CN106328862A - Preparation method for crosslinked polyimide gel polymer electrolyte membrane - Google Patents
Preparation method for crosslinked polyimide gel polymer electrolyte membrane Download PDFInfo
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- CN106328862A CN106328862A CN201610729379.9A CN201610729379A CN106328862A CN 106328862 A CN106328862 A CN 106328862A CN 201610729379 A CN201610729379 A CN 201610729379A CN 106328862 A CN106328862 A CN 106328862A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method for a crosslinked polyimide gel polymer electrolyte membrane. The method comprises the following steps of (1) performing a crosslinking reaction: dissolving soluble polyimide by an aprotic solvent, and performing the crosslinking reaction of the dissolved polyimide and a silane coupling agent with amino groups to obtain a coating A; (2) performing curing and film-forming: performing the curing process on the coating A, removing the solvent, and drying to obtain a membrane B; and (3) performing swelling: dipping the membrane B in a lithium ion battery electrolytic solution for swelling to obtain the crosslinked polyimide gel polymer electrolyte membrane. According to the method, the imide groups on the polyimide are mainly used to react with the amino groups on silane, and the imide groups and the amino groups are subjected to low-temperature crosslinking, so that the obtained crosslinked polyimide has more excellent heat stability; the crosslinked polyimide gel polymer electrolyte membrane prepared according to the preparation method has high heat stability, high liquid absorption amount and strength, and good wettability and ion conductivity; and the preparation process is simple, is simple and convenient to control, and is safer and more environment-friendly, efficient and energy-saving.
Description
Technical field
The present invention relates to technical field of lithium ion, particularly relate to a kind of crosslinked polyimide gel polymer electrolyte
The preparation method of barrier film.
Background technology
Along with economic fast development, people are increasing to the demand of the energy, simultaneously Global climate change shadow significantly
Ringing the survival and development of the mankind, the low carbon development based on low energy consumption, low emission, low stain day by day becomes world's tide
Stream.One of Main way that lithium ion battery develops as new forms of energy, has been widely applied to various mobile communication equipment, hands
Hold in instrument and automobile.
The lithium ion battery circulated in the market predominantly uses liquid electrolyte, but lithium salts holds during using
Easily formation of deposits dendrite on negative pole, may puncture barrier film, causes internal short-circuit of battery and battery fluid leakage, exists serious
Potential safety hazard；Although lithium ion polymer battery has high-energy-density, the advantages such as arbitrary shape can be processed into, meet little
Type demand miniaturization, the gel polymer electrolyte barrier film of existing lithium ion polymer battery is mainly in dry method or wet
Method barrier film coating on base films Kynoar and copolymer thereof, this fluoropolymer is absorption portion by electrolyte solvent portion swells
Point electrolyte and form polymer sol-gel；But fusing point is about the thermoplastic Kynoar of 160 DEG C at collosol and gel
Under state, the dimensional stability effect to barrier film is extremely limited, and the most at high temperature this coating is often dissolved；And it is difficult
The garbage of the fluoropolymer of degraded has serious harm to environment；Therefore the gel polymer electrolyte of a kind of safety and environmental protection is found
Matter becomes problem demanding prompt solution.
Summary of the invention
It is an object of the invention to propose a kind of heat stability height and the crosslinked polyimide gelatin polymer of safety and environmental protection
The preparation method of electrolyte membrance.
For reaching this purpose, the present invention by the following technical solutions:
The preparation method of a kind of crosslinked polyimide gel polymer electrolyte barrier film, comprises the steps:
(1) cross-linking reaction: after using aprotic solvent to dissolve the polyimides of solubility, then with the silane with amino
Coupling agent carries out cross-linking reaction, obtains coating A；
(2) film-forming: after the coating A that step (1) obtains is carried out curing process, then washing removal solvent, be dried
To thin film B；
(3) swelling action: described thin film B is immersed lithium-ion battery electrolytes swelling, obtain crosslinked polyimide gel
Polymer electrolyte diaphragm.
