CN113078349A - Preparation method of Rb-doped ternary composite solid electrolyte - Google Patents
Preparation method of Rb-doped ternary composite solid electrolyte Download PDFInfo
- Publication number
- CN113078349A CN113078349A CN202110320451.3A CN202110320451A CN113078349A CN 113078349 A CN113078349 A CN 113078349A CN 202110320451 A CN202110320451 A CN 202110320451A CN 113078349 A CN113078349 A CN 113078349A
- Authority
- CN
- China
- Prior art keywords
- solid electrolyte
- source
- rubidium
- ionic liquid
- doped
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011206 ternary composite Substances 0.000 title claims abstract description 18
- 239000002608 ionic liquid Substances 0.000 claims abstract description 35
- 239000002002 slurry Substances 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 18
- 229920000307 polymer substrate Polymers 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000003825 pressing Methods 0.000 claims abstract description 12
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 20
- 229910052744 lithium Inorganic materials 0.000 claims description 19
- 239000000919 ceramic Substances 0.000 claims description 18
- 239000002270 dispersing agent Substances 0.000 claims description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 229910021525 ceramic electrolyte Inorganic materials 0.000 claims description 11
- 229910052701 rubidium Inorganic materials 0.000 claims description 10
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 9
- 229910052715 tantalum Inorganic materials 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 6
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 claims description 6
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 2
- 229910017569 La2(CO3)3 Inorganic materials 0.000 claims description 2
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 claims description 2
- 229960001633 lanthanum carbonate Drugs 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000026 rubidium carbonate Inorganic materials 0.000 claims description 2
- 229940102127 rubidium chloride Drugs 0.000 claims description 2
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 2
- ZIRLXLUNCURZTP-UHFFFAOYSA-I tantalum(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Ta+5] ZIRLXLUNCURZTP-UHFFFAOYSA-I 0.000 claims description 2
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims description 2
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 claims 1
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 claims 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 12
- 239000003792 electrolyte Substances 0.000 abstract description 11
- 239000002131 composite material Substances 0.000 abstract description 9
- 150000002500 ions Chemical group 0.000 abstract description 6
- 239000002223 garnet Substances 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 229910001419 rubidium ion Inorganic materials 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 239000007790 solid phase Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 12
- 239000000758 substrate Substances 0.000 description 8
- -1 polytetrafluoroethylene Polymers 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910003480 inorganic solid Inorganic materials 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical compound [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 description 1
- RVSGESPTHDDNTH-UHFFFAOYSA-N alumane;tantalum Chemical compound [AlH3].[Ta] RVSGESPTHDDNTH-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- CMGJQFHWVMDJKK-UHFFFAOYSA-N lanthanum;trihydrate Chemical compound O.O.O.[La] CMGJQFHWVMDJKK-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920000379 polypropylene carbonate Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003826 uniaxial pressing Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
-
- 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
- H01M10/058—Construction or manufacture
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a preparation method of Rb-doped ternary composite solid electrolyte, which comprises the steps of dissolving LLTZRO powder synthesized by a solid phase chemical ball milling method into dispersion liquid, stirring to form slurry, pouring the slurry on two sides of a polymer substrate, drying, pressing into a sheet, fully soaking in functional ionic liquid, and airing. In the composite solid electrolyte, rubidium ions form large-aperture ion gaps and channels for increasing ion transmission in the LLZTO garnet solid electrolyte, so that the ion conductivity of a garnet crystal structure is improved; meanwhile, the composite solid electrolyte taking the polymer as the main body is formed, the flexible processing performance of the electrolyte is improved on the basis of keeping the ionic conductivity, the ionic liquid is modified and impregnated into the flaky electrolyte, the ionic liquid can fully fill up tiny gaps in the structure and bridge LLZTO particles, an effective channel is formed for lithium ions, the conductivity is improved, and the ultrathin solid electrolyte sheet can be formed under the condition of sheet forming.
