A wide-temperature high-voltage polyallyl carbonate-based polymer electrolyte

Abstract

A wide-temperature, high-pressure polyallyl carbonate-based polymer electrolyte belongs to the field of lithium-ion battery technology. The electrolyte comprises polyallyl carbonate or a copolymer thereof, a conductive lithium salt, and a porous support material. The preparation process of this polymer electrolyte is simple and easy to control, and it possesses excellent mechanical properties; its room-temperature ionic conductivity (25°C) is >10. ‑3 S cm ‑1 The ionic conductivity at 5℃ is >10. ‑4 S cm ‑1 The ionic conductivity at -20°C is >10. ‑4 S cm ‑1 Electrochemical window at room temperature (25°C) > 4.8V (vs. Li + / Li); 5℃ electrochemical window > 5.3V (vs. Li + The polyallyl carbonate polymer (poly(Li)) exhibits excellent compatibility with high-voltage cathode materials, and batteries assembled from it demonstrate superior cycle performance at both room temperature and low temperature. This invention relates to a polyallyl carbonate polymer that can be used as a high-voltage resistant electrolyte material in all-solid-state lithium-ion batteries at both room temperature and low temperature.

Description

Technical Field

[0001] This invention relates to lithium-ion battery technology, specifically to the polymerization and curing of allyl carbonate-based monomers or multi-component comonomers containing allyl carbonate under the action of an initiator, and the composite of these monomers with conductive lithium salts and porous support materials to obtain lithium-ion battery polymer electrolytes and polyallyl carbonate-based lithium-ion battery polymer electrolytes for application in all-solid-state lithium-ion batteries at different temperatures. Background Technology

[0002] Lithium-ion batteries are widely used in electrochemical energy storage due to their high energy density and reliability. Currently, commercially available lithium batteries primarily use two types of electrolytes: organic liquid electrolytes and gel polymer electrolytes. Both types of electrolytes have high ionic conductivity, effectively wetting the electrodes and forming a stable solid electrolyte film on the electrode surface, resulting in good performance. However, both types of electrolytes contain a significant amount of organic solvents, such as ethylene carbonate, dimethyl carbonate, propylene carbonate, and diethyl carbonate. Because organic liquid electrolytes typically possess high chemical activity, volatility, and flammability, they pose significant safety hazards to lithium-ion batteries, severely hindering their further popularization. Solid-state electrolytes, free of organic solvents, can significantly improve the safety performance of lithium-ion batteries and have gained widespread acceptance. All-solid-state electrolytes mainly include inorganic solid-state electrolytes and polymer electrolytes. While inorganic solid-state electrolytes suffer from complex manufacturing processes and poor interfacial compatibility, polymer electrolytes have gained widespread acceptance due to their good compatibility with lithium metal, high thermal stability, simple manufacturing processes, good flexibility, and adjustable shape and size. An ideal polymer electrolyte should possess the following advantages: 1. Ionic conductivity close to that of a liquid electrolyte; 2. Good compatibility with electrodes; 3. A wide electrochemical window; and 4. Simple preparation process. However, to date, it is difficult for polymer electrolytes to simultaneously meet all of these advantages.

