CN114388880A - NASICON structure lithium ion solid electrolyte material and preparation method and application thereof - Google Patents
NASICON structure lithium ion solid electrolyte material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 73
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 64
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 57
- 239000002228 NASICON Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 14
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 20
- 229910052744 lithium Inorganic materials 0.000 claims description 20
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- 239000002001 electrolyte material Substances 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- 239000002210 silicon-based material Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 238000007580 dry-mixing Methods 0.000 claims description 6
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 6
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 6
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 6
- 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 5
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 5
- 239000004254 Ammonium phosphate Substances 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 239000005696 Diammonium phosphate Substances 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- QOKYJGZIKILTCY-UHFFFAOYSA-J hydrogen phosphate;zirconium(4+) Chemical compound [Zr+4].OP([O-])([O-])=O.OP([O-])([O-])=O QOKYJGZIKILTCY-UHFFFAOYSA-J 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 abstract description 8
- 239000007774 positive electrode material Substances 0.000 abstract description 8
- 239000003792 electrolyte Substances 0.000 abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 239000010703 silicon Substances 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 16
- 238000009826 distribution Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000002227 LISICON Substances 0.000 description 1
- 229910011250 Li3Zr2Si2PO12 Inorganic materials 0.000 description 1
- 229910000857 LiTi2(PO4)3 Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a lithium ion solid electrolyte material with an NASICON structure, a preparation method and application thereof, wherein the chemical general formula of the lithium ion solid electrolyte material with the NASICON structure is Li(x‑4y+9)ZrySixP(3‑x)O12(ii) a X is more than 0 and less than 3, and y is more than or equal to 1 and less than or equal to 2. The lithium ion solid electrolyte material with the NASICON structure contains stable zirconium and silicon elements, so that compared with other solid electrolytes, the lithium ion solid electrolyte material with the NASICON structure has the advantages that the chemical property is more stable in the process of charging and discharging of a battery when being used as an electrolyte layer in a lithium ion battery, the lithium ion solid electrolyte material does not react with positive and negative electrode materials, and the lithium ion solid electrolyte material is good in compatibility with the positive and negative electrode materials. The preparation method of the NASICON structure lithium ion solid electrolyte material is a high-temperature solid phase method, and the preparation method is simple and easy to implement and has low costLow cost, high safety and easy realization of industrial production.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a lithium ion solid electrolyte material with an NASICON structure, and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high voltage, low self-discharge rate, high energy density and the like, so the lithium ion battery gradually replaces the continuously expanded application field of the traditional battery. However, with the increasing energy density of lithium ion batteries and the upsizing of energy storage modules, the potential safety hazard of lithium ion batteries is always the first problem to be solved by researchers. The electrolyte is one of the key components of a high specific energy secondary lithium battery. Although the electrode material is a prerequisite for determining the energy density of a secondary lithium battery, the energy density is related to the reaction kinetics, the cycle stability and the safety thereof, which are directly related to the electrolyte. At present, the secondary lithium battery mainly uses liquid electrolyte, and the secondary lithium battery using the liquid electrolyte has potential safety hazards of internal short circuit, liquid leakage, combustion, even explosion and the like. In order to solve the above problems, researchers have proposed the idea of replacing the conventional liquid organic electrolyte with a solid electrolyte.
Solid electrolytes generally include two major types, the first type is inorganic solid electrolytes, the second type is electrolytes composed of polymers, lithium salts and fillers, and inorganic solid electrolytes including perovskite type, NASICON type, LISICON type, Li3N, glassy solid electrolytes and the like are currently studied and have a great prospect. The NASICON type solid electrolyte has the advantages of good structural stability and high porosity, but the common LiTi2(PO4)3The active property of titanium causes the material to have the defects of instability to lithium and easy generation of electronic conduction, so that the application of the solid electrolyte in the aspect of lithium batteries is limited to a great extent. The new solid electrolyte formed by replacing titanium with silicon and zirconium has the advantages of stable property and high conductivity, but is mainly prepared by a replacement method at present, so that the production efficiency is low and the process is complicated. Therefore, a simpler and more efficient preparation method is needed.
