CN109728342A - A kind of selfreparing composite solid electrolyte, quasi-solid electrolyte and lithium battery - Google Patents
A kind of selfreparing composite solid electrolyte, quasi-solid electrolyte and lithium battery Download PDFInfo
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- CN109728342A CN109728342A CN201811564924.9A CN201811564924A CN109728342A CN 109728342 A CN109728342 A CN 109728342A CN 201811564924 A CN201811564924 A CN 201811564924A CN 109728342 A CN109728342 A CN 109728342A
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- solid electrolyte
- selfreparing
- electrolyte
- composite
- composite solid
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 132
- 239000002131 composite material Substances 0.000 title claims abstract description 115
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 56
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000003792 electrolyte Substances 0.000 claims abstract description 56
- 229920006299 self-healing polymer Polymers 0.000 claims abstract description 25
- 229910003480 inorganic solid Inorganic materials 0.000 claims abstract description 24
- 239000011244 liquid electrolyte Substances 0.000 claims abstract description 21
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 18
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 7
- 230000005611 electricity Effects 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000002223 garnet Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 210000001787 dendrite Anatomy 0.000 abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 26
- 239000002002 slurry Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- 229910052786 argon Inorganic materials 0.000 description 13
- 210000004027 cell Anatomy 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- -1 formula 2 Chemical class 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 6
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 6
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000004087 circulation Effects 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 229910008251 Zr2O2 Inorganic materials 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 229940044658 gallium nitrate Drugs 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000035876 healing Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 125000006091 1,3-dioxolane group Chemical class 0.000 description 1
- 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 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910009866 Ti5O12 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- PHDNGVHIVIYFJP-UHFFFAOYSA-N [Zr].[La].[Li] Chemical compound [Zr].[La].[Li] PHDNGVHIVIYFJP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
The present invention relates to field of batteries, more particularly to a kind of selfreparing composite solid electrolyte, quasi-solid electrolyte and lithium battery.The selfreparing composite solid electrolyte includes self-healing polymers and inorganic solid electrolyte, and the self-healing polymers include selfreparing group, and the selfreparing group is selected from urea groups.Selfreparing composite solid electrolyte butt of the invention is bent, with flexibility, it is able to suppress the growth of Li dendrite, the service life that there is composite solid electrolyte self-repair function battery can be improved, the quasi-solid electrolyte that fraction of electrolyte containing lithium salt is prepared, which is added, in selfreparing composite solid electrolyte can make electrolyte keep higher conductivity, the content that liquid electrolyte containing lithium salt can be reduced simultaneously, improves the safety of battery.
Description
Technical field
The present invention relates to field of batteries, more particularly to a kind of selfreparing composite solid electrolyte, quasi-solid electrolyte and
Lithium battery.
Background technique
Lithium metal has high specific capacity (3860mAh g-1) and minimum electrochemical potentials (- 3.040V is relative to standard
Hydrogen electrode), it is the ideal negative electrode material for preparing lithium battery.However the development of lithium metal battery is but limited to take off/embedding lithium repeatedly
Uncontrollable lithium electro-deposition behavior causes the growth of Li dendrite to cause battery short circuit and energy loss in cyclic process.And solid
The coulombic efficiency that the generation of electrolyte interface layer (Solid Electrolyte Interphase, SEI) will cause battery reduces
It is deteriorated with cycle performance of battery.SEI layers are caused to collapse in addition, the expansion of lithium an- ode immense volume can be such that interfacial stress constantly accumulates
The continuous increase collapsed with cell interface resistance.
Currently, the method for improving lithium an- ode stability, which specifically includes that, introduces artificial SEI layers, interface protective layer, electrolysis
Matter additive etc. and the lithium metal pillared composite for constructing 3D, however since the lower conductivity of boundary layer and poor machinery are steady
It is qualitative that battery is caused to be only capable of using at lower current densities, at the same electrolyte additive it is continuous consumption can also make it is cell performance
Can constantly it decline, and the introducing of additional pillared composite can also reduce the energy density of battery entirety.
Summary of the invention
The purpose of the present invention is to provide a kind of selfreparing composite solid electrolyte, quasi-solid electrolyte and lithium batteries, originally
The selfreparing composite solid electrolyte of invention has self-repair function, inhibits the growth of Li dendrite, composite solid electrolyte has
The service life of battery can be improved in self-repair function, and fraction of electrolysis containing lithium salt is added in selfreparing composite solid electrolyte
The composite electrolyte (i.e. quasi-solid electrolyte) that liquid is prepared can make electrolyte keep higher conductivity, while can reduce
The content of liquid electrolyte containing lithium salt improves the safety of battery to overcome the drawbacks described above of the prior art.
In order to achieve the above objects and other related objects, an aspect of of the present present invention provides a kind of selfreparing composite solid electrolysis
Matter, the selfreparing composite solid electrolyte include self-healing polymers and inorganic solid electrolyte, the self-healing polymers
Including selfreparing group, the selfreparing group is selected from urea groups.
In certain embodiments of the present invention, at least part of end group of the self-healing polymers includes the selfreparing
Group.
