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CN117673458A - In-situ preparation method of solid-state lithium battery with reaction selectivity and all-solid-state battery - Google Patents

In-situ preparation method of solid-state lithium battery with reaction selectivity and all-solid-state battery Download PDF

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CN117673458A
CN117673458A CN202211007574.2A CN202211007574A CN117673458A CN 117673458 A CN117673458 A CN 117673458A CN 202211007574 A CN202211007574 A CN 202211007574A CN 117673458 A CN117673458 A CN 117673458A
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赵金保
张鹏
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
    • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
    • 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
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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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Abstract

The invention discloses an in-situ preparation method of a solid-state lithium battery with reaction selectivity and an all-solid-state battery thereof. The solid electrolyte is prepared by means of initiation and irradiation of an amine catalyst, and polymerization and crosslinking are efficiently and quantitatively completed at room temperature by utilizing a sulfhydryl-alkene click reaction. The method is suitable for preparing solid-state batteries of pure polymer solid-state electrolytes. Under the action of a catalyst or high-energy rays, generated free radicals can be captured by sulfhydryl groups preferentially, and sulfur free radicals generated preferentially attack carbon-carbon double bonds to generate C-S bonds through sulfhydryl-alkene click reaction, so that the preparation of the polymer solid electrolyte with high efficiency and high selectivity is realized. The method can be used for preparing the pure polymer solid-state battery in situ, can be used for carrying out directional structural design on the electrolyte, improves the compatibility of the electrolyte and an interface, optimizes the ion conduction path in the electrolyte and improves the performance of the solid-state lithium battery.

Description

In-situ preparation method of solid-state lithium battery with reaction selectivity and all-solid-state battery
Technical Field
The invention belongs to the technical field of new energy, and particularly relates to preparation of a solid-state lithium battery.
Background
The lithium battery has the advantages of high energy density, high output power, high voltage, small self-discharge, wide working temperature range, no memory effect, environmental friendliness and the like, and is one of the most important energy storage devices, so that the lithium battery is widely applied to the fields of electric vehicles, rail transit, large-scale energy storage, aerospace and the like. However, the traditional liquid lithium ion battery adopts liquid electrolyte, so that potential safety hazards such as easy leakage, easy volatilization, easy combustion and the like exist, side reactions are easy to occur with electrodes in the charge and discharge process, gas production can be decomposed under high voltage, and the capacity of the battery is irreversibly attenuated. Therefore, in order to further improve the energy density of lithium batteries and the safety of lithium batteries, research into solid-state lithium batteries has been attracting attention of researchers of energy storage science.
The solid electrolyte is used as one of the key materials of the solid lithium battery, so that a series of potential safety hazards caused by leakage and volatilization of the liquid electrolyte are avoided, the short circuit of the battery caused by the fact that lithium dendrites pierce through a diaphragm under long circulation can be effectively avoided, and the safety of the battery is improved. In addition, the solid electrolyte has a wider electrochemical window, so that the high-voltage positive electrode material can be applied to the solid battery, and the energy density of the lithium battery is further improved. Therefore, the development of all-solid-state lithium ion batteries is of great importance for the development of all-force-driven lithium ion batteries. The solid electrolyte is largely classified into a polymer solid electrolyte and an inorganic solid electrolyte. Whether polymer solid electrolyte or inorganic solid electrolyte, the problems of low ionic conductivity at room temperature and electrode interface compatibility need to be solved, and the problems are often solved by an in-situ solid state method. However, the free radicals generated by the traditional in-situ solid state mode are random, and the participating reaction is non-selective, so that the in-situ prepared electrolyte has the problem of low structural accuracy.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an in-situ preparation method of a solid-state lithium battery with reaction selectivity and an all-solid-state battery thereof. In order to improve the room temperature ion conductivity, interface compatibility and structural accuracy of the polymer electrolyte, the click reaction is used in the design of the solid electrolyte, the high selectivity of the thiol-ene click reaction is utilized to accurately design the polymer solid electrolyte and construct a continuous interface-bulk ion conduction path, and a preparation method with reaction selectivity and accuracy is provided for the in-situ preparation of the all-solid-state battery.
One of the technical schemes adopted for solving the technical problems is as follows:
an in-situ preparation method of a solid lithium battery with reaction selectivity comprises the following steps:
s1: under the protective atmosphere, grinding and mixing the anode material and the conductive agent uniformly according to a certain proportion, adding a certain amount of binder and solvent and mixing uniformly, and uniformly coating the obtained slurry on an aluminum foil to prepare an anode plate; and grinding and mixing the cathode material and the conductive agent uniformly according to a certain proportion, adding a certain amount of binder and solvent and mixing uniformly, and uniformly coating the obtained slurry on a copper foil to prepare the cathode sheet.
