CN112490433A - Solid-state battery and method for improving rate capability and safety of solid-state battery - Google Patents
Solid-state battery and method for improving rate capability and safety of solid-state battery Download PDFInfo
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- CN112490433A CN112490433A CN202011222235.7A CN202011222235A CN112490433A CN 112490433 A CN112490433 A CN 112490433A CN 202011222235 A CN202011222235 A CN 202011222235A CN 112490433 A CN112490433 A CN 112490433A
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- 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
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
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Abstract
The invention belongs to the technical field of solid-state batteries, and particularly relates to a solid-state battery and a method for improving the rate capability and the safety of the solid-state battery, wherein the method for improving the rate capability and the safety of the solid-state battery comprises the following steps: and placing the solid-state battery cell into a chamber of the atomic layer deposition equipment for nano-scale protective layer deposition, wherein the solid-state battery cell comprises a porous current collector. The invention provides a solid-state battery with a nano protective layer and a method for improving the rate capability and safety of the solid-state battery, which solve the problems that the rate capability of the existing solid-state battery is poor and the existing solid-state battery adopts a lithium metal cathode or a sulfide electrolyte and the like which are unstable in air.
Description
Technical Field
The invention belongs to the technical field of solid-state batteries, and particularly relates to a solid-state battery and a method for improving the rate capability and safety of the solid-state battery.
Background
The prior art and the defects are as follows:
the solid-state battery uses solid positive and negative electrodes and a solid electrolyte, does not contain any liquid, and all materials are composed of solid materials. The inorganic solid electrolyte material adopted by the solid-state battery is nonflammable and nonvolatile, has no leakage problem, and is expected to overcome the lithium dendrite phenomenon, so that the all-solid-state battery based on the inorganic solid electrolyte is expected to have very high safety characteristic, and the polymer solid electrolyte still has certain combustible risk, but the safety is also greatly improved compared with a liquid-state electrolyte battery containing a combustible solvent. However, in the solid-state battery, for example, metal lithium is used as a negative electrode, or a sulfide electrolyte is used, and when the battery package is broken, the metal lithium or the sulfide electrolyte is exposed to the air and reacts with water or oxygen in the air to generate flammable gas or toxic gas, so that the solid-state battery still has potential safety hazard.
The current solid-state battery is assembled by cold isostatic pressing or hot pressing, the solid-state battery has poor multiplying power performance due to large contact resistance of a solid interface, and the stable conductive buffer layer is generally introduced to eliminate or weaken the space charge effect, inhibit the generation of an interface layer and reduce the interface resistance. At present, the atomic layer deposition technology mainly coats and deposits electrode materials or electrode pole pieces, and is used for improving the interface compatibility of solid electrolyte materials and the electrode materials or reducing the interface resistance. According to related art search, no atomic layer deposition technology is currently employed for subsequent processing of solid-state battery cells.
CN 107851840 a, nano-engineered coatings for anode active materials, cathode active materials and solid state electrolytes for reducing corrosion and enhancing battery cycle life, and a method of manufacturing batteries comprising the nano-engineered coatings. Also disclosed is a solid-state battery comprising a solid electrolyte layer having a solid electrolyte particle coated with a protective coating layer having a thickness of 100nm or less. The protective coating is obtained by Atomic Layer Deposition (ALD) or Molecular Layer Deposition (MLD).
CN 108539250A, an all-solid-state lithium battery and a preparation method thereof, wherein ALD is adopted to coat metal oxide, metal phosphate, metal fluoride or metal sulfide on the surface of a positive electrode material, and the positive electrode material is heated and reacts with residual alkaline substances on the surface of the positive electrode material to form a LiXaYb solid electrolyte layer, so that the pH value of the positive electrode material is reduced, the internal resistance of the solid battery is reduced, and the cycle performance and the rate capability of the battery are improved.
CN 109980183A, atomic layer deposition processing method for improving solid state battery positive electrode circulation stability, atomic layer deposition processing positive electrode, in positive electrode particle gap and surface deposition transition layer, has advantages such as the positive electrode charge-discharge stability of greatly promoting solid state battery.
In all of the patents, electrode materials or electrode plates are processed, and pores are still present in the electrode plates and the electrolyte after the battery is assembled, so that the problem of high interface impedance is also present. According to related technology search, the subsequent treatment after the assembly of the solid-state battery cell is mainly heating or pressurizing, and the atomic layer deposition technology is not adopted for the subsequent treatment of the solid-state battery cell at present.
The difficulty and significance for solving the technical problems are as follows:
therefore, based on the problems, the solid-state battery with the nano protective layer and the method for improving the rate capability and the safety of the solid-state battery have important practical significance in solving the problems that the rate capability of the existing solid-state battery is poor and the existing solid-state battery is unstable in air due to the adoption of a lithium metal negative electrode or a sulfide electrolyte and the like.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provide a solid-state battery with a nano protective layer and a method for improving the rate capability and safety of the solid-state battery, which solve the problems that the rate capability of the existing solid-state battery is poor and the existing solid-state battery adopts a lithium metal cathode or a sulfide electrolyte and the like which are unstable in the air.
