CN110808409A - Polymer lithium secondary battery and in-situ preparation method thereof - Google Patents
Polymer lithium secondary battery and in-situ preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a polymer lithium secondary battery and an in-situ preparation method thereof. The invention replaces the existing heat curing method, can continuously use the plate and the diaphragm used in the preparation of the common liquid electrolyte battery, has the advantages of little change on the equipment and the materials used in the traditional process, convenience, high efficiency, more types of selectable monomers and prepolymers, no introduction of impurities, capability of being carried out at normal temperature and the like, and has good industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of new energy, and particularly relates to a polymer lithium secondary battery and an in-situ preparation method thereof.
Background
Lithium secondary batteries are playing more and more important roles in various fields of energy storage because of their advantages such as high energy density, high output voltage, and good cycle performance. In the current common liquid electrolyte lithium secondary battery, the liquid electrolyte is mainly LiPF6、LiN(SO2C2F5)2The lithium salt is dissolved in a polar aprotic organic solvent (e.g., a mixture of carbonates: ethylene carbonate and dimethyl carbonate, etc.). The liquid electrolyte battery has the defects of easy liquid leakage, easy chemical side reaction with electrodes and the like, so that the safety and the service life of the liquid electrolyte battery are severely restricted, and the use temperature range of the battery is limited within 55 ℃ by the polar organic solvents. In order to avoid these problems of liquid electrolytes in lithium secondary batteries, polymer lithium ion batteries have been produced.
The polymer lithium secondary battery is a lithium secondary battery assembled by replacing a liquid electrolyte with a diaphragm system by a dry polymer electrolyte, and the polymer electrolyte can be in an all-solid form or a liquid-solid binary gel form. But the conductivity of the all-solid polymer electrolyte is too low, so that the gel-state polymer electrolyte has better application prospect.
In the current preparation process of the polymer electrolyte battery, compared with the mode of respectively preparing a positive pole piece, a negative pole piece and a polymer electrolyte, and then assembling and packaging the positive pole piece, the negative pole piece and the polymer electrolyte; the process method for forming the gel polymer electrolyte membrane by pouring the polymer precursor solution into the battery semi-finished product in which the positive and negative electrode assemblies and the porous diaphragm are placed in advance and then directly crosslinking/polymerizing in situ has the advantages of simple process and higher efficiency, can directly use the pole piece and the diaphragm of the conventional lithium ion battery under the condition of not carrying out special modification or change, is more suitable for large-scale production and the like, and has incomparable advantages in industrial production. The in-situ crosslinking/polymerizing gel polymer battery process, which is mainly used at present, places a roll-type or stack-type electrode assembly, which is composed of electrode plates and porous separators, in a pouch, injects a thermally polymerizable polyethylene oxide (PEO) -based monomer or oligomer crosslinking agent and an electrolyte composition thereto, and thermally cures the injected material. However, the common thermal-initiated crosslinking/polymerization method needs to introduce impurities such as an initiator, the crosslinking and polymerization materials are limited, and the high temperature required by the reaction often has adverse effects on battery components such as a positive electrode material, and the practical application of in-situ preparation of the polymer lithium secondary battery is greatly limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a polymer lithium secondary battery and an in-situ preparation method thereof, and solves the problems in the background art.
One of the technical schemes adopted by the invention for solving the technical problems is as follows: the method comprises the steps of pouring precursor solution with irradiation crosslinking or irradiation polymerization property into a packaged battery semi-finished product, and carrying out in-situ crosslinking or polymerization on the precursor solution through ionizing radiation to form a polymer electrolyte membrane to prepare the lithium secondary battery.
In a preferred embodiment of the present invention, the precursor solution is prepared by dissolving a polymer monomer having a radiation crosslinking or radiation polymerization property, a prepolymer and a lithium salt in an aprotic organic solvent.