Disclosure of Invention
The embodiment of the invention provides an NASICON structure lithium ion solid electrolyte material, a preparation method and application thereof, and the NASICON structure lithium ion solid electrolyte material contains stable zirconium and silicon elements, and has the advantages of more stable chemical property expression in the charge and discharge processes of a battery, no reaction with positive and negative electrode materials and good compatibility with the positive and negative electrode materials when being used as an electrolyte layer in a lithium ion battery compared with other solid electrolytes. The preparation method of the NASICON structure lithium ion solid electrolyte material provided by the invention has the advantages of easily available and cheap raw materials, simple preparation method and easy realization of industrial mass production.
In a first aspect, embodiments of the present invention provide a lithium ion solid state electrolyte material with a NASICON structure, where the chemical general formula of the lithium ion solid state electrolyte material with a NASICON structure is Li(x-4y+9)ZrySixP(3-x)O12；0＜x＜3，1≤y≤2。
In a second aspect, an embodiment of the present invention provides a preparation method of the NASICON structure lithium ion solid state electrolyte material according to the first aspect, where the preparation method is a high temperature solid phase method, and includes:
weighing raw materials according to a proportion, and uniformly mixing the raw materials in a dry mixing or wet mixing mode to obtain a mixed material;
placing the mixed material in high-temperature treatment equipment for heat treatment to obtain a precursor;
the precursor is subjected to graded crushing treatment to obtain the lithium ion solid electrolyte material with the NASICON structure, and the particle size is 500nm-50 mu m;
the chemical general formula of the lithium ion solid electrolyte material with the NASICON structure is Li(x-4y+9)ZrySixP(3-x)O12Wherein x is more than 0 and less than 3, and y is more than or equal to 1 and less than or equal to 2.
Preferably, the raw materials comprise: a lithium-containing compound, a zirconium-containing compound, a silicon-containing compound, and a phosphorus-containing compound;
the lithium-containing compound includes: one or more of lithium carbonate, lithium hydroxide, lithium oxide or lithium phosphate; the particle size of the lithium-containing compound particles is between 20nm and 50 mu m;
the zirconium-containing compound includes: one or more of zirconium oxide, zirconium hydroxide, zirconium silicate or zirconium hydrogen phosphate; the particle size of the particles of the zirconium-containing compound is between 20nm and 50 mu m;
the silicon-containing compound includes: silicon dioxide and/or silicon monoxide; the particle size of the particles of the silicon-containing compound is between 20nm and 50 mu m;
the phosphorus-containing compound includes: one or more of lithium phosphate, ammonium phosphate, diammonium phosphate, ammonium dihydrogen phosphate or phosphorus pentoxide; the particle size of the particles of the phosphorus-containing compound is between 20nm and 50 mu m.
Preferably, the dry mixing comprises: one of mixing with a ball mill, mixing with a double motion mixer, or mixing with a high speed mixer;
the wet mixing comprises: one of ball milling mixing, sand milling mixing or dispersion mixing.
Preferably, the heat treatment apparatus comprises: one of a box furnace, a tube furnace, a track kiln, a rotary kiln or a pusher kiln.
Preferably, the heat treatment comprises: heating to 900-1300 ℃ at the heating rate of 0.5-12 ℃/min, preserving the heat for 5-30 hours, and naturally cooling to room temperature.
Preferably, the apparatus for the classification crushing treatment comprises: one of a jaw crusher, a cone crusher, an impact crusher, a hammer crusher, a roll crusher, a flat jet mill, a fluidized bed jet mill, a circulating jet mill, an impact crusher, an expansion crusher, a ball mill crusher, a high-speed rotation projection crusher or a high-speed rotation impact crusher.
In a third aspect, an embodiment of the present invention provides a separator including the NASICON-structured lithium ion solid state electrolyte material described in the first aspect.
In a fourth aspect, an embodiment of the present invention provides a lithium battery, including the separator according to the third aspect.
