CN116111179A - Wide-temperature high-pressure polyallylcarbonate-based polymer electrolyte - Google Patents

Wide-temperature high-pressure polyallylcarbonate-based polymer electrolyte Download PDF

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CN116111179A
CN116111179A CN202111323541.4A CN202111323541A CN116111179A CN 116111179 A CN116111179 A CN 116111179A CN 202111323541 A CN202111323541 A CN 202111323541A CN 116111179 A CN116111179 A CN 116111179A
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尉海军
丁培沛
郭现伟
林志远
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Beijing University of Technology
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Abstract

A wide temperature high pressure polyallylcarbonate based polymer electrolyte belongs to the technical field of lithium ion batteries. The electrolyte comprises a polyolefinPropyl carbonate or its copolymer, conductive lithium salt and porous supporting material. The preparation process of the polymer electrolyte is simple and easy to control, and has excellent mechanical properties; room temperature ion (25 ℃) conductivity > 10 ‑3 S cm ‑1 Ion conductivity at 5 ℃ of > 10 ‑4 S cm ‑1 Ion conductivity at minus 20 ℃ is more than 10 ‑4 S cm ‑1 The electrochemical window at room temperature (25 ℃) is > 4.8V (vs. Li + Li); electrochemical window > 5.3V at 5 deg.C (vs. Li) + Li) has good compatibility with high-voltage positive electrode materials, and the assembled battery has excellent cycle performance at room temperature and low temperature. The polyallylcarbonate polymer can be used as a high-voltage-resistant electrolyte material and can be applied to all-solid-state lithium ion batteries at room temperature and low temperature.

Description

Wide-temperature high-pressure polyallylcarbonate-based polymer electrolyte
Technical Field
The invention relates to a lithium ion battery technology, in particular to a lithium ion battery polymer electrolyte obtained by polymerizing and curing allyl carbonate-based monomer or allyl carbonate-containing multicomponent comonomer under the action of an initiator and compositing conductive lithium salt and a porous supporting material, and application of the polyallyl carbonate-based lithium ion battery polymer electrolyte in different temperatures of an all-solid-state lithium ion battery.
Background
The lithium ion battery is widely applied to the field of electrochemical energy storage due to high energy density and good reliability. Currently, there are two main types of electrolytes used in commercial lithium batteries: one is an organic liquid electrolyte and the other is a gel polymer electrolyte. Both electrolytes have higher ionic conductivity, can effectively infiltrate the electrode and form a stable solid electrolyte membrane on the surface of the electrode, and have better performance. However, both the two electrolytes contain more organic solvents, such as ethylene carbonate, dimethyl carbonate, propylene carbonate, diethyl carbonate and the like, and the organic liquid electrolyte generally has the characteristics of high chemical activity, volatility, easy ignition and the like, so that the lithium ion battery has great potential safety hazard and is seriously hindered from further popularization. The solid electrolyte does not contain an organic solvent, can obviously improve the safety performance of the lithium ion battery, and is widely accepted. The all-solid electrolyte mainly includes an inorganic solid electrolyte and a polymer electrolyte. For the defects of complex preparation process, poor interface compatibility and the like of inorganic solid electrolyte, the polymer electrolyte has been widely accepted due to the advantages of good compatibility with lithium metal, high thermal stability, simple preparation process, good flexibility, adjustable shape and size and the like. The ideal polymer electrolyte should possess the following advantages: 1. near the ionic conductivity of the liquid electrolyte; 2. the electrode has good compatibility with the electrode; 3. a wide electrochemical window; 4. the preparation process is simple. However, it has been difficult to satisfy the above advantages simultaneously with the polymer electrolyte.
