CN114583257A - Gel electrolyte precursor solution, integrated gel solid-state lithium battery and preparation method thereof - Google Patents
Gel electrolyte precursor solution, integrated gel solid-state lithium battery and preparation method thereof Download PDFInfo
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- 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
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Abstract
The invention provides a gel electrolyte precursor solution, an integrated gel solid-state lithium battery and a preparation method thereof, and belongs to the technical field of solid-state batteries. The invention eliminates high impedance caused by insufficient contact among components in the solid-state battery by a mode of forming the solid electrolyte by in-situ gel, and greatly improves the energy utilization rate, the coulombic efficiency and the cycle life of the solid-state battery. In addition, the invention completely avoids the solvent volatilization step in the production of the common polymer electrolyte process, the solvent utilization rate is 100 percent, and the production cost and the complexity are reduced. In addition, the integrated battery element can be used as an independent integrated battery cell unit for subsequent stacking and assembling, and the assembling efficiency of the solid-state battery can be greatly improved. The integrated structure forming process is compatible with the large-scale preparation process and production equipment of the conventional liquid battery, and provides great convenience for commercialization of the gel solid lithium battery.
Description
Technical Field
The invention relates to the technical field of solid-state batteries, in particular to a gel electrolyte precursor solution, an integrated gel solid-state lithium battery and a preparation method thereof.
Background
Lithium ion batteries have been used in various portable electronic devices, electric vehicles, and energy storage grids for renewable energy sources such as wind energy and solar energy as the most widely used energy storage technology at present. As the market demands higher and higher for high specific energy lithium battery products, the safety performance and cycle performance of the battery face greater challenges. At present, organic electrolyte is used in commercial lithium ion batteries, and the batteries can generate a large amount of heat under the abnormal conditions of impact, overcharge, internal short circuit and the like, so that the thermal runaway of the batteries is caused. The solid-state battery has the advantages that the inherent safety property of the solid-state battery is the hot direction in the battery research field, the solid-state electrolyte has excellent electrochemical stability, flame retardant property and higher mechanical strength, and the safety performance of the battery can be ensured while high specific energy is considered.
Nevertheless, solid-state lithium batteries also have some of the more common problems, such as: the conductivity of the solid electrolyte at room temperature is insufficient, the interface wettability among electrode material particles is poor, the stability of a multilayer structure of the battery is poor, and the rate performance, the capacity exertion and the endurance time of the battery are influenced. In addition, the polymer electrolyte has the problem of high-temperature volatilization of organic solvents in the preparation process, and the preparation of the inorganic electrolyte inevitably needs a high-temperature calcination process, and the processes all need energy consumption, thereby greatly increasing the production and manufacturing cost of the solid-state battery.
Disclosure of Invention
The invention aims to provide a gel electrolyte precursor solution, an integrated gel solid-state lithium battery and a preparation method thereof, which realize the effect of simultaneously finishing the molding of a solid electrolyte and the integrated assembly of the solid-state battery, have compatible preparation process with the existing liquid-state battery production system, greatly simplify the preparation process of the solid electrolyte, and improve the energy utilization rate, the coulombic efficiency and the cycle life of the solid-state battery.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a gel electrolyte precursor solution, which comprises a lithium ion electrolytic solution and 1, 3-dioxolane; the volume ratio of the lithium ion electrolytic solution to the 1, 3-dioxolane is (0.5-2): (0.2 to 1.5);
the lithium ion electrolytic solution comprises lithium hexafluorophosphate and a carbonate electrolyte; the concentration of lithium hexafluorophosphate in the lithium ion electrolytic solution is 0.1-2.5 mol/L.
Preferably, the carbonate electrolyte is one or more of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate.
Preferably, when the carbonate electrolytes are a plurality of kinds of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate, the volumes of the carbonate electrolytes are equal.
The invention provides a preparation method of an integrated gel solid-state lithium battery, which comprises the following steps: and injecting the gel electrolyte precursor solution into the space among the lithium battery positive plate, the polymer porous membrane electrolyte frame and the negative plate, and carrying out in-situ gelation to obtain the integrated gel solid-state battery.
