CN109509911B - Preparation method of fluoro-material gel polymer electrolyte membrane and lithium ion battery - Google Patents

Preparation method of fluoro-material gel polymer electrolyte membrane and lithium ion battery Download PDF

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CN109509911B
CN109509911B CN201811308167.9A CN201811308167A CN109509911B CN 109509911 B CN109509911 B CN 109509911B CN 201811308167 A CN201811308167 A CN 201811308167A CN 109509911 B CN109509911 B CN 109509911B
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唐伟超
李素丽
赵伟
袁号
李俊义
徐延铭
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Zhuhai Cosmx Battery Co Ltd
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Abstract

The invention provides a preparation method of a fluoro-material gel polymer electrolyte membrane in order to obtain an electrolyte membrane with high electrochemical stability, belonging to the technical field of lithium ion batteries, and the scheme comprises the following steps: adding 5-50 parts by weight of fluorine-containing vinyl monomer, 40-80 parts by weight of gellable monomer and 0-3 parts by weight of polyethylene glycol methacrylate-based monomer into 100-300 parts by weight of solvent, continuously introducing nitrogen, uniformly stirring, adding 0.05-1.00 part by weight of initiator, reacting for 24 hours at 60 ℃, and purifying to obtain polymer A; step two: adding 30-80 parts of polymer A and 0-20 parts of filler into 100-300 parts of solvent, uniformly stirring in a dry nitrogen atmosphere, adding 0-2.00 parts of hydroxyl crosslinking agent into a mixed system, uniformly coating the mixed solution on a smooth mold, and reacting in the nitrogen atmosphere; step three: after the reaction, the obtained product was dried in vacuum to obtain a fluoro-product gel polymer electrolyte membrane.

Description

Preparation method of fluoro-material gel polymer electrolyte membrane and lithium ion battery
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a fluoro-material gel polymer electrolyte membrane and a lithium ion battery.
Background
The lithium ion battery has the advantages of high voltage, no memory effect, wide working temperature range, environmental friendliness and the like, and is widely applied to the fields of electric automobiles, digital codes, large-scale energy storage, national defense and military and the like. At present, a commercialized lithium ion battery mainly adopts liquid electrolyte, and the liquid electrolyte has safety problems of liquid leakage, flammability, explosion and the like due to external collision, extrusion, heating and the like in the use process of the lithium ion battery, so that the large-scale application of the lithium ion battery is severely limited. At present, although there is a certain measure for improving the safety of a liquid lithium ion battery, the effect is very little, and in order to improve the energy density and the safety performance of the lithium ion battery, it is urgently needed to develop a lithium ion battery with high energy density and high safety.
The solid-state battery adopts the solid-state electrolyte material, so that the problems of leakage, flammability and the like of the liquid electrolyte of the lithium ion battery are solved, and the safety of the lithium ion battery can be effectively improved. The solid electrolyte mainly comprises three systems of oxide, sulfide and polymer, the oxide electrolyte has the problems of poor interface contact, difficult thickness control and the like, and the sulfide electrolyte has the problems of high cost, harsh production conditions and the like; the all-solid polymer electrolyte has the problems of low conductivity and the like. In order to solve the safety problem, the gel polymer electrolyte comes along, and the gel polymer electrolyte has the characteristics of high conductivity, good interface contact, easiness in processing, low cost and the like, and is always a key research direction in novel electrolytes.
The fluorine-containing polymer is always the main material in the lithium ion battery, and the Chinese patent application with the publication number of CN201710181998.3 discloses a single-ion polymer electrolyte formed by copolymerizing sodium styrene sulfonate and fluorine-containing acrylate, wherein the conductivity is too low to be industrially applied although the transference number of lithium ions is high. Chinese patent application No. CN 201610487646.6 discloses a method for preparing an electrolyte membrane by copolymerization of sodium styrene sulfonate, polyethylene glycol methacrylate, hexafluorobutyl methacrylate, and ethylene carbonate, wherein a perfluoroalkyl group with strong electron withdrawing property is introduced into the molecular layer, and the structure can promote ionization of lithium ions to a certain extent, improve the mechanical properties of the electrolyte membrane, but the effect is limited. The current patents and literature reports that although the individual performances are outstanding, the performances are still a certain distance away from industrial application.
Disclosure of Invention
The invention aims to provide a preparation method of a fluoro-material gel polymer electrolyte membrane, and the prepared composite gel polymer electrolyte membrane has higher lithium ion conductivity, better mechanical strength and better electrochemical window stability at room temperature.
