CN109037769B - Preparation method of gel polymer electrolyte with composite carbonic acid cross-linked structure - Google Patents
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Abstract
A preparation method of a gel polymer electrolyte with a composite carbonic acid cross-linked structure comprises the following steps: adding a carbonic acid structural cross-linking agent, a gellable monomer, a functional polymer, an inorganic filler and/or a fast ion conductor and a solvent into a reactor together, and continuously introducing inert gas into the reactor for stirring to form a uniform precursor solution; adding an initiator into the precursor solution, continuously stirring in an inert gas atmosphere to obtain a mixed solution, uniformly coating the mixed solution on a mold, evaporating the solvent to obtain a crosslinked polymer film, and carrying out an initiation reaction on the crosslinked polymer film in the inert gas atmosphere; and after the initiation reaction is finished, carrying out vacuum drying to obtain the gel polymer electrolyte. According to the invention, the carbonate multi-alkenyl structural monomer is used as a cross-linking agent to be cross-linked and copolymerized with the gel monomer, and the liquid absorption rate and the conductivity of the gel polymer electrolyte can be effectively improved by introducing the carbonic acid cross-linked structure.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a gel polymer electrolyte.
Background
Compared with batteries such as lead-acid storage batteries, nickel-metal hydride batteries and nickel-insulated batteries, the lithium ion battery has the characteristics of high voltage, high energy density, long service life, low self-discharge, no memory effect, environmental friendliness and the like, and is widely applied to the fields of power equipment, digital equipment and the like in recent years. The lithium ion battery mainly comprises a positive pole piece, a negative pole piece, a diaphragm and electrolyte, most of the lithium ion batteries on the market adopt liquid electrolyte, and the application range of the lithium ion battery is limited because the risks of electrolyte leakage, flammability, explosion and the like can exist in the use process of the battery. The main method for solving the safety problem of the liquid electrolyte at present is to modify the existing electrolyte system by using a modified material, but the method addresses both the symptoms and the root causes, and does not fundamentally solve the safety problem of the lithium ion battery caused by the liquid electrolyte.
The solid-state lithium ion battery is always considered to be the next generation lithium ion battery which is closest to practical use, and the solid-state lithium ion battery adopts non-liquid electrolyte, so that the problems of liquid leakage, flammability, explosion and the like of the liquid-state lithium ion battery can be fundamentally solved. The non-liquid electrolyte used by the solid lithium ion battery mainly comprises a polymer electrolyte, an oxide electrolyte and a sulfide electrolyte, wherein the oxide electrolyte has low conductivity and poor interface contact, and the sulfide electrolyte has the problems of high cost, harsh production conditions and the like, so the polymer electrolyte becomes a research and development hotspot of the non-liquid electrolyte.
The polymer electrolyte is divided into gel polymer electrolyte and all-solid-state polymer electrolyte, and the gel polymer electrolyte has lithium ion conductivity comparable to liquid electrolyte and has certain mechanical property. At present, gel polymer electrolytes mainly comprise systems such as polymethyl methacrylate, polyvinylidene fluoride-hexafluoropropylene, polyacrylonitrile, polyether and the like, are generally prepared by methods such as copolymerization, crosslinking and the like, and are prepared into the gel polymer electrolytes by pore-forming and liquid-absorbing. The polymethyl methacrylate system has better liquid absorption rate, but has poor mechanical property after being formed into gel, and is easy to dissolve in electrolyte; the polyvinylidene fluoride system and the polyvinylidene fluoride-hexafluoropropylene system have strong electronegativity, but have poor film forming property and compatibility with a lithium cathode, and have higher cost; the polyacrylonitrile system has strong polarity, but is easy to crystallize and has poor mechanical property; the polyether system has good liquid absorption rate but poor electrochemical stability.
In order to improve the performance of gel polymer electrolyte, the chinese invention patent with patent number 201310476395.8 adopts butyl acrylate, styrene, methyl methacrylate and acrylonitrile as raw materials to prepare copolymer type gel polymer, the system adopts a plurality of gel monomers for copolymerization, although different material systems have advantages, the advantages and the disadvantages of the material systems are not compatible with each other, for example, the mechanical property of styrene is good but the liquid absorption rate is poor, the liquid absorption rate of methyl methacrylate is good but the materials are brittle, the conductivity and the mechanical property in the gel polymer electrolyte after copolymerization are not perfectly compatible, and the cycle performance of the assembled battery is not good. The chinese patent publication No. CN104393336B discloses that nano-composite fiber reinforced gel polymer electrolyte is prepared by using nano-silica, polymethyl methacrylate, and polyvinylidene fluoride as raw materials and nano-composite fibers as a skeleton support structure, but the patent only simply performs physical compounding on the polymethyl methacrylate, the polyvinylidene fluoride, and the nano-silica, and the prepared nano-composite fiber reinforced gel polymer electrolyte has relatively low conductivity.
