CN111987347B - Phosphate solid electrolyte, solid-phase synthesis method and equipment thereof, and solid-state battery - Google Patents
Phosphate solid electrolyte, solid-phase synthesis method and equipment thereof, and solid-state battery Download PDFInfo
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- CN111987347B CN111987347B CN202010572532.8A CN202010572532A CN111987347B CN 111987347 B CN111987347 B CN 111987347B CN 202010572532 A CN202010572532 A CN 202010572532A CN 111987347 B CN111987347 B CN 111987347B
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- 238000000034 method Methods 0.000 title claims abstract description 70
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 52
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 51
- 239000010452 phosphate Substances 0.000 title claims abstract description 49
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 42
- 238000010532 solid phase synthesis reaction Methods 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 132
- 239000000843 powder Substances 0.000 claims abstract description 121
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 25
- 238000001354 calcination Methods 0.000 claims abstract description 24
- -1 phosphate compound Chemical class 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 17
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 15
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 15
- 150000003608 titanium Chemical class 0.000 claims abstract description 15
- 229910006210 Li1+xAlxTi2-x(PO4)3 Inorganic materials 0.000 claims abstract description 6
- 229910006212 Li1+xAlxTi2−x(PO4)3 Inorganic materials 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 63
- 230000002209 hydrophobic effect Effects 0.000 claims description 55
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000010439 graphite Substances 0.000 claims description 16
- 229910002804 graphite Inorganic materials 0.000 claims description 16
- 239000000919 ceramic Substances 0.000 claims description 15
- 239000003575 carbonaceous material Substances 0.000 claims description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 238000000354 decomposition reaction Methods 0.000 claims description 12
- 239000004408 titanium dioxide Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 7
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000012071 phase Substances 0.000 abstract description 33
- 239000012535 impurity Substances 0.000 abstract description 17
- 238000005245 sintering Methods 0.000 abstract description 15
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 75
- 235000021317 phosphate Nutrition 0.000 description 42
- 238000000498 ball milling Methods 0.000 description 33
- 238000003756 stirring Methods 0.000 description 17
- 229910052593 corundum Inorganic materials 0.000 description 16
- 239000010431 corundum Substances 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 15
- 238000002441 X-ray diffraction Methods 0.000 description 14
- 229910001220 stainless steel Inorganic materials 0.000 description 13
- 239000010935 stainless steel Substances 0.000 description 13
- 239000013078 crystal Substances 0.000 description 12
- 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 description 9
- 239000008103 glucose Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000011324 bead Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000013067 intermediate product Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 5
- 229910052863 mullite Inorganic materials 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000001722 carbon compounds Chemical class 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910003480 inorganic solid Inorganic materials 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000002228 NASICON Substances 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000002699 waste material Substances 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—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
-
- 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)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
The application discloses a phosphate solid electrolyte, a solid-phase synthesis method thereof, equipment and a solid-state battery, wherein the synthesis method comprises the following steps: mixing lithium salt, aluminum salt, titanium salt, a phosphate compound, a carbon source and a solvent according to a preset proportion to obtain a mixture; drying the mixture at a first temperature after primary mixing to obtain dried powder; placing the dried powder in a first container, and pre-burning for a first time at a second temperature to obtain pre-burned powder; placing the pre-sintered powder in a second container after secondary mixing, and calcining for a second time at a third temperature to obtain Li1+xAlxTi2‑x(PO4)3A solid electrolyte material; wherein the third temperature is higher than the second temperature. The method effectively solves the problem of material sticking in the sintering process, ensures that pure-phase materials can be obtained in the subsequent sintering step, and avoids the generation of impurity phases.
Description
Technical Field
The application relates to the field of materials, in particular to a phosphate solid electrolyte, a solid-phase synthesis method and equipment thereof, and a solid-state battery.
Background
A large amount of volatile, inflammable and explosive organic solvents exist in the lithium ion battery, and serious potential safety hazards are brought to the battery. Compared with liquid electrolyte, the inorganic solid electrolyte has obvious advantages in safety and thermal stability, so that the all-solid-state lithium ion battery using the inorganic solid electrolyte is considered as a means for fundamentally solving the safety problem of the lithium ion battery, and has strong promotion effect on the development of new energy automobiles and energy storage batteries.
Among the inorganic solid electrolytes, the phosphate solid electrolyte Li of NASICON type1+xAlxTi2-x(PO4)3Has the advantages of higher conductivity, stability to air, good electrochemical stability, low cost and the like,therefore, the method has great application prospect in the development of all-solid-state lithium batteries. The high temperature solid phase method is the most commonly used method for preparing NASICON type lithium ion electrolytes. The raw materials are ground and mixed according to a certain proportion, then are placed in a ceramic container, and are subjected to high-temperature calcination for a long time in an air atmosphere to form a phase. In the high temperature solid phase process, it is desirable to use inorganic phosphates as a source of phosphate, the most common and least expensive phosphates including phosphoric acid and ammonium phosphates. However, phosphoric acid is inevitably generated in the process of temperature rise, and the phosphoric acid has obvious corrosiveness to the ceramic container at higher temperature, so that on one hand, a synthesized product is bonded in the ceramic container and is difficult to take out, and the ceramic container is damaged; on the other hand, the loss of the phosphorus element causes that the element proportion in the product is difficult to control, the product has impurity phases, and the product conductivity is lower.
Disclosure of Invention
The application aims to provide a phosphate solid electrolyte, a solid-phase synthesis method and equipment thereof, and a solid-state battery, and aims to overcome the technical defects of the synthesis process of the phosphate solid electrolyte in the prior art.
