WO2021052363A1 - Polymer lithium secondary battery and in-situ preparation method therefor - Google Patents

Abstract

A polymer lithium secondary battery and an in-situ preparation method therefor. The polymer lithium secondary battery is prepared by initiating cross-linking or polymerization of a precursor liquid by high-energy ionizing irradiation. An existing thermal curing method is replaced with the method. A board and a diaphragm used in preparation of a common liquid electrolyte battery can be continuously used; few changes are made to equipment and materials used in traditional processes; advantages such as convenience and high efficiency, more available monomer and prepolymer types, no impurity introduction, and operability at normal temperature are achieved; a good industrial application prospect is provided.

Description

Polymer lithium secondary battery and in-situ manufacturing method thereof Technical field

The invention belongs to the technical field of new energy, and specifically relates to a polymer lithium secondary battery and an in-situ manufacturing method thereof.

Background technique

Lithium secondary batteries are playing an increasingly important role in various fields of energy storage because of their high energy density, high output voltage, and good cycle performance. In the current common liquid electrolyte lithium secondary batteries, the liquid electrolyte is mainly to _{dissolve LiPF 6} , LiN(SO ₂ C ₂ F ₅ ) ₂ and other lithium salts in a polar aprotic organic solvent (such as a mixture of carbonates) : Ethylene carbonate and dimethyl carbonate, etc.). Due to its shortcomings such as easy leakage and chemical side reactions with electrodes, the safety and service life of liquid electrolyte batteries are severely restricted, and these polar organic solvents limit the battery's operating temperature range to 55°C . In order to avoid these problems with liquid electrolytes in lithium secondary batteries, polymer lithium-ion batteries have emerged.

The polymer lithium secondary battery is a lithium secondary battery assembled by a "dry" polymer electrolyte instead of a liquid electrolyte and a diaphragm system. The polymer electrolyte can be in all solid state or in liquid-solid binary state. Glue form. However, due to the low conductivity of the all-solid polymer electrolyte, the gel-state polymer electrolyte presents a better application prospect.

In the current polymer electrolyte battery preparation process, compared to the method of separately preparing the positive and negative pole pieces and the polymer electrolyte, and then assemble and encapsulate the assembly; in the battery semi-finished product where the positive and negative components and the porous diaphragm are placed in advance The process method of pouring polymer precursor solution inside, and then directly crosslinking/polymerizing in situ to form gel polymer electrolyte membrane has simple process and higher efficiency, and can directly use conventional lithium without special modification or change. The pole pieces and diaphragms of ion batteries are more suitable for large-scale production and other unparalleled advantages in industrial production. In addition, the in-situ crosslinking/polymerization method can better construct the electrode/electrolyte interface layer, which is beneficial to polymer batteries. Obtain excellent electrochemical performance. At present, the main in-situ crosslinking/polymerization gel polymer battery process is to place a jelly-roll type or stacked type electrode assembly composed of electrode plates and porous diaphragms in a bag, and inject heat into it. Polymerized polyethylene oxide (PEO) monomer or oligomer crosslinking agent and electrolyte composition, and thermally cure the injected material. However, ordinary thermally initiated crosslinking/polymerization methods need to introduce impurities such as initiators, and the materials for crosslinking and polymerization are limited. At the same time, the high temperature required for the reaction often has an adverse effect on the battery components such as the cathode material, which greatly limits the in-situ Practical application of preparing polymer lithium secondary battery.

Summary of the invention

The purpose of the present invention is to overcome the shortcomings of the prior art and provide a polymer lithium secondary battery and an in-situ manufacturing method thereof, which solves the above-mentioned problems in the background art.

One of the technical solutions adopted by the present invention to solve its technical problems is to provide an in-situ manufacturing method for polymer lithium secondary batteries, in which a semi-finished product of the battery is filled with radiation cross-linking or radiation polymerization properties. The precursor solution is cross-linked or polymerized in situ by ionizing radiation to form a polymer electrolyte membrane to prepare a lithium secondary battery.