The technical scheme adopted by the invention for solving the technical problems in the prior art is as follows:
a method for improving the rate capability and the safety of a solid-state battery comprises the following steps: and placing the solid-state battery cell into a chamber of the atomic layer deposition equipment for nano-scale protective layer deposition, wherein the solid-state battery cell comprises a porous current collector.
The invention can also adopt the following technical scheme:
in the method for improving the rate capability and the safety of the solid-state battery, further, the method for improving the rate capability and the safety of the solid-state battery comprises the following steps:
the method comprises the following steps: preparing a positive electrode: mixing the positive active material, the conductive agent, the binder and the solvent, performing ball milling or stirring to obtain positive slurry, coating the positive slurry on a porous positive current collector, and drying to obtain the electrode.
Step two: preparing solid electrolyte slurry: mixing a polymer electrolyte precursor, an inorganic solid electrolyte material, a lithium salt and a solvent, and performing ball milling or stirring to obtain solid electrolyte slurry;
step three: treating the positive electrode by using solid electrolyte slurry: spraying or coating the solid electrolyte slurry obtained in the step two on the surface of the anode electrode obtained in the step two, and then drying to obtain a solid battery anode electrode;
step four: preparation of a solid electrolyte membrane: independently forming a film by the solid electrolyte slurry obtained in the step two through coating and drying processes or forming a film by taking a porous material as a support;
step five: assembling the battery: stacking and assembling the solid-state battery anode electrode obtained in the step three with the solid electrolyte membrane and the metal lithium cathode obtained in the step four in sequence, and obtaining a solid-state battery cell through cold isostatic pressing or hot pressing;
step six: atomic layer deposition treatment: placing the solid-state battery cell obtained in the fifth step into a cavity of atomic layer deposition equipment, and introducing a gas precursor pulse into the cavity for reaction so as to deposit a nano protective layer in the pores and the surfaces of the solid-state battery;
step seven: packaging the solid-state battery: welding the current collector of the solid battery cell and the lug together after the atomic layer deposition treatment, and carrying out vacuum packaging by adopting an aluminum plastic film.
In the method for improving the rate capability and the safety of the solid-state battery, further, the method for improving the rate capability and the safety of the solid-state battery comprises the following steps:
the method comprises the following steps: preparing a composite positive electrode: mixing a positive electrode active material, a conductive agent, a binder, an electrolyte precursor polymer, an inorganic solid electrolyte material, a lithium salt and a solvent, performing ball milling or stirring to obtain a composite positive electrode slurry, coating the positive electrode slurry on a porous positive electrode current collector, and drying to obtain a composite positive electrode;
step two: preparation of a solid electrolyte membrane: mixing a polymer electrolyte precursor, a solid electrolyte material, a lithium salt and a solvent, and performing ball milling or stirring to obtain solid electrolyte slurry, wherein the solid electrolyte slurry is independently formed into a film through the processes of coating and drying or is supported by a porous material to form a film;
step three: preparing a composite negative electrode: mixing a negative electrode active material, a conductive agent, a binder, a polymer electrolyte precursor, an inorganic solid electrolyte material, a lithium salt and a solvent, performing ball milling or stirring to obtain a composite negative electrode slurry, coating the negative electrode slurry on a porous negative electrode current collector, and drying to obtain a composite negative electrode;
step four: assembling the battery: stacking and assembling the composite positive electrode obtained in the step one, the solid electrolyte membrane obtained in the step two and the composite negative electrode obtained in the step three in sequence, and obtaining a solid battery cell through cold isostatic pressing or hot pressing;
step five: atomic layer deposition treatment: placing the solid-state battery cell obtained in the step four into a cavity of atomic layer deposition equipment, and introducing a gas precursor pulse into the cavity for reaction so as to deposit a nano protective layer in the pores and the surfaces of the solid-state battery;
step six: packaging the solid-state battery: welding the current collector of the solid battery cell obtained in the step five after the atomic layer deposition treatment with the lug together, and performing vacuum packaging by adopting an aluminum plastic film.