Preferably, the polymer porous membrane electrolyte frame comprises polypropylene, a polyethylene microporous membrane, a polystyrene micro-nano fiber membrane, a polyacrylonitrile micro-nano fiber membrane, a polybenzimidazole micro-nano fiber membrane, a polyetherimide micro-nano fiber membrane, a polyethylene terephthalate micro-nano fiber membrane, a polyvinylidene fluoride micro-nano fiber membrane, a poly (vinylidene fluoride-co-hexafluoropropylene) micro-nano fiber membrane, a polycaprolactone micro-nano fiber membrane, a polylactic acid micro-nano fiber membrane, a polyvinyl acetate micro-nano fiber membrane, a natural cellulose micro-nano fiber membrane, a chitin micro-nano fiber membrane or a chitosan micro-nano fiber membrane.
Preferably, the reaction temperature of the in-situ gel is 15-45 ℃ and the reaction time is 0.5-48 h.
Preferably, the positive plate includes lithium cobaltate, lithium manganate, lithium iron phosphate or lithium nickel cobalt manganese.
Preferably, the negative electrode sheet comprises a graphite negative electrode sheet, a silicon-carbon negative electrode sheet or a lithium negative electrode sheet.
Preferably, the injection is performed under argon protection conditions.
The invention provides an integrated gel solid-state lithium battery prepared by the preparation method in the scheme.
The invention provides a precursor solution of a gel electrolyte, which comprises a lithium ion electrolytic solution and 1, 3-dioxolane; the volume ratio of the lithium ion electrolytic solution to the 1, 3-dioxolane is (0.5-2): (0.2 to 1.5); the lithium ion electrolytic solution comprises lithium hexafluorophosphate and carbonate electrolyte; the concentration of lithium hexafluorophosphate in the lithium ion electrolytic solution is 1 mol/L. The precursor solution of the gel electrolyte provided by the invention can form gel at normal temperature, and can be used as the electrolyte of a solid lithium battery.
The invention provides a preparation method of an integrated gel solid-state lithium battery, which comprises the following steps: and injecting the gel electrolyte precursor solution into the space among the lithium battery positive plate, the polymer porous membrane electrolyte frame and the negative plate, and carrying out in-situ gelation to form the integrated gel solid-state battery. The invention eliminates high impedance caused by insufficient contact among components in the solid-state battery by a mode of forming the solid electrolyte by in-situ gel, and greatly improves the energy utilization rate, the coulombic efficiency and the cycle life of the solid-state battery.
In addition, the invention completely avoids the solvent volatilization step in the production of the common polymer electrolyte process, the solvent utilization rate is 100 percent, and the production cost and the complexity are reduced.
In addition, the integrated battery element can be used as an independent integrated battery cell unit for subsequent stacking and assembling, and the assembling efficiency of the solid-state battery can be greatly improved.
The integrated structure forming process is compatible with the large-scale preparation process and production equipment of the conventional liquid battery, and provides great convenience for commercialization of the gel solid lithium battery.
Drawings
FIG. 1 is a schematic structural diagram of an integrated gel solid-state lithium battery provided by the present invention;
fig. 2 is a graph of the charge-discharge cycle tested for the battery prepared in example 2;
fig. 3 is a graph of the charge and discharge cycles tested for the battery prepared in example 3.
Detailed Description
The invention provides a precursor solution of a gel electrolyte, which comprises a lithium ion electrolytic solution and 1, 3-dioxolane; the volume ratio of the lithium ion electrolytic solution to the 1, 3-dioxolane is (0.5-2): (0.2 to 1.5);
the lithium ion electrolytic solution comprises lithium hexafluorophosphate and a carbonate electrolyte; the concentration of lithium hexafluorophosphate in the lithium ion electrolytic solution is 0.1-2.5 mol/L, preferably 0.5-2 mol/L, and more preferably 1 mol/L.
In the present invention, the starting materials used are all commercially available products well known in the art, unless otherwise specified.