In a preferred embodiment of the present invention, the precursor solution is made by dissolving polymer monomers, prepolymers and lithium salts with radiation crosslinking or radiation polymerization properties in an aprotic organic solvent.

In a preferred embodiment of the present invention, it includes the following steps:

1) The polymer monomer, prepolymer, lithium salt, and crosslinking agent are dissolved in an aprotic organic solvent in a mass ratio of 1-9:1-4:1-4:0-1 to prepare a precursor solution;

2) Place the welded positive and negative pole pieces and porous insulating film into the battery packaging film, and connect the tabs;

3) Pour the precursor solution into the battery packaging film and package the battery;

4) The encapsulated battery is irradiated with gamma rays or high-energy electron beams with a radiation dose of 0.1-500 KGy to achieve in-situ crosslinking or polymerization of the precursor solution to prepare a lithium secondary battery.

In a preferred embodiment of the present invention, the polymer monomer is a double bond functional group or epoxy functional group monomer containing a vinyl group or an acrylic group, including acrylate, acrylonitrile, methoxyacrylate, acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, glycidyl methacrylate, ethylene carbonate, propylene carbonate, ethylene oxide, acrylic acid, styrene, fluoride, phosphazene, siloxane, acetic acid At least one of esters.

In a preferred embodiment of the present invention, the prepolymer is a polymer with or without side chains with aliphatic chains, ether segments, ester segments, and silicon-oxygen bond units in the main chain, Including polyethylene glycol, polyethylene glycol methacrylate, polyvinyl carbonate, polyvinyl alcohol, polyethylene oxide, polycarbonate, polymethacrylic acid, polyacrylonitrile, polyphosphazene, segregation At least one of vinyl fluoride.

In a preferred embodiment of the present invention, the crosslinking agent is a multifunctional organic substance and its surface-modified nano-inorganic powder, including polyethylene glycol diacrylate, divinylbenzene, N,N-methylene bis acrylamide (the MBA), diisocyanates, ethyl orthosilicate, and a surface hydroxyl group-containing nano-SiO _2, nano-TiO ₂ nano-Al ₂ O _3, and the rear coupling surface-modified nano-SiO _2, nano-TiO _2. Nano Al ₂ O ₃ .

In a preferred embodiment of the present invention, the lithium salt includes LiTFSI, LiClO ₄ , LiPF ₆ , LiCl, LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , LiAsF ₆ , LiSbF ₆ , LiAlCl ₄ , CH ₃ SO ₃ Li , LiBF ₄ , also includes lithium salts with functional groups that can undergo radiation crosslinking or radiation polymerization, grafting, including organic lithium salts that can undergo radiation crosslinking, such as lithium lower aliphatic carboxylates, and can achieve radiation crosslinking. According to polymerization, grafted double bond monomer lithium salt such as 2-acrylamide-2-methylpropanesulfonate lithium (AMPSLi), styrene trifluoromethanesulfonimide lithium (STFSILi).

In a preferred embodiment of the present invention, the aprotic organic solvent includes ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), propylene carbonate (PC), methyl ethyl carbonate Ester (EMC), 1,3-dioxolane (DOL), dimethyl ether (DME), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), N,N-dimethyl methyl At least one of amide (DMF), N,N-dimethylacetamide (DMAc), acetone, tetrahydrofuran (THF), and acetonitrile.

Examples of the positive electrode material include layered compounds such as LiCoO ₂ , ternary materials, olivine-type compounds such as LiFePO ₄ , spinel materials such as nickel-manganese high-voltage materials, etc. The types and proportions of conductive agents and binders added are different. However, the selection of conductive agent, binder, and current collector only needs to meet the normal working requirements of the electrode.

Examples of the negative electrode material include graphite negative electrode, silicon carbon negative electrode, and lithium metal negative electrode. According to needs, conductive agents, adhesives, selected conductive agents, adhesives, and current collectors can be added as long as they meet the requirements of the electrode.