In certain embodiments of the present invention, the self-healing polymers are in such as formula 1,2 compound represented of formula
One or two kinds of combinations,
In certain embodiments of the present invention, the self-healing polymers are selected from compound as shown in Equation 1 and such as formulas 2
Compound combination, wherein compound as shown in Equation 1 and the molar ratio selected from such as compound of formula 2 are 1:1~6:1.
In certain embodiments of the present invention, the selfreparing composite solid electrolyte further includes any of the following conditions
Item is multinomial:
A1) the selfreparing composite solid electrolyte be layer body, the selfreparing composite solid electrolyte with a thickness of 10
~80 μm, preferably 10~50 μm；
A2) inorganic solid electrolyte is selected from the oxide of cubic garnet structure, is preferably selected from GaxLi7- 3xLa3Zr2O12, wherein 0≤x≤0.5, the partial size of the inorganic solid electrolyte is 200~1000nm；
A3) inorganic solid electrolyte is 10~50% in the quality accounting of selfreparing composite solid electrolyte, preferably
It is 20~40%.
The preparation method of another aspect of the present invention offer selfreparing composite solid electrolyte, comprising: prepare inorganic solid-state
The inorganic solid electrolyte is added in self-healing polymers and obtains dispersion by electrolyte, coating, drying.
Another aspect of the present invention provides a kind of composite electrolyte, and the composite electrolyte includes of the present invention reviews one's lessons by oneself
Multiple composite solid electrolyte and liquid electrolyte, the liquid electrolyte the quality accounting of composite electrolyte be 10%~
60%, preferably 20%~50%, the liquid electrolyte includes lithium salts.
The preparation method of another aspect of the present invention offer composite electrolyte, comprising: multiple to selfreparing of the present invention
It closes in solid electrolyte and liquid electrolyte containing lithium salt is added.
Another aspect of the present invention provides selfreparing composite solid electrolyte and/or composite electrolyte of the present invention in electricity
Purposes in pond.
Another aspect of the present invention provides a kind of lithium battery, including selfreparing composite solid electrolyte of the present invention
And/or composite electrolyte of the present invention.
Detailed description of the invention
Fig. 1 is selfreparing mechanism figure of the invention.
Fig. 2 is scanning electron microscope (SEM) map of the selfreparing composite solid electrolyte of the embodiment of the present invention 1.
Fig. 3 is the optics map of the selfreparing composite solid electrolyte of the embodiment of the present invention 1.
Fig. 4 is the selfreparing optics map of the selfreparing composite solid electrolyte of the embodiment of the present invention 1.
Fig. 5 is selfreparing scanning electron microscope (SEM) map of the selfreparing composite solid electrolyte of the embodiment of the present invention 1.
Fig. 6 is the performance comparison figure for the lithium Symmetrical cells that the embodiment of the present invention 7 and comparative example 1 are prepared respectively.
Fig. 7 is that the LTO/Li half-cell 0.2C first charge-discharge voltage that the embodiment of the present invention 8 and comparative example 2 are prepared respectively is bent
Line.
Fig. 8 is that the LTO/Li half-cell 1C first charge-discharge voltage that the embodiment of the present invention 8 and comparative example 2 are prepared respectively is bent
Line.
Fig. 9 is the performance comparison under the LTO/Li half-cell different multiplying that the embodiment of the present invention 8 and comparative example 2 are prepared respectively
Figure.
Figure 10 is the LTO/Li half-cell 0.2C first charge-discharge voltage curve of comparative example 3 of the present invention preparation.
Specific embodiment
The following detailed description of selfreparing composite solid electrolyte, quasi-solid electrolyte and lithium battery according to the present invention.
First aspect present invention provides a kind of selfreparing composite solid electrolyte, the selfreparing composite solid electrolyte packet
Self-healing polymers and inorganic solid electrolyte are included, the self-healing polymers include selfreparing group, the selfreparing group
Selected from urea groups.The self-repair function of electrolyte can be achieved due to the effect of hydrogen bond for the selfreparing group of the self-healing polymers.
By taking urea groups as an example, as shown in Figure 1, hydrogen bond selfreparing mechanism, which is urea groups, forms cross-linked structure by Hydrogenbond, after material damage
Section is contacted, realizes material selfreparing using the interaction between hydrogen bond.
In selfreparing composite solid electrolyte provided by the present invention, at least part of end group packet of self-healing polymers
Include the selfreparing group.
In selfreparing composite solid electrolyte provided by the present invention, the self-healing polymers are selected from such as formula 1,2 institute of formula
The combination of one or both of the compound shown,
In selfreparing composite solid electrolyte provided by the present invention, the self-healing polymers are selected from as shown in Equation 1
The combination of compound and the compound such as formula 2, wherein compound as shown in Equation 1 and the molar ratio selected from such as compound of formula 2
For 1:1~6:1,1:1~4:1 or 4:1~6:1, preferably 4:1.
In selfreparing composite solid electrolyte provided by the present invention, the film thickness of the composite solid electrolyte is 10~
80 μm, 10~50 μm or 50~80 μm, preferably 10~50 μm.
In selfreparing composite solid electrolyte provided by the present invention, the inorganic solid electrolyte is selected from cubic garnet
The oxide of structure.More specifically, the inorganic solid electrolyte is selected from the oxide of the lithium lanthanum zirconium of gallium doping, and chemical general formula is
GaxLi7-3xLa3Zr2O12, wherein 0≤x≤0.5.
