CN117886614A - Fibrous ceramic inorganic material, preparation method and application thereof, and lithium battery solid polymer electrolyte - Google Patents
Fibrous ceramic inorganic material, preparation method and application thereof, and lithium battery solid polymer electrolyte Download PDFInfo
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- CN117886614A CN117886614A CN202410302304.7A CN202410302304A CN117886614A CN 117886614 A CN117886614 A CN 117886614A CN 202410302304 A CN202410302304 A CN 202410302304A CN 117886614 A CN117886614 A CN 117886614A
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 45
- 239000007787 solid Substances 0.000 title claims abstract description 45
- 239000000919 ceramic Substances 0.000 title claims abstract description 41
- 229910010272 inorganic material Inorganic materials 0.000 title claims abstract description 41
- 239000011147 inorganic material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- 239000012266 salt solution Substances 0.000 claims abstract description 24
- 241000233866 Fungi Species 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 21
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000835 fiber Substances 0.000 claims abstract description 16
- 241000894006 Bacteria Species 0.000 claims abstract description 14
- 150000002603 lanthanum Chemical class 0.000 claims abstract description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 10
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 60
- 239000011256 inorganic filler Substances 0.000 claims description 32
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 32
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 27
- 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 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 19
- 238000012258 culturing Methods 0.000 claims description 15
- 239000001963 growth medium Substances 0.000 claims description 14
- 238000004108 freeze drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- 239000001888 Peptone Substances 0.000 claims description 8
- 108010080698 Peptones Proteins 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- 235000019319 peptone Nutrition 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 3
- 210000001787 dendrite Anatomy 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 239000002657 fibrous material Substances 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 81
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 25
- 239000000243 solution Substances 0.000 description 22
- 239000002131 composite material Substances 0.000 description 19
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical group [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 12
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 9
- 230000001954 sterilising effect Effects 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 210000004027 cell Anatomy 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000011244 liquid electrolyte Substances 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 238000004659 sterilization and disinfection Methods 0.000 description 5
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 3
- XRNHBMJMFUBOID-UHFFFAOYSA-N [O].[Zr].[La].[Li] Chemical compound [O].[Zr].[La].[Li] XRNHBMJMFUBOID-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Inorganic Fibers (AREA)
Abstract
The invention belongs to the technical field of lithium batteries, and provides a fibrous ceramic inorganic material, a preparation method and application thereof, and a lithium battery solid polymer electrolyte. The preparation method of the invention comprises the following steps: performing first culture on the fibrous fungus spores to obtain fibrous fungus; performing second culture on the fiber bacteria in a metal salt solution to obtain a precursor; roasting the precursor to obtain the fibrous ceramic inorganic material; the metal salts in the metal salt solution comprise lithium salt, lanthanum salt and zirconyl nitrate. The ceramic material has excellent ion conductivity, and the fibrous material is a continuous and elongated dot-like material. The fibrous ceramic inorganic material constructs an ion passage in the solid polymer electrolyte, is favorable for ion transmission in the solid polymer electrolyte, and can further inhibit lithium dendrites.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a fibrous ceramic inorganic material, a preparation method and application thereof, and a lithium battery solid polymer electrolyte.
Background
Batteries are widely used in portable electronic products, electric vehicles, and large-scale energy storage using intermittent renewable energy sources (such as wind energy, water energy, and solar energy). Among commercial batteries, lithium ion batteries are becoming mainstream due to their high energy density.
Conventional lithium ion batteries generally use a liquid electrolyte which has high lithium ion conductivity and promotes good wetting of the electrode surfaces, so that commercial organic liquid electrolytes are still widely used in lithium batteries.
However, liquid electrolytes often suffer from low ion selectivity, insufficient electrochemical and thermal stability, and the like, and in particular present safety risks (e.g., electrolyte leakage, fire and explosion). All of these problems with liquid electrolytes have prevented large-scale commercialization of lithium ion batteries.
To address the safety risk, replacing liquid electrolytes with solid electrolytes is currently the most widespread choice. Solid Polymer Electrolytes (SPEs) have excellent mechanical properties and ease of preparation. Polyethylene oxide (PEO) is widely studied in solid polymer electrolytes, but the low ionic conductivity of PEO at room temperature severely affects its development.
