CN111463429B - Preparation method of high specific energy zinc-nickel battery positive electrode slurry - Google Patents

Preparation method of high specific energy zinc-nickel battery positive electrode slurry Download PDF

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CN111463429B
CN111463429B CN202010188931.4A CN202010188931A CN111463429B CN 111463429 B CN111463429 B CN 111463429B CN 202010188931 A CN202010188931 A CN 202010188931A CN 111463429 B CN111463429 B CN 111463429B
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nickel
slurry
mixed
additive
rare earth
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CN111463429A (en
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柯娃
马永泉
陈经宁
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Shandong Hetai New Energy Co ltd
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Shandong Hetai New Energy Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

Abstract

The invention provides a preparation method of high specific energy zinc-nickel battery anode slurry, firstly nickel salt and Bi are mixed according to the sequence2O3The rare earth additive and the binder are dry-mixed to obtain dry powder, the prepared dry powder, nickel powder and pure water are subjected to primary wet mixing to obtain mixed slurry, and finally, polytetrafluoroethylene emulsion and the mixed slurry are subjected to secondary wet mixing. The invention sets the adding sequence and mixing process of the slurry, when the nickel salt and the additive are dry mixed, the nickel salt, the bismuth trioxide and the rare earth additive are mixed to ensure the combination of the nickel salt and the additive, finally, the binder particles are added to be attached to the surface layer of the mixture, the mixture is ensured to be uniformly dispersed after water dissolving, no obvious agglomeration occurs, then, the polytetrafluoroethylene emulsion is slowly added at a constant speed for further fixation, so that the raw materials are uniformly dispersed, through the two steps of operation, the viscosity degree of the slurry is increased, the connecting force between the slurry and the matrix is greatly improved, and the cycle life of the battery is prolonged.

