CN117855581A - Composite solid electrolyte for improving stability of negative electrode interface of all-solid-state lithium metal battery and preparation method - Google Patents
Composite solid electrolyte for improving stability of negative electrode interface of all-solid-state lithium metal battery and preparation method Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 101
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000011575 calcium Substances 0.000 claims abstract description 41
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 33
- 239000003792 electrolyte Substances 0.000 claims abstract description 32
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 30
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 30
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- 239000000945 filler Substances 0.000 claims abstract description 19
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 7
- 239000002070 nanowire Substances 0.000 claims abstract description 7
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 7
- 125000005587 carbonate group Chemical group 0.000 claims abstract description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 32
- -1 polypropylene carbonate Polymers 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 15
- 239000002033 PVDF binder Substances 0.000 claims description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 12
- 238000005266 casting Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000003949 imides Chemical class 0.000 claims description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920001940 conductive polymer Polymers 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000002322 conducting polymer Substances 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 2
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 2
- 229920000131 polyvinylidene Polymers 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 13
- 210000001787 dendrite Anatomy 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 abstract description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 39
- 238000012360 testing method Methods 0.000 description 29
- 239000002904 solvent Substances 0.000 description 12
- 238000011056 performance test Methods 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 239000011268 mixed slurry Substances 0.000 description 9
- 239000011149 active material Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910010710 LiFePO Inorganic materials 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000006230 acetylene black Substances 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910010941 LiFSI Inorganic materials 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910006270 Li—Li Inorganic materials 0.000 description 2
- KNMXTLXXEIIWIN-UHFFFAOYSA-H O.O.O.O.O.O.O.O.O.O.O.O.P(=O)([O-])([O-])[O-].[Ca+2].P(=O)([O-])([O-])[O-].[Ca+2].[Ca+2] Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.P(=O)([O-])([O-])[O-].[Ca+2].P(=O)([O-])([O-])[O-].[Ca+2].[Ca+2] KNMXTLXXEIIWIN-UHFFFAOYSA-H 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 238000010952 in-situ formation Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- 235000019801 trisodium phosphate Nutrition 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical group [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
The invention discloses a composite solid electrolyte for improving the stability of a negative electrode interface of an all-solid-state lithium metal battery and a preparation method thereof. The composite solid electrolyte comprises 50-85% of high molecular polymer, 10-45% of lithium salt and 2-10% of superfine CHANW filler containing calcium vacancies according to mass percentage; the superfine CHANW filler containing calcium vacancies is a hydroxyapatite nanowire with carbonate groups substituted for part of phosphate groups. The superfine carbonic acid hydroxyapatite nanowire containing calcium vacancies can promote the formation of a solid electrolyte interface layer rich in inorganic matters on the surface of the negative electrode, remarkably reduce the interface impedance of the all-solid-state lithium ion battery, and inhibit the growth of lithium dendrites of the lithium metal negative electrode. The all-solid-state lithium metal battery assembled by adopting the solid-state electrolyte can realize stable circulation with long service life and good multiplying power performance, and meanwhile, the safety performance of the battery is greatly improved, so that the composite solid-state electrolyte has great commercial application prospect.
Description
Technical Field
The invention belongs to the technical field of solid-state batteries, and particularly relates to a composite solid-state electrolyte for improving the stability of an anode interface of an all-solid-state lithium battery and a preparation method thereof.
Background
As the lithium ion battery is portableThe requirements on safety and energy density of the mobile equipment, the energy storage device, the electric automobile and other fields are increasing widely. Lithium metal has a high theoretical specific capacity (3860 mAh g) -1 ) And low electrode potential (-3.04V compared to standard hydrogen electrodes), lithium Metal Batteries (LMBs) are a promising alternative to Lithium Ion Batteries (LIBs). The solid electrolyte can obviously reduce potential safety hazards such as combustion, explosion and the like on one hand, and is beneficial to improving the energy density of the lithium ion battery on the other hand, so that the all-solid lithium metal battery becomes one of the most promising energy storage devices in the future. However, current commercialization of all-solid-state lithium metal batteries is limited by their short cycle life. The low coulombic efficiency and capacity decay caused by unstable solid electrolyte interface layers (SEI) and dendrite growth present challenges for practical applications of all-solid-state lithium metal batteries. The cycle life of lithium metal batteries is primarily limited by non-uniform lithium deposition/stripping, which results in exposure of large amounts of lithium to the electrolyte and loss of active lithium due to dead lithium formation. Therefore, improving the interface compatibility of the lithium metal cathode and the electrolyte is the most effective method for improving the performance of the lithium metal all-solid-state battery at present.