Disclosure of Invention
In view of the above, the invention aims to provide a fibrous ceramic inorganic material, a preparation method and application thereof, and a lithium battery solid polymer electrolyte. The lithium battery solid polymer electrolyte prepared by the prepared fibrous ceramic inorganic material has high ion conductivity at room temperature.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a fibrous ceramic inorganic material, which comprises the following steps:
performing first culture on the fibrous fungus spores to obtain fibrous fungus;
performing second culture on the fiber bacteria in a metal salt solution to obtain a precursor;
roasting the precursor to obtain the fibrous ceramic inorganic material;
the metal salts in the metal salt solution comprise lithium salt, lanthanum salt and zirconyl nitrate.
Preferably, the first culture medium comprises 10-15 g glucose, 8-10 g peptone and 500mL deionized water; the temperature of the first culture is 25-35 ℃ and the time is 36-48 h; the first culture is performed in a shaking incubator.
Preferably, the molar ratio of lithium salt, lanthanum salt and zirconyl nitrate is 8.4:3:2; the concentration of zirconyl nitrate in the metal salt solution is 0.1-0.2 mol/L;
the temperature of the second culture is 25-35 ℃ and the time is 24-36 h; the second culture is performed in a shaking incubator.
Preferably, after the second culturing, the method further comprises: washing and freeze-drying the product obtained after the second culture in sequence; the cleaned reagent is deionized water; the freeze drying temperature is-80 ℃ and the time is 1-2 days.
Preferably, the roasting temperature is 700-900 ℃ and the time is 1-2 hours.
The invention also provides the fibrous ceramic inorganic material obtained by the preparation method.
The invention also provides application of the fibrous ceramic inorganic material in the solid polymer electrolyte of the lithium battery.
The invention also provides a lithium battery solid polymer electrolyte, which comprises a first film layer, a second film layer and a third film layer which are sequentially laminated;
the preparation raw materials of the first film layer comprise acetonitrile, lithium bis (trifluoromethanesulfonyl) imide and polyethylene oxide;
the preparation raw materials of the second film layer comprise acetonitrile, lithium bis (trifluoromethanesulfonyl) imide, polyethylene oxide and inorganic filler; the inorganic filler is the fibrous ceramic inorganic material according to the technical scheme;
the preparation raw materials of the third film layer are consistent with those of the first film layer.
Preferably, in the preparation raw materials of the first film layer, the dosage ratio of acetonitrile, lithium bis (trifluoromethanesulfonyl) imide to polyethylene oxide is 15mL: 200-400 mg:1g.
Preferably, in the preparation raw materials of the second film layer, the dosage ratio of acetonitrile, lithium bistrifluoromethylsulfonyl imide, polyethylene oxide and inorganic filler is 15mL: 200-400 mg:1g: 200-400 mg.
The invention provides a preparation method of a fibrous ceramic inorganic material, which comprises the following steps: performing first culture on the fibrous fungus spores to obtain fibrous fungus; performing second culture on the fiber bacteria in a metal salt solution to obtain a precursor; roasting the precursor to obtain the fibrous ceramic inorganic material; the metal salts in the metal salt solution comprise lithium salt, lanthanum salt and zirconyl nitrate. The ceramic material has excellent ion conductivity, and the fibrous material is a continuous and elongated dot-like material. The fibrous ceramic inorganic material constructs an ion passage in the solid polymer electrolyte, is favorable for ion transmission in the solid polymer electrolyte, and can further inhibit lithium dendrites. The fibrous ceramic inorganic material is lithium lanthanum zirconium oxygen/biomass fiber, wherein lithium lanthanum zirconium oxygen can conduct lithium ions in a polymer electrolyte, and the biomass fiber can enable the lithium lanthanum zirconium oxygen to keep fibrous morphology.