In a first aspect, the present application provides a solid-phase synthesis method of a phosphate solid electrolyte, comprising the following steps:
mixing lithium salt, aluminum salt, titanium salt, a phosphate compound, a carbon source and a solvent according to a preset proportion to obtain a mixture;
drying the mixture at a first temperature after primary mixing to obtain dried powder;
placing the dried powder in a first container, and pre-burning for a first time at a second temperature to obtain pre-burned powder;
placing the pre-sintered powder in a second container after secondary mixing, and calcining for a second time at a third temperature to obtain Li1+xAlxTi2-x(PO4)3A solid electrolyte material; wherein the third temperature is higher than the second temperature.
Further, the carbon source includes an inorganic carbon material and/or an organic carbon material.
Further, the preset proportion is that the ratio of the sum of the masses of the lithium salt, the aluminum salt, the titanium salt and the phosphate to the mass of the carbon source is 1 (0.001-0.12).
Further, the lithium salt comprises one or more of lithium carbonate, lithium nitrate, lithium hydroxide and lithium acetate; the aluminum salt comprises aluminum nitrate and/or aluminum oxide; the titanium salt is titanium dioxide; the phosphoric acid compound is one or more of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and triammonium phosphate; the solvent comprises water and/or ethanol.
Further, the materials used by the first container and the second container are the same, or the materials used by the first container and the second container are different, or the materials used by the first container and the second container are partially the same.
Further, the material used for the inner surface of the first container is a hydrophobic material, and the hydrophobic material is in a stable state at the second temperature; the material used for the second container is in a stable state at the third temperature; the stable state is a state that the material does not physically react at the corresponding temperature, and the material does not chemically react or does not chemically react with air.
Further, the hydrophobic material is not separable from the inner surface of the first container, and/or the hydrophobic material is separable from the inner surface of the first container.
Further, the hydrophobic material comprises graphite, and the material used for the second container comprises at least one of ceramic and metal.
Further, the second temperature is in the range of 150-500 ℃; the first time length is 1-5 h.
Further, the third temperature is in the range of 700-1000 ℃; the second time length is 5-20 h.
On the other hand, the application provides a phosphate solid electrolyte prepared by the solid-phase synthesis method.
In another aspect, the present application provides a solid-state battery comprising a phosphate solid electrolyte prepared by the above-described solid-phase synthesis method.
In another aspect, the present application provides an apparatus for performing the above solid phase synthesis method, the apparatus comprising the first container, the material used for the inner surface of the first container is a hydrophobic material, and the hydrophobic material is in a stable state at the second temperature; the hydrophobic material is not separable from a surface of the first container, and/or the hydrophobic material is separable from a surface of the first container; the stable state is a state in which the hydrophobic material does not physically react at the corresponding temperature, and the hydrophobic material itself does not chemically react or the hydrophobic material itself does not chemically react with air.
The beneficial effect of this application:
according to the method, a carbon source is added in the preparation process of the phosphate solid electrolyte, the sintering process is further divided into two steps, the first step adopts a relatively low temperature for pre-sintering (the relatively low temperature refers to a low sintering temperature relative to the second step), so that decomposition of a phosphate compound occurs in the pre-sintering process, synthesis of a solid electrolyte material does not occur, the intermediate product phosphoric acid is fully absorbed in a porous structure of the carbon source, corrosion of the phosphoric acid to a first container is effectively prevented, the problem of material adhesion in the sintering process is effectively solved, pure-phase materials can be obtained in the subsequent sintering step, and no impurity phase is generated.
Drawings
FIG. 1 is an X-ray diffraction pattern of a sample obtained in example 1 of the present invention;
fig. 2 is a photograph of prefired powder in a first container after prefiring at step S3 of example 1 of the present invention;
fig. 3 is a photograph of prefired powder in a first container after prefiring at step S3 of example 2 of the present invention;
fig. 4 is a photograph of prefired powder in a first container after prefiring at step S3 of example 3 of the present invention;
fig. 5 is a photograph of prefired powder in a first container after prefiring at step S3 of example 5 of the present invention;
fig. 6 is a photograph of prefired powder in a first container after prefiring at step S3 of comparative example 1 of the present invention.
The implementation, functional features and advantages of the objectives of the present application will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present application will be described clearly and completely with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The application provides a solid-phase synthesis method of a phosphate solid electrolyte, which comprises the following steps:
s1, mixing lithium salt, aluminum salt, titanium salt, a phosphate compound, a carbon source and a solvent according to a preset proportion to obtain a mixture;
s2, drying the mixture at a first temperature after primary mixing to obtain dried powder;
s3, placing the dried powder in a first container, and pre-burning for a first time at a second temperature to obtain pre-burned powder;
s4, placing the pre-sintered powder in a second container after secondary mixing, and calcining for a second time at a third temperature to obtain Li1+xAlxTi2-x(PO4)3A solid electrolyte material; wherein the third temperature is higher than the second temperature.
In step S1 of the embodiment of the present application, the amount of lithium salt, aluminum salt, titanium salt, and phosphoric acid compound added in the above predetermined ratio may be determined according to the finally synthesized Li1+xAlxTi2-x(PO4)3The proportion of each element in the solid electrolyte and the amount of the solid electrolyte which is expected to be synthesized are calculated; the carbon source is added in the amount of lithium salt, aluminum salt, titanium salt and phosphorusCalculating the mass sum of the acid salts according to a certain proportion; the amount of the solvent is enough to mix various materials uniformly, and the amount of the solvent is not limited in the present application and can be adjusted by a person skilled in the art according to actual conditions. The mixing in step S1 is a preliminary simple mixing, placing several materials together, stirring or shaking slightly.