[0003] In 1973, Wright et al. reported that PEO-based polymer electrolytes could be used as electrolyte materials for solid-state batteries, and this was later confirmed by Armand et al. However, subsequent in-depth research revealed that PEO-based polymer electrolytes exhibit low ionic conductivity (~10⁻⁶) at room temperature. -7 S cm -1The low electrochemical stability window of polycarbonate electrolytes (PCEs) prevents them from meeting market demands and hinders their widespread use and promotion. Subsequently, researchers reported numerous types of electrolytes, such as polyvinylidene fluoride (PVDF), PVDF-hexafluoropropylene (PVDF-HFA), polyacrylonitrile (PAC), and polymethyl methacrylate (PMMA). These polymers are often used as gel polymer electrolytes, which exhibit high ionic conductivity. However, due to their low mechanical strength, they are prone to internal short circuits under severe impacts. Polyoxyethylene (POE) and polyoxypropylene (POP) can be used as all-solid-state polymer electrolytes; however, their low ionic conductivity limits their applications. Therefore, many researchers have focused on developing novel polymer electrolyte systems, with polymers containing strongly polar carbonate groups [-O-(C=O)-O-] attracting widespread attention. Patent number CN 105591154A describes a polycarbonate-based all-solid-state polymer electrolyte with a room-temperature ionic conductivity of 2 × 10⁻⁶. -5 Scm -1 ~1×10 -3 S cm -1 The electrochemical window is greater than 4V. Patent No. CN 105702919A describes a method for preparing a lithium battery electrode containing an interface-stabilized polymer material and its application in solid-state lithium batteries. A polymer electrolyte is prepared using polyvinyl carbonate (PVCA) or its copolymers, which can form a coating film on the electrode surface, effectively suppressing the damage to the electrode material and the decomposition of the solid electrolyte on the positive and negative electrode surfaces during charging and discharging. Patent CN 111138596A describes a polymer electrolyte and a lithium-ion battery including the polymer electrolyte. The described polymer electrolyte is a semi-solid electrolyte containing at least one carbonate structure, one ester structure, one boron structure, and one fluorine structure; wherein the carbonate structure, ester structure, boron structure, and fluorine structure can be combined to form different chain segments. The polymer electrolyte is prepared using an in-situ polymerization method, and this polymer electrolyte has good anionic affinity for lithium salts and high conductivity (>10). -3 S cm -1 However, due to the large amount of organic solvent additives in semi-solid polymer electrolytes, significant safety hazards remain, as they can easily cause internal short circuits in the battery during severe impacts. The polymer electrolytes mentioned above all possess high ionic conductivity and good interfacial stability, but their low electrochemical window (<4.7V) makes them unsuitable for use in high-voltage cathode material systems.

[0004] To address the aforementioned issues, we have developed a novel polyallyl carbonate-based polymer electrolyte, prepared using allyl carbonate, lithium salt, and a porous support material. This polymer electrolyte exhibits a simple and easily controllable preparation process, excellent mechanical properties, and a room-temperature ionic conductivity (25°C) > 10.-3 S cm -1 The ionic conductivity at 5℃ is >10. -4 Scm -1 The ionic conductivity at -20°C is >10. -4 S cm -1 Electrochemical window at room temperature (25°C) > 4.8V (vs. Li + / Li); 5℃ electrochemical window > 5.3V (vs. Li + This polymer electrolyte exhibits excellent compatibility with high-voltage cathode materials and effectively suppresses the growth of lithium dendrites in the anode. The solid-state lithium-ion battery can operate for extended periods at both room and low temperatures. Furthermore, the polymer electrolyte possesses good flexibility, making it suitable for flexible lithium-ion battery devices in wearable electronic devices. Summary of the Invention

[0005] The purpose of this invention is to provide a wide-temperature, high-pressure polyallyl carbonate-based lithium-ion battery polymer electrolyte, its preparation method, and its application.

[0006] The technical solution of this invention is as follows:

[0007] A wide-temperature, high-pressure polyallyl carbonate-based lithium-ion battery polymer electrolyte, wherein the polymer electrolyte material includes polyallyl carbonate monomer or copolymer thereof, conductive lithium salt, initiator or catalyst, and is supported by a porous support material.

[0008] The mass fraction of the polyallyl carbonate group or its copolymer in the electrolyte material is 40%-80%; the mass fraction of the conductive lithium salt in the electrolyte material is 10%-50%; and the mass fraction of the catalyst is 0.01-10% of the mass of the allyl carbonate group or its copolymer.