Drawings
FIG. 1 shows LLZO@MF-H obtained in example 1 2 O and LLZO@MF-C obtained in example 3 2 H 6 X-ray diffraction (XRD) pattern of O;
FIG. 2 is LLZO@MF-H obtained in example 1 2 O and LL obtained in example 3ZO@MF-C 2 H 6 O Scanning Electron Microscope (SEM), wherein the left graph is LLZO@MF-H 2 SEM of O, LLZO@MF-C on the right 2 H 6 SEM image of O;
FIG. 3 is an EIS diagram of a symmetrical cell composed of the composite solid polymer electrolyte thin films obtained in examples 1 to 4, wherein (a) is an EIS diagram of a symmetrical cell composed of the composite solid polymer electrolyte thin films obtained in examples 1 and 3, and (b) is an EIS diagram of a symmetrical cell composed of the composite solid polymer electrolyte thin films obtained in examples 2 and 4;
FIG. 4 is a graph showing that the composite solid polymer electrolyte film obtained in example 2 was at 0.1mA/cm 2 Lithium symmetric battery deposition-stripping cycle test under current density;
FIG. 5 is a graph showing that the composite solid polymer electrolyte film obtained in example 2 was at 0.1mA/cm 2 Lithium deposition-stripping curve after 500 hours of cycling at current density.
Detailed Description
The invention provides a preparation method of a fibrous ceramic inorganic material, which comprises the following steps:
performing first culture on the fibrous fungus spores to obtain fibrous fungus;
performing second culture on the fiber bacteria in a metal salt solution to obtain a precursor;
roasting the precursor to obtain the fibrous ceramic inorganic material;
the metal salts in the metal salt solution comprise lithium salt, lanthanum salt and zirconyl nitrate.
In the present invention, the raw materials used in the present invention are preferably commercially available products unless otherwise specified.
The invention carries out first culture on the fibrous fungus spores to obtain fibrous fungus.
In the present invention, the fibrous fungus spores are preferably commercially available products. In the invention, the culture medium for the first culture preferably comprises 10-15 g of glucose, 8-10 g of peptone and 500mL of deionized water, and in the specific embodiment of the invention, the culture medium for the first culture preferably comprises 10g of glucose, 8g of peptone and 500mL of deionized water. In the present invention, the preparation method of the first culture medium preferably includes: mixing the preparation raw materials, and sequentially carrying out high-temperature sterilization and irradiation sterilization; the temperature of the high-temperature sterilization is preferably 121 ℃, and the time is preferably 15-30 min; the radiation sterilization rays are preferably ultraviolet rays; the irradiation sterilization time is preferably 15-30 min. In the invention, the temperature of the first culture is preferably 25-35 ℃ and the time is preferably 36-48 h; the first cultivation is preferably carried out in a shaking incubator.
After the first culturing, the present invention preferably further comprises: washing the first cultured fibrous fungus spores; the cleaning reagent is preferably ethanol or deionized water.
After the fiber bacteria are obtained, the fiber bacteria are subjected to second culture in a metal salt solution to obtain a precursor.
In the present invention, the metal salt in the metal salt solution includes lithium salt, lanthanum salt and zirconyl nitrate. In the present invention, the molar ratio of the lithium salt, lanthanum salt and zirconyl nitrate is preferably 8.4:3:2; the concentration of zirconyl nitrate in the metal salt solution is preferably 0.1-0.2 mol/L. In the present invention, the lithium salt is preferably lithium nitrate; the lanthanum salt is preferably lanthanum nitrate. In the present invention, the solvent of the metal salt solution is preferably water or ethanol, and more preferably ethanol.
In the invention, the temperature of the second culture is preferably 25-35 ℃ and the time is preferably 24-36 h; the second cultivation is preferably carried out in a shaking incubator.
After the second culturing, the present invention preferably further comprises: and washing and freeze-drying the product obtained after the second culture in sequence. In the present invention, the cleaning agent is preferably deionized water. In the present invention, the temperature of the freeze-drying is preferably-80 ℃ and the time is preferably 1 to 2 days.
After the precursor is obtained, the precursor is roasted to obtain the fibrous ceramic inorganic material.
In the invention, the roasting temperature is preferably 700-900 ℃ and the time is preferably 1-2 h. In the present invention, the baking atmosphere is preferably air.