S2: mixing lithium salt, a precursor and a free radical capturing agent containing sulfhydryl groups with a solvent in a protective gas atmosphere to obtain a precursor solution, and pouring the precursor solution into a porous support film;
s3: and in the protective gas atmosphere, drying the solvent of the poured porous support film, assembling the solvent, the positive plate and the negative plate into a soft-package battery, and carrying out in-situ curing on the precursor solution of the assembled soft-package battery by triggering an amine catalyst or ionizing radiation to obtain the all-solid-state secondary battery.
Further, the free radical scavenger containing mercapto group comprises at least one of polyethylene glycol dithiol, dithioglycol, 1, 5-pentanedithiol, 2' - (1, 2-ethylenedioxy) diethyl mercaptan, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (mercaptoacetic acid) or dipentaerythritol hexa (3-mercaptopropionate).
The amine catalyst comprises triethylamine, n-hexylamine and the like. The amine catalyst may be added to the precursor solution.
Further, the radiation dose is 10-200 KGy.
Further, the lithium salt includes lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium difluorosulfimide (LiWSI), lithium difluorooxalato borate (LiDFOB), lithium bisoxalato borate (LiBOB), lithium hexafluorophosphate (LiPF) 6 ) Or lithium perchlorate (LiClO) 4 ) At least one of them.
Further, in the step S2, the lithium salt content is 10-80 wt% of the solvent mass.
Further, the precursor comprises at least one of a polymer or a prepolymer. Preferably, the precursor comprises a polymer, and may further comprise a prepolymer. The polymer comprises at least one of polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), polyethylene oxide (PEO), chlorinated Polyethylene (PEC), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (P (VDF-HFP)); the prepolymer is a monomer containing vinyl and propenyl double bond functional groups or epoxy functional groups, and comprises at least one of acrylic ester, acrylonitrile, polyethylene glycol diacrylate, methoxy acrylic ester, acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, glycidyl methacrylate, allyl alcohol glycidyl ether, ethylene carbonate, vinylene carbonate, propylene carbonate, acrylic acid, styrene, siloxane, acetate, 1,3, 5-triallyl isocyanurate, triallyl cyanurate, pentaerythritol tetraacrylate, pentaerythritol glycidyl ether, isopentyl tetraacrylate, 3, 9-divinyl-2, 4,8, 10-tetraoxaspiro [5.5] undecane and neopentyl glycol dimethacrylate.
Further, the mass ratio of the lithium salt, the polymer, the prepolymer and the free radical trapping agent containing sulfhydryl groups is 10-50: 10 to 150: 50-150: 50-150.
Further, the solvent is water or aprotic organic solvent, including at least one of ethylene carbonate, propylene carbonate, N-methylpyrrolidone, triethylamine, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, acetone, tetrahydrofuran and acetonitrile.
Further, among the solvents used in the precursor solution, saturated ester-based organic solvents such as fluoroethylene carbonate (FEC) may be included.
Further, the positive electrode material includes a layered compound such as LiCoO 2 Ternary materials, olivine compounds, e.g. LiFePO 4 The types and proportions of the added conductive agent and the binder are not limited, and the selection of the conductive agent, the binder and the current collector only meets the normal working requirements of the electrode. Examples of the anode material include graphite anode, silicon carbon anode, lithium metal anode; according to the requirement, a conductive agent and a binder can be added, and the selected conductive agent, binder and current collector only meet the electrode requirements. Specifically, the conductive agent adopted by the positive electrode is, for example, acetylene black, and the mass ratio of the positive electrode material to the conductive agent is, for example, 7-9: 0.5 to 1; the conductive agent used for the negative electrode is, for example, conductive graphite, and the mass ratio of the negative electrode material to the conductive agent is, for example, 7 to 9:0.5 to 1; the binder used for the positive electrode is, for example, polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), SN, or the like, and the binder used for the negative electrode is, for example, CMC-SBR (sodium carboxymethyl cellulose and styrene butadiene rubber), or the like.
The second technical scheme adopted by the invention for solving the technical problems is as follows:
the all-solid-state battery prepared by the in-situ preparation method of the solid-state lithium battery with reaction selectivity.
The equipment, reagents, processes, parameters, etc. according to the present invention are conventional equipment, reagents, processes, parameters, etc. unless otherwise specified, and are not exemplified.
All ranges recited herein are inclusive of all point values within the range.
In the present invention, the "room temperature" is a conventional ambient temperature, and may be 10 to 30 ℃.
