CN114927679B - Lithium battery negative electrode slurry and manufacturing method thereof - Google Patents
Lithium battery negative electrode slurry and manufacturing method thereof Download PDFInfo
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- 239000011267 electrode slurry Substances 0.000 title claims abstract description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 238000003756 stirring Methods 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 21
- 239000010703 silicon Substances 0.000 claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 239000002109 single walled nanotube Substances 0.000 claims abstract description 16
- 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 12
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 12
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000004537 pulping Methods 0.000 claims abstract description 11
- 238000004898 kneading Methods 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 238000007580 dry-mixing Methods 0.000 claims abstract description 9
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 9
- 239000010439 graphite Substances 0.000 claims abstract description 9
- 239000006258 conductive agent Substances 0.000 claims abstract description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 239000007773 negative electrode material Substances 0.000 claims description 9
- 238000007790 scraping Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000011856 silicon-based particle Substances 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 229920000126 latex Polymers 0.000 claims description 3
- 239000004816 latex Substances 0.000 claims description 3
- 238000005253 cladding Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 3
- 230000002411 adverse Effects 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000007865 diluting Methods 0.000 abstract description 2
- 239000012530 fluid Substances 0.000 description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910013458 LiC6 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000013060 biological fluid Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 210000002726 cyst fluid Anatomy 0.000 description 1
- 210000000805 cytoplasm Anatomy 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000019580 granularity Nutrition 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000012886 linear function Methods 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 210000004880 lymph fluid Anatomy 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000036962 time dependent Effects 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
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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
The invention relates to a lithium battery negative electrode slurry and a preparation method thereof, wherein the lithium battery negative electrode slurry comprises a solvent, a binder and powder, and the powder comprises the following components in parts by weight: 35-45 parts of graphite, 53-55 parts of silicon cathode, 0.18-0.4 part of conductive agent, 0.22-0.6 part of single-walled carbon nanotube and 1.0-1.8 parts of sodium carboxymethyl cellulose; the solvent comprises deionized water and N-methyl pyrrolidone. The preparation method comprises dry mixing, kneading, diluting, pulping and slowly stirring and vacuumizing. Compared with the prior art, the invention can improve the energy density, and provides a novel mixed pulping method which can improve the stability of the slurry and reduce the adverse effect caused by coating.
Description
Technical Field
The invention relates to the technical field of lithium battery processing, in particular to lithium battery negative electrode slurry and a manufacturing method thereof.
Background
In the manufacturing process of the electrode of the lithium ion battery, the positive electrode slurry consists of an adhesive, a conductive agent, a positive electrode material and the like; the negative electrode slurry is composed of a binder, graphite carbon powder and the like. The preparation of the anode slurry and the cathode slurry comprises a series of processes of mixing, dissolving, dispersing and the like between liquid and between liquid and solid materials, and the processes are accompanied by temperature, viscosity, environment and the like. In the positive and negative electrode slurry, the dispersibility and uniformity of the granular active substances directly influence the movement of lithium ions between two electrodes of a battery, so that the mixing and dispersion of the slurry of each electrode plate material in the production of the lithium ion battery are important, and the quality of the slurry dispersion directly influences the quality of the subsequent production of the lithium ion battery and the performance of the product thereof.
Lithium ion battery electrode slurries are one type of fluid, and generally the fluid can be divided into newtonian and non-newtonian fluids. The non-Newtonian fluid can be divided into a swelling plastic fluid, a time-dependent non-Newtonian fluid, a pseudoplastic fluid, a Bingham plastic fluid and the like. Newtonian fluid is a low viscosity fluid that deforms very easily after being subjected to a force, and the shear stress is proportional to the deformation rate, and is a fluid in which the shear stress at any point is a linear function of the shear deformation rate. Many fluids in nature are newtonian. Most pure liquids such as water and alcohol, light oil, low molecular compound solutions, low-speed flowing gases and the like are Newtonian fluids. Non-newtonian fluids refer to fluids that do not satisfy newtonian viscosity laws of experiment, i.e., fluids whose shear stress and shear strain rate are not linear. Non-newtonian fluids are widely found in life, production and nature. Concentrated solutions and suspensions of high molecular weight polymers and the like are typically non-newtonian fluids. Most biological fluids belong to the non-newtonian fluids as defined now. Various body fluids such as human body blood, lymph fluid, and cyst fluid, and "semifluid" such as cytoplasm are non-newtonian fluids.
The electrode slurry is composed of a plurality of raw materials with different specific gravities and different granularities, and is formed by mixing and dispersing solid-liquid phases, and the formed slurry belongs to non-Newtonian fluid. Lithium battery slurry can be divided into positive electrode slurry and negative electrode slurry, and the properties of the slurry are quite different due to different slurry systems (oily and aqueous).
