CN111952597A - Composite positive plate, preparation method thereof and solid-state battery - Google Patents
Composite positive plate, preparation method thereof and solid-state battery Download PDFInfo
- Publication number
- CN111952597A CN111952597A CN202010625488.2A CN202010625488A CN111952597A CN 111952597 A CN111952597 A CN 111952597A CN 202010625488 A CN202010625488 A CN 202010625488A CN 111952597 A CN111952597 A CN 111952597A
- Authority
- CN
- China
- Prior art keywords
- lithium
- positive plate
- gas
- positive electrode
- solid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
-
- 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
-
- 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 invention belongs to the technical field of batteries, and particularly relates to a preparation method of a composite positive plate, which comprises the following steps: dissolving a polymer and a first lithium salt in a first solvent to form a mixed slurry; and obtaining a positive plate, depositing the mixed slurry on the surface of one side of the positive plate, which is far away from the current collector, and drying to form a protective layer to obtain the composite positive plate. The preparation method of the composite positive plate provided by the invention has simple and convenient process, is suitable for industrial large-scale production and application, and the protective layer in the prepared composite positive plate can effectively isolate the direct contact between the high-energy intercalation positive material and the solid electrolyte so as to avoid the problem of interface incompatibility; and the lithium ion conductive material has better lithium ion conductivity, can reduce the interface impedance of the contact between the anode of the solid-state battery and the electrolyte, reduces the ohmic internal resistance of the solid-state battery, and is beneficial to improving the charge and discharge performance of the battery.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a composite positive plate, a preparation method thereof and a solid-state battery.
Background
Conventional lithium ion batteries face more and more safety problems, wherein volatile, flammable and combustible organic electrolytes are one of the main factors causing the safety problems of the lithium ion batteries. The solid-state battery is used as a new generation of lithium ion battery technology, and has the outstanding advantages of good safety, high energy density and the like on the basis of inheriting the advantages of the traditional lithium ion battery. The choice of the positive electrode material is an important factor affecting the energy density of a solid-state lithium battery. Currently, most solid-state lithium battery systems researched by many use lithium iron phosphate (LFP) anodes, because LFP anodes have better interface compatibility with the existing solid-state electrolytes, the existing layered anode materials of solid-state lithium batteries, such as Lithium Cobaltate (LCO), lithium nickelate, lithium manganate, lithium nickel manganese manganate (NCM), etc., have the problem of poor matching with the solid-state electrolytes. Wherein the reaction energy of the garnet-type oxide electrolyte (e.g., LLZO) with the fully lithiated layered positive electrode material is zero, but during charging, the LLZO reacts with the semi-lithiated positive electrode. Due to the presence of the transition metal, a reaction between the organic electrolyte PEO and the layered positive electrode material also occurs, reducing the usable electrochemical window of the PEO electrolyte. These become obstacles for the application of the layered positive electrode material in the solid-state lithium battery, and seriously hinder the improvement of the energy density of the solid-state lithium battery.
At present, the problem of matching and compatibility between the anode material and the electrolyte is solved, and the improvement of the battery performance is one of the research hotspots of the solid-state battery at present. In some prior arts, the problem of incompatibility of the interface of the positive electrode active material and the polymer solid electrolyte is solved by additionally coating the positive electrode material, but the additional coating process is complicated, and the coating is not uniform, so that complete protection of the positive electrode material or the electrolyte cannot be realized. In some prior art, atomic deposition is adopted to deposit transition layers in gaps and surfaces of positive electrode particles, so that stability of a solid battery positive electrode in a charging and discharging process is improved, but the atomic layer deposition method is very expensive, has high requirements on instruments and equipment, and is not suitable for industrial large-scale production processes. At present, an effective method for improving the stability of the anode material of the solid-state battery is still lacked.
Disclosure of Invention
The invention aims to provide a preparation method of a composite positive plate, and aims to solve the technical problems of poor matching and compatibility between a positive material and a solid electrolyte, complex positive coating process, high cost and the like in the conventional positive plate.
Another object of the present invention is to provide a composite positive electrode sheet.
Another object of the present invention is to provide a solid-state battery.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a preparation method of a composite positive plate comprises the following steps:
dissolving a polymer and a first lithium salt in a first solvent to form a mixed slurry;
and obtaining a positive plate, depositing the mixed slurry on the surface of one side of the positive plate, which is far away from the current collector, and drying to form a protective layer to obtain the composite positive plate.
Preferably, the thickness of the protective layer is 1-4 microns.
Preferably, in the mixed slurry, the mass ratio of the polymer to the first lithium salt is (1.5-3): 1.
preferably, the polymer is selected from: at least one of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyacrylonitrile derivatives, polyvinyl chloride and polyvinyl fluoride; and/or the presence of a gas in the gas,
the first lithium salt is selected from: at least one of lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (difluorosulfonimide) and lithium bis (trifluoromethylsulfonimide); and/or the presence of a gas in the gas,
the first solvent is selected from: at least one of N, N-dimethylacetamide, dimethylformamide, N-methylpyrrolidone and acetone.
Preferably, the step of obtaining the positive electrode sheet includes: and mixing the positive electrode material, the binder, the conductive agent, the second lithium salt, the plasticizer and the second solvent, and depositing the mixture on the current collector to obtain the positive electrode plate.