In order to achieve the purpose, the invention adopts the following technical scheme:
the method comprises the following steps: adding 5-50 parts by weight of fluorine-containing vinyl monomer, 40-80 parts by weight of gellable monomer and 0-10 parts by weight of polyethylene glycol methacrylate-based monomer into 100-300 parts by weight of solvent, keeping the atmosphere of nitrogen or inert gas, stirring at a rotating speed of 100-800 r/min for 10min-120min, then adding 0.05-1.00 part by weight of initiator, then reacting at 60-110 ℃ for 5-48 h, and purifying to obtain polymer A;
step two: adding 30-80 parts by weight of polymer A and 0-20 parts by weight of filler into 100-300 parts by weight of solvent, stirring at a rotating speed of 100-800 r/min in a dry nitrogen or inert gas atmosphere, stirring for 1-10 hours, then adding 0-2.00 parts by weight of hydroxyl crosslinking agent into a mixed system, uniformly coating the mixed solution on a mold with a smooth surface, introducing dry nitrogen or inert gas into a vacuum drying oven, and reacting for 6-24 hours at a temperature of 60-100 ℃ in the dry nitrogen or inert gas atmosphere;
step three: and after the reaction is finished, drying the membrane for 30-60 hours in a vacuum drying oven at the temperature of 90-98 ℃ by taking nitrogen or inert gas as replacement gas to obtain the fluoro-compound gel polymer electrolyte membrane.
Preferably, the structural formula of the fluorine-containing vinyl monomer in the step one is shown in the specification
Figure BDA0001854230000000031
ToAt least one, wherein R is-H, -CH3Or a-F group; structural formula-CxHyFzWherein x, y, z are positive integers, and-CxHyFzMedium X, Y, Z satisfies the saturated structure; structural formula-CaHbFcWherein a, b, C are positive integers, and-CaHbFcWherein a, b and c satisfy a saturated structure; r2And R4is-CAHBFCODA, B, C, D belongs to an integer, A is more than or equal to 0, B is more than or equal to 0, C is more than or equal to 0, and D is more than or equal to 0.
Preferably, in the step one, the gellable monomer is one or a combination of polyethylene glycol methyl ether methacrylate, polyethylene glycol methyl ether acrylate, polyethylene glycol methyl methacrylate, polyethylene glycol monoallyl ether, methyl methacrylate, isobutyl methacrylate, methoxyethyl methacrylate, hydroxypropyl methacrylate, tert-butyl methacrylate, hydroxyethyl methacrylate and acrylonitrile.
Preferably, the polyethylene glycol methacrylate group in the step one is one or a combination of several of polyethylene glycol methyl methacrylate (molecular weight 300-2500) and polyethylene glycol monoallyl ether (molecular weight 100-2400).
Preferably, the solvent in the first step and the second step is one or a combination of several of toluene, acetonitrile, tetrahydrofuran, benzene, acetone, dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone.
Preferably, in the first step, the initiator is one or a combination of several of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide and benzoyl peroxide tert-butyl ester.
Preferably, in the second step, the filler is one or a combination of more of nano-silica (particle size of 7-700 nm), nano-titania, nano-alumina, nano-zirconia, diatomite, bentonite, kaolin, attapulgite, lithium phosphate, lithium titanate, lithium titanium phosphate, lithium titanium aluminum phosphate, lithium lanthanum titanate, lithium lanthanum tantalate, lithium germanium aluminum phosphate, lithium aluminosilicate, lithium silicon phosphate, lithium lanthanum titanate, boron trioxide doped lithium phosphate, lithium lanthanum platinum and lithium lanthanum platinum aluminum oxide.
Preferably, the hydroxyl crosslinking agent in the second step is one or a combination of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), Lysine Diisocyanate (LDI), adipaldehyde, glutaraldehyde, adipoyl chloride, aliphatic polycarbodiimide, aromatic polycarbodiimide, and genipin.
The lithium ion battery comprises a positive electrode, a negative electrode and the fluoro-material gel polymer electrolyte membrane prepared by the preparation method.
