CN109244538A - Based on Semi-IPN structural polymer electrolyte and preparation method thereof, solid lithium ion battery - Google Patents
Based on Semi-IPN structural polymer electrolyte and preparation method thereof, solid lithium ion battery Download PDFInfo
- Publication number
- CN109244538A CN109244538A CN201811136661.1A CN201811136661A CN109244538A CN 109244538 A CN109244538 A CN 109244538A CN 201811136661 A CN201811136661 A CN 201811136661A CN 109244538 A CN109244538 A CN 109244538A
- Authority
- CN
- China
- Prior art keywords
- polymer dielectric
- polymer
- lithium
- type compounds
- polyoxyethylene
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000005518 polymer electrolyte Substances 0.000 title claims description 35
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 29
- 239000007787 solid Substances 0.000 title claims description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 146
- 229920000642 polymer Polymers 0.000 claims abstract description 129
- -1 polyoxyethylene Polymers 0.000 claims abstract description 124
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 97
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 65
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 65
- 239000003989 dielectric material Substances 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 29
- 229910052744 lithium Inorganic materials 0.000 claims description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 27
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 239000003999 initiator Substances 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 12
- 150000004291 polyenes Chemical class 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 229960002645 boric acid Drugs 0.000 claims description 6
- 235000010338 boric acid Nutrition 0.000 claims description 6
- 239000006193 liquid solution Substances 0.000 claims description 6
- LSRGXLRLWFDKNR-UHFFFAOYSA-N FC(F)(F)[S] Chemical compound FC(F)(F)[S] LSRGXLRLWFDKNR-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- 150000002466 imines Chemical class 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 claims description 2
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 claims description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- LJRSZGKUUZPHEB-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxypropoxy)propoxy]propyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COC(C)COC(=O)C=C LJRSZGKUUZPHEB-UHFFFAOYSA-N 0.000 claims 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 description 25
- 239000002202 Polyethylene glycol Substances 0.000 description 17
- 229920001223 polyethylene glycol Polymers 0.000 description 17
- 238000006116 polymerization reaction Methods 0.000 description 17
- 238000012360 testing method Methods 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 8
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 230000037427 ion transport Effects 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 125000004386 diacrylate group Chemical group 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920000867 polyelectrolyte Polymers 0.000 description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
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
- H01M10/056—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
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
The present invention provides a kind of polymer dielectrics and preparation method thereof, the polymer dielectric is the polymer dielectric based on Semi-IPN structure, it polymerize to form network skeleton structure including polyenoid based compound, the polyoxyethylene type compounds being filled in the network skeleton structure, and the lithium salts being complexed with the network skeleton structure, the polyoxyethylene type compounds.The mechanical property and ionic conductivity of polymer can be improved in polymer dielectric provided by the invention.
Description
Technical field
The invention belongs to technical field of lithium ion, more particularly to it is a kind of based on Semi-IPN structural polymer electrolyte and
Preparation method and a kind of solid lithium ion battery.
Background technique
Lithium ion battery is a kind of secondary cell (rechargeable battery), it relies primarily on lithium ion and moves between a positive electrode and a negative electrode
It moves and carrys out work.In charge and discharge process, Li+Insertion and deintercalation back and forth between two electrodes: when charging, Li+From positive deintercalation,
It is embedded in cathode by electrolyte, cathode is in lithium-rich state；It is then opposite when electric discharge.Lithium ion battery has energy density height, work
The advantages that making voltage height, having extended cycle life, is widely used in the energy storage of mobile electronic device, automobile, electric system etc..
Currently, commercialized lithium ion battery, since electrolyte is incendive organic solution, there is leakage, burning,
The danger of explosion.Compared to liquid lithium ionic cell, solid state lithium battery due to, electrochemical window mouth width good with high-temperature stability,
The advantages that security performance is high, energy density is high, receives significant attention and studies.Solid polymer electrolyte, because it has well
Flexibility and tensile and shear property, more than glass transition temperature there is good ionic conductivity, it is easily prepared at flexibility
Bent battery has the possibility of heavy industrialization application.Currently, the polymer dielectric of most study is polyethylene glycol oxide
Base electrolyte, such polymer dielectric viscoplasticity is good, has preferable compatibility with cathode of lithium.But polyethylene oxide base is electrolysed
For matter as many polymer, mechanical performance is not strong, and ionic conductivity is relatively low.For this purpose, the side such as technical staff is by being blended, copolymerization
Method improves polymer machinery intensity, reduces crystallinity.Blending method is relatively easy, but to raising polymer dielectric mechanical property
Energy effect is not high；The reaction process of copolymerization mode is complex, it is difficult to and the extent of reaction is controlled very well, be easy to cause polymerization excessively,
Influence polymer dielectric performance.
Summary of the invention
The purpose of the present invention is to provide one kind based on Semi-IPN structural polymer electrolyte and preparation method thereof pond, it is intended to
Solve the problems, such as that existing polyethylene glycol oxide base electrolyte mechanical performance is not strong, ionic conductivity is relatively low.
Another aspect of the present invention provides a kind of containing the above-mentioned solid lithium ion based on Semi-IPN structural polymer electrolyte
Battery.
For achieving the above object, The technical solution adopted by the invention is as follows:
A kind of polymer dielectric, the polymer dielectric are the polymer dielectric based on Semi-IPN structure, including
Polyenoid based compound polymerize to form network skeleton structure, the polyoxyethylene type compounds being filled in the network skeleton structure,
And the lithium salts being complexed with the network skeleton structure, the polyoxyethylene type compounds.
Preferably, it is total to be selected from polyoxyethylene, polyoxypropylene and polyoxyethylene polyoxypropylene for the polyoxyethylene type compounds
At least one of polymers.