Wright et al reported in 1973, after which Armand et al confirmed that it could be found as an electrolyte material for solid-state batteries. However, in subsequent intensive studies, it was found that ion conductivity was low (-10) due to the presence of PEO-based polymer electrolytes at room temperature -7 S cm -1 ) And a lower electrochemical stability window, can not meet the market demand, and can not be widely used and popularized. Researchers have thereafter reported a number of classes of electrolytes, such as: polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyacrylonitrile, polymethyl methacrylate. These polymers are commonly used as gel polymer electrolytes having high ionic conductivity, but are liable to short-circuit the inside of the battery upon severe impact due to low mechanical strength of the gel polymer electrolyte. Polyoxyethylene, polyoxypropylene may be used as an all-solid polymer electrolyte, however, low ionic conductivity limits their applications. Thus, many scholars have been working on developing polymer electrolytes with novel systems containing highly polar carbonate groups [ -O- (C=O) -O ]]Polymers have attracted considerable attention from researchers. Patent No. CN 105591154A describes an all-solid polymer electrolyte of the polycarbonate type having an ionic conductivity of 2X 10 at room temperature -5 S cm -1 ～1×10 -3 S cm -1 The electrochemical window is greater than 4V. Patent number CN 105702919a describes a method for preparing lithium battery electrodes comprising an interfacial stable polymer material and its use in solid state lithium batteries. The polymer electrolyte is prepared by using polyvinyl carbonate (PVCA) or a copolymer thereof, a covering film can be formed on the surface of the electrode, and the damage of the electrode material and the decomposition of the solid electrolyte on the surface of the anode and the cathode in the charge and discharge process can be effectively inhibited. Patent CN 111138596A describes a polymer electrolyte and a lithium ion battery comprising the polymer electrolyte. The polymer electrolyte is described as a semi-solid electrolyte comprising at least one carbonate structure, one ester structureA boron structure and a fluorine structure; wherein the carbonate structure, the ester structure, the boron structure and the fluorine structure may be combined with each other into different segments. The polymer electrolyte is prepared by an in-situ polymerization method, has better anion affinity with lithium salt and higher conductivity (> 10) -3 S cm -1 ) However, since a large amount of organic solution additives exist in the semi-solid polymer electrolyte, there is still a great safety hazard, and the inside of the battery is easily made short at the time of severe impact. The polymer electrolyte provided by the method has higher ionic conductivity and good interface stability, but has a low electrochemical window (less than 4.7V), and is not suitable for being applied to a high-voltage positive electrode material system.
In view of the above problems, we have developed a novel polyallylcarbonate-based polymer electrolyte prepared using allyl carbonate, lithium salt and a porous support material. The preparation process of the polymer electrolyte is simple and easy to control, and has excellent mechanical properties; room temperature ion (25 ℃) conductivity > 10 -3 S cm -1 Ion conductivity at 5 ℃ of > 10 -4 S cm -1 Ion conductivity at minus 20 ℃ is more than 10 -4 S cm -1 The electrochemical window at room temperature (25 ℃) is > 4.8V (vs. Li + Li); electrochemical window > 5.3V at 5 deg.C (vs. Li) + Li); the polymer electrolyte has good compatibility with a high-voltage positive electrode material, and can effectively inhibit the growth of lithium negative electrode dendrites; the solid-state lithium ion battery can work for a long time at room temperature and low temperature. Meanwhile, the polymer electrolyte has good flexibility, and is also suitable for flexible lithium ion battery devices of wearable electronic equipment.
Disclosure of Invention
The invention aims to provide a wide-temperature high-pressure polyallylcarbonate-based lithium ion battery polymer electrolyte, and a preparation method and application thereof.
The technical scheme of the invention is as follows:
a polymer electrolyte of a wide-temperature high-pressure polyallylcarbonate-based lithium ion battery comprises a polyallylcarbonate monomer or a copolymer thereof, conductive lithium salt, an initiator or a catalyst, and is supported by a porous support material.
The mass fraction of the polyallylcarbonate group or the copolymer thereof in the electrolyte material is 40% -80%; the mass fraction of the conductive lithium salt in the electrolyte material is 10% -50%; the mass fraction of the catalyst is 0.01-10% of the mass of allyl carbonate groups or copolymers thereof.
The structural unit of the corresponding allyl carbonate monomer in the polymer has the following general formula:
Figure BDA0003345401620000031
wherein R is one or more of alkyl, alkoxy, fluorine-containing functional group, boron-containing functional group, ester-containing functional group and nitrogen-containing functional group.
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-sultone (PST), vinyl Acetate (VA), cyanoacrylate (ECA), 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 the following: lithium hexafluorophosphate (LiPF) 6 ) Lithium perchlorate (LiClO) 4 ) Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiLiWSI), lithium bis (oxalato) borate (LiBOB), lithium bis (trifluoromethanesulfonyl) methyllithium [ LiC (SO) 2 CF 3 ) 3 ]Lithium difluorooxalato borate (LiDFOB);
the porous supporting material is one or more of the following: cellulose nonwoven fabric, polyethylene nonwoven fabric, polypropylene nonwoven fabric, glass fiber nonwoven fabric, polytetrafluoroethylene nonwoven fabric;
the initiator or catalyst is one of the following: dibutyl tin dilaurate, dibutyl tin bis (acetylacetonate), azobisisoheptonitrile (ABVN), azobisisobutyronitrile (AIBN), dimethyl Azobisisobutyrate (AIBME), benzoyl Peroxide (BPO), t-butyl benzoyl peroxide (TBPB), methyl Ethyl Ketone Peroxide (MEKPO), platinum water (Pt).