In selfreparing composite solid electrolyte provided by the present invention, the partial size of the inorganic solid electrolyte be selected from
200~1000nm, 200~300nm, 300~600nm or 600~1000nm, preferably 300~600nm.
In selfreparing composite solid electrolyte provided by the present invention, the inorganic solid electrolyte is in selfreparing composite solid
The quality accounting of state electrolyte is 10~50%, 10~20%, 20~40% or 40~50%, the inorganic solid electrolyte
It is preferably 20~40% in the quality accounting of selfreparing composite solid electrolyte.Within the scope of above-mentioned quality accounting, selfreparing is multiple
Close solid state electrolysis mass-energy has preferable mechanical performance and self-reparing capability simultaneously.
The preparation method of second aspect of the present invention offer selfreparing composite solid electrolyte, comprising: prepare inorganic solid-state electricity
The inorganic solid electrolyte is added in self-healing polymers and obtains dispersion by Xie Zhi, and coated, drying process is made.
In the preparation method of selfreparing composite solid electrolyte provided by the present invention, the system of the inorganic solid electrolyte
Standby includes the in the mixed solvent that gallium nitrate, lithium nitrate, lanthanum nitrate, acetylacetone,2,4-pentanedione zirconium are dissolved in alcohol-water, controls alcohol-water
Volume ratio is 2:1~5:1, and citric acid, which is added, to be complexed metal ion in solution sufficiently to obtain uniform colloidal sol.Gained colloidal sol is first
It is heated 4 hours at 60~90 DEG C, then heats to 180~200 DEG C and continue to obtain gel in heating 8~12 hours, finally 200
Xerogel is sufficiently dried to obtain at~250 DEG C.Gained xerogel is placed in Muffle furnace and is calcined 4~6 hours for 700~1000 DEG C,
Oxide inorganic solid electrolyte can be obtained after cooling.
In the preparation method of selfreparing composite solid electrolyte provided by the present invention, the selfreparing composite solid electrolysis
The preparation of matter includes being dispersed in self-healing polymers in non-water system dispersing agent, and inorganic oxide electrolyte is then added and stirs
It mixes 8~12 hours, slurry is concentrated in agitating and heating under the conditions of 50~100 DEG C, and control stock quality concentration is 40~60%, and by institute
It obtains slurry and stands progress deaeration processing in 0~1 hour.Slurry is coated on by substrate using plate applicator, by gained composite solid
Dielectric film is placed in 60~80 DEG C drying 10~12 hours in heating plate, is then transferred to 60~80 in the glove box full of argon gas
DEG C continue to obtain selfreparing composite solid electrolyte in dry 8~10 hours.
In the preparation method of selfreparing composite solid electrolyte provided by the present invention, divide in composite solid electrolyte preparation
Powder is selected from n,N-Dimethylformamide, N-Methyl pyrrolidone, acetonitrile, ethyl alcohol, dimethyl sulfoxide, one of acetone or more
Kind.The substrate is selected from one of polytetrafluoroethylene (PTFE), copper foil, aluminium foil or a variety of.
The third aspect of the present invention provides a kind of composite electrolyte, and the composite electrolyte includes of the present invention reviews one's lessons by oneself
Multiple composite solid electrolyte and liquid electrolyte, the liquid electrolyte the quality accounting of composite electrolyte be 10%~
60%, preferably 20%~50%, the liquid electrolyte includes lithium salts.The composite electrolyte is quasi-solid electrolyte, institute
State quasi-solid electrolyte be it is a kind of between liquid electrolyte and it is all solid state between solid-liquid mixing electrolyte, it can be to greatest extent
Ground keeps the high mobility of liquid electrolyte, while having the performance steady in a long-term of solid electrolyte.
In composite electrolyte provided by the present invention, the liquid electrolyte is 10% in the quality accounting of composite electrolyte
~60%, 10~20%, 20~50%, 50~60%, preferably 20%~50%.
In composite electrolyte provided by the present invention, the liquid electrolyte includes lithium salts, and the lithium salts is selected from double trifluoros
One of sulfonyloxy methyl imine lithium, lithium nitrate, lithium hexafluoro phosphate, lithium perchlorate or a variety of combinations, mole of the lithium salts
Concentration is selected from 0.5~1.5mol L-1。
In composite electrolyte provided by the present invention, solvent is selected from ethylene carbonate, carbonic acid two in the liquid electrolyte
One of ethyl ester, methyl ethyl carbonate, 1,3- dioxolanes, glycol dimethyl ether, diethylene glycol dimethyl ether are a variety of.
The fourth aspect of the present invention provides the preparation method of aforementioned composite electrolyte, is included in glove box multiple to selfreparing
Liquid electrolyte containing lithium salt, which is added, in conjunction solid electrolyte butt can be obtained composite electrolyte, i.e. quasi-solid electrolyte.
In the preparation method of composite electrolyte provided by the present invention, the additional amount of the liquid electrolyte containing lithium salt is
20~40 μ L.
In the preparation method of composite electrolyte provided by the present invention, the environment of the glove box is small in water, oxygen value
In the glove box full of argon gas of 1ppm.
The fifth aspect of the present invention provides selfreparing composite solid electrolyte and/or composite electrolyte of the present invention in electricity
Purposes in pond.
