CN106549187B - A kind of dielectric film and its preparation method and application containing amphoteric ion full solid state polymer - Google Patents
A kind of dielectric film and its preparation method and application containing amphoteric ion full solid state polymer Download PDFInfo
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- CN106549187B CN106549187B CN201610959515.3A CN201610959515A CN106549187B CN 106549187 B CN106549187 B CN 106549187B CN 201610959515 A CN201610959515 A CN 201610959515A CN 106549187 B CN106549187 B CN 106549187B
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- 239000007787 solid Substances 0.000 title claims abstract description 55
- 229920000642 polymer Polymers 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 44
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 33
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 17
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 229920001843 polymethylhydrosiloxane Polymers 0.000 claims abstract description 12
- 238000001291 vacuum drying Methods 0.000 claims abstract description 10
- -1 methyl hydrogen Chemical compound 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 238000004132 cross linking Methods 0.000 claims abstract description 6
- 239000003377 acid catalyst Substances 0.000 claims abstract description 3
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 claims abstract 4
- 229910001416 lithium ion Inorganic materials 0.000 claims description 33
- 150000002500 ions Chemical class 0.000 claims description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- MWQJGSUQGMJVCS-UHFFFAOYSA-N N=[S+]C(F)(F)F.[Li] Chemical compound N=[S+]C(F)(F)F.[Li] MWQJGSUQGMJVCS-UHFFFAOYSA-N 0.000 claims description 9
- 239000004809 Teflon Substances 0.000 claims description 9
- 229920006362 Teflon® Polymers 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- GBCKRQRXNXQQPW-UHFFFAOYSA-N n,n-dimethylprop-2-en-1-amine Chemical compound CN(C)CC=C GBCKRQRXNXQQPW-UHFFFAOYSA-N 0.000 abstract description 22
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract description 5
- 229920000570 polyether Polymers 0.000 abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052744 lithium Inorganic materials 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 24
- 239000011259 mixed solution Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 7
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 7
- 229920006280 packaging film Polymers 0.000 description 7
- 239000012785 packaging film Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- 230000004899 motility Effects 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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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
- H01M10/058—Construction or manufacture
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Primary Cells (AREA)
Abstract
The invention discloses a kind of dielectric film and its preparation method and application containing amphoteric ion full solid state polymer.By poly- (methyl hydrogen silicomethane), N, N- dimethylallylamine, allyl capped polyethers, 1,3- propyl sultone, lithium salts and crosslinking agent are made the full solid state polymer electrolyte of the present invention.PMHS, PEO, DMAA are sufficiently mixed in toluene, chloroplatinic acid catalyst reaction is added；The product of preparation is reacted with 1,3-PS again；The product of above-mentioned reaction is mixed into lithium salts, crosslinking agent in acetonitrile solvent, and crosslinking forms a film to get amphoteric ion full solid state polymer electrolyte film is contained in vacuum drying oven after being sufficiently stirred.The present invention's increases substantially containing zwitterionic full solid state polymer electrolyte conductivity, reaches 3.39 × 10 at room temperature‑4S·cm‑1, electrochemical window is more than 5V, can be used for lithium secondary battery.
Description
Technical field
The present invention relates to a kind of dielectric film and its preparation method and application containing amphoteric ion full solid state polymer.
Background technology
With the development of the social economy, demand of the people to the energy increasingly increases, at the same it is dirty in global warming, air
It contaminates that the problems such as serious is especially prominent, drastically influences the development and existence of human society, therefore this height of lithium rechargeable battery
The green mobile energy storage device of effect is shown one's talent, and the Main way of Future New Energy Source development is become, and lithium ion battery is not only at present
It is widely used in the mobile electrons such as smart mobile phone, laptop, stereo set, game machine, digital camera, palm PC to set
It is standby, also it is increasingly used in electric vehicle, unmanned plane, earth orbital flight device, airline carriers of passengers etc..
Current market sales of lithium ion battery mainly uses carbonates liquid electrolyte systems, although having higher
Ionic conductivity, but organic solvent has and is easy that leakage, flash-point is relatively low, easy firing, the characteristics such as volatile, toxic, in mistake
It fills, collide, squeezing etc. in special circumstances, it may occur however that the safety accidents such as leakage, burning, explosion, to the personal property of user
Safety causes certain threat, it would therefore be highly desirable to which it is higher and disclosure satisfy that all solid state poly- of business application to develop security performance
Polymer electrolyte.
