CN104681817B - A kind of nickel-hydrogen secondary battery negative electrode material - Google Patents
A kind of nickel-hydrogen secondary battery negative electrode material Download PDFInfo
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- CN104681817B CN104681817B CN201310638203.9A CN201310638203A CN104681817B CN 104681817 B CN104681817 B CN 104681817B CN 201310638203 A CN201310638203 A CN 201310638203A CN 104681817 B CN104681817 B CN 104681817B
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Abstract
The present invention provides a kind of nickel-hydrogen secondary battery negative electrode material, and the material is the composite of the core shell structure with metal oxide clad, and core material is hydrogen storage alloy particle, and clad is made up of metal oxide.The nickel-hydrogen secondary battery negative electrode material of the present invention passes through surface clad oxide; enhance the adhesion of metal oxide and hydrogen storing alloy powder; make metal oxide being more evenly distributed on hydrogen storing alloy powder surface; effectively play protective effect of the metal oxide on hydrogen bearing alloy surface; reduce the dissolving of hydrogen bearing alloy surface-element; the cyclical stability of hydrogen bearing alloy is improved, reduces self discharge.The nickel-hydrogen secondary battery negative electrode material price of the present invention is cheap, and preparation technology is simple, has higher charge specific capacity, good cyclical stability and relatively low self-discharge rate in aqueous slkali.
Description
Technical field
The present invention relates to a kind of nickel-hydrogen secondary battery negative electrode material, more particularly to it is a kind of with metal oxide clad
The nickel-hydrogen secondary battery negative electrode material of core shell structure, belongs to field of metal material surface treatment.
Background technology
Nickel-hydrogen secondary cell has the characteristics that good capacity height, security, memory-less effect and to zero environmental, is international
The important directions of upper secondary cell research and development, it is all to be applied to hybrid vehicle, compact battery, electric tool etc. at present
It is multi-field.Hydrogen bearing alloy is as the emphasis that negative electrode active material is always Ni-MH battery research.In recent years, with the depth of research
Enter, there is AB3-3.8The novel rare-earth Mg base hydrogen bearing alloy of structure is remote high because its alloy electrode capacity is up to 360-410mAh/g
In traditional AB5Type hydrogen storage alloy, and be gradually applied in commercially producing.But special construction and Mg due to such alloy etc.
The presence of perishable element so that alloy is efflorescence, oxidation, the corrosion-resistant during charge and discharge cycles the problems such as compared with AB5Type
Alloy is more serious, have impact on the performances such as circulating battery stability and spray charging precipitator, greatly limit the hair of its application technology
Exhibition.
It is to improve the important method of its performance that surface treatment is carried out to alloy.Cladding or modification have improvement alloy conductive
Can, the material of alloy efficiency for charge-discharge, heavy-current discharge performance and cyclical stability etc. is improved, the comprehensive of alloy can be improved
Energy.The surface coating method studied mainly by reducing process in hydrogen storing alloy powder Surface coating Ni, Cu, Pd, Co or wherein
Two kinds of mixture accelerates the migration rate of alloy surface electric charge, so as to improve high power to improve the electro catalytic activity of alloyed powder
Rate discharge capability, meet electrode high rate during charging-discharging.Also it is avoided that hydrogen bearing alloy rare earth elements to surface segregation simultaneously
And oxidation, slow down alloy pulverization.But metal is coated there is also some shortcomings, as coated after Cu by multiple charge and discharge cycles copper quilt
Oxidation and gradual solution modeling, cause short circuit.Although other cladding metals have higher stability and urged in alkaline solution
Change activity, but its cost is higher, preparation technology is more complicated.
Some researchs are added from the decay resistance for improving alloy surface in electrolyte or electrode material in recent years
Appropriate additive metal oxide, improve the activity function of alloy electrode or the cyclical stability of electrode.Pass through blending
Mode adds the combination defective tightness of metal oxide, alloying pellet and metal oxide, the addition effect of a small amount of metal oxide
Fruit and unobvious, and the addition for increasing metal oxide can influence the capacity of alloy.
