CN108550906A - A kind of preparation method of compound all-solid polymer electrolyte film - Google Patents
A kind of preparation method of compound all-solid polymer electrolyte film Download PDFInfo
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Abstract
A kind of preparation method of compound all-solid polymer electrolyte film, includes the following steps：Carbonate functional vinyl monomer and polyether structure monomer are stirred with solvent under atmosphere of inert gases, initiator is then added, is reacted in atmosphere of inert gases, carbonate functional ethylenic copolymer is obtained after dry purification；Obtained carbonate functional ethylenic copolymer is added with inorganic filler or fast-ionic conductor in solvent and is uniformly mixed, lithium salts is added and stirs to get uniformly mixed mixed liquor；Mixed liquor is uniformly coated on mold, after being dried in vacuo solvent evaporated, obtains compound all-solid polymer electrolyte film.The dielectric film of the present invention, which has, preferably protects liquid rate, higher lithium ion conductivity, more superior mechanical property, good machining property, better electrochemical stability and better application prospect.
Description
Technical field
The invention belongs to be used in technical field of lithium ion more particularly to a kind of full solid state polymer lithium ion battery
Composite electrolyte membrane preparation method.
Background technology
The advantages that lithium ion battery is due to its energy density height, good reliability, the development advanced by leaps and bounds in recent years.
Lithium ion battery includes mainly positive plate, negative plate, diaphragm and electrolyte, and electrolyte is mostly organic carbonate solvents.Due to
The safety issues such as there is leakage, catch fire, explode in lithium ion battery, to limit answering for lithium ion battery in use
Use range.Full solid state polymer lithium ion battery has many advantages, such as that energy density is high, it is wide with operating temperature to have a safety feature, and electricity
There is no liquid electrolyte inside pond, becomes the hot spot of lithium ion battery research frontier.
All solid state electrolyte used by all-solid lithium-ion battery is mainly polyethers, makrolon, poly- methyl-prop at present
The series polymers such as e pioic acid methyl ester, polyacrylonitrile, the ether oxygen structural unit with negatively charged in polyether structure polymer, can
Dissociation lithium salts simultaneously transmits lithium ion, therefore the polymer dielectric of polyether structure is always the research hotspot in the field.Polyethers knot
Structure polymer main representative is polyethylene glycol oxide (PEO), and it is low, mechanical strong that polyethylene glycol oxide is primarily present room temperature lithium ion conductivity
The problems such as degree difference and not good enough electrochemical stability.
To improve polyethylene glycol oxide disadvantage, the Chinese invention patent application of Publication No. CN105633475A discloses one kind
The polymer dielectric of copolymeric structure is prepared using methoxypolyethylene glycol methacrylate and methyl methacrylate as monomer, though
The lithium ion conductivity of the right polymer dielectric at room temperature is higher than the lithium ion conductivity of polyethylene glycol oxide, but mechanical performance is not
It is ideal.The Chinese invention patent of Patent No. 200780020101.3 discloses one kind using polyethylene glycol oxide and styrene as monomer
The polymer dielectric of block structure is prepared, which reduces the crystallization of polyethylene glycol oxide by introducing polystyrene structure
Degree is to improve conductivity.It is polymerize with methyl methacrylate and styryl structures with polyether structure, to a certain extent can
The conductivity of polymer at room temperature is improved, however since polymethyl methacrylate and polystyrene structure do not lead lithium, lead to it
Copolymer conductivity is not high and electrochemical stability is not good enough.
Invention content
It is obtained compound the purpose of the present invention is to provide a kind of preparation method of compound all-solid polymer electrolyte film
Full solid state polymer electrolyte film at room temperature have higher lithium ion conductivity, more excellent mechanical strength and preferably
Electrochemical stability.
To achieve the goals above, the present invention takes following technical solution：
A kind of preparation method of compound all-solid polymer electrolyte film, includes the following steps：
Carbonate functional vinyl monomer and polyether structure monomer are stirred with solvent under atmosphere of inert gases,
The mass fraction of carbonate functional vinyl monomer and polyether structure monomer is respectively 10~80 parts and 20~90 parts, is then added
The initiator for entering 0.1~1 mass parts, is reacted in atmosphere of inert gases, and carbonate functional second is obtained after dry purification
Alkenyl copolymers；
Obtained carbonate functional ethylenic copolymer is added with inorganic filler or fast-ionic conductor in solvent and is stirred
It is uniformly mixed, carbonate functional ethylenic copolymer and the mass fraction of inorganic filler or fast-ionic conductor are respectively 10~80
Part and 0~50 part, the lithium salts for adding 10~60 mass parts stirs to get uniformly mixed mixed liquor；
Mixed liquor is uniformly coated on mold, after being dried in vacuo solvent evaporated, obtains compound full solid state polymer electrolysis
Plasma membrane.
