CN104269557B - The application process of a kind of zinc cathode additive agent in zinc-nickel secondary batteries - Google Patents

The application process of a kind of zinc cathode additive agent in zinc-nickel secondary batteries Download PDF

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Publication number
CN104269557B
CN104269557B CN201410508038.XA CN201410508038A CN104269557B CN 104269557 B CN104269557 B CN 104269557B CN 201410508038 A CN201410508038 A CN 201410508038A CN 104269557 B CN104269557 B CN 104269557B
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zinc
application
mass parts
hydrotalcite
negative
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CN201410508038.XA
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CN104269557A (en
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杨占红
冯召宾
张政
王婷婷
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中南大学
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/626Metals
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/364Composites as mixtures
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a kind of application of zinc cathode additive agent of zinc-nickel secondary batteries. Can improve deformation and the dendrite of zinc oxide by this application, and improve other performances such as electric conductivity, resistivity, depositional configuration and speed. Solved the poor and low problem of anionic zinc-base hydrotalcite specific discharge capacity of deformation, dendrite and the cycle performance of zinc oxide simultaneously. By the present invention, can obtain good cycle performance and high ratio discharge capacity simultaneously, be conducive to the marketization of zinc-nickel secondary batteries.

Description

The application process of a kind of zinc cathode additive agent in zinc-nickel secondary batteries

Technical field

The present invention relates to the application process of a kind of zinc cathode additive agent in zinc-nickel secondary batteries.

Background technology

Alkali zinc nickel secondary cell has that specific energy is large, specific power is high, stable operating voltage, cheap feature. But,The problem such as deformation and the dendrite main cause of active material zinc is the dissolving of active material in alkaline electrolyte, for example, and in chargingIn process, active material zinc deposition is inhomogeneous, and this has caused the formation of current-density gradient, thus cause zinc deformation andDendrite.

For this difficult problem, people are doing a lot of research aspect the improvement of zinc negative pole. By adding additive to be in zinc negative poleImprove an important channel of electrode electro Chemical performance. The additive generally adopting in zinc electrode at present and studying mainly containsThree classes: corrosion inhibitor as mercury substitute, inorganic additive and organic additive. In patent documentation CN1971978A, by inorganic additive hydrogen-oxygenThereby change calcium and add the deformation that can reduce the dissolving of active material in alkaline electrolyte in zinc electrode and slow down zinc electrode to. Enter oneStep research discovery, the distortion why calcium hydroxide can slow down zinc electrode is that it can be in alkaline electro because in cyclic processSeparate in liquid and generate novel substance-zincic acid calcium that a kind of solubility is lower. Therefore there is the directly activity as zinc electrode by zincic acid calcium of researcherMaterial, has obtained good effect. But the shortcoming that uses this active material is that it can reduce the capacity of zinc negative pole greatly.

Also there is researcher using metal, metal oxide or the hydroxide with higher overpotential of hydrogen evolution as changing for mercury additiveProperty zinc electrode. This additive mainly contains the metals such as In, Bi, Sn, Ga, Tl. These metals can change by characteristic separatelyEnter zinc negative pole. Meanwhile, researcher has also done a lot of improvement to electrolyte, in electrolyte, adds boric acid, phosphoric acid, fluorineChange potassium, organic inhibitor etc. are the solubility in alkaline electrolyte for reducing zinc electrode, thereby improve zinc electrode performance. ButThese additives still do not have to improve well the cycle performance of zinc negative pole.

In patent documentation 201110167284.X, using a kind of anionic zinc-base hydrotalcite directly as zinc negative electrode active material, thoughSo its cyclicity improves, but it is lower than discharge capacity, can not meet the demand of market to zinc-nickel secondary batteries.

Summary of the invention

The object of the invention is to the application in zinc-nickel secondary batteries by zinc cathode additive agent, obtain good cyclicity simultaneouslyEnergy and high ratio discharge capacity. Improve deformation and the dendrite of active material zinc, and improve electric conductivity, resistivity, depositional configuration andOther performance such as speed; Be conducive to the marketization of zinc-nickel secondary batteries.

