CN117923454B - Titanium aluminum lithium phosphate material, diaphragm, preparation method of diaphragm and battery - Google Patents
Titanium aluminum lithium phosphate material, diaphragm, preparation method of diaphragm and battery Download PDFInfo
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- CN117923454B CN117923454B CN202410107674.5A CN202410107674A CN117923454B CN 117923454 B CN117923454 B CN 117923454B CN 202410107674 A CN202410107674 A CN 202410107674A CN 117923454 B CN117923454 B CN 117923454B
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- lithium
- aluminum
- phosphate material
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- aluminum titanium
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- 239000000463 material Substances 0.000 title claims abstract description 99
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000007790 solid phase Substances 0.000 claims abstract description 70
- 238000005245 sintering Methods 0.000 claims abstract description 61
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims abstract description 53
- 239000010936 titanium Substances 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 29
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 23
- CNRZQDQNVUKEJG-UHFFFAOYSA-N oxo-bis(oxoalumanyloxy)titanium Chemical compound O=[Al]O[Ti](=O)O[Al]=O CNRZQDQNVUKEJG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 21
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011574 phosphorus Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 28
- 229920000098 polyolefin Polymers 0.000 claims description 14
- PPQREHKVAOVYBT-UHFFFAOYSA-H aluminium carbonate Inorganic materials [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 claims description 10
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 10
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 10
- 238000005266 casting Methods 0.000 claims description 10
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 10
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 10
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- -1 aluminum titanium oxide compound Chemical class 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 4
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 4
- 229910002706 AlOOH Inorganic materials 0.000 claims description 3
- 229910003890 H2TiO3 Inorganic materials 0.000 claims description 3
- 229910009973 Ti2O3 Inorganic materials 0.000 claims description 3
- 229910009815 Ti3O5 Inorganic materials 0.000 claims description 3
- 229910010416 TiO(OH)2 Inorganic materials 0.000 claims description 3
- 229910003080 TiO4 Inorganic materials 0.000 claims description 3
- 229910010298 TiOSO4 Inorganic materials 0.000 claims description 3
- 229910008558 TiSO4 Inorganic materials 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 229910001679 gibbsite Inorganic materials 0.000 claims description 3
- KADRTWZQWGIUGO-UHFFFAOYSA-L oxotitanium(2+);sulfate Chemical compound [Ti+2]=O.[O-]S([O-])(=O)=O KADRTWZQWGIUGO-UHFFFAOYSA-L 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000007600 charging Methods 0.000 abstract description 13
- 238000001556 precipitation Methods 0.000 abstract description 7
- 238000007599 discharging Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000126 substance Substances 0.000 description 21
- 239000007784 solid electrolyte Substances 0.000 description 20
- 150000002500 ions Chemical class 0.000 description 18
- 230000008569 process Effects 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000012528 membrane Substances 0.000 description 14
- 229910009515 Li1.5Al0.5Ti1.5(PO4)3 Inorganic materials 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 229910006210 Li1+xAlxTi2-x(PO4)3 Inorganic materials 0.000 description 4
- 229910006212 Li1+xAlxTi2−x(PO4)3 Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910012465 LiTi Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- BDVMTRCCIQHRBL-UHFFFAOYSA-J phosphonato phosphate;titanium(4+) Chemical compound [Ti+4].[O-]P([O-])(=O)OP([O-])([O-])=O BDVMTRCCIQHRBL-UHFFFAOYSA-J 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
- B29C69/001—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore a shaping technique combined with cutting, e.g. in parts or slices combined with rearranging and joining the cut parts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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
-
- 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a titanium aluminum lithium phosphate material, a diaphragm, a preparation method of the diaphragm and a battery, and belongs to the technical field of batteries. The preparation method of the lithium aluminum titanium phosphate material comprises the following steps: carrying out first solid-phase sintering on the first mixture obtained by solid-phase mixing of aluminum oxide and titanium oxide to obtain an aluminum titanium oxide material with a molecular formula of Al xTi2‑xOk, wherein x is more than 0 and less than 2, and k=4-0.5 x; and carrying out solid-phase mixing on the aluminum titanium oxide, the phosphorus source and the lithium source, and then carrying out second solid-phase sintering to obtain the titanium aluminum lithium phosphate material with the molecular formula of Li yAlxTi2‑x(PO4)3, wherein y-x=1, x is more than 0 and less than 2, and y is more than 1 and less than 3. The lithium aluminum titanium phosphate material has higher ionic conductivity, good surface morphology and higher purity. The battery with the diaphragm prepared from the material has higher safety, excellent low-temperature multiplying power charging and discharging capability, no lithium precipitation during low-temperature charging and high low-temperature charging constant current ratio.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a titanium aluminum lithium phosphate material, a diaphragm, a preparation method of the diaphragm and a battery.