According to the preparation method of the polyallylcarbonate-based lithium ion battery polymer electrolyte, the allyl carbonate-based monomer or the allyl carbonate-containing multicomponent comonomer is subjected to vacuum heating and curing under the action of an initiator or a catalyst to obtain the all-solid-state polymer electrolyte; the method mainly comprises the following steps:
1) Adding conductive lithium salt into allyl carbonate-based monomer solution or multi-component comonomer solution containing allyl carbonate, and fully stirring to obtain uniform solution;
2) Adding an initiator or a catalyst into the solution;
3) Coating or immersing the allyl carbonate-based electrolyte mixed solution obtained in the step 2) into a porous supporting material, and then carrying out vacuum heating curing at 60-120 ℃ for 2-12 hours to obtain the all-solid-state polymer electrolyte.
The monomer copolymerized with the allyl carbonate monomer is one or more of Methyl Methacrylate (MMA) and other methacrylate derivatives, acrylonitrile (AN), acrylamide (AM), maleic Anhydride (MAH), allyl-1, 3-sultone (PST), vinyl Acetate (VA), cyanoacrylate (ECA), ethylene carbonate (VEC), vinylene Carbonate (VCA) and lithium acrylate (LiMAA), and the mass fraction of the allyl carbonate structural unit in the copolymer is 10% -90%;
the conductive lithium salt is one or more of the following: lithium hexafluorophosphate (LiPF) 6 ) Lithium perchlorate (LiClO) 4 ) Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiLiWSI), lithium bis (oxalato) borate (LiBOB), lithium bis (trifluoromethanesulfonyl) methyllithium [ LiC (SO) 2 CF 3 ) 3 ]Lithium difluorooxalato borate (LiDFOB);
the porous supporting material is one or more of the following: cellulose nonwoven fabric, polyethylene nonwoven fabric, polypropylene nonwoven fabric, glass fiber nonwoven fabric, polytetrafluoroethylene nonwoven fabric;
the initiator or catalyst is one of the following: dibutyl tin dilaurate, dibutyl tin bis (acetylacetonate), azobisisoheptonitrile (ABVN), azobisisobutyronitrile (AIBN), dimethyl Azobisisobutyrate (AIBME), benzoyl Peroxide (BPO), t-butyl benzoyl peroxide (TBPB), methyl Ethyl Ketone Peroxide (MEKPO), platinum water (Pt).
The invention provides a polymer solid lithium ion battery of a polyallylcarbonate-based polymer electrolyte, which is characterized by comprising the following components: the positive electrode, the negative electrode and the polymer electrolyte provided by the invention, which is arranged between the positive electrode and the negative electrode and has the functions of a diaphragm and an electrolyte;
the polymer solid lithium ion battery is characterized in that: the positive electrode active material is lithium iron phosphate (LiFeO) 4 ) Lithium Nickel Cobalt Aluminate (NCA), lithium rich materials (LLOs), lithium cobalt oxide (LiCoO) 2 ) Lithium ion fluorophosphate, nickel cobalt lithium manganate, lithium manganese oxide, lithium manganate, lithium nickel manganate, lithium iron manganese phosphate, lithium nickelate (LiNiO) 2 ) One or more of the following; 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.