Compared with the background technology, the technical proposal has the following advantages:
the invention provides an in-situ preparation method of a solid lithium battery with reaction selectivity and an all-solid lithium battery thereof, wherein a solid electrolyte is prepared by means of initiation and irradiation of an amine catalyst, and polymerization and crosslinking are efficiently and quantitatively completed at room temperature by utilizing a sulfhydryl-alkene click reaction. The method is suitable for preparing solid-state batteries of pure polymer solid-state electrolytes. Under the action of a catalyst or high-energy rays, generated free radicals can be captured by sulfhydryl groups preferentially, and sulfur free radicals generated preferentially attack carbon-carbon double bonds to generate C-S bonds through sulfhydryl-alkene click reaction, so that the preparation of the polymer solid electrolyte with high efficiency and high selectivity is realized. The click reaction is used in the design of the solid electrolyte, the polymer solid electrolyte is accurately designed, a continuous interface-bulk ion conduction path is constructed, the compatibility of the electrolyte and the interface is improved, the ion conduction path in the electrolyte is optimized, the performance of the solid lithium battery is improved, and the preparation method with reaction selectivity and accuracy is provided for the in-situ preparation of the all-solid-state battery.
Drawings
FIG. 1 is an infrared spectrum of an electrolyte of a battery of example 1 of the present invention before and after irradiation curing; wherein: the upper curve represents before curing and the lower curve represents after curing. The disappearance of the stretching vibration peak of the thiol and carbon-carbon double bond can be seen in combination with fig. 1, indicating complete curing.
Fig. 2 is an SEM image of each part of the batteries of example 1 and comparative example 1 of the present invention; wherein: (a) is a cross-sectional SEM image of the solid electrolyte of the battery of example 1 after radiation curing, (b) is a cross-sectional SEM image of the precursor and the porous cellulose film of comparative example 1 without radiation curing, and (c) is a cross-sectional SEM image of the porous cellulose film of example 1 before curing. It can be seen in connection with fig. 2 that full cure can only be achieved by radiation curing.
Fig. 3 is a plot of the first turn voltage versus capacity for a solid state lithium battery after radiation curing according to example 1 of the present invention. It can be seen in conjunction with fig. 3 that the battery employing example 1 can function properly.
FIG. 4 is an optical comparison of the electrolyte after irradiation curing and ultraviolet curing of example 1 and comparative example 3 of the present invention, respectively; wherein: after irradiation (left), after ultraviolet irradiation (right).
Detailed Description
The invention is further described below with reference to the drawings and examples.
The specific technical scheme of the embodiment of the invention is as follows:
s1: under the protective atmosphere, grinding and mixing the anode material and the conductive agent uniformly according to a certain proportion, adding a certain amount of binder and solvent and mixing uniformly, and uniformly coating the obtained slurry on an aluminum foil to prepare an anode plate; and grinding and mixing the cathode material and the conductive agent uniformly according to a certain proportion, adding a certain amount of binder and solvent and mixing uniformly, and uniformly coating the obtained slurry on a copper foil to prepare the cathode sheet.
S2: mixing lithium salt, a precursor and a free radical capturing agent containing sulfhydryl groups with a solvent in a protective gas atmosphere to obtain a precursor solution, and pouring the precursor solution into a porous support film;
s3: and in the protective gas atmosphere, drying the solvent of the poured porous support film, assembling the solvent, the positive plate and the negative plate into a soft-package battery, and carrying out in-situ curing on the precursor solution of the assembled soft-package battery by triggering an amine catalyst or ionizing radiation to obtain the all-solid-state secondary battery.
The lithium salt content is 10-80 wt% of the solvent.
The radiation dose is 10-200 KGy.
Example 1
(1) Preparing a positive plate and a negative plate: liNi is added to 0.8 Co 0.1 Mn 0.1 O 2 The positive electrode material and acetylene black (conductive agent) are ground and mixed uniformly according to a certain proportion (mass ratio of 7-9:0.5-1), PEO (binder) accounting for 10wt% and solvent N-methyl pyrrolidone are added and stirred uniformly, and the obtained slurry is coated on an aluminum foil uniformly to prepare a positive electrode plate; grinding and mixing a silicon-carbon anode material, conductive graphite (conductive agent) and CMC-SBR (binder) according to a certain proportion (mass ratio of 7-9:0.5-1:0.5-1), uniformly stirring with water, and uniformly coating the obtained slurry on a copper foil to prepare the anode sheet.
(2) Preparing a precursor solution: the lithium salt is LiTFSI; the precursor comprises a polymer and a prepolymer, wherein the polymer is prepared from PEO and PVDF according to a mass ratio of 1:1, mixing, wherein the prepolymer is prepared from polyethylene glycol diacrylate, methoxy acrylate and ethylene carbonate according to the mass ratio of 1:2 to 8:1 to 9, mixing; the free radical scavenger containing mercapto group is pentaerythritol tetra (3-mercaptopropionic acid). The lithium salt, the polymer, the prepolymer and the free radical trapping agent containing sulfhydryl are mixed according to the mass ratio of 10-50: 10 to 150: 50-150: and after mixing in the proportion of 50-150, adding acetonitrile, and uniformly mixing to obtain a precursor solution.
