CN115117440B - Oxide solid electrolyte sheet and preparation method and application thereof - Google Patents
Oxide solid electrolyte sheet and preparation method and application thereof Download PDFInfo
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003792 electrolyte Substances 0.000 claims abstract description 41
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 27
- 230000009467 reduction Effects 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 57
- 229920000642 polymer Polymers 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 37
- 229910003002 lithium salt Inorganic materials 0.000 claims description 35
- 159000000002 lithium salts Chemical class 0.000 claims description 35
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- -1 polyethylene carbonate Polymers 0.000 claims description 24
- 238000005303 weighing Methods 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- 229910052786 argon Inorganic materials 0.000 claims description 12
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 12
- 229920001940 conductive polymer Polymers 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910010252 TiO3 Inorganic materials 0.000 claims description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 claims description 6
- 229910009496 Li1.5Al0.5Ge1.5 Inorganic materials 0.000 claims description 6
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 6
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 4
- 125000004386 diacrylate group Chemical group 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims 3
- 238000000576 coating method Methods 0.000 abstract description 12
- 239000011248 coating agent Substances 0.000 abstract description 11
- 239000007787 solid Substances 0.000 abstract description 9
- 238000005245 sintering Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 9
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 5
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 3
- 229910013063 LiBF 4 Inorganic materials 0.000 description 3
- 229910012305 LiPON Inorganic materials 0.000 description 3
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000005486 organic electrolyte Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000671 polyethylene glycol diacrylate Polymers 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical class [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 238000000348 solid-phase epitaxy Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002203 sulfidic glass Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses an oxide solid electrolyte sheet, a preparation method and application thereof, wherein the oxide solid electrolyte is subjected to gradient coating treatment, so that the contact problem between rigid solids is effectively relieved by polymer electrolyte coating, the wettability of an interface and the inside of the electrolyte sheet is increased, and the impedance is reduced; and simultaneously effectively relieves the stability problem of the electrolyte sheet at the interface. Coating the positive electrode side of the high-voltage platform by adopting a high-voltage-resistant polymer electrolyte, so that the oxidation resistance of the high-voltage-resistant polymer electrolyte is improved; the reduction-resistant polymer electrolyte is used for coating one side of the cathode with stronger reducibility, so that the reduction resistance is improved, and the polymer electrolyte with high ion conductivity is used for coating the middle electrolyte, so that the overall conductivity is improved. The oxide solid electrolyte prepared by the invention does not need excessive preparation pressure and battery stack pressure, does not need sintering, and reduces the process steps and the manufacturing cost. The all-solid battery assembled from the electrolyte has excellent electrochemical properties.
Description
Technical Field
The invention belongs to the technical field of all-solid-state battery systems, and relates to a method for preparing an oxide solid-state electrolyte sheet, the oxide solid-state electrolyte sheet prepared by the method, and application of the electrolyte sheet in preparing a solid-state battery.
Background
At present, the traditional fossil energy still occupies a great proportion in global energy consumption, however, the further development is severely limited by the non-uniform distribution and non-renewable property of the fossil energy in geography, and the requirements of people on portable equipment, power grid level scale energy storage, a fifth generation (5G) mobile network, electric automobiles and the like are also difficult to meet. However, at present, a liquid organic electrolyte solution is mostly adopted in the commercialized lithium ion battery, the boiling point of the organic electrolyte solution is low, the organic electrolyte solution is toxic, in practical application, leakage of the electrolyte solution can occur, and dangerous events such as explosion of the battery can even be caused due to improper operation. In recent years, all-solid-state lithium metal batteries have been rapidly developed. Numerous studies have focused on high-safety solid state electrolytes (SPEs).
Currently mainstream solid electrolytes can be classified into oxide, sulfide, and polymer solid electrolytes. Sulfide solid electrolyte has good room temperature ionic conductivity, but has severe requirements on preparation environment and a narrow voltage window; the polymer solid electrolyte has good processability and flexibility and low cost, but the room-temperature ionic conductivity limits the further application; the oxide solid electrolyte has higher intrinsic ionic conductivity and mechanical strength, but the electrolyte is strong in rigidity, difficult to flake, a rigid interface exists between the electrolyte and the anode and the cathode, and a grain boundary exists in the electrolyte, so that the overall conductivity of the electrolyte flake is reduced. Modified for its shortcomings, is expected to further solve its application in all-solid-state batteries.