The room-temperature conductivity of full solid state polymer electrolyte (SPE) is relatively low, is the master that cannot be satisfied commercially use requirement
Want reason.PEO is most common polymer electrolyte at present, however conductivity is relatively low under PEO and lithium salts mixed room temperature, is needed
It to be further modified, improve the conductivity of polymer at room temperature.Currently, the main method for improving conductivity has grafting, blending, is total to
The methods of poly-, addition inorganic filler.Since PMHS segments are soft, motility is good, and PEO is grafted to PMHS side chains, not only may be used
To reduce PEO crystallinity, and the advantage that PMHS sub-chain motions can be utilized good, the electric conductivity of PEO segments is further increased,
Amphoteric ion is further introduced into PMHS side chains, can not only form new lithium ion mobility channel, improves conductivity, Er Qieke
By improving cell interface performance, to play the role of improving electrochemical stability, therefore prepare electric conductivity and stability is equal
The polymer dielectric film for the lithium ion battery applications that can be met the requirements.
Invention content
The purpose of the present invention is to solve existing full solid state polymer electrolyte room-temperature conductivities low, electrochemical window is not
High problem.The present invention provides a kind of dielectric film containing amphoteric ion full solid state polymer and preparation method thereof and use
On the way.
The full solid state polymer electrolyte film of the present invention is prepared by following steps：
Preparation method containing amphoteric ion full solid state polymer electrolyte includes the following steps：
A, it by hydrosilylation, prepares side chain while being grafted PEO and zwitterionic polymethyl hydrogen siloxane,
Shown in structure such as formula (1):
M/n≤0.04 in formula (1), x=3~20, R are-N (CH3)2-。
B, the polymer prepared in step a and lithium salts, crosslinking agent are dissolved in acetonitrile or acetone solvent, are stirred at room temperature
Mix, pour into Teflon mould after mixing, be placed in heat drying in vacuum drying oven, crosslinking film forming, prepare containing
Zwitterionic full solid state polymer electrolyte film.
Preferably, the step a is specific as follows：
1) it is sufficiently mixed PMHS and organic solvent to obtain solution A, then mixes DMAA, PEO, catalyst and organic solvent
It closes uniformly, obtains solution B, solution A is preheated to 40~60 DEG C, under inert gas atmosphere, solution B is slowly added dropwise into A, drip
Add rear mixed liquor the reaction was continued at 40~60 DEG C 2~3h, then raises temperature to 70~90 DEG C of reactions until C=C disappears, reaction terminates
Organic solvent is removed, product C is obtained；
2) it is sufficiently mixed product C and organic solvent to obtain solution D, 45~60 DEG C is preheated in inert gas environment, it will
1,3- propyl sultone is added in solution D, is reacted 16~20 hours at 45~60 DEG C, removes organic solvent and obtains product E, product
E is formula (1) structure.
Preferably, DMAA and molar ratio≤0.04 PEO in the step 1)；Organic solvent described in step 1) is
Toluene, step 1) catalyst are chloroplatinic acid, are fed intake as 10~40ppm, and preferably chloroplatinic acid catalyst feeds intake as 20ppm.
Preferably, the organic solvent described in step 2) is tetrahydrofuran；The amount and step of 1,3- propyl sultone is added
1) it is 1 that the DMAA being added in, which meets molar ratio,:1.
Preferably, lithium salts used is bis trifluoromethyl sulfimide lithium, the PEO satisfactions [EO] of lithium salts amount used and addition:
[Li+]=5~40.
Preferably, added crosslinking agent is triethyleneglycol divinylether, and the addition of crosslinking agent is polymerization prepared by step a
The 5~10% of amount of substance.
The invention also discloses the dielectric film containing amphoteric ion full solid state polymer prepared by the method, features
It is：The conductivity at room temperature containing amphoteric ion full solid state polymer electrolyte film is 10-4S·cm-1More than,
The room temperature electrochemical window is stablized in 5V or more.
Contain amphoteric ion full solid state polymer electrolyte film answering in lithium ion battery the invention also discloses described
With.