(3) And pouring the precursor solution into a porous cellulose film under a protective atmosphere, drying most of the solvent, assembling the precursor solution and the positive and negative plates into a soft package battery, and carrying out in-situ crosslinking and curing on the precursor solution in the soft package under the irradiation dose of high-energy electron beam irradiation of 100KGy to obtain the solid-state lithium battery.
Comparative example 1
The difference between comparative example 1 and example 1 is that: in comparative example 1, no radiation curing was used.
(1) Preparing a positive plate and a negative plate: liNi is added to 0.8 Co 0.1 Mn 0.1 O 2 The positive electrode material and acetylene black (conductive agent) are ground and mixed uniformly according to a certain proportion (mass ratio of 7-9:0.5-1), PEO (binder) accounting for 10wt% and solvent N-methyl pyrrolidone are added and stirred uniformly, and the obtained slurry is coated on an aluminum foil uniformly to prepare a positive electrode plate; grinding and mixing a silicon-carbon anode material, conductive graphite (conductive agent) and CMC-SBR (binder) according to a certain proportion (mass ratio of 7-9:0.5-1:0.5-1), uniformly stirring with water, and uniformly coating the obtained slurry on a copper foil to prepare the anode sheet.
(2) Preparing a precursor solution: the lithium salt is LiTFSI; the precursor comprises a polymer and a prepolymer, wherein the polymer is prepared from PEO and PVDF according to a mass ratio of 1:1, mixing, wherein the prepolymer is prepared from polyethylene glycol diacrylate, methoxy acrylate and ethylene carbonate according to the mass ratio of 1:2 to 8:1 to 9, mixing; the free radical scavenger containing mercapto group is pentaerythritol tetra (3-mercaptopropionic acid). The lithium salt, the polymer, the prepolymer and the free radical trapping agent containing sulfhydryl are mixed according to the proportion of 10 to 50:10 to 150: 50-150: and after mixing in a mass ratio of 50-150, adding acetonitrile, and uniformly mixing to obtain a precursor solution.
(3) And pouring the precursor solution into a porous cellulose film under a protective atmosphere, drying most of the solvent, and assembling the precursor solution and the positive and negative plates into a soft package battery to obtain the solid-state battery.
Example 2
Example 2 differs from example 1 in that: catalyst initiation was used in example 2.
(1) Preparing a positive plate and a negative plate: liNi is added to 0.8 Co 0.1 Mn 0.1 O 2 The positive electrode material and acetylene black (conductive agent) are ground and mixed uniformly according to a certain proportion (mass ratio of 7-9:0.5-1), PEO (binder) accounting for 10wt% and solvent N-methyl pyrrolidone are added and stirred uniformly, and the obtained slurry is coated on an aluminum foil uniformly to prepare a positive electrode plate; grinding and mixing a silicon-carbon anode material, conductive graphite (conductive agent) and CMC-SBR (binder) according to a certain proportion (mass ratio of 7-9:0.5-1:0.5-1), uniformly stirring with water, and uniformly coating the obtained slurry on a copper foil to prepare the anode sheet.
(2) Preparing a precursor solution: the lithium salt is LiTFSI; the precursor comprises a polymer and a prepolymer, wherein the polymer is prepared from PEO and PVDF according to a mass ratio of 1:1, mixing, wherein the prepolymer is prepared from polyethylene glycol diacrylate, methoxy acrylate, ethylene carbonate and triethylamine according to the mass ratio of 1:2 to 8:1 to 9:0.1 mixing; the free radical scavenger containing mercapto group is pentaerythritol tetra (3-mercaptopropionic acid). The lithium salt, the polymer, the prepolymer and the free radical trapping agent containing sulfhydryl are mixed according to the mass ratio of 10-50: 10 to 150: 50-150: and after mixing in the proportion of 50-150, adding acetonitrile, and uniformly mixing to obtain a precursor solution.
(3) And pouring the precursor solution in a porous cellulose film under a protective atmosphere, drying most of the solvent, assembling the precursor solution and the positive and negative plates to form a soft-package battery, standing at 40 ℃ for 12 hours, and enabling the precursor solution to realize in-situ crosslinking and solidification in a die through triethylamine catalysis to obtain the solid-state lithium battery.
Comparative example 2
The difference between comparative example 2 and example 2 is that: the precursor in comparative example 2 contained no polymer and was cured without using a catalyst.
(1) Preparing a positive plate and a negative plate: liNi is added to 0.8 Co 0.1 Mn 0.1 O 2 The positive electrode material and acetylene black (conductive agent) are ground and mixed uniformly according to a certain proportion (mass ratio of 7-9:0.5-1), PEO (binder) accounting for 10wt% and solvent N-methyl pyrrolidone are added and stirred uniformly, and the obtained slurry is coated on an aluminum foil uniformly to prepare a positive electrode plate; grinding and mixing a silicon-carbon anode material, conductive graphite (conductive agent) and CMC-SBR (binder) according to a certain proportion (mass ratio of 7-9:0.5-1:0.5-1), uniformly stirring with water, and uniformly coating the obtained slurry on a copper foil to prepare the anode sheet.
