CN112635770A - Lithium ion battery pre-lithiation positive pole piece and preparation method of lithium ion battery - Google Patents
Lithium ion battery pre-lithiation positive pole piece and preparation method of lithium ion battery Download PDFInfo
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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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
- 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
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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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
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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
The invention provides a lithium ion battery prelithiation positive pole piece and a preparation method of a lithium ion battery. The preparation method of the lithium ion battery prelithiation positive pole piece comprises the following steps: and coating the positive electrode slurry on the surface of the current collector, and drying and rolling to obtain the positive electrode piece. The prelithiation positive pole piece can realize the improvement of the first-cycle coulomb efficiency of the lithium ion battery, and can keep the specific energy of the battery at a higher level.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and relates to a lithium ion battery prelithiation positive pole piece and a preparation method of a lithium ion battery.
Background
At present, lithium ion batteries occupy an indispensable position in human life, and from electronic communication to traffic travel, none of the lithium ion batteries play an energy supply role. With the improvement of the quality of life of people, the capacity requirement of the lithium ion battery is increased. As an important component of lithium ion batteries, negative electrode materials have a significant impact on the performance of lithium ion batteries. The negative electrode material of the commercial lithium ion battery is mainly a carbon material and a silicon-carbon material, and compared with the positive electrode material, the specific capacity of the negative electrode material is higher, but the first-week coulombic efficiency of the negative electrode material is usually lower, the carbon material can reach 90%, and the silicon-based material can only reach 80%. The reason for this phenomenon is that during the first cycle of charge and discharge of the lithium ion battery, part of lithium ions and electrolyte components generate an SEI film on the surface of the negative electrode material, and a part of capacity is lost, resulting in lower first cycle coulombic efficiency. Low coulombic efficiency means that more positive electrode material needs to be proportioned to make up for this partial capacity loss. The increase in the proportion of the positive electrode material leads to an increase in the overall weight of the battery and a decrease in the energy density.
In order to solve the problem of low first-pass efficiency of the negative electrode material, a prelithiation technology is researched. The prelithiation strategy is currently mainly applied to lithium ion batteries, and the main purpose of the prelithiation strategy is to offset lithium ions consumed in the formation process of the lithium ion batteries, so that the first efficiency of the batteries is improved. The method mainly comprises three methods: the pre-formation of the negative plate, such as CN 105190958B, CN 110178252A, and CN 110521033 a, can maximally simulate the formation of an SEI film, but the operation is complicated, and large-scale application is difficult to realize; the lithium powder added into the negative electrode, such as CN 108321438A and CN 110010863A, can be added in the negative electrode pulping process, and can also be sprayed on the surface of the negative electrode plate, so that the operation is relatively simple and convenient, but the operation safety of the lithium powder is difficult to guarantee; the positive electrode is supplemented with a prelithiated material, e.g. CN 108365174A, e.g. Li2O2Etc. can provide rich Li+The material can be directly added in the positive electrode pulping process, the safety is relatively guaranteed, production equipment and processes can be reserved to a large extent, but the prelithiation material still exists in the battery after releasing lithium ions, occupies a certain mass, and reduces the mass specific energy of the prelithiation material.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a pre-lithiation positive pole piece of a lithium ion battery and a preparation method of the lithium ion battery.
In order to achieve the technical effect, the invention adopts the following technical scheme:
one of the objectives of the present invention is to provide a lithium ion battery prelithiation positive electrode plate, where the positive electrode plate includes a current collector and a positive electrode slurry disposed on the surface of the current collector, and the positive electrode slurry includes lithium nitride.
In the present invention, lithium nitride is selected as the prelithiation material. The lithium nitride has high theoretical specific capacity which reaches 2309mAh/g, so that the first cycle coulombic efficiency of the battery can be improved by only adding a small amount of lithium nitride. Meanwhile, lithium nitride is used as a prelithiation material, and nitrogen generated by decomposition does not generate side reaction with each material in the battery, so that no adverse effect is caused. And for the flexible package battery, the process preparation process comprises an air-extracting and sealing process, so that nitrogen generated by pre-lithiation can be effectively removed. In summary, the addition of lithium nitride to the positive electrode as a prelithiation material can achieve the goals of both improving first-week coulombic efficiency and ensuring specific energy of the battery.