In the present invention, the fibrous ceramic inorganic material is named LLZO@MF.
The invention also provides the fibrous ceramic inorganic material obtained by the preparation method.
In the present invention, the ceramic material has excellent ion conductivity, and the fibrous material is a continuous and extended dot-like material. The fibrous ceramic inorganic material constructs an ion passage in the solid polymer electrolyte, is favorable for ion transmission in the solid polymer electrolyte, and can further inhibit lithium dendrites.
The invention also provides application of the fibrous ceramic inorganic material in the solid polymer electrolyte of the lithium battery.
The invention also provides a lithium battery solid polymer electrolyte, which comprises a first film layer, a second film layer and a third film layer which are sequentially laminated;
the preparation raw materials of the first film layer comprise acetonitrile, lithium bis (trifluoromethanesulfonyl) imide and polyethylene oxide;
the preparation raw materials of the second film layer comprise acetonitrile, lithium bis (trifluoromethanesulfonyl) imide, polyethylene oxide and inorganic filler; the inorganic filler is the fibrous ceramic inorganic material according to the technical scheme;
the preparation raw materials of the third film layer are consistent with those of the first film layer.
The lithium battery solid polymer electrolyte provided by the invention comprises a first film layer; the thickness of the first film layer is preferably 25 μm. In the invention, the preparation raw materials of the first film layer comprise acetonitrile, lithium bis (trifluoromethanesulfonyl) imide and polyethylene oxide; in the preparation raw materials of the first film layer, the dosage ratio of acetonitrile, lithium bis (trifluoromethanesulfonyl) imide to polyethylene oxide is preferably 15mL: 200-400 mg:1g.
In the present invention, the preparation method of the first film layer preferably includes the following steps: adding lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) into acetonitrile, and then adding polyethylene oxide to perform heating and stirring mixing to obtain a first film material liquid; and pouring the first film layer feed liquid on a template, and carrying out vacuum drying to obtain the first film layer. In the present invention, the temperature of the heating and stirring mixture is preferably 50 ℃ and the time is preferably 24 hours. In the present invention, the template is preferably a polytetrafluoroethylene template. In the present invention, the temperature of the vacuum drying is preferably 60℃and the time is preferably 24 hours.
The lithium battery solid polymer electrolyte provided by the invention comprises a second film layer which is laminated on the first film layer, wherein the thickness of the second film layer is preferably 50 mu m. In the invention, the preparation raw materials of the second film layer comprise acetonitrile, lithium bis (trifluoromethanesulfonyl) imide, polyethylene oxide and inorganic filler; the inorganic filler is the fibrous ceramic inorganic material according to the technical scheme. In the invention, the usage ratio of acetonitrile, lithium bistrifluoro methanesulfonimide, polyethylene oxide and inorganic filler in the preparation raw material of the second film layer is preferably 15mL: 200-400 mg:1g: 200-400 mg.
In the present invention, the preparation method of the second film layer preferably includes the following steps: adding lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) into acetonitrile, then adding polyethylene oxide and inorganic filler, heating, stirring and mixing to obtain a second film material liquid; and pouring the second film material liquid on the first film, and performing vacuum drying to obtain the second film. In the present invention, the temperature of the heating and stirring mixture is preferably 50 ℃ and the time is preferably 24 hours. In the present invention, the temperature of the vacuum drying is preferably 60℃and the time is preferably 24 hours.
The lithium battery solid polymer electrolyte provided by the invention comprises a third film layer which is laminated on the second film layer, wherein the thickness of the third film layer is preferably 25 mu m. In the present invention, the preparation raw materials of the third film layer are identical to those of the first film layer, and the preparation methods are the same, and are not described herein.
The fibrous ceramic inorganic material, the preparation method and application thereof, and the solid polymer electrolyte for lithium battery provided by the present invention are described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Step 1: culturing the fiber bacteria: 10g glucose, 8g peptone were added to an Erlenmeyer flask containing 500mL deionized water. Sealing with a breathable sealing film, sterilizing at 121deg.C for 15 min, and irradiating with ultraviolet rays for 15 min to obtain culture medium. The fibrous fungus spores are added into the culture medium, then the conical flask is placed in a shaking incubator at 35 ℃ for culturing for 36 hours, and then the cultured fibrous fungus is taken out, and the culture medium is washed by absolute ethyl alcohol or deionized water.