At present, graphite adopted by a negative electrode is used as a main material, and pulping is divided into dry pulping and wet pulping. The capacity of the prior art cannot meet the requirement, the theoretical gram capacity of the graphite material in the cathode is 372mAh/g (1 lithium ion is intercalated into every 6 carbon atoms to form a LiC6 structure), but the practical maximum capacity is about 330-350mAh/g. At present, the maximum limit of the high-end product reaches 360-365mAh/g, the theoretical capacity is close to that of the high-end product, but the graphite negative electrode material gradually reaches the upper limit, so that new materials and new processes with higher energy density are needed to meet the demands.
Disclosure of Invention
The invention aims to provide lithium battery negative electrode slurry and a manufacturing method thereof, so as to improve energy density.
The aim of the invention can be achieved by the following technical scheme: the lithium battery negative electrode slurry comprises a solvent, a binder and powder, wherein the powder comprises the following components in parts by weight: 35-45 parts of graphite, 53-55 parts of silicon cathode, 0.18-0.4 part of conductive agent, 0.22-0.6 part of single-walled carbon nanotube and 1.0-1.8 parts of sodium carboxymethyl cellulose; the solvent comprises deionized water and N-methyl pyrrolidone.
In the invention, the silicon cathode is silicon oxide and composite material SiO-C.
In the invention, the reason for adding the single-wall carbon nano tube is that the volume of silicon is greatly expanded in the charge and discharge process of the battery, and cracks are caused after the expansion, so that the silicon cathode particles are formed, the connection among the silicon cathode material particles is broken, and the silicon cathode battery is rapidly attenuated. The single-walled carbon nanotubes can solve the problem and simultaneously meet the fundamental problem of the application of the silicon negative electrode in lithium batteries. Due to the advantages of good conductivity, high strength, high flexibility and the like, the single-wall carbon nano tube has less addition in the proportion of ingredients, can meet the capability of forming cladding and connection in the material, can cover the surfaces of silicon particles after being introduced into a silicon anode, and can establish high-conductivity and durable connection among the silicon particles. The single-wall carbon nano tube can effectively prolong the cycle life of the silicon cathode, and the battery with high silicon content can meet the requirement of the cycle life by adding the single-wall carbon nano tube.
Preferably, the binder is styrene-butadiene rubber latex.
Preferably, the solid content of the negative electrode slurry is 55% ± 5%.
The preparation method of the lithium battery negative electrode slurry comprises the following steps:
(1) Dry blending: dry-mixing graphite, a conductive agent and part of sodium carboxymethylcellulose to obtain first powder, dry-mixing a silicon anode and a single-wall carbon nanotube to obtain second powder, and dry-mixing the first powder and the second powder to obtain a dry mixed material;
(2) Kneading: adding deionized water into the dry mixed material, stirring, adding residual sodium carboxymethylcellulose, and continuously kneading;
(3) Dilution: adding deionized water and N-methylpyrrolidone, and stirring;
(4) Pulping: adding a binder and stirring;
(5) Slowly stirring and vacuumizing: and (5) vacuumizing and continuously stirring.
Preferably, in the step (1), parameters of obtaining the first powder, the second powder and the dry mixture are: the stirring revolution is 20-80rpm, the rotation is 500-2000rpm, the stirring time is 2-5min, and the temperature is 15-40 ℃.
Preferably, in step (2), the parameters after adding deionized water to the dry blend are: the stirring revolution is 30-80rpm, the rotation is 1000-3000rpm, the stirring time is 10-20min, and the wall scraping treatment is carried out in the process at 25+/-10 ℃.
Preferably, in the step (2), the stirring revolution is 20-50rpm, the autorotation is 500-2000rpm, the stirring time is 10-20min, and the wall scraping treatment is carried out in the process, wherein the temperature is 25+/-10 ℃ when the residual sodium carboxymethyl cellulose is added and continuously kneaded.
Preferably, in the step (3), the stirring revolution is 20-50rpm, the rotation is 500-1000rpm, the stirring time is 30-90min, the wall scraping treatment is carried out in the process, and the temperature is kept at 25+/-10 ℃.
Preferably, in the step (4), the stirring revolution is 20-30rpm, the rotation is 500-800rpm, the stirring time is 10-30min, the slurry is cooled during the process, and the temperature is kept at 25+/-10 ℃.
Preferably, in the step (5), the vacuum degree is-0.095-0.085 Mpa, the stirring revolution is 10-20rpm, the autorotation is 200-500rpm, the stirring time is 30-60min, the slurry is cooled during the process, and the temperature is kept at 25+/-10 ℃.