The polymer solid lithium ion battery is characterized in that: the preparation of the positive electrode comprises the following steps: the preparation of the positive electrode material comprises the following steps: grinding and mixing 50-90% of positive electrode active material and 5-30% of conductive agent acetylene black, adding 1-15% of polyvinylidene fluoride (PVDF), 1-15% of electrolyte mixed solution and 1-methyl-2 pyrrolidone, and grinding and mixing to obtain a positive electrode material, wherein the 1-methyl-2 pyrrolidone is used for adjusting viscosity and is not added into the composition of the positive electrode material in percentage by mass; (2) Coating the anode material on the surface of an aluminum foil, and vacuum drying to obtain an anode;
or the metal lithium and the metal lithium alloy can be directly used as the corresponding negative electrode;
or preparing the negative electrode, comprising the following steps: (1) preparation of a negative electrode material: grinding and mixing 35-85% of negative electrode active material and 5-30% of conductive agent acetylene black; adding polyvinylidene fluoride (PVDF) accounting for 5-20% of the mass fraction, 1-20% of electrolyte mixed solution and 1-methyl-2 pyrrolidone, and grinding and mixing to obtain a cathode material; wherein 1-methyl-2 pyrrolidone is used for adjusting viscosity and is not counted in the mass percentage composition of the anode material; and (2) coating the surface of the copper foil, and drying to obtain the negative electrode.
The composition of the electrolyte mixed solution in the positive electrode material and the negative electrode material is as follows: the electrolyte mixed solution comprises 40-80% of allyl carbonate by mass percent, 10-50% of conductive lithium salt by mass percent of electrolyte mixed solution, and 0.1-10% of initiator or catalyst by mass percent of allyl carbonate or copolymer monomer thereof; the specific selection ranges of the respective substances in the electrolyte mixture are the same as those of the respective substances of the polycarbonate-based polymer electrolyte material described above.
The preparation process of the battery comprises the following steps: ex-situ assembly process-positive electrode, negative electrode and solid polymer electrolyte as described above; (2): in-situ assembling process, the electrolyte mixed solution is injected into a battery system of a positive electrode, a diaphragm and a negative electrode, and is solidified at 60-120 ℃.
The polymer electrolyte is applied to an all-solid-state lithium ion battery at the temperature of-20 ℃ to 80 ℃.
The innovation and the practicability of the invention are as follows:
the invention prepares the solid polymer electrolyte for the first time by using allyl carbonate-based monomer or a mixture containing allyl carbonate multicomponent comonomer, conductive lithium salt and porous supporting material. The polymer electrolyte has very high ionic conductivity (> 10) at room temperature -3 S cm -1 ) Ion conductivity at-20 ℃ below zero is 2.75X10 -4 S cm -1 Electrochemical window (> 4.8V vs. Li) + /Li). Meanwhile, when the polymer electrolyte is assembled into a solid lithium ion battery, a protective layer can be formed on the surfaces of electrode materials and metal lithium of the lithium battery, so that damage of electrode crystals caused by intercalation and deintercalation of lithium ions can be effectively inhibited, and further the long-cycle stability of the lithium battery is improved. And is combined withIn addition, the polymer electrolyte can be prepared by in-situ polymerization without adding an organic solvent in the preparation process of the polymer electrolyte, so that potential safety hazards and environmental pollution are eliminated, and the safety and the practicability of the lithium battery are greatly improved. The lithium ion battery 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.
Drawings
FIG. 1 is a graph showing the linear voltammogram of Polymer electrolyte preparation example 1.
FIG. 2 shows charge and discharge curves of a lithium ion battery at different temperatures in preparation example 7 of a solid-state lithium ion battery
Fig. 3 is a graph showing the cycling performance at 25 c of the lithium ion battery in preparation example 7 of a solid-state lithium ion battery.
Detailed Description
The invention is illustrated by the following specific examples, which are included to provide a better understanding of the invention and are not intended to limit the scope of the invention in any way.
Preparation of a polymer electrolyte:
example 1
3g of Allyl Methyl Carbonate (AMC), 0.8g of lithium bistrifluoromethane sulfonyl imide (LiTFSI) were dissolved in 5ml of N-methylpyrrolidone (NMP) in a glove box filled with argon, and stirred to dissolve completely; 0.1g of Azobisisobutyronitrile (AIBN) was added thereto and stirred uniformly. On a polytetrafluoroethylene mould, a whatman diaphragm is used as a porous supporting framework, and the uniformly stirred mixture is scraped on two sides of the whatman diaphragm; heating in a vacuum drying oven at 80 ℃ for 10 hours to solidify into a film.
Example 2
1g of Allyl Methyl Carbonate (AMC), 1g of Methyl Methacrylate (MMA), and 0.25g of lithium bistrifluoromethane sulfonimide (LiTFSI) were dissolved in 1.5ml of N-methylpyrrolidone (NMP) in a glove box filled with argon, and stirred at room temperature to completely dissolve the materials; 0.02g of Azobisisobutyronitrile (AIBN) was added thereto and stirred uniformly. On a polytetrafluoroethylene mould, taking a cellulose diaphragm as a porous supporting framework, and scraping and coating the uniformly stirred mixture on two sides of the cellulose diaphragm; heating in a vacuum drying oven at 80 ℃ for 10 hours to solidify into a film.