Preferably, the polyenoid based compound is in double methacrylate class compound, triacrylate class compound
It is at least one.
Preferably, the double methacrylate class compound is selected from polyethyleneglycol diacrylate, tripropylene glycol dipropyl
At least one of olefin(e) acid ester.
Preferably, the triacrylate class compound is selected from trimethylolpropane trimethacrylate, pentaerythrite 3 third
At least one of olefin(e) acid ester.
Preferably, the polyoxyethylene type compounds polymerize the matter to form network skeleton structure with the polyenoid based compound
Amount is than being 10:1~10:5.
Preferably, the lithium salts is selected from bis trifluoromethyl sulphur imine lithium, trifluoromethyl sulfonic acid lithium, lithium perchlorate, hexafluoro phosphorus
One of sour lithium, hexafluoroarsenate lithium, LiBF4, dioxalic acid lithium borate, difluorine oxalic acid boracic acid lithium.
It preferably, is in terms of 100% by the total weight of the polymer dielectric, the weight percentage of the lithium salts is
20%~80%.
Correspondingly, a kind of method for preparing polymer electrolytes, the polymer dielectric is based on Semi-IPN structure
Polymer dielectric, the method for preparing polymer electrolytes the following steps are included:
The mixed solution of polyoxyethylene type compounds, polyenoid based compound and lithium salts is provided；
Initiator is added in the mixed solution, mixed processing obtains polymer dielectric precursor solution；
It is deposited on described on substrate to polymer dielectric precursor solution, is reacted under the conditions of 60-80 DEG C, it is described more
Alkenyl compound polymerize to form network skeleton structure, and the polyoxyethylene type compounds are filled in the network skeleton structure,
Between the lithium salts and the polyoxyethylene type compounds network skeleton structure, the lithium salts and the polyoxyethylene type compounds
Between be complexed, form the polymer poly polymer electrolyte of Semi-IPN structure.
Preferably, the mixed solution of the polyoxyethylene type compounds, polyenoid based compound and lithium salts, using following methods
Preparation:
The polyoxyethylene type compounds are dissolved in anhydrous solvent, polyoxyethylene type compounds solution is configured；
The polyenoid based compound is added in the polyoxyethylene type compounds solution, carries out mixed processing, configuration is poly-
Close object precursor solution；
Lithium salts is added in the polybenzazole precursor liquid solution, mixed processing obtains polyoxyethylene type compounds, polyene-based
The mixed solution of compound and lithium salts.
Preferably, the substrate is positive plate.
Preferably, the anhydrous solvent is selected from acetonitrile, tetrahydrofuran, dimethyl sulfoxide, n,N-Dimethylformamide, N, N-
At least one of dimethyl acetamide etc..
Preferably, the initiator is selected from azodiisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, dilauryl
At least one of peroxide, di-tert-butyl peroxide.
Preferably, the quality of the initiator is the 0.2%~3% of the polyene-based compound quality.
And a kind of solid lithium ion battery, polymer dielectric, the polymer dielectric are of the present invention poly-
Polymer electrolyte；Or the polymer dielectric is the polymer dielectric of the method for the invention preparation.
The polymer dielectric of half interpenetrating network structure provided by the invention, on the one hand, pass through the friendship of polyenoid based compound
Connection forms the network skeleton structure of high resiliency and rigidity, and the mechanical property of polymer dielectric can be improved；On the other hand, described
Polyoxyethylene base electrolyte is filled in network skeleton structure, forms mutual through structure, can inhibit polyoxyethylene electrolyte
Crystallization, to improve ionic conductivity.And the polymer dielectric of half interpenetrating network structure provided by the invention, due to described
Polyoxyethylene base electrolyte is filled in the mechanical property of the polymer dielectric of network skeleton structure formation and ionic conductivity obtains
To enhancing, therefore the self-supporting polymer dielectric without support frame can be formed.In addition, high-intensitive crosslinking interpenetrating polymerization
Object electrolyte can avoid being similar to conventional polyoxyethylene base electrolyte under the conditions of high temperature test, and melting occur causes battery to go out
Existing micro-short circuit even short circuit phenomenon.
The method for preparing polymer electrolytes of half interpenetrating network structure provided by the invention, with polyoxyethylene chemical combination
Object, polyenoid based compound add initiator after being mixed to form mixed solution with lithium salts collectively as the main substance of electrolyte
It is uniformly mixed, then by initiated polymerization after obtained polymer dielectric precursor solution deposition, obtains semi-intercrossing network knot
The polymer dielectric of structure.In this method, before polymerization reaction, polyoxyethylene type compounds, polyenoid based compound and lithium salts
The uniform deposition on substrate, thus in the polymer dielectric of subsequent obtained half interpenetrating network structure, polyoxyethylene
Class compound, the evenly dispersed of lithium salts provide condition, are conducive to the polymer dielectric for obtaining stable electrochemical property.This hair
The polymer dielectric for the half interpenetrating network structure that bright method is prepared has preferable mechanical property and ionic conductivity.
Solid lithium ion battery provided by the invention containing polymer dielectric of the present invention, therefore has preferable
Mechanical property and chemical property.
Detailed description of the invention
Fig. 1 is the electricity of the polymer dielectric ionic conductance test for the half interpenetrating network structure that the embodiment of the present invention 1 provides
Solve plasma membrane impedance schematic diagram；
Fig. 2 is the polymer dielectric voltage stability window test for the half interpenetrating network structure that the embodiment of the present invention 2 provides
Result schematic diagram；
Fig. 3 is the polymer dielectric measuring mechanical property signal of half interpenetrating network structure provided in an embodiment of the present invention
Figure.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indication or suggestion relative importance or implicitly indicates the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include one or more of the features.In the description of the present invention,
The meaning of " plurality " is two or more, unless otherwise specifically defined.
