CN1279638C

CN1279638C - Hydrogen-absorbing alloy, method of surface modification of the alloy, negative electrode for battery and alkaline secondary battery

Info

Publication number: CN1279638C
Application number: CNB2003101197894A
Authority: CN
Inventors: 河野龙兴; 鹤田慎司; 神田基
Original assignee: Toshiba Corp
Current assignee: Toshiba Corp
Priority date: 1996-01-22
Filing date: 1997-01-22
Publication date: 2006-10-11
Anticipated expiration: 2017-01-22
Also published as: CN1279637C; CN1154198C; KR100241813B1; CN1505190A; KR970060558A; CN1162197A; CN1505189A

Abstract

A hydrogen-absorbing alloy which is excellent in stability in an aqueous solution and in mechanical pulverizability is disclosed. This hydrogen-absorbing alloy contains an alloy represented by the following general formula (I): <paragraph lvl=''0''><in-line-formula>Mg2M1y (I)</in-line-formula>wherein M1 is at least one element selected (excluding Mg, elements which are capable of causing an exothermic reaction with hydrogen, Al and B) from elements which are incapable of causing an exothermic reaction with hydrogen; and y is defined as 1<y<=1.5.

Description

Hydrogen bearing alloy, the battery cathode that contains hydrogen bearing alloy and alkaline secondary cell

The application is that the application number submitted on January 22nd, 1997 is the dividing an application of application of 97100420.X.

The present invention relates to a kind of hydrogen bearing alloy, hydrogen bearing alloy surface modifying method, battery and alkaline secondary cell negative electrode.

As everyone knows, hydrogen bearing alloy can stably absorb and store the tens thousand of times of hydrogen to own vol (calculating with gas under the normal temperature and pressure), can be safely, easily store, keep and transport hydrogen as the energy, so it has caused people's attention as a kind of promising material.By making full use of the performance difference between the different hydrogen bearing alloys, it also to be studied in the application aspect chemical heat pump and the compressor, some of them have developed into practical stage.In recent years, extensively carried out hydrogen bearing alloy electrode material and metal hydride secondary battery (as, nickel-hydrogen secondary cell) application study of aspect, this is because hydrogen bearing alloy is being inhaled, had high catalytic activity in the hydrogen discharge reaction, and is that the hydrogen that relies on storage to go in the alloy comes work as the battery of the energy.

In view of the physics and the chemical characteristic of hydrogen bearing alloy probably is applied in numerous areas, therefore, it is regarded as one of important raw and processed materials of futurity industry.

The metal that can inhale hydrogen with constituting hydrogen adsorbing alloy can be can with the simple substance material of hydrogen generation exothermic reaction, can form the metal (as platinum family element, group of the lanthanides family element and alkali earth metal) of stable compound with hydrogen; Or comprise the alloy that above-mentioned metal and other metal form.One of advantage of this alloy is that the bond strength of metal and hydrogen can suitably be weakened, and the result inhales hydrogen discharge reaction and relatively easily carries out.Two of advantage is that alloy inhales, puts the variation (glacing flatness) and the similar performance of relation (equalizing pressure, plateau pressure) between hydrogen characteristic and the required Hydrogen Vapor Pressure of reaction, equilibrium region scope (land regions), the equalizing pressure in suction hydrogen process and all can improve.Three of advantage is to improve the physics and the chemical stability of alloy.

Conventional hydrogen bearing alloy is divided into following a few class: promptly, and (1) AB ₅(as LaNi ₅, CaNi ₅); (2) AB ₂Type is (as MgZn ₂, ZrNi ₂); (3) AB type (as TiNi, TiTe); (4) A ₂Type B is (as Mg ₂Ni, Ca ₂Fe) and other type (as cluster), wherein A represent can and the metallic element of hydrogen generation exothermic reaction, B is other kind metallic element.The LaNi of (1) type wherein ₅, some alloys of the Laves phase alloy of (2) type and (3) type can react and stable chemical performance with hydrogen, at normal temperatures so the candidate material that they are used as electrode for secondary battery obtains broad research.

But A ₂There is following point in the Type B hydrogen bearing alloy.That is alloy has very strong absorption hydrogen ability, in case almost can not discharge after hydrogen is adsorbed; Suction, hydrogen discharge reaction can only (about 200-300 ℃) just can carry out when temperature is quite high; Even react, reaction speed is very slow; Chemical stability is quite low, especially in the aqueous solution; This alloy is sticking usually and hard, therefore is difficult to pulverize.According to these facts,, seldom use A except storing and transportation of hydrogen ₂The Type B hydrogen bearing alloy.Although it is big that it inhales hydrogen volume than other class type hydrogen storage alloy, be calculated by weight to two to several times.If so above-mentioned A ₂The problem that the Type B hydrogen bearing alloy exists is resolved, and it can not only equally with other hydrogen bearing alloy be used in same field so, but also may open up the purposes in other frontier.

By the way, up to this point, the theoretical paper of more existing (5) class type hydrogen storage alloys, but almost still do not have the actual report that uses and test.

Simultaneously, the open 6-768.7 of Japan Patent has disclosed a kind of Mg base hydrogen bearing alloy, is expressed from the next: Mg _2-xNi _1-yA _yB _x(wherein x is 0.1-1.5; Y is 0.1-1.5; A is a kind of element among Sn, Sb and the Bi; B is a kind of element among Li, Na, K and the Al).The example of this alloy has:

Mg _1.5Al _0.5Ni _0.7Sn _0.3Or Mg _1.8Al _0.2

Ni _0.8Sn _0.2。In this publication, also disclosed the negative material that this hydrogen bearing alloy can be used as alkaline secondary cell.But, because the hydrogen bearing alloy that this publication discloses is mainly A ₂The Type B alloy, very poor at its hydrogen storage property of normal temperature scope.Therefore, put hydrogen for it can be inhaled at normal temperatures and pressures, the method that discloses in this publication is at the surface coverage layer of metal nickel compound of this hydrogen bearing alloy or the gloomy compound of stone.

As above-mentioned explanation, A ₂Type B hydrogen bearing alloy and other class type hydrogen storage alloy have distinct characteristics: in light weight, that capacity reaches the cost of raw material greatly is low.Because it mainly is made up of alkaline-earth metal and iron family element.But A ₂The Type B hydrogen bearing alloy also has above-mentioned said variety of issue simultaneously.

Therefore, one of the object of the invention provides a kind of hydrogen bearing alloy, its stable chemical performance (especially in the aqueous solution), and easy mechanical crushing.

Another purpose of the present invention provides a kind of hydrogen bearing alloy, its hydrogen sucking function, and hydrogen sucking function especially at room temperature is improved.

Still a further object of the present invention provides the surface-active method of a kind of change hydrogen bearing alloy, makes hydrogen bearing alloy fully inhale hydrogen easily.

The further purpose of the present invention provides the alkaline secondary cell that the very stable secondary battery negative pole of electrode reaction and charge and discharge cycle performance are improved.

Further object of the present invention is the method that a kind of evaluation of exploitation contains Mg hydrogen bearing alloy inefficacy speed.Based on the method, can provide to be fit to the actual negative pole that uses, in electrode reaction with have in the alkaline secondary cell of this kind negative pole, its invertibity and stability are very high.

That is,, provide the hydrogen bearing alloy of the alloy that contains following general formula (2) expression by the present invention:

Mg ₂M1 _y

Wherein M1 be selected from (except that Mg, can with element, Al and the B of the anti-heat of hydrogen generation heat release) can not with at least a element in the element of hydrogen generation exothermic reaction; The scope of y is 1＜y≤1.5.

By the present invention, further provide the hydrogen bearing alloy of the alloy that contains following general formula (II) expression:

Mg _2-xM2 _xM1 _y ……(II)

Wherein M2 be selected from (except that Mg) can and the element of element, Al and the B of hydrogen generation exothermic reaction in be selected from element; M1 be at least a can not with at least a element in the element (except that Mg and M2) of hydrogen generation exothermic reaction, the scope of x is 0＜x≤1.0; The scope of y is 1＜y≤2.5.

In addition, by the present invention, also provide the hydrogen bearing alloy of the alloy that contains following general formula (III) expression:

M _2-xM2 _xM1 _y ……(III)

Wherein M is at least a element that is selected among Be, Ca, Sr, Ba, Y, Ra, La, Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu, Ti, Zr, Hf, Pd and the Pt; M2 be selected from can and element, Al and the B of hydrogen generation exothermic reaction at least a element (except that M) M1 be selected from can not with at least a element in the element (except that Mg and M2) of hydrogen generation exothermic reaction; The scope of x is 0.01＜x≤1.0; The scope of y is 0.5＜y≤1.5.

In addition, by the present invention, further provide the method that comprises with the step on the solution-treated hydrogen bearing alloy surface of containing the R-X compound, wherein R represents alkyl, alkenyl, alkynyl, aryl or its substituting group; X represents halogen.

Have, by the present invention, further provide a kind of hydrogen bearing alloy, in adopting the X-ray diffraction spectrogram of CuK α as radiation source, the scope of half-breadth (half-width) Δ (2 θ) at least one peak is 0.2 a °≤Δ (2 θ)≤50 ° in three highest peaks.

In addition, by the present invention, further provide to contain 10% or the hydrogen bearing alloy of more Mg, in adopting the X-ray diffraction spectrogram of CuK α as radiation source, near half-breadth Δ (2 θ at the peak that occurs 20 ° ₁) scope be 0.3 °≤Δ (2 θ ₁)≤10 °; Near the scope of the half-breadth Δ (2 θ 2) at the peak that occurs 40 ° is 0.3 a °≤Δ (2 θ 2)≤10 °.

In addition,, also provide the method for hydrogen bearing alloy surface modification, comprised the step of carrying out mechanical treatment under a vacuum or inert gas or the nitrogen atmosphere by the present invention.

Also have,, further provide the method for hydrogen bearing alloy surface modification, comprise the step of under vacuum or inert gas or the nitrogen atmosphere hydrogen bearing alloy being carried out mechanical treatment by the present invention.

Have, by the present invention, provide a kind of battery cathode, this negative pole comprises the hydrogen bearing alloy of the alloy that contains following general formula (I) expression

Mg ₂M1 _y ……(I)

Wherein M1 be selected from can not with at least a element (except that element, Al and the B of Mg and Hydrogen Energy generation exothermic reaction) in the element of hydrogen generation exothermic reaction; The scope of y is 1＜y≤1.5.

By the present invention, a kind of alkaline secondary cell further is provided, the negative pole of this battery comprises the hydrogen bearing alloy of the alloy that contains following general formula (I) expression:

Mg ₂M1y ……(I)

Wherein M1 be selected from can not with at least a element (except that element, Al and the B of Mg, energy and hydrogen generation exothermic reaction) of hydrogen generation exothermic reaction; The scope of y is 1＜y≤1.5.

By the present invention, a kind of battery cathode is provided, this negative pole comprises the hydrogen bearing alloy of the alloy that contains following general formula (II) expression;

Mg ₂-xM2xM1y ……(II)

Wherein M2 be selected from can and element, Al and the B (except that Mg) of hydrogen generation exothermic reaction at least a element; M1 be selected from can not with at least a element in the element (except that Mg and M2) of hydrogen generation exothermic reaction; The scope of x is 0＜x≤1.0; The scope of y is 1＜y≤2.5.

By the present invention, a kind of alkaline secondary cell further is provided, the negative pole of this battery comprises the hydrogen bearing alloy of the alloy that contains following general formula (II) expression

Mg _2-xM2xM1y ……(II)

By the present invention, the battery cathode that contains hydrogen bearing alloy is provided, this hydrogen bearing alloy is in adopting the X-ray diffraction spectrogram of CuK α as radiation source, and the scope of the half-breadth Δ (2 θ) at least one peak is 0.2 a °≤Δ (2 θ)≤50 ° in three highest peaks.

By the present invention, a kind of alkaline secondary cell further is provided, the negative pole of this battery contains a kind of hydrogen bearing alloy, this hydrogen bearing alloy is in adopting the X-ray diffraction spectrogram of CuK α as radiation source, and the scope of the half-breadth Δ (2 θ) at least one peak is 0.2 a °≤Δ (2 θ)≤50 ° in three highest peaks.

By the present invention, a kind of battery cathode is provided, this negative pole comprises the hydrogen bearing alloy that contains the Mg element, wherein, when this negative pole soaks in the alkaline aqueous solution of 6N-8N alkali metal hydroxide, have under (a) normal temperature, magnesium ion enter eluting rate in the aqueous solution be no more than the 0.5mg/kg alloy/hour, be no more than in the time of 60 ℃ the 4mg/kg alloy/hour, and (b) under the normal temperature, the component element of alloy enter eluting rate in the aqueous solution be no more than the 1.5mg/kg alloy/hour, be no more than in the time of 60 ℃ the 20mg/kg alloy/hour.

By the present invention, a kind of alkaline secondary cell also is provided, this battery comprises the negative pole that is positioned over the hydrogen bearing alloy that contains the Mg element in the shell, at staggered relatively anodal of shell and be arranged between the two barrier film, and to wherein injecting electrolyte;

Wherein, filling and hermetic electrolyte liquid in battery case, 30 days or the longer time after, the Mg ion concentration is no more than 2.2mg/L in the electrolyte.

By the present invention, further provide the hydrogen bearing alloy of the alloy that contains following general formula (V) expression:

(Mg _1-xM3 _x)20- _yM4 ……(V)

Wherein M4 is at least a element that is selected among Ni, Fe, Co, Cu, Zn, Sn and the Si; M3 is at least a element that is selected from the electronegativity element higher than Mg (except that the M4 element); The scope of x is 0＜x＜0.5; The scope of y is 0≤y＜18.

In addition, by the present invention, provide the hydrogen bearing alloy of the alloy that contains following general formula (VI) expression:

(Mg _1-xM5 _x) _20-yM6 ………(VI)

Wherein M5 is selected from doubly at least a element of 1-1.5 that atomic radius is Mg (electronegativity than the high element of Mg except); M6 is at least a element that is selected among Ni, Fe, Co, Cu, Zn, Sn and the Si; The scope of x is 0＜x＜0.5; The scope of y is 0≤y＜18.

In addition, by the present invention, also provide a kind of hydrogen bearing alloy, it is to be formed by the mixture that includes following component:

A kind of alloy with storage hydrogen character and

At least a additive, this additive be selected from (a) IA family element, IIA family element, group III A element, IVA family element, VA family element, VIA family element, VIIA family element, VIIIA family element, IB family element, IIB family element, IIIB family element, IVB family element, VB family element and, the alloy that is combined to form by arbitrary element in (a) of at least a element in the group vib element, (b) and (c) oxide of arbitrary element in (a);

This mixture vacuum or inert gas or nitrogen atmosphere under carry out mechanical treatment.

In addition, by the present invention, further provide a kind of hydrogen bearing alloy, this hydrogen bearing alloy comprises:

A kind of alloy with storage hydrogen character; With

The additive of 0.01-50% (volume), it is that flat footpath particle diameter is the powder of 0.01-100 μ m, and be scattered in the alloy, be selected from least a element in (a) IA family element, IIA family element, group III A element, IVA family element, VA family element, VIA family element, VIIA family element, VIIIA family element, IB family element, IIB family element, IIIB family element, IVB family element, VB family element and the group vib element; (b) alloy that is combined to form by arbitrary element in (a) and (c) oxide of arbitrary element in (a);

In addition, by the present invention, further provide a kind of alkaline secondary cell, the negative pole of this battery comprises the hydrogen bearing alloy of the alloy that contains following general formula (V) expression:

(Mg _1-xM3 _x) _20-yM4 ……(V)

In addition, by the present invention, provide a kind of alkaline secondary cell, the negative pole of this battery comprises the hydrogen bearing alloy of the alloy that contains following general formula (VI) expression

(Mg _1-xM5 _x) _20-yM6 ……(VI)

Wherein M5 is selected from least a in the 1-1.5 element (removing the element higher than Mg electronegativity) doubly that atomic radius is Mg; M6 is at least a element that is selected among Fe, Ni, Co, Cu, Zn, Sn and the Si; The scope of x is 0＜x＜0.5; The scope of y is 0≤y＜18.

In addition, by the present invention, further provide a kind of alkaline secondary cell, the negative pole of this battery contains hydrogen bearing alloy, and this hydrogen bearing alloy is formed by a kind of mixture, and this mixture comprises:

A kind of alloy with suction hydrogen character; With

At least a additive, this additive are selected from alloy that at least a element in (a) IA family element, IIA family element, IIIA family element, IVA family element, VA family element, VIA family element, VIIA family element, VIIIA family element, IB family element, IIB family element, IIIB family element, IVB family element, VB family element and the group vib element, (b) be combined to form by arbitrary element in (a) and (c) by the oxide of arbitrary element in (a);

This mixture is carried out mechanical treatment under vacuum or inert gas or nitrogen atmosphere.

In addition, by the present invention, also provide to comprise a kind of alkaline secondary cell, the negative pole of this battery contains hydrogen bearing alloy, and this hydrogen bearing alloy is formed by a kind of mixture, and this mixture comprises:

A kind of alloy with suction hydrogen character; With

The additive of 0.01-50% (volume), it is that average grain diameter is the powder of 0.01-100 μ m, and be scattered in the alloy, be selected from least a element in (a) IA family element, IIA family element, IIIA family element, IVA family element, VA family element, VIA family element, VIIA family element, VIIIA family element, IB family element, IIB family element, IIIB family element, IVB family element, VB family element and the group vib element; (b) alloy that is combined to form by arbitrary element in (a); (c) oxide of arbitrary element in (a).

Other purpose of the present invention and advantage will propose in will narrating in the back, say to a certain extent, and promptly be conspicuous from specification, also can obtain by enforcement of the present invention.Objects and advantages of the present invention can also draw in conjunction with claims.

Brief description of drawings

The accompanying drawing of a book part has illustrated the preferred embodiments of the invention as an illustration, and with the detailed description of top general introduction and the following embodiment preferred that will provide, is used to illustrate principle of the present invention.

Fig. 1 is the Mg/Ni alloy phase diagram.

Fig. 2 is the La/Ni alloy phase diagram.

Fig. 3 is the part perspective view of cylinder type secondary battery of the present invention.

Fig. 4 is Mg ₂Ni _yGraph of a relation between middle y value and the Mg elution amount.

Fig. 5 can bear the part perspective view of the method for testing of maximum stress for the explanation alloy strip.

Fig. 6 for the suction of explanation in the example of the present invention, put the block diagram of hydrogen process temperature sweep type measurement mechanism.

Fig. 7 raises and pressure variation relation figure (pressure reduces and the hydrogen of hydrogen adsorbing alloy is directly proportional) with the temperature of comparative example 3 and 17 for hydrogen bearing alloy example 16 and 17

Fig. 8 is that the temperature of hydrogen bearing alloy example 18 and comparative example 3 raises and pressure variation relation figure

The Mg of the unmodified and surface modification in surface when Fig. 9 is 25 ℃ ₂The Ni hydrogen bearing alloy is inhaled pressure variation in the hydrogen process.

Figure 10 is the relation between the cycle-index of simulated battery of example 151 negative poles and comparative example 20 negative poles.

Figure 11 is the cycle-index and the discharge capacity graph of a relation of the simulated battery of example 242 negative poles and comparative example 20 negative poles

Figure 12 contains Mg for mechanical treatment ₂The mixture of Ni and Ni and the X-ray diffractogram of the hydrogen bearing alloy that obtains.

The alloy that contains following formula (I) representative according to a kind of hydrogen bearing alloy of one embodiment of the invention:

Mg ₂M1 _y ……(I)

M1 is at least a element that is selected from the element (except that element, Al and the B of Mg, energy and hydrogen generation exothermic reaction) of discord hydrogen generation exothermic reaction; The scope of y is 1＜y≤1.5.

The example of M1 element is Fe, Ni, Co, Ag, Cd, Mn, In, Se, Si, Ge and Pb.M1 can be a single-element, also can be the mixture that contains two or more these elements.The preferred example of M1 is the electronegativity element higher than Mg, i.e. Fe, Ni, Co, Ag, Cd, Mn, In, Se, Sn, Ge and Pb.Especially, the hydrogen bearing alloy that contains the such iron family element of Fe, Ni, Co is preferred, because this class alloy stable performance and have the ability that hydrogen is put in good suction.Most preferred M1 element is the electronegativity element higher than Mg.If this element is 10% (atom) or the alloy Mg that forms still less the time with pure Mg addition _1-wM _1wThe unit cell volume of (0＜w≤0.1) is littler than pure Mg, and the example of these elements is: Mn, Ag, Cd and In.

Table 1 is the alloy that formed by above-mentioned substituted element and Mg and the unit cell volume of pure Mg.Adopt the alloy powder X-ray diffraction method, obtain lattice constant, calculate the data in the table 1, suppose that these crystal structures all are the hexagonal crystal systems as pure Mg according to diffraction pattern.

In addition, if Mg _1-wM1 _wMutually middle w value surpasses 0.1, Mg _1-wM1 _wThe phase crystal structure is different with hexagonal crystal structure, because addition element M1, the variation of Mg unit cell volume can't accurately be estimated.Therefore, the scope of w is defined as 0＜w≤0.1.But, if even w surpasses 0.1, Mg _1-wM1 _wStill keep hexagonal crystal structure mutually, can surpass 0.1 scope three meaning use element M 1 in the w value so.Table 1

Alloying component	Unit cell volume (nm ³)
Alloying component	Unit cell volume (nm ³)	Mg (pure Mg)	0.0462
Mg _0.99Ag _0.01	0.0459	Mg (pure Mg)	0.0462
Mg _0.99Ag _0.01	0.0459	Mg _0.9Cd _0.1	0.0452
Mg _0.95In _0.05	0.0460	Mg _0.9Cd _0.1	0.0452

The reason of y value within 1＜y≤1.5 scopes that limits M1 element in the general formula (I) can be interpreted as described below and (a) influence to hydrogen; (b) relevant to chemical stability such as reducibleness with machinability.

(a) to the influence of hydrogen

If have the Mg of hydrogen absorption capacity and the ratio of M1 (almost can not form hydride) to be made as 2: y should be y=1 according to stoichiometry viewpoint y value and (that is, is Mg ₂M1).But, if in fact the y value is made as 1 or less than 1, the problem of chemical stability and mechanical crushing aspect may appear in the alloy that obtains, the theme that the present invention that Here it is will solve.On the contrary, if the y value is excessive, some other undesirable problem may produce in actual use.For example, if the y value is used microscopic examination greater than 2, such result appears in the alloy that obtains, and promptly no longer is Mg ₂The crystal structure of M1 type, and become MgM1 ₂Type alloy, i.e. Laves phase.This MgM1 ₂The type alloy also has hydrogen absorption capacity, still, calculates MgM1 by weight ₂Type absorption hydrogen capacity only is Mg ₂40～70% of M1 type alloy.Therefore excessive y value is disadvantageous aspect capacity density.

(b) to the influence of chemical stability and reducibleness

Usually, only as Mg: M1=2: in the time of 1, just form Mg ₂The M1 type hydrogen storage alloy.Therefore, if some composition fluctuation keeps Mg so fully as Mg or the M1 increase or the minimizing of alloy part ₂M1 type structure is impossible, and its mechanism can be explained with reference to following phasor.Mg shown in Figure 1 ₂Ni (Mg-Ni system) phasor is Mg ₂The exemplary of M1 type alloy.Figure 2 shows that AB ₅Type alloy LaNi ₅(La-Ni system) phasor.These phasors occur in " binary alloy phase diagram " (american society for metals, nineteen ninety version).From Fig. 1,2 Mg as can be seen ₂Ni is to be to be represented by a vertical line in the phasor at Mg-Ni, and Lavis is to be represented by some enlarged area in the phasor at La-Ni.This can ascribe to is making LaNi ₅In the production process of alloy, even bath component virtually completely can be produced and LaNi when the regulation composition fluctuates up and down ₅Identical alloy.But for Mg ₂M1 if bath component is formed fluctuation up and down in regulation, produces Mg ₂Ni solid solution and unnecessary composition two-phase eutectic, that is, represent the equation Mg of positive number: Ni=2 at Y: among the Y, if Y＜1, Mg ₂Ni and excessive Mg form eutectic and dissolve each other; If Y＞1, Mg ₂Ni and Mg ₂Ni ₂Or Mg ₂Ni, Mg ₂, Ni ₂Form eutectic with Ni.

The chemical stability of Mg such as anticorrosive and non-oxidizability are not as Ni, toughness and plasticity ratio Ni height.On the other hand, Mg ₂Ni and Mg ₂Ni ₂Compare Mg ₂The resistivity of Ni in water and oxygen is stronger, is particularly inhaling under the hydrogen state, and the polarizability of Mg2Ni structure (ionization) is higher.Therefore, y＜1 o'clock, even reduce the y value, there is high viscosity Mg in the alloy grain border, and enables to resist mechanical stress, but chemical stability and comminuted all very poor.On the contrary, when y＞1, discord Mg dissolves each other Mg ₂The Ni surface is by Mg ₂Ni or Ni surround, thereby have improved chemical stability.In addition, when y＞1, the alloy that obtains has very high rigidity, but crystal boundary contains the unnecessary low viscosity Ni of enrichment mutually, may cause brittle fracture easily.So adopting mechanical means to pulverize alloy may carry out easily.

Explain that as above-mentioned when Mg and M1 component ratio are expressed as Mg: M1=2: during y, one of condition that realizes improving mechanical crushing is y＞1.Simultaneously, do not rely on MgM1 in order to keep the alloy available capacity ₂Phase, the upper limit of y should be set at 1.5, and in order to guarantee alloy stability, the scope of y should be made as: 1＜y≤1.5 in addition.

When Mg and M1 component ratio are expressed as Mg: M1=2: during y, the lower limit of y surpasses 1, satisfies in theory.But in fact alloy exists composition fluctuation and segregation, so one of condition that obtains alloy is that the every part of alloy all is that the even one-tenth by y＞1 is grouped into.Particularly (a) if alloy with so-called method for annealing production, wherein, the melt of component element is poured in the mold container after with induction furnace or arc furnace fusing in the identical mode of preparation common metal ingot casting, this moment, the y value was preferably 1.05 or more; (b) if alloy is like this preparation, be about to above-mentioned melt and one low temperature/high heat capacity material such as transfer roller or liquid and contact and make melt quenching, or make above-mentioned melt cast Quench in air or in the liquid and produce alloy, the y value is preferably 1.02 or more; And (c) by prescription the mixing of several simple metal or alloy with the alloy that formation has predetermined composition, then, do not adopt smelting process to make alloy mixture hot rolling, hot pressing or mechanical mixture (mechanical alloying method); The y value is preferably 1.02 or more.