Further, the carbonate functional vinyl monomer be with carbonate structural and can poly bis key carbonyldioxy it is poly-
Close monomer.
Further, the carbonate functional vinyl monomer is vinyl ethylene carbonate, allyl methyl carbonic acid
One or more of ester, propylene carbonate ethyl ester, cis- -3- hexenols methyl carbonate, formic acid diester, allyl phenyl ester.
Further, the polyether structure monomer is methoxypolyethylene glycol methacrylate or methoxypolyethylene glycol propylene
At least one of acid esters.
Further, the solvent be acetonitrile, tetrahydrofuran, acetone, methyl pyrrolidone, N, N- dimethyl amides,
One or more of ethyl acetate, sulfolane.
Further, the initiator is azodiisobutyronitrile, azobisisoheptonitrile, azo-bis-iso-dimethyl, mistake
One or more of Benzoyl Oxide, benzoyl peroxide tert-butyl ester.
Further, the inorganic filler is nano silicon dioxide, nano-titanium dioxide, nano-aluminium oxide, nanometer
One or more of zirconium oxide, diatomite, bentonite, kaolin or attapulgite.
Further, the fast-ionic conductor be lithium phosphate, lithium titanate, titanium phosphate lithium, titanium phosphate aluminium lithium, lanthanium titanate lithium,
Tantalic acid lanthanum lithium, phosphoric acid germanium aluminium lithium, lithium aluminosilicate, silicon phosphate lithium, lanthanium titanate lithium, diboron trioxide doping phosphoric acid lithium, lanthanum platinum lithium, lanthanum
One or more of lithium platinum alumina.
Further, the lithium salts is lithium perchlorate, lithium hexafluoro phosphate, di-oxalate lithium borate, LiODFB, three
In methyl fluoride Sulfonic Lithium, LiBF4, double trifluoromethanesulfonimide lithiums, dimalonic acid boric acid, malonato lithium borate
One or more.
Further, it after initiator being added, is stirred with the speed of 100~600r/min at a temperature of 50~100 DEG C, lazy
Property gas shield under react 4~48h.
By above technical scheme it is found that the present invention uses carbonate functional vinyl structure monomer and polyether structure monomer
Polymerization prepares carbonate functional polyvinyl, and structural carbonate and polyether structure is made to pass through polyethylene backbone in molecular layer
Face combines, and the electrochemical stability for remaining carbonate functionalities structure is good, mechanical property is good and has the function of the characteristics of leading lithium,
To achieve the effect that improve conductivity at room temperature, is compared with conventional polyethylene oxide electrolyte, there is higher room temperature
Lithium ion conductivity, lower crystallization degree, good machining property, better electrochemical stability and preferably application
Foreground.
Specific implementation mode
In order to which above and other objects of the present invention, feature and advantage can be become apparent from, the embodiment of the present invention cited below particularly,
It is described below in detail.
The composite electrolyte membrane of the present invention is carbonate functional ethylenic copolymer all solid state electrolyte film, preparation side
Method includes the following steps：
Carbonate functional vinyl monomer and polyether structure monomer are stirred with solvent under atmosphere of inert gases,
Wherein, the mass fraction of carbonate functional vinyl monomer and polyether structure monomer is respectively 10~80 parts and 20~90 parts,
Then initiator is added, the mass fraction of initiator is 0.1~1 part, with 100~600r/min's at a temperature of 50~100 DEG C
Speed stirs, and reacts 4~48h (hour) under inert gas protection, and it is total to obtain carbonate functional vinyl after dry purification
Polymers；
Obtained carbonate functional ethylenic copolymer is added with inorganic filler or fast-ionic conductor in solvent and is stirred
The mass fraction of mixing, carbonate functional ethylenic copolymer and inorganic filler or fast-ionic conductor be respectively 10~80 parts and
0~50 part, with speed stirring 2~6h of stirring of 1000~3000r/min, the lithium salts of 10~60 mass parts is then added, with
Speed stirring 1.5~2h of stirring of 1000~3000r/min, obtains uniformly mixed mixed liquor；
Mixed liquor is uniformly coated on Teflon mould, 24~48h is dried in vacuo at a temperature of 60~100 DEG C,
After solvent evaporated, carbonate functional ethylenic copolymer dielectric film is obtained.