Based on the background, the invention adopts a gradient coating method, adopts polymer electrolytes with high pressure resistance, high conductivity and reduction resistance to carry out in-situ coating on oxide solid electrolytes, then respectively places three coated oxide solid powders at upper, middle and lower positions, presses the three coated oxide solid powders into tablets, the oxide coated by the high pressure resistance polymer corresponds to a high pressure positive electrode material, the high conductivity coating is positioned in the middle, and the oxide coated by the reduction resistance polymer at the lower layer contacts with a lithium metal negative electrode, thereby realizing interface compatibility of the positive electrode and the negative electrode. The preparation method of the electrolyte not only realizes high compactness of the oxide solid electrolyte under the condition of no sintering, but also improves the stability of the electrolyte. The method reduces the preparation cost of the oxide solid electrolyte and improves the electrochemical performance of the oxide solid electrolyte and the battery.
Disclosure of Invention
The invention provides a preparation process of an oxide solid electrolyte with a wide electrochemical stability window and compact inside. The preparation method comprises the following specific steps:
an oxide solid state electrolyte sheet comprising:
a high pressure resistant polymer-coated oxide solid electrolyte (a);
a high-conductivity polymer electrolyte-coated oxide solid electrolyte (B); and
A reduction-resistant polymer electrolyte-coated oxide solid electrolyte (C);
The three coated oxide solid electrolyte structures are a-B-C from top to bottom (as shown in fig. 1), wherein: the part A contacts the anode of the battery, so that the oxidation resistance of the electrolyte can be improved; the C part contacts the cathode of the battery, and has stronger reduction resistance and stability; and part B is responsible for rapid ion conduction, thus forming an oxide solid electrolyte with a wide electrochemical stability window and dense interior.
The invention also discloses a preparation method of the oxide solid electrolyte sheet, which comprises the following steps:
(1) Preparing high-pressure resistant polymer coated oxide solid electrolyte powder (A);
(2) Preparing high-conductivity polymer electrolyte coated oxide solid electrolyte powder (B);
(3) Preparing reduction-resistant polymer electrolyte coated oxide solid electrolyte powder (C);
(4) And (3) preparing the composite oxide solid electrolyte sheet.
Further, the preparation of the high-pressure resistant polymer-coated oxide solid electrolyte powder (a) of step (1) includes:
① Weighing the high-pressure resistant polymer and lithium salt in a glove box filled with argon to obtain a first mixture for standby, wherein the mass ratio of the lithium salt to the high-pressure resistant polymer is 1: 1-20;
② Adding oxide solid electrolyte powder into the first mixture to obtain a second mixture for standby; the mass ratio of the oxide solid electrolyte powder to the first mixture is 1:10 to 99;
③ Adding a proper amount of solvent into the second mixture, wherein the mass ratio of the solvent to the second mixture is 1: 5-50, adding a solvent, stirring for 12-24 hours at a temperature of 20-85 ℃ under a closed condition, and continuing to carry out ultrasonic treatment for 20min at a power of 240-960W to obtain a dispersion liquid;
④ Stirring the dispersion liquid in a glove box filled with argon at 60-100 ℃ to volatilize the solution completely, and continuously drying the solution for 24-72 hours under the vacuum condition at 60-120 ℃ to obtain the high-pressure-resistant polymer-coated oxide solid electrolyte powder (A).
Further, the high pressure resistant polymer of step ① is selected from any one or more of the following:
Polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polyethylene glycol diacrylate-polyacrylonitrile copolymer (PEGDA-PAN), polyacrylonitrile (PAN), polyethylene glycol diacrylate (PEGDA), polymethyl methacrylate (PMMA), polyethylene carbonate (PVC), nitrile polyvinyl alcohol (PVA-CN);
The lithium salt in the step ① comprises the following components in mass ratio 1: 1-10, selected from any two of the following:
Lithium perchlorate (LiClO 4), lithium hexafluorophosphate (LiPF 6), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium hexafluoroarsenate (LiAsF 6), lithium tetrafluoroborate (LiBF 4), lithium difluorooxalato borate (liodbb), lithium bis (fluorosulfonyl) imide (LFSI);
the oxide solid electrolyte powder of step ② is selected from one or more of the following:
Li0.34La0.567TiO3(LLTO)、Li7La3Zr2O12(LLZO)、Li6.4La3Zr1.4Ta0.6O12(LLZTO)、Li2.88PO3.73N0.14(LiPON)、Li1.3Al0.3Ti1.7(PO4)3(LATP)、Li1.5Al0.5Ge1.5P3O12;
the solvent of step ③ is selected from any one or more of the following:
One or more of acetone, acetonitrile, N-methyl pyrrolidone, N-dimethylformamide, ethanol, propanol, N-butanol, isopropanol, ethylene glycol and tetrahydrofuran.