(2) Preparing a precursor solution: the lithium salt is LiTFSI; the precursor comprises a prepolymer, wherein the prepolymer is prepared from polyethylene glycol diacrylate, methoxy acrylate and ethylene carbonate according to the mass ratio of 1:2 to 8:1 to 9, mixing; the free radical scavenger containing mercapto group is pentaerythritol tetra (3-mercaptopropionic acid). The lithium salt, the prepolymer and the free radical trapping agent containing sulfhydryl are mixed according to the mass ratio of 10-50: 50-150: and after mixing in the proportion of 50-150, adding acetonitrile, and uniformly mixing to obtain a precursor solution.
(3) And pouring the precursor solution into a porous cellulose film under a protective atmosphere, drying most of the solvent, and assembling the precursor solution and the positive and negative plates into a soft package battery to obtain the solid-state battery.
Comparative example 3
Comparative example 3 differs from example 1 in that: comparative example 3 employed ultraviolet curing and failed to achieve integration of the positive and negative electrodes with the solid electrolyte.
(1) Preparing a positive plate and a negative plate: liNi is added to 0.8 Co 0.1 Mn 0.1 O 2 The positive electrode material and acetylene black (conductive agent) are ground and mixed uniformly according to a certain proportion (mass ratio of 7-9:0.5-1), PEO (binder) accounting for 10wt% and solvent N-methyl pyrrolidone are added and stirred uniformly, and the obtained slurry is coated on an aluminum foil uniformly to prepare a positive electrode plate; grinding and mixing a silicon-carbon anode material, conductive graphite (conductive agent) and CMC-SBR (binder) uniformly according to a certain proportion (mass ratio of 7-9:0.5-1:0.5-1), stirring uniformly with water, and uniformly coating the obtained slurry on a copper foilAnd (3) preparing the negative plate.
(2) Preparing a precursor solution: the lithium salt is LiTFSI; the precursor comprises a polymer and a prepolymer, wherein the polymer is prepared from PEO and PVDF according to a mass ratio of 1:1, mixing, wherein the prepolymer is prepared from polyethylene glycol diacrylate, methoxy acrylate, ethylene carbonate and triethylamine according to the mass ratio of 1:2 to 8:1 to 9:0.1 mixing; the free radical scavenger containing mercapto group is pentaerythritol tetra (3-mercaptopropionic acid). The lithium salt, the polymer, the prepolymer and the free radical trapping agent containing sulfhydryl are mixed according to the mass ratio of 10-50: 10 to 150: 50-150: and after mixing in the proportion of 50-150, adding acetonitrile, and uniformly mixing to obtain a precursor solution.
(3) And pouring the precursor solution into a porous cellulose film under a protective atmosphere, drying most of the solvent, assembling the precursor solution and the positive and negative plates into a soft package battery, and irradiating the battery under an ultraviolet lamp (with the power of 750W and the irradiation time of 1800 s) to crosslink and solidify the precursor solution, thus assembling the solid battery.
Because the ultraviolet lamp has poor penetrability and can not penetrate through the battery shell or the soft package to realize crosslinking and curing, the crosslinking and curing of the positive (negative) electrode and the single side of the precursor can only be realized, and the integral integration of the battery can not be realized. As shown in fig. 4, the optical diagram of the electrolyte membrane after different curing modes in the soft package: the left side is the irradiated film of example 1, the right side is the ultraviolet light of comparative example 3, and the ultraviolet light curing mode cannot be used for initiating crosslinking curing through the soft package, so that liquid infiltrates into the paper, and the electrolyte film cured by irradiation does not infiltrate.
Example 3
Example 3 differs from example 1 in that: the precursor solution of example 3 contains a certain amount of saturated ester organic solvent FEC, so that the prepared solid electrolyte has better high-voltage oxidation resistance.
(1) Preparing a positive plate and a negative plate: liNi is added to 0.8 Co 0.1 Mn 0.1 O 2 The anode material and acetylene black (conductive agent) are ground and mixed uniformly according to a certain proportion (mass ratio of 7-9:0.5-1),adding PEO (binder) accounting for 10 weight percent and N-methyl pyrrolidone serving as a solvent, uniformly stirring, and uniformly coating the obtained slurry on an aluminum foil to prepare a positive plate; grinding and mixing a silicon-carbon anode material, conductive graphite (conductive agent) and CMC-SBR (binder) according to a certain proportion (mass ratio of 7-9:0.5-1:0.5-1), uniformly stirring with water, and uniformly coating the obtained slurry on a copper foil to prepare the anode sheet.