The invention has the beneficial effects that:
the invention is different from the traditional polyethylene oxide polymer electrolyte, adopts a molecular design method, the main chain adopts a gel structure and a fluorine-containing vinyl structure, a gel polymer electrolyte matrix with the gel structure and the fluorine-containing structure is formed under certain reaction conditions, simultaneously, a polyether monomer with hydroxyl is copolymerized to obtain the hydroxyl-containing gel polymer electrolyte matrix, after the hydroxyl-containing gel polymer electrolyte matrix is effectively mixed with functional fillers and the like, a specific hydroxyl crosslinking agent is selected to crosslink a polymer electrolyte system to form the polymer electrolyte with the controllable crosslinking structure, the structure can effectively connect an ether oxygen structure with a gel structure and a fluorine-containing structure macromolecule on a molecular level, the polymer system has three special structures of polyether with the crosslinking structure, the gel structure and the fluorine-containing structure, the three special structures have good affinity with the electrolyte and high liquid absorption rate, the effect of improving the room-temperature ionic conductivity of the gel polymer electrolyte is achieved.
The crosslinking degree of the polymer system can be controlled by controlling the addition amount of the crosslinking agent, the reaction degree and the like, when the crosslinking degree is in a certain range, the polymer electrolyte has good interface contact of linear polymers and good mechanical properties of the crosslinked polymers, and meanwhile, the polymer system contains a polyether structure, a gel structure and a fluorine-containing structure, has good liquid retention rate for the liquid absorption rate of the electrolyte, high conductivity and good mechanical properties, and has good application potential.
Drawings
FIG. 1 is a molecular structure diagram of 1H,1H, 2H-perfluoro-1-hexene;
FIG. 2 is a molecular structure diagram of 4,4,5,6,6, 6-octafluoro-2-hexene;
FIG. 3 is a molecular structure diagram of hexafluoropropylene dimer;
FIG. 4 is a molecular structure diagram of hexafluorobutyl acrylate;
FIG. 5 is a molecular structural diagram of hexafluorobutyl methacrylate;
FIG. 6 is a molecular structural diagram of octafluoropentyl methacrylate;
FIG. 7 is a molecular structural diagram of heptafluorobutyl acrylate;
FIG. 8 is a molecular structure diagram of 2,2,3,3,4,4, 4-heptafluoro-butyl methacrylate.
Detailed Description
In order to make the above and other objects, features and advantages of the present invention more apparent, embodiments of the present invention are described in detail below:
the first embodiment is as follows:
the fluoro-species gel polymer electrolyte membrane according to the present embodiment is a copolymer electrolyte membrane of a gellable monomer and a fluorine-containing vinyl monomer, and the preparation method thereof includes the steps of:
the method comprises the following steps: adding 5-50 parts by weight of fluorine-containing vinyl monomer, 40-80 parts by weight of gellable monomer and 0-10 parts by weight of polyethylene glycol methacrylate-based monomer into 100-300 parts by weight of solvent, keeping the atmosphere of nitrogen or inert gas, stirring at a rotating speed of 100-800 r/min for 10min-120min, then adding 0.05-1.00 part by weight of initiator, then reacting at 60-110 ℃ for 5-48 h, and purifying to obtain polymer A;
step two: adding 30-80 parts by weight of polymer A and 0-20 parts by weight of filler into 100-300 parts by weight of solvent, stirring at a rotating speed of 100-800 r/min in a dry nitrogen or inert gas atmosphere, stirring for 1-10 hours, then adding 0-2.00 parts by weight of hydroxyl crosslinking agent into a mixed system, uniformly coating the mixed solution on a mold with a smooth surface, introducing nitrogen or inert gas into a vacuum drying oven, and reacting for 6-24 hours at a temperature of 60-100 ℃ in a nitrogen or inert gas atmosphere;
step three: and after the reaction is finished, drying the membrane for 30-60 hours in a vacuum drying oven at the temperature of 90-98 ℃ by taking nitrogen or inert gas as replacement gas to obtain the fluoro-compound gel polymer electrolyte membrane.
Preferably, the structural formula of the fluorine-containing vinyl monomer in the step one is shown in the specification
Figure BDA0001854230000000061
Wherein R is-H, -CH3Or a-F group; structural formula-CxHyFzWherein x, y, z are positive integers, and-CxHyFzMedium X, Y, Z satisfies the saturated structure; structural formula-CaHbFcWherein a, b, C are positive integers, and-CaHbFcWherein a, b and c satisfy a saturated structure; r2And R4is-CAHBFCODA, B, C, D belongs to an integer, A is more than or equal to 0, B is more than or equal to 0, C is more than or equal to 0, and D is more than or equal to 0.
Preferably, in the step one, the gellable monomer is one or a combination of polyethylene glycol methyl ether methacrylate, polyethylene glycol methyl ether acrylate, polyethylene glycol methyl methacrylate, polyethylene glycol monoallyl ether, methyl methacrylate, isobutyl methacrylate, methoxyethyl methacrylate, hydroxypropyl methacrylate, tert-butyl methacrylate, hydroxyethyl methacrylate and acrylonitrile.