Preferably, the positive electrode material is selected from: at least one of lithium cobaltate, lithium nickelate, lithium manganate, lithium nickel cobalt aluminate, lithium-rich manganese base and spinel lithium nickel manganate; and/or the presence of a gas in the gas,
the binder is selected from: at least one of polyvinylidene fluoride, polyacrylic acid, sodium carboxymethylcellulose, styrene butadiene rubber; and/or the presence of a gas in the gas,
the conductive agent is selected from: at least one of conductive carbon black, acetylene black, ketjen black, single-walled carbon nanotubes, multi-walled carbon nanotubes, and graphene; and/or the presence of a gas in the gas,
the second lithium salt is selected from: at least one of lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (difluorosulfonimide) and lithium bis (trifluoromethylsulfonimide); and/or the presence of a gas in the gas,
the plasticizer is selected from: at least one of succinonitrile, ionic liquid and polyethylene glycol; and/or the presence of a gas in the gas,
the second solvent is selected from: at least one of N, N-dimethylacetamide, dimethylformamide, N-methylpyrrolidone and acetone.
Correspondingly, the composite positive plate comprises a positive plate and a protective layer coated on the surface of one side, far away from a current collector, of the positive plate, wherein the protective layer comprises a polymer and a first lithium salt.
Preferably, the thickness of the protective layer is 1-4 microns; and/or the presence of a gas in the gas,
in the protective layer, the mass ratio of the polymer to the first lithium salt is (1.5-3): 1; and/or the presence of a gas in the gas,
the polymer is selected from: at least one of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyacrylonitrile derivatives, polyvinyl chloride and polyvinyl fluoride; and/or the presence of a gas in the gas,
the first lithium salt is selected from: at least one of lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (difluorosulfonimide) and lithium bis (trifluoromethylsulfonimide).
Accordingly, a solid-state battery comprising the composite positive electrode sheet prepared by the above method, or comprising the above composite positive electrode sheet.
Preferably, the solid-state battery is a solid-state lithium battery including: at least one solid electrolyte in inorganic system, organic system and organic-inorganic composite system.
The preparation method of the composite positive plate comprises the steps of firstly dissolving a polymer and a first lithium salt in a first solvent to form mixed slurry, then depositing the mixed slurry on the surface of one side of the positive plate, which is far away from a current collector, and drying to form a protective layer, thus obtaining the positive plate. The composite positive plate is particularly suitable for solid batteries, and in the using process, the surface of the composite positive plate containing the protective layer is arranged at one side close to the solid electrolyte, on one hand, a protective layer is formed on the surface of the positive plate, and the protective layer contains a polymer and a first lithium salt, so that the direct physical contact between a positive material and the solid electrolyte can be effectively avoided, the problem of interface incompatibility is further avoided, and the application of a layered positive material or a high-voltage positive material in the solid battery is realized; on the other hand, the first lithium salt in the protective layer has better lithium ion conduction performance, so that the interface impedance of the contact between the anode of the solid-state battery and the electrolyte can be reduced, and the first lithium salt has good ionic conductivity to ensure the lithium ion transmission between the anode plate and the electrolyte, thereby reducing the ohmic internal resistance of the solid-state battery and being beneficial to improving the charge and discharge performance of the battery. The preparation method of the composite positive plate provided by the invention is simple and convenient in process and is suitable for industrial large-scale production and application.
The composite positive plate provided by the invention comprises a positive plate and a protective layer coated on the outer surface of one side of the positive plate, which is far away from a current collector, wherein the protective layer comprises a polymer and a first lithium salt, so that the direct contact between a high-energy intercalation positive material and a solid electrolyte can be effectively isolated, the problem of interface incompatibility can be avoided, the application of a layered positive material or a high-voltage positive material in a solid battery can be realized, the composite positive plate has better lithium ion conduction performance, the interface impedance of the contact between the positive electrode and the electrolyte of the solid battery can be reduced, and the good ionic conductivity is realized to ensure the lithium ion transmission between the positive plate and the electrolyte, so that the ohmic internal resistance of the solid battery is reduced, and the charging and discharging performance of the battery can be improved.
The solid-state battery provided by the invention comprises the composite positive plate which has good interface compatibility with a solid electrolyte, low interface impedance and good ion conduction, so that the ohmic resistance of the solid-state battery is reduced, the charge and discharge performance of the battery is improved, the stability of the battery is enhanced, and the service life of the battery is prolonged.
Drawings
Fig. 1 is a sectional scanning electron microscope image of the composite positive electrode sheet provided in example 1 of the present invention.
Fig. 2 is a cross-sectional scanning electron microscope image of the composite positive electrode sheet provided in example 2 of the present invention.
Fig. 3 is a cross-sectional scanning electron microscope image of the composite positive electrode sheet provided in example 3 of the present invention.
Fig. 4 is a cross-sectional scanning electron microscope image of the composite positive electrode sheet provided in example 4 of the present invention.
Fig. 5 is a cycle test chart of the coin cells of example 1 and comparative example 1 of the present invention.
Fig. 6 is a cycle test chart of the coin cells of examples 2 and 3 of the present invention and comparative example 2.
Fig. 7 is a cycle test chart of the coin cells of example 4 of the invention and comparative example 3.