The application of zinc cathode additive agent in zinc-nickel secondary batteries, is characterized in that, this zinc cathode additive agent is anionicZinc-base hydrotalcite, application process comprises:

(1) zinc oxide using the anionic zinc-base hydrotalcite of 4-40 mass parts as additive, 40-76 mass parts is as workProperty material, 8-15 mass parts other zinc-containing substances of conductive agent, 5-15 mass parts carry out mechanical mixture and obtain negative material and mixThing;

(2) dispersant of 5-10 mass parts is dissolved in the deionized water of 35-50 mass parts, obtains dispersant solution;

(3) step (2) gained dispersant solution is joined in the negative material mixture of step (1), then strongly stirringMix down and add binder solution, the negative material mixture weight that binder solution and step (1) obtain, than being 1-5:100, obtainsTo uniform viscosity zinc cathode size;

(4) the viscosity zinc cathode size of step (3) is rolled to becoming even thin slice, cut compressing tablet and dry, obtain zinc negative poleProduct pole piece.

In step (1), the addition of anionic zinc-base hydrotalcite is preferably 15-35 mass parts.

The more preferably 20-25 mass parts of addition of anionic zinc-base hydrotalcite in step (1).

In step (1), the addition of zinc oxide is preferably 40-70 mass parts.

The more preferably 50-60 mass parts of addition of zinc oxide in step (1).

In step (1), the addition of conductive agent is preferably 8-12 mass parts, and the addition of other zinc-containing substances is preferably 8-12 matterAmount part.

The more preferably 8-10 mass parts of addition of conductive agent in step (1), the addition of other zinc-containing substances is furtherBe preferably 8-10 mass parts.

By above-mentioned preferred, can obtain better cycle performance and higher ratio discharge capacity.

The anion of described anionic zinc-base hydrotalcite is CO3 2-、BO3 3-、PO4 3-、AsO4 3-、SO4 2-、OH-、F-、Cl-、Benzoate anion, phthalic acid root, ethanedioic acid root, succinic, DBSA root, dodecyl sulphate root, 12One in alkyl azochlorosulfonate.

Cation in described anionic zinc-base hydrotalcite is Sn2+、Cu2+、Ba2+、Ca2+、Sr2+、Mg2+、In3+、Bi3+、La3+、Nd3+、Ce3+、Pr3+、Sb3+、Ga3+、Tl3+、Al3+In one or more.

Described conductive agent is a kind of or and several in electrically conductive graphite, conductive carbon black, acetylene black, indium powder, aluminium powder, glass putty or copper powderKind;

Described other zinc-containing substances are one in zinc powder, zinc oxide, zinc-indium, zinc-indium-bismuth, zinc-Xi or zinc-Sn-In alloy powderPlant or two kinds; Described dispersant be neopelex, 12 sodium alkyl sulfate ﹑ softex kws,Inferior sodium phosphate, hexamethylenetetramine, Ju Yi bis-Chun ﹑ tetrabutyl phosphonium bromide An ﹑ thiocarbamide, teabrom, polyethylene glycol octyl groupOne or more in phenyl ether;

Described binding agent be polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose, polyvinyl alcohol, fluoropolymer, polyethylene, rubber orOne or more in waterglass.

Described anionic zinc-base hydrotalcite is preferably carbonate type zinc-tin aluminum hydrotalcite.