The embodiment of the invention provides a kind of polymer dielectric, the polymer dielectric is based on Semi-IPN structure
Polymer dielectric, including polyenoid based compound polymerize to form network skeleton structure, are filled in the network skeleton structure
Polyoxyethylene type compounds, and the lithium salts being complexed with the network skeleton structure, the polyoxyethylene type compounds.
The polymer dielectric of half interpenetrating network structure provided by the invention, on the one hand, pass through the friendship of polyenoid based compound
Connection forms the network skeleton structure of high resiliency and rigidity, and the mechanical property of polymer dielectric can be improved；On the other hand, described
Polyoxyethylene base electrolyte is filled in network skeleton structure, forms mutual through structure, can inhibit polyoxyethylene electrolyte
Crystallization, to improve ionic conductivity.And the polymer dielectric of half interpenetrating network structure provided by the invention, due to described
Polyoxyethylene base electrolyte is filled in the mechanical property of the polymer dielectric of network skeleton structure formation and ionic conductivity obtains
To enhancing, therefore the self-supporting polymer dielectric without support frame can be formed.In addition, high-intensitive crosslinking interpenetrating polymerization
Object electrolyte can avoid being similar to conventional polyoxyethylene base electrolyte under the conditions of high temperature test, and melting occur causes battery to go out
Existing micro-short circuit even short circuit phenomenon.
Specifically, polyenoid based compound polymerize to form network structure composition polymer dielectric in the embodiment of the present invention
It is insufficient to solve polyethylene glycol oxide base class electrolyte mechanical property to improve the mechanical property of polymer dielectric for skeleton structure
The problem of.Herein, it is notable that for constructing the alkenyl compound of polymer dielectric skeleton structure of the embodiment of the present invention
It is necessary for polyenoid based compound.When using monoene based compound as raw material, since polymerization reaction site is single, end reaction
Obtained product forms chain structure, cannot get the network structure product of the embodiment of the present invention.
Preferably, the polyenoid based compound is in double methacrylate class compound, triacrylate class compound
It is at least one.The polyenoid based compound of preferred type not only has preferable reactivity, is capable of forming network skeleton structure；
Moreover, polymerizeing the network skeleton structure to be formed using double methacrylate class compound, triacrylate class compound, itself is to lithium
Ion has certain conduction, to avoid the introducing due to other high molecular materials that lithium ion conductivity is caused obviously to drop
Low problem.
In some embodiments, the double methacrylate class compound is selected from polyethyleneglycol diacrylate, two contractings 3 third
At least one of omega-diol diacrylate.
In some embodiments, the triacrylate class compound is selected from trimethylolpropane trimethacrylate, season penta
At least one of tetrol triacrylate.
Preferred above-mentioned double methacrylate class compound, triacrylate class compound have high reaction activity, intermolecular
Cross-linking effect it is obvious, to form relatively compact network skeleton structure, assign the polymer of the half interpenetrating network structure
The excellent mechanical property of electrolyte and preferable lithium ion conductivity.
On this basis, the polyoxyethylene type compounds are uniformly filled in the polyenoid based compound and polymerize to form network
In the gap of skeleton structure, the polymer dielectric based on Semi-IPN structure is formed as a result,.Thus, on the one hand, by introducing power
The higher network skeleton structure of intensity is learned, mechanical strength of the polyoxyethylene type compounds as electrolyte when is improved.Separately
On the one hand, the polyoxyethylene base electrolyte is filled in network skeleton structure, forms mutual through structure, can inhibit polyoxy second
The electrolytelike crystallization of alkene, to improve ionic conductivity.Since the polyoxyethylene base electrolyte is filled in network skeleton knot
The mechanical property and ionic conductivity for the polymer dielectric being configured to are enhanced, therefore can be formed without support frame
Self-supporting polymer dielectric.In addition, high-intensitive crosslinking interpenetrating polymer electrolyte, can avoid being similar to conventional polyoxyethylene
There is the micro-short circuit even short circuit phenomenon that melting causes battery to occur under the conditions of high temperature test in base electrolyte.
Specifically, the polyoxyethylene type compounds are preferably selected from but are not limited to polyoxyethylene, polyoxypropylene and polyoxy second
At least one of alkene poiyoxypropylene copolymer.
In the embodiment of the present invention, the dosage of the polyenoid based compound has the mechanics and electric property of polymer dielectric
Certain influence.Specifically, being not enough to be formed network skeleton structure will polymerize when the dosage of the polyenoid based compound is very few
Object electrolyte is filled wherein.When the dosage of the polyenoid based compound is excessive, on the one hand, polyene-based compound molecule is relatively
To be intensive, intermolecular relative distance shortens, and (is not mixed also equal with polyoxyethylene type compounds, in the mixed process of lithium salts at it
It is even), it is easy to happen polymerization reaction, it is difficult to form a film.On the other hand, when the dosage for stating polyenoid based compound is excessive, polyenoid
Based compound polymerize the specific gravity increase to form network skeleton structure, although polyenoid based compound polymerize to form network skeleton structure sheet
Body has certain lithium ion transport performance, but its lithium ion transport performance does not have polyoxyethylene type compounds good.Therefore, when more
When the dosage of alkenyl compound is excessive, the influence (lithium ion transport reduced performance) to lithium ion transport performance is more obvious.When
Given this, it is preferred that the polyoxyethylene type compounds polymerize the matter to form network skeleton structure with the polyenoid based compound
Amount is than being 10:1~10:5, at this point, the obtained polymer dielectric based on Semi-IPN structure, not only has excellent mechanical property
Can, and polyenoid based compound polymerize that form influence of the network skeleton structure to lithium ion transport performance itself smaller, exists in addition
In the structure, the electrolytelike crystallization of polyoxyethylene is inhibited, and therefore, also improves ionic conductivity.As most preferred embodiment,
It is preferred that the polyoxyethylene type compounds polymerize with the polyenoid based compound to be formed network skeleton structure mass ratio be 10:2.