The solid electrolyte material with the NASICON structure provided by the invention contains stable zirconium and silicon elements, so that compared with other solid electrolytes, the solid electrolyte material is more stable in chemical property expression in the charge and discharge process of a lithium ion battery when being used as an electrolyte layer in the lithium ion battery, has the advantages of no reaction with positive and negative electrode materials and good compatibility with the positive and negative electrode materials. The preparation method of the NASICON structure lithium ion solid electrolyte material provided by the embodiment of the invention is a high-temperature solid phase method, and has the advantages of easily available and cheap raw materials, simple preparation method and easy realization of industrial mass production.
Drawings
The technical solutions of the embodiments of the present invention are further described in detail with reference to the accompanying drawings and embodiments.
Fig. 1 is a flowchart of a method for producing a NASICON-structured lithium ion solid-state electrolyte material according to an embodiment of the present invention;
fig. 2 is an X-ray diffraction pattern (XRD) of the NASICON-structured lithium ion solid state electrolyte material provided in example 1 of the present invention;
FIG. 3 is a volume particle size distribution curve of a NASICON structure lithium ion solid state electrolyte material provided in example 1 of the present invention;
FIG. 4 is an XRD pattern of a lithium ion solid state electrolyte material of NASICON structure provided in example 2 of the present invention;
FIG. 5 is a volume particle size distribution curve of a NASICON structure lithium ion solid state electrolyte material provided in example 2 of the present invention;
FIG. 6 is an XRD pattern of a lithium ion solid state electrolyte material of NASICON structure provided in example 3 of the present invention;
fig. 7 is a volume particle size distribution curve of the NASICON-structured lithium ion solid state electrolyte material provided in example 3 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples, but it should be understood that these examples are for the purpose of illustration only and are not to be construed as limiting the invention in any way, i.e., not as limiting the scope of the invention.
The embodiment of the invention provides a lithium ion solid electrolyte material with an NASICON structure, and a lithium ion solid electrolyte with an NASICON structureThe chemical general formula of the material is Li(x-4y+9)ZrySixP(3-x)O12；0＜x＜3，1≤y≤2。
An embodiment of the present invention provides a preparation method of the NASICON-structured lithium ion solid-state electrolyte material in the first aspect, where the preparation method is a high-temperature solid-phase method, and the preparation method includes:
the raw materials comprise: a lithium-containing compound, a zirconium-containing compound, a silicon-containing compound, and a phosphorus-containing compound;
in the actual preparation, because the condition of little volatilization of lithium and phosphorus exists in the high-temperature preparation process, the lithium and the phosphorus need to be slightly excessive in the selection of the actual raw material proportion, and the excessive range is between 2 and 20 percent;
the lithium-containing compound includes: one or more of lithium carbonate, lithium hydroxide, lithium oxide or lithium phosphate; the particle size of the lithium-containing compound particles is between 20nm and 50 mu m;
the zirconium-containing compound includes: one or more of zirconium oxide, zirconium hydroxide, zirconium silicate or zirconium hydrogen phosphate; the particle size of the particles of the zirconium-containing compound is between 20nm and 50 mu m;
the silicon-containing compound includes: silicon dioxide and/or silicon monoxide; the particle size of the particles of the silicon-containing compound is between 20nm and 50 mu m;
the phosphorus-containing compounds include: one or more of lithium phosphate, ammonium phosphate, diammonium phosphate, ammonium dihydrogen phosphate or phosphorus pentoxide; the particle size of the particles of the phosphorus-containing compound is between 20nm and 50 mu m;
the dry mixing comprises the following steps: one of mixing with a ball mill, mixing with a double motion mixer, or mixing with a high speed mixer;
the wet mixing comprises the following steps: one of ball milling mixing, sand milling mixing or dispersion mixing.
the apparatus for heat treatment comprises: one of a box furnace, a tube furnace, a track kiln, a rotary kiln or a pusher kiln.