Further illustrating, described aprotic solvent includes N,N-dimethylacetamide, DMF, N-methyl
Ketopyrrolidine, dimethyl sulfoxide, Allyl carbonate, acetone, oxolane, hexamethylene, pentane, octane, heptane, hexane, hexamethylene
Ketone, toluene Ketohexamethylene, acetonitrile, ethyl acetate, butyl acetate, butanone, butanone, espeleton, methylisobutylketone, ethylene carbonate
Ester, dimethyl carbonate, Ethyl methyl carbonate, diethyl carbonate, benzene,toluene,xylene, Nitrobenzol, dioxane, carbon tetrachloride,
Any one or more combination in tetrachloroethylene, chloroform, dichloromethane, trichloro-benzenes, ether, ethyl methyl ether, butyl ether, pyridine.
Further illustrating, the described silane coupler with amino includes gamma-aminopropyl-triethoxy-silane, γ-ammonia third
Base trimethoxy silane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropyltriethoxy two
Methoxy silane, N-β (aminoethyl)-gamma-aminopropyl-triethoxy-silane, N-β (aminoethyl)-γ-aminopropyltriethoxy diethoxy
Base silane, phenylaminomethyl triethoxysilane, phenylaminomethyl trimethoxy silane, 3-[2-(2-aminoethylamino) second
Base amino] propyl trimethoxy silicane, at least one in polyamino alkyltrialkoxysilaneand.
Further illustrating, curing process described in step (2) is by the described independent film-forming of coating A or by described coating
A is coated on porous substrate, and described porous substrate is non-woven fabrics, paper, cellulose membrane, polyethylene porous membrane, polypropylene porous
Any one in film, polyethylene and polypropylene composite materials perforated membrane.
Further illustrating, the coating method of the described coating A in step (2) is silk screen, roller coat, impregnate, spray, scraper is coated with
Cloth, it is cast and drenches any one that cover.
Preferably, described in step (2), the temperature of curing process is 20～120 DEG C, and the time of solidification is 10s～5h.
Beneficial effects of the present invention: the system of a kind of crosslinked polyimide gel polymer electrolyte barrier film that the present invention proposes
Preparation Method, reacts with the amino on silane mainly by the imide group on polyimides, it is achieved that crosslinked at low temperature, has
Versatility, it is thus achieved that the polyimides of crosslinking there is more excellent heat stability, it is to avoid in barrier film, collosol and gel state is poly-
The problem that vinylidene heat stability at high temperature is low, the crosslinked polyimide gel polymerisation obtained by preparation method of the present invention
Thing electrolyte membrance has high thermal stability, liquid absorption and intensity height, wellability and the good conductivity of ion, preparation technology letter
Single, that manipulation is easy feature；And described polyimides can also reclaim monomer by hydrolysis, thus solves for fluorine-containing
Polymer is difficult to degraded and reclaims and cause the problem of environmental pollution, more safety and environmental protection and energy-efficient.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of the imide group of one embodiment of the invention；
Detailed description of the invention
Further illustrate technical scheme below in conjunction with the accompanying drawings and by detailed description of the invention.
The preparation method of a kind of crosslinked polyimide gel polymer electrolyte barrier film, comprises the steps:
(1) cross-linking reaction: after using aprotic solvent to dissolve the polyimides of solubility, then with the silane with amino
Coupling agent carries out cross-linking reaction, obtains coating A；
(2) film-forming: after the coating A that step (1) obtains is carried out curing process, then washing removal solvent, be dried
To thin film B；
(3) swelling action: described thin film B is immersed lithium-ion battery electrolytes swelling, obtain crosslinked polyimide gel
Polymer electrolyte diaphragm.
The preparation method of a kind of crosslinked polyimide gel polymer electrolyte barrier film that the present invention proposes, mainly uses
Carry out cross-linking reaction with the silane coupler first polyimides with solubility of amino, then the polyimides after crosslinking is passed through
Lithium-ion battery electrolytes is swelling and absorbs partial electrolyte liquid, thus obtains described crosslinked polyimide gel polymer electrolyte
Barrier film；The method of polyimides crosslinking at present typically requires the hot conditions of a few Baidu, and the present invention is sub-mainly by polyamides
Imide group on amine reacts with the amino on silane, it is achieved that crosslinked at low temperature, has versatility, it is thus achieved that the polyamides of crosslinking
Imines has more excellent heat stability, it is to avoid the Kynoar of collosol and gel state at high temperature thermally-stabilised in barrier film
Property low problem, the crosslinked polyimide gel polymer electrolyte barrier film obtained by preparation method of the present invention has high heat stability
Property, liquid absorption and intensity height, wellability and the good conductivity of ion, preparation technology is simple, the feature that manipulation is easy；And it is described
Polyimides can also reclaim monomer by hydrolysis, thus solve the fluoropolymer recovery that is difficult to degrade and cause environmental pollution
Problem, more safety and environmental protection and energy-efficient.Wherein said soluble polyimide can be any one soluble poly
Acid imide, processes convenient.