The sixth aspect of the present invention provides a kind of lithium battery, including anode, cathode, further includes selfreparing of the present invention
Composite solid electrolyte and/or composite electrolyte of the present invention.
In lithium battery provided by the present invention, positive material is selected from cobalt acid lithium, LiFePO4, nickel ion doped, nickel cobalt
One of LiMn2O4 is a variety of, and the anode further includes binder, conductive agent, and the mass fraction of binder is 5~15%, leads
The mass fraction of electric agent is 5~15%.
In lithium battery provided by the present invention, cathode is in natural graphite, artificial graphite, lithium titanate, lithium metal, silicon
One or more.
The beneficial effects of the present invention are:
Selfreparing composite solid electrolyte butt of the invention is bent, have flexibility, and can selfreparing, be able to suppress lithium
The growth of dendrite, the service life that there is composite solid electrolyte self-repair function battery can be improved.
The addition of selfreparing composite solid electrolyte can make composite electrolyte of the invention (i.e. quasi-solid electrolyte)
With self-repair function, quasi-solid electrolyte has good conductivity, can stablize lithium an- ode and can effectively inhibit lithium
The growth of dendrite reduces reacting between lithium metal and electrolyte, while can reduce the content of liquid electrolyte containing lithium salt, mentions
The safety of high battery.
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
In the following embodiments, reagent, material and the instrument used such as not special explanation, it is commercially available to obtain
?
One, the preparation of selfreparing composite solid electrolyte
Embodiment 1
(1)Ga0.25Li6.25La3Zr2O12The preparation of inorganic solid electrolyte
According to Ga0.25Li6.25La3Zr2O12Stoichiometric ratio weigh gallium nitrate, lithium nitrate, lanthanum nitrate, levulinic respectively
Ketone zirconium is uniformly dissolved in the in the mixed solvent of alcohol-water, and wherein the content of lithium nitrate wants excess 10% to make up high-temperature calcination process
The loss of middle lithium source.The volume ratio of ethyl alcohol and water is 4:1, and cation in the abundant complex solution of citric acid is then added and obtains white
Colloidal sol, and then heated 4 hours under the conditions of 60 DEG C, then heat to 180 degree and heat and obtain gel in 10 hours, and 250
Gel is sufficiently dried to obtain xerogel under the conditions of DEG C.Gained xerogel is placed in 800 DEG C of calcinings in Muffle furnace and obtains oxygen within 5 hours
Compound solid electrolyte.
(2) preparation of selfreparing composite solid electrolyte
Take 0.3g by such as compound of formula 1 and formula 2 is that the self-healing polymers that 4:1 is mixed to get are dissolved in 1.2g in molar ratio
In ethyl alcohol, the Ga that 0.128g partial size is 500nm is then added0.25Li6.25La3Zr2O2Solid electrolyte, at room temperature magnetic agitation
12 hours.Then slurry is placed in stirring in 60 DEG C of heating plates to be concentrated into the mass concentration of slurry is 40~50%, then will slurry
Material stands 1 hour and is de-gassed.Using plate cladding process, slurry is evenly applied in polytetrafluoroethylene (PTFE) substrate, is arranged
Blade thickness is 250 μm.Slurry is evenly applied in substrate, 60 DEG C of heating in heating plate are set in transfer after film layer stands 2 hours
10 hours, it is then transferred to the glove box (H full of argon gas2O≤1ppm, O2≤ 1ppm) in 60 DEG C continue heating 12 hours
Keep it sufficiently dry.
Fig. 2 is scanning electron microscope (SEM) map of the selfreparing composite solid electrolyte of the embodiment of the present invention 1.It can be with from Fig. 2
Find out, inorganic solid electrolyte even particulate dispersion is in the substrate of polymer, average grain diameter 500nm.
Fig. 3 is the optics map of the selfreparing composite solid electrolyte of the embodiment of the present invention 1.From figure 3, it can be seen that reviewing one's lessons by oneself
Multiple composite solid electrolyte has flexibility well, and average thickness is 25 microns.
Fig. 4 is the selfreparing optics map of the selfreparing composite solid electrolyte of the embodiment of the present invention 1.It can from Fig. 4
Out, the slight crack at room temperature after half an hour in electrolyte has apparent healing, and slight crack almost heals after two hours, this card
The self-reparing capability of selfreparing composite solid electrolyte is illustrated.
Fig. 5 is selfreparing scanning electron microscope (SEM) map of the selfreparing composite solid electrolyte of the embodiment of the present invention 1.From
Fig. 5 can be seen that after after an hour, and slight crack has apparent healing, this further demonstrates selfreparing composite solid from microcosmic
The self-repair function of state electrolyte.
Embodiment 2
(1)Ga0.5Li5.5La3Zr2O12The preparation of inorganic solid electrolyte
According to Ga0.5Li5.5La3Zr2O12Stoichiometric ratio weigh gallium nitrate, lithium nitrate, lanthanum nitrate, acetylacetone,2,4-pentanedione respectively
Zirconium is uniformly dissolved in the in the mixed solvent of alcohol-water, and wherein the content of lithium nitrate wants excess 10% to make up in high-temperature calcination process
The loss of lithium source.The volume ratio of ethyl alcohol and water is 4:1, and cation in the abundant complex solution of citric acid is then added and obtains white
And then colloidal sol heats 4 hours under the conditions of 60 DEG C, then heat to 180 degree heating and obtain gel in 10 hours, and at 250 DEG C
Under the conditions of gel is sufficiently dried to obtain xerogel.Gained xerogel is placed in 800 DEG C of calcinings in Muffle furnace to be aoxidized within 5 hours
Object solid electrolyte.
