CN113421991B - Negative electrode plate containing pre-lithium silica material, preparation method of negative electrode plate and lithium ion battery - Google Patents
Negative electrode plate containing pre-lithium silica material, preparation method of negative electrode plate and lithium ion battery Download PDFInfo
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- CN113421991B CN113421991B CN202110672116.XA CN202110672116A CN113421991B CN 113421991 B CN113421991 B CN 113421991B CN 202110672116 A CN202110672116 A CN 202110672116A CN 113421991 B CN113421991 B CN 113421991B
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- 239000000463 material Substances 0.000 title claims abstract description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 30
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 13
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 13
- 239000011267 electrode slurry Substances 0.000 claims abstract description 73
- 238000000576 coating method Methods 0.000 claims abstract description 65
- 239000011248 coating agent Substances 0.000 claims abstract description 61
- 239000006256 anode slurry Substances 0.000 claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 claims abstract description 42
- 238000001035 drying Methods 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 229920001296 polysiloxane Polymers 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000006258 conductive agent Substances 0.000 claims description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 239000006257 cathode slurry Substances 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 239000002070 nanowire Substances 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 8
- -1 pinholes Substances 0.000 abstract description 7
- 239000007789 gas Substances 0.000 description 43
- 239000002002 slurry Substances 0.000 description 15
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004278 EU approved seasoning Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910007562 Li2SiO3 Inorganic materials 0.000 description 1
- YJSAVIWBELEHDD-UHFFFAOYSA-N [Li].[Si]=O Chemical compound [Li].[Si]=O YJSAVIWBELEHDD-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009530 blood pressure measurement Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction 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
- 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
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
-
- 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 application discloses a preparation method of a negative electrode plate containing a pre-lithium silica material, which comprises the steps of coating negative electrode slurry containing the pre-lithium silica material on the plate, and specifically comprises the following steps: determining the limit shelf time of the anode slurry according to the gas production speed of the anode slurry; and finishing coating and drying the anode slurry required by the electrode plate within the limit rest time after the anode slurry is prepared so as to obtain the anode plate. According to the preparation method of the negative electrode plate, the gas production speed of the negative electrode slurry is maintained at a lower speed within the limit shelf time, so that the problems of tail during coating, pinholes, air holes, particles, scratches, material dropping and the like after the plate is dried caused by gas production of the negative electrode slurry in the coating process can be effectively avoided, the negative electrode plate with smooth and flat surface is obtained, and the yield of the negative electrode plate product is improved.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a negative electrode plate containing a pre-lithium silica material, a preparation method of the negative electrode plate and a lithium ion battery.
Background
The lithium ion battery has the advantages of high working voltage, long cycle service life, no memory effect, small self-discharge, environmental friendliness and the like, and is widely applied to portable electronic products and electric automobiles. At present, a commercial lithium ion battery mainly adopts a graphite anode material, but the theoretical specific capacity of the lithium ion battery is only 372mAh/g, and the requirement of the lithium ion battery on high energy density in the future cannot be met. The existing Si has the theoretical capacity of 4200mAh/g, but has the expansion of 300 percent, so that the circulation performance is influenced, and the market popularization and application are constrained. The corresponding silicon oxide material has better cycle performance, but has low efficiency for the first time. At the time of the first charge, 20 to 50% of lithium is consumed for SEI film formation, which greatly reduces the first coulombic efficiency.
At present, an effective way for improving the first effect of the silicon-oxygen material is to dope lithium into the silicon-oxygen material in advance so as to react the irreversible lithium-consuming phase part in the silicon-oxygen material in advance. The existing industrialized method is to directly coat a lithium layer on the surface of the pole piece, so as to achieve the effect of reducing the consumption of positive electrode lithium. However, the method has high requirements on the operation environment and has great potential safety hazard, so that the method is difficult to realize industrialized popularization. Under the current state of technology development, obtain first effect promotion ubiquitous processability poor problem through carrying out lithium in advance at the material end, mainly show: the aqueous slurry has serious gas production, low viscosity, tailing during coating, pinholes, air holes, particles, scratches, seasonings and the like after the pole piece is dried. The main reasons for this problem are: a large amount of Li2SiO3, li4SiO4 phases, and even Li2O, lixSi exist in the material after the pre-lithium, and these components are easily reacted with water, showing strong basicity leading to poor processability.