The present invention grafts to PEO on the side chain of PMHS, to reduce glass transition temperature, to reduce solid polymer
The crystallinity of electrolyte, since the electric action of PEO is only happened at noncrystalline domain, conductance can be improved by reducing crystallinity
Rate, simultaneously because PMHS main chains are softer, motility is strong, can reinforce the sub-chain motion ability of PEO, play and further increase
The effect of conductivity.In PMHS side chain graft amphoteric ions, can play the role of further increasing conductivity, the reason is that both sexes
Ion (sulfobetaines) can promote electron delocalization, while sulfonic acid group is easily by the attack of electrophilic group, it is easier to it is low
The Li of cloud density+It interacts, plays and promote lithium salts dissociation, form new lithium ion mobility channel, reach into one
Step improves the effect of conductivity；On the other hand, due to introducing amphoteric ion, increase the interface stability of electrolyte with it is compatible
Property, so that polymer electrolyte electrochemical window is improved.
Compared with prior art, the invention has the advantages that：1, the vitrifying of polymer dielectric is reduced
Transition temperature, to reduce crystallinity；2, electrolyte leakage and the safety decomposed existing for liquid electrolyte can be solved to ask
Topic；3, room-temperature conductivity reaches 3.39 × 10-4S·cm-1, decomposition voltage is more than 5V, basically reaches commercially use demand；4,
It can be processed into arbitrary shape, meet different cell shapes demands.The present invention can make full solid state polymer electrolyte in lithium ion
It is more widely used in battery.
Specific implementation mode
With reference to embodiment, the present invention will be further described.These examples only describe the typical of the present invention, but
The invention is not limited thereto.
In all examples provided by the invention, the raw material provided can be obtained from market buying.
The synthesis of 1 Siloxane-Oxyalkylene Copolymers of embodiment
A certain amount of polymethyl hydrogen siloxane (PMHS) is weighed, mixes and is added in the three-necked flask of 50ml with suitable toluene,
It moves in oil bath pan and heats, by appropriate allyl capped polyethers (PEO) (m(PEO):m(PMHS)=2), by appropriate Speier catalyst
It is added in normal pressure funnel after being uniformly dispersed in toluene solvant, in N2Under atmosphere, mixed liquor in normal pressure funnel is instilled three dropwise
It in mouthful flask, is reacted certain time at 50 DEG C first, is then heated to 80 DEG C of reaction certain times, until the reaction was complete by PEO,
Product passes through n-hexane washing impurity-removing, and revolving removes solvent, obtains Siloxane-Oxyalkylene Copolymers (PEO-g-PMHS).
The preparation of 2 polymer Li-ion battery of embodiment
(1) Siloxane-Oxyalkylene Copolymers prepared in embodiment 1 are placed in 100ml round-bottomed flasks, are then added suitable
Crosslinking agent and bis trifluoromethyl sulfimide lithium (LiTFSI) are measured, lithium salts amount is added and meets [EO]:[Li+]=20:1, in acetonitrile
It is sufficiently stirred, is uniformly mixed in solvent.
(2) mixed solution in (1) is poured into Teflon mould, is subsequently placed in vacuum drying oven, is dried in vacuo
Obtain all solid state modified polymer electrolyte film.
(3) anode, full solid state polymer electrolyte film and cathode are stacked togather, is sealed in button cell or plastic-aluminum combined
In packaging film, it is compacted into full solid state polymer lithium ion battery.
The preparation of 3 polymer Li-ion battery of embodiment
(1) a certain amount of polymethyl hydrogen siloxane (PMHS) is weighed, the three-necked flask that 50ml is added is mixed with suitable toluene
In, it moves in oil bath pan and heats, by allyl capped polyethers (PEO) (m(PEO):m(PMHS)=2), N, N- dimethylallylamine
(DMAA)(n(DMAA):n(PEO)=1:20) it is added after mixing in normal pressure funnel in toluene with suitable Speier catalyst,
Then in N2Under atmosphere, mixed liquor in normal pressure funnel is instilled in three-necked flask dropwise, reacts certain time at 50 DEG C first, with
After be heated to 80 DEG C of reaction certain times, mixed solution becomes shallow yellow transparent solution from water white transparency, and product passes through n-hexane
Washing impurity-removing, revolving obtain grafting DMAA and PEO modified polyorganosiloxanes.
