CN113921803A - Lithium supplementing method for lithium ion battery - Google Patents
Lithium supplementing method for lithium ion battery Download PDFInfo
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- CN113921803A CN113921803A CN202111173659.3A CN202111173659A CN113921803A CN 113921803 A CN113921803 A CN 113921803A CN 202111173659 A CN202111173659 A CN 202111173659A CN 113921803 A CN113921803 A CN 113921803A
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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
- 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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
Li additive used for lithium supplement8SnO6A method for supplementing lithium to a lithium ion battery. Aiming at the phenomenon that certain negative electrode materials of the lithium ion battery have low first charge-discharge efficiency, a lithium supplement additive Li is added on the positive electrode side8SnO6The method can supplement lithium for the lithium ion battery, and can obviously improve the discharge capacity, specific energy and cycle of the lithium ion battery. It is characterized in that: (1) the lithium ion battery has good lithium supplementing effect, and the performance of the lithium ion battery can be obviously improved; (2) convenient use and low cost, and only a proper amount of Li serving as a lithium supplement additive is required to be added into the positive electrode slurry8SnO6The method is compatible with the current preparation process of the lithium ion battery, and no additional production equipment is needed; (3) the requirement on the environment is low, and the environment is poor,strict water removal and drying environments are not required; (4) safe and has no risk of fire and explosion.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a lithium supplementing method of a lithium ion batteryThe method is carried out. Mainly aiming at the defect of low first coulombic efficiency of hard carbon, silicon carbon and other cathode materials, a proper amount of Li serving as a lithium supplement additive material is added to one side of a cathode material8SnO6The lithium ion battery has the advantages that lithium loss caused by low first charge-discharge efficiency of negative electrode materials such as hard carbon, silicon carbon and the like is compensated, the quantity of reversibly deintercalated lithium ions is increased, and the energy density of the lithium ion battery is further increased.
Background
In recent years, with the explosion of the electric automobile industry, various portable electronic products and the field of large-scale energy storage, higher requirements are put forward on the energy density and the high-capacity performance of the lithium ion battery, and the lithium ion battery is required to have the characteristics of higher energy density and power density, better safety, longer service life and the like. However, when the lithium ion battery is subjected to the first cycle, processes such as formation of a negative electrode SEI (Solid Electrolyte Interphase), deactivation of negative electrode material particles due to falling off, and irreversible deposition of lithium metal occur in both the half cell and the full cell, active lithium ions in the positive electrode material are consumed, and the available energy of the lithium ion battery is reduced. Therefore, in order to solve the above-mentioned difficulties, a lithium supplement technology is important (mainly for all batteries using graphite, silicon carbon, etc. as negative electrode materials), and the purpose of lithium supplement is mainly to pre-compensate active lithium loss during first cycle charge and discharge of a lithium ion battery, that is, loss of lithium ions in the positive electrode material that cannot be normally extracted due to insertion into the negative electrode, and further to improve the energy density of the battery. Currently, the prelithiation method is divided into two types, negative prelithiation and positive prelithiation. The negative electrode prelithiation is subdivided into a chemical method and an electrochemical method, namely, a lithium-containing chemical reagent is used for carrying out chemical reaction with the negative electrode to reduce and supplement lithium; or the battery is preassembled with the negative electrode and the lithium sheet, and the lithium ions are reduced at the negative electrode by utilizing small current charging, so that the negative electrode is lithiated. The method comprises the following steps of pre-lithiating the positive electrode, namely adding a high-lithium (multi-lithium) additive to the positive electrode in a homogenizing process, wherein the high-lithium additive irreversibly migrates to the negative electrode in a first charging process, and then lithiating the negative electrode. The prelithiation process has the following advantages: (1) the first-week reversible capacity of the battery and the actual energy density of the battery are increased; (2) the volume of the negative electrode material (graphite, silicon carbon and the like) is pre-expanded, the breakage of material particles in the lithium embedding process is reduced, and the mechanical stability and the cycle performance of the negative electrode material are further improved; (3) some prelithiation techniques can pre-form artificial SEI films in place of the formation step of lithium ion batteries. In summary, in consideration of various advantages of the lithium supplement technology, the lithium supplement by the lithium supplement additive is an effective way for improving the energy density of the lithium ion battery.