Detailed Description
In order to make the purpose, technical solution and technical effect of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention is clearly and completely described, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
The embodiment of the invention provides a preparation method of a composite positive plate, which comprises the following steps:
s10, dissolving a polymer and a first lithium salt in a first solvent to form mixed slurry;
s20, obtaining a positive plate, depositing the mixed slurry on the surface of one side, far away from a current collector, of the positive plate, and drying to form a protective layer to obtain the composite positive plate.
According to the preparation method of the composite positive plate provided by the embodiment of the invention, firstly, the polymer and the first lithium salt are dissolved in the first solvent to form mixed slurry, then the mixed slurry is deposited on the surface of one side of the positive plate, which is far away from the current collector, and is dried to form the protective layer, so that the positive plate is obtained. The composite positive plate is particularly suitable for a solid battery, and in the using process, the surface of the composite positive plate containing the protective layer is arranged at one side close to a solid electrolyte, so that on one hand, a protective layer is formed on the surface of the positive plate, and the protective layer contains a polymer and a first lithium salt, so that the direct physical contact between a positive material and the solid electrolyte can be effectively avoided, the problem of interface incompatibility is further avoided, and the application of a layered positive material or a high-voltage positive material in the solid battery is realized; on the other hand, the first lithium salt in the protective layer has better lithium ion conduction performance, so that the interface impedance of the contact between the anode of the solid-state battery and the electrolyte can be reduced, and the first lithium salt has good ionic conductivity to ensure the lithium ion transmission between the anode plate and the electrolyte, thereby reducing the ohmic internal resistance of the solid-state battery and being beneficial to improving the charge and discharge performance of the battery. The preparation method of the composite positive plate provided by the embodiment of the invention is simple and convenient in process and suitable for industrial large-scale production and application.
Specifically, in the above step S10, the polymer and the first lithium salt are dissolved in the first solvent to form a mixed slurry. According to the embodiment of the invention, the polymer and the first lithium salt are dissolved in the solvent to form the mixed slurry, wherein the polymer not only plays roles of a protective layer framework and auxiliary film formation, but also can effectively avoid the problem of interface incompatibility caused by direct contact between the cathode material and the solid electrolyte. The first lithium salt has the conductivity of lithium ions, and reduces the interface impedance between the positive electrode material and the electrolyte, so that the ohmic internal resistance of the solid-state battery is reduced, and the charging and discharging performance of the battery is improved.
In some embodiments, the mass ratio of the polymer to the first lithium salt in the mixed slurry is (1.5-3): 1. in the mixed slurry of the embodiment of the invention, the mass ratio of the polymer to the first lithium salt is (1.5-3): 1, the mixed slurry composed of the polymer and the first lithium salt in the proportion effectively ensures the ion conduction, the interface barrier function and the film forming property of the protective layer. If the polymer content in the mixed slurry is too high, the ion conduction of the protective layer is reduced, thereby affecting the lithium ion conduction and increasing the thickness of the protective layer; if the content of the first lithium salt is too high, not only the film forming property of the protective layer is affected, but also the lithium salt is unnecessarily wasted. In some specific embodiments, the mass ratio of the polymer and the first lithium salt in the mixed slurry may be 1.5: 1. 1.8: 1. 2: 1. 2.2: 1. 2.5: 1. 2.8: 1 or 3: 1.
in some embodiments, the polymer is selected from: at least one of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyacrylonitrile derivatives, polyvinyl chloride and polyvinyl fluoride. The polymers adopted by the embodiment of the invention not only have better high voltage resistance, but also have good stability, and have better chemical stability for anode materials and electrolytes, and in addition, the polymers also have better film-forming property and good film stability.
In some embodiments, the first lithium salt is selected from: at least one of lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (difluorosulfonimide) and lithium bis (trifluoromethylsulfonimide). The lithium salts adopted by the embodiment of the invention can be dissociated to obtain lithium ions, have high ionic conductivity and stability, are beneficial to the ionic conduction between the positive plate and the electrolyte, and can not react with other substances in the battery when the battery works in a high-pressure and high-temperature environment.
In some embodiments, the first solvent is selected from: at least one of N, N-dimethylacetamide, dimethylformamide, N-methylpyrrolidone and acetone. The solvents adopted by the embodiment of the invention have better dissolving effect on the polymer and the first lithium salt, and form uniform mixed slurry.
Specifically, in step S20, obtaining a positive plate, depositing the mixed slurry on a surface of the positive plate away from the current collector, and drying to form a protective layer, thereby obtaining the composite positive plate. According to the embodiment of the invention, the mixed slurry is deposited on the surface of one side of the positive plate, which is far away from the current collector, and a protective layer is formed on the surface of the positive plate, so that the composite positive plate is prepared. In the using process, the surface of the composite positive plate containing the protective layer is arranged on one side close to the solid electrolyte, and through the protective layer, the problem of interface incompatibility between the positive electrode material and the solid electrolyte can be effectively avoided, the cycle stability and the service life of the battery are improved, the lithium ion conductive performance is good, the interface impedance of the contact between the positive electrode of the solid battery and the electrolyte is reduced, and meanwhile, the ionic conductivity is good so as to ensure the lithium ion transmission between the positive plate and the electrolyte, so that the ohmic internal resistance of the solid battery is reduced, and the charging and discharging performance of the battery is favorably improved.