[0009] The general formula of the allyl carbonate monomer structural unit in the polymer is as follows:

[0010]

[0011] Wherein R is one or more of alkyl, alkoxy, fluorine-containing, boron-containing, ester-containing, and nitrogen-containing functional groups.

[0012] The monomer copolymerized with the allyl carbonate monomer is one or more of methyl methacrylate (MMA) or other methacrylate derivatives, acrylonitrile (AN), acrylamide (AM), maleic anhydride (MAH), allyl-1,3-sulfonyl lactone (PST), vinyl acetate (VA), cyanoacrylate (ECA), ethylene ethylene carbonate (VEC), vinylene carbonate (VCA), and lithium acrylate (LiMAA), and the mass fraction of the allyl carbonate monomer in the copolymer is 10%-90%.

[0013] The conductive lithium salt is one or more of the following: lithium hexafluorophosphate (LiPF6), lithium perchlorate (LiClO4), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(oxalateborate)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)methyl [LiC(SO2CF3)3], and lithium difluorooxalateborate (LiDFOB);

[0014] The porous support material is one or more of the following: cellulose nonwoven fabric, polyethylene nonwoven fabric, polypropylene nonwoven fabric, glass fiber nonwoven fabric, and polytetrafluoroethylene nonwoven fabric.

[0015] The initiator or catalyst is one of the following: dibutyltin dilaurate, bis(acetylacetonate) dibutyltin, azobisisoheptanenitrile (ABVN), azobisisobutyronitrile (AIBN), dimethyl azobisisobutyrate (AIBME), benzoyl peroxide (BPO), tert-butyl peroxide (TBPB), methyl ethyl ketone peroxide (MEKPO), or platinum solution (Pt).

[0016] The above-mentioned method for preparing a polyallyl carbonate-based lithium-ion battery polymer electrolyte involves vacuum heating and curing an allyl carbonate-based monomer or a multi-component comonomer containing allyl carbonate under the action of an initiator or catalyst to obtain an all-solid polymer electrolyte. The main steps include the following:

[0017] 1) Add conductive lithium salt to an allyl carbonate monomer solution or a multi-component comonomer solution containing allyl carbonate and stir thoroughly to obtain a homogeneous solution.

[0018] 2) Add an initiator or catalyst to the above solution;

[0019] 3) Coat or immerse the allyl carbonate-based electrolyte mixture obtained in step 2) into a porous support material, and then cure it under vacuum at 60-120°C for 2-12 hours to obtain an all-solid polymer electrolyte.

[0020] The monomers copolymerized with the allyl carbonate monomers are one or more of methyl methacrylate (MMA) and other methacrylate derivatives, acrylonitrile (AN), acrylamide (AM), maleic anhydride (MAH), allyl-1,3-sulfonyl lactone (PST), vinyl acetate (VA), cyanoacrylate (ECA), ethylene ethylene carbonate (VEC), vinylene carbonate (VCA), lithium acrylate (LiMAA), and the mass fraction of the allyl carbonate structural unit in the copolymer is 10%-90%.

[0021] The conductive lithium salt is one or more of the following: lithium hexafluorophosphate (LiPF6), lithium perchlorate (LiClO4), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(oxalateborate)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)methyl [LiC(SO2CF3)3], and lithium difluorooxalateborate (LiDFOB);

[0022] The porous support material is one or more of the following: cellulose nonwoven fabric, polyethylene nonwoven fabric, polypropylene nonwoven fabric, glass fiber nonwoven fabric, and polytetrafluoroethylene nonwoven fabric.

[0023] The initiator or catalyst is one of the following: dibutyltin dilaurate, bis(acetylacetonate) dibutyltin, azobisisoheptanenitrile (ABVN), azobisisobutyronitrile (AIBN), dimethyl azobisisobutyrate (AIBME), benzoyl peroxide (BPO), tert-butyl peroxide (TBPB), methyl ethyl ketone peroxide (MEKPO), or platinum solution (Pt).