In the invention, the volume ratio of the lithium ion electrolytic solution to the 1, 3-dioxolane is preferably (0.5-2): 1, more preferably (1 to 1.5): 1. in the present invention, the 1, 3-dioxolane is preferably anhydrous grade 1, 3-dioxolane having a purity of 99.9% or more. In the present invention, the 1, 3-dioxolane functions as a monomer for forming a polymer electrolyte; the lithium hexafluorophosphate has the functions of providing free-swimming lithium ions and serving as an initiator of polymerization reaction; the carbonate electrolyte has the function of improving the ion conductivity of the gel solid electrolyte.
In the present invention, the carbonate electrolyte is preferably one or more of ethylene carbonate, dimethyl carbonate, and ethyl methyl carbonate. In the present invention, when the carbonate electrolyte is a plurality of kinds of ethylene carbonate, dimethyl carbonate, and ethyl methyl carbonate, the volumes of the respective carbonate electrolytes are preferably equal. In the embodiment of the present invention, the carbonate electrolyte specifically includes: the volume ratio is 1: 1 Ethylene Carbonate (EC)/dimethyl carbonate (DMC) in a volume ratio of 1: 1: 1 Ethylene Carbonate (EC)/dimethyl carbonate (DMC)/Ethyl Methyl Carbonate (EMC) or a volume ratio of 1: 1 Ethylene Carbonate (EC)/diethyl carbonate (DEC).
The precursor solution of the gel electrolyte provided by the invention can form gel through spontaneous ring-opening polymerization reaction at normal temperature, and is used as the electrolyte of a solid lithium battery.
The preparation method of the electrolyte precursor solution has no special requirements, and lithium hexafluorophosphate can be directly dissolved in the carbonate electrolyte and the 1, 3-dioxolane.
The invention provides a preparation method of an integrated gel solid-state lithium battery, which comprises the following steps: and injecting the gel electrolyte precursor solution into the space among the lithium battery positive plate, the polymer porous membrane electrolyte frame and the negative plate, and carrying out in-situ gelation to form the integrated gel solid-state battery.
The invention has no special requirements on the specific types of the positive plate, the negative plate and the polymer porous membrane electrolyte framework, and the positive plate, the negative plate and the polymer porous membrane electrolyte framework which are well known in the field can be commercialized.
In the invention, the polymer porous membrane electrolyte frame can be specifically polypropylene, polyethylene microporous membrane, polystyrene micro-nano fiber membrane, polyacrylonitrile micro-nano fiber membrane, polybenzimidazole micro-nano fiber membrane, polyetherimide micro-nano fiber membrane, polyethylene terephthalate micro-nano fiber membrane, polyvinylidene fluoride micro-nano fiber membrane, poly (vinylidene fluoride-co-hexafluoropropylene) micro-nano fiber membrane, polycaprolactone micro-nano fiber membrane, polylactic acid micro-nano fiber membrane, polyvinyl acetate micro-nano fiber membrane, natural cellulose micro-nano fiber membrane, chitin micro-nano fiber membrane or chitosan micro-nano fiber membrane; the positive plate can be lithium cobaltate, lithium manganate, lithium iron phosphate or lithium nickel cobalt manganese; the negative electrode sheet can be a graphite negative electrode sheet, a silicon-carbon negative electrode sheet or a lithium negative electrode sheet.
The invention has no special requirement on the injection time of the gel electrolyte precursor solution, and the appropriate injection time can be selected according to the type of the battery. In the invention, when the integrated gel solid-state lithium battery is a button solid-state battery, the invention preferably places the positive plate in the positive shell of the battery, then covers the polymer porous membrane electrolyte frame, injects the gel electrolyte precursor solution into the positive plate and the polymer porous membrane electrolyte frame, then covers the negative plate, stands for 1h to ensure that the gel electrolyte precursor solution fully permeates into the pores of the electrode particles, and then assembles the button battery according to the conventional sequence. When the integrated gel solid-state lithium battery is a film-shaped soft package battery, the invention preferably fixes a positive electrode tab and a negative electrode tab on a positive plate and a negative plate respectively by welding, and the positive plate, the polymer porous membrane electrolyte frame and the negative plate are laminated in turn and are arranged in an aluminum-plastic film with sealed sides; and injecting the gel electrolyte precursor solution into the stacked battery under the argon atmosphere, and standing for 1h to fully soak the gel electrolyte precursor solution.