(2) Preparing a precursor solution: the lithium salt is LiTFSI; the precursor comprises a polymer and a prepolymer, wherein the polymer is prepared from PEO and PVDF according to a mass ratio of 1:1, the prepolymer is prepared by mixing polyethylene glycol diacrylate, methoxy acrylate, ethylene carbonate and FEC (fluoroethylene carbonate) according to the mass ratio of 1:2 to 8:1 to 9:1 to 9, mixing; the free radical scavenger containing mercapto group is pentaerythritol tetra (3-mercaptopropionic acid). The lithium salt, the polymer, the prepolymer and the free radical trapping agent containing sulfhydryl are mixed according to the mass ratio of 10-50: 10 to 150: 50-150: 50-150 to obtain a precursor solution.
(3) And pouring the precursor solution into a porous cellulose film under a protective atmosphere, drying most of the solvent, assembling the precursor solution and the positive and negative plates into a soft package battery, and enabling the precursor solution to be crosslinked and solidified in situ in a die under the irradiation dose of high-energy electron beam irradiation of 100KGy to obtain the solid-state lithium battery.
Example 4
Example 4 differs from example 1 in that: the binder in the positive electrode material of example 4 contains PVDF and SN to improve ion conduction at the internal interface of the positive electrode while avoiding the use of an ester organic solvent.
(1) Preparing a positive plate and a negative plate: liNi is added to 0.8 Co 0.1 Mn 0.1 O 2 The positive electrode material and acetylene black (conductive agent) are ground and mixed uniformly according to a certain proportion (mass ratio is 7-9:0.5-1), PVDF accounting for 5wt%, SN accounting for 5wt% and a certain amount of N-methyl pyrrolidone solvent are added and stirred uniformly, and the obtained slurry is uniformly coated on an aluminum foil to prepare a positive electrode plate; grinding and mixing the silicon-carbon anode material, the conductive graphite (conductive agent) and CMC-SBR (binder) uniformly according to a certain proportion (the mass ratio is 7-9:0.5-1:0.5-1), and mixing withAnd uniformly stirring water, and uniformly coating the obtained slurry on a copper foil to prepare the negative plate.
(2) Preparing a precursor solution: the lithium salt is LiTFSI; the precursor comprises a polymer and a prepolymer, wherein the polymer is prepared from PEO and PVDF according to a mass ratio of 1:1, mixing, wherein the prepolymer is prepared from polyethylene glycol diacrylate, methoxy acrylate and ethylene carbonate according to the mass ratio of 1:2 to 8:1 to 9, mixing; the free radical scavenger containing mercapto group is pentaerythritol tetra (3-mercaptopropionic acid). The lithium salt, the polymer, the prepolymer and the free radical trapping agent containing sulfhydryl are mixed according to the mass ratio of 10-50: 10 to 150: 50-150: and after mixing in the proportion of 50-150, adding acetonitrile, and uniformly mixing to obtain a precursor solution.
(3) And pouring the precursor solution into a porous cellulose film under a protective atmosphere, drying most of the solvent, assembling the precursor solution and the positive and negative plates into a soft package battery, and enabling the precursor solution to be crosslinked and solidified in situ in a die under the irradiation dose of high-energy electron beam irradiation of 100KGy to obtain the solid-state lithium battery.
Example 5
Example 5 differs from example 4 in that: the positive electrode material of example 5 was a lithium manganate positive electrode material.
(1) Preparing a positive plate and a negative plate: grinding and mixing a lithium manganate anode material and acetylene black (conductive agent) uniformly according to a certain proportion (mass ratio of 7-9:0.5-1), adding PVDF accounting for 5wt%, SN accounting for 5wt% and a certain amount of N-methyl pyrrolidone solvent, stirring uniformly, and uniformly coating the obtained slurry on an aluminum foil to prepare an anode plate; grinding and mixing a silicon-carbon anode material, conductive graphite (conductive agent) and CMC-SBR (binder) according to a certain proportion (mass ratio of 7-9:0.5-1:0.5-1), uniformly stirring with water, and uniformly coating the obtained slurry on a copper foil to prepare the anode sheet.
(2) Preparing a precursor solution: the lithium salt is LiTFSI; the precursor comprises a polymer and a prepolymer, wherein the polymer is prepared from PEO and PVDF according to a mass ratio of 1:1, mixing, wherein the prepolymer is prepared from polyethylene glycol diacrylate, methoxy acrylate and ethylene carbonate according to the mass ratio of 1:2 to 8:1 to 9, mixing; the free radical scavenger containing mercapto group is pentaerythritol tetra (3-mercaptopropionic acid). The lithium salt, the polymer, the prepolymer and the free radical trapping agent containing sulfhydryl are mixed according to the mass ratio of 10-50: 10 to 150: 50-150: and after mixing in the proportion of 50-150, adding acetonitrile, and uniformly mixing to obtain a precursor solution.