Preferably, the polyethylene glycol methacrylate group in the step one is one or a combination of several of polyethylene glycol methyl methacrylate (molecular weight 300-2500) and polyethylene glycol monoallyl ether (molecular weight 100-2400).
Preferably, the solvent in the first step and the second step is one or a combination of several of toluene, acetonitrile, tetrahydrofuran, benzene, acetone, dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone.
Preferably, in the first step, the initiator is one or a combination of several of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide and benzoyl peroxide tert-butyl ester.
Preferably, in the second step, the filler is one or a combination of more of nano-silica (particle size of 7-700 nm), nano-titania, nano-alumina, nano-zirconia, diatomite, bentonite, kaolin, attapulgite, lithium phosphate, lithium titanate, lithium titanium phosphate, lithium titanium aluminum phosphate, lithium lanthanum titanate, lithium lanthanum tantalate, lithium germanium aluminum phosphate, lithium aluminosilicate, lithium silicon phosphate, lithium lanthanum titanate, boron trioxide doped lithium phosphate, lithium lanthanum platinum and lithium lanthanum platinum aluminum oxide.
Preferably, the hydroxyl crosslinking agent in the second step is one or a combination of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), Lysine Diisocyanate (LDI), adipaldehyde, glutaraldehyde, adipoyl chloride, aliphatic polycarbodiimide, aromatic polycarbodiimide, and genipin.
The lithium ion battery comprises a positive electrode, a negative electrode and the fluoro-material gel polymer electrolyte membrane prepared by the preparation method.
The present invention will be further illustrated by the following specific examples. The reagents, materials and instruments used in the following description are all conventional reagents, conventional materials and conventional instruments, which are commercially available, and the reagents may be synthesized by a conventional synthesis method, if not specifically described.
Example 1
A fluoro-species gel polymer electrolyte membrane is a copolymer electrolyte membrane of a gellable monomer and a fluorine-containing vinyl monomer, and is prepared by a method comprising the steps of:
the method comprises the following steps: adding 3 parts by weight of 1H,1H, 2H-perfluoro-1-hexene, 2 parts by weight of octafluoropentyl methacrylate, 50 parts by weight of polyethylene glycol methyl ether acrylate, 30 parts by weight of methyl methacrylate, 2 parts by weight of polyethylene glycol methyl methacrylate with the molecular weight of 300 and 1 part by weight of polyethylene glycol monoallyl ether with the molecular weight of 2400 into 100 parts by weight of toluene, continuously introducing nitrogen, stirring at the rotating speed of 800r/min for 10min, then adding 1.00 part by weight of azobisisobutyronitrile, reacting at the temperature of 60 ℃ for 48H, and purifying to obtain a polymer A;
step two: adding 80 parts of polymer A, 8 parts of nano silicon dioxide, 8 parts of lithium titanate and 4 parts of lithium aluminosilicate into 100 parts of acetonitrile, stirring at a rotating speed of 400r/min in a dry nitrogen atmosphere for 6 hours, then adding 1 part of Toluene Diisocyanate (TDI) into a mixed system, uniformly coating the mixed solution on a mold with a smooth surface, and reacting at 60 ℃ for 24 hours in a vacuum drying oven in a nitrogen atmosphere;
step three: after the reaction, the obtained product was dried at 90 ℃ for 60 hours in a nitrogen atmosphere to obtain a fluorinated gel polymer electrolyte membrane.
The lithium ion battery comprises a positive electrode, a negative electrode and the fluoro-material gel polymer electrolyte membrane prepared by the method. The preparation method comprises the following steps: and preparing the prepared fluoro-material gel polymer electrolyte membrane, the positive plate and the negative plate into a lithium ion battery cell by adopting a winding process or a lamination process, injecting electrolyte into the battery cell, standing, and performing vacuum packaging by adopting an aluminum-plastic film to obtain the composite gel polymer electrolyte lithium ion battery.