Example 3
1.38g of Allyl Methyl Carbonate (AMC), 1g of Acrylonitrile (AN), 0.4g of lithium bistrifluoromethane sulfonimide (LiTFSI) were dissolved in 1.5ml of N-methylpyrrolidone (NMP) in a glove box filled with argon, and stirred at room temperature to dissolve completely; 0.02g of dibutyltin bis (acetylacetonate) was added thereto and stirred uniformly. On a polytetrafluoroethylene mould, a whatman diaphragm is used as a porous supporting framework, and the uniformly stirred mixture is scraped on two sides of the whatman diaphragm; heating in a vacuum drying oven at 80 ℃ for 10 hours to solidify into a film.
Example 4
1.8g of Allyl Methyl Carbonate (AMC), 0.5g of Acrylamide (AM), 0.65g of lithium perchlorate (LiClO) were placed in a glove box filled with argon 4 ) Dissolving in 2ml tetrahydrofuran, stirring at room temperature to dissolve completely; 0.02g of dibutyltin bis (acetylacetonate) was added thereto and stirred uniformly. On a polytetrafluoroethylene mould, taking a cellulose diaphragm as a porous supporting framework, and scraping and coating the uniformly stirred mixture on two sides of the cellulose diaphragm; heating in a vacuum drying oven at 80 ℃ for 10 hours to solidify into a film.
Example 5
2.3g of allyl succinimidyl carbonate (ALOC-OSU), 1g of Maleic Anhydride (MAH), 0.8g of lithium perchlorate (LiClO) 4 ) Dissolving in 2ml tetrahydrofuran, stirring at room temperature to dissolve completely; 0.05g of platinum water (Pt) was added and stirred uniformly. On a polytetrafluoroethylene mould, a non-woven fabric diaphragm is used as a porous supporting framework, and the uniformly stirred mixture is scraped and coated on two sides of the non-woven fabric diaphragm; heating in a vacuum drying oven at 80 ℃ for 10 hours to solidify into a film.
Example 6
5g of allyl tert-butyl peroxycarbonate (TBAC), 3g of allyl-1, 3-sultone (PST) and 1.23g of lithium bistrifluoromethane-sulfonyl imide (LiTFSI) are dissolved in 5ml of dimethyl sulfoxide, and the mixture is stirred at room temperature to be completely dissolved; 0.08g of platinum water (Pt) was added and stirred uniformly. On a polytetrafluoroethylene mould, a whatman diaphragm is used as a porous supporting framework, and the uniformly stirred mixture is scraped on two sides of the whatman diaphragm; heating in a vacuum drying oven at 80 ℃ for 10 hours to solidify into a film.
Electrolyte thickness: the thickness of the block polymer electrolyte was measured using a micrometer (precision 0.01 mm), 3 points on the film were arbitrarily taken for measurement, and the average value was calculated.
Ion conductivity: the polymer electrolyte was sandwiched by two stainless steel gaskets, and the button cell of assembly 2032 was used to measure impedance according to the formula
Figure BDA0003345401620000071
Wherein L is the thickness of the polymer electrolyte, S is the area of the stainless steel gasket, and R is the measured impedance value.
Electrochemical window: polymer electrolyte is clamped by stainless steel and lithium sheets, a 2032 button cell is assembled, linear volt-ampere scanning measurement is carried out, the initial voltage is 2.8V, the highest potential is 5.5V, and the scanning speed is 1mV S -1 。
Figure BDA0003345401620000081
Preparation of a solid-state lithium ion battery:
example 7
Uniformly grinding 200mg of lithium cobaltate and 25mg of acetylene black serving as a conductive agent for 40min; adding 25mg of binder polyvinylidene fluoride, 6mg of electrolyte mixed solution and 200 mu L of 1-methyl-2 pyrrolidone, and uniformly grinding for 40min; coating the aluminum foil surface, and drying at 80 ℃ for 8 hours under vacuum condition to obtain a positive electrode material; the positive electrode sheet was cut into a round sheet with r=0.6 mm, and the polymer electrolyte in example 1 was prepared using the above polymer electrolyte to assemble a solid state lithium ion half cell, and then metal lithium was used as a negative electrode.