Step 2: in an Erlenmeyer flask, a metal salt (molar ratio of lithium nitrate, lanthanum nitrate, and zirconyl nitrate: 8.4:3:2) was dissolved in deionized water to form a metal salt solution, wherein the concentration of lithium nitrate was 0.42mol/L, the concentration of lanthanum nitrate was 0.15mol/L, and the concentration of zirconyl nitrate was 0.1 mol/L.
Step 3: transferring the fiber bacteria obtained in the step 1 into the metal salt solution obtained in the step 2, and placing the conical flask into a shaking incubator at 35 ℃ for culturing for 24 hours.
Step 4: washing the product cultured in the step 3 by deionized water, and freeze-drying for 2 days at the temperature of-80 ℃ to obtain a dried precursor.
Step 5: calcining the precursor dried in the step 4 at 900 ℃ in an air atmosphere for 2 hours to obtain a fibrous ceramic inorganic material which is marked as LLZO@MF-H 2 O。
Step 6: 200mg of lithium bistrifluoromethanesulfonimide (LiTFSI) was added to 15mL of anhydrous acetonitrile, followed by adding 1g of polyethylene oxide (PEO) with stirring at 50℃and stirring with heating for 24 hours. Thereafter, the solution was cast on a polytetrafluoroethylene template and dried in vacuo at 60℃for 24 hours to synthesize a first film layer having a thickness of about 25 μm and containing no inorganic filler.
Step 7: the solution in step 6 was repeatedly prepared and 200mg of the fibrous ceramic inorganic material obtained in step 5 was additionally added. Thereafter, the solution was cast on the first film layer formed in step 6, and vacuum-dried at 60℃for 24 hours, to synthesize a second film layer containing an inorganic filler to a thickness of about 50. Mu.m.
Step 8: repeatedly preparing the solution in the step 6, and pouring the solution in the stepAnd (3) drying the second film layer formed in the step 7 for 24 hours at 60 ℃ in vacuum, and finally synthesizing two layers of three-layer films without inorganic filler and one layer of film with inorganic filler, wherein the film with inorganic filler is sandwiched and named as a composite solid polymer electrolyte film PEO-LLZO@MF-H 2 O-200。
Example 2
Step 1: culturing the fiber bacteria: 10g glucose, 8g peptone were added to an Erlenmeyer flask containing 500mL deionized water. Sealing with a breathable sealing film, sterilizing at 121deg.C for 15 min, and irradiating with ultraviolet rays for 15 min to obtain culture medium. Adding the fibrous fungus spores into the obtained culture medium, placing the conical flask into a shaking incubator at 35 ℃ for culturing for 36 hours, taking out the cultured fibrous fungus, and washing the culture medium with absolute ethyl alcohol or deionized water.
Step 2: in an Erlenmeyer flask, a metal salt (molar ratio of lithium nitrate, lanthanum nitrate, and zirconyl nitrate: 8.4:3:2) was dissolved in deionized water to form a metal salt solution, wherein the concentration of lithium nitrate was 0.42mol/L, the concentration of lanthanum nitrate was 0.15mol/L, and the concentration of zirconyl nitrate was 0.1 mol/L.
Step 3: transferring the fiber bacteria obtained in the step 1 into the metal salt solution obtained in the step 2, and placing the conical flask into a shaking incubator at 35 ℃ for culturing for 24 hours.
Step 4: washing the product cultured in the step 3 by deionized water, and freeze-drying for 2 days at the temperature of-80 ℃ to obtain a dried precursor.
Step 5: calcining the precursor dried in the step 4 at 900 ℃ in an air atmosphere for 2 hours to obtain a fibrous ceramic inorganic material which is marked as LLZO@MF-H 2 O。
Step 6: 400mg of lithium bistrifluoromethanesulfonimide (LiTFSI) was added to 15mL of anhydrous acetonitrile, followed by 1g of polyethylene oxide (PEO) with stirring at 50℃and stirring with heating for 24 hours. Thereafter, the solution was cast on a polytetrafluoroethylene template and dried in vacuo at 60℃for 24 hours to synthesize a first film layer having a thickness of about 25 μm and containing no inorganic filler.