(2) 50ml tri- is added after dissolving grafting DMAA and the PEO modified polyorganosiloxane prepared in (1) in tetrahydrofuran
In mouth flask, then by a certain amount of 1,3- propyl sultone (n(1,3-PS)):n(DMAA)=1:1) it is added in three-necked flask, in N2Gas
Under atmosphere, 50 DEG C of reaction appropriate times, product removes solvent through revolving, obtains amphoteric ion and Siloxane-Oxyalkylene Copolymers (ZW-
Co-PEO-g-PMHS) polymer electrolyte.
(3) ZW-co-PEO-g-PMHS prepared in (2) is placed in 100ml round-bottomed flasks, appropriate crosslinking is then added
Agent and bis trifluoromethyl sulfimide lithium (LiTFSI) are added lithium salts amount and meet [EO]:[Li+]=20:1, in acetonitrile solvent
It is sufficiently stirred, is uniformly mixed.
(4) mixed solution in (3) is poured into Teflon mould, is subsequently placed in vacuum drying oven, is dried in vacuo
Obtain all solid state modified polymer electrolyte film.
(5) anode, full solid state polymer electrolyte film and cathode are stacked togather, is sealed in button cell or plastic-aluminum combined
In packaging film, it is compacted into full solid state polymer lithium ion battery.
The preparation of 4 polymer Li-ion battery of embodiment
(1) a certain amount of polymethyl hydrogen siloxane (PMHS) is weighed, the three-necked flask that 50ml is added is mixed with suitable toluene
In, it moves in oil bath pan and heats.By allyl capped polyethers (PEO) (m(PEO):m(PMHS)=2), N, N- dimethylallylamine
(DMAA)(n(DMAA):n(PEO)=1:10) it is added after mixing in normal pressure funnel in toluene with suitable Speier catalyst,
Then in N2Under atmosphere, mixed liquor in normal pressure funnel is instilled in three-necked flask dropwise, reacts certain time at 50 DEG C first, with
After be heated to 80 DEG C of reaction certain times, mixed solution becomes shallow yellow transparent solution from water white transparency, and product passes through n-hexane
Washing impurity-removing, revolving obtain grafting DMAA and PEO modified polyorganosiloxanes.
(2) the grafting DMAA prepared in (1) the and PEO polysiloxanes being modified is dissolved in tetrahydrofuran, 50ml is added
In three-necked flask, then by a certain amount of 1,3- propyl sultone (n(1,3-PS):n(DMAA)=1:1) it is added in three-necked flask, in N2Gas
Under atmosphere, 50 DEG C of reaction appropriate times, product removes solvent through revolving, obtains amphoteric ion and Siloxane-Oxyalkylene Copolymers (ZW-
Co-PEO-g-PMHS) polymer electrolyte.
(3) ZW-co-PEO-g-PMHS prepared in (2) is placed in 100ml round-bottomed flasks, appropriate crosslinking is then added
Agent and bis trifluoromethyl sulfimide lithium (LiTFSI) are added lithium salts amount and meet [EO]:[Li+]=20:1, in acetonitrile solvent
It is sufficiently stirred, is uniformly mixed.
(4) mixed solution in (3) is poured into Teflon mould, is subsequently placed in vacuum drying oven, is dried in vacuo
Obtain all solid state modified polymer electrolyte film.
(5) anode, full solid state polymer electrolyte film and cathode are stacked togather, is sealed in button cell or plastic-aluminum combined
In packaging film, it is compacted into full solid state polymer lithium ion battery.
The preparation of 5 polymer Li-ion battery of embodiment
(1) a certain amount of polymethyl hydrogen siloxane (PMHS) is weighed, the three-necked flask that 50ml is added is mixed with suitable toluene
In, it moves in oil bath pan and heats, by allyl capped polyethers (PEO) (m(PEO):m(PMHS)=2), N, N- dimethylallylamine
(DMAA)(n(DMAA):n(PEO)=1:5) it is added after mixing in normal pressure funnel in toluene with suitable Speier catalyst,
Then in N2Under atmosphere, mixed liquor in normal pressure funnel is instilled in three-necked flask dropwise, reacts certain time at 50 DEG C first, with
After be heated to 80 DEG C of reaction certain times, mixed solution becomes shallow yellow transparent solution from water white transparency, and product passes through n-hexane
Washing impurity-removing, revolving obtain grafting DMAA and PEO modified polyorganosiloxanes.