In a preferred embodiment of the present invention, the method comprises the following steps:
1) mixing a polymer monomer, a prepolymer, a lithium salt and a crosslinking agent in a ratio of 1-9: 1-4: 1-4: dissolving the mixture in an aprotic organic solvent in a mass ratio of 0-1 to prepare a precursor solution;
2) placing the positive and negative pole pieces and the porous insulating film with the welded lugs into a battery packaging film, and connecting the lugs;
3) pouring a precursor solution into the battery packaging film, and packaging the battery;
4) and irradiating the packaged battery with gamma rays or high-energy electron beams, wherein the radiation dose is 0.1-500 KGy, so that in-situ crosslinking or polymerization of the precursor solution is realized, and the lithium secondary battery is prepared.
In a preferred embodiment of the present invention, the polymer monomer is a double bond functional group or epoxy functional group monomer containing vinyl and propenyl groups, and includes at least one of acrylate, acrylonitrile, methoxy acrylate, acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, glycidyl methacrylate, ethylene carbonate, propylene carbonate, ethylene oxide, acrylic acid, styrene, fluoride, phosphazene, siloxane, and acetate.
In a preferred embodiment of the present invention, the prepolymer is a polymer with or without side chains and a main chain with a fatty chain, an ether segment, an ester segment, a siloxane unit, and includes at least one of polyethylene glycol, polyethylene glycol methacrylate, polyvinyl carbonate, polyvinyl alcohol, polyethylene oxide, polycarbonate, polymethacrylic acid, polyacrylonitrile, polyphosphazene, and vinylidene fluoride.
In a preferred embodiment of the present invention, the crosslinking agent is a multifunctional organic substance and a surface-modified nano inorganic powder thereof, and includes polyethylene glycol diacrylate, divinyl benzene, N-Methylene Bisacrylamide (MBA), diisocyanate, tetraethoxysilane, and nano SiO with hydroxyl on the surface2TiO 2 nanoparticles2Nano Al2O3And nano SiO modified by coupling agent surface2TiO 2 nanoparticles2Nano Al2O3。
In a preferred embodiment of the present invention, the lithium salt includes LiTFSI and LiClO4、LiPF6、LiCl、、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、LiBF4Also includes the components capable of generating radiation crosslinking or radiation polymerization,Grafted lithium salts with functional groups, including organic lithium salts that can be radiation crosslinked, such as lithium lower aliphatic carboxylates, and grafted lithium salts of monomers with double bonds that can effect radiation polymerization, such as lithium 2-acrylamido-2-methylpropanesulfonate (AMPSLi), lithium Styrene Trifluoromethanesulfonylimide (STFSILIi).
In a preferred embodiment of the present invention, the aprotic organic solvent includes at least one of Ethylene Carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Propylene Carbonate (PC), Ethyl Methyl Carbonate (EMC), 1, 3-Dioxolane (DOL), dimethyl ether (DME), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), acetone (acetone), Tetrahydrofuran (THF), and Acetonitrile (Acetonitrile).
Examples of the positive electrode material include layered compounds such as LiCoO2Ternary materials, olivine-type compounds such as LiFePO4And spinel materials such as nickel-manganese high-voltage materials, 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 needs to meet the normal working requirements of the electrode.
Examples of the anode material include graphite anodes, silicon carbon anodes, lithium metal anodes. According to the requirement, a conductive agent and a binder can be added, and the selected conductive agent, the binder and the current collector only need to meet the electrode requirement.
The porous insulating film comprises a common PP or PE diaphragm, a porous cellulose film and a non-woven fabric film which is made of stable polymers such as polyimide and the like and has enough mechanical strength. The electronic insulating film is selected to meet the requirements of being capable of separating the positive electrode from the negative electrode, having high porosity and having sufficient mechanical strength and flexibility.
In a preferred embodiment of the present invention, the radiation dose is 10 to 200 KGy.
The second technical scheme adopted by the invention for solving the technical problems is as follows: the polymer lithium secondary battery comprises a polymer lithium ion battery and a polymer lithium battery, and is prepared by adopting the in-situ preparation method of the polymer lithium secondary battery, wherein the polymer electrolyte is in a gel state.
The invention relates to the application of the in-situ preparation process in chemical power systems such as polymer lithium secondary batteries and the like and various polymer batteries prepared by the preparation process.