The manufacturing process of the invention can be carried out by adopting a double-planetary stirrer.
Compared with the prior art, the invention has the following advantages:
1. According to the invention, through the formula design of the negative electrode slurry, the energy density can be improved, the problem of connection fracture between silicon negative electrode particles in the charging and discharging process of the battery is relieved through the single-wall carbon nano tube, and the cycle life is prolonged;
2. the invention provides a novel mixed pulping method, which can improve the stability of slurry and reduce the adverse effect caused by coating.
Detailed Description
The following examples of the present invention are described in detail, and are given by way of illustration of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
The negative electrode slurry of the lithium battery mainly comprises the following components:
Powder 1: first negative electrode material (graphite): 35% -45%, and the total added amount is denoted as A;
powder 2: second anode material (silicon anode): 53-55%, the total added amount is denoted as B;
Note that: the ratio of the first negative electrode material to the second negative electrode material is 94-96.5%;
powder 3: conductive agent: SP (Carbon ECP): 0.18% -0.4%, and the total added amount is marked as C;
powder 4: single-wall carbon nanotubes: 0.22% -0.6%, and the addition amount is marked as D;
binder (SBR): 1.0% -1.6% (sbr=styrene-butadiene rubber latex), the total added is denoted as E;
powder 5: CMC (sodium carboxymethyl cellulose): 1.0% -1.8%, and the total added amount is denoted as F;
solvent 1: deionized water, the total added amount is denoted as G;
Solvent 2: NMP, total added was designated H;
The total weight of the solvent was noted as N, with deionized water accounting for 75% and NMP 25%;
the total weight of the powder is denoted as P;
The total weight of the slurry was designated M:
a) The viscosity of the cathode is controlled to be 5000-15000cps;
b) The solid content is 55 percent plus or minus 5 percent
C) The weight of the solvent is added according to the proportion and the total weight of the slurry;
d) Attention was paid to the effect of temperature and humidity on viscosity (25 ℃.+ -. 5 ℃)
The preparation method comprises the following process steps:
1. dry blending (3 steps of dry blending);
2. Kneading (kneading is in two steps);
3. diluting;
4. Pulping;
5. Slowly stirring and vacuumizing.
The method comprises the following specific steps:
The first step: dry blending
1) Dry-blending three powders of the first negative electrode material (a sufficient amount of the first negative electrode material) and the conductive agent (C sufficient amount of the first negative electrode material) and 60% of the first negative electrode material (F) (i.e., 60% of the total weight of CMC), and stirring and revolving the three powders: 20-80rpm, autorotation: 500-2000rpm, stirring time: 2-5min; setting specific parameters according to devices with different volumes;
2) Simultaneously adding a second cathode material (adding a sufficient amount of B) and single-wall carbon nano tubes (adding a sufficient amount of D) into another stirrer for dry mixing, stirring and revolution: 20-80rpm, autorotation: 500-2000rpm, stirring time: 2-5min;
note that: the two steps are carried out in different stirring equipment simultaneously;
3) And adding the powder after the two steps of mixing into the same stirring equipment for dry mixing, stirring and revolving: 20-80rpm, autorotation: 500-2000rpm, stirring time: 2-5min; finally forming the required dry mixed material;
The process needs to cool and circulate the materials, ensures the consistency of the materials, and suggests the temperature to be between 15 and 40 ℃;
And a second step of: kneading
1) Adding the solvent 1 into the dry mixed material prepared in the first step, wherein the adding amount is added according to the solid content of 75 percent, and stirring and revolving: 30-80rpm, autorotation: 1000-3000rpm, stirring time: 10-20min; wall scraping treatment is needed in the process, meanwhile, the temperature of the slurry is guaranteed to be reduced, and the temperature is kept at 25+/-10 ℃;
2) Kneading was continued by adding the remaining 40% cmc after 1) ended, and stirring revolution: 20-50rpm, autorotation: 500-2000rpm, stirring time: 10-20min; wall scraping treatment is needed in the process, meanwhile, the temperature of the slurry is guaranteed to be reduced, and the temperature is kept at 25+/-10 ℃;
And a third step of: dilution of
All remaining solvents (solvent 1 and solvent 2) were added, and: all the solvent remaining is added here means the solvent required for setting the solids content of 55% minus the solvent used during kneading;
stirring and revolution: 20-50rpm, autorotation: 500-1000rpm, stirring time: 30-90min; wall scraping treatment is needed in the process, meanwhile, the temperature of the slurry is guaranteed to be reduced, and the temperature is kept at 25+/-10 ℃;
Fourth step: pulping
Adding SBR, stirring and revolving: 20-30rpm, autorotation: 500-800rpm, stirring time: 10-30min; cooling the slurry in the process, and simultaneously ensuring that the slurry is cooled and the temperature is kept at 25+/-10 ℃;
Fifth step: slowly stirring and vacuumizing
Vacuum pumping is started, the vacuum degree is-0.095-0.085 Mpa, and stirring revolution is carried out: 10-20rpm, autorotation: 200-500rpm, stirring time: 30-60min; and cooling the slurry in the process, and simultaneously ensuring that the slurry is cooled and the temperature is kept at 25+/-10 ℃.
