CN103540822A - Cobalt carbide material for hydrogen storage as well as preparation method thereof and hydrogen storage electrode and battery prepared from material and battery - Google Patents
Cobalt carbide material for hydrogen storage as well as preparation method thereof and hydrogen storage electrode and battery prepared from material and battery Download PDFInfo
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- CN103540822A CN103540822A CN201210248288.5A CN201210248288A CN103540822A CN 103540822 A CN103540822 A CN 103540822A CN 201210248288 A CN201210248288 A CN 201210248288A CN 103540822 A CN103540822 A CN 103540822A
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- 239000000463 material Substances 0.000 title claims abstract description 94
- 239000001257 hydrogen Substances 0.000 title claims abstract description 93
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 93
- 238000003860 storage Methods 0.000 title claims abstract description 84
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 75
- 239000010941 cobalt Substances 0.000 title claims abstract description 75
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 75
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 27
- 239000000956 alloy Substances 0.000 claims abstract description 27
- 229910002056 binary alloy Inorganic materials 0.000 claims abstract description 16
- 239000011232 storage material Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims description 32
- 150000002431 hydrogen Chemical class 0.000 claims description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 238000000498 ball milling Methods 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 9
- 238000005260 corrosion Methods 0.000 abstract description 15
- 230000007797 corrosion Effects 0.000 abstract description 15
- 238000007599 discharging Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 6
- 229910020791 La—Mg—Ni Inorganic materials 0.000 abstract 3
- 238000013329 compounding Methods 0.000 abstract 3
- 239000002585 base Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000003701 mechanical milling Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000009461 vacuum packaging Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910019001 CoSi Inorganic materials 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000011664 signaling Effects 0.000 description 1
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- 238000013112 stability test Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a cobalt carbide material for hydrogen storage as well as a preparation method thereof and a hydrogen storage electrode and a battery prepared from the material and a battery. The cobalt carbide material for hydrogen storage is formed by compounding a CoCX binary alloy and a La-Mg-Ni-based alloy. According to the cobalt carbide material for hydrogen storage disclosed by the embodiment of the invention, the cobalt carbide material is formed by compounding the CoCX binary alloy with the La-Mg-Ni-based alloy, so that characteristics that the CoCX binary alloy is easy to activate and good in cycle performance and characteristics that the La-Mg-Ni-based alloy is low in hydrogen re-discharging temperature and strong in corrosion resistance are combined, and therefore, the cobalt carbide material for hydrogen storage formed by compounding can be used for reversibly adsorbing and discharging hydrogen; according to the hydrogen storage electrode prepared from the hydrogen storage material, a simulated battery assembled under normal temperature and normal pressure has the advantages of being extremely high in discharging capacity, dynamic performance and cycle performance as well as excellent in corrosion resistance, and the like.
Description
Technical field
The present invention relates to material technology field, more specifically, the present invention relates to cobalt carbide material and preparation method thereof and the hydrogen-storage electrode of being prepared by this material and battery for Chu Qing.
Background technology
The hydrogen storage material of series of new attracts much attention in recent years, Here it is Ni, Co compound MX.For example, the Yang Han of Wuhan University western for study group ball milled (mechanical alloying method) synthesized CoP, under the large electric current of 300mA/g, discharge, except initial pot-life, from 30 weeks, its circulation volume just remained on about 310mAh/g until 100 weeks.Adopt the synthetic CoB of chemical reduction method, more than loading capacity has reached 600mAh/g first, be stabilized in 300mAh/g left and right since the 3rd week, after circulation in 100 weeks, capacity still remains on 260mAh/g.NiB, CoB, CoP, the preparation in succession of CoSi etc., has opened a broader visual field to us, therefore, can attempt preparing some these serial novel materials.
Summary of the invention
The present invention one of is intended to solve the problems of the technologies described above at least to a certain extent or at least provides a kind of useful business to select.
