CN106549187A - A kind of dielectric film containing amphion full solid state polymer and its production and use - Google Patents
A kind of dielectric film containing amphion full solid state polymer and its production and use Download PDFInfo
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Abstract
The invention discloses a kind of dielectric film containing amphion full solid state polymer and its production and use.The full solid state polymer electrolyte of the present invention by poly- (methyl hydrogen silicomethane), N, make by N DMAAs, allyl capped polyethers, 1,3 propyl group sultone, lithium salts and crosslinking agent.PHMS, 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, is crosslinked film forming after being sufficiently stirred in vacuum drying oven, obtains final product containing amphion full solid state polymer electrolyte film.The present invention's increases substantially containing zwitterionic full solid state polymer electrolyte electrical conductivity, and room temperature is issued to 3.39 × 10‑4S·cm‑1, electrochemical window can be used for lithium secondary battery more than 5V.
Description
Technical field
The present invention relates to a kind of dielectric film containing amphion full solid state polymer and its production and use.
Background technology
With the development of social economy, people increasingly increase to the demand of the energy, while dirty in global warming, air
The problems such as contaminating serious is especially prominent, drastically influence 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 becomes the Main way of Future New Energy Source development, and current lithium ion battery is not only
It is widely used in the mobile electrons such as smart mobile phone, notebook computer, stereo set, game machine, digital camera, palm PC to set
It is standby, also more and more it is applied to the aspects such as electric automobile, unmanned plane, earth orbital flight device, airline carriers of passengers.
The lithium ion battery main Bian carbonates liquid electrolyte systems sold in the market, although have higher
Ionic conductivity, but organic solvent has the characteristic such as easy leakage, relatively low flash-point, easy firing, volatile, poisonous, in mistake
Fill, collide, extruding etc. in particular cases, it may occur however that reveal, burning, the security incident such as blast, the personal property to user
Safety causes certain threat, it would therefore be highly desirable to 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 meet commercially use requirement
Want reason.PEO is the most frequently used polymer electrolyte at present, but conductance is relatively low under PEO and lithium salts mixed room temperature, is needed
Further to be modified, improve the electrical conductivity under polymer room temperature.At present, the main method for improving electrical conductivity has grafting, blending, is total to
The methods such as poly-, addition inorganic filler.As PHMS segments are soft, motility is good, PEO is grafted to PHMS side chains, not only may be used
To reduce PEO crystallinity, and the advantage that PHMS sub-chain motions can be utilized good, the electric conductivity of PEO segments is further improved,
Amphion is introduced into PHMS side chains further, new lithium ion mobility passage not only can be formed, improve electrical conductivity, Er Qieke
By improving cell interface performance, to play a part of to improve electrochemical stability, therefore prepare electric conductivity and stability is equal
The polymer dielectric film of the lithium ion battery applications for requiring can be met.
The content of the invention
The invention aims to solve that existing full solid state polymer electrolyte room-temperature conductivity is low, electrochemical window not
High problem.The invention provides a kind of dielectric film containing amphion 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 amphion full solid state polymer electrolyte is comprised the following steps：
A, by hydrosilylation, prepare side chain while being grafted PEO and zwitterionic poly- (methyl hydrogen silicomethane),
Shown in its 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 be dissolved in into acetonitrile or acetone solvent, stirred under room temperature
Mix, pour into after being well mixed in Teflon mould, be placed in heat drying in vacuum drying oven, be crosslinked film forming, prepare containing
Zwitterionic full solid state polymer electrolyte film.
Preferably, described step a is specific as follows：
1) PHMS is sufficiently mixed with organic solvent and obtains solution A, subsequently DMAA, PEO, catalyst and organic solvent are mixed
Close uniform, obtain solution B, solution A is preheated to into 40～60 DEG C, under inert gas atmosphere, solution B is slowly added dropwise in A, drip
Plus rear mixed liquor continues 2～3h of reaction at 40～60 DEG C, then raise temperature to 70～90 DEG C of reactions and disappear up to C=C, reaction terminates
Organic solvent is removed, product C is obtained；
2) product C is sufficiently mixed with organic solvent and obtains solution D, in inert gas environment, be preheated to 45～60 DEG C, will
During 1,3- propyl group sultone adds solution D, react 16～20 hours at 45～60 DEG C, remove organic solvent and obtain product E, product
E is formula (1) structure.