(3) And pouring the precursor solution into a porous cellulose film under a protective atmosphere, drying most of the solvent, assembling the precursor solution and the positive and negative plates into a soft package battery, and enabling the precursor solution to be crosslinked and solidified in situ in a die under the irradiation dose of high-energy electron beam irradiation of 100KGy to obtain the solid-state lithium battery.
Example 6
Example 6 differs from example 4 in that: the positive electrode material of example 6 was a lithium iron phosphate positive electrode material.
(1) Preparing a positive plate and a negative plate: grinding and mixing a lithium iron phosphate anode material and acetylene black (conductive agent) uniformly according to a certain proportion (mass ratio of 7-9:0.5-1), adding PVDF accounting for 5wt%, SN accounting for 5wt% and a certain amount of N-methylpyrrolidone solvent, stirring uniformly, and uniformly coating the obtained slurry on an aluminum foil to prepare an anode plate; grinding and mixing a silicon-carbon anode material, conductive graphite (conductive agent) and CMC-SBR (binder) according to a certain proportion (mass ratio of 7-9:0.5-1:0.5-1), uniformly stirring with water, and uniformly coating the obtained slurry on a copper foil to prepare the anode sheet.
(2) Preparing a precursor solution: the lithium salt is LiTFSI; the precursor comprises a polymer and a prepolymer, wherein the polymer is prepared from PEO and PVDF according to a mass ratio of 1:1, mixing, wherein the prepolymer is prepared from polyethylene glycol diacrylate, methoxy acrylate and ethylene carbonate according to the mass ratio of 1:2 to 8:1 to 9, mixing; the free radical scavenger containing mercapto group is pentaerythritol tetra (3-mercaptopropionic acid). The lithium salt, the polymer, the prepolymer and the free radical trapping agent containing sulfhydryl are mixed according to the mass ratio of 10-50: 10 to 150: 50-150: and after mixing in the proportion of 50-150, adding acetonitrile, and uniformly mixing to obtain a precursor solution.
(3) And pouring the precursor solution into a porous cellulose film under a protective atmosphere, drying most of the solvent, assembling the precursor solution and the positive and negative plates into a soft package battery, and enabling the precursor solution to be crosslinked and solidified in situ in a die under the irradiation dose of high-energy electron beam irradiation of 100KGy to obtain the solid-state lithium battery.
Example 7
Example 7 differs from example 6 in that: in example 7 the polymer consisted of PEC and PVDF, the prepolymer consisted of polyethylene glycol diacrylate, methoxy acrylate, vinylene carbonate, the free radical scavenger containing mercapto group consisted of pentaerythritol tetrakis (3-mercaptopropionic acid), 2' - (1, 2-ethylenedioxy) bis-ethanethiol.
(1) Preparing a positive plate and a negative plate: grinding and mixing a lithium iron phosphate anode material and acetylene black (conductive agent) uniformly according to a certain proportion (mass ratio of 7-9:0.5-1), adding PVDF accounting for 5wt%, SN accounting for 5wt% and a certain amount of N-methylpyrrolidone solvent, stirring uniformly, and uniformly coating the obtained slurry on an aluminum foil to prepare an anode plate; grinding and mixing a silicon-carbon anode material, conductive graphite (conductive agent) and CMC-SBR (binder) according to a certain proportion (mass ratio of 7-9:0.5-1:0.5-1), uniformly stirring with water, and uniformly coating the obtained slurry on a copper foil to prepare the anode sheet.
(2) Preparing a precursor solution: the lithium salt is LiTFSI; the precursor comprises a polymer and a prepolymer, wherein the polymer is prepared from PEC and PVDF according to a mass ratio of 1:1, mixing, wherein the prepolymer is prepared from polyethylene glycol diacrylate, methoxy acrylate and vinylene carbonate according to the mass ratio of 1-5: 1 to 5:1 to 5, mixing; the free radical trapping agent containing mercapto group is pentaerythritol tetra (3-mercaptopropionic acid) ester and 2,2- (1, 2-ethanediyl dioxy) diethyl mercaptan, and the mass ratio is 1-10: 1 to 3. The lithium salt, the polymer, the prepolymer and the free radical trapping agent containing sulfhydryl are mixed according to the mass ratio of 10-50: 10 to 150: 50-150: and after mixing in the proportion of 50-150, adding acetonitrile, and uniformly mixing to obtain a precursor solution.
(3) And pouring the precursor solution into a porous cellulose film under a protective atmosphere, drying most of the solvent, assembling the precursor solution and the positive and negative plates into a soft package battery, and enabling the precursor solution to be crosslinked and solidified in situ in a die under the irradiation dose of high-energy electron beam irradiation of 100KGy to obtain the solid-state lithium battery.