(2) composite solid electrolyte
The self-healing polymers for taking 0.3g as shown in Equation 1 are uniformly dissolved in 1.2g ethyl alcohol, and 0.128g partial size is then added and is
The Ga of 500nm0.25Li6.25La3Zr2O2Solid electrolyte, at room temperature magnetic agitation 12 hours.Slurry is then placed in 60 DEG C to add
It is 40~50% that stirring, which is concentrated into the mass concentration of slurry, on hot plate, and slurry is then stood 1 hour and is de-gassed.Using
Slurry is evenly applied in polytetrafluoroethylene (PTFE) substrate by plate cladding process, and setting blade thickness is 250 μm.Slurry is uniformly applied
It is overlying in substrate, transfer is set and heated 10 hours for 60 DEG C in heating plate after film layer stands 2 hours, is then transferred to full of argon gas
Glove box (H2O≤1ppm, O2≤ 1ppm) in 60 DEG C continue heating and make within 12 hours it sufficiently dry.
Embodiment 3
(1)Ga0.25Li6.25La3Zr2O12The preparation of inorganic solid electrolyte
According to Ga0.25Li6.25La3Zr2O12Stoichiometric ratio weigh a certain amount of gallium oxide respectively, lithium carbonate, oxidation
Lanthanum, zirconium oxide, wherein the content of lithium carbonate wants excess 10% to make up the loss of lithium source in high-temperature calcination process.Solid powder is first
First ball milling 15h and then 900 DEG C of roasting 6h, continues thereafter with ball milling 15h and obtains electrolyte powder.
(2) composite solid electrolyte
The self-healing polymeric compounds for taking 0.3g as shown in Equation 2 are dissolved in 1.2g ethyl alcohol, and 0.3g is then added
Ga0.25Li6.25La3Zr2O2Solid electrolyte, at room temperature magnetic agitation 12 hours.Then slurry is placed in 60 DEG C of heating plates
The mass concentration that stirring is concentrated into slurry is 40~50%, and slurry is then stood 1 hour and is de-gassed.It is applied using plate
Method is covered, slurry is evenly applied in polytetrafluoroethylene (PTFE) substrate, setting blade thickness is 250 μm.Slurry is evenly applied to base
On bottom, transfer is set and is heated 10 hours for 60 DEG C in heating plate after film layer stands 2 hours, is then transferred to the gloves full of argon gas
Case (H2O≤1ppm, O2≤ 1ppm) in 60 DEG C continue heating and make within 12 hours it sufficiently dry.
Two, the preparation of composite electrolyte (quasi-solid electrolyte)
Embodiment 4
In the glove box full of argon gas that water, oxygen value are respectively less than 1ppm, the selfreparing composite solid that is obtained to embodiment 1
30 μ L electrolyte containing lithium salt are added in electrolyte butt can be obtained quasi-solid electrolyte.
Embodiment 5
In the glove box full of argon gas that water, oxygen value are respectively less than 1ppm, the selfreparing composite solid that is obtained to embodiment 2
30 μ L electrolyte containing lithium salt are added in electrolyte butt can be obtained quasi-solid electrolyte.
Embodiment 6
In the glove box full of argon gas that water, oxygen value are respectively less than 1ppm, the selfreparing composite solid that is obtained to embodiment 3
30 μ L electrolyte containing lithium salt are added in electrolyte butt can be obtained quasi-solid electrolyte.
Three, the preparation of lithium Symmetrical cells and battery performance test
Embodiment 7
In the glove box (H for being full of argon gas2O≤1ppm, O2≤ 1ppm) in, successively according to lithium piece, the quasi- solid-state of embodiment 4
Electrolyte, lithium piece sequence assemble lithium Symmetrical cells, by after assembled battery standing 0.5 hour at room temperature respectively in 3mA
cm-2-1mAh cm-2, 5mA cm-2-1mAh cm-2, 10mA cm-2-1mAh cm-2, 20mA cm-2-1mAh cm-2Condition into
The charge-discharge performance of row battery is tested.Test results are shown in figure 6.
Comparative example 1
In the glove box (H for being full of argon gas2O≤1ppm, O2≤ 1ppm) in, successively according to lithium piece, commercialization Celgard 2325
Diaphragm, lithium piece sequence assemble lithium Symmetrical cells, by after assembled battery standing 0.5 hour at room temperature respectively in 1mA cm-2-
1mAh cm-2, 3mA cm-2-1mAh cm-2, 5mA cm-2-1mAh cm-2, 10mA cm-2-1mAh cm-2Condition carry out battery
Charge-discharge performance test.Test results are shown in figure 6.