In some embodiments, the protective layer has a thickness of 1 to 4 microns. The thickness of the protective layer in the composite positive plate provided by the embodiment of the invention is 1-4 microns, the protective layer with the thickness can effectively solve the problem of interface contact between the positive plate and an electrolyte, and meanwhile, the composite positive plate is ensured to have better ionic conductivity. In some embodiments, the thickness of the protective layer in the composite positive electrode sheet may be 1 micron, 1.5 microns, 2 microns, 2.5 microns, 3 microns, or 4 microns.
In some embodiments, the step of obtaining the positive electrode tab comprises: and mixing the positive electrode material, the binder, the conductive agent, the second lithium salt, the plasticizer and the second solvent, and depositing on the current collector to obtain the positive electrode plate. The embodiment of the invention has no strict requirement on the selection of each component material in the positive plate, and can be suitable for any positive plate. In some embodiments, the positive electrode material is selected from: at least one of lithium cobaltate, lithium nickelate, lithium manganate, lithium nickel cobalt aluminate, lithium-rich manganese base and spinel lithium nickel manganate. In some embodiments, the binder is selected from: at least one of polyvinylidene fluoride, polyacrylic acid, sodium carboxymethyl cellulose, styrene butadiene rubber. In some embodiments, the conductive agent is selected from: at least one of conductive carbon black, acetylene black, ketjen black, single-walled carbon nanotubes, multi-walled carbon nanotubes and graphene. In some embodiments, the second lithium salt is selected from: at least one of lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (difluorosulfonimide) and lithium bis (trifluoromethylsulfonimide). In some embodiments, the plasticizer is selected from: at least one of succinonitrile, ionic liquid and polyethylene glycol. In some embodiments, the second solvent is selected from: at least one of N, N-dimethylacetamide, dimethylformamide, N-methylpyrrolidone and acetone. The positive plate formed by combining the positive materials in the embodiments of the invention has higher specific capacity and excellent electrochemistry performance, and can effectively improve the capacity of the battery.
The composite positive plate prepared by the embodiment of the invention is suitable for any solid-state battery, and is particularly suitable for a solid-state lithium battery. The problem of poor matching of the anode material and solid electrolytes such as inorganic garnet type oxide electrolytes (lithium lanthanum zirconium oxygen LLZO, lithium lanthanum zirconium tantalum oxygen LLZTO system), organic electrolytes PEO and the like can be obviously improved, the stability of the solid battery is improved, and the service life of the solid battery is prolonged.
Correspondingly, the embodiment of the invention also provides a composite positive plate, which comprises a positive plate and a protective layer coated on the surface of one side, far away from the current collector, of the positive plate, wherein the protective layer comprises a polymer and a first lithium salt.
The composite positive plate provided by the embodiment of the invention comprises a positive plate and a protective layer coated on the outer surface of one side of the positive plate, which is far away from a current collector, wherein the protective layer comprises a polymer and a first lithium salt, so that the direct contact between a high-energy intercalation positive material and a solid electrolyte can be effectively isolated, the problem of interface incompatibility can be avoided, the application of a layered positive material or a high-voltage positive material in a solid battery can be realized, the composite positive plate has better lithium ion conduction performance, the interface impedance of the contact between the positive electrode and the electrolyte of the solid battery can be reduced, and the composite positive plate has good ionic conductivity to ensure the lithium ion transmission between the positive plate and the electrolyte, so that the ohmic internal resistance of the solid battery is reduced, and the charging and discharging performance of the battery can. .
The composite positive plate of the embodiment of the invention can be prepared by any one of the methods of the embodiments.
In some embodiments, the protective layer has a thickness of 1 to 4 microns.
In some embodiments, in the protective layer, the mass ratio of the polymer to the first lithium salt is (1.5 to 3): 1.
in some embodiments, the polymer is selected from: at least one of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyacrylonitrile derivatives, polyvinyl chloride and polyvinyl fluoride.
In some embodiments, the first lithium salt is selected from: at least one of lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (difluorosulfonimide) and lithium bis (trifluoromethylsulfonimide).
The technical effects of the above embodiments of the present invention are discussed in detail in the foregoing, and are not described herein again.
Correspondingly, the embodiment of the invention also provides a solid-state battery, and the solid-state battery comprises the composite positive plate prepared by the method or comprises the composite positive plate.
The solid-state battery provided by the embodiment of the invention comprises the composite positive plate which has good interface compatibility with an electrolyte, low interface impedance and good ion conduction, so that the ohmic resistance of the solid-state battery is reduced, the charge and discharge performance of the battery is improved, the stability of the battery is enhanced, and the service life of the battery is prolonged.
In some embodiments, the solid-state battery is a solid-state lithium battery, wherein the solid-state electrolyte comprises: at least one of an inorganic system, an organic system, and an organic-inorganic composite system. In some embodiments, solid-state electrolytes include, but are not limited to: inorganic garnet type oxide electrolyte (lithium lanthanum zirconium oxygen LLZO, lithium lanthanum zirconium tantalum oxygen LLZTO system), organic-PEO system, and organic-inorganic composite system. In the solid-state lithium battery provided by the embodiment of the invention, the protective layer exists between the anode and the solid-state electrolyte, so that the problem of interface incompatibility can be avoided, and further the application of high-energy anode materials such as a layered anode material or a high-voltage anode material in the solid-state lithium battery (a PEO system and a LLZTO system) is realized. In addition, the presence of the polymer may improve poor physical contact between the pole piece and the solid-state electrolyte, and the presence of the lithium salt may improve ion conduction. The lithium conductive protective layer can reduce the interface impedance of solid-solid contact of the solid-state lithium battery, and has good ionic conductivity so as to ensure the lithium ion transmission between the positive electrode side and the solid-state electrolyte.
