CN1976097A - Nickel-hydrogen secondary battery negative electrode and battery and producing method thereof - Google Patents
Nickel-hydrogen secondary battery negative electrode and battery and producing method thereof Download PDFInfo
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- CN1976097A CN1976097A CNA2005101260026A CN200510126002A CN1976097A CN 1976097 A CN1976097 A CN 1976097A CN A2005101260026 A CNA2005101260026 A CN A2005101260026A CN 200510126002 A CN200510126002 A CN 200510126002A CN 1976097 A CN1976097 A CN 1976097A
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 53
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims description 23
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 76
- 239000000956 alloy Substances 0.000 claims abstract description 76
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 22
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 238000003860 storage Methods 0.000 claims description 41
- 239000000463 material Substances 0.000 claims description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- 239000003792 electrolyte Substances 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 22
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 239000000853 adhesive Substances 0.000 claims description 16
- 230000001070 adhesive effect Effects 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- 239000000470 constituent Substances 0.000 claims description 7
- 239000000654 additive Substances 0.000 abstract description 10
- 230000000996 additive effect Effects 0.000 abstract description 9
- 239000011230 binding agent Substances 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 2
- 239000007773 negative electrode material Substances 0.000 abstract 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 41
- 229910000531 Co alloy Inorganic materials 0.000 description 21
- VQVNCTNULYBZGL-UHFFFAOYSA-N cobalt yttrium Chemical compound [Co].[Y] VQVNCTNULYBZGL-UHFFFAOYSA-N 0.000 description 21
- 229910018095 Ni-MH Inorganic materials 0.000 description 9
- 229910018477 Ni—MH Inorganic materials 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 229910000990 Ni alloy Inorganic materials 0.000 description 8
- 238000003825 pressing Methods 0.000 description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 7
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 7
- LUMYORYTBJPPFC-UHFFFAOYSA-N [Co].[Ni].[Y] Chemical compound [Co].[Ni].[Y] LUMYORYTBJPPFC-UHFFFAOYSA-N 0.000 description 6
- 235000011837 pasties Nutrition 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229910018007 MmNi Inorganic materials 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- IKBUJAGPKSFLPB-UHFFFAOYSA-N nickel yttrium Chemical compound [Ni].[Y] IKBUJAGPKSFLPB-UHFFFAOYSA-N 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- DEXZEPDUSNRVTN-UHFFFAOYSA-K yttrium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Y+3] DEXZEPDUSNRVTN-UHFFFAOYSA-K 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000001996 bearing alloy Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- GFDKELMFCRQUSG-UHFFFAOYSA-N yttrium;trihydrate Chemical compound O.O.O.[Y] GFDKELMFCRQUSG-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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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- Battery Electrode And Active Subsutance (AREA)
Abstract
A negative electrode of NiH secondary battery is prepared as coating negative electrode material on negative electrode base body; forming negative electrode material by alloy stored with hydrogen, binder and alloy additive; forming alloy additive by yttrium and metal with oxyhydrogen composite catalytic ability. The NiH secondary battery applying said negative electrode is also disclosed.
Description
Technical field
The invention relates to nickel-hydrogen secondary battery negative electrode and battery and their preparation method.
Background technology
Alkaline secondary cell mainly comprises nickel-hydrogen secondary cell, NI-G secondary cell and Ni-MH secondary battery.Compare with the NI-G secondary cell, nickel-hydrogen secondary cell has energy height, advantages such as the pollution of no cadmium.
Nickel-hydrogen secondary cell generally comprises electrode group and the alkaline electrolyte that is sealed in the battery container.Described electrode group comprises positive pole, negative pole and dividing plate.Positive pole comprises anodal conducting base and coating and/or is filled in positive electrode on the anodal conducting base that described positive electrode contains as the nickel hydroxide powder of major constituent and adhesive; Negative pole comprises negative pole conducting base and coating and/or is filled in negative material on the negative pole conducting base that described negative material contains as the hydrogen-storage alloy of major constituent and adhesive.Described dividing plate is arranged between positive pole and the negative pole, has electrical insulation capability and liquid retainability energy, and described electrode group and alkaline electrolyte are contained in the battery case together.Described battery container is generally gone back the double as cathode terminal.