Compared with the background technology, the technical scheme has the following advantages:
the irradiation method is used for preparing the polymer lithium secondary battery in situ, the plate and the diaphragm used in the preparation of the common liquid electrolyte battery can be continuously used in an in-situ crosslinking/polymerization mode, the change of equipment and materials used in the traditional process is less, the operation is convenient and rapid, the in-situ preparation of the polymer film can be rapidly carried out in large batch, and the method is suitable for large-scale production. Meanwhile, compared with a polymer lithium secondary battery prepared in situ by a thermal curing method, the method can be carried out at normal temperature without introducing impurities such as an initiator, the influence of the rising temperature on the anode and cathode materials is avoided, the cross-linking polymerization of the electrolyte precursor liquid can be uniformly initiated in the battery without the influence of the shape of the battery, and the method is more suitable for industrial production.
Drawings
Fig. 1 is a photograph of a polymer lithium ion battery prepared in example 1.
Fig. 2 is a photograph of a gel-state polymer electrolyte after irradiation in example 1.
Fig. 3 is a voltage-capacity curve of the polymer lithium ion pouch battery prepared in example 1.
Figure 4 is a graph comparing the EIS impedance of the pouch cells of example 1 and comparative example 1.
Detailed Description
The invention is explained in detail below with reference to the drawings and examples:
example 1
Referring to FIGS. 1-2, a polymer lithium secondary battery of the present embodiment uses ternary LiNi0.8Co0.1Mn0.1O2Preparing positive pole piece with positive material as active material, preparing negative pole piece with silicon-carbon negative material as negative active material, welding tabs, using common Polyethylene (PE) diaphragm as porous insulating film to block contact between positive and negative poles, and using polyimide adhesive tape to separate positive and negative pole pieces and diaphragmAnd (4) fixing, reserving a passage for filling the precursor solution to the anode and cathode spacing films, putting the passage into the aluminum plastic film with three sealed sides, and exposing the lugs.
Mixing polyethylene oxide (PEO) with a prepolymer molecular weight of 100000 with a crosslinking agent polyethylene glycol diacrylate (PEGDA) in a ratio of 4: 1, and taking LiClO4As lithium salt, the ratio O/Li of ethoxy chain segment unit and lithium ion in prepolymer and crosslinking agent is 8, dissolving the above substances in ethylene carbonate/dimethyl carbonate (EC/DMC) mixed solvent under inert atmosphere, wherein the mass ratio of ethylene carbonate to dimethyl carbonate in the mixed solvent is 1: 1. and (3) pouring the dissolved precursor solution into the soft package battery, sealing the soft package battery by using a heat sealing machine in the gap between the positive pole piece and the negative pole piece.
And irradiating the packaged soft package battery with gamma rays to obtain an irradiation dose of 100KGy, and performing in-situ crosslinking on the precursor liquid in the soft package battery to obtain the polymer lithium secondary battery of the embodiment.
Comparative example 1
Comparative example 1 differs from example 1 in that:
with ternary LiNi0.8Co0.1Mn0.1O2The anode material is used as an active material to prepare an anode plate, the silicon-carbon cathode material is used as a cathode active material to prepare a cathode plate, and the tabs are respectively welded.
Mixing polyethylene oxide (PEO) with a prepolymer molecular weight of 100000 with a crosslinking agent polyethylene glycol diacrylate (PEGDA) in a ratio of 4: 1, and taking LiClO4As lithium salt, the ratio O/Li of ethoxy chain segment unit and lithium ion in prepolymer and crosslinking agent is 8, dissolving the above substances in ethylene carbonate/dimethyl carbonate (EC/DMC) mixed solvent under inert atmosphere, wherein the mass ratio of ethylene carbonate to dimethyl carbonate in the mixed solvent is 1: 1. and coating the dissolved precursor solution on a common Polyethylene (PE) diaphragm.
And irradiating the Polyethylene (PE) diaphragm attached with the precursor solution by gamma rays with the irradiation dose of 100KGy to enable the precursor solution to be crosslinked in situ.
And (3) using a cross-linked composite polymer electrolyte membrane to separate the contact of the positive electrode and the negative electrode, using a polyimide adhesive tape to fix the positive electrode plate, the negative electrode plate and the polymer electrolyte membrane, and putting the positive electrode plate, the negative electrode plate and the polymer electrolyte membrane into an aluminum plastic film with three sealed sides and exposing the electrode lugs. And sealing the soft package battery by using a heat sealing machine.