[0024] This invention provides a polymer solid-state lithium-ion battery with a polyallyl carbonate-based polymer electrolyte, characterized in that it comprises: a positive electrode, a negative electrode, and the polymer electrolyte of this invention, which serves as both a separator and an electrolyte, and is placed between the positive and negative electrodes.

[0025] The polymer solid-state lithium-ion battery described above is characterized in that: the positive electrode active material is one or more of lithium iron phosphate (LiFeO4), lithium nickel cobalt aluminum oxide (NCA), lithium-rich materials (LLOs), lithium cobalt oxide (LiCoO2), lithium-ion fluorophosphate, lithium nickel cobalt manganese oxide, lithium manganese oxide, lithium manganese oxide, lithium nickel manganese oxide, lithium manganese iron phosphate, and lithium nickel oxide (LiNiO2); the negative electrode active material is one or more of lithium metal, lithium metal alloy, carbon silicon composite material, lithium titanate, graphite, lithium metal nitride, antimony oxide, carbon germanium composite material, and lithium titanium oxide.

[0026] The polymer solid-state lithium-ion battery is characterized in that the preparation of the positive electrode includes the following steps: (1) the preparation of the positive electrode material, including the following steps: grinding and mixing 50-90% of the positive electrode active material and 5-30% of the conductive agent acetylene black, adding 1-15% of the polyvinylidene fluoride (PVDF), 1-15% of the electrolyte mixture and 1-methyl-2-pyrrolidone to obtain the positive electrode material, wherein 1-methyl-2-pyrrolidone is used to adjust the viscosity and is not included in the mass percentage composition of the positive electrode material; (2) coating the positive electrode material on the surface of aluminum foil and vacuum drying to obtain the positive electrode;

[0027] Alternatively, metallic lithium or lithium alloys can be directly used as the corresponding negative electrode;

[0028] Alternatively, the preparation of the negative electrode includes the following steps: (1) Preparation of negative electrode material: 35-85% of negative electrode active material and 5-30% of conductive agent acetylene black are ground and mixed; 5-20% of polyvinylidene fluoride (PVDF), 1-20% of electrolyte mixture and 1-methyl-2-pyrrolidone are added and ground and mixed to obtain negative electrode material; 1-methyl-2-pyrrolidone is used to adjust viscosity and is not included in the mass percentage composition of negative electrode material; (2) Coating on the surface of copper foil and drying to obtain negative electrode.

[0029] The electrolyte mixture in the positive and negative electrode materials is composed of the following components: allyl carbonate accounts for 40-80% of the electrolyte mixture by mass, conductive lithium salt accounts for 10-50% of the electrolyte mixture by mass, and the initiator or catalyst accounts for 0.1-10% of the mass of allyl carbonate or its copolymer monomers. The specific selection range of each substance in the electrolyte mixture is the same as the selection range of each substance in the polycarbonate-based polymer electrolyte material described above.

[0030] The battery manufacturing processes include (1): non-in-situ assembly process --- positive electrode, negative electrode and the above-mentioned solid polymer electrolyte; (2): in-situ assembly process --- inject the above-mentioned electrolyte mixture into the battery system of positive electrode, separator and negative electrode, and cure at 60-120℃.

[0031] The present invention relates to the application of polymer electrolytes in all-solid-state lithium-ion batteries at temperatures ranging from -20°C to 80°C.

[0032] The innovation and practicality of this invention lie in:

