CN108365262A - A kind of 3D networks hybrid inorganic-organic all solid state electrolyte and a kind of lithium secondary battery - Google Patents
A kind of 3D networks hybrid inorganic-organic all solid state electrolyte and a kind of lithium secondary battery Download PDFInfo
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- CN108365262A CN108365262A CN201810130352.7A CN201810130352A CN108365262A CN 108365262 A CN108365262 A CN 108365262A CN 201810130352 A CN201810130352 A CN 201810130352A CN 108365262 A CN108365262 A CN 108365262A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 101
- 239000007787 solid Substances 0.000 title claims abstract description 74
- 229910052744 lithium Inorganic materials 0.000 title claims description 40
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002105 nanoparticle Substances 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 28
- 239000003822 epoxy resin Substances 0.000 claims abstract description 28
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 28
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 27
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 27
- 239000011159 matrix material Substances 0.000 claims abstract description 27
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 27
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 26
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 17
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 30
- -1 Kynoar Polymers 0.000 claims description 28
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229920001451 polypropylene glycol Polymers 0.000 claims description 9
- 150000002118 epoxides Chemical class 0.000 claims description 8
- 150000004820 halides Chemical class 0.000 claims description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 229920000098 polyolefin Polymers 0.000 claims description 6
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 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
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 claims description 3
- 229910009496 Li1.5Al0.5Ge1.5 Inorganic materials 0.000 claims description 3
- 229910005317 Li14Zn(GeO4)4 Inorganic materials 0.000 claims description 3
- 229910010615 Li6.75La3 Inorganic materials 0.000 claims description 3
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- QRMHDYCPNIVCBO-UHFFFAOYSA-N [SH2]=N.[F] Chemical compound [SH2]=N.[F] QRMHDYCPNIVCBO-UHFFFAOYSA-N 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 229960002645 boric acid Drugs 0.000 claims description 3
- 235000010338 boric acid Nutrition 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 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
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 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
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920000333 poly(propyleneimine) Polymers 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 102200027768 rs199475567 Human genes 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- ZHJQNCRLAJBKPV-UHFFFAOYSA-N C(C1CO1)C(C(C(O)CC1CO1)O)O.OCC(C)(CO)C Chemical compound C(C1CO1)C(C(C(O)CC1CO1)O)O.OCC(C)(CO)C ZHJQNCRLAJBKPV-UHFFFAOYSA-N 0.000 claims 1
- 239000004593 Epoxy Substances 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 229910052785 arsenic Inorganic materials 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 abstract description 18
- 238000009396 hybridization Methods 0.000 abstract description 7
- 239000007784 solid electrolyte Substances 0.000 description 36
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 33
- 238000003756 stirring Methods 0.000 description 23
- 239000007788 liquid Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 229910001416 lithium ion Inorganic materials 0.000 description 15
- 239000012528 membrane Substances 0.000 description 15
- 239000002243 precursor Substances 0.000 description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 14
- 239000002585 base Substances 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- 239000004809 Teflon Substances 0.000 description 10
- 229920006362 Teflon® Polymers 0.000 description 10
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- 239000006185 dispersion Substances 0.000 description 8
- 230000005611 electricity Effects 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000010422 painting Methods 0.000 description 6
- 210000001787 dendrite Anatomy 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000006193 liquid solution Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000219991 Lythraceae Species 0.000 description 2
- 235000014360 Punica granatum Nutrition 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 150000002576 ketones Chemical class 0.000 description 2
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- GDKZTIJXNRGQLT-UHFFFAOYSA-N 1,5-bis(oxiran-2-yl)pentane-2,3,4-triol Chemical compound C1OC1CC(O)C(O)C(O)CC1CO1 GDKZTIJXNRGQLT-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical class CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- PPPGBRSJYRPWKP-UHFFFAOYSA-N fluoroethene;1,1,2,3,3,3-hexafluoroprop-1-ene Chemical compound FC=C.FC(F)=C(F)C(F)(F)F PPPGBRSJYRPWKP-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 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
-
- 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)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
The present invention provides a kind of 3D networks organic inorganic hybridization all solid state electrolytes, including：Three-dimensional network polymer electrolyte matrix as 3D network organic inorganic hybridization all solid state electrolyte skeletons；And it is scattered in the aggregate and lithium salts of the oxide electrolyte nano particle or oxide electrolyte nano particle inside the three-dimensional network polymer electrolyte matrix；The three-dimensional network polymer electrolyte matrix is obtained by reaction monomers, diglycidyl ether type epoxy resin and its derivative, crosslinking agent and linear polymer with epoxy group by ring-opening polymerization.
Description
Technical field
The invention belongs to lithium secondary battery technical fields, and in particular to a kind of all solid state electricity of 3D networks hybrid inorganic-organic
Solve matter and a kind of lithium secondary battery.