Comparative example 2
Comparative example 2 differs from example 1 in that: comparative example 2 was made in situ using a conventional thermal curing process.
With ternary LiNi0.8Co0.1Mn0.1O2Preparing a positive pole piece by taking the positive pole material as an active material, preparing a negative pole piece by taking the silicon-carbon negative pole material as a negative pole active material, respectively welding pole lugs, taking a common Polyethylene (PE) diaphragm as a porous insulating film to prevent the positive pole and the negative pole from contacting, fixing the positive pole piece, the negative pole piece and the diaphragm by using a polyimide adhesive tape, reserving a passage for filling a precursor solution into a positive and negative diaphragm, filling the passage into an aluminum-plastic film with three sealed sides, and exposing the pole lugs.
Mixing polyethylene oxide (PEO) with a prepolymer molecular weight of 100000 with a crosslinking agent polyethylene glycol diacrylate (PEGDA) in a ratio of 4: 1, and taking LiClO4And (2) as lithium salt, the ratio O/Li of ethoxy chain segment units to lithium ions in the prepolymer and the crosslinking agent is 8, the lithium salt, the prepolymer and the crosslinking agent are dissolved in an ethylene carbonate/dimethyl carbonate (EC/DMC) mixed solvent, and the mass ratio of ethylene carbonate to dimethyl carbonate in the mixed solvent is 1: 1. and (3) pouring the dissolved precursor solution into the soft package battery, sealing the soft package battery by using a heat sealing machine in the gap between the positive pole piece and the negative pole piece.
And heating the packaged soft package battery at 70 ℃ for 10 hours to enable the prepolymer to be crosslinked in situ in the soft package battery.
Example 2
Example 2 differs from example 1 in that: preparing a positive pole piece by taking a lithium cobaltate positive pole material as an active material, preparing a negative pole piece by taking a graphite negative pole material as a negative pole active material, respectively welding pole lugs, taking a porous cellulose film as a porous insulating film to prevent the positive pole and the negative pole from contacting, fixing the positive pole and the negative pole pieces and a diaphragm by using a polyimide adhesive tape, reserving a passage for filling a precursor solution into a positive and negative diaphragm, filling the passage into an aluminum plastic film with three sealed sides, and exposing the pole lugs.
Taking polyethylene glycol (PEG) with a molecular weight of 600 and Methyl Methacrylate (MMA) monomers, mixing the polyethylene glycol (PEG) and the Methyl Methacrylate (MMA) monomers in a ratio of 1: 1, taking lithium trifluoromethanesulfonylimide (LiTFSI) as a lithium salt, mixing the lithium salt with polyethylene glycol (PEG600) with the average molecular weight of 600, wherein the mass ratio of Methyl Methacrylate (MMA) monomer is 1: and 4, dissolving the substances in an acetonitrile solvent in an inert atmosphere, pouring the dissolved precursor solution into a soft-package battery, and sealing the aluminum-plastic film in the gap between the positive and negative pole pieces by using a heat sealing machine.
And irradiating the packaged soft package battery with a high-energy electron beam with an irradiation dose of 100KGy to enable the precursor solution to be crosslinked in situ in the soft package battery.
Example 3
Example 3 differs from example 1 in that: preparing a positive pole piece by taking a lithium iron phosphate positive pole material as an active material, taking lithium metal as a negative pole, respectively welding pole lugs, taking a polypropylene (PP) diaphragm as a porous insulating film to prevent the positive pole and the negative pole from contacting, fixing the positive pole, the negative pole and the diaphragm by using a polyimide adhesive tape, reserving a passage for filling a precursor solution into an interval film between the positive pole and the negative pole, filling the passage into an aluminum plastic film with three sealed sides, and exposing the pole lugs.