In the present invention, the injection is performed under argon protection conditions. The invention has no special requirement on the injection amount of the gel electrolyte precursor solution, and can ensure that the positive plate, the polymer porous membrane electrolyte frame and the negative plate are fully soaked.
In the invention, the reaction temperature of the in-situ gel is preferably 15-45 ℃, and more preferably 20-40 ℃; the time of the in-situ gel reaction is preferably 0.5 to 48 hours, more preferably 2 to 30 hours, and further preferably 5 to 20 hours. The invention eliminates high impedance caused by insufficient contact among components in the solid-state battery by a mode of forming the solid electrolyte by in-situ gel, and greatly improves the energy utilization rate, the coulombic efficiency and the cycle life of the solid-state battery.
The invention provides an integrated gel solid-state lithium battery prepared by the preparation method in the scheme. As shown in fig. 1, the integrated gel solid-state lithium battery provided by the invention comprises a negative electrode, a positive electrode and a gel electrolyte filled between the negative electrode and the positive electrode; the gel electrolyte encapsulates a porous electrolyte framework. In the present invention, the type of the integrated gel solid state lithium battery preferably includes a button type solid state battery or a film type pouch battery.
The gel electrolyte precursor solution, the integrated gel solid state lithium battery and the method for manufacturing the same according to the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
This example is a button solid state battery, assembled using a battery model CR2025, using a battery assembly comprising: 16.2mm by 1.0mm steel sheet, 15.4mm by 1.1mm spring piece, the following steps were all performed under argon atmosphere.
(1) Lithium hexafluorophosphate (LiPF)6) Dissolving in a solvent with the volume ratio of 1: 1 Ethylene Carbonate (EC)/dimethyl carbonate (DMC), to obtain a lithium ion battery electrolyte in which lithium hexafluorophosphate (LiPF) is present6) The concentration of (A) is 1 mol/L; mixing the lithium ion battery electrolyte with a 1,3 Dioxolane (DOL) solvent, wherein the volume ratio of the two is 1: 1, stirring for 10 minutes to obtain a uniform gel electrolyte precursor solution;
(2) placing a lithium cobaltate positive plate with the diameter of 11mm cut in advance into a battery positive shell, and then covering a poly (vinylidene fluoride-co-hexafluoropropylene) micro-nano fiber membrane with the diameter of 20mm cut in advance;
(3) injecting 60 mu L of gel electrolyte precursor solution into the positive electrode and the poly (vinylidene fluoride-b-hexafluoropropylene) film, and then covering a graphite negative electrode sheet with the diameter of 13.5 mm; standing for 1h to ensure that the precursor solution of the gel electrolyte fully permeates into pores of the electrode particles;
and placing the steel sheet, the carbon sheet and the negative electrode shell in sequence to assemble the button cell, standing the cell at room temperature for 24 hours, and obtaining the solid-state lithium battery with the integrated structure after the in-situ gel reaction is sufficient.
Example 2
This example is a button solid state battery, assembled using a battery model CR2025, using a battery assembly comprising: 16.2mm by 1.0mm steel sheet, 15.4mm by 1.1mm spring piece, the following steps were all performed under argon atmosphere.
(1) Mixing lithium hexafluorophosphate (LiPF)6) Dissolving in a solvent with the volume ratio of 1: 1: 1 Ethylene Carbonate (EC)/dimethyl carbonate (DMC)/Ethyl Methyl Carbonate (EMC) to obtain a lithium ion battery electrolyte in which lithium hexafluorophosphate (LiPF) is present6) The concentration of (A) is 1 mol/L; mixing the lithium ion battery electrolyte with a 1,3 Dioxolane (DOL) solvent, wherein the volume ratio of the two is 1.25: 1, stirring for 15 minutes to obtain uniform gel electrolyte precursor solutionLiquid;
(2) placing a lithium iron phosphate positive plate which is cut in advance and has the diameter of 11mm into a battery positive shell, and then covering a polyetherimide micro-nano fiber membrane which is cut in advance and has the diameter of 20 mm;
(3) injecting 50 mu L of gel electrolyte precursor solution into the positive electrode and the polyetherimide film, and then covering a lithium negative electrode sheet with the diameter of 13.5 mm; standing for 1h to ensure that the precursor solution of the gel electrolyte fully permeates into pores of the electrode particles;
(4) and placing the steel sheet, the carbon sheet and the negative electrode shell in sequence to assemble the button battery, standing the battery for 36 hours at room temperature, and obtaining the gel solid-state lithium battery with the integrated structure after the in-situ gel reaction is sufficient.