The polymer electrolyte has the advantages of easy mass preparation, flexibility, low price and the like, and becomes the most popular electrolyte in all-solid-state batteries. However, the formation of lithium dendrites on the surface of lithium metal remains one of the greatest challenges faced by polymer-based all-solid lithium metal batteries. The solid electrolyte interface layer (SEI) formed by the reaction between the lithium metal anode and the electrolyte can regulate the morphology of lithium deposition/exfoliation and control the cycling stability of the lithium battery, so that the formation of SEI having excellent ion conducting properties on the lithium metal surface is critical to maintain the cycling stability of an all-solid lithium metal battery. Chinese patent CN 114497719A discloses an interface connection layer of a solid-state battery to achieve a stable contact interface and rapid ion transmission, however, the connection layer needs to be additionally added in the process of assembling the battery, which is not beneficial to the improvement of energy density, and the process is complicated and is not beneficial to the mass production. Therefore, it is critical to improve the above problems to form an SEI layer having good ion conductivity in situ on a lithium anode.
Disclosure of Invention
The invention aims to provide a composite solid electrolyte for improving the stability of a cathode interface of a polymer-based all-solid-state lithium battery and a preparation method thereof. The composite solid electrolyte is used in an all-solid-state lithium metal battery, can realize stable circulation with long service life and good multiplying power performance, and meanwhile, the safety performance of the composite solid electrolyte is greatly improved.
In order to achieve the technical purpose, the following technical scheme is adopted:
the composite solid electrolyte for improving the stability of the negative electrode interface of the all-solid-state lithium battery comprises, by mass, 50% -85% of high-molecular polymer, 10% -45% of lithium salt and 2% -10% of superfine CHANW filler containing calcium vacancies; wherein the superfine CHANW filler containing calcium vacancies is a hydroxyapatite nanowire with carbonate substituted part of phosphate.
The superfine CHANW containing calcium vacancies promotes the reduction reaction kinetics of electrolyte lithium salt on the surface of the anode to form a solid electrolyte interface layer (SEI) rich in inorganic matters, thereby improving the interface stability of the lithium metal anode and inhibiting the generation of lithium dendrites.
According to the scheme, the molar ratio of phosphate to carbonate in the CHANW filler containing calcium vacancies is 0.1-0.5:1, and Ca/P is 2-6. Wherein Ca/P refers to calcium ions (Ca 2+ ) With phosphate ions (PO) 4 3- ) Molar ratio of (2).
According to the scheme, the CHANW filler containing calcium vacancies is prepared by mixing calcium phosphate dodecahydrate, sodium carbonate and trisodium phosphate for hydrothermal reaction.
According to the scheme, the diameter of the nanowire in the superfine CHANW filler containing calcium vacancies is less than or equal to 5nm.
According to the scheme, the high molecular polymer with ion conductivity is one or a combination of more of polyethylene oxide, polypropylene carbonate, polyvinyl carbonate, polyfluoro ethylene carbonate, polyvinylidene carbonate, polyimide, polyacrylonitrile, polyvinylidene fluoride and polyvinylidene fluoride-hexafluoropropylene.
According to the scheme, the electrolyte lithium salt is lithium difluorophosphate (LiPO 2 F 2 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium hexafluorophosphate (LiPF) 6 ) One or more of lithium difluorooxalato borate (LiDFOB), lithium bisoxalato borate (LiBOB), lithium bisfluorosulfonyl imide (LiLSI), or lithium bistrifluoromethanesulfonyl imide (LiTFSI).
The preparation method of the composite solid electrolyte for improving the stability of the negative electrode interface of the all-solid-state lithium battery comprises the following specific steps:
1) Dispersing superfine CHANW filler containing calcium vacancies in an organic solvent, adding an ion-conducting polymer and electrolyte lithium salt after stirring and fully dispersing, and stirring to form uniform mixed viscous slurry;
2) Casting the mixed viscous slurry obtained in the step 1) into a mould, and vacuum drying after volatilizing the organic solvent to obtain the superfine CHANW improved composite solid electrolyte containing calcium vacancies.
According to the above scheme, in the step 1), the superfine CHANW containing calcium vacancies is dispersed in an organic solvent in an environment with a water oxygen content of less than 0.1 ppm.
According to the scheme, in the step 1), the organic solvent is one or more of tetrahydrofuran, octadecyl ether-6, methylcyclohexane, anhydrous acetonitrile, N-N dimethylformamide and acetone.