Background
The lithium ion battery is the most mature lithium secondary battery at present and is widely applied to the fields of 3C digital codes, electric automobiles, energy storage and the like. The electrolyte is an important component of the lithium ion battery, and the traditional lithium ion battery adopts an organic liquid electrolyte, has the defects of easy volatilization, easy leakage, poor shock resistance and the like, and has potential safety hazard. The development of all-solid-state lithium ion batteries based on solid electrolytes can solve the potential safety hazard caused by liquid electrolytes. The inorganic solid electrolyte has the advantages of safety, easiness in preparation, high mechanical strength, gao Shiwen crystal grain conductivity, high lithium ion mobility, excellent electrochemical stability and the like. Of the inorganic solid electrolytes, lithium aluminum titanium phosphate Li 1+xAlxTi2-x(PO4)3 (LATP) has a theoretical ionic conductivity of up to 10 -3 S/cm at room temperature, approaching commercial electrolyte levels and is of particular concern. In addition, the material does not contain rare and expensive metals such as lanthanum, zirconium, germanium and the like, and only contains common elements such as lithium, aluminum, titanium, phosphorus and oxygen, so the commercialization prospect is clear.
The conventional methods for synthesizing lithium aluminum titanium phosphate mainly comprise a solid-phase sintering method, a liquid-phase precipitation method, a sol-gel method and the like, wherein the solid-phase sintering method and the liquid-phase precipitation method are simple in process and are suitable for industrial mass production, but when the LATP solid electrolyte is prepared by adopting the traditional solid-phase sintering process, on one hand, elements involved in the LATP solid electrolyte are easy to agglomerate, on the other hand, the required sintering temperature is above 1050 ℃, so that lithium salt is volatilized at high temperature to cause loss of lithium in a sintered product to cause impure product, and in addition, the preparation energy consumption is relatively large. The liquid phase precipitation method can produce waste liquid which is easy to pollute the environment, has higher requirements on reaction equipment, and the final material has high price and is not suitable for commercial application.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a titanium aluminum lithium phosphate material, a diaphragm, a preparation method of the titanium aluminum lithium phosphate material, and a battery, so as to solve or improve the technical problems.
The application can be realized as follows:
In a first aspect, the invention provides a preparation method of a lithium aluminum titanium phosphate material, which comprises the following steps: carrying out first solid-phase sintering on the first mixture obtained by solid-phase mixing of aluminum oxide and titanium oxide to obtain an aluminum titanium oxide material with a molecular formula of Al xTi2-xOk, wherein x is more than 0 and less than 2, and k=4-0.5 x;
And carrying out solid-phase mixing on the aluminum titanium oxide, the phosphorus source and the lithium source, and then carrying out second solid-phase sintering to obtain the titanium aluminum lithium phosphate material with the molecular formula of Li yAlxTi2-x(PO4)3, wherein y-x=1, x is more than 0 and less than 2, and y is more than 1 and less than 3.
In an alternative embodiment, the aluminum oxide includes at least one of Al2O3、Al2O3·3H2O、Al2(CO3)3、AlOOH、Al(OH)3、Al2(SO4)3 and Al (NO 3)3;
or, the titanium oxide includes at least one of TiO2、H2TiO3、TiO、Ti3O5、Ti2O3、TiOSO4、TiO(OH)2、Ti2(SO4)3、TiSO4、H4TiO4 and Ti (NO 3)4).
In an alternative embodiment, the temperature of the first solid phase sintering is 900-1400 ℃ and the time of the first solid phase sintering does not exceed 48 hours.
In an alternative embodiment, the second solid phase sintering is performed at a temperature of 350-900 ℃ for a period of no more than 48 hours.
In an alternative embodiment, the phosphorus source comprises at least one of ammonium dihydrogen phosphate and phosphoric acid;
or, the lithium source includes at least one of lithium carbonate and lithium dihydrogen phosphate.
In a second aspect, the present application provides a lithium aluminum titanium phosphate material prepared by the preparation method of any one of the foregoing embodiments.
In a third aspect, the present application provides a separator comprising the titanium aluminum lithium phosphate material of the foregoing embodiments.
In a fourth aspect, the present application provides a method for preparing a separator according to the foregoing embodiment, comprising the steps of: melt-extruding polyolefin and the lithium aluminum titanium phosphate material in any of the previous embodiments to obtain a casting sheet; stretching the casting sheet to obtain a stretched film; and rolling and cutting the stretched film to obtain the diaphragm.
In an alternative embodiment, the method of preparation comprises at least one of the following features:
Characteristic one: the weight of the lithium aluminum titanium phosphate material is less than the weight of the polyolefin;
And the second characteristic is: the average grain diameter of the lithium aluminum titanium phosphate is less than or equal to 1 mu m;
and (3) the following characteristics: the polyolefin has a weight average molecular weight of 10 to 500 tens of thousands.
In a fifth aspect, the present application provides a battery comprising the separator of the foregoing embodiment.
The beneficial effects of the application include:
The aluminum oxide and titanium oxide are mixed and sintered to prepare the aluminum-titanium oxide precursor creatively, so that an aluminum source and a titanium source react first, and atomic-level uniform mixing of substances is ensured under the condition of solid-phase reaction. On the basis, by mixing the aluminum titanium oxide compound with the phosphorus source and the lithium source in a solid phase and performing solid phase sintering for the second time, on one hand, the two-to-two reactions among substances possibly occurring during the co-sintering of the four substances in the prior art can be effectively avoided, the probability of generating a heterogeneous phase is reduced, and the purity of a product is improved; on the other hand, the temperature of the second solid phase sintering is lower, so that volatilization and loss of lithium can be avoided or reduced; in addition, the finally obtained lithium aluminum titanium phosphate material has good surface morphology and good performance (such as ion conductivity and the like).
The preparation method of the lithium aluminum titanium phosphate material is simple, the conditions are easy to control, and the cost is low.