In the embodiment of the present invention, the lithium salts is dispersed in polyenoid based compound and polymerize to form network skeleton structure and polyoxy second
In the Semi-IPN structure that vinyl compound is formed, and it is complexed with the network skeleton structure, the polyoxyethylene type compounds.
In some embodiments, the lithium salts is selected from bis trifluoromethyl sulphur imine lithium, trifluoromethyl sulfonic acid lithium, perchloric acid
One of lithium, lithium hexafluoro phosphate, hexafluoroarsenate lithium, LiBF4, dioxalic acid lithium borate, difluorine oxalic acid boracic acid lithium.
It preferably, is in terms of 100% by the total weight of the polymer dielectric, the weight percentage of the lithium salts is
20%~80%.If the lithium salt content is too low, battery conductance rate is reduced；If the lithium salt content is excessively high, lithium salts due to
Reunite, can equally reduce battery conductance rate.
Polymer dielectric provided in an embodiment of the present invention can be prepared by following methods.
Correspondingly, the embodiment of the invention provides a kind of method for preparing polymer electrolytes, the polymer dielectric
For the polymer dielectric based on Semi-IPN structure, the method for preparing polymer electrolytes the following steps are included:
S01., the mixed solution of polyoxyethylene type compounds, polyenoid based compound and lithium salts is provided；
S02. initiator is added in the mixed solution, mixed processing obtains polymer dielectric precursor solution；
S03. it is deposited on described on substrate to polymer dielectric precursor solution, is reacted under the conditions of 60-80 DEG C, institute
It states polyenoid based compound to polymerize to form network skeleton structure, the polyoxyethylene type compounds are filled in the network skeleton structure
In, between the lithium salts and the polyoxyethylene type compounds network skeleton structure, the lithium salts and the polyoxyethylene
It closes and is complexed between object, form the polymer poly polymer electrolyte of Semi-IPN structure.
The method for preparing polymer electrolytes of half interpenetrating network structure provided in an embodiment of the present invention, with polyoxyethylene
Compound, polyenoid based compound are collectively as the main substance of electrolyte, and after being mixed to form mixed solution with lithium salts, addition is drawn
It sends out agent to be uniformly mixed, then by initiated polymerization after obtained polymer dielectric precursor solution deposition, obtains Semi-IPN net
The polymer dielectric of network structure.In this method, before polymerization reaction, polyoxyethylene type compounds, polyenoid based compound and
The lithium salts uniform deposition on substrate, thus in the polymer dielectric of subsequent obtained half interpenetrating network structure, polyoxy
Ethylene compounds, the evenly dispersed of lithium salts provide condition, are conducive to the polymer dielectric for obtaining stable electrochemical property.
The polymer dielectric for the half interpenetrating network structure that the method for the present invention is prepared has preferable mechanical property and ionic conductance
Rate.
Specifically, the mixing for providing polyoxyethylene type compounds, polyenoid based compound and lithium salts is molten in above-mentioned steps S01
Liquid.The polyoxyethylene type compounds in polyoxyethylene, polyoxypropylene and poloxalkol at least
It is a kind of.
Preferably, the polyenoid based compound is in double methacrylate class compound, triacrylate class compound
It is at least one.Specific preferred, the double methacrylate class compound is selected from polyethyleneglycol diacrylate, tripropylene glycol
At least one of diacrylate.Specific preferred, the triacrylate class compound is selected from trimethylolpropane tris third
At least one of olefin(e) acid ester, pentaerythritol triacrylate.Preferably, the polyoxyethylene type compounds and the polyene-based
Compound polymerize to be formed network skeleton structure mass ratio be 10:1~10:5.Preferably, the lithium salts is selected from bis trifluoromethyl
Sulphur imine lithium, trifluoromethyl sulfonic acid lithium, lithium perchlorate, lithium hexafluoro phosphate, hexafluoroarsenate lithium, LiBF4, dioxalic acid boric acid
One of lithium, difluorine oxalic acid boracic acid lithium.It is further preferred that being institute in terms of 100% by the total weight of the polymer dielectric
The weight percentage for stating lithium salts is 20%~80%.
Wherein, the preferred type of polyoxyethylene type compounds, the preferred type of polyenoid based compound, polyoxyethylene chemical combination
The relative amount of object and polyenoid based compound, the content of lithium salts and its type selection bring influence, as described above, in order to save
About length, details are not described herein again.
In some embodiments, polyoxyethylene type compounds, polyenoid based compound and lithium salts can be dissolved in simultaneously molten
In agent, the mixed solution of configuration polyoxyethylene type compounds, polyenoid based compound and lithium salts.
Compared to general polymer dielectric, the polymer electrolytic provided in an embodiment of the present invention based on Semi-IPN structure
Matter may not need porous separator as support frame, reduce the quality of dielectric film, and mechanical property with higher and
Chemical property.
In some preferred embodiments, the mixed solution of the polyoxyethylene type compounds, polyenoid based compound and lithium salts,
It is prepared using following methods:
S011. the polyoxyethylene type compounds are dissolved in anhydrous solvent, configure polyoxyethylene type compounds solution.
S012. the polyenoid based compound is added in the polyoxyethylene type compounds solution, carries out mixed processing, matches
Set polybenzazole precursor liquid solution；
S013. be added lithium salts in the polybenzazole precursor liquid solution, mixed processing, obtain polyoxyethylene type compounds,
The mixed solution of polyenoid based compound and lithium salts.