(2) the grafting DMAA prepared in (1) the and PEO polysiloxanes being modified is dissolved in dissolve in tetrahydrofuran and is added
In 50ml three-necked flasks, then by a certain amount of 1,3-propane sultone (n1,3-PS):n(DMAA)=1:1) it is added in three-necked flask,
N2Under atmosphere, 50 DEG C of reaction appropriate times, product obtains amphoteric ion and Siloxane-Oxyalkylene Copolymers through rotating away solvent
(ZW-co-PEO-g-PMHS) polymer electrolyte.
(3) ZW-co-PEO-g-PMHS prepared in (2) is placed in 100ml round-bottomed flasks, appropriate crosslinking is then added
Agent and bis trifluoromethyl sulfimide lithium (LiTFSI) are added lithium salts amount and meet [EO]:[Li+]=20:1, in acetonitrile solvent
It is sufficiently stirred, is uniformly mixed.
(4) mixed solution in (3) is poured into Teflon mould, is subsequently placed in vacuum drying oven, is dried in vacuo
Obtain all solid state modified polymer electrolyte film.
(5) anode, full solid state polymer electrolyte film and cathode are stacked togather, is sealed in button cell or plastic-aluminum combined
In packaging film, it is compacted into full solid state polymer lithium ion battery.
The preparation of 6 polymer Li-ion battery of embodiment
(1) ZW-co-PEO-g-PMHS prepared in embodiment (3) is placed in 100ml round-bottomed flasks, is then added
Appropriate crosslinking agent and bis trifluoromethyl sulfimide lithium (LiTFSI) are added lithium salts amount and meet [EO]:[Li+]=8:1, in acetonitrile
It is sufficiently stirred, is uniformly mixed in solvent.
(2) mixed solution in (1) is poured into Teflon mould, is subsequently placed in vacuum drying oven, is dried in vacuo
Obtain all solid state modified polymer electrolyte film.
(3) anode, full solid state polymer electrolyte film and cathode are stacked togather, is sealed in button cell or plastic-aluminum combined
In packaging film, it is compacted into full solid state polymer lithium ion battery.
The preparation of 7 polymer Li-ion battery of embodiment
(1) ZW-co-PEO-g-PMHS prepared in embodiment (3) is placed in 100ml round-bottomed flasks, is then added
Appropriate crosslinking agent and bis trifluoromethyl sulfimide lithium (LiTFSI) are added lithium salts amount and meet [EO]:[Li+]=14:1, in second
It is sufficiently stirred, is uniformly mixed in nitrile solvent.
(2) mixed solution in (1) is poured into Teflon mould, is subsequently placed in vacuum drying oven, is dried in vacuo
Obtain all solid state modified polymer electrolyte film.
(3) anode, full solid state polymer electrolyte film and cathode are stacked togather, is sealed in button cell or plastic-aluminum combined
In packaging film, it is compacted into full solid state polymer lithium ion battery.
The preparation of 8 polymer Li-ion battery of embodiment
(1) ZW-co-PEO-g-PMHS prepared in embodiment (3) is placed in 100ml round-bottomed flasks, is then added
Appropriate crosslinking agent and bis trifluoromethyl sulfimide lithium (LiTFSI) are added lithium salts amount and meet [EO]:[Li+]=26:1, in second
It is sufficiently stirred, is uniformly mixed in nitrile solvent.
(2) mixed solution in (1) is poured into Teflon mould, is subsequently placed in vacuum drying oven, is dried in vacuo
Obtain all solid state modified polymer electrolyte film.
(3) anode, full solid state polymer electrolyte film and cathode are stacked togather, is sealed in button cell or plastic-aluminum combined
In packaging film, it is compacted into full solid state polymer lithium ion battery.
The performance test of (25 DEG C) is shown in Table 1 under full solid state polymer lithium ion battery room temperature prepared by embodiment 2~8
| Conductivity (10-4S·cm-1) | Electrochemical window (V) | |
| Embodiment 2 | 1.32 | 4.1 |
| Embodiment 3 | 3.39 | 5.2 |
| Embodiment 4 | 1.77 | 5.4 |
| Embodiment 5 | 0.75 | 5.1 |
| Embodiment 6 | 1.83 | 4.9 |
| Embodiment 7 | 2.81 | 5.0 |
| Embodiment 8 | 0.86 | 4.8 |
As shown in Table 1, the full solid state polymer electrolyte room-temperature conductivity that prepared by the present invention significantly improves, especially electric
Chemical window is significantly improved, and substantially increases the security performance of lithium ion battery；This thin-film material has centainly simultaneously
Mechanical strength and good processing performance can solve the problems, such as that electrolyte leakage easily occurs for liquid electrolyte, and the present invention makes entirely
Solid polymer electrolyte being more widely applied in the lithium secondary battery.