Fig. 6 is the performance comparison figure for the lithium Symmetrical cells that the embodiment of the present invention 7 and comparative example 1 are prepared respectively.In 3mA cm-2,1mAh cm-2Under the conditions of, it is not observed in preceding ten circulations using the lithium Symmetrical cells of commercial 2325 diaphragm of Celgard
Apparent voltage fluctuation, ten circulation after voltage fluctuation gradually increase.This show the increase battery polarization with cycle-index by
It is gradually bigger.Especially in biggish current density (10mA cm-2, 20mA cm-2) under especially it is observed that apparent voltage wave
Dynamic, this, which illustrates high current density also, can make to increase using the battery polarization of commercialization 2325 diaphragm of Celgard.And use quasi- solid-state
The lithium Symmetrical cells of electrolyte show stable charge and discharge platform in charge and discharge cycles, and with the increase of cycle-index electricity
Pressure is still very stable not to observe apparent voltage fluctuation, and overpotential is much smaller than using commercialization 2325 diaphragm of Celgard
Lithium Symmetrical cells.In 3mA cm-2,1mAh cm-2Under the conditions of, the polarization using the lithium Symmetrical cells of quasi-solid electrolyte only has
36mV and can stablize circulation 1000 times.Especially in superhigh-current-density (10mA cm-2, 20mA cm-2) under the conditions of, it adopts
Lower overpotential is still shown with the lithium battery of quasi-solid electrolyte, and still it is observed that stable charge and discharge platform,
Its overpotential is significantly lower than the lithium Symmetrical cells using commercialization 2325 diaphragm of Celgard, wherein 10mA cm-2-1mAh cm-2Item
The overpotential of battery is 150mV, 20mA cm under part-2-1mAh cm-2Under the conditions of overpotential be 240mV.Especially in 20mA
cm-2-1mAh cm-2Under the conditions of use hybrid solid-state electrolyte lithium battery can with overlength stablize circulation 1500 times.Therefore, it uses
Better performance is shown under the big multiplying power of lithium Symmetrical cells and long-time cycling condition of quasi-solid electrolyte.It also probes into simultaneously
Large capacity (10mA cm-2-10mAh cm-2) under the conditions of battery charge-discharge performance, the lithium using hybrid solid-state electrolyte is symmetrical
Battery can stablize circulation 200 hours and show lesser battery polarization.This shows the lithium battery using quasi-solid electrolyte
The battery face amount of superelevation can be provided in practical applications.
Four, the preparation of LTO/Li half-cell and battery performance test
Embodiment 8
(1)Li4Ti5O12The preparation method of electrode slice
Li is weighed respectively according to the mass ratio of 8:1:14Ti5O12, Kynoar (PVDF), then Super P is added
Nmp solvent prepares electrode slurry, the revolving speed that electrode slurry is placed in 500rpm in batch mixer is mixed 30s, then 2000rpm revolving speed is mixed
10min, and uniform electrode slurry can be obtained in degassing 10min under 2200rpm revolving speed.
Using plate cladding process, slurry is evenly applied in copper foil substrate, is transferred in vacuum drying oven after standing 2 hours
60 DEG C drying 12 hours.Electrode slice after drying is punched out the disk for being cut into that diameter is 12mm after twin rollers roll-in.
(2) preparation of polyvinylidene difluoride film
Certain weight poly (vinylidene fluoride) is uniformly dissolved in nmp solvent, the mass concentration for controlling PVDF is 0.05g ml-1, so
It is evenly applied in substrate of glass afterwards, control blade thickness is 50 μm.Film layer is stood 2 hours, is then transferred to
The drying 12 hours of 60 DEG C of vacuum drying oven.
(3) preparation of LTO/Li half-cell
In the glove box (H for being full of argon gas2O≤1ppm, O2≤ 1ppm) in, it is successively (quasi- according to lithium piece, composite electrolyte membrane
Solid electrolyte), Li4Ti5O12The sequence of electrode slice assembles lithium battery.Wherein, at composite electrolyte membrane (quasi-solid electrolyte)
And Li4Ti5O12To add one layer of PVDF thin film between electrode slice, by assembled battery standing 0.5 hour, at room temperature at different times
Electrochemical property test is carried out under rate, wherein test voltage is 1.1-2.4V.
Comparative example 2
In the glove box (H for being full of argon gas2O≤1ppm, O2≤ 1ppm) in, successively according to lithium piece, commercialization Celgard 2325
Diaphragm, Li4Ti5O12The sequence of electrode slice assembles lithium battery.By assembled battery standing 0.5 hour, at room temperature at different times
Electrochemical property test is carried out under rate, wherein test voltage is 1.1-2.4V.
Comparative example 3
In the glove box (H for being full of argon gas2O≤1ppm, O2≤ 1ppm) in, successively according to lithium piece, pure PVDF diaphragm,
Li4Ti5O12The sequence of electrode slice assembles lithium battery.By assembled battery standing 0.5 hour, at room temperature under different multiplying into
Row electrochemical property test, wherein test voltage is 1.1-2.4V.
Fig. 7 is that the LTO/Li half-cell 0.2C first charge-discharge voltage that the embodiment of the present invention 8 and comparative example 2 are prepared respectively is bent
Line.As can be seen from Figure 7: using the ratio that discharges for the first time under the conditions of the LTO/Li half-cell 0.2C of commercialization 2325 diaphragm of Celgard
Capacity is 149mAh g-1, and use LTO/Li half-cell of the embodiment 8 based on the quasi-solid electrolyte preparation of embodiment 4 for the first time
Specific discharge capacity is up to 157mAh g-1, compared to use half-cell of the comparative example 2 based on commercial 2325 diaphragm of Celgard in 0.2C
Under the conditions of show higher specific capacity.