With other method ratio, because method (a) cooling stage is slower, the easier generation of segregation, it is very difficult to obtain uniform alloy, but because its production method is quite simple, it has obtained using the most widely.According to (c) method, the uniformity of alloy more is subject to the working condition influence, so according to working condition, the lower limit of y needs to improve.On the contrary, can obtain mass ratio alloy uniformly according to method (b).Produce the after annealing processing method if adopt the optimized production conditioned disjunction to adopt, can improve the uniformity of composition and tissue, work as the y value so and remain on 1.01 or higher, target of the present invention may reach.Judge that uniformity can adopt various surface analysis methods (as EDX, X ray spectroscope or EPMA that energy disperses, electro-probe micro analyzer), utilizes electron microscope or X-ray diffraction method.For example according to surface analysis method, to the component distributing test of alloy part structure, wherein 90% or the more parts surface by same phase composition, this alloy can be considered as uniformly.On the other hand, according to the X-ray diffraction method, the diffraction maximum of Mg or M1 or single-element size and the ratio that derives between the diffraction maximum size of these elements are represented by percentage in the foundry alloy, if ratio is no more than overall 5% uniformity that can be considered as alloy.

According to these results, even the alloy of producing with other production method, the lower range that can expect y is 1.01 to 1.10.

Hydrogen bearing alloy of the present invention can be the alloy by general formula (I) expression, and it contains and surpasses 20% (atom) VB family and group vib element.

As above-mentioned explanation, hydrogen bearing alloy of the present invention comprises the alloy by general formula (I) expression: Mg ₂M1 _y(wherein M1 be can not with the element (except that element, Al and the B of Mg, energy and hydrogen generation exothermic reaction) of hydrogen generation exothermic reaction at least a, the scope of y is 1＜y≤1.5).That is, the hydrogen bearing alloy shown in the general formula (I) is characterised in that y or M1 such as Ni greater than 1 less than 1.5, and its chemical property is stable, has excellent mechanical crushing, shows A ₂Type B alloy such as Mg ₂Ni intrinsic high hydrogen absorption capacity.

Therefore, also can keep excellent hydrogen absorption capacity according to hydrogen bearing alloy of the present invention even when the hydrogen reaction of the oxidizing gas such with containing a small amount of oxygen or water vapour.In addition,, also be difficult to change its hydrogen absorption capacity, enlarged the scope of application of alloy like this even hydrogen bearing alloy according to the present invention contacts with the aqueous solution.

Further, in general, owing to inhale, put lattice dilatation and contraction that hydrogen causes hydrogen bearing alloy gradually, thereby cause the hydrogen bearing alloy physical property to change (as bulk density, contact resistance and conductivity).If the variation of these physical propertys has caused problem, can adopt the alloy powder of pulverizing in advance to avoid these problems.Because the hydrogen bearing alloy that the present invention proposes is than the habitual Mg that resembles ₂This A of Ni ₂The easier efflorescence of Type B alloy, the problem of above-mentioned proposition solves easily.

As above-mentioned explanation, carry out preliminary treatment before use by the represented hydrogen bearing alloy of the present invention of general formula (I) and carry out easily, and in use can control reliably easily.Therefore, be particularly suitable as the electrode material of secondary cell by the hydrogen bearing alloy of general formula (I) expression.

The hydrogen bearing alloy of another embodiment of the present invention contains the alloy by following formula (II) representative:

Mg _2-xM2 _xM1 _y ……(II)

Wherein M2 be selected from can and element, Al and the B (except that Mg) of hydrogen generation exothermic reaction at least a element; M1 is at least a element (except Mg and the M2) that is selected from the element of discord hydrogen generation exothermic reaction; The scope of x is 0＜x≤1.0; The scope of y is 1＜y≤2.5.

As the example of M1, can select same element for use with reference to general formula (I).

Can and the example of hydrogen generation exothermic reaction or element (except that Mg) that can spontaneous formation hydrogen compound be alkali earth metal such as Be, Ca and Ba; Rare earth element such as Y, Ra, La, Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Lu; IVA family element such as Ti, Zr and Hf; VIIIA family element such as Pd and Pt.M2 can use the mixture of single-element or two kinds of more kinds of these elements.

M2 preferably from Al, B and can and hydrogen generation exothermic reaction and than electronegativity than selecting (except that Mg) the higher element of Mg, promptly M2 is at least a element that is selected among B, Be, Y, Pd, Ti, Zr, Hf, Th, V, Nb, Ta, Pa and the Al.If the selected element of M2 has higher electronegativity than Mg, can reduce electronegativity difference between alloy and the hydrogen, and make the hydrogen instability on the lattice position, thereby improve the hydrogen sucking function of alloy.Particularly, this alkaline-earth metal energy of Be and Mg form the alloy of stable chemical performance.On the other hand, Ti, the Zr and the Hf that belong to IVA family element have very high activity to hydrogen, can form hydride.

In addition, M2 preferably selects (except that Mg) from the element of Al, B and energy and hydrogen generation exothermic reaction, if in pure Mg, adds 10% (atom) or M2 still less, the Mg of the alloy that obtains _1-wM1 _wThe unit cell volume of phase (0＜w≤0.1) is littler than pure Mg, i.e. at least a element that should preferably select from Li and Al of M2.

According to the scope of x in the following true restriction general formula (II), promptly when x greater than 1.0 the time, Mg ₂M1 _yHydrogen sucking function (glacing flatness of hydrogen absorption capacity, land regions and invertibity) very poor, in some cases, can not keep crystal structure, so the scope of x is preferably 0.05≤x≤0.5.

According to the scope of y in the following true restriction general formula (II), promptly be set at greater than 1 the time when the y value, the explanation of the alloy that can represent with reference to mutual-through type (I) can obtain same advantage.On the other hand, when the y value surpasses 2.5, not only the hydrogen absorption capacity of hydrogen bearing alloy reduces, crystal structure itself variation simultaneously, so y preferably should be 1.01≤y≤1.5, more preferably 1.02≤y≤1.5 are preferably 1.05≤y≤1.5 especially.

Hydrogen bearing alloy of the present invention by general formula (II) expression preferably contains 20% (atom) VB family or group vib element at most.

As above-mentioned explanation, with the hydrogen bearing alloy of the present invention of general formula (II) expression: Mg _2-xM2 _xM1 _y(wherein M2 is at least a element among energy and hydrogen generation exothermic reaction element, Al and the B (except that Mg); M1 be can not with at least a element in the element (except that Mg and M2) of hydrogen generation exothermic reaction; The scope of x is 0＜x≤1.0; The scope of y is 1＜y≤2.5).Promptly because the hydrogen bearing alloy of being represented by general formula (II) is characterised in that part Mg is replaced by the element such as the Al of M2 representative, with general A ₂The Type B hydrogen bearing alloy is compared, and particularly at a lower temperature, its hydrogen sucking function is improved, and keeps A simultaneously ₂The Type B hydrogen bearing alloy intrinsic high hydrogen absorption capacity.And by the represented hydrogen bearing alloy of general formula (II) compare hydrogen absorption capacity bigger (by weight calculate) with general rare earth based hydrogen bearing alloy, production cost is lower, weight is lighter.And, the y value that is characterised in that its M1 such as Ni with the hydrogen bearing alloy of general formula (II) expression greater than 1 less than 2.5, so stable chemical performance, mechanical crushing excellent performance.

Therefore, hydrogen bearing alloy of the present invention is even can keep bigger hydrogen absorption capacity in also during with the hydrogen reaction that contains a small amount of as oxygen or this product oxidizing gas of water vapour.Have, even when contacting with the aqueous solution, the hydrogen absorption capacity of oxygen uptake alloy of the present invention is difficult to change, and has therefore expanded the purposes of alloy again.

As above-mentioned explanation, the hydrogen bearing alloy of being represented by general formula (II) of the present invention can reduce suction hydrogen temperature, can keep A simultaneously ₂The Type B hydrogen bearing alloy intrinsic high hydrogen absorption capacity.In addition, anticipate before use and use in the control of condition carry out easily.So, be particularly suitable as the electrode material of secondary cell by the hydrogen bearing alloy of general formula (II) expression.

The hydrogen bearing alloy of another embodiment of the present invention contains the alloy of following formula (III) expression:

M _2-xM2 _xM1 _y ……(III)

Wherein M is at least a element that is selected among Be, Ca, Sr, Ba, Y, Ra, La, Ce, Pr, Pm, Sm, En, Gd, Tb, Dy, Ho, Er, Tm, Lu, Ti, Zr, Hf, Pd and the Pt; M2 be selected from can and element, Al and the B (except that M) of hydrogen generation exothermic reaction at least a element; M1 be selected from can not with at least a element in the element (except that Mg and M2) of hydrogen generation exothermic reaction; The scope of x is 0.01＜x≤1.0; The scope of y is 0.5＜y≤1.5.

As the example of M2, can select same element for use with reference to general formula (II).

The example of the preferred compositions of M, M2 and M1 is to comprise that Zr is M, and Fe is that M1, Cr are the ternary alloy three-partalloy of M2 and comprises that Zr is that M, Ni and Co are that M1, V are the quaternary alloy of M2.

Based on the following fact, the scope of y and x in the restriction general formula (III).That is, if y is less than 0.5, M, M1 will separate out mutually with M2, hydrogen adsorbing alloy intrinsic characteristic to lose, the chemical property of hydrogen bearing alloy becomes unstable simultaneously, the lower limit that therefore preferably sets the y value is not lower than 1 (as 1.01).In addition, the y value surpasses at 2.0 o'clock, and hydrogen bearing alloy not only hydrogen absorption capacity reduces, and crystal structure changes, so the y value upper limit preferably is decided to be 1.5.

If the x value is less than 0.01, hydrogen bearing alloy no longer has excellent low temperature and inhales hydrogen character, on the other hand, when x greater than 1.0 the time, not only crystal structure changes hydrogen bearing alloy but also A ₂The inherent characteristic of Type B alloy disappears, so the preferable range of x value is 0.05 to 0.5.

By above-mentioned explanation, hydrogen bearing alloy of the present invention comprises the alloy by general formula (III) expression:

M _2-xM2 _xM1 _y, wherein M is at least a element that is selected among Be, Ca, Sr, Ba, Y, Ra, La, Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu, Ti, Zr, Hf, Pd and the Pt; M2 be selected from can and element, Al and the B of hydrogen generation exothermic reaction at least a (except that M) element; M1 is selected to provide at least a element in the element (except that Mg and M2) of thermal response with hydrogen; The scope of x is 0.01＜x≤1.0; The scope of y is 0.5＜y≤1.5.Promptly because the hydrogen bearing alloy of representing with general formula (III) is characterised in that part M such as Zr are replaced by element such as A1 by the M2 representative, with general A ₂The Type B hydrogen bearing alloy is compared, and its hydrogen sucking function especially can be improved in the performance aspect the reduction suction hydrogen temperature, has kept A simultaneously ₂The Type B hydrogen bearing alloy intrinsic high hydrogen absorption capacity.In addition by the hydrogen bearing alloy of general formula (III) expression than rare earth based hydrogen bearing alloy hydrogen absorption capacity bigger (calculating by weight), cost is lower, weight is lighter.

Therefore, can reduce by the hydrogen bearing alloy of the present invention of general formula (III) expression and inhale the hydrogen temperature and keep A simultaneously ₂The Type B hydrogen bearing alloy intrinsic big hydrogen absorption capacity.In addition, because the hydrogen bearing alloy of being represented by general formula (III) can maintain A ₂The Type B hydrogen bearing alloy intrinsic high hydrogen absorption capacity, so this alloy is particularly suitable as the electrode material of secondary cell.

The hydrogen bearing alloy of another embodiment of the present invention comprises the alloy by following general formula (V) expression:

(Mg _1-xM3 _x) _20-yM4 ……(V)

Wherein M4 is at least a element that is selected among Ni, Fe, Co, Cu, Zn, Sn and the Si; M3 is at least a element that is selected from the electronegativity element higher than Mg (except that M4); The scope of x is 0＜x＜0.5; The scope of y is 0≤y＜18.

Example as the electronegativity M3 element higher than Mg (except that the M4 element) is Al (1.5), Mn (1.5), Ta (1.5), V (1.6), Cr (1.6), Nb (1.6), Ga (1.6), In (1.7), Ge (1.8), Pb (1.8), Mo (1.8), Re (1.9), AG (1.9), B (2.0), C (2.5), P (2.1), Ir (2.2), Rh (2.2), Ru (2.2), Os (2.2), Pt (2.2), Au (2.4), Se (2.4), S (2.5), Sc (1.3), Zr (1.4), Hf (1.3), Pd (1.8) and Tl (1.8).The electronegativity data of parenthetic each metallic element of data representation, it is that polarity number from each metallic element obtains, and can be used alone or in combination these elements.

Based on the following fact, limit x and the scope of y in general formula (V).That is, when x surpasses 0.5, the changes in crystal structure of alloy causes the decreased performance of Mg base alloy during Datong District very much, so the preferable range of x is 0.01≤x≤0.4, x is limited in this scope, can increase hydrogen.On the other hand, when the y value surpassed 18, reduced the position of storage hydrogen in the alloy, so hydrogen decline, so the preferable range of y value is 1≤y≤17.5.

The hydrogen bearing alloy that contains the alloy of general formula (V) expression and meet above-mentioned explanation has good suction, hydrogen discharging performance.

Below be the alloy that draws according to the electronegativity point of view and the variation of the bond strength between the hydrogen, that is, change by Mg component in the above-mentioned general formula (V) in the stability of hydrogen in the alloy and to be caused by the replacement of the M3 element as Pt and Zr.

Such relation is arranged usually, in most of the cases, the electronegativity difference of metallic element and hydrogen is big more in the metal hydride, the bond strength of metal and hydrogen is big more, can think that also the electronegativity difference between alloy and the hydrogen increases, metal-hydrogen key ions binding performance increases, and stabilized hydrogen is inhaled in reinforced metal-hydrogen bond thereby raising thus.In other words, when replacing Mg with the electronegativity M3 element of element as Al and Ag so higher than Mg, the electronegativity difference diminishes between metal and the hydrogen, so hydrogen stability in crystal lattice weakens.

So, when replacing the position of Mg than the high element al of Mg and the such M3 element of Ag with electronegativity, hydrogen instability in the crystal lattice, thereby improve the hydrogen bearing alloy performance and help the production of alloy.

On the other hand, in the above-mentioned general formula (V) M4 such as Ni to the character of improving hydrogen bearing alloy and promote that the release of the hydrogen that alloy has adsorbed is effective.Because the electronegativity of M4 is than Mg height, and be the element of discord hydrogen generation exothermic reaction, promptly can not spontaneous formation hydride.

As above-mentioned explanation and general Mg ₂Ni type alloy phase ratio, the hydrogen bearing alloy of the present invention that contains the alloy of being represented by general formula (V) can significantly improve hydrogen sucking function, especially hydrogen.Compare with general rare earth metal type hydrogen storage alloy, hydrogen bearing alloy of the present invention has actual advantage: the Unit Weight hydrogen increases, and production cost reduces, weight saving.

The hydrogen bearing alloy of another embodiment of the present invention comprises the alloy by following general formula (VI) expression:

(Mg _1-xM5 _x) _20-yM6 ……(VI)

Wherein M5 be selected from least a element in 1 to 1.5 times the element that atomic radius is Mg (except that electronegativity than the high element of Mg); M6 is at least a element that is selected among Ni, Fe, Co, Cu, Zn, Sn and the Si; The scope of x is 0＜x＜0.5; The scope of y is 0≤y＜18.

If M5 element atomic radius surpasses 1.5 times of Mg, be difficult to form single alloy phase, cause the hydrogen sucking function of alloy to descend, the element as by the M5 representative can use Ca, Sr, K and Na.In these M5 elements, Ca and Sr are preferred elements.

Based on the following true scope that limits middle x of general formula (VI) and y.Promptly when x surpassed 0.5, crystal structure of alloy altered a great deal, the performance depreciation of Mg base alloy simultaneously, the preferable range of x is 0.01≤x≤0.4, x in this preferable range the time absorption hydrogen amount increase.On the other hand, when the y value surpasses 18, inhale the hydrogen position in the alloy and reduce, thereby hydrogen reduces, the preferable range of y value is 1≤y≤17.5.

The hydrogen bearing alloy that comprises by general formula (VI) alloy expression and that meet above-mentioned explanation has good suction, hydrogen discharging performance.

That is, when the position of Mg in the alloy be by atomic radius be 1 to 1.5 times element of Mg atom such as Sr atom when replacing alloy the catalytic activity of hydrogen is increased, therefore improve hydrogen sucking function.

On the other hand, for example Ni can improve the hydrogen sucking function of hydrogen bearing alloy to M6 effectively and the release of the hydrogen that promotes to have adsorbed in the alloy in the above-mentioned general formula (VI), element discord hydrogen generation exothermic reaction because M6 is higher than electronegativity Mg promptly can not spontaneous formation hydride.

According to above-mentioned explanation and Mg commonly used ₂Ni type alloy phase ratio, the hydrogen bearing alloy hydrogen sucking function of the present invention that comprises the alloy of being represented by general formula (VI) is significantly increased, and particularly hydrogen increases.Compare with general rare-earth type hydrogen bearing alloy, hydrogen bearing alloy of the present invention also has many real advantage: the Unit Weight hydrogen increases, and production cost reduces, weight saving.

The method that the present invention carries out surface modification to hydrogen bearing alloy comprises uses the R-X compound, and wherein R represents alkyl, alkenyl, alkynyl, aryl or its substituting group, and X is a halogen, the step that hydrogen bearing alloy is handled.

The example of these hydrogen bearing alloys is (1) AB ₅Type (LaNi for example ₅, CaNi ₅); (2) B ₂A ₂Type (MgZn for example ₂, ZrNi ₂); (3) AB type (for example TiNi, TiFe); (4) A ₂Type B (Mg for example ₂Ni, Ca ₂Fe).

The inventive method can be used for the hydrogen bearing alloy that another kind comprises the alloy of being represented by following general formula (IV):

Mg _2-xM2 _xM1 _y ……(IV)

Wherein M2 be selected from can and element, Al and the B of hydrogen generation exothermic reaction at least a element (except that Mg); M1 be selected from can not with at least a element (except that Mg and M2) in the element of hydrogen generation exothermic reaction; The scope of x is 0≤x≤1.0; The scope of y is 0.5＜y≤2.5.

As the example of M1 in the general formula (IV), can select same element for use with reference to general formula (I).

As the example of M2 in the general formula (IV), can select same element for use with reference to general formula (II).

In the inventive method, preferably use above-mentioned AB ₅Type, A ₂Type B or contain the hydrogen bearing alloy of the alloy of general formula (IV) expression.

The active order of above-mentioned R-X compound is iodide＞bromide＞chloride, and wherein R represents alkyl, alkenyl, alkynes base, aryl or its substituting group, and X represents halogen.The example of R-X compound is: iodomethane, bromine ethene, 1,2-methylene bromide, 1,2-diiodomethane.

This R-X compound (halide) preferably reacts with hydrogen bearing alloy in the presence of solvent, thereby makes alloy surface modifying.

The example of this solvent is: ether, oxolane (THF), di ether, di-n-butyl ether, Di Iso Propyl Ether, diethylene glycol dimethyl ether, dioxanes and dimethoxy-ethane (DME).These solvents can be used alone or as a mixture, preferred ether and THF.When the R-X compound was alkyl halide, alkenyl halide, aryl halide, ether solvent was preferred.On the other hand, when selected R-X compound is alkenyl compound or aryl compound, the preferred THF that uses with high coordination intensity.When reacting in ether, bromide and iodide react easily in the R-X compound.The bromide of chloride or replacement has than low activity in these R-X compounds, can react in THF.

Some factor is determined the suitable concn of above-mentioned R-X compound in solvent below considering

(1) halid activity (when using SA halide, concentration should increase).

(2) cause the possibility (when using aryl chloride and benzyl chloride, may cause coupling reaction) of side reaction so these halide concentrations are low.

(3) solubility of product and stability (when halid solubility was low, halid concentration should be low, and ie in solution is a saturated concentration or when higher, has solid matter and separate out when cooling, so increased inhomogeneities).

For reaction is carried out easily, can in the solution that contains the R-X compound, add catalyst.The example of this type of catalyst is many cyclic condensations hydrocarbon, as: pentalene (pentalene), indenes, naphthalene, Azulene, Heptalene, biphenyl, indacene, Pi, acenaphthene, fluorenes, phenalene, phenanthrene, anthracene, fluoranthene, acephenathrylene, subunit anthracene, terphenyl (triphenylene), pyrene, Ya En, aphthacene, Pleiadene, picene, perylene, pentaphene, tentacene, connection four benzene, hexaphene, hexacene, rubicene, cool, trinaphthylene, pentacene, heptacene, pinanthrene and ovalene.Anthracene is only in these compounds.When the hydrogen bearing alloy that contains Mg was used the THF solution-treated of the R-X compound that is added with anthracene, the mixture of anthracene and Mg was had an effect, and generates equilibrium products between them.Therefore, only anthracene is joined in the reaction system of being represented by following reaction equation (3), must promote reaction to carry out, therefore may carry out alloy surface modifying better to positive direction as catalyst.

Surface modifying method of the present invention has superiority in commercial Application, and this surface modification of the present invention is to add R-Ms (M: the hydrogen bearing alloy composition) reaction system is dewatered and activation in the primary reaction system in advance.

The method of the hydrogen bearing alloy surface modification that proposes with the present invention particularly and do not have the alloy phase ratio of surface modification, can improve the performance and the activity of hydrogen bearing alloy.

Therefore, one of method of the hydrogen sucking function of improvement hydrogen bearing alloy is that it is carried out surface modification treatment.Be that the activity of hydrogen bearing alloy in inhaling the hydrogen process caused by surface segregation mechanism, therefore, this activity it is believed that it is with relevant at the easiness and the catalyst performance of alloy surface formation Catalytic Layer.When with R-X compound treatment hydrogen bearing alloy, the part component element M that constitutes hydrogen bearing alloy carries out following reaction:

M+R-X→R-MX (1)

Or

M+αR-X→αR-MXα (2)

When surface treatment is carried out in these reactions, hydrogen bearing alloy surface or near the slight segregation of generation and producing thereon as the activity of such catalysts site.

For example when handling Mg with bromoethane ₂During the Ni type hydrogen storage alloy, the Mg in the hydrogen bearing alloy carries out following reaction

(3)

Along with this reaction (surface modification), Mg ₂The Ni surface oxide film is removed, and therefore the Ni that exposes works to decompose the catalyst of hydrogen when absorbing hydrogen, has improved the absorption hydrogen performance thus.

The example of the element (except the Mg) of energy and the reaction of R-X compound is rare earth element Ln (Ln: lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, dysprosium, holmium, erbium, thulium, ytterbium and ruthenium), during room temperature under atmosphere, argon gas or blanket of nitrogen, these lanthanide series and 1,2-ethylidene periodide produce LnI by following reaction equation in THF solution ₂

(4)

These rare earth elements of La, Nd, Sm and Ln are active especially, they and 1, the 2-ethylidene periodide reactive order of living is La＞Nd＞Sm＞Lu.

For example work as LaNi ₅Type hydrogen storage alloy is with 1, and when the 2-ethylidene periodide was handled, the La in the hydrogen bearing alloy carried out following reaction.

(5)

After this reaction (surface modification), cover LaNi ₅The oxidation film on surface is removed, and therefore the Ni that exposes works to decompose the catalyst of hydrogen when absorbing hydrogen, so improved the hydrogen sucking function of hydrogen bearing alloy.

After the processing of R-X compound solution, the only residual a spot of halogen in hydrogen bearing alloy surface (for example) less than 1%, the result is that the proper property of hydrogen bearing alloy can not weakened basically.

Another feature of hydrogen bearing alloy of the present invention is, in three highest peaks of CuK α as the X-ray diffractogram of radiation source, half-breadth Δ (2 θ) scope that has a peak at least is 0.2 a °≤Δ (2 θ)≤50 °.Three highest peaks of term refer to the independent pulse peak of three maximums in the X-ray diffraction peak herein.

Hydrogen bearing alloy component type example is (1) AB ₅Type (routine LgNi ₅, CaNi ₅);

(2) AB ₂Type (routine MgZn ₂, ZrNi ₂); (3) AB type (for example TiNi, TiFe); (4) A ₂Type B (routine Mg ₂Ni, Ca ₂Fe)

Hydrogen bearing alloy preferably contains the composition with the alloy of following formula (V) expression:

Mg _2-xM2 _xM1 _y……(IV)

Wherein M2 be selected from can and element, Al and the B of hydrogen generation exothermic reaction at least a (except that Mg) element; M ₁It is at least a element (except that Mg and M2) that is selected from the element of discord hydrogen generation exothermic reaction; The scope of x is 0≤x≤1.0; The scope of y is 0.5＜y≤2.5.

As the example of M1 in the formula (IV), can select same element for use with reference to general formula (I).

As the example of M2 in the formula (IV), can select same element for use with reference to general formula (II).

Especially, Mg content reaches 10% or more hydrogen bearing alloy such as Mg ₂In Ni and the hydrogen bearing alloy by general formula (IV) expression, doing the doing in the X-ray diffractogram of radiation source with Cuk α, near the scope of the half-breadth Δ of diffraction maximum 20 ° (2 θ 1) is 0.3 a °≤Δ (2 θ 1)≤10 °, and near the scope of the half-breadth Δ of diffraction maximum 40 ° (2 θ 2) is 0.3 a °≤Δ (2 θ 2)≤10 °.

According to the following true half-breadth scope that limits.That is, if Δ (2 θ)＜0.2 °, the suction hydrogen speed of alloy becomes very slow; On the other hand, if Δ (2 θ)＞50 °, hydrogen-absorbing ability descends, so preferred half-breadth is 0.3 a °≤Δ (2 θ)≤10 °.

If the crystallite dimension so that D represents hydrogen bearing alloy preferably is limited to it between 0.8nm≤D≤50nm.If use the hydrogen bearing alloy of crystallite dimension in this scope, the diffusion admittance of hydrogen can strengthen and diffusion length can reduce, and hydrogen bearing alloy is inhaled as a result, hydrogen discharging performance will be enhanced.So control the reasons are as follows of crystallite dimension: even D is less than 0.8nm, and the hydrogen-absorbing ability of alloy may reduce; In addition if D greater than 50nm, the diffusion admittance of hydrogen is with blocked.

Hydrogen bearing alloy surface modifying method according to another embodiment of the present invention comprises a step of hydrogen bearing alloy being carried out mechanical treatment under vacuum or inert gas or nitrogen atmosphere.

The mechanical treatment of above-mentioned surface modification can be realized by following method.That is, at first hydrogen bearing alloy is put into ball mill container,, by the collision of wall and ball alloy is clashed into then such as externally swing ball mill, spiral ball mill, rotary ball mill or grinder (attriter).