According to the scheme, in the step 1), after the ion conductor polymer and the electrolyte lithium salt are added, stirring is carried out for 5-12 hours at 50-60 ℃ to form uniform mixed viscous slurry.
According to the above scheme, in the step 2), the vacuum drying conditions are as follows: drying at 60-80deg.C for 10-24 hr to completely remove residual solvent.
According to the above scheme, in the step 2), the mold is a polytetrafluoroethylene mold.
There is provided the use of the above composite solid electrolyte in an all-solid lithium battery.
An all-solid-state lithium battery is provided, comprising a positive electrode, a negative electrode and the above composite solid-state electrolyte between the positive and negative electrodes.
According to the scheme, the mass ratio of the active material, the conductive agent, the binder and the composite solid electrolyte in the positive electrode of the all-solid lithium battery is 7: (1-2): (0.5-1): (0.5-1).
According to the scheme, the active material in the positive electrode is lithium manganate (LiMn 2 O 4 ) Lithium cobalt oxide (LiCoO) 2 ) Lithium iron phosphate (LiFePO) 4 ) Lithium nickelate (LiNiO) 2 ) Lithium iron manganese phosphate (LiFe) 0.2 Mn 0.8 PO 4 ) Lithium nickel manganese (LiNi) 0.5 Mn 1.5 O 4 ) One of nickel cobalt manganese or nickel cobalt aluminum ternary materials; the negative electrode material is one of a metal lithium sheet or a metal lithium alloy.
According to the scheme, the superfine CHANW containing calcium vacancies promotes the reduction reaction kinetics of electrolyte lithium salt on the surface of the anode to form a solid electrolyte interface layer (SEI) rich in inorganic matters, so that the interface stability of the lithium metal anode is improved, and the generation of lithium dendrites is inhibited.
The beneficial effects of the invention are as follows:
the invention provides a composite solid electrolyte for improving the stability of an anode interface of an all-solid-state lithium battery, which comprises an ultrafine CHANW filler containing calcium vacancies; in the superfine CHANW filler containing calcium vacancies, the negative divalent carbonate replaces part of the negative trivalent phosphate of the hydroxyapatite, so as to balance charges and generate negatively charged calcium vacancies. The superfine CHANW filler containing calcium vacancies is introduced into the polymer-based electrolyte, and electrons at the calcium vacancies are transferred to the electrolyte lithium salt in the process of reducing the lithium salt to promote the reduction reaction kinetics of the electrolyte lithium salt on the surface of the negative electrode, and finally, an SEI layer which is mainly made of lithium fluoride and is rich in inorganic matters is formed on the surface of lithium metal in situ, wherein the inorganic components of the SEI layer mainly originate from the reduction decomposition of the lithium salt, and the SEI layer with excellent performance can be formed without additionally introducing other film forming additives or artificial interface layers. The SEI layer rich in inorganic matters not only promotes the transmission of lithium ions at an interface and obviously reduces the interface impedance of the all-solid-state lithium ion battery, but also induces the uniform deposition and stripping of lithium ions, thereby inhibiting the generation of lithium dendrites; the obtained composite solid electrolyte is used for an all-solid-state lithium metal battery, can realize long-life stable circulation and good multiplying power performance, and meanwhile, the safety performance of the composite solid-state electrolyte is greatly improved, so that the composite solid-state electrolyte has great commercial application prospect.
Drawings
The following description is presented in conjunction with the accompanying drawings to provide a further understanding of the invention, and the following drawings are merely illustrative of some embodiments of the invention and are not to be construed as limiting the scope of the invention. Other relevant drawings may be made by those of ordinary skill in the art without undue burden from these drawings.
FIG. 1 is a TEM of the ultra-fine CHANW used in example 2.
Fig. 2 is a schematic diagram of the in situ formation of an inorganic-rich SEI layer from ultra-fine CHANW induced lithium salts containing calcium vacancies and the key role of the SEI layer in an all-solid-state lithium metal battery.
Fig. 3 is a cyclic voltammogram of a li||cu battery assembled from the composite solid state electrolytes of examples 2, 4, 5 and comparative examples 1, 3, 4, wherein fig. 3a is example 2 and comparative example 1, fig. 3b is example 4 and comparative example 3, and fig. 3c is example 5 and comparative example 4.