After the diaphragm containing the titanium aluminum lithium phosphate material is further prepared into a battery, the use safety of the battery is improved, and the corresponding battery has the advantages of high safety, excellent low-temperature rate charging and discharging capability, no lithium precipitation during low-temperature charging, high low-temperature charging constant current ratio and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of an aluminum oxide of example 1 of the present invention;
FIG. 2 is an SEM image of the titanium oxide of example 1 of the present invention;
FIG. 3 is an SEM image of an aluminum titanium oxide material prepared in example 1 of the present invention;
FIG. 4 is an XRD pattern of the aluminum titanium oxide material prepared in example 1 of the present invention;
FIG. 5 is an XRD pattern of a lithium aluminum titanium phosphate material prepared in example 1 of the present invention;
FIG. 6 is an SEM image of lithium aluminum titanium phosphate material prepared in example 1 of the present invention;
fig. 7 is a schematic structural view of a separator prepared in example 3 of the present invention.
Icon: 11-polyolefin PE; lithium titanium aluminum 12-phosphate material.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The titanium aluminum lithium phosphate material, the diaphragm, the preparation method thereof and the battery provided by the application are specifically described below.
The application provides a preparation method of a lithium aluminum titanium phosphate material, which comprises the following steps: carrying out first solid-phase sintering on the first mixture obtained by solid-phase mixing of aluminum oxide and titanium oxide to obtain an aluminum titanium oxide material with a molecular formula of Al xTi2-xOk, wherein x is more than 0 and less than 2, and k=4-0.5 x;
And carrying out solid-phase mixing on the aluminum titanium oxide, the phosphorus source and the lithium source, and then carrying out second solid-phase sintering to obtain the titanium aluminum lithium phosphate material with the molecular formula of Li yAlxTi2-x(PO4)3, wherein y-x=1, x is more than 0 and less than 2, and y is more than 1 and less than 3.
The aluminum oxide described above may include, by way of example and not limitation, at least one of Al2O3、Al2O3·3H2O、Al2(CO3)3、AlOOH、Al(OH)3、Al2(SO4)3 and Al (NO 3)3).
The titanium oxide may include, by way of example and not limitation, at least one of TiO2、H2TiO3、TiO、Ti3O5、Ti2O3、TiOSO4、TiO(OH)2、Ti2(SO4)3、TiSO4、H4TiO4 and Ti (NO 3)4).
The molar ratio of Al in the aluminum oxide to Ti in the titanium oxide satisfies x (2-x), where x may be taken from any value in the range of 0 (not included) to 2 (not included).
In the present application, the temperature of the first solid phase sintering may be 900 to 1400 ℃, such as 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃, 1400 ℃, or the like, or any other value within the range of 900 to 1400 ℃.
The time of the first solid phase sintering is not more than 48h, such as 48h, 42h, 36h, 30h, 24h, 18h, 12h, 6h or 2h, etc. Too long sintering time not only wastes energy, but also has a negative impact on the properties of the material.
The phosphorus source may include, by way of example and not limitation, at least one of monoammonium phosphate and phosphoric acid.
The lithium source may include, by way of example and not limitation, at least one of lithium carbonate and lithium dihydrogen phosphate.
The molar ratio of P in the phosphorus source, li in the lithium source, and Al in the aluminum titanium oxide material satisfies 3:y:x, where y can be taken from a number in the range of 1 (not included) to 3 (not included) and satisfies y-x=1.
In the present application, the temperature of the second solid phase sintering may be 350 to 900 ℃, such as 350 to 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, etc., or any other value within the range of 350 to 900 ℃.
The time of the second solid phase sintering is not more than 48h, such as 48h, 42h, 36h, 30h, 24h, 18h, 12h, 6h or 2h, etc. Too long sintering time not only wastes energy, but also has a negative impact on the properties of the material.
It should be noted that, when preparing the lithium titanium aluminum phosphate material by the conventional solid-phase sintering method, the phosphorus source, the titanium source, the aluminum source and the lithium source are mixed together and then sintered, in the process, firstly, the materials are difficult to mix uniformly, and the elements are easy to agglomerate after diffusion during sintering; secondly, the four substances can react pairwise in the sintering process, so that the generation of impurity phases is caused, and the purity of the product is reduced; and thirdly, the corresponding sintering temperature is 1050 ℃ or above, under the high-temperature sintering condition, lithium salt is easy to volatilize, so that the loss of lithium in a sintered product is high, the product is impure, and the corresponding preparation energy consumption is high and the cost is high.
The aluminum oxide and titanium oxide are mixed and sintered to prepare the aluminum-titanium oxide precursor creatively, so that an aluminum source and a titanium source react first, and atomic-level uniform mixing of substances is ensured under the condition of solid-phase reaction. On the basis, by mixing the aluminum titanium oxide compound with the phosphorus source and the lithium source in a solid phase and performing solid phase sintering for the second time, on one hand, the two-to-two reactions among substances possibly occurring during the co-sintering of the four substances in the prior art can be effectively avoided, the probability of generating a heterogeneous phase is reduced, and the purity of a product is improved; on the other hand, the temperature of the second solid phase sintering is lower, so that volatilization and loss of lithium can be avoided or reduced; in addition, the finally obtained lithium aluminum titanium phosphate material has good surface morphology and good performance (such as ion conductivity and the like).