Table 1 comparative battery cycle capacity retention ratios of inventive example 1 and comparative examples 1 and 2
Table 1 shows the discharge capacity comparisons after 50 cycles at a rate of 0.5C at room temperature for example 1, comparative example 1 and comparative example 2 according to the present invention. As can be seen from the data of table 1, example 1 has better cycle stability and capacity retention, and analysis of example 1 and comparative example 1 shows that the solid-state battery prepared by the radiation curing method has better performance, and radiation curing is indispensable in the art. In addition, the precursor needs to contain a certain amount of polymer to avoid the short circuit of the battery, so that the preparation of a more complete solid-state battery is realized.
The foregoing description is only illustrative of the preferred embodiments of the present invention, and therefore should not be taken as limiting the scope of the invention, for all changes and modifications that come within the meaning and range of equivalency of the claims and specification are therefore intended to be embraced therein.

Claims (10)

1. The in-situ preparation method of the solid lithium battery with reaction selectivity is characterized by comprising the following steps of: comprising the following steps:
s1: uniformly mixing a positive electrode material, a conductive agent, a binder and a solvent, uniformly coating the obtained slurry on an aluminum foil, and preparing a positive electrode plate; uniformly mixing a negative electrode material, a conductive agent, a binder and a solvent, uniformly coating the obtained slurry on a copper foil, and preparing a negative electrode plate;
s2: mixing lithium salt, a precursor and a free radical capturing agent containing sulfhydryl with a solvent to obtain a precursor solution, and pouring the precursor solution into a porous support membrane;
s3: and drying the solvent of the poured porous support film, assembling the porous support film, the positive electrode plate and the negative electrode plate into a soft-package battery, and initiating or ionizing radiation on the assembled soft-package battery through an amine catalyst to enable the precursor solution to be cured in situ, so that the all-solid-state battery is obtained.
2. The method for in-situ preparation of a solid-state battery with reaction selectivity according to claim 1, wherein: the free radical trapping agent containing the mercapto group comprises at least one of polyethylene glycol dithiol, dithioglycol, 1, 5-pentanedithiol, 2' - (1, 2-ethylenedioxy) diethyl mercaptan, trimethylolpropane tri (3-mercaptopropionate), pentaerythritol tetra (mercaptoacetic acid) or dipentaerythritol hexa (3-mercaptopropionate).
3. The method for in-situ preparation of a solid-state battery with reaction selectivity according to claim 1, wherein: the amine catalyst comprises triethylamine or n-hexylamine; the amine catalyst is added to the precursor solution.
4. The method for in-situ preparation of a solid-state battery with reaction selectivity according to claim 1, wherein: the radiation dose is 10-200 KGy.
5. The method for in-situ preparation of a solid-state battery with reaction selectivity according to claim 1, wherein: the lithium salt comprises at least one of lithium bis (trifluoromethylsulfonyl) imide, lithium difluorosulfimide, lithium difluorooxalato borate, lithium bisoxalato borate, lithium hexafluorophosphate or lithium perchlorate.
6. The method for in-situ preparation of a solid-state battery with reaction selectivity according to claim 1, wherein: in the step S2, the content of the lithium salt is 10-80 wt% of the mass of the solvent.
7. The method for in-situ preparation of a solid-state battery with reaction selectivity according to claim 1, wherein: the precursor comprises at least one of a polymer or a prepolymer; the polymer comprises at least one of polymethyl methacrylate, polyacrylonitrile, polyethylene oxide, chlorinated polyethylene, polyvinylidene fluoride or polyvinylidene fluoride-hexafluoropropylene copolymer; the prepolymer comprises at least one of acrylic acid ester, acrylonitrile, polyethylene glycol diacrylate, methoxy acrylic acid ester, acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, glycidyl methacrylate, allyl alcohol glycidyl ether, ethylene carbonate, vinylene carbonate, propylene carbonate, acrylic acid, styrene, siloxane, acetate, 1,3, 5-triallyl isocyanurate, triallyl cyanurate, pentaerythritol tetraacrylate, pentaerythritol glycidyl ether, isopentyl tetraacrylate, 3, 9-divinyl-2, 4,8, 10-tetraoxaspiro [5.5] undecane or neopentyl glycol dimethacrylate.
8. The method for in-situ preparation of a solid-state battery with reaction selectivity according to claim 1, wherein: the solvent comprises at least one of water, ethylene carbonate, propylene carbonate, N-methylpyrrolidone, triethylamine, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, acetone, tetrahydrofuran or acetonitrile.
9. The method for in-situ preparation of a solid-state battery with reaction selectivity according to claim 1, wherein: the positive electrode material comprises a layered compound, a ternary material, an olivine-type compound or a spinel material; the negative electrode material comprises a graphite negative electrode, a silicon carbon negative electrode or a lithium metal negative electrode.
10. An all-solid-state battery prepared by the in-situ preparation method of a solid-state lithium battery having reaction selectivity according to any one of claims 1 to 9.
CN202211007574.2A 2022-08-22 2022-08-22 In-situ preparation method of solid-state lithium battery with reaction selectivity and all-solid-state battery Pending CN117673458A (en)

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