Description

Preparation method of high specific energy zinc-nickel battery positive electrode slurry
Technical Field
The invention relates to battery slurry, in particular to zinc-nickel battery anode slurry.
Background
The new high specific energy zinc-nickel battery has the characteristics of high specific energy, high specific power, high working voltage and high open-circuit voltage, and the negative electrode material zinc of the battery is rich in reserve in nature, low in price and good in application prospect. Is a secondary battery which can be recycled. However, the cycle times of the high specific energy zinc-nickel battery are limited, and the development of the high specific energy zinc-nickel battery is greatly restricted.
In the high-specific energy zinc-nickel battery, the active substances are not tightly combined with the matrix, so that the active substances are softened and fall off; meanwhile, since the positive active material generally contains a large amount of components, it is difficult to achieve absolutely sufficient uniform dispersion of the positive active material in the preparation of the slurry, and the uniformity of the battery is poor. In addition, the forming state and viscosity of the paste affect the subsequent manufacturing process, while the viscosity of the paste prepared by the prior art is low, and the thickness of the pole piece cannot be ensured, so that the consistency and the service life of the battery are affected.
Disclosure of Invention
The preparation method of the high-specific-energy zinc-nickel battery anode slurry aims to solve the problem that the active substance is not tightly combined with a matrix to soften and fall off due to uneven mixing of the anode material of the existing high-specific-energy zinc-nickel battery, improve the electrode charging acceptance capacity, and improve the specific energy and the cycle life of the zinc-nickel battery.
The technical scheme of the invention provides a preparation method of high specific energy zinc-nickel battery anode slurry, which mainly comprises three steps of dry mixing, primary wet mixing and secondary wet mixing, and the process comprises the following steps:
(1) dry blending
Putting nickel salt and an additive into a mixing device, controlling the dry mixing time to be 3-10min, and controlling the stirring speed in the process to be 30-150 Rpm; the additive is Bi2O3Rare earth additives and binders; the raw materials are added with nickel salt and Bi in sequence2O3Rare earth additives and binders;
(2) one-time wet mixing
Uniformly mixing the dry powder uniformly mixed in the step (1) with nickel powder and pure water, wherein the wet mixing time is controlled to be 10-60min, and the process stirring speed is controlled to be 80-250 Rpm;
(3) secondary wet mixing: stirring the polytetrafluoroethylene emulsion and the mixed slurry obtained in the step (2) for 10-40min at 200-500Rpm to prepare a mixed paste;
the paste in the process comprises the following components in parts by weight: 30-45 parts of dry powder, 20-35 parts of nickel powder, 10-15 parts of pure water and 0.1-2 parts of polytetrafluoroethylene emulsion.
Further, the mass ratio of the raw materials in the step (1) is nickel salt: bi2O3: rare earth additive: binder (100-: (5-10): (5-10): (2-6).
Further, the rare earth additive is La2O3，Y2O3，Dy2O3，Nd2O3One kind of (1).
Further, the nickel salt is nickel hydroxide, and the binder is one of HEC (hydroxyethyl cellulose), EMC (ethyl methyl cellulose), MHEC (hydroxyethyl methyl cellulose), CMC (carboxymethyl cellulose).
Further, the nickel powder and the pure water in the step (2) are simultaneously added into the dry powder prepared in the step (1).
Further, the adding time of the pure water in the step (2) is 0.5-2 min.
Further, in the step (3), the polytetrafluoroethylene emulsion is added into the mixed slurry at a constant speed, and the adding time is controlled to be 5-8 min.
Further, the prepared mixed paste is slurry with the viscosity of 2000-30000 mpas.
The invention has the advantages and beneficial effects that: the invention sets the adding sequence (nickel salt, additive, polytetrafluoroethylene emulsion) and mixing process of the slurry, when the nickel salt and the additive are dry mixed, the nickel salt, the bismuth trioxide and the rare earth additive are mixed to ensure the combination of the nickel salt and the additive, then binder particles are added to be attached to the surface layer of the mixture finally, the mixture is ensured to be uniformly dispersed after water dissolving, no obvious agglomeration occurs, then PTFE emulsion (polytetrafluoroethylene) is slowly added at a constant speed for further fixing, the anode slurry is uniformly dispersed, through the two steps of operation, the viscosity degree of the slurry is increased, the prepared slurry is in a slurry shape, but the bonding property is strong, the binder in the material can play a bonding role to the maximum extent, the connecting force between the slurry and a matrix is greatly improved, and the cycle life of the battery is prolonged.
Drawings
FIG. 1 is a graph showing the cycle life test results of the positive electrode of the present invention
Detailed Description
The present invention will be further described with reference to the following embodiments.
Example 1
The embodiment provides a preparation method of high-specific-energy zinc-nickel battery positive electrode slurry, which comprises the following process steps:
(1) dry blending
Putting nickel hydroxide and an additive into a mixing device, controlling the dry mixing time to be 3min, and controlling the stirring speed to be 30 Rpm; the additive is Bi2O3、La2O3And HEC; the raw materials are added with nickel salt and Bi in sequence2O3The rare earth additive and the binder are nickel salt in a mass ratio: bi2O3: rare earth additive: binder 100: 5: 5: 2;
(2) one-time wet mixing
Uniformly mixing the uniformly mixed dry powder in the step (1) with nickel powder and pure water, wherein the wet mixing time is controlled to be 10min, and the process stirring speed is controlled to be 250 Rpm; wherein the adding time of the pure water is 0.5 min;