Background technology
Lithium ion battery has high-energy-density density, operating voltage high, and self-discharge rate is low, fast charging and discharging, service life
The advantages such as long and memory-less effect (J.Power Sources., 2011,196:8651-8655) so that lithium ion battery is recognized
To be large-scale power battery optimal selection.However the low energy density of graphite cathode leads to the energy of current lithium ion battery
For density usually in 200Wh/kg or so, this seriously constrains extensive use of the lithium ion battery on electric vehicle.With pure electricity
Electrical automobile is commercialized the acceleration of process, and there is an urgent need to further increase energy density (the energy density 300Wh/ of lithium ion battery
Kg or more).Using lithium metal as cathode, battery energy density can be greatly improved, is mainly due to lithium metal in lithium two
Theoretical specific energy density in primary cell negative material is up to 3860mAh/g, while the use of lithium metal also makes no collector electricity
The preparation of pole is possibly realized, to greatly improve battery energy density.However, lithium an- ode in charge and discharge cycles easily because of lithium
Ion inhomogeneous deposition causes lithium dendrite growth to bring safety problem, and huge challenge is brought for the application of metal lithium electrode
(Energ.Environ.Sci.,2013,7(2):513-537).In addition, being currently being widely used volatile and flammable liquid has
Solvent easily causes the safety problem (J.Power in cyclic process as Current commercial lithium-ion battery electrolytes
Sources.,2012,208:210-224), simultaneously because liquid state organic electrolyte and diaphragm unstable electrification under high voltages
It learns performance and so that the energy density of lithium ion battery is difficult to improve.Replace traditional organic liquid electricity using solid polymer electrolyte
Solution liquid is considered as the effective way for promoting lithium battery safety.In all-solid lithium-ion battery, all solid state electrolysis materials
Material is free of any liquid component, can directly play the role of electrolyte and diaphragm (J.Power Sources., 2015,
282:299-322), and solid electrolyte can effectively inhibit lithium dendrite growth.The basic demand of solid electrolyte be it is high from
Electron conductivity, suitable mechanical strength and the electrode interface stablized.The energy density of all-solid lithium-ion battery is higher than current lithium
Ion battery, it is considered to be one of most promising next generation's high-energy-density lithium battery system.So far, it prepares while simultaneous
It is still at this stage to have high ionic conductivity, low electrode/electrolyte interface impedance, the good polymer electrolyte of mechanical strength
Huge technological challenge (Chem.Rev., 2014,114 (23):11503-11618).Therefore, exploitation is directed to high-energy density lithium
The New Solid electrolyte of battery system is expected to that the energy density and safety guarantee of existing lithium ion battery is substantially improved, has
Important actual application value (Nature., 2001,414:359–367).
Patent CN106876784A and CN106941190A individually disclose a kind of PEO bases solid polymer electrolyte membrane and
Pomegranate type LLZO solid oxide electrolytes.There are room temperatures for PEO bases solid polymer electrolyte membrane disclosed in CN106876784A
, easily there is short circuit, it is difficult to meet actual operation requirements in the problems such as ionic conductivity low and high temperature mechanical property and poor thermal stability.
And pomegranate type LLZO solid oxide electrolytes room-temperature conductivity disclosed in CN106941190A is high, but electrolyte sheet thickness is big
And easy embrittlement, cause cell interface resistance high, greatly reduces the gravimetric energy density and volume energy density of battery, it is difficult to prepare
Large capacity battery core.Therefore current solid electrolyte critical issue is to prepare high-lithium ion conductivity, highly oxidation resistant current potential, take into account
Mechanical property and ionic conduction characteristic can completely inhibit the hybrid inorganic-organic solid-state that Li dendrite pierces through in life cycle management
Dielectric film realizes the fusion of high mechanical properties and high ionic conductivity, solves current electrolyte intermediate ion conductivity and mechanics
Performance is difficult to the problem taken into account.
Invention content
In view of this, the technical problem to be solved in the present invention be to provide a kind of 3D networks hybrid inorganic-organic it is all solid state
Electrolyte and a kind of lithium secondary battery, 3D networks hybrid inorganic-organic all solid state electrolyte provided by the invention have higher
Conductivity, while it has both excellent mechanical property and flexibility, excellent thermostabilization and dimensional stability, solves current poly-
Polymer electrolyte intermediate ion conductivity is difficult to the problem taken into account with mechanical property, improves the safety of lithium battery.
The present invention provides a kind of 3D networks hybrid inorganic-organic all solid state electrolytes, including：
Three-dimensional network polymer electrolyte matrix as 3D network hybrid inorganic-organic all solid state electrolyte skeletons；
And be scattered in oxide electrolyte nano particle inside the three-dimensional network polymer electrolyte matrix or
The aggregate and lithium salts of oxide electrolyte nano particle；
The three-dimensional network polymer electrolyte matrix is by the reaction monomers with epoxy group, diglycidyl ether type epoxy
Resin and its derivative, crosslinking agent and linear polymer are obtained by ring-opening polymerization.
Preferably, the linear polymer is selected from polyacrylonitrile, polymethyl methacrylate, Kynoar, polyphenyl second
Alkene, Kynoar-hexafluoropropene, polypropylene oxide, polyethylene glycol oxide, polysiloxanes, polyurethane or one kind in polysulfones or
A variety of, the range of number-average molecular weight of the linear polymer is 100,000~4,000,000.
Preferably, the lithium salts is selected from lithium perchlorate, hexafluoroarsenate lithium, lithium hexafluoro phosphate, LiBF4, trifluoromethyl
It is one or more in Sulfonic Lithium, trifluoromethane sulfonic acid imine lithium, double fluorine sulfimide lithiums and difluorine oxalic acid boracic acid lithium.
Preferably, the molar ratio of the lithium salts and the linear polymer is 1：(4~50).
Preferably, the one kind or more of the reaction monomers with epoxy group in glycidol ethers compound
Kind.
Preferably, the glycidol ethers compound is selected from 3- glycidyl ether oxypropyltriethoxysilanes, gathers
Ethylene glycol diglycidylether, poly- (propylene glycol) diglycidyl ether, neopentylglycol diglycidyl ether and poly- (dimethyl silica
Alkane) it is one or more in diglycidyl ether.
Preferably, the number-average molecular weight of the reaction monomers with epoxy group is 300~20000Da.
Preferably, the number-average molecular weight of the reaction monomers with epoxy group is 500~10000Da.
Preferably, the diglycidyl ether type epoxy resin and its number-average molecular weight of derivative are 400~20000Da,
Epoxide number 160~290.
Preferably, the diglycidyl ether type epoxy resin and its derivative are E44, E51, E52, E54, E55 and E56D
In it is one or more.
Preferably, the crosslinking agent is the compound at least contained there are one amido.
Preferably, the crosslinking agent be selected from containing at least one amido compound, the compound be selected from alkane and its
Derivative, polyene hydrocarbons and their derivates, polyalkylene oxide and its derivative or cellulose and its derivates.
Preferably, the derivative of the alkane is selected from the halides of alkane, and the derivative of the polyolefin is selected from polyolefin
Halides, the polyalkylene oxide derivative be selected from polyalkylene oxide halides, the polyalkylene oxide be selected from polyethylene oxide
Or polypropylene oxide.