Be accompanied by the carrying out of nickel-hydrogen cell charging and discharging circulation, the oxidation resistance of the hydrogen-storage alloy powder in the nickel-hydrogen battery negative pole material descends, especially anodal precipitated oxygen during battery overcharge, further impel the hydrogen-storage alloy oxidation, cause the decline of the actual hydrogen storage capacity of hydrogen-storage alloy negative pole, promptly cause hydrogen-storage alloy negative pole charge acceptance to descend, inside battery hydrogen dividing potential drop rises during charging, causes inner pressure of battery to rise.Inner pressure of battery is elevated to a certain degree, battery safety valve is opened, when gas is emitted, electrolyte also can overflow, and causes electrolyte solution loss, and the internal resistance of cell increases, thereby along with the carrying out of charge and discharge cycles, discharge capacity of the cell descends, and finally shortens battery life.
In order to improve the oxidation resistance of hydrogen-storage alloy negative pole, Japanese patent laid-open 6-215765 discloses the method for adding yttrium and compound thereof in the hydrogen-storage alloy negative pole.Add yttrium and compound thereof in the hydrogen-storage alloy negative pole, make the surface-coated yttrium of hydrogen-storage alloy or its compound, the negative pole oxidation is suppressed during battery overcharge; Even along with charge and discharge cycles, hydrogen-storage alloy cracks because hydrogen-expansion and contraction are put in suction, thereby form under the situation of unsalted surface, because yttrium and compound thereof are dissolved in the electrolyte, separate out at the hydrogen-storage alloy unsalted surface then, thereby still can play the effect that suppresses the negative pole oxidation.But said method only can solve the oxidation resistance of hydrogen-storage alloy itself.Because there is the liberation of hydrogen side reaction in negative pole in the Ni-MH battery charging process, and anodal precipitated oxygen when overcharging.Though the nickel-hydrogen battery negative pole design capacity is higher than positive pole, because hydrogen-storage alloy negative pole hydrogen-oxygen recombination velocity is slower, the hydrogen-oxygen of generation is accumulated at inside battery, cause inner pressure of battery to rise.When inner pressure of battery is elevated to a certain degree, battery safety valve is opened, electrolyte overflows with gas, causes electrolyte exhaustion, internal resistance increase, discharge capacity of the cell to descend, and final battery cycle life shortens.Therefore, the interior pressure performance and the cycle performance of existing nickel-hydrogen secondary cell are relatively poor.
Summary of the invention
The objective of the invention is to overcome the interior pressure performance and the relatively poor shortcoming of cycle performance of the nickel-hydrogen secondary cell that prior art makes, provide a kind of and can improve the interior pressure performance of nickel-hydrogen secondary cell and nickel-hydrogen secondary battery negative electrode of cycle performance and preparation method thereof.
Another object of the present invention provides nickel-hydrogen secondary cell and preparation method thereof.
The inventor is by discovering, has only the oxidation resistance of improving hydrogen-storage alloy itself simultaneously and the oxygen ability that disappears, i.e. hydrogen-oxygen compound ability could really improve the interior pressure performance and the cycle performance of nickel-hydrogen secondary cell.Therefore, the inventor focuses on the hydrogen-oxygen compound ability that improves hydrogen-storage alloy, and has finally finished the present invention.
The invention provides a kind of nickel-hydrogen secondary battery negative electrode, this negative pole comprises negative pole conducting base and coating and/or is filled in negative material on the negative pole conducting base, described negative material contains as the hydrogen-storage alloy of major constituent and adhesive, wherein, described negative material also contains a kind of alloy addition, the metal that this alloy addition contains yttrium and has hydrogen-oxygen composite catalyzing ability.
The invention provides a kind of preparation method of nickel-hydrogen secondary battery negative electrode, this method comprises the negative material coating and/or is filled on the negative pole conducting base, described negative material contains as the hydrogen-storage alloy of major constituent and adhesive, wherein, described negative material also contains a kind of alloy addition, the metal that this alloy addition contains yttrium and has hydrogen-oxygen composite catalyzing ability.
The invention provides a kind of nickel-hydrogen secondary cell, this battery comprises electrode group and alkaline electrolyte, and described electrode group and alkaline electrolyte are sealed in the battery container, and described electrode group comprises positive pole, negative pole and dividing plate, wherein, described negative pole is a negative pole provided by the invention.
The present invention also provides a kind of preparation method of nickel-hydrogen secondary cell, this method comprises positive pole, negative pole and dividing plate is prepared into an electrode group, the electrode group and the electrolyte that obtain are sealed in the battery case, and wherein, described negative pole is a nickel-hydrogen secondary battery negative electrode provided by the invention.