Disclosure of Invention
The invention aims to provide a preparation method of a gel polymer electrolyte with high lithium ion conductivity and good mechanical strength at room temperature.
In order to achieve the purpose, the invention adopts the following technical solutions:
a preparation method of a gel polymer electrolyte with a composite carbonic acid cross-linked structure comprises the following steps:
s1, adding 0.1-10 parts by mass of carbonic acid structural cross-linking agent, 70-95 parts by mass of gellable monomer, 0-5 parts by mass of functional polymer, 0-50 parts by mass of inorganic filler and/or fast ion conductor and solvent into a reactor, and continuously introducing inert gas into the reactor for stirring to form uniform precursor solution;
s2, adding 0.1-1 part by mass of an initiator into the precursor solution, continuously stirring in an inert gas atmosphere to obtain a mixed solution, uniformly coating the mixed solution on a mold, evaporating the solvent to obtain a cross-linked polymer film, and carrying out an initiation reaction on the cross-linked polymer film in the inert gas atmosphere;
and S3, after the initiation reaction is finished, carrying out vacuum drying to obtain the gel polymer electrolyte.
More specifically, the carbonic acid structure crosslinking agent is a polymerizable monomer having both a carbonic acid structure and a polypolyalkenyl group.
More specifically, the structural formula of the carbonic acid structural cross-linking agent is as follows:
More specifically, the carbonic acid structure cross-linking agent is one or more of bis (vinyl) carbonate, 2-ethoxycarbonyloxyethyl-2-methylpropyl-2-enoate, 2-propenyl-2-propyl-2-oxycarbonyloxy-2-enoate, 2- [ [ (2-allyloxy) carbonyl ] oxy ] propyl methacrylate and oxydi-2, 1-ethanediyldivinyl dicarbonate.
More specifically, the gellable monomer is one or 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.
More specifically, the functional polymer is one or more of polyvinylidene fluoride, poly (vinylidene fluoride-hexafluoropropylene), high molecular polyethylene, polypropylene, polystyrene, polyethylene oxide and polycarbonate.
More specifically, the initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide and benzoyl peroxide tert-butyl ester.
More specifically, the inorganic filler is one or more of nano silicon dioxide, nano titanium dioxide, nano aluminum oxide, nano zirconia, diatomite, bentonite, kaolin or attapulgite.
More specifically, the fast ion conductor is lithium phosphate, lithium titanate, lithium titanium phosphate, lithium aluminum titanium phosphate, lithium lanthanum titanate, lithium lanthanum tantalate, lithium aluminum germanium phosphate, lithium aluminosilicate, lithium silicon phosphate, lithium lanthanum titanate, boron trioxide doped lithium phosphate, lithium lanthanum platinum aluminum oxide, LISICON, NASICON, Li2S-P2S5、Li2S-SiS2、Li2S-GeS2、Li2S-B2S3、Li2S-MeS2-P2S5One or more of them.
More specifically, the crosslinked polymer film is subjected to thermal initiation reaction under the inert gas atmosphere, the reaction temperature is 60-120 ℃, and the reaction time is 2-36 h.
According to the technical scheme, the carbonate functionalized multi-alkenyl structure monomer is used as the cross-linking agent, the carbonate multi-alkenyl structure and the gel monomer structure are effectively combined on the molecular level by a molecular design method, and the prepared electrolyte not only keeps the advantages of good mechanical property, stable electrochemical property, high liquid absorption rate and the like of the carbonate structure, but also has the advantages of high conductivity and the like of the gel monomer; and a carbonate structure is introduced at the molecular level, so that compared with the conventional gel polymer electrolyte, the gel polymer electrolyte has better electrochemical stability, higher liquid absorption rate, better conductivity and good mechanical property.
Detailed Description
In order to make the aforementioned and other objects, features and advantages of the invention more apparent, embodiments of the invention are described in detail below.