The heat treatment comprises the following steps: heating to 900-1300 ℃ at the heating rate of 0.5-12 ℃/min, preserving the heat for 5-30 hours, and naturally cooling to room temperature.
the apparatus for the classification crushing treatment comprises: one of a jaw crusher, a cone crusher, a counterattack crusher, a hammer crusher, a roller crusher, a flat jet mill, a fluidized bed jet mill, a circulating jet mill, an impact crusher, an expansion crusher, a ball mill crusher, a high-speed rotation projection crusher or a high-speed rotation impact crusher;
the chemical general formula of the prepared NASICON structure lithium ion solid electrolyte material is Li(x-4y+9)ZrySixP(3-x)O12Wherein x is more than 0 and less than 3, and y is more than or equal to 1 and less than or equal to 2.
The embodiment of the invention provides a diaphragm, which comprises the NASICON structure lithium ion solid electrolyte material, and the diaphragm can be applied to a lithium battery.
In order to better understand the technical scheme provided by the invention, the following specific examples respectively illustrate the preparation process and the characteristics of the lithium ion solid electrolyte material with the NASICON structure.
Example 1
The embodiment provides a preparation method of a lithium ion solid electrolyte material with an NASICON structure.
The method comprises the following specific steps:
weighing 1.55 parts of lithium carbonate 5 mu m powder, 2 parts of zirconium dioxide 3 mu m powder, 2 parts of silicon dioxide powder and 1.15 parts of ammonium dihydrogen phosphate 10 mu m powder according to a molar ratio, adding the mixture into a ball milling tank, and carrying out ball milling for 12 hours to obtain a mixed material, wherein the particle size of the mixed material is 700 nm;
placing the mixed material in a box-type heating furnace, heating to 900 ℃ at the speed of 3 ℃/min in the air atmosphere, preserving the temperature for 15 hours, and cooling to room temperature to obtain a precursor;
the precursor is firstly subjected to preliminary crushing by a jaw crusher and a roller crusher, and then is subjected to graded crushing by an impact crusher to form powder with the particle size of 5 mu m, so as to obtain the micron-sized NASICON structure lithium ion solid electrolyte material with the chemical formula of Li3Zr2Si2PO12。
Lithium ion solid electrolyte material Li with NASICON structure prepared in the example3Zr2Si2PO12As shown in fig. 2, has characteristic peaks at 20.0 °, 27.0 °, 35.6 °, 43.8 °, and 53.5 °.
Lithium ion solid electrolyte material Li with NASICON structure prepared in the example3Zr2Si2PO12The volume particle size distribution curve is shown in FIG. 3, and the average particle diameter D50 is 5 μm.
Example 2
The embodiment provides a preparation method of a lithium ion solid electrolyte material with an NASICON structure.
The method comprises the following specific steps:
weighing 3.55 parts of lithium hydroxide 5 mu m powder and 1.86 parts of zirconium dioxide 3 mu m powder according to a molar ratio, adding 1.92 parts of silicon dioxide powder and 1.15 parts of ammonium phosphate 12 mu m powder into a ball milling tank, adding deionized water, and carrying out ball milling for 8 hours to obtain a mixed material, wherein the particle size of the mixed material is about 500 nm;
drying the mixed material, placing the dried mixed material in a tubular heating furnace, heating the mixed material to 860 ℃ at the speed of 1 ℃/min, preserving the heat for 15 hours, and cooling the mixed material to room temperature to obtain a precursor;
the precursor is firstly subjected to preliminary crushing by a jaw crusher and a roller crusher, and then is subjected to graded crushing by a flat jet mill to obtain powder with the particle size of 3 mu m, so as to obtain the lithium ion solid electrolyte material with the micron-sized NASICON structure, wherein the chemical formula is Li3.48Zr1.86Si1.92P1.08O12。
Lithium ion solid electrolyte material Li with NASICON structure prepared in the example3.48Zr1.86Si1.92P1.08O12As shown in figure 4, at 20.The positions of 0 degrees, 27.0 degrees, 35.6 degrees, 43.8 degrees and 53.5 degrees have characteristic peaks.
Lithium ion solid electrolyte material Li with NASICON structure prepared in the example3.48Zr1.86Si1.92P1.08O12The volume particle size distribution curve is shown in FIG. 5, and the average particle diameter D50 is 3 μm.
Example 3
The embodiment provides a preparation method of a lithium ion solid electrolyte material with an NASICON structure.