For this reason, one object of the present invention be to propose a kind ofly to inhale that hydrogen discharging temperature is low, corrosion resistance strong, the easy storage hydrogen cobalt carbide material of activation, good cycle.
According to the storage hydrogen cobalt carbide material of the embodiment of the present invention, by CoC
xbinary alloy and La-Mg-Ni-base alloy are compounded to form.
According to the storage hydrogen cobalt carbide material of the embodiment of the present invention, owing to adopting CoC
xbinary alloy and La-Mg-Ni-base alloy are composited, and combine CoC
xbinary alloy easily activates, the multiple feature that hydrogen discharging temperature is low, corrosion resistance is strong of the feature of good cycle and La-Mg-Ni-base alloy, the storage hydrogen being compounded to form can reversible suction be put hydrogen with cobalt carbide material, and the simulated battery that the hydrogen-storage electrode that uses this hydrogen storage material to prepare is assembled at normal temperatures and pressures has high loading capacity, dynamic performance, cycle performance and the superior advantages such as corrosion resistance; Making finished product battery can have different purposes, has great application and DEVELOPMENT PROSPECT; And preparation technology of the present invention is simple, safe.
In addition, storage hydrogen cobalt carbide material according to the above embodiment of the present invention, can also have following additional technical characterictic:
According to one embodiment of present invention, the chemical constitution of described La-Mg-Ni-base alloy is La
0.8mg
0.2ni
0.8mn
0.1co
0.5al
0.1.
According to one embodiment of present invention, described storage hydrogen uses the chemical constitution of cobalt carbide material as shown in formula I,
CoC
X-（La
0.8Mg
0.2Ni
0.8Mn
0.1Co
0.5Al
0.1)
Y （Ⅰ）
Wherein, X=1,2 or 3, and 0≤Y≤0.9.
Another object of the present invention is to propose a kind of preparation method of cobalt carbide material for hydrogen that stores up, and comprises the following steps: a) take respectively CoC
xbinary alloy also mixes with La-Mg-Ni-base alloy powder, obtains powder mix; B) powder mix 5～80 hours described in mechanical ball milling under argon gas atmosphere, obtains described hydrogen storage material.
According to one embodiment of present invention, the chemical constitution of described La-Mg-Ni-base alloy is La
0.8mg
0.2ni
0.8mn
0.1co
0.5al
0.1.
According to one embodiment of present invention, described storage hydrogen uses the chemical constitution of cobalt carbide material as shown in formula I,
CoC
X-（La
0.8Mg
0.2Ni
0.8Mn
0.1Co
0.5Al
0.1)
Y （Ⅰ）
Wherein, X=1,2 or 3, and 0≤Y≤0.9.
The invention allows for the preparation method of cobalt carbide material for another kind of storage hydrogen, comprise the following steps: a) take respectively CoC
xbinary alloy also mixes with La-Mg-Ni-base alloy powder, obtains powder mix; B) after described powder mix is ground, in tube furnace under argon gas atmosphere sintering, obtain described hydrogen storage material.
According to one embodiment of present invention, in described step a), the chemical constitution of described La-Mg-Ni-base alloy is La
0.8mg
0.2ni
0.8mn
0.1co
0.5al
0.1.
According to one embodiment of present invention, described storage hydrogen uses the chemical constitution of cobalt carbide material as shown in formula I,
CoC
X-（La
0.8Mg
0.2Ni
0.8Mn
0.1Co
0.5Al
0.1)
Y （Ⅰ）
Wherein, X=1,2 or 3, and 0≤Y≤0.9.
According to one embodiment of present invention, in described step b), sintering temperature is 500～800 ℃.
According to one embodiment of present invention, in described step b), sintering time is 5～25 hours.
A further object of the present invention is to propose a kind of hydrogen-storage electrode, and described hydrogen-storage electrode is compounded to form with cobalt carbide material by nickel powder with according to the storage hydrogen described in above-described embodiment.