The carbonate functional vinyl monomer of the present invention be with carbonate structural and can poly bis key carbonyldioxy polymerize it is single
Body, can be vinyl ethylene carbonate, Allyl methyl carbonate, propylene carbonate ethyl ester, cis- -3- hexenols methyl carbonate,
One or more of formic acid diester, allyl phenyl ester.
The polyether structure monomer of the present invention is methoxypolyethylene glycol methacrylate (molecular weight 300~20000) or gathers
At least one of ethylene glycol monomethyl ether acrylate (molecular weight 480~5000).
Solvent used in the present invention can be acetonitrile, tetrahydrofuran, acetone, methyl pyrrolidone, N, N- dimethyl amides,
One or more of ethyl acetate, sulfolane.Initiator can be azodiisobutyronitrile (AIBN), azobisisoheptonitrile
(ABVI), in azo-bis-iso-dimethyl (AIBME), benzoyl peroxide (BPO), the benzoyl peroxide tert-butyl ester (TBPB)
One or more.Inorganic filler can be nano silicon dioxide, nano-titanium dioxide, nano-aluminium oxide, nano zircite,
One or more of diatomite, bentonite, kaolin or attapulgite.Fast-ionic conductor can be lithium phosphate (Li3PO4), metatitanic acid
Lithium (Li4Ti5O12), titanium phosphate lithium [LiTi2(PO4)3], titanium phosphate aluminium lithium [LiAlXTi2-X(PO4)3], lanthanium titanate lithium
(Li0.35La0.57TiO3), tantalic acid lanthanum lithium (Li0.35La0.57Ta0.8O3), phosphoric acid germanium aluminium lithium [Li1.5Al0.5Ge1.5(PO4)3], sial
Sour lithium (LiAlSiO4), silicon phosphate lithium (Li3.5Si0.5P0.5O4), lanthanium titanate lithium (Li0.35La0.57TiO3), diboron trioxide doping
Lithium phosphate (Li3PO4:B2O3), lanthanum platinum lithium [LLZO Li(7-X)La3Zr(2-X)MXO12, 0.15≤M≤0.25, (M=Al, Ta,
W ...)], lanthanum lithium platinum alumina [Al-LLZO, LISICON, NASICON, Li2S-P2S5、Li2S-SiS2、Li2S-GeS2、Li2S-
B2S3、Li2S-MeS2-P2S5One or more of (Me=Si, Ge, Sn, Al etc.)].
The lithium salts of the present invention can be lithium perchlorate (LiClO4), lithium hexafluoro phosphate (LiPF6), di-oxalate lithium borate
(LiBOB), LiODFB (LiDFBD), trifluoromethyl sulfonic acid lithium (LiCF3SO3), LiBF4 (LiBF4), double three
One kind in fluoromethane sulfimide lithium (LiTFSI), dimalonic acid boric acid (LiBMB), malonato lithium borate (LiMOB)
Or it is several.
Below by specific embodiment, the present invention is further illustrated.Reagent, the material arrived used in following the description
Material and instrument such as not special explanation, are conventional reagent, conventional material and conventional instrument, commercially available, institute
The reagent being related to can also be synthesized by conventional synthesis process and be obtained.
Embodiment 1
The preparation method of the compound semisolid dielectric film of the present embodiment includes the following steps：
By the methoxypolyethylene glycol methacrylate (molecule of the vinyl ethylene carbonate of 10 mass parts and 40 mass parts
300) and together with the methoxypolyethylene glycol acrylate of 50 mass parts (molecular weight 5000) and tetrahydrofuran amount is added in reactor,
Maintaining nitrogen purge and continue to stir into reactor, the azodiisobutyronitrile of 0.1 mass parts be then added, at 50 DEG C, with
The speed of 100r/min stirs, and reacts 48h under inert gas protection, and it is total to obtain carbonate functional vinyl after dry purification
Polymers；
The carbonate functional ethylenic copolymer of 80 mass parts is added in part tetrahydrofuran of 200 mass parts, with
The speed of 2000r/min stirs 5h, and the lithium perchlorate of 10 mass parts is then added, and stirs 2h with the speed of 2000r/min, obtains
Uniformly mixed mixed liquor；
Mixed liquor is uniformly coated on Teflon mould, with 60 DEG C of vacuum drying 36h under nitrogen atmosphere, is obtained
To compound all-solid polymer electrolyte film.