Disclosure of Invention
The invention aims to provide a lithium supplementing method of a lithium ion battery. By adding a lithium supplement additive Li into the anode of the lithium ion battery8SnO6The lithium ion battery is supplemented with lithium in the first charging process, and the purposes of improving the capacity, energy density and cycle performance of the lithium ion battery are further achieved.
A lithium supplement method for a lithium ion battery anode material comprises the following specific steps;
1) the anode material of the lithium ion battery and the lithium supplement additive material Li8SnO6Mixing at a certain ratio.
2) Adding conductive carbon black into N-methyl pyrrolidone (NMP) dissolved with a certain amount of PVDF binder, and stirring in vacuum to mix uniformly. Then adding the Li into the solution8SnO6And the mixture of the anode material is stirred for 2 to 10 hours in vacuum again and mixed evenly.
3) And (3) uniformly coating the stirred positive slurry on a current collector aluminum foil by using a coating machine, and drying to obtain the positive plate.
4) And preparing the lithium ion battery negative pole piece according to the process similar to the steps.
5) Cutting the prepared positive and negative electrode pieces into electrode pieces with certain shapes. And fully baking under the circulating condition of vacuum and dry nitrogen to remove trace moisture in the pole piece.
6) And adopting a lamination process to alternately stack and arrange the positive plate, the diaphragm and the negative plate, or adopting a winding process to wind the positive plate, the diaphragm and the negative plate into a winding core.
7) And fully baking the coiled core again in a vacuum drying box.
8) And injecting the electrolyte into the battery cell in an anhydrous drying room or a glove box for removing water and oxygen.
9) And sequentially carrying out charge-discharge activation, standing aging and formation on the battery core after liquid injection to obtain the lithium ion battery with the lithium supplement effect.
As a preferred technical scheme, Li in the step 1)8SnO6The mass fraction of the mixture of the positive electrode material and the positive electrode material is 0.5-5%.
As a preferable technical scheme, in the step 3), the mass fraction of PVDF in the positive plate (without the current collector) is 1-7%, and Li8SnO6And the mass fraction of the mixture of the positive electrode material and the positive electrode material in the positive electrode sheet (without the current collector) is 90-97%.
Preferably, in the step 4), the negative electrode material is a hard carbon negative electrode, a SiO negative electrode or a Si/C composite negative electrode.
Compared with the prior art, the invention has the following beneficial effects compared with the negative electrode lithium supplement technology:
(1) in the aspect of convenience, the existing production process is not required to be changed, new equipment is not required to be introduced, and only a proper amount of Li is added into the positive electrode slurry8SnO6Preparing a sample;
(2) in the aspect of safety, potential safety hazards caused by spraying lithium powder in the process of lithium supplement of the negative electrode are avoided;
(3) is environment-friendly and easy for industrial implementation.
Drawings
FIG. 1 is Li containing a lithium supplement additive prepared in example 18SnO6SEM image of the NCM523 positive electrode sheet.
Fig. 2 is a graph of cycle performance of the lithium ion battery having a lithium supplement effect prepared in example 1.
Fig. 3 is a graph of cycle performance of the lithium ion battery having a lithium supplement effect prepared in example 2.
FIG. 4 is Li containing a lithium supplement additive prepared in example 38SnO6SEM image of the NCM523 positive electrode sheet.
Detailed Description
The invention provides a lithium supplementing method of a novel lithium supplementing additive for a lithium ion battery, wherein the lithium supplementing method comprises the step of supplementing a lithium additive material Li8SnO6Specific embodiments that function in the positive electrode material are further described below with respect to specific embodiments of the present invention.