As a preferable technical solution of the present invention, the positive electrode slurry further includes a conductive agent, a binder, a positive electrode material, and a solvent.
Preferably, the mass ratio of the lithium nitride to the conductive agent to the binder to the positive electrode material is (0.5-3): 1-4): 1-3): 90-97.5, such as 1.0:1.5:1.5:96, 1.2:2.0:1.8:95, 2.0:2.0:2.0:94 or 2.5:3:2.5:92, but not limited to the enumerated values, and other non-enumerated values within the numerical range are also applicable.
As a preferred technical solution of the present invention, the positive electrode material includes any one of or a combination of at least two of a lithium iron phosphate material, a nickel cobalt manganese material, a nickel cobalt aluminum material or a lithium cobaltate, and a lithium manganate material, and the combination is typically, but not limited to, as an example: a combination of a lithium iron phosphate material and a nickel cobalt manganese material, a combination of a nickel cobalt manganese material and a lithium cobaltate material, a combination of a nickel cobalt aluminum material and a lithium iron phosphate material, a combination of a lithium iron phosphate material, a nickel cobalt aluminum material and a lithium manganate material, and the like.
Preferably, the conductive agent comprises any one of, or a combination of at least two of, conductive carbon black, conductive graphite, carbon nanotubes, graphene or carbon fibers, typical but non-limiting examples of which are: combinations of conductive carbon black and conductive graphite, combinations of conductive graphite and carbon nanotubes, combinations of carbon nanotubes and graphene, combinations of carbon fibers and conductive carbon black or conductive carbon black, graphene and carbon nanotubes, and the like.
Preferably, the binder comprises polyvinylidene fluoride and/or polytetrafluoroethylene.
Preferably, the solvent comprises any one of, or a combination of at least two of, N-dimethylformamide, N-methylpyrrolidone, or cyclohexanone, typical but non-limiting examples of which are: a combination of N, N-dimethylformamide and N-methylpyrrolidone, a combination of N-methylpyrrolidone and cyclohexanone, a combination of cyclohexanone and N, N-dimethylformamide, a combination of N, N-dimethylformamide, N-methylpyrrolidone and cyclohexanone, or the like.
In a preferred embodiment of the present invention, the lithium nitride paste is disposed outside the positive electrode paste.
As a preferred technical solution of the present invention, the composition of the lithium nitride slurry includes lithium nitride, a conductive agent, a binder, and a solvent;
preferably, the mass ratio of the lithium nitride to the conductive agent to the binder is (0.5-1): 2-3): 6-7.5, such as 0.6:2.1:7.3, 0.7:2.2:7.1, 0.8:2.5:6.7 or 0.9:2.8:6.3, but not limited to the enumerated values, and other values within the range of the enumerated values are also applicable.
Preferably, the conductive agent comprises any one of, or a combination of at least two of, conductive carbon black, conductive graphite, carbon nanotubes, graphene or carbon fibers, typical but non-limiting examples of which are: combinations of conductive carbon black and conductive graphite, combinations of conductive graphite and carbon nanotubes, combinations of carbon nanotubes and graphene, combinations of carbon fibers and conductive carbon black or conductive carbon black, graphene and carbon nanotubes, and the like.
Preferably, the binder comprises polyvinylidene fluoride and/or polytetrafluoroethylene.
Preferably, the solvent comprises any one of, or a combination of at least two of, N-dimethylformamide, N-methylpyrrolidone, or cyclohexanone, typical but non-limiting examples of which are: a combination of N, N-dimethylformamide and N-methylpyrrolidone, a combination of N-methylpyrrolidone and cyclohexanone, a combination of cyclohexanone and N, N-dimethylformamide, a combination of N, N-dimethylformamide, N-methylpyrrolidone and cyclohexanone, or the like.