Embodiment 2
The preparation method of the dielectric film of the present embodiment is as follows：
By the Allyl methyl carbonate of 20 mass parts, the methoxypolyethylene glycol methacrylate (molecule of 40 mass parts
Amount is 20000) and reaction is added in the methoxypolyethylene glycol acrylate of 40 mass parts (molecular weight 480) together with methyl pyrrolidone
In device, maintaining nitrogen purge and continues to stir into reactor, the benzoyl peroxide of 1 mass parts is then added, at 100 DEG C,
It is stirred with the speed of 600r/min, reacts 4h under inert gas protection, carbonate functional vinyl is obtained after dry purification
Copolymer；
400 mass parts are added in the carbonate functional ethylenic copolymer of 10 mass parts and the lanthanum platinum lithium of 50 mass parts
In tetrahydrofuran, 2h is stirred with the speed of 1000r/min, double trifluoromethanesulfonimide lithiums of 60 mass parts are then added, with
The speed of 1000r/min stirs 1.5h, obtains uniformly mixed mixed liquor；
Mixed liquor is uniformly coated on Teflon mould, under nitrogen atmosphere for 24 hours with 100 DEG C of vacuum drying,
Obtain compound all-solid polymer electrolyte film.
Embodiment 3
The preparation method of the dielectric film of the present embodiment is as follows：
By the propylene carbonate ethyl ester of 20 mass parts, the methoxypolyethylene glycol methacrylate (molecular weight of 40 mass parts
950) it and together with the methoxypolyethylene glycol acrylate of 40 mass parts (molecular weight 1000) and acetonitrile is added in reactor, to reaction
Maintaining nitrogen purge and continue to stir in device, the azobisisoheptonitrile of 0.5 mass parts is then added, at 60 DEG C, with 300r/min
Speed stirring, react under inert gas protection for 24 hours, carbonate functional ethylenic copolymer obtained after dry purification；
By the carbonate functional ethylenic copolymer of 80 mass parts and the nano zircite of 5 mass parts, 15 mass parts
Lithium titanate is added in the tetrahydrofuran of 600 mass parts, stirs 6h with the speed of 3000r/min, the four of 15 mass parts are then added
Lithium fluoroborate stirs 1.5h with the speed of 3000r/min, obtains uniformly mixed mixed liquor；
Mixed liquor is uniformly coated on Teflon mould, under nitrogen atmosphere for 24 hours with 100 DEG C of vacuum drying,
Obtain compound all-solid polymer electrolyte film.
Embodiment 4
The preparation method of the dielectric film of the present embodiment is as follows：
By the cis- -3- hexenols methyl carbonate of 30 mass parts, the propylene carbonate ethyl ester of 20 mass parts and 50 mass parts
Methoxypolyethylene glycol methacrylate (molecular weight 10000) and acetone are added in reactor together, persistently lead into reactor
Nitrogen simultaneously continues to stir, and the azo-bis-iso-dimethyl of 0.75 mass parts is then added, at 55 DEG C, with the speed of 500r/min
Degree stirring reacts 36h, carbonate functional ethylenic copolymer is obtained after dry purification under inert gas protection；
The carbonate functional ethylenic copolymer of 80 mass parts is added in the tetrahydrofuran of 400 mass parts, with
The speed of 2500r/min stirs 5h, and the di-oxalate lithium borate of 20 mass parts is then added, and 2h is stirred with the speed of 1500r/min,
Obtain uniformly mixed mixed liquor；
Mixed liquor is uniformly coated on Teflon mould, with 60 DEG C of vacuum drying 36h under nitrogen atmosphere, is obtained
To compound all-solid polymer electrolyte film.