Taking (polyethylene glycol) PEG with the average molecular weight of 600 as a prepolymer, taking monomer lithium salt styrene lithium trifluoromethanesulfonylimide (STFSILI) with double bonds as lithium salt, enabling the ratio O/Li of an ethoxy chain segment unit and lithium ions in the prepolymer to be 8, and taking a silane coupling agent KH570 as a surface modification nano SiO2The cross-linking agent accounts for 5 percent by mass, and is dissolved in diethyl carbonate (DEC) solvent under inert atmosphere, the dissolved precursor solution is poured into a soft package battery, and the aluminum plastic film is sealed by a heat sealing machine in the gap between a positive pole piece and a negative pole piece.
And irradiating the packaged soft package battery with a high-energy electron beam with an irradiation dose of 150KGy to enable the precursor solution to be crosslinked in situ in the soft package battery.
Example 4
Example 4 differs from example 1 in that: preparing a positive pole piece by taking a lithium manganate positive pole material as an active material, preparing a negative pole piece by taking a lithium metal negative pole material as a negative active material, welding pole lugs respectively, taking a Polyethylene (PE) diaphragm as a porous insulating film to prevent the positive pole and the negative pole from contacting, fixing the positive pole and the negative pole pieces and the diaphragm by using a polyimide tape, reserving a passage for filling a precursor solution into a positive and negative diaphragm, filling the passage into an aluminum-plastic film with three sealed sides, and exposing the pole lugs.
Taking polyethylene glycol methacrylate (PEGMA) and Methyl Methacrylate (MMA) monomers, mixing the following components in a ratio of 1: 1, taking lithium trifluoromethanesulfonylimide (LiTFSI) as a lithium salt, wherein the mass ratio of the lithium salt to a polymerization monomer is 1: and 4, dissolving the substances in an acetone solvent in an inert atmosphere, pouring the dissolved precursor solution into a soft-package battery, and sealing the aluminum plastic film in the gap between the positive and negative pole pieces by using a heat sealing machine.
And irradiating the packaged soft package battery with a high-energy electron beam with an irradiation dose of 75KGy to polymerize the precursor liquid in situ in the soft package battery.
Example 5
Example 5 differs from example 1 in that: with ternary LiNi1/3Co1/3Mn1/3O2Preparing a positive pole piece by taking the positive pole material as an active material, preparing a negative pole piece by taking the silicon-carbon negative pole material as a negative pole active material, welding pole lugs respectively, taking a polypropylene (PP) diaphragm as a porous insulating film to prevent the positive pole and the negative pole from contacting, fixing the positive pole and the negative pole pieces and the diaphragm by using a polyimide adhesive tape, reserving a passage for filling a precursor solution into a positive and negative diaphragm spacing film, filling the passage into an aluminum-plastic film with three sealed sides, and exposing the pole lugs.
Taking polyethylene glycol methacrylate (PEGMA) and 2-acrylamide-2-lithium methyl propane sulfonate (AMPSLi) monomers, mixing the monomers in a ratio of 1: 1, dissolving the substances in N, N-Dimethylformamide (DMF) solvent in an inert atmosphere, pouring the dissolved precursor solution into a soft-package battery, sealing the gap between a positive electrode plate and a negative electrode plate by using a heat sealing machine, and sealing the aluminum-plastic film.
And irradiating the packaged soft package battery with a high-energy electron beam with an irradiation dose of 50KGy to polymerize the precursor liquid in situ in the soft package battery.
Example 6
Example 6 differs from example 1 in that: with ternary LiNi0.6Co0.2Mn0.2O2The positive pole piece and the graphite negative pole material are prepared by taking the positive pole material as an active materialPreparing a negative pole piece for a negative active material, respectively welding pole lugs, taking a cellulose acetate porous film as a porous insulating film to prevent the contact of a positive pole and a negative pole, fixing the positive pole piece, the negative pole piece and a diaphragm by using a polyimide adhesive tape, reserving a passage for filling a precursor solution into a positive-negative electrode diaphragm, filling the passage into an aluminum-plastic film with three sealed sides, and exposing the pole lugs.
Taking polyethylene glycol-600 (PEG-600), polyethylene carbonate (PEC) and lithium Styrene Trifluoromethanesulfonimide (STFSILI) monomers, mixing the following raw materials in a proportion of 1: 1: 1, dissolving the above substances in diethyl carbonate (DEC) in an inert atmosphere, pouring the dissolved precursor solution into a soft-package battery, sealing the gap between a positive electrode plate and a negative electrode plate by using a heat sealing machine, and sealing the aluminum-plastic film.