Example 2
A fluoro-species gel polymer electrolyte membrane is a copolymer electrolyte membrane of a gellable monomer and a fluorine-containing vinyl monomer, and is prepared by a method comprising the steps of:
the method comprises the following steps: according to the weight parts, 20 parts of 4,4,5,6,6, 6-octafluoro-2-hexene-containing polymer A, 30 parts of hexafluorobutyl methacrylate, 30 parts of isobutyl methacrylate, 10 parts of polyethylene glycol methyl ether methacrylate, 1 part of polyethylene glycol methyl methacrylate with the molecular weight of 2500 and 5 parts of polyethylene glycol monoallyl ether with the molecular weight of 100 are added into 300 parts of benzene, argon is continuously introduced, the mixture is stirred for 120min at the rotating speed of 100r/min, then 0.05 part of benzoyl peroxide is added, the mixture is reacted for 36h at the temperature of 110 ℃, and the polymer A is obtained after purification treatment;
step two: adding 30 parts of polymer A, 5 parts of nano aluminum oxide, 4 parts of lithium titanium aluminum phosphate and 2 parts of lithium lanthanum tantalate into 200 parts of tetrahydrofuran, stirring at the rotating speed of 800r/min in a dry argon atmosphere, stirring for 1h, then adding 0.5 part of isophorone diisocyanate (IPDI) into a mixed system, uniformly coating the mixed solution on a mold with a smooth surface, and reacting for 6h at 100 ℃ in a vacuum drying oven in the argon atmosphere;
step three: after the reaction, the mixture was dried at 98 ℃ for 30 hours under an argon atmosphere to obtain a fluoro-product gel polymer electrolyte membrane.
The lithium ion battery comprises a positive electrode, a negative electrode and the fluoro-material gel polymer electrolyte membrane prepared by the method. The preparation method comprises the following steps: and preparing the prepared fluoro-material gel polymer electrolyte membrane, the positive plate and the negative plate into a lithium ion battery cell by adopting a winding process or a lamination process, injecting electrolyte into the battery cell, standing, and performing vacuum packaging by adopting an aluminum-plastic film to obtain the composite gel polymer electrolyte lithium ion battery.
Example 3
A fluoro-species gel polymer electrolyte membrane is a copolymer electrolyte membrane of a gellable monomer and a fluorine-containing vinyl monomer, and is prepared by a method comprising the steps of:
the method comprises the following steps: adding 6 parts by weight of hexafluorobutyl acrylate, 4 parts by weight of hexafluoropropylene dimer, 30 parts by weight of methoxyethyl methacrylate, 30 parts by weight of acrylonitrile, 9.5 parts by weight of polyethylene glycol methyl methacrylate with the molecular weight of 1000 and 0.5 part by weight of polyethylene glycol monoallyl ether with the molecular weight of 1000 into 200 parts by weight of N-methylpyrrolidone, continuously introducing dry helium, stirring at the rotating speed of 500r/min for 60min, then adding 0.5 part by weight of azobisisoheptonitrile, then reacting at the temperature of 70 ℃ for 24h, and obtaining a polymer A after purification treatment;
step two: adding 80 parts of polymer A, 2 parts of nano zirconia, 3 parts of lithium titanium phosphate, 5 parts of lithium lanthanum titanate and 5 parts of lithium lanthanum platinum aluminum oxide into 300 parts of benzene, stirring at a rotating speed of 100r/min in a dry helium atmosphere for 10 hours, then adding 0.8 part of diphenylmethane diisocyanate (MDI) into a mixed system, uniformly coating the mixed solution on a mold with a smooth surface, and reacting at 80 ℃ for 12 hours in a vacuum drying oven in the helium atmosphere;
step three: and after the reaction is finished, drying the membrane for 50 hours at the temperature of 95 ℃ in a helium atmosphere to obtain the fluoro-product gel polymer electrolyte membrane.
The lithium ion battery comprises a positive electrode, a negative electrode and the fluoro-material gel polymer electrolyte membrane prepared by the method. The preparation method comprises the following steps: and preparing the prepared fluoro-material gel polymer electrolyte membrane, the positive plate and the negative plate into a lithium ion battery cell by adopting a winding process or a lamination process, injecting electrolyte into the battery cell, standing, and performing vacuum packaging by adopting an aluminum-plastic film to obtain the composite gel polymer electrolyte lithium ion battery.