The invention also aims to provide a preparation method of the lithium ion battery prelithiation positive pole piece, which comprises the following steps: and coating the slurry on the surface of a current collector, and drying and rolling to obtain the positive pole piece.
As a preferred technical scheme of the invention, the surface of the positive pole piece is coated with the lithium nitride slurry to obtain the positive pole piece with the lithium nitride coating.
The invention also aims to provide a preparation method of the pre-lithiated lithium ion battery, which comprises the following steps:
(1) sequentially laminating at least one pre-lithiated positive pole piece and at least one negative pole piece of the lithium ion battery, arranging a diaphragm between the adjacent positive pole piece and the negative pole piece, packaging the diaphragm and an electrolyte together to form a soft package battery, and reserving an air bag;
(2) standing the soft package battery obtained in the step (1);
(3) after standing, charging the soft package battery to ensure that Li in the lithium nitride+Is fully embedded in the groundThe negative pole piece;
(4) and carrying out air extraction and sealing on the soft package battery and cutting off the air bag.
In the invention, the negative pole piece is prepared by coating negative pole slurry on a current collector, wherein the negative pole slurry comprises a binder, a conductive agent, a negative pole material and a solvent. Wherein the negative electrode material comprises any one or a combination of at least two of natural graphite, artificial graphite, a silicon-carbon material or a silicon-oxygen material. The binder, the conductive agent and the solvent are the same as the raw materials used by the positive pole piece. The proportions of binder, conductive agent, and anode material are conventional in the art and will not be described in detail herein.
In the present invention, the electrolyte may be an ether solvent system or an ester solvent system. The air bag can be arranged on the positive electrode side of the battery cell and also can be arranged on the negative electrode side.
In a preferred embodiment of the present invention, the temperature of the standing in the step (2) is 25 to 60 ℃, for example, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃ or 55 ℃, but the temperature is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the standing time in step (2) is 1-24 h, such as 1h, 3h, 10h, 12h, 15h, 18h, 20h or 22h, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
As a preferable technical scheme of the invention, the charging mode in the step (3) is constant-current constant-voltage charging.
Preferably, the current of the constant-current and constant-voltage charging is 0.001-1C, and the cut-off voltage is 3.8-4.5V; the constant current and voltage is 1.5-4.5V, and the charging is carried out until the current is 0.001-1C.
The current for constant current and constant voltage charging may be 0.01C, 0.05C, 0.1C, 0.2C, 0.5C, 0.8C, 1C, etc., and the off-voltage may be 3.85V, 3.90V, 3.95V, 4.00V, 4.05V, 4.10V, 4.15V, etc., but is not limited to the values listed, and other values not listed in the above numerical ranges are also applicable. The voltage of the constant-current constant-voltage charging is 1.5-4.2V, and the cut-off current is 0.001-1C.
The voltage for the constant-current constant-voltage charging may be 2.0V, 2.5V, 3.0V, 3.5V, or 4.0V, and the off-current may be 0.01C, 0.05C, 0.1C, 0.2C, 0.5C, 0.8C, or 1C, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned ranges of values are also applicable.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention provides a lithium ion battery prelithiation positive pole piece and a preparation method of the lithium ion battery, wherein the prelithiation slurry can realize the improvement of the first-week coulombic efficiency of the lithium ion battery, the first-week coulombic efficiency can be improved by 2-3%, meanwhile, the mass specific energy of the battery can be kept at a higher level, and the specific energy can be improved by 2-4%.
Drawings
FIG. 1 is a schematic diagram of a method for preparing a positive electrode plate in examples 1 to 3 of the present invention;
FIG. 2 is a schematic view of a method for manufacturing a positive electrode sheet in examples 4 to 6 of the present invention;
FIG. 3 is a schematic illustration of a lamination pattern in an embodiment of the present invention;
fig. 4 is a schematic diagram of a pouch battery package according to an embodiment of the present invention;
in the figure: 1-positive pole piece, 2-diaphragm, 3-negative pole piece.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
The embodiment provides a preparation method of a pre-lithiated lithium ion battery, which includes the following steps:
(1) sequentially laminating a positive pole piece and a negative pole piece, arranging a diaphragm between the adjacent positive pole piece and the negative pole piece, packaging the diaphragm and electrolyte together to form a soft package battery, and reserving an air bag;
(2) standing the soft package battery obtained in the step (1) for 24 hours at 25 ℃;
(3) after standing, carrying out constant-current and constant-voltage charging on the soft package battery, wherein the current is 0.01C, and the cut-off voltage is 3.8V; the constant-current constant-voltage charging voltage is 3.8V, the cut-off current is 0.01C, and Li in the lithium nitride is obtained+Fully embedded into the negative pole piece;
(4) and carrying out air extraction and sealing on the soft package battery and cutting off the air bag.