The content of the invention
It is poor for rare earth and magnesium-based hydrogen storage alloy cycle life in the prior art, metal Shortcomings are coated, and pass through
The problem of metal oxide that simple blend mode is added is with alloying pellet combination defective tightness, it is an object of the invention to provide
A kind of nickel-hydrogen secondary battery negative electrode material, the material have good circulation stability and a spray charging precipitator, and cost is cheap.
To achieve the above object, the present invention uses following technical scheme：
A kind of nickel-hydrogen secondary battery negative electrode material, the material are compound for the core shell structure with metal oxide clad
Material, core material are hydrogen storage alloy particle, and clad is made up of metal oxide.
Wherein, the clad accounts for the 0.1%~5% of composite gross weight, the granularity of metal oxide for 50nm~
500nm。
Preferably, the composition of the hydrogen bearing alloy is Ln1-xMgxNiy-a-bAlaMb, wherein, Ln is rare earth element, Y, Ti, Zr
In one or more, the one or more in M Co, Mn, Fe, Zn, Sn, Si, Cu, V, Nb, Mo, P, B, Ta, Cr, Ga, In,
X, a, b, y represent the mol ratio between each alloying element respectively, and meet 0≤x≤0.25,0.05≤a≤0.3,0≤b≤
0.5,2.8≤y≤3.9.
Preferably, described metal oxide layer is TiO2、ZrO2、ZnO、SnO2、CoO、Co2O3、NiO、Cu2O、Fe2O3、
Cr2O3、Al2O3、In2O3、SbO、CdO、Mn2O3、MoO3、WO3、CeO2、Y2O3、La2O3、Nd2O3In one or more of mixing
Oxide.
The preparation method of nickel-hydrogen secondary battery negative electrode material of the present invention is：Hydrogen storing alloy powder is added and is dispersed with metal oxygen
It is sufficiently mixed in the solution of compound, is dried in vacuo at 60~90 DEG C.The content of the metal oxide disperseed in solution is
1wt.%~20wt.%.The solution of dispersing metal oxides can select the mixing of water or water and water-miscible organic solvent
Thing, wherein also including 0.1wt.%~2wt.% property-modifying additive.Surfactant, silicon can be selected as property-modifying additive
One or more in alkane coupling agent, titanate coupling agent, aluminate coupling agent, aliphatic acid.
The advantage of the invention is that：
The nickel-hydrogen secondary battery negative electrode material of the present invention by surface clad oxide, enhance metal oxide and
The adhesion of hydrogen storing alloy powder, metal is aoxidized being more evenly distributed on hydrogen storing alloy powder surface, effectively play metal oxide
Protective effect on hydrogen bearing alloy surface, the dissolving of hydrogen bearing alloy surface-element is reduced, improves the cyclical stability of hydrogen bearing alloy,
Reduce self discharge.
The nickel-hydrogen secondary battery negative electrode material price of the present invention is cheap, and preparation technology is simple, has in aqueous slkali higher
Charge specific capacity, good cyclical stability and relatively low self-discharge rate.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the hydrogen storing alloy powder after Surface coating in embodiment 1.
Embodiment
The invention will be further described by the following examples.
In the following Examples and Comparative Examples, hydrogen bearing alloy ingot casting is prepared using magnetic suspension induction melting first, to it
It is broken into after being heat-treated more than 200 mesh powders.The hydrogen-bearing alloy powder is uniformly mixed with metal oxide dispersion,
It is dried in vacuo at 60 DEG C~90 DEG C, the hydrogen storing alloy powder after being surface-treated.
By the hydrogen storing alloy powder after being surface-treated and nickel powder, (mass ratio of hydrogen storing alloy powder and nickel powder is 1:4) mix
Manufactured electrode is made with nickel hydroxide electrode composition battery, mercuric oxide electrode as reference electrode, 6mol/L potassium hydroxide solutions
The test of cycle life and self discharge is carried out for electrolyte.At a temperature of 25 DEG C, 60mAg-1Constant current charge-discharge 5 times is to alloy electricity
Pole carries out activation process and measures electrochemistry capacitance.300mA·g-1Constant current charge-discharge circulates 100 weeks and measures capability retention.Will
Electrode places 180h under the conditions of 25 DEG C, measures the spray charging precipitator of alloy electrode.