Description
Technical Field
The invention belongs to the technical field of preparation of solid electrolytes obtained by lithium ion batteries, and particularly relates to an Rb-doped garnet-type LLZTO solid electrolyte, a polymer and ionic liquid compounded solid electrolyte and a preparation method thereof.
Background
With the rapid development of new energy electric vehicles, lithium ion batteries with high energy density are highly valued by more and more researchers. In conventional liquid electrolytes, unstable deposition and dendrite growth of lithium metal on the negative electrode can cause a series of safety problems, which severely hamper the development of lithium metal negative electrodes. Compared with liquid electrolyte, the solid electrolyte has high ionic conductivity, good mechanical strength, incombustibility and chemical stability, can perfectly solve the safety problem of lithium dendrites of the lithium battery, and can match a lithium metal cathode with a high-voltage anode to prepare the all-solid-state lithium battery with higher energy density. The development of solid electrolyte is one of the most critical to all-solid batteries, and researchers have attracted great interest because it contains inorganic solid electrolyte or nano inorganic filler, and also contains polymer electrolyte, and has good machinability, flexibility and reasonable ionic conductivity.
One of the methods for increasing the conductivity of the inorganic solid electrolyte is to improve by means of doping with a metal element. For example, chinese patent CN109052473A discloses an industrial preparation method of a garnet-type solid electrolyte co-doped with tantalum and aluminum, wherein the expression is Li6.4xLa3Zr2xTaxAl0.2O12Wherein x is 0.2-0.5, and the crystal structure of the lanthanum lithium zirconate cubic phase is stabilized by co-doping tantalum aluminum element, so that the ionic conductivity is improved. Another effective method for improving the conductivity of solid electrolyte is to prepare inorganic solid electrolyte and polymer solid electrolyte into composite solid electrolyte, for example, Chinese patent document CN106450424A discloses a polymer composite solid electrolyte, its preparation method and application, which comprises drying polyethylene oxide, inorganic solid electrolyte and lithium bis (trifluoromethanesulfonylimide) at 50 deg.C and 120 deg.C respectively, and drying at the same timeDissolving in acetonitrile to obtain a uniform mixed solution. And pouring the prepared mixed solution into a polytetrafluoroethylene mold, volatilizing the acetonitrile solvent in vacuum, and drying at 50 ℃ in vacuum to obtain the solid electrolyte. These modified solid electrolytes still have problems in terms of insufficient lithium ion conductivity and the like.
Disclosure of Invention
Aiming at the defects of the modified solid electrolyte on the lithium ion conduction performance, the invention aims to provide a preparation method of the Rb compound doped LLZTO ceramic matrix, polymer and ionic liquid compounded solid electrolyte.
The technical scheme adopted by the invention for solving the problems is as follows:
a preparation method of a sandwich-shaped ternary composite solid electrolyte doped with Rb comprises the following steps:
(1) preparation of rubidium-doped LLZTO solid electrolyte: adding a lithium source, a lanthanum source, a zirconium source, a tantalum source and a rubidium source into a dispersing agent, mixing for 12-24 hours in a ball mill at 100-600 r/min, sintering at 700-1200 ℃, ball-milling into powder, and adding the dispersing agent to form rubidium-doped LLZTO slurry;
(2) infiltrating the rubidium-doped LLZTO slurry obtained in the step (1) into two surfaces of a polymer substrate, drying in a vacuum furnace at 100-120 ℃, and pressing into a sheet ceramic electrolyte with the thickness of 50-100 microns under the pressure of 50-500 MPa;
(3) soaking the flaky ceramic electrolyte obtained in the step (2) in an ionic liquid for 12-24 h, and then drying at 100-120 ℃ in vacuum to obtain a solid electrolyte compounded by the LLZTO ceramic matrix, the polymer and the ionic liquid, namely the Rb-doped sandwich-shaped ternary composite solid electrolyte.
According to the scheme, N-methylpyrrolidone NMP is adopted as the dispersing agent in the step (1).