Example 3
This example is a button solid state battery, assembled using a battery model CR2025, using a battery assembly comprising: 16.2mm by 1.0mm steel sheet, 15.4mm by 1.1mm spring piece, the following steps were all performed under argon atmosphere.
(1) Mixing lithium hexafluorophosphate (LiPF)6) Dissolving in a solvent with the volume ratio of 1: 1: 1 Ethylene Carbonate (EC)/dimethyl carbonate (DMC)/Ethyl Methyl Carbonate (EMC) to obtain a lithium ion battery electrolyte in which lithium hexafluorophosphate (LiPF) is present6) The concentration of (A) is 1 mol/L; mixing the lithium ion battery electrolyte with a 1,3 Dioxolane (DOL) solvent, wherein the volume ratio of the two is 1.25: 1, stirring for 15 minutes to obtain a uniform gel electrolyte precursor solution;
(2) placing a lithium iron phosphate positive plate which is cut in advance and has the diameter of 11mm into a battery positive shell, and then covering a PP diaphragm which is cut in advance and has the diameter of 20 mm;
(3) injecting 50 mu L of gel electrolyte precursor solution into the positive electrode and the polyetherimide film, and then covering a graphite negative electrode sheet with the diameter of 13.5 mm; standing for 1h to ensure that the precursor solution of the gel electrolyte fully permeates into pores of the electrode particles;
(4) and placing the steel sheet, the carbon sheet and the negative electrode shell in sequence to assemble the button cell, standing the cell at room temperature for 24 hours, and obtaining the solid-state lithium battery with the integrated structure after the in-situ gel reaction is sufficient.
Example 4
The embodiment is a film-shaped soft package battery, a lithium iron phosphate positive plate and a graphite negative plate are used, a vinylidene fluoride micro-nano fiber membrane is used as a solid electrolyte porous frame, the size of the electrode plate is 6cm × 6cm, and the size of the vinylidene fluoride micro-nano fiber membrane is 6.6cm × 6.6 cm.
(1) Carrying out ultrasonic welding on a positive electrode lug and a negative electrode lug, respectively fixing the positive electrode lug and the negative electrode lug on a cut positive plate and a cut negative plate, sequentially overlapping the positive plate, the vinylidene fluoride micro-nano fiber membrane and the negative electrode plate, and filling the laminated positive plate, the vinylidene fluoride micro-nano fiber membrane and the negative electrode plate into an aluminum-plastic membrane with side sealing;
(2) under an argon atmosphere, lithium hexafluorophosphate (LiPF)6) Dissolving in a solvent with the volume ratio of 1: 1: 1 Ethylene Carbonate (EC)/dimethyl carbonate (DMC)/Ethyl Methyl Carbonate (EMC) to obtain a lithium ion battery electrolyte in which lithium hexafluorophosphate (LiPF) is present6) The concentration of (A) is 1 mol/L; mixing the lithium ion battery electrolyte with a 1,3 Dioxolane (DOL) solvent, wherein the volume ratio of the two is 1.5: 1, stirring for 15 minutes to obtain a uniform gel electrolyte precursor solution;
(3) and under the argon atmosphere, 0.5ml of the gel electrolyte precursor solution is injected into the stacked batteries, and the batteries are kept stand for 1h to fully soak the gel electrolyte precursor solution.
(4) And finally, carrying out vacuum heat final sealing on the battery to finish the packaging of the battery, standing the battery for 36 hours at room temperature, and obtaining the film-shaped solid lithium battery with an integrated structure after the in-situ gel reaction is sufficient.