In order to make the above implementation details and operations of the present invention clearly understood by those skilled in the art and to make the progress of the composite positive electrode sheet and the preparation method thereof obviously reflected, the above technical solution is illustrated by a plurality of examples below.
Example 1
A composite positive plate and a button battery comprise the following steps:
dissolving/dispersing a positive electrode material LCO, a conductive agent SP, a binder PVDF, (a plasticizer succinonitrile + lithium salt LiTFSI) in a solvent NMP according to the proportion of (7-9.5): (0.2-1): 0.1-1), and fully stirring for 8 hours to obtain a composite positive electrode slurry, smearing, and heating in vacuum at 100 ℃ for drying overnight to obtain a positive electrode sheet;
dissolving/dispersing the binder PVDF and the lithium salt LiTFSI in the solvent DMF according to the proportion (1-5) of 1 for fully stirring for 8 hours, and mixing the slurry;
thirdly, scraping the mixed slurry onto the surface of the positive plate obtained in the step I, and heating and drying the surface of the positive plate in vacuum at 80 ℃ overnight to obtain a composite positive plate containing a protective layer, wherein the thickness of the protective layer is about 1 micron, as shown in the attached drawing 1;
and fourthly, sequentially placing the composite positive plate, the LLZTO solid electrolyte sheet, the lithium sheet, the gasket and the elastic sheet into the stainless steel shell of the button cell in a stacking manner, and assembling the button cell.
Example 2
A composite positive plate and a button battery comprise the following steps:
firstly, dissolving/dispersing a nickel cobalt lithium manganate positive electrode material NCM811, a conductive agent SP, a binder PVDF, (a plasticizer succinonitrile + a lithium salt LiTFSI) in a solvent NMP according to the proportion of (7-9.5): (0.2-1): 0.2-1: (0.1-1) to fully stir for 8 hours to obtain a composite positive electrode slurry, smearing, and heating and drying overnight at 100 ℃ in vacuum to obtain a positive electrode sheet;
dissolving/dispersing the binder PVDF and the lithium salt LiTFSI in the solvent DMF according to the proportion (1-5) of 1 for fully stirring for 8 hours, and mixing the slurry;
thirdly, scraping the mixed slurry on the surface of the positive plate obtained in the step I, and heating and drying the surface of the positive plate in vacuum at 80 ℃ overnight to obtain a composite positive plate containing a protective layer, wherein the thickness of the protective layer is about 1.2 microns, as shown in the attached figure 2;
and fourthly, sequentially placing the composite positive plate, the LLZTO solid electrolyte sheet, the lithium sheet, the gasket and the elastic sheet into the stainless steel shell of the button cell in a stacking manner, and assembling the button cell.
Example 3
A composite positive plate and a button battery comprise the following steps:
firstly, dissolving/dispersing a nickel cobalt lithium manganate positive electrode material NCM811, a conductive agent SP, a binder PVDF, (a plasticizer succinonitrile + a lithium salt LiTFSI) in a solvent NMP according to the proportion of (7-9.5): (0.2-1): 0.2-1: (0.1-1) to fully stir for 8 hours to obtain a composite positive electrode slurry, smearing, and heating and drying overnight at 100 ℃ in vacuum to obtain a positive electrode sheet;
dissolving/dispersing the binder PVDF and the lithium salt LiTFSI in the solvent DMF according to the proportion (1-5) of 1 for fully stirring for 8 hours, and mixing the slurry;
thirdly, scraping the mixed slurry on the surface of the positive plate obtained in the step I, and heating and drying the surface of the positive plate in vacuum at 80 ℃ overnight to obtain a composite positive plate containing a protective layer, wherein the thickness of the protective layer is about 1.7 microns, as shown in the attached figure 3;
and fourthly, sequentially placing the composite positive plate, the LLZTO solid electrolyte sheet, the lithium sheet, the gasket and the elastic sheet into the stainless steel shell of the button cell in a stacking manner, and assembling the button cell.
Example 4
A composite positive plate and a button battery comprise the following steps:
dissolving/dispersing a lithium-rich manganese-based positive electrode material Li-rich, a conductive agent SP, a binder PVDF, (a plasticizer succinonitrile + a lithium salt LiTFSI) in a solvent NMP according to the proportion of (7-9.5): (0.2-1): 0.1-1), and fully stirring for 8 hours to obtain a composite positive electrode slurry, coating the composite positive electrode slurry on a carbon-coated aluminum foil, and heating and drying overnight at 80 ℃ under vacuum to obtain a positive electrode sheet;
dissolving/dispersing the binder PVDF and the lithium salt LiTFSI in the solvent DMF according to the proportion (1-5) of 1 for fully stirring for 8 hours, and mixing the slurry;
thirdly, scraping the mixed slurry on the surface of the positive plate obtained in the step I, and heating and drying the surface of the positive plate in vacuum at 80 ℃ overnight to obtain a composite positive plate containing a protective layer, wherein the thickness of the protective layer is about 3.2 microns, as shown in the attached figure 4;
and fourthly, sequentially placing the composite positive plate, the LLZTO solid electrolyte sheet, the lithium sheet, the gasket and the elastic sheet into the stainless steel shell of the button cell in a stacking manner, and assembling the button cell.