Further, the preparation of the high-conductivity polymer electrolyte coated oxide solid electrolyte powder (B) of step (2) includes:
① Weighing a certain mass of high ion conductive polymer monomer, an initiator and lithium salt into a mortar in a glove box filled with argon to obtain a first mixture for standby; the mass ratio of the initiator to the polymer monomer to the lithium salt is 1: 95-99: 25-150;
② Adding oxide solid electrolyte powder into the first mixture, wherein the mass ratio of the oxide solid electrolyte powder to the first mixture is 1: 10-99 to obtain a second mixture;
③ Grinding the second mixture for 30-100 min, and then heating, wherein the temperature is 60-150 ℃ for 4-12 h, so as to obtain the oxide solid electrolyte powder (B) coated by the high-conductivity polymer.
Further, the Gao Lizi conductive polymer monomer of step ① is selected from any one or more of the following:
Polyethylene oxide (PEO), methyl Methacrylate (MMA), acrylonitrile (AN), ethylene carbonate (VC), 1, 3-Dioxolane (DOL), tetrahydrofuran (THF);
the lithium salt of step ① is selected from any two of the following:
Lithium perchlorate (LiClO 4), lithium hexafluorophosphate (LiPF 6), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium hexafluoroarsenate (LiAsF 6), lithium tetrafluoroborate (LiBF 4), lithium difluorooxalato borate (liodbb), lithium bis (fluorosulfonyl) imide (LFSI);
The initiator in step ① is selected from any one of the following:
azobisisobutyronitrile, dibenzoyl peroxide;
the oxide solid electrolyte powder of step ② is selected from one or more of the following:
Li0.34La0.567TiO3(LLTO)、Li7La3Zr2O12(LLZO)、Li6.4La3Zr1.4Ta0.6O12(LLZTO)、Li2.88PO3.73N0.14(LiPON)、Li1.3Al0.3Ti1.7(PO4)3(LATP)、Li1.5Al0.5Ge1.5P3O12.
further, the preparation of the reduction-resistant polymer electrolyte coated oxide solid electrolyte powder (C) of step (3) includes:
① Weighing a certain mass of reduction-resistant polymer and lithium salt in a glove box filled with argon to obtain a first mixture for later use; the mass ratio of the polymer to the lithium salt is 1:1 to 10;
② Weighing a certain amount of oxide solid electrolyte powder, and adding the oxide solid electrolyte powder into the first mixture to obtain a second mixture, wherein the mass ratio of the oxide solid electrolyte to the first mixture is 1: and (2) ball milling the second mixture in a ball mill at a rotating speed of 480-640 r/min for 4-8 h to obtain the reduction-resistant polymer electrolyte coated oxide solid electrolyte powder (C).
Further, the reduction resistant polymer of step ① is selected from any one or more of the following:
Polyethylene oxide (PEO), polyethylene glycol diacrylate (PEGDA), polymethyl methacrylate (PMMA), polyethylene carbonate (PVC), nitrile polyvinyl alcohol (PVA-CN);
The lithium salt in step ① is selected from any one of the following:
Lithium perchlorate (LiClO 4), lithium hexafluorophosphate (LiPF 6), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium hexafluoroarsenate (LiAsF 6), lithium tetrafluoroborate (LiBF 4), lithium difluorooxalato borate (liodbb), lithium bis (fluorosulfonyl) imide (LFSI);
the oxide solid electrolyte powder of step ② is selected from one or more of the following:
Li0.34La0.567TiO3(LLTO)、Li7La3Zr2O12(LLZO)、Li6.4La3Zr1.4Ta0.6O12(LLZTO)、Li2.88PO3.73N0.14(LiPON)、Li1.3Al0.3Ti1.7(PO4)3(LATP)、Li1.5Al0.5Ge1.5P3O12.