The gel polymer electrolyte has a cross-linked carbonic acid structure, and the preparation method comprises the following steps:
s1, adding 0.1-10 parts by mass of carbonic acid structure cross-linking agent, 70-95 parts by mass of gellable monomer, 0-5 parts by mass of functional polymer, 0-50 parts by mass of inorganic filler and/or fast ion conductor and solvent into a reactor, continuously introducing inert gas into the reactor, and continuously stirring at the speed of 100-500 r/min to form uniform precursor solution;
s2, adding 0.1-1 part by mass of an initiator into the precursor solution, continuously stirring for 1-24 hours at a speed of 100-600 r/min in an inert gas atmosphere to obtain a mixed solution, uniformly coating the mixed solution on a mold, evaporating the solvent to obtain a cross-linked polymer film with a certain thickness, and carrying out an initiation reaction on the cross-linked polymer film in the inert gas atmosphere;
and S3, after the initiation reaction is finished, vacuum drying is carried out for 24-48 h at the temperature of 60-100 ℃, and the gel polymer electrolyte with the cross-linked carbonic acid structure is obtained.
And (3) assembling the prepared electrolyte, the anode material and the cathode material into a polymer lithium ion battery core by adopting a conventional process, encapsulating and baking the polymer lithium ion battery core, injecting a proper amount of electrolyte, and then carrying out hot pressing formation, secondary sealing, sorting, OCV (open circuit control) and packaging to obtain the lithium ion gel polymer battery.
The carbonic acid structure cross-linking agent used in the preparation of the precursor solution is a polymeric monomer which simultaneously has a carbonic acid structure and a polymerizable polyene group, and the structural formula is as follows:
The carbonic acid structure crosslinking agent can be one or more of bis (vinyl) carbonate, 2-ethoxycarbonyloxyethyl-2-methylpropyl-2-enoate, 2-propenyl-2-propyl-2-oxycarbonyloxy-2-enoate, 2- [ [ (2-allyloxy) carbonyl ] oxy ] propyl methacrylate and oxydi-2, 1-ethanediyl divinyl dicarbonate.
The gellable monomer can be one or more of polyethylene glycol methyl ether methacrylate with the molecular weight of 300-20000, polyethylene glycol methyl ether acrylate with the molecular weight of 480-5000, polyethylene glycol methyl methacrylate with the molecular weight of 300-2500, polyethylene glycol monoallyl ether with the molecular weight of 100-2400, methyl methacrylate, isobutyl methacrylate, methoxyethyl methacrylate, hydroxypropyl methacrylate, tert-butyl methacrylate, hydroxyethyl methacrylate and acrylonitrile.
The functional polymer can be one or more of polyvinylidene fluoride, poly (vinylidene fluoride-hexafluoropropylene), high molecular polyethylene, polypropylene, polystyrene, polyethylene oxide and polycarbonate.
The solvent is conventional solvent, and can be one or more of acetonitrile, tetrahydrofuran, acetone, methyl pyrrolidone, N-dimethyl diamide, ethyl acetate and sulfolane.
The initiator used for carrying out the initiation reaction can be one or more of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide and benzoyl peroxide tert-butyl ester.
The inorganic filler may be nanoSilicon dioxide, nano titanium dioxide, nano aluminum oxide, nano zirconia, diatomite, bentonite, kaolin, attapulgite and the like; the fast ion conductor may be lithium phosphate (Li)3PO4) Lithium titanate (Li)4Ti5O12) Lithium titanium phosphate [ LiTi ]2(PO4)3]Lithium aluminum titanium phosphate [ LiAl ]XTi2-X(PO4)3]Lithium lanthanum titanate (Li)0.35La0.57TiO3) Lanthanum lithium tantalate (Li)0.35La0.57Ta0.8O3) Lithium aluminum germanium phosphate [ Li ]1.5Al0.5Ge1.5(PO4)3]Lithium aluminosilicate (LiAlSiO)4) Lithium silicophosphate (Li)3.5Si0.5P0.5O4) Boron trioxide doped lithium phosphate (Li)3PO4:B2O3) Lanthanum platinum lithium [ LLZO Li(7-X)La3Zr(2-X)MXO12 0.15≤M≤0.25(M＝Al、Ta、W……)]Lanthanum lithium platinum aluminum oxide (Al-LLZO), LISICON, NASICON, Li2S-P2S5、Li2S-SiS2、Li2S-GeS2、Li2S-B2S3、Li2S-MeS2-P2S5(Me is one or more of Si, Ge, Sn, Al, etc.).