Therefore, poor processability is still a common problem for pre-lithium silicone materials, and is also a difficulty in preparing negative electrode sheets containing pre-lithium silicone materials.
Disclosure of Invention
The purpose of the application is to provide a negative electrode plate containing a pre-lithium silica material, a preparation method thereof and a lithium ion battery.
In order to achieve the above purpose, the present application adopts the following technical scheme:
the first aspect of the application discloses a preparation method of a negative electrode plate containing a pre-lithium silica material, which comprises the steps of coating negative electrode slurry containing the pre-lithium silica material on the plate, and specifically comprises the following steps:
determining the limit shelf time of the anode slurry according to the gas production speed of the anode slurry;
and finishing coating and drying the anode slurry required by the electrode plate within the limit rest time after the anode slurry is prepared so as to obtain the anode plate.
The key point of the preparation method of the negative electrode plate is that before the negative electrode slurry coated on the plate is prepared, the limit shelf time is determined according to the gas production speed of the negative electrode slurry containing the pre-lithium silica material, the time of coating and drying the negative electrode slurry is controlled, and the coating and drying of the negative electrode slurry are completed within the limit shelf time. In the limit rest time, the gas production speed of the anode slurry is maintained at a lower speed, so that the problems of tailing during coating, pinholes, air holes, particles, scratches, material dropping and the like after the electrode plate is dried caused by gas production of the anode slurry in the coating process can be effectively avoided, the anode plate with smooth and even surface is obtained, and the yield of anode plate products is improved.
In one implementation of the present application, determining the limit shelf time of the anode slurry according to the gas production rate of the anode slurry specifically includes:
placing the negative electrode slurry in a closed container, and recording the gas pressure of the closed container and the corresponding negative electrode slurry shelf time to obtain a pressure curve of the negative electrode slurry gas production;
determining the limit shelf time of the cathode slurry according to the pressure curve;
preferably, the volume of the negative electrode slurry is not less than 80% of the volume of the closed container.
It can be understood that placing the anode slurry in the closed container means that the anode slurry just prepared is placed in the closed container, so that the ultimate shelf time of the anode slurry is determined according to the gas production rate change trend of the anode slurry by recording the shelf time of the anode slurry and the gas pressure of the closed container and establishing a pressure curve to analyze the gas production rate change of the anode slurry.
In one implementation of the present application, determining the limit shelf time of the negative electrode slurry according to the pressure curve specifically includes:
and acquiring a slope turning point of the pressure curve, and taking the rest time of the negative electrode slurry corresponding to the slope turning point of the pressure curve as the limit rest time.
It can be understood that, the slope analysis of the pressure curve is used for analyzing the change process of the gas production speed of the negative electrode slurry, and the slope turning point of the pressure curve, namely the rest time corresponding to the turning point of the negative electrode slurry gas production speed from slow rotation is used as the limit rest time of the negative electrode slurry, so that the gas production speed of the negative electrode slurry in the limit rest time is ensured to be slower, the negative electrode slurry is further coated and dried in the limit rest time, and the problems of tailing during coating, pinholes, air holes, particles, scratches, dropping and the like after the drying of a pole piece caused by the quicker gas production of the negative electrode slurry are avoided.
In one implementation of the present application, determining the limit shelf time of the anode slurry according to the gas production rate of the anode slurry further includes:
and calculating the preset coating quantity of the negative electrode slurry required by the pole piece according to the limit shelf time, and preparing the negative electrode slurry required by the pole piece according to the preset coating quantity.