The porous insulating film includes ordinary PP or PE membranes, porous cellulose films, and non-woven films made of various materials such as polyimide and other stable polymers with sufficient mechanical strength. Choose an electronic insulating film that can separate the positive and negative electrodes, has high porosity, and has sufficient mechanical strength and flexibility.

In a preferred embodiment of the present invention, the radiation dose is 10-200 KGy.

The second technical solution adopted by the present invention to solve its technical problem is to provide a polymer lithium secondary battery, including a polymer lithium ion battery and a polymer lithium battery, using the principle of the above-mentioned polymer lithium secondary battery. The polymer electrolyte is in a gel state.

The invention relates to the application of the in-situ preparation process in chemical power supply systems such as polymer lithium secondary batteries, and the preparation of various polymer batteries through the preparation process.

Compared with the background technology, this technical solution has the following advantages:

The lithium polymer secondary battery is prepared in situ by the irradiation method, and the in-situ crosslinking/polymerization method can continue to use the plates and diaphragms used in the preparation of ordinary liquid electrolyte batteries, with few changes to traditional process equipment and materials, and easy operation It is fast and can be made in situ quickly in large quantities and is suitable for large-scale production. At the same time, compared to the in-situ polymer lithium secondary battery made by the thermal curing method, it can be carried out at room temperature without introducing impurities such as initiators, avoiding the influence of elevated temperature on the positive and negative materials, and at the same time, it can be Affected by the shape of the battery, the cross-linking polymerization of the electrolyte precursor solution is uniformly initiated inside the battery, which is more suitable for industrial production.

Description of the drawings

Figure 1 is a photograph of the polymer lithium ion battery prepared in Example 1.

FIG. 2 is a photograph of the gel polymer electrolyte after irradiation in Example 1. FIG.

FIG. 3 is a voltage-capacity curve of the polymer lithium ion soft pack battery prepared in Example 1. FIG.

Fig. 4 is a comparison of EIS impedance diagrams of soft-pack batteries of Example 1 and Comparative Example 1.

detailed description

The content of the present invention will be described in detail below with reference to the drawings and embodiments:

Example 1

As shown in Figures 1-2, a polymer lithium secondary battery of this embodiment uses ternary LiNi _0.8 Co _0.1 Mn _0.1 O ₂ as the active material to prepare the positive electrode sheet, and the silicon-carbon negative electrode material is made from the negative electrode active material. For the negative pole piece, weld the tabs separately, use the ordinary polyethylene (PE) diaphragm as a porous insulating film to separate the positive and negative poles from contacting, and fix the positive and negative pole pieces and the diaphragm with polyimide tape, leaving it to the positive and negative The electrode spacer film is filled with the path of the precursor liquid, and the three-sided sealed aluminum plastic film is put into the aluminum plastic film to expose the electrode ears.

Take prepolymer polyethylene oxide (PEO) with a molecular weight of 100,000 and crosslinking agent polyethylene glycol diacrylate (PEGDA) at a mass ratio of 4:1, and take LiClO ₄ as the lithium salt, prepolymer and crosslinking The ratio of the ethoxy segment unit to the lithium ion in the coupling agent is O/Li=8. Under an inert atmosphere, dissolve the above-mentioned substances in a mixed solvent of ethylene carbonate/dimethyl carbonate (EC/DMC), and carbonic acid in the mixed solvent The mass ratio of vinyl ester to dimethyl carbonate is 1:1. Pour the dissolved precursor solution into the soft-pack battery, and seal the soft-pack battery with a heat sealer in the gap between the positive and negative pole pieces.

The packaged soft-pack battery was irradiated with a γ-ray irradiation dose of 100 KGy, so that the precursor was cross-linked in situ inside the soft-pack battery to prepare the polymer lithium secondary battery of this embodiment.