When carrying out this kind mechanical treatment in airtight container, described processing can or vacuumize at filling argon gas or inert gas, certain the time, but also carry out in the drying receptacle of filling hydrogen.When using airtight container, because bump carries out through wall, the sealing position of container will be because of becoming flexible through being impacted.Therefore the safety in order to seal can be taked dual cap seal or with inert gas cleaning container or be evacuated.More preferably when forming inert gas atmosphere, control the purity of inert gas.By way of example, the oxygen content of preferably controlling inert gas is within 100ppm, and water vapour is within 50ppm.For anti-oxidation, hydrogen storage alloy particle is the same with metallic particles to be handled in inert gas.

Adopt externally swing ball mill and similar machinery to carry out mechanical treatment 1 to 1000 hour.If the processing time is less than 1 hour, hydrogen bearing alloy is difficult to obtain desirable hydrogen absorption characteristic; On the other hand, if the processing time surpasses 000 hour, oxidizing process slowly will take place, and production cost can improve also.

Behind mechanical treatment, the desirable granularity of hydrogen bearing alloy should be 0.1 to 50 μ m, if necessary, can also heat-treat hydrogen bearing alloy.Treatment temperature is determined by the hydrogen bearing alloy composition.In the case, this temperature is preferably between 100 to 500 ℃.Under certain situation, have such possibility, that is: behind the mechanical treatment, the elemental constituent of mixing in the mixture may flock together with alloy.This gathering may improve the hydrogen sucking function of alloy effectively.In this case, the desired proportions of this gathering is 10% (weight) or more.

According to the method for hydrogen bearing alloy surface modification of the present invention, might greatly improve initial activity, activity and the hydrogen sucking function of alloy.This method is included in the step of under a vacuum or inert gas or the nitrogen atmosphere hydrogen bearing alloy being carried out mechanical treatment.

Can adopt any means in the following method that the hydrogen sucking function of hydrogen bearing alloy is improved: (1) is surface coating modified; (2) topochemistry method modification; (3) mechanochemical reaction modification; (4) coating modification; (5) be used in combination x radiation x.According to surface modifying method of the present invention, (3) kind method, promptly the mechanochemistry method can significantly improve the initial activity of hydrogen bearing alloy and the hydrogen sucking function of hydrogen bearing alloy.

According to mechanically modifying method of the present invention, not only can change the basic structure of alloying pellet, also can change its physical property by the variation of surface texture.In other words, promptly can change the interior energy of hydrogen bearing alloy.In addition, because the refinement of particle has generated unsalted surface, surface energy is improved.

According to mechanically modifying method of the present invention, hydrogen bearing alloy surface and structure change, thereby produce stress, can cause structural damage like this.The variation of atom or molecular migration and lattice arrangement causes that potential energy increases.Because this series of effects, make the selectivity of improving catalytic action and putting forward catalytic reaction become possibility.

One of result that modification is handled is the crystal defect in the hydrogen bearing alloy.In this case, these defectives comprise: the admissible thermodynamics lattice defect, plasticity distorts in ideal crystal, and promptly in the surface modification treatment process, the mechanical energy of generation causes the plastic deformation of crystal; The heat distortion, promptly because of non-uniform temperature in the crystal or phase transformation, the local distortion of giving birth to heat and producing; And the distortion that causes of phase transformation residual stress.Utilize above these effects also may improve the hydrogen sucking function of hydrogen bearing alloy.

These hydrogen bearing alloy samples through after the mechanically modifying processing have produced expansion with Cuk α as the X-ray diffraction peak outline line that radiation source obtains.Usually outline line expansion in peak is caused the variation of (a) crystallite dimension by following factor; (b) heterogeneous deformation (stain)

With regard to (a), crystallite dimension D can be expressed by following Scherrer ' s equation:

D＝(0.9λ)/(Δ(2θ)cosθ) (6)

D: crystallite dimension;

Δ (2 θ): show half-breadth;

λ: used X ray wavelength;

θ: the Bragg angle of diffracted ray.

Equally, crystallite dimension ε also can be by following Stokes and Wilson The Representation Equation:

ε＝λ/(βicosθ) (7)

ε: crystallite dimension;

β i: integral breadth;

λ: used X ray wavelength;

θ: the Bragg angle of diffracted ray.

Hydrogen bearing alloy is after above-mentioned mechanical means is handled, and its X-ray diffraction peak broadens, and by top two equations as can be known, this causes crystallite dimension to reduce to cause because of mechanical treatment.

By (b) as can be known, the crystal grain distortion also is to cause one of reason that the X-ray diffraction peak broadens.The crystal grain distortion is because the change of interplanar distance and fluctuation cause.By the Stokes-Wilson equation as can be known, concern and can express between crystal grain heterogeneous deformation η and the diffracted ray integral breadth β i ' by following formula:

βi’＝2ηtanθ (8)

Further, owing to the peak profile that crystallite dimension changes and two kinds of effects of heterogeneous deformation cause broadens and can be expressed by following Hall equation:

β＝βi+β′i (9)

So behind the mechanical treatment, it is because crystallite dimension changes and produce the result of heterogeneous deformation that hydrogen bearing alloy peak wide wheel line broadens.Correspondingly, the hydrogen sucking function of alloy can improve by controlling this two factor.Be alloy grain during, can strengthen the diffusion admittance of hydrogen because of the mechanical treatment refinement.And having dwindled diffusion length, the result just can improve suction, the hydrogen discharging performance of hydrogen bearing alloy.Preferred size 0.8nm≤D≤the 50nm of this crystal grain.Further, the Impact energy of mechanical treatment is huge, is enough to change the hydrogen bearing alloy interplanar distance, causes lattice asymmetric of hydrogen bearing alloy thus.In other words, owing to produce crystal grain deformation,, can influence suction, the hydrogen discharging performance of hydrogen bearing alloy at an easy rate by changing the intracell energy.

Broadening of hydrogen bearing alloy peak outline line after mechanical treatment represented by apparent half-breadth (apparenthalf-width) Δ (2 θ), shown in equation (6), its scope is 0.2 °≤Δ (2 θ)≤50 ° preferably, is more preferably 0.3 °≤Δ (2 θ)≤10 °.

Another embodiment of hydrogen bearing alloy of the present invention is formed by a mixture, and this mixture comprises:

A kind of alloy with hydrogen sucking function and

At least a additive, this additive are selected from by (a) IA family element (Li for example, Na, Rb, Ca, Sr, Ba etc.), IIA family element (Be for example, Mg, Rb, Cs etc.), group III A element (routine Sc, Y etc.), element (the Ti of IVA family, Zr and Hf), element (the V of VA family, Nb and Ta), element (the Cr of VIA family, Mo and W), VIIA family element (Mn for example, Re etc.), element (the Fe of VIIIA family, Ru, Os, Co, Rh, Ir, Ni, Pd and Pt), element (the Cu of IB family, Ag and Au), element (the Zn of IIB family, Cd and Hg), element (the B of IIIB family, Al, Ga, In, Ti etc.), element (the C of IVB family, Si, Ge, Sn and Pb), element (the P of VB family, As, Sb and Bi) and group vib element (routine S, Se, Te etc.) at least a element in; (b) alloy that forms by above-mentioned (a) element combination in any and that (c) oxide of any element is formed in above-mentioned (a) in a group is at least a;

Said mixture carries out mechanical treatment in vacuum or under inert gas or nitrogen atmosphere.

As for above-mentioned alloy, can use A with hydrogen sucking function ₂The Type B alloy or by the alloy of aforementioned formula (IV) to (IV) expression (wherein A be selected from can with the element of hydrogen generation exothermic reaction, and B be selected from can not with the element of hydrogen generation exothermic reaction.Especially, by general formula (V) or (VI) represented alloy be more preferred.

The element of aforementioned (a), the oxide of the alloy of aforementioned (b) and aforementioned (c) is had on the alloy of inhaling hydrogen character because they are adsorbed on consumingly, all can be used as hydrogenation catalyst nuclear.

In front in (a), present the element of high catalytic activity when preferably selecting those and H-H reaction for use.If consider this element is used for battery, the element of be positive when preferably selecting for use (heat absorption) with H-H reaction, or in the reaction of negative electrode (hydrogen electrode), have the element of exchange current density io greatly.The example of this dvielement has V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ru, Co, Rh, Ir, Pd, Ni, Pt, Cu, Ag, Au etc.

About the alloy in above-mentioned (b), should preferably those present the more alloy of high catalytic activity, this high activity plays synergy from each component element in the alloy in the hydrogen electrode reaction, and it is higher than the catalytic activity sum that derives from each component element.Specially suitable this class alloy example has Ti-Ni type alloy, Ni-Zr type alloy, Co-Mo type alloy, Ru-V type alloy, Pt-W type alloy, Pd-W type alloy, Pt-Pd type alloy, V-Co type alloy, V-Ni type alloy, V-Fe type alloy, Mo-Co type alloy, Mo-Ni type alloy, W-Ni type alloy and W-Co type alloy.In these alloys, MoCo ₃, WCo ₃, MoNi ₃And WNi ₃Be preferred.Because these alloys have high catalytic activity and are suitable for improving the hydrogen sucking function of hydrogen bearing alloy.

As for the oxide of above-mentioned (c), preferably those can provide the oxide of big exchange current density io.The preferred example of this type oxide is FeO ₂, RuO ₂, CoO, CO ₂O ₃, RhO ₂, IrO ₂And NiO.

Said mixture is preferably by such forming: with the stereometer of alloy with hydrogen absorption characteristic, contain the above-mentioned additive of 0.01-70% (volume).If the amount of additive less than 0.01% (volume), just is difficult to improve the suction hydrogen rate of hydrogen bearing alloy; On the other hand, if the consumption of additive greater than 70% (volume), then the hydrogen of hydrogen bearing alloy reduces.The preferred content of additive is 1-50% (volume).

As for the mechanical processing method of above-mentioned surface modification, can adopt equipment same as described above, that is, for example externally swing ball mill, spiral ball mill, screw grinding machine or grinder.

When for example adopting the externally swing ball mill, mechanical treatment 1-1000 hour in the same manner as described above.

Because being a mixture, hydrogen bearing alloy of the present invention forms, this mixture comprises a kind of alloy and at least a additive with hydrogen sucking function, and this additive is selected from least a element in (a) IA family element, IIA family element, group III A element, IVA family element, VA family element, VIA family element, VIIA family element, VIIIA family element, IB family element, IIB family element, IIIB family element, IVB family element, VB family element and the group vib element; (b) alloy that forms by above-mentioned (a) element combination in any and that (c) oxide of any element is formed in above-mentioned (a) in a group is at least a; The mixture that obtains is carried out mechanical treatment in vacuum or inert gas or hydrogen, the initial activity of hydrogen bearing alloy and hydrogen sucking function can be significantly increased as a result.

That is to say that the suction hydrogen activity of hydrogen bearing alloy is formed the easiness of Catalytic Layer and the Effect on Performance of Catalytic Layer when inhaling hydrogen.Because these factors, just may utilize the advantageous effects of aforementioned alloy surface modifying method to improve the hydrogen sucking function of hydrogen bearing alloy.

Correspondingly, according to hydrogen bearing alloy of the present invention, for further improving the hydrogen sucking function of hydrogen bearing alloy, add the above-mentioned additive that accounts for hydrogen sucking function alloy volume 0.01-70%, the mixture that obtains is carried out mechanical treatment in vacuum or inert gas or hydrogen atmosphere, adhered to catalytic core for hydrogenation thus.By this mechanical treatment, when inhaling hydrogen, at alloy surface with hydrogen sucking function and near surface thereof, adsorbing catalytic core consumingly, played the effect of promotion hydrogenation, thereby improved the initial activity of alloy, so can significantly improve the initial activity and the hydrogen sucking function of hydrogen bearing alloy in view of the above.

For example, with Ni with predetermined ratio with have the Mg of hydrogen sucking function ₂Ni type alloy mixes, and the mixture that obtains is carried out mechanical treatment in inert gas (as argon gas) atmosphere, and Ni will be adsorbed in alloy surface, plays the effect of hydroperoxide decomposition catalyst when inhaling hydrogen, and the result has improved the hydrogen bearing alloy hydrogen sucking function.In addition, use this mechanical processing method after, the alloy grain size reduces, thereby has increased alloying pellet interface ratio, and produces inhomogeneous deformation in crystal, and then is more conducive to the absorption of hydrogen.

Another embodiment of hydrogen bearing alloy of the present invention comprises a kind of the have alloy of hydrogen absorption characteristic and at least a powder additive of 0.01-70% (volume), its average grain diameter is 0.01-100 μ m and is scattered in the described alloy, is selected from by (a) IA family element (as Li, Na, Rb, Ca, Sr, Ba etc.), IIA family element is (as Be, Mg, Rb, Cs etc.), the group III A element is (as Sc, Y etc.), element (the Ti of IVA family, Zr and Hf), element (the V of VA family, Nb and Ta), element (the Cr of VIA family, Mo and W), VIIA family element is (as Mn, Re etc.), element (the Fe of VIIIA family, Ru, Os, Co, Rh, In, Ni, Pd and Pt), element (the Cu of IB family, Ag and Au), element (the Zn of IIB family, Cd and Hg), IIIB family element (B for example, Al, Gu, Zn, Ti etc.), element (the C of IVB family, Si, Ge, Sn and Pb), element (the P of VB family, As, Sb and Bi) and the group vib element (as S, Se, Te etc.) at least a element in; (b) alloy that forms by above-mentioned (a) element combination in any and (c) oxide of arbitrary element is formed in above-mentioned (a) one group.

As aforementioned alloy, A with hydrogen sucking function ₂The Type B alloy (wherein A be can with the element of hydrogen generation exothermic reaction, B for can not with the element of hydrogen generation exothermic reaction) or all can use by the represented alloy of aforementioned formula (IV) to (VI).Contain general formula (V) or (VI) hydrogen bearing alloy of represented alloy be preferred.

All additives, the various elements of promptly aforementioned (a), alloy (b) and oxide (c) when they are adsorbed in the hydrogen bearing alloy surface with hydrogen sucking function consumingly, all can be used as the hydrogenation catalytic core.As these additives, the aforesaid same type of material that is used for hydrogen bearing alloy of the present invention all can be used.

The reasons are as follows of control additive powder granularity.If promptly the additive powder particle size is less than 0.01 μ m, then be difficult to improve the hydrogen sucking function of hydrogen bearing alloy; On the other hand, if the additive powder particle size, then can reduce the suction hydrogen speed of hydrogen bearing alloy greater than 100 μ m.Preferred additive powder particle size is 0.1-50 μ m.

Qualification is dispersed in the reasons are as follows of additive volume in the hydrogen bearing alloy with hydrogen sucking function.If promptly the shared volume of powder additive is less than 0.01%, then be difficult to improve the suction hydrogen speed of hydrogen bearing alloy; On the other hand, if the shared volume of powder additive greater than 70%, the hydrogen of hydrogen bearing alloy will reduce.The shared volume of additive is 1-50% more preferably.

As the method for in the alloy of hydrogen absorption characteristic is arranged, disperseing to add powder additive, can adopt following the whole bag of tricks, as described additive is being mixed the method for carrying out aforesaid mechanical treatment with described alloy, add method, quick quenching technique, atomizing sputtering method, galvanoplastic, CVD method, cathode vacuum sputtering method, mechanical alloying method, roll process, liquid cohesion (sol-gel) method of additive during alloy melting.

This embodiment according to hydrogen bearing alloy of the present invention, the ratio of aforementioned additive with certain particle size with 0.01-70% (volume) is dispersed in the alloy with hydrogen sucking function, cause the hydrogenation catalytic core to be adsorbed on the alloy, significantly improved the initial activity of alloy like this.Can significantly improve the initial activity and the hydrogen sucking function of hydrogen bearing alloy in view of the above.

With reference to garden column type nickel-hydrogen secondary cell alkaline secondary cell of the present invention is further explained.

With reference to Fig. 3, in garden cylindrical outer cover 1, place electrode core assembly 5, core assembly is reeled by positive pole 2, barrier film 3 and negative pole 4 and is formed, and negative pole 4 is arranged on the outermost layer of electrode core assembly 5, so that electrically contact with shell 1, alkalinous metal electrolyte reinjects.Seal cover 7 is placed in the upper opening of garden cylindrical shell 1; Seal cover is the garden sheet of perforate 6 in the middle of.The insulated enclosure circle 8 of ring-type is inserted between the upper inside wall of the outward flange of seal cover 7 and open cell shell 1.The inside press seal of end edge with garden cylindrical outer cover 1 open enclosure makes seal cover 7 be locked on the shell 1 through sealing ring 8.One end of positive wire 9 links to each other with anodal 2, the other end links to each other with the lower surface of seal cover 7, shape like the positive terminal 10 of carnival hat shape be installed in seal cover 7 above, to cover perforate 6, rubber safety valve 11 is placed between seal cover 7 and the positive terminal 10, to seal perforate 6.Pad 12 is round insulation sheets with holes, covers on positive terminal 10, and the projection of terminal 10 is stretched out from the opening of pad 12.Envelope tube 13 is used for sealing all peripheries of pad 12, the outer wall of battery case 1 and the bottom periphery of battery case 1.

To explain in detail positive pole 2, barrier film 3, negative pole 4 and electrolyte below.

(1) anodal 2

Anodal 2 can be by being that hydroxide nickel powder adding electric conducting material is made in active material, and mixture and polymer-binder and water mixing furnishing paste with obtaining are filled in the electrode substrate then, and dry back is pressed reservation shape and is shaped.

Can use cobalt oxide or cobalt hydroxide as electric conducting material.

The example of polymer-binder is carboxymethyl cellulose, methylcellulose, Sodium Polyacrylate and polytetrafluoroethylene.

The example of conductive matrices is metal nickel screen, stainless (steel) wire, nickel plating stainless (steel) wire or sponge shape, fibrous or felted porous metal bodies.

(2-1) negative pole

Negative pole can prepare by add electric conducting material in hydrogen storing alloy powder, and with the mixture and polymer-binder and water mixing furnishing paste that obtain, then paste mixture is filled in the conductive matrices, after the drying, presses reservation shape and is shaped.

The example of hydrogen bearing alloy is the alloy by following (1) to (a 5) expression.

(1) the above-mentioned hydrogen bearing alloy that contains by the represented alloy of general formula (I), (II), (V), (VI).

(2) use the Cuk alpha ray as in three highest peaks in the X-ray diffraction spectrogram of radiation source, the half-breadth Δ (2 θ) that has a peak at least is 0.2 a °≤Δ (2 θ)≤50 °, is preferably the hydrogen bearing alloy of 0.3 °≤Δ (2 θ)≤10 °.The crystalline size D of this hydrogen bearing alloy is preferably in 0.8nm≤D≤50nm scope.

(3) in vacuum or under inert gas or hydrogen atmosphere condition, through the hydrogen bearing alloy of mechanical treatment.

(4) by the formed hydrogen bearing alloy of a kind of mixture, this mixture comprises a kind of alloy with hydrogen absorption characteristic; With at least a additive, this additive is selected from by at least a element in (a) IA family, IIA family, IIIA family, IVA family, VA family, VIA family, VIIA family, VIIIA family, IB family, IIB family, IIIB family, IVB family, VB family and the group vib element; (b) by the formed alloy of combination of listed arbitrary element in (a); (c) (a) in a group of forming of the oxide of listed any element; In vacuum or under inert gas or nitrogen atmosphere condition, described mixture is carried out mechanical treatment.

(5) a kind of hydrogen bearing alloy, this alloy comprises a kind ofly having the alloy of hydrogen absorption characteristic and the average grain diameter of 0.01-50% (volume) is the Powdered additive of 0.01-100 μ m, it is scattered in the described alloy, and this additive is selected from by at least a element in (a) IA family, IIA family, IIIA family, IVA family, VA family, VIA family, VIIA family, VIIIA family, IB family, IIB family, IIIB family, IVB family, VB family and the group vib element; (b) (a) in the formed alloy of combination of listed arbitrary element; (c) (a) in a group of forming of the oxide of listed any element.

Hydrogen bearing alloy in above-mentioned (3) to (5) or have in the alloy of hydrogen absorption characteristic, those hydrogen bearing alloys that contain by the represented alloy of general formula (IV) to (VI) are preferred.

As polymer-binder, can use and the material identical materials that is used as positive pole.

As electric conducting material, for example can use carbon black.

The example of conductive matrices is the substrate of two dimension, for example rigid plate of punch metal, expanding metal, porous, nickel screen and three-dimensional matrix, for example, the porous metal bodies of felted, biscuit substrate.

As the raw material of negative pole, will comprise by general formula (I) and (II) hydrogen bearing alloy of alloy of expression be optimized determining the optimal values of content of magnesium in the alloy so that improve its reactivity and improve the resistance matter of hydrogen bearing alloy simultaneously.That is, improve hydrogen bearing alloy and inhaled/putting stability in hydrogen or the charge.And, under the condition of using this negative pole, can produce all extraordinary alkaline secondary cell of capacity and charge/discharge characteristics.

Above-mentioned general formula (V) and (VI) hydrogen bearing alloy of represented alloy be characterised in that significant improvement is arranged on hydrogen absorption characteristic, especially with traditional Mg ₂Ni type alloy phase than the time hydrogen increase.Another of this hydrogen bearing alloy is characterised in that with traditional rare earth element type hydrogen storage alloy and compares that the hydrogen of Unit Weight is bigger, and manufacturing expense is more cheap, and weight is lighter.Therefore, the alkaline secondary cell of the negative pole that contains this hydrogen bearing alloy, particularly superior on capacity and charge/discharge characteristics as negative pole.

Say that further the negative pole of the hydrogen bearing alloy of above-mentioned containing (2) to (a 5) represented alloy will demonstrate bigger capacity and better charge/discharge characteristics as the alkaline secondary cell of negative pole.

(2-2) negative pole 4

This negative pole 4 comprises the hydrogen bearing alloy that contains magnesium.When negative pole being immersed in the 6N-8N alkali metal hydroxide aqueous solution, (a) at normal temperatures, the elution rate of magnesium ion in alkali metal hydroxide aqueous solution be not more than 0.5 milligram of/kilogram alloy/hour, or in the time of 60 ℃, the elution rate of magnesium ion in alkali metal hydroxide aqueous solution be not more than 4 milligrams of/kilogram alloys/hour, and (b) at normal temperatures, the elution rate of alloy compositions element in alkali metal hydroxide aqueous solution is not more than 1.5 milligrams of/kilogram alloys 1 hour, or in the time of 60 ℃, the elution rate of alloy compositions element in alkali metal hydroxide aqueous solution be not more than 20 milligrams of/kilogram alloys/hour.

The present inventor has set up the method that a kind of evaluation contains magnesium hydrogen bearing alloy deterioration velocity.The inventor finds on the basis of this method, and the negative pole that includes hydrogen bearing alloy has satisfied invertibity and stability in electrode reaction.

In alkali metal hydroxide aqueous solution, the elution rate of the ion of hydrogen bearing alloy, promptly corrosion rate is a parameter of expression alloy static stability.Therefore only normally can not determine the stability of a dynamic circulation on this static stability.This is because dynamic characteristic affects the cyclical stability of hydrogen bearing alloy consumingly, for example, is inhaling/is putting in the hydrogen process, and is influential to the strain of alloy lattice by the hydrogen between alloy lattice.In addition, by contacting with external additive or,, can determining the static characteristic that alloy is intrinsic with method of modifying chemistry or physics by surface treatment.

Consider this point, use multiple contain magnesium, different mutually on the composition, with the hydrogen bearing alloy that diverse ways is handled, adopt several method to make negative pole (hydrogen electrode), anticathode is estimated.The result shows that concerning having higher reversible hydrogen bearing alloy, suitable following condition person is only excellent on stability.

The feature that is negative pole is, when negative pole is immersed in the hydroxide aqueous solution of 6N-8N, (a) only with regard to magnesium, at normal temperatures, the elution rate of magnesium ion in alkali metal hydroxide aqueous solution be not more than 0.5 milligram of/kilogram alloy/hour, or in the time of 60 ℃, the elution rate of magnesium ion in alkali metal hydroxide aqueous solution be not more than 4 milligrams of/kilogram alloys/hour, and (b) with regard to whole elements, at normal temperatures, the elution rate of alloy compositions element in alkali metal hydroxide aqueous solution be not more than 1.5 milligrams of/kilogram alloys/hour, or in the time of 60 ℃, the elution rate of alloy compositions element in alkali metal hydroxide aqueous solution be not more than 20 milligrams of/kilogram alloys/hour.

So the reason of elution rate is as follows under definite 60 ℃ the temperature: that is to say, with regard to the hydrogen bearing alloy that reality is used, the ion elution rate of alloy is lower at normal temperatures, its order of magnitude be 0.5 milligram of/kilogram alloy/hour, therefore need to quicken elution of reactive speed to save Measuring Time and to improve certainty of measurement.

Therefore, also might use another set point to represent the in fact elution rate of same order, it is to measure elution rate to estimate the characteristic of negative pole under different temperatures.But it is worthless using the high temperature that surpasses 60 ℃.Because alloy composition is different with processing mode, the fluctuation of measuring temperature will cause side effect.

Make the most frequently used method of negative pole and be to use hydrogen bearing alloy: when hydrogen bearing alloy is immersed in the alkali metal hydroxide aqueous solution of 6N-10N with following feature, at normal temperatures, the elution rate of magnesium ion in alkali metal hydroxide aqueous solution be not more than 0.5 milligram of/kilogram alloy/hour, or in the time of 60 ℃, the elution rate of magnesium ion in the alkali metal hydroxide alkaline aqueous solution be not more than 4 milligrams of/kilogram alloys/hour, and at normal temperatures, alloy compositions element total elution rate in the alkali metal hydroxide dehydrating solution be not more than 1.5 milligrams of/kilogram alloys/hour, or in the time of 60 ℃ alloy compositions element total elution rate in the alkali metal hydroxide dehydrating solution be not more than 20 milligrams of/kilogram alloys/hour.

(3) barrier film 3

Barrier film 3 can be made of non woven cloth in polymer, for example, and polypropylene non-woven fabric, nylon nonwoven fabrics or the nonwoven fabrics that constitutes by polypropylene fibre and nylon fiber.Especially, become hydrophilic polypropylene non-woven fabric to be more suitable for through surface treatment as barrier film.

(4) alkali metal electrolysis liquid

The example of alkali metal electrolysis liquid is NaOH (NaOH) aqueous solution, lithium hydroxide (LiOH) aqueous solution, potassium hydroxide (KOH) aqueous solution, the mixed aqueous solution of NaOH (NaOH) and lithium hydroxide (LiOH), the mixed aqueous solution of potassium hydroxide (KOH) and lithium hydroxide (LiOH), the mixed aqueous solution of NaOH (NaOH), potassium hydroxide (KOH) and lithium hydroxide (LiOH).