Contain alloy addition in the negative material of nickel-hydrogen secondary cell provided by the invention, the metal that this alloy addition contains yttrium and has hydrogen-oxygen composite catalyzing ability.Therefore can improve the oxidation resistance of hydrogen-storage alloy and the oxygen ability that disappears simultaneously, i.e. hydrogen-oxygen compound ability, thus improve the interior pressure performance and the cycle performance of nickel-hydrogen secondary cell.
Description of drawings
Fig. 1 is the addition of expression yttrium cobalt alloy powder and the graph of a relation of inner pressure of battery;
Fig. 2 is the addition of expression yttrium cobalt alloy powder and the graph of a relation of cycle performance of battery;
Embodiment
Nickel-hydrogen secondary battery negative electrode provided by the invention comprises negative pole conducting base and coating and/or is filled in negative material on the negative pole conducting base, described negative material contains as the hydrogen-storage alloy of major constituent and adhesive, wherein, described negative material also contains a kind of alloy addition, the metal that this alloy addition contains yttrium and has hydrogen-oxygen composite catalyzing ability.
Wherein, described metal with hydrogen-oxygen composite catalyzing ability is cobalt and/or nickel.For the yttrium cobalt alloy, because cobalt element is soluble in the electrolyte, in battery charging process, can be reduced to metallic cobalt again, to separate out in the hydrogen-storage alloy surface, not molten cobalt is then still stayed the hydrogen-storage alloy surface.And metallic yttrium element itself is comparatively active, easily is oxidized to yttria (Y
2O
3) or yttrium hydroxide (Y (OH)
3), also be coated on the hydrogen-storage alloy surface, form the superpacket coating of yttria or yttrium hydroxide and metallic cobalt like this on the hydrogen-storage alloy surface, wherein, yttria or yttrium hydroxide can improve the oxidation resistance of hydrogen-storage alloy itself, metallic cobalt then has hydrogen-oxygen composite catalyzing ability, can improve the oxygen ability that disappears of hydrogen-storage alloy itself, thereby the yttrium cobalt alloy can improve the interior pressure performance and the cycle performance of nickel-hydrogen secondary cell.For yttrium nickel alloy or yttrium cobalt-nickel alloy, because nickel itself also has hydrogen-oxygen composite catalyzing ability, so yttrium nickel alloy or yttrium cobalt-nickel alloy also can improve the cycle life of Ni-MH battery.
Weight with described hydrogen-storage alloy is benchmark, and the content of described alloy addition is 0.2-15 weight %, is preferably 1-10 weight %.
Total weight with described alloy addition is a benchmark, and the content of yttrium is 5-60 weight %, is preferably 10-50 weight %.
Form to described alloy addition does not have special requirement, is preferably powder, can make this alloy mix, distribute more even in negative material like this.There is no particular limitation to the particle size of powder, is preferably the 0.5-25 micron, more preferably the 1-20 micron.
According to the negative pole of nickel-hydrogen secondary cell provided by the invention, except negative material contained described alloy addition provided by the invention, other structure and material can use and well known to a person skilled in the art structure and material.
Described hydrogen-storage alloy can be selected from can be as any hydrogen-storage alloy of alkaline secondary cell negative electrode key component, and this hydrogen-storage alloy can produce alkaline electrolyte in electrochemical reaction hydrogen absorbs, and, the reversible hydrogen ground of absorption is resolved.Described hydrogen-storage alloy has been done detailed description in CN1159793C.
The kind of described adhesive and content are conventionally known to one of skill in the art, and for example, described adhesive can be selected from carboxymethyl cellulose, hydroxypropyl methylcellulose, methylcellulose, Sodium Polyacrylate, the polytetrafluoroethylene one or more; In general, according to the difference of adhesive therefor kind, be benchmark with the weight of described hydrogen bearing alloy, the content of adhesive is 0.01-5 weight %, is preferably 0.02-3 weight %.
Described negative pole conducting base can use the various known negative pole conducting bases that are used for nickel-hydrogen secondary cell, as matrix, perforated metal panel or the expanded metal of nickel foam substrate, felt piece structure.
According to the preparation method of nickel-hydrogen secondary battery negative electrode provided by the invention, except negative material contained described alloy addition provided by the invention, other step was conventionally known to one of skill in the art.For example, can adopt conventional method that negative material is coated in described negative pole conducting base.For example, negative material is mixed into pasty state, applies and/or be filled on the described negative pole conducting base, drying, pressing mold or pressing mold not can obtain described negative pole.Wherein, solvent can be selected from any solvent that can make described mixture form pasty state, is preferably water.The consumption of solvent can make described pastel have viscosity and flowability, can be coated on the described conducting base to get final product.In general, be benchmark with the weight of hydrogen-storage alloy, the content of described solvent is 10-30 weight %, is preferably 15-25 weight %.Wherein, drying, the method for pressing mold and condition are conventionally known to one of skill in the art.
