WO2021121066A1 - 正极材料及其制备方法和应用 - Google Patents
正极材料及其制备方法和应用 Download PDFInfo
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- electrode material
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 72
- 239000013078 crystal Substances 0.000 claims abstract description 60
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 59
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 27
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 22
- 150000002500 ions Chemical class 0.000 claims abstract description 15
- -1 nickel-cobalt-manganese-aluminum Chemical compound 0.000 claims abstract description 7
- 229910052796 boron Inorganic materials 0.000 claims description 73
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 64
- 239000002019 doping agent Substances 0.000 claims description 63
- 239000011248 coating agent Substances 0.000 claims description 58
- 239000010406 cathode material Substances 0.000 claims description 57
- 239000002243 precursor Substances 0.000 claims description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 34
- 229910052744 lithium Inorganic materials 0.000 claims description 34
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 31
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 30
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 25
- 229910001416 lithium ion Inorganic materials 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 229910018626 Al(OH) Inorganic materials 0.000 claims description 3
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 3
- 229910019440 Mg(OH) Inorganic materials 0.000 claims description 3
- 229910021314 NaFeO 2 Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 39
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract description 13
- 229910001453 nickel ion Inorganic materials 0.000 abstract description 13
- 230000014759 maintenance of location Effects 0.000 abstract description 12
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011572 manganese Substances 0.000 description 30
- 238000012360 testing method Methods 0.000 description 16
- 238000001228 spectrum Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000007704 transition Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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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
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
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- 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
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
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- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
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- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- 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
Definitions
- the present invention belongs to the technical field of lithium ion batteries. Specifically, the present invention relates to a positive electrode material and a preparation method and application thereof.
- an object of the present invention is to provide a positive electrode material and its preparation method and application.
- the positive electrode material has a low content of divalent nickel ions, a low degree of lithium-nickel mixing, a stable crystal structure, a high cycle retention rate and thermal stability, a prolonged service life and improved safety.
- the present invention provides a cathode material.
- the general formula of the cathode material is Li a Ni 1-xyz Co x Mn y Al z M b O 2 , wherein, 1.04 ⁇ a ⁇ 1.08, 0.04 ⁇ x ⁇ 0.08, 0.025 ⁇ y ⁇ 0.06, 0.03 ⁇ z ⁇ 0.09, 0.015 ⁇ b ⁇ 0.06, M is B and selected from Zr and Al, B, Ti, Mg, Na, Ca, At least one of Nb, Ba, Si, P, W, and Sr.
- the cathode material of the embodiment of the present invention compared with the existing nickel-cobalt-manganese-aluminum cathode material, the cathode material is doped with M ions.
- M ions Through the doping of M ions, the content of divalent nickel ions can be reduced, thereby reducing the content of nickel from (003 )
- the amount of nickel ions that transition from the crystal plane to the (104) crystal plane reduces the degree of lithium-nickel mixing and stabilizes the crystal structure of the cathode material, thereby increasing the cycle retention and thermal stability of the material, so as to extend the service life of the material and increase Its safety.
- cathode material according to the foregoing embodiment of the present invention may also have the following additional technical features:
- the value range of b is 0.02 ⁇ b ⁇ 0.03.
- the positive electrode material has an ⁇ -NaFeO 2 type layered structure similar to LiCoO 2 , and the crystal type of the positive electrode material belongs to the R-3m space group of the hexagonal crystal system.
- the 2 ⁇ angle of the positive electrode material on the (003) crystal plane is around 18.74 degrees, preferably the positive electrode material is 18.74 ⁇ 0.2 degrees on the (003) crystal plane 2 ⁇ angle, and the positive electrode material is in (003)
- the half-width of the diffraction peak of the crystal plane is 0.0550-0.0700.
- the 2 ⁇ angle of the positive electrode material on the (104) crystal plane is around 44.4 degrees, preferably the positive electrode material is 44.4 ⁇ 0.2 degrees on the (104) crystal plane 2 ⁇ angle, and the positive electrode material is in the (003) crystal plane.
- the ratio of the half-width of the diffraction peak of the plane to the half-width of the diffraction peak on the (104) crystal plane is 1.45-1.6.