Preferably, the crosslinking agent is one or more in polyethyleneimine, polypropyleneimine, polyetheramine.
Preferably, the number-average molecular weight of the crosslinking agent is 230 to 10000Da.
Preferably, reaction monomers, diglycidyl ether type epoxy resin and its derivative with epoxy group, crosslinking
The mass ratio of agent is (1~3):(1~3):(4~8).
Preferably, the oxide electrolyte nano particle is selected from Li14Zn(GeO4)4、LiZr2Si2PO12、
Li1.3Al0.3Ti1.7(PO4)3、Li1.5Al0.5Ge1.5P3O12、Li7La3Zr2O12And Li6.75La3Zr1.75Ta0.25O12In one kind or
A variety of, grain size is 50nm~900nm, and the grain size of the aggregate of the oxide electrolyte nano particle is 1 μm~5 μm.
Preferably, the oxide electrolyte nano-particle accounts for reaction monomers with epoxy group, diglycidyl ether type
The weight percent of the sum of epoxy resin and its derivative and crosslinking agent quality is 20wt%~50wt%, the linear polymer
Account for the weight of the sum of reaction monomers, diglycidyl ether type epoxy resin and its derivative and crosslinking agent quality with epoxy group
Percentage is 5wt%~30wt%.
Preferably, the thickness of all solid state electrolyte is 20~200 μm.
The present invention also provides a kind of lithium secondary batteries, including above-mentioned 3D networks hybrid inorganic-organic all solid state electrolyte.
Compared with prior art, the present invention provides a kind of 3D networks hybrid inorganic-organic all solid state electrolytes, including：
Three-dimensional network polymer electrolyte matrix as 3D network hybrid inorganic-organic all solid state electrolyte skeletons；And it is scattered in
Oxide electrolyte nano particle inside the three-dimensional network polymer electrolyte matrix or oxide electrolyte nanometer
The aggregate and lithium salts of grain；The three-dimensional network polymer electrolyte matrix is by the reaction monomers with epoxy group, shrink
Ethoxylated glycerol type epoxy resin and its derivative, crosslinking agent and linear polymer are obtained by ring-opening polymerization.Side of the present invention
Method is using functional and highly cross-linked molecular structure fine and close three-dimensional polymer matrix as skeleton, by oxide electrolyte nanometer
Grain and lithium salts are uniformly implemented in polymer electrolyte matrix in situ, are prepared with multi-level lithium ion conducting channel
3D network hybrid inorganic-organic solid electrolytes.In the method for the present invention in 3D networks hybrid inorganic-organic solid electrolyte structure
The advantages of being effectively combined polymer dielectric and inorganic oxide electrolyte, crosslinked polymer electrolyte network assign hydridization
The good flexibility of electrolyte and adhesiveness, inorganic oxide electrolyte nano particle have high hardness and wide electrochemistry
Stability window can effectively inhibit lithium dendrite growth.
The result shows that 3D network hydridization all solid state electrolytes prepared by the method for the present invention realize ionic conductivity and mechanics
Performance organically blends, and conductivity at room temperature is up to 3.68 × 10-5S cm-1, it is far above PEO+ lithium salts base all solid state electrolytes
Room-temperature conductivity (conductivity at room temperature be 1.52 × 10-5S cm-1), the ionic conductivity at 80 DEG C is 1.04 × 10-3S
cm-1(ionic conductivity at 80 DEG C of PEO+ lithium salts bases all solid state electrolyte is 5.43 × 10-4S cm-1), reach practical application water
It is flat.It has both excellent mechanical property and flexibility (tensile strength 10.8Mpa, elastic deformation 125%, and PEO+ simultaneously
The tensile strength of lithium salts base all solid state electrolyte is only 0.62Mpa), excellent thermostabilization and dimensional stability solve current
Polymer dielectric intermediate ion conductivity is difficult to the problem taken into account with mechanical property, improves the safety of lithium battery.
Description of the drawings
Fig. 1 is the flow signal of the preparation method of 3D networks hybrid inorganic-organic all solid state electrolyte provided by the invention
Figure；
Fig. 2 is the structural schematic diagram of Teflon mould；
Fig. 3 is the surface topography map of 3D network hybrid inorganic-organic solid electrolyte membranes made from embodiment 1；
Fig. 4 is thermal weight loss (TGA) curve of 3D network hybrid inorganic-organic solid electrolytes made from embodiment 1；
Fig. 5 is the mechanical property figure of 3D network hybrid inorganic-organic solid electrolytes made from embodiment 1；
Fig. 6 is the thermal dimensional stability figure of 3D network hybrid inorganic-organic solid electrolytes made from embodiment 1；
Fig. 7 is the ionic conductivity and temperature relation of 3D network hybrid inorganic-organic solid electrolytes made from embodiment 1
Curve graph.
Specific implementation mode
The present invention provides a kind of 3D networks hybrid inorganic-organic all solid state electrolytes, including：
Three-dimensional network polymer electrolyte matrix as 3D network hybrid inorganic-organic all solid state electrolyte skeletons；
And be scattered in oxide electrolyte nano particle inside the three-dimensional network polymer electrolyte matrix or
The aggregate and lithium salts of oxide electrolyte nano particle；
The three-dimensional network polymer electrolyte matrix is by the reaction monomers with epoxy group, diglycidyl ether type epoxy
Resin and its derivative, crosslinking agent and linear polymer are obtained by ring-opening polymerization.
3D networks hybrid inorganic-organic all solid state electrolyte provided by the invention includes miscellaneous as 3D network organic and inorganics
Change the three-dimensional network polymer electrolyte matrix of all solid state electrolyte skeleton.
Wherein, the three-dimensional network polymer electrolyte matrix is by the reaction monomers with epoxy group, glycidol ether
Type epoxy resin and its derivative, crosslinking agent and linear polymer are obtained by ring-opening polymerization.