According to nickel-hydrogen secondary cell provided by the present invention, described dividing plate is arranged between positive pole and the negative pole, and it has electrical insulation capability and liquid retainability energy, and described electrode group and alkaline electrolyte are contained in the battery case together.Described dividing plate can be selected from various dividing plates used in the alkaline secondary cell, as polyolefine fiber nonwoven fabrics and the surperficial chip component of introducing hydrophilic fibre or handling through sulfonation.The position of described dividing plate, character and kind are conventionally known to one of skill in the art.
Anode can be selected from the used positive pole of various nickel-hydrogen secondary cells, and it can commercially obtain, and also can adopt existing method preparation.Described anodal conducting base is a nickel-hydrogen secondary cell anodal conducting base commonly used, as matrix, perforated metal panel or the expanded metal of nickel foam substrate, felt piece structure.
The described positive electrode of nickel-hydrogen secondary cell contains nickel hydroxide and adhesive, and described adhesive can adopt adhesive used in the negative pole.The content of adhesive is conventionally known to one of skill in the art, is generally the 0.01-5 weight % of nickel hydroxide, is preferably 0.02-3 weight %.
Can also contain additive in the described positive electrode, the kind of described additive and content are conventionally known to one of skill in the art.For example, described additive can be selected from the metal of cobalt, zinc and in the compound one or more.In general, in element, described content of additive is the 0-15 weight % of nickel hydroxide, is preferably 2-10 weight %.In positive electrode, add cobalt additive and can improve the conductivity that reaches between the positive active material between positive active material and the conducting base.In positive electrode, introduce additive such as zinc and can improve battery stability of structure in charge and discharge process, thereby improve the cycle life of battery.Detailed introduction has been done in acting on of these additives among the CN1159793C.
The preparation method of described positive pole can adopt conventional preparation method.For example,, also have additive to be blended into pasty state sometimes, apply and/or be filled on the described conducting base described nickel hydroxide, adhesive and solvent, drying, pressing mold or pressing mold not can obtain described positive pole.Wherein, described solvent can be selected from any solvent that can make described mixture form pasty state, is preferably water.The consumption of solvent can make described pastel have viscosity, can be coated on the described conducting base to get final product.In general, the content of described solvent is the 15-40 weight % of nickel hydroxide, is preferably 20-35 weight %.Wherein, drying, the method for pressing mold and condition are conventionally known to one of skill in the art.
Described electrolyte is the used electrolyte of alkaline secondary cell, as in potassium hydroxide aqueous solution, sodium hydrate aqueous solution, the lithium hydroxide aqueous solution one or more.The injection rate of electrolyte is generally 0.9-1.6g/Ah, the concentration of electrolyte be generally 6-8 rub/liter.
According to the preparation method of nickel-hydrogen secondary cell provided by the invention, except described negative material contained described alloy addition provided by the invention, other step was conventionally known to one of skill in the art.In general, will between described positive pole for preparing and the negative pole dividing plate be set, constitute an electrode group, this electrode group is contained in the battery container, inject electrolyte, then that battery container is airtight, can obtain alkaline secondary cell provided by the invention.
To the present invention be described in more detail by embodiment below.
This example illustrates nickel-hydrogen secondary battery negative electrode provided by the invention and battery and their preparation method.
(1) preparation of negative pole
With 100 weight portions commercial consist of MmNi
3.55Co
0.75Mn
0.4Al
0.3MmNi
5The carboxymethyl cellulose binder of series hydrogen storage alloy, 0.5 weight portion, (average grain diameter of powder is 1.5 microns to 2 weight portion yttrium cobalt alloy powder, wherein yttrium accounts for 20 weight % of alloy powder total weight), reach 20 parts of weight deionized waters and fully stir, be mixed into pasty slurry.This slurry is coated on the Punching steel strip equably, oven dry, roll-in then, cuts to make and be of a size of 172 millimeters * 42.5 millimeters * 0.5 millimeter negative pole, wherein, the amount of negative material is about 9 grams.