- the ratio of the diffraction peak intensity of the (003) crystal plane to the diffraction peak intensity of the (104) crystal plane of the positive electrode material is 2.45 ⁇ I 003 /I 104 ⁇ 3.05.
- M is B and at least one selected from Zr, Al, and W, preferably M is a combination of B, Zr, and Al or a combination of B, Zr, Al, and W.
- the present invention provides a method for preparing the above-mentioned positive electrode material. According to an embodiment of the present invention, the method includes:
- calcined product with a lithium source and other dopants, and the other dopants include those selected from Zr and Al, Ti, Mg, Na, Ca, Nb, Ba, Si, P, W, and Sr.
- At least one ion source substance At least one ion source substance;
- the dried product is mixed with an aluminum source coating agent and a boron source coating agent and then subjected to heat treatment, so as to obtain the positive electrode material.
- a precursor material with more orderly grain size growth direction, greater specific surface area and strength can be obtained .
- the precursor reacts to obtain a pure single-crystal quaternary cathode material instead of a single-crystal material.
- the dried product is packaged with the aluminum source by a dry method.
- the coating agent and the boron source coating agent are uniformly mixed and then subjected to heat treatment.
- the boron source acts as a fluxing agent to uniformly coat the aluminum source on the surface of the positive electrode material to obtain cycle retention and thermal stability.
- a positive electrode material with high life and safety.
- the method for preparing a positive electrode material according to the foregoing embodiment of the present invention may also have the following additional technical features:
- the positive electrode precursor material is selected from at least one of Ni 1-xyz Co x Mn y Al z (OH) 2 , Ni 1-xyz Co x Mn y Al z CO 3 , Among them, 0.04 ⁇ x ⁇ 0.08, 0.04 ⁇ y ⁇ 0.06, 0.03 ⁇ z ⁇ 0.09, preferably 0.03 ⁇ y ⁇ 0.06, and more preferably 0.04 ⁇ y ⁇ 0.06.
- the boron source dopant and the boron source dopant are independently selected from at least one of B 2 O 3 and H 3 BO 3.
- the mass ratio of the positive electrode precursor material to the boron source dopant is 1:0.001-0.002.
- the pre-sintering temperature is 900-1000° C., and the time is 10-15 h.
- the mass ratio of the calcined product to the lithium source and the dopant is 480:260-280:1-10.
- the lithium source is selected from at least one of LiOH and Li 2 CO 3.
- the other dopants are those containing at least one ion source selected from Zr and Al, Ti, Mg, Na, Ca, Nb, Ba, Si, P, W, and Sr. substance.
- the dopant is selected from Zr(OH) 4 , ZrO 2 , Al 2 O 3 , TiO 2 , Mg(OH) 2 , NaCl, CaCl 2 , Nb 2 O 5 , BaCl 2. At least one of SiO 2 , H 3 PO 3 , WO 3, and SrO.
- the calcination temperature is 830-880°C, and the time is 12-17h.
- the mass ratio of the dried product to the aluminum source coating agent and the boron source coating agent is 1:0.001-0.003:0.0015-0.007.
- the aluminum source coating agent is selected from at least one of Al 2 O 3 , Al(OH) 3 , and AlF 3.
- the temperature of the heat treatment is 400-600°C, and the time is 6-8h.
- the present invention provides a lithium ion battery.
- the lithium ion battery has the above-mentioned positive electrode material or the positive electrode material prepared by the above-mentioned method for preparing the positive electrode material.
- the lithium ion battery of the embodiment of the present invention because the lithium ion battery has the above-mentioned positive electrode material, and the positive electrode material is doped with M ions to reduce the content of divalent nickel ions, thereby reducing the transition from the (003) crystal plane.
- the amount of nickel ions to the (104) crystal plane reduces the degree of lithium-nickel mixing in the positive electrode material, so that the crystal structure of the positive electrode material is stable, which is beneficial to improve the cycle retention and thermal stability of the lithium ion battery, and prolong the service life of the battery And improve its safety.
- the present invention provides an automobile.
- the automobile has the above-mentioned lithium ion battery.
- the automobile of the embodiment of the present invention because the automobile has the above-mentioned lithium-ion battery, the automobile can meet the long-distance requirement under the high cycle retention rate, thermal stability, service life and safety performance of the above-mentioned lithium ion battery , And can significantly reduce potential safety hazards.