Comparative example 1

The difference between Comparative Example 1 and Example 1 lies in:

The ternary LiNi _0.8 Co _0.1 Mn _0.1 O ₂ positive electrode material is used as the active material to prepare the positive electrode pole piece, and the silicon carbon negative electrode material is used as the negative electrode active material to make the negative electrode pole piece, and the tabs are welded separately.

Take prepolymer polyethylene oxide (PEO) with a molecular weight of 100,000 and crosslinking agent polyethylene glycol diacrylate (PEGDA) at a mass ratio of 4:1, and take LiClO ₄ as the lithium salt, prepolymer and crosslinking The ratio of the ethoxy segment unit to the lithium ion in the coupling agent is O/Li=8. Under an inert atmosphere, dissolve the above substances in a mixed solvent of ethylene carbonate/dimethyl carbonate (EC/DMC), and carbonic acid in the mixed solvent. The mass ratio of vinyl ester to dimethyl carbonate is 1:1. The dissolved precursor liquid is coated on a common polyethylene (PE) membrane.

The polyethylene (PE) membrane attached with the precursor liquid was irradiated with a radiation dose of 100 KGy with gamma rays to cross-link the precursor liquid in situ.

Use the cross-linked composite polymer electrolyte membrane to cut off the contact between the positive and negative electrodes, fix the positive and negative pole pieces and the polymer electrolyte membrane with polyimide tape, and put them into the three-sided sealed aluminum-plastic film and expose it Extremely ear. Seal the soft pack battery with a heat sealer.

Comparative example 2

The difference between Comparative Example 2 and Example 1 is that: Comparative Example 2 is made in situ by a traditional thermal curing method.

The ternary LiNi _0.8 Co _0.1 Mn _0.1 O ₂ positive electrode material is used as the active material to prepare the positive electrode pole piece, and the silicon carbon negative electrode material is used as the negative electrode active material to make the negative electrode pole piece. The porous insulating film cuts off the contact between the positive and negative electrodes, and fix the positive and negative pole pieces and the separator with polyimide tape, leaving a path for pouring the precursor liquid to the positive and negative separators, and put it into a three-sided sealed aluminum plastic The tabs are exposed in the membrane.

Take prepolymer polyethylene oxide (PEO) with a molecular weight of 100,000 and crosslinking agent polyethylene glycol diacrylate (PEGDA) at a mass ratio of 4:1, and take LiClO ₄ as the lithium salt, prepolymer and crosslinking The ratio of the ethoxy segment unit to the lithium ion in the coupling agent is O/Li=8. The above substances are dissolved in a mixed solvent of ethylene carbonate/dimethyl carbonate (EC/DMC). The mass ratio of methyl ester is 1:1. Pour the dissolved precursor solution into the soft-pack battery, and seal the soft-pack battery with a heat sealer in the gap between the positive and negative pole pieces.

The encapsulated soft-pack battery is heated at 70° C. for 10 hours, so that the prepolymer is cross-linked in situ inside the soft-pack battery.

Example 2

The difference between Example 2 and Example 1 is that the anode electrode is made of lithium cobalt oxide cathode material as the active material, and the anode electrode is made of graphite anode material as the anode active material. The tabs are welded separately, and the porous cellulose film is used as the The porous insulating film cuts off the contact between the positive and negative electrodes, and fix the positive and negative pole pieces and the separator with polyimide tape, leaving a path for pouring the precursor liquid to the positive and negative separators, and put it into a three-sided sealed aluminum plastic The tabs are exposed in the membrane.

Take the polyethylene glycol (PEG) with a molecular weight of 600 and mix with methyl methacrylate (MMA) monomers in a mass ratio of 1:1, and take lithium trifluoromethylsulfonimide (LiTFSI) as the lithium salt, lithium salt The mass ratio of the monomers to polyethylene glycol (PEG600) and methyl methacrylate (MMA) with an average molecular weight of 600 is 1:4. Under an inert atmosphere, dissolve the above substances in an acetonitrile solvent. The precursor solution is poured into the soft pack battery, and the aluminum-plastic film is sealed with a heat sealer in the gap between the positive and negative pole pieces.