Claims (10)
1. a kind of preparation method containing amphoteric ion full solid state polymer electrolyte, it is characterised in that：The method includes with
Lower step：
A, it by hydrosilylation, prepares side chain while being grafted PEO and zwitterionic polymethyl hydrogen siloxane, structure
As shown in formula (1):
M/n≤0.04 in formula (1), x=3~20, R are-N (CH3)2-；
B, the polymer prepared in step a and lithium salts, crosslinking agent are dissolved in acetonitrile or acetone solvent, are stirred at room temperature, mixed
Poured into Teflon mould after closing uniformly, be placed in heat drying in vacuum drying oven, crosslinking film forming, prepare containing both sexes from
The full solid state polymer electrolyte film of son.
2. a kind of preparation method containing amphoteric ion full solid state polymer electrolyte as described in claim 1, feature exist
It is specific as follows in the step a：
1) it is sufficiently mixed PMHS and organic solvent to obtain solution A, DMAA, PEO, catalyst is uniformly mixed with organic solvent,
Solution B is obtained, solution A is preheated to 40~60 DEG C, under inert gas atmosphere, solution B is slowly added dropwise into A, is mixed after dropwise addition
Liquid the reaction was continued at 40~60 DEG C 2~3h is closed, then raises temperature to 70~90 DEG C of reactions until C=C disappears, reaction, which terminates to remove, to be had
Solvent obtains product C；
2) it is sufficiently mixed product C and organic solvent to obtain solution D, 45~60 DEG C is preheated in inert gas environment, by 1,3-
Propyl sultone is added in solution D, is reacted 16~20 hours at 45~60 DEG C, removes organic solvent and obtains product E, product E is
For formula (1) structure.
3. a kind of preparation method containing amphoteric ion full solid state polymer electrolyte as claimed in claim 2, feature exist
DMAA and molar ratio≤0.04 PEO in the step 1)；Organic solvent described in step 1) is toluene, and step 1) is urged
Agent is chloroplatinic acid, is fed intake as 10~40ppm.
4. a kind of preparation method containing amphoteric ion full solid state polymer electrolyte as claimed in claim 2, feature exist
Organic solvent described in step 2) is tetrahydrofuran；The molar ratio of 1,3- propyl sultone and DMAA are 1:1.
5. a kind of preparation method containing amphoteric ion full solid state polymer electrolyte as claimed in claim 3, feature exist
It feeds intake as 20ppm in the chloroplatinic acid catalyst.
6. a kind of preparation method containing amphoteric ion full solid state polymer electrolyte as described in claim 1, feature exist
In lithium salts used be bis trifluoromethyl sulfimide lithium.
7. a kind of preparation method containing amphoteric ion full solid state polymer electrolyte as described in claim 1 or 4, feature
Meet [EO] in lithium salts amount used and the PEO of addition:[Li+]=5~40.
8. a kind of preparation method containing amphoteric ion full solid state polymer electrolyte as described in claim 1, feature exist
In added crosslinking agent be triethyleneglycol divinylether, the addition of crosslinking agent be polymer quality prepared by step a 5~
10%.
9. a kind of dielectric film containing amphoteric ion full solid state polymer prepared by method as described in claim 1, feature
It is：The conductivity at room temperature containing amphoteric ion full solid state polymer electrolyte film is 10-4S·cm-1More than,
Room temperature electrochemical window is stablized in 5V or more.
10. the application containing amphoteric ion full solid state polymer electrolyte film in lithium ion battery as claimed in claim 9.