In the method for improving the rate capability and safety of the solid-state battery, further, the positive active material includes, but is not limited to, layered LiCoO2、LiNiO2、LiNixCo1-xO2、LiFexMn1-xPO4(0≤x≤1)、LiNi1/3Mn1/ 3Co1/3O2、LiNi0.8Mn0.1Co0.1O2、LiNi0.6Mn0.2Co0.2O2And LiNi0.5Mn0.2Co0.3O2、LiNi0.85Co0.1Al0.05O2、LiMn2O4、LiNi0.5Mn1.5O4、CrxOyOne or more of the above;
the polymer electrolyte precursor comprises but is not limited to one or more of polyethylene oxide (PEO), polyethylene glycol (PEG), Polyacrylonitrile (PAN), Polymethacrylate (PMMA) and polypropylene carbonate (PPC);
the inorganic solid electrolyte material includes, but is not limited to, perovskite (Li)3xLa(2/3)-xTiO3Where x is 0.01. ltoreq. x.ltoreq.0.33), garnet type (Li)5La3Nb2O12、Li5La3Ta2O12、Li6.4La3Zr1.4Ta0.6O12) NASICON type (Li)1.3Ti1.7Al0.3(PO4)3、Li1+xAlxGe2-x(PO4)3Wherein x is more than or equal to 0 and less than or equal to 0.65), thio-LISICON type (Li)4-xGe1- xPxS4Where x is 0-1, Li7P2S8I、Li2S-P2S5) And anti-perovskite type Li3One or more of OCl;
the conductive agent comprises one or more of Super p, acetylene black, vapor-grown carbon fiber VGCF, carbon nanotube CNTs and graphene;
the binder comprises but is not limited to one or more of polyvinylidene fluoride PVDF, polyvinylidene fluoride-hexafluoropropylene PVDF-HFP, polytetrafluoroethylene PTFE, cyano rubber NBR and sodium carboxymethylcellulose CMC;
the lithium salt includes, but is not limited to, lithium hexafluorophosphate LiPF6Lithium hexafluoroarsenate LiAsF6Lithium bis (trifluoromethanesulfonylimide) LiTFSI, lithium bis (fluorosulfonylimide) LiFSI, lithium bis (oxalato) borate LiBOB, lithium difluoro (oxalato) borate LiDFOB and lithium perchlorate LiClO4One or more of them.
The solvent comprises one or more of acetone, acetonitrile, tetrahydrofuran THF, N-methylpyrrolidone NMP, N-dimethylformamide DMF, dimethyl carbonate DMC and dimethyl sulfoxide DMSO.
In the method for improving rate capability and safety of solid-state battery, further, the nano protective layer includes, but is not limited to, aluminum oxide Al2O3Silicon dioxide SiO2Lithium phosphate Li3PO4And one or more of LiPON, wherein the deposition thickness of the nano protective layer is 2-100 nm.
In the method for improving the rate capability and safety of the solid-state battery, further, the porous positive electrode current collector includes, but is not limited to, one of a punched aluminum foil, an aluminum wire mesh, and a foamed aluminum.
In the method for improving the rate capability and safety of the solid-state battery, further, the porous negative current collector includes, but is not limited to, one of a punched copper foil, a copper wire mesh, a foamed copper, a punched nickel foil, a nickel wire mesh, and a foamed nickel;
the negative active material includes but is not limited to one or more of metallic lithium, metallic lithium alloy, graphite, soft carbon, hard carbon, nano silicon, porous silicon, silicon/carbon composite, sulfur and lithium titanate.
A solid-state battery is manufactured by the method for improving the rate capability and safety of the solid-state battery.
In conclusion, the invention has the following advantages and positive effects:
1. according to the invention, the solid-state battery cell is placed in the atomic layer deposition equipment cavity and comprises the porous current collector, so that the nano protective layer is constructed on all open pores and surfaces of the solid-state battery cell, the interface contact resistance is reduced, the multiplying power performance of the solid-state battery is improved, the reaction of a battery material and oxygen or water is inhibited, and the safety of the solid-state battery is further improved.
2. According to the invention, the punched metal foil or the metal wire mesh or the foam metal is used as a current collector of the solid-state battery, the solid-state battery cell is assembled, and the atomic layer deposition equipment is used for depositing the solid-state battery cell. The protective layer can strengthen the contact between the electrolyte inside and the electrode layer and between the electrolyte and the electrode material, thereby reducing the interface contact resistance and improving the rate performance of the solid-state battery.
Drawings
Fig. 1 is a schematic diagram of a solid-state battery cell structure according to embodiments 1 and 4.
Fig. 2 is a schematic diagram of a solid-state battery cell structure according to embodiments 2 and 3.
Fig. 3 is a graph comparing the electrical properties of the cells treated by the present invention and the untreated cells described in example 1 after the encapsulation test.
Fig. 4 is a graph comparing the rate performance of the battery cell treated by the method of the present invention and the battery cell not treated in example 2 after the packaging test.
Fig. 5 is a graph comparing the electrical properties of the cells treated by the present invention and the untreated cells described in example 3 after the encapsulation test.
Fig. 6 is a graph comparing the electrical properties of the cells treated by the present invention and the untreated cells described in example 4 after the packaging test.
Detailed Description
The present invention will be described in detail with reference to fig. 1 to 6.