The method comprises the following specific steps:
weighing 3.2 parts of lithium hydroxide 5 mu m powder and 2 parts of zirconium hydroxide 4 mu m powder according to a molar ratio, adding 2.15 parts of silicon dioxide powder and 0.45 part of phosphorus pentoxide 10 mu m powder into a ball milling tank, adding absolute ethyl alcohol, and carrying out ball milling for 6 hours to obtain a mixed material, wherein the particle size of the mixed material is 900 nm;
drying the mixed material, placing the dried mixed material in a tubular heating furnace, heating the mixed material to 950 ℃ at the speed of 5 ℃/min, preserving the heat for 12 hours, and cooling the mixed material to room temperature to obtain a precursor;
the precursor is firstly subjected to preliminary crushing by a jaw crusher and a roller crusher, and then is subjected to graded crushing by a flat jet mill to obtain powder with the particle size of 3 mu m, so as to obtain the lithium ion solid electrolyte material with the micron-sized NASICON structure, wherein the chemical formula is Li3.15Zr2Si2.15P0.85O12。
Lithium ion solid electrolyte material Li with NASICON structure prepared in the example3.15Zr2Si2.15P0.85O12As shown in fig. 6, the XRD pattern of (a) has characteristic peaks at positions of 20.0 °, 27.0 °, 35.6 °, 43.8 °, and 53.5 °.
Lithium ion solid electrolyte material Li with NASICON structure prepared in the example3.15Zr2Si2.15P0.85O12The volume particle size distribution curve of (2) is shown in FIG. 7, and the average particle diameter D50 is 3 μm.
Example 4
The embodiment provides a preparation method of a lithium ion solid electrolyte material with an NASICON structure.
The method comprises the following specific steps:
weighing 3.6 parts of lithium hydroxide 5 mu m powder, 1.9 parts of zirconium hydroxide 4 mu m powder, 2.15 parts of silicon dioxide powder and 0.45 part of phosphorus pentoxide 10 mu m powder according to a molar ratio, adding into a ball milling tank, adding absolute ethyl alcohol, and carrying out ball milling for 6 hours, wherein the particle size of the mixture is 900 nm;
drying the mixed material, placing the dried mixed material in a tubular heating furnace, heating the mixed material to 1000 ℃ at the speed of 8 ℃/min, preserving the heat for 10 hours, and cooling the mixed material to room temperature to obtain a precursor;
the precursor is firstly subjected to primary crushing by a jaw crusher and a roller crusher, and then is crushed and classified into powder with the size of 16 mu m by a flat jet mill to obtain a micron-sized solid electrolyte material with the chemical formula of Li3.55Zr1.9Si2.15P0.85O12。
The solid electrolyte material with the NASICON structure provided by the invention contains stable zirconium and silicon elements, so that compared with other solid electrolytes, the solid electrolyte material is more stable in chemical property expression in the charge and discharge process of a lithium ion battery when being used as an electrolyte layer in the lithium ion battery, has the advantages of no reaction with positive and negative electrode materials and good compatibility with the positive and negative electrode materials. . The preparation method of the NASICON structure lithium ion solid electrolyte material provided by the embodiment of the invention is a high-temperature solid phase method, and has the advantages of easily available and cheap raw materials, simple preparation method and easy realization of industrial mass production.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. The lithium ion solid electrolyte material with NASICON structure is characterized in that the NAS is made of a material with NASICON structureThe chemical general formula of the lithium ion solid electrolyte material with the ICON structure is Li(x-4y+9)ZrySixP(3-x)O12；0＜x＜3，1≤y≤2。
2. A method for preparing the NASICON structure lithium ion solid state electrolyte material of claim 1, wherein the method for preparing is a high temperature solid phase method, comprising:
weighing raw materials according to a proportion, and uniformly mixing the raw materials in a dry mixing or wet mixing mode to obtain a mixed material;
placing the mixed material in high-temperature treatment equipment for heat treatment to obtain a precursor;
the precursor is subjected to graded crushing treatment to obtain the lithium ion solid electrolyte material with the NASICON structure, and the particle size is 500nm-50 mu m;
the chemical general formula of the lithium ion solid electrolyte material with the NASICON structure is Li(x-4y+9)ZrySixP(3-x)O12Wherein x is more than 0 and less than 3, and y is more than or equal to 1 and less than or equal to 2.