According to one embodiment of present invention, described nickel powder and described storage hydrogen are 2～4:1 by the weight ratio of cobalt carbide material.
Another object of the present invention is to propose a kind of battery, and described battery comprises the hydrogen-storage electrode described in above-described embodiment.
Additional aspect of the present invention and advantage in the following description part provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Accompanying drawing explanation
Above-mentioned and/or additional aspect of the present invention and advantage accompanying drawing below combination obviously and is easily understood becoming the description of embodiment, wherein:
Fig. 1 stores up the preparation method's of cobalt carbide material schematic flow sheet for hydrogen according to an embodiment of the invention;
Fig. 2 stores up the preparation method's of cobalt carbide material schematic flow sheet for hydrogen in accordance with another embodiment of the present invention;
Fig. 3 uses cobalt carbide material at the cyclic discharge capacity schematic diagram of different Ball-milling Times according to storage hydrogen according to the present invention, and wherein A represents that Ball-milling Time is the storage hydrogen cobalt carbide material of 10 hours, and B represents that Ball-milling Time is the storage hydrogen cobalt carbide material of 20 hours;
Fig. 4 is the cobalt carbide material ball milling SEM of 20 hours figure for storage hydrogen according to the present invention;
Fig. 5 is that wherein C represents that Y is 0.5 storage hydrogen cobalt carbide material according to cobalt carbide material cyclic discharge capacity schematic diagram for the storage hydrogen of different proportionings of the present invention;
Fig. 6 is that wherein C represents that Y is 0.5 storage hydrogen cobalt carbide material according to the storage hydrogen according to the present invention cobalt carbide material ball milling cyclic voltammetry curve figure of 20 hours;
Fig. 7 is that wherein C represents that Y is 0.5 storage hydrogen cobalt carbide material according to the storage hydrogen according to the present invention cobalt carbide material ball milling interchange resistance figure of 20 hours.
Embodiment
Describe embodiments of the invention below in detail, the example of described embodiment is shown in the drawings.Below by the embodiment being described with reference to the drawings, be exemplary, only for explaining the present invention, and can not be interpreted as limitation of the present invention.
First, describe according to the storage hydrogen cobalt carbide material of the embodiment of the present invention.
According to storage hydrogen cobalt carbide material of the present invention, by CoC
xbinary alloy and La-Mg-Ni-base alloy are compounded to form.
About described CoC
xbinary alloy, Co, C material has good chemical property, as corrosion-resistant in alkali lye in C material, and has good electroconductibility, and Co material has good help to hydrogen storage property, can, by its coated other materials, improve the chemical property of encapsulated material.
About La-Mg-Ni-base alloy, its chemical constitution is preferably La
0.8mg
0.2ni
0.8mn
0.1co
0.5al
0.1.
Particularly, described storage hydrogen by the chemical constitution of cobalt carbide material preferably as shown in formula I,
CoC
X-（La
0.8Mg
0.2Ni
0.8Mn
0.1Co
0.5Al
0.1)
Y（Ⅰ）
Wherein, X=1,2 or 3, and 0≤Y≤0.9.
According to the storage hydrogen cobalt carbide material of the embodiment of the present invention, inhale that hydrogen discharging temperature is low, corrosion resistance strong, easily activation, good cycle, and can reversible suction put hydrogen, the simulated battery that the hydrogen-storage electrode that uses this hydrogen storage material to prepare is assembled at normal temperatures and pressures has high loading capacity, dynamic performance, cycle performance and the superior advantages such as corrosion resistance; Making finished product battery can have different purposes, has great application and DEVELOPMENT PROSPECT; And preparation technology of the present invention is simple, safe.
It should be noted that, unrestricted by the preparation method of cobalt carbide material according to the storage hydrogen of the embodiment of the present invention.