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
S1, adding 0.1 part by mass of bis (vinyl) carbonate, 25 parts by mass of polyethylene glycol methyl ether methacrylate (molecular weight 300), 25 parts by mass of polyethylene glycol methyl ether acrylate (molecular weight 5000), 25 parts by mass of polyethylene glycol monoallyl ether (molecular weight 2400), 20 parts by mass of methyl methacrylate, 2 parts by mass of polyvinylidene fluoride, 5 parts by mass of nano-silica, 5 parts by mass of nano-alumina, 20 parts by mass of lanthanum lithium titanate, 20 parts by mass of germanium aluminum lithium phosphate and N, N-dimethyl diamide into a reactor, continuously introducing nitrogen into the reactor, and continuously stirring at the rotating speed of 500r/min until the mixture is uniform to obtain a precursor solution;
s2, adding 1 part by mass of benzoyl peroxide into the precursor solution, continuously stirring for 24 hours at a speed of 600r/min in an inert gas atmosphere to obtain a mixed solution, uniformly coating the mixed solution on a mold, evaporating the solvent to obtain a crosslinked polymer film, and carrying out thermal initiation reaction on the crosslinked polymer film in the inert gas atmosphere, wherein the reaction temperature is 100 ℃ and the reaction time is 24 hours;
and S3, after the initiation reaction is finished, drying for 48 hours in vacuum at the temperature of 60 ℃ to obtain the gel polymer electrolyte.
In the embodiment, the functional polymer, the inorganic filler and the fast ion conductor are added into the precursor solution, the functional polymer can improve the film forming performance and the mechanical property of the polymer system before polymerization, so that the film forming at the later stage is facilitated, and the functional polymer also has a certain lithium conducting function and can increase the conductivity of lithium ions. Inorganic filler and fast ion conductor are added, the inorganic filler can improve the mechanical property of the polymer electrolyte on one hand, and can reduce the crystallization degree of the polymer on the other hand, thereby improving the conductivity of the polymer; and the inorganic filler having a porous structure can also adsorb gas or trace water generated during the preparation or use of the battery. The addition of the fast ionic conductor can also reduce the crystallization degree of the polymer electrolyte and improve the conductivity of the polymer electrolyte, and the small-particle fast ionic conductor also has the function of improving the mechanical property of the polymer electrolyte; and the fast ion conductor has the function of lithium conduction, can also play a role in the lithium ion conductivity of the polymer electrolyte, and does not repeatedly conflict with the inorganic filler.
Example 2
S1, adding 10 parts by mass of 2-ethoxycarbonyloxyethyl-2-methylpropyl-2-enoate, 20 parts by mass of polyethylene glycol methyl ether methacrylate (molecular weight 20000), 5 parts by mass of polyethylene glycol methyl methacrylate (molecular weight 2500), 5 parts by mass of polyethylene glycol methyl ether acrylate (molecular weight 480), 30 parts by mass of isobutyl methacrylate, 15 parts by mass of polyethylene glycol monoallyl ether (molecular weight 100), 3 parts by mass of polycarbonate, 2 parts by mass of poly (vinylidene fluoride-hexafluoropropylene), 10 parts by mass of nano titanium dioxide, 10 parts by mass of lithium aluminosilicate and methyl pyrrolidone into a reactor, continuously introducing nitrogen into the reactor and continuously stirring at a rotating speed of 400r/min until the mixture is uniform to obtain a precursor solution;
s2, adding 0.8 part by mass of benzoyl peroxide tert-butyl ester into the precursor solution, continuously stirring for 1h at a speed of 400r/min in an inert gas atmosphere to obtain a mixed solution, uniformly coating the mixed solution on a mold, evaporating the solvent to obtain a crosslinked polymer film, and carrying out thermal initiation reaction on the crosslinked polymer film in the inert gas atmosphere at the reaction temperature of 120 ℃ for 2 h;
and S3, after the initiation reaction is finished, drying for 36h in vacuum at 100 ℃ to obtain the gel polymer electrolyte.