Comparative example 1
A composite positive plate and a button battery comprise the following steps:
dissolving/dispersing a positive electrode material LCO, a conductive agent SP, a binder PVDF, (a plasticizer succinonitrile + lithium salt LiTFSI) in a solvent NMP according to the proportion of (7-9.5): (0.2-1): 0.1-1), and fully stirring for 8 hours to obtain a composite positive electrode slurry, smearing, and heating in vacuum at 100 ℃ for drying overnight to obtain a positive electrode sheet;
and secondly, sequentially putting the positive plate, the LLZTO solid electrolyte sheet, the lithium sheet, the gasket and the elastic sheet into the stainless steel shell of the button cell in a stacking manner, and assembling the button cell.
Comparative example 2
A composite positive plate and a button battery comprise the following steps:
firstly, dissolving/dispersing a nickel cobalt lithium manganate positive electrode material NCM811, a conductive agent SP, a binder PVDF, (a plasticizer succinonitrile + a lithium salt LiTFSI) in a solvent NMP according to the proportion of (7-9.5): (0.2-1): 0.2-1: (0.1-1) to fully stir for 8 hours to obtain a composite positive electrode slurry, smearing, and heating and drying overnight at 100 ℃ in vacuum to obtain a positive electrode sheet;
and secondly, sequentially putting the positive plate, the LLZTO solid electrolyte sheet, the lithium sheet, the gasket and the elastic sheet into the stainless steel shell of the button cell in a stacking manner, and assembling the button cell.
Comparative example 3
A composite positive plate and a button battery comprise the following steps:
dissolving/dispersing a lithium-rich manganese-based positive electrode material Li-rich, a conductive agent SP, a binder PVDF, (a plasticizer succinonitrile + a lithium salt LiTFSI) in a solvent NMP according to the proportion of (7-9.5): (0.2-1): 0.1-1), and fully stirring for 8 hours to obtain a composite positive electrode slurry, coating the composite positive electrode slurry on a carbon-coated aluminum foil, and heating and drying overnight at 80 ℃ under vacuum to obtain a positive electrode sheet;
and secondly, sequentially putting the positive plate, the LLZTO solid electrolyte sheet, the lithium sheet, the gasket and the elastic sheet into the stainless steel shell of the button cell in a stacking manner, and assembling the button cell.
Furthermore, in order to verify the advancement of the composite positive plate and the button cell prepared in the embodiments 1 to 3 of the present invention, the embodiments of the present invention were subjected to performance tests.
Test example 1
In the test example of the present invention, the cross sections of the composite positive electrode sheets prepared in examples 1 to 4 were tested by scanning electron microscopy, and the electron microscopy images are respectively shown in fig. 1 to 4. As can be seen, the surface of each of the composite positive plates prepared in examples 1 to 4 has a protective layer with a uniform thickness of 1 to 4 μm.
Test example 2
The test examples of the invention respectively test the cycle performance of the button batteries prepared in examples 1 to 4 and comparative examples 1 to 3, and the test results are respectively shown in the attached figures 5 to 7, wherein the abscissa is the cycle number, the left ordinate is the specific capacity, and the right ordinate is the coulombic efficiency.
The test results shown in fig. 5 to 7 show that the button cells prepared in the embodiments 1 to 4 of the present invention effectively improve the cycling stability of the button cells due to the adoption of the composite positive plate coated with the protective layer.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The preparation method of the composite positive plate is characterized by comprising the following steps:
dissolving a polymer and a first lithium salt in a first solvent to form a mixed slurry;
and obtaining a positive plate, depositing the mixed slurry on the surface of one side of the positive plate, which is far away from the current collector, and drying to form a protective layer to obtain the composite positive plate.
2. The method for preparing a composite positive electrode sheet according to claim 1, wherein the thickness of the protective layer is 1 to 4 μm.
3. The method for producing a composite positive electrode sheet according to claim 1, wherein the mass ratio of the polymer to the first lithium salt in the mixed slurry is (1.5 to 3): 1.
4. the method for producing a composite positive electrode sheet according to any one of claims 1 to 3, wherein the polymer is selected from the group consisting of: at least one of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyacrylonitrile derivatives, polyvinyl chloride and polyvinyl fluoride; and/or the presence of a gas in the gas,
the first lithium salt is selected from: at least one of lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (difluorosulfonimide) and lithium bis (trifluoromethylsulfonimide); and/or the presence of a gas in the gas,
the first solvent is selected from: at least one of N, N-dimethylacetamide, dimethylformamide, N-methylpyrrolidone and acetone.
5. The method for producing a composite positive electrode sheet according to claim 4, wherein the step of obtaining a positive electrode sheet comprises: and mixing the positive electrode material, the binder, the conductive agent, the second lithium salt, the plasticizer and the second solvent, and depositing the mixture on the current collector to obtain the positive electrode plate.