[0033] This invention is the first to prepare a solid polymer electrolyte from a mixture of allyl carbonate-based monomers or multi-component comonomers containing allyl carbonate, a conductive lithium salt, and a porous support material. This polymer electrolyte exhibits a very high ionic conductivity (>10) at room temperature.-3 S cm -1 The ionic conductivity at -20℃ is 2.75×10⁻⁶. -4 S cm -1 Electrochemical window (>4.8V vs. Li) + (Li). Simultaneously, when this polymer electrolyte is assembled into a solid-state lithium-ion battery, it can form a protective layer on the surface of the lithium battery electrode material and metallic lithium, effectively suppressing the damage to the electrode crystals caused by lithium-ion insertion and extraction, thereby improving the long-cycle stability of the lithium battery. Furthermore, the polymer electrolyte of this invention can be prepared without adding organic solvents, using in-situ polymerization to eliminate safety hazards and environmental pollution, greatly improving the safety and practicality of lithium batteries. It can be applied to all-solid-state lithium batteries (including lithium-sulfur batteries), all-solid-state lithium-ion batteries, and other secondary high-energy lithium batteries. Attached Figure Description

[0034] Figure 1 Linear voltammetric scan curves from Example 1 of polymer electrolyte preparation.

[0035] Figure 2 Charge-discharge curves of lithium-ion batteries at different temperatures in Example 7 of solid-state lithium-ion battery preparation

[0036] Figure 3 Cycle performance of the lithium-ion battery at 25°C in Example 7 for solid-state lithium-ion battery preparation. Detailed Implementation

[0037] The present invention will be illustrated by specific embodiments below. These embodiments are provided to better understand the present invention and are by no means intended to limit the scope of the present invention.

[0038] Preparation of polymer electrolytes:

[0039] Example 1

[0040] In an argon-filled glove box, 3g of allyl methyl carbonate (AMC) and 0.8g of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) were dissolved in 5ml of N-methylpyrrolidone (NMP) and stirred until completely dissolved. 0.1g of azobisisobutyronitrile (AIBN) was then added and stirred evenly. Using a Whatman membrane as a porous support framework, the well-stirred mixture was coated onto both sides of a polytetrafluoroethylene mold. The mixture was then cured in a vacuum drying oven at 80°C for 10 hours to form a film.

[0041] Example 2

[0042] In an argon-filled glove box, 1g of allyl methyl carbonate (AMC), 1g of methyl methacrylate (MMA), and 0.25g of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) were dissolved in 1.5ml of N-methylpyrrolidone (NMP) and stirred at room temperature until completely dissolved. 0.02g of azobisisobutyronitrile (AIBN) was then added and stirred evenly. Using a cellulose membrane as a porous support framework, the well-stirred mixture was coated onto both sides of a polytetrafluoroethylene mold. The mixture was then cured in a vacuum drying oven at 80°C for 10 hours to form a film.

[0043] Example 3

[0044] In an argon-filled glove box, 1.38 g of allyl methyl carbonate (AMC), 1 g of acrylonitrile (AN), and 0.4 g of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) were dissolved in 1.5 ml of N-methylpyrrolidone (NMP) and stirred at room temperature until completely dissolved. 0.02 g of dibutyltin bis(acetylacetonate) was then added and stirred thoroughly. Using a Whatman membrane as a porous support framework, the well-stirred mixture was coated onto both sides of a polytetrafluoroethylene (PTFE) mold. The mixture was then cured in a vacuum drying oven at 80°C for 10 hours to form a film.

[0045] Example 4

[0046] In an argon-filled glove box, 1.8 g of allyl methyl carbonate (AMC), 0.5 g of acrylamide (AM), and 0.65 g of lithium perchlorate (LiClO4) were dissolved in 2 ml of tetrahydrofuran and stirred at room temperature until completely dissolved. Then, 0.02 g of dibutyltin bis(acetylacetonate) was added and stirred evenly. Using a cellulose membrane as a porous support framework, the well-stirred mixture was coated onto both sides of a polytetrafluoroethylene mold. The mixture was then cured into a film by heating in a vacuum drying oven at 80°C for 10 hours.

[0047] Example 5

[0048] Dissolve 2.3g of allyl succinimide carbonate (ALOC-OSU), 1g of maleic anhydride (MAH), and 0.8g of lithium perchlorate (LiClO4) in 2ml of tetrahydrofuran and stir at room temperature until completely dissolved. Add 0.05g of platinum solution (Pt) and stir evenly. On a polytetrafluoroethylene mold, using a nonwoven fabric membrane as a porous support framework, coat the well-stirred mixture onto both sides of the nonwoven fabric membrane. Cure the film by heating at 80℃ in a vacuum drying oven for 10 hours.