The positive pole piece is prepared by mixing lithium nitride, conductive carbon black, polyvinylidene fluoride and lithium iron phosphate with N, N-dimethylformamide according to the mass ratio of 0.5:1:1:97.5 to prepare positive pole slurry and coating the positive pole slurry on the surface of a current collector.
Example 2
The embodiment provides a preparation method of a pre-lithiated lithium ion battery, which includes the following steps:
(1) sequentially laminating a positive pole piece and a negative pole piece, arranging a diaphragm between the adjacent positive pole piece and the negative pole piece, packaging the diaphragm and electrolyte together to form a soft package battery, and reserving an air bag;
(2) standing the soft package battery obtained in the step (1) for 6 hours at the temperature of 60 ℃;
(3) after standing, carrying out constant-current constant-voltage charging on the soft-package battery, wherein the current is 0.05C, the cut-off voltage is 4.2V, the constant-current constant-voltage charging voltage is 4.0V, and the cut-off current is 0.01C; making Li in lithium nitride+Fully embedded into the negative pole piece;
(4) and carrying out air extraction and sealing on the soft package battery and cutting off the air bag.
The positive pole piece is prepared by mixing lithium nitride, conductive graphite, polytetrafluoroethylene and lithium iron phosphate with N, N-dimethylformamide according to the mass ratio of 3:4:3:90 to obtain positive pole slurry and coating the positive pole slurry on the surface of a current collector.
Example 3
The embodiment provides a preparation method of a pre-lithiated lithium ion battery, which includes the following steps:
(1) sequentially laminating a positive pole piece and a negative pole piece, arranging a diaphragm between the adjacent positive pole piece and the negative pole piece, packaging the diaphragm and electrolyte together to form a soft package battery, and reserving an air bag;
(2) standing the soft package battery obtained in the step (1) for 10 hours at the temperature of 45 ℃;
(3) after standing, carrying out constant-current constant-voltage charging on the soft-package battery, wherein the current is 0.1C, the cut-off voltage is 4.0V, the constant-current constant-voltage charging voltage is 4.0V, and the cut-off current is 0.01C; making Li in lithium nitride+Fully embedded into the negative pole piece;
(4) and carrying out air extraction and sealing on the soft package battery and cutting off the air bag.
The positive pole piece is prepared by mixing lithium nitride, conductive graphite, polyvinylidene fluoride and lithium iron phosphate with N, N-dimethylformamide according to the mass ratio of 2.0:2.5:2.0:93.5 to obtain positive pole slurry and coating the positive pole slurry on the surface of a current collector.
Example 4
The embodiment provides a preparation method of a pre-lithiated lithium ion battery, which comprises the following steps except for the preparation method of a positive pole piece: mixing conductive graphite, polyvinylidene fluoride and lithium iron phosphate with N, N-dimethylformamide according to the mass ratio of 2.5:2.0:95.5 to prepare positive electrode slurry, coating the positive electrode slurry on the surface of a current collector, and then coating the positive electrode slurry prepared by mixing lithium nitride, conductive graphite and polyvinylidene fluoride with N, N-dimethylformamide according to the mass ratio of 0.5:2:7.5 to prepare lithium nitride slurry. The other conditions were the same as in example 3.