Further illustrating, described aprotic solvent includes N,N-dimethylacetamide, DMF, N-methyl
Ketopyrrolidine, dimethyl sulfoxide, Allyl carbonate, acetone, oxolane, hexamethylene, pentane, octane, heptane, hexane, hexamethylene
Ketone, toluene Ketohexamethylene, acetonitrile, ethyl acetate, butyl acetate, butanone, butanone, espeleton, methylisobutylketone, ethylene carbonate
Ester, dimethyl carbonate, Ethyl methyl carbonate, diethyl carbonate, benzene,toluene,xylene, Nitrobenzol, dioxane, carbon tetrachloride,
Any one or more combination in tetrachloroethylene, chloroform, dichloromethane, trichloro-benzenes, ether, ethyl methyl ether, butyl ether, pyridine.By
Autoprotolysis reaction in described aprotic solvent is the faintest or not certainly pass tendency, and have the strongest solvability,
Using above preferred described aprotic solvent to dissolve the polyimides of described solubility, its solvability is strong, simultaneously
Proton solvent is avoided to affect chemical reaction.
Further illustrating, the described silane coupler with amino includes gamma-aminopropyl-triethoxy-silane, γ-ammonia third
Base trimethoxy silane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropyltriethoxy two
Methoxy silane, N-β (aminoethyl)-gamma-aminopropyl-triethoxy-silane, N-β (aminoethyl)-γ-aminopropyltriethoxy diethoxy
Base silane, phenylaminomethyl triethoxysilane, phenylaminomethyl trimethoxy silane, 3-[2-(2-aminoethylamino) second
Base amino] propyl trimethoxy silicane, at least one in polyamino alkyltrialkoxysilaneand.Silicon by described band amino
The polyimides of the described solubility after alkane coupling agent and dissolving carries out cross-linking reaction, so that imide group therein and silicon
Amino reaction on alkane, forms amido link, and the hydrolysis of the alkoxyl of recycling silane coupler obtains the polyimides of crosslinking, i.e.
Described coating A.
Further illustrating, curing process described in step (2) is by the described independent film-forming of coating A or by described coating
A is coated on porous substrate, and described porous substrate is non-woven fabrics, paper, cellulose membrane, polyethylene porous membrane, polypropylene porous
Any one in film, polyethylene and polypropylene composite materials perforated membrane.Described coating A is coated on described porous substrate and is solidified into
Film, thus provide preferable mechanical strength by base material, i.e. optimize the mechanical characteristic of barrier film.
Further illustrating, the coating method of the described coating A in step (2) is silk screen, roller coat, impregnate, spray, scraper is coated with
Cloth, it is cast and drenches any one that cover.Film forming can be carried out by any of the above coating method, easy to operate simply, film forming is imitated
The best.
Preferably, described in step (2), the temperature of curing process is 20～120 DEG C, and the time of solidification is 10s～5h.Root
Certain solidification temperature and hardening time is set, so that described coating A forms stable thin film according to different conditions of cure
It is swelling that described thin film B is dipped in described lithium battery electrolytes by B, beneficially later stage, forms good stability and the high friendship of intensity
Connection polyimides gel polymer electrolyte barrier film.
The polyimides of described solubility can be fluorine-containing, any one soluble polyimide of silicon, phosphorus, but do not limits
Fixed, can be selected for the polyimides of the solubility of other structures, i.e. possess solubility.