Correspondingly, the application provides a lithium aluminum titanium phosphate material which is prepared by the preparation method.
The lithium aluminum titanium phosphate material has higher surface morphology, higher ion conductivity and higher purity.
In addition, the application also provides a diaphragm which contains the titanium aluminum lithium phosphate material and is beneficial to improving the use safety of the battery.
Correspondingly, the application also provides a preparation method of the diaphragm, which can comprise the following steps: carrying out melt extrusion on polyolefin and the lithium aluminum titanium phosphate material to obtain a casting sheet; stretching the casting sheet to obtain a stretched film; and rolling and cutting the stretched film to obtain the diaphragm.
In the preparation process of the diaphragm, the weight of the lithium aluminum titanium phosphate material is less than that of polyolefin. That is, the weight ratio of lithium aluminum titanium phosphate material to polyolefin is less than 50:50, such as may be 49:51, 40:60, 30:70, 20:80, 10:90, etc.
In some embodiments, the average particle size of the lithium aluminum titanium phosphate is 1 μm or less, for example, 1 μm, 0.8 μm, 0.6 μm, 0.5 μm, 0.2 μm, or the like.
In some embodiments, the polyolefin may have a weight average molecular weight of 10 to 500 tens of thousands, such as 10, 50, 100, 200, 300, 400, or 500 tens of thousands, or the like.
In addition, the equipment and other preparation conditions (such as the preparation raw materials, the pore-forming agent, the selection and the use amount of the pore-forming agent, the stretching parameters, etc.) used in the steps related to the separator can refer to the prior art, and are not described in detail herein.
Further, the application also provides a battery which contains the separator.
The battery has the advantages of high safety, excellent low-temperature multiplying power charging and discharging capability, no lithium precipitation during low-temperature charging, high low-temperature charging constant current ratio and the like.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment provides a lithium aluminum titanium phosphate material, the chemical formula of which is Li 1.3Al0.3Ti1.7(PO4)3, and the preparation method comprises the following steps:
s1: aluminum oxide Al 2O3 (SEM image shown in FIG. 1) and titanium oxide TiO 2 (SEM image shown in FIG. 2) were solid phase mixed at a molar ratio of Al to Ti of 0.3:1.7 to give a first mixture.
S2: and carrying out primary solid-phase sintering on the first mixture at 1400 ℃ for 24 hours to obtain the aluminum titanium oxide material with the chemical formula of Al 0.3Ti1.7O3.85.
The SEM image of the aluminum titanium oxide material is shown in fig. 3, and the XRD image is shown in fig. 4. In FIG. 4, PDF#81-0030 is (Al 2Ti)O5, PDF#89-0555 is Ti 0.924O2.
S3: and (3) carrying out solid-phase mixing on the aluminum titanium oxide material and lithium dihydrogen phosphate as well as ammonium dihydrogen phosphate according to the molar ratio of Al to Li to P of 0.3:1.3:3 to obtain a second mixture.
S4: and carrying out second solid-phase sintering on the second mixture at 900 ℃ for 12 hours to obtain the lithium aluminum titanium phosphate material with the chemical formula of Li 1.3Al0.3Ti1.7(PO4)3.
The reaction equation involved in the second solid phase sintering process includes:
20Al0.3Ti1.7O3.85+26LiH2PO4+34NH4H2PO4→20Li1.3Al0.3Ti1.7(PO4)3+77H2O↑+34NH3↑.
The XRD pattern of the lithium aluminum titanium phosphate material obtained in this example is shown in FIG. 5, wherein PDF#35-0754 is LiTi 2(PO4)3, and it can be seen from FIG. 5: the obtained lithium aluminum titanium phosphate material has less impurity peaks and higher purity.
The SEM of the lithium aluminum titanium phosphate material obtained in this example is shown in fig. 6, and it can be seen from fig. 6 that the obtained lithium aluminum titanium phosphate material has a good surface morphology.
The lithium aluminum titanium phosphate material prepared in the embodiment is pressed into a solid electrolyte membrane, the solid electrolyte membrane is cut into a wafer with the diameter of 19mm, a symmetrical battery is assembled by clamping the wafer between two stainless steel gaskets, then an electrochemical workstation is connected, and impedance test is carried out at the room temperature of 25 ℃ to obtain the body impedance value of the sample to be tested. Calculating the ion conductivity according to the formula sigma=l/(a×rb), wherein sigma is the ion conductivity in S/cm; l is the thickness of the tablet, and the unit is cm; a is the area of the tablet, and the unit is cm 2; rb is the bulk impedance of the sample to be measured in Ω. Wherein L is 0.015cm, A is 2.84cm 2, rb is 5.8 Ω, and σ is calculated to be 9.1X10 -4 S/cm.
Example 2
The embodiment provides a lithium aluminum titanium phosphate material, the chemical formula of which is Li 1.5Al0.5Ti1.5(PO4)3, and the preparation method comprises the following steps:
s1: the aluminum oxide Al 2(CO3)3 and the titanium oxide TiO are mixed in solid phase according to the mole ratio of 0.5:1.5 of Al to Ti to obtain a first mixture.
S2: and carrying out primary solid-phase sintering on the first mixture at 900 ℃ for 12 hours to obtain the aluminum titanium oxide material Al 0.5Ti1.5O3.75.