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| CN108091418A (en) * | 2018-01-31 | 2018-05-29 | 苏州维洛克电子科技有限公司 | A kind of novel conductive film |
| CN108808099B (en) * | 2018-05-23 | 2020-04-28 | 浙江大学 | Preparation method and application of modified polysiloxane-based solid electrolyte membrane |
| CN108615937B (en) * | 2018-05-25 | 2020-01-14 | 北京新能源汽车股份有限公司 | Polymer electrolyte, solid electrolyte membrane and lithium ion battery |
| CN108899579B (en) * | 2018-06-14 | 2021-03-05 | 北京工业大学 | Preparation of self-crosslinking composite solid electrolyte and all-solid-state lithium ion battery formed by same |
| CN109935476B (en) * | 2019-03-08 | 2021-03-26 | 齐鲁工业大学 | Amphoteric gel polymer electrolyte with good performance and preparation and application thereof |
| CN112448027B (en) * | 2019-09-03 | 2021-10-22 | 华南师范大学 | Blended gel polymer electrolyte and preparation method and application thereof |
| CN110571470B (en) * | 2019-09-16 | 2021-05-11 | 上海汽车集团股份有限公司 | Fluorine-containing modified polysiloxane solid electrolyte and preparation method and application thereof |
| CN111162308B (en) * | 2019-12-02 | 2022-10-28 | 常州乾艺智能制造科技有限公司 | Preparation method of novel low-lattice-energy lithium salt for solid lithium battery |
| CN112625592B (en) * | 2020-10-26 | 2022-03-25 | 上海汽车集团股份有限公司 | Preparation method of lithium metal interface modification layer |
| CN112615049B (en) * | 2020-12-21 | 2023-01-03 | 中创新航技术研究院(江苏)有限公司 | Solid electrolyte and battery comprising the same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020019213A (en) * | 2000-09-05 | 2002-03-12 | 김순택 | Lithium secondary battery |
| CN1464002A (en) * | 2002-06-12 | 2003-12-31 | 中国科学院化学研究所 | Comb shaped polysiloxane and solid electrolyte produced therefrom and process for preparing the same |
| CN1738072A (en) * | 2005-09-01 | 2006-02-22 | 复旦大学 | Dye sensitization nanocrystalline solar battery based on dendroid compounds and its preparing method |
| CN1880354A (en) * | 2005-06-13 | 2006-12-20 | 中国科学院化学研究所 | Whole solid state/gelatin polymer solid electrolyte and its dedicated polymer and preparation method |
| EP2991153A1 (en) * | 2014-08-28 | 2016-03-02 | Samsung Electronics Co., Ltd. | Composite electrolyte and lithium battery including the same |
| CN106030721A (en) * | 2014-02-17 | 2016-10-12 | 富士胶片株式会社 | Solid electrolyte composition, battery electrode sheet and all-solid secondary battery using same, and method for producing these |
-
2016
- 2016-10-27 CN CN201610959515.3A patent/CN106549187B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020019213A (en) * | 2000-09-05 | 2002-03-12 | 김순택 | Lithium secondary battery |
| CN1464002A (en) * | 2002-06-12 | 2003-12-31 | 中国科学院化学研究所 | Comb shaped polysiloxane and solid electrolyte produced therefrom and process for preparing the same |
| CN1880354A (en) * | 2005-06-13 | 2006-12-20 | 中国科学院化学研究所 | Whole solid state/gelatin polymer solid electrolyte and its dedicated polymer and preparation method |
| CN1738072A (en) * | 2005-09-01 | 2006-02-22 | 复旦大学 | Dye sensitization nanocrystalline solar battery based on dendroid compounds and its preparing method |
| CN106030721A (en) * | 2014-02-17 | 2016-10-12 | 富士胶片株式会社 | Solid electrolyte composition, battery electrode sheet and all-solid secondary battery using same, and method for producing these |
| EP2991153A1 (en) * | 2014-08-28 | 2016-03-02 | Samsung Electronics Co., Ltd. | Composite electrolyte and lithium battery including the same |
Non-Patent Citations (3)
| Title |
|---|
| Effect of zwitterions on electrochemical properties of oligoether-based;Mitsutake Suematsu et al;《Electrochimica Acta》;20141212;第175卷;全文 * |
| Li+ ion transport in ionic liquid-based electrolytes and the influence of sulfonate-based zwitterion additives;F. Wohde et al;《Solid State Ionics》;20160131;第284卷;全文 * |
| The additive effect of zwitterion and nano-particles on ion;N. Byrne et al;《Electrochimica Acta》;20050102;第50卷;全文 * |
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