Beneficial effect of the present invention

The present invention, by the application of zinc cathode additive agent in zinc-nickel secondary batteries, has obtained good cycle performance and high simultaneouslyCompare discharge capacity. In the prior art, known use zinc oxide in nickel-zinc cell time, there is the poor problem of cycle performance, andThere is the problem lower than discharge capacity in anionic zinc-base hydrotalcite, the existence of these problems has limited it greatly at nickel-zinc cellIn application, and existingly improve one's methods or have various deficiencies, can not well address the above problem. And in prior artAlthough also attempted zinc oxide to use together with hydrotalcite, its basic ideas are all to improve as active material using hydrotalciteThe deformation of zinc negative pole and dendrite, although can improve cycle performance from certain angle, but there is the problem lower than discharge capacity;And in zinc-nickel cell field, hydrotalcite is the negative material that a kind of known resultant effect is better than zinc oxide, therefore, using waterWhen talcum, the conventional thought of prior art is that the more excellent hydrotalcite of combination property is used as active material. And the present inventionInventor by using anionic zinc-base hydrotalcite as additive with zinc oxide as active material fit applications, and by controlMake its content, be surprised to find that and can obtain good cycle performance and high ratio discharge capacity simultaneously, thereby proposed the present invention.And found through experiments, the present invention can improve deformation and the dendrite of active material zinc, and improves electric conductivity, resistivity, depositionOther performance such as form and speed. Solved the poor and anionic zinc-base water of deformation, dendrite and the cycle performance of zinc oxide simultaneouslyThe problem that talcum specific discharge capacity is low. The solution of these problems, concerning battery industry, is highly profitable, and is conducive to zinc-nickel twoThe marketization of primary cell.

Brief description of the drawings

Fig. 1 is the pure ZnO electrode containing the ZnO electrode of 24% hydrotalcite additive, comparative example 1 prepared of embodiment 2 and rightThe CV curve comparison figure of the pure Zn-Sn-Al-LDH electrode of ratio 2.

As can be seen from the figure, compare and pure ZnO electrode, contain oxidation peak and the reduction of the ZnO electrode of 24% hydrotalcite additiveSpike potential is poor less, and this explanation is better containing the invertibity of the ZnO electrode of 24% hydrotalcite additive. From figure, also can simultaneouslyGo out, the oxidation peak area that contains the ZnO electrode of 24% hydrotalcite additive is greater than the oxidation peak area of pure Zn-Sn-Al-LDH electrode,This explanation is greater than the latter containing the capacity of the ZnO electrode of 24% hydrotalcite.

Fig. 2 is that embodiment 2 preparations are containing the ZnO electrode of 24% hydrotalcite additive, pure ZnO electrode and the contrast of comparative example 1The charging platform comparison diagram of the pure Zn-Sn-Al-LDH electrode of example 2. As can be seen from the figure, compare and pure ZnO electrode and pureZn-Sn-Al-LDH electrode, has shown lower charging platform containing the ZnO electrode of 24% hydrotalcite additive, and this shows containing 24%The ZnO electrode of hydrotalcite additive has less resistance, also can suppress better the liberation of hydrogen of electrode simultaneously, improves filling of electrodeElectrical efficiency.

Fig. 3 is the pure ZnO electrode containing the ZnO electrode of 24% hydrotalcite additive, comparative example 1 prepared of embodiment 2 and rightThe discharge capacity curve comparison figure of the pure Zn-Sn-Al-LDH electrode of ratio 2. As can be seen from the figure, compare and pure ZnO electrode,Shown better cycle performance containing the ZnO electrode of 24% hydrotalcite additive, this explanation adds the cyclicity of ZnO after hydrotalciteCan obtain improving greatly. From figure, also can find out, the ratio electric discharge that contains the ZnO electrode of 24% hydrotalcite additive is held simultaneouslyAmount will be higher than pure Zn-Sn-Al-LDH electrode, and this shows that making zinc negative active core-shell material with the ZnO that adds hydrotalcite additive can showWork improves the ratio discharge capacity of zinc negative pole.

Detailed description of the invention

Be intended to further illustrate the present invention below in conjunction with embodiment, and unrestricted the present invention.