And irradiating the packaged soft package battery with a high-energy electron beam to obtain an irradiation dose of 100KGy, so that the precursor solution is polymerized in situ in the soft package battery.
Example 7
Example 7 differs from example 1 in that: with ternary LiNi1/3Co1/3Mn1/3O2Preparing a positive pole piece by taking the positive pole material as an active material, preparing a negative pole piece by taking the silicon negative pole material as a negative pole active material, respectively welding pole lugs, taking a polyvinylidene fluoride (PVDF) electrostatic spinning film as a porous insulating film to prevent the positive pole and the negative pole from contacting, fixing the positive pole piece, the negative pole piece and a diaphragm by using a polyimide adhesive tape, reserving a passage for filling a precursor solution into a positive and negative spacing film, filling the passage into an aluminum-plastic film with three sealed sides, and exposing the pole lugs.
Mixing polyethylene oxide (PEO) with a prepolymer molecular weight of 100000 with a cross-linking agent of tetraethoxysilane in a ratio of 9: 1, and taking LiCF3SO3As lithium salt, the ratio O/Li of ethoxy chain segment unit and lithium ion in prepolymer and crosslinking agent is 8, dissolving the above substances in ethylene carbonate/diethyl carbonate (EC/DEC) mixed solvent under inert atmosphere, wherein the mass ratio of ethylene carbonate to diethyl carbonate in the mixed solvent is 1: 1. and (3) pouring the dissolved precursor solution into the soft package battery, sealing the soft package battery by using a heat sealing machine in the gap between the positive pole piece and the negative pole piece.
And irradiating the packaged soft package battery with gamma rays to obtain an irradiation dose of 75KGy, so that the precursor solution is crosslinked in situ in the soft package battery.
Comparison of impedance Properties of batteries
The resistance properties of example 1 and comparative example 1 were measured and the results are shown in FIG. 4.
Second, comparison of the cycle Capacity Retention ratio
The cycle capacity retention of example 1 and comparative example 2 was determined and the results are given in the following table:
TABLE 1 comparison of the cycle capacity retention of example 1 with comparative example 2
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (10)
1. An in-situ preparation method of a polymer lithium secondary battery is characterized in that: and (3) pouring a precursor solution with irradiation crosslinking or irradiation polymerization property into the packaged battery semi-finished product, and carrying out in-situ crosslinking or polymerization on the precursor solution through ionizing radiation to form a polymer electrolyte membrane to prepare the lithium secondary battery.
2. The in-situ preparation method of a polymer lithium secondary battery according to claim 1, wherein: the precursor solution is prepared by dissolving polymer monomers with the property of radiation crosslinking or radiation polymerization, a prepolymer and a lithium salt in an aprotic organic solvent.
3. The in-situ preparation method of a polymer lithium secondary battery according to claim 2, comprising the steps of:
1) mixing a polymer monomer, a prepolymer, a lithium salt and a crosslinking agent in a ratio of 1-9: 1-4: 1-4: dissolving the mixture in an aprotic organic solvent in a mass ratio of 0-1 to prepare a precursor solution;
2) placing the positive and negative pole pieces and the porous insulating film with the welded lugs into a battery packaging film, and connecting the lugs;
3) pouring a precursor solution into the battery packaging film, and packaging the battery;
4) and irradiating the packaged battery with gamma rays or high-energy electron beams, wherein the radiation dose is 0.1-500 KGy, so that in-situ crosslinking or polymerization of the precursor solution is realized, and the lithium secondary battery is prepared.
4. The in-situ preparation method of a polymer lithium secondary battery according to claim 3, wherein: the polymer monomer is a double-bond functional group or epoxy functional group monomer containing vinyl and propenyl, and comprises at least one of acrylate, acrylonitrile, methoxy acrylate, acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, glycidyl methacrylate, ethylene carbonate, propylene carbonate, ethylene oxide, acrylic acid, styrene, fluoride, phosphazene, siloxane and acetate.