Preferably, the step 1) in DMAA and PEO molar ratio≤0.04；Step 1) described in organic solvent be
Toluene, step 1) catalyst is chloroplatinic acid, is fed intake as 10～40ppm, preferred chloroplatinic acid catalyst feeds intake as 20ppm.
Preferably, step 2) described in organic solvent be tetrahydrofuran；Add the amount and right of 1,3- propyl group sultone
It is required that the DMAA added in 2 meets mol ratio for 1:1.
Preferably, lithium salts used is bis trifluoromethyl sulfimide lithium, lithium salts amount used and PEO satisfactions [EO] for adding:
[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 amphion full solid state polymer prepared by methods described, its feature
It is：The described conductivity at room temperature containing amphion full solid state polymer electrolyte film is 10-4S·cm-1More than,
The room temperature electrochemical window is stable in more than 5V.
The invention also discloses the answering in lithium ion battery containing amphion full solid state polymer electrolyte film
With.
The present invention grafts to PEO on the side chain of PHMS, to reduce glass transition temperature, so as to reduce solid polymer
The degree of crystallinity of electrolyte, as the electric action of PEO simply occurs in noncrystalline domain, therefore reduction degree of crystallinity can improve conductance
Rate, simultaneously because PHMS main chains are soft, motility is strong, can strengthen the sub-chain motion ability of PEO, play and further improve
The effect of electrical conductivity.In PHMS side chain graft amphions, can play a part of further to improve electrical conductivity, reason is both sexes
Ion (sulfobetaines) can promote electron delocalization, at the same sulfonic acid group easily by electrophilic group attack, it is easier to it is low
The Li of cloud density+Generation interacts, and plays promotion lithium salts dissociation, forms new lithium ion mobility passage, reach into one
Step improves the effect of electrical conductivity；On the other hand, due to introduce amphion, increased the interface stability of electrolyte with it is compatible
Property, it is improved polymer electrolyte electrochemical window.
Compared with prior art, the invention has the advantages that：1st, reduce the vitrifying of polymer dielectric
Transition temperature, so as to reduce degree of crystallinity；2nd, the electrolyte leakage and the safety decomposed that can solve liquid electrolyte presence is asked
Topic；3rd, room-temperature conductivity reaches 3.39 × 10-4S·cm-1, decomposition voltage basically reaches commercially use demand more than 5V；4、
Arbitrary shape can be processed into, different cell shapes demands are met.The present invention can make full solid state polymer electrolyte in lithium ion
It is more widely used in battery.
Specific embodiment
With reference to embodiment, the present invention will be further described.Typical case description of these examples only to the present invention, but
The invention is not restricted to this.
It is all the present invention provide examples in, there is provided raw material can from market buying obtain.
The synthesis of 1 Siloxane-Oxyalkylene Copolymers of embodiment
Weigh a certain amount of poly- (methyl hydrogen silicomethane) (PHMS), mix the there-necked flask for adding 50ml with appropriate toluene
In, heat in moving to oil bath pan, by appropriate allyl capped polyethers (PEO) (m(PEO):m(PHMS)=2), appropriate Speier is catalyzed
During agent adds normal pressure funnel after being uniformly dispersed in toluene solvant, in N2Under atmosphere, mixed liquor in normal pressure funnel is dropwise instilled
In there-necked flask, certain hour is reacted at 50 DEG C first, be subsequently heated to 80 DEG C of reaction certain hours, until PEO has reacted
Entirely, through n-hexane washing impurity-removing, revolving removes solvent, obtains Siloxane-Oxyalkylene Copolymers (PEO-g-PHMS) product.
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 subsequently added suitable
Amount crosslinking agent and bis trifluoromethyl sulfimide lithium (LiTFSI), add lithium salts amount to meet [EO]:[Li+]=20:1, in acetonitrile
It is sufficiently stirred in solvent, is well mixed.
(2) mixed solution in (1) is poured in Teflon mould, is subsequently placed in vacuum drying oven, be vacuum dried
Obtain all solid state modified polymer electrolyte film.
(3) positive pole, full solid state polymer electrolyte film and negative pole are stacked togather, is sealed in button cell or plastic-aluminum combined
In packaging film, full solid state polymer lithium ion battery is compacted into.
The preparation of 3 polymer Li-ion battery of embodiment
(1) weigh a certain amount of poly- (methyl hydrogen silicomethane) (PHMS), mix three mouthfuls of burnings for adding 50ml with appropriate toluene
In bottle, heat in moving to oil bath pan, by allyl capped polyethers (PEO) (m(PEO):m(PHMS)=2), N, N- DMAAs
(DMAA)(n(DMAA):n(PEO)=1:20) in adding normal pressure funnel after being well mixed in toluene with appropriate Speier catalyst,
Subsequently in N2Under atmosphere, mixed liquor in normal pressure funnel is dropwise instilled in there-necked flask, certain hour is reacted at 50 DEG C first, with
After be heated to 80 DEG C of reaction certain hours, mixed solution is changed into shallow yellow transparent solution from water white transparency, and product is through n-hexane
Washing impurity-removing, revolving obtain being grafted DMAA and PEO modified polyorganosiloxanes.
(2) 50ml tri- is added after dissolve the grafting DMAA and PEO modified polyorganosiloxane prepared in (1) in tetrahydrofuran
In mouth flask, subsequently by a certain amount of 1,3- propyl group sultone (n(1,3-PS)):n(DMAA)=1:1) in adding there-necked flask, in N2Gas
Under atmosphere, 50 DEG C of reaction appropriate times, product Jing revolvings remove solvent, obtain amphion and Siloxane-Oxyalkylene Copolymers (ZW-
Co-PEO-g-PHMS) polymer electrolyte.
(3) ZW-co-PEO-g-PHMS prepared in (2) is placed in 100ml round-bottomed flasks, is subsequently added appropriate crosslinking
Agent and bis trifluoromethyl sulfimide lithium (LiTFSI), add lithium salts amount to meet [EO]:[Li+]=20:1, in acetonitrile solvent
It is sufficiently stirred for, is well mixed.
(4) mixed solution in (3) is poured in Teflon mould, is subsequently placed in vacuum drying oven, be vacuum dried
Obtain all solid state modified polymer electrolyte film.
(5) positive pole, full solid state polymer electrolyte film and negative pole are stacked togather, is sealed in button cell or plastic-aluminum combined
In packaging film, full solid state polymer lithium ion battery is compacted into.
The preparation of 4 polymer Li-ion battery of embodiment
(1) weigh a certain amount of poly- (methyl hydrogen silicomethane) (PHMS), mix three mouthfuls of burnings for adding 50ml with appropriate toluene
In bottle, heat in moving to oil bath pan.By allyl capped polyethers (PEO) (m(PEO):m(PHMS)=2), N, N- DMAAs
(DMAA)(n(DMAA):n(PEO)=1:10) in adding normal pressure funnel after being well mixed in toluene with appropriate Speier catalyst,
Subsequently in N2Under atmosphere, mixed liquor in normal pressure funnel is dropwise instilled in there-necked flask, certain hour is reacted at 50 DEG C first, with
After be heated to 80 DEG C of reaction certain hours, mixed solution is changed into shallow yellow transparent solution from water white transparency, and product is through n-hexane
Washing impurity-removing, revolving obtain being grafted DMAA and PEO modified polyorganosiloxanes.
(2) the modified polysiloxanes of the grafting DMAA and PEO prepared in (1) is dissolved in tetrahydrofuran, adds 50ml
In there-necked flask, subsequently by a certain amount of 1,3- propyl group sultone (n(1,3-PS):n(DMAA)=1:1) in adding there-necked flask, in N2Gas
Under atmosphere, 50 DEG C of reaction appropriate times, product Jing revolvings remove solvent, obtain amphion and Siloxane-Oxyalkylene Copolymers (ZW-
Co-PEO-g-PHMS) polymer electrolyte.
(3) ZW-co-PEO-g-PHMS prepared in (2) is placed in 100ml round-bottomed flasks, is subsequently added appropriate crosslinking
Agent and bis trifluoromethyl sulfimide lithium (LiTFSI), add lithium salts amount to meet [EO]:[Li+]=20:1, in acetonitrile solvent
It is sufficiently stirred for, is well mixed.
(4) mixed solution in (3) is poured in Teflon mould, is subsequently placed in vacuum drying oven, be vacuum dried
Obtain all solid state modified polymer electrolyte film.
(5) positive pole, full solid state polymer electrolyte film and negative pole are stacked togather, is sealed in button cell or plastic-aluminum combined
In packaging film, full solid state polymer lithium ion battery is compacted into.
The preparation of 5 polymer Li-ion battery of embodiment
(1) weigh a certain amount of poly- (methyl hydrogen silicomethane) (PHMS), mix three mouthfuls of burnings for adding 50ml with appropriate toluene
In bottle, heat in moving to oil bath pan, by allyl capped polyethers (PEO) (m(PEO):m(PHMS)=2), N, N- DMAAs
(DMAA)(n(DMAA):n(PEO)=1:5) in adding normal pressure funnel after being well mixed in toluene with appropriate Speier catalyst,
Subsequently in N2Under atmosphere, mixed liquor in normal pressure funnel is dropwise instilled in there-necked flask, certain hour is reacted at 50 DEG C first, with
After be heated to 80 DEG C of reaction certain hours, mixed solution is changed into shallow yellow transparent solution from water white transparency, and product is through n-hexane
Washing impurity-removing, revolving obtain being grafted DMAA and PEO modified polyorganosiloxanes.
(2) the modified polysiloxanes of the grafting DMAA and PEO prepared in (1) is dissolved in dissolving in tetrahydrofuran to add
In 50ml there-necked flasks, subsequently by a certain amount of PS (n1,3-PS):n(DMAA)=1:1) in adding there-necked flask,
N2Under atmosphere, 50 DEG C of reaction appropriate times, product Jing rotate away solvent, obtain amphion and Siloxane-Oxyalkylene Copolymers
(ZW-co-PEO-g-PHMS) polymer electrolyte.
(3) ZW-co-PEO-g-PHMS prepared in (2) is placed in 100ml round-bottomed flasks, is subsequently added appropriate crosslinking
Agent and bis trifluoromethyl sulfimide lithium (LiTFSI), add lithium salts amount to meet [EO]:[Li+]=20:1, in acetonitrile solvent
It is sufficiently stirred for, is well mixed.
(4) mixed solution in (3) is poured in Teflon mould, is subsequently placed in vacuum drying oven, be vacuum dried
Obtain all solid state modified polymer electrolyte film.
(5) positive pole, full solid state polymer electrolyte film and negative pole are stacked togather, is sealed in button cell or plastic-aluminum combined
In packaging film, full solid state polymer lithium ion battery is compacted into.
The preparation of 6 polymer Li-ion battery of embodiment
(1) ZW-co-PEO-g-PHMS prepared in embodiment (3) is placed in 100ml round-bottomed flasks, is subsequently added
Appropriate crosslinking agent and bis trifluoromethyl sulfimide lithium (LiTFSI), add lithium salts amount to meet [EO]:[Li+]=8:1, in acetonitrile
It is sufficiently stirred in solvent, is well mixed.
(2) mixed solution in (1) is poured in Teflon mould, is subsequently placed in vacuum drying oven, be vacuum dried
Obtain all solid state modified polymer electrolyte film.
(3) positive pole, full solid state polymer electrolyte film and negative pole are stacked togather, is sealed in button cell or plastic-aluminum combined
In packaging film, full solid state polymer lithium ion battery is compacted into.
The preparation of 7 polymer Li-ion battery of embodiment
(1) ZW-co-PEO-g-PHMS prepared in embodiment (3) is placed in 100ml round-bottomed flasks, is subsequently added
Appropriate crosslinking agent and bis trifluoromethyl sulfimide lithium (LiTFSI), add lithium salts amount to meet [EO]:[Li+]=14:1, in second
It is sufficiently stirred in nitrile solvent, is well mixed.
(2) mixed solution in (1) is poured in Teflon mould, is subsequently placed in vacuum drying oven, be vacuum dried
Obtain all solid state modified polymer electrolyte film.
(3) positive pole, full solid state polymer electrolyte film and negative pole are stacked togather, is sealed in button cell or plastic-aluminum combined
In packaging film, full solid state polymer lithium ion battery is compacted into.
The preparation of 8 polymer Li-ion battery of embodiment
(1) ZW-co-PEO-g-PHMS prepared in embodiment (3) is placed in 100ml round-bottomed flasks, is subsequently added
Appropriate crosslinking agent and bis trifluoromethyl sulfimide lithium (LiTFSI), add lithium salts amount to meet [EO]:[Li+]=26:1, in second
It is sufficiently stirred in nitrile solvent, is well mixed.
(2) mixed solution in (1) is poured in Teflon mould, is subsequently placed in vacuum drying oven, be vacuum dried
Obtain all solid state modified polymer electrolyte film.
(3) positive pole, full solid state polymer electrolyte film and negative pole are stacked togather, is sealed in button cell or plastic-aluminum combined
In packaging film, full solid state polymer lithium ion battery is compacted into.Full solid state polymer lithium ion battery prepared by embodiment 2～8
The performance test of (25 DEG C) under room temperature is shown in Table 1
| Electrical 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 electricity
Chemical window is significantly improved, and substantially increases the security performance of lithium ion battery；This thin-film material has certain simultaneously
Mechanical strength and good processing characteristics, can solve the problems, such as that liquid electrolyte easily occurs electrolyte leakage, 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 amphion full solid state polymer electrolyte, it is characterised in that：Methods described include with
Lower step：
A, by hydrosilylation, prepare side chain while being grafted PEO and zwitterionic poly- (methyl hydrogen silicomethane), its knot
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 be dissolved in into acetonitrile or acetone solvent, stir under room temperature, mix
Close it is uniform after pour in Teflon mould, be placed in heat drying in vacuum drying oven, be crosslinked film forming, prepare containing both sexes from
The full solid state polymer electrolyte film of son.
2. a kind of preparation method containing amphion full solid state polymer electrolyte as claimed in claim 1, its feature exist
It is specific as follows in described step a：
1) PHMS is sufficiently mixed with organic solvent and obtains solution A, DMAA, PEO, catalyst are well mixed with organic solvent,
Solution B is obtained, solution A is preheated to into 40～60 DEG C, under inert gas atmosphere, solution B is slowly added dropwise in A, mixed after dropwise addition
Close liquid and continue 2～3h of reaction at 40～60 DEG C, then raise temperature to 70～90 DEG C of reactions and disappear up to C=C, reaction terminates removing to be had
Machine solvent, obtains product C；
2) product C is sufficiently mixed with organic solvent and obtains solution D, 45～60 DEG C are preheated in inert gas environment, by 1,3-
During propyl group sultone adds solution D, react 16～20 hours at 45～60 DEG C, remove organic solvent and obtain product E, product E is
For formula (1) structure.
3. a kind of preparation method containing amphion full solid state polymer electrolyte as claimed in claim 2, its feature exist
In the step 1) in DMAA and PEO molar ratio≤0.04；Step 1) described in organic solvent be toluene, step 1) urge
Agent is chloroplatinic acid, is fed intake as 10～40ppm.
4. a kind of preparation method containing amphion full solid state polymer electrolyte as claimed in claim 2, its feature exist
In step 2) described in organic solvent be tetrahydrofuran；1,3- propyl group sultone is 1 with the mol ratio of DMAA:1.