The encapsulated soft-pack battery is irradiated with a high-energy electron beam with an irradiation dose of 100KGy, so that the precursor liquid is cross-linked in situ inside the soft-pack battery.

Example 3

The difference between Example 3 and Example 1 is that the positive electrode is prepared with lithium iron phosphate as the active material, lithium metal is used as the negative electrode, the tabs are welded separately, and the polypropylene (PP) diaphragm is used as a porous insulating film to separate the positive and negative electrodes. If the electrodes are in contact, fix the positive and negative electrodes and the diaphragm with polyimide tape, leave a path for pouring the precursor solution to the positive and negative electrodes, and put them into the aluminum-plastic film sealed on three sides and expose the lugs.

Take the (polyethylene glycol) PEG with an average molecular weight of 600 as the prepolymer, and take the monomer lithium salt with double bond styrene trifluoromethanesulfonimide lithium (STFSILi) as the lithium salt to make the prepolymer ethoxylate The ratio of the segment unit to the lithium ion is O/Li=8, and the silane coupling agent KH570 surface-modified nano-SiO ₂ is used as the cross-linking agent. The mass fraction of the cross-linking agent is 5%. Under an inert atmosphere, the above The substance is dissolved in diethyl carbonate (DEC) solvent, and the dissolved precursor solution is poured into the soft pack battery. The gap between the positive and negative pole pieces is sealed with a heat sealer to seal the aluminum-plastic film.

The packaged soft-pack battery is irradiated with a high-energy electron beam with an irradiation dose of 150KGy, so that the precursor liquid is cross-linked in situ inside the soft-pack battery.

Example 4

The difference between Example 4 and Example 1 lies in the fact that lithium manganate cathode material is used as the active material to prepare positive pole pieces, and the lithium metal negative electrode material is used as the negative active material to make negative pole pieces. The tabs are welded separately, and the polyethylene (PE) ) The diaphragm is used as a porous insulating film to separate the positive and negative electrodes from contact, and the positive and negative pole pieces and the diaphragm are fixed with polyimide tape, leaving a path for pouring the precursor solution to the positive and negative electrode spacers, and then sealing them on three sides. The lugs are exposed in the aluminum plastic film.

Take polyethylene glycol methacrylate (PEGMA) and methyl methacrylate (MMA) monomers and mix at a mass ratio of 1:1, and take lithium trifluoromethanesulfonimide (LiTFSI) as the lithium salt. The mass ratio to polymerized monomer is 1:4. Under an inert atmosphere, dissolve the above-mentioned substances in acetone solvent, and pour the dissolved precursor into the pouch battery. The gap between the positive and negative pole pieces is used. The heat sealer seals the aluminum plastic film.

The packaged soft-pack battery is irradiated with a high-energy electron beam with an irradiation dose of 75KGy, so that the precursor solution is polymerized in-situ inside the soft-pack battery.

Example 5

The difference between Example 5 and Example 1 is that the ternary LiNi _1/3 Co _1/3 Mn _1/3 O ₂ positive electrode material is used as the active material to prepare the positive electrode sheet, and the silicon carbon negative electrode material is used as the negative electrode active material to make the negative electrode. Weld the tabs separately, use the polypropylene (PP) separator as a porous insulating film to separate the positive and negative poles from contact, and fix the positive and negative poles and the separator with polyimide tape, leaving the separator film facing the positive and negative poles. Fill the path of the precursor liquid at the place, put it into the aluminum plastic film sealed on three sides and expose the tabs.

Take polyethylene glycol methacrylate (PEGMA) and 2-acrylamide-2-methyl propane sulfonate lithium (AMPSLi) monomer and mix in a mass ratio of 1:1, and dissolve the above substances in an inert atmosphere Pour the dissolved precursor solution into the soft pack battery in N,N-dimethylformamide (DMF) solvent, and seal the aluminum-plastic film in the gap between the positive and negative pole pieces with a heat sealer.