Embodiment 5
The preparation method of the dielectric film of the present embodiment is as follows：
By the formic acid diester of 20 mass parts, the carbonic acid third of the cis- -3- hexenols methyl carbonate of 10 mass parts, 10 mass parts
The methoxypolyethylene glycol methacrylate (molecular weight 20000) and N, N- dimethyl amide of alkene ethyl ester and 60 mass parts are together
It is added in reactor, maintaining nitrogen purge and continues to stir into reactor, the benzoyl peroxide uncle of 0.8 mass parts is then added
Butyl ester is stirred at 80 DEG C, with the speed of 400r/min, is reacted under inert gas protection for 24 hours, and carbonic acid is obtained after dry purification
Ester functional ethylenic copolymer；
By the Li of the carbonate functional ethylenic copolymer and 5 mass parts of 60 mass parts2S-MeS2-P2S5It is added 400 parts
In tetrahydrofuran, 5h is stirred with the speed of 2000r/min, the LiODFB of 25 mass parts is then added, with 2000r/
The speed of min stirs 2h, obtains uniformly mixed mixed liquor；
Mixed liquor is uniformly coated on Teflon mould, with 60 DEG C of vacuum drying 36h under nitrogen atmosphere, is obtained
To compound all-solid polymer electrolyte film.
Embodiment 6
The preparation method of the dielectric film of the present embodiment is as follows：
By the allyl phenyl ester of 30 mass parts, the methoxypolyethylene glycol methacrylate (molecular weight of 40 mass parts
20000), the methoxypolyethylene glycol acrylate (molecular weight 3000) and sulfolane of 40 mass parts are added in reactor together, to
Maintaining nitrogen purge and continue to stir in reactor, the benzoyl peroxide of 0.7 mass parts be then added, at 100 DEG C, with
The speed of 400r/min stirs, and reacts 40h under inert gas protection, and it is total to obtain carbonate functional vinyl after dry purification
Polymers；
300 parts of tetrahydrochysenes are added in the carbonate functional ethylenic copolymer of 70 mass parts and the lanthanium titanate lithium of 5 mass parts
In furans, 4h is stirred with the speed of 2500r/min, the dimalonic acid boric acid of 25 mass parts is then added, with the speed of 2500r/min
Degree stirring 2h, obtains uniformly mixed mixed liquor；
Mixed liquor is uniformly coated on Teflon mould, with 60 DEG C of vacuum drying 36h under nitrogen atmosphere, is obtained
To compound all-solid polymer electrolyte film.
Embodiment 7
The preparation method of the dielectric film of the present embodiment is as follows：
By the allyl phenyl ester of 20 mass parts of propylene carbonate ethyl ester of 40 mass parts, 20 mass parts formic acid diester,
The methoxypolyethylene glycol methacrylate (molecular weight 5000) of 15 mass parts and the methoxypolyethylene glycol acrylate of 5 mass parts
(molecular weight 2000) and ethyl acetate are added in reactor together, maintaining nitrogen purge and continue to stir into reactor, then plus
The azodiisobutyronitrile for entering 0.4 mass parts is stirred at 60 DEG C, with the speed of 400r/min, is reacted under inert gas protection
48h obtains carbonate functional ethylenic copolymer after dry purification；
400 mass are added in the carbonate functional ethylenic copolymer of 70 mass parts and the phosphoric acid germanium aluminium lithium of 5 mass parts
In the tetrahydrofuran of part, 5h is stirred with the speed of 2000r/min, double trifluoromethanesulfonimides of 15 mass parts are then added
Lithium stirs 2h with the speed of 2000r/min, obtains uniformly mixed mixed liquor；
Mixed liquor is uniformly coated on Teflon mould, with 60 DEG C of vacuum drying 36h under nitrogen atmosphere, is obtained
To compound all-solid polymer electrolyte film.
The compound all-solid polymer electrolyte film that Examples 1 to 7 is prepared and commercial polyethylene glycol oxide electrolysis
Matter carries out conductivity at room temperature rate, electrochemical window and tensile strength test, and test result is as follows shown in table.
Conductivity it can be seen from the result of upper table under conventional polyethylene oxide polymer electrolyte room temperature is 1.26
×10-5S/cm, electrochemical window 3.8V, the conductivity under polymer dielectric room temperature of the invention is about 10-6S/cm, tool
There are more superior conductivity at room temperature, electrochemical window and tensile strength, polymer dielectric of the invention to be adopted from structure
Cyclic carbonate ester structure is introduced with molecular design method since cyclic carbonate has many advantages, such as that high voltage, mechanical property are good to change
It has been apt to the properties of polymer dielectric, has made it have better application potential.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to embodiment illustrated herein, and is to fit to consistent with the principles and novel features disclosed in this article
Widest range.