3. The method of manufacturing according to claim 2, wherein the raw material comprises: a lithium-containing compound, a zirconium-containing compound, a silicon-containing compound, and a phosphorus-containing compound;
the lithium-containing compound includes: one or more of lithium carbonate, lithium hydroxide, lithium oxide or lithium phosphate; the particle size of the lithium-containing compound particles is between 20nm and 50 mu m;
the zirconium-containing compound includes: one or more of zirconium oxide, zirconium hydroxide, zirconium silicate or zirconium hydrogen phosphate; the particle size of the particles of the zirconium-containing compound is between 20nm and 50 mu m;
the silicon-containing compound includes: silicon dioxide and/or silicon monoxide; the particle size of the particles of the silicon-containing compound is between 20nm and 50 mu m;
the phosphorus-containing compound includes: one or more of lithium phosphate, ammonium phosphate, diammonium phosphate, ammonium dihydrogen phosphate or phosphorus pentoxide; the particle size of the particles of the phosphorus-containing compound is between 20nm and 50 mu m.
4. The production method according to claim 2, wherein the dry mixing includes: one of mixing with a ball mill, mixing with a double motion mixer, or mixing with a high speed mixer;
the wet mixing comprises: one of ball milling mixing, sand milling mixing or dispersion mixing.
5. The method for preparing as claimed in claim 2, wherein the apparatus for heat treatment comprises: one of a box furnace, a tube furnace, a track kiln, a rotary kiln or a pusher kiln.
6. The method of manufacturing according to claim 2, wherein the heat treatment includes: heating to 900-1300 ℃ at the heating rate of 0.5-12 ℃/min, preserving the heat for 5-30 hours, and naturally cooling to room temperature.
7. The method of claim 2, wherein the apparatus for the step-crushing treatment comprises: one of a jaw crusher, a cone crusher, an impact crusher, a hammer crusher, a roll crusher, a flat jet mill, a fluidized bed jet mill, a circulating jet mill, an impact crusher, an expansion crusher, a ball mill crusher, a high-speed rotation projection crusher or a high-speed rotation impact crusher.
8. A separator comprising the NASICON structure lithium ion solid state electrolyte material according to claim 1.
9. A lithium battery comprising the separator according to claim 8.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102468486A (en) * | 2010-11-02 | 2012-05-23 | 三星Sdi株式会社 | Positive active material for lithium secondary battery and method of manufacturing same |
| CN108933282A (en) * | 2018-07-11 | 2018-12-04 | 中国科学院宁波材料技术与工程研究所 | NASICON structure sodion solid electrolytes, preparation method and solid-state sodium-ion battery |
| CN110277586A (en) * | 2019-06-26 | 2019-09-24 | 上海空间电源研究所 | A kind of lithium ion solid electrolyte and preparation method thereof |
| CN111480256A (en) * | 2018-04-20 | 2020-07-31 | 株式会社Lg化学 | Electrolyte for lithium secondary battery and lithium secondary battery comprising the same |
-
2022
- 2022-01-19 CN CN202210061299.6A patent/CN114388880A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102468486A (en) * | 2010-11-02 | 2012-05-23 | 三星Sdi株式会社 | Positive active material for lithium secondary battery and method of manufacturing same |
| CN111480256A (en) * | 2018-04-20 | 2020-07-31 | 株式会社Lg化学 | Electrolyte for lithium secondary battery and lithium secondary battery comprising the same |
| CN108933282A (en) * | 2018-07-11 | 2018-12-04 | 中国科学院宁波材料技术与工程研究所 | NASICON structure sodion solid electrolytes, preparation method and solid-state sodium-ion battery |
| CN110277586A (en) * | 2019-06-26 | 2019-09-24 | 上海空间电源研究所 | A kind of lithium ion solid electrolyte and preparation method thereof |
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