Preferably, the preset ratio is that the ratio of the sum of the masses of the lithium salt, the aluminum salt, the titanium salt and the phosphate to the mass of the carbon source is 1 (0.001-0.12). For example, 1:0.001, 1:0.005, 1:0.006, 1:0.007, 1:0.01, 1:0.02, 1:0.03, 1:0.04, 1:0.05, 1:0.06, 1:0.07, 1:0.08, 1:0.09, 1:0.1, 1:0.11, 1:0.12, etc. can be used.
In step S2, the above-mentioned primary mixing is used to uniformly disperse the mixture, wherein the primary mixing manner includes, but is not limited to, ball milling with a ball mill, stirring with a stirrer, dispersing with a disperser, and the like, and any manner that can achieve the purpose of uniformly dispersing the mixture should be included in the primary mixing of the present application. The first temperature is a temperature for drying the uniformly dispersed mixture, and is used for drying the solvent, and preferably, the first temperature is a volatilization temperature of the solvent or is slightly higher than the volatilization temperature of the solvent. The drying time in step S2 is not specifically limited, and the mixture may be dried.
In step S3, the first container is used for placing the dried powder and carrying the dried powder to burn in at a second temperature. The shape and capacity of the first container are not particularly limited to that which can be achieved to contain the reaction product.
In step S4, the second container is used for placing the calcined powder and carrying the calcined powder to calcine at a third temperature. The shape and capacity of the second container are not particularly limited in this application so as to be able to accommodate the reaction product. The above-mentioned secondary compounding is used for dispersing the pre-sintering powder evenly, wherein the secondary compounding mode includes but is not limited to ball milling with a ball mill, stirring with a stirrer, dispersing with a disperser, etc., and all modes that can realize the purpose of dispersing the mixture evenly should be included in the secondary compounding of this application. Specifically, the secondary mixing process comprises mixing the pre-sintered powder with a certain amount of solvent, dispersing uniformly, and drying the solvent. The solvent is added into the secondary mixed material in an amount that the pre-sintered powder can be uniformly mixed, and the drying temperature is that the solvent can be dried.
In the embodiment of the application, a proper amount of carbon source is added in the solid-phase synthesis process of the phosphate solid electrolyte, the carbon source is fully mixed with lithium salt, aluminum salt, titanium salt, phosphoric acid compound and solvent and then dried, and the lithium salt, the aluminum salt, the titanium salt and the phosphoric acid compound are uniformly dispersed on the periphery side of the carbon source. In the pre-burning process of step S3, at the second temperature, the decomposition reaction of the phosphate compound occurs to generate phosphoric acid, and the porous structure of the carbon source can be timely adsorbed by the phosphoric acid generated by the decomposition reaction, so that in step S4, the problem that the phosphoric acid corrodes the second container and causes material adhesion is avoided. By the solid phase synthesis method, the synthesized product is powdery, is easy to take out and industrial production, and meanwhile, the product has accurate proportion of each element, high purity and higher ionic conductivity.
The carbon source of the embodiments of the present application includes an inorganic carbon material and/or an organic carbon material. Wherein the inorganic carbon material includes but is not limited to at least one of graphite and activated carbon; the organic carbon material includes, but is not limited to, at least one of glucose and sucrose. The porous structure of the inorganic carbon material can be used for timely adsorbing phosphoric acid generated in the pre-burning process. In the pre-firing step S3, the decomposition reaction of the organic carbon material occurs earlier than the decomposition reaction of the phosphoric acid compound, and a carbon compound having a porous structure is generated, and the carbon compound having a porous structure is also used for adsorbing phosphoric acid generated later. In the present application, the carbon source is preferably an organic carbon material, because the organic carbon material has a larger specific surface area of the porous carbon compound formed in the pre-firing process, which is more favorable for sufficient adsorption of phosphoric acid.
The lithium salt in the embodiment of the application comprises one or more of lithium carbonate, lithium nitrate, lithium hydroxide and lithium acetate; the aluminum salt includes aluminum nitrate and/or aluminum oxide; the titanium salt is titanium dioxide; the phosphoric acid compound is one or more of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and triammonium phosphate; the solvent comprises water and/or ethanol.
In some embodiments of the present application, the first container and the second container are made of the same material. The materials of the first container and the second container are in a stable state at a third temperature, and the stable state is a state that the materials do not physically react and do not chemically react with each other or the materials do not chemically react with air at the corresponding temperature. For example, the material may be a ceramic, including but not limited to mullite, corundum, etc., a metal, including but not limited to nickel, platinum, silver, etc., and the like.
In other embodiments of the present application, the materials used for the first and second containers are different. The material of the first container is in a stable state at the second temperature, the stable state being a state in which the material does not physically react and the material itself does not chemically react or the material itself does not chemically react with air at the corresponding temperature. For example, the material of the first container may be graphite or the like, and the material of the second container may be ceramic, including but not limited to mullite, corundum, etc., metal, including but not limited to nickel, platinum, silver, etc., and the like.
In still other embodiments of the present application, the first container and the second container are made of the same material. For example, the first vessel comprises graphite and at least one of a ceramic, a metal, and the second vessel is a ceramic, a metal, the ceramic including but not limited to mullite, corundum, and the like, and the metal including but not limited to nickel, platinum, silver, and the like.