In this way, first polyoxyethylene type compounds are dissolved in anhydrous solvent, configure polyoxyethylene chemical combination
After object solution, polyenoid based compound is added, is conducive to the evenly dispersed of polyoxyethylene type compounds and polyenoid based compound.Into
One step, lithium salts is added in polybenzazole precursor liquid solution, through mixed processing, so that three uniformly mixes, and is formed in deposition
Liquid phase film layer in it is evenly dispersed, and then when aggregating into network structure, be capable of forming that network structure uniformity is good, polyoxyethylene
Class compound and lithium salts are dispersed in the polymer dielectric based on Semi-IPN structure in network structure.
Specifically, the anhydrous solvent as solvent, can not only preferably dissolve polyoxyethylene type compounds, polyene-based
Object and lithium salts are closed, even and if also not reacting in a heated condition with any one in above-mentioned raw materials.Preferably, described
Anhydrous solvent is in acetonitrile, tetrahydrofuran, dimethyl sulfoxide, n,N-Dimethylformamide, n,N-dimethylacetamide etc.
It is at least one.Preferred anhydrous solvent has preferable dissolubility, meanwhile, boiling point is lower, removes after being conducive to film forming.
In some embodiments, lithium salts is added in the polybenzazole precursor liquid solution, the mode of mixed processing is preferably selected
It is selected as stir process.In order to enable polyoxyethylene type compounds, polyenoid based compound and lithium salts are uniformly dispersed, mixing time is preferred
It is 12-24 hours.
In above-mentioned steps S02, the embodiment of the present invention is not directly by the initiator and polyoxyethylene type compounds, polyene-based
Compound and lithium salts are added simultaneously, but are added in the mixed solution of polyoxyethylene type compounds, polyenoid based compound and lithium salts
Initiator causes polyenoid based compound and polymerization reaction occurs so that initiator be avoided to add overlong time, thus when influencing film forming
Polyenoid based compound polymerize the uniformity to form network skeleton structure and polyoxyethylene type compounds and lithium salts dispersion it is uniform
Property, and then influence the chemical property of polymer dielectric.
Preferably, in order to enable initiator is uniformly dispersed in mixed solution, effectively occurred with guaranteeing that polymerization reaction is stablized,
After initiator is added, mixed processing is carried out using agitating mode.Specifically, the time of stirring is 2-10 hours.
In some embodiments, the initiator be selected from azodiisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide,
At least one of dilauryl peroxide, di-tert-butyl peroxide.Above-mentioned initiator can effectively cause polyene-based
The polymerization reaction between object is closed, meanwhile, other side reactions between raw material will not be introduced.
Preferably, the quality of the initiator is the 0.2%~3% of the polyene-based compound quality.If the initiation
The content of agent is too low, then is difficult to cause the polymerization reaction between polyenoid based compound, in addition cannot cause polyenoid based compound it
Between polymerization reaction；If the too high levels of the initiator, initiator remain in polymer dielectric, filled in lithium ion battery
Side reaction occurs in discharge process, influences performance of lithium ion battery, especially reduces the capacity of lithium ion battery.
In above-mentioned steps S03, formation liquid phase film on substrate is deposited on to polymer dielectric precursor solution by described.Its
In, the substrate can be hard substrate, the material of hard substrate, it should not under polymeric reaction condition of the embodiment of the present invention,
It reacts with the ingredient in liquid phase film, and itself will not change in polymeric reaction condition of the embodiment of the present invention.?
In some embodiments, the substrate is polyfluortetraethylene plate.
With in some embodiments, the substrate is positive plate, it is hereby achieved that polymer dielectric film and positive plate one
Body structure simplifies lithium ion battery manufacture craft.
Further, it is reacted under the conditions of 60-80 DEG C, the polyenoid based compound polymerize to form network skeleton structure, institute
It states polyoxyethylene type compounds to be filled in the network skeleton structure, the lithium salts and the polyoxyethylene type compounds network
Be complexed between skeleton structure, between the lithium salts and the polyoxyethylene type compounds, formed have high mechanical strength and
The polymer poly polymer electrolyte of the Semi-IPN structure of elasticity.Preferably, the reaction time is 5-24 hours.
Compared to general polymer dielectric, the polymer electrolytic based on Semi-IPN structure of preparation of the embodiment of the present invention
Matter improves the mechanical property of polymer dielectric, therefore, may not need porous due to foring cross-linked network skeleton structure
Property diaphragm reduces the quality of dielectric film as support frame.
And the embodiment of the invention also provides a kind of solid lithium ion battery, including polymer dielectric, the polymerizations
Object electrolyte is polymer dielectric of the present invention；Or the polymer dielectric is the poly- of the method for the invention preparation
Polymer electrolyte.
Solid lithium ion battery provided in an embodiment of the present invention containing polymer dielectric of the present invention, therefore has
Preferable mechanical property and chemical property.
Polymer dielectric provided in an embodiment of the present invention is as described above, specifically, the polymer dielectric is base
It polymerize to form network skeleton structure in the polymer dielectric of Semi-IPN structure, including polyenoid based compound, is filled in the net
Polyoxyethylene type compounds in network skeleton structure, and with the network skeleton structure, the polyoxyethylene type compounds network
The lithium salts of conjunction.Composition and its structural analysis in the polymer dielectric, preparation process are as described above, in order to save a piece
Width, details are not described herein again.
In embodiment, the solid lithium ion battery further includes positive plate and negative electrode tab.In some embodiments, positive
Piece and negative electrode tab are oppositely arranged, and the polymer dielectric is arranged between the positive plate and the negative electrode tab.