And (3) performance testing:
the battery prepared in example 2 was subjected to a charge-discharge cycle test at room temperature under 0.2C conditions, and the test results are shown in fig. 2. As can be seen from fig. 2, the initial specific capacity of the solid-state battery is 162mAh/g (the theoretical specific capacity of lithium iron phosphate is 170mAh/g, the capacity exertion rate reaches 95%) at a rate of 0.2C, the discharge specific capacity after 60 cycles of cycling is 160mAh/g, the capacity retention rate is 99%, and the coulombic efficiency is greater than 99.9%, which proves that the integrated gel solid-state lithium battery has excellent electrochemical performance.
The battery prepared in example 3 was subjected to a charge-discharge cycle test at room temperature under 0.5C conditions, and the test results are shown in fig. 3. As can be seen from FIG. 3, the solid-state battery can stably circulate 150 circles under the rate of 0.5C, the specific discharge capacity is kept at 156mAh/g, the capacity is not attenuated, the coulombic efficiency is more than 99.8%, and the solid-state battery has excellent charge and discharge performance and long cycle life.
According to the embodiment, the invention provides the preparation method of the integrated gel solid-state lithium battery, and the high impedance caused by insufficient contact among the components in the solid-state battery is eliminated in an in-situ gel mode, so that the energy utilization rate, the coulomb efficiency and the cycle life of the solid-state battery are greatly improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The gel electrolyte precursor solution is characterized by comprising a lithium ion electrolyte solution and 1, 3-dioxolane; the volume ratio of the lithium ion electrolytic solution to the 1, 3-dioxolane is (0.5-2): (0.2 to 1.5);
the lithium ion electrolytic solution comprises lithium hexafluorophosphate and a carbonate electrolyte; the concentration of lithium hexafluorophosphate in the lithium ion electrolytic solution is 0.1-2.5 mol/L.
2. A gel electrolyte precursor solution according to claim 1, wherein the carbonate-based electrolyte is one or more of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate.
3. A gel electrolyte precursor solution according to claim 1, wherein when the carbonate-based electrolytes are a plurality of ethylene carbonate, dimethyl carbonate, and ethyl methyl carbonate, the volumes of the respective carbonate-based electrolytes are equal.
4. A preparation method of an integrated gel solid-state lithium battery comprises the following steps: injecting the gel electrolyte precursor solution of any one of claims 1 to 3 between a positive plate, a polymer porous membrane electrolyte frame and a negative plate of a lithium battery, and carrying out in-situ gelation to obtain an integrated gel solid-state battery.
5. The preparation method according to claim 4, wherein the polymer porous membrane electrolyte framework comprises polypropylene, polyethylene microporous membrane, polystyrene micro-nanofiber membrane, polyacrylonitrile micro-nanofiber membrane, polybenzimidazole micro-nanofiber membrane, polyetherimide micro-nanofiber membrane, polyethylene terephthalate micro-nanofiber membrane, polyvinylidene fluoride micro-nanofiber membrane, poly (vinylidene fluoride-co-hexafluoropropylene) micro-nanofiber membrane, polycaprolactone micro-nanofiber membrane, polylactic acid micro-nanofiber membrane, polyvinyl acetate micro-nanofiber membrane, natural cellulose micro-nanofiber membrane, chitin micro-nanofiber membrane or chitosan micro-nanofiber membrane.
6. The preparation method of claim 4, wherein the reaction temperature of the in-situ gel is 15-45 ℃ and the reaction time is 0.5-48 h.
7. The production method according to claim 4, wherein the positive electrode sheet includes lithium cobaltate, lithium manganate, lithium iron phosphate, or lithium nickel cobalt manganate.
8. The production method according to claim 4, wherein the negative electrode sheet comprises a graphite negative electrode sheet, a silicon-carbon negative electrode sheet, or a lithium negative electrode sheet.
9. The method of claim 4, wherein the injecting is performed under argon protection conditions.
10. An integrated gel solid state lithium battery prepared by the preparation method of any one of claims 4 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117276686A (en) * | 2023-11-22 | 2023-12-22 | 中自环保科技股份有限公司 | Preparation method of solid-state battery based on cation in-situ polymerization |
| CN117276686B (en) * | 2023-11-22 | 2024-03-01 | 中自环保科技股份有限公司 | Preparation method of solid-state battery based on cation in-situ polymerization |
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