Fig. 4 is an electrochemical impedance spectrum of the lfp||li battery cycle 0.1C assembled in examples 1-3 (fig. 4 a) and comparative examples 1-2 (fig. 4 b) after 5 cycles.
Fig. 5 is a graph of voltage versus time for Li symmetric cells assembled in examples 1-3 (fig. 5 a-c) and comparative examples 1-2 (fig. 5 d-e) of the present invention.
Fig. 6 is a charge-discharge curve of LFP Li batteries assembled in example 2 and comparative example 1 of the present invention at 0.2C for 20 th, 40 th and 60 th cycles, respectively; wherein the upper graph shows the cycle performance, the lower graph shows the charge-discharge curve of example 2, and the lower graph shows the charge-discharge curve of comparative example 1.
Fig. 7 is the rate performance of lfp||li batteries assembled in example 2 and comparative example 1 of the present invention.
Fig. 8 is a scanning electron microscope image of the surface of lithium metal after 100h cycle of the Li-Li battery assembled in example 2 (left image) and comparative example 1 (right image) of the present invention.
Fig. 9 is an XPS characterization of the composition of the lithium metal surface after 100h cycling of the assembled Li batteries of example 2 (fig. 9 a) and comparative example 1 (fig. 9 b) of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In examples 1-5 and comparative examples 1-4 of the present invention, the following materials were selected, respectively:
the high molecular polymer with ion conductivity is polyethylene oxide (PEO) with a molecular weight of 60 ten thousand, which is produced by Shanghai Ala Biochemical technologies Co.
The electrolyte lithium salt is lithium bistrifluoromethyl sulfonate imide (LiTFSI), available from dormer reagent company.
Respectively dissolving calcium phosphate dodecahydrate, sodium carbonate and trisodium phosphate in deionized water according to different molar ratios, then mixing and stirring the above solutions, adding the mixture into a hydrothermal kettle to react for 12 hours at 100 ℃, and centrifugally washing the reacted product to obtain the superfine hydroxyapatite carbonate nanowires with calcium vacancies in different P/C ratios (namely molar ratios of phosphate radicals and carbonate radicals).
However, the use of the polymer, the lithium electrolyte salt and the ultra-fine CHANW filler containing calcium vacancies in this example is not limiting, and one skilled in the art may use other conventional nano-materials such as the polymer, lithium electrolyte salt and inorganic nano-dielectric calcium vacancies listed in this invention to prepare the composite solid electrolyte of this invention.
Example 1
A preparation method of a composite solid electrolyte for improving the stability of an all-solid-state lithium battery cathode interface comprises the following specific steps:
1) In a glove box having a water-oxygen content of less than 0.1ppm, 5 mass% of a calcium-vacancy-containing ultrafine CHANW filler (P/C ratio of 0.18, ca/P ratio of 5.5) relative to the PEO polymer was dispersed in tetrahydrofuran, and stirred to obtain a uniform mixed solution.
2) PEO polymer and lithium salt LiTFSI (PEO (molar amount based on molecular mass of PEO monomer) to LiTFSI were added to the mixed solution at a molar ratio of 8: 1) After fully stirring for 10 hours at 60 ℃, uniform mixed slurry with certain viscosity is obtained.
3) Casting the slurry obtained in the step 2 into a polytetrafluoroethylene mould, standing in a glove box to volatilize most of the solvent, transferring to a vacuum oven, fully drying at the temperature of 60 ℃ for 24 hours, taking out and demoulding to obtain the composite solid electrolyte, namely PLNW-18, and slicing for later use.
The composite solid electrolyte prepared by the embodiment is selected, and a symmetric battery is assembled by taking a lithium sheet as a symmetric electrode to perform lithium removal performance test; liFePO with active material 4 The pole piece of the lithium ion battery is a positive pole, and the metal lithium piece is a negative pole for full battery cycle performance test, wherein an active substance LiFePO in the positive pole 4 The mass ratio of the conductive agent acetylene black, the binder polyvinylidene fluoride (PVDF) and the composite solid electrolyte is as follows: 7:2:0.5:0.5.
wherein the impedance and CV tests are performed on an Autolab and EC-LAB electrochemical workstations, respectively; the symmetrical battery and full battery charge and discharge tests are carried out on a blue battery tester, the test temperature is 60 ℃, and the full battery test voltage range is as follows: 2.7-4.0V.