In one implementation of the present application, calculating the preset coating amount of the negative electrode slurry required for the pole piece according to the limit shelf time includes:
obtaining the coating rate of the negative electrode slurry;
calculating a preset coating amount according to the coating rate, the width of the coated pole piece, the coating surface density and the limit rest time;
preferably, the coating rate is from 10 to 1000m/h, more preferably from 120 to 1000m/h;
preferably, the width of the coated pole piece is: 0.2 to 1m, more preferably 0.38 to 1m;
preferably, the coating surface density is 5-40mg/cm 2 More preferably 5-35mg/cm 2 。
In one implementation of the present application, the negative electrode slurry includes a negative electrode active material including a pre-lithiated silicone material;
preferably, the negative active material further comprises graphite;
preferably, the negative electrode slurry further comprises an aqueous binder, wherein the aqueous binder comprises at least one of carboxymethyl cellulose, styrene-butadiene rubber and polyacrylic acid;
preferably, the negative electrode slurry further includes a solvent, the solvent including water;
preferably, the negative electrode slurry further comprises a carbon-based conductive agent, wherein the carbon-based conductive agent comprises at least one of carbon black, carbon nanotubes and carbon nanowires;
preferably, the pre-lithium silicone material: graphite: conductive agent: and (2) a binder: the mass ratio of water is 1:b:c:d:e, wherein b is more than or equal to 0 and less than or equal to 20, more preferably b is more than or equal to 10 and less than or equal to 20, c is more than or equal to 0 and less than or equal to 0.2, more preferably b is more than or equal to 0.1 and less than or equal to 0.2, d is more than or equal to 0.01 and less than or equal to 0.05, more preferably b is more than or equal to 0.3 and less than or equal to 0.5,0.6 and less than or equal to 1.5, and more preferably b is more than or equal to 1.0 and less than or equal to 1.5.
The second aspect of the application also discloses a negative electrode plate prepared by the preparation method.
The third aspect of the application also discloses a lithium ion battery adopting the negative electrode plate.
Due to the adoption of the technical scheme, the beneficial effects of the application are that:
the preparation method of the negative electrode plate is characterized in that before preparing the negative electrode slurry coated on the plate, the limit shelf time is determined according to the gas production speed of the negative electrode slurry containing the pre-lithium silica material, the time of coating and drying the negative electrode slurry is controlled, and the coating and drying of the negative electrode slurry are completed within the limit shelf time. In the limit rest time, the gas production speed of the anode slurry is maintained at a lower speed, so that the problems of tailing during coating, pinholes, air holes, particles, scratches, material dropping and the like after the electrode plate is dried caused by gas production of the anode slurry in the coating process can be effectively avoided, the anode plate with smooth and even surface is obtained, and the yield of anode plate products is improved.
Drawings
Fig. 1 shows a pressure graph of the anode slurry gas production in example 1.
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments. In the following embodiments, numerous specific details are set forth in order to provide a better understanding of the present application. However, one skilled in the art will readily recognize that some of the features may be omitted, or replaced by other elements, materials, or methods in different situations. In some instances, some operations associated with the present application have not been shown or described in the specification to avoid obscuring the core portions of the present application, and may not be necessary for a person skilled in the art to describe in detail the relevant operations based on the description herein and the general knowledge of one skilled in the art.
Furthermore, the described features, operations, or characteristics of the description may be combined in any suitable manner in various embodiments. Also, various steps or acts in the method descriptions may be interchanged or modified in a manner apparent to those of ordinary skill in the art. Thus, the various orders in the description are for clarity of description of only certain embodiments, and are not meant to be required, unless otherwise indicated, to be followed.
All materials of the present application are not particularly limited in their sources, and may be commercially available or prepared according to conventional methods well known to those skilled in the art.
The purity of all the raw materials is not particularly limited, and the present invention is preferably carried out with analytically pure or conventional purity in the field of lithium ion battery materials.
The embodiment provides a preparation method of a negative electrode plate containing a pre-lithium silica material, which comprises the steps of coating negative electrode slurry containing the pre-lithium silica material on the plate, and specifically comprises the following steps:
determining the limit shelf time of the anode slurry according to the gas production speed of the anode slurry;
and finishing coating and drying the anode slurry required by the electrode plate within the limit rest time after the anode slurry is prepared so as to obtain the anode plate.