Step 7: the solution in step 6 was repeatedly prepared and 400mg of the fibrous ceramic inorganic material obtained in step 5 was additionally added. Thereafter, the solution was cast on the first film layer formed in step 6, and vacuum-dried at 60℃for 24 hours, to synthesize a second film layer containing an inorganic filler to a thickness of about 50. Mu.m.
Step 8: repeatedly preparing the solution in the step 6, pouring the solution on the second film layer formed in the step 7, and vacuum drying at 60 ℃ for 24 hours to finally synthesize two layers of three-layer films without inorganic filler and one layer of three-layer film with inorganic filler, wherein the films with inorganic filler are sandwiched and named as a composite solid polymer electrolyte film PEO-LLZO@MF-H 2 O-400。
Example 3
Step 1: culturing the fiber bacteria: 10g glucose, 8g peptone were added to an Erlenmeyer flask containing 500mL deionized water. Sealing with a breathable sealing film, sterilizing at 121deg.C for 15 min, and irradiating with ultraviolet rays for 15 min to obtain culture medium. The fibrous spores were added to the above medium. Then, the flask was placed in a shaking incubator at 35℃for 36 hours, and the cultured fibrous fungus was taken out and the medium was washed with absolute ethanol or deionized water.
Step 2: in an Erlenmeyer flask, a metal salt (molar ratio of lithium nitrate, lanthanum nitrate, and zirconyl nitrate: 8.4:3:2) was dissolved in ethanol to form a metal salt solution, wherein the concentration of lithium nitrate was 0.42mol/L, the concentration of lanthanum nitrate was 0.15mol/L, and the concentration of zirconyl nitrate was 0.1 mol/L.
Step 3: transferring the fiber bacteria obtained in the step 1 into the metal salt solution obtained in the step 2, and placing the conical flask into a shaking incubator at 35 ℃ for culturing for 24 hours.
Step 4: washing the product cultured in the step 3 by ethanol, and freeze-drying for 2 days at the temperature of-80 ℃ to obtain a dried precursor.
Step 5: calcining the precursor dried in the step 4 at 700 ℃ for 2 hours in an air atmosphere to obtain a fibrous ceramic inorganic material, which is marked as LLZO@MF-C 2 H 6 O。
Step 6: 200mg of lithium bistrifluoromethanesulfonimide (LiTFSI) was added to 15mL of anhydrous acetonitrile, followed by adding 1g of polyethylene oxide (PEO) with stirring at 50℃and stirring with heating for 24 hours. Thereafter, the solution was cast on a polytetrafluoroethylene template and dried in vacuo at 60℃for 24 hours to synthesize a first film layer having a thickness of about 25 μm and containing no inorganic filler.
Step 7: the solution in step 6 was repeatedly prepared and 200mg of the fibrous ceramic inorganic material obtained in step 5 was additionally added. Thereafter, the solution was cast onto the first film layer formed in step 6 and dried in vacuo at 60 ℃ for 24 hours. A second film layer containing an inorganic filler was synthesized to a thickness of about 50 μm.
Step 8: repeatedly preparing the solution in the step 6, pouring the solution on the second film layer formed in the step 7, and vacuum drying at 60 ℃ for 24 hours to finally synthesize two layers of three-layer films without inorganic filler and one layer of three-layer film with inorganic filler, wherein the films with inorganic filler are sandwiched and named as a composite solid polymer electrolyte film PEO-LLZO@MF-C 2 H 6 O-200。
Example 4
Step 1: culturing the fiber bacteria: 10g glucose, 8g peptone were added to an Erlenmeyer flask containing 500mL deionized water. Sealing with a breathable sealing film, sterilizing at 121deg.C for 15 min, and irradiating with ultraviolet rays for 15 min to obtain culture medium. The fibrous fungus spores are added into the culture medium, then the conical flask is placed in a shaking incubator at 35 ℃ for culturing for 36 hours, and then the cultured fibrous fungus is taken out, and the culture solution is washed by absolute ethyl alcohol or deionized water.