Example 3
S1, adding 5 parts by mass of 2-propenyl-2-propyl-2-oxycarbonyloxy-2-enoate, 10 parts by mass of polyethylene glycol methyl ether methacrylate (molecular weight 950), 10 parts by mass of polyethylene glycol methyl ether acrylate (molecular weight 1000), 20 parts by mass of polyethylene glycol methyl methacrylate (molecular weight 300), 10 parts by mass of methoxyethyl methacrylate, 40 parts by mass of acrylonitrile, 3 parts by mass of polyethylene oxide and acetonitrile into a reactor, continuously introducing nitrogen into the reactor, and continuously stirring at the rotating speed of 100r/min until the mixture is uniform to obtain a precursor solution;
s2, adding 0.5 part by mass of azobisisobutyronitrile into the precursor solution, continuously stirring for 10 hours at a speed of 100r/min in an inert gas atmosphere to obtain a mixed solution, uniformly coating the mixed solution on a mold, evaporating the solvent to obtain a crosslinked polymer film, and carrying out thermal initiation reaction on the crosslinked polymer film in the inert gas atmosphere at the reaction temperature of 60 ℃ for 10 hours;
and S3, after the initiation reaction is finished, drying the mixture in vacuum for 24 hours at the temperature of 90 ℃ to obtain the gel polymer electrolyte.
Example 4
S1, adding 1 part by mass of 2- [ [ (2-allyloxy) carbonyl ] oxy ] propyl methacrylate, 20 parts by mass of polyethylene glycol methyl methacrylate (molecular weight 1000), 10 parts by mass of polyethylene glycol monoallyl ether (molecular weight 2000), 40 parts by mass of hydroxypropyl methacrylate, 5 parts by mass of nano zirconium oxide, 5 parts by mass of lanthanum platinum lithium and tetrahydrofuran into a reactor, continuously introducing nitrogen into the reactor, and continuously stirring at the rotating speed of 200r/min until the mixture is uniform to obtain a precursor solution;
s2, adding 0.1 part by mass of azobisisoheptonitrile into the precursor solution, continuously stirring for 20 hours at a speed of 300r/min in an inert gas atmosphere to obtain a mixed solution, uniformly coating the mixed solution on a mold, evaporating the solvent to obtain a crosslinked polymer film, and carrying out thermal initiation reaction on the crosslinked polymer film under the inert gas at the reaction temperature of 80 ℃ for 16 hours;
and S3, after the initiation reaction is finished, drying for 40h in vacuum at 65 ℃ to obtain the gel polymer electrolyte.
Example 5
S1, adding 8 parts by mass of 2- [ [ (2-allyloxy) carbonyl ] oxy ] propyl methacrylate, 25 parts by mass of polyethylene glycol monoallyl ether (molecular weight 2400), 30 parts by mass of methyl methacrylate, 30 parts by mass of acrylonitrile, 4 parts by mass of polystyrene, 20 parts by mass of lanthanum lithium platinum aluminum oxide, 10 parts by mass of nano silicon dioxide and tetrahydrofuran into a reactor, continuously introducing nitrogen into the reactor, and continuously stirring at the rotating speed of 300r/min until the mixture is uniform to obtain a precursor solution;
s2, adding 0.6 part by mass of benzoyl peroxide tert-butyl ester into the precursor solution, continuously stirring for 12 hours at the speed of 500r/min to obtain a mixed solution, uniformly coating the mixed solution on a mold, evaporating the solvent to obtain a crosslinked polymer film, and carrying out thermal initiation reaction on the crosslinked polymer film in an inert gas atmosphere, wherein the reaction temperature is 110 ℃ and the reaction time is 36 hours;
and S3, after the initiation reaction is finished, drying for 30h in vacuum at 70 ℃ to obtain the gel polymer electrolyte.
Example 6
S1, adding 9 parts by mass of oxydi-2, 1-ethanediyldivinyl dicarbonate, 50 parts by mass of polyethylene glycol methyl ether methacrylate (molecular weight 950), 15 parts by mass of tert-butyl methacrylate, 15 parts by mass of hydroxyethyl methacrylate, 1 part by mass of polycarbonate, 20 parts by mass of boron trioxide-doped lithium phosphate, 20 parts by mass of nano aluminum oxide and tetrahydrofuran into a reactor, continuously introducing nitrogen into the reactor, and continuously stirring at the rotating speed of 400r/min until the mixture is uniform to obtain a precursor solution;
s2, adding 0.9 mass part of dimethyl azodiisobutyrate into the precursor solution, continuously stirring for 6 hours at the speed of 200r/min to obtain a mixed solution, uniformly coating the mixed solution on a mold, evaporating the solvent to obtain a crosslinked polymer film, and carrying out thermal initiation reaction on the crosslinked polymer film in an inert gas atmosphere, wherein the reaction temperature is 90 ℃ and the reaction time is 30 hours;
and S3, after the initiation reaction is finished, drying for 44 hours in vacuum at the temperature of 80 ℃ to obtain the gel polymer electrolyte.
