CN111180659B - Preparation method of lithium ion battery cathode slurry - Google Patents
Preparation method of lithium ion battery cathode slurry Download PDFInfo
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- CN111180659B CN111180659B CN201911389623.1A CN201911389623A CN111180659B CN 111180659 B CN111180659 B CN 111180659B CN 201911389623 A CN201911389623 A CN 201911389623A CN 111180659 B CN111180659 B CN 111180659B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000006257 cathode slurry Substances 0.000 title claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 180
- 239000002002 slurry Substances 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 70
- 230000008569 process Effects 0.000 claims abstract description 61
- 239000011230 binding agent Substances 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000498 cooling water Substances 0.000 claims abstract description 32
- 239000008367 deionised water Substances 0.000 claims abstract description 30
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 30
- 239000007773 negative electrode material Substances 0.000 claims abstract description 21
- 239000006258 conductive agent Substances 0.000 claims abstract description 16
- 239000011812 mixed powder Substances 0.000 claims abstract description 15
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 11
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 11
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 11
- 229940047670 sodium acrylate Drugs 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000007790 scraping Methods 0.000 claims abstract description 4
- 239000011267 electrode slurry Substances 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 9
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 8
- 239000013543 active substance Substances 0.000 claims description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- -1 transition metal nitrides Chemical class 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- 239000002931 mesocarbon microbead Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 3
- 239000002733 tin-carbon composite material Substances 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 3
- QWJYDTCSUDMGSU-UHFFFAOYSA-N [Sn].[C] Chemical class [Sn].[C] QWJYDTCSUDMGSU-UHFFFAOYSA-N 0.000 claims 1
- 150000001721 carbon Chemical class 0.000 claims 1
- 239000006182 cathode active material Substances 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 20
- 239000006185 dispersion Substances 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 1
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
- H01M4/04—Processes of manufacture in general
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of lithium ion battery cathode slurry, which comprises the following steps: stirring the negative active material, the conductive agent and the first binder sodium carboxymethyl cellulose dry powder to obtain mixed powder; adding a second binder polyacrylonitrile-sodium acrylate and deionized water, and stirring in vacuum to obtain a dough-like first slurry; stopping the machine to scrape the paddle and the wall, adding deionized water, and starting vacuum stirring to obtain second slurry. Stopping the machine, scraping the bottom of the shovel, and continuously stirring in vacuum to obtain third slurry; adding a third binder multipolymer, and starting vacuum stirring to obtain a fourth slurry; and adjusting the viscosity of the fourth slurry, starting reverse stirring to obtain negative slurry, and preparing a negative pole piece by using the negative slurry. The circulating cooling water is required to be started in the vacuum stirring process. The invention adds different binders for three times, and the prepared slurry has stable state, no layering, uniform dispersion and no precipitation. The negative pole piece made of the slurry has good cohesiveness, low rebound rate and good electrolyte wettability.
Description
Technical Field
The invention relates to a preparation method of lithium ion battery cathode slurry, belonging to the field of lithium ion battery manufacturing.
Background
The lithium ion battery has the advantages of high energy density, high voltage platform, wide temperature application range, no memory effect, environmental friendliness and the like, and the advantages enable the lithium ion battery to occupy the core position of a power battery. The production and manufacture of lithium ion batteries are closely connected by individual process steps. In general, the production of lithium batteries includes a pole piece manufacturing process, a battery assembly process, and a final liquid injection, pre-charging, formation, and aging process. In the three-stage process, each process can be divided into several key processes, and each step has a great influence on the final performance of the battery. In the stage of pole piece manufacturing process, four processes of slurry preparation, slurry coating, pole piece rolling and pole piece slitting can be subdivided.
The electrode slurry is composed of a plurality of raw materials with different specific gravities and different particle sizes, and is formed by mixing and dispersing solid and liquid phases, and belongs to non-Newtonian fluid. The lithium battery slurry can be divided into two types of positive electrode slurry and negative electrode slurry, and the properties of the slurry are different due to different slurry systems (oil and water). The negative electrode slurry mixing and dispersing process of the lithium ion battery has great influence on the overall process of the lithium ion battery, and is one of the most important links in the whole process. The problems to be solved are to improve the caking property of the negative pole piece and the wetting property of the electrolyte and reduce the rebound rate.