Example 8
Uniformly grinding 220mg of lithium iron phosphate and 45mg of acetylene black serving as a conductive agent for 40min; adding 15mg of binder polyvinylidene fluoride, 15mg of electrolyte mixed solution and 150 mu L of 1-methyl-2 pyrrolidone, and uniformly grinding for 40min; coating the aluminum foil surface, and drying at 80 ℃ for 8 hours under vacuum condition to obtain a positive electrode material; and cutting the positive plate into a circular plate with R=0.6mm, and assembling the solid-state lithium ion half battery by adopting the polymer electrolyte. Then, metallic lithium is used as a negative electrode.
Example 9
Uniformly grinding 200mg of nickel cobalt lithium aluminate and 40mg of conductive agent acetylene black for 40min; adding 15mg of binder polyvinylidene fluoride, 15mg of electrolyte mixed solution and 150 mu L of 1-methyl-2 pyrrolidone, and uniformly grinding for 40min; coating the aluminum foil surface, and drying at 80 ℃ for 8 hours under vacuum condition to obtain a positive electrode material; and cutting the positive plate into a circular plate with R=0.6mm, and assembling the solid-state lithium ion half battery by adopting the polymer electrolyte. Then, metallic lithium is used as a negative electrode.

Claims (10)

1. The polymer electrolyte of the wide-temperature high-pressure polyallylcarbonate-based lithium ion battery is characterized in that the polymer electrolyte material comprises polyallylcarbonate monomers or copolymers thereof, conductive lithium salt, an initiator or a catalyst, and is supported by a porous support material.
2. A wide temperature and high pressure polyallylcarbonate-based lithium ion battery polymer electrolyte according to claim 1, wherein the mass fraction of the polyallylcarbonate-based or copolymer thereof in the electrolyte material is 40% to 80%; the mass fraction of the conductive lithium salt in the electrolyte raw material is 10% -50%; the mass fraction of the catalyst is 0.01-10% of the mass of allyl carbonate groups or copolymers thereof.
3. A wide temperature and high pressure polyallylcarbonate based lithium ion battery polymer electrolyte according to claim 1, wherein the corresponding allylcarbonate based monomer structural unit in the polymer has the formula:
Figure FDA0003345401610000011
wherein R is one or more of alkyl, alkoxy, fluorine-containing functional group, boron-containing functional group, ester-containing functional group and nitrogen-containing functional group.
4. A wide temperature and high pressure polyallylcarbonate based lithium ion battery polymer electrolyte as in claim 1 wherein the monomer copolymerized with the allylcarbonate based monomer is one or more of Methyl Methacrylate (MMA) or other methacrylate derivatives, acrylonitrile (AN), acrylamide (AM), maleic Anhydride (MAH), allyl-1, 3-sultone (PST), vinyl Acetate (VA), cyanoacrylate (ECA), ethylene carbonate (VEC), vinylene Carbonate (VCA), lithium acrylate (LiMAA), the mass fraction of allylcarbonate based monomer in the copolymer being 10% to 90%;
the conductive lithium salt is one or more of the following: lithium hexafluorophosphate (LiPF) 6 ) Lithium perchlorate (LiClO) 4 ) Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiLiWSI), lithium bis (oxalato) borate (LiBOB), lithium bis (trifluoromethanesulfonyl) methyllithium [ LiC (SO) 2 CF 3 ) 3 ]Lithium difluorooxalato borate (LiDFOB);
the porous supporting material is one or more of the following: cellulose nonwoven fabric, polyethylene nonwoven fabric, polypropylene nonwoven fabric, glass fiber nonwoven fabric, polytetrafluoroethylene nonwoven fabric;
the initiator or catalyst is one of the following: dibutyl tin dilaurate, dibutyl tin bis (acetylacetonate), azobisisoheptonitrile (ABVN), azobisisobutyronitrile (AIBN), dimethyl Azobisisobutyrate (AIBME), benzoyl Peroxide (BPO), t-butyl benzoyl peroxide (TBPB), methyl Ethyl Ketone Peroxide (MEKPO), platinum water (Pt).