further, the preparation of the composite oxide solid electrolyte sheet of step (4) includes:
① Adding 0.1-0.5 g of oxide solid electrolyte powder (A) coated by high-pressure resistant polymer into a cold pressing mold, and pressurizing for 2-10 min under 15-60 MPa to obtain an electrolyte sheet A;
② The electrolyte sheet A is not required to be demoulded, 0.1 to 0.5g of oxide solid electrolyte powder (B) coated by the high conductive polymer is continuously added into a cold pressing mold, and the electrolyte sheet A-B is obtained after pressurizing for 2 to 10 minutes under 15 to 60 MPa;
③ The A-B electrolyte sheet is not required to be demoulded, 0.1 to 0.5g of oxide solid electrolyte powder (C) coated by the reduction-resistant polymer electrolyte is continuously added into a cold-pressing mold, and the pressure is increased for 2 to 10 minutes under 15 to 60MPa, so that the A-B-C electrolyte sheet is obtained;
④ And (3) continuously pressurizing the A-B-C electrolyte sheet for 5-15 min under 45-80 MPa, and demolding to obtain the composite oxide solid electrolyte sheet.
The invention also discloses an oxide solid electrolyte sheet prepared by the preparation method.
The invention also discloses an application of the oxide solid electrolyte sheet in preparing a solid-state battery, which comprises the following steps:
Assembling the obtained oxide solid electrolyte sheet into a blocking battery and a full battery, performing metal spraying treatment on two sides of the ABC sheet, assembling into a steel sheet pair sedimentation tank, and testing the ion conductivity of the steel sheet pair sedimentation tank; the anode adopts LiFePO 4, and the cathode adopts metal Li.
Compared with the prior art, the invention has the following advantages:
(1) The coating treatment is adopted for the rigid oxide electrolyte, and the problems of large platelet boundary impedance and interface impedance of the traditional oxide solid electrolyte are overcome by utilizing the flexibility and easy processing property of the polymer electrolyte;
(2) The gradient coating treatment is adopted, the positive electrode is coated by high-pressure resistant polymer electrolyte, the electrolyte at one side of the negative electrode is coated by reduction resistant polymer, and the electrolyte in the bulk phase is coated by high-ion conductive polymer, so that the method can simultaneously improve the high-pressure resistance, the reduction resistance, the interface compatibility and the overall performance of the battery of the electrolyte;
(3) The oxide electrolyte is coated by adopting the organic polymer, so that good interface contact and wettability inside the battery can be realized without excessively high preparation pressure and battery stack pressure, meanwhile, a sintering step is omitted, and the process steps and the manufacturing cost of the oxide solid electrolyte are greatly reduced.
Drawings
FIG. 1 (a) is a schematic structural diagram of a gradient coated oxide solid electrolyte; fig. 1 (b) is a surface scanning electron micrograph of the electrolyte.
Fig. 2 is a graph of all solid state battery cycle performance data assembled from electrolytes.
FIG. 3 is a sweep voltammogram of a gradient coated oxide solid electrolyte.
Detailed Description
The following embodiments are provided to further illustrate the technical scheme of the present invention, but not to limit the technical scheme, and all modifications and equivalent substitutions are included in the scope of the present invention without departing from the spirit and scope of the technical scheme.