Example 2
A preparation method of a composite solid electrolyte for improving the stability of an all-solid-state lithium battery cathode interface comprises the following specific steps:
1) In a glove box having a water oxygen content of less than 0.1ppm, 5 mass% of ultrafine CHANW containing calcium vacancies (P/C ratio of 0.36 and Ca/P ratio of 2.7) relative to PEO polymer was dispersed in tetrahydrofuran and stirred to obtain a uniform mixed solution.
2) PEO polymer and lithium salt LiTFSI (molar ratio of PEO to LiTFSI 8: 1) After fully stirring for 10 hours at 60 ℃, uniform mixed slurry with certain viscosity is obtained.
3) Casting the slurry obtained in the step 2 into a polytetrafluoroethylene mould, standing in a glove box to volatilize most of the solvent, transferring to a vacuum oven, fully drying at the temperature of 60 ℃ for 24 hours, taking out and demoulding to obtain the composite solid electrolyte, namely PLNW-36, and slicing for later use.
The composite solid electrolyte prepared by the embodiment is selected, copper foil is used as a working electrode, and metal lithium is used as a counter electrode to assemble a battery for cyclic voltammetry test; the lithium sheets are used as symmetrical electrodes to assemble a symmetrical battery for lithium removal and insertion performance test; liFePO with active material 4 The pole piece of the lithium ion battery is a positive pole, and the metal lithium piece is a negative pole for full battery cycle performance test, wherein an active substance LiFePO in the positive pole 4 The mass ratio of the conductive agent acetylene black, the binder polyvinylidene fluoride (PVDF) and the solid electrolyte (PEO and LiTFSI) is as follows: 7:2:0.5:0.5.
wherein the impedance and CV tests are performed on an Autolab and EC-LAB electrochemical workstations, respectively; the symmetrical battery and full battery charge and discharge tests are carried out on a blue battery tester, the test temperature is 60 ℃, and the full battery test voltage range is as follows: 2.7-4.0V.
Example 3
A preparation method of a composite solid electrolyte for improving the stability of an all-solid-state lithium battery cathode interface comprises the following specific steps:
1) In a glove box having a water-oxygen content of less than 0.1ppm, 5 mass% of ultrafine CHANW containing calcium vacancies (P/C ratio of 0.5 and Ca/P ratio of 2.2) relative to PEO polymer was dispersed in tetrahydrofuran and stirred to obtain a uniform mixed solution.
2) PEO polymer and lithium salt LiTFSI (molar ratio of PEO to LiTFSI 8: 1) After fully stirring for 10 hours at 60 ℃, uniform mixed slurry with certain viscosity is obtained.
3) Casting the slurry obtained in the step 2 into a polytetrafluoroethylene mould, standing in a glove box to volatilize most of the solvent, transferring to a vacuum oven, fully drying at the temperature of 60 ℃ for 24 hours, taking out and demoulding to obtain the composite solid electrolyte, namely PLNW-50, and slicing for later use.
The composite solid electrolyte prepared by the embodiment is selected, and a symmetric battery is assembled by taking a lithium sheet as a symmetric electrode to perform lithium removal performance test; liFePO with active material 4 The pole piece of (2) is positive pole, and the metal lithium pieceFull cell cycle performance test for negative electrode, wherein active material LiFePO in positive electrode 4 The mass ratio of the conductive agent acetylene black, the binder polyvinylidene fluoride (PVDF) and the solid electrolyte (PEO and LiTFSI) is as follows: 7:2:0.5:0.5.
wherein the impedance and CV tests are performed on an Autolab and EC-LAB electrochemical workstations, respectively; the symmetrical battery and full battery charge and discharge tests are carried out on a blue battery tester, the test temperature is 60 ℃, and the full battery test voltage range is as follows: 2.7-4.0V.
Example 4
A preparation method of a composite solid electrolyte for improving the stability of an all-solid-state lithium battery cathode interface comprises the following specific steps:
1) In a glove box having a water oxygen content of less than 0.1ppm, 5 mass% of ultrafine CHANW containing calcium vacancies (36% P/C ratio, 2.7 Ca/P ratio) was dispersed in tetrahydrofuran and stirred to obtain a homogeneous mixed solution.
2) PEO polymer and lithium salt LiFSI (the molar ratio of PEO to LiFSI is 8: 1) After fully stirring for 10 hours at 60 ℃, uniform mixed slurry with certain viscosity is obtained.
3) Casting the slurry obtained in the step 2 into a polytetrafluoroethylene mould, standing in a glove box to volatilize most of the solvent, transferring to a vacuum oven, fully drying at the temperature of 60 ℃ for 24 hours, taking out and demoulding to obtain the composite solid electrolyte, marking the composite solid electrolyte as PLFSNW, and slicing for later use.