(3) secondary wet mixing: stirring the polytetrafluoroethylene emulsion and the mixed slurry at 200Rpm for 10min according to the proportion, wherein the polytetrafluoroethylene emulsion is added into the mixed slurry at a constant speed, and the adding time is controlled to be 5min, so as to prepare a mixed paste body, and the mixed paste body is the slurry with the viscosity of 2000-;
the paste in the process comprises the following components in parts by weight: 30 parts of dry powder, 20 parts of nickel powder, 10 parts of pure water and 0.1 part of polytetrafluoroethylene emulsion.
Example 2
The embodiment provides a preparation method of high-specific-energy zinc-nickel battery positive electrode slurry, which comprises the following process steps:
(1) dry blending
Putting nickel hydroxide and an additive into a mixing device, controlling the dry mixing time to be 10min, and controlling the stirring speed to be 150 Rpm; the additive is Bi2O3、Y2O3And EMC; the raw materials are added with nickel salt and Bi in sequence2O3The rare earth additive and the binder are nickel salt in a mass ratio: bi2O3: rare earth additive: binder 150: 10: 10: 6;
(2) one-time wet mixing
Uniformly mixing the uniformly mixed dry powder in the step (1) with nickel powder and pure water, wherein the wet mixing time is controlled to be 60min, and the process stirring speed is controlled to be 80 Rpm; wherein the adding time of the pure water is 2 min;
(3) secondary wet mixing: stirring the polytetrafluoroethylene emulsion and the mixed slurry at 500Rpm for 40min according to the proportion, wherein the polytetrafluoroethylene emulsion is added into the mixed slurry at a constant speed, and the adding time is controlled to be 8min, so as to prepare a mixed paste body, and the mixed paste body is the slurry with the viscosity of 2000-;
the paste in the process comprises the following components in parts by weight: 45 parts of dry powder, 35 parts of nickel powder, 15 parts of pure water and 2 parts of polytetrafluoroethylene emulsion.
Example 3
The embodiment provides a preparation method of high-specific-energy zinc-nickel battery positive electrode slurry, which comprises the following process steps:
(1) dry blending
Putting nickel hydroxide and an additive into a mixing device, controlling the dry mixing time to be 5min, and controlling the stirring speed to be 90 Rpm; the additive is Bi2O3、Dy2O3And a MHEC; the raw materials are added with nickel salt and Bi in sequence2O3The rare earth additive and the binder are nickel salt in a mass ratio: bi2O3: rare earth additive: binder 120: 8: 7: 4;
(2) one-time wet mixing
Uniformly mixing the uniformly mixed dry powder in the step (1) with nickel powder and pure water, wherein the wet mixing time is controlled to be 30min, and the process stirring speed is controlled to be 180 Rpm; wherein the adding time of the pure water is 1 min;
(3) secondary wet mixing: stirring the polytetrafluoroethylene emulsion and the mixed slurry at 250Rpm for 25min according to the proportion, wherein the polytetrafluoroethylene emulsion is added into the mixed slurry at a constant speed, and the adding time is controlled to be 6min, so as to prepare a mixed paste body, and the mixed paste body is the slurry with the viscosity of 2000-;
the paste in the process comprises the following components in parts by weight: 40 parts of dry powder, 25 parts of nickel powder, 12 parts of pure water and 1.5 parts of polytetrafluoroethylene emulsion.
Example 4
The embodiment provides a preparation method of high-specific-energy zinc-nickel battery positive electrode slurry, which comprises the following process steps:
(1) dry blending
Putting nickel hydroxide and an additive into a mixing device, controlling the dry mixing time to be 8min and controlling the stirring speed to be 120 Rpm; the additive is Bi2O3、Nd2O3And CMC; the raw materials are added with nickel salt and Bi in sequence2O3Rare earth additiveAnd a binder, wherein the raw materials in mass ratio are nickel salt: bi2O3: rare earth additive: binder 140: 8: 6: 3;
(2) one-time wet mixing
Uniformly mixing the uniformly mixed dry powder in the step (1) with nickel powder and pure water, wherein the wet mixing time is controlled to be 45min, and the process stirring speed is controlled to be 150 Rpm; wherein the adding time of the pure water is 1 min;
(3) secondary wet mixing: stirring the polytetrafluoroethylene emulsion and the mixed slurry at 350Rpm for 30min according to the proportion, wherein the polytetrafluoroethylene emulsion is added into the mixed slurry at a constant speed, and the adding time is controlled to be 7min, so as to prepare a mixed paste body, and the mixed paste body is the slurry with the viscosity of 2000-;
the paste in the process comprises the following components in parts by weight: 35 parts of dry powder, 30 parts of nickel powder, 14 parts of pure water and 1 part of polytetrafluoroethylene emulsion.
The result of the cycle number test of the anode body obtained by the invention is shown in figure 1, and the test result shows that the capacity of the anode sheet prepared by the method is very gently attenuated within 400 cycles, the attenuation rate is very small, the initial capacity is 8Ah, the capacity can still be kept at about 7.5Ah after the anode sheet is cycled for 400 times, and the attenuation rate is only 6.25%; compared with the lead-acid battery sold on the market, the capacity attenuation after 370 times of circulation exceeds 21%, and the cycle life of the zinc-nickel battery is greatly prolonged.
Materials, reagents and experimental equipment related to the embodiment of the invention are all commercial products in accordance with the field of battery element preparation if no special description is provided.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, modifications and decorations can be made without departing from the core technology of the present invention, and these modifications and decorations shall also fall within the protection scope of the present invention. Any changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.