(2) Zheng Ji preparation
With the nickel hydroxide of 100 weight portions, the CoO of 5 parts of weight (cobalt protoxide), the carboxymethyl cellulose binder of 0.2 part of weight reaches 30 parts of weight deionized waters and fully stirs, and is mixed into pasty slurry.Get regular-type foam nickel, be made into 91 millimeters * 42 millimeters * 1.4 millimeters nickel foam substrate after pressure, the cut-parts, nickel strap 20 millimeters * 1.5 millimeters * 0.2 millimeter of the centre position of nickel foam substrate spot welding, nickel strap exposes 10 millimeters of nickel screens, fill the above-mentioned slurry that obtains, oven dry, roll-in make and are of a size of 91 millimeters * 42 millimeters * 1.4 millimeters positive pole then.Wherein, the content of positive electrode is about 8 grams.
(3) assembling of battery
The positive pole that negative pole, dividing plate grafted polypropylene diaphragm, (2) that (1) is obtained obtain stacks gradually the electrode group that is wound into scroll, the electrode that obtains is assembled in the AA shaped steel shell, (electrolyte is KOH and LiOH mixed aqueous solution to add electrolyte 1.1g/Ah, the LiOH that contains 30 weight %KOH and 15 grams per liters in the mixed aqueous solution), make Ni-MH battery A1 (AA-1800mAh) after the sealing.
Embodiment 2-6
This example illustrates nickel-hydrogen secondary battery negative electrode provided by the invention and battery and their preparation method.
Make Ni-MH battery A2-A6 (AA-1800mAh) respectively according to the method identical with embodiment 1, different is that the addition of yttrium cobalt alloy powder is respectively 0.5 weight %, 1 weight %, 4 weight %, 7 weight % and the 10 weight % of hydrogen-storage alloy.
This example illustrates nickel-hydrogen secondary battery negative electrode provided by the invention and battery and their preparation method.
Make Ni-MH battery A7 (AA-1800mAh) respectively according to the method identical with embodiment 1, different is, in the process of preparation negative pole, (average grain diameter of this alloy powder is 5 microns to add the yttrium Ni alloy powder, wherein yttrium accounts for 45 weight % of alloy powder total weight), the yttrium cobalt alloy powder that replaces embodiment 1 to add, the addition of yttrium Ni alloy powder is 2 weight % of hydrogen-storage alloy.
This example illustrates nickel-hydrogen secondary battery negative electrode provided by the invention and battery and their preparation method.
Make Ni-MH battery A8 (AA-1800mAh) respectively according to the method identical with embodiment 1, different is, in the process of preparation negative pole, (average grain diameter of this alloy powder is 5 microns to add yttrium nickel cobalt (alloy) powder, wherein yttrium accounts for 15 weight % of alloy powder total weight, nickel element accounts for 30 weight % of alloy powder total weight), the yttrium cobalt alloy powder that replaces embodiment 1 to add, the addition of yttrium nickel cobalt (alloy) powder is 2 weight % of hydrogen-storage alloy.
Comparative example 1
Adopt the method identical with embodiment 1 to make reference Ni-MH battery CA1 respectively, different is in the process for preparing negative pole, not add yttrium cobalt alloy powder.
Comparative example 2
Adopt the method identical to make reference Ni-MH battery CA2 respectively with embodiment 1, different is, in the process of preparation negative pole, add the yttrium cobalt alloy powder that yttria powder (average grain diameter is 1.5 microns) replaces embodiment 1 to add, the addition of yttria powder is 2 weight % of hydrogen-storage alloy.
Battery performance test
Inner pressure of battery is measured: above-mentioned nickel-hydrogen secondary cell A1-A8 that obtains and reference nickel-hydrogen secondary cell CA1-CA2 measure inner pressure of battery through after discharging and recharging activation for the first time with 1C (1800mA) current charges in the time of 120 minutes.Inner pressure of battery is measured by loading onto manometric method in the battery steel shell bottom, and measurement result is as shown in table 1 below.
Cycle performance of battery is measured: above-mentioned nickel-hydrogen secondary cell A1-A8 that obtains and reference nickel-hydrogen secondary cell CA1-CA2 are through after discharging and recharging activation for the first time, with 0.2C (360mA) current charges 7.5 hours, and be aided with simultaneously-Δ V=10mV control, it is 1V that 1C is discharged to cell voltage, after finishing, each charge or discharge all shelved 15 minutes, 70% o'clock the cycle-index of reducing to initial capacity with discharge capacity of the cell is represented the cycle performance of battery, the cycle-index cycle performance of the bright battery of multilist more is good more, and measurement result is as shown in table 1.