5. The method for preparing the wide-temperature high-pressure polyallylcarbonate-based lithium ion battery polymer electrolyte according to any one of claims 1 to 4, wherein the allyl carbonate-based monomer or the allyl carbonate-containing multicomponent comonomer is subjected to vacuum heating and curing under the action of an initiator or a catalyst to obtain the all-solid-state polymer electrolyte; the method mainly comprises the following steps:
1) Adding conductive lithium salt into allyl carbonate-based monomer solution or multi-component comonomer solution containing allyl carbonate, and fully stirring to obtain uniform solution;
2) Adding an initiator or a catalyst into the solution;
3) Coating or immersing the allyl carbonate-based electrolyte mixed solution obtained in the step 2) into a porous supporting material, and then carrying out vacuum heating curing at 60-120 ℃ for 2-12 hours to obtain the all-solid-state polymer electrolyte.
6. A polymer solid state lithium ion battery of a polyallylcarbonate-based polymer electrolyte, comprising: the positive electrode, the negative electrode and the polymer electrolyte which is arranged between the positive electrode and the negative electrode and has the functions of a diaphragm and an electrolyte; the polymer electrolyte is a wide temperature and high voltage polyallylcarbonate-based lithium ion battery polymer electrolyte as defined in any one of claims 1 to 4.
7. The polymer solid lithium ion battery of claim 6, wherein the positive electrode active material is lithium iron phosphate (LiFeO 4 ) Lithium Nickel Cobalt Aluminate (NCA), lithium rich materials (LLOs), lithium cobalt oxide (LiCoO) 2 ) Lithium ion fluorophosphate, nickel cobalt lithium manganate, lithium manganese oxide, lithium manganate, lithium nickel manganate, lithium iron manganese phosphate, lithium nickelate (LiNiO) 2 ) One or more of the following; 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;
the preparation of the positive electrode comprises the following steps: the preparation of the positive electrode material comprises the following steps: grinding and mixing 50-90% of positive electrode active material and 5-30% of conductive agent acetylene black, adding 1-15% of polyvinylidene fluoride (PVDF), 1-15% of electrolyte mixed solution and 1-methyl-2 pyrrolidone, and grinding and mixing to obtain a positive electrode material, wherein the 1-methyl-2 pyrrolidone is used for adjusting viscosity and is not added into the composition of the positive electrode material in percentage by mass; (2) Coating the anode material on the surface of an aluminum foil, and vacuum drying to obtain an anode;
or the metal lithium and the metal lithium alloy can be directly used as the corresponding negative electrode;
or preparing the negative electrode, comprising the following steps: (1) preparation of a negative electrode material: grinding and mixing 35-85% of negative electrode active material and 5-30% of conductive agent acetylene black; adding polyvinylidene fluoride (PVDF) accounting for 5-20% of the mass fraction, 1-20% of electrolyte mixed solution and 1-methyl-2 pyrrolidone, and grinding and mixing to obtain a cathode material; wherein 1-methyl-2 pyrrolidone is used for adjusting viscosity and is not counted in the mass percentage composition of the anode material; and (2) coating the surface of the copper foil, and drying to obtain the negative electrode.
8. The polymer solid lithium ion battery of the polyallylcarbonate-based polymer electrolyte according to claim 7, wherein the composition of the electrolyte mixture in the positive electrode material and the negative electrode material is: the electrolyte mixed solution comprises 40-80% of allyl carbonate by mass percent, 10-50% of conductive lithium salt by mass percent of electrolyte mixed solution, and 0.1-10% of initiator or catalyst by mass percent of allyl carbonate or copolymer monomer thereof; the specific selection ranges of the respective substances in the electrolyte mixed solution are the same as those of the respective substances of the above-described polycarbonate-based polymer electrolyte raw material.
9. The method for preparing a polymer solid lithium ion battery of polyallylcarbonate-based polymer electrolyte according to claim 6, comprising two processes, (1): ex-situ assembly process-positive electrode, negative electrode and solid polymer electrolyte as described above; (2): in-situ assembling process, the electrolyte mixed solution is injected into a battery system of a positive electrode, a diaphragm and a negative electrode, and is solidified at 60-120 ℃.
10. The use of a wide temperature and high pressure polyallylcarbonate-based lithium ion battery polymer electrolyte as defined in any one of claims 1 to 4 in an all-solid-state lithium ion battery at a temperature of-20 ℃ to 80 ℃.
CN202111323541.4A 2021-11-09 2021-11-09 Wide-temperature high-pressure polyallylcarbonate-based polymer electrolyte Pending CN116111179A (en)

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