Fig. 8 is the first charge-discharge under the conditions of the LTO/Li half-cell 1C that the embodiment of the present invention 8 and comparative example 2 are prepared respectively
Voltage curve.As can be seen from the figure: being discharged for the first time using the half-cell based on commercial 2325 diaphragm of Celgard under this condition
Specific capacity is 129mAh g-1, and use the half-cell first discharge specific capacity of the quasi-solid electrolyte preparation based on embodiment 4 can
To reach 143mAh g-1, to be apparently higher than the half-cell discharge specific capacity using commercialization 2325 diaphragm of Celgard.
Fig. 9 is the performance comparison figure under LTO/Li half-cell different multiplying prepared by the embodiment of the present invention 8 and comparative example 2.
As can be seen from the figure: using based on embodiment 4 quasi-solid electrolyte preparation LTO/Li half-cell ratio using Celgard every
The half-cell of film shows better high rate performance.
Figure 10 is the LTO/Li half-cell 0.2C first charge-discharge voltage curve of comparative example 3 of the present invention.Comparative example 3 is to adopt
Use pure PVDF as the performance of the LTO/Li half-cell of diaphragm.As can be seen from Figure 10: using based on pure PVDF as diaphragm
LTO/Li half-cell, first discharge specific capacity only have 128mAh g-1, performance will be lower than solid using the standard based on embodiment 4
The performance of the LTO/Li half-cell of state electrolyte preparation.
The above, only presently preferred embodiments of the present invention, not to the present invention in any form with substantial limitation,
It should be pointed out that under the premise of not departing from the method for the present invention, can also be made for those skilled in the art
Several improvement and supplement, these are improved and supplement also should be regarded as protection scope of the present invention.All those skilled in the art,
Without departing from the spirit and scope of the present invention, when made using disclosed above technology contents it is a little more
Dynamic, modification and the equivalent variations developed, are equivalent embodiment of the invention；Meanwhile all substantial technologicals pair according to the present invention
The variation, modification and evolution of any equivalent variations made by above-described embodiment, in the range of still falling within technical solution of the present invention.
Claims (10)
1. a kind of selfreparing composite solid electrolyte, the selfreparing composite solid electrolyte includes self-healing polymers and inorganic
Solid electrolyte, the self-healing polymers include selfreparing group, and the selfreparing group is selected from urea groups.
2. selfreparing composite solid electrolyte according to claim 1, which is characterized in that the self-healing polymers are at least
Partial end group includes the selfreparing group.
3. selfreparing composite solid electrolyte according to claim 1, which is characterized in that the self-healing polymers are selected from
Such as the combination of one or both of formula 1,2 compound represented of formula,
4. selfreparing composite solid electrolyte according to claim 1, which is characterized in that the self-healing polymers are selected from
The combination of compound and the compound such as formula 2 as shown in Equation 1, wherein compound as shown in Equation 1 and the compound such as formula 2
Molar ratio be 1:1~6:1.
5. selfreparing composite solid electrolyte according to claim 1, which is characterized in that the selfreparing composite solid electricity
Solution matter further includes any one or multinomial of the following conditions:
A1) the selfreparing composite solid electrolyte be layer body, the selfreparing composite solid electrolyte with a thickness of 10~80 μ
M, preferably 10~50 μm；
A2) inorganic solid electrolyte is selected from the oxide of cubic garnet structure, is preferably selected from GaxLi7-3xLa3Zr2O12,
Wherein 0≤x≤0.5, the partial size of the inorganic solid electrolyte are 200~1000nm；
A3) inorganic solid electrolyte is 10~50%, preferably 20 in the quality accounting of selfreparing composite solid electrolyte
~40%.
6. the preparation method of described in any item selfreparing composite solid electrolytes according to claim 1~5, comprising: preparation nothing
The inorganic solid electrolyte is added in self-healing polymers and obtains dispersion by machine solid electrolyte, coating, drying.
7. a kind of composite electrolyte, the composite electrolyte includes selfreparing composite solid as claimed in any one of claims 1 to 5
State electrolyte and liquid electrolyte, the liquid electrolyte are 10%~60% in the quality accounting of composite electrolyte, preferably
20%~50%, the liquid electrolyte includes lithium salts.
8. the preparation method of composite electrolyte according to claim 7, comprising: described in any item to Claims 1 to 5
Liquid electrolyte containing lithium salt is added in selfreparing composite solid electrolyte.
9. selfreparing composite solid electrolyte described in any claim and/or according to claim according to claim 1~5
The purposes of composite electrolyte described in 7 in the battery.