According to the scheme, in the step (2), the polymer substrate is selected from one of PEO, PAN, PEC, PVP, PVDF, PPC and the like, the polymer substrate film is selected from one of PEO, PAN, PEC, PVP, PVDF and PPC, and the film thickness is controlled to be 50-100 mu m.
According to the scheme, the ionic liquid in the step (3) is selected from lithium-containing ionic liquidBody ([ EMI ]0.8Li0.2][TFSI]) Loaded as guest molecules into the sheet ceramic electrolyte.
According to the scheme, the lithium source is lithium hydroxide (LiOH) and lithium carbonate (Li)2CO3) Lithium perchlorate (LiClO)4) One or more of lithium bis (trifluoromethyl) sulfonyl imide (LiTFSI) and the like; the lanthanum source is lanthanum oxide (La)2O3) Lanthanum hydroxide (La (OH)3) Lanthanum carbonate (La)2(CO3)3) One or more of the following; the source of zirconium is selected from zirconium oxide (ZrO)2) Zirconium hydroxide (Zr (OH)4) Zirconium carbonate (ZrOCO)3) And the like; rubidium carbonate (Rb) is adopted as rubidium salt2CO3) Rubidium chloride (RbCl)3) Rubidium nitrate (Rb (NO)3)3) Rubidium hydroxide (RbOH), etc.; the tantalum source being tantalum oxide (Ta)2O5) And tantalum hydroxide (Ta (OH)5) And the like.
According to the scheme, the lithium source, the lanthanum source, the zirconium source, the tantalum source and the rubidium source are (7-8) in terms of the molar ratio of metal elements Li, La, Zr, Ta and Rb: 3: 2: (0.5-1.5): (0-1); wherein, the amount of the rubidium source is not 0, and the lithium source is 5-10 wt% in excess.
Compared with the prior art, the invention has the beneficial effects that:
firstly, the Rb doped, ionic liquid and polymer compounded ternary solid electrolyte forms large-aperture ion gaps and channels for increasing ion transmission in the LLZTO garnet solid electrolyte due to doping of rubidium ions with larger ionic radius than lithium ions, so that the rapid mobility of the lithium ions in the garnet crystal structure is improved; meanwhile, the composite solid electrolyte taking a polymer as a main body is formed by taking polymer solid electrolytes such as PEO, PVP, PVDF, PPC and the like as substrates, the flexible processing performance of the electrolyte is improved on the basis of keeping the ionic conductivity, the ionic liquid is modified and soaked into the interior of the flaky electrolyte, the ionic liquid can fully fill up tiny gaps in the structure, and LLZTO particles are bridged, so that an effective channel is formed for lithium ions, the resistance of a cathode contact interface can be effectively reduced, the lithium ion conduction is promoted, the conductivity is improved, and ultrathin solid electrolyte sheets can be formed under the condition of sheet forming. Therefore, the Rb doped, ionic liquid and polymer compounded ternary solid electrolyte prepared by the invention has high lithium ion conductivity and excellent flexible processability.
Drawings
Fig. 1 is a plot of the lithium ion diffusion rates of comparative example 1 and rubidium-doped PEO/ionic liquid sandwich-like ternary composite solid-state electrolyte (example 1).
Fig. 2 is an impedance spectrum of comparative example 2 and rubidium-doped PEO/ionic liquid sandwich-like ternary composite solid electrolyte (example 4).
Fig. 3 is arrhenius diagrams of the solid electrolytes of comparative examples 1 and 2 and examples 1 and 2.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the present invention is not limited to the following examples.
In the following examples, Ionic liquids [ EMI ]0.8Li0.2][TFSI]Purchased from Linzhou science technologies, Inc.