The material used for the inner surface of the first container in the embodiment of the application is a hydrophobic material, and the hydrophobic material is in a stable state at the second temperature; the material used for the second container is in a stable state at the third temperature; the stable state is a state that the material does not physically react at the corresponding temperature, and the material does not chemically react or does not chemically react with air. The hydrophobic material is adopted to avoid the infiltration of the intermediate product phosphoric acid, so that the corrosion of the phosphoric acid to the first container is avoided, the adhesion of reaction products is caused, the deviation of the element proportion of the product can be avoided, the product is easy to take out, the proportion is accurate, and the beneficial effects of the product quality and the production capacity are greatly improved.
In some embodiments of the present application, the hydrophobic material is not separable from the inner surface of the first container. The first container is integrally prepared from hydrophobic materials; or the first container main body is made of other materials, the hydrophobic material is compounded on the inner surface of the first container through deposition, adhesion, mechanical pressing and other modes, and the composite material can be directly used in the production process, so that the operation is simple and convenient. The other material here is different from the hydrophobic material and satisfies the other material in a stable state at the second temperature.
In other embodiments of the present application, the hydrophobic material is detachable from an inner surface of the first container. The first container main body is made of other materials, the hydrophobic material is arranged on the inner surface of the first container through direct placement and the like, the replacement of the inner surface of the hydrophobic material is facilitated, the maintenance of the first container is facilitated, the cleaning time is reduced, the acceleration of production is facilitated, and the productivity is improved. For example, a film made of a hydrophobic material is applied to the inner surface of the first container. The other material here is different from the hydrophobic material and satisfies the other material in a stable state at the second temperature.
In still other embodiments of the present application, the inner surface of the first container has both a non-separable hydrophobic material and a separable hydrophobic material. The structure of the first container of this embodiment combines the advantages of the two aforementioned structures, is favorable to maintaining the first container on the one hand, and on the other hand has further guaranteed that under the unexpected circumstances such as separable hydrophobic material breaks, intermediate product phosphoric acid can not react with first container, has improved the purity and the productivity of product, has prolonged the life of first container, and has ensured the stability of technology.
Preferably, the hydrophobic material comprises graphite; the material used for the second container comprises at least one of ceramics and metal. Ceramics include, but are not limited to, mullite, corundum, and the like, metals include, but are not limited to, nickel, platinum, silver, and the like
The second temperature in the embodiment of the present application ranges from 150 ℃ to 500 ℃; the first time length is 1-5 h. For example, the second temperature may be 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃ or the like. The first time period is 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, etc. At this second temperature, a decomposition reaction of the phosphoric acid compound and a decomposition reaction of the organic carbon material occur. Preferably, in step S3, when the temperature is increased from room temperature to the second temperature, the decomposition reaction of the organic carbon material is advantageously completed and then the decomposition reaction of the phosphoric acid compound is started by using a multi-stage temperature increase manner.
The third temperature in the embodiment of the present application ranges from 700 ℃ to 1000 ℃; the second time length is 5-20 h. For example, the third temperature may be 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃ or the like. The second time period is 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, etc. At the third temperature, the carbon source is decomposed at a high temperature to discharge the generated gas, and the lithium salt, the aluminum salt, the titanium salt and the phosphoric acid are phase-formed by high-temperature calcination to generate Li1+ xAlxTi2-x(PO4)3A solid electrolyte material.
The embodiment of the application provides a phosphate solid electrolyte, which is prepared by the solid-phase synthesis method. The phosphate solid electrolyte synthesized by the solid-phase synthesis method provided by the embodiment of the application has the advantages of accurate proportion of elements, high purity, less impurity phase and high conductivity.
The application provides a solid-state battery, which comprises a phosphate solid electrolyte prepared by the solid-phase synthesis method. The solid-state battery of the phosphate solid electrolyte synthesized by the solid-phase method in the embodiment of the application has the advantages of high ion transmission speed, good high-rate performance and long service life in the charging and discharging processes.
The embodiment of the application also provides equipment for implementing the solid-phase synthesis method, which comprises a first container, wherein the material used for the inner surface of the first container is a hydrophobic material, and the hydrophobic material is in a stable state at a second temperature; the hydrophobic material is not separable from a surface of the first container, and/or the hydrophobic material is separable from a surface of the first container; the stable state is a state in which the hydrophobic material does not physically react at the corresponding temperature, and the hydrophobic material itself does not chemically react or the hydrophobic material itself does not chemically react with air. Preferably, the hydrophobic material comprises graphite.
In some embodiments of the present application, the hydrophobic material is not separable from the inner surface of the first container. The first container is integrally prepared from hydrophobic materials; or the first container main body is made of other materials, the hydrophobic material is compounded on the inner surface of the first container through deposition, adhesion, mechanical pressing and other modes, and the composite material can be directly used in the production process, so that the operation is simple and convenient. The other material here is different from the hydrophobic material and satisfies the other material in a stable state at the second temperature.
In other embodiments of the present application, the hydrophobic material is detachable from an inner surface of the first container. The first container main body is made of other materials, the hydrophobic material is arranged on the inner surface of the first container through direct placement and the like, the replacement of the inner surface of the hydrophobic material is facilitated, the maintenance of the first container is facilitated, the cleaning time is reduced, the acceleration of production is facilitated, and the productivity is improved. For example, a film made of a hydrophobic material is applied to the inner surface of the first container. The other material here is different from the hydrophobic material and satisfies the other material in a stable state at the second temperature.
In still other embodiments of the present application, the inner surface of the first container has both a non-separable hydrophobic material and a separable hydrophobic material. The structure of the first container of this embodiment combines the advantages of the two aforementioned structures, is favorable to maintaining the first container on the one hand, and on the other hand has further guaranteed that under the unexpected circumstances such as separable hydrophobic material breaks, intermediate product phosphoric acid can not react with first container, has improved the purity and the productivity of product, has prolonged the life of first container, and has ensured the stability of technology.