The linear polymer is selected from polyacrylonitrile, polymethyl methacrylate, Kynoar, polystyrene, gathers partially
It is one or more in vinyl fluoride-hexafluoropropene, polypropylene oxide, polyethylene glycol oxide, polysiloxanes, polyurethane or polysulfones.Institute
State linear polymer range of number-average molecular weight be 100,000~4,000,000, preferably 500,000~3,000,000, more preferably 1,000,000~
2000000.
The reaction monomers with epoxy group are one or more in glycidol ethers compound, preferably
, the glycidol ethers compound is selected from 3- glycidyl ether oxypropyltriethoxysilanes, polyethylene glycol diglycidyl
Glycerin ether, poly- (propylene glycol) diglycidyl ether, neopentylglycol diglycidyl ether and poly- (dimethyl siloxane) two shrink are sweet
It is one or more in oily ether.
The number-average molecular weight of the reaction monomers with epoxy group be 300~20000Da, preferably 500~
10000Da, more preferably 500,1000,2000,3000 or 6000Da.
The molecular weight of the diglycidyl ether type epoxy resin and its derivative be 400~20000Da, preferably 500~
10000Da, more preferably 1000~8000Da；Epoxide number 160~290, preferably 180~270, more preferably 200~250.
Preferably, the diglycidyl ether type epoxy resin and its derivative are E44, E51, E52, E54, E55 and E56D
In it is one or more.
The crosslinking agent be selected from containing at least one amido compound, the compound be selected from alkane hydrocarbons and their derivates,
Polyene hydrocarbons and their derivates, polyalkylene oxide and its derivative or cellulose and its derivates.
Crosslinking agent of the present invention is selected from straight chain aminated compounds, branch aminated compounds or with dissaving structure
Aminated compounds.
Preferably, the derivative of the alkane is selected from the halides of alkane, and the derivative of the polyolefin is selected from polyolefin
Halides, the polyalkylene oxide derivative be selected from polyalkylene oxide halides, the polyalkylene oxide be selected from polyethylene oxide
Or polypropylene oxide.It is furthermore preferred that the one kind or more of the crosslinking agent in polyethyleneimine, polypropyleneimine, polyetheramine
Kind.
In the present invention, the number-average molecular weight of the crosslinking agent be 230 to 10000Da, preferably 230,400,1000,
2000,4000 or 5000Da.
The matter of reaction monomers, diglycidyl ether type epoxy resin and its derivative with epoxy group, crosslinking agent
Amount is than being (1~3):(1~3):(4~8), preferably (1.5~2.5):(1.5~2.5):(5~7).
The linear polymer accounts for reaction monomers, diglycidyl ether type epoxy resin and its derivative with epoxy group
It is 5wt%~30wt%, preferably 10wt%~25wt% with the weight percent of the sum of crosslinking agent quality, more preferably
15wt%~20wt%.
3D networks hybrid inorganic-organic all solid state electrolyte provided by the invention further includes being scattered in the three-dimensional network to gather
The oxide electrolyte nano particle of polymer electrolyte intrinsic silicon or the aggregate of oxide electrolyte nano particle and
Lithium salts.
The lithium salts is inorganic lithium salt or organic lithium salt, preferably lithium perchlorate (LiClO4), hexafluoroarsenate lithium
(LiAsF6), lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4), trifluoromethyl sulfonic acid lithium (LiCF3SO4), trifluoromethyl
One kind or more in sulfimide lithium (LiTFSI), double fluorine sulfimide lithiums (LiFSI) and difluorine oxalic acid boracic acid lithium (LiDFOB)
Kind.
The molar ratio of the lithium salts and the linear polymer is 1：(4~50), preferably 1：(5~45), more preferably
1：(10~40), further preferably 1：(20~30).
The oxide electrolyte nano particle is selected from Li14Zn(GeO4)4、LiZr2Si2PO12、Li1.3Al0.3Ti1.7
(PO4)3、Li1.5Al0.5Ge1.5P3O12、Li7La3Zr2O12And Li6.75La3Zr1.75Ta0.25O12In it is one or more, grain size is
50nm~900nm, preferably 100nm~800nm, more preferably 300~500nm.
The oxide electrolyte nano-particle accounts for reaction monomers, diglycidyl ether type epoxy resin with epoxy group
And its weight percent of the sum of derivative and crosslinking agent quality is 20wt%~50wt%, preferably 25wt%~45wt%,
More preferably 30wt%~40wt%.
The thickness of the 3D networks hybrid inorganic-organic all solid state electrolyte be 20~200 μm, preferably 50~180 μm,
More preferably 100~150 μm.
The present invention also provides a kind of preparation methods of above-mentioned 3D networks hybrid inorganic-organic all solid state electrolyte, including
Following steps：
A) linear polymer, lithium salts and solvent are mixed, obtain mixed solution；
B) by reaction monomers, diglycidyl ether type epoxy resin and its derivative with epoxy group, crosslinking agent, oxidation
Object electrolyte nano particle and solvent mixing, obtain mixed dispersion liquid；
C) mixed solution and the mixed dispersion liquid are mixed, obtain reaction precursor liquid solution；
D the reaction precursor liquid solution) is injected in mold or is coated on matrix surface, heating is reacted, after drying,
Obtain 3D network hybrid inorganic-organic all solid state electrolytes；
Step A) and step B) limited without sequence.
Specifically, in the present invention, step A) described in solvent and step B) described in solvent be preferably organic molten
It is one or more in agent, more preferably arene, alicyclic hydrocarbon type, halogenated hydrocarbons, ethers and ketone and other organic solvents.
In some specific embodiments of the present invention, step A) described in solvent and step B) described in solvent independent be selected from third
Ketone, hexamethylene, toluene, chloroform, N,N-dimethylformamide, acetonitrile, tetrahydrofuran, DMAC N,N' dimethyl acetamide or N- methyl pyrroles
Pyrrolidone.
The present invention is not particularly limited the mixed solution and the preparation sequence of the mixed dispersion liquid.
Mixed solution is obtained with after mixed dispersion liquid, the mixed solution and the mixed dispersion liquid are mixed,
Obtain reaction precursor liquid solution.