Comparative example 1
A preparation method of a LLZTO garnet type solid-state battery comprises the following steps:
mixing LiOH, La (OH)3、ZrO2、Ta(OH)5According to a molar ratio of 7: 3: 2: 0.5 adding a dispersing agent NMP, fully mixing for 15h in a ball mill at 600r/min, roasting for 12h at 1200 ℃ and grinding for 6h to form powder, adding the dispersing agent to form LLZTO slurry, drying in a vacuum furnace at 120 ℃, and pressing into a flaky ceramic electrolyte with the thickness of 75 microns by a tabletting machine under 100MPa in a uniaxial pressure static pressure mode to serve as a reference sample.
Comparative example 2
A preparation method of a PEO/ionic liquid sandwich-shaped ternary composite solid electrolyte (undoped Rb) comprises the following steps:
(a) LLZTO solid electrolyte powder prepared first: mixing LiOH, La (OH)3、ZrO2、Ta(OH)5According to a molar ratio of 7: 3: 2: 0.5, adding a dispersing agent, fully mixing for 15h at 600r/min in a ball mill, roasting for 12h at the high temperature of 1200 ℃, ball-milling for 6h to form powder, and adding the dispersing agent to form LLZTO slurry;
(b) the LLZTO ceramic slurry is poured on two sides of a PEO substrate film with 80 μm polymer, the ceramic slurry is kept to be soaked on two sides of the polymer substrate, then the polymer substrate is dried in a vacuum furnace at 120 ℃, and a sheet-shaped ceramic electrolyte with the thickness of 100 μm is pressed by a single-shaft pressing way under the pressure of 100 MPa;
(c) soaking a flaky electrolyte in an ionic liquid ([ EMI ] to form a thin electrolyte0.8Li0.2][TFSI]) And (3) drying the mixture at 120 ℃ in vacuum for 24h to form a thin solid electrolyte, adding ionic liquid to improve the ionic conductivity, and preparing the LLZTO ceramic-based, polymer and ionic liquid composite solid electrolyte.
Example 1
A preparation method of a sandwich-shaped ternary composite solid electrolyte doped with Rb comprises the following steps:
(a) preparing rubidium-doped LLZTO solid electrolyte powder: mixing LiOH, La (OH)3、ZrO2、Ta(OH)5、RbCl3According to a molar ratio of 7: 3: 2: 0.5: 0.2, adding a dispersing agent, fully mixing for 15h at 600r/min in a ball mill, roasting for 12h at the high temperature of 800 ℃, ball-milling for 6h to form powder, and adding the dispersing agent to form rubidium-doped LLZTO slurry;
(b) pouring LLZTRO ceramic slurry onto two sides of 80 μm polymer PEO substrate, soaking the ceramic slurry into two sides of the polymer substrate, drying in 120 deg.C vacuum furnace, and pressing into 100 μm sheet ceramic electrolyte by uniaxial pressing at 100 MPa;
(c) soaking a flaky electrolyte in an ionic liquid (EMI)0.8Li0.2][TFSI]) And (3) drying the solid electrolyte formed into a sheet at 120 ℃ in vacuum for 12h, adding ionic liquid to improve the ionic conductivity, and preparing the Rb doped LLZTO ceramic-based polymer-ionic liquid composite solid electrolyte.
Example 2
A preparation method of a sandwich-shaped ternary composite solid electrolyte doped with Rb comprises the following steps:
(a) preparing rubidium-doped LLZTO solid electrolyte powder: mixing LiOH, La (OH)3、ZrO2、Ta(OH)5、RbCl3According to a molar ratio of 7: 3: 2: 0.5: 0.5, adding a dispersing agent, fully mixing for 15h at 600r/min in a ball mill, roasting for 12h at the high temperature of 1000 ℃, ball-milling for 6h to form powder, and adding the dispersing agent to form rubidium-doped LLZTO slurry;
(b) pouring the LLZTO ceramic slurry onto a substrate with two surfaces of polymer PEO with the thickness of 80 μm to enable the ceramic slurry to be soaked on the two surfaces of the polymer substrate, then putting the polymer substrate into a vacuum furnace with the temperature of 120 ℃ for drying, and pressing the polymer substrate into flaky ceramic electrolyte with the thickness of 100 μm by a single-shaft pressing mode under the pressure of 200 MPa;
(c) soaking a flaky electrolyte in an ionic liquid (EMI)0.8Li0.2][TFSI]) And (3) drying the solid electrolyte in vacuum at 100 ℃ for 12h to form a thin sheet, adding ionic liquid to improve the ionic conductivity, and preparing the Rb doped LLZTO ceramic matrix, polymer and ionic liquid compounded solid electrolyte.