The preparation method of an embodiment 1-crosslinked polyimide gel polymer electrolyte barrier film, comprises the steps:
(1) cross-linking reaction: the fluorine-containing copolyimide of 1g that viscosity is 0.6dL/g is joined DMAC N,N' dimethyl acetamide
Solution carries out dissolving to obtain mass fraction be the solution of 5%, and adds 0.1g γ-aminopropyltrimethoxysilane and cross-link
Reaction, stirs 20min, obtains coating A under room temperature；
(2) film-forming: use silk screen to be coated on polyfluortetraethylene plate by the coating A that step (1) obtains, put into 80 DEG C
Baking oven solidifies 5min, then uses 50wt% ethanol water to carry out washing to remove after solvent, dry and obtain thin film B；
(3) swelling action: described thin film B is immersed lithium-ion battery electrolytes swelling, the wherein master of lithium battery electrolytes
Composition is wanted to include Allyl carbonate: ethylene carbonate: diethyl carbonate=50:25:25, LiPF6(concentration is 1.0mol/L),
Soak 2 hours under room temperature, it is thus achieved that crosslinked polyimide gel polymer electrolyte barrier film, and it is solidifying to test described crosslinked polyimide
The pick up of xanthan polymer electrolyte membrance is 450%.
The preparation method of a comparative example 1-crosslinked polyimide gel polymer electrolyte barrier film, including walking as follows
Rapid:
(1) dissolve: the fluorine-containing copolyimide of the 1g (same as in Example 1) that viscosity is 0.6dL/g is joined N, N-
Carrying out in dimethylacetamide solution dissolving acquisition mass fraction is the solution of 5%, obtains coating A；
(2) film-forming: use silk screen to be coated on polyfluortetraethylene plate by the coating A that step (1) obtains, put into 80 DEG C
Baking oven solidifies 5min, then uses 50wt% ethanol water to carry out washing to remove after solvent, dry and obtain thin film B；
(3) swelling action: being immersed in lithium-ion battery electrolytes by described thin film B, wherein lithium battery electrolytes is main
Composition includes Allyl carbonate: ethylene carbonate: diethyl carbonate=50:25:25, LiPF6(concentration is 1.0mol/L), in room
Temperature is lower soaks 2 hours, finds that described thin film B dissolves.
With comparative example 1, embodiment 1 is carried out contrast understand, in comparative example 1, will be by fluorine-containing copolyimide
It is coated after dissolving in the thin film B immersion lithium-ion battery electrolytes that solidification obtains, finds that described thin film B is dissolved；And it is real
Execute and carry out cross-linking reaction with γ-aminopropyltrimethoxysilane after fluorine-containing copolyimide is dissolved by example 1, then be coated
Solidification obtains thin film B, immerses in lithium-ion battery electrolytes and does not finds that thin film B is dissolved, it is thus achieved that crosslinked polyimide gel
Polymer electrolyte diaphragm has a high-liquid absorbing rate of 450%, thus the crosslinking that obtained by silane coupler cross-linking reaction of explanation
The heat stability of polyimides is higher, and the liquid absorption of the crosslinked polyimide gel polymer electrolyte barrier film being prepared into is with strong
Degree height, wellability and the good conductivity of ion；Such as the infrared spectrum of imide group that Fig. 1 is embodiment 1, as seen from the figure, hand over
After connection, imide group:
The symmetrical stretching vibration 1722cm of C=O-1With asymmetrical stretching vibration 1785cm-1；Weaken
The stretching vibration 1371cm of C-N-1Weaken
1660cm-1Occur that the stretching vibration of amide group C=O absorbs (amide I)
1540cm-1Occur that amide group C-NH bending vibration absorbs (amide II)
Illustrate that imide group reacts with amino on silane, form amido link.
1100cm-1Near occur in that Si-O stretching vibration absorb, illustrate that silane reacts with polyimides.
The preparation method of an embodiment 2-crosslinked polyimide gel polymer electrolyte barrier film, comprises the steps:
(1) cross-linking reaction: the fluorine-containing copolyimide of 1g that viscosity is 1.8dL/g is joined N-Methyl pyrrolidone molten
Liquid carries out dissolving to obtain mass fraction be the solution of 5%, and adds 0.06g gamma-aminopropyl-triethoxy-silane and cross-link
Reaction, stirs 20min, obtains coating A under room temperature；
(2) film-forming: use silk screen to be coated on polyethylene porous membrane by the coating A that step (1) obtains, put into 50 DEG C
Baking oven solidifies 1min, then uses 50wt% ethanol water to carry out washing to remove after solvent, dry and obtain thin film B, wherein, institute
The thickness stating polyethylene porous membrane is 9 μm, and porosity is 60vol%；
(3) swelling action: described thin film B is immersed lithium-ion battery electrolytes swelling, the wherein master of lithium battery electrolytes
Composition is wanted to include Allyl carbonate: ethylene carbonate: diethyl carbonate=50:25:25, LiPF6(concentration is 1.0mol/L),
Soak 2 hours under room temperature, it is thus achieved that crosslinked polyimide gel polymer electrolyte barrier film, and it is solidifying to test described crosslinked polyimide
The pick up of xanthan polymer electrolyte membrance is 360%.