Example 1:
A method for preparing an oxide solid electrolyte sheet, comprising:
step one: preparation of high pressure resistant polymer coated oxide solid electrolyte powder
(1) Weighing a certain mass of high-pressure-resistant polymer and lithium salt in a glove box filled with argon, wherein the lithium salt is double salt, and the mass ratio of the high-pressure-resistant polymer to the lithium salt is 1:1, the ratio of lithium salt to polymer is 1:10; the high pressure resistant polymer is Polyacrylonitrile (PAN); the lithium salt is lithium bis (trifluoromethanesulfonyl imide) (LiTFSI) or lithium difluoro (oxalato) borate (LiODFB). After weighing, adding the mixture into a white transparent glass bottle with a magnet;
(2) Adding oxide solid electrolyte into the glass bottle in the above steps, wherein the mass ratio of the oxide solid electrolyte to the polymer electrolyte (the sum of the mass of the high-pressure resistant polymer and the mass of the lithium salt) is 1: the oxide solid electrolyte powder is Li 6.4La3Zr1.4Ta0.6O12 (LLZTO);
(3) Adding a proper amount of solvent, namely N-methyl pyrrolidone, into the glass bottle in the step, wherein the mass ratio of the solvent to the solid (oxide solid electrolyte powder, polymer and lithium salt) is 1:20, adding a solvent, stirring for 18h under a closed condition at a temperature of 75 ℃, and continuing ultrasonic treatment with power of 960W for 20min to obtain a uniform dispersion;
(4) Opening the cover of the glass bottle, vigorously stirring the dispersion liquid in a glove box filled with argon at 80 ℃ to completely volatilize the solution, finally obtaining oxide solid electrolyte powder uniformly coated by polymer electrolyte, and continuously drying the obtained powder for 48 hours under the vacuum condition at 120 ℃ to obtain high-pressure-resistant polymer-coated oxide solid electrolyte powder (A) for further removing the solvent;
step two: preparation of high conductivity polymer electrolyte coated oxide solid electrolyte powder (B):
(1) Weighing a certain mass of high ion conductive polymer monomer, initiator and lithium salt in a glove box filled with argon, wherein the mass ratio of the initiator to the polymer monomer to the lithium salt is 1:95:95; the high ion conductive polymer monomer is Methyl Methacrylate (MMA); the lithium salt is lithium bis (trifluoromethanesulfonyl) imide (LiTFSI). After the weighing is finished, all the materials are added into a mortar;
(2) Adding an oxide solid electrolyte into the glass bottle in the above steps, wherein the mass ratio of the oxide solid electrolyte to the polymer electrolyte (the sum of the mass of the polymer and the mass of the lithium salt) is 1:10, the oxide solid electrolyte powder is Li 6.4La3Zr1.4Ta0.6O12 (LLZTO);
(3) Grinding the mixture in the mortar for 30min until the mixture is in a uniform viscous state;
(4) Carrying out heat treatment on the mixture in the viscous state, and continuing for 4 hours at 80 ℃ to initiate polymerization of polymer monomers, so as to uniformly form high-conductivity polymer on the surface of the oxide solid powder, and finally obtaining oxide solid electrolyte powder (B) coated by the high-conductivity polymer;
Step three: preparation of reduction-resistant polymer electrolyte-coated oxide solid electrolyte powder (C):
(1) Weighing a certain mass of reduction-resistant polymer and lithium salt in a glove box filled with argon, wherein the mass ratio of the polymer to the lithium salt is 1:1.5; the reduction resistant polymer is polyethylene oxide (PEO); the lithium salt is lithium hexafluorophosphate (LiPF 6);
(2) Weighing a certain amount of oxide solid electrolyte, wherein the mass ratio of the oxide solid electrolyte to the polymer electrolyte (the sum of the mass of the polymer and the mass of the lithium salt) is 1:19, the oxide solid electrolyte powder was Li 6.4La3Zr1.4Ta0.6O12 (LLZTO). And then adding the weighed polymer, lithium salt and oxide solid electrolyte into a ball milling tank, ball milling for 4 hours in a ball mill at a rotating speed of 480r/min, so that the polymer is uniformly coated on the oxide solid electrolyte, and finally obtaining oxide solid electrolyte powder (C) coated by the reduction-resistant polymer electrolyte.
Step four: preparation of oxide solid electrolyte sheet:
(1) Adding 0.1g of powder A into a cold pressing mold, regulating the pressure to 15MPa, and obtaining an A electrolyte sheet obtained from the powder A for 2 min;
(2) The obtained electrolyte sheet A is not required to be demoulded, a proper amount of B is continuously added into a die, the mass is 0.15g, and the electrolyte sheet A-B is obtained by pressing the electrolyte sheet A on a cold press for 2min under the pressure of 15 MPa;
(3) The obtained A-B electrolyte sheet is not required to be demoulded, a proper amount of C is continuously added into a die, the mass is 0.1g, and the A-B-C electrolyte sheet is obtained by pressing the die on a cold press for 2min under the pressure of 15 MPa;
(4) Continuously pressurizing the obtained A-B-C electrolyte sheet to 60MPa, continuously demolding for 10min to obtain a compact composite oxide solid electrolyte sheet for later use;
(5) Assembling the obtained gradient coated oxide solid electrolytic piece into a blocking battery and a full battery, performing metal spraying treatment on two sides of the ABC piece, assembling into a steel piece pair sedimentation tank, and testing the ion conductivity of the steel piece pair sedimentation tank; the positive electrode adopts LiFePO 4, the negative electrode adopts metal Li, and the electrochemical performance of the full battery is tested.