Example 1:
will supplement lithium additive Li8SnO6Is uniformly mixed with the ternary cathode material NCM523 (Li)8SnO6Mass fraction in the mixture was 0.5%). Adding conductive carbon black into NMP solution of PVDF, stirring in vacuum to mix them uniformly, then adding the above-mentioned Li into the above-mentioned slurry8SnO6And the mixture of the positive electrode material is again stirred for 10 hours in vacuum to obtain uniform slurry. The amounts of PVDF and conductive carbon black added to the slurry were adjusted so that the mass fraction of PVDF in the solid matter added to NMP was 1%, and Li8SnO6And the mass fraction of the mixture of the positive electrode material in the solid matter added to NMP was 97%. And uniformly coating the stirred slurry on a current collector aluminum foil by using a coating machine, and drying to obtain the positive plate. And preparing the hard carbon negative pole piece by adopting a similar process flow. And (3) after the positive plate and the negative plate are sufficiently dried in a vacuum drying box by adopting a circulation process of vacuumizing and charging dry nitrogen, the positive plate, the diaphragm and the negative plate are sequentially and alternately stacked and arranged by adopting a lamination process, and then are packaged by adopting an aluminum-plastic film, so that the lithium ion battery core is obtained. Placing the obtained battery core in a vacuum drying box, and fully baking for 8 hours by adopting a circulation process of vacuumizing and charging dry nitrogen; after electrolyte is injected into the battery cell, the lithium ion battery with the lithium supplementing effect is obtained through standing, formation, secondary sealing and aging in sequence.
Example 2:
will supplement lithium additive Li8SnO6Uniformly mixed with the ternary cathode material NCA (Li)8SnO6Mass fraction in the mixture is 5%). Adding conductive carbon black into NMP solution of PVDF, stirring in vacuum to mix them uniformly, then adding the above-mentioned Li into the above-mentioned slurry8SnO6And the mixture of the anode material is stirred for 2 hours in vacuum again to obtainTo a homogeneous slurry. The amounts of PVDF and conductive carbon black added to the slurry were adjusted so that the mass fraction of PVDF in the solid matter added to NMP was 5%, and Li8SnO6And the mass fraction of the mixture of the positive electrode material in the solid matter added to NMP was 93%. And uniformly coating the stirred slurry on a current collector aluminum foil by using a coating machine, and drying to obtain the positive plate. And preparing the SiO/graphite composite negative pole piece by adopting a similar process flow. And (3) after the positive plate and the negative plate are sufficiently dried in a vacuum drying box by adopting a circulation process of vacuumizing and charging dry nitrogen, the positive plate, the diaphragm and the negative plate are sequentially and alternately stacked and arranged by adopting a lamination process, and then the positive plate, the diaphragm and the negative plate are packaged by adopting an aluminum shell to obtain the lithium ion battery core. Placing the obtained battery core in a vacuum drying box, and fully baking for 14 hours by adopting a circulation process of vacuumizing and charging dry nitrogen again; after electrolyte is injected into the battery cell, the lithium ion battery with the lithium supplementing effect is obtained through standing, formation, welding, sealing and aging in sequence.