The embodiments and advantages of the present application are illustrated below by specific examples and comparative examples.
Example 1
S1, 50mL of water, 6.20 g of lithium carbonate, 1.99 g of alumina, 17.72 g of titanium dioxide, 44.95 g of ammonium dihydrogen phosphate and 0.75g of glucose were added to a 2L stainless steel pot, respectively, to obtain a mixture.
S2, adding 200 g of ball milling beads with the diameter of 3mm into a stainless steel tank, and carrying out ball milling and stirring for 4 hours at the stirring speed of 200 rpm. And (3) placing the ball milling tank in a blast oven, and drying for 10 hours at 120 ℃ to obtain dried powder.
S3, taking 10 g of the dried powder prepared in the step S2, presintering the powder for 2 hours at 400 ℃ in a muffle furnace by using a first container to obtain presintering powder, naturally cooling the powder, and taking out the presintering powder; the first container is a graphite container.
S4, mixing the pre-sintered powder for the second time, wherein the mixing step for the second time comprises the steps of adding 30mL of ethanol into the pre-sintered powder, carrying out ball milling for 3 hours, then placing the mixture into a blast oven, and drying the mixture for 8 hours at the temperature of 100 ℃; then the dried material is burnt in a muffle furnace for 5 hours at 900 ℃ by a second container to obtain a phosphate solid electrolyte product; the second container is a corundum container.
As shown in fig. 2, which is a photo of the calcined powder in the first container after the calcination in step S3, the powder product will not adhere to the surface of the first container/the second container during the two calcination processes in step S3 and step S4, and the product is easy to be taken out. The crystal phase structure of the product is analyzed by adopting an X-ray diffraction technology, an X-ray diffraction pattern is shown in figure 1, and the phosphate solid electrolyte product has no impurity phase. And (3) ball-milling the obtained phosphate solid electrolyte product in a planetary ball mill at the rotating speed of 500rpm for 12 hours by using 1.5 wt% of polyvinyl butyral as a binder and ethanol as a ball milling agent. And (3) drying the ball-milled slurry in a 50 ℃ oven, maintaining the pressure of the dry powder at 5Mpa for 10min, and pressing into a wafer with the thickness of 2 mm. Sputtering a layer of gold film on two ends of the wafer to form ion blocking electrodes, and testing the ion conductivity of the material by AC impedance technology, wherein the total ion conductivity of the material is 5.71 multiplied by 10- 4S/cm。
Example 2
S1, 50mL of water, 6.20 g of lithium carbonate, 1.99 g of alumina, 17.72 g of titanium dioxide, 44.95 g of ammonium dihydrogen phosphate and 0.75g of glucose were added to a 2L stainless steel pot, respectively, to obtain a mixture.
S2, adding 200 g of ball milling beads with the diameter of 3mm, and carrying out ball milling and stirring for 4 hours at the stirring speed of 200 rpm. And (3) placing the ball milling tank in a blast oven, and drying for 10 hours at 120 ℃ to obtain dried powder.
S3, taking 10 g of the dried powder prepared in the step S2, burning the powder for 2 hours at 400 ℃ in a muffle furnace by using a first container to obtain pre-burnt powder, and naturally cooling the pre-burnt powder and taking out the pre-burnt powder; the first container is a corundum container.
S4, mixing the pre-sintered powder for the second time, wherein the mixing step for the second time comprises the steps of adding 30mL of ethanol into the pre-sintered powder, carrying out ball milling for 3 hours, then placing the mixture into a blast oven, and drying the mixture for 8 hours at the temperature of 100 ℃; burning the dried material in a muffle furnace for 5 hours at 900 ℃ by using a second container to obtain a phosphate solid electrolyte product; the second container is a corundum container.
As shown in fig. 3, which is a photograph of the calcined powder in the first container after the calcination in step S3, the powder product slightly adhered to the surface of the corundum container during the calcination in step S3. In the calcining process of the step S4, the powder product can not be adhered to the surface of the corundum container, and the product is easy to take out. The crystal phase structure of the product is analyzed by adopting an X-ray diffraction technology, and the product has no impurity phase. The obtained powder was tested for ionic conductivity in the same manner as in example 1, and found to be 2.51X 10-4S/cm。
Example 3
The glucose in example 1 was changed to activated carbon in an amount of 0.75g, and the first vessel was a ceramic vessel having graphite paper laid on the surface.
The rest of the procedure was the same as in example 1.
As shown in fig. 4, which is a photograph of the calcined powder in the first container after the calcination in step S3, the powder product was slightly adhered to the surface of the first container during the calcination in step S3. The powder product does not adhere to the second container during the calcination of step S4On the surface, the product is easy to take out. The crystal phase structure of the product is analyzed by adopting an X-ray diffraction technology, and the phosphate solid electrolyte product has no impurity phase. The obtained powder was tested for ionic conductivity in the same manner as in example 1, and found to be 2.49X 10-4S/cm。
Example 4
The amount of glucose used in example 2 was increased to 1.5 grams, the first vessel being a mullite vessel.
The rest of the procedure was the same as in example 2.
The powder product slightly adheres to the first container during the calcination in step S3. The powder product does not adhere to the surface of the second container during the calcination in step S4, and the product is easily taken out. The crystal phase structure of the product is analyzed by adopting an X-ray diffraction technology, and the product has no impurity phase. The obtained powder was tested for ionic conductivity in the same manner as in example 1, and found to be 4.82X 10-4S/cm。
Example 5
The amount of activated carbon used in example 3 was increased to 1.5 grams, and the first vessel was a ceramic vessel having a graphite coating on its surface.