The present invention can be described there is no specifically limited to the mixed solution and the mixed dispersion liquid hybrid mode
Mixed solution pours into mixed dispersion liquid, or mixed dispersion liquid is poured into mixed solution.The mixing time be 2~
12h, preferably 4~10h, more preferably 6~8h.
Wherein, the weight percent content that the linear polymer accounts for precursor solution is 5%~30%, preferably 10%
~25%, more preferably 15%~20%.
The reaction precursor liquid solution is injected in mold or is coated on matrix surface, heating is reacted, after drying, obtained
To 3D network hybrid inorganic-organic all solid state electrolytes.
In the present invention, the precursor solution is formed into the mode of dielectric film there is no specifically limited, it can be by institute
It states precursor solution painting to pour into mold, the mold is preferably Teflon mould, and the Teflon mould is preferred
For circular die, diameter is preferably 6~20cm, more preferably 10~15cm.The precursor solution pours into the mold
Thickness is preferably 20~200 μm, more preferably 50~150 μm, further preferably 70~120 μm.
Precursor solution can also be coated on matrix surface, wherein there is no special for mode of the present invention to the coating
Different limitation, can be poured on matrix surface, form certain thickness film, or be the coating methods such as spraying, spin coating, precursor solution
It is preferably 20~200 μm in the thickness for the film that described matrix surface is formed, more preferably 50~150 μm, further preferably 70
~120 μm.
Then, heating is reacted, and the temperature of reaction is preferably 60~120 DEG C, more preferably 80~100 DEG C；Time is excellent
It is selected as 12~36 hours, more preferably 16~32 hours, further preferably 20~28 hours.
Finally, heating reaction product is dried, obtains 3D network hybrid inorganic-organic all solid state electrolytes.
Referring to Fig. 1, Fig. 1 is all solid state electrolysis of 3D networks hybrid inorganic-organic all solid state electrolyte provided by the invention
The flow diagram of matter.In Fig. 1, reaction monomers first, reaction monomers second and reaction monomers third are corresponded to respectively with epoxy group
Reaction monomers, diglycidyl ether type epoxy resin and its derivative and crosslinking agent；Oxide solid electrolyte nano particle is
Oxide electrolyte nano particle.
Detailed process is：By reaction monomers, diglycidyl ether type epoxy resin and its derivative with epoxy group, friendship
Join agent and oxide electrolyte nano particle mixing after, be that lithium salts is mixed with the mixture of linear polymer, then into
Row heating reaction, obtains 3D network hybrid inorganic-organic all solid state electrolytes (3D-HSPE).
The present invention also provides a kind of lithium secondary batteries, including above-mentioned 3D networks hybrid inorganic-organic all solid state electrolyte.
The method of the present invention is using functional and highly cross-linked molecular structure fine and close three-dimensional polymer matrix as skeleton, by oxygen
Compound electrolyte nano particle and lithium salts are uniformly implemented in polymer electrolyte matrix in situ, are prepared with multi-level
The 3D network hybrid inorganic-organic solid electrolytes in lithium ion conducting channel.3D networks hybrid inorganic-organic in the method for the present invention
The advantages of polymer dielectric and inorganic oxide electrolyte have been effectively combined in solid electrolyte structure, cross-linked polymer electricity
It solves matter network and assigns the good flexibility of hydridization electrolyte and adhesiveness, inorganic oxide electrolyte nano particle has high
Hardness and wide electrochemical stability window, can effectively inhibit lithium dendrite growth.
The result shows that 3D network hydridization all solid state electrolytes prepared by the method for the present invention realize ionic conductivity and mechanics
Performance organically blends, and conductivity at room temperature is up to 3.68 × 10-5S cm-1, it is far above PEO+ lithium salts base all solid state electrolytes
Room-temperature conductivity (conductivity at room temperature be 1.52 × 10-5Scm-1), the ionic conductivity at 80 DEG C is 1.04 × 10-3S
cm-1(ionic conductivity at 80 DEG C of PEO+ lithium salts bases all solid state electrolyte is 5.43 × 10-4S cm-1), reach practical application water
It is flat.It has both excellent mechanical property and flexibility, excellent thermostabilization and dimensional stability simultaneously, solves present polymer
Electrolyte intermediate ion conductivity is difficult to the problem taken into account with mechanical property, improves the safety of lithium battery.
For a further understanding of the present invention, with reference to embodiment to 3D networks hybrid inorganic-organic provided by the invention
The all solid state electrolyte and lithium secondary battery of all solid state electrolyte illustrate, and protection scope of the present invention is not by following implementation
The limitation of example.
Embodiment 1
The present embodiment is related to a kind of preparation method of 3D networks hybrid inorganic-organic solid electrolyte, the method includes
Following steps：
(1) polyethylene glycol oxide (PEO, Mn=600000) of 0.10g is added in the beaker A of 25ml, then uses liquid-transfering gun
The acetonitrile of 2.0g is added dropwise, stirring 2h makes it completely dissolved, and 0.55gLiTFSI is then added, and continuing stirring, to form water white transparency molten
Liquid；
(2) 0.10g polyethyleneglycol diglycidylethers (Mn=500), 0.06g are sequentially added in the beaker B of 25ml
BisphenolA-glycidol ether epoxy resin E51 (epoxide number 186) and 0.4g polyetheramines (Mn=2000) are added in beaker,
The acetonitrile of 2.0g is added dropwise with liquid-transfering gun, is eventually adding 1.2g LAGP nano particle (grain sizes：300 ± 10nm), stirring 6h mixing is equal
It is even, form white presoma mixed liquor.
(3) solution in beaker A is poured into beaker B, after quickly stirring 6h, obtains uniformly mixed precursors mixing
Liquid；Presoma mixed liquor painting is poured into Teflon mould, 80 DEG C of reactions of constant temperature obtain white 3D networks afterwards for 24 hours to be had
Machine-inorganic hybridization all solid state electrolyte film；It is put into after solid electrolyte membrane obtained is dried spare in glove box.