Below, in conjunction with Fig. 1 and Fig. 2,2 kinds of preferred preparation methods' of cobalt carbide material flow process for storage hydrogen according to the present invention is described.As shown in Figure 1, according to one embodiment of present invention, described storage hydrogen can comprise the following steps by the preparation method of cobalt carbide material:
A) take respectively CoC
xbinary alloy also mixes with La-Mg-Ni-base alloy powder, obtains powder mix;
B) powder mix 5～80 hours described in mechanical ball milling under argon gas atmosphere, obtains described hydrogen storage material.
Thus, can make inhale that hydrogen discharging temperature is low, corrosion resistance strong, the easy storage hydrogen cobalt carbide material of activation, good cycle, and preparation method is simple, safe, is applicable to promoting the use of.
Method and apparatus about mechanical ball milling is not particularly limited, as long as described powder mix ball milling under argon gas atmosphere can be obtained to described hydrogen storage material, consider cost and equipment feasibility, preferably, described ball-grinding machine is ball grinder and ball mill, and the working method of ball milling specifically can comprise:
Powder mix is added in ball grinder, tighten ball grinder, with high-purity argon gas protection, being filled with the argon gas time is 5～6 hours, after having inflated, ball grinder is placed in to ball mill and carries out ball milling, and control drum's speed of rotation is 450rpm.In mechanical milling process, along with the carrying out of ball milling, metal powder can be bonded on ball grinder tank wall, and grinding efficiency declines.Cooling for preventing from that high temperature is to synthetic unfavorable, constantly shut down carrying out, about 10h of the timed interval stops machine No. one time, takes off ball grinder and strikes tank.After metal-powder is struck, with mortar, grind, cross 200 mesh sieves, sampling is preserved, and remaining material packs ball grinder into, more again uses argon shield, and upper machine carries out ball milling, repeats aforesaid operations to stipulating Ball-milling Time, obtains Chu Qing cobalt carbide material.
Rotten in order to prevent that Chu Qing from occurring with cobalt carbide material, can with cobalt carbide material product, adopt vacuum packaging to store the storage hydrogen of preparing gained.
As shown in Figure 2, according to another embodiment of the invention, described storage hydrogen can comprise the following steps by the preparation method of cobalt carbide material:
A) take respectively CoC
xbinary alloy also mixes with La-Mg-Ni-base alloy powder, obtains powder mix;
B) after described powder mix is ground, in tube furnace under argon gas atmosphere sintering, obtain described hydrogen storage material.
In order to guarantee that powder mix can fully react, the temperature of sintering in tube furnace of the powder mix after grinding is preferably 500～800 ℃, and sintering time is preferably 5～25 hours, can obtain Chu Qing cobalt carbide material, and adopts vacuum packaging to store.
According to aforesaid method prepare gained storage hydrogen with cobalt carbide material inhale that hydrogen discharging temperature is low, corrosion resistance strong, easily activation, good cycle, and can reversible suction put hydrogen, the simulated battery that the hydrogen-storage electrode that uses this hydrogen storage material to prepare is assembled at normal temperatures and pressures has high loading capacity, dynamic performance, cycle performance and the superior advantages such as corrosion resistance; Making finished product battery can have different purposes, has great application and DEVELOPMENT PROSPECT; And preparation technology of the present invention is simple, safe.Next, describe according to the hydrogen-storage electrode of the embodiment of the present invention.
About described hydrogen-storage electrode, it will be appreciated that, described hydrogen-storage electrode is by nickel powder and according to aforesaid method, prepare gained storage hydrogen and be compounded to form with cobalt carbide material, wherein, described nickel powder and described storage hydrogen are that 2～4:1 is preferred by the weight ratio of cobalt carbide material, and described nickel powder and described storage hydrogen are 3:1 by the weight ratio of cobalt carbide material.