Handle electrode material or electrode sheet among the prior art, the battery equipment is accomplished the inside hole that still has of back electrode sheet and electrolyte, consequently still has the great problem of interface impedance, and this patent is deposited at the electric core aspect, can fill inside hole, reduces interparticle and interface resistance. In addition, the safety of the battery cell is not improved by a plurality of patents, and the protective layer can inhibit the reaction of a battery material (especially, metal lithium and sulfide electrolyte, wherein the metal lithium can react with water in the air to release hydrogen, and the sulfide electrolyte can react with the water to release hydrogen sulfide gas) and water vapor after the battery package is damaged, so that the safety is improved.
In order to further understand the contents, features and effects of the present invention, the following embodiments are illustrated and described in detail with reference to the accompanying drawings:
example 1
a) 1.7g LiFePO were weighed40.2g of SP and 0.1g of PVDF, and adding 20ml of NMP solvent after mixing, and stirring for 3 hours to obtain electrode slurry;
b) coating the slurry obtained in the step a) on a 10-micron thick aluminum wire mesh by using a 200-micron scraper, drying at 100 ℃, and then performing vacuum drying at 110 ℃ for 6 hours to obtain a positive electrode;
c) mixing and dissolving 0.55g of PEO, 0.45g of LiTFSI and 0.4g of LLZTO in 10ml of acetonitrile, coating 0.5ml of solution on the positive electrode obtained in the step b), drying at 50 ℃ for 12h to obtain a composite positive electrode, and cutting the electrode into phi 16mm wafers serving as composite positive electrode wafers;
d) putting 5ml of the solution prepared in the step c) into a mold with the diameter of 20mm, and drying the solution for 24 hours at the temperature of 50 ℃ to obtain a solid electrolyte sheet;
e) sequentially attaching the composite positive pole piece obtained in the step c) to the solid electrolyte sheet obtained in the step d) and a phi 16mm metal lithium sheet, and pressing by an oil press to obtain a solid battery cell;
f) placing the solid battery cell obtained in the step e) into an atomic layer deposition chamber under a dry atmosphere, adopting water and trimethylaluminum as precursors, and depositing Al with the thickness of about 30nm through 100 deposition cycles2O3A layer, obtaining a processed solid-state battery cell;
g) and (3) packaging the processed solid-state battery cell obtained in the step f) by using a button cell sealing machine, and then testing under the conditions of constant temperature of 60 ℃, voltage range of 2.5-4.0V and current density of 10 mA/g.
h) The untreated solid-state battery cell obtained in the steps a) to e) of the present embodiment is packaged by a button cell sealing machine, and then tested under the conditions of constant temperature of 60 ℃, voltage range of 2.5-4.0V, and current density of 10mA/g, which is compared with g).
Example 2
a) 1.6g of LiNi was weighed0.85Co0.1Al0.05O20.2g of SP, 0.05g of PVDF, 0.05g of PPC and 0.025g of LiFSI, adding 10ml of THF solvent after mixing, and stirring for 6 hours at 50 ℃ to obtain composite anode slurry;
b) coating the composite anode slurry obtained in the step a) on 15 mu m foamed aluminum by adopting a 0.15mm scraper, drying at 60 ℃, then carrying out vacuum drying at 80 ℃ for 10h to obtain a composite anode electrode, and cutting the electrode into a phi 16mm wafer serving as a composite anode pole piece;
c) weighing 0.1g of PPC, 0.5g of LiFSI and 0.15g of LAGP powder, mixing, adding 6ml of DMC solvent, stirring for 6h at 60 ℃, taking 1ml of DMC solvent, placing in a mold with the diameter of 20mm, and drying for 24h at 60 ℃ to obtain a solid electrolyte sheet;
d) weighing 1.6g of graphite, 0.2g of acetylene black, 0.05g of PVDF, 0.05g of PPC and 0.025g of LiFSI, mixing, adding 10ml of THF solvent, and stirring at 50 ℃ for 6 hours to obtain composite cathode slurry;
e) coating the composite negative electrode slurry obtained in the step d) on a 10-micron copper wire mesh by adopting a 0.1mm scraper, drying at 60 ℃, then carrying out vacuum drying at 80 ℃ for 10 hours to obtain a composite negative electrode, and cutting the electrode into a phi 16mm wafer serving as a composite negative electrode piece;
f) sequentially attaching the solid electrolyte sheet obtained in the step c) and the composite negative electrode sheet obtained in the step e) to the composite positive electrode sheet obtained in the step b), and pressing by using an oil press to obtain a solid battery cell;
g) placing the solid battery cell obtained in the step f) into an atomic layer deposition chamber under a dry atmosphere, and depositing Li with the thickness of about 2nm by using water, bis (trimethylsilyl) amido lithium LiHMDS and trimethyl phosphate as precursors through 20 deposition cycles3PO4A layer, obtaining a processed solid-state battery cell;
h) and g) packaging the processed solid-state battery cell by using a button cell sealing machine, and then testing under the conditions of constant temperature of 25 ℃, voltage range of 2.5-4.2V and current density of 20 mA/g.
i) Obtaining an untreated solid-state battery cell in the steps a) to f) of the embodiment, packaging the untreated solid-state battery cell by using a button cell sealing machine, and then sequentially testing the untreated solid-state battery cell for ten weeks at constant temperature of 25 ℃ and voltage of 2.5-4.2V by multiplying power of 0.1C, 0.2C, 0.5C, 1C and 0.1C in a charging and discharging cycle manner, and comparing the result with h).