Example 3
A preparation method of a sandwich-shaped ternary composite solid electrolyte doped with Rb comprises the following steps:
(a) preparing rubidium-doped LLZTO solid electrolyte powder: mixing LiOH, La (OH)3、ZrO2、Ta(OH)5、RbCl3According to a molar ratio of 7: 3: 2: 1: 1, adding a dispersing agent, fully mixing for 15h in a ball mill at 600r/min, roasting for 15h at the high temperature of 1100 ℃, ball-milling for 6h to form powder, and adding the dispersing agent to form rubidium-doped LLZTO slurry;
(b) pouring the LLZTO ceramic slurry onto the two-sided substrate of the polymer to enable the ceramic slurry to be soaked into the two sides of the PAN substrate of the polymer, then putting the PAN substrate of the polymer into a vacuum furnace at 120 ℃ for drying, and pressing the PAN substrate of the polymer into a flaky ceramic electrolyte with the thickness of 75 microns by a single-shaft pressing machine under the pressure of 300 MPa;
(c) soaking flake electrolyte in ionic liquidBody (EMI)0.8Li0.2][TFSI]) And (3) drying the solid electrolyte in vacuum at 100 ℃ for 18h to form a thin sheet, adding ionic liquid to improve the ionic conductivity, and preparing the Rb doped LLZTO ceramic-based polymer-ionic liquid composite solid electrolyte.
Example 4
A preparation method of a sandwich-shaped ternary composite solid electrolyte doped with Rb comprises the following steps:
(a) preparing rubidium-doped LLZTO solid electrolyte powder: mixing LiOH, La (OH)3、ZrO2、Ta(OH)5、RbCl3According to the molar ratio of 8: 3: 2: 1.5: 1, adding a dispersing agent, fully mixing for 15h in a ball mill at 600r/min, roasting for 15h at the high temperature of 1200 ℃, ball-milling for 6h to form powder, and adding the dispersing agent to form rubidium-doped LLZTO slurry;
(b) pouring the LLZTO ceramic slurry onto a polymer substrate with two surfaces to enable the ceramic slurry to be soaked on two sides of PVDF (polyvinylidene fluoride) of the polymer substrate, then putting the polymer substrate into a 120 ℃ vacuum furnace for drying, and pressing the polymer substrate into flaky ceramic electrolyte with the thickness of 100 microns by a single-shaft pressing machine under the pressure of 50-500 MPa;
(c) soaking the flaky electrolyte in Ionic Liquid (ILs) for 24h, drying at 100 ℃ in vacuum to form the flaky solid electrolyte, adding the ionic liquid to improve the ionic conductivity, and preparing the Rb doped LLZTO ceramic-based polymer and ionic liquid compounded solid electrolyte.
As can be seen from FIGS. 1 and 2, the ternary composite solid electrolyte prepared by the preparation method of the invention is doped with rubidium and compounded with PEO and ILs, so that the diffusion rate of lithium ions in the solid electrolyte is increased, and the interface impedance is reduced.
As can be seen from FIG. 3, the conductivity of the rubidium-doped PEO/ILs composite ternary composite solid electrolyte is greatly improved compared with that of the comparative example, and Rb is+The doping can further improve the conductivity of the solid electrolyte.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and changes can be made without departing from the inventive concept of the present invention, and these modifications and changes are within the protection scope of the present invention.