Example 5
The embodiment provides a preparation method of a pre-lithiated lithium ion battery, which comprises the following steps except for the preparation method of a positive pole piece: the preparation method comprises the steps of mixing conductive graphite, polyvinylidene fluoride and lithium iron phosphate with N, N-dimethylformamide according to the mass ratio of 2.5:2.0:95.5 to prepare anode slurry, coating the anode slurry on the surface of a current collector, and then coating the anode slurry prepared by mixing lithium nitride, conductive graphite and polyvinylidene fluoride with N, N-dimethylformamide according to the mass ratio of 1:3:6 to prepare the lithium nitride slurry. The other conditions were the same as in example 3.
Example 6
The embodiment provides a preparation method of a pre-lithiated lithium ion battery, which comprises the following steps except for the preparation method of a positive pole piece: mixing lithium nitride, conductive graphite, polyvinylidene fluoride and lithium iron phosphate with N, N-dimethylformamide according to the mass ratio of 2.5:2.0:95.5 to prepare anode slurry, coating the anode slurry on the surface of a current collector, and then coating the anode slurry prepared by mixing the lithium nitride, the conductive graphite and the polyvinylidene fluoride with N, N-dimethylformamide according to the mass ratio of 0.8:2.2:7.0 to prepare the lithium nitride slurry. The other conditions were the same as in example 3.
Example 7
The embodiment provides a preparation method of a pre-lithiated lithium ion battery, which comprises the step (3) of constant-current and constant-voltage charging, wherein the current is 0.1C, the cut-off voltage is 4.5V, the constant-current and constant-voltage charging voltage is 4.0V, and the cut-off current is 0.01C. The other conditions were the same as in example 3.
Example 8
The embodiment provides a preparation method of a pre-lithiated lithium ion battery, which comprises the step (3) of constant-current and constant-voltage charging, wherein the current is 0.1C, the cut-off voltage is 4.5V, the constant-current and constant-voltage charging voltage is 4.5V, and the cut-off current is 0.01C. The other conditions were the same as in example 3.
Example 9
The embodiment provides a preparation method of a pre-lithiated lithium ion battery, which comprises the step (3) of constant-current and constant-voltage charging, wherein the current is 0.5C, the cut-off voltage is 4.0V, the constant-current and constant-voltage charging voltage is 4.0V, and the cut-off current is 0.01C. The other conditions were the same as in example 3.
Comparative example
In this comparative example, the conditions were the same as in example 4 except that no lithium nitride coating was applied.
The negative electrode plate used in examples 1 to 9 and comparative example was prepared by mixing conductive graphite, sodium carboxymethyl cellulose (CMC), Styrene Butadiene Rubber (SBR), and artificial graphite in a mass ratio of 1.8: 1.2: 1.6: 95.4 mixing with deionized water to prepare cathode slurry, and coating the cathode slurry on the surface of the current collector to prepare the cathode. The diaphragm used was a double-sided ceramic coated diaphragm.
The results of first-week coulombic efficiencies and specific energies of the prelithiated lithium ion batteries prepared in examples 1 to 9 and comparative example are shown in table 1.
The first week coulombic efficiency and specific energy test method comprises the following steps: the batteries prepared in each example and comparative example were formed, and then charged at a constant current of 0.2C (specifically, based on the design capacity of each battery), and the cut-off voltage was 3.65V. Then, a discharge test was performed, and constant current discharge was performed at 0.2C (specifically, based on the design capacity of each cell), and the voltage was cut off at 2.5V.
Calculating the measured capacity C1 in the charging stage and the measured capacity C2 in the discharging stage, wherein the first-week coulombic efficiency is C2/C1 × 100%;
measuring the mass of the battery as M, the voltage of a discharge platform as V, and the specific energy of mass as C2V/M in Wh/kg;
TABLE 1
| First week coulomb efficiency% | Specific energy/Wh kg-1 | |
| Example 1 | 93.5 | 170 |
| Example 2 | 94.7 | 175 |
| Example 3 | 94.3 | 173 |
| Example 4 | 92.9 | 168 |
| Example 5 | 93.4 | 170 |
| Example 6 | 93.7 | 170 |
| Example 7 | 94.7 | 174 |
| Example 8 | 94.9 | 174 |
| Example 9 | 95.1 | 175 |
| Comparative example | 92.4 | 165 |
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. The pre-lithiated positive pole piece of the lithium ion battery is characterized by comprising a current collector and positive pole slurry arranged on the surface of the current collector, wherein the positive pole slurry comprises lithium nitride.