The reaction equation involved in the first solid phase sintering process includes:
Al2(CO3)3+6TiO+3O2→4Al0.5Ti1.5O3.75+3CO2。
S3: and (3) carrying out solid-phase mixing on the aluminum titanium oxide material and lithium carbonate as well as ammonium dihydrogen phosphate according to the molar ratio of Al to Li to P of 0.5:1.5:3 to obtain a second mixture.
S4: and (3) carrying out second solid-phase sintering on the second mixture at 350 ℃ for 12 hours to obtain the lithium aluminum titanium phosphate material with the chemical formula of Li 1.5Al0.5Ti1.5(PO4)3.
The reaction equation involved in the second solid phase sintering process comprises ：4Al0.5Ti1.5O3.75+6LiH2PO4+6NH4H2PO4→4Li1.5Al0.5Ti1.5(PO4)3+15H2O↑+6NH3↑.
The lithium aluminum titanium phosphate material prepared in the embodiment is pressed into a solid electrolyte membrane, the solid electrolyte membrane is cut into a wafer with the diameter of 19mm, a symmetrical battery is assembled by clamping the wafer between two stainless steel gaskets, then an electrochemical workstation is connected, and impedance test is carried out at the room temperature of 25 ℃ to obtain the body impedance value of the sample to be tested. Calculating the ion conductivity according to the formula sigma=l/(a×rb), wherein sigma is the ion conductivity in S/cm; l is the thickness of the tablet, and the unit is cm; a is the area of the tablet, and the unit is cm 2; rb is the bulk impedance of the sample to be measured in Ω. Wherein L is 0.015cm, A is 2.84cm 2, rb is 6.0 Ω, and σ is calculated to be 8.8X10 -4 S/cm.
Example 3
The embodiment provides a lithium aluminum titanium phosphate material, the chemical formula of which is Li 1.5Al0.5Ti1.5(PO4)3, and the preparation method comprises the following steps:
s1: the aluminum oxide Al 2(CO3)3 and the titanium oxide TiO are mixed in solid phase according to the mole ratio of 0.5:1.5 of Al to Ti to obtain a first mixture.
S2: and carrying out primary solid-phase sintering on the first mixture at 1200 ℃ for 12 hours to obtain the aluminum titanium oxide material Al 0.5Ti1.5O3.75.
The reaction equation involved in the first solid phase sintering process includes:
Al2(CO3)3+6TiO+3O2→4Al0.5Ti1.5O3.75+3CO2。
S3: and (3) carrying out solid-phase mixing on the aluminum titanium oxide material and lithium carbonate as well as ammonium dihydrogen phosphate according to the molar ratio of Al to Li to P of 0.5:1.5:3 to obtain a second mixture.
S4: and (3) carrying out second solid-phase sintering on the second mixture at 500 ℃ for 12 hours to obtain the lithium aluminum titanium phosphate material with the chemical formula of Li 1.5Al0.5Ti1.5(PO4)3.
The reaction equation involved in the second solid phase sintering process comprises ：4Al0.5Ti1.5O3.75+6LiH2PO4+6NH4H2PO4→4Li1.5Al0.5Ti1.5(PO4)3+15H2O↑+6NH3↑.
The lithium aluminum titanium phosphate material prepared in the embodiment is pressed into a solid electrolyte membrane, the solid electrolyte membrane is cut into a wafer with the diameter of 19mm, a symmetrical battery is assembled by clamping the wafer between two stainless steel gaskets, then an electrochemical workstation is connected, and impedance test is carried out at the room temperature of 25 ℃ to obtain the body impedance value of the sample to be tested. Calculating the ion conductivity according to the formula sigma=l/(a×rb), wherein sigma is the ion conductivity in S/cm; l is the thickness of the tablet, and the unit is cm; a is the area of the tablet, and the unit is cm 2; rb is the bulk impedance of the sample to be measured in Ω. Wherein L is 0.015cm, A is 2.84cm 2, rb is 5.9 Ω, and σ is calculated to be 8.9X10 -4 S/cm.
Example 4
The embodiment provides a diaphragm, and a preparation method thereof comprises the following steps:
S1: feeding: the polyolefin PE with the weight average molecular weight of 50 ten thousand and the lithium aluminum titanium phosphate material with the chemical formula of Li 1.3Al0.3Ti1.7(PO4)3 (average particle size D 50 =1 μm) prepared in the example 1 are pretreated according to the weight ratio of 10:1, and then are conveyed to an extrusion system.
S2: casting: and (3) extruding a melt from a die head after the pretreated raw materials are melted and plasticized in a double-screw extrusion system, and forming a casting sheet after the melt is cast.
In the above process, the extruder temperature was 180 ℃.
S3: stretching: and (3) stretching the casting sheet at a certain temperature (130 ℃) for 5 times longitudinally, and stretching the casting sheet at a certain temperature for 2 times transversely to obtain the diaphragm containing the lithium aluminum titanium phosphate.
The structural schematic of the separator is shown in fig. 7, which includes a polyolefin PE 11 and a lithium titanium aluminum phosphate material 12.