Chinese patent CN20191006025.4 discloses a preparation method of high-power graphite cathode slurry, which comprises the steps of uniformly mixing solid materials, adding a first binder in batches to prepare a coarse material, adding a surfactant and water into the coarse material, and adding a second binder to obtain uniform and stable cathode slurry. No agglomeration and delamination occur in the preparation process, and the dispersion time is short.
Chinese patent CN201810109468.2 discloses a negative electrode slurry and a preparation method and use thereof, the preparation method of the negative electrode slurry comprises the following steps: mixing and stirring a first binder and a dispersant with 60-70% of water to prepare a glue solution; step b): mixing the glue solution with a negative active material, and then mixing and stirring the mixture with water to obtain a slurry intermediate product; step c), mixing and stirring the obtained slurry intermediate product, a second binder and the residual amount of water to obtain the negative electrode slurry; by using the method, the production efficiency is improved, and the negative electrode slurry which is good in stability, not easy to settle, good in dispersion effect and high in binding power with the negative electrode current collector is obtained.
Chinese patent cn201711393630.x discloses a lithium ion battery negative electrode slurry and a preparation method thereof, wherein the lithium ion battery negative electrode slurry comprises a negative electrode active material, a conductive agent, a binder and a solvent; the binder includes a first binder, the first binder being an acrylic polymer. The lithium ion battery cathode slurry provided by the invention adopts the acrylic polymer or the mixture of the acrylic polymer and other binders as the binders, so that the obtained lithium ion battery cathode slurry can keep non-layering, non-precipitation and stable viscosity for a long time, and the stability of the lithium ion battery cathode slurry is greatly improved.
However, in the production process, the problems of poor adhesion of the negative electrode plate, high rebound rate of the negative electrode plate, poor wettability of the electrolyte and the like often occur when the negative electrode slurry is prepared into the negative electrode plate.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a method for preparing a negative electrode slurry for a lithium ion battery. The negative pole slurry prepared by the method has the advantages of good adhesion, low rebound rate and good electrolyte wettability when being used for preparing the negative pole piece.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
adding a negative electrode active substance, a conductive agent and sodium carboxymethyl cellulose dry powder serving as a first binder into a stirring kettle, and stirring to obtain mixed powder; adding a second binder polyacrylonitrile-sodium acrylate and deionized water, and stirring in vacuum to obtain a dough-like first slurry. Stopping the machine to scrape the paddle and the wall, adding deionized water into the first slurry, and starting vacuum stirring to obtain a second slurry. Stopping the machine, scraping the bottom of the shovel, and continuing vacuum stirring to obtain third slurry. And adding the third binder multipolymer, and starting vacuum stirring to obtain fourth slurry. And adjusting the viscosity of the fourth slurry, starting reverse stirring to obtain negative slurry, preparing a negative pole piece by using the negative slurry, testing the peel strength and the electrolyte wettability of the pole piece, and calculating the rebound rate of the pole piece after full charging.
Furthermore, the negative electrode active material accounts for 90-98%, the conductive agent accounts for 0.3-2%, and the first binder sodium carboxymethyl cellulose accounts for 0.3-2%.
Further, the negative active material is one or a mixture of more of artificial graphite, natural graphite, hard carbon, mesocarbon microbeads, transition metal nitrides, transition metal oxide carbon composite materials, lithium titanate carbon composite materials, silicon carbon or tin carbon composite materials.
Further, the conductive agent is one or a mixture of more of conductive carbon black, conductive graphite, carbon nanotubes, carbon fibers and graphene.
Further, the second binder polyacrylonitrile-sodium acrylate accounts for 1% -3%.