In some embodiments, the positive plate includes collector and the positive-active material being formed on the collector
The bed of material.Specifically, the anode active material layer includes positive electrode active materials, the positive electrode active materials be may be selected from but not limited to
For at least one of LiFePO4, cobalt acid lithium, LiMn2O4 or nickle cobalt lithium manganate.
In some embodiments, the negative electrode tab includes collector and the negative electrode active material that is formed on the collector
The bed of material.Specifically, the anode active material layer includes negative electrode active material, the negative electrode active material be may be selected from but not limited to
For at least one of lithium metal, lithium titanate or graphite.
It is illustrated combined with specific embodiments below.
Embodiment 1
A kind of method for preparing polymer electrolytes, the polymer dielectric are the electrostrictive polymer based on Semi-IPN structure
Xie Zhi, the method for preparing polymer electrolytes the following steps are included:
Polyethylene glycol oxide, polyethylene glycol dimethacrylate, lithium salts, acetonitrile are added to the container to uniformly mixed, formation
Clarify sticky solution.Wherein, polyethylene glycol oxide and polyethylene glycol dimethacrylate mass ratio are 10:2；Lithium salts dosage is pressed
1/12 (molar ratio) of ethyoxyl measures addition in polymer dielectric, is uniformly mixed.
The initiator of polyethylene glycol dimethacrylate quality 1% is added in the above solution, is uniformly mixed.
Above-mentioned solution is coated on polyfluortetraethylene plate, 80 DEG C of initiation polymerizations obtain Semi-IPN topology convergence after drying
Object electrolyte.
In the polymer dielectric of the Semi-IPN structure, polyethylene glycol dimethacrylate forms network skeleton knot
Structure, polyoxyethylene type compounds are filled in the network skeleton structure, lithium salts and the network skeleton structure, the polyoxy second
Vinyl compound complexing.
The ionic conductivity of the polymer dielectric for the half interpenetrating network structure that embodiment 1 is prepared about 5*10-5Scm-1, the dielectric film impedance schematic diagram of ionic conductance test is as shown in Figure 1, as seen from Figure 1, embodiment 1 is prepared partly mutual
The polymer dielectric film bulk resistance for wearing network structure is about 50 Ω, with preferable conductivity.
Embodiment 2
A kind of method for preparing polymer electrolytes, difference from example 1 is that, using polyoxyethylene-polyoxy
Propylene copolymer substitutes polyethylene glycol oxide.
The ionic conductivity of the polymer dielectric for the half interpenetrating network structure that embodiment 2 is prepared about 5.8*10- 5Scm-1, voltage stability window test result schematic diagram as shown in Fig. 2, from Figure 2 it can be seen that embodiment 2 be prepared it is Semi-IPN
The polymer interpenetrating dielectric film of network structure can be stabilized in 0-4.5V not to be decomposed.
Embodiment 3
A kind of method for preparing polymer electrolytes, difference from example 1 is that, using tripropylene glycol two
Acrylate substitutes polyethylene glycol dimethacrylate.
Embodiment 4
A kind of method for preparing polymer electrolytes, difference from example 1 is that, using trimethylolpropane tris
Acrylate substitutes polyethylene glycol dimethacrylate.
Embodiment 5
A kind of method for preparing polymer electrolytes, difference from example 1 is that, using three propylene of pentaerythrite
Acid esters substitutes polyethylene glycol dimethacrylate.
Embodiment 6-10
A kind of preparation method of solid lithium ion battery, comprising the following steps:
Positive plate preparation: polyoxyethylene and lithium salts are dissolved in acetonitrile, and wherein polyoxyethylene and lithium salts ratio press polyoxy
Ethylene ethyoxyl/Li (molar ratio) is 1:12 calculating, is uniformly mixed, and polyelectrolyte solution is formed, and mass concentration is
10%；Then uniformly mixed iron phosphate serving as positive active material and conductive black is added, mass concentration respectively accounts for 80% and 10%；
12h is stirred, is stirred.The slurry that will be prepared is coated on aluminium foil, and dry 12h at 80-100 DEG C, then film-making obtains
To anode pole piece.
The polymer dielectric of the half interpenetrating network structure of embodiment 1-5 preparation is provided respectively.
With the positive plate of above-mentioned preparation, polymer dielectric, negative metal lithium successively lamination, solid state lithium battery is produced.
Embodiment 11
A kind of preparation method of solid lithium ion battery, comprising the following steps:
Positive plate preparation: polyoxyethylene and lithium salts are dissolved in acetonitrile, and wherein polyoxyethylene and lithium salts ratio press polyoxy
Ethylene ethyoxyl/Li (molar ratio) is 1:12 calculating, is uniformly mixed, and polyelectrolyte solution is formed, and mass concentration is
10%；Then uniformly mixed iron phosphate serving as positive active material and conductive black is added, mass concentration respectively accounts for 80% and 10%；
12h is stirred, is stirred.The slurry that will be prepared is coated on aluminium foil, and dry 12h at 80-100 DEG C, then film-making obtains
To anode pole piece.
The polymer dielectric of half interpenetrating network structure, the polymer dielectric and reality of the half interpenetrating network structure are provided
Apply example 1 the difference is that: by above-mentioned solution be coated to anode extremely on, 80 DEG C of initiation polymerize, and Semi-IPN knot is obtained after drying
Structure polymer dielectric and the integrated structure of positive plate.
With the integral structure of the positive plate of above-mentioned preparation and polymer dielectric, negative metal lithium lamination, produce solid
State lithium battery, wherein positive plate is oppositely arranged with negative metal lithium, and polymer dielectric is located in positive plate and negative metal lithium
Between.