Example 5
The embodiment provides a battery, which is prepared by the following steps:
Adding a binder PVDF into NMP according to a mass ratio of 1:8, stirring to obtain a glue solution, then mixing a commercially available 8-series nickel cobalt lithium manganate ternary TLP813 material, a conductive agent acetylene black and the glue solution according to a mass ratio of 97:1:2, and stirring under the action of a vacuum stirrer until the system is uniform, thus obtaining an anode slurry; and uniformly coating the positive electrode slurry on a positive electrode current collector, airing at room temperature, transferring to an oven for continuous drying, and then carrying out cold pressing and cutting according to required specifications to obtain the positive electrode plate. Mixing negative electrode active material graphite, conductive agent acetylene black, thickener CMC and binder SBR according to the mass ratio of 96.2:0.8:1.2:1.8, adding solvent deionized water into the mixed material formed by the mixing, and stirring under the action of a vacuum stirrer until the system is uniform to obtain negative electrode slurry; and uniformly coating the negative electrode slurry on a negative electrode current collector, airing at room temperature, transferring to an oven for continuous drying, and then carrying out cold pressing and cutting according to required specifications to obtain a negative electrode plate. And (3) stacking the positive electrode plate, the lithium titanium aluminum phosphate Li 1.3Al0.3Ti1.7(PO4)3 diaphragm prepared in the embodiment 4 and the negative electrode plate in sequence, so that the battery cell is obtained after assembly. Placing the battery cell assembly into an inner cavity of a battery shell, drying, and then injecting electrolyte into the inner cavity of the battery shell, wherein the electrolyte solvent is ethylene carbonate, and the solute is lithium hexafluorophosphate (1 mol/L); and (3) performing procedures of sealing, standing, formation, capacity division and the like to obtain the square lithium ion battery. The square battery has a capacity of 20Ah, a thickness of 15mm, a width of 119mm and a height of 208mm.
Comparative example 1
Referring to example 2 of Chinese patent No. CN117246989A, a titanium aluminum lithium phosphate composite material is prepared, which comprises the following specific steps:
S1: 48.0285kg of lithium carbonate, 15.294kg of aluminum oxide, 332.715kg of titanium pyrophosphate and 16.2927kg of titanium dioxide are weighed and dispersed in 200kg of deionized water and put into a stirring cylinder to be mixed to obtain a first mixture, wherein the rotation speed of the stirring cylinder is 500rpm, and the stirring time is 2 hours;
S2: sanding the first mixture to obtain a mixture with the D 50 particle size of 0.8 mu m, transferring the mixture with the D 50 particle size of 0.8 mu m into a fine grinding cylinder, and grinding to obtain a second mixture with the D 50 particle size of 0.2 mu m;
s3: spray drying the second mixture to obtain a third mixture, wherein the spray drying process is that the inlet temperature is 260 ℃, the outlet temperature is 105 ℃, the spray gun pressure is 0.4MPa, and the frequency is 16Hz;
S4: taking a sagger, putting the third mixture into the sagger and placing the sagger into a high-temperature furnace for sintering to obtain a fourth mixture. Sintering at 900 deg.c, heating at 5 deg.c/min for 5 hr, cooling at 1 deg.c/min to 100 deg.c, and opening the furnace door to take out the fourth mixture;
s5: crushing the fourth mixture by using a pair roller machine to obtain the titanium aluminum lithium phosphate solid electrolyte.
The lithium aluminum titanium phosphate Li 1.3Al0.3Ti1.7(PO4)3 material prepared in the comparative example is pressed into a solid electrolyte membrane, the solid electrolyte membrane is cut into a wafer with the diameter of 19mm, a symmetrical battery is assembled by clamping the wafer between two stainless steel gaskets, then an electrochemical workstation is connected, and impedance test is carried out at the room temperature of 25 ℃ to obtain the body impedance value of the sample to be tested. Calculating the ion conductivity according to the formula sigma=l/(a×rb), wherein sigma is the ion conductivity in S/cm; l is the thickness of the tablet, and the unit is cm; a is the area of the tablet, and the unit is cm 2; rb is the bulk impedance of the sample to be measured in Ω. Wherein L is 0.015cm, A is 2.84cm 2, rb is 12.6Ω, and σ is calculated to be 4.2X10 -4 S/cm.
As can be seen from comparison of the example 1, the example 2 and the comparative example 1, the ionic conductivity of the lithium aluminum titanium phosphate material in the example is improved by more than one time compared with that of the comparative example, and meanwhile, the material obtained in the example maintains high purity and good surface morphology.
Comparative example 2
The comparative example provides a lithium aluminum titanium phosphate material, the chemical formula of which is Li 1.5Al0.5Ti1.5(PO4)3, and the preparation method comprises the following steps:
s1: aluminum oxide Al 2(CO3)3, titanium oxide TiO and lithium carbonate as well as ammonium dihydrogen phosphate are subjected to solid phase mixing according to the mole ratio of Li, al, ti and P of 1.5:0.5:1.5:3 to obtain a mixture.
S2: and (3) performing solid-phase sintering on the mixture at 350 ℃ to obtain the lithium aluminum titanium phosphate material with the chemical formula of Li 1.5Al0.5Ti1.5(PO4)3.
The reaction equation involved in the solid phase sintering process includes:
Al2(CO3)3+6TiO+3O2+6LiH2PO4+6NH4H2PO4→4Li1.5Al0.5Ti1.5(PO4)3+15H2O↑+6NH3↑+3CO2↑.