6. The method for preparing a composite positive electrode sheet according to claim 5, wherein the positive electrode material is selected from the group consisting of: at least one of lithium cobaltate, lithium nickelate, lithium manganate, lithium nickel cobalt aluminate, lithium-rich manganese base and spinel lithium nickel manganate; and/or the presence of a gas in the gas,
the binder is selected from: at least one of polyvinylidene fluoride, polyacrylic acid, sodium carboxymethylcellulose, styrene butadiene rubber; and/or the presence of a gas in the gas,
the conductive agent is selected from: at least one of conductive carbon black, acetylene black, ketjen black, single-walled carbon nanotubes, multi-walled carbon nanotubes, and graphene; and/or the presence of a gas in the gas,
the second lithium salt is selected from: at least one of lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (difluorosulfonimide) and lithium bis (trifluoromethylsulfonimide); and/or the presence of a gas in the gas,
the plasticizer is selected from: at least one of succinonitrile, ionic liquid and polyethylene glycol; and/or the presence of a gas in the gas,
the second solvent is selected from: at least one of N, N-dimethylacetamide, dimethylformamide, N-methylpyrrolidone and acetone.
7. The composite positive plate is characterized by comprising a positive plate and a protective layer coated on the surface of one side, far away from a current collector, of the positive plate, wherein the protective layer comprises a polymer and a first lithium salt.
8. The composite positive electrode sheet according to claim 7, wherein the protective layer has a thickness of 1 to 4 μm;
in the protective layer, the mass ratio of the polymer to the first lithium salt is (1.5-3): 1; and/or the presence of a gas in the gas,
the polymer is selected from: at least one of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyacrylonitrile derivatives, polyvinyl chloride and polyvinyl fluoride; and/or the presence of a gas in the gas,
the first lithium salt is selected from: at least one of lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (difluorosulfonimide) and lithium bis (trifluoromethylsulfonimide).
9. A solid-state battery comprising the composite positive electrode sheet produced by the method according to any one of claims 1 to 6, or comprising the composite positive electrode sheet according to any one of claims 8 to 9.
10. The solid-state battery according to claim 9, wherein the solid-state battery is a lithium solid-state battery comprising: at least one solid electrolyte in inorganic system, organic system and organic-inorganic composite system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010625488.2A CN111952597A (en) | 2020-07-02 | 2020-07-02 | Composite positive plate, preparation method thereof and solid-state battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010625488.2A CN111952597A (en) | 2020-07-02 | 2020-07-02 | Composite positive plate, preparation method thereof and solid-state battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111952597A true CN111952597A (en) | 2020-11-17 |
Family
ID=73337879
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010625488.2A Pending CN111952597A (en) | 2020-07-02 | 2020-07-02 | Composite positive plate, preparation method thereof and solid-state battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111952597A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114583246A (en) * | 2022-02-21 | 2022-06-03 | 南昌大学 | Solid-state lithium ion battery and preparation method thereof |
| CN114784276A (en) * | 2022-04-13 | 2022-07-22 | 北京理工大学 | Composite material with electronic and ionic conductivity, preparation method and application thereof |
| CN116315186A (en) * | 2023-05-17 | 2023-06-23 | 中创新航科技集团股份有限公司 | Battery cell |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106229447A (en) * | 2016-08-10 | 2016-12-14 | 东莞永蓝电子科技有限公司 | A kind of lithium ion battery |
| CN108365165A (en) * | 2018-02-06 | 2018-08-03 | 哈尔滨工业大学 | A kind of solid state lithium battery and preparation method thereof of novel electrolytes complex method |
| CN108963205A (en) * | 2018-06-12 | 2018-12-07 | 天津力神电池股份有限公司 | A kind of solid state lithium battery of NEW TYPE OF COMPOSITE anode and its preparation method and application |
| CN108963328A (en) * | 2018-06-12 | 2018-12-07 | 天津力神电池股份有限公司 | Solid state lithium battery and preparation method based on multi-functional layered composite solid electrolyte |
| CN109119591A (en) * | 2018-08-17 | 2019-01-01 | 张家港市国泰华荣化工新材料有限公司 | A kind of solid state battery anode composite and preparation method thereof |
| CN109256525A (en) * | 2018-08-28 | 2019-01-22 | 长沙矿冶研究院有限责任公司 | A kind of all-solid-state battery high-compactness flexible electrical pole piece and preparation method thereof |
| CN109786817A (en) * | 2019-01-23 | 2019-05-21 | 蜂巢能源科技有限公司 | Solid state lithium battery and its application and the method for preparing the solid electrolyte membrane that non-woven fabrics enhances |
| CN110034275A (en) * | 2019-04-25 | 2019-07-19 | 上海空间电源研究所 | A kind of sulfide solid state battery buffer layer and preparation method thereof and solid state battery |
| CN110212160A (en) * | 2019-06-26 | 2019-09-06 | 上海空间电源研究所 | A kind of solid state battery ion transport layers and preparation method thereof and solid state battery |
| CN110518250A (en) * | 2019-09-06 | 2019-11-29 | 深圳先进技术研究院 | Plasticizing anode of high positive active material carrying capacity and preparation method thereof, solid state battery |
| CN110556574A (en) * | 2019-08-12 | 2019-12-10 | 北京协同创新研究院 | Multilayer solid electrolyte, preparation method thereof, solid battery and electronic equipment |