Further, the third binder multipolymer is one or a mixture of two of styrene-butadiene rubber and acrylic acid polymer, and accounts for 0.4-3% of the total weight of the binder multipolymer.
The invention adopts the structure to obtain the following beneficial effects: according to the preparation method of the lithium ion battery cathode slurry, different binders are added for three times, and the prepared slurry is stable in state, free of layering, uniform in dispersion and free of precipitation. The negative pole piece made of the slurry has good cohesiveness, low rebound rate and good electrolyte wettability.
Detailed Description
The technical solutions of the present invention will be described in further detail with reference to specific implementations, and all the portions of the present invention that are not described in detail in the technical features or the connection relationships of the present invention are the prior art.
The invention provides a preparation method of lithium ion battery cathode slurry, which comprises the steps of adding a cathode active substance, a conductive agent and sodium carboxymethyl cellulose dry powder serving as a first binder into a stirring kettle, and stirring to obtain mixed powder; adding a second binder polyacrylonitrile-sodium acrylate and deionized water, and stirring in vacuum to obtain a dough-like first slurry. Stopping the machine to scrape the paddle and the wall, adding deionized water into the first slurry, and starting vacuum stirring to obtain a second slurry. Stopping the machine, scraping the bottom of the shovel, and continuing vacuum stirring to obtain third slurry. And adding the third binder multipolymer, and starting vacuum stirring to obtain fourth slurry. And adjusting the viscosity of the fourth slurry, starting reverse stirring to obtain negative slurry, and preparing a negative pole piece by using the negative slurry. The circulating cooling water is started in the whole vacuum stirring process.
Preferably, the negative electrode active material accounts for 90% -98%, the conductive agent accounts for 0.3% -2%, and the first binder carboxymethylcellulose sodium accounts for 0.3% -2%.
Preferably, the negative active material is one or a mixture of more of artificial graphite, natural graphite, hard carbon, mesocarbon microbeads, transition metal nitrides, transition metal oxide carbon composite materials, lithium titanate carbon composite materials, silicon carbon or tin carbon composite materials.
Preferably, the conductive agent is one or a mixture of more of conductive carbon black, conductive graphite, carbon nanotubes, carbon fibers and graphene.
Preferably, the second adhesive polyacrylonitrile-sodium acrylate accounts for 1% -3%.
Preferably, the third binder multipolymer is one or a mixture of two of styrene-butadiene rubber and acrylic acid polymer, and accounts for 0.4-3% of the total weight of the composite material.
The negative pole piece is prepared by the negative pole slurry, the peel strength and the electrolyte wettability of the pole piece are tested, and the rebound rate of the pole piece after being fully charged is calculated.
In order to facilitate understanding of the present invention, the technical solution of the present invention is further described below with reference to examples and comparative examples, which are currently commonly used in the production process of negative electrode slurry. The applicant states that the present invention is illustrated in detail by the following examples, but the present invention is not limited to the above detailed process flow, i.e. it is not meant that the present invention should be implemented by relying on the following process flow. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Example one
a. Adding artificial graphite (negative electrode active substance), SP (conductive agent) and sodium carboxymethylcellulose (first binder) dry powder into a stirring kettle according to the proportion of 97.1:0.5:0.5, rotating the stirring kettle at 500rpm, revolving at 15rpm, and stirring for 20min to obtain mixed powder;
b. adding 1.3 percent of polyacrylonitrile-sodium acrylate (second binder) and deionized water into the mixed powder, wherein the mass of the deionized water accounts for 52 percent of that of the negative active material, starting stirring, revolving the stirring kettle at 35rpm, stirring for 50min, and starting circulating cooling water in the stirring process to obtain a first paste in a dough shape, wherein the vacuum degree in the stirring process is-85 to-100 KPa.
c. Stopping the machine to scrape the paddle and the wall, adding deionized water into the first slurry, wherein the mass of the deionized water accounts for 48% of that of the negative active material, starting vacuum stirring, rotating the stirring kettle at 1500rpm, revolving at 40rpm, stirring for 15min, wherein the vacuum degree in the stirring process is-85 to-100 KPa, and starting circulating cooling water in the stirring process to obtain a second slurry.