The composite solid electrolyte prepared in this example was selected, and a cyclic voltammetry test was performed on an EC-LAB electrochemical workstation with copper foil as the working electrode and lithium metal as the counter electrode assembly cell, with a CV test performed at a sweep rate of 0.1mV S -1 。
Example 5
A preparation method of a composite solid electrolyte for improving the stability of an all-solid-state lithium battery cathode interface comprises the following specific steps:
1) In a glove box having a water oxygen content of less than 0.1ppm, 5 mass% of ultrafine CHANW containing calcium vacancies (P/C ratio of 0.36 and Ca/P ratio of 2.7) relative to PEO polymer was dispersed in tetrahydrofuran and stirred to obtain a uniform mixed solution.
2) PEO polymer and lithium salt lipfob (molar ratio of PEO to lipfob is 8: 1) After fully stirring for 10 hours at 60 ℃, uniform mixed slurry with certain viscosity is obtained.
3) Casting the slurry obtained in the step 2 into a polytetrafluoroethylene mould, standing in a glove box to volatilize most of the solvent, transferring to a vacuum oven, fully drying at the temperature of 60 ℃ for 24 hours, taking out and demoulding to obtain the composite solid electrolyte, namely PLFBNW, and slicing for later use.
The composite solid electrolyte prepared in this example was selected, and a cyclic voltammetry test was performed on an EC-LAB electrochemical workstation with copper foil as the working electrode and lithium metal as the counter electrode assembly cell, with a CV test performed at a sweep rate of 0.1mV S -1 。
Comparative example 1
This comparative example prepared a polymer solid electrolyte as follows:
1) An amount of PEO and electrolyte lithium salt LiTFSI (molar ratio of PEO to LiTFSI 8: 1) After fully stirring for 10 hours at 60 ℃, uniform mixed slurry with certain viscosity is obtained.
2) Casting the slurry obtained in the step 1 on a polytetrafluoroethylene mould, standing in a glove box to volatilize most of the solvent, transferring to a vacuum oven, taking out and demoulding after the solvent is fully dried for 24 hours at the temperature of 60 ℃ in vacuum to obtain a solid electrolyte, marking the solid electrolyte as PL, and slicing for standby.
The composite solid electrolyte prepared in this comparative example was selected, and a battery was assembled with a steel sheet as a blocking electrode for ion conductivity testing; the lithium sheets are used as symmetrical electrodes to assemble a symmetrical battery for lithium removal and insertion performance test; liFePO with active material 4 The pole piece of the lithium ion battery is a positive pole, and the metal lithium piece is a negative pole for full battery cycle performance test, wherein an active substance LiFePO in the positive pole 4 The mass ratio of the conductive agent acetylene black, the binder polyvinylidene fluoride (PVDF) and the solid electrolyte (PEO and LiTFSI) is as follows: 7:2:0.5:0.5.
wherein the impedance test is performed on an Autolab electrochemical workstation; the symmetrical battery and full battery charge and discharge tests are carried out on a blue battery tester, the test temperature is 60 ℃, and the full battery test voltage range is as follows: 2.7-4.0V.
Comparative example 2
This comparative example prepared a composite solid electrolyte as follows:
1) In a glove box with the water-oxygen content lower than 0.1ppm, 5 percent (relative to PEO polymer) of calcium-vacancy-containing carbonic acid hydroxyapatite nanorods (the P/C ratio is 0.36 and the Ca/P ratio is 2.7) are dispersed in tetrahydrofuran, and uniform mixed solution is obtained through stirring.
2) PEO polymer and lithium salt LiTFSI (molar ratio of PEO to LiTFSI 8: 1) After sufficient stirring at 60 ℃, uniform mixed slurry with certain viscosity is obtained.
3) Casting the slurry obtained in the step 2 into a polytetrafluoroethylene mould, standing in a glove box to volatilize most of the solvent, transferring to a vacuum oven, fully drying at the temperature of 60 ℃ for 24 hours, taking out and demoulding to obtain the composite solid electrolyte, marking the composite solid electrolyte as PLNR, and slicing for later use.