The invention changes the traditional wet pulping process, changes the defects of the prior art and improves the capacity and the performance of the battery at the same time:
the following table shows that the single-wall carbon nano tube added in the invention can solve the defect of the silicon cathode when the silicon carbon cathode is singly used and has lower cycle life.
Table 1 comparison of various negative electrode properties
The silicon cathode with the SiO content of 15-25%, the specific capacity of 1500mAh/g and the 1500-cycle silicon cathode can be manufactured by adding the single-wall carbon nano tube into the silicon cathode mixture, and the silicon cathode basically meets the requirements of high energy density, high rate capability and high cost performance.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (9)
1. The preparation method of the lithium battery negative electrode slurry is characterized by comprising a solvent, a binder and powder, wherein the powder comprises the following components in parts by weight: 35-45 parts of graphite, 53-55 parts of silicon cathode, 0.18-0.4 part of conductive agent, 0.22-0.6 part of single-walled carbon nanotube and 1.0-1.8 parts of sodium carboxymethyl cellulose; the solvent comprises deionized water and N-methyl pyrrolidone;
the single-walled carbon nanotubes can cover the surfaces of the silicon particles and establish highly conductive and durable connection between the silicon particles, thereby forming cladding and connection inside the negative electrode material;
The manufacturing method comprises the following steps:
(1) Dry blending: dry-mixing graphite, a conductive agent and part of sodium carboxymethylcellulose to obtain first powder, dry-mixing a silicon anode and a single-wall carbon nanotube to obtain second powder, and dry-mixing the first powder and the second powder to obtain a dry mixed material;
(2) Kneading: adding deionized water into the dry mixed material, stirring, adding residual sodium carboxymethylcellulose, and continuously kneading;
(3) Dilution: adding deionized water and N-methylpyrrolidone, and stirring;
(4) Pulping: adding a binder and stirring;
(5) Slowly stirring and vacuumizing: and (5) vacuumizing and continuously stirring.
2. The method for preparing a negative electrode slurry for a lithium battery according to claim 1, wherein the binder is styrene-butadiene rubber latex.
3. The method for manufacturing the negative electrode slurry for the lithium battery according to claim 1, wherein the solid content of the negative electrode slurry is 55% ± 5%.
4. The method for producing a negative electrode slurry for a lithium battery according to claim 1, wherein in the step (1), parameters at the time of obtaining the first powder, the second powder, and the dry mixture are: the stirring revolution is 20-80rpm, the rotation is 500-2000rpm, the stirring time is 2-5min, and the temperature is 15-40 ℃.
5. The method of claim 1, wherein in step (2), the parameters after deionized water is added to the dry mixture are as follows: the stirring revolution is 30-80rpm, the rotation is 1000-3000rpm, the stirring time is 10-20min, and the wall scraping treatment is carried out in the process at 25+/-10 ℃.
6. The method for producing a negative electrode slurry for a lithium battery according to claim 1, wherein in the step (2), stirring revolution is 20-50rpm, autorotation is 500-2000rpm, stirring time is 10-20min, wall scraping treatment is performed during the stirring, and the temperature is 25 ℃ ± 10 ℃ when the remaining sodium carboxymethyl cellulose is added and kneaded continuously.
7. The method for producing a negative electrode slurry for a lithium battery according to claim 1, wherein in the step (3), stirring revolution is 20 to 50rpm, rotation is 500 to 1000rpm, stirring time is 30 to 90min, wall scraping treatment is performed during the process, and the temperature is kept at 25 ℃ ± 10 ℃.
8. The method for producing a negative electrode slurry for a lithium battery according to claim 1, wherein in the step (4), stirring revolution is 20-30rpm, rotation is 500-800rpm, stirring time is 10-30min, slurry cooling is performed during the process, and the temperature is kept at 25 ℃ ± 10 ℃.
9. The method for producing a negative electrode slurry for a lithium battery according to claim 1, wherein in the step (5), the vacuum degree is-0.095 to 0.085Mpa, the revolution under stirring is 10 to 20rpm, the rotation is 200 to 500rpm, the stirring time is 30 to 60 minutes, the slurry is cooled during the process, and the temperature is kept at 25 ℃ ± 10 ℃.
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