The packaged soft-pack battery is irradiated with a high-energy electron beam with an irradiation dose of 50KGy, so that the precursor solution is polymerized in-situ inside the soft-pack battery.

Example 6

The difference between Example 6 and Example 1 is that the ternary LiNi _0.6 Co _0.2 Mn _0.2 O ₂ positive electrode material is used as the active material to prepare the positive pole piece, and the graphite negative electrode material is the negative electrode active material to make the negative pole piece, and the tabs are welded separately. , Use the cellulose acetate porous film as a porous insulating film to separate the positive and negative electrodes from contact, fix the positive and negative pole pieces and the separator with polyimide tape, leaving a path for pouring the precursor liquid to the positive and negative separators. It is put into the aluminum plastic film sealed on three sides and the tabs are exposed.

Take polyethylene glycol-600 (PEG-600), polyvinyl carbonate (PEC), and styrene trifluoromethanesulfonimide lithium (STFSILi) monomers at a mass ratio of 1:1:1 and mix them in an inert atmosphere Next, dissolve the above-mentioned substances in diethyl carbonate (DEC), pour the dissolved precursor solution into the soft pack battery, and seal the aluminum-plastic film in the gap between the positive and negative pole pieces with a heat sealer.

The packaged soft-pack battery is irradiated with a high-energy electron beam with an irradiation dose of 100KGy, so that the precursor solution is polymerized in-situ inside the soft-pack battery.

Example 7

The difference between Example 7 and Example 1 is that the ternary LiNi _1/3 Co _1/3 Mn _1/3 O ₂ positive electrode material is used as the active material to prepare the positive pole piece, and the silicon negative electrode material is used as the negative electrode active material to make the negative pole piece. , Weld the tabs separately, use the PVDF electrospun membrane as a porous insulating film to separate the positive and negative poles from contact, and fix the positive and negative pole pieces and the diaphragm with polyimide tape, leaving it out to the positive The negative spacer film is filled with the precursor fluid channel, and it is put into the aluminum plastic film sealed on three sides and the tabs are exposed.

Take prepolymer polyethylene oxide (PEO) with a molecular weight of 100,000 and mix with crosslinking agent ethyl orthosilicate in a mass ratio of 9:1, take LiCF ₃ SO ₃ as the lithium salt, prepolymer and crosslinking agent The ratio of the ethoxy segment unit to the lithium ion is O/Li=8. Under an inert atmosphere, the above substances are dissolved in a mixed solvent of ethylene carbonate/diethyl carbonate (EC/DEC), and the mixed solvent contains ethylene carbonate, The mass ratio of diethyl carbonate is 1:1. Pour the dissolved precursor solution into the soft-pack battery, and seal the soft-pack battery with a heat sealer in the gap between the positive and negative pole pieces.

The packaged soft-pack battery is irradiated with a radiation dose of 75KGy with gamma rays, so that the precursor solution is cross-linked in situ inside the soft-pack battery.

1. Battery impedance performance comparison

The impedance performance of Example 1 and Comparative Example 1 were measured, and the results are shown in FIG. 4.

2. Comparison of cyclic capacity retention rate

The cycle capacity retention rates of Example 1 and Comparative Example 2 were measured, and the results are as follows:

Table 1 Comparison of the cycle capacity retention rate of Example 1 and Comparative Example 2

The above are only preferred embodiments of the present invention, so the scope of implementation of the present invention cannot be limited accordingly. That is to say, equivalent changes and modifications made according to the scope of the patent of the present invention and the contents of the specification should still be covered by the present invention. Within range.

Industrial applicability

The invention discloses a polymer lithium secondary battery and an in-situ manufacturing method thereof. The polymer lithium secondary battery is prepared by initiating crosslinking or polymerization of a precursor liquid by high-energy ionization radiation. The invention replaces the existing thermal curing method, can continue to use the plates and diaphragms used in the preparation of ordinary liquid electrolyte batteries, has little modification to the traditional process equipment and materials, is convenient and efficient, and has more selectable monomer and prepolymer types. There are many advantages, no impurities are introduced, and it can be carried out at room temperature. It has good industrial application prospects and industrial practicability.