[0049] Example 6

[0050] Dissolve 5g of allyl tert-butyl peroxycarbonate (TBAC), 3g of allyl-1,3-sulfonyl lactone (PST), and 1.23g of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in 5ml of dimethyl sulfoxide and stir at room temperature until completely dissolved. Add 0.08g of platinum solution (Pt) and stir evenly. On a polytetrafluoroethylene mold, using a Whatman membrane as a porous support framework, coat the well-stirred mixture onto both sides of the Whatman membrane. Cure the film by heating at 80°C in a vacuum drying oven for 10 hours.

[0051] Electrolyte thickness: The thickness of the block polymer electrolyte was measured using a micrometer (accuracy 0.01 mm). Three points on the membrane were randomly selected for measurement, and the average value was calculated.

[0052] Ionic conductivity: The impedance of a 2032 coin cell was measured by assembling a polymer electrolyte using two stainless steel gaskets, according to the formula... Where L is the thickness of the polymer electrolyte, S is the area of ​​the stainless steel gasket, and R is the measured impedance value.

[0053] Electrochemical window: A 2032 coin cell was assembled using stainless steel and lithium foil to sandwich the polymer electrolyte. Linear voltammetry measurements were performed with an onset voltage of 2.8V, a maximum potential of 5.5V, and a scan rate of 1mV / s. -1 .

[0054]

[0055] Fabrication of solid-state lithium-ion batteries:

[0056] Example 7

[0057] 200 mg of lithium cobalt oxide and 25 mg of conductive agent acetylene black were uniformly ground for 40 min; 25 mg of binder polyvinylidene fluoride, 6 mg of electrolyte mixture and 200 μL of 1-methyl-2-pyrrolidone were added and uniformly ground for 40 min; the mixture was coated on the surface of aluminum foil and dried at 80 °C for 8 h under vacuum to obtain the positive electrode material; the positive electrode sheet was cut into a circular piece with R = 0.6 mm, and a solid lithium-ion half cell was assembled using the polymer electrolyte in Example 1 prepared by the above polymer electrolyte, and then lithium metal was used as the negative electrode.

[0058] Example 8

[0059] 220 mg of lithium iron phosphate and 45 mg of conductive agent acetylene black were uniformly ground for 40 min; 15 mg of binder polyvinylidene fluoride, 15 mg of electrolyte mixture and 150 μL of 1-methyl-2-pyrrolidone were added and uniformly ground for 40 min; the mixture was then coated onto the surface of aluminum foil and dried at 80 °C under vacuum for 8 h to obtain the positive electrode material; the positive electrode sheet was cut into circular pieces with R = 0.6 mm, and a solid-state lithium-ion half-cell was assembled using the above polymer electrolyte. Then, metallic lithium was used as the negative electrode.

[0060] Example 9

[0061] 200 mg of lithium nickel cobalt aluminum oxide and 40 mg of conductive agent acetylene black were uniformly ground for 40 min; 15 mg of binder polyvinylidene fluoride, 15 mg of electrolyte mixture and 150 μL of 1-methyl-2-pyrrolidone were added and uniformly ground for 40 min; the mixture was then coated onto the surface of aluminum foil and dried at 80 °C under vacuum for 8 h to obtain the positive electrode material; the positive electrode sheet was cut into circular pieces with R = 0.6 mm, and a solid-state lithium-ion half-cell was assembled using the above polymer electrolyte. Then, lithium metal was used as the negative electrode.