Embodiment 1
Magnetic suspension induction melting prepared composition is used as La0.4Sm0.3Nd0.15Mg0.15Ni3.35Al0.15Hydrogen bearing alloy casting
Ingot, crushed under 1198K after heat treatment 10h and take 300~400 mesh powders.By the TiO that granularity is 100nm2Powder is dispersed
In the aqueous solution of the titanate coupling agent containing 0.3wt%, metal oxide content 3wt.%.Will be with solution homogenous quantities
Hydrogen storing alloy powder add in the dispersion soln and be sufficiently mixed, be dried in vacuo at 80 DEG C.
As shown in figure 1, for the scanning electron microscope (SEM) photograph of the present embodiment hydrogen storing alloy powder after Surface coating, can from figure
Arrive, oxide is evenly distributed on alloyed powder surface, forms clad on surface, plays to alloy protective effect.
By the hydrogen storing alloy powder after being surface-treated and nickel powder, (mass ratio of hydrogen storing alloy powder and nickel powder is 1:4) mix
Manufactured electrode is made with nickel hydroxide electrode composition battery, mercuric oxide electrode as reference electrode, 6mol/L potassium hydroxide solutions
The test of cycle life and self discharge is carried out for electrolyte.At a temperature of 25 DEG C, 60mAg-1Constant current charge-discharge 5 times is to alloy electricity
Pole carries out activation process, and alloy electrode activated in discharge and recharge in first week, measured maximum discharge capacity 371.3mAh/g.
300mA·g-1Constant current charge-discharge circulates 100 weeks and measures capability retention 94.2%.Electrode is placed into 180h under the conditions of 25 DEG C,
Measure the spray charging precipitator 74.3% of alloy electrode.
Comparative example 1
Magnetic suspension induction melting prepared composition is used as La0.4Sm0.3Nd0.15Mg0.15Ni3.35Al0.15Hydrogen bearing alloy casting
Ingot, crushed under 1198K after heat treatment 10h and take 300~400 mesh powders.By this hydrogen storing alloy powder and nickel powder (hydrogen storing alloy powder
Mass ratio with nickel powder is 1:4) electrode being mixed and nickel hydroxide electrode composition battery, mercuric oxide electrode is as reference electricity
Pole, 6mol/L potassium hydroxide solutions carry out the test of cycle life and self discharge as electrolyte.At a temperature of 25 DEG C, 60mA
g-1Constant current charge-discharge 5 times carries out activation process to alloy electrode, and alloy electrode activates in discharge and recharge in first week, measures maximum and put
Capacitance 368.5mAh/g.300mA·g-1Constant current charge-discharge circulates 100 weeks and measures capability retention 89.7%.By electrode 25
180h is placed under the conditions of DEG C, measures the spray charging precipitator 55.9% of alloy electrode.
Embodiment 2
Magnetic suspension induction melting prepared composition is used as La0.4Sm0.3Nd0.15Mg0.15Ni3.35Al0.15Hydrogen bearing alloy casting
Ingot, crushed under 1198K after heat treatment 10h and take 300~400 mesh powders.By the CeO that granularity is 200nm2With Y2O3Mixing
Powder is dispersed in the aqueous solution of the titanate coupling agent containing 0.3wt.%, metal oxide content 5wt.%.Will
Add in the dispersion soln and be sufficiently mixed with the hydrogen storing alloy powder of solution homogenous quantities, be dried in vacuo at 80 DEG C.
By the hydrogen storing alloy powder after being surface-treated and nickel powder, (mass ratio of hydrogen storing alloy powder and nickel powder is 1:4) mix
Manufactured electrode is made with nickel hydroxide electrode composition battery, mercuric oxide electrode as reference electrode, 6mol/L potassium hydroxide solutions
The test of cycle life and self discharge is carried out for electrolyte.At a temperature of 25 DEG C, 60mAg-1Constant current charge-discharge 5 times is to alloy electricity
Pole carries out activation process, and alloy electrode activated in discharge and recharge in first week, measured maximum discharge capacity 365.4mAh/g.