Preparation method about hydrogen-storage electrode is not particularly limited, and preferably, the concrete complex method of described hydrogen-storage electrode can comprise:
Measure the aforesaid method according to the present invention and prepare gained storage hydrogen cobalt carbide material sample, add Ni powder, the mass ratio of controlling nickel powder and sample is 3:1, in crucible, mix, at 30MPa, depress to the alloy electrode plate that diameter is about 1cm, record in detail all accurate weighing datas, rear calculated activity amount.With two foam metal nickels that diameter is about 2cm, clamp alloy electrode plates again, with the pressure compacting of 20MPa, then, at the Bian Shangdian of the nickel foam sheet metallic nickel sheet of burn-oning, obtain hydrogen-storage electrode.
Preparation process according to battery of the present invention is described below.The preparation of anode pole piece: positive electrode material is sintered type Ni (OH)
2, cut out two capacity much larger than the rectangle pole piece of capacity of negative plates, by two Ni (OH)
2be with spot welding with a Ni, obtain anode pole piece for one section of pole piece.
Take above-mentioned hydrogen-storage electrode as cathode pole piece, described anode pole piece, hydrogen-storage electrode and Hg/HgO reference electrode are assembled, coordinate the KOH aqueous solution of 6mol/L as electrolytic solution, just can obtain the simulated battery of three-electrode system.
Below in conjunction with specific embodiment, the preparation method of cobalt carbide material for storage hydrogen according to the present invention is described.
First be ready to ball grinder, in ball milling ball in the mass ratio of ball and bead to be about the effect of ball in 2:1(be to pulverize macrobead, the effect of bead is to make it refinement), ball powder mass ratio is 20:1, each jar estimates just to fill 10～20 grams, powder.
Take respectively the CoC that mol ratio is identical
xbinary alloy also mixes with La-Mg-Ni-base alloy powder, obtains powder mix, and powder mix is added in ball grinder; tighten ball grinder, with high-purity argon gas protection, being filled with the argon gas time is 5～6 hours; after having inflated, ball grinder is placed in to ball mill and carries out ball milling, control drum's speed of rotation is 450rpm.In mechanical milling process, along with the carrying out of ball milling, metal powder can be bonded on ball grinder tank wall, and grinding efficiency declines.Cooling for preventing from that high temperature is to synthetic unfavorable, constantly shut down carrying out, about 10h of the timed interval stops machine No. one time, takes off ball grinder and strikes tank.After metal-powder is struck, with mortar, grind, cross 200 mesh sieves, sampling is preserved, and remaining material packs ball grinder into, more again uses argon shield, and upper machine carries out ball milling, repeats aforesaid operations to stipulating Ball-milling Time, obtains Chu Qing cobalt carbide material.
The storage hydrogen of preparing gained through mechanical spheroidal graphite 10h and 20h reaches respectively 280mAh/g and 260mAh/g(as shown in Figure 3 with cobalt carbide material initial discharge capacity), and cycle life is very stable.
Below by experimental example, above-described embodiment being prepared to gained storage hydrogen detects with cobalt carbide material.
Experimental example 1
The microstructure that scanning electronic microscope (SEM) can be used for observing specimen surface, the various physical signallings that mainly utilize fine focusing electron beam to eject when sample surfaces scans are modulated into picture.Instrument adopts the X-650 of HIT type scanning electron microscope instrument, operating voltage 20KV.
Fig. 4 is cobalt carbide material SEM figure for the ball milling storage hydrogen of 20 hours, the La after ball milling
0.8mg
0.2ni
0.8mn
0.1co
0.5al
0.1there is very large surface-area, can be adsorbed on CoC
xsurface occupies macroparticle room to help the absorption of hydrogen, and has Corrosion Protection and catalytic performance.
Experimental example 2
By different, measure than mixed C oC
xand La
0.8mg
0.2ni
0.8mn
0.1co
0.5al
0.1material, obtains Chu Qing cobalt carbide material CoC
x-(La
0.8mg
0.2ni
0.8mn
0.1co
0.5al
0.1)
y, it is carried out to charge-discharge test.