In addition, beaker can be substituted with container, wherein container be not with reactant or the container of solvent reaction, Ke Yishi
Glass container can also be the easy or ceramic vessel of stainless steel.Different size of appearance can be selected according to the scale of reaction
Device.A kind of stirring and dissolving of step can also be summarised as the sub-step of dissolving, and this dissolving can be nature dissolving, the purpose is to
Each component dissolving is complete.
In step (3), Teflon mould is used, be the reeded, bottom surface of tool is circular vessel, opener
Ware.It is the structural schematic diagram of Teflon mould referring to Fig. 2, Fig. 2.The drying steps of solid electrolyte membrane can be drying,
It can also be vacuum drying, can also spontaneously dry.If necessary to use, can be placed on it is spare in glove box or baking oven,
If necessary to store, need to be placed in the environment for keeping its drying.
By measuring, the thickness for the 3D network hybrid inorganic-organic all solid state electrolytes that the present embodiment is prepared is 104
μm, the room-temperature conductivity measured is 3.68 × 10-5S cm-1。
The surface topography of 3D networks hybrid inorganic-organic all solid state electrolyte is as shown in figure 3, Fig. 3 made from the present embodiment
For the surface topography map of 3D networks hybrid inorganic-organic solid electrolyte membrane made from embodiment 1.Wherein, (a) is embodiment 1
The optical photograph on the surface of 3D networks hybrid inorganic-organic solid electrolyte membrane obtained (b) is 3D nets made from embodiment 1
The stereoscan photograph of network hybrid inorganic-organic solid electrolyte membrane.From figure 3, it can be seen that prepared 3D networks it is organic-nothing
Machine hydridization all solid state electrolyte surface shows fine and close cross-linked network structure, and oxide electrolyte nano-particle uniformly divides
Cloth is in a polymer matrix.
Thermogravimetric curve such as Fig. 4 of 3D networks hybrid inorganic-organic all solid state electrolyte made from the present embodiment.By Fig. 4
It is found that hydridization solid polymer membrane initial decomposition temperature is up to 300 DEG C, show that the solid electrolyte membrane has excellent thermostabilization
Property, meet the requirement on lithium secondary battery enough.The heat decomposition temperature of reference PEO+LiTFSI is only 150 DEG C, high
Easy decomposition failure under temperature.
The bending property of 3D networks hybrid inorganic-organic solid electrolyte is as shown in figure 5, Fig. 5 is made from the present embodiment
The mechanical property figure of 3D networks hybrid inorganic-organic solid electrolyte made from embodiment 1.In Fig. 5, a is prepared by embodiment 1
The finished figure of 3D network hybrid inorganic-organic solid electrolytes, b are 3D network hybrid inorganic-organic solid-states prepared by embodiment 1
The form photo that electrolyte is wound on a column, c are 3D network hybrid inorganic-organics solid-state electricity prepared by embodiment 1
Solve the stress-strain curve of matter.
As shown in Figure 5, which has excellent flexibility and mechanical property, it is not easy to be broken.Lithium two
Primary cell assembles and use in the process all may be by certain outer force effect, therefore the mechanical property of solid electrolyte is characterization
Whether it meets an important indicator of practical application.This experiment is strong using the stretching for measuring solid electrolyte under certain condition
It spends and characterizes the mechanical characteristic of polymer dielectric with tension fracture elongation rate.By solid electrolyte membrane be cut into 10mm wide,
The batten of 50mm long is measured respectively with the CMT6104 type universal electrical puller systems of MTS industrialsystems companies of the U.S.
The tensile strength of polymer dielectric film, rate of extension are 5mm min-1.Sample thickness passes through the limited public affairs of Shanghai Measuring and Cutting Tools Plant
G103 type electronic digital display outside micrometers are taken charge of to measure.After tested, 3D networks hybrid inorganic-organic solid-state electricity made from the present embodiment
The tensile strength for solving matter is 10.8Mpa, elastic deformation 125%.
And the tensile strength of PEO+ lithium salts base all solid state electrolytes (preparation method is referring to embodiment 2) is only 0.62Mpa
The thermal dimensional stability of 3D networks hybrid inorganic-organic solid electrolyte made from the present embodiment was as shown in fig. 6, should
Solid electrolyte places 3h at 80 DEG C, and any contraction does not occur for size.On the contrary, PEO+LiTFSI solid electrolyte (preparation methods
Referring to embodiment 2) there is gross distortion, short circuit easily occurs and causes lithium battery safety problem.Illustrate 3D network hybrid inorganic-organics
Solid electrolyte has excellent thermal dimensional stability, and lithium battery safety can be greatly improved.
The ionic conductivity of 3D networks hybrid inorganic-organic all solid state electrolyte made from the present embodiment is bent with temperature relation
Line chart is as shown in fig. 7, its conductivity at room temperature is 3.68 × 10-5S cm-1, it is far above all solid state electrolysis of PEO+LiTFSI bases
The conductivity at room temperature (1.52 × 10 of matter-5S cm-1), the ionic conductivity at 80 DEG C is 1.04 × 10-3S cm-1(PEO+ lithiums
Ionic conductivity at 80 DEG C of alkali all solid state electrolyte (preparation method is referring to embodiment 2) is only 5.43 × 10-4S cm-1),
Reach actual application level.The linear relationship of ionic conductivity and temperature show ionic conductivity vary with temperature relationship meet Ah
Human relations Nice ionic conductive mechanism.
Embodiment 2
The present embodiment is related to a kind of preparation method of PEO+ lithium salts base all solid state electrolyte reference, and the method includes such as
Lower step：
(1) PEO (Mn=100000) of 0.72g is added in the beaker of 25ml, the acetonitrile of 6.0g is then added dropwise, stirring makes
It is completely dissolved, and then weighs 0.59g LiTFSI, and stirring 6h is uniformly mixed.Above-mentioned solution is poured into clean polytetrafluoroethylene (PTFE)
In mold, it is positioned in vacuum drying oven in 60 DEG C of constant temperature drying 8h after standing a period of time, obtains all solid state electricity of PEO+ lithium salts bases
PEO bases solid electrolyte membrane obtained is put into spare in glove box by Xie Zhi.