300mA·g-1Constant current charge-discharge circulates 100 weeks and measures capability retention 95.8%.Electrode is placed into 180h under the conditions of 25 DEG C,
Measure the spray charging precipitator 72.3% of alloy electrode.
Embodiment 3
Magnetic suspension induction melting prepared composition is used as La0.4Sm0.3Nd0.15Mg0.15Ni3.35Al0.15Hydrogen bearing alloy casting
Ingot, crushed under 1198K after heat treatment 10h and take 300~400 mesh powders.By the Co that granularity is 100nm2O3Powder is dispersed
In the aqueous solution of the aluminate coupling agent containing 0.2wt.%, metal oxide content 4wt.%.Will be with solution homogeneity
The hydrogen storing alloy powder of amount is added in the dispersion soln and is sufficiently mixed, and is dried in vacuo at 80 DEG C.
By the hydrogen storing alloy powder after being surface-treated and nickel powder, (mass ratio of hydrogen storing alloy powder and nickel powder is 1:4) mix
Manufactured electrode is made with nickel hydroxide electrode composition battery, mercuric oxide electrode as reference electrode, 6mol/L potassium hydroxide solutions
The test of cycle life and self discharge is carried out for electrolyte.At a temperature of 25 DEG C, 60mAg-1Constant current charge-discharge 5 times is to alloy electricity
Pole carries out activation process, and alloy electrode activated in discharge and recharge in first week, measured maximum discharge capacity 373.1mAh/g.
300mA·g-1Constant current charge-discharge circulates 100 weeks and measures capability retention 92.3%.Electrode is placed into 180h under the conditions of 25 DEG C,
Measure the spray charging precipitator 73.3% of alloy electrode.
Embodiment 4
Magnetic suspension induction melting prepared composition is used as La0.63Sm0.2Mg0.17Ni3.0Co0.4Al0.1Hydrogen bearing alloy casting
Ingot, crushed under 1223K after heat treatment 10h and take 300~400 mesh powders.By the Fe that granularity is 200nm2O3Powder is dispersed
In the aqueous solution of the aluminate coupling agent containing 0.2wt.%, metal oxide content 3.5wt.%.Will be same with solution
The hydrogen storing alloy powder of quality is added in the dispersion soln and is sufficiently mixed, and is dried in vacuo at 80 DEG C.
By the hydrogen storing alloy powder after being surface-treated and nickel powder, (mass ratio of hydrogen storing alloy powder and nickel powder is 1:4) mix
Manufactured electrode is made with nickel hydroxide electrode composition battery, mercuric oxide electrode as reference electrode, 6mol/L potassium hydroxide solutions
The test of cycle life and self discharge is carried out for electrolyte.At a temperature of 25 DEG C, 60mAg-1Constant current charge-discharge 5 times is to alloy electricity
Pole carries out activation process, and alloy electrode activated in discharge and recharge in first week, measured maximum discharge capacity 370.7mAh/g.
300mA·g-1Constant current charge-discharge circulates 100 weeks and measures capability retention 91.4%.Electrode is placed into 180h under the conditions of 25 DEG C,
Measure the spray charging precipitator 71.6% of alloy electrode.
Embodiment 5
Magnetic suspension induction melting prepared composition is used as La0.63Sm0.2Mg0.17Ni3.0Co0.4Al0.1Hydrogen bearing alloy casting
Ingot, crushed under 1223K after heat treatment 10h and take 300~400 mesh powders.By the Al that granularity is 200nm2O3Powder is dispersed
In the aqueous solution of the aluminate coupling agent containing 0.2wt.%, metal oxide content 1.5wt.%.Will be same with solution
The hydrogen storing alloy powder of quality is added in the dispersion soln and is sufficiently mixed, and is dried in vacuo at 80 DEG C.