| CN111244537A (en) * | 2020-02-24 | 2020-06-05 | 南方科技大学 | Composite solid electrolyte, solid battery and preparation method thereof |
-
2020
- 2020-07-02 CN CN202010625488.2A patent/CN111952597A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106229447A (en) * | 2016-08-10 | 2016-12-14 | 东莞永蓝电子科技有限公司 | A kind of lithium ion battery |
| CN108365165A (en) * | 2018-02-06 | 2018-08-03 | 哈尔滨工业大学 | A kind of solid state lithium battery and preparation method thereof of novel electrolytes complex method |
| CN108963205A (en) * | 2018-06-12 | 2018-12-07 | 天津力神电池股份有限公司 | A kind of solid state lithium battery of NEW TYPE OF COMPOSITE anode and its preparation method and application |
| CN108963328A (en) * | 2018-06-12 | 2018-12-07 | 天津力神电池股份有限公司 | Solid state lithium battery and preparation method based on multi-functional layered composite solid electrolyte |
| CN109119591A (en) * | 2018-08-17 | 2019-01-01 | 张家港市国泰华荣化工新材料有限公司 | A kind of solid state battery anode composite and preparation method thereof |
| CN109256525A (en) * | 2018-08-28 | 2019-01-22 | 长沙矿冶研究院有限责任公司 | A kind of all-solid-state battery high-compactness flexible electrical pole piece and preparation method thereof |
| CN109786817A (en) * | 2019-01-23 | 2019-05-21 | 蜂巢能源科技有限公司 | Solid state lithium battery and its application and the method for preparing the solid electrolyte membrane that non-woven fabrics enhances |
| CN110034275A (en) * | 2019-04-25 | 2019-07-19 | 上海空间电源研究所 | A kind of sulfide solid state battery buffer layer and preparation method thereof and solid state battery |
| CN110212160A (en) * | 2019-06-26 | 2019-09-06 | 上海空间电源研究所 | A kind of solid state battery ion transport layers and preparation method thereof and solid state battery |
| CN110556574A (en) * | 2019-08-12 | 2019-12-10 | 北京协同创新研究院 | Multilayer solid electrolyte, preparation method thereof, solid battery and electronic equipment |
| CN110518250A (en) * | 2019-09-06 | 2019-11-29 | 深圳先进技术研究院 | Plasticizing anode of high positive active material carrying capacity and preparation method thereof, solid state battery |
| CN111244537A (en) * | 2020-02-24 | 2020-06-05 | 南方科技大学 | Composite solid electrolyte, solid battery and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114583246A (en) * | 2022-02-21 | 2022-06-03 | 南昌大学 | Solid-state lithium ion battery and preparation method thereof |
| CN114784276A (en) * | 2022-04-13 | 2022-07-22 | 北京理工大学 | Composite material with electronic and ionic conductivity, preparation method and application thereof |
| CN114784276B (en) * | 2022-04-13 | 2023-10-27 | 北京理工大学 | Composite material with electronic and ionic conductivity, preparation method and application thereof |
| CN116315186A (en) * | 2023-05-17 | 2023-06-23 | 中创新航科技集团股份有限公司 | Battery cell |
| CN116315186B (en) * | 2023-05-17 | 2023-08-18 | 中创新航科技集团股份有限公司 | Battery cell |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111244537A (en) | Composite solid electrolyte, solid battery and preparation method thereof | |
| CN105932225A (en) | Preparation method of improved room temperature electron ion fast transfer electrode slice for solid-state secondary lithium battery | |
| CN111430788A (en) | Composite solid electrolyte membrane, preparation method and solid lithium battery | |
| CN111640940A (en) | Negative plate and secondary battery | |
| CN111162309B (en) | Solid electrolyte-anode composite material and preparation and application methods thereof | |
| CN110380133A (en) | A kind of transition zone design method of inorganic solid electrolyte and positive interpolar | |
| CN111952597A (en) | Composite positive plate, preparation method thereof and solid-state battery | |
| CN111244409A (en) | Solid electrolyte-anode composite material and preparation and application thereof | |
| CN112259803B (en) | Lithium ion laminated core and application thereof | |
| CN110707287A (en) | Metallic lithium cathode, preparation method thereof and lithium battery | |
| CN113140731B (en) | All-solid-state lithium battery and preparation method thereof | |
| CN114665065A (en) | Positive pole piece and preparation method and application thereof | |
| CN111653732A (en) | Positive electrode material, positive electrode plate and lithium ion battery | |
| WO2023236843A1 (en) | Composite positive-electrode lithium-supplementing additive, and preparation method therefor and use thereof | |
| CN113451586A (en) | Electrode plate of secondary battery, secondary battery and preparation method of secondary battery | |
| CN115172653A (en) | Composite positive electrode, solid-state lithium ion secondary battery, and electric device | |
| CN113745636A (en) | Solid-state lithium battery and preparation method thereof | |
| CN111900458A (en) | Composite solid electrolyte and preparation method thereof | |
| CN113889595A (en) | Preparation method of solid electrolyte coated graphite composite material | |
| CN109411700B (en) | Positive pole piece applied to all-solid-state lithium ion battery and preparation method thereof | |
| CN215644574U (en) | Electrode plate of secondary battery and secondary battery | |
| CN115036458B (en) | Lithium ion battery | |
| CN112701347B (en) | Electrochemical device and electronic equipment | |
| CN115295771A (en) | Positive electrode composite material, preparation method thereof, positive electrode plate and secondary battery | |
| CN114220975A (en) | Lithium-rich manganese-based positive pole piece and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201117 |
|
| RJ01 | Rejection of invention patent application after publication |