The gel polymer electrolyte membranes prepared in examples 1 to 6 were subjected to room temperature conductivity and liquid absorption tests with conventional polyethylene oxide electrolyte membranes, polyacrylonitrile electrolyte membranes, and polymethyl methacrylate electrolyte membranes, the test methods were in accordance with the industry standards, and the test results are shown in table 1.
TABLE 1
From the results of table 1, it is understood that the room temperature ionic conductivity and the liquid absorption rate of the carbonic acid structure crosslinked gel polymer electrolytes prepared in examples 1 to 6 are substantially superior to those of the existing polyethylene oxide electrolyte, polyacrylonitrile electrolyte and polymethyl methacrylate electrolyte. And the carbonic acid crosslinked structure gel polymers prepared in examples 1 to 6 were electrolyzedAll substances have the applied ionic conductivity (> 10)-3S/cm), and proving that the introduction of a carbonic acid cross-linked structure can effectively improve the liquid absorption rate and the conductivity of the gel polymer electrolyte.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. The preparation method of the gel polymer electrolyte with the composite carbonic acid crosslinked structure is characterized by comprising the following steps of:
adding 0.1-10 parts by mass of a carbonic acid structure cross-linking agent, 70-95 parts by mass of a polyether structure gellable monomer, 0-5 parts by mass of a functional polymer, 0-50 parts by mass of an inorganic filler and/or a fast ion conductor and a solvent into a reactor together, and continuously introducing an inert gas into the reactor for stirring to form a uniform precursor solution, wherein the carbonic acid structure cross-linking agent is a carbonic ester functionalized multi-alkenyl structure monomer, and the structural formula of the carbonic acid structure cross-linking agent is as follows:
wherein R1, R2, R3 and R4 are all CxHyOzX, y and z are integers, x is more than or equal to 0, y is more than or equal to 0, z is more than or equal to 0, and the carbonic acid structural cross-linking agent is bis (vinyl) carbonate, 2-ethoxycarbonyloxyethyl-2-methylpropyl-2-olefine acid ester, 2-propenyl-2-propyl-2-oxycarbonyloxy-2-olefine acid ester, 2- [ [ (2-allyloxy) carbonyl group]Oxy radical]One or more of propyl methacrylate and oxy-di-2, 1-ethanediyl divinyl dicarbonate;
adding 0.1-1 part by mass of an initiator into the precursor solution, continuously stirring in an inert gas atmosphere to obtain a mixed solution, uniformly coating the mixed solution on a mold, evaporating the solvent to obtain a crosslinked polymer film, and carrying out an initiation reaction on the crosslinked polymer film in the inert gas atmosphere;
and after the initiation reaction is finished, vacuum drying is carried out to obtain the cross-linked polycarbonate-polyether gel polymer electrolyte with the carbonate functional group on the cross-linked structure.
2. The method for preparing a composite carbonic acid crosslinked structure gel polymer electrolyte according to claim 1, wherein: the monomer capable of being gelled is one or 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.
3. The method for preparing a composite carbonic acid crosslinked structure gel polymer electrolyte according to claim 1, wherein: the functional polymer is one or more of polyvinylidene fluoride, poly (vinylidene fluoride-hexafluoropropylene), high molecular polyethylene, polypropylene, polystyrene, polyethylene oxide and polycarbonate.
4. The method for preparing a composite carbonic acid crosslinked structure gel polymer electrolyte according to claim 1, wherein: the initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide and benzoyl peroxide tert-butyl ester.
5. The method for preparing a composite carbonic acid crosslinked structure gel polymer electrolyte according to claim 1, wherein: the inorganic filler is one or more of nano silicon dioxide, nano titanium dioxide, nano aluminum oxide, nano zirconia, diatomite, bentonite, kaolin or attapulgite.