According to the present invention, alkaline secondary cell comprises the negative pole that includes the hydrogen bearing alloy that contains magnesium that is enclosed in the battery case, positive pole and the barrier film relative with negative pole, diaphragm clip between both positive and negative polarity, the alkali metal electrolysis liquid of annotating in the battery case,

Wherein, after filling alkali metal electrolysis liquid in battery case and sealing, after 30 days or longer time, the concentration of magnesium ion in alkali metal electrolysis liquid is no more than 2.2 mg/litre.

Ion concentration in the described secondary cell electrolyte is limited to the situation that reason in this scope please refer to alkaline secondary cell.

In general, in alkaline secondary cell, the amount of electrolyte has qualification, even therefore a spot of ion is eluted in the electrolyte, also will cause electrolyte intermediate ion concentration to increase significantly.In addition, because the elution rate of ion reduces along with the increase of wash-out ion concentration in the electrolyte, so in the short relatively time, the speed that electrolyte intermediate ion concentration increases will be reduced to an insignificant degree.Say that further with regard to the negative pole (hydrogen electrode) of low deterioration velocity, described as negative pole of the present invention, at the beginning, the elution rate of negative pole intermediate ion is lower.According to these facts, can suppose 30 days after electrolyte is packed into after, the ion concentration in the battery electrolyte remains unchanged substantially.Therefore, with regard to the electrolyte in the battery, the ion concentration in the electrolyte can be assumed to be a parameter.

Just as explained above, according to another embodiment of the invention, the detection method that contains magnesium hydrogen bearing alloy deterioration velocity by foundation, produce in electrode reaction, by have satisfied invertibity and stability, the negative pole that comprises hydrogen bearing alloy is possible as the alkaline secondary cell of negative pole.Therefore, it is possible producing the high power capacity alkaline secondary cell that substitutes traditional alkaline secondary cell (nickel-cadmium cell, or the nickel-based battery of use LaNi5 type hydrogen storage alloy) according to the present invention.

Simultaneously, in alkaline secondary cell, restriction magnesium ion wash-out is gone into amount in the electrolyte also can suppress the internal short-circuit that the formation because of dendritic crystalline substance causes effectively.

Below, by preferred embodiment, the present invention will be described in more detail.

(embodiment 1-5, comparative example 1-6)

Mg and Ni are melted in the dielectric heating oven that is full of under the argon gas atmosphere, prepare 11 kinds thus and have Mg ₂The hydrogen bearing alloy (the y value is listed in the following table 2) that Niy forms.

The diameter of 11 kinds of hydrogen storage alloy particles obtaining is adjusted into 45-75 μ m, then every kind of alloy of predetermined quantity is immersed in respectively be heated in the potassium hydroxide aqueous solution of 8N 60 ℃ 5 hours.Subsequently, measure the concentration that is eluted to the magnesium ion in this aqueous solution respectively.From this measurement result, calculate the concentration of the magnesium ion of the relative value of magnesium ion of wash-out and every mole of magnesium wash-out.Wash-out concentration by setting pure magnesium is 100, calculates the relative value of the magnesium of wash-out, the results are shown in the following table 2.In addition, the standard value that the amount of wash-out is obtained divided by the ratio of magnesium in the alloy is shown among Fig. 4.

On the other hand, being ground into diameter is that 75 μ m or more short grained every kind of hydrogen bearing alloy are respectively put in the measuring body container, under the condition of 300 ℃ and 10atm, hydrogen is passed in this container, after 24 hours, calculate hydrogen the alloy from the decline of pressure.Table is in following table 2 as a result.

Table 2

	Mg ₂Ni _yComposition		The Mg concentration of wash-out		Hydrogen (Mg _zNi _yH _xIn z)
	Mg ₂Ni _yComposition		The Mg concentration of wash-out			Mg: Ni atomic ratio	y	Relative value	The mol ratio of Mg in the alloy
	Comparative example 1	100∶0	0	100		Mg: Ni atomic ratio	y	Relative value	The mol ratio of Mg in the alloy	1.00	0
Comparative example 2	Comparative example 1	100∶0	0	100	75∶25	0.667	19	0.25	1.4	1.00	0
Comparative example 2	Comparative example 3	2∶1	1.000	18	75∶25	0.667	19	0.25	1.4	0.27	3.2
Embodiment 1	Comparative example 3	2∶1	1.000	18	40∶21	1.050	0	0.12	3.4	0.27	3.2
Embodiment 1	Embodiment 2	64∶36	1.125	7	40∶21	1.050	0	0.12	3.4	0.11	3.5

Table 2 (continuing)

Embodiment 3	5∶3	1.200	7	0.11	3.3
Embodiment 3	5∶3	1.200	7	0.11	3.3	Embodiment 4	8∶5	1.250	8	0.13	3.0
Embodiment 5	4∶3	1.500	10	0.18	2.3	Embodiment 4	8∶5	1.250	8	0.13	3.0
Embodiment 5	4∶3	1.500	10	0.18	2.3	Comparative example 4	8∶7	1.750	105	1.97	0.7
Comparative example 5	50∶50	2.000	145	2.90	0.4	Comparative example 4	8∶7	1.750	105	1.97	0.7
Comparative example 5	50∶50	2.000	145	2.90	0.4	Comparative example 6	1∶2	4.000	240	7.20	0.5

As can be seen from Table 2, with regard to Mg ₂Ni _y, when the y value of expression Ni amount hour, the amount of the Mg ion of wash-out is littler than the amount of pure Mg wash-out.Yet when the y value surpassed 1.5, the amount of the Mg ion of wash-out sharply increased.Particularly, when the y value in the hydrogen bearing alloy was in 1＜y≤1.5 scopes, the amount of the Mg ion of wash-out reduced.In addition, when the y value of representing the Ni amount is near 1, Mg ₂Ni _yHydrogen absorption characteristic do not have significant change.But when the y value surpasses 1.5, the hydrogen absorption characteristic rapid deterioration.In view of these results, can find out, work as Mg ₂Ni _yIn y value in the determined 1＜y of the present invention≤1.5 scopes the time, can obtain having the fabulous chemical stability and the hydrogen bearing alloy of hydrogen absorption characteristic.

(embodiment 6 and comparative example 7)

Mg and Ni are melted in the dielectric heating oven that is full of argon gas, are respectively Mg thereby prepared two kinds of compositions ₂Ni _1.5(embodiment 6) and Mg ₂Ni _0.84The hydrogen bearing alloy of (comparative example 7).

Every kind of hydrogen bearing alloy piece material cuts into five kinds of lath-shaped alloy samples respectively with diamond cutter.Because any defective that forms or scrambling can cause or impel alloy fracture,, carry out following stress test afterwards so these samples must be that the diamond paste of 0.3 μ m carries out surface finish and handles with particle size on the lath-shaped alloy surface.As shown in Figure 5, measured the maximum stress of every kind of lath-shaped sample.That is, arrange and spacing is that support stick 22 upper supports of 20mm lath-shaped sample 21 in pair of parallel.Then, on lath-shaped sample 21, on this point midway, apply weight 23, cause 21 bendings of lath-shaped sample, measure simultaneously and cause lath-shaped sample 21 crooked required pressure, and on this based measurement, calculate maximum stress parallel support stick.

Calculate maximum stress according to the formula of listing below.In this formula, W (mm) represents the width of lath-shaped alloy sample; T (mm) represents the thickness of lath-shaped alloy sample; Distance between support stick is decided to be 20mm, and crooked required power is defined as f/N, and σ represents maximum stress.σ/10 ⁶Nm ^-2=moment/section modulus

＝(20f/4)/(wt ²/6)

＝5f/6wt ²

The maximum stress of every kind of lath-shaped alloy sample of Ce Dinging is listed in the following table 3 in this way.

Table 3

		Specimen size		Breaking load N	Moment	10 ³Nm	Section modulus 10 ^-9m	Maximum stress 10 ⁶Nm ^-2
		Specimen size							Thickness (mm)	Width (mm)
		Embodiment 6	Sample 1						Thickness (mm)	Width (mm)	0.49	10.1	2.05	10.2	0.41	25.2
Sample 2	0.50		Sample 1	9.9	2.83	14.2	0.41	34.5			0.49	10.1	2.05	10.2	0.41	25.2
Sample 2	0.50		Sample 3	9.9	2.83	14.2	0.41	34.5	0.65	9.6	3.14	15.7	0.67	23.3
Sample 4	1.03		Sample 3	10.3	11.3	56.3	1.82	30.9	0.65	9.6	3.14	15.7	0.67	23.3
Sample 4	1.03		Sample 5	10.3	11.3	56.3	1.82	30.9	1.05	10.1	11.7	58.4	1.85	31.6
Comparative example 7	Sample 1		Sample 5	0.37	9.7	2.45	12.3	0.22	1.05	10.1	11.7	58.4	1.85	31.6	55.3
	Sample 1	Sample 2	0.60	0.37	9.7	2.45	12.3	0.22	10.6	6.20	31.0	0.64	48.7		55.3
	Sample 3	Sample 2	0.60	0.60	10.9	5.39	26.9	0.65	10.6	6.20	31.0	0.64	48.7	41.3
	Sample 3	Sample 4	1.22	0.60	10.9	5.39	26.9	0.65	10.5	26.9	134	2.60	51.8	41.3
	Sample 5	Sample 4	1.22	1.30	10.3	27.7	138	2.92	10.5	26.9	134	2.60	51.8	47.3

As can be seen from Table 3, composition is Mg ₂Ni _1.5The lath-shaped hydrogen bearing alloy of (embodiment 6) and composition are Mg ₂Ni _0.84The lath-shaped hydrogen bearing alloy sample of (comparative example 7) is compared, and the former has low stress and fabulous machinability (comprising pulverability).

When the plane of disruption of hydrogen bearing alloy among the embodiment 6 was surveyed with scanning electron microscopy (SEM), susceptible of proof from the photo that obtains, the plane of disruption were by a large amount of Mg ₂Ni phase and minor N i or other phase compositions are at Mg ₂The granule boundary of Ni phase has the phase of a spot of high Mg content.Same structure has also obtained confirmation in EPMA (electron detection microscopic analyzer) test.Specifically, with regard to the hydrogen bearing alloy of embodiment 6, based on entire area, the area of high Mg content phase is 8-9%, Mg ₂Ni is 90% or more with the area of only being made up of Ni that occupies mutually mutually.In the hydrogen bearing alloy SEM of comparative example 7 photo, Mg ₂Ni has occupied most area mutually by what Ni formed mutually with only.Simultaneously, at Mg ₂Recognize considerable high Mg content phase on the crystal boundary of Ni phase.Specifically, the area of high Mg content phase be entire area 20% or more.

Result according to embodiment 6 and comparative example 7 can find out, the composition distribution consistency degree (Mg that records on the alloy fracture face ₂The Ni phase) be 90% or higher alloy, its stability and mechanical pulverability are excellent.

(embodiment 7-14 and comparative example 8-10)

11 kinds consist of Mg _2-xM2 _xM1 _yHydrogen bearing alloy piece material list in the following table 4.

From these hydrogen bearing alloy piece material, prepare many sizes lath-shaped alloy sample identical with the sample of embodiment 6.Then, the maximum stress by using testing apparatus shown in Fig. 5 and calculating formula mentioned above to measure these samples.Obtain that the results are shown in Table 4.

Table 4

	Hydrogen bearing alloy Mg _2-xM2 _xM1 _y	The y value	Maximum stress 10 ⁶Nm ^-2
	Hydrogen bearing alloy Mg _2-xM2 _xM1 _y	The y value	Maximum stress 10 ⁶Nm ^-2	Embodiment 7	Mg ₂Ni _0.95Fe _0.1	1.05	28.1
Embodiment 8	Mg ₂Ni _0.95Co _0.1	1.05	28.6	Embodiment 7	Mg ₂Ni _0.95Fe _0.1	1.05	28.1
Embodiment 8	Mg ₂Ni _0.95Co _0.1	1.05	28.6	Embodiment 9	Mg ₂Ni _0.9Cu _0.2	1.10	31.2
Embodiment 10	Mg _1.9Ca _0.1Ni _1.1	1.10	28.2	Embodiment 9	Mg ₂Ni _0.9Cu _0.2	1.10	31.2
Embodiment 10	Mg _1.9Ca _0.1Ni _1.1	1.10	28.2	Embodiment 11	Mg _1.9La _0.1Ni _1.1	1.10	29.3
Embodiment 12	Mg ₂Ni _0.9Sn _0.25	1.15	30.2	Embodiment 11	Mg _1.9La _0.1Ni _1.1	1.10	29.3
Embodiment 12	Mg ₂Ni _0.9Sn _0.25	1.15	30.2	Embodiment 13	Mg ₂Ni ₁Se _0.1	1.10	34.9
Embodiment 14	Mg _1.9Ca _0.1Ni _0.9Sn _0.15	1.05	30.8	Embodiment 13	Mg ₂Ni ₁Se _0.1	1.10	34.9
Embodiment 14	Mg _1.9Ca _0.1Ni _0.9Sn _0.15	1.05	30.8	Comparative example 8	Mg ₂Ni _0.95Fe _0.05	1.00	44.8
Comparative example 9	Mg _1.9Al _0.1Ni _0.9	0.90	54.3	Comparative example 8	Mg ₂Ni _0.95Fe _0.05	1.00	44.8
Comparative example 9	Mg _1.9Al _0.1Ni _0.9	0.90	54.3	Comparative example 10	Mg ₂Ni _0.45Sn _0.45	0.90	53.3

From table 4, can find out significantly, consist of Mg _2-xM2 _xM1 _yThe time, shown in embodiment 7-14, when the y value greater than 1 the time, available maximum stress is about 30 * 106Nm ^-2On the contrary, among the comparative example 8-10, the y value is not more than 1, and its maximum stress is about 50 * 10 ⁶Nm ^-2This shows that power required in comparative example 8-10 is than high by tens percent in embodiment 7-14.

(embodiment 15)

Make the Mg that includes scheduled volume and Ni and consist of Mg by method for annealing ₂Ni _yHydrogen bearing alloy.Then, this alloy is sealed in the quartz ampoule that is full of argon gas.Under 500 ℃ temperature, slowly annealed about one month, therefore, made and consisted of Mg ₂Ni _1.01Hydrogen bearing alloy.

The hydrogen bearing alloy that makes is immersed in the alkali metal hydroxide aqueous solution, and measures the amount of the magnesium ion of wash-out.The result is, the relative quantity of the magnesium ion of wash-out is 9, and divided by 66.4%, promptly the value that obtains of the magnesium amount in the alloy is 0.14 this amount, and this shows that this alloy has excellent chemical stability.

The hydrogen testing apparatus is inhaled/put to Fig. 6 a kind of temperature scanning type that explained through diagrams, and this device is used to estimate the hydrogen bearing alloy from embodiment 16 preparations.Referring to Fig. 6, hydrogen cylinder 31 links to each other with sample container 33 by pipeline 32.The mid portion of pipeline 32 has fork, and the far-end of arm 34 links to each other with vacuum pump 35.Pressure gauge 36 is installed on the arm 34 fork parts.Press first valve 37 on the pipeline 32 between hydrogen cylinder 31 and the sample container 33 ₁, second valve 37 ₂Order (from hydrogen cylinder 31) two valves are installed.At first valve 37 ₁With second valve 37 ₂Between the part of pipeline 32 link to each other with accumulator 38.In addition, the 3rd valve 37 ₃Be installed on the arm 34 between vacuum pump 35 and the pressure gauge 36.Sample container 33 has been equipped with heater 39.Thermocouple 40 is inserted into the inside of sample container 33.Temperature controller 42 with computer 41 controls links to each other with heater 39 with thermocouple 40, so that from the basis of thermocouple 40 detecting temperatures, adjusts the temperature of heater 39.The self-recorder 43 that computerizeds control links to each other with temperature controller 42 with pressure gauge 36.

(embodiment 16 and 17, comparative example 11 and 12)

Prepare and consist of Mg _2-xThe multiple hydrogen bearing alloy of M2xM1y, but Mg _2-xM2 _xHave nothing in common with each other with M1y and x, y value, promptly they are to form to be respectively Mg _1.9Al _0.1Ni _1.05(M1=Ni, M2=Al, x=0.1, y=1.05; Embodiment 16), Mg _1.9Al _0.1Ni (M1=Ni, M2=Al, x=0.1, y=1; Comparative example 11), Mg _1.9Mn _0.1Ni _1.05(M1=Ni, M2=Mn, x=0.1, y=1.05; Embodiment 17), Mg _1.9Mn _0.1Ni (M1=Ni, M2=Mn, x=0.1, y=1; Comparative example 12) and Mg ₂The alloy of Ni (comparative example 3).

Then, every kind of hydrogen bearing alloy is respectively charged in the sample container 33.After this, close first valve 37 ₁, open second valve 37 ₂With the 3rd valve 37 ₃In this case, start vacuum pump 35, extract the air in pipeline 32, arm 34, accumulator 38 and the sample container 33 out.Then, closing second valve 37 ₂With the 3rd valve 37 ₃Afterwards, open first valve, thus they are used hydrogen exchange so that from hydrogen cylinder 31, hydrogen is defeated by pipeline 32, arm 34, accumulator 38 and sample container 33.Subsequently, closing first valve 37 ₁The time, calculate the amounts of hydrogen of input from the pressure gauge that pressure gauge 36 shows.Then, open second valve 37 ₂, make the hydrogen of input enter into sample container 33, and,, the temperature in the sample container 33 risen with constant rate of speed by control to thermocouple 40 and temperature controller 42 with thermocouple 40 its temperature of control.Simultaneously, the heater 39 that receives this control signal has write down the temperature of sample container 33.At this moment, can detect the variation of any pressure in the sample container 33 by pressure gauge 36, and in self-recorder 43, note.Because the pressure that rising caused of temperature variation in the sample container 33 (it is that hydrogen bearing alloy suction hydrogen causes that temperature reduces) is shown among Fig. 7.

As can be seen from Figure 7, with Mg _1.9Al _0.1Ni hydrogen bearing alloy (comparative example 11) is compared Mg _1.9Al _0.1Ni _1.05Hydrogen bearing alloy (embodiment 16) can be inhaled hydrogen under lower temperature.With Mg _1.9Mn _0.1Ni hydrogen bearing alloy (comparative example 12) is compared Mg _2.9Mn _0.1Ni _1.05Hydrogen bearing alloy (embodiment 17) also can be inhaled hydrogen under lower temperature.Especially, compare with the hydrogen bearing alloy that substitutes M2 with Mn among the embodiment 17, inhale the hydrogen temperature or be suitable for inhaling aspect the temperature of hydrogen reducing, the hydrogen bearing alloy that substitutes M2 with Al among the embodiment 16 is better.And, with Mg ₂Ni hydrogen bearing alloy (comparative example 3) is compared, and embodiment 16 and 17 hydrogen bearing alloy have fabulous hydrogen absorption capacity.Therefore can find out that when M2 (Al or Mn) substituted part Mg, when keeping fabulous hydrogen absorption capacity, it was possible reducing the temperature that is suitable for inhaling hydrogen.

In another experiment, by using Mg _1.9Al _0.1Ni _1.05(embodiment 16), Mg _1.9Mn _0.1Ni _1.05(embodiment 17), Mg _1.9Al _0.1Ni (comparative example 11) and Mg ₂Ni (comparative example 3) hydrogen bearing alloy has carried out the research of inhaling hydrogen concentration and inhaling correlation between the hydrogen temperature.Determine thus and inhale hydrogen required temperature when H/M=0.1 (ratio of the number of hydrogen atoms that this expression absorbs and the atomicity of hydrogen bearing alloy is 0.1).In addition, use the concentration of measuring the magnesium of the relative value of the magnesium density of wash-out in embodiment 16 and 17, comparative example 11 and 3 alloys and every mole of magnesium wash-out as method same as described in the embodiment 1.In this case, the relative value of the magnesium ion concentration of wash-out is 100 from pure magnesium by setting, and calculates the relative value of the magnesium ion concentration of wash-out.Obtain that the results are shown in Table 5.

Table 5

	Hydrogen bearing alloy Mg _2-xM2 _xM1 _y	The y value	The Mg concentration of wash-out		Temperature (℃)
			The Mg concentration of wash-out			Relative value	Every mole ratio of Mg in the alloy
			Embodiment 16	Mg _1.9Al _0.1Ni _1.05		Relative value	Every mole ratio of Mg in the alloy	1.05	7	0.11	70
Comparative example 11	Mg _1.9Al _0.1Ni	1.00	Embodiment 16	Mg _1.9Al _0.1Ni _1.05	17	0.27	75	1.05	7	0.11	70
Comparative example 11	Mg _1.9Al _0.1Ni	1.00	Embodiment 17	Mg _1.9Ni _1.06Mn _0.1	17	0.27	75	1.16	7	0.12	110
Comparative example 3	Mg ₂Ni	1.00	Embodiment 17	Mg _1.9Ni _1.06Mn _0.1	18	0.27	140	1.16	7	0.12	110

Can find out significantly that from table 5 when using when partly substituting Mg and its y value greater than 1 hydrogen bearing alloy with M2 (Al or Mn), the chemical stability that obtains low suction hydrogen temperature and improve alloy is possible.

(embodiment 18)

Prepared and consisted of Mg _1.9Al _0.1Ni _0.55(Mg _2-xM2 _xM1 _yIn M1=Ni and Co, M2=Al, x=0.1, hydrogen bearing alloy y=1.10).Then, with the device shown in Fig. 6, tested with the method identical that the pressure that causes changes because the sample container temperature rises (it is that hydrogen bearing alloy suction hydrogen causes that temperature reduces) with embodiment 16.Obtained the characteristic curve of this alloy shown in Figure 8.From Mg ₂The result that the Ni hydrogen bearing alloy obtains also is shown among Fig. 8.

As shown in Figure 8, substitute M1 in the hydrogen bearing alloy, when keeping fabulous hydrogen absorption capacity, can reduce the temperature that is suitable for inhaling hydrogen with Ni and Co.

In another experiment, as described in example 1 above, tested the concentration of the magnesium of the relative value of the magnesium density of wash-out in the present embodiment alloy and every mole of magnesium wash-out with same method.In this case, the concentration value of the magnesium ion of wash-out is 100 from pure magnesium by setting, and calculates the relative value of magnesium ion concentration.Consequently, the relative value of the concentration of wash-out is 8, and the concentration of the magnesium of every mole of magnesium wash-out is 0.13 in the alloy.

(

embodiment

19 and 20, comparative example 13)

Prepared the multiple M of consisting of _2-xThe hydrogen bearing alloy of M2xM1y, but its M _2-xM2x and M1 component and x, y value are variant.That is alloy Zr, _1.9V _0.1Fe _1.05(M=Zr, M1=Fe, M2=V, x=0.1, y=1.05; Embodiment 19), alloy Zr _1.9Cr _0.1Fe _1.05(M=Zr, M1=Fe, M2=Cr, x=0.1, y=1.05; Embodiment 20), and alloy Zr ₂Fe (comparative example 13).Then, with the experimental provision shown in Fig. 6, tested with the method identical that the pressure that causes changes because the sample container temperature rises (it is that hydrogen bearing alloy suction hydrogen causes that temperature descends) with embodiment 16.Simultaneously, also measured relevant suction hydrogen until the required temperature of H/M=0.1 (number of hydrogen atoms that this expression absorbs and the ratio of the atomicity in the hydrogen bearing alloy are 0.1).The results are shown in the following table 6.

Table 6

	Hydrogen bearing alloy Mg _2-xM2 _xM1 _y	The Y value	Temperature (℃)
	Hydrogen bearing alloy Mg _2-xM2 _xM1 _y	The Y value	Temperature (℃)	Embodiment 19 embodiment 20 comparative examples 13	Zr _1.9V _0.1Fe _1.05 Zr _1.9Cr _0.1Fe _1.05 Zr ₂Fe	1.16 1.16 1.00	340 295 380

From table 6, can find out significantly, work as Zr=M, M2 (V and Cr) partly substitute M and

When the y value of M1 surpasses 1 (embodiment 19 and 20), might realize inhaling the reduction of hydrogen temperature according to the hydrogen bearing alloy of top each condition formation.

(embodiment 21-26, comparative example 3,14,15)

At first, Mg, Ni, Ag, Cd, Ca, Pd, Al, In, Co and Ti are melted in the dielectric heating oven that is full of argon gas, have prepared 9 kinds of hydrogen bearing alloys.The composition Mg of every kind of alloy _2-xM2xM1y lists in the table 7.

Then, every kind of alloy is put into container 33 respectively as sample.Close first valve 37 thereafter, ₁, open second valve 37 ₂With the 3rd valve 37 ₃In this case, start vacuum pump 35, extract the air in pipeline 32, arm 34, accumulator 38 and the sample container 33 out.Close second valve 37 then ₂With the 3rd valve 37 ₃, open first valve 37 ₁,, thereby finish hydrogen exchange so that make the hydrogen in the hydrogen cylinder 31 enter into pipeline 32, arm 34, accumulator 38 and sample container 33.Subsequently, closing first valve 37 ₁After, open second valve 37 ₂, make the hydrogen of input enter into sample container 33, verify the pressure and temperature of record in the self-recorder 43.

With regard to embodiment 21-26 and comparative example 3,14,15, when hydrogen exchange, adjust the pressure of hydrogen cylinder 31 in advance, so that the pressure (initial pressure) in the control sample container 33 remains on about 10atm, and the initial measurement temperature is set at room temperature (about 25 ℃).

Subsequently, by the control of computer 41 and temperature controller 42, the temperature in the control sample container 33 rises with the speed of 0.5 ℃ of per minute.Simultaneously, the heater 39 that receives this control signal has detected the temperature in the sample container 33.At this moment, by pressure gauge 36 and self-recorder 43, measure and note the variation of the pressure and temperature in the sample container 33.

On the other hand, monitor that the pressure in the sample container 33 changes, this pressure changes owing to temperature in the aforesaid operations rises and causes.And be reduced to the basis with this pressure, determine that H/M=0.1 (promptly, the number of hydrogen atoms that every atom absorbs in the alloy reaches 0.1) time temperature can make hydrogen bearing alloy finish the minimum temperature standard of inhaling H-H reaction as one, and, as described in example 1 above, measured the concentration of the magnesium of the relative value of the magnesium density of wash-out in the alloy of embodiment 21-26 and comparative example 3,14,15 and every mole of magnesium wash-out with same method.In this case, the relative value of the magnesium ion concentration of wash-out is 100 from pure magnesium by setting, and calculates the relative value of wash-out magnesium ion concentration.The results are shown in the following table 7.

