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
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- solid state
- full solid
- polymer electrolyte
- state polymer
- amphoteric ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610959515.3A CN106549187B (en) | 2016-10-27 | 2016-10-27 | A kind of dielectric film and its preparation method and application containing amphoteric ion full solid state polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610959515.3A CN106549187B (en) | 2016-10-27 | 2016-10-27 | A kind of dielectric film and its preparation method and application containing amphoteric ion full solid state polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106549187A CN106549187A (en) | 2017-03-29 |
| CN106549187B true CN106549187B (en) | 2018-11-02 |
Family
ID=58393906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610959515.3A Active CN106549187B (en) | 2016-10-27 | 2016-10-27 | A kind of dielectric film and its preparation method and application containing amphoteric ion full solid state polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106549187B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106549187A (en) | 2017-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106549187B (en) | A kind of dielectric film and its preparation method and application containing amphoteric ion full solid state polymer | |
| Yang et al. | Review of ionic liquids containing, polymer/inorganic hybrid electrolytes for lithium metal batteries | |
| CN108808099A (en) | A kind of preparation method and purposes of modified polyorganosiloxane based solid electrolyte film | |
| CN103208651B (en) | A kind of siloxy group solid electrolyte and Synthesis and applications thereof | |
| Crowther et al. | Primary Li-air cell development | |
| CN101003630B (en) | Cyclic carbonate-modified siloxane and method for producing the same, non-aqueous electrolyte solution, secondary cell and capacitor | |
| CN110676509B (en) | Room-temperature solid polymer electrolyte and preparation method thereof, electrode/electrolyte composite and preparation method and application thereof | |
| CN106898812B (en) | A kind of solid polymer electrolyte and preparation method thereof and anode composite and solid lithium ion battery | |
| Zhang et al. | Organic electrolyte design for rechargeable batteries: From lithium to magnesium | |
| KR101954601B1 (en) | Organic-inorganic composite solid electrolyte, lithium secondary cell comprising the same, and manufacturing method for the lithium secondary cell | |
| JP2012518248A (en) | High energy non-aqueous battery based on ionic conductive gel, its production method and its use | |
| Wang et al. | Organosilicon‐Based Functional Electrolytes for High‐Performance Lithium Batteries | |
| CN109065947B (en) | Controllable photocuring PEG solid topological structure polymer electrolyte and preparation method thereof | |
| Wang et al. | Fluorosilane compounds with oligo (ethylene oxide) substituent as safe electrolyte solvents for high-voltage lithium-ion batteries | |
| CN106785032B (en) | A kind of lithium ion battery polymer dielectric and preparation method | |
| CN108428931B (en) | Ionic liquid polymer composite solid electrolyte, preparation method thereof and lithium ion battery | |
| CN107925126A (en) | Additive, all solid state secondary battery and its manufacture method of all solid state secondary battery | |
| CN102964372A (en) | Halogenosilane functionalized carbonate electrolyte material, its preparation method and application in lithium-ion battery electrolyte solution | |
| Zhang et al. | Cross-linked nanohybrid polymer electrolytes with POSS cross-linker for solid-state lithium ion batteries | |
| US7473491B1 (en) | Electrolyte for electrochemical cell | |
| CN105556726B (en) | Ion transmission material, the preparation method for including its dielectric film and the dielectric film | |
| CN106916308A (en) | Polymer and preparation method thereof and solid polymer electrolyte and all-solid lithium-ion battery | |
| Wu et al. | Lithium-ion transport enhancement with bridged ceramic-polymer interface | |
| CN107180998B (en) | A kind of electrolyte and lithium ion battery | |
| Wang et al. | Poly (ethylene oxide)–silica hybrid materials for lithium battery application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |