CN109962288A - Solid polymer electrolyte, preparation method and lithium secondary battery - Google Patents
Solid polymer electrolyte, preparation method and lithium secondary battery Download PDFInfo
- Publication number
- CN109962288A CN109962288A CN201711405541.2A CN201711405541A CN109962288A CN 109962288 A CN109962288 A CN 109962288A CN 201711405541 A CN201711405541 A CN 201711405541A CN 109962288 A CN109962288 A CN 109962288A
- Authority
- CN
- China
- Prior art keywords
- polymer electrolyte
- lithium
- solid polymer
- solid
- secondary battery
- 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.)
- Pending
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
- H01M10/052—Li-accumulators
-
- 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
-
- 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
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
-
- 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
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of solid polymer electrolyte and preparation method thereof for lithium secondary battery, and the lithium secondary battery containing the solid polymer electrolyte.The solid polymer electrolyte for lithium secondary battery includes divinyl macromer functional polymer, secondary matrix polymer, lithium salts and diene functional groups' crosslinking agent, with diene functional groups' crosslinking agent diels-Alder reversible addition reaction can occur for the divinyl macromer functional polymer as main matrix polymer.
Description
Technical field
The solid polymer electrolyte and preparation method thereof that the present invention relates to a kind of for lithium secondary battery, and containing should
The lithium secondary battery of solid polymer electrolyte.
Background technique
At this stage, increasingly serious with energy and environment situation, energy storage and power lithium secondary battery receive increasingly
More concerns and research.There are the safety such as unstability under leakage, high temperature for the liquid electrolyte as used in traditional lithium secondary battery
Problem, research and development all solid lithium secondary battery are one of the possible technique schemes for promoting lithium battery safety, wherein solid-state
Electrolyte is the core and emphasis of all solid lithium secondary battery exploitation.Compared to inorganic solid electrolyte, polymer solid electrolysis
Matter is light with its, excellent viscoplasticity, film-forming process, the characteristics such as stable chemical property, as all solid state electrolyte
It is had great advantages when with diaphragm.But polymer-based solid state electrolytic thin-membrane is in independent film forming, forming processes and high temperature work
Under the conditions of work, it may appear that the structures such as cavity or micro-damage so that positive and negative anodes substance can not be obstructed, and then cause the failure of battery.
Summary of the invention
In view of the foregoing, it is necessary to provide one kind can be automatically repaired cavity or micro-damage it is isostructural for lithium it is secondary
The solid electrolyte of battery.
A kind of solid polymer electrolyte for lithium secondary battery, including divinyl macromer functional polymer, secondary matrix
Polymer, lithium salts and diene functional groups' crosslinking agent, the divinyl macromer functional polymer, can be with as main matrix polymer
Diels-Alder reversible addition reaction occurs for diene functional groups' crosslinking agent.
A kind of preparation method of the solid polymer electrolyte for lithium secondary battery, includes the following steps:
Divinyl macromer functional polymer, secondary matrix polymer and lithium salts are added in organic solvent and dissolved, solid-state is obtained
Electrolyte glue A；
Diene functional groups' crosslinking agent is added in organic solvent and is dissolved, solution B is obtained；
It is dry after film of casting by solid electrolyte glue A and solution B hybrid reaction in an inert atmosphere, it obtains
The solid polymer electrolyte.
A kind of lithium secondary battery, including positive electrode, negative electrode material and the solid-state as described above for being used for lithium secondary battery
Polymer dielectric.
Compared with prior art, the invention has the following advantages:
1, the present invention prepared by solid polymer electrolyte in divinyl macromer functional polymer and dienophile crosslinking
It is interacted and is crosslinked by diels-Alder (Diels-Alder) between agent, there is preferably mechanical performance.
2, solid polymer electrolyte prepared by the present invention has self-healing properties, when it is using in the lithium secondary battery
When, in the case where there is cavity or micro-damage, partial short-circuit generates high temperature, promotes Diels-Alder cycloaddition reversible reaction
Progress, the self-repairability of solid polymer electrolyte is realized, to improve use of the solid electrolyte in battery applications
Service life and safety.
3, Diels-Alder cycloaddition reversible reaction does not need catalyst, ensure that solid polymer electrolyte system
Consistency, stable electrochemical property are controllable.
4, the preparation method of solid polymer electrolyte provided by the invention has that simple process, reaction is controllable, the period is short
The features such as.
Detailed description of the invention
Fig. 1 is the schematic diagram in a preferred embodiment of the present invention for the solid polymer electrolyte of lithium secondary battery.
Fig. 2 is that solid electrolyte assembles solid state battery 0.5C circulation conservation rate and follows in the embodiment of the present invention 1 and comparative example 1
Ring number relational graph.
Main element symbol description
Nothing
The present invention that the following detailed description will be further explained with reference to the above drawings.
Specific embodiment
Below in conjunction with the attached drawing in embodiment of the present invention, the technical solution in embodiment of the present invention is carried out clear
Chu is fully described by, it is clear that described embodiment is only some embodiments of the invention, rather than whole realities
Apply mode.
Based on the embodiment in the present invention, those of ordinary skill in the art institute without making creative work
The every other embodiment obtained, shall fall within the protection scope of the present invention.
All technical and scientific terms used herein with to belong to those skilled in the art of the invention usual
The meaning of understanding is identical.Term as used herein in the specification of the present invention is intended merely to description specific embodiment
Purpose, it is not intended that in limitation the present invention.
Except as otherwise explaining, reagent, software and the instrument that do not explain especially involved in following embodiment, are all conventional commercials
Product or open source.
As shown in Figure 1, present pre-ferred embodiments provide a kind of solid polymer electrolyte for lithium secondary battery, packet
Include divinyl macromer functional polymer, secondary matrix polymer, lithium salts and diene functional groups' crosslinking agent, the divinyl macromer function
It is anti-with diene functional groups' crosslinking agent the reversible addition of diels-Alder to occur for group's polymer as main matrix polymer
It answers.
Above-mentioned term " Diels-Alder reaction " has its conventional meaning, be a kind of organic reaction (specifically
A kind of cycloaddition reaction), conjugated diene is reacted with substituted olefine (commonly referred to as dienophile) generates substituted cyclohexene.Even if new
Some atoms among the ring of formation are not carbon atoms, this reaction can continue to carry out.Some Diels-Alder reactions
It is reversible, such ring decomposition reaction is called inverse Diels-Alder reaction or inverse Diels-Alder reacts (retro-
Diels-Alder)。
Specific embodiment according to the present invention, the divinyl macromer functional polymer include furans list sealing end polyoxyethylene
Alkene (mFuran-PEO), furans bi-end-blocking polyethylene glycol (dFuran-PEG), pyrroles singly block polyethylene glycol oxide (mPyrrole-
) or at least one of pyrroles's bi-end-blocking polyethylene glycol (dPyrrole-PEG) PEO.Wherein, the furans list blocks polyoxygenated
Ethylene and pyrroles singly block the molecular weight of polyethylene glycol oxide not less than 60W, and furans bi-end-blocking polyethylene glycol and pyrroles's bi-end-blocking are poly-
The molecular weight of ethylene glycol is not less than 2000.
Specific embodiment according to the present invention, the secondary matrix polymer include polyvinylidene fluoride (PVDF), gather
In vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polymethyl methacrylate (PMMA) or polyvinyl alcohol (PVA) extremely
Few one kind.
Specific embodiment according to the present invention, the lithium salts include bis- (fluoroform sulphonyl) imine lithiums (LiTFSI),
Bis- (fluorine sulphonyl) imine lithiums (LiTSI), lithium perchlorate (LiClO4), dioxalic acid lithium borate (LiBOB) or lithium phosphate (LiPO4) in
At least one.
Specific embodiment according to the present invention, diene functional groups' crosslinking agent include maleimide and its N-
Substitutive derivative, such as N-phenylmaleimide, N- alkyl maleimide.Preferably, the alkyl is the alkane of 1-6 carbon
Base.
Specific embodiment according to the present invention, in the solid polymer electrolyte, the divinyl macromer functional group polymerization
Object, secondary matrix polymer, lithium salts and diene functional groups' crosslinking agent mass ratio be 1:0.3-0.7:0.1-0.6:0.5-
2。
Another preferred embodiment of the present invention also provides a kind of preparation of solid polymer electrolyte for lithium secondary battery
Method includes the following steps:
S1, divinyl macromer functional polymer, secondary matrix polymer and lithium salts are added in organic solvent and dissolved, consolidate
State electrolyte glue A；
S2, diene functional groups' crosslinking agent is added in organic solvent and is dissolved, obtain solution B；
S3, by solid electrolyte glue A and solution B hybrid reaction in an inert atmosphere, it is dry after film of casting,
Obtain the solid polymer electrolyte.
Specific embodiment according to the present invention, the divinyl macromer functional polymer include furans list sealing end polyoxyethylene
Alkene (mFuran-PEO), furans bi-end-blocking polyethylene glycol (dFuran-PEG), pyrroles singly block polyethylene glycol oxide (mPyrrole-
) or at least one of pyrroles's bi-end-blocking polyethylene glycol (dPyrrole-PEG) PEO.Wherein, the furans list blocks polyoxygenated
Ethylene and pyrroles singly block the molecular weight of polyethylene glycol oxide not less than 60W, and furans bi-end-blocking polyethylene glycol and pyrroles's bi-end-blocking are poly-
The molecular weight of ethylene glycol is not less than 2000.
Specific embodiment according to the present invention, the secondary matrix polymer include polyvinylidene fluoride (PVDF), gather
In vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polymethyl methacrylate (PMMA) or polyvinyl alcohol (PVA) extremely
Few one kind.
Specific embodiment according to the present invention, the lithium salts include bis- (fluoroform sulphonyl) imine lithiums (LiTFSI),
Bis- (fluorine sulphonyl) imine lithiums (LiTSI), lithium perchlorate (LiClO4), dioxalic acid lithium borate (LiBOB) or lithium phosphate (LiPO4) in
At least one.
Specific embodiment according to the present invention, diene functional groups' crosslinking agent include maleimide and its N-
Substitutive derivative, such as N-phenylmaleimide, N- alkyl maleimide.Preferably, the alkyl is the alkane of 1-6 carbon
Base.
Specific embodiment according to the present invention, the organic solvent include acetonitrile, acetone, dimethylformamide (DMF)
Or at least one of N-Methyl pyrrolidone (NMP).
Specific embodiment according to the present invention, by divinyl macromer functional polymer, secondary matrix polymer in step S1
It is added in organic solvent and dissolves with lithium salts, further comprise: dissolving 4-12h in the case where temperature is 30-90 DEG C of stirring condition, stand
It is cooling, obtain solid electrolyte glue A.
Further, the quality of the divinyl macromer functional polymer, secondary matrix polymer, lithium salts and organic solvent of addition
Than for 1:0.3-0.7:0.1-0.6:10-20.
Specific embodiment according to the present invention diene functional groups' crosslinking agent is added in organic solvent in step S2
Dissolution, further comprises: dissolving under 20-60 DEG C of stirring condition, obtain solution B.
Further, the mass ratio of the diene functional groups' crosslinking agent and organic solvent of addition is 0.5-2:5-10.
Specific embodiment according to the present invention, when organic solvent chooses acetonitrile or acetone, solution temperature is no more than 35
DEG C, drying temperature is no more than 50 DEG C.
Specific embodiment according to the present invention, by solid electrolyte glue A and solution B in inert gas ring in step S3
Under border when hybrid reaction, it is stirred to react 18-36h at 30-80 DEG C, stands and defoams, after film of being cast, 40-80 DEG C of vacuum drying
8-24h obtains the solid polymer electrolyte.
Further, the inert gas is nitrogen.
Another preferred embodiment of the present invention also provides a kind of lithium secondary battery, including positive electrode, negative electrode material and above-mentioned
Solid polymer electrolyte for lithium secondary battery.
Specific embodiment according to the present invention, the positive electrode include cobalt acid lithium, lithium nickelate, LiMn2O4, ferric phosphate
At least one of lithium, nickle cobalt lithium manganate, vanadic anhydride, molybdenum trioxide or titanium disulfide；The negative electrode material includes carbon materials
At least one of material, tin and its alloy, silicon and its alloy, lithium metal and its alloy.
Lithium secondary battery provided by the invention contains self-repair type all solid state electrolyte.When all solid state electrolyte exists
After being damaged, part generates high temperature and reviewing one's lessons by oneself for solid electrolyte film may be implemented by Diels-Alder reversible reaction
Renaturation energy.There is preferably circulation and security performance using all solid lithium secondary battery of all solid state electrolyte building.
Embodiment
It is special below to lift preferred embodiment to allow the present invention to be clearer and more comprehensible, it elaborates, protection scope of the present invention is not
It is limited by the following examples.It is all within marrow and principle of the invention, any modification, equivalent replacement, improvement and so on,
It should all be included in the protection scope of the present invention.
Embodiment 1
In drying shed, 1 part of (by mass, similarly hereinafter) furans list sealing end polyethylene glycol oxide, 0.3 part are gathered into inclined difluoro second
Alkene, 0.1 part of bis- (fluoroform sulphonyl) imine lithium are added in 10 parts of acetonitriles, dissolve 8h in the case where temperature is 30 DEG C of stirring condition,
Cooling is stood, solid electrolyte glue A is obtained；
0.5 part of maleimide is dissolved in 5 parts of acetonitriles under 30 DEG C of stirring conditions, obtains solution B；
In N2Under protection, solid electrolyte glue A is mixed with solution B, 30 DEG C are stirred to react 18h, defoaming are stood, through molten
Liquid is cast after film, and 40 DEG C of vacuum drying 22h are to get to solid polymer electrolyte.
In the solid polymer electrolyte, containing 1 part of furans list sealing end polyethylene glycol oxide, 0.3 part of polyvinylidene fluoride,
0.1 part of bis- (fluoroform sulphonyl) imine lithium and 0.5 part of maleimide.
Through measuring, all solid state electrolyte Tg is -55.2 DEG C and 51 DEG C；Tensile strength is 9.2MPa, elongation at break
210%.The self-repair type polymer base all solid state electrolyte film is packed into test cell, measures its lithium-ion electric at 80 DEG C
Conductance is 8.3 × 10-4S/cm。
Comparative example 1
In drying shed, by 0.5 part of polyethylene glycol oxide, 0.5 part of polyethylene glycol, 0.4 part of polyvinyl alcohol, 0.2 part of dioxalic acid
Lithium borate is added in 18 parts of DMF, dissolves 12h in the case where temperature is 70 DEG C of stirring condition, stands cooling, obtain solid electrolyte glue
Liquid；Stand defoaming, after solution-cast film, 80 DEG C vacuum drying for 24 hours to get arrive common solid-state polymer dielectric.
In the solid polymer electrolyte, contain 0.5 part of polyethylene glycol oxide, 0.5 part of polyethylene glycol, 0.4 part of polyethylene
Alcohol, 0.2 part of dioxalic acid lithium borate.
Through measuring, all solid state electrolyte Tg is -48 DEG C and 57 DEG C；Tensile strength is 2.8MPa, elongation at break
120%.The common solid-state polymer dielectric is packed into test cell, measuring its lithium ion conductivity at 80 DEG C is 4.2
×10-4S/cm。
From in above embodiments 1 and comparative example 1 as can be seen that diene in self-repair type all solid state electrolyte in embodiment 1
It is crosslinked, mechanical property between the PEO and PEG and the crosslinking agent of dienophile of body sealing end there are Diels-Alder interaction
It can be substantially better than unmodified all solid state electrolyte in comparative example 1, the former tensile strength is 3.28 times of the latter, and extension at break is also big
In the latter.Since Diels-Alder interaction is that high-temperature and reversible reacts, it is crosslinked the application temperature condition in all solid state electrolyte
Can't excessively confine the movement of polymeric matrix segment down, thus the migration of lithium ion does not receive influence, in embodiment 1 from
Repairing type all solid state electrolyte still maintains the original excellent electric property of solid electrolyte, and conductivity even up to compares
2 times or so of unmodified solid electrolyte conductivity in example 1.
Referring to fig. 2, Fig. 2 is that solid electrolyte prepared in the embodiment of the present invention 1 and comparative example 1 assembles solid state battery
0.5C recycles conservation rate and circulating ring number relation curve.From Figure 2 it can be seen that the assembled solid state battery of ordinary construction solid electrolyte
Service life (in the case of circulation conservation rate > 80%) is only 84 circles；And circulation longevity of the solid state battery at 0.5C in the embodiment of the present invention
Life has reached 300 circles.This illustrates that the reaction of Diels-Alder thermal reversion is to micro-damage under stronger mechanical performance and high temperature
It repairs and to the depression effect of Li dendrite, so that the service life of the assembled solid state battery of self-repair type all solid state electrolyte mentions significantly
Height has preferable safety.In addition, there is the phenomenon that single-point diving (at Fig. 2 red circle) in the cyclic process middle and later periods, but
Capacity is brought into normal play in following cycle immediately, this also has benefited from the case where there is micro-damage, partial short-circuit, generates heat
Amount, promotes the progress of Diels-Alder [4+2] cycloaddition reversible reaction, to realize oneself of polymer-based solid state electrolyte
Prosthetic.
Embodiment 2
In drying shed, by 1 part of furans bi-end-blocking polyethylene glycol, 0.7 part of Kynoar-hexafluoropropylene copolymer, 0.6
Bis- (fluorine sulphonyl) imine lithiums of part are added in 20 parts of acetone, dissolve 4h in the case where temperature is 30 DEG C of stirring condition, stand cooling, obtain
Solid electrolyte glue A；
2 parts of N-phenylmaleimides are dissolved in 10 parts of acetone under 30 DEG C of stirring conditions, obtain solution B；
In N2Under protection, solid electrolyte glue A is mixed with solution B, 30 DEG C are stirred to react 30h, defoaming are stood, through molten
Liquid is cast after film, and 50 DEG C of vacuum drying 8h are to get to solid polymer electrolyte.
In the solid polymer electrolyte, contain 1 part of furans bi-end-blocking polyethylene glycol, 0.7 part of Kynoar-hexafluoro
Propylene copolymer, 0.6 part of bis- (fluorine sulphonyl) imine lithium and 2 parts of N-phenylmaleimides.
Embodiment 3
In drying shed, 1 part of pyrroles is singly blocked into polyethylene glycol oxide, 0.5 part of polymethyl methacrylate, 0.3 part
LiClO4It is added in 15 parts of DMF, dissolves 12h in the case where temperature is 50 DEG C of stirring condition, stand cooling, obtain solid electrolyte glue
Liquid A；
1 part of N- butyl maleimide is dissolved in 7 parts of DMF under 50 DEG C of stirring conditions, obtains solution B；
In N2Under protection, solid electrolyte glue A is mixed with solution B, 50 DEG C are stirred to react 36h, defoaming are stood, through molten
Liquid is cast after film, and 60 DEG C of vacuum drying 14h are to get to solid polymer electrolyte.
In the solid polymer electrolyte, polyethylene glycol oxide, 0.5 part of polymethylacrylic acid are singly blocked containing 1 part of pyrroles
Methyl esters, 0.3 part of LiClO4With 1 part of N- butyl maleimide.
Embodiment 4
In drying shed, 1 part of pyrroles's bi-end-blocking polyethylene glycol, 0.6 part of polyvinyl alcohol, 0.5 part of dioxalic acid lithium borate are added
Enter in 17 parts of NMP, 10h is dissolved under stirring condition at a temperature of 90 °C, stands cooling, obtain solid electrolyte glue A；
1.5 parts of bismaleimide are dissolved in 8 parts of NMP under 90 DEG C of stirring conditions, obtain solution B；
In N2Under protection, solid electrolyte glue A is mixed with solution B, 90 DEG C are stirred to react 28h, defoaming are stood, through molten
Liquid is cast after film, and 80 DEG C of vacuum drying 18h are to get to solid polymer electrolyte.
In the solid polymer electrolyte, contain 1 part of pyrroles's bi-end-blocking polyethylene glycol, 0.6 part of polyvinyl alcohol, 0.5 part
Dioxalic acid lithium borate and 1.5 parts of bismaleimide.
The above is only better embodiment of the invention, not the limitation to the present invention in any form, though
So the present invention is disclosed above by better embodiment, but is not intended to limit the invention, any technology people for being familiar with this profession
Member, without departing from the scope of the present invention, when the technology contents using the disclosure above are modified or are modified
For the equivalent implementations of equivalent variations, but without departing from the technical solutions of the present invention, according to the technical essence of the invention
To any simple modification, equivalent change and modification that embodiment of above is done, the range of technical solution of the present invention is still fallen within
It is interior.
Claims (10)
1. a kind of solid polymer electrolyte for lithium secondary battery, including divinyl macromer functional polymer, secondary matrix are poly-
Conjunction object, lithium salts and diene functional groups' crosslinking agent, the divinyl macromer functional polymer, can be with parents as main matrix polymer
Diels-Alder reversible addition reaction occurs for divinyl macromer functional group crosslinking agent.
2. solid polymer electrolyte according to claim 1, which is characterized in that the divinyl macromer functional polymer packet
Include furans list sealing end polyethylene glycol oxide, furans bi-end-blocking polyethylene glycol, pyrroles singly block polyethylene glycol oxide or pyrroles's bi-end-blocking is poly-
At least one of ethylene glycol.
3. solid polymer electrolyte according to claim 1, which is characterized in that the secondary matrix polymer includes poly-
At least one of vinylidene fluoride, Kynoar-hexafluoropropylene copolymer, polymethyl methacrylate or polyvinyl alcohol.
4. solid polymer electrolyte according to claim 1, which is characterized in that the lithium salts includes bis- (fluoroforms
Sulphonyl) imine lithium, at least one of bis- (fluorine sulphonyl) imine lithium, lithium perchlorate, dioxalic acid lithium borate or lithium phosphates.
5. solid polymer electrolyte according to claim 1, which is characterized in that diene functional groups' crosslinking agent
Including maleimide and its N- substitutive derivative.
6. solid polymer electrolyte according to claim 1, which is characterized in that in the solid polymer electrolyte,
The divinyl macromer functional polymer, secondary matrix polymer, lithium salts and diene functional groups' crosslinking agent mass ratio be 1:
0.3-0.7:0.1-0.6:0.5-2。
7. a kind of preparation method of the solid polymer electrolyte for lithium secondary battery, includes the following steps:
Divinyl macromer functional polymer, secondary matrix polymer and lithium salts are added in organic solvent and dissolved, solid state electrolysis is obtained
Matter glue A；
Diene functional groups' crosslinking agent is added in organic solvent and is dissolved, solution B is obtained；
It is dry after film of casting by solid electrolyte glue A and solution B hybrid reaction in an inert atmosphere, it obtains described
Solid polymer electrolyte.
8. the preparation method of solid polymer electrolyte according to claim 7, which is characterized in that the organic solvent packet
Include at least one of acetonitrile, acetone, dimethylformamide or N-Methyl pyrrolidone.
9. the preparation method of solid polymer electrolyte according to claim 7, which is characterized in that by solid electrolyte glue
Liquid A and solution B in an inert atmosphere hybrid reaction when, 18-36h is stirred to react at 30-80 DEG C, stands defoaming, casting applies
After film, 40-80 DEG C of vacuum drying 8-24h obtains the solid polymer electrolyte.
10. a kind of lithium secondary battery, including positive electrode, negative electrode material and described in any one of claims 1-6 it is used for lithium two
The solid polymer electrolyte of primary cell.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711405541.2A CN109962288A (en) | 2017-12-22 | 2017-12-22 | Solid polymer electrolyte, preparation method and lithium secondary battery |
| PCT/CN2018/094696 WO2019119779A1 (en) | 2017-12-22 | 2018-07-05 | Solid polymer electrolyte, preparation method therefor, and lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711405541.2A CN109962288A (en) | 2017-12-22 | 2017-12-22 | Solid polymer electrolyte, preparation method and lithium secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109962288A true CN109962288A (en) | 2019-07-02 |
Family
ID=66994427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711405541.2A Pending CN109962288A (en) | 2017-12-22 | 2017-12-22 | Solid polymer electrolyte, preparation method and lithium secondary battery |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN109962288A (en) |
| WO (1) | WO2019119779A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114050315A (en) * | 2021-12-02 | 2022-02-15 | 华东理工大学 | High-room-temperature ionic conductivity solid polymer composite electrolyte for metal lithium battery and preparation method thereof |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10797314B2 (en) | 2016-07-29 | 2020-10-06 | Blue Current, Inc. | Compliant solid-state ionically conductive composite materials and method for making same |
| US11581570B2 (en) | 2019-01-07 | 2023-02-14 | Blue Current, Inc. | Polyurethane hybrid solid ion-conductive compositions |
| US11394054B2 (en) | 2019-12-20 | 2022-07-19 | Blue Current, Inc. | Polymer microspheres as binders for composite electrolytes |
| KR20220121243A (en) | 2019-12-20 | 2022-08-31 | 블루 커런트, 인크. | Composite electrolyte with binder |
| JP2023521050A (en) * | 2020-04-04 | 2023-05-23 | ブルー カレント、インコーポレイテッド | Non-Byproduct Generation Method for Solid State Hybrid Electrolyte |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103181016A (en) * | 2010-09-13 | 2013-06-26 | 加利福尼亚大学董事会 | Ionic gel electrolyte, energy storage devices, and methods of manufacture thereof |
| CN104008791A (en) * | 2014-06-09 | 2014-08-27 | 合肥工业大学 | Self-repairing conductive material with 'sushi' structure and manufacturing method thereof |
| US20150344639A1 (en) * | 2014-05-30 | 2015-12-03 | Pall Corporation | Self-assembling polymers - i |
| CN106633555A (en) * | 2016-09-14 | 2017-05-10 | 同济大学 | Polyvinyl alcohol membrane with self-repair function implemented by aid of dynamic covalent bonds and method for preparing polyvinyl alcohol membrane |
| CN107474234A (en) * | 2017-08-01 | 2017-12-15 | 大连理工大学 | Functionalization/thermal reversion crosslinked polyethers and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2694758B1 (en) * | 1992-08-14 | 1994-10-21 | Centre Nat Rech Scient | Crosslinkable copolymers obtained by polycondensation and ionically conductive material containing them. |
| JP4859264B2 (en) * | 1997-12-01 | 2012-01-25 | アセップ・インク | Perfluorinated sulfone salts and their use as ionic conducting materials |
| JP2005104846A (en) * | 2003-09-26 | 2005-04-21 | Tosoh Corp | Quaternary ammonium ambient-temperature molten salt and its manufacturing method |
-
2017
- 2017-12-22 CN CN201711405541.2A patent/CN109962288A/en active Pending
-
2018
- 2018-07-05 WO PCT/CN2018/094696 patent/WO2019119779A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103181016A (en) * | 2010-09-13 | 2013-06-26 | 加利福尼亚大学董事会 | Ionic gel electrolyte, energy storage devices, and methods of manufacture thereof |
| US20150344639A1 (en) * | 2014-05-30 | 2015-12-03 | Pall Corporation | Self-assembling polymers - i |
| CN104008791A (en) * | 2014-06-09 | 2014-08-27 | 合肥工业大学 | Self-repairing conductive material with 'sushi' structure and manufacturing method thereof |
| CN106633555A (en) * | 2016-09-14 | 2017-05-10 | 同济大学 | Polyvinyl alcohol membrane with self-repair function implemented by aid of dynamic covalent bonds and method for preparing polyvinyl alcohol membrane |
| CN107474234A (en) * | 2017-08-01 | 2017-12-15 | 大连理工大学 | Functionalization/thermal reversion crosslinked polyethers and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114050315A (en) * | 2021-12-02 | 2022-02-15 | 华东理工大学 | High-room-temperature ionic conductivity solid polymer composite electrolyte for metal lithium battery and preparation method thereof |
| CN114050315B (en) * | 2021-12-02 | 2023-02-24 | 华东理工大学 | High room temperature ionic conductivity solid polymer composite electrolyte for metal lithium battery and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019119779A1 (en) | 2019-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109962288A (en) | Solid polymer electrolyte, preparation method and lithium secondary battery | |
| CN109546207A (en) | A kind of composite solid polymer electrolyte film and its preparation method and application | |
| JP6999425B2 (en) | Lithium ion gel battery | |
| CN110048156B (en) | Solid electrolyte and preparation method and application thereof | |
| US7279251B1 (en) | Lithium secondary battery comprising a super fine fibrous polymer separator film and its fabrication method | |
| KR101351897B1 (en) | Electrolyte for electrochemical device, the preparation method thereof and electrochemical device comprising the same | |
| US20090026662A1 (en) | Hybrid polymer electrolyte, a lithium secondary battery comprising the hybrid polymer electrolyte and their fabrication methods | |
| KR101322694B1 (en) | Electrolyte for electrochemical device, the preparation method thereof and electrochemical device comprising the same | |
| CN109065945A (en) | A kind of solid electrolyte membrane and its preparation method and application | |
| CN105703004B (en) | The preparation method of gel electrolyte battery core | |
| CN102244292A (en) | Lithium ion battery ionic liquid based gel polymer electrolyte as well as preparation and applications thereof | |
| CN109575187B (en) | Preparation method of crosslinked polymer electrolyte, semi-solid polymer battery and preparation method | |
| CN105591154A (en) | Polycarbonate all-solid-state polymer electrolyte, all-solid-state secondary lithium battery made of same and preparation and application thereof | |
| CN110600797A (en) | Preparation method of polymer-inorganic composite electrolyte | |
| CN110534795A (en) | The preparation method and solid state battery of solid state battery | |
| CN101747642B (en) | Gel polymer electrolyte, polymer battery and preparing method | |
| CN110048158A (en) | A kind of in-situ polymerization ELECTRODE WITH BILAYER POLYMERIC object dielectric film and its preparation method and application | |
| Sun et al. | Ultra-robust polyimide nanofiber separators with shutdown function for advanced lithium-ion batteries | |
| CN114335536B (en) | Plastic crystal modified positive electrode solid-state battery and preparation method thereof | |
| CN111934020B (en) | High-pressure-resistant all-solid-state lithium battery interface layer and in-situ preparation method and application thereof | |
| CN109818055A (en) | A kind of electrolyte of the anti-thermal runaway of width warm area and its serondary lithium battery of composition | |
| CN114335700A (en) | Solid electrolyte membrane and preparation method thereof, secondary battery and preparation method | |
| CN113711411A (en) | Electrolyte membrane for all-solid-state battery and all-solid-state battery comprising same | |
| CN107946642A (en) | It is a kind of suitable for polymer dielectric of high-voltage anode material and preparation method thereof | |
| KR20010037100A (en) | Polymer electrolyte, method for preparing the same, and lithium secondary battery employing the same |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190702 |
|
| RJ01 | Rejection of invention patent application after publication |