5. a kind of preparation method containing amphion full solid state polymer electrolyte as claimed in claim 3, its feature exist
Feed intake as 20ppm in described chloroplatinic acid catalyst.
6. a kind of preparation method containing amphion full solid state polymer electrolyte as claimed in claim 1, its feature exist
In lithium salts used be bis trifluoromethyl sulfimide lithium.
7. a kind of preparation method containing amphion full solid state polymer electrolyte as described in claim 1 or 4, its feature
[EO] is met with the PEO for adding in lithium salts amount used:[Li+]=5～40.
8. a kind of preparation method containing amphion full solid state polymer electrolyte as claimed in claim 1, its feature exist
In added crosslinking agent be triethyleneglycol divinylether, the addition of crosslinking agent be polymer quality prepared by step a 5～
10%.
9. the dielectric film containing amphion full solid state polymer that prepared by a kind of method as claimed in claim 1, its feature
It is：The described conductivity at room temperature containing amphion full solid state polymer electrolyte film is 10-4S·cm-1More than,
The room temperature electrochemical window is stable in more than 5V.
10. application as claimed in claim 9 containing amphion full solid state polymer electrolyte film in lithium ion battery.
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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 |
| CN108615937A (en) * | 2018-05-25 | 2018-10-02 | 北京新能源汽车股份有限公司 | Polymer dielectric, solid electrolyte membrane and lithium ion battery |
| CN108808099A (en) * | 2018-05-23 | 2018-11-13 | 浙江大学 | A kind of preparation method and purposes of modified polyorganosiloxane based solid electrolyte film |
| CN108899579A (en) * | 2018-06-14 | 2018-11-27 | 北京工业大学 | A kind of all-solid lithium-ion battery of self-crosslinking composite solid electrolyte prepared and its constitute |
| CN109935476A (en) * | 2019-03-08 | 2019-06-25 | 齐鲁工业大学 | Ampholytic gels polymer dielectric and its preparation, application with superperformance |
| CN110571470A (en) * | 2019-09-16 | 2019-12-13 | 上海汽车集团股份有限公司 | fluorine-containing modified polysiloxane solid electrolyte and preparation method and application thereof |
| CN111162308A (en) * | 2019-12-02 | 2020-05-15 | 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 |
| CN112448027A (en) * | 2019-09-03 | 2021-03-05 | 华南师范大学 | Blended gel polymer electrolyte and preparation method and application thereof |
| CN112615049A (en) * | 2020-12-21 | 2021-04-06 | 凯博能源科技有限公司 | Solid electrolyte and battery comprising the same |
| CN112625592A (en) * | 2020-10-26 | 2021-04-09 | 上海汽车集团股份有限公司 | Preparation method of lithium metal interface modification layer |
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 |
|---|
| F. WOHDE ET AL: "Li+ ion transport in ionic liquid-based electrolytes and the influence of sulfonate-based zwitterion additives", 《SOLID STATE IONICS》 * |
| MITSUTAKE SUEMATSU ET AL: "Effect of zwitterions on electrochemical properties of oligoether-based", 《ELECTROCHIMICA ACTA》 * |
| N. BYRNE ET AL: "The additive effect of zwitterion and nano-particles on ion", 《ELECTROCHIMICA ACTA》 * |
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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 |
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| CN108615937A (en) * | 2018-05-25 | 2018-10-02 | 北京新能源汽车股份有限公司 | Polymer dielectric, solid electrolyte membrane and lithium ion battery |
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| 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 |
| CN110571470A (en) * | 2019-09-16 | 2019-12-13 | 上海汽车集团股份有限公司 | fluorine-containing modified polysiloxane solid electrolyte and preparation method and application thereof |
| CN111162308A (en) * | 2019-12-02 | 2020-05-15 | 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 |
| 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 |
| CN112625592A (en) * | 2020-10-26 | 2021-04-09 | 上海汽车集团股份有限公司 | Preparation method of lithium metal interface modification layer |
| 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 |
| CN112615049A (en) * | 2020-12-21 | 2021-04-06 | 凯博能源科技有限公司 | Solid electrolyte and battery comprising the same |
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