d. Stopping the machine to scrape the bottom of the shovel, continuing vacuum stirring, rotating the stirring kettle at 2000rpm, revolving at 35rpm, stirring for 40min, wherein the vacuum degree in the stirring process is-85 to-100 KPa, and circulating cooling water is started in the stirring process to obtain third slurry.
e. And adding 0.6% of styrene butadiene rubber (third binder) into the third slurry, starting vacuum stirring, rotating the stirring kettle at 2000rpm, revolving at 30rpm, stirring for 45min, wherein the vacuum degree in the stirring process is-85 to-100 KPa, and starting circulating cooling water in the stirring process to obtain a fourth slurry.
f. Adjusting the viscosity of the fourth slurry, starting reverse stirring, revolving at 15rpm, stirring for 15min, starting circulating cooling water with the vacuum degree of-85 to-100 KPa in the stirring process to obtain negative electrode slurry, preparing a negative electrode plate by using the negative electrode slurry, testing the peeling strength and the electrolyte wettability of the electrode plate, and calculating the rebound rate of the electrode plate after full charging.
Example two
a. Adding artificial graphite (negative electrode active substance), SP (conductive agent) and sodium carboxymethylcellulose (first binder) dry powder into a stirring kettle according to a ratio of 96.5:0.5:1.2, rotating the stirring kettle at 500rpm, revolving at 15rpm, and stirring for 20min to obtain mixed powder;
b. adding 1% of polyacrylonitrile-sodium acrylate (second binder) and deionized water into the mixed powder, wherein the mass of the deionized water accounts for 52% of that of the negative active material, starting stirring, revolving the stirring kettle at 35rpm, stirring for 50min, and starting circulating cooling water in the stirring process to obtain the first paste in a dough shape, wherein the vacuum degree in the stirring process is-85 to-100 KPa.
c. Stopping the machine to scrape the paddle and the wall, adding deionized water into the first slurry, wherein the mass of the deionized water accounts for 48% of that of the negative active material, starting vacuum stirring, rotating the stirring kettle at 1500rpm, revolving at 40rpm, stirring for 15min, wherein the vacuum degree in the stirring process is-85 to-100 KPa, and starting circulating cooling water in the stirring process to obtain a second slurry.
d. Stopping the machine to scrape the bottom of the shovel, continuing vacuum stirring, rotating the stirring kettle at 2000rpm, revolving at 35rpm, stirring for 40min, wherein the vacuum degree in the stirring process is-85 to-100 KPa, and circulating cooling water is started in the stirring process to obtain third slurry.
e. And adding 0.8% of styrene butadiene rubber (third binder) into the third slurry, starting vacuum stirring, rotating the stirring kettle at 2000rpm, revolving at 30rpm, stirring for 45min, wherein the vacuum degree in the stirring process is-85 to-100 KPa, and starting circulating cooling water in the stirring process to obtain a fourth slurry.
f. Adjusting the viscosity of the fourth slurry, starting reverse stirring, revolving at 15rpm, stirring for 15min, starting circulating cooling water with the vacuum degree of-85 to-100 KPa in the stirring process to obtain negative electrode slurry, preparing a negative electrode plate by using the negative electrode slurry, testing the peeling strength and the electrolyte wettability of the electrode plate, and calculating the rebound rate of the electrode plate after full charging.
EXAMPLE III
a. Adding artificial graphite (negative electrode active substance), SP (conductive agent) and sodium carboxymethylcellulose (first binder) dry powder into a stirring kettle according to the proportion of 97.2:0.5:0.4, rotating the stirring kettle at 500rpm, revolving at 15rpm, and stirring for 20min to obtain mixed powder;
b. adding 1.5% of polyacrylonitrile-sodium acrylate (second binder) and deionized water into the mixed powder, wherein the mass of the deionized water accounts for 52% of that of the negative active material, starting stirring, revolving the stirring kettle at 35rpm, stirring for 50min, and starting circulating cooling water in the stirring process to obtain the first paste in a dough shape, wherein the vacuum degree in the stirring process is-85 to-100 KPa.