Claims (10)

1. An in-situ manufacturing method of polymer lithium secondary battery is characterized in that: a precursor solution with radiation cross-linking or radiation polymerization properties is poured into the semi-finished product of the battery, and the precursor solution is subjected to in-situ cross-linking through ionizing radiation. Lithium secondary battery is prepared by linking or polymerizing to form a polymer electrolyte membrane.
2. The in-situ manufacturing method of polymer lithium secondary battery according to claim 1, characterized in that: the precursor solution is made of polymer monomers and prepolymers with radiation crosslinking or radiation polymerization properties. And lithium salt is made by dissolving in aprotic organic solvent.
3. The in-situ manufacturing method of polymer lithium secondary battery according to claim 2, characterized in that it comprises the following steps:

   1) The polymer monomer, prepolymer, lithium salt, and crosslinking agent are dissolved in an aprotic organic solvent in a mass ratio of 1-9:1-4:1-4:0-1 to prepare a precursor solution;

   2) Place the welded positive and negative pole pieces and porous insulating film into the battery packaging film, and connect the tabs;

   3) Pour the precursor solution into the battery packaging film and package the battery;

   4) The encapsulated battery is irradiated with gamma rays or high-energy electron beams with a radiation dose of 0.1-500 KGy to achieve in-situ crosslinking or polymerization of the precursor solution to prepare a lithium secondary battery.
4. The in-situ manufacturing 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 a vinyl group or an acrylic group. Including acrylate, acrylonitrile, methoxyacrylate, acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, glycidyl methacrylate, ethylene carbonate, propylene carbonate, ethylene oxide, acrylic acid , At least one of styrene, fluoride, phosphazene, siloxane, and acetate.
5. The in-situ manufacturing method of a polymer lithium secondary battery according to claim 3, characterized in that: the prepolymer has aliphatic chains, ether segments, ester segments, silicon Polymers with or without side chains of oxygen bond units, including polyethylene glycol, polyethylene glycol methacrylate, polyvinyl carbonate, polyvinyl alcohol, polyethylene oxide, polycarbonate, At least one of polymethacrylic acid, polyacrylonitrile, polyphosphazene, and vinylidene fluoride.
6. The in-situ manufacturing method of polymer lithium secondary battery according to claim 3, characterized in that: the crosslinking agent is a multifunctional organic substance and its surface-modified nano-inorganic powder, including polyethylene two Alcohol diacrylate, divinylbenzene, N,N-methylenebisacrylamide, diisocyanate, ethyl orthosilicate, and nano-SiO ₂ , nano-TiO ₂ , nano-Al ₂ O ₃ with hydroxyl groups on the surface, and _{Nano SiO 2} , nano TiO ₂ , and nano Al ₂ O ₃ after surface modification of the coupling agent.
7. The in-situ manufacturing method of a polymer lithium secondary battery according to claim 3, wherein the lithium salt comprises LiTFSI, LiClO ₄ , LiPF ₆ , LiCl, LiCF ₃ SO ₃ , LiCF ₃ CO _2. LiAsF ₆ , LiSbF ₆ , LiAlCl ₄ , CH ₃ SO ₃ Li, LiBF ₄ , AMPSLi, STFSILi.
8. The in-situ manufacturing method of a polymer lithium secondary battery according to claim 3, wherein the aprotic organic solvent comprises ethylene carbonate, dimethyl carbonate, diethyl carbonate, propylene carbonate , Ethyl methyl carbonate, 1,3-dioxolane, dimethyl ether, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide , At least one of acetone, tetrahydrofuran and acetonitrile.
9. The in-situ manufacturing 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 it is prepared by the in-situ manufacturing method of the polymer lithium secondary battery according to any one of claims 1-9.

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