Table 7

	Hydrogen bearing alloy Mg _2-xM2 _xM1 _y	The Y value (℃)	The Mg concentration of elution		Temperature (℃)
			The Mg concentration of elution			Relative value	The mol ratio of Mg in the alloy
			Embodiment			Relative value	The mol ratio of Mg in the alloy
21	Mg ₂Ag _0.22Ni _1.11	1.11	Embodiment	7	0.11	120
21	Mg ₂Ag _0.22Ni _1.11	1.11	Comparative example 14	7	0.11	120	Mg _1.9Al _0.1Ni	1.00	17	0.27	75
Embodiment 22	Mg ₂Co _1.24In _0.35	1.59	Comparative example 14	8	0.14	110	Mg _1.9Al _0.1Ni	1.00	17	0.27	75
Embodiment 22	Mg ₂Co _1.24In _0.35	1.59	Embodiment 23	8	0.14	110	Mg ₂Co _1.11In _0.11	1.22	9	0.15	150
Embodiment 24	Mg _1.5Ca _0.5Ni _1.5Ag _0.5	2.00	Embodiment 23	7	0.19	115	Mg ₂Co _1.11In _0.11	1.22	9	0.15	150
Embodiment 24	Mg _1.5Ca _0.5Ni _1.5Ag _0.5	2.00	Embodiment 25	7	0.19	115	Mg _1.76Ca _0.5Ni _1.5Ag _0.38	1.88	7	0.15	110
Embodiment 26	Mg ₂Ni _1.25In _0.25W _0.25	1.75	Embodiment 25	6	0.11	125	Mg _1.76Ca _0.5Ni _1.5Ag _0.38	1.88	7	0.15	110
Embodiment 26	Mg ₂Ni _1.25In _0.25W _0.25	1.75	Comparative example 3	6	0.11	125	Mg ₂Ni	1.00	18	0.27	140
Comparative example 15	Mg ₂Co	1.00	Comparative example 3	58	0.87	170	Mg ₂Ni	1.00	18	0.27	140

From table 7, can find out significantly, compare with 15, use the hydrogen bearing alloy of embodiment 21-26, realize that the chemical stability of inhaling the reduction of hydrogen temperature and improving alloy is possible with comparative example 3,14.

(embodiment 27-38 and comparative example 16)

Listed 13 kinds of hydrogen bearing alloys in the table 8, each alloy has (Mg _1-xM3 _x) _20-yThe general formula (V) of M4 (x is defined as 0＜x＜0.5, and y is defined as 0＜y＜18).They are respectively put in the sample container 33.Then, close first valve 37 ₁, open second valve 37 ₂With the 3rd valve 37 ₃, in this case, start vacuum pump 35, extract the air in pipeline 32, arm 34, accumulator 38 and the sample container 33 out.Close second valve 37 then ₂With the 3rd valve 37 ₃, open first valve 37 ₁,, thereby finished hydrogen exchange so that make the hydrogen in the hydrogen cylinder 31 enter into pipeline 32, arm 34, accumulator 38 and sample container 33.Close first valve 37 subsequently ₁, the system pressure that shows from pressure gauge 36 calculates the amounts of hydrogen of importing this moment.Open second valve 37 then ₂, make the hydrogen of input enter into sample container 33.Temperature with thermocouple 40 test samples containers 33.At this moment, control thermocouple 40 and temperature controller 42 are to keep the temperature constant in the sample container 33.In this case, can measure pressure in the sample container 33 by pressure gauge 36 changes and is recorded on the self-recorder 43.

By using above-mentioned tester, measured the hydrogen-absorption speed of every kind of hydrogen bearing alloy in the time of 100 ℃.In the hydrogen with scheduled volume is input in the sample container 1 hour, hydrogen amount (wt%) expression that this hydrogen-absorption speed absorbs with hydrogen bearing alloy.The results are shown in the following table 8.

Table 8

	Hydrogen bearing alloy	Hydrogen-absorption speed
	Hydrogen bearing alloy	Hydrogen-absorption speed	Comparative example 16	Mg ₄Ni	1.0
Embodiment 27	(Mg _0.5V _0.5) ₂₀Zn _0.3Ni _0.7	7.2	Comparative example 16	Mg ₄Ni	1.0
Embodiment 27	(Mg _0.5V _0.5) ₂₀Zn _0.3Ni _0.7	7.2	Embodiment 28	(Mg _0.85Mn _0.15) ₁₇Ni _0.9Cu _0.1	6.6
Embodiment 29	(Mg _0.8S _0.2) _7.8Ni	4.7	Embodiment 28	(Mg _0.85Mn _0.15) ₁₇Ni _0.9Cu _0.1	6.6
Embodiment 29	(Mg _0.8S _0.2) _7.8Ni	4.7	Embodiment 30	(Mg _0.7C _0.3) ₆Ni _0.5Co _0.5	4.5
Embodiment 31	(Mg _0.6Ru _0.4) ₄Ni _0.3Fe _0.7	4.0	Embodiment 30	(Mg _0.7C _0.3) ₆Ni _0.5Co _0.5	4.5
Embodiment 31	(Mg _0.6Ru _0.4) ₄Ni _0.3Fe _0.7	4.0	Embodiment 32	(Mg _0.9Pt _0.1) ₅Si _0.2Ni _0.8	4.2
Embodiment 33	(Mg _0.5Pd _0.5) ₈Cu	5.0	Embodiment 32	(Mg _0.9Pt _0.1) ₅Si _0.2Ni _0.8	4.2
Embodiment 33	(Mg _0.5Pd _0.5) ₈Cu	5.0	Embodiment 34	(Mg _0.8Au _0.1Al _0.1) ₁₄Ni	6.2
Embodiment 35	(Mg _0.99Mn _0.01) _7.8Ni _0.8Fe _0.2	4.9	Embodiment 34	(Mg _0.8Au _0.1Al _0.1) ₁₄Ni	6.2
Embodiment 35	(Mg _0.99Mn _0.01) _7.8Ni _0.8Fe _0.2	4.9	Embodiment 36	(Mg _0.7Ti _0.3) ₁₇Ni _0.3Co _0.7	6.5
Embodiment 37	(Mg _0.9Nb _0.1) ₁₀Ni	5.3	Embodiment 36	(Mg _0.7Ti _0.3) ₁₇Ni _0.3Co _0.7	6.5
Embodiment 37	(Mg _0.9Nb _0.1) ₁₀Ni	5.3	Embodiment 38	(Mg _0.8Ag _0.2) ₈Ni _0.8Fe _0.2	5.0

Can find out significantly from table 8, compare that the hydrogen bearing alloy of the content of magnesium with increase by using embodiment 27-28 can increase the hydrogen of alloy significantly and improve the hydrogen absorption characteristic of alloy with the hydrogen bearing alloy of comparative example 16.

(embodiment 39-50 and comparative example 17)

Listed 13 kinds of Powdered hydrogen bearing alloys in the table 9, every kind of alloy has (Mg _1-xM3x) _20-yM4The general formula (V) of (x is defined as 0＜x＜0.5, and y limits 0≤y＜18).At first, these Powdered alloys are mixed by 1: 1 weight ratio with electrolytic copper powder respectively, (internal diameter: 10mm), the resulting mixture of 1g is applied 10, the pressure compacting of 000kg 5 minutes obtains particle thus in the particle molding apparatus.Then this particle is clipped in the middle of the Ni silk screen spot welding and compacting.Subsequently, this compacts links to each other with the Ni lead by spot welding.Thereby 13 kinds of different types of hydrogen-bearing alloy electrodes (negative pole) have been made.

The hydrogen-bearing alloy electrode that makes thus is immersed in the potassium hydroxide aqueous solution of 8N with the sintrered nickel counterelectrode respectively, under 25 ℃ temperature, carries out the charge test then.In the test of this charge, each circulation comprises the following steps, promptly, with the current charges of every gram hydrogen bearing alloy 100mA 10 hours, after 10 minutes, with the current discharge of every gram hydrogen bearing alloy 20mA, up to the voltage with respect to mercuric oxide electrode reduce to-during 0.5V till.Carry out this charge repeatedly so that obtain the maximum discharge capacity of every kind of negative pole.The results are shown in the following table 9 of this loop test.

Table 9

	Hydrogen bearing alloy	Discharge capacity (mAh/g)
	Hydrogen bearing alloy	Discharge capacity (mAh/g)	Comparative example 17	Mg _3.5Ni	15
Embodiment 39	(Mg _0.8Ta _0.2) _7.8Cu _0.4Ni _0.6	410	Comparative example 17	Mg _3.5Ni	15
Embodiment 39	(Mg _0.8Ta _0.2) _7.8Cu _0.4Ni _0.6	410	Embodiment 40	(Mg _0.6Os _0.4) ₉Ni _0.5Cu _0.5	420
Embodiment 41	(Mg _0.7Re _0.3) ₁₅Si _0.4Ni _0.6	710	Embodiment 40	(Mg _0.6Os _0.4) ₉Ni _0.5Cu _0.5	420
Embodiment 41	(Mg _0.7Re _0.3) ₁₅Si _0.4Ni _0.6	710	Embodiment 42	(Mg _0.98Ir _0.02) ₁₀Ni _0.6Co _0.4	425
Embodiment 43	(Mg _0.8Rh _0.2) ₈Ni	405	Embodiment 42	(Mg _0.98Ir _0.02) ₁₀Ni _0.6Co _0.4	425
Embodiment 43	(Mg _0.8Rh _0.2) ₈Ni	405	Embodiment 44	(Mg _0.97C _0.03) ₃Ni _0.2Fe _0.8	120
Embodiment 45	(Mg _0.9Ag _0.1) ₁₄Cu	640	Embodiment 44	(Mg _0.97C _0.03) ₃Ni _0.2Fe _0.8	120
Embodiment 45	(Mg _0.9Ag _0.1) ₁₄Cu	640	Embodiment 46	(Mg _0.5Al _0.5) _7.8Ni	420
Embodiment 47	(Mg _0.94P _0.06) ₁₀Ni _0.6Co _0.4	415	Embodiment 46	(Mg _0.5Al _0.5) _7.8Ni	420
Embodiment 47	(Mg _0.94P _0.06) ₁₀Ni _0.6Co _0.4	415	Embodiment 48	(Mg _0.9In _0.1) ₈Ni	390
Embodiment 49	(Mg _0.8Pt _0.2) ₅Ni	180	Embodiment 48	(Mg _0.9In _0.1) ₈Ni	390
Embodiment 49	(Mg _0.8Pt _0.2) ₅Ni	180	Embodiment 50	(Mg _0.8Au _0.2) ₃Ni _0.2Fe _0.8	135

From table 9, can find out significantly, contain by general formula (V) (Mg _1-xM3 _x) _20-yM4) represented alloy and the negative pole of comparing the hydrogen bearing alloy with higher Mg content with the hydrogen bearing alloy of comparative example 17 can increase the hydrogen of alloy effectively and improve the hydrogen absorption characteristic of alloy significantly.

(embodiment 51-60 and comparative example 18)

Listed in the following table 10 and had (Mg _1-xM3 _x) _20-y11 kinds of alloys of the general formula (V) of M4 (x is defined as 0＜x＜0.5, and y is defined as 0≤y＜18) by using as shown in Figure 6 suction/put the hydrogen characteristic test device, have been measured the hydrogen of these 11 kinds of hydrogen bearing alloys in the time of 25 ℃ respectively.In this case, in 20 hours after being input to predetermined amounts of hydrogen in the sample container, the hydrogen amount (wt%) that absorbs with hydrogen bearing alloy is expressed as hydrogen.The results are shown in the following table 10.

Table 10

	Hydrogen bearing alloy	Hydrogen (wt%)
	Hydrogen bearing alloy	Hydrogen (wt%)	Comparative example 18	Mg _3.2Ni	0.5
Embodiment 51	(Mg _0.9Y _0.1) _7.8Zn _0.1Ni _0.9	4.8	Comparative example 18	Mg _3.2Ni	0.5
Embodiment 51	(Mg _0.9Y _0.1) _7.8Zn _0.1Ni _0.9	4.8	Embodiment 52	(Mg _0.7Sc _0.3) ₅Cu _0.8Ni _0.2	4.2
Embodiment 53	(Mg _0.6La _0.4) ₃Ni _0.5Co _0.5	3.1	Embodiment 52	(Mg _0.7Sc _0.3) ₅Cu _0.8Ni _0.2	4.2
Embodiment 53	(Mg _0.6La _0.4) ₃Ni _0.5Co _0.5	3.1	Embodiment 54	(Mg _0.6Hf _0.2Pt _0.2) ₄Fe	4.0
Embodiment 55	(Mg _0.5Zr _0.5) ₁₀Cu _0.5Ni _0.5	5.3	Embodiment 54	(Mg _0.6Hf _0.2Pt _0.2) ₄Fe	4.0
Embodiment 55	(Mg _0.5Zr _0.5) ₁₀Cu _0.5Ni _0.5	5.3	Embodiment 56	(Mg _0.8Pb _0.2) ₅Ni	4.2
Embodiment 57	(Mg _0.9Y _0.1) ₈Sn _0.4Ni _0.6	5.0	Embodiment 56	(Mg _0.8Pb _0.2) ₅Ni	4.2
Embodiment 57	(Mg _0.9Y _0.1) ₈Sn _0.4Ni _0.6	5.0	Embodiment 58	(Mg _0.4In _0.4W _0.2) _7.8Ni	4.8
Embodiment 59	(Mg _0.7La _0.3) ₁₇Cu _0.3Ni _0.7	6.6	Embodiment 58	(Mg _0.4In _0.4W _0.2) _7.8Ni	4.8
Embodiment 59	(Mg _0.7La _0.3) ₁₇Cu _0.3Ni _0.7	6.6	Embodiment 60	(Mg _0.9Tl _0.1) ₉Si _0.05Co _0.95	5.0

From table 10, can find out significantly, use and contain the hydrogen absorption characteristic that the hydrogen bearing alloy higher than the hydrogen bearing alloy Mg content of comparative example 17 can increase the hydrogen of alloy effectively and improve alloy significantly.

(embodiment 61-71 and comparative example 19)

Listed in the following table 11 and had (Mg ₁-xM3x) _20-y12 kinds of Powdered hydrogen bearing alloys of the general formula (V) of M4 (x is defined as 0＜x＜0.5, and y is defined as 0≤y＜18).At first these Powdered alloys are mixed by 1: 1 weight ratio with electrolytic copper powder respectively, (internal diameter: 10mm) the resulting mixture of 1g is applied 10, the pressure of 000kg is suppressed 5 minutes to obtain particle at the particle molding apparatus.Then this particle is clipped in the middle of the Ni silk screen spot welding and compacting.Subsequently compacts is linked to each other with the Ni lead through spot welding.Thereby 12 kinds of different types of hydrogen-bearing alloy electrodes (negative pole) have been made.

The hydrogen-bearing alloy electrode that makes thus is immersed in the aqueous solution of potassium hydroxide of 8N with the sintrered nickel counterelectrode respectively, under 25 ℃ temperature, carries out the charge test then.In this charge test, each circulation comprises the following steps, that is, every gram hydrogen bearing alloy was with the current charges of 100mA 10 hours, after 10 minutes, every gram hydrogen bearing alloy with the current discharge of 20mA up to the voltage with respect to mercuric oxide electrode reduce to-during 0.5V till.Carry out this charge repeatedly so that obtain the maximum discharge capacity of every kind of negative pole.The results are shown in the following table 11 of this loop test.

Table 11

	Hydrogen bearing alloy	Discharge capacity (mAh/g)
	Hydrogen bearing alloy	Discharge capacity (mAh/g)	Comparative example 19	Mg _4.0Ni	25
Embodiment 61	(Mg _0.9Ce _0.1) ₈Zn _0.3Ni _0.7	420	Comparative example 19	Mg _4.0Ni	25
Embodiment 61	(Mg _0.9Ce _0.1) ₈Zn _0.3Ni _0.7	420	Embodiment 62	(Mg _0.85La _0.05C _0.1) ₁₃Fe	510
Embodiment 63	(Mg _0.7Pr _0.3) _7.8Ni	410	Embodiment 62	(Mg _0.85La _0.05C _0.1) ₁₃Fe	510
Embodiment 63	(Mg _0.7Pr _0.3) _7.8Ni	410	Embodiment 64	(Mg _0.25Zr _0.4Mo _0.35) ₃Ni	125
Embodiment 65	(Mg _0.8Sm _0.2) ₅Si _0.3Cu _0.7	200	Embodiment 64	(Mg _0.25Zr _0.4Mo _0.35) ₃Ni	125
Embodiment 65	(Mg _0.8Sm _0.2) ₅Si _0.3Cu _0.7	200	Embodiment 66	(Mg _0.5Y _0.4Al _0.1) ₄Co	180
Embodiment 67	(Mg _0.9Zr _0.1) ₉Si _0.2Ni _0.8	390	Embodiment 66	(Mg _0.5Y _0.4Al _0.1) ₄Co	180
Embodiment 67	(Mg _0.9Zr _0.1) ₉Si _0.2Ni _0.8	390	68 embodiment	(Mg _0.8In _0.2) _7.8Zn _0.4Cu _0.6	370
Embodiment 69	(Mg _0.99Hf _0.01) ₃Sn _0.2Ni _0.8	110	68 embodiment	(Mg _0.8In _0.2) _7.8Zn _0.4Cu _0.6	370
Embodiment 69	(Mg _0.99Hf _0.01) ₃Sn _0.2Ni _0.8	110	Embodiment 70	(Mg _0.8Hf _0.2) ₄Ni	175
Embodiment 71	(Mg _0.8Y _0.2) ₈Cu _0.5Ni _0.5	390	Embodiment 70	(Mg _0.8Hf _0.2) ₄Ni	175

From table 11, can find out significantly, compare with the hydrogen bearing alloy of comparative example 19, the negative pole (embodiment 61-71) that is made of the general formula (V) of (Mg1-xM3x) 20-yM4 hydrogen bearing alloy represented and that contain higher Mg amount can increase the hydrogen of alloy effectively and improve the hydrogen absorption characteristic of alloy significantly.

(embodiment 72-74)

Below table 12 in listed have (Mg1-xM3x) 20-yM4 three kinds of hydrogen bearing alloys of general formula (VI) of (x is defined as 0＜x＜0.5, and y is defined as 0≤y＜18).By using as shown in Figure 6 suction/put the hydrogen characteristic test device, tested the hydrogen in the time of 25 ℃ respectively.In this case, predetermined amounts of hydrogen was input in the sample container in 20 hours, the hydrogen amount (wt%) that hydrogen bearing alloy absorbs is expressed as hydrogen.The results are shown in the following table 12.

In addition, above-mentioned Powdered hydrogen bearing alloy is mixed by 1: 1 weight ratio with electrolytic copper powder respectively.In the particle molding apparatus, the resulting mixture of 1g is applied 10, the pressure of 000kg is suppressed 5 minutes to obtain particle.Then this particle is clipped in the middle of the Ni silk screen spot welding and compacting.By spot welding with compacts with link to each other with the Ni lead.Thereby 3 kinds of different types of hydrogen-bearing alloy electrodes (negative pole) have been made.

The hydrogen-bearing alloy electrode that makes thus is immersed in the aqueous solution of potassium hydroxide of 8N with the sintrered nickel counterelectrode respectively, under 25 ℃ temperature, carries out the charge test then.In the test of this charge, each circulation comprises the following steps, promptly, every gram hydrogen bearing alloy was with the current charges of 100mA 10 hours, after 10 minutes, every gram hydrogen bearing alloy is with the current discharge of 20mA, up to the voltage with respect to mercuric oxide electrode reduce to-during 0.5V till.Carry out this charge repeatedly so that obtain the maximum discharge capacity of every kind of negative pole.The results are shown in the following table 12 of this loop test.

Table 12

	Hydrogen bearing alloy	Hydrogen (wt%)	Discharge capacity (mAh/g)
	Hydrogen bearing alloy	Hydrogen (wt%)	Discharge capacity (mAh/g)	Embodiment 72	(Mg _0.85Ca _0.15) ₁₆Ni _0.8Cu _0.2	6.4	650
Embodiment 73	(Mg _0.7Ca _0.3) ₁₅Fe _0.3Co _0.7	6.0	720	Embodiment 72	(Mg _0.85Ca _0.15) ₁₆Ni _0.8Cu _0.2	6.4	650
Embodiment 73	(Mg _0.7Ca _0.3) ₁₅Fe _0.3Co _0.7	6.0	720	Embodiment 74	(Mg _0.8Sr _0.2) ₁₁Co _0.05Cu _0.95	5.5	580

From table 12, can find out significantly, in the hydrogen bearing alloy of embodiment 72-74, the position of Mg is replaced by Mg1-1.5 element (except that than the higher element of Mg elecrtonegativity) doubly by M5 or atomic radius, and M6 is at least one element among Ni, Fe, Co, Cu, Zn, Sn and the Si, these alloys have increased hydrogen significantly, have improved hydrogen absorption characteristic.

The negative pole that contains above-mentioned hydrogen bearing alloy can increase its discharge capacity respectively and improve its charge/discharge characteristics, also is understandable.

(embodiment 75)

Contain Mg ₂The hydrogen bearing alloy of Ni is put in the round-bottomed flask that is equipped with agitating device, dropping funel and cooling water pipe, with vacuum pump the air in the flask is extracted out, charges into argon gas after with heating gun ledge being heated.Subsequently, THF is joined in the flask, argon gas can be flow into wherein.Under condition of stirring, 1-bromo-3-ethane splashes in the flask lentamente by dropping funel, allows hydrogen bearing alloy and 1-bromo-3-ethane react.When dripping end, stop to stir, make hydrogen bearing alloy precipitate.The hydrogen bearing alloy of filtering-depositing then obtains the hydrogen bearing alloy of surface modification.

With suction shown in Figure 6/put the hydrogen characteristic test device, measured hydrogen absorption characteristic through hydrogen bearing alloy surface modification and long time without surface modification.When the hydrogen of predetermined joins in the reaction vessel, change by the pressure of control in the reaction vessel and to carry out this test.

Specifically, at first every kind of hydrogen bearing alloy is put into sample container 33 respectively.Then, close first valve 37 ₁, open second valve 37 ₂With the 3rd valve 37 ₃, in this case, start vacuum pump 35, extract the air in pipeline 32, arm 34, accumulator 38 and the sample container 33 out.Then, close second valve 37 ₂With the 3rd valve 37 ₃, open first valve 37 ₁,, thereby finish hydrogen exchange so that the hydrogen in the hydrogen cylinder 31 enters into pipeline 32, arm 34, accumulator 38 and sample container 33.Closing first valve 37 subsequently ₁The time, calculate the amounts of hydrogen of input from the pressure gauge that pressure gauge 36 shows.Open second valve 37 thereafter, ₂, make the hydrogen of input enter into sample container 33, with the temperature of thermocouple test samples container 33.At this moment, control thermocouple 40 and temperature controller 42 are to keep the temperature constant in the sample container 33.Observing pressure in the sample container 33 from pressure gauge 36 changes and is recorded on the self-recorder 43.In the time of 25 ℃, Mg before and after the surface modification ₂The Ni hydrogen bearing alloy is shown among Fig. 9 owing to the pressure that suction hydrogen causes changes (it is that hydrogen bearing alloy suction hydrogen causes that temperature reduces).

From Fig. 9, can find out significantly, with regard to the hydrogen bearing alloy of long time without surface modification,, not find that also significant pressure changes, thereby keeping a constant compression force even apply predetermined hydrogen pressure.Yet, just through the Mg of surface modification ₂The Ni hydrogen bearing alloy applies predetermined hydrogen pressure and has changed its internal pressure sharp.Therefore confirm that a large amount of hydrogen is absorbed by alloy.In addition, compare, might reduce through the hydrogen bearing alloy of surface modification and inhale about 200 ℃ of hydrogen temperature with traditional hydrogen bearing alloy.That is to say, with regard to traditional Mg ₂The Ni hydrogen bearing alloy, unless temperature quite high (200 ℃-300 ℃), suction/hydrogen discharge reaction will can not take place or be very slow.When use resembles among the embodiment 75 hydrogen bearing alloy through surface modification, near room temperature, inhale by contrast ,/hydrogen discharge reaction is possible.

(embodiment 76-106)

Below having among the table 13-15 hydrogen bearing alloy of listed composition handle according to the surface modifying method identical with embodiment 75.Before surface modification and after tested the variation of they hydrogen absorption characteristics.In this test, used suction as shown in Figure 6/put hydrogen characteristic test device.It the results are shown among the following table 13-15, and in these tables, symbol x represents the number of hydrogen atom, that is, and and the MHx that in hydrogen bearing alloy, absorbs.