c. Stopping the machine to scrape the paddle and the wall, adding deionized water into the first slurry, wherein the mass of the deionized water accounts for 48% of that of the negative active material, starting vacuum stirring, rotating the stirring kettle at 1500rpm, revolving at 40rpm, stirring for 15min, wherein the vacuum degree in the stirring process is-85 to-100 KPa, and starting circulating cooling water in the stirring process to obtain a second slurry.
d. Stopping the machine to scrape the bottom of the shovel, continuing vacuum stirring, rotating the stirring kettle at 2000rpm, revolving at 35rpm, stirring for 40min, wherein the vacuum degree in the stirring process is-85 to-100 KPa, and circulating cooling water is started in the stirring process to obtain third slurry.
e. And adding 0.4% of styrene butadiene rubber (third binder) into the third slurry, starting vacuum stirring, rotating the stirring kettle at 2000rpm, revolving at 30rpm, stirring for 45min, wherein the vacuum degree in the stirring process is-85 to-100 KPa, and starting circulating cooling water in the stirring process to obtain a fourth slurry.
f. Adjusting the viscosity of the fourth slurry, starting reverse stirring, revolving at 15rpm, stirring for 15min, starting circulating cooling water with the vacuum degree of-85 to-100 KPa in the stirring process to obtain negative electrode slurry, preparing a negative electrode plate by using the negative electrode slurry, testing the peeling strength and the electrolyte wettability of the electrode plate, and calculating the rebound rate of the electrode plate after full charging.
Comparative example 1
a. Adding artificial graphite (negative electrode active material), SP (conductive agent) and sodium carboxymethylcellulose (first binder) dry powder into a stirring kettle at a ratio of 96.5:0.5:1.2, rotating the stirring kettle at 500rpm, revolving at 15rpm, and stirring for 20min to obtain mixed powder. Adding deionized water into the mixed powder, wherein the mass of the deionized water accounts for 52% of that of the negative active material, starting stirring, revolving the stirring kettle at 35rpm, stirring for 50min, and starting circulating cooling water during stirring to obtain a dough-like first slurry, wherein the vacuum degree during stirring is-85 to-100 KPa;
b. stopping the machine to scrape the paddle and the wall, adding deionized water into the first slurry, wherein the mass of the deionized water accounts for 48% of that of the negative active material, starting vacuum stirring, rotating the stirring kettle at 1500rpm, revolving at 40rpm, stirring for 15min, wherein the vacuum degree in the stirring process is-85 to-100 KPa, and starting circulating cooling water in the stirring process to obtain second slurry;
c. stopping the machine to scrape the bottom of the shovel, continuing vacuum stirring, enabling the stirring kettle to rotate at 2000rpm and revolve at 35rpm, stirring for 40min, enabling the vacuum degree in the stirring process to be minus 85 to minus 100KPa, and starting circulating cooling water in the stirring process to obtain third slurry;
d. adding 1.8% of styrene-butadiene rubber into the third slurry, starting vacuum stirring, rotating the stirring kettle at 2000rpm, revolving at 30rpm, stirring for 45min, wherein the vacuum degree in the stirring process is-85 to-100 KPa, and starting circulating cooling water in the stirring process to obtain a fourth slurry;
e. adjusting the viscosity of the fourth slurry, starting reverse stirring, revolving at 15rpm, stirring for 15min, starting circulating cooling water with the vacuum degree of-85 to-100 KPa in the stirring process to obtain negative electrode slurry, preparing a negative electrode plate by using the negative electrode slurry, testing the peeling strength and the electrolyte wettability of the electrode plate, and calculating the rebound rate of the electrode plate after full charging.