5. The in-situ preparation method of a polymer lithium secondary battery according to claim 3, wherein: the prepolymer is a polymer with or without a side chain and a main chain with an aliphatic chain, an ether chain segment, an ester chain segment and a siloxane bond unit, and comprises at least one of polyethylene glycol, polyethylene glycol methacrylate, polyvinyl carbonate, polyvinyl alcohol, polyethylene oxide, polycarbonate, polymethyl methacrylate, polyacrylonitrile, polyphosphazene and vinylidene fluoride.
6. The in-situ preparation method of a polymer lithium secondary battery according to claim 3, wherein: the cross-linking agent is a multifunctional organic matter and surface-modified nano inorganic powder thereof, and comprises polyethylene glycol diacrylate, divinyl benzene, N-methylene bisacrylamide, diisocyanate, tetraethoxysilane and nano SiO containing hydroxyl on the surface2TiO 2 nanoparticles2Nano Al2O3And nano SiO modified by coupling agent surface2TiO 2 nanoparticles2Nano Al2O3。
7. The in-situ preparation method of a polymer lithium secondary battery according to claim 3, wherein: the lithium salt comprises LiTFSI and LiClO4、LiPF6、LiCl、、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、LiBF4、AMPSLi、STFSILi。
8. The in-situ preparation method of a polymer lithium secondary battery according to claim 3, wherein: the aprotic organic solvent comprises at least one of ethylene carbonate, dimethyl carbonate, diethyl carbonate, propylene carbonate, ethyl methyl carbonate, 1, 3-dioxolane, dimethyl ether, N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, acetone, tetrahydrofuran and acetonitrile.
9. The in-situ preparation method of a polymer lithium secondary battery according to claim 3, wherein: the radiation dose is 10-200 KGy.
10. A polymer lithium secondary battery characterized in that: the in-situ preparation method of the polymer lithium secondary battery according to any one of claims 1 to 9.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910875429.8A CN110808409A (en) | 2019-09-17 | 2019-09-17 | Polymer lithium secondary battery and in-situ preparation method thereof |
| PCT/CN2020/115576 WO2021052363A1 (en) | 2019-09-17 | 2020-09-16 | Polymer lithium secondary battery and in-situ preparation method therefor |
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| CN111326789A (en) * | 2020-03-09 | 2020-06-23 | 天津中电新能源研究院有限公司 | Semi-interpenetrating network flame-retardant solid lithium ion electrolyte, solid lithium battery and preparation method |
| CN111934020A (en) * | 2020-07-14 | 2020-11-13 | 华中科技大学 | High-pressure-resistant all-solid-state lithium battery interface layer and in-situ preparation method and application thereof |
| CN112366359A (en) * | 2020-03-03 | 2021-02-12 | 厦门大学 | Production method and application of lithium battery |
| WO2021052363A1 (en) * | 2019-09-17 | 2021-03-25 | 厦门大学 | Polymer lithium secondary battery and in-situ preparation method therefor |
| CN112687948A (en) * | 2020-12-22 | 2021-04-20 | 双登集团股份有限公司 | Solid-state battery with improved interface performance and preparation method thereof |
| CN112838262A (en) * | 2021-01-10 | 2021-05-25 | 中南大学 | Preparation method of polyamide-based gel polymer electrolyte with multi-network structure |
| CN113851707A (en) * | 2021-09-30 | 2021-12-28 | 蜂巢能源科技有限公司 | Gel electrolyte, preparation method thereof and battery |
| CN114156531A (en) * | 2021-10-21 | 2022-03-08 | 东风汽车集团股份有限公司 | Composite solid electrolyte and preparation method thereof |
| CN114335695A (en) * | 2021-12-24 | 2022-04-12 | 上海工程技术大学 | In-situ generated silicon dioxide composite solid polymer electrolyte and application thereof in lithium battery |
| CN114530627A (en) * | 2020-11-06 | 2022-05-24 | 纳米及先进材料研发院有限公司 | Secondary lithium ion battery comprising in-situ thermosetting solid composite electrolyte |
| CN114614097A (en) * | 2022-02-28 | 2022-06-10 | 合肥国轩高科动力能源有限公司 | Electrolyte for ternary cathode material lithium ion battery and manufacturing method of lithium ion battery |
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