Comparative example 1
A kind of method for preparing polymer electrolytes, the method for preparing polymer electrolytes the following steps are included:
Polyethylene glycol oxide, lithium salts, acetonitrile are added to the container to uniformly mixed, the sticky solution of formation clarification.Wherein, lithium salts
Dosage measures addition by 1/12 (molar ratio) of ethyoxyl in polymer dielectric, is uniformly mixed.
Above-mentioned solution is coated on nonwoven cloth diaphragm, nonwoven cloth diaphragm is lain on polyfluortetraethylene plate, 80 DEG C of initiations
Polymerization, obtains polymer dielectric film after drying.
The polymer dielectric that the embodiment 3-5 crosslinking interpenetrating polymer electrolyte provided and comparative example 1 provide is adopted
Mechanics Performance Testing is carried out with pulling method.The results show that the crosslinking interpenetrating polymer electrolyte that embodiment 3-5 is provided is shown
Very strong mechanical performance, as shown in Figure 3；And the polymer dielectric that comparative example 1 provides can not be difficult to individually form a film, and can not draw
Stretch test.
The polymer dielectric that the embodiment 1-5 crosslinking interpenetrating polymer electrolyte provided and comparative example 1 are provided into
The test of row ionic conductivity, test result is as follows shown in table 1.
Table 1
| Embodiment | Conductivity at room temperature/Scm-1 |
| Embodiment 1 | 5.0*10-5 |
| Embodiment 2 | 5.8*10-5 |
| Embodiment 3 | 4.2*10-5 |
| Embodiment 4 | 4.8*10-5 |
| Embodiment 5 | 5.2*10-5 |
| Comparative example 1 | 5.5*10-5 |
Seen from table 1, crosslinking interpenetrating polymer electrolyte provided in an embodiment of the present invention, can effectively provide mechanical property
On the basis of energy, there is preferable ionic conductivity.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of polymer dielectric, which is characterized in that the polymer dielectric is the electrostrictive polymer based on Semi-IPN structure
Xie Zhi, including polyenoid based compound polymerize to form network skeleton structure, the polyoxyethylene being filled in the network skeleton structure
Class compound, and the lithium salts being complexed with the network skeleton structure, the polyoxyethylene type compounds.
2. polymer dielectric as described in claim 1, which is characterized in that the polyoxyethylene type compounds are selected from polyoxy second
At least one of alkene, polyoxypropylene and poloxalkol.
3. polymer dielectric as described in claim 1, which is characterized in that the polyenoid based compound is selected from double methacrylate
At least one of class compound, triacrylate class compound.
4. polymer dielectric as claimed in claim 3, which is characterized in that the double methacrylate class compound is selected from poly- second
At least one of omega-diol diacrylate, tri (propylene glycol) diacrylate；
The triacrylate class compound in trimethylolpropane trimethacrylate, pentaerythritol triacrylate extremely
Few one kind.
5. polymer dielectric according to any one of claims 1-4, which is characterized in that the polyoxyethylene type compounds with
The polyenoid based compound polymerize to be formed network skeleton structure mass ratio be 10:1~10:5.
6. polymer dielectric according to any one of claims 1-4, which is characterized in that the lithium salts is selected from bis trifluoromethyl
Sulphur imine lithium, trifluoromethyl sulfonic acid lithium, lithium perchlorate, lithium hexafluoro phosphate, hexafluoroarsenate lithium, LiBF4, dioxalic acid boric acid
One of lithium, difluorine oxalic acid boracic acid lithium；And/or
It is in terms of 100% by the total weight of the polymer dielectric, the weight percentage of the lithium salts is 20%~80%.
7. a kind of method for preparing polymer electrolytes, which is characterized in that the polymer dielectric is based on Semi-IPN structure
Polymer dielectric, the method for preparing polymer electrolytes the following steps are included:
The mixed solution of polyoxyethylene type compounds, polyenoid based compound and lithium salts is provided；
Initiator is added in the mixed solution, mixed processing obtains polymer dielectric precursor solution；
It is deposited on described on substrate to polymer dielectric precursor solution, is reacted under the conditions of 60-80 DEG C, the polyene-based
Compound polymerize to form network skeleton structure, and the polyoxyethylene type compounds are filled in the network skeleton structure, described
Between lithium salts and the polyoxyethylene type compounds network skeleton structure, between the lithium salts and the polyoxyethylene type compounds
It is complexed, forms the polymer poly polymer electrolyte of Semi-IPN structure.
8. method for preparing polymer electrolytes as claimed in claim 7, which is characterized in that the polyoxyethylene chemical combination
The mixed solution of object, polyenoid based compound and lithium salts, is prepared using following methods:
The polyoxyethylene type compounds are dissolved in anhydrous solvent, polyoxyethylene type compounds solution is configured；
The polyenoid based compound is added in the polyoxyethylene type compounds solution, carries out mixed processing, configures polymer
Precursor solution；
Lithium salts is added in the polybenzazole precursor liquid solution, mixed processing obtains polyoxyethylene type compounds, polyene-based chemical combination
The mixed solution of object and lithium salts.
9. method for preparing polymer electrolytes as claimed in claim 8, which is characterized in that the substrate is positive plate；With/
Or
The anhydrous solvent is selected from acetonitrile, tetrahydrofuran, dimethyl sulfoxide, n,N-Dimethylformamide, N, N- dimethylacetamide
At least one of amine etc.；And/or
The initiator is selected from azodiisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, dilauryl peroxide, two
At least one of tert-butyl peroxide；And/or
The quality of the initiator is the 0.2%~3% of the polyene-based compound quality.