The thickness for the PEO+ lithium salts base all solid state electrolyte films that the present embodiment is prepared is 180 μm, and room-temperature conductivity is
1.52×10-5S cm-1。
Embodiment 3
The present embodiment is related to a kind of preparation method of 3D networks hybrid inorganic-organic all solid state electrolyte film, the method
Include the following steps：
(1) polyethylene glycol oxide (Mn=1000000) of 0.12g is added in the beaker A of 25ml, is then added dropwise with liquid-transfering gun
The acetonitrile of 2.0g, stirring 2h make it completely dissolved, and 0.55gLiTFSI is then added, and continue stirring and form colourless transparent solution；
(2) 0.15g polyethyleneglycol diglycidylethers (Mn=1000), 0.05g are sequentially added in the beaker B of 25ml
BisphenolA-glycidol ether epoxy resin E44 (epoxide number 190) and 0.4g polyetheramines (Mn=1000) are added in beaker,
The acetonitrile of 2.0g is added dropwise with liquid-transfering gun, is eventually adding 0.3g LAGP nano particle (grain sizes：500 ± 20nm), stirring 6h mixing is equal
It is even, form white presoma mixed liquor.
(3), solution in beaker A is poured into beaker B, after quickly stirring 6h, it is mixed obtains uniformly mixed precursors
Close liquid；Presoma mixed liquor painting is poured into Teflon mould, isothermal reaction obtains white 3D networks afterwards for 24 hours to be had
Machine-inorganic hybridization all solid state electrolyte film；It is put into after solid electrolyte membrane obtained is dried spare in glove box.
The thickness for the 3D network hybrid inorganic-organic all solid state electrolytes that the present embodiment is prepared is 125 μm, is measured
Room-temperature conductivity is 1.34 × 10-5S cm-1。
Embodiment 4
The present embodiment is related to a kind of preparation method of 3D networks hybrid inorganic-organic all solid state electrolyte film, the method
Include the following steps：
(1) polyethylene glycol oxide (Mn=4000000) of 0.24g is added in the beaker A of 25ml, is then added dropwise with liquid-transfering gun
The acetonitrile of 2.0g, stirring 2h make it completely dissolved, and 0.64gLiTFSI is then added, and continue stirring and form colourless transparent solution；
(2) 0.15g polyethyleneglycol diglycidylethers (Mn=2000), 0.05g are sequentially added in the beaker B of 25ml
BisphenolA-glycidol ether epoxy resin E51 (epoxide number 195) and 0.4g polyetheramines (Mn=2000) are added in beaker,
The acetonitrile of 2.0g is added dropwise with liquid-transfering gun, is eventually adding 0.6g LAGP nano particle (grain sizes：500 ± 20nm), stirring 6h mixing is equal
It is even, form white presoma mixed liquor.
(3), solution in beaker A is poured into beaker B, after quickly stirring 6h, it is mixed obtains uniformly mixed precursors
Close liquid；Presoma mixed liquor painting is poured into Teflon mould, white 3D networks are obtained after isothermal reaction 12h to be had
Machine-inorganic hybridization all solid state electrolyte film；It is put into after solid electrolyte membrane obtained is dried spare in glove box.
The thickness for the 3D network hybrid inorganic-organic all solid state electrolytes that the present embodiment is prepared is 100 μm, is measured
Room-temperature conductivity is 2.94 × 10-5S cm-1。
Embodiment 5
The present embodiment is related to a kind of preparation method of 3D networks hybrid inorganic-organic all solid state electrolyte film, the method
Include the following steps：
(1) polyacrylonitrile (Mn=130000) of 0.12g is added in the beaker A of 25ml, is then added dropwise with liquid-transfering gun
The acetonitrile of 2.0g, stirring 2h make it completely dissolved, and 0.45g LiTFSI are then added, and continue stirring and form colourless transparent solution；
(2) 0.15g polyethyleneglycol diglycidylethers (Mn=500), 0.05g are sequentially added in the beaker B of 25ml
BisphenolA-glycidol ether epoxy resin E44 (epoxide number 195) and 0.4g polyetheramines (Mn=2000) are added in beaker,
The acetonitrile of 2.0g is added dropwise with liquid-transfering gun, is eventually adding 0.6g LLZO nano particle (grain sizes：900 ± 50nm), stirring 6h mixing is equal
It is even, form white presoma mixed liquor.
(3), solution in beaker A is poured into beaker B, after quickly stirring 6h, it is mixed obtains uniformly mixed precursors
Close liquid；Presoma mixed liquor painting is poured into Teflon mould, isothermal reaction obtains white 3D networks afterwards for 24 hours to be had
Machine-inorganic hybridization all solid state electrolyte film；It is put into after solid electrolyte membrane obtained is dried spare in glove box.
The thickness for the 3D network hybrid inorganic-organic all solid state electrolytes that the present embodiment is prepared is 110 μm, is measured
Room-temperature conductivity is 6.0 × 10-6S cm-1。
Embodiment 6
The present embodiment is related to a kind of preparation method of 3D networks hybrid inorganic-organic all solid state electrolyte film, the method
Include the following steps：
(1) polysiloxanes (Mn=100000) of 0.24g is added in the beaker A of 25ml, is then added dropwise with liquid-transfering gun
The n,N-Dimethylformamide of 2.0g, stirring 2h make it completely dissolved, and 0.2g LiTFSI are then added, and continue stirring and form nothing
Color clear solution；
(2) 0.15g polyethyleneglycol diglycidylethers (Mn=2000), 0.05g are sequentially added in the beaker B of 25ml
BisphenolA-glycidol ether epoxy resin E44 (epoxide number 165) and 0.4g polyetheramines (Mn=2000) are added in beaker,
The acetonitrile of 2.0g is added dropwise with liquid-transfering gun, is eventually adding 0.3g LLZO micron particles (grain sizes：5 ± 0.5 μm), stirring 6h mixing is equal
It is even, form white presoma mixed liquor.