Step 2: in an Erlenmeyer flask, a metal salt (molar ratio of lithium nitrate, lanthanum nitrate, and zirconyl nitrate: 8.4:3:2) was dissolved in ethanol to form a metal salt solution, wherein the concentration of lithium nitrate was 0.42mol/L, the concentration of lanthanum nitrate was 0.15mol/L, and the concentration of zirconyl nitrate was 0.1 mol/L.
Step 3: and (3) transferring the product obtained in the step (1) into the metal salt solution obtained in the step (2), and placing the conical flask in a shaking incubator at 35 ℃ for culturing for 24 hours.
Step 4: washing the cultured cellosilk in the step 3 with ethanol, and freeze-drying at-80 ℃ for 2 days to obtain a dried precursor.
Step 5: calcining the precursor dried in the step 4 at 700 ℃ for 2 hours in an air atmosphere to obtain a fibrous ceramic inorganic material, which is marked as LLZO@MF-C 2 H 6 O。
Step 6: 200mg of lithium bistrifluoromethanesulfonimide (LiTFSI) was added to 15mL of anhydrous acetonitrile, followed by adding 1g of polyethylene oxide (PEO) with stirring at 50℃and stirring with heating for 24 hours. Thereafter, the solution was cast on a polytetrafluoroethylene template and dried in vacuo at 60℃for 24 hours to synthesize a first film layer having a thickness of about 25 μm and containing no inorganic filler.
Step 7: the solution in step 6 was repeatedly prepared and 400mg of the fibrous ceramic inorganic material obtained in step 5 was additionally added. Thereafter, the solution was cast on the first film layer formed in step 6, and vacuum-dried at 60℃for 24 hours, to synthesize a second film layer containing an inorganic filler to a thickness of about 50. Mu.m.
Step 8: repeatedly preparing the solution in the step 6, pouring the solution on the second film layer formed in the step 7, and vacuum drying at 60 ℃ for 24 hours to finally synthesize two layers of three-layer films without inorganic filler and one layer of three-layer film with inorganic filler, wherein the films with inorganic filler are sandwiched and named as a composite solid polymer electrolyte film PEO-LLZO@MF-C 2 H 6 O-400。
FIG. 1 shows LLZO@MF-H obtained in example 1 2 O and LLZO@MF-C obtained in example 3 2 H 6 The XRD pattern of O can be seen from FIG. 1: exhibiting characteristic peaks that are clearly consistent with PDF cards.
FIG. 2 is LLZO@MF-H obtained in example 1 2 O and LLZO@MF-C obtained in example 3 2 H 6 SEM of O, wherein the left graph is LLZO@MF-H 2 SEM of O, LLZO@MF-C on the right 2 H 6 SEM image of O. As can be seen from fig. 2: illustrating the successful synthesis of fibrous ceramic inorganic materials.
The composite solid polymer electrolyte thin films obtained in examples 1, 2, 3 and 4 were assembled with stainless steel sheets, respectively, and were pretreated in a vacuum oven at 60 ℃ for 2 hours. EIS was tested in an electrochemical workstation at 25℃to calculate composite solid polymers in examples 1, 2, 3 and 4, respectivelyThe ionic conductivity of the electrolyte thin film was shown in fig. 3, and fig. 3 shows EIS diagrams of symmetrical cells composed of the composite solid polymer electrolyte thin films obtained in examples 1 to 4, wherein (a) shows EIS diagrams of symmetrical cells composed of the composite solid polymer electrolyte thin films obtained in examples 1 and 3, and (b) shows EIS diagrams of symmetrical cells composed of the composite solid polymer electrolyte thin films obtained in examples 2 and 4. As shown in fig. 3: the ionic conductivities of the composite solid polymer electrolyte films of examples 1, 2, 3 and 4 were 9.13×10, respectively, according to the formula σ=l/(r×s) (the real part value of the inflection point of the R-C semicircle and the straight line is the total impedance R, L is the thickness (about 100 microns), and S is the electrode effective area) -5 、2.26×10 -4 、8.38×10 -5 And 1.56X10 -4 S/m。
The composite solid polymer electrolyte membrane obtained in example 2 was assembled with a lithium sheet in a glove box and pre-treated for 2 hours at 60 ℃ in a vacuum oven. The interfacial stability of lithium metal and the composite solid polymer electrolyte film was tested in a blue electric system at 60℃and the results are shown in FIG. 4, FIG. 4 being that the composite solid polymer electrolyte film obtained in example 2 was at 0.1mA/cm 2 And (3) testing the deposition-stripping cycle of the lithium symmetrical battery under the current density. As shown in FIG. 4, at 0.1mA/cm 2 The charge and discharge can be performed for more than 500 hours at a current density of 0.5 hours each.