10. a kind of solid lithium ion battery, including polymer dielectric, which is characterized in that the polymer dielectric is right
It is required that the described in any item polymer dielectrics of 1-6；Or the polymer dielectric is any one of claim 7-9 the method
The polymer dielectric of preparation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811136661.1A CN109244538A (en) | 2018-09-28 | 2018-09-28 | Based on Semi-IPN structural polymer electrolyte and preparation method thereof, solid lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811136661.1A CN109244538A (en) | 2018-09-28 | 2018-09-28 | Based on Semi-IPN structural polymer electrolyte and preparation method thereof, solid lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109244538A true CN109244538A (en) | 2019-01-18 |
Family
ID=65057875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811136661.1A Pending CN109244538A (en) | 2018-09-28 | 2018-09-28 | Based on Semi-IPN structural polymer electrolyte and preparation method thereof, solid lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109244538A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110233288A (en) * | 2019-06-03 | 2019-09-13 | 深圳市比克动力电池有限公司 | Full solid state polymer electrolyte and preparation method thereof with half interpenetrating network structure |
| CN111276739A (en) * | 2020-03-26 | 2020-06-12 | 华中科技大学 | In-situ preparation method and application of semi-interpenetrating polymer electrolyte |
| CN111499876A (en) * | 2020-04-17 | 2020-08-07 | 东北师范大学 | Reticular polymer and preparation method thereof, semi-interpenetrating network polymer electrolyte and polymer lithium battery |
| CN112038694A (en) * | 2020-09-14 | 2020-12-04 | 浙江大学 | Three-layer composite electrolyte with sandwich structure and preparation method and application thereof |
-
2018
- 2018-09-28 CN CN201811136661.1A patent/CN109244538A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110233288A (en) * | 2019-06-03 | 2019-09-13 | 深圳市比克动力电池有限公司 | Full solid state polymer electrolyte and preparation method thereof with half interpenetrating network structure |
| CN110233288B (en) * | 2019-06-03 | 2020-12-01 | 深圳市比克动力电池有限公司 | All-solid-state polymer electrolyte with semi-interpenetrating network structure and preparation method thereof |
| CN111276739A (en) * | 2020-03-26 | 2020-06-12 | 华中科技大学 | In-situ preparation method and application of semi-interpenetrating polymer electrolyte |
| CN111499876A (en) * | 2020-04-17 | 2020-08-07 | 东北师范大学 | Reticular polymer and preparation method thereof, semi-interpenetrating network polymer electrolyte and polymer lithium battery |
| CN111499876B (en) * | 2020-04-17 | 2021-04-20 | 东北师范大学 | Reticular polymer and preparation method thereof, semi-interpenetrating network polymer electrolyte and polymer lithium battery |
| CN112038694A (en) * | 2020-09-14 | 2020-12-04 | 浙江大学 | Three-layer composite electrolyte with sandwich structure and preparation method and application thereof |
| CN112038694B (en) * | 2020-09-14 | 2021-11-23 | 浙江大学 | Three-layer composite electrolyte with sandwich structure and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Gel polymer electrolyte based on PVDF-HFP matrix composited with rGO-PEG-NH2 for high-performance lithium ion battery | |
| CN105591154B (en) | The all solid state serondary lithium battery and its preparation of polycarbonate-based full solid state polymer electrolyte and its composition and application | |
| CN100499226C (en) | Process for producing polyradical compound and battery | |
| CN109244538A (en) | Based on Semi-IPN structural polymer electrolyte and preparation method thereof, solid lithium ion battery | |
| CN109786820B (en) | Boron-containing plastic crystal polymer and preparation method and application thereof | |
| Chai et al. | Biodegradable composite polymer as advanced gel electrolyte for quasi-solid-state lithium-metal battery | |
| CN108598569B (en) | A kind of three-dimensional network gel polymer electrolyte material and its preparation method and application | |
| CN101747642B (en) | Gel polymer electrolyte, polymer battery and preparing method | |
| CN109346767A (en) | A kind of solid polymer electrolyte and its application in lithium metal battery | |
| CN103570873B (en) | A kind of composition for gel polymer electrolyte, gel polymer electrolyte and electrochemical appliance | |
| CN108598564A (en) | A kind of solid polymer electrolyte and its preparation method and application | |
| CN108923064B (en) | Solid polymer electrolyte, preparation method thereof and lithium ion secondary battery | |
| WO2021098685A1 (en) | Solid-state polymer electrolyte, preparation method therefor, and lithium battery | |
| CN110249456A (en) | Lithium ion battery anode and lithium ion battery | |
| CN104170130A (en) | Cathode active material composition and lithium secondary battery comprising same | |
| CN108242563A (en) | A kind of high voltage withstanding alkyl tin groups, alkyl silane groups lithium battery polymer dielectric, preparation method and its application in solid lithium battery | |
| CN101595580B (en) | Polyradical compound-conductive material composite body, method for producing the same, and battery using the same | |
| CN112599859A (en) | Preparation method of high-energy-density power battery | |
| CN111211299A (en) | Modified lithium ion battery positive electrode material coated with strong electronegative organic matter layer and preparation method thereof | |
| CN111261872A (en) | Organic electrode material and preparation method and application thereof | |
| CN109888369A (en) | A kind of all solid state electrolyte and preparation method thereof and a kind of lithium battery | |
| CN103427113A (en) | Gel polymer electrolyte, polymer battery, and preparation method thereof | |
| CN111129583B (en) | Gel electrolyte and preparation method of lithium ion battery containing gel electrolyte | |
| CN105958117A (en) | Nano particle doped gel polymer electrolyte, preparation method thereof and application | |
| CN117219847A (en) | Composite electrolyte film, preparation method thereof and application thereof in solid-state lithium battery |
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 |