The rest of the procedure was the same as in example 3.
As shown in fig. 5, which is a photo of the calcined powder in the first container after the calcination in step S3, the powder product will not adhere to the surface of the first container/the second container during the two calcination processes in step S3 and step S4, and the product is easy to be taken out. The crystal phase structure of the product is analyzed by adopting an X-ray diffraction technology, and the phosphate solid electrolyte product has no impurity phase. The obtained powder was tested for ionic conductivity in the same manner as in example 1, and found to be 4.67X 10-4S/cm。
Example 6
Changing the step S3 in the embodiment 1 into 10 g of the dried powder obtained in the step S2, pre-burning the dried powder for 2 hours at 200 ℃ in a muffle furnace by using a first container to obtain pre-burned powder, and naturally cooling the pre-burned powder and taking out the pre-burned powder; the first container is a graphite container.
Step S4 is changed into a step S, the pre-sintered powder is mixed for the second time, and the step of mixing for the second time comprises the steps of adding 30mL of ethanol into the pre-sintered powder, carrying out ball milling for 3 hours, then placing the mixture into a blast oven, and drying the mixture for 8 hours at the temperature of 100 ℃; then the dried material is burnt in a muffle furnace for 1000 ℃ for 5 hours by a second container to obtain a phosphate solid electrolyte product; the second container is a corundum container.
The rest of the procedure was the same as in example 1.
In the two calcining processes of the step S3 and the step S4, the powder product is not adhered to the surface of the first container/the second container, and the product is easy to take out. The crystal phase structure of the product is analyzed by adopting an X-ray diffraction technology, and the phosphate solid electrolyte product has no impurity phase. The obtained powder was tested for ionic conductivity in the same manner as in example 1, and found to be 5.67X 10-4S/cm。
Example 7
Changing the step S4 in the embodiment 1 into a step of mixing the pre-sintered powder for the second time, wherein the step of mixing the materials for the second time comprises the steps of adding 30mL of ethanol into the pre-sintered powder, carrying out ball milling for 3 hours, then placing the mixture into a blast oven, and drying the mixture for 8 hours at the temperature of 100 ℃; then the dried material is burnt in a muffle furnace for 5 hours at 800 ℃ by a second container to obtain a phosphate solid electrolyte product; the second container is a corundum container.
The rest of the procedure was the same as in example 1.
In the two calcining processes of the step S3 and the step S4, the powder product is not adhered to the surface of the first container/the second container, and the product is easy to take out. The crystal phase structure of the product is analyzed by adopting an X-ray diffraction technology, and the phosphate solid electrolyte product has no impurity phase. The obtained powder was tested for ionic conductivity in the same manner as in example 1, and found to be 2.26X 10-4S/cm。
Example 8
S1, 50mL of water, 7.04 g of lithium hydroxide, 14.64 g of aluminum nitrate, 17.72 g of titanium dioxide, 51.59 g of diammonium phosphate and 0.75g of glucose were added to a 2L stainless steel pot, respectively, to obtain a mixture.
S2, adding 200 g of ball milling beads with the diameter of 3mm into a stainless steel tank, and carrying out ball milling and stirring for 4 hours at the stirring speed of 200 rpm. And (3) placing the ball milling tank in a blast oven, and drying for 10 hours at 120 ℃ to obtain dried powder.
S3, taking 10 g of the dried powder prepared in the step S2, presintering the powder for 2 hours at 400 ℃ in a muffle furnace by using a first container to obtain presintering powder, naturally cooling the powder, and taking out the presintering powder; the first container is a graphite container.
S4, mixing the pre-sintered powder for the second time, wherein the mixing step for the second time comprises the steps of adding 30mL of ethanol into the pre-sintered powder, carrying out ball milling for 3 hours, then placing the mixture into a blast oven, and drying the mixture for 8 hours at the temperature of 100 ℃; then the dried material is burnt in a muffle furnace for 8 hours at 900 ℃ by a second container to obtain a phosphate solid electrolyte product; the second container is a corundum container.
In the two calcining processes of the step S3 and the step S4, the powder product is not adhered to the surface of the first container/the second container, and the product is easy to take out. The crystal phase structure of the product is analyzed by adopting an X-ray diffraction technology, and the phosphate solid electrolyte product has no impurity phase. The obtained powder was tested for ionic conductivity in the same manner as in example 1, and found to be 5.45X 10-4S/cm。
Example 9
S1, 50mL of water, 11.56 g of lithium nitrate, 1.99 g of alumina, 17.72 g of titanium dioxide, 45.06 g of phosphoric acid and 15 g of glucose were added to a 2L stainless steel can, respectively, to obtain a mixture.
S2, adding 200 g of ball milling beads with the diameter of 3mm into a stainless steel tank, and carrying out ball milling and stirring for 4 hours at the stirring speed of 200 rpm. And (3) placing the ball milling tank in a blast oven, and drying for 10 hours at 120 ℃ to obtain dried powder.
S3, taking 10 g of the dried powder prepared in the step S2, presintering the powder for 1 hour at 500 ℃ in a muffle furnace by using a first container to obtain presintering powder, naturally cooling the powder, and taking out the presintering powder; the first container is a graphite container.