Embodiment 1

The analytically pure ANN aluminium nitrate nonahydrate of the analytically pure zinc nitrate hexahydrate of 36 mass parts and 10 mass parts is dissolved in to 100 matterIn the deionized water of amount part, pure the analysis of 1.5 mass parts stannous chloride is dissolved in the watery hydrochloric acid (0.1%) of 50 mass parts, willAbove-mentioned two kinds of solution mix formation salting liquid. The NaOH of 3.2 mass parts and 2.12 mass parts sodium carbonate are dissolved inIn the deionized water of 50 mass parts, form aqueous slkali. Under strong mechanical agitation, salting liquid and aqueous slkali is per second with oneSpeed is added drop-wise in the three-necked bottle under the inert gas shielding that fills 50 mass parts deionized waters, and controlling pH value of solution is 10.0, continuesThe continuous 60min that stirs, hydro-thermal reaction 12h at 120 DEG C, finally carried out Lv ﹑ washing to precipitation, and dry 12h is at 60 DEG CObtain carbonate type zinc-tin aluminum hydrotalcite additive.

By 0.4g zinc-tin aluminium ternary hydrotalcite additive obtained above, 3.6g zinc negative electrode active material zinc oxide, 0.5g acetyleneBlack, 0.5g zinc powder carries out ground and mixed and obtains negative material mixture in mortar; 0.1g neopelex is dissolved inIn 1ml deionized water, gained solution is added drop-wise in negative material mixture; 0.05g binding agent polyvinylidene fluoride is dissolved in to 6mlIn deionized water, gained solution is added drop-wise in negative material mixture, then continues to be ground to uniform mud; By mud and glassOn glass plate, roll into the thin slice of even thickness with glass bar, be cut into the square sheets of 1cm × 1cm with blade, be sandwiched in 2cm × 10cm'sOn copper mesh collector, compressing tablet is made the zinc negative pole utmost point, the anodal sintrered nickel anode pole piece that dimensions is 5cm × 5cm, the both positive and negative polarity of adoptingBe sandwiched in respectively electrolytic cell and make open cell, electrolyte is 6mol/LKOH and saturated burnett's solution.

Embodiment 2

Zinc-tin aluminium ternary hydrotalcite additive 1.2g, zinc negative electrode active material zinc oxide 2.8g, acetylene that embodiment 1 is obtained0.5g, zinc powder 0.5g carry out ground and mixed and obtain negative material mixture in mortar; By molten 0.1g neopelexIn 1ml deionized water, gained solution is added drop-wise in negative material mixture; 0.05g binding agent polyvinylidene fluoride is dissolved inIn 6ml deionized water, gained solution is added drop-wise in negative material mixture, then continues to be ground to uniform mud; By mudWith the thin slice of rolling into even thickness on glass plate with glass bar, be cut into the square sheets of 1cm × 1cm with blade, be sandwiched in 2cm × 10cmCopper mesh collector on compressing tablet make the zinc negative pole utmost point, anodal adopt the sintrered nickel anode pole piece that dimensions is 5cm × 5cm, positive and negativeThe utmost point is sandwiched in respectively electrolytic cell and makes open cell, and electrolyte is 6mol/LKOH and saturated burnett's solution.

Embodiment 3

Zinc-tin aluminium ternary hydrotalcite additive 1.5g, zinc negative electrode active material zinc oxide 2.5g, acetylene black that embodiment 1 is obtained0.5g, zinc powder 0.5g carry out ground and mixed and obtain negative material mixture in mortar; By molten 0.1g neopelexIn 1ml deionized water, gained solution is added drop-wise in negative material mixture; 0.05g binding agent polyvinylidene fluoride is dissolved inIn 6ml deionized water, gained solution is added drop-wise in negative material mixture, then continues to be ground to uniform mud; By mudWith the thin slice of rolling into even thickness on glass plate with glass bar, be cut into the square sheets of 1cm × 1cm with blade, be sandwiched in 2cm × 10cmCopper mesh collector on compressing tablet make the zinc negative pole utmost point, anodal adopt the sintrered nickel anode pole piece that dimensions is 5cm × 5cm, positive and negativeThe utmost point is sandwiched in respectively electrolytic cell and makes open cell, and electrolyte is 6mol/LKOH and saturated burnett's solution.