In addition, since the raw materials of the material are oxides Al 2(CO3)3, titanium oxide TiO, lithium carbonate and ammonium dihydrogen phosphate, the mixed local area is also accompanied by other hetero-phase reactions, so the purity of the material is not high, and the ionic conductivity of the material is low. The hetero-phase reaction equation is as follows:
Al2(CO3)3+6TiO+3O2→4Al0.5Ti1.5O3.75+3CO2；
8TiO+4LiH2PO4+12NH4H2PO4→4LiTi2(PO4)3+22H2O↑+12NH3↑+25O2↑;
Al2(CO3)3+3LiH2PO4→Li3Al2(PO4)3+3H2O↑+3CO2↑.
The lithium titanium aluminum phosphate material prepared in the comparative example is pressed into a solid electrolyte membrane, the solid electrolyte membrane is cut into a wafer with the diameter of 19mm, a symmetrical battery is assembled by clamping the wafer between two stainless steel gaskets, then the wafer is connected with an electrochemical workstation, and impedance test is carried out at the room temperature of 25 ℃ to obtain the body impedance value of a sample to be tested. Calculating the ion conductivity according to the formula sigma=l/(a×rb), wherein sigma is the ion conductivity in S/cm; l is the thickness of the tablet, and the unit is cm; a is the area of the tablet, and the unit is cm 2; rb is the bulk impedance of the sample to be measured in Ω. Wherein L is 0.015cm, A is 2.84cm 2, rb is 18.1 Ω, and σ is calculated to be 2.9X10 -4 S/cm.
Comparative example 3
The comparative example provides a lithium aluminum titanium phosphate material, the chemical formula of which is Li 1.5Al0.5Ti1.5(PO4)3, and the preparation method comprises the following steps:
s1: the aluminum oxide Al 2(CO3)3 and the titanium oxide TiO are mixed in solid phase according to the mole ratio of 0.5:1.5 of Al to Ti to obtain a first mixture.
S2: and carrying out primary solid-phase sintering on the first mixture at 1500 ℃ for 60 hours to obtain the aluminum titanium oxide material Al 0.5Ti1.5O3.75.
The reaction equation involved in the first solid phase sintering process includes:
Al2(CO3)3+6TiO+3O2→4Al0.5Ti1.5O3.75+3CO2。
S3: and (3) carrying out solid-phase mixing on the aluminum titanium oxide material and lithium carbonate as well as ammonium dihydrogen phosphate according to the molar ratio of Al to Li to P of 0.5:1.5:3 to obtain a second mixture.
S4: and (3) carrying out second solid-phase sintering on the second mixture at 350 ℃ for 12 hours to obtain the lithium aluminum titanium phosphate material with the chemical formula of Li 1.5Al0.5Ti1.5(PO4)3.
The reaction equation involved in the second solid phase sintering process comprises ：4Al0.5Ti1.5O3.75+6LiH2PO4+6NH4H2PO4→4Li1.5Al0.5Ti1.5(PO4)3+15H2O↑+6NH3↑.
The lithium titanium aluminum phosphate material prepared in the comparative example is pressed into a solid electrolyte membrane, the solid electrolyte membrane is cut into a wafer with the diameter of 19mm, a symmetrical battery is assembled by clamping the wafer between two stainless steel gaskets, then the wafer is connected with an electrochemical workstation, and impedance test is carried out at the room temperature of 25 ℃ to obtain the body impedance value of a sample to be tested. Calculating the ion conductivity according to the formula sigma=l/(a×rb), wherein sigma is the ion conductivity in S/cm; l is the thickness of the tablet, and the unit is cm; a is the area of the tablet, and the unit is cm 2; rb is the bulk impedance of the sample to be measured in Ω. Wherein L is 0.015cm, A is 2.84cm 2, rb is 12.3 Ω, and σ is calculated to be 4.3X10 -4 S/cm.
Comparative example 4
The comparative example provides a lithium aluminum titanium phosphate material, the chemical formula of which is Li 1.5Al0.5Ti1.5(PO4)3, and the preparation method comprises the following steps:
s1: the aluminum oxide Al 2(CO3)3 and the titanium oxide TiO are mixed in solid phase according to the mole ratio of 0.5:1.5 of Al to Ti to obtain a first mixture.
S2: and carrying out primary solid-phase sintering on the first mixture at 900 ℃ for 12 hours to obtain the aluminum titanium oxide material Al 0.5Ti1.5O3.75.
The reaction equation involved in the first solid phase sintering process includes:
Al2(CO3)3+6TiO+3O2→4Al0.5Ti1.5O3.75+3CO2。
S3: and (3) carrying out solid-phase mixing on the aluminum titanium oxide material and lithium carbonate as well as ammonium dihydrogen phosphate according to the molar ratio of Al to Li to P of 0.5:1.5:3 to obtain a second mixture.
S4: and (3) carrying out second solid-phase sintering on the second mixture at 1200 ℃ for 12 hours to obtain the lithium aluminum titanium phosphate material with the chemical formula of Li 1.5Al0.5Ti1.5(PO4)3.
The reaction equation involved in the second solid phase sintering process comprises ：4Al0.5Ti1.5O3.75+6LiH2PO4+6NH4H2PO4→4Li1.5Al0.5Ti1.5(PO4)3+15H2O↑+6NH3↑.