10. a kind of lithium battery, including as described in Claims 1 to 5 any claim selfreparing composite solid electrolyte and/
Or composite electrolyte as claimed in claim 7.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110767937A (en) * | 2019-11-21 | 2020-02-07 | 四川新敏雅电池科技有限公司 | Composite polymer solid electrolyte and lithium battery |
| CN111029647A (en) * | 2019-12-20 | 2020-04-17 | 中国电子科技集团公司第十八研究所 | Electrolyte with self-repairing function and preparation method of solid-state battery |
| CN111162314A (en) * | 2019-12-25 | 2020-05-15 | 中国科学院青岛生物能源与过程研究所 | Self-repairing polymer electrolyte based on dynamic chemical bond and application of self-repairing polymer electrolyte in secondary lithium battery |
| CN112687971A (en) * | 2020-12-28 | 2021-04-20 | 中国电子科技集团公司第十八研究所 | Self-repairing functional interface layer of solid-state battery and construction method |
| CN118431547A (en) * | 2024-07-02 | 2024-08-02 | 蜂巢能源科技股份有限公司 | Composite solid electrolyte and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170062830A1 (en) * | 2015-08-31 | 2017-03-02 | The Board Of Trustees Of The Leland Stanford Junior University | High performance battery anodes with polymeric coatings |
| CN106515165A (en) * | 2016-11-15 | 2017-03-22 | 复旦大学 | Self-healing capacitive intelligent skin with high sensitivity and preparation method thereof |
| US20170237119A1 (en) * | 2014-03-12 | 2017-08-17 | The Regents Of The University Of Colorado, A Body Corporate | Li-ion electrolyte membrane facilitated by a self-healing polymer matrix, and associated battery |
| CN107154512A (en) * | 2017-05-05 | 2017-09-12 | 华中科技大学 | A kind of polymer dielectric and its preparation and application with self-healing function |
| CN108598560A (en) * | 2018-02-27 | 2018-09-28 | 北京匠芯电池科技有限公司 | Composite solid electrolyte and its preparation method and application |
| CN108598561A (en) * | 2018-03-08 | 2018-09-28 | 浙江大学 | A kind of quasi- solid lithium ion conducting electrolyte and its preparation method and application |
| WO2018231731A2 (en) * | 2017-06-09 | 2018-12-20 | The Regents Of The University Of California | Self-forming solid state batteries and self-healing solid electrolytes |
-
2018
- 2018-12-20 CN CN201811564924.9A patent/CN109728342B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170237119A1 (en) * | 2014-03-12 | 2017-08-17 | The Regents Of The University Of Colorado, A Body Corporate | Li-ion electrolyte membrane facilitated by a self-healing polymer matrix, and associated battery |
| US20170062830A1 (en) * | 2015-08-31 | 2017-03-02 | The Board Of Trustees Of The Leland Stanford Junior University | High performance battery anodes with polymeric coatings |
| CN106515165A (en) * | 2016-11-15 | 2017-03-22 | 复旦大学 | Self-healing capacitive intelligent skin with high sensitivity and preparation method thereof |
| CN107154512A (en) * | 2017-05-05 | 2017-09-12 | 华中科技大学 | A kind of polymer dielectric and its preparation and application with self-healing function |
| WO2018231731A2 (en) * | 2017-06-09 | 2018-12-20 | The Regents Of The University Of California | Self-forming solid state batteries and self-healing solid electrolytes |
| CN108598560A (en) * | 2018-02-27 | 2018-09-28 | 北京匠芯电池科技有限公司 | Composite solid electrolyte and its preparation method and application |
| CN108598561A (en) * | 2018-03-08 | 2018-09-28 | 浙江大学 | A kind of quasi- solid lithium ion conducting electrolyte and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| YI CUI等: "《High-Performance Lithium Metal Negative Electrode with a Soft and Flowable Polymer Coating》", 《ACS ENERGY LETTERS》 * |
| YI CUI等: "《Self-healing chemistry enables the stable operation of silicon microparticle anodes for high-energy lithium-ion batteries》", 《NATURE CHEMISTRY》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110767937A (en) * | 2019-11-21 | 2020-02-07 | 四川新敏雅电池科技有限公司 | Composite polymer solid electrolyte and lithium battery |
| CN110767937B (en) * | 2019-11-21 | 2022-05-24 | 四川新敏雅电池科技有限公司 | Composite polymer solid electrolyte and lithium battery |
| CN111029647A (en) * | 2019-12-20 | 2020-04-17 | 中国电子科技集团公司第十八研究所 | Electrolyte with self-repairing function and preparation method of solid-state battery |
| CN111029647B (en) * | 2019-12-20 | 2023-07-18 | 中国电子科技集团公司第十八研究所 | Preparation method of electrolyte with self-repairing function and solid-state battery |
| CN111162314A (en) * | 2019-12-25 | 2020-05-15 | 中国科学院青岛生物能源与过程研究所 | Self-repairing polymer electrolyte based on dynamic chemical bond and application of self-repairing polymer electrolyte in secondary lithium battery |
| CN111162314B (en) * | 2019-12-25 | 2023-05-09 | 中国科学院青岛生物能源与过程研究所 | Self-repairing polymer electrolyte based on dynamic chemical bond and application of self-repairing polymer electrolyte in secondary lithium battery |
| CN112687971A (en) * | 2020-12-28 | 2021-04-20 | 中国电子科技集团公司第十八研究所 | Self-repairing functional interface layer of solid-state battery and construction method |
| CN118431547A (en) * | 2024-07-02 | 2024-08-02 | 蜂巢能源科技股份有限公司 | Composite solid electrolyte and preparation method and application thereof |
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