Example 3
a) 1.6g of LiNi was weighed0.5Mn0.2Co0.3O20.2g of SP, 0.05g of PVDF, 0.05g of NBR and 0.05g of LiFSI, adding 10ml of THF solvent after mixing, and stirring for 6 hours at 50 ℃ to obtain composite anode slurry;
b) coating the composite anode slurry obtained in the step a) on a 13-micron punched aluminum foil by adopting a 0.15mm scraper, drying at 60 ℃, then carrying out vacuum drying at 80 ℃ for 10 hours to obtain a composite anode electrode, and cutting the electrode into a phi 16mm wafer serving as a composite anode pole piece;
c) weighing 1.6g of graphite, 0.2g of VGCF, 0.05g of PVDF, 0.05g of NBR and 0.05g of LiFSI, mixing, adding 10ml of DMF solvent, and stirring at 50 ℃ for 6 hours to obtain composite cathode slurry;
d) coating the composite negative electrode slurry obtained in the step c) on a 10-micron copper wire mesh by adopting a 0.1mm scraper, drying at 60 ℃, then carrying out vacuum drying at 80 ℃ for 10 hours to obtain a composite negative electrode, and cutting the electrode into a phi 16mm wafer serving as a composite negative electrode piece;
e) sequentially attaching the composite positive pole piece obtained in the step b) to an LLZO solid electrolyte sheet with the diameter phi of 20mm and the thickness of 0.2mm and the composite negative pole piece obtained in the step d), and pressing by an oil press to obtain a solid battery cell;
f) placing the solid battery cell obtained in the step e) into an atomic layer deposition chamber under a dry atmosphere, and depositing Li with the thickness of about 30nm by 300 deposition cycles by using water, bis (trimethylsilyl) amido lithium LiHMDS and trimethyl phosphate as precursors3PO4A layer, obtaining a processed solid-state battery cell;
g) and (3) packaging the processed solid-state battery cell obtained in the step f) by using a button cell sealing machine, and then testing under the conditions of constant temperature of 25 ℃, voltage range of 2.5-4.2V and current density of 20 mA/g.
h) Obtaining an untreated solid-state battery cell by the steps a) to e) in the embodiment, packaging the untreated solid-state battery cell by using a button cell sealing machine, and then testing the untreated solid-state battery cell under the conditions of constant temperature of 25 ℃, voltage range of 2.5-4.2V and current density of 20mA/g, and comparing the untreated solid-state battery cell with the battery cell g).
Example 4
a) 0.07g LiCoO was weighed out2、0.005g SP、0.025g Li7P3S11Mixing and grinding to obtain composite anode powder, putting a stainless steel wire mesh with the diameter of phi 10mm and the thickness of 15 mu m into a grinding tool with the diameter of phi 10mm, adding the composite anode powder, and pressing the mixture in an oil press at the pressure of 300MPa to obtain a composite anode piece;
b) placing 0.1g Li on the composite positive electrode sheet obtained in a)7P3S11A solid electrolyte, pressed at 300MPa pressure in an oil press;
c) putting a lithium indium alloy sheet with the diameter of 10mm into the solid electrolyte side obtained in the step b), and pressing by an oil press under the pressure of 300MPa to obtain a solid battery cell;
d) placing the solid battery cell obtained in the step c) into an atomic layer deposition chamber under a dry atmosphere, adopting water and trimethylaluminum as precursors, and depositing Al with the thickness of about 100nm through 333 deposition cycles2O3A layer, obtaining a processed solid-state battery cell;
e) packaging the processed solid-state battery cell obtained in the step d) by using a button cell sealing machine, and then testing under the conditions of constant temperature of 25 ℃, voltage range of 2-3.8V and current density of 10 mA/g.
f) Obtaining an untreated solid-state battery cell by the steps a) to c) of the embodiment, packaging the untreated solid-state battery cell by a button cell sealing machine, and then testing the untreated solid-state battery cell under the conditions of constant temperature of 25 ℃, voltage range of 2-3.8V and current density of 10mA/g, comparing with the step e).