S4, mixing the pre-sintered powder for the second time, wherein the mixing step for the second time comprises the steps of adding 30mL of ethanol into the pre-sintered powder, carrying out ball milling for 3 hours, then placing the mixture into a blast oven, and drying the mixture for 8 hours at the temperature of 100 ℃; then the dried material is burnt in a muffle furnace for 700 ℃ for 20 hours by a second container to obtain a phosphate solid electrolyte product; the second container is a corundum container.
Twice of step S3 and step S4The powder product can not be adhered to the surface of the first container/the second container in the calcining process, and the product is easy to take out. The crystal phase structure of the product is analyzed by adopting an X-ray diffraction technology, and the phosphate solid electrolyte product has no impurity phase. The obtained powder was tested for ionic conductivity in the same manner as in example 1, and found to be 1.51X 10-4S/cm。
Example 10
S1, 50mL of ethanol, 13.02 g of lithium acetate, 1.99 g of alumina, 17.72 g of titanium dioxide, 58.23 g of triammonium phosphate and 0.75g of glucose were added to a 2L stainless steel pot, respectively, to obtain a mixture.
S2, adding 200 g of ball milling beads with the diameter of 3mm into a stainless steel tank, and carrying out ball milling and stirring for 4 hours at the stirring speed of 200 rpm. And (3) placing the ball milling tank in a blast oven, and drying for 10 hours at 120 ℃ to obtain dried powder.
S3, taking 10 g of the dried powder prepared in the step S2, presintering the powder for 5 hours at 150 ℃ in a muffle furnace by using a first container to obtain presintering powder, naturally cooling the powder, and taking out the presintering powder; the first container is a graphite container.
S4, mixing the pre-sintered powder for the second time, wherein the mixing step for the second time comprises the steps of adding 30mL of ethanol into the pre-sintered powder, carrying out ball milling for 3 hours, then placing the mixture into a blast oven, and drying the mixture for 8 hours at the temperature of 100 ℃; then the dried material is burnt in a muffle furnace for 5 hours at 900 ℃ by a second container to obtain a phosphate solid electrolyte product; the second container is a corundum container.
In the two calcining processes of the step S3 and the step S4, the powder product is not adhered to the surface of the first container/the second container, and the product is easy to take out. The crystal phase structure of the product is analyzed by adopting an X-ray diffraction technology, and the phosphate solid electrolyte product has no impurity phase. The obtained powder was tested for ionic conductivity in the same manner as in example 1, and found to be 2.29X 10-4S/cm。
Comparative example 1
S1, 50mL of water, 6.20 g of lithium carbonate, 1.99 g of alumina, 17.72 g of titanium dioxide and 44.95 g of ammonium dihydrogen phosphate were put in a 2L stainless steel pot, respectively, to obtain a mixture.
S2, adding 200 g of ball milling beads with the diameter of 3mm into a stainless steel tank, and carrying out ball milling and stirring for 4 hours at the stirring speed of 200 rpm. And (3) placing the ball milling tank in a blast oven, and drying for 10 hours at 120 ℃ to obtain dried powder.
S3, taking 10 g of the dried powder prepared in the step S2, burning the powder for 2 hours in a muffle furnace at 400 ℃ by using a first container to obtain pre-burnt powder, and naturally cooling the pre-burnt powder and taking out the powder; the first container is a graphite container.
S4, mixing the pre-sintered powder for the second time, wherein the mixing step for the second time comprises the steps of adding 30mL of ethanol into the pre-sintered powder, carrying out ball milling for 3 hours, then placing the mixture into a blast oven, and drying the mixture for 8 hours at the temperature of 100 ℃; then the dried material is burnt in a muffle furnace for 5 hours at 900 ℃ by a second container to obtain a phosphate solid electrolyte product; the second container is a corundum container.
As shown in fig. 6, which is a photograph of the calcined powder in the first container after the calcination in step S3, the powder product was agglomerated on the surface of the first container during the calcination in step S3 and was difficult to take out. The crystal phase structure of the product is analyzed by adopting an X-ray diffraction technology, and the product has impurity phases. The obtained powder was tested for ionic conductivity in the same manner as in example 1, and found to be 7.41X 10- 5S/cm。
Comparative example 2
S1, 50mL of water, 6.20 g of lithium carbonate, 1.99 g of alumina, 17.72 g of titanium dioxide and 44.95 g of ammonium dihydrogen phosphate were put in a 2L stainless steel pot, respectively, to obtain a mixture.
S2, adding 200 g of ball milling beads with the diameter of 3mm into a stainless steel tank, and carrying out ball milling and stirring for 4 hours at the stirring speed of 200 rpm. And (3) placing the ball milling tank in a blast oven, and drying for 10 hours at 120 ℃ to obtain dried powder.
S3, taking 10 g of the dried powder prepared in the step S2, and burning the dried powder in a muffle furnace for 5 hours at 900 ℃ by using a second container to obtain a phosphate solid electrolyte product; the second container is a corundum container.
In the calcining process of the step S3, the powder product is agglomerated on the surface of the second container, and the caking is serious and difficult to take out. The crystal phase structure of the product is analyzed by adopting an X-ray diffraction technology, and the product has impurity phases. The resulting powder was subjected to ion-charging in the same manner as in example 1The result of the conductivity test was 8.8X 10-6S/cm。
From the results of the above examples and comparative examples, it is apparent that the addition of the carbon source during the preparation of the phosphate solid electrolyte has an effect of solving the phenomenon of the sticking on the container in which the material to be sintered is placed. The inventors of the present application found that a carbon source can effectively adsorb phosphoric acid produced by decomposition of a phosphoric acid compound, and have not been known to the public before. On the basis of the discovery, the sintering process is further divided into two steps, the first step adopts a relatively low temperature to perform pre-sintering (the relatively low temperature refers to a low sintering temperature relative to the second step), so that decomposition of phosphate compounds occurs in the pre-sintering process, and synthesis of solid electrolyte materials does not occur, so that the intermediate product phosphoric acid is fully absorbed in a porous structure of a carbon source, corrosion of the first container by the phosphoric acid is effectively prevented, and pure-phase materials can be obtained in the subsequent sintering step, and no impurity phase is generated.