Charge/discharge capacity and stability test process are: electrode before test in electrolytic solution static 20min so that it fully infiltrates; Then with constant current charge 300min, standing 10min after power-off, then constant-current discharge, stopping potential is-0.5V vs Hg/HgO electrode that then standing 10min, circulates tens times with this.Whole process is carried out online control with the Wuhan LAND of Lan electricity Electronics Co., Ltd. battery test system by computer.The every 300s of whole process is by computer recording one secondary data.While calculating alloy capacity, should deduct the quality of the nickel powder in electrode, only the actual content with alloy calculates.
Experimental result: simple CoC
xthe maximum discharge capacity of material reaches 360mAhg
-1, simple La
0.8mg
0.2ni
0.8mn
0.1co
0.5al
0.1material maximum discharge capacity reaches 277mAh g
-1, when Y=0.5, play loading capacity and reach respectively 407mAh g
-1, much larger than its theoretical value calculated value (as shown in Figure 5).Therefore, Chu Qing is not CoC with cobalt carbide material
xand La
0.8mg
0.2ni
0.8mn
0.1co
0.5al
0.1the simple mixing of material, exists and interacts between the two.
Experimental example 3
To the ball milling sample CoC of 20 hours
x-(La
0.8mg
0.2ni
0.8mn
0.1co
0.5al
0.1)
0.5carry out cyclic voltammetry, adopt CHI660B type electrochemical workstation and computer interconnection record data, adopt three-electrode system (experimental electrode employing is prepared gained storage hydrogen according to the embodiment of the present invention 1 and is prepared from cobalt carbide material) test loop volt-ampere, utilize potentiostat within the scope of-1.2V-0.4V, the speed of sweeping with 1mv/s scans, and the choppy sea electric potential signal receiving is called cyclic voltammetry curve (as shown in Figure 6).
Experimental result: two peaks of redox are all very obvious, be in respectively-0.62V(vs Hg/HgO) and-0.98V(vsHg/HgO), Δ=0.37V, illustrates that matrix material has good reversibility.
Experimental example 4
To the ball milling sample CoC of 20 hours
x-(La
0.8mg
0.2ni
0.8mn
0.1co
0.5al
0.1)
0.5carry out ac impedance measurement, adopt CHI660B type electrochemical workstation and computer interconnection record data, adopt three-electrode system (experimental electrode employing is prepared gained storage hydrogen according to the embodiment of the present invention 1 and is prepared from cobalt carbide material) test alternating-current impedance, take range of frequency as 10
4-10
-2hZ, the sine wave disturbance signal function that sweep velocity is 5mv/s is in electrode system, by the response of electrode system, obtains electrode impedance, according to zview matching software to data fitting, infer electrode process equivalent electrical circuit, and analyze, obtain exchanging resistance figure (as shown in Figure 7).
Experimental result: sample corrosion potential is higher, and corrosion electric current density is little, illustrates that the corrosion resistance of composite alloy electrode in alkali lye strengthens.
In the description of this specification sheets, the description of reference term " embodiment ", " some embodiment ", " example ", " concrete example " or " some examples " etc. means to be contained at least one embodiment of the present invention or example in conjunction with specific features, structure, material or the feature of this embodiment or example description.In this manual, the schematic statement of above-mentioned term is not necessarily referred to identical embodiment or example.And the specific features of description, structure, material or feature can be with suitable mode combinations in any one or more embodiment or example.
Although illustrated and described embodiments of the invention, those having ordinary skill in the art will appreciate that: in the situation that not departing from principle of the present invention and aim, can carry out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited by claim and equivalent thereof.
Claims (14)
1. a storage hydrogen cobalt carbide material, is characterized in that, by CoC
xbinary alloy and La-Mg-Ni-base alloy are compounded to form.
2. storage hydrogen cobalt carbide material according to claim 1, is characterized in that, the chemical constitution of described La-Mg-Ni-base alloy is La
0.8mg
0.2ni
0.8mn
0.1co
0.5al
0.1.