Claims

1. A wide-temperature high-voltage polyallyl carbonate-based lithium-ion battery polymer electrolyte, characterized by, The polymer electrolyte material comprises a polyallyl carbonate-based monomer or a copolymer thereof, a conductive lithium salt, an initiator or a catalyst, and is supported by a porous support material; The mass fraction of the polyallyl carbonate-based monomer or the copolymer thereof in the electrolyte material is 40%-80%; the mass fraction of the conductive lithium salt in the electrolyte raw material is 10%-50%; and the mass fraction of the catalyst is 0.01-10% of the mass of the allyl carbonate-based monomer or the copolymer thereof; The corresponding allyl carbonate-based monomer structural unit in the polymer has the following general formula: ； R is one or more of an alkyl group, an alkoxy group, a fluorine-containing functional group, a boron-containing functional group, an ester-containing functional group, and a nitrogen-containing functional group; The polymer electrolyte has an ionic conductivity > 10 -3 S cm at room temperature -1 at -20 °C of 2.75 x 10 -4 S cm -1 An electrochemical window of > 4.8 V vs. Li + / Li.

2. The wide temperature and high voltage poly(allyl carbonate)-based lithium-ion battery polymer electrolyte according to claim 1, characterized in that, The monomer copolymerized with the allyl carbonate-based monomer is one or more of methyl methacrylate (MMA) or other methacrylate derivatives, acrylonitrile (AN), acrylamide (AM), maleic anhydride (MAH), allyl-1,3-sulfonic acid lactone (PST), vinyl acetate (VA), cyanoacrylate (ECA), vinyl ethylene carbonate (VEC), vinylene carbonate (VCA), and lithium acrylate (LiMAA), and the mass fraction of the allyl carbonate-based monomer in the copolymer is 10%-90%; The conductive lithium salt is one or more of lithium hexafluorophosphate (LiPF6), lithium perchlorate (LiClO4), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)methylide [LiC(SO2CF3)3], and lithium difluoro(oxalato)borate (LiDFOB); The porous support material is one or more of cellulose non-woven fabric, polyethylene non-woven fabric, polypropylene non-woven fabric, glass fiber non-woven fabric, and polytetrafluoroethylene non-woven fabric; The initiator or the catalyst is one of dilauryl tin dibutyl, bis(acetylacetone) dibutyl tin, azobisisoheptyl nitrile (ABVN), azobis isobutyronitrile (AIBN), dimethyl azobis isobutyrate (AIBME), benzoyl peroxide (BPO), tert-butyl benzoyl peroxide (TBPB), methyl ethyl ketone peroxide (MEKPO), and platinum gold water (Pt).

3. A process for the preparation of a wide temperature and high voltage poly(allyl carbonate)-based polymer electrolyte for lithium-ion batteries according to any one of claims 1-2, characterized in that, The allyl carbonate-based monomer or the multi-component copolymer monomer containing the allyl carbonate is solidified under vacuum heating in the presence of the initiator or the catalyst to obtain a full-solid-state polymer electrolyte. The main steps include the following: 1) A conductive lithium salt is added to an allyl carbonate-based monomer solution or a multi-component copolymer monomer solution containing the allyl carbonate, and the mixture is stirred to obtain a uniform solution; 2) An initiator or a catalyst is added to the solution; 3) The allyl carbonate-based electrolyte mixed solution obtained in step 2) is coated or immersed in a porous support material, and then solidified under vacuum heating at 60-120 ºC for 2-12 hours to obtain a full-solid-state polymer electrolyte.

4. A solid state polymer lithium ion battery comprising a polyallyl carbonate based polymer electrolyte, characterized in that, The method comprises the following steps: 1) Preparing an allyl carbonate-based monomer solution or a multi-component copolymer monomer solution containing the allyl carbonate; 2) Adding a conductive lithium salt to the solution and stirring to obtain a uniform solution; 3) Adding an initiator or a catalyst to the solution; 4) Coating or immersing the solution obtained in step 3) in a porous support material, and then solidifying under vacuum heating at 60-120 ºC for 2-12 hours to obtain a full-solid-state polymer electrolyte. The positive electrode, the negative electrode, and the polymer electrolyte having the functions of a separator and an electrolyte between the positive electrode and the negative electrode; the polymer electrolyte is a wide-temperature and high-voltage polyallyl carbonate-based lithium ion battery polymer electrolyte according to any one of claims 1-2.