In summary, the present invention provides a solid-state battery with a nano-protective layer and a method for improving the rate capability and safety of the solid-state battery, which solve the problems of poor rate capability of the current solid-state battery and instability of the lithium metal cathode or sulfide electrolyte in the air.
The present invention has been described in detail with reference to the above examples, but the description is only for the preferred examples of the present invention and should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (8)
1. A method for improving the rate capability and safety of a solid-state battery is characterized in that: the method for improving the rate capability and the safety of the solid-state battery comprises the following steps: and placing the solid-state battery cell into a chamber of the atomic layer deposition equipment for nano-scale protective layer deposition, wherein the solid-state battery cell comprises a porous current collector.
2. The method for improving the rate capability and safety of the solid-state battery according to claim 1, wherein: the method for improving the rate capability and the safety of the solid-state battery comprises the following steps:
the method comprises the following steps: preparing a positive electrode: mixing the positive active material, the conductive agent, the binder and the solvent, performing ball milling or stirring to obtain positive slurry, coating the positive slurry on a porous positive current collector, and drying to obtain the electrode.
Step two: preparing solid electrolyte slurry: mixing a polymer electrolyte precursor, an inorganic solid electrolyte material, a lithium salt and a solvent, and performing ball milling or stirring to obtain solid electrolyte slurry;
step three: treating the positive electrode by using solid electrolyte slurry: spraying or coating the solid electrolyte slurry obtained in the step two on the surface of the anode electrode obtained in the step two, and then drying to obtain a solid battery anode electrode;
step four: preparation of a solid electrolyte membrane: independently forming a film by the solid electrolyte slurry obtained in the step two through coating and drying processes or forming a film by taking a porous material as a support;
step five: assembling the battery: stacking and assembling the solid-state battery anode electrode obtained in the step three with the solid electrolyte membrane and the metal lithium cathode obtained in the step four in sequence, and obtaining a solid-state battery cell through cold isostatic pressing or hot pressing;
step six: atomic layer deposition treatment: placing the solid-state battery cell obtained in the fifth step into a cavity of atomic layer deposition equipment, and introducing a gas precursor pulse into the cavity for reaction so as to deposit a nano protective layer in the pores and the surfaces of the solid-state battery;
step seven: packaging the solid-state battery: welding the current collector of the solid battery cell and the lug together after the atomic layer deposition treatment, and carrying out vacuum packaging by adopting an aluminum plastic film.
3. The method for improving the rate capability and safety of the solid-state battery according to claim 1, wherein: the method for improving the rate capability and the safety of the solid-state battery comprises the following steps:
the method comprises the following steps: preparing a composite positive electrode: mixing a positive electrode active material, a conductive agent, a binder, an electrolyte precursor polymer, an inorganic solid electrolyte material, a lithium salt and a solvent, performing ball milling or stirring to obtain a composite positive electrode slurry, coating the positive electrode slurry on a porous positive electrode current collector, and drying to obtain a composite positive electrode;
step two: preparation of a solid electrolyte membrane: mixing a polymer electrolyte precursor, a solid electrolyte material, a lithium salt and a solvent, and performing ball milling or stirring to obtain solid electrolyte slurry, wherein the solid electrolyte slurry is independently formed into a film through the processes of coating and drying or is supported by a porous material to form a film;
step three: preparing a composite negative electrode: mixing a negative electrode active material, a conductive agent, a binder, a polymer electrolyte precursor, an inorganic solid electrolyte material, a lithium salt and a solvent, performing ball milling or stirring to obtain a composite negative electrode slurry, coating the negative electrode slurry on a porous negative electrode current collector, and drying to obtain a composite negative electrode;
step four: assembling the battery: stacking and assembling the composite positive electrode obtained in the step one, the solid electrolyte membrane obtained in the step two and the composite negative electrode obtained in the step three in sequence, and obtaining a solid battery cell through cold isostatic pressing or hot pressing;
step five: atomic layer deposition treatment: placing the solid-state battery cell obtained in the step four into a cavity of atomic layer deposition equipment, and introducing a gas precursor pulse into the cavity for reaction so as to deposit a nano protective layer in the pores and the surfaces of the solid-state battery;
step six: packaging the solid-state battery: welding the current collector of the solid battery cell obtained in the step five after the atomic layer deposition treatment with the lug together, and performing vacuum packaging by adopting an aluminum plastic film.