The preparation method of an embodiment 3-crosslinked polyimide gel polymer electrolyte barrier film, comprises the steps:
(1) cross-linking reaction: the siliceous copolyimide of 1g that viscosity is 1.8dL/g is joined N, N-dimethylacetamide
Carrying out in the mixed solution of amine/Allyl carbonate (8:2) dissolving acquisition mass fraction is the solution of 5%, and adds 0.02g phenylamino
Ylmethyl trimethoxy silane and 0.06g gamma-aminopropyl-triethoxy-silane carry out cross-linking reaction, stir 20min under room temperature,
To coating A；
(2) film-forming: be impregnated in by polypropylene porous film in the coating A that step (1) obtains, puts in 120 DEG C of baking ovens
Solidification 10s, then use 50wt% ethanol water to carry out washing to remove after solvent, dry and obtain thin film B, wherein, described poly-third
The thickness of alkene perforated membrane is 12 μm, and porosity is 45vol%；
(3) swelling action: described thin film B is immersed lithium-ion battery electrolytes swelling, the wherein master of lithium battery electrolytes
Composition is wanted to include Allyl carbonate: ethylene carbonate: diethyl carbonate=50:25:25, LiPF6(concentration is 1.0mol/L),
Soak 2 hours under room temperature, it is thus achieved that crosslinked polyimide gel polymer electrolyte barrier film, and it is solidifying to test described crosslinked polyimide
The pick up of xanthan polymer electrolyte membrance is 290%.
The preparation method of an embodiment 4-crosslinked polyimide gel polymer electrolyte barrier film, comprises the steps:
(1) cross-linking reaction: the phosphorous copolyimide of 1g that viscosity is 1.2dL/g is joined N, N-dimethyl formyl
Carrying out in the mixed solution of amine/dimethyl carbonate/hexamethylene (5:4:1) dissolving acquisition mass fraction is the solution of 5%, and adds
0.02gN-β (aminoethyl)-γ-aminopropyltrimethoxysilane and 0.06gN-β (aminoethyl)-γ-aminopropyltriethoxy dimethoxy
Base silane carries out cross-linking reaction, stirs 20min, obtain coating A under room temperature；
(2) film-forming: coating A roller coat step (1) obtained is on polyethylene and polypropylene composite materials perforated membrane, 25
Solidify 5h under conditions of DEG C, then use 50wt% ethanol water to carry out washing to remove after solvent, dry and obtain thin film B, wherein,
The thickness of described polyethylene and polypropylene composite materials perforated membrane is 10 μm, and porosity is 56vol%；
(3) swelling action: described thin film B is immersed lithium-ion battery electrolytes swelling, the wherein master of lithium battery electrolytes
Composition is wanted to include Allyl carbonate: ethylene carbonate: diethyl carbonate=2:1:1, LiPF6(concentration is 1.0mol/L), in room
Temperature is lower soaks 2 hours, it is thus achieved that crosslinked polyimide gel polymer electrolyte barrier film, and tests described crosslinked polyimide gel
The pick up of polymer electrolyte diaphragm is 325%.
The preparation method of an embodiment 5-crosslinked polyimide gel polymer electrolyte barrier film, comprises the steps:
(1) cross-linking reaction: the polyimides that the 1g that viscosity is 1.0dL/g contains full-cream ring structure is joined dimethyl sulfoxide
Carrying out in solution dissolving acquisition mass fraction is the solution of 5%, and adds 0.03gN-β (aminoethyl)-γ-aminopropyl three ethoxy
Base silane and 0.05gN-β (aminoethyl)-γ-aminopropyltriethoxy diethoxy silane carry out cross-linking reaction, stir under room temperature
20min, obtains coating A；
(2) film-forming: be sprayed on electrospun fibers element film by the coating A that step (1) obtains, puts into 40 DEG C of baking ovens
Middle solidification 6min, then use 50wt% ethanol water to carry out washing to remove after solvent, dry and obtain thin film B, wherein, described fibre
The thickness of dimension element film is 8.5 μm, and porosity is 48vol%；
(3) swelling action: described thin film B is immersed lithium-ion battery electrolytes swelling, the wherein master of lithium battery electrolytes
Composition is wanted to include Allyl carbonate: ethylene carbonate: diethyl carbonate=2:1:1, LiPF6(concentration is 1.0mol/L), in room
Temperature is lower soaks 2 hours, it is thus achieved that crosslinked polyimide gel polymer electrolyte barrier film, and tests described crosslinked polyimide gel
The pick up of polymer electrolyte diaphragm is 350%.