Example 4
A fluoro-species gel polymer electrolyte membrane is a copolymer electrolyte membrane of a gellable monomer and a fluorine-containing vinyl monomer, and is prepared by a method comprising the steps of:
the method comprises the following steps: according to parts by weight, adding 25 parts of hexafluorobutyl acrylate, 5 parts of methacrylic acid-2, 2,3,3,4,4, 4-heptafluoro-butyl ester, 10 parts of heptafluorobutyl acrylate, 30 parts of methoxyethyl methacrylate, 20 parts of tert-butyl methacrylate, 1 part of polyethylene glycol methyl methacrylate with the molecular weight of 500 and 1 part of polyethylene glycol monoallyl ether with the molecular weight of 1200 into 250 parts of N, N-dimethylformamide, continuously introducing neon, stirring at the rotating speed of 200r/min for 100min, then adding 0.8 part of benzoyl peroxide tert-butyl ester, then reacting for 5h at the temperature of 110 ℃, and purifying to obtain a polymer A;
step two: adding 60 parts of polymer A, 5 parts of nano titanium dioxide, 6 parts of lithium aluminum germanium phosphate and 3 parts of boron trioxide doped lithium phosphate into 200 parts of tetrahydrofuran, stirring at the rotating speed of 600r/min in a dry neon atmosphere for 8 hours, then adding 2 parts of Hexamethylene Diisocyanate (HDI) into a mixed system, uniformly coating the mixed solution on a mold with a smooth surface, and reacting at 70 ℃ for 10 hours in a vacuum drying oven in the neon atmosphere;
step three: and after the reaction is finished, drying the membrane for 40 hours at 90 ℃ in a neon atmosphere to obtain the fluoride gel polymer electrolyte membrane.
The lithium ion battery comprises a positive electrode, a negative electrode and the fluoro-material gel polymer electrolyte membrane prepared by the method. The preparation method comprises the following steps: and preparing the prepared fluoro-material gel polymer electrolyte membrane, the positive plate and the negative plate into a lithium ion battery cell by adopting a winding process or a lamination process, injecting electrolyte into the battery cell, standing, and performing vacuum packaging by adopting an aluminum-plastic film to obtain the composite gel polymer electrolyte lithium ion battery.
Example 5
A fluoro-species gel polymer electrolyte membrane is a copolymer electrolyte membrane of a gellable monomer and a fluorine-containing vinyl monomer, and is prepared by a method comprising the steps of:
the method comprises the following steps: adding 20 parts by weight of hexafluorobutyl methacrylate, 10 parts by weight of octafluoropentyl methacrylate, 20 parts by weight of hydroxypropyl methacrylate, 20 parts by weight of hydroxyethyl methacrylate, 3 parts by weight of polyethylene glycol methyl methacrylate with the molecular weight of 1000 and 4 parts by weight of polyethylene glycol monoallyl ether with the molecular weight of 2400 into 150 parts by weight of benzene, continuously introducing nitrogen, stirring at the rotating speed of 600r/min for 40min, then adding 0.9 part of dimethyl azodiisobutyrate, then reacting at 80 ℃ for 12h, and purifying to obtain a polymer A;
step two: adding 50 parts by weight of polymer A, 6 parts by weight of lithium phosphate, 3 parts by weight of lithium silicophosphate and 9 parts by weight of lithium lanthanum titanate into 250 parts by weight of acetone, stirring at a rotating speed of 500r/min in a dry nitrogen atmosphere for 3 hours, then adding 1 part by weight of dicyclohexylmethane diisocyanate (HMDI) into a mixed system, uniformly coating the mixed solution on a mold with a smooth surface, and reacting for 20 hours at 90 ℃ in a vacuum drying oven in a nitrogen atmosphere;
step three: after the reaction, the obtained product was dried at 98 ℃ for 48 hours in a nitrogen atmosphere to obtain a fluoro-product gel polymer electrolyte membrane.
The lithium ion battery comprises a positive electrode, a negative electrode and the fluoro-material gel polymer electrolyte membrane prepared by the method. The preparation method comprises the following steps: and preparing the prepared fluoro-material gel polymer electrolyte membrane, the positive plate and the negative plate into a lithium ion battery cell by adopting a winding process or a lamination process, injecting electrolyte into the battery cell, standing, and performing vacuum packaging by adopting an aluminum-plastic film to obtain the composite gel polymer electrolyte lithium ion battery.
Example 6
A fluoro-species gel polymer electrolyte membrane is a copolymer electrolyte membrane of a gellable monomer and a fluorine-containing vinyl monomer, and is prepared by a method comprising the steps of:
the method comprises the following steps: adding 20 parts by weight of hexafluorobutyl acrylate, 20 parts by weight of methyl methacrylate, 20 parts by weight of isobutyl methacrylate, 20 parts by weight of acrylonitrile, 10 parts by weight of polyethylene glycol methyl ether methacrylate, 2 parts by weight of polyethylene glycol methyl methacrylate with the molecular weight of 500 and 2 parts by weight of polyethylene glycol monoallyl ether with the molecular weight of 1200 into 300 parts by weight of N-methyl pyrrolidone, continuously introducing argon, stirring for 30min at the rotating speed of 700r/min, then adding 1 part by weight of benzoyl peroxide, then reacting for 30h at the temperature of 90 ℃, and purifying to obtain a polymer A;
step two: adding 80 parts of polymer A, 10 parts of lanthanum platinum lithium and 10 parts of lithium phosphate into 300 parts of acetonitrile, stirring at a rotating speed of 400r/min in a dry argon gas atmosphere, stirring for 9 hours, then adding 2 parts of Hexamethylene Diisocyanate (HDI) into a mixed system, uniformly coating the mixed solution on a mold with a smooth surface, and reacting for 24 hours at 100 ℃ in a vacuum drying oven in an argon gas atmosphere;
step three: after the reaction, the obtained product was dried at 90 ℃ for 50 hours in an argon atmosphere to obtain a fluoro-product gel polymer electrolyte membrane.