The key point of the preparation method of the negative electrode plate is that before the negative electrode slurry coated on the plate is prepared, the limit shelf time is determined according to the gas production speed of the negative electrode slurry containing the pre-lithium silica material, the time of coating and drying the negative electrode slurry is controlled, and the coating and drying of the negative electrode slurry are completed within the limit shelf time. In the limit rest time, the gas production speed of the anode slurry is maintained at a lower speed, so that the problems of tailing during coating, pinholes, air holes, particles, scratches, material dropping and the like after the electrode plate is dried caused by gas production of the anode slurry in the coating process can be effectively avoided, the anode plate with smooth and even surface is obtained, and the yield of anode plate products is improved.
The coating and drying method of the negative electrode sheet in this embodiment may be a conventional coating and drying method of the negative electrode slurry, which is not particularly limited herein.
In one implementation manner of this embodiment, in order to measure the gas production speeds of different anode slurries more accurately, determining the limit rest time of the anode slurry according to the gas production speeds of the anode slurry specifically includes:
placing the now-manufactured anode slurry in a closed container, and recording the gas pressure of the closed container and the corresponding anode slurry shelf time to obtain a pressure curve of the anode slurry gas production;
and determining the limit shelf time of the cathode slurry according to the pressure curve.
It is understood that the negative electrode slurry placed in the closed container means the negative electrode slurry which is just prepared, and the formulation of the negative electrode slurry is the same as that of the negative electrode slurry to be coated on the pole piece. And placing the anode slurry in a closed container, and analyzing the gas production rate change of the anode slurry by recording the anode slurry shelf time and the gas pressure of the closed container and establishing a pressure curve, so as to determine the limit shelf time of the anode slurry according to the gas production rate change trend of the anode slurry.
In a specific implementation manner of this embodiment, in order to ensure accuracy of a measurement result, a volume of the negative electrode slurry in the closed container is not less than 80% of a volume of the closed container, and the smaller the remaining space in the closed container is, the more accurate the gas pressure change recorded in the closed container after the slurry gas is produced, so that the more accurate the limit shelf time obtained according to the pressure curve is.
In a specific implementation manner of the embodiment, the pressure gauge is used for recording the pressure in the closed container, meanwhile, a certain reserved space is reserved in the container, the reserved space is used for preventing slurry from generating gas and bubbling to pollute the pressure gauge, and the size of the pressure gauge is not particularly limited.
In one implementation manner of this embodiment, in order to keep the surface of the negative electrode sheet smooth and flat after the negative electrode slurry is coated and dried in the rest time, determining the limit rest time of the negative electrode slurry according to the pressure curve specifically includes:
and acquiring a slope turning point of the pressure curve, and taking the rest time of the negative electrode slurry corresponding to the slope turning point of the pressure curve as the limit rest time.
It will be appreciated that after the slurry is left for a period of time, water reacts with residual alkali, lithium and other substances in the slurry through the coating layer of the pre-lithium silica material to release gas, and meanwhile, the pH of the slurry is increased, and the stability of the slurry is destroyed by too high pH, so that the slurry is settled. When the gas production speed is obviously increased, the slurry is gradually settled, so that the rest time is not longer than the corresponding rest time when the gas production speed starts to be obviously increased, and the rest time is the limit rest time of the slurry.
According to the method, the change process of the gas production speed of the anode slurry is analyzed through the slope of the pressure curve, the slope turning point of the pressure curve, namely the rest time corresponding to the turning point of the anode slurry gas production speed from slow rotation speed is used as the limit rest time of the anode slurry, so that the gas production speed of the anode slurry in the limit rest time is low, the anode slurry is coated and dried in the limit rest time, and the problems of tailing during coating, pinholes, air holes, particles, scratches, dropping and the like caused by the fact that the anode slurry gas production speed is high, and the problems of pinholes, particles, scratches, dropping and the like are avoided after the electrode plate is dried are solved.