The preparation method of an embodiment 6-crosslinked polyimide gel polymer electrolyte barrier film, comprises the steps:
(1) cross-linking reaction: 6FDA and triptycene diamidogen that 1g viscosity is 1.3dL/g are polymerized the polyimides obtained and put into
Carrying out dissolving acquisition mass fraction in ethyl acetate/Ketohexamethylene/acetone (2:2:1) mixed solution is the solution of 5%, and adds
0.05gN-β (aminoethyl)-gamma-aminopropyl-triethoxy-silane and 0.05gN-β (aminoethyl)-γ-aminopropyltriethoxy diethoxy
Base silane carries out cross-linking reaction, stirs 20min, obtain coating A under room temperature；
(2) film-forming: coating A scraper for coating step (1) obtained, on polyethylene porous membrane, puts into 60 DEG C of baking ovens
Middle solidification 1min, then use 50wt% ethanol water to carry out washing to remove after solvent, dry and obtain thin film B, wherein, poly-second
The thickness of alkene perforated membrane is 8 μm, and porosity is 52vol%；
(3) swelling action: described thin film B is immersed lithium-ion battery electrolytes swelling, the wherein master of lithium battery electrolytes
Composition is wanted to include Allyl carbonate: ethylene carbonate: diethyl carbonate=2:1:1, LiPF6(concentration is 1.0mol/L), in room
Temperature is lower soaks 2 hours, it is thus achieved that crosslinked polyimide gel polymer electrolyte barrier film, and tests described crosslinked polyimide gel
The pick up of polymer electrolyte diaphragm is 270%.
The know-why of the present invention is described above in association with specific embodiment.These describe and are intended merely to explain the present invention's
Principle, and limiting the scope of the invention can not be construed to by any way.Based on explanation herein, the technology of this area
Personnel need not pay performing creative labour can associate other detailed description of the invention of the present invention, and these modes fall within
Within protection scope of the present invention.
Claims (6)
1. the preparation method of a crosslinked polyimide gel polymer electrolyte barrier film, it is characterised in that: comprise the steps:
(1) cross-linking reaction: after using aprotic solvent to dissolve the polyimides of solubility, then silane coupled with amino
Agent carries out cross-linking reaction, obtains coating A；
(2) film-forming: after the coating A that step (1) obtains is carried out curing process, then washing removal solvent, be dried to obtain thin
Film B；
(3) swelling action: described thin film B is immersed lithium-ion battery electrolytes swelling, obtain crosslinked polyimide gel polymerisation
Thing electrolyte membrance.
The preparation method of a kind of crosslinked polyimide gel polymer electrolyte barrier film the most according to claim 1, it is special
Levy and be: described aprotic solvent include DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, N-Methyl pyrrolidone, two
Methyl sulfoxide, Allyl carbonate, acetone, oxolane, hexamethylene, pentane, octane, heptane, hexane, Ketohexamethylene, toluene hexamethylene
Ketone, acetonitrile, ethyl acetate, butyl acetate, butanone, butanone, espeleton, methylisobutylketone, ethylene carbonate, carbonic acid diformazan
Ester, Ethyl methyl carbonate, diethyl carbonate, benzene,toluene,xylene, Nitrobenzol, dioxane, carbon tetrachloride, tetrachloroethylene, chlorine
Any one or more combination in imitative, dichloromethane, trichloro-benzenes, ether, ethyl methyl ether, butyl ether, pyridine.