The inventors of the present application have further found that, in terms of the selection of the carbon source, the effect of the organic carbon source such as glucose is better than that of the inorganic carbon source, because the organic carbon source is decomposed first in the pre-sintering process to generate a porous loose structure, and further, the organic carbon source can sufficiently absorb phosphoric acid. Moreover, from the results of the above examples and comparative examples, the addition of the carbon source also contributes to the improvement of the conductivity of the product, which is related to the proper control of the ratio of each element in the product, but the excessive carbon source is not favorable for the improvement of the productivity and causes the waste of raw materials.
The inventors of the present application have further optimized the kind of the first container in the burn-in process, giving a preferred kind of material for the first container. When the surface of the first container is made of a hydrophobic material such as graphite, the powder sticking phenomenon during the pre-firing process is greatly suppressed. The hydrophobic material is adopted to further avoid the infiltration of the intermediate product phosphoric acid, so that the corrosion of the phosphoric acid to the first container is avoided, the adhesion of reaction products is avoided, the deviation of the element proportion of the product can be avoided, the product is easy to take out, the proportion is accurate, and the beneficial effects of greatly improving the product quality and the production capacity are achieved.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, apparatus, article, or method that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, apparatus, article, or method. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a process, apparatus, article, or method that includes the element.
The above description is only a preferred embodiment of the present application, and not intended to limit the scope of the present application, and all modifications of equivalent structures and equivalent processes, which are made by the contents of the specification and the drawings of the present application, or which are directly or indirectly applied to other related technical fields, are also included in the scope of the present application.
Claims (11)
1. A solid-phase synthesis method of a phosphate solid electrolyte is characterized by comprising the following steps:
mixing lithium salt, aluminum salt, titanium salt, a phosphate compound, a carbon source and a solvent according to a preset proportion to obtain a mixture;
drying the mixture at a first temperature after primary mixing to obtain dried powder;
placing the dried powder in a first container, and presintering the dried powder for a first time at a second temperature, wherein the second temperature is 150-500 ℃, so that the decomposition of the phosphoric acid compound occurs in the presintering process, and the synthesis of the solid electrolyte does not occur;
placing the pre-sintered powder in a second container after secondary mixing, and calcining for a second time at a third temperature to obtain Li1+xAlxTi2-x(PO4)3A solid electrolyte material; wherein the third temperature is higher than the second temperature, and the range of the third temperature is 700 ℃At 1000 ℃, the carbon source is removed by oxidation at the third temperature;
the material used for the inner surface of the first container is a hydrophobic material, and the hydrophobic material is in a stable state at the second temperature; the material used for the second container is in a stable state at the third temperature; the stable state is a state that the material does not physically react at the corresponding temperature, and the material does not chemically react or does not chemically react with air.
2. The solid phase synthesis method of claim 1, wherein the carbon source comprises an inorganic carbon material and/or an organic carbon material.
3. The solid-phase synthesis method according to claim 1, wherein the ratio of the sum of the mass of the lithium salt, the aluminum salt, the titanium salt and the phosphate compound to the mass of the carbon source is 1 (0.001 to 0.12).
4. The solid phase synthesis method of claim 1, wherein the lithium salt comprises one or more of lithium carbonate, lithium nitrate, lithium hydroxide, and lithium acetate; the aluminum salt comprises aluminum nitrate and/or aluminum oxide; the titanium salt is titanium dioxide; the phosphoric acid compound is one or more of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and triammonium phosphate; the solvent comprises water and/or ethanol.
5. The solid phase synthesis method of claim 1, wherein the first vessel and the second vessel are made of different materials or are made of partially the same material.
6. The solid phase synthesis method of claim 1, wherein the hydrophobic material is not separable from the inner surface of the first vessel, and/or the hydrophobic material is separable from the inner surface of the first vessel.
7. The solid phase synthesis method of claim 1, wherein the hydrophobic material comprises graphite, and the material used for the second container comprises at least one of ceramic and metal.
8. The solid phase synthesis method of claim 1, wherein the first time period is 1-5 hours.
9. The solid phase synthesis method of claim 1, wherein the second time period is 5 to 20 hours.
10. A phosphate solid electrolyte prepared by the solid-phase synthesis method according to any one of claims 1 to 9.
11. A solid-state battery comprising the phosphate solid electrolyte prepared by the solid-phase synthesis method according to any one of claims 1 to 9.
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| CN106129464A (en) * | 2015-12-09 | 2016-11-16 | 天津金牛电源材料有限责任公司 | A kind of synthetic method of solid ceramic electrolyte titanium phosphate aluminum lithium |
| CN108091928A (en) * | 2017-12-13 | 2018-05-29 | 桑顿新能源科技有限公司 | A kind of Organic-inorganic composite solid electrolyte and preparation method |
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Denomination of invention: Phosphate solid electrolyte and its solid-state synthesis method, equipment, solid-state battery Granted publication date: 20210803 Pledgee: Agricultural Bank of China Limited by Share Ltd. Xiamen Tongan branch Pledgor: Xiamen Guna new energy materials Co.,Ltd. Registration number: Y2024980018914 |