Claims (10)
1. a kind of preparation method of compound all-solid polymer electrolyte film, which is characterized in that include the following steps：
Carbonate functional vinyl monomer and polyether structure monomer are stirred with solvent under atmosphere of inert gases, carbonic acid
The mass fraction of ester functional vinyl monomer and polyether structure monomer is respectively 10~80 parts and 20~90 parts, is then added
The initiator of 0.1~1 mass parts, is reacted in atmosphere of inert gases, and carbonate functional ethylene is obtained after dry purification
Base co-polymer；
Obtained carbonate functional ethylenic copolymer is added with inorganic filler or fast-ionic conductor in solvent and is stirred
Uniformly, the mass fraction of carbonate functional ethylenic copolymer and inorganic filler or fast-ionic conductor be respectively 10~80 parts and
0~50 part, the lithium salts for adding 10~60 mass parts stirs to get uniformly mixed mixed liquor；
Mixed liquor is uniformly coated on mold, after being dried in vacuo solvent evaporated, obtains compound all-solid polymer electrolyte film.
2. the preparation method of compound all-solid polymer electrolyte film as described in claim 1, it is characterised in that：The carbonic acid
Ester functional vinyl monomer be with carbonate structural and can poly bis key carbonyldioxy polymerized monomer.
3. the preparation method of compound all-solid polymer electrolyte film as claimed in claim 1 or 2, it is characterised in that：It is described
Carbonate functional vinyl monomer be vinyl ethylene carbonate, Allyl methyl carbonate, propylene carbonate ethyl ester, it is cis--
One or more of 3- hexenols methyl carbonate, formic acid diester, allyl phenyl ester.
4. the preparation method of compound all-solid polymer electrolyte film as described in claim 1, it is characterised in that：The polyethers
Structures alone is at least one of methoxypolyethylene glycol methacrylate or methoxypolyethylene glycol acrylate.
5. the preparation method of compound all-solid polymer electrolyte film as described in claim 1, it is characterised in that：The solvent
For acetonitrile, tetrahydrofuran, acetone, methyl pyrrolidone, N, one kind in N- dimethyl amides, ethyl acetate, sulfolane or
It is several.
6. the preparation method of compound all-solid polymer electrolyte film as described in claim 1, it is characterised in that：The initiation
Agent is azodiisobutyronitrile, azobisisoheptonitrile, azo-bis-iso-dimethyl, benzoyl peroxide, benzoyl peroxide uncle
One or more of butyl ester.
7. the preparation method of compound all-solid polymer electrolyte film as described in claim 1, it is characterised in that：It is described inorganic
Filler is nano silicon dioxide, nano-titanium dioxide, nano-aluminium oxide, nano zircite, diatomite, bentonite, kaolinite
One or more of soil or attapulgite.
8. the preparation method of compound all-solid polymer electrolyte film as described in claim 1, it is characterised in that：It is described soon from
Sub- conductor is lithium phosphate, lithium titanate, titanium phosphate lithium, titanium phosphate aluminium lithium, lanthanium titanate lithium, tantalic acid lanthanum lithium, phosphoric acid germanium aluminium lithium, aluminosilicate
One or more of lithium, silicon phosphate lithium, lanthanium titanate lithium, diboron trioxide doping phosphoric acid lithium, lanthanum platinum lithium, lanthanum lithium platinum alumina.
9. the preparation method of compound all-solid polymer electrolyte film as described in claim 1, it is characterised in that：The lithium salts
For lithium perchlorate, lithium hexafluoro phosphate, di-oxalate lithium borate, LiODFB, trifluoromethyl sulfonic acid lithium, LiBF4,
One or more of double trifluoromethanesulfonimide lithiums, dimalonic acid boric acid, malonato lithium borate.
10. the preparation method of compound all-solid polymer electrolyte film as described in claim 1, it is characterised in that：Addition is drawn
It after sending out agent, is stirred with the speed of 100~600r/min at a temperature of 50~100 DEG C, reacts 4~48h under inert gas protection.