The preparation method of a kind of crosslinked polyimide gel polymer electrolyte barrier film the most according to claim 1, it is special
Levy and be: the described silane coupler with amino includes gamma-aminopropyl-triethoxy-silane, γ-aminopropyl trimethoxy silicon
Alkane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, N-
β (aminoethyl)-gamma-aminopropyl-triethoxy-silane, N-β (aminoethyl)-γ-aminopropyltriethoxy diethoxy silane, phenylamino
MTES, phenylaminomethyl trimethoxy silane, 3-[2-(2-aminoethylamino) ethylamino] propyl group three
At least one in methoxy silane, polyamino alkyltrialkoxysilaneand.
The preparation method of a kind of crosslinked polyimide gel polymer electrolyte barrier film the most according to claim 1, it is special
Levy and be: described in step (2), curing process is for by the described independent film-forming of coating A or to be coated on porous by described coating A
On base material, described porous substrate be non-woven fabrics, paper, cellulose membrane, polyethylene porous membrane, polypropylene porous film, polyethylene and
Any one in polypropylene composite materials perforated membrane.
The preparation method of a kind of crosslinked polyimide gel polymer electrolyte barrier film the most according to claim 1, it is special
Levy and be: the coating method of the described coating A in step (2) is silk screen, roller coat, impregnate, spray, scraper for coating, be cast and drench
Cover any one.
The preparation method of a kind of crosslinked polyimide gel polymer electrolyte barrier film the most according to claim 1, it is special
Levy and be: the temperature of curing process described in step (2) is 20 DEG C～120 DEG C, and the time of solidification is 10s～5h.
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| CN201610729379.9A CN106328862A (en) | 2016-08-25 | 2016-08-25 | Preparation method for crosslinked polyimide gel polymer electrolyte membrane |
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| CN201610729379.9A CN106328862A (en) | 2016-08-25 | 2016-08-25 | Preparation method for crosslinked polyimide gel polymer electrolyte membrane |
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| CN111477951A (en) * | 2020-04-14 | 2020-07-31 | 宁德新能源科技有限公司 | Composite electrolyte and electrochemical and electronic device using the same |
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| CN114695953A (en) * | 2020-12-28 | 2022-07-01 | 荣盛盟固利新能源科技有限公司 | High-voltage high-safety polyimide gel polymer electrolyte, preparation method and application thereof, and lithium ion battery |
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| CN109119572A (en) * | 2018-08-01 | 2019-01-01 | 乳源东阳光氟树脂有限公司 | Polyimides lithium battery diaphragm and preparation method thereof and lithium battery comprising the diaphragm |
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| CN109193027A (en) * | 2018-09-05 | 2019-01-11 | 四川大学 | A kind of lithium ion polymer electrolyte film and the preparation method and application thereof |
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| CN111630687A (en) * | 2018-10-11 | 2020-09-04 | 旭化成株式会社 | Lithium ion battery using cross-linked separator |
| CN111630687B (en) * | 2018-10-11 | 2022-11-01 | 旭化成株式会社 | Lithium ion battery using cross-linked separator |
| US11670822B2 (en) | 2018-10-11 | 2023-06-06 | Asahi Kasei Kabushiki Kaisha | Separator having silane-modified polyolefin and polyethylene, and method for producing the same |
| US11837750B2 (en) | 2018-10-11 | 2023-12-05 | Asahi Kasei Kabushiki Kaisha | Lithium ion battery using crosslinkable separator |
| CN110760225A (en) * | 2019-10-31 | 2020-02-07 | 深圳中科瑞能实业有限公司 | Production method of gel polymer electrolyte porous membrane |
| CN110931850A (en) * | 2019-11-19 | 2020-03-27 | 上海大学 | Polysiloxane composite electrolyte, application thereof and preparation method thereof |
| CN110931850B (en) * | 2019-11-19 | 2023-03-24 | 上海大学 | Polysiloxane composite electrolyte, application thereof and preparation method thereof |
| CN111403666A (en) * | 2020-04-13 | 2020-07-10 | 上海极紫科技有限公司 | Composition of high-temperature-resistant lithium battery diaphragm and preparation and crosslinking methods thereof |
| CN111477951A (en) * | 2020-04-14 | 2020-07-31 | 宁德新能源科技有限公司 | Composite electrolyte and electrochemical and electronic device using the same |
| CN114695953A (en) * | 2020-12-28 | 2022-07-01 | 荣盛盟固利新能源科技有限公司 | High-voltage high-safety polyimide gel polymer electrolyte, preparation method and application thereof, and lithium ion battery |
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