2. The prelithiated positive electrode sheet of the lithium-ion battery of claim 1, wherein the positive electrode slurry further comprises a conductive agent, a binder, a positive electrode material, and a solvent.
Preferably, the mass ratio of the lithium nitride to the conductive agent to the binder to the positive electrode material is (0.5-3): 1-4): 1-3): 90-97.5.
3. The pre-lithiated positive electrode sheet of a lithium ion battery according to claim 1 or 2, wherein the positive electrode material comprises any one of a lithium iron phosphate material, a nickel cobalt manganese material, a nickel cobalt aluminum material, a lithium cobaltate or a lithium manganate material, or a combination of at least two of them;
preferably, the conductive agent comprises any one of conductive carbon black, conductive graphite, carbon nanotubes, graphene or carbon fibers or a combination of at least two of the same;
preferably, the binder comprises polyvinylidene fluoride and/or polytetrafluoroethylene;
preferably, the solvent comprises any one of N, N-dimethylformamide, N-methylpyrrolidone or cyclohexanone, or a combination of at least two thereof.
4. The positive electrode plate as claimed in any one of claims 1 to 3, wherein a lithium nitride paste is disposed outside the positive electrode paste.
5. The positive electrode sheet according to claim 4, wherein the composition of the lithium nitride paste comprises lithium nitride, a conductive agent, a binder and a solvent;
preferably, the mass ratio of the lithium nitride to the conductive agent to the binder is (0.5-1): 2-3): 6-7.5;
preferably, the conductive agent comprises any one of conductive carbon black, conductive graphite, carbon nanotubes, graphene or carbon fibers or a combination of at least two of the same;
preferably, the binder comprises polyvinylidene fluoride and/or polytetrafluoroethylene;
preferably, the solvent includes N, N-dimethylformamide, N-methylpyrrolidone, cyclohexanone, and the like.
6. A preparation method of the lithium ion battery prelithiation positive pole piece according to any one of claims 1 to 5, characterized in that the preparation method comprises: and coating the positive electrode slurry on the surface of the current collector, and drying and rolling to obtain the positive electrode piece.
7. The preparation method of claim 6, wherein the surface of the positive pole piece is coated with lithium nitride slurry to obtain the positive pole piece with the lithium nitride coating.
8. A preparation method of a pre-lithiated lithium ion battery is characterized by comprising the following steps:
(1) sequentially laminating at least one positive pole piece and at least one negative pole piece according to any one of claims 1 to 5, or winding, wherein a diaphragm is arranged between the adjacent positive pole piece and the negative pole piece, the diaphragm and an electrolyte are packaged together to form a soft package battery, and an air bag is reserved;
(2) standing the soft package battery obtained in the step (1);
(3) after standing, charging the soft package battery to ensure that Li in the lithium nitride+Fully embedded into the negative pole piece;
(4) and carrying out air extraction and sealing on the soft package battery and cutting off the air bag.
9. The preparation method according to claim 8, wherein the temperature of the standing in the step (2) is 25-60 ℃;
preferably, the standing time in the step (2) is 1-24 h.
10. The method according to claim 8, wherein the charging method in step (3) is constant current and constant voltage charging;
preferably, the current of the constant-current and constant-voltage charging is 0.001-1C, and the cut-off voltage is 3.8-4.5V; the constant current and voltage is 1.5-4.5V, and the charging is carried out until the current is 0.001-1C.
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| CN114243090A (en) * | 2021-12-17 | 2022-03-25 | 中国科学院电工研究所 | Lithium pre-embedding device and method of lithium ion energy storage device |
| CN114976016A (en) * | 2022-06-29 | 2022-08-30 | 广州小鹏汽车科技有限公司 | Positive electrode material for solid-state battery, method for producing same, solid-state battery, and vehicle |
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