The lithium ion battery comprises a positive electrode, a negative electrode and the fluoro-material gel polymer electrolyte membrane prepared by the method. The preparation method comprises the following steps: and preparing the prepared fluoro-material gel polymer electrolyte membrane, the positive plate and the negative plate into a lithium ion battery cell by adopting a winding process or a lamination process, injecting electrolyte into the battery cell, standing, and performing vacuum packaging by adopting an aluminum-plastic film to obtain the composite gel polymer electrolyte lithium ion battery.
Example 7
A fluoro-species gel polymer electrolyte membrane is a copolymer electrolyte membrane of a gellable monomer and a fluorine-containing vinyl monomer, and is prepared by a method comprising the steps of:
the method comprises the following steps: adding 15 parts of 1H,1H, 2H-perfluoro-1-hexene, 15 parts of hexafluorobutyl acrylate, 20 parts of methyl methacrylate, 20 parts of tert-butyl methacrylate and 40 parts of acrylonitrile into 100 parts of toluene, continuously introducing nitrogen, stirring at the rotating speed of 200r/min for 90min, then adding 0.8 part of benzoyl peroxide, then reacting at 100 ℃ for 10H, and purifying to obtain a polymer A;
step two: adding 40 parts of polymer A, 4 parts of nano-silica, 3 parts of diatomite and 3 parts of attapulgite into 200 parts of acetonitrile, stirring at the rotating speed of 700r/min in a dry nitrogen atmosphere for 7 hours, then uniformly coating the mixed solution on a mold with a smooth surface, and reacting at 60 ℃ for 18 hours in a vacuum drying oven in the nitrogen atmosphere;
step three: after the reaction, the obtained product was dried at 96 ℃ for 30 hours in a nitrogen atmosphere to obtain a fluoro-product gel polymer electrolyte membrane.
The lithium ion battery comprises a positive electrode, a negative electrode and the fluoro-material gel polymer electrolyte membrane prepared by the method. The preparation method comprises the following steps: and preparing the prepared fluoro-material gel polymer electrolyte membrane, the positive plate and the negative plate into a lithium ion battery cell by adopting a winding process or a lamination process, injecting electrolyte into the battery cell, standing, and performing vacuum packaging by adopting an aluminum-plastic film to obtain the composite gel polymer electrolyte lithium ion battery.
The composite gel polymer electrolyte membranes prepared in examples 1 to 7 and the gel-able polymer electrolyte were subjected to room temperature conductivity and liquid absorption rate tests, and the test results are shown in the following table.
Figure BDA0001854230000000141
From the results of the above table, it can be seen that the room temperature ionic conductivity and the liquid absorption rate of the crosslinked gel polymer electrolytes containing fluorine structures prepared in examples 1 to 7 are substantially superior to those of the existing polyethylene oxide electrolyte, polyacrylonitrile electrolyte and polymethyl methacrylate electrolyte. Furthermore, the polyether cross-linked structure fluorine-containing gel polymer electrolytes prepared in examples 1 to 7 all have higher ionic conductanceRate (> 10)-3S/cm), and the introduction of the fluorine-containing structure is proved to be capable of effectively improving the liquid absorption rate and the conductivity of the gel polymer electrolyte.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A method for preparing a fluoro-species gel polymer electrolyte membrane, comprising the steps of:
the method comprises the following steps: adding 5-50 parts by weight of fluorine-containing vinyl monomer, 40-80 parts by weight of gellable monomer and 2-10 parts by weight of polyethylene glycol methacrylate monomer into 100-300 parts by weight of solvent, keeping the atmosphere of nitrogen or inert gas, stirring at a rotating speed of 100-800 r/min for 10-120 min, then adding 0.05-1.00 part of initiator, then reacting at 60-110 ℃ for 5-48 h, and purifying to obtain polymer A;
step two: adding 30-80 parts by weight of polymer A and 0-20 parts by weight of filler into 100-300 parts by weight of solvent, stirring at a rotating speed of 100-800 r/min in a dry nitrogen or inert gas atmosphere, stirring for 1-10 hours, then adding 0.5-2.00 parts by weight of hydroxyl crosslinking agent into a mixed system, uniformly coating the mixed solution on a mold with a smooth surface, introducing dry nitrogen or inert gas into a vacuum drying oven, and reacting for 6-24 hours at 60-100 ℃ in the dry nitrogen or inert gas atmosphere;
step three: and after the reaction is finished, drying the membrane for 30-60 hours in a vacuum drying oven at the temperature of 90-98 ℃ by taking nitrogen or inert gas as replacement gas to obtain the fluoro-compound gel polymer electrolyte membrane.