The composite solid electrolyte prepared in this comparative example was selected, and a battery was assembled with a steel sheet as a blocking electrode for ion conductivity testing; the lithium sheets are used as symmetrical electrodes to assemble a symmetrical battery for lithium removal and insertion performance test; liFePO with active material 4 The pole piece of the lithium ion battery is a positive pole, and the metal lithium piece is a negative pole for full battery cycle performance test, wherein an active substance LiFePO in the positive pole 4 The mass ratio of the conductive agent acetylene black, the binder polyvinylidene fluoride (PVDF) and the solid electrolyte (PEO and LiTFSI) is as follows: 7:2:0.5:0.5.
wherein the impedance and CV tests are performed on an Autolab and EC-LAB electrochemical workstations, respectively; the symmetrical battery and full battery charge and discharge tests are carried out on a blue battery tester, the test temperature is 60 ℃, and the full battery test voltage range is as follows: 2.7-4.0V.
Comparative example 3
This comparative example prepared a polymer solid electrolyte as follows:
1) An amount of PEO and electrolyte lithium salt LiFSI (PEO to LiFSI molar ratio of 8: 1) After sufficient stirring at 60 ℃, uniform mixed slurry with certain viscosity is obtained.
2) Casting the slurry obtained in the step 1 on a polytetrafluoroethylene mould, standing in a glove box to volatilize most of the solvent, transferring to a vacuum oven, taking out and demoulding after the solvent is fully dried for 24 hours at the temperature of 60 ℃ in vacuum to obtain a solid electrolyte, marking the solid electrolyte as PLFS, and then slicing for standby.
The composite solid electrolyte prepared in this comparative example was selected and subjected to cyclic voltammetry using copper foil as the working electrode and lithium sheets as the counter electrode assembly cells.
Wherein the cyclic voltammetric test is performed on an EC-LAB electrochemical workstation with a sweep rate of 0.1mV S -1 。
Comparative example 4
This comparative example prepared a polymer solid electrolyte as follows:
1) An amount of PEO and electrolyte lithium salt lipfob (molar ratio PEO to lipfob of 8: 1) After sufficient stirring at 60 ℃, uniform mixed slurry with certain viscosity is obtained.
2) Casting the slurry obtained in the step 1 on a polytetrafluoroethylene mould, standing in a glove box to volatilize most of the solvent, transferring to a vacuum oven, taking out and demoulding after the solvent is fully dried for 24 hours at the temperature of 60 ℃ in vacuum to obtain a solid electrolyte, marking the solid electrolyte as PLFB, and slicing for later use.
The composite solid electrolyte prepared in this comparative example was selected and subjected to cyclic voltammetry using copper foil as the working electrode and lithium sheets as the counter electrode assembly cells.
Wherein the cyclic voltammetric test is performed on an EC-lab electrochemical workstation with a sweep rate of 0.1mV S -1 。
FIG. 1 is a TEM of the ultra-fine CHANW filler used in example 2, where the diameter ranges from 1.5 to 2.0nm.
Fig. 2 is a schematic diagram of the in situ formation of an inorganic-rich SEI layer from ultra-fine CHANW induced lithium salts containing calcium vacancies and the key role of the SEI layer in an all-solid-state lithium metal battery. The uniform inorganic-rich SEI formed on the surface of lithium metal can promote the transmission of lithium ions, induce the uniform deposition of lithium ions and inhibit the generation of lithium dendrites.
Fig. 3 is a cyclic voltammogram of the li||cu battery assembled with the composite solid state electrolytes of examples 2, 4, 5 and comparative examples 1, 3, 4, respectively. As can be seen from the figure, examples 2, 4, and 5 all have sharp CV peaks that are evident compared to the comparative examples, indicating that the kinetics of the reduction reaction of lithium salts is improved in the cha nw-containing electrolyte.
Fig. 4 is an electrochemical impedance spectrum of lfp||li battery cycles 0.1C assembled in examples 1-3 and comparative examples 1-2 of the present invention after 5 cycles. It can be seen that the impedance of the lfp||li battery in the example system after 5 cycles of 0.1C is smaller than that of the comparative example, which indicates that the interface stability is better in the battery containing the CHANW, and the cycle stability of the battery is more favorable.
Fig. 5 is a graph of voltage versus time for Li-Li symmetric batteries assembled in examples 1-3 and comparative examples 1-2 of the present invention. The polarization voltages of the examples are all smaller than that of the comparative examples, and the cyclic stability of the examples is significantly better than that of the comparative examples, wherein the all-solid-state lithium symmetric battery assembled in example 2 can be stably cycled for up to 1750 hours.
Fig. 6 is a cycle performance at 0.2C of LFP Li batteries assembled in example 2 and comparative example 1 of the present invention. The cycle stability (80% capacity retention after 420 cycles) and specific capacity of example 2 were significantly better than those of comparative example 1.