Comparative example II
a. Adding artificial graphite (negative electrode active material), SP (conductive agent) and sodium carboxymethylcellulose (first binder) dry powder into a stirring kettle according to the ratio of 97.2:0.5:0.6, rotating the stirring kettle at 500rpm, revolving at 15rpm, and stirring for 20min to obtain mixed powder. Adding deionized water into the mixed powder, wherein the mass of the deionized water accounts for 52% of that of the negative active material, starting stirring, revolving the stirring kettle at 35rpm, stirring for 50min, and starting circulating cooling water during stirring to obtain a dough-like first slurry, wherein the vacuum degree during stirring is-85 to-100 KPa;
b. stopping the machine to scrape the paddle and the wall, adding deionized water into the first slurry, wherein the mass of the deionized water accounts for 48% of that of the negative active material, starting vacuum stirring, rotating the stirring kettle at 1500rpm, revolving at 40rpm, stirring for 15min, wherein the vacuum degree in the stirring process is-85 to-100 KPa, and starting circulating cooling water in the stirring process to obtain second slurry;
c. stopping the machine to scrape the bottom of the shovel, continuing vacuum stirring, enabling the stirring kettle to rotate at 2000rpm and revolve at 35rpm, stirring for 40min, enabling the vacuum degree in the stirring process to be minus 85 to minus 100KPa, and starting circulating cooling water in the stirring process to obtain third slurry;
d. adding 1.7% of acrylic polymer into the third slurry, starting vacuum stirring, rotating the stirring kettle at 2000rpm, revolving at 30rpm, stirring for 45min, wherein the vacuum degree in the stirring process is-85 to-100 KPa, and starting circulating cooling water in the stirring process to obtain a fourth slurry;
e. adjusting the viscosity of the fourth slurry, starting reverse stirring, revolving at 15rpm, stirring for 15min, starting circulating cooling water with the vacuum degree of-85 to-100 KPa in the stirring process to obtain negative electrode slurry, preparing a negative electrode plate by using the negative electrode slurry, testing the peeling strength and the electrolyte wettability of the electrode plate, and calculating the rebound rate of the electrode plate after full charging.
The test results after the above case implementation are shown in table one:
table one test results
The full-charge rebound rate in the table is (thickness of the pole piece after full charge-thickness of the pole piece after rolling)/thickness of the pole piece after rolling.
The method for testing wettability of the pole piece in the table is as follows: taking rolled negative pole pieces, wherein the negative pole pieces are respectively divided into five sections for sampling, sucking three drops of electrolyte on each pole piece by a pipettor, recording the time required by the electrolyte to completely soak the pole pieces by a stopwatch, and simultaneously observing whether the electrolyte is uniformly diffused on the surfaces of the pole pieces or not and the shape is regular.
The data in the table one show that, the slurry is prepared by adding different binders three times, and the negative pole piece is prepared by using the slurry, compared with the negative pole piece prepared by the traditional mass production process in the comparative example, the stripping strength represents the cohesiveness of the pole piece, and the greater the stripping strength, the greater the cohesiveness of the pole piece. Compared with the traditional mass production process, the pole piece prepared by the method has high peel strength, which shows that the cohesiveness is better, the data in the table shows that the full-electricity rebound rate is lower, the time for the electrolyte to uniformly infiltrate the pole piece is characterized by the wettability of the electrolyte, the shorter the time is, the better the wettability of the electrolyte is shown, and the data in the table shows that the pole piece prepared by the method has shorter time for the electrolyte to uniformly infiltrate the pole piece, which shows that the wettability of the electrolyte is better.