Table 13

	Hydrogen bearing alloy	X (before handling)	X (handling the back)
	Hydrogen bearing alloy	X (before handling)	X (handling the back)	Embodiment 75	Mg ₂Ni	0	3.0
Embodiment 76	Mg ₂Cu	0	2.0	Embodiment 75	Mg ₂Ni	0	3.0
Embodiment 76	Mg ₂Cu	0	2.0	Embodiment 77	Mg ₂Co	0	3.5
Embodiment 78	Mg ₂Fe	0	4.0	Embodiment 77	Mg ₂Co	0	3.5
Embodiment 78	Mg ₂Fe	0	4.0	Embodiment 79	LaNi ₅	0.1	6.0
Embodiment 80	MmNi ₅	0	3.0	Embodiment 79	LaNi ₅	0.1	6.0
Embodiment 80	MmNi ₅	0	3.0	Embodiment 81	CaNi ₅	0	4.0
Embodiment 82	TiFe	0.1	0.5	Embodiment 81	CaNi ₅	0	4.0
Embodiment 82	TiFe	0.1	0.5	Embodiment 83	TiCo	0	0.5
Embodiment 84	ZrMn ₂	0.1	3.0	Embodiment 83	TiCo	0	0.5
Embodiment 84	ZrMn ₂	0.1	3.0	Embodiment 85	ZrNi ₂	0.1	3.0

Table 14

	Hydrogen bearing alloy	X (before handling)	X (handling the back)
	Hydrogen bearing alloy	X (before handling)	X (handling the back)	Embodiment 86	Mg ₂Ni _0.8Co _0.2	0	2.3
Embodiment 87	Mg ₂Ni _0.9Co _0.2	0	2.9	Embodiment 86	Mg ₂Ni _0.8Co _0.2	0	2.3
Embodiment 87	Mg ₂Ni _0.9Co _0.2	0	2.9	Embodiment 88	Mg _2.1Ni _1.8Fe _0.1	0	3.0
Embodiment 89	Mg ₂Ni _0.7Mo _0.2Rh _0.2	0	3.1	Embodiment 88	Mg _2.1Ni _1.8Fe _0.1	0	3.0
Embodiment 89	Mg ₂Ni _0.7Mo _0.2Rh _0.2	0	3.1	Embodiment 90	Mg _1.8Zr _0.2Ni	0	2.5
Embodiment 91	Mg _1.3Y _0.5Ni	0	2.0	Embodiment 90	Mg _1.8Zr _0.2Ni	0	2.5
Embodiment 91	Mg _1.3Y _0.5Ni	0	2.0	Embodiment 92	Mg ₂Ir _0.1Ni	0	2.4
Embodiment 93	Mg _1.9Al _0.1Ni _0.9Mn _0.2	0	3.5	Embodiment 92	Mg ₂Ir _0.1Ni	0	2.4
Embodiment 93	Mg _1.9Al _0.1Ni _0.9Mn _0.2	0	3.5	Embodiment 94	Mg ₂Cu _0.5Cd _0.5	0	1.6
Embodiment 95	Mg ₂Cu _0.8Pd _0.4	0	2.0	Embodiment 94	Mg ₂Cu _0.5Cd _0.5	0	1.6

Table 15

	Hydrogen bearing alloy	X (before handling)	X (handling the back)
	Hydrogen bearing alloy	X (before handling)	X (handling the back)	Embodiment 96	Mg ₂Ti _0.1Ni	0	2.3
Embodiment 97	Mg ₂Nb _0.1Ni _1.2	0	3.1	Embodiment 96	Mg ₂Ti _0.1Ni	0	2.3
Embodiment 97	Mg ₂Nb _0.1Ni _1.2	0	3.1	Embodiment 98	Mg ₂Ta _0.1Ni _1.8	0	2.8
Embodiment 99	LaAl _0.3Ni _3.8Mn _0.4Co _0.5	0.5	5.0	Embodiment 98	Mg ₂Ta _0.1Ni _1.8	0	2.8
Embodiment 99	LaAl _0.3Ni _3.8Mn _0.4Co _0.5	0.5	5.0	Embodiment 100	NmAl _0.6Ni _3.7Mn _0.3Zr _0.4	1.0	5.0
Embodiment 101	CaAl _0.4Ni _4.0Mn _0.5Si _0.1	0.7	4.5	Embodiment 100	NmAl _0.6Ni _3.7Mn _0.3Zr _0.4	1.0	5.0
Embodiment 101	CaAl _0.4Ni _4.0Mn _0.5Si _0.1	0.7	4.5	Embodiment 102	TiFe _0.4Mn _0.5	0.2	2.1
Embodiment 103	TiMn _1.6Co _0.1	0	2.6	Embodiment 102	TiFe _0.4Mn _0.5	0.2	2.1
Embodiment 103	TiMn _1.6Co _0.1	0	2.6	Embodiment 104	ZrCo _1.1Mn _1.3	0.2	3.0
Embodiment 105	Zr _0.6Ti _0.4V _0.6Ni _1.1Mn _0.2	0.1	3.5	Embodiment 104	ZrCo _1.1Mn _1.3	0.2	3.0
Embodiment 105	Zr _0.6Ti _0.4V _0.6Ni _1.1Mn _0.2	0.1	3.5	Embodiment 106	ZrMn _0.6V _0.2Ni1.5Co _0.1	0.2	3.1

From table 13-15, can find out significantly, when the hydrogen bearing alloy surface modification, activate its surface, therefore can improve the hydrogen absorption characteristic of alloy.

(embodiment 107)

Mg ₂The Ni hydrogen bearing alloy is put in the double-canopy rustless steel container with stainless steel ball, is full of the argon gas that contains 1ppm or oxygen still less and 0.5ppm or water still less thereafter in the container.After the O-ring seals sealing, rustless steel container carried out ball-milling treatment (a kind of mechanical treatment) 100 hours, and its rotary speed is 200rpm.

Measured through mechanical treatment and without the hydrogen absorption characteristic of the hydrogen bearing alloy of mechanical treatment with suction shown in Figure 6/put hydrogen characteristic test device.When the hydrogen of predetermined is imported in the reaction vessel, by this test of pressure variation having carried out in the control reaction vessel.

Specifically, at first every kind of hydrogen bearing alloy is respectively charged in the sample container 33, closes first valve 37 then ₁, open second valve 37 ₂With the 3rd valve 37 ₃In this case, start vacuum pump 35, extract the air in pipeline 32, arm 34, accumulator 38 and the sample container 33 out.Close second valve 37 then ₂With the 3rd valve 37 ₃, open first valve 37 ₁, so that make the hydrogen in the hydrogen cylinder 31 enter into pipeline 32, arm 34, accumulator 38 and sample container 33, so the hydrogen exchange of finishing.Subsequently, closing first valve 37 ₁The time, calculate the amounts of hydrogen of input from the pressure gauge that pressure gauge 36 shows.Open second valve 37 then ₂, make the hydrogen of input enter into sample container 33, with the temperature of thermocouple 40 test samples containers 33.Simultaneously, control thermocouple 40 and temperature controller 42 are so that the temperature constant in the maintenance sample container 33.At this moment, can measure pressure in the sample container 33 by pressure gauge 36 changes and is recorded on the self-recorder 43.

In the time of 25 ℃, this hydrogen storage alloy particle before mechanical treatment with after the table 16 of hydrogen absorption characteristic below listing in.

(embodiment 108)

Mg with 0.5 mole ₂The Ni hydrogen bearing alloy mixes with 0.5 mole of Ni powder as the catalyst nucleus, and the mixture that obtains is put in the double-canopy rustless steel container with stainless steel ball.Thereafter be full of the argon gas that contains 1ppm or oxygen still less and 0.5ppm or water content still less in the container, after the sealing ring sealing, rustless steel container carried out ball-milling treatment (a kind of mechanical treatment) 100 hours, and its rotary speed is 200rpm.

Measured through mechanical treatment and without the Mg of mechanical treatment with suction shown in Figure 6/put hydrogen characteristic test device ₂The hydrogen absorption characteristic of Ni hydrogen bearing alloy.The hydrogen absorption characteristic of this hydrogen bearing alloy is listed in the following table 16 in the time of 25 ℃.

(embodiment 109-150)

Hydrogen bearing alloy with listed composition among the following table 16-19 according to embodiment 107 in identical method carry out mechanical treatment, measured the variation of they hydrogen absorption characteristics before and after surface modification.In this test, used suction shown in Figure 6/put hydrogen characteristic test device.The results are shown among the following table 16-19.In these tables, symbol x represents the number of hydrogen, i.e. the number of the MHx that absorbs in the hydrogen bearing alloy.

Table 16

	Hydrogen bearing alloy	X (before handling)	X (handling the back)
	Hydrogen bearing alloy	X (before handling)	X (handling the back)	Embodiment 107	Mg ₂Ni	0	3.0
Embodiment 108	Mg ₂Ni (Ni mixed)	0	3.5	Embodiment 107	Mg ₂Ni	0	3.0
Embodiment 108	Mg ₂Ni (Ni mixed)	0	3.5	Embodiment 109	Mg ₂Cu	0	2.5
Embodiment 110	Mg ₂Co	0	3.8	Embodiment 109	Mg ₂Cu	0	2.5
Embodiment 110	Mg ₂Co	0	3.8	Embodiment 111	Mg ₂Fe	0	4.4
Embodiment 112	LaNi ₅	0.1	6.0	Embodiment 111	Mg ₂Fe	0	4.4
Embodiment 112	LaNi ₅	0.1	6.0	Embodiment 113	MmNi ₅	0	3.5
Embodiment 114	CaNi ₅	0	4.5	Embodiment 113	MmNi ₅	0	3.5
Embodiment 114	CaNi ₅	0	4.5	Embodiment 115	TiFe	0.1	1.6
Embodiment 116	TiCo	0	1.8	Embodiment 115	TiFe	0.1	1.6
Embodiment 116	TiCo	0	1.8	Embodiment 117	ZrNi ₂	0.1	3.2
Embodiment 118	ZrNi ₂	0.1	3.6	Embodiment 117	ZrNi ₂	0.1	3.2

Table 17

	Hydrogen bearing alloy	X (before handling)	X (handling the back)
	Hydrogen bearing alloy	X (before handling)	X (handling the back)	Embodiment 119	Mg ₂Ni _0.7Cu _0.3	0	2.9
Embodiment 120	Mg ₂Ni _0.9Co _0.2	0	3.4	Embodiment 119	Mg ₂Ni _0.7Cu _0.3	0	2.9
Embodiment 120	Mg ₂Ni _0.9Co _0.2	0	3.4	Embodiment 121	Mg ₂Ni _0.8Fe _0.1	0	3.5
Embodiment 122	Mg ₂Ni _0.7Rh _0.2Ru _0.2	0	3.7	Embodiment 121	Mg ₂Ni _0.8Fe _0.1	0	3.5
Embodiment 122	Mg ₂Ni _0.7Rh _0.2Ru _0.2	0	3.7	Embodiment 123	Mg _1.9Zr _0.1Ni	0	3.0
Embodiment 124	Mg _1.8Cr _0.1Ni	0	2.6	Embodiment 123	Mg _1.9Zr _0.1Ni	0	3.0
Embodiment 124	Mg _1.8Cr _0.1Ni	0	2.6	Embodiment 125	Mg ₂Mo _0.1Ni	0	2.4
Embodiment 126	Mg _1.9V _0.1Ni _0.9Mn _0.2	0	3.4	Embodiment 125	Mg ₂Mo _0.1Ni	0	2.4
Embodiment 126	Mg _1.9V _0.1Ni _0.9Mn _0.2	0	3.4	Embodiment 127	Mg ₂Cu _0.5W _0.5	0	1.6
Embodiment 128	Mg ₂Cu _0.7Cd _0.4	0	2.0	Embodiment 127	Mg ₂Cu _0.5W _0.5	0	1.6

Table 18

	Hydrogen bearing alloy	X (before handling)	X (handling the back)
	Hydrogen bearing alloy	X (before handling)	X (handling the back)	Embodiment 129	Mg ₂Y _0.1Ni _1.1	0	2.3
Embodiment 130	Mg ₂Ir _0.1Ni _1.5	0	3.1	Embodiment 129	Mg ₂Y _0.1Ni _1.1	0	2.3
Embodiment 130	Mg ₂Ir _0.1Ni _1.5	0	3.1	Embodiment 131	Mg ₂Pt _0.1Ni _1.9	0	2.8
Embodiment 132	LaAl _0.3Ni _3.5Mn _0.4Co _0.7	0.5	6.0	Embodiment 131	Mg ₂Pt _0.1Ni _1.9	0	2.8
Embodiment 132	LaAl _0.3Ni _3.5Mn _0.4Co _0.7	0.5	6.0	Embodiment 133	MmAl _0.3Ni _4.1Mn _0.3Co _0.3	1.0	6.0
Embodiment 134	CaAl _0.3Ni _4.3Mn _0.4	0.6	5.5	Embodiment 133	MmAl _0.3Ni _4.1Mn _0.3Co _0.3	1.0	6.0
Embodiment 134	CaAl _0.3Ni _4.3Mn _0.4	0.6	5.5	Embodiment 135	TiFe _0.6Mn _0.3	0.3	2.1
Embodiment 136	TiMn _0.6Co _0.4	0	2.5	Embodiment 135	TiFe _0.6Mn _0.3	0.3	2.1
Embodiment 136	TiMn _0.6Co _0.4	0	2.5	Embodiment 137	ZrCo _0.9Mn _1.1	0.1	3.5
Embodiment 138	Zr _0.5Ti _0.5V _0.7Ni _1.3	0.2	3.9	Embodiment 137	ZrCo _0.9Mn _1.1	0.1	3.5
Embodiment 138	Zr _0.5Ti _0.5V _0.7Ni _1.3	0.2	3.9	Embodiment 139	ZrMn _0.5V _0.3Ni _1.5	0.1	3.4

Table 19

	Hydrogen bearing alloy	X (before handling)	X (handling the back)
	Hydrogen bearing alloy	X (before handling)	X (handling the back)	Embodiment 140	(Mg _0.8Al _0.2)Ni	0	2.0
Embodiment 141	(Mg _0.6V _0.4) ₈Fe _0.7Cu _0.3	0	2.6	Embodiment 140	(Mg _0.8Al _0.2)Ni	0	2.0
Embodiment 141	(Mg _0.6V _0.4) ₈Fe _0.7Cu _0.3	0	2.6	Embodiment 142	(Mg _0.5Ba _0.25Cr _0.25) ₁₀ Co	0	3.1
Embodiment 143	(Mg _0.9Mn _0.05Ti _0.05) ₄Si _0.6Zn _0.4	0	2.8	Embodiment 142	(Mg _0.5Ba _0.25Cr _0.25) ₁₀ Co	0	3.1
Embodiment 143	(Mg _0.9Mn _0.05Ti _0.05) ₄Si _0.6Zn _0.4	0	2.8	Embodiment 144	(Mg _0.7Mo _0.3) ₅Cu _0.8Ni _0.2	0	2.5
Embodiment 145	(Mg _0.8Ca _0.2) ₁₁ Ni	0	2.2	Embodiment 144	(Mg _0.7Mo _0.3) ₅Cu _0.8Ni _0.2	0	2.5
Embodiment 145	(Mg _0.8Ca _0.2) ₁₁ Ni	0	2.2	Embodiment 146	(Mg _0.5Sr _0.5) ₆Co _0.5Fe _0.5	0	3.0
Embodiment 147	(Mg _0.7Li _0.3) ₇Zn _0.5Ni _0.5	0	2.1	Embodiment 146	(Mg _0.5Sr _0.5) ₆Co _0.5Fe _0.5	0	3.0
Embodiment 147	(Mg _0.7Li _0.3) ₇Zn _0.5Ni _0.5	0	2.1	Embodiment 148	(Mg _0.8La _0.1Y _0.1) ₁₅ Cu	0	2.9
Embodiment 149	(Mg _0.8Na _0.05K _0.15) ₉Ni _0.9Cu _0.1	0	3.2	Embodiment 148	(Mg _0.8La _0.1Y _0.1) ₁₅ Cu	0	2.9
Embodiment 149	(Mg _0.8Na _0.05K _0.15) ₉Ni _0.9Cu _0.1	0	3.2	Embodiment 150	(Mg _0.6Sr _0.2La _0.2) ₁₃Ni _0.8Cu _0.2Co _0.2	0	2.9

From table 16-19, can find out significantly that the mechanical treatment hydrogen bearing alloy has activated the surface of alloy, therefore can improve the hydrogen absorption characteristic of hydrogen bearing alloy.

(embodiment 151)

The hydrogen-bearing alloy powder that makes among the embodiment 108 is mixed with electrolytic copper powder by 1: 1 weight ratio.(internal diameter: 10mm), the resulting mixture of 1g is applied 20 tons pressure compacting 3 minutes to obtain particle in the particle molding apparatus.Then this particle is clipped in the middle of the Ni silk screen spot welding and compacting.Subsequently, by spot welding compacts is linked to each other with the Ni lead.Thereby made hydrogen-bearing alloy electrode (negative pole).

(comparative example 20)

Except using Mg without mechanical treatment ₂The Ni hydrogen bearing alloy is as outside the raw material, prepares hydrogen-bearing alloy electrode (negative pole) with the method identical with embodiment 151.

The negative pole of embodiment 151 and comparative example 20 is immersed in the potassium hydroxide aqueous solution of 8N with the sintrered nickel counterelectrode respectively, carries out the charge test then under 25 ℃ temperature.In the test of this charge, every gram hydrogen bearing alloy is with the current charges of 100mA 10 hours, and after 10 minutes, every gram hydrogen bearing alloy is with the current discharge of 100mA, up to the voltage with respect to mercuric oxide electrode reduce to-during 0.5V till.Carry out this charge repeatedly, it the results are shown among Figure 10.In Figure 10, symbol A is without the charge/discharge characteristics curve of the negative pole of mechanical treatment in the comparative example 20.Symbol B is through the charge/discharge characteristics curve of the negative pole of mechanical treatment among the embodiment 151.

Can find out significantly that from Figure 10 with regard to comparative example 20 (charge/discharge characteristics curve A), it can not carry out charge/discharge at normal temperatures, shows its discharge off capacity.By contrast, with regard to embodiment 151 (charge/discharge characteristics curve B), its discharge capacity of circulating for the first time is 750mAh/g.Obviously, it is possible improving discharge capacity significantly by mechanical treatment.Therefore, can think usually that mechanical treatment is a method of improving battery (being equipped with the negative pole that contains hydrogen bearing alloy) flash-over characteristic effectively.

(embodiment 152-155 and comparative example 20)

With Mg ₂The Ni hydrogen bearing alloy is put in the double-canopy rustless steel container with stainless steel ball, is full of the argon gas that contains 1ppm or oxygen still less and 0.5ppm or water content still less then in the rustless steel container.After the O-ring seals sealing, this rustless steel container carries out 2 hours, 50 hours, 200 hours, 800 hours ball-milling treatment (a kind of mechanical treatment) respectively, and their rotary speed is controlled to be 200rpm.Thereby made the hydrogen-bearing alloy powder of four kinds of surface modifications.

With with identical method described in the embodiment 151, will prepare hydrogen-bearing alloy electrode (negative pole) through mechanical treatment and without the hydrogen bearing alloy of mechanical treatment.These negative poles are immersed in the potassium hydroxide aqueous solution of 8N with counterelectrode respectively, carry out the charge test then under 25 ℃ temperature.In the test of this charge, charge with the method identical with embodiment 151.Recorded their maximum discharge capacity.The results are shown in Table 20 in this charge test, and the average particulate diameter of the hydrogen-bearing alloy powder in these hydrogen-bearing alloy powders and the comparative example 20 is also listed in the table 20.

Table 20

	Processing time (h)	Average particulate diameter (μ m)	Discharge capacity (mAh/g)
	Processing time (h)	Average particulate diameter (μ m)	Discharge capacity (mAh/g)	Comparative example 20	0	80	0
Embodiment 152	2	20	115	Comparative example 20	0	80	0
Embodiment 152	2	20	115	Embodiment 153	50	6	523
Embodiment 154	200	2	617	Embodiment 153	50	6	523
Embodiment 154	200	2	617	Embodiment 155	800	1	658

Can find out significantly that from table 20 along with the increase of mechanical treatment time, the average particulate diameter of hydrogen bearing alloy reduces pro rata.Therefore it is possible increasing discharge capacity.

(embodiment 156-162 and comparative example 20)

Mg ₂The Ni hydrogen bearing alloy is put in the double-canopy rustless steel container with stainless steel ball, is full of the argon gas that contains 1ppm or oxygen still less and 0.5ppm or water still less then in the rustless steel container.After the O-ring seals sealing, rustless steel container carried out respectively 3 hours, 40 hours, 300 hours, 650 hours, 800 hours, 900 hours and 1000 hours ball-milling treatment (a kind of mechanical treatment).Their rotary speed is controlled to be 200rpm.Thereby made the hydrogen-bearing alloy powder of seven kinds of surface modifications.

Described with embodiment 151, will prepare hydrogen-bearing alloy electrode (negative pole) with same method through mechanical treatment and without the hydrogen bearing alloy of mechanical treatment.These negative poles are immersed in the potassium hydroxide aqueous solution of 8N with counterelectrode (sintered nickel electrode) respectively, carry out the charge test then under 25 ℃ temperature.In the test of this charge, charge with the method identical with embodiment 151, measured their maximum discharge capacity.The results are shown in Table 21 in this charge test.Δ (2 θ of hydrogen bearing alloy in embodiment 156-162 and the comparative example 20 ₂) (in the x-ray diffraction pattern that obtains as radiation source with the CuK alpha ray, the half-breadth at least one peak in three intense lines) value also lists in the table 21.

Table 21

	Processing time (h)	Δ(2θ2) (°)	Discharge capacity (mAh/g)
	Processing time (h)	Δ(2θ2) (°)	Discharge capacity (mAh/g)	Comparative example 20	0	0.1	0
Embodiment 156	3	0.5	142	Comparative example 20	0	0.1	0
Embodiment 156	3	0.5	142	Embodiment 157	40	1.2	503
Embodiment 158	300	3.4	631	Embodiment 157	40	1.2	503
Embodiment 158	300	3.4	631	Embodiment 159	650	5.1	649
Embodiment 160	800	9.5	653	Embodiment 159	650	5.1	649
Embodiment 160	800	9.5	653	Embodiment 161	900	25.1	630
Embodiment 162	1000	41.3	535	Embodiment 161	900	25.1	630

Can find out significantly that from table 21 along with the increase of mechanical treatment time, the crystallite dimension of hydrogen-bearing alloy powder reduces pro rata, increase Δ (2 θ simultaneously ₂) value.Thereby the increase discharge capacity is possible.

(embodiment 163-167 and comparative example 20)

With Mg ₂The Ni hydrogen bearing alloy is put in the double-canopy rustless steel container with stainless steel ball, is full of the argon gas that contains 1ppm or oxygen still less and 0.5ppm or water still less then in the rustless steel container.With after the O-ring seals sealing, rustless steel container carries out the ball-milling treatment (a kind of mechanical treatment) of 0.5 hour, 2.5 hours, 15 hours, 250 hours and 700 hours respectively.Their rotary speed is controlled to be 200rpm.Thereby made the hydrogen-bearing alloy powder of 5 kinds of surface modifications.

As described in embodiment 151, prepare hydrogen-bearing alloy electrode (negative pole) with identical method through mechanical treatment and without the hydrogen bearing alloy of mechanical treatment.These negative poles are immersed in the potassium hydroxide aqueous solution of 8N with counterelectrode (sintered nickel electrode) respectively, carry out the charge test then under 25 ℃ temperature.In the test of this charge, charge with the method identical with embodiment 151, measured their maximum discharge capacity.The crystallite dimension of hydrogen bearing alloy is listed in the following table 22 in the result of charge and discharge cycles test and embodiment 163-167 and the comparative example 20.

Table 22

	Processing time (h)	The size of crystal grain (nm)	Discharge capacity (mAh/g)
	Processing time (h)	The size of crystal grain (nm)	Discharge capacity (mAh/g)	Comparative example 20	0	111.5	0
Embodiment 163	0.5	56.2	13	Comparative example 20	0	111.5	0
Embodiment 163	0.5	56.2	13	Embodiment 164	2.5	37.5	124
Embodiment 165	15	23.2	323	Embodiment 164	2.5	37.5	124
Embodiment 165	15	23.2	323	Embodiment 166	250	5.1	626
Embodiment 167	700	2.2	651	Embodiment 166	250	5.1	626

Can find out significantly that from table 22 along with the increase of mechanical treatment time, the crystallite dimension of hydrogen bearing alloy reduces pro rata, it is possible therefore increasing discharge capacity.

(embodiment 168-172 and comparative example 21,22)

Mg ₂The Ni hydrogen bearing alloy is put in the double-canopy rustless steel container with stainless steel ball, and this rustless steel container is promptly handled under vacuum, inert gas (nitrogen, argon gas or helium), hydrogen, oxygen and the air conditions at seven kinds of atmospheric conditions.After the sealing ring sealing, rustless steel container carries out 100 hours ball-milling treatment (a kind of mechanical treatment), and their rotary speed is controlled to be 200rpm.Thereby made the hydrogen-bearing alloy powder of seven kinds of surface modifications.

As described in embodiment 151, these hydrogen bearing alloys through mechanical treatment prepare hydrogen-bearing alloy electrode (negative pole) with same method.These negative poles are immersed in the potassium hydroxide aqueous solution of 8N with counterelectrode (sintered nickel electrode) respectively, then under 25 ℃ temperature, carry out the charge test and have measured their maximum discharge capacity with the method identical with embodiment 151.The results are shown in Table 23 in this charge test.

Table 23

	Handle atmosphere	Discharge capacity (mAh/g)
	Handle atmosphere	Discharge capacity (mAh/g)	Embodiment 168	Argon gas (99.999%)	605
Embodiment 169	Vacuum	402	Embodiment 168	Argon gas (99.999%)	605
Embodiment 169	Vacuum	402	Embodiment 170	Nitrogen (99.999%)	513
Embodiment 171	Helium (99.999%)	526	Embodiment 170	Nitrogen (99.999%)	513
Embodiment 171	Helium (99.999%)	526	Embodiment 172	Hydrogen (99.99999%)	650
Comparative example 21	Oxygen (99.999%)	0	Embodiment 172	Hydrogen (99.99999%)	650
Comparative example 21	Oxygen (99.999%)	0	Comparative example 22	Air	0

Embodiment 168-172 from table 23 can obviously find out, carries out mechanical treatment in vacuum or under the atmosphere of inert gas or hydrogen and meets the requirements.If mechanical treatment is to carry out under this atmosphere, it is possible increasing discharge capacity.

(embodiment 173-219 and comparative example 20)

Hydrogen bearing alloy with listed composition among the following table 24-27 carries out mechanical treatment under different condition, thereby has finished surface treatment.

As described in embodiment 151, these hydrogen bearing alloys through mechanical treatment prepare hydrogen storage alloy negative with same method.These negative poles are immersed in the potassium hydroxide aqueous solution of 8N with counterelectrode (sintered nickel electrode) respectively then, under 25 ℃ temperature, fill/and electric loop test with the method identical with embodiment 151, measured their maximum discharge capacity, it the results are shown among the table 24-27.The maximum discharge capacity of comparative example 20 is also listed among the table 24-27.