5. A solid state polymer lithium ion battery containing a polyallyl carbonate based polymer electrolyte according to claim 4, characterized in that, The positive electrode active material is one or more of lithium iron phosphate (LiFeO4), lithium nickel cobalt aluminum oxide (NCA), lithium-rich material (LLOs), lithium cobalt oxide (LiCoO2), lithium ion fluorophosphoric acid lithium, lithium nickel cobalt manganese oxide, lithium manganese oxide, lithium manganese oxide, lithium nickel manganese oxide, lithium manganese iron phosphate, lithium nickel oxide (LiNiO2); the negative electrode active material is one or more of metal lithium, metal lithium alloy, carbon-silicon composite material, lithium titanate, graphite, lithium metal nitride, antimony oxide, carbon-germanium composite material, lithium titanium oxide; The preparation of the positive electrode includes the following steps: (1) preparation of the positive electrode material, including the following steps: grinding and mixing 50-90% by mass fraction of the positive electrode active material, 5-30% by mass fraction of the conductive agent acetylene black, adding 1-15% by mass fraction of polyvinylidene fluoride (PVDF), 1-15% of the electrolyte mixture, and 1-methyl-2-pyrrolidone to obtain the positive electrode material; 1-methyl-2-pyrrolidone is used to adjust the viscosity and is not included in the mass percentage composition of the positive electrode material; (2) coating the positive electrode material on the surface of an aluminum foil and vacuum drying to obtain the positive electrode; The metal lithium and the metal lithium alloy can be directly used as the corresponding negative electrode; Alternatively, the preparation of the negative electrode includes the following steps: (1) preparation of the negative electrode material: grinding and mixing 35-85% by mass fraction of the negative electrode active material and 5-30% by mass fraction of the conductive agent acetylene black; adding 5-20% by mass fraction of polyvinylidene fluoride (PVDF), 1-20% of the electrolyte mixture, and 1-methyl-2-pyrrolidone to obtain the negative electrode material; 1-methyl-2-pyrrolidone is used to adjust the viscosity and is not included in the mass percentage composition of the negative electrode material; (2) coating on the surface of a copper foil and drying to obtain the negative electrode.

6. A solid state polymer lithium ion battery containing a polyallyl carbonate based polymer electrolyte according to claim 5, characterized in that, The composition of the electrolyte mixture in the positive electrode material and the negative electrode material is as follows: the mass fraction of the electrolyte mixture component allyl carbonate-based monomer or its copolymer is 40-80%, the mass fraction of the conductive lithium salt in the electrolyte mixture is 10-50%, and the mass fraction of the initiator or catalyst is 0.1-10% of the mass of the allyl carbonate-based monomer or its copolymer monomer; the specific selection range of each substance in the electrolyte mixture is the same as the selection range of each substance in the above-mentioned polyallyl carbonate-based polymer electrolyte raw material.

7. A method for preparing a solid polymer lithium-ion battery containing a polyallyl carbonate-based polymer electrolyte according to claim 5, characterized in that, Two processes are included, (1): non-in-situ assembly process---the positive electrode, the negative electrode, and the above-mentioned polymer electrolyte; (2): in-situ assembly process---injecting the above-mentioned electrolyte mixture into the battery system of the positive electrode, the separator, and the negative electrode, and solidifying at 60-120 ℃.

8. The application of a wide-temperature and high-voltage polyallyl carbonate-based lithium ion battery polymer electrolyte according to any one of claims 1-2 in a full-solid-state lithium ion battery under temperature conditions of -20 ℃-80 ℃.

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