Claims (6)
1. A preparation method of an Rb-doped ternary composite solid electrolyte is characterized by comprising the following steps:
(1) preparation of rubidium-doped LLZTO solid electrolyte: adding a lithium source, a lanthanum source, a zirconium source, a tantalum source and a rubidium source into a dispersing agent, ball-milling and mixing for 12-24 hours, sintering at a high temperature of 700-1200 ℃, ball-milling into powder, and adding the dispersing agent to form rubidium-doped LLZTO slurry;
(2) infiltrating the rubidium-doped LLZTO slurry obtained in the step (1) into two surfaces of a polymer substrate, drying the polymer substrate in a vacuum furnace at 100-120 ℃, and pressing the polymer substrate into a sheet ceramic electrolyte with the thickness of 50-100 microns under the pressure of 50-500 MPa;
(3) and (3) soaking the flaky ceramic electrolyte obtained in the step (2) in ionic liquid for 12-24 h, and then drying at 100-120 ℃ in vacuum to obtain a solid electrolyte compounded by the LLZTO ceramic matrix, the polymer and the ionic liquid, namely the Rb doped ternary composite solid electrolyte.
2. The method of claim 1, wherein the dispersant in step (1) is N-methylpyrrolidone.
3. The method of claim 1, wherein the polymer substrate film in step (2) is selected from one of PEO, PAN, PEC, PVP, PVDF and PPC, and the film thickness is controlled to be 50-100 μm.
4. The method of claim 1, wherein the ionic liquid in step (3) is lithium-containing ionic liquid [ EMI ] that is used as the ionic liquid0.8Li0.2][TFSI]。
5. The method for preparing an Rb-doped ternary composite solid electrolyte according to claim 1, wherein the lithium source is one or more selected from the group consisting of lithium hydroxide, lithium carbonate, lithium perchlorate and lithium bis (trifluoromethyl) sulfonimide; the lanthanum source is selected from one or more of lanthanum oxide, lanthanum hydroxide and lanthanum carbonate; the zirconium source is selected from at least one or more of zirconium oxide, zirconium hydroxide and zirconium carbonate; the rubidium source is selected from one of rubidium carbonate, rubidium chloride, rubidium nitrate and rubidium hydroxide; the tantalum source is selected from one of tantalum oxide and tantalum hydroxide.
6. The method for preparing the Rb doped ternary composite solid electrolyte according to claim 1, wherein the molar ratio of the lithium source, the lanthanum source, the zirconium source, the tantalum source and the rubidium source in terms of metal ions is (7-8): 3: 2: (0.5-1.5): (0-1); wherein the amount of rubidium source is other than 0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110320451.3A CN113078349A (en) | 2021-03-25 | 2021-03-25 | Preparation method of Rb-doped ternary composite solid electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110320451.3A CN113078349A (en) | 2021-03-25 | 2021-03-25 | Preparation method of Rb-doped ternary composite solid electrolyte |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113078349A true CN113078349A (en) | 2021-07-06 |
Family
ID=76611592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110320451.3A Pending CN113078349A (en) | 2021-03-25 | 2021-03-25 | Preparation method of Rb-doped ternary composite solid electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113078349A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244293A (en) * | 2011-06-09 | 2011-11-16 | 中南大学 | Method for preparing ionic liquid plasticized composite polymer electrolyte for lithium ion battery |
| CN106654364A (en) * | 2016-10-20 | 2017-05-10 | 中国科学院大学 | Ion liquid composite full-solid polymer electrolyte and preparation method and application thereof |
| CN107492681A (en) * | 2017-08-09 | 2017-12-19 | 上海纳晓能源科技有限公司 | Solid electrolyte film and preparation method thereof |
| CN110247108A (en) * | 2019-07-08 | 2019-09-17 | 光鼎铷业(广州)集团有限公司 | A kind of preparation method of rubidium doped garnet type composite solid electrolyte film |