4. The method for improving the rate capability and safety of the solid-state battery according to claim 2 or 3, wherein: the positive active material includes, but is not limited to, layered LiCoO2、LiNiO2、LiNixCo1-xO2、LiFexMn1-xPO4(0≤x≤1)、LiNi1/3Mn1/3Co1/3O2、LiNi0.8Mn0.1Co0.1O2、LiNi0.6Mn0.2Co0.2O2And LiNi0.5Mn0.2Co0.3O2、LiNi0.85Co0.1Al0.05O2、LiMn2O4、LiNi0.5Mn1.5O4、CrxOyOne or more of the above;
the polymer electrolyte precursor comprises but is not limited to one or more of polyethylene oxide (PEO), polyethylene glycol (PEG), Polyacrylonitrile (PAN), Polymethacrylate (PMMA) and polypropylene carbonate (PPC);
the inorganic solid electrolyte material includes, but is not limited to, perovskite (Li)3xLa(2/3)-xTiO3Where x is 0.01. ltoreq. x.ltoreq.0.33), garnet type (Li)5La3Nb2O12、Li5La3Ta2O12、Li6.4La3Zr1.4Ta0.6O12) NASICON type (Li)1.3Ti1.7Al0.3(PO4)3、Li1+xAlxGe2-x(PO4)3Wherein x is more than or equal to 0 and less than or equal to 0.65), thio-LISICON type (Li)4-xGe1- xPxS4Where x is 0-1, Li7P2S8I、Li2S-P2S5) And anti-perovskite type Li3One or more of OCl;
the conductive agent comprises one or more of Super p, acetylene black, vapor-grown carbon fiber VGCF, carbon nanotube CNTs and graphene;
the binder comprises but is not limited to one or more of polyvinylidene fluoride PVDF, polyvinylidene fluoride-hexafluoropropylene PVDF-HFP, polytetrafluoroethylene PTFE, cyano rubber NBR and sodium carboxymethylcellulose CMC;
the lithium salt includes, but is not limited to, lithium hexafluorophosphate LiPF6Lithium hexafluoroarsenate LiAsF6Lithium bis (trifluoromethanesulfonylimide) LiTFSI, lithium bis (fluorosulfonylimide) LiFSI, lithium bis (oxalato) borate LiBOB, lithium difluoro (oxalato) borate LiDFOB and lithium perchlorate LiClO4One or more of them.
The solvent comprises one or more of acetone, acetonitrile, tetrahydrofuran THF, N-methylpyrrolidone NMP, N-dimethylformamide DMF, dimethyl carbonate DMC and dimethyl sulfoxide DMSO.
5. The method for improving the rate capability and safety of the solid-state battery according to claim 2 or 3, wherein: the nano protective layer includes but is not limited to aluminum oxide Al2O3Silicon dioxide SiO2Lithium phosphate Li3PO4And one or more of LiPON, wherein the deposition thickness of the nano protective layer is 2-100 nm.
6. The method for improving the rate capability and safety of the solid-state battery according to claim 2, wherein: the porous positive current collector includes, but is not limited to, one of a punched aluminum foil, an aluminum wire mesh, and foamed aluminum.
7. The method for improving the rate capability and safety of the solid-state battery according to claim 3, wherein: the porous negative current collector comprises but is not limited to one of a punched copper foil, a copper wire mesh, a foamed copper, a punched nickel foil, a nickel wire mesh and a foamed nickel;
the negative active material includes but is not limited to one or more of metallic lithium, metallic lithium alloy, graphite, soft carbon, hard carbon, nano silicon, porous silicon, silicon/carbon composite, sulfur and lithium titanate.
8. A solid-state battery characterized by: the solid-state battery is prepared by the method for improving the rate capability and the safety of the solid-state battery according to claim 2 or 3.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113381065A (en) * | 2021-05-21 | 2021-09-10 | 万向一二三股份公司 | Polymer composite solid electrolyte and preparation method and application thereof |
| CN115233188A (en) * | 2022-07-22 | 2022-10-25 | 南京理工大学 | Piece-level Ni-Al 2 O 3 Preparation method of porous energy material |
| CN116454367A (en) * | 2023-06-13 | 2023-07-18 | 常州欣盛半导体技术股份有限公司 | Solid-state battery and method for producing same |
| WO2023240530A1 (en) * | 2022-06-16 | 2023-12-21 | 宁德时代新能源科技股份有限公司 | Battery component protection method and device, secondary battery, battery module, battery pack, and electric apparatus |
| WO2023240531A1 (en) * | 2022-06-16 | 2023-12-21 | 宁德时代新能源科技股份有限公司 | Protection method and device for secondary battery, secondary battery, battery module, battery pack, and electric device |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244231A (en) * | 2010-05-14 | 2011-11-16 | 中国科学院物理研究所 | Method for cladding surfaces of active material of anode and/or anode and methods manufacturing anode and battery |
| CN103928704A (en) * | 2014-04-14 | 2014-07-16 | 南京安普瑞斯有限公司 | Lithium ion battery and manufacturing method thereof |