As shown in fig. 2, which is an electrochemical window test of the prepared electrolyte, the decomposition voltage thereof is as high as 5V, illustrating the wide electrochemical window thereof. As shown in fig. 3, the performance of the solid-state battery prepared by the electrolyte sheet subjected to gradient coating is different from that of the battery not subjected to gradient coating, the discharge specific capacity is higher, the interface impedance is small, the cycle performance is stable, the strategy is proved to alleviate the side reaction of the anode interface and the cathode interface, and the compatibility of the interface is improved.
Example 2:
A method for preparing an oxide solid electrolyte sheet, comprising:
The process steps are the same as in example 1 except that the high ion conductive polymer monomer used in step two (1) is changed to 1, 3-Dioxolane (DOL); the same effect can be achieved by changing the lithium salt used to lithium bis (fluorosulfonyl) imide (LFSI).
Example 3:
A method for preparing an oxide solid electrolyte sheet, comprising:
The same procedure as in example 1 was followed except that the oxide solid electrolyte powder used in each step was replaced with Li 0.34La0.567TiO3 (LLTO).
The foregoing is only a preferred embodiment of the present invention, but the design concept of the present invention is not limited thereto, and any person skilled in the art will be able to make insubstantial modifications of the present invention within the scope of the present invention disclosed herein by this concept, which falls within the actions of invading the protection scope of the present invention.
Claims (6)
1. A method for preparing an oxide solid electrolyte sheet, comprising:
(1) Preparation of high pressure resistant polymer coated oxide solid electrolyte powder (a):
(1.1) weighing the high-pressure resistant polymer and lithium salt in a glove box filled with argon to obtain a first mixture for later use; the mass ratio of the lithium salt to the high-pressure resistant polymer is 1: 1-20;
(1.2) adding oxide solid electrolyte powder to the first mixture to obtain a second mixture for later use; the mass ratio of the oxide solid electrolyte powder to the first mixture is 1:10 to 99;
(1.3) adding a solvent into the second mixture, stirring for 12-24 h at 20-85 ℃ under a closed condition, and performing ultrasonic treatment for 20min at a power of 240-960W to obtain a dispersion liquid for later use; the mass ratio of the solvent to the second mixture is 1:5 to 50 percent;
(1.4) maintaining the dispersion liquid in a glove box filled with argon at 60-100 ℃ to volatilize the solution completely, and continuously drying the solution for 24-72 hours under the vacuum condition at 60-120 ℃ to obtain high-pressure-resistant polymer-coated oxide solid electrolyte powder (A);
(2) Preparation of high conductivity polymer electrolyte coated oxide solid electrolyte powder (B):
(2.1) weighing the high ion conductive polymer monomer, the initiator and the lithium salt in a glove box filled with argon to obtain a first mixture for later use; the mass ratio of the initiator to the high ion conductive polymer monomer to the lithium salt is 1: 95-99: 25-150;
(2.2) adding an oxide solid electrolyte powder to the first mixture to obtain a second mixture; the mass ratio of the oxide solid electrolyte powder to the first mixture is 1:10 to 99;
(2.3) grinding the second mixture for 30-100 min, and then heating the mixture for 4-12 h at 60-150 ℃ to obtain high-conductivity polymer coated oxide solid electrolyte powder (B);
(3) Preparation of reduction-resistant polymer electrolyte-coated oxide solid electrolyte powder (C):
(3.1) weighing the reduction-resistant polymer and lithium salt in a glove box filled with argon to obtain a first mixture for later use; the mass ratio of the reduction-resistant polymer to the lithium salt is 1:1 to 10;
(3.2) weighing oxide solid electrolyte powder, adding the oxide solid electrolyte powder into the first mixture to obtain a second mixture, and ball-milling the second mixture in a ball mill at a rotating speed of 480-640 r/min for 4-8 hours to obtain reduction-resistant polymer electrolyte coated oxide solid electrolyte powder (C); the mass ratio of the oxide solid electrolyte to the first mixture is 1:10 to 99;