The invention and its embodiments have been described above, without this being limitative. In summary, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (5)
1. The preparation method of the lithium ion battery cathode slurry is characterized by comprising the following steps:
a. adding a negative electrode active substance, a conductive agent and first binder sodium carboxymethyl cellulose dry powder into a stirring kettle, and stirring the stirring kettle for 15-30min at the rotation speed of 400-600rpm and the revolution speed of 10-20rpm to obtain mixed powder;
wherein, the negative active substance accounts for 90 to 98 percent, the conductive agent accounts for 0.3 to 2 percent, and the first binder sodium carboxymethyl cellulose accounts for 0.3 to 2 percent;
b. adding a second binder polyacrylonitrile-sodium acrylate and deionized water into the mixed powder, wherein the mass of the deionized water accounts for 52% of that of the negative active material, starting stirring, revolving the stirring kettle at 30-40rpm, stirring for 40-60min, and starting circulating cooling water in the stirring process to obtain a first paste in a dough shape, wherein the vacuum degree in the stirring process is-85 to-100 KPa;
c. stopping scraping a paddle and a wall, adding deionized water into the first slurry, wherein the mass of the deionized water accounts for 48% of that of the cathode active material, starting vacuum stirring, rotating the stirring kettle at 1000-2000rpm, revolving at 30-45rpm, stirring for 8-20min, keeping the vacuum degree of the stirring process at-85 to-100 KPa, and starting circulating cooling water in the stirring process to obtain second slurry;
d. stopping the machine to scrape the bottom of the shovel, continuing vacuum stirring, stirring for 35-50min at the stirring kettle autorotation speed of 1500-2000rpm and revolution speed of 30-45rpm, wherein the vacuum degree in the stirring process is-85 to-100 KPa, and circulating cooling water is started in the stirring process to obtain third slurry;
e. adding a third binder multipolymer into the third slurry, starting vacuum stirring, rotating the stirring kettle at 1000-2000rpm, revolving at 20-40rpm, stirring for 35-50min, starting circulating cooling water in the stirring process at-85 to-100 KPa to obtain a fourth slurry;
f. adjusting the viscosity of the fourth slurry, starting reverse stirring, revolving at 10-20rpm, stirring for 10-30min, starting circulating cooling water to obtain negative electrode slurry with the vacuum degree of-85 to-100 KPa in the stirring process, and preparing a negative electrode plate by using the negative electrode slurry.
2. The method for preparing the negative electrode slurry of the lithium ion battery according to claim 1, wherein the negative electrode active material in the step a is one or more of artificial graphite, natural graphite, hard carbon, mesocarbon microbeads, transition metal nitrides, transition metal oxide carbon composites, lithium titanate carbon composites, silicon carbon or tin carbon composites.
3. The preparation method of the lithium ion battery negative electrode slurry according to claim 1, wherein the conductive agent in the step a is one or more of conductive carbon black, conductive graphite, carbon nanotubes, carbon fibers and graphene.
4. The preparation method of the lithium ion battery cathode slurry according to claim 1, wherein the second binder polyacrylonitrile-sodium acrylate in the step b accounts for 1% -3%.
5. The method for preparing the lithium ion battery negative electrode slurry according to claim 1, wherein the third binder multipolymer in the step e is one or a mixture of two of styrene butadiene rubber and acrylic acid polymer, and the proportion of the third binder multipolymer is 0.4-3%.
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| CN112054201A (en) * | 2020-09-10 | 2020-12-08 | 昆山宝创新能源科技有限公司 | Negative electrode slurry, negative electrode plate and preparation method and application thereof |
| CN112909261B (en) * | 2021-05-08 | 2022-04-01 | 蜂巢能源科技有限公司 | Composite binder and preparation method and application thereof |
| CN114050236B (en) * | 2021-11-05 | 2023-05-12 | 包头昊明稀土新电源科技有限公司 | Rare earth power supply negative electrode slurry and slurry process |
| CN114864877A (en) * | 2022-05-20 | 2022-08-05 | 湖北亿纬动力有限公司 | Preparation method and application of negative pole piece |
| CN115347192A (en) * | 2022-09-21 | 2022-11-15 | 湖北亿纬动力有限公司 | Thick cathode electrode and preparation method and application thereof |
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Denomination of invention: A preparation method of negative electrode slurry for lithium-ion batteries Effective date of registration: 20231124 Granted publication date: 20210312 Pledgee: Jiangxi Guangxin Rural Commercial Bank Co.,Ltd. Pledgor: JIANGXI ANC NEW ENERGY TECHNOLOGY Co.,Ltd. Registration number: Y2023980067648 |