Table 24

	Alloy with hydrogen storage property	Additive	Processing time (h)	Discharge capacity (mAh/g)
	Alloy with hydrogen storage property	Additive	Processing time (h)	Discharge capacity (mAh/g)	Comparative example 20	Mg ₂Ni	--	--	0
Embodiment 173	Mg ₂Ni	Ni	100	751	Comparative example 20	Mg ₂Ni	--	--	0
Embodiment 173	Mg ₂Ni	Ni	100	751	Embodiment 174	Mg ₂Ni	--	1	78
Embodiment 175	Mg ₂Ni	--	25	452	Embodiment 174	Mg ₂Ni	--	1	78
Embodiment 175	Mg ₂Ni	--	25	452	Embodiment 176	Mg ₂Ni	--	100	605
Embodiment 177	Mg ₂Ni	Ni	500	825	Embodiment 176	Mg ₂Ni	--	100	605
Embodiment 177	Mg ₂Ni	Ni	500	825	Embodiment 178	Mg ₂Ni	Co	100	752
Embodiment 179	Mg ₂Ni	Fe	100	703	Embodiment 178	Mg ₂Ni	Co	100	752
Embodiment 179	Mg ₂Ni	Fe	100	703	Embodiment 180	Mg ₂Ni	WCO ₃	100	642
Embodiment 181	Mg ₂Ni	IrO ₂	100	750	Embodiment 180	Mg ₂Ni	WCO ₃	100	642
Embodiment 181	Mg ₂Ni	IrO ₂	100	750	Embodiment 182	Mg ₂Cu	Cu	100	502

Table 25

	Alloy with hydrogen storage property	Additive	Processing time (h)	Discharge capacity (mAh/g)
	Alloy with hydrogen storage property	Additive	Processing time (h)	Discharge capacity (mAh/g)	Embodiment 183	Mg ₂CO	CO	100	712
Embodiment 184	Mg ₂Fe	Fe	100	745	Embodiment 183	Mg ₂CO	CO	100	712
Embodiment 184	Mg ₂Fe	Fe	100	745	Embodiment 185	LaNi ₅	--	--	274
Embodiment 186	LaNi ₅	Pt	100	321	Embodiment 185	LaNi ₅	--	--	274
Embodiment 186	LaNi ₅	Pt	100	321	Embodiment 187	LaNi ₅	MoCo ₃	100	325
Embodiment 188	LaNi ₅	CoO	100	290	Embodiment 187	LaNi ₅	MoCo ₃	100	325
Embodiment 188	LaNi ₅	CoO	100	290	Embodiment 189	MmNi ₅	Rh	100	123
Embodiment 190	CaNi ₅	MoNi ₃	100	150	Embodiment 189	MmNi ₅	Rh	100	123
Embodiment 190	CaNi ₅	MoNi ₃	100	150	Embodiment 191	TiFe	Pd		100	154
Embodiment 192	TiCo	FeO		100	Embodiment 191	TiFe	Pd		100	154	111
Embodiment 192	TiCo	FeO		100	Embodiment 193	ZrMn ₂	Wni ₃	100	148		111
Embodiment 194	ZrNi ₂	Au	100	85	Embodiment 193	ZrMn ₂	Wni ₃	100	148

Table 26

	Alloy with hydrogen storage property	Additive	Processing time (h)	Discharge capacity (mAh/g)
	Alloy with hydrogen storage property	Additive	Processing time (h)	Discharge capacity (mAh/g)	Embodiment 195	Mg ₂Ni _0.8Co _0.2	Ag	100	650
Embodiment 196	Mg ₂Ni _0.6Co _0.5	Ir	100	730	Embodiment 195	Mg ₂Ni _0.8Co _0.2	Ag	100	650
Embodiment 196	Mg ₂Ni _0.6Co _0.5	Ir	100	730	Embodiment 197	Mg ₂Ni _0.7Fe _0.2	V	50	360
Embodiment 198	Mg ₂Al _0.2Ni _0.8Mn _0.2	CoO	100	850	Embodiment 197	Mg ₂Ni _0.7Fe _0.2	V	50	360
Embodiment 198	Mg ₂Al _0.2Ni _0.8Mn _0.2	CoO	100	850	Embodiment 199	Mg _1.9B _0.1Ni	NiO	100	605
Embodiment 200	Mg _1.8C _0.1Ni	Pd	500	625	Embodiment 199	Mg _1.9B _0.1Ni	NiO	100	605
Embodiment 200	Mg _1.8C _0.1Ni	Pd	500	625	Embodiment 201	Mg ₂Au _0.1Ni	Cr	200	652
Embodiment 202	Mg _1.8Al _0.2Ni _0.8Cr _0.2	Ni	100	800	Embodiment 201	Mg ₂Au _0.1Ni	Cr	200	652
Embodiment 202	Mg _1.8Al _0.2Ni _0.8Cr _0.2	Ni	100	800	Embodiment 203	Mg ₂Cu _0.8Co _0.2	Mn	100	503
Embodiment 204	Mg ₂Cu _0.7Sn _0.5	Co ₃O ₄	100	524	Embodiment 203	Mg ₂Cu _0.8Co _0.2	Mn	100	503
Embodiment 204	Mg ₂Cu _0.7Sn _0.5	Co ₃O ₄	100	524	Embodiment 205	Mg ₂Au _0.1Ni _1.3	Ru	100	605
Embodiment 206	Mg ₂Ni _1.6Ag _0.1	Mo	100	553	Embodiment 205	Mg ₂Au _0.1Ni _1.3	Ru	100	605
Embodiment 206	Mg ₂Ni _1.6Ag _0.1	Mo	100	553	Embodiment 207	Mg ₂Al _0.1Ni _1.9	RhO ₂	100	502

Table 27

	Alloy with hydrogen storage property	Additive	Processing time (h)	Discharge capacity (mAh/g)
	Alloy with hydrogen storage property	Additive	Processing time (h)	Discharge capacity (mAh/g)	Embodiment 208	Mg ₂Fe _0.5Ni _0.6Zn _0.1	W	100	645
Embodiment 209	LaAl _0.3Ni _3.7Mn _0.5Co _0.5	VCO ₃	100	285	Embodiment 208	Mg ₂Fe _0.5Ni _0.6Zn _0.1	W	100	645
Embodiment 209	LaAl _0.3Ni _3.7Mn _0.5Co _0.5	VCO ₃	100	285	Embodiment 210	LaAl _0.4Ni _4.4Zr _0.2	Ru	100	231
Embodiment 211	LaAl _0.3Ni _3.7Mn _0.5Co _0.5	VNi ₃	100	265	Embodiment 210	LaAl _0.4Ni _4.4Zr _0.2	Ru	100	231
Embodiment 211	LaAl _0.3Ni _3.7Mn _0.5Co _0.5	VNi ₃	100	265	Embodiment 212	MmAl _1.0Ni _3.5Si _0.5	Nb	100	284
Embodiment 213	MmNi _3.6Mn _0.4Ti _0.3Co _0.7	WPt ₃	100	205	Embodiment 212	MmAl _1.0Ni _3.5Si _0.5	Nb	100	284
Embodiment 213	MmNi _3.6Mn _0.4Ti _0.3Co _0.7	WPt ₃	100	205	Embodiment 214	MmAl _0.2Ni _3.8Mn _0.5Cu _0.5	Ta	100	250
Embodiment 215	TiFe _0.8Mn _0.1	Co ₂O ₃	100	211	Embodiment 214	MmAl _0.2Ni _3.8Mn _0.5Cu _0.5	Ta	100	250
Embodiment 215	TiFe _0.8Mn _0.1	Co ₂O ₃	100	211	Embodiment 216	TiCo _0.6Mn _0.5	V	100	260
Embodiment 217	Zr _0.6Ti _0.4V _0.6Ni _1.3	Au	100	390	Embodiment 216	TiCo _0.6Mn _0.5	V	100	260
Embodiment 217	Zr _0.6Ti _0.4V _0.6Ni _1.3	Au	100	390	Embodiment 218	ZrCo _1.0Mn _1.3	RuO ₂	100	350
Embodiment 219	ZrV _0.3Ni _1.4Mn _0.6	Ta	100	380	Embodiment 218	ZrCo _1.0Mn _1.3	RuO ₂	100	350

24-27 can clearly find out from table, and after hydrogen bearing alloy carried out mechanical treatment, the discharge capacity of alloy increased, and charge-discharge characteristic has obtained remarkable improvement.

(embodiment 220)

Smelt the Mg that obtains with high-frequency methods ₂Ni gold and 20% (volume) are (with Mg ₂The Ni alloy is the basis) the Ni powder (a kind of additive) that plays catalyst action mixes, and then mixture put into the rustless steel container of Double layer lid with stainless steel ball.Charge into the argon gas that contains 1ppm or oxygen still less, 0.5ppm or water still less in the container, container is sealed with O type circle thereafter, ball milling (mechanical treatment) 100 hours, and rotary speed is controlled at per minute 200 changes.

Then, in the time of 25 ℃, put the suction hydrogen rate of hydrogen characteristic evaluation apparatus measurement for Evaluation alloy with suction shown in Figure 6.The hydrogen amount MHV that alloy was absorbed in 10 hours behind the hydrogen of the suction hydrogen rate V of alloy with input scheduled volume in reaction vessel represents.The result is shown in table 28.

(embodiment 221～241)

Shown in table 28, the alloy that will have a hydrogen absorption characteristic mixes with the additive that certain volume percentage (based on hydrogen bearing alloy) plays catalyst action respectively, and carries out mechanical treatment with the condition identical with embodiment 220.

Adopt suction shown in Figure 6 to put the hydrogen characteristic evaluation apparatus, use with the same method of embodiment 220 and measure its storage hydrogen rate 25 ℃ the time.Through mechanical means alloy of handling and the Mg that does not pass through mechanical treatment ₂The result of Ni alloy (comparative example 20) is shown in table 28.

Table 28

	Alloy with hydrogen storage property	Additive	Additive total amount (Vol%)	Before the V mechanical treatment	Behind the V mechanical treatment
	Alloy with hydrogen storage property	Additive	Additive total amount (Vol%)	Before the V mechanical treatment	Behind the V mechanical treatment	Comparative example 120	Mg ₂Ni	-	-	0	-
Embodiment 220	Mg ₂Ni	Ni	20	0	3.3	Comparative example 120	Mg ₂Ni	-	-	0	-
Embodiment 220	Mg ₂Ni	Ni	20	0	3.3	Embodiment 221	Mg ₂Ni _0.5Cu _0.5	Pd	51	0	2.7
Embodiment 222	Mg ₂Ni _0.75Co _0.25	MoCo ₃	32	0	3.9	Embodiment 221	Mg ₂Ni _0.5Cu _0.5	Pd	51	0	2.7
Embodiment 222	Mg ₂Ni _0.75Co _0.25	MoCo ₃	32	0	3.9	Embodiment 223	Mg ₂Ni _0.75Fe _0.25	RuO ₃	61	0	3.2
Embodiment 224	Ti ₂Ni	MmNi ₅	5	0	1.9	Embodiment 223	Mg ₂Ni _0.75Fe _0.25	RuO ₃	61	0	3.2
Embodiment 224	Ti ₂Ni	MmNi ₅	5	0	1.9	Embodiment 225	LaNi ₅	V	37	0.1	6.0
Embodiment 226	MmNi ₅	MgZn ₂	21	0	3.6	Embodiment 225	LaNi ₅	V	37	0.1	6.0
Embodiment 226	MmNi ₅	MgZn ₂	21	0	3.6	Embodiment 227	CaNi ₅	Hf	9	0	4.8
Embodiment 228	MgNi ₂	La ₃Ni	42	0	3.4	Embodiment 227	CaNi ₅	Hf	9	0	4.8
Embodiment 228	MgNi ₂	La ₃Ni	42	0	3.4	Embodiment 229	VNi ₂	ZrFe ₂	13	0	3.7

(continuing)

Table 28 (continuing)

	Alloy with hydrogen storage property	Additive	Additive total amount (vol%)	Before the V mechanical treatment	Behind the V mechanical treatment
	Alloy with hydrogen storage property	Additive	Additive total amount (vol%)	Before the V mechanical treatment	Behind the V mechanical treatment	Embodiment 230	TiNi	Ir	46	0	1.9
Embodiment 231	LaNi	V ₄Ti	84	0.1	2.6	Embodiment 230	TiNi	Ir	46	0	1.9
Embodiment 231	LaNi	V ₄Ti	84	0.1	2.6	Embodiment 232	Vni	Ni	29	0.1	2.3
Embodiment 233	LaNi ₃	Ca ₂Fe	34	0.1	4.2	Embodiment 232	Vni	Ni	29	0.1	2.3
Embodiment 233	LaNi ₃	Ca ₂Fe	34	0.1	4.2	Embodiment 234	Vni ₃	Mg ₂Ni	55	0	4.1
Embodiment 235	La ₂Ni ₇	Pt	42	0.1	7.6	Embodiment 234	Vni ₃	Mg ₂Ni	55	0	4.1
Embodiment 235	La ₂Ni ₇	Pt	42	0.1	7.6	Embodiment 236	Zr ₂Ni ₇	Mg ₂Cu	63	0	6.9
Embodiment 237	La ₂Ni ₃	ZrNi ₂	2	0.2	3.6	Embodiment 236	Zr ₂Ni ₇	Mg ₂Cu	63	0	6.9
Embodiment 237	La ₂Ni ₃	ZrNi ₂	2	0.2	3.6	Embodiment 238	Ca ₂Ni ₃	Mo	27	0.1	3.1
Embodiment 239	La ₇Ni ₃	TiNi	13	0.1	4.2	Embodiment 238	Ca ₂Ni ₃	Mo	27	0.1	3.1
Embodiment 239	La ₇Ni ₃	TiNi	13	0.1	4.2	Embodiment 240	La ₃Ni	Co ₃O ₄	73	0.2	8.1
Embodiment 241	V ₃Ni	Co	58	0	7.6	Embodiment 240	La ₃Ni	Co ₃O ₄	73	0.2	8.1

Can find out obviously from table 28, embodiment 220～241 handles the hydrogen bearing alloy that comprises hydrogen bearing alloy that contains the Ni that is not less than 5% (volume) and the mixture that adds additive such as metallic addition and obtain with mechanical means, and it inhales hydrogen rate and hydrogen storage property significantly is improved.

(embodiment 242)

The hydrogen-bearing alloy powder of embodiment 220 is mixed with electrolytic copper powder by 1: 1 weight ratio, the mixture of the 1g that obtains is joined in the mould of internal diameter 10mm, under the pressure of 20000kg, suppressed 3 minutes, obtain particle.This particle is clipped in the Ni net, and periphery is by spot welding and compacting respectively.Then, compacts is linked to each other with the Ni lead-in wire through spot welding, make hydrogen-bearing alloy electrode (negative pole) thus.

The hydrogen electrode that makes thus is immersed in the potassium hydroxide aqueous slkali of 8N with the sintrered nickel counterelectrode.Under 25 ℃, carry out the charging and discharging loop test then.Each charge and discharge cycles was made up of several steps: every gram hydrogen bearing alloy is with the current charges of 100mA 10 hours, fill 10 minutes after, every gram hydrogen bearing alloy is with the current discharge of 20mA, until the voltage with respect to mercuric oxide electrode reduce to-during 0.5V till.

The comparison of the cyclic discharge capacity characteristic of comparative example 20 (containing the Mg2Ni that does not pass through aforementioned mechanical treatment) negative electrode and the cyclic discharge capacity characteristic of embodiment 242 negative electrodes is marked respectively by curve a and b in Figure 11.Apparent in Figure 11, contain the Mg that does not pass through aforementioned mechanical treatment ₂The negative electrode of Ni can not discharge and recharge at normal temperatures that (curve a).On the other hand, the negative electrode that contains the hydrogen bearing alloy of embodiment 220 is 832mAh/g in the discharge capacity of circulation for the first time.This just demonstrates the material of crossing with mechanical treatment, and discharge capacity has had remarkable increase.

(embodiment 243～253)

According to the part by weight shown in the table 29, with nickel and Mg ₂The Ni alloy mixes, and makes 12 kinds of hydrogen bearing alloys, and resulting mixture is handled in the mode identical with embodiment 220.

Subsequently, adopt the method identical, measure the suction hydrogen rate of every kind of hydrogen bearing alloy with embodiment 220.

Adopt every kind hydrogen bearing alloy use with example 242 same method and be made into negative electrode thereafter.The negative electrode that obtains thus is immersed in the KOH aqueous slkali of 8N with the sintrered nickel antipole respectively, under 25 ℃, carries out charge and discharge cycles, measure maximum discharge capacity.

The result who obtains lists in the table 29 with the result of comparative example 20.

Figure 12 shows that the XRD diffraction spectrogram that changes with Ni.In Figure 12, that A shows is sample Mg ₂The diffraction spectrogram of Ni+5% volume Ni; That B shows is sample Mg ₂The diffraction spectrogram of Ni+10% (volume) Ni; That C shows is sample Mg ₂The diffraction spectrogram of Ni+15% (volume) Ni; That D shows is sample Mg ₂The diffraction spectrogram of Ni+18% (volume) Ni; That E shows is sample Mg ₂The diffraction spectrogram of Ni+22% (volume) Ni; That F shows is sample Mg ₂The diffraction spectrogram of Ni+25% (volume) Ni; That G shows is sample Mg ₂The diffraction spectrogram of Ni+33% (volume) Ni.Apparent from Figure 12, along with Ni content increases, at Mg ₂In the X-ray diffraction spectrogram of Ni, broaden pro rata, increased apparent half-breadth value Δ (2 θ so significantly at contiguous 20 ° of peak values with contiguous 40 ° _{20 °}With 2 θ _{40 °}).

Table 29

	The content of nickel (vol%)	Inhale hydrogen rate V	Discharge capacity (mAh/g)
	The content of nickel (vol%)	Inhale hydrogen rate V	Discharge capacity (mAh/g)	Comparative example embodiment 20	0	0	0
Embodiment 243	5.1	2.1	525	Comparative example embodiment 20	0	0	0
Embodiment 243	5.1	2.1	525	Embodiment 244	9.7	2.2	544
Embodiment 245	13.9	2.5	645	Embodiment 244	9.7	2.2	544
Embodiment 245	13.9	2.5	645	Embodiment 246	17.7	3.0	751
Embodiment 247	21.2	3.1	790	Embodiment 246	17.7	3.0	751
Embodiment 247	21.2	3.1	790	Embodiment 248	24.4	3.2	805
Embodiment 249	30.0	3.3	832	Embodiment 248	24.4	3.2	805
Embodiment 249	30.0	3.3	832	Embodiment 250	34.5	3.4	850
Embodiment 251	39.2	3.6	900	Embodiment 250	34.5	3.4	850
Embodiment 251	39.2	3.6	900	Embodiment 252	49.8	3.7	920
Embodiment 253	65.9	2.8	700	Embodiment 252	49.8	3.7	920

Can find out obviously that from table 29 suction hydrogen rate and discharge capacity are along with the increase of Ni content improves the highest 50% (volume) that can be of Ni content.But, when the content of Ni surpasses 50% (volume), inhale the hydrogen rate and but decline to a great extent.

(embodiment 254～275)

According to the listed volume ratio of table 30, multiple additives is mixed with multiple alloy with hydrogen storage property, and with the mixture that obtains to carry out mechanical treatment to prepare 22 kinds of hydrogen bearing alloys with embodiment 220 described identical modes.

Then, adopt resulting each hydrogen bearing alloy, according to preparing negative electrode with the same method of embodiment 242, and the negative electrode that will so obtain is immersed in the KOH aqueous slkali of 8N with the sintrered nickel counterelectrode.Under 25 ℃, carry out charge and discharge cycles then, measure maximum discharge capacity.

The result of resulting result and comparative example 20 is shown in table 30.

Table 30

	Alloy with hydrogen storage property	Additive	Additive total amount (vol%)	(mAh/g) discharge capacity
	Alloy with hydrogen storage property	Additive	Additive total amount (vol%)	(mAh/g) discharge capacity	Comparative example 20	Mg ₂Ni	-	-	0
Embodiment 254	Mg ₂Ni	Ni	65	820	Comparative example 20	Mg ₂Ni	-	-	0
Embodiment 254	Mg ₂Ni	Ni	65	820	Embodiment 255	Mg ₂Ni _0.5Cu _0.5	wNi ₃	31	728
Embodiment 256	Mg ₂Ni _0.75Co _0.25	NimO	27	826	Embodiment 255	Mg ₂Ni _0.5Cu _0.5	wNi ₃	31	728
Embodiment 256	Mg ₂Ni _0.75Co _0.25	NimO	27	826	Embodiment 257	Mg ₂Ni _0.75Co _0.25	LaNi ₅	48	850
Embodiment 258	Ti ₂Ni	Au	3	302	Embodiment 257	Mg ₂Ni _0.75Co _0.25	LaNi ₅	48	850
Embodiment 258	Ti ₂Ni	Au	3	302	Embodiment 259	LaNi ₅	V ₂O ₅	63	350
Embodiment 260	MmNi ₅	ZrFe ₂	22	285	Embodiment 259	LaNi ₅	V ₂O ₅	63	350
Embodiment 260	MmNi ₅	ZrFe ₂	22	285	Embodiment 261	CaNi ₅	OB	38	350
Embodiment 262	MgNi ₂	TiNi	52	442	Embodiment 261	CaNi ₅	OB	38	350
Embodiment 262	MgNi ₂	TiNi	52	442	Embodiment 263	VNi ₂	Wco3	8	419

Table 30 (continuing)

	Alloy with hydrogen storage property	Additive	Additive total amount (vol%)	(mAh/g) discharge capacity
	Alloy with hydrogen storage property	Additive	Additive total amount (vol%)	(mAh/g) discharge capacity	Embodiment 264	TiNi	Zr ₂Ni ₇	26	374
Embodiment 265	LaNi	Ti	64	355	Embodiment 264	TiNi	Zr ₂Ni ₇	26	374
Embodiment 265	LaNi	Ti	64	355	Embodiment 266	VNi	Ni	14	480
Embodiment 267	LaNi ₃	RuO ₂	17	450	Embodiment 266	VNi	Ni	14	480
Embodiment 267	LaNi ₃	RuO ₂	17	450	Embodiment 268	VNi ₃	Co	56	401
Embodiment 269	La ₂Ni ₇	Ta	35	360	Embodiment 268	VNi ₃	Co	56	401
Embodiment 269	La ₂Ni ₇	Ta	35	360	Embodiment 270	Zr ₂Ni ₇	Na ₂Ni	2	364
Embodiment 271	La ₂Ni ₃	ZrNi ₂	42	222	Embodiment 270	Zr ₂Ni ₇	Na ₂Ni	2	364
Embodiment 271	La ₂Ni ₃	ZrNi ₂	42	222	Embodiment 272	Ca ₂Ni ₃	LaNi	29	211
Embodiment 273	La ₇Ni ₃	V ₃Ni	51	503	Embodiment 272	Ca ₂Ni ₃	LaNi	29	211
Embodiment 273	La ₇Ni ₃	V ₃Ni	51	503	Embodiment 274	La ₃Ni	Co ₂O ₃	38	450
Embodiment 275	V ₃Ni	Rf	7	700	Embodiment 274	La ₃Ni	Co ₂O ₃	38	450

Can find out obviously that from table 30 hydrogen bearing alloy of handling with mechanical means has increased discharge capacity, has improved charge-discharge characteristic significantly.

(embodiment 276～279 and comparative example 20)

The Mg that will obtain with the high-frequency melting method ₂Ni alloy and LaNi5 alloy mix by 80: 20 volume ratio.The mixture that obtains is handled the different time by the mechanical means identical with example 220, obtain 4 kinds of different hydrogen bearing alloys.

Then, measure Δ (the 2 θ 2) value (using the half-breadth value of Cuk α) and the suction hydrogen rate of each hydrogen bearing alloy respectively as near the peak of radiogenic X-ray diffraction spectrogram 40 °.

Method according to identical with example 242 adopts every kind of hydrogen bearing alloy to make negative pole respectively, is immersed in the KOH aqueous slkali of 8N with the sintrered nickel counterelectrode, carries out charge and discharge cycles then under 25 ℃, measures maximum discharge capacity.

The Mg that does not handle of result who obtains and comparative example 20 through mechanical means ₂The result of Ni lists in the table 31 together.

Table 31

	Processing time (h)	Δ(2θ ₂)(°)	Inhale hydrogen rate V	Discharge capacity (mAh/g)
	Processing time (h)	Δ(2θ ₂)(°)	Inhale hydrogen rate V	Discharge capacity (mAh/g)	Comparative example 20	0	0.07	0.6	150
Embodiment 276	5	0.60	1.9	463	Comparative example 20	0	0.07	0.6	150
Embodiment 276	5	0.60	1.9	463	Embodiment 277	50	1.50	2.4	621
Embodiment 278	400	3.70	3.4	860	Embodiment 277	50	1.50	2.4	621
Embodiment 278	400	3.70	3.4	860	Embodiment 279	700	6.10	3.5	871

Can find out obviously that from table 31 the mechanical treatment time is long more, the diameter of crystal grain is more little, has produced uneven distortion in the crystal simultaneously.So Δ (2 θ ₂) the value increase, store up hydrogen rate and discharge capacity simultaneously and also obtained very big increase.

(embodiment 280～284 and comparative example 23,24)

70% (volume) Mg ₂Ni alloy and 30% (volume) Co powder is placed in the rustless steel container of Double layer lid with stainless steel ball.Then under seven kinds of different atmospheric conditions, promptly use the method identical to carry out mechanical treatment under vacuum, argon gas, nitrogen, helium, hydrogen, oxygen and the air conditions with example 220, prepare the hydrogen-bearing alloy powder of 7 kinds of surface modifications.

Measure the suction hydrogen rate of the hydrogen-bearing alloy powder of these modifications then.

Thereafter, method according to identical with example 242 adopts the hydrogen bearing alloy of these modifications to make negative electrode respectively, and the negative pole that obtains is immersed in the KOH aqueous slkali of 8N with the sintrered nickel counterelectrode, under 25 ℃, carry out charge and discharge cycles then, measure maximum discharge capacity.

Its result is shown in table 32.

Table 32

	Handle gas	Inhale hydrogen rate V	(mAh/g) discharge capacity
	Handle gas	Inhale hydrogen rate V	(mAh/g) discharge capacity	Embodiment 280	Argon(99.999％)	2.4	610
Embodiment 281	Vacuum	2.0	415	Embodiment 280	Argon(99.999％)	2.4	610
Embodiment 281	Vacuum	2.0	415	Embodiment 282	Nitrogen(99.999％)	2.2	550
Embodiment 283	Helium(99.999％)	2.1	531	Embodiment 282	Nitrogen(99.999％)	2.2	550
Embodiment 283	Helium(99.999％)	2.1	531	Embodiment 284	Hydrogen(99.99999％)	2.7	672
Comparative example 23	Oxygen(99.999％)	0	0	Embodiment 284	Hydrogen(99.99999％)	2.7	672
Comparative example 23	Oxygen(99.999％)	0	0	Comparative example 24	Air	0	0

Can find out obviously that from table 32 the suction hydrogen rate of carrying out the hydrogen bearing alloy of mechanical treatment under vacuum, inert gas or nitrogen atmosphere condition improves a lot, and the discharge capacity that contains the negative electrode of these hydrogen bearing alloys improves a lot also.

(embodiment 285～306)

The powder additive of predetermined particle diameter is joined in the alloy with hydrogen storage property shown in table 33, and the mixture that obtains is handled the different time according to the mechanical means identical with embodiment 220, obtain 22 kinds of different hydrogen bearing alloys.

Then, measure the suction hydrogen rate of every kind of alloy according to the method identical with embodiment 220.

After this,, make negative electrode with these hydrogen bearing alloys, and the negative electrode that obtains is immersed in the KOH aqueous slkali of 8N with the sintrered nickel counterelectrode, under 25 ℃, carry out charge and discharge cycles then, measure maximum discharge capacity according to the method identical with embodiment 242.