Comparative example 1

4g zinc negative electrode active material zinc oxide, 0.5g acetylene black, 0.5g zinc powder are carried out to ground and mixed in mortar and obtain negative poleMaterial blends; 0.1g neopelex is dissolved in 1ml deionized water, and gained solution is added drop-wise to negative material to be mixedIn thing; 0.05g binding agent polyvinylidene fluoride is dissolved in 6ml deionized water, and gained solution is added drop-wise to negative material mixtureIn, then continue to be ground to uniform mud; By mud and the thin slice of rolling into even thickness on glass plate with glass bar, use bladeBe cut into the square sheets of 1cm × 1cm, be sandwiched in compressing tablet on the copper mesh collector of 2cm × 10cm and make the zinc negative pole utmost point, the anodal chi that adoptsVery little specification is the sintrered nickel anode pole piece of 5cm × 5cm, and both positive and negative polarity is sandwiched in respectively electrolytic cell and makes open cell, and electrolyte is6mol/LKOH and saturated burnett's solution.

Comparative example 2

4g zinc negative electrode active material zinc-tin aluminium ternary hydrotalcite, 0.5g acetylene black, 0.5g zinc powder are ground in mortar mixedClose and obtain negative material mixture; 0.1g neopelex is dissolved in 1ml deionized water, and gained solution is added drop-wise to negativeIn utmost point material blends; 0.05g binding agent polyvinylidene fluoride is dissolved in 6ml deionized water, and gained solution is added drop-wise to negative poleIn material blends, then continue to be ground to uniform mud; By mud with on glass plate, roll into the thin of even thickness with glass barSheet, is cut into the square sheets of 1cm × 1cm with blade, and be sandwiched in compressing tablet on the copper mesh collector of 2cm × 10cm and make the zinc negative pole utmost point,The sintrered nickel anode pole piece that anodal employing dimensions is 5cm × 5cm, both positive and negative polarity is sandwiched in respectively electrolytic cell and makes open cell, electricitySeparating liquid is 6mol/LKOH and saturated burnett's solution.

Battery performance test:

Above-described embodiment and comparative example are assembled to the battery obtaining and are following activation processing: 0.1C charging 10h, shelve 15min,After be discharged to 1.2V with 0.2C, then shelve 15min; So charge and discharge 5 times, complete activation. Then at room temperature (25 ± 2 DEG C)Under with 1C current charges, 1C electric discharge, the cycle life of zinc-nickel secondary batteries is measured in circulation. After test cell circulation 200 timesStop test. Test result is shown in Fig. 1,2,3.

Claims (9)