(4) Preparation of composite oxide solid electrolyte sheet:
(4.1) adding 0.1-0.5 g of oxide solid electrolyte powder (A) coated by high-pressure resistant polymer into a cold pressing mold, and pressurizing for 2-10 min under 15-60 MPa to obtain an electrolyte sheet A;
(4.2) continuously adding 0.1-0.5 g of oxide solid electrolyte powder (B) coated by high conductive polymer into a cold pressing mold without demoulding, and pressurizing for 2-10 min under 15-60 MPa to obtain an A-B electrolyte sheet;
(4.3) continuously adding 0.1-0.5 g of oxide solid electrolyte powder (C) coated by the reduction-resistant polymer electrolyte into a cold-pressing mold without demoulding, and pressurizing for 2-10 min under 15-60 MPa to obtain the A-B-C electrolyte sheet;
(4.4) continuously pressurizing the A-B-C electrolyte sheet for 5-15 min under 45-80 MPa, and demolding to obtain the composite oxide solid electrolyte sheet; wherein:
the high pressure resistant polymer of step (1.1) is selected from any one or more of the following:
Polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyethylene glycol diacrylate-polyacrylonitrile copolymer, polyacrylonitrile, polyethylene glycol diacrylate, polymethyl methacrylate, polyethylene carbonate, and nitrile polyvinyl alcohol;
The Gao Lizi conductive polymer monomer of step (2.1) is selected from any one or more of the following:
polyethylene oxide, methyl methacrylate, acrylonitrile, ethylene carbonate, 1, 3-dioxolane, tetrahydrofuran;
the reduction-resistant polymer of step (3.1) is selected from any one or more of the following:
Polyethylene oxide, polyethylene glycol diacrylate, polymethyl methacrylate, polyethylene carbonate, and nitrile polyvinyl alcohol.
2. The method of manufacturing according to claim 1, wherein:
step (1.1) the lithium salt consists of the following components in mass ratio 1: 1-10, selected from any two of the following:
Lithium perchlorate, lithium hexafluorophosphate, lithium bistrifluoromethane sulfonimide, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium difluorooxalato borate, lithium bistrifluorosulfonimide;
the oxide solid electrolyte powder of step (1.2) is selected from one or more of the following:
Li0.34La0.567TiO3、Li7La3Zr2O12、Li6.4La3Zr1.4Ta0.6O12、Li2.88PO3.73N0.14、Li1.3Al0.3Ti1.7(PO4)3、Li1.5Al0.5Ge1.5P3O12;
the solvent of step (1.3) is selected from any one or more of the following:
Acetone, acetonitrile, N-methylpyrrolidone, N-dimethylformamide, ethanol, propanol, N-butanol, isopropanol, ethylene glycol, tetrahydrofuran.
3. The method of manufacturing according to claim 1, wherein:
the lithium salt in step (2.1) is selected from any two of the following:
Lithium perchlorate, lithium hexafluorophosphate, lithium bistrifluoromethane sulfonimide, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium difluorooxalato borate, lithium bistrifluorosulfonimide;
The initiator in the step (2.1) is selected from any one of the following:
azobisisobutyronitrile, dibenzoyl peroxide;
The oxide solid electrolyte powder of step (2.2) is selected from one or more of the following:
Li0.34La0.567TiO3、Li7La3Zr2O12、Li6.4La3Zr1.4Ta0.6O12、Li2.88PO3.73N0.14、Li1.3Al0.3Ti1.7(PO4)3、Li1.5Al0.5Ge1.5P3O12.
4. The method of manufacturing according to claim 1, wherein:
the lithium salt in the step (3.1) is selected from any one of the following:
Lithium perchlorate, lithium hexafluorophosphate, lithium bistrifluoromethane sulfonimide, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium difluorooxalato borate, lithium bistrifluorosulfonimide;
The oxide solid electrolyte powder of step (3.2) is selected from one or more of the following:
Li0.34La0.567TiO3、Li7La3Zr2O12、Li6.4La3Zr1.4Ta0.6O12、Li2.88PO3.73N0.14、Li1.3Al0.3Ti1.7(PO4)3、Li1.5Al0.5Ge1.5P3O12.
5. an oxide solid electrolyte sheet produced by the production method according to any one of claims 1 to 4.
6. Use of the oxide solid electrolyte sheet according to claim 5 for the preparation of a solid-state battery.
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