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| CN111864275A (en) * | 2019-04-26 | 2020-10-30 | 北京卫蓝新能源科技有限公司 | Battery cell, preparation method thereof and lithium ion battery |
| CN112864469A (en) * | 2021-01-28 | 2021-05-28 | 北京工业大学 | Method for modifying polymer solid polyelectrolyte |
| CN114267815A (en) * | 2020-09-16 | 2022-04-01 | 郑州宇通集团有限公司 | Composite positive electrode for solid-state battery, preparation method of composite positive electrode and solid-state lithium battery |
| CN114551993A (en) * | 2021-07-20 | 2022-05-27 | 万向一二三股份公司 | Three-dimensional PEO polymer composite solid electrolyte containing modified inorganic filler, preparation method and solid lithium ion battery |
| CN115084637A (en) * | 2022-05-19 | 2022-09-20 | 吉林省东驰新能源科技有限公司 | Inorganic-organic composite solid electrolyte and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103647107A (en) * | 2013-11-28 | 2014-03-19 | 中国东方电气集团有限公司 | All-solid-state electrolyte membrane of lithium ion battery and preparation method thereof |
| CN105591154A (en) * | 2015-02-13 | 2016-05-18 | 中国科学院青岛生物能源与过程研究所 | Polycarbonate all-solid-state polymer electrolyte, all-solid-state secondary lithium battery made of same and preparation and application thereof |
| CN105655635A (en) * | 2014-11-11 | 2016-06-08 | 宁德时代新能源科技股份有限公司 | Composite solid polymer electrolyte membrane, preparation method thereof and polymer lithium battery |
| CN105826603A (en) * | 2016-04-06 | 2016-08-03 | 中国科学院青岛生物能源与过程研究所 | Vinylene carbonate-based lithium ion battery polymer electrolyte and preparation method as well as application thereof |
| 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 |
-
2018
- 2018-04-24 CN CN201810374629.0A patent/CN108550906A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103647107A (en) * | 2013-11-28 | 2014-03-19 | 中国东方电气集团有限公司 | All-solid-state electrolyte membrane of lithium ion battery and preparation method thereof |
| CN105655635A (en) * | 2014-11-11 | 2016-06-08 | 宁德时代新能源科技股份有限公司 | Composite solid polymer electrolyte membrane, preparation method thereof and polymer lithium battery |
| CN105591154A (en) * | 2015-02-13 | 2016-05-18 | 中国科学院青岛生物能源与过程研究所 | Polycarbonate all-solid-state polymer electrolyte, all-solid-state secondary lithium battery made of same and preparation and application thereof |
| CN105826603A (en) * | 2016-04-06 | 2016-08-03 | 中国科学院青岛生物能源与过程研究所 | Vinylene carbonate-based lithium ion battery polymer electrolyte and preparation method as well as application thereof |
| 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 |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109546212A (en) * | 2018-11-26 | 2019-03-29 | 中南大学 | Solid polymer electrolyte preparation method and its solid secondary batteries |
| CN109546212B (en) * | 2018-11-26 | 2022-05-20 | 广东聚圣科技有限公司 | Solid polymer electrolyte preparation method and solid secondary battery thereof |
| CN109755641A (en) * | 2019-03-18 | 2019-05-14 | 珠海光宇电池有限公司 | A kind of composite material and preparation method and lithium ion battery |
| CN111864275A (en) * | 2019-04-26 | 2020-10-30 | 北京卫蓝新能源科技有限公司 | Battery cell, preparation method thereof and lithium ion battery |
| CN111864275B (en) * | 2019-04-26 | 2021-10-15 | 北京卫蓝新能源科技有限公司 | Battery cell, preparation method thereof and lithium ion battery |
| CN114267815A (en) * | 2020-09-16 | 2022-04-01 | 郑州宇通集团有限公司 | Composite positive electrode for solid-state battery, preparation method of composite positive electrode and solid-state lithium battery |
| CN112864469A (en) * | 2021-01-28 | 2021-05-28 | 北京工业大学 | Method for modifying polymer solid polyelectrolyte |
| CN114551993A (en) * | 2021-07-20 | 2022-05-27 | 万向一二三股份公司 | Three-dimensional PEO polymer composite solid electrolyte containing modified inorganic filler, preparation method and solid lithium ion battery |
| CN114551993B (en) * | 2021-07-20 | 2023-10-03 | 万向一二三股份公司 | Three-dimensional PEO polymer composite solid electrolyte containing modified inorganic filler, preparation method and solid lithium ion battery |
| CN115084637A (en) * | 2022-05-19 | 2022-09-20 | 吉林省东驰新能源科技有限公司 | Inorganic-organic composite solid electrolyte and application thereof |
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