The result who obtains lists in the table 33 with the disperse volume of aforesaid powder additive and the result of comparative example 20.

Table 33

	Alloy with hydrogen storage property	Additive	Particle diameter (μ m)	Dispersion rate (vol%)	Inhale the hydrogen rate	Discharge capacity (mAh/g)
	Alloy with hydrogen storage property	Additive	Particle diameter (μ m)	Dispersion rate (vol%)	Inhale the hydrogen rate	Discharge capacity (mAh/g)	Comparative example 20	Mg ₂Ni	-	-	0	0	0
Embodiment 285	Mg ₂Ni	Ni	0.001	30	3.0	743	Comparative example 20	Mg ₂Ni	-	-	0	0	0
Embodiment 285	Mg ₂Ni	Ni	0.001	30	3.0	743	Embodiment 286	Mg ₂Ni _0.6Cu _0.4	Zr	0.513	17	2.8	700
Embodiment 287	Mg ₂Ni _0.7Cu _0.3	MoNi ₃	8.15	0.4	3.3	824	Embodiment 286	Mg ₂Ni _0.6Cu _0.4	Zr	0.513	17	2.8	700
Embodiment 287	Mg ₂Ni _0.7Cu _0.3	MoNi ₃	8.15	0.4	3.3	824	Embodiment 288	Mg ₂Ni _0.95Fe _0.15	Co ₂O ₃	0.692	16	3.4	856
Embodiment 289	Ti ₂Ni	Ag	3.68	0.7	3.0	290	Embodiment 288	Mg ₂Ni _0.95Fe _0.15	Co ₂O ₃	0.692	16	3.4	856
Embodiment 289	Ti ₂Ni	Ag	3.68	0.7	3.0	290	Embodiment 290	LaNi ₅	ZrNi ₂	5.1	30	5.0	381
Embodiment 291	MmNi ₅	W	35.7	4.3	5.5	256	Embodiment 290	LaNi ₅	ZrNi ₂	5.1	30	5.0	381
Embodiment 291	MmNi ₅	W	35.7	4.3	5.5	256	Embodiment 292	CaNi ₅	ZrFe ₃	0.325	17	5.8	348
Embodiment 293	MgNi ₂	V	0.013	32	3.1	431	Embodiment 292	CaNi ₅	ZrFe ₃	0.325	17	5.8	348
Embodiment 293	MgNi ₂	V	0.013	32	3.1	431	Embodiment 294	VNi ₂	Mg ₂Ni	12.0	0.5	3.8	409
Embodiment 295	TiNi	Tc	1.35	2.5	2.0	368	Embodiment 294	VNi ₂	Mg ₂Ni	12.0	0.5	3.8	409

Table 33 (continuing)

	Alloy with hydrogen storage property	Additive	Particle diameter (μ m)	Dispersion rate (vol%)	Inhale the hydrogen rate	Discharge capacity (mAh/g)
	Alloy with hydrogen storage property	Additive	Particle diameter (μ m)	Dispersion rate (vol%)	Inhale the hydrogen rate	Discharge capacity (mAh/g)	Embodiment 296	LaNi	Mg ₂Cu	2.31	26	2.7	351
Embodiment 297	VNi	LaNi ₅	0.052	1.8	3.0	360	Embodiment 296	LaNi	Mg ₂Cu	2.31	26	2.7	351
Embodiment 297	VNi	LaNi ₅	0.052	1.8	3.0	360	Embodiment 298	LaNi ₃	Ti ₂Ni	0.016	45	4.8	425
Embodiment 299	VNi ₃	TiFe	0.894	3.6	4.9	431	Embodiment 298	LaNi ₃	Ti ₂Ni	0.016	45	4.8	425
Embodiment 299	VNi ₃	TiFe	0.894	3.6	4.9	431	Embodiment 300	La ₂Ni ₇	Zr ₂Fe	0.953	23	10.1	367
Embodiment 301	Zr ₂Ni ₇	IrO ₂	22.3	0.02	9.5	356	Embodiment 300	La ₂Ni ₇	Zr ₂Fe	0.953	23	10.1	367
Embodiment 301	Zr ₂Ni ₇	IrO ₂	22.3	0.02	9.5	356	Embodiment 302	La ₂Ni ₃	MmNi ₅	0.413	8.9	3.6	218
Embodiment 303	Ca ₂Ni ₃	Rh	40.5	48	3.8	209	Embodiment 302	La ₂Ni ₃	MmNi ₅	0.413	8.9	3.6	218
Embodiment 303	Ca ₂Ni ₃	Rh	40.5	48	3.8	209	Embodiment 304	La ₇Ni ₃	WCo ₃	35.36	0.06	4.0	482
Embodiment 305	La ₃Ni	Ru	0.156	31	8.5	503	Embodiment 304	La ₇Ni ₃	WCo ₃	35.36	0.06	4.0	482
Embodiment 305	La ₃Ni	Ru	0.156	31	8.5	503	Embodiment 306	V ₃Ni	Cr	8.91	15	9.0	690

Can obviously find out from table 33, although Mg ₂The suction hydrogen rate V of Ni is approximately 0～0.5 at normal temperatures, when powder additive such as Ni powder are joined the hydrogen bearing alloy with hydrogen storage property, in the time of for example in the hydrogen bearing alloy among the embodiment 285～306, alloy hydrogen absorption characteristic at normal temperatures is improved, and the charge-discharge characteristic of negative electrode has also obtained very big improvement simultaneously.

(embodiment 307～326)

The powder of predetermined particle diameter is joined shown in table 34, general formula in (V) and the alloy with hydrogen absorption characteristic (VI), the mixture that obtains according to the method mechanical treatment different time identical with embodiment 220, is obtained 20 kinds of different hydrogen bearing alloys thus.

Measure the storage hydrogen rate of every kind of hydrogen bearing alloy then respectively according to the method identical with embodiment 20.

, according to embodiment 242 identical method, respectively with these hydrogen bearing alloys make negative electrode, the negative electrode that obtains is immersed in the KOH aqueous slkali of 8N with the sintrered nickel counterelectrode, under 25 ℃, carry out charge and discharge cycles then, measure maximum discharge capacity thereafter.

Its result lists in table 34 with the disperse volume of aforesaid powder additive.

Table 34

	Alloy with hydrogen storage property	Additive	Particle diameter (μ m)	Dispersion rate (vol%)	Inhale the hydrogen rate	Discharge capacity (mAh/g)
	Alloy with hydrogen storage property	Additive	Particle diameter (μ m)	Dispersion rate (vol%)	Inhale the hydrogen rate	Discharge capacity (mAh/g)	Embodiment 307	(Mg _0.8Mn _0.2) ₄ Ni	Co		5	3.2	2.8	456
Embodiment 308	(Mg _0.6Cr _0.4) ₁₂Co _0.3Cu _0.7	CaNi ₅	20	15.3	3.0	391	Embodiment 307	(Mg _0.8Mn _0.2) ₄ Ni	Co		5	3.2	2.8	456
Embodiment 308	(Mg _0.6Cr _0.4) ₁₂Co _0.3Cu _0.7	CaNi ₅	20	15.3	3.0	391	Embodiment 309	(Mg _0.8Al _0.1B _0.1) ₄ Fe	TiFe		35	8.6	1.6	530
Embodiment 310	(Mg _0.9Mo _0.1) ₁₁Si	Ni	0.1	25.2	3.1	700	Embodiment 309	(Mg _0.8Al _0.1B _0.1) ₄ Fe	TiFe		35	8.6	1.6	530
Embodiment 310	(Mg _0.9Mo _0.1) ₁₁Si	Ni	0.1	25.2	3.1	700	Embodiment 311	(Mg _0.7Ru _0.3) ₁₃Sn _0.5Zn _0.5	V	3	40.1	2.6	621
Embodiment 312	(Mg _0.8Pd _0.1W _0.1) ₁₀Ni	Ti ₂Ni	18	55.3	2.2	313	Embodiment 311	(Mg _0.7Ru _0.3) ₁₃Sn _0.5Zn _0.5	V	3	40.1	2.6	621
Embodiment 312	(Mg _0.8Pd _0.1W _0.1) ₁₀Ni	Ti ₂Ni	18	55.3	2.2	313	Embodiment 313	(Mg _0.7Zr _0.3) ₅Ni _0.9Cu _0.1	Co ₃Mo	50	1.2	2.1	215
Embodiment 314	(Mg _0.9C _0.1) ₁₅Ni _0.9Co _0.1	Ni	0.9	11.6	2.9	400	Embodiment 313	(Mg _0.7Zr _0.3) ₅Ni _0.9Cu _0.1	Co ₃Mo	50	1.2	2.1	215
Embodiment 314	(Mg _0.9C _0.1) ₁₅Ni _0.9Co _0.1	Ni	0.9	11.6	2.9	400	Embodiment 315	(Mg _0.7Ge _0.3) ₉ Fe	ZrMnNi		23	31.2	3.1	390
Embodiment 316	(Mg _0.8P _0.1Ti _0.1) ₃Cu	Pt	11	0.6	2.6	280	Embodiment 315	(Mg _0.7Ge _0.3) ₉ Fe	ZrMnNi		23	31.2	3.1	390

Table 34 (continuing)

	Alloy with hydrogen storage property	Additive	Particle diameter (μ m)	Dispersion rate (vol%)	Inhale the hydrogen rate	Discharge capacity (mAh/g)
	Alloy with hydrogen storage property	Additive	Particle diameter (μ m)	Dispersion rate (vol%)	Inhale the hydrogen rate	Discharge capacity (mAh/g)	Embodiment 317	(Mg _0.9K _0.1) ₃Ni	NiP	0.5	19.3	2.2	431
Embodiment 318	(Mg _0.6Ca _0.4) ₁₄Co _0.5Ni _0.5	Mo	1.3	60.2	1.3	320	Embodiment 317	(Mg _0.9K _0.1) ₃Ni	NiP	0.5	19.3	2.2	431
Embodiment 318	(Mg _0.6Ca _0.4) ₁₄Co _0.5Ni _0.5	Mo	1.3	60.2	1.3	320	Embodiment 319	(Mg _0.8Ca _0.1Sr _0.1) ₁₂ Zn	Pd		5	45.3	2.9	800
Embodiment 320	(Mg _0.5Ba _0.5) ₁₀Cu _0.7Ni _0.3	V ₄Ti	13	1.2	3.0	293	Embodiment 319	(Mg _0.8Ca _0.1Sr _0.1) ₁₂ Zn	Pd		5	45.3	2.9	800
Embodiment 320	(Mg _0.5Ba _0.5) ₁₀Cu _0.7Ni _0.3	V ₄Ti	13	1.2	3.0	293	Embodiment 321	(Mg _0.8Na _0.2) ₁₆ Fe	NiB		8	16.3	2.2	411
Embodiment 322	(Mg _0.7La _0.2Li _0.1) ₅Si	LaNi ₄Al	15	21.6	2.6	393	Embodiment 321	(Mg _0.8Na _0.2) ₁₆ Fe	NiB		8	16.3	2.2	411
Embodiment 322	(Mg _0.7La _0.2Li _0.1) ₅Si	LaNi ₄Al	15	21.6	2.6	393	Embodiment 323	(Mg _0.8Y _0.1Ca _0.1) ₂₀Ni _0.8 Co _0.1Cu _0.1	Ni	0.05	30.3	2.5	516
Embodiment 324	(Mg _0.6Sr _0.4) ₅ Cu	Au		21	9.6	2.1	Embodiment 323	(Mg _0.8Y _0.1Ca _0.1) ₂₀Ni _0.8 Co _0.1Cu _0.1	Ni	0.05	30.3	2.5	516	290
Embodiment 324	(Mg _0.6Sr _0.4) ₅ Cu	Au		21	9.6	2.1	Embodiment 325	(Mg _0.9Li _0.1) ₈Ni	B	0.8	51.2	1.3	410	290
Embodiment 326	(Mg _0.6La _0.4) ₄ Co	CaAlNi	₄	3	3.2	2.2	Embodiment 325	(Mg _0.9Li _0.1) ₈Ni	B	0.8	51.2	1.3	410	391

Can find out obviously that from table 34 at normal temperatures, for being the hydrogen bearing alloy of the embodiment 307～326 that powder additive such as Ni powder obtain in (V) and the alloy with hydrogen storage property (VI), its hydrogen storage property improves greatly at general formula.

(embodiment 327～332 and comparative example 25～27)

To consisting of Mg _1.9Al _0.1Ni _1.05Hydrogen bearing alloy in, add carbon dust and polytetrafluoroethylene in varing proportions.The mixture that obtains is rolled into chip shape, and thin slice is online attached to Ni with pressure.Be prepared into 9 kinds of hydrogen electrodes (negative electrode).The hydrophobicity of hydrogen electrode and ion eluting rate, the variation of the pressure when forming composite sheet with the composition of electrode such as polytetrafluoroethylene content with the Ni net changes.

The hydrogen electrode that obtains thus is soaked in the KOH alkaline solution of 8N, carries out the charge and discharge cycles test then at normal temperatures.In discharging and recharging, charging is to charge 10 hours with 100mA by every gram hydrogen bearing alloy, and discharge is to discharge with 200mA by every gram hydrogen bearing alloy, reduces to-0.5V until its voltage with respect to mercuric oxide electrode.The capacity of the 20th circulation discharge and the proportionate relationship of the 3rd cyclic discharge capacity and ion eluting rate are as shown in table 35.The ion eluting rate is that hydrogen electrode was soaked in alkali metal hydroxide aqueous solution 5 hours, uses the amount of the component of ICP (inductively coupled plasma) spectrophotometer wash-out then.The consumption of the alkali metal hydroxide aqueous solution in the hydrogen electrode is approximately every gram alloy 100ml.

Table 35

	Ionic species	Aqueous slkali	Solution temperature ℃	Eluting rate milligram/kilogram alloy/hour	/ the 3 circulation of the 20th circulation of eluting rate (%)
	Ionic species	Aqueous slkali	Solution temperature ℃	Eluting rate milligram/kilogram alloy/hour		Embodiment 327	Mg	8N KOH	25	0.3	70
Embodiment 328	Mg	6N KOH	25	0.5	65	Embodiment 327	Mg	8N KOH	25	0.3	70
Embodiment 328	Mg	6N KOH	25	0.5	65	Embodiment 329	Mg	7N KOH 1N LiOH	25	0.4	77
Embodiment 330	Mg	9N KOH		60	1.2	Embodiment 329	Mg	7N KOH 1N LiOH	25	0.4	77	75
Embodiment 330	Mg	9N KOH		60	1.2	Embodiment 331	Mg+Al	8N KOH	25	1.0	72	75
Embodiment 332	Mg+Al	8N KOH		60	3.4	Embodiment 331	Mg+Al	8N KOH	25	1.0	72	68
Embodiment 332	Mg+Al	8N KOH		60	3.4	Comparative example 25	Mg	8N KOH	25	0.7	32	68
Comparative example 26	Mg	9N KOH		60	2.3	Comparative example 25	Mg	8N KOH	25	0.7	32	43
Comparative example 26	Mg	9N KOH		60	2.3	Comparative example 27	Mg+Al	8N KOH	25	4.8	30	43

(embodiment 333～341)

With different ratios the hydrogen bearing alloy shown in the table 36 is mixed with carbon dust and polytetrafluoroethylene, then mixture is rolled into thin slice, thin slice is online attached to Ni with pressure, makes 8 kinds of hydrogen-bearing alloy electrodes.

The hydrogen electrode that obtains thus is immersed in the KOH aqueous solution of 8N, carries out the charge and discharge cycles test at normal temperatures according to the method identical with embodiment 327.According to the method identical with embodiment 327, measure the proportionate relationship and the ion eluting rate of the capacity of the capacity of the 20th circulation discharge and the 3rd circulation discharge, the result is shown in table 36.

Table 36

	Hydrogen bearing alloy	Ionic species
	Hydrogen bearing alloy	Ionic species	Embodiment 333	Mg ₂Ni _1.125	Magnesium
Embodiment 334	Mg ₂Co _1.1In _0.11	All elements	Embodiment 333	Mg ₂Ni _1.125	Magnesium
Embodiment 334	Mg ₂Co _1.1In _0.11	All elements	Embodiment 335	MgNi _1.11Ag _0.22	Magnesium
Embodiment 336	Mg _1.8Al _0.3Ni _0.9Pd _0.3	Magnesium	Embodiment 335	MgNi _1.11Ag _0.22	Magnesium
Embodiment 336	Mg _1.8Al _0.3Ni _0.9Pd _0.3	Magnesium	Embodiment 337	Mg _1.8Al _0.3Ni _0.9Pd _0.3	Magnesium
Embodiment 338	Mg _1.6Al _0.3NiMn _0.2	All elements	Embodiment 337	Mg _1.8Al _0.3Ni _0.9Pd _0.3	Magnesium
Embodiment 338	Mg _1.6Al _0.3NiMn _0.2	All elements	Embodiment 339	Mg _1.6Al _0.3Ni _0.7Mn _0.2Co _0.2	All elements
Embodiment 340	Mg _1.8Al _0.3Ni _0.9Pd _0.3(pruinescence invade bubble in the hydrochloric acid of 0.01N 30 seconds)	Magnesium	Embodiment 339	Mg _1.6Al _0.3Ni _0.7Mn _0.2Co _0.2	All elements
Embodiment 340		Magnesium	Embodiment 341	Mg _1.8Al _0.2Ni _0.95Pt _0.05	Magnesium

Table 36

	Aqueous slkali	Solution temperature ℃	Eluting rate milligram/kilogram alloy/hour	The 20 circulation of eluting rate/circulation for the third time
	Aqueous slkali	Solution temperature ℃	Eluting rate milligram/kilogram alloy/hour		Embodiment 333	8N KOH	25	0.2	65
Embodiment 334	8N KOH	25	2.1	72	Embodiment 333	8N KOH	25	0.2	65
Embodiment 334	8N KOH	25	2.1	72	Embodiment 335	8N KOH	25	0.2	76
Embodiment 336	8N KOH	25	0.2	78	Embodiment 335	8N KOH	25	0.2	76
Embodiment 336	8N KOH	25	0.2	78	Embodiment 337	8N KOH	60	4.2	77
Embodiment 338	7N KOH 1N LiOH	60	0.5	70	Embodiment 337	8N KOH	60	4.2	77
Embodiment 338	7N KOH 1N LiOH	60	0.5	70	Embodiment 339	9N KOH	60	3.4	80
Embodiment 340	8N KOH	25	0.2	76	Embodiment 339	9N KOH	60	3.4	80
Embodiment 340	8N KOH	25	0.2	76	Embodiment 341	8N KOH	25	0.2	74

Shown in table 35 and 36, formed a simulated battery with the hydrogen electrode that contains hydrogen bearing alloy (embodiment 327 to 341) as negative electrode, it is characterized in that, when described negative pole is immersed in the alkali metal hydroxide aqueous solution of 6～8N, (a) at normal temperatures, the eluting rate of Mg ion in alkali metal hydroxide aqueous solution is no more than per hour per kilogram alloy 0.5mg, and in the time of 60 ℃, the eluting rate of Mg ion in alkali metal hydroxide aqueous solution is no more than per hour per kilogram alloy 4mg; (b) at normal temperatures, the eluting rate of the component element of alloy in alkali metal hydroxide aqueous solution is no more than per hour per kilogram alloy 1.5mg, in the time of 60 ℃, the eluting rate of the component element of alloy in alkali metal hydroxide aqueous solution is no more than per hour per kilogram alloy 20mg; Compare with the simulated battery of forming as negative electrode with the hydrogen electrode (comparative example 25-27) of the hydrogen bearing alloy that does not reach above-mentioned condition, it has higher capacity.

(embodiment 342～348 and comparative example 28)

Stack a paste Ni electrode (positive electrode) respectively on embodiment 327,333 to 335,338 to 340 and comparative example 27 resulting hydrogen electrodes (negative electrode), the centre separates with nylon nonwoven fabrics.Then, the compound that obtains is wound into a cylinder and makes 8 kinds of electrode groups thus.These electrode groups are inserted in the AA type battery case, add the KOH solution of 8N subsequently.With the lid that has safety valve it is sealed then, obtain 8 kinds of AA type nickel-hydrogen secondary cells thus.

The charge and discharge cycles test will be carried out under the battery condition below that obtain thus.Charging was by the current charges of every gram hydrogen bearing alloy 50mA 10 hours, and discharge is undertaken by the electric current of every gram hydrogen bearing alloy 20mA, when its voltage with respect to mercuric oxide electrode is reduced to 0.9V till.Repeat this circulation, the capacity of the 3rd circulation time and the capacity of the 20th circulation time are compared.After 30 day battery is broken thereafter.Magnesium ion is eluted to amount ICP (inductively coupled plasma) spectrometer measurement in the electrolyte.The result is shown in table 37.

Table 37

	The hydrogen electrode that uses	Ionic species	Concentration mg/l	/ the 3 circulation of 20 circulations of eluting rate (%)
	The hydrogen electrode that uses	Ionic species	Concentration mg/l	/ the 3 circulation of 20 circulations of eluting rate (%)	Embodiment 342	Example 327	Mg	1.2	68
Embodiment 343	Example 333	Mg	1.1	63	Embodiment 342	Example 327	Mg	1.2	68
Embodiment 343	Example 333	Mg	1.1	63	Embodiment 344	Example 334	Mg	1.7	57
Embodiment 345	Example 335	Mg	1.2	62	Embodiment 344	Example 334	Mg	1.7	57
Embodiment 345	Example 335	Mg	1.2	62	Embodiment 346	Example 338	Mg	1.3	59
Embodiment 347	Example 339	Mg	1.2	66	Embodiment 346	Example 338	Mg	1.3	59
Embodiment 347	Example 339	Mg	1.2	66	Embodiment 348	Example 340	Mg	1.4	78
Comparative example 28	Comparative Example 27	Mg	2.8	34	Embodiment 348	Example 340	Mg	1.4	78

Can obviously find out from table 37, satisfy following condition: promptly in battery case, adding alkali metal electrolysis liquid and sealing, after 30 days, the concentration of Mg ion in electrolyte is no more than the battery of the embodiment 343～349 of 2.2mg/l, compare with the battery of the comparative example 28 that does not satisfy above-mentioned condition, it has higher capacity.

As mentioned above, hydrogen bearing alloy of the present invention not only has in light weight and characteristics high power capacity, and owing to have good low temperature hydrogen storage property and good chemical stability, but the range of application of this alloy strengthens, can outside the application of the alloy of routine, use, applicable to various fields (as storing and transportation of hydrogen, store with the conversion of transportation heat energy, heat energy and mechanical energy, separate with purified hydrogen, hydrogen isotope separate, contain hydrogen as the catalyst of battery, synthetic chemistry and the thermal sensor of active material etc.).Utilize the great majority in these alloys, also can develop many new applications.

Further, according to hydrogen bearing alloy of the present invention and surface modifying method, can activate alloy at an easy rate and improve its hydrogen storage property.Therefore, use this kind alloy to do battery cathode, can obtain to have the battery of high power capacity.

In addition, according to negative pole of the present invention and alkaline secondary cell, make the discharging and recharging of hydrogen bearing alloy of containing magnesium react the possibility that becomes, and up to the present the conventional hydrogen bearing alloy that contains magnesium can not discharge and recharge reaction.In addition, when keeping high power capacity, it can also be in the stability that keeps for a long time discharging and recharging.

Of the present invention other advantage and to improve be conspicuous for the person of ordinary skill of the art.Therefore scope of the present invention is not limited to described detailed description, representational device and illustrative embodiment herein.Therefore, under situation about not breaking away from, can carry out various modifications to the present invention by appended claim and the spiritual or general notion that equivalent limited thereof.

Claims

1. hydrogen bearing alloy, it comprises by the represented alloy of following general formula (II):

Mg _2-xM2 _xM1 _y (II)

Wherein M1 is at least a element that is selected among Fe, Ni, Co, Ag, Cd, Mn, In, Se, Sn, Ge and the Pb; M2 is at least a element that is selected among Li, B, Be, Ca, Ba, Y, Ra, La, Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu, Ti, Zr, Hf, Pd, Pt, Th, V, Nb, Ta, Pa and the Al; The scope of x is 0＜x≤1.0, and the scope of y is 1＜y≤2.5.

2. according to the hydrogen bearing alloy of claim 1, the electronegativity of wherein said M1 is than Mg height, based on pure magnesium, if its consumption is 10 atom % or lower, and the Mg of the alloy that then obtains _1-wM1 _wThe unit cell volume of phase is littler than the unit cell volume of pure Mg, wherein 0＜W≤0.1.

3. according to the hydrogen bearing alloy of claim 1, wherein, described M1 is at least a element that is selected from Ag, Cd, Mn, In, Fe, Ni and Co.

4. according to the hydrogen bearing alloy of claim 1, wherein, the electronegativity of the M2 described in the general formula (II) is than Mg height.

5. according to the hydrogen bearing alloy of claim 4, wherein, described M2 is at least a element that is selected among B, Be, Y, Pd, Ti, Zr, Hf, Th, V, Nb, Ta, Pa and the Al.

6. according to the hydrogen bearing alloy of claim 1, wherein, in the general formula (II), based on pure Mg, if the consumption of M2 is 10 atom % or lower, the Mg of the alloy that obtains _1-wM1 _wThe unit cell volume of phase is littler than the unit cell volume of pure magnesium, wherein 0≤W≤0.1.

7. according to the hydrogen bearing alloy of claim 6, wherein, described M2 is at least a element that is selected among Li and the Al.

8. according to the hydrogen bearing alloy of claim 1, wherein, the scope of x is 0.01≤x≤1.0 in the general formula (II).

9. according to the hydrogen bearing alloy of claim 1, wherein, the scope of y is 1.01≤y≤2.5 in the general formula (II).

10. according to the hydrogen bearing alloy of claim 1, wherein, the scope of y is 1.02≤y≤2.5 in the general formula (II).

11. according to the hydrogen bearing alloy of claim 1, wherein, the scope of y is 1.05≤y≤2.5 in the general formula (II).

12, the battery cathode that contains hydrogen bearing alloy, described hydrogen bearing alloy comprise the alloy by following general formula (II) expression:

Mg _2-xM2 _xM1 _y (II)

13, according to the negative pole of claim 12, the M1 in its formula of (II) is Ni.

14, according to the negative pole of claim 12, the M2 in its formula of (II) is Pd.

15, according to the negative pole of claim 12, the scope of the y in its formula of (II) is 1.01≤y≤1.5.

16, a kind of alkaline secondary cell that comprises the negative pole that contains hydrogen bearing alloy, this hydrogen bearing alloy contain the alloy of useful following general formula (II) expression:

Mg _2-xM2 _xM1 _y (II)