The lithium titanium aluminum phosphate material prepared in the comparative example is pressed into a solid electrolyte membrane, the solid electrolyte membrane is cut into a wafer with the diameter of 19mm, a symmetrical battery is assembled by clamping the wafer between two stainless steel gaskets, then the wafer is connected with an electrochemical workstation, and impedance test is carried out at the room temperature of 25 ℃ to obtain the body impedance value of a sample to be tested. Calculating the ion conductivity according to the formula sigma=l/(a×rb), wherein sigma is the ion conductivity in S/cm; l is the thickness of the tablet, and the unit is cm; a is the area of the tablet, and the unit is cm 2; rb is the bulk impedance of the sample to be measured in Ω. Wherein L is 0.015cm, A is 2.84cm 2, rb is 11.9 Ω, and σ is calculated to be 4.4X10 -4 S/cm.
Comparative example 5
The commercially available polyolefin PE separator was used in place of the lithium aluminum titanium phosphate Li 1.3Al0.3Ti1.7(PO4)3 separator used in example 5 to prepare square lithium ion batteries of the same size.
Test examples
The two batteries obtained in example 5 and comparative example 5 were tested for their needle punching safety performance and their charge and discharge performance at-10 ℃. Wherein, at room temperature (25+/-5) DEG C, the battery is charged and discharged to obtain discharge capacity C1; then the battery is fully charged at room temperature, the battery core is placed in an environment of minus 10 ℃, the battery core is left for 4 hours to discharge to obtain discharge capacity C2, C2/C1×100% is low-temperature performance, and the test result is shown in table 1.
Table 1 test results
As can be seen from table 1: compared with comparative example 5, the battery of example 5 has an improvement in the needle punching safety passing rate from 0% to 60%, while having a 20% improvement in the low-temperature discharge performance. The battery is subjected to constant-current and constant-voltage charging at the temperature of minus 10 ℃ with the 0.1C multiplying power, the example 5 has higher constant-current ratio and is improved by about 20 percent, and meanwhile, the charging interface of the battery prepared in the example 5 does not separate out lithium.
Further, it can be seen from comparative examples 1 to 4 and comparative examples 1 to 4 that: the ionic conductivities of example 1, example 2, example 3 and example 4 were improved by more than 2 times compared to comparative example 1. In comparative example 2, the lithium source, the titanium source, the aluminum source and the phosphorus source have the lowest ionic conductivity because of more impurity phases of materials formed by one-step solid phase mixed sintering. Comparative examples 3 and 4 have a somewhat reduced electrical conductivity of the material compared to the examples due to the excessive sintering temperature or time.
In conclusion, the lithium aluminum titanium phosphate material provided by the application has the characteristics of ultrahigh ion conductivity, good surface morphology and high purity. The battery of the diaphragm prepared by the material has the advantages of high safety, excellent low-temperature multiplying power charging and discharging capability, low-temperature charging without lithium precipitation and high low-temperature charging constant current ratio.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The preparation method of the lithium aluminum titanium phosphate material is characterized by comprising the following steps of: carrying out first solid-phase sintering on the first mixture obtained by solid-phase mixing of aluminum oxide and titanium oxide to obtain an aluminum titanium oxide material with a molecular formula of Al xTi2-xOk, wherein x is more than 0 and less than 2, and k=4-0.5 x;
Mixing the aluminum titanium oxide compound, a phosphorus source and a lithium source in a solid phase, and then performing solid phase sintering for the second time to obtain a titanium aluminum lithium phosphate material with a molecular formula of Li yAlxTi2-x(PO4)3, wherein y-x=1, x is more than 0 and less than 2, and y is more than 1 and less than 3;
The aluminum oxide includes at least one of Al2O3、Al2O3·3H2O、Al2(CO3)3、AlOOH、Al(OH)3、Al2(SO4)3 and Al (NO 3)3;
the titanium oxide includes at least one of TiO2、H2TiO3、TiO、Ti3O5、Ti2O3、TiOSO4、TiO(OH)2、Ti2(SO4)3、TiSO4、H4TiO4 and Ti (NO 3)4;
the temperature of the first solid phase sintering is 900-1400 ℃, and the time of the first solid phase sintering is not more than 48 hours; the temperature of the second solid phase sintering is 350-900 ℃, and the time of the second solid phase sintering is not more than 48 hours;
the lithium aluminum titanium phosphate material is used for preparing a battery diaphragm.
2. The method of preparing according to claim 1, wherein the phosphorus source comprises at least one of ammonium dihydrogen phosphate and phosphoric acid;
or, the lithium source includes at least one of lithium carbonate and lithium dihydrogen phosphate.
3. A lithium aluminum titanium phosphate material, characterized by being prepared by the preparation method of claim 1 or 2.
4. A separator comprising the lithium aluminum titanium phosphate material according to claim 3.
5. A method of preparing the separator of claim 4, comprising the steps of: carrying out melt extrusion on polyolefin and the lithium aluminum titanium phosphate material of claim 3 to obtain a casting sheet; stretching the casting sheet to obtain a stretched film; and rolling and cutting the stretched film to obtain the diaphragm.
6. The method of manufacture of claim 5, comprising at least one of the following features:
Characteristic one: the weight of the lithium aluminum titanium phosphate material is less than that of polyolefin;
And the second characteristic is: the average grain diameter of the lithium aluminum titanium phosphate is less than or equal to 1 mu m;
and (3) the following characteristics: the polyolefin has a weight average molecular weight of 10 to 500 tens of thousands.
7. A battery, characterized in that, the battery comprising the separator according to claim 6.
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