3. storage hydrogen cobalt carbide material according to claim 2, is characterized in that, described storage hydrogen uses the chemical constitution of cobalt carbide material as shown in formula I,
CoC
X-（La
0.8Mg
0.2Ni
0.8Mn
0.1Co
0.5Al
0.1)
Y（Ⅰ）
Wherein, X=1,2 or 3, and 0≤Y≤0.9.
4. a hydrogen-storage electrode, is characterized in that, by nickel powder with according to the storage hydrogen described in claim 1-3 any one, with cobalt carbide material, is compounded to form.
5. hydrogen-storage electrode according to claim 4, is characterized in that, described nickel powder and described storage hydrogen are 2～4:1 by the weight ratio of cobalt carbide material.
6. a battery, is characterized in that, comprises the hydrogen-storage electrode described in claim 4 or 5.
7. store up a preparation method for cobalt carbide material for hydrogen, it is characterized in that, comprise the following steps:
A) take respectively CoC
xbinary alloy also mixes with La-Mg-Ni-base alloy powder, obtains powder mix;
B) powder mix 5～80 hours described in mechanical ball milling under argon gas atmosphere, obtains described hydrogen storage material.
8. the preparation method of cobalt carbide material for storage hydrogen according to claim 7, is characterized in that, the chemical constitution of described La-Mg-Ni-base alloy is La
0.8mg
0.2ni
0.8mn
0.1co
0.5al
0.1.
9. the preparation method of cobalt carbide material for kind storage hydrogen according to claim 8, is characterized in that, described storage hydrogen uses the chemical constitution of cobalt carbide material as shown in formula I,
CoC
X-（La
0.8Mg
0.2Ni
0.8Mn
0.1Co
0.5Al
0.1)
Y（Ⅰ）
Wherein, X=1,2 or 3, and 0≤Y≤0.9.
10. store up a preparation method for cobalt carbide material for hydrogen, it is characterized in that, comprise the following steps:
A) take respectively CoC
xbinary alloy also mixes with La-Mg-Ni-base alloy powder, obtains powder mix;
B) after described powder mix is ground, in tube furnace under argon gas atmosphere sintering, obtain described hydrogen storage material.
The preparation method of cobalt carbide material for 11. kind storage hydrogen according to claim 10, is characterized in that, in described step a), the chemical constitution of described La-Mg-Ni-base alloy is La
0.8mg
0.2ni
0.8mn
0.1co
0.5al
0.1.
The preparation method of cobalt carbide material for 12. kind storage hydrogen according to claim 11, is characterized in that, described storage hydrogen uses the chemical constitution of cobalt carbide material as shown in formula I,
CoC
X-（La
0.8Mg
0.2Ni
0.8Mn
0.1Co
0.5Al
0.1)
Y（Ⅰ）
Wherein, X=1,2 or 3, and 0≤Y≤0.9.
13. according to the preparation method of the storage hydrogen use cobalt carbide material described in any one in claim 10-12, it is characterized in that, in described step b), sintering temperature is 500～800 ℃.
14. according to the preparation method of the storage hydrogen use cobalt carbide material described in any one in claim 10-12, it is characterized in that, in described step b), sintering time is 5～25 hours.
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| CN106887345A (en) * | 2017-02-20 | 2017-06-23 | 兰州理工大学 | For the preparation method of the high conductivity cobalt carbide of fake capacitance electrode material |
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| CN102534338A (en) * | 2011-12-27 | 2012-07-04 | 彩虹集团公司 | Cobalt carbide material for hydrogen storage and preparation method thereof |
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| US20090155688A1 (en) * | 2007-12-05 | 2009-06-18 | Sanyo Electric Co., Ltd. | Alkaline storage cell |
| CN102534338A (en) * | 2011-12-27 | 2012-07-04 | 彩虹集团公司 | Cobalt carbide material for hydrogen storage and preparation method thereof |
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