| US20150207171A1 (en) * | 2012-08-16 | 2015-07-23 | The Regents Of The University Of California | Thin film electrolyte based 3d micro-batteries |
| CN108539250A (en) * | 2018-03-30 | 2018-09-14 | 武汉艾特米克超能新材料科技有限公司 | A kind of solid lithium battery and preparation method thereof |
| US20180309166A1 (en) * | 2017-04-24 | 2018-10-25 | GM Global Technology Operations LLC | Passivation of sulfide, oxide, and oxysulfide glass electrolyte films for lithium metal batteries |
| CN109494351A (en) * | 2018-11-22 | 2019-03-19 | 罗伯特·博世有限公司 | Solid lithium battery, cathode and their preparation method for solid lithium battery |
| CN109768334A (en) * | 2018-12-25 | 2019-05-17 | 中国电子科技集团公司第十八研究所 | Preparation method of bipolar solid-state lithium secondary battery |
| CN109841817A (en) * | 2019-03-01 | 2019-06-04 | 同济大学 | For the modification lithium base composite negative pole material of solid state battery and its preparation and application |
| CN109980183A (en) * | 2017-12-27 | 2019-07-05 | 中国电子科技集团公司第十八研究所 | Method for improving cycle stability of anode for solid-state battery by atomic layer deposition treatment |
| CN110544762A (en) * | 2018-05-29 | 2019-12-06 | 深圳格林德能源有限公司 | Coating film for inhibiting peripheral expansion of flexible package lithium ion battery cell and preparation method thereof |
| CN111342124A (en) * | 2020-03-09 | 2020-06-26 | 天津中电新能源研究院有限公司 | Cell hot-pressing integrated molding solid-state battery and preparation method thereof |
-
2020
- 2020-11-05 CN CN202011222235.7A patent/CN112490433A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244231A (en) * | 2010-05-14 | 2011-11-16 | 中国科学院物理研究所 | Method for cladding surfaces of active material of anode and/or anode and methods manufacturing anode and battery |
| US20150207171A1 (en) * | 2012-08-16 | 2015-07-23 | The Regents Of The University Of California | Thin film electrolyte based 3d micro-batteries |
| CN103928704A (en) * | 2014-04-14 | 2014-07-16 | 南京安普瑞斯有限公司 | Lithium ion battery and manufacturing method thereof |
| US20180309166A1 (en) * | 2017-04-24 | 2018-10-25 | GM Global Technology Operations LLC | Passivation of sulfide, oxide, and oxysulfide glass electrolyte films for lithium metal batteries |
| CN109980183A (en) * | 2017-12-27 | 2019-07-05 | 中国电子科技集团公司第十八研究所 | Method for improving cycle stability of anode for solid-state battery by atomic layer deposition treatment |
| CN108539250A (en) * | 2018-03-30 | 2018-09-14 | 武汉艾特米克超能新材料科技有限公司 | A kind of solid lithium battery and preparation method thereof |
| CN110544762A (en) * | 2018-05-29 | 2019-12-06 | 深圳格林德能源有限公司 | Coating film for inhibiting peripheral expansion of flexible package lithium ion battery cell and preparation method thereof |
| CN109494351A (en) * | 2018-11-22 | 2019-03-19 | 罗伯特·博世有限公司 | Solid lithium battery, cathode and their preparation method for solid lithium battery |
| CN109768334A (en) * | 2018-12-25 | 2019-05-17 | 中国电子科技集团公司第十八研究所 | Preparation method of bipolar solid-state lithium secondary battery |
| CN109841817A (en) * | 2019-03-01 | 2019-06-04 | 同济大学 | For the modification lithium base composite negative pole material of solid state battery and its preparation and application |
| CN111342124A (en) * | 2020-03-09 | 2020-06-26 | 天津中电新能源研究院有限公司 | Cell hot-pressing integrated molding solid-state battery and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113381065A (en) * | 2021-05-21 | 2021-09-10 | 万向一二三股份公司 | Polymer composite solid electrolyte and preparation method and application thereof |
| WO2023240530A1 (en) * | 2022-06-16 | 2023-12-21 | 宁德时代新能源科技股份有限公司 | Battery component protection method and device, secondary battery, battery module, battery pack, and electric apparatus |
| WO2023240531A1 (en) * | 2022-06-16 | 2023-12-21 | 宁德时代新能源科技股份有限公司 | Protection method and device for secondary battery, secondary battery, battery module, battery pack, and electric device |
| US20240258584A1 (en) * | 2022-06-16 | 2024-08-01 | Contemporary Amperex Technology Co., Limited | Protection method and device for secondary battery, secondary battery, battery module, battery pack, and electric apparatus |
| CN115233188A (en) * | 2022-07-22 | 2022-10-25 | 南京理工大学 | Piece-level Ni-Al 2 O 3 Preparation method of porous energy material |
| CN115233188B (en) * | 2022-07-22 | 2024-05-17 | 南京理工大学 | Sheet grade Ni-Al2O3Preparation method of porous energy material |
| CN116454367A (en) * | 2023-06-13 | 2023-07-18 | 常州欣盛半导体技术股份有限公司 | Solid-state battery and method for producing same |
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