2. The method for producing a fluoro-species gel polymer electrolyte membrane according to claim 1, wherein: step one, the structural formula of the fluorine-containing vinyl monomer is shown as
Figure FDA0002800420460000011
Wherein R is-H, -CH3Or a-F group; structural formula-CxHyFzWherein x, y, z are positive integers, and-CxHyFzMedium X, Y, Z satisfies the saturated structure; structural formula-CaHbFcWherein a, b, C are positive integers, and-CaHbFcWherein a, b and c satisfy a saturated structure; r2And R4is-CAHBFCODA, B, C, D belongs to an integer, A is more than or equal to 0, B is more than or equal to 0, C is more than or equal to 0, and D is more than or equal to 0.
3. The method for producing a fluoro-species gel polymer electrolyte membrane according to claim 1, wherein: the gellable monomer in the step one is one or a combination of more of polyethylene glycol methyl ether methacrylate, polyethylene glycol methyl ether acrylate, polyethylene glycol methyl methacrylate, polyethylene glycol monoallyl ether, methyl methacrylate, isobutyl methacrylate, methoxyethyl methacrylate, hydroxypropyl methacrylate, tert-butyl methacrylate, hydroxyethyl methacrylate and acrylonitrile.
4. The method for producing a fluoro-species gel polymer electrolyte membrane according to claim 1, wherein: the polyethylene glycol methyl acrylate is one or a combination of polyethylene glycol methyl methacrylate and polyethylene glycol monoallyl ether, the molecular weight of the polyethylene glycol methyl methacrylate is 300-2500, and the molecular weight of the polyethylene glycol monoallyl ether is 100-2400.
5. The method for producing a fluoro-species gel polymer electrolyte membrane according to claim 1, wherein: in the first step and the second step, the solvent is one or a combination of several of toluene, acetonitrile, tetrahydrofuran, benzene, acetone, dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone.
6. The method for producing a fluoro-species gel polymer electrolyte membrane according to claim 1, wherein: the initiator in the first step is one or a combination of a plurality of azodiisobutyronitrile, azodiisoheptonitrile, dimethyl azodiisobutyrate, benzoyl peroxide and benzoyl peroxide tert-butyl ester.
7. The method for producing a fluoro-species gel polymer electrolyte membrane according to claim 1, wherein: in the second step, the filler is one or a combination of more of nano silicon dioxide, nano titanium dioxide, nano aluminum oxide, nano zirconium oxide, diatomite, bentonite, kaolin, attapulgite, lithium phosphate, lithium titanate, lithium titanium phosphate, lithium aluminum titanium phosphate, lanthanum lithium titanate, lanthanum lithium tantalate, lithium aluminum germanium phosphate, lithium aluminosilicate, lithium silicon phosphate, lanthanum lithium titanate, boron trioxide doped lithium phosphate, lanthanum platinum lithium and lanthanum lithium platinum aluminum oxide.
8. The method for producing a fluoro-species gel polymer electrolyte membrane according to claim 1, wherein: step two, the hydroxyl crosslinking agent is one or a combination of several of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), Lysine Diisocyanate (LDI), adipaldehyde, glutaraldehyde, adipoyl chloride, aliphatic polycarbodiimide, aromatic polycarbodiimide and genipin.
9. The method for producing a fluoro-species gel polymer electrolyte membrane according to claim 7, wherein: the particle size of the nano silicon dioxide is 7-700 nm.
10. A lithium ion battery comprising the fluoro-species gel polymer electrolyte membrane of any one of claims 1 to 8, wherein: the composition of the electrolyte comprises a positive electrode, a negative electrode and a fluoro-compound gel polymer electrolyte membrane.
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