| WO2020252427A1 (en) * | 2019-06-13 | 2020-12-17 | Ampcera Inc. | A solid-state electrolyte membrane |
-
2021
- 2021-03-25 CN CN202110320451.3A patent/CN113078349A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244293A (en) * | 2011-06-09 | 2011-11-16 | 中南大学 | Method for preparing ionic liquid plasticized composite polymer electrolyte for lithium ion battery |
| CN106654364A (en) * | 2016-10-20 | 2017-05-10 | 中国科学院大学 | Ion liquid composite full-solid polymer electrolyte and preparation method and application thereof |
| CN107492681A (en) * | 2017-08-09 | 2017-12-19 | 上海纳晓能源科技有限公司 | Solid electrolyte film and preparation method thereof |
| WO2020252427A1 (en) * | 2019-06-13 | 2020-12-17 | Ampcera Inc. | A solid-state electrolyte membrane |
| CN110247108A (en) * | 2019-07-08 | 2019-09-17 | 光鼎铷业(广州)集团有限公司 | A kind of preparation method of rubidium doped garnet type composite solid electrolyte film |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111653820B (en) | Solid electrolyte and application thereof | |
| Kim et al. | Research progresses of garnet-type solid electrolytes for developing all-solid-state Li batteries | |
| Chen et al. | Synthesis of Ta and Ca doped Li7La3Zr2O12 solid-state electrolyte via simple solution method and its application in suppressing shuttle effect of Li-S battery | |
| US10305096B2 (en) | Method for producing electrode active material and electrode active material | |
| Xu et al. | Recent advances in the interface design of solid-state electrolytes for solid-state energy storage devices | |
| Wei et al. | Challenges, fabrications and horizons of oxide solid electrolytes for solid‐state lithium batteries | |
| Zhang et al. | Recent advances of Li7La3Zr2O12-based solid-state lithium batteries towards high energy density | |
| CN108899579A (en) | A kind of all-solid lithium-ion battery of self-crosslinking composite solid electrolyte prepared and its constitute | |
| CN111834662B (en) | Interface functional layer, preparation method thereof and lithium ion battery | |
| Zhou et al. | Production of Ta-doped Li7La3Zr2O12 solid electrolyte with high critical current density | |
| CN113871588A (en) | Lithium battery core-shell cathode material, lithium battery containing lithium battery core-shell cathode material and preparation method of lithium battery | |
| CN112993233A (en) | Lithium supplement material of lithium ion battery and preparation method and application thereof | |
| CN113078350A (en) | Preparation method of rubidium-doped high-conductivity LLZTO/PEO composite solid electrolyte | |
| Zhao et al. | Current challenges and perspectives of garnet-based solid-state electrolytes | |
| Ferrer-Nicomedes et al. | Introducing an ionic conductive matrix to the cold-sintered Li1. 3Al0. 3Ti1. 7 (PO4) 3-based composite solid electrolyte to enhance the electrical properties | |
| CN114566702B (en) | Sandwich integrated all-solid-state polymer electrolyte membrane, preparation method and application thereof | |
| CN113078349A (en) | Preparation method of Rb-doped ternary composite solid electrolyte | |
| CN115020795A (en) | Lithium salt-free composite solid electrolyte membrane and preparation method thereof | |
| CN113851697B (en) | Preparation method and application of thin layered solid electrolyte membrane | |
| CN112510254B (en) | Novel sulfide solid electrolyte and preparation method and application thereof | |
| CN114695949A (en) | Acrylic fiber-based ceramic composite nanofiber solid electrolyte and preparation method thereof | |
| JP2022081804A (en) | Manufacturing method of solid electrolyte and manufacturing method of secondary battery | |
| CN111370754A (en) | Preparation method of ultrathin electrolyte film and all-solid-state battery | |
| Langer et al. | Li 7 La 3 Zr 2 O 12 and Poly (Ethylene Oxide) Based Composite Electrolytes | |
| Mosa et al. | Sol–Gel Materials for Batteries and Fuel Cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210706 |
|
| RJ01 | Rejection of invention patent application after publication |