In one implementation manner of this embodiment, after determining the limit rest time of the anode slurry according to the gas production rate of the anode slurry, the method further includes:
and calculating the preset coating quantity of the negative electrode slurry required by the pole piece according to the limit shelf time, and preparing the slurry required by the pole piece according to the preset coating quantity.
In one implementation manner of this embodiment, calculating the preset coating amount of the negative electrode slurry required for the pole piece according to the limit rest time includes:
obtaining the coating rate of the negative electrode slurry;
calculating a preset coating amount according to the coating rate, the width of the coated pole piece, the coating surface density and the limit rest time;
in a specific implementation of this embodiment, the coating rate is 120/h;
in a specific implementation of this embodiment, the width of the coated pole piece is 0.38m;
in one specific implementation of this embodiment, the coated surface density is 35mg/cm 2 。
Specifically, according to the preset coating amount and the mass ratio of each component in the negative electrode slurry formula, the feeding amount of each component in the negative electrode slurry is calculated, and different components are mixed according to the feeding amount, so that the negative electrode slurry to be coated on the negative electrode plate is prepared. And finishing coating and drying the anode slurry required by the electrode plate within the limit rest time after the anode slurry with the preset coating amount is prepared, so as to obtain the anode plate.
In one implementation of this embodiment, the negative electrode slurry includes a negative electrode active material including a pre-lithium silicone material, which is used to reduce positive electrode lithium consumption, increase battery capacity, and increase first coulombic efficiency.
In one implementation of this embodiment, the negative electrode active material further includes graphite, which is used to further increase the initial efficiency and improve the battery cycle stability.
In one implementation of this embodiment, the negative electrode slurry further includes a binder, the binder including at least one of carboxymethyl cellulose and styrene butadiene rubber;
in one implementation of this embodiment, the negative electrode slurry further includes a solvent, the solvent including water.
In one implementation of this embodiment, the negative electrode slurry further includes a conductive agent, the conductive agent including carbon black.
In a specific implementation manner of this embodiment, the pre-lithium silicone material: graphite: conductive carbon black: carboxymethyl cellulose: styrene-butadiene rubber: the mass ratio of water is 5:38:1:2:1:53.
The second aspect of the embodiment also discloses a negative electrode plate prepared by adopting the preparation method.
The third aspect of the embodiment also discloses a lithium ion battery adopting the negative electrode plate.
Example 1
1. Preparation of negative electrode slurry test sample
The mass ratio of the substances is as follows: graphite: conductive carbon black: CMC: SBR: water=5:38:1:2:1:53, negative electrode slurry test samples were prepared, total sample mass 500g.
Pressure measurement and limit rest time calculation: taking a sample of 450g of negative electrode slurry for testing, putting the sample into a high-pressure reaction kettle with a pressure gauge and a volume of 500mL, sealing the high-pressure reaction kettle well, and recording the putting time of the sample and the pressure value displayed by the pressure gauge. According to the slurry rest time and the pressure value corresponding to the pressure gauge, a pressure curve is produced, as shown in fig. 1, wherein the time corresponding to the slope turning point of the pressure curve, namely the point at which the gas production speed starts to obviously rise, is the limit rest time of the cathode slurry, and is 7 hours.
Calculating the feeding amount: the coating rate of the coater is 120m/h, the width of the coated pole piece is 0.38m, and the coating surface density is 35mg/cm 2 The coating time was 7h, so the total length of coating was 840 meters, the coating area was 319.2 square meters, and the preset coating weight was 117.72kg. According to the proportion, the feeding amount of the pre-lithium silicon oxide A is 12kg, the feeding amount of graphite is 95kg, and the other materials are added according to the proportion.
Preparing a negative electrode slurry: pre-lithium silicone article a: graphite: conductive carbon black: CMC: SBR: water = 5:38:1:2:1:53 to make a slurry.
And (3) coating and drying: and coating and drying the slurry in a coating machine for storage immediately after the slurry is prepared.
The foregoing description of specific embodiments has been presented only to facilitate an understanding of the invention and is not intended to limit the invention. Several simple deductions, modifications or substitutions may also be made by a person skilled in the art to which the invention pertains, based on the idea of the invention.