FIG. 5 is a graph showing that the composite solid polymer electrolyte film obtained in example 2 was at 0.1mA/cm 2 The lithium deposition-stripping curve after 500 hours of cycling at current density can be seen from fig. 5: voltage polarization of 100mV indicates smooth lithium ion conduction. I.e., lithium ions are extracted from the lithium sheet and pass through the electrolyte layer to be successfully deposited on the other side of the lithium sheet. In addition, the polarization voltage remained unchanged, proving that the interface impedance or bulk impedance remained unchanged.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A method for preparing a fibrous ceramic inorganic material, comprising the steps of:
performing first culture on the fibrous fungus spores to obtain fibrous fungus;
performing second culture on the fiber bacteria in a metal salt solution to obtain a precursor;
roasting the precursor to obtain the fibrous ceramic inorganic material;
the metal salts in the metal salt solution comprise lithium salt, lanthanum salt and zirconyl nitrate.
2. The method of claim 1, wherein the first culture medium comprises 10-15 g glucose, 8-10 g peptone and 500mL deionized water; the temperature of the first culture is 25-35 ℃ and the time is 36-48 h; the first culture is performed in a shaking incubator.
3. The method according to claim 1, wherein the molar ratio of the lithium salt, lanthanum salt and zirconyl nitrate is 8.4:3:2; the concentration of zirconyl nitrate in the metal salt solution is 0.1-0.2 mol/L;
the temperature of the second culture is 25-35 ℃ and the time is 24-36 h; the second culture is performed in a shaking incubator.
4. The method according to claim 1 or 3, wherein after the second culturing, further comprising: washing and freeze-drying the product obtained after the second culture in sequence; the cleaned reagent is deionized water; the freeze drying temperature is-80 ℃ and the time is 1-2 days.
5. The method according to claim 1, wherein the baking temperature is 700-900 ℃ and the baking time is 1-2 hours.
6. A fibrous ceramic inorganic material obtained by the method according to any one of claims 1 to 5.
7. Use of the fibrous ceramic inorganic material of claim 6 in a solid polymer electrolyte for a lithium battery.
8. The solid polymer electrolyte of the lithium battery is characterized by comprising a first film layer, a second film layer and a third film layer which are sequentially laminated;
the preparation raw materials of the first film layer comprise acetonitrile, lithium bis (trifluoromethanesulfonyl) imide and polyethylene oxide;
the preparation raw materials of the second film layer comprise acetonitrile, lithium bis (trifluoromethanesulfonyl) imide, polyethylene oxide and inorganic filler; the inorganic filler is the fibrous ceramic inorganic material of claim 6;
the preparation raw materials of the third film layer are consistent with those of the first film layer.
9. The solid polymer electrolyte of lithium battery according to claim 8, wherein the ratio of acetonitrile, lithium bis (trifluoromethanesulfonyl) imide to polyethylene oxide in the raw materials for preparing the first film layer is 15mL: 200-400 mg:1g.
10. The solid polymer electrolyte of lithium battery according to claim 8, wherein the second film layer is prepared from acetonitrile, lithium bis (trifluoromethanesulfonyl) imide, polyethylene oxide and inorganic filler in an amount ratio of 15mL: 200-400 mg:1g: 200-400 mg.
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