Table 1
| The embodiment numbering | The battery numbering | The powder kind of adding | Addition (weight %) | Inner pressure of battery (atmospheric pressure) | Cycle performance (inferior) |
| | A1 | Yttrium cobalt alloy powder | 2.0 | 6.7 | 667 |
| | A2 | Yttrium cobalt alloy powder | 0.5 | 12.1 | 511 |
| | A3 | Yttrium cobalt alloy powder | 1.0 | 7.0 | 658 |
| | A4 | Yttrium cobalt alloy powder | 4.0 | 6.5 | 670 |
| | A5 | Yttrium cobalt alloy powder | 7.0 | 6.4 | 675 |
| | A6 | Yttrium cobalt alloy powder | 10.0 | 6.4 | 679 |
| | A7 | The yttrium Ni alloy powder | 2.0 | 7.1 | 640 |
| | A8 | Yttrium nickel cobalt (alloy) powder | 2.0 | 6.8 | 658 |
| Comparative example 1 | CA1 | - | 0 | 20.1 | 303 |
| Comparative example 2 | CA2 | Yttria | 2.0 | 20.9 | 454 |
Utilize the inner voltage detecting result of battery A1-A6 and CA1 to obtain the addition of yttrium cobalt alloy powder and the relation of inner pressure of battery, as shown in Figure 1.
Utilize the cycle performance of battery measurement result of battery A1-A6 and CA1 to obtain the addition of yttrium cobalt alloy powder and the relation of cycle performance of battery, as shown in Figure 2.
As depicted in figs. 1 and 2, the interpolation of yttrium cobalt alloy powder can reduce the internal resistance of battery and improve the cycle-index of battery, when addition is 1 weight %, interior significantly reduction and the cycle-index of pressing significantly improves, when but addition surpasses 10 weight %, interior degree of pressing performance and cycle performance to improve is limited, considers that from the cost aspect addition of yttrium cobalt alloy powder is preferably 1-10 weight %.
From the result shown in the table 1 as can be seen, compare with reference cell, because be added with yttrium cobalt alloy powder, yttrium Ni alloy powder or yttrium nickel cobalt (alloy) powder in the negative material of nickel-hydrogen secondary cell provided by the invention, the interior pressure performance and the cycle performance of battery provided by the invention have obtained remarkable improvement.
Claims (10)
1, a kind of nickel-hydrogen secondary battery negative electrode, this negative pole comprises negative pole conducting base and coating and/or is filled in negative material on the negative pole conducting base, described negative material contains as the hydrogen-storage alloy of major constituent and adhesive, it is characterized in that, described negative material also contains a kind of alloy addition, the metal that this alloy addition contains yttrium and has hydrogen-oxygen composite catalyzing ability.
2, negative pole according to claim 1, wherein, described metal with hydrogen-oxygen composite catalyzing ability is cobalt and/or nickel.
3, negative pole according to claim 1 wherein, is a benchmark with the weight of described hydrogen-storage alloy, and the content of described alloy addition is 1-10 weight %.
4, negative pole according to claim 1 wherein, is a benchmark with the total weight of alloy addition, and the content of yttrium is 10-50 weight %.
5, the preparation method of the described nickel-hydrogen secondary battery negative electrode of claim 1, this method comprises the negative material coating and/or is filled on the negative pole conducting base, described negative material contains as the hydrogen-storage alloy of major constituent and adhesive, it is characterized in that, described negative material also contains a kind of alloy addition, the metal that this alloy addition contains yttrium and has hydrogen-oxygen composite catalyzing ability.
6, method according to claim 5, wherein, described metal with hydrogen-oxygen composite catalyzing ability is cobalt and/or nickel.
7, negative pole according to claim 5 wherein, is a benchmark with the weight of described hydrogen-storage alloy, and the content of described alloy addition is 1-10 weight %.
8, negative pole according to claim 5 wherein, is a benchmark with the total weight of alloy addition, and the content of yttrium is 10-50 weight %.
9, a kind of nickel-hydrogen secondary cell, this battery comprises electrode group and alkaline electrolyte, and described electrode group and alkaline electrolyte are sealed in the battery container, and described electrode group comprises positive pole, negative pole and dividing plate, it is characterized in that described negative pole is any described negative pole among the claim 1-4.
10, the preparation method of the described nickel-hydrogen secondary cell of claim 9, this method comprises positive pole, negative pole and dividing plate is prepared into an electrode group, the electrode group and the electrolyte that obtain are sealed in the battery case, it is characterized in that, described negative pole is any described negative pole among the claim 1-4.
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