By the hydrogen storing alloy powder after being surface-treated and nickel powder, (mass ratio of hydrogen storing alloy powder and nickel powder is 1:4) mix
Manufactured electrode is made with nickel hydroxide electrode composition battery, mercuric oxide electrode as reference electrode, 6mol/L potassium hydroxide solutions
The test of cycle life and self discharge is carried out for electrolyte.At a temperature of 25 DEG C, 60mAg-1Constant current charge-discharge 5 times is to alloy electricity
Pole carries out activation process, and alloy electrode activated in discharge and recharge in first week, measured maximum discharge capacity 370.7mAh/g.
300mA·g-1Constant current charge-discharge circulates 100 weeks and measures capability retention 94.1%.Electrode is placed into 180h under the conditions of 25 DEG C,
Measure the spray charging precipitator 75.3% of alloy electrode.
Comparative example 2
Magnetic suspension induction melting prepared composition is used as La0.63Sm0.2Mg0.17Ni3.0Co0.4Al0.1Rare earth and magnesium-based hydrogen storage
Alloy cast ingot, crushed under 1223K after heat treatment 10h and take 300~400 mesh powders.By this hydrogen storing alloy powder and nickel powder (hydrogen storage
The mass ratio of alloyed powder and nickel powder is 1:4) electrode being mixed and nickel hydroxide electrode composition battery, mercuric oxide electrode conduct
Reference electrode, 6mol/L potassium hydroxide solutions carry out the test of cycle life and self discharge as electrolyte.At a temperature of 25 DEG C,
60mA·g-1Constant current charge-discharge 5 times carries out activation process to alloy electrode, and alloy electrode is activated in discharge and recharge in first week, measured
Maximum discharge capacity 365.3mAh/g.300mA·g-1Constant current charge-discharge circulates 100 weeks and measures capability retention 84.2%.By electricity
180h is placed in pole under the conditions of 25 DEG C, measures the spray charging precipitator 56.1% of alloy electrode.
Embodiment 6
Magnetic suspension induction melting prepared composition is used as La0.55Nd0.1Gd0.2Zr0.05Mg0.1Ni3.0Co0.3Al0.15It is dilute
Native Mg base hydrogen bearing alloy ingot casting, crushed under 1198K after heat treatment 10h and take 300~400 mesh powders.It is 100nm's by granularity
ZrO2Powder is dispersed in the aqueous solution of the titanate coupling agent containing 0.2wt.%, and metal oxide content is
1.0wt.%.Hydrogen storing alloy powder with solution homogenous quantities is added in the dispersion soln and is sufficiently mixed, vacuum is done at 80 DEG C
It is dry.
By the hydrogen storing alloy powder after being surface-treated and nickel powder, (mass ratio of hydrogen storing alloy powder and nickel powder is 1:4) mix
Manufactured electrode is made with nickel hydroxide electrode composition battery, mercuric oxide electrode as reference electrode, 6mol/L potassium hydroxide solutions
The test of cycle life and self discharge is carried out for electrolyte.At a temperature of 25 DEG C, 60mAg-1Constant current charge-discharge 5 times is to alloy electricity
Pole carries out activation process, and alloy electrode activated in discharge and recharge in first week, measured maximum discharge capacity 368.7mAh/g.
300mA·g-1Constant current charge-discharge circulates 100 weeks and measures capability retention 93.2%.Electrode is placed into 180h under the conditions of 25 DEG C,
Measure the spray charging precipitator 70.7% of alloy electrode.
Comparative example 3
Magnetic suspension induction melting prepared composition is used as La0.55Nd0.1Gd0.2Zr0.05Mg0.1Ni3.0Co0.3Al0.15It is dilute
Native Mg base hydrogen bearing alloy ingot casting, crushed under 1198K after heat treatment 10h and take 300~400 mesh powders.By this hydrogen storing alloy powder
(mass ratio of hydrogen storing alloy powder and nickel powder is 1 with nickel powder:4) electrode being mixed and nickel hydroxide electrode composition battery, oxygen
Change mercury electrode and the test of cycle life and self discharge is carried out as electrolyte as reference electrode, 6mol/L potassium hydroxide solutions.