(3), solution in beaker A is poured into beaker B, after quickly stirring 6h, it is mixed obtains uniformly mixed precursors
Close liquid；Presoma mixed liquor painting is poured into Teflon mould, white 3D networks are obtained after isothermal reaction 12h to be had
Machine-inorganic hybridization all solid state electrolyte film；It is put into after solid electrolyte membrane obtained is dried spare in glove box.
The thickness for the 3D network hybrid inorganic-organic all solid state electrolytes that the present embodiment is prepared is 115 μm, is measured
Room-temperature conductivity is 2.3 × 10-6S cm-1。
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (20)
1. a kind of 3D networks hybrid inorganic-organic all solid state electrolyte, which is characterized in that including：
Three-dimensional network polymer electrolyte matrix as 3D network hybrid inorganic-organic all solid state electrolyte skeletons；
And it is scattered in the oxide electrolyte nano particle inside the three-dimensional network polymer electrolyte matrix or oxidation
The aggregate and lithium salts of object electrolyte nano particle；
The three-dimensional network polymer electrolyte matrix is by reaction monomers, diglycidyl ether type epoxy resin with epoxy group
And its derivative, crosslinking agent and linear polymer are obtained by ring-opening polymerization.
2. all solid state electrolyte according to claim 1, which is characterized in that the linear polymer be selected from polyacrylonitrile,
Polymethyl methacrylate, Kynoar, polystyrene, Kynoar-hexafluoropropene, polypropylene oxide, polyoxyethylene
It is one or more in alkene, polysiloxanes, polyurethane or polysulfones, the range of number-average molecular weight of the linear polymer is 100,000~
4000000.
3. all solid state electrolyte according to claim 1, which is characterized in that the lithium salts is selected from lithium perchlorate, hexafluoro arsenic
Sour lithium, lithium hexafluoro phosphate, LiBF4, trifluoromethyl sulfonic acid lithium, trifluoromethane sulfonic acid imine lithium, double fluorine sulfimide lithiums and
It is one or more in difluorine oxalic acid boracic acid lithium.
4. all solid state electrolyte according to claim 1, which is characterized in that the lithium salts rubs with the linear polymer
You are than being 1：(4~50).
5. all solid state electrolyte according to claim 1, which is characterized in that the reaction monomers choosing with epoxy group
From one or more in glycidol ethers compound.
6. all solid state electrolyte according to claim 5, which is characterized in that the glycidol ethers compound is selected from 3-
It is glycidyl ether oxypropyltriethoxysilane, polyethyleneglycol diglycidylether, poly- (propylene glycol) diglycidyl ether, new
It is one or more in neopentyl glycol diglycidyl glycerin ether and poly- (dimethyl siloxane) diglycidyl ether.
7. all solid state electrolyte according to claim 1, which is characterized in that the reaction monomers with epoxy group
Number-average molecular weight is 300~20000Da.
8. all solid state electrolyte according to claim 1, which is characterized in that the reaction monomers with epoxy group
Number-average molecular weight is 500~10000Da.
9. all solid state electrolyte according to claim 1, which is characterized in that the diglycidyl ether type epoxy resin and its
The number-average molecular weight of derivative is 400~20000Da, epoxide number 160~290.
10. all solid state electrolyte according to claim 1, which is characterized in that the diglycidyl ether type epoxy resin and
Its derivative is one or more in E44, E51, E52, E54, E55 and E56D.
11. all solid state electrolyte according to claim 1, which is characterized in that the crosslinking agent is at least containing there are one amine
The compound of base.
12. all solid state electrolyte according to claim 11, which is characterized in that the crosslinking agent is selected from containing at least one
The compound of amido, the compound are selected from alkane hydrocarbons and their derivates, polyene hydrocarbons and their derivates, polyalkylene oxide and its derivative
Or cellulose and its derivates.
13. all solid state electrolyte according to claim 12, which is characterized in that the derivative of the alkane is selected from alkane
Halides, the derivative of the polyolefin is selected from the halides of polyolefin, the derivative of the polyalkylene oxide is selected from polyalkylene oxide
Halides, the polyalkylene oxide be selected from polyethylene oxide or polypropylene oxide.
14. all solid state electrolyte according to claim 11, which is characterized in that the crosslinking agent be selected from polyethyleneimine,
It is one or more in polypropyleneimine, polyetheramine.
15. all solid state electrolyte according to claim 11, which is characterized in that the number-average molecular weight of the crosslinking agent is
230 to 10000Da.
16. all solid state electrolyte according to claim 1, which is characterized in that the reaction monomers with epoxy group,
The mass ratio of diglycidyl ether type epoxy resin and its derivative, crosslinking agent is (1~3):(1~3):(4~8).
17. all solid state electrolyte according to claim 1, which is characterized in that the oxide electrolyte nano particle choosing
From Li14Zn(GeO4)4、LiZr2Si2PO12、Li1.3Al0.3Ti1.7(PO4)3、Li1.5Al0.5Ge1.5P3O12、Li7La3Zr2O12With
Li6.75La3Zr1.75Ta0.25O12In it is one or more, grain size be 50nm~900nm, the oxide electrolyte nano particle
Aggregate grain size be 1 μm~5 μm.
18. all solid state electrolyte according to claim 1, which is characterized in that the oxide electrolyte nano-particle accounts for
The weight hundred of reaction monomers, diglycidyl ether type epoxy resin and its derivative and the sum of crosslinking agent quality with epoxy group
Point than being 20wt%~50wt%, the linear polymer accounts for reaction monomers with epoxy group, diglycidyl ether type epoxy
The weight percent of the sum of resin and its derivative and crosslinking agent quality is 5wt%~30wt%.
19. all solid state electrolyte according to claim 1, which is characterized in that the thickness of all solid state electrolyte is 20
~200 μm.
20. a kind of lithium secondary battery, which is characterized in that including the 3D networks described in claim 1~19 any one it is organic-nothing
Machine hydridization all solid state electrolyte.
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