FIG. 7 is a graph showing the rate performance of LFP Li batteries assembled in example 2 and comparative example 1 of the present invention, and the average capacity at 5.0C was 113Ah g -1 . The specific capacities at different magnifications shown in example 2 are all significantly higher than those of comparative example 1.
Fig. 8 is a scanning electron microscope image of the surface of lithium metal after cycling of the Li battery assembled in example 2 and comparative example 1 of the present invention. The figure shows that the surface of lithium metal is smooth and no lithium dendrite is generated after the cycle in the symmetrical battery of example 2, whereas the surface of lithium metal is rough and there is significant lithium dendrite generation after the cycle in the symmetrical battery of comparative example 1.
Fig. 9 is an XPS characterization of the composition of the lithium metal surface after cycling of the assembled Li batteries of inventive example 2 and comparative example 1. Fig. 9 (a) shows that the symmetric battery of example 2 has a smooth surface of lithium metal after being cycled to form a larger amount of inorganic product, particularly LiF, than the battery of comparative example 1 of fig. 9 (b), mainly because in the battery containing the CHANW, the CHANW promotes the reduction reaction of lithium salt at the interface of the negative electrode, thereby generating a larger amount of inorganic product derived from decomposition of lithium salt, wherein a large amount of LiF plays a good role in protecting the interface of the negative electrode, not only suppressing the interface reaction, but also suppressing the generation of lithium dendrites.
It will be understood that modifications and variations will be apparent to those skilled in the art from the foregoing description, and it is intended that all such modifications and variations be included within the scope of the following claims.
Claims (10)
1. The composite solid electrolyte for improving the interface stability of the cathode of the all-solid-state lithium battery is characterized by comprising 50-85% of high molecular polymer, 10-45% of lithium salt and 2-10% of superfine CHANW filler containing calcium vacancies in percentage by mass; wherein the superfine CHANW filler containing calcium vacancies is a hydroxyapatite nanowire with carbonate substituted part of phosphate.
2. The composite solid state electrolyte of claim 1 wherein the molar ratio of phosphate to carbonate in the calcium vacancy-containing CHANW filler is from 0.1 to 0.5:1 and ca/P is from 2 to 6.
3. The composite solid state electrolyte of claim 1 wherein the diameter of the nanowires in the ultra-fine CHANW filler containing calcium vacancies is 5nm or less.
4. The composite solid electrolyte of claim 1, wherein the solid state electrolyte comprises,
the high molecular polymer with ion conductivity is one or a combination of more of polyethylene oxide, polypropylene carbonate, polyvinyl carbonate, polyfluoro ethylene carbonate, polyvinylidene carbonate, polyimide, polyacrylonitrile, polyvinylidene fluoride and polyvinylidene fluoride-hexafluoropropylene;
the electrolyte lithium salt is one or more of lithium difluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium difluorooxalato borate, lithium bisoxalato borate, lithium bisfluorosulfonyl imide or lithium bistrifluoromethanesulfonyl imide.
5. A method for preparing the composite solid electrolyte for improving the interface stability of the cathode of an all-solid-state lithium battery according to any one of claims 1 to 4, which is characterized by comprising the following specific steps:
1) Dispersing superfine CHANW filler containing calcium vacancies in an organic solvent, adding an ion-conducting polymer and electrolyte lithium salt after stirring and fully dispersing, and stirring to form uniform mixed viscous slurry;
2) Casting the mixed viscous slurry obtained in the step 1) into a mould, and vacuum drying after volatilizing the organic solvent to obtain the superfine CHANW improved composite solid electrolyte containing calcium vacancies.
6. The method according to claim 5, wherein in the step 1), the organic solvent is one or more of tetrahydrofuran, octadecyl ether-6, methylcyclohexane, anhydrous acetonitrile, N-N dimethylformamide and acetone.
7. The method according to claim 5, wherein in the step 1), after adding the ion conductive polymer and the lithium salt electrolyte, the mixture is stirred at 50 to 60 ℃ for 5 to 12 hours to form a uniform mixed viscous slurry.
8. Use of the composite solid electrolyte of any one of claims 1-4 in an all-solid lithium battery.
9. An all-solid lithium battery comprising the composite solid electrolyte of any one of claims 1-4.
10. The all-solid-state lithium battery of claim 9, further comprising a positive electrode and a negative electrode, wherein the composite solid-state electrolyte is located between the positive electrode and the negative electrode.
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