At a temperature of 25 DEG C, 60mAg-1Constant current charge-discharge 5 times carries out activation process to alloy electrode, and alloy electrode was in charge and discharge in first week
Electricity activates, and measures maximum discharge capacity 369.3mAh/g.300mA·g-1Constant current charge-discharge, which circulates, measures capacity holding for 100 weeks
Rate 87.3%.Electrode is placed into 180h under the conditions of 25 DEG C, measures the spray charging precipitator 54.3% of alloy electrode.
Claims (2)
1. a kind of nickel-hydrogen secondary battery negative electrode material, it is characterised in that the material is the nucleocapsid with metal oxide clad
The composite of structure, core material are hydrogen storage alloy particle, and clad is made up of metal oxide；The group of the hydrogen bearing alloy
As Ln1-xMgxNiy-a-bAlaMb, wherein, Ln is rare earth element, the one or more in Y, Ti, Zr, M Co, Mn, Fe, Zn,
One or more in Sn, Si, Cu, V, Nb, Mo, P, B, Ta, Cr, Ga, In, x, a, b, y are represented between each alloying element respectively
Mol ratio, and meet 0≤x≤0.25,0.05≤a≤0.3,0≤b≤0.5,2.8≤y≤3.9；The clad accounts for compound
The 0.1%~5% of material gross weight；The granularity of metal oxide is 50nm~500nm in the clad；
The preparation method of the material is：Hydrogen storing alloy powder is added to be dispersed with the solution of metal oxide and is sufficiently mixed,
It is dried in vacuo at 60~90 DEG C；The content of the GOLD FROM PLATING SOLUTION category oxide is 1wt.%~20wt.%；The solution be water or
The mixture of person's water and water-miscible organic solvent, wherein also including 0.1wt.%~2wt.% property-modifying additive；The modification
Additive is the one or more in surfactant, silane coupler, titanate coupling agent, aluminate coupling agent.
2. nickel-hydrogen secondary battery negative electrode material according to claim 1, it is characterised in that described metal oxide layer is
TiO2、ZrO2、ZnO、SnO2、CoO、Co2O3、NiO、Cu2O、Fe2O3、Cr2O3、Al2O3、In2O3、SbO、CdO、Mn2O3、MoO3、
WO3、CeO2、Y2O3、La2O3、Nd2O3In one or more of mixed oxides.
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| CN105642883B (en) * | 2016-01-12 | 2018-01-16 | 华南理工大学 | A kind of core shell structure magnesium-base hydrogen storage material |
| CN106811616B (en) * | 2017-02-21 | 2018-08-21 | 淄博君行电源技术有限公司 | Capacitive Ni-MH power cell Zinc oxide-base hydrogen-storage alloy |
| CN107808959A (en) * | 2017-10-27 | 2018-03-16 | 郑州汉东科技有限公司 | A kind of hydrogen storing alloy powder and its surface treatment method |
| CN115312738B (en) * | 2022-09-01 | 2025-02-14 | 燕山大学 | A Pr-doped metal oxide/La-Y-Ni composite material and its preparation method and application |
| CN115394991A (en) * | 2022-09-16 | 2022-11-25 | 金山科创有限公司 | Negative electrode material and preparation method thereof, nickel-metal hydride secondary battery using the negative electrode material |
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| CN1510774A (en) * | 2002-12-25 | 2004-07-07 | 三洋电机株式会社 | Hydrogen storing alloy for alkali secondary battery and alkali secondary battery |
| CN1185732C (en) * | 1996-12-27 | 2005-01-19 | 佳能株式会社 | Powdery material, electrode member, method for manufacturing same and secondary cell |
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| JP2002246016A (en) * | 2001-02-16 | 2002-08-30 | Mitsui Mining & Smelting Co Ltd | Surface treatment method for hydrogen storage alloy, and surface coated hydrogen storage alloy |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1185732C (en) * | 1996-12-27 | 2005-01-19 | 佳能株式会社 | Powdery material, electrode member, method for manufacturing same and secondary cell |
| CN1510774A (en) * | 2002-12-25 | 2004-07-07 | 三洋电机株式会社 | Hydrogen storing alloy for alkali secondary battery and alkali secondary battery |
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