1. the application of zinc cathode additive agent in zinc-nickel secondary batteries, is characterized in that, this zinc cathode additive agent is cloudyIonic zinc-base hydrotalcite, application process comprises:
(1) zinc oxide using the anionic zinc-base hydrotalcite of 15-35 mass parts as additive, 40-76 mass parts asThe conductive agent of active material, 8-15 mass parts, other zinc-containing substances of 5-15 mass parts carry out mechanical mixture and obtain negative pole materialMaterial mixture;
(2) dispersant of 5-10 mass parts is dissolved in the deionized water of 35-50 mass parts, obtains dispersant solution;
(3) step (2) gained dispersant solution is joined in the negative material mixture of step (1), then by forceUnder strong stirring, add binder solution, the negative material mixture weight ratio that binder solution and step (1) obtain is1-5:100, obtains uniform viscosity zinc cathode size;
(4) the viscosity zinc cathode size of step (3) is rolled to becoming even thin slice, cut compressing tablet and dry, obtain zinc negative poleFinished product pole piece.
2. application according to claim 1, is characterized in that, in step (1), the addition of zinc oxide is 40-70Mass parts.
3. application according to claim 1, is characterized in that, in step (1), anionic zinc-base hydrotalcite addsDosage is 20-25 mass parts.
4. according to the application described in claim 1 or 3, it is characterized in that, in step (1), the addition of zinc oxide is 50-60Mass parts.
5. application according to claim 4, is characterized in that, in step (1), the addition of conductive agent is 8-12Mass parts, the addition of other zinc-containing substances is 8-12 mass parts.
6. application according to claim 4, is characterized in that, in step (1), the addition of conductive agent is 8-10Mass parts, the addition of other zinc-containing substances is 8-10 mass parts.
7. according to the application described in claim 1 or 3, it is characterized in that the moon of described anionic zinc-base hydrotalciteIon is CO3 2-、BO3 3-、PO4 3-、AsO4 3-、SO4 2-、OH-、F-、Cl-, benzoate anion, phthalic acid root, second twoOne in acid group, succinic, DBSA root, dodecyl sulphate root, dodecyl sodium sulfonate root; DescribedAnionic zinc-base hydrotalcite in cation be Sn2+、Cu2+、Ba2+、Ca2+、Sr2+、Mg2+、In3+、Bi3+、La3+、Nd3+、Ce3+、Pr3+、Sb3+、Ga3+、Tl3+、Al3+In one or more.
8. application according to claim 1, is characterized in that, described conductive agent be electrically conductive graphite, conductive carbon black,One or more in indium powder, aluminium powder, glass putty or copper powder; Described other zinc-containing substances be zinc powder, zinc oxide, zinc-indium,One or both in zinc-indium-bismuth, zinc-Xi or zinc-Sn-In alloy powder; Described dispersant be neopelex,12 sodium alkyl sulfate ﹑ softex kws, inferior sodium phosphate, hexamethylenetetramine, poly-second two alcohol ﹑ tetra-fourthsOne or more in base bromination An ﹑ thiocarbamide, teabrom, Triton X-100; Described binding agent is poly-fourOne in PVF, sodium carboxymethylcellulose, polyvinyl alcohol, fluoropolymer, polyethylene, rubber or waterglass or severalKind.
9. application according to claim 1, is characterized in that, described anionic zinc-base hydrotalcite is carbonate typeZinc-tin aluminum hydrotalcite.
CN201410508038.XA 2014-09-28 2014-09-28 The application process of a kind of zinc cathode additive agent in zinc-nickel secondary batteries CN104269557B (en)

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CN104617268B (en) * 2015-01-23 2017-03-15 重庆大学 A kind of nickel-zinc cell zinc load material and its preparation method and application
CN105161702B (en) * 2015-10-26 2017-08-04 新乡市超力新能源有限公司 A kind of cathode active material of zinc-nickel battery, Zinc-nickel battery negative plate and zinc-nickel cell
CN106654277A (en) * 2016-11-29 2017-05-10 先雪峰 Application of additive, electrode slurry, additive slurry, cathode or anode of lithium ion battery, preparation method of cathode or anode of lithium ion battery and lithium ion battery
CN106450337A (en) * 2016-12-14 2017-02-22 先雪峰 Application of additive, electrode slurry, additive slurry, positive electrode or negative electrode of lithium ion battery, preparation method of positive electrode or negative electrode of lithium ion battery, and lithium ion battery
CN107681118A (en) * 2017-09-03 2018-02-09 河南师范大学 Iron nickel secondary batteries negative plate and preparation method thereof and the iron nickel secondary batteries using the negative plate

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CN102263260B (en) * 2011-06-21 2013-04-24 中南大学 Application of zinc based polynary hydrotalcite in preparation of zinc negative pole of zinc-nickel secondary battery
CN102263262B (en) * 2011-06-21 2013-09-11 中南大学 Method for using anionic zinc houghite for preparing zinc cathode of zinc-nickel secondary battery
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