Example 3:
will supplement lithium additive Li8SnO6And anode material LiFePO4Mixing homogeneously (Li)8SnO6Mass fraction in the mixture was 3%). Adding conductive carbon black into NMP solution of PVDF, stirring in vacuum to mix them uniformly, then adding the above-mentioned Li into the above-mentioned slurry8SnO6And the mixture of the positive electrode material is stirred for 8 hours in vacuum again to obtain uniform slurry. The amounts of PVDF and conductive carbon black added to the slurry were adjusted so that the mass fraction of PVDF in the solid matter added to NMP was 7%, and Li8SnO6And the mass fraction of the mixture of the positive electrode material in the solid matter added to NMP was 90%. And uniformly coating the stirred slurry on a current collector aluminum foil by using a coating machine, and drying to obtain the positive plate. And preparing the Si/C composite negative pole piece by adopting a similar process flow. And (3) fully drying the positive plate and the negative plate in a vacuum drying box by adopting a circulation process of vacuumizing and charging dry nitrogen, winding the positive plate, the diaphragm and the negative plate into a winding core by adopting a winding process, and packaging by adopting an aluminum-plastic film to obtain the lithium ion battery core. Placing the obtained battery cell in a vacuum drying box and thenFully baking for 11 hours by adopting a circulation process of vacuumizing and charging dry nitrogen; after electrolyte is injected into the battery cell, the lithium ion battery with the lithium supplementing effect is obtained through standing, formation, secondary sealing and aging in sequence.
Claims (5)
1. Li additive used for lithium supplement8SnO6A method for supplementing lithium to a lithium ion battery.
2. The method of supplementing lithium according to claim 1, wherein:
2.1. the anode material of the lithium ion battery and the lithium supplement additive material Li8SnO6Mixing at a certain ratio.
2.2. Carbon black is put into N-methyl pyrrolidone (NMP) dissolved with a certain amount of PVDF binder, and the mixture is stirred in vacuum to be mixed evenly. Then adding the Li into the solution8SnO6And the mixture of the anode material is stirred for 2 to 10 hours in vacuum again and mixed evenly.
2.3. And (3) uniformly coating the stirred positive slurry on a current collector aluminum foil by using an automatic coating machine, and drying to obtain the positive plate.
2.4. And preparing the lithium ion battery negative pole piece according to the process similar to the steps.
2.5. Cutting the prepared positive and negative electrode pieces into electrode pieces with certain shapes. And fully baking under the circulating condition of vacuum and dry nitrogen to remove trace moisture in the pole piece.
2.6. And adopting a lamination process to alternately stack and arrange the positive plate, the diaphragm and the negative plate, or adopting a winding process to wind the positive plate, the diaphragm and the negative plate into a winding core.
2.7. And fully baking the coiled core obtained by the method in a vacuum drying oven again.
2.8. And injecting the electrolyte into the battery cell in an anhydrous drying room or a glove box for removing water and oxygen.
2.9. And sequentially carrying out charge-discharge activation, standing aging and formation on the battery core after liquid injection to obtain the lithium ion battery with the lithium supplement effect.
3. The positive electrode material of claim 2.1 including but not limited to LiCoO2Ternary positive electrode materials (NCM333, NCM523, NCM622, NCM712, NCM811, and NCA), LiFePO4Etc.; li8SnO6The mass fraction of the mixture of the positive electrode material and the positive electrode material is 0.5-5%.
4. The positive electrode sheet prepared according to claims 2.2 and 2.3, wherein the mass fraction of PVDF in the positive electrode sheet (without current collector) is 1-7%, and Li8SnO6And the mass fraction of the mixture of the positive electrode material and the positive electrode material in the positive electrode sheet (without the current collector) is 90-97%.
5. The negative pole piece prepared according to the claim 2.4, wherein the negative pole material is a hard carbon negative pole, a SiO/graphite composite negative pole or a Si/C composite negative pole.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115472784A (en) * | 2022-08-16 | 2022-12-13 | 北京航空航天大学 | Na 3 Ti 2 (PO 4 ) 3 Preparation method of positive electrode and application of positive electrode in sodium ion battery |
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2021
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115472784A (en) * | 2022-08-16 | 2022-12-13 | 北京航空航天大学 | Na 3 Ti 2 (PO 4 ) 3 Preparation method of positive electrode and application of positive electrode in sodium ion battery |
| CN115472784B (en) * | 2022-08-16 | 2023-07-14 | 北京航空航天大学 | Na (Na) 3 Ti 2 (PO 4 ) 3 Preparation method of positive electrode and application of positive electrode in sodium ion battery |
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