Claims (9)
1. The preparation method of the negative electrode plate containing the pre-lithium silica material comprises the steps of coating the negative electrode slurry containing the pre-lithium silica material on the plate, and is characterized by comprising the following steps:
determining the limit shelf time of the anode slurry according to the gas production speed of the anode slurry, and specifically comprising the following steps: firstly, placing the negative electrode slurry in a closed container, and recording the gas pressure of the closed container and the corresponding negative electrode slurry shelf time to obtain a pressure curve of the gas production of the negative electrode slurry; and then determining the limit shelf time of the cathode slurry according to the pressure curve, wherein the method specifically comprises the following steps: acquiring a slope turning point of the pressure curve, and taking the rest time of the anode slurry corresponding to the slope turning point of the pressure curve as a limit rest time;
finishing coating and drying the anode slurry required by the anode sheet within the limit rest time after the anode slurry is prepared so as to obtain the anode sheet;
the volume of the negative electrode slurry in the closed container is not less than 80% of the volume of the closed container;
the negative electrode slurry includes an aqueous binder;
the negative electrode slurry further includes a solvent including water.
2. The method according to claim 1, wherein determining the limit shelf time of the anode slurry from the gas production rate of the anode slurry further comprises:
and calculating the preset coating quantity of the negative electrode slurry required by the pole piece according to the limit shelf time, and preparing the negative electrode slurry required by the pole piece according to the preset coating quantity.
3. The method according to claim 2, wherein the calculating the preset coating amount of the negative electrode slurry required for the electrode sheet according to the limit rest time specifically comprises:
obtaining the coating rate of the negative electrode slurry;
calculating a preset coating amount according to the coating rate, the width of the coated pole piece, the coating surface density and the limit rest time;
the coating rate is 10-1000m/h;
the width of the coated pole piece is as follows: 0.2-1m;
the density of the coating surface is 4-30mg/cm 2 。
4. The method of manufacturing according to claim 3, wherein the negative electrode slurry includes a negative electrode active material including a pre-lithiated silicone material;
the negative active material further includes graphite;
the negative electrode slurry further includes a carbon-based conductive agent.
5. The method according to claim 4, wherein the aqueous binder comprises at least one of carboxymethyl cellulose, styrene-butadiene rubber, and polyacrylic acid.
6. The method according to claim 4, wherein the carbon-based conductive agent comprises at least one of carbon black, carbon nanotubes, and carbon nanowires.
7. The method of claim 4, wherein the pre-lithiated silicone material: graphite: conductive agent: and (2) a binder: the mass ratio of water is 1:b:c:d:e, wherein b is more than or equal to 0 and less than or equal to 20, c is more than or equal to 0 and less than or equal to 0.2, d is more than or equal to 0.01 and less than or equal to 0.05,0.6 and e is more than or equal to 0 and less than or equal to 1.5.
8. A negative electrode sheet comprising a pre-lithiated silicone material prepared by the method of any one of claims 1-7.
9. A lithium ion battery employing the negative electrode tab of claim 8.
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| JP5862227B2 (en) * | 2011-11-22 | 2016-02-16 | 日産自動車株式会社 | Method for producing negative electrode for non-aqueous electrolyte secondary battery |
| JP5910188B2 (en) * | 2012-03-09 | 2016-04-27 | トヨタ自動車株式会社 | Battery electrode manufacturing method and manufacturing apparatus |
| KR101902071B1 (en) * | 2015-10-26 | 2018-11-02 | 주식회사 엘지화학 | Negative electrode active particle and method for manufacturing the same |
| WO2018061536A1 (en) * | 2016-09-30 | 2018-04-05 | 信越化学工業株式会社 | Negative electrode active material, mixed negative electrode active material substance, and method for producing negative electrode active material |
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| JP2004349079A (en) * | 2003-05-21 | 2004-12-09 | Canon Inc | Lithium secondary battery electrode structure, manufacturing method of same, secondary battery having the structure and manufacturing method of same |
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