Claims (6)

1. The preparation method of the high specific energy zinc-nickel battery anode slurry is characterized by comprising the following steps:
(1) dry blending
Putting nickel salt and an additive into a mixing device, controlling the dry mixing time to be 3-10min, and controlling the stirring speed in the process to be 30-150 Rpm; the additive is Bi2O3Rare earth additives and binders; the raw materials are added with nickel salt and Bi in sequence2O3Rare earth additives and binders; the raw materials are nickel salt and Bi in a mass ratio203Rare earth additive and binder (100-;
(2) one-time wet mixing
Uniformly mixing the dry powder uniformly mixed in the step (1) with nickel powder and pure water, wherein the wet mixing time is controlled to be 10-60min, and the process stirring speed is controlled to be 80-250Rpm, wherein the nickel powder and the pure water are simultaneously added into the dry powder prepared in the step (1);
(3) secondary wet mixing
Stirring the polytetrafluoroethylene emulsion and the mixed slurry prepared in the step (2) for 10-40min at 200-500Rpm to prepare a mixed paste;
the paste in the mixing process comprises the following components in parts by weight: 30-45 parts of dry powder, 20-35 parts of nickel powder, 10-15 parts of pure water and 0.1-2 parts of polytetrafluoroethylene emulsion.
2. The method of claim 1, wherein the rare earth additive is La2O3，Y2O3，Dy2O3，Nd2O3One kind of (1).
3. The method for preparing the positive electrode slurry of the high specific energy zinc-nickel battery according to claim 1, wherein the nickel salt is nickel hydroxide, and the binder is one of HEC, EMC, MHEC, CMC.
4. The method for preparing the positive electrode slurry of the high specific energy zinc-nickel battery according to claim 1, wherein the pure water is added in the step (2) for 0.5-2 min.
5. The method for preparing the positive electrode slurry of the high-specific-energy zinc-nickel battery as claimed in claim 1, wherein the polytetrafluoroethylene emulsion in the step (3) is added into the mixed slurry at a constant speed, and the adding time is controlled to be 5-8 min.
6. The method for preparing the positive electrode slurry of the high-specific-energy zinc-nickel battery as claimed in claim 1, wherein the prepared mixed paste is a slurry with viscosity of 2000-30000 mpas.
CN202010188931.4A 2020-03-18 2020-03-18 Preparation method of high specific energy zinc-nickel battery positive electrode slurry Active CN111463429B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56143671U (en) * 1980-03-29 1981-10-29
CN101207200A (en) * 2006-12-20 2008-06-25 北京有色金属研究总院 Ni(OH)2 anode active materials for high temperature Ni-MH electrokinetic cell and preparation method thereof
CN103647054A (en) * 2013-11-13 2014-03-19 河南师范大学 Nickel-based cell anode, its preparation method and nickel-based cell by using anode
CN110600716A (en) * 2019-10-17 2019-12-20 超威电源集团有限公司 Positive electrode slurry of high-specific-energy zinc-nickel battery and positive electrode slurry making method
CN110729457A (en) * 2019-10-22 2020-01-24 益阳科力远电池有限责任公司 Method for manufacturing positive plate of nickel battery

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5616171B2 (en) * 2009-09-28 2014-10-29 富士フイルム株式会社 Polymer composite piezoelectric body and piezoelectric element using the same
CN102024994B (en) * 2010-11-30 2011-12-28 辽宁九夷三普电池有限公司 Nickel-zinc secondary battery and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56143671U (en) * 1980-03-29 1981-10-29
CN101207200A (en) * 2006-12-20 2008-06-25 北京有色金属研究总院 Ni(OH)2 anode active materials for high temperature Ni-MH electrokinetic cell and preparation method thereof
CN103647054A (en) * 2013-11-13 2014-03-19 河南师范大学 Nickel-based cell anode, its preparation method and nickel-based cell by using anode
CN110600716A (en) * 2019-10-17 2019-12-20 超威电源集团有限公司 Positive electrode slurry of high-specific-energy zinc-nickel battery and positive electrode slurry making method
CN110729457A (en) * 2019-10-22 2020-01-24 益阳科力远电池有限责任公司 Method for manufacturing positive plate of nickel battery

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