6. Such as rightThe method for preparing a gel polymer electrolyte with a composite carbonic acid crosslinked structure according to claim 1, which is characterized in that: the fast ion conductor is lithium phosphate, lithium titanate, lithium titanium phosphate, lithium aluminum titanium phosphate, lithium lanthanum titanate, lithium lanthanum tantalate, lithium aluminum germanium phosphate, lithium aluminosilicate, lithium silicon phosphate, lithium lanthanum titanate, boron trioxide doped lithium phosphate, lithium platinum lanthanum, lithium platinum aluminum oxide, lithium titanate, boron trioxide doped lithium aluminum oxide, lithium lanthanum platinum aluminum oxide, lithium titanate doped lithium lanthanum lithium titanate, lithium titanate doped lithium aluminum oxide, lithium lanthanum platinum aluminum oxide, lithium titanate doped lithium lanthanum platinum aluminum oxide, lithium titanate doped lithium titanate, lithium titanate doped lithium aluminum oxide, lithium titanate doped lithium titanate, lithium titanate doped lithium lanthanum platinum aluminum oxide, lithium titanate doped lithium titanate, lithium titanate doped lithium titanate, lithium titanate doped lithium titanate, lithium titanate platinum aluminum oxide, lithium titanate, lithium doped lithium titanate, lithium titanate, lithium titanate, lithium titanate, lithium titanate, lithium titanate, lithium titanate, lithium titanate, lithium2S-P2S5、Li2S-SiS2、Li2S-GeS2、Li2S-B2S3、Li2S-MeS2-P2S5One or more of them.
7. The method for preparing a composite carbonic acid crosslinked structure gel polymer electrolyte according to claim 1, 3, 4, 5 or 6, characterized in that: the crosslinked polymer film is subjected to thermal initiation reaction in an inert gas atmosphere, the reaction temperature is 60-120 ℃, and the reaction time is 2-36 h.
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| CN113036209A (en) * | 2021-03-01 | 2021-06-25 | 刘迪 | High-rate polymer lithium battery and processing method |
| CN113845143B (en) * | 2021-09-23 | 2023-07-28 | 内江师范学院 | Bentonite modified metatitanic acid type lithium ion sieve precursor and preparation method thereof |
| CN115084637B (en) * | 2022-05-19 | 2023-07-14 | 吉林省东驰新能源科技有限公司 | Inorganic-organic composite solid electrolyte and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1164862A (en) * | 1995-08-23 | 1997-11-12 | 三井石油化学工业株式会社 | Novel acrylates, novel allyl ethers, novel allyl carbonates, acrylate polymers, allyl ether polymers, allyl carbonate polymers, and solid polyelectrolytes |
| CN1210613A (en) * | 1996-12-03 | 1999-03-10 | 三井化学株式会社 | Gel-form solid polymer electrolyte |
| CN107492680A (en) * | 2017-07-26 | 2017-12-19 | 哈尔滨工业大学无锡新材料研究院 | A kind of vinylene carbonate and polyethylene glycol（Methyl）Acrylate base polymer electrolyte and preparation method thereof |
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| CN101033323A (en) * | 2006-03-09 | 2007-09-12 | Nec东金株式会社 | Polymer gel electrolyte and polymer secondary battery using the same |
| CN101807717A (en) * | 2010-04-20 | 2010-08-18 | 诺莱特科技(苏州)有限公司 | Gel electrolyte, preparation method thereof, battery using gel electrolyte and preparation method thereof |
| CN105826603B (en) * | 2016-04-06 | 2018-06-19 | 中国科学院青岛生物能源与过程研究所 | A kind of polymerized thylene carbonate vinyl ester lithium ion battery polymer electrolyte and its preparation method and application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1164862A (en) * | 1995-08-23 | 1997-11-12 | 三井石油化学工业株式会社 | Novel acrylates, novel allyl ethers, novel allyl carbonates, acrylate polymers, allyl ether polymers, allyl carbonate polymers, and solid polyelectrolytes |
| CN1210613A (en) * | 1996-12-03 | 1999-03-10 | 三井化学株式会社 | Gel-form solid polymer electrolyte |
| CN107492680A (en) * | 2017-07-26 | 2017-12-19 | 哈尔滨工业大学无锡新材料研究院 | A kind of vinylene carbonate and polyethylene glycol（Methyl）Acrylate base polymer electrolyte and preparation method thereof |
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