- Fig. 1 is a schematic flow chart of a method for preparing a cathode material according to an embodiment of the present invention
- Fig. 2 shows the corrected XRD spectrum of the positive electrode material obtained in Example 1;
- Fig. 3 shows the corrected XRD spectrum of the positive electrode material obtained in Example 4.
- Fig. 4 shows the corrected XRD spectrum of the cathode material obtained in Example 6;
- FIG. 5 shows the corrected XRD spectrum of the positive electrode material obtained in Example 8.
- Fig. 6 shows the corrected XRD spectrum of the positive electrode material obtained in Example 9;
- FIG. 7 shows the corrected XRD spectrum of the positive electrode material obtained in Comparative Example 1.
- the present invention provides a cathode material.
- the general formula of the cathode material is Li a Ni 1-xyz Co x Mn y Al z M b O 2 , where 1.04 ⁇ a ⁇ 1.08, 0.04 ⁇ x ⁇ 0.08, 0.025 ⁇ y ⁇ 0.06 (preferably 0.03 ⁇ y ⁇ 0.06, more preferably 0.04 ⁇ y ⁇ 0.06), 0.03 ⁇ z ⁇ 0.09, 0.015 ⁇ b ⁇ 0.06, preferably 0.02 ⁇ b ⁇ 0.03, M is B and at least one selected from Zr and Al, B, Ti, Mg, Na, Ca, Nb, Ba, Si, P, W, and Sr.
- the positive electrode material is doped with M ions.
- M ions the content of divalent nickel ions can be reduced, thereby reducing the transition from (003) crystal plane to (104)
- the amount of nickel ions on the crystal plane reduces the degree of lithium-nickel mixing, so that the crystal structure of the cathode material is stabilized, thereby improving the cycle retention and thermal stability of the material, so as to extend the service life of the material and improve its safety.
- a can be 1.04/1.05/1.06/1.07/1.08
- x can be 0.04/0.05/0.06/0.0.7/0.08
- y can be 0.04/0.05/0.06
- z can be 0.03/0.04/0.05/0.06/0.0. 7/0.0.8/0.09
- b can be 0.015/0.02/0.03/0.04/0.05/0.06.
- too low a will result in low material capacity and cycle performance, and too high will result in high residual alkali , Affect the stability of the slurry during the later homogenization; if x is too low, it will affect the layered structure of the material, if it is too high, it will reduce the actual capacity and increase the material cost; if y is too low, the safety performance and structural stability of the material will decrease , Too high will destroy the layered structure of the material and reduce the specific capacity of the material; too low z will cause poor thermal stability of the material, too high will cause the material capacity to be low; too low b will lead to the cycle and thermal stability of the material Poor performance, too high will also make the cycle and thermal stability of the material poor.
- the above-mentioned positive electrode material has an ⁇ -NaFeO 2 type layered structure similar to LiCoO 2 , and the crystal type of the positive electrode material belongs to the R-3m space group of the hexagonal crystal system.
- the 2 ⁇ angle of the positive electrode material on the (003) crystal plane is around 18.74 degrees, preferably the positive electrode material on the (003) crystal plane 2 ⁇ angle is 18.74 ⁇ 0.2 degrees, and the half peak of the diffraction peak of the positive electrode material on the (003) crystal plane
- the width is 0.0550-0.0700. The inventor found that too high a half-value width indicates that the grain size of the material is smaller, and the deviation from the complete crystal is greater, that is, poor crystallinity; too low a half-value width indicates that the material has a better capacity under large currents. difference. The material within the above range has moderate grain size and excellent electrical properties.
- the 2 ⁇ angle of the positive electrode material on the (104) crystal plane is around 44.4 degrees, preferably the positive electrode material has a 2 ⁇ angle of 44.4 ⁇ 0.2 degrees on the (104) crystal plane, and the half-width of the diffraction peak on the (003) crystal plane is equal to 104)
- the ratio of the half-width of the diffraction peak of the crystal plane is 1.45-1.6. The inventor found that the material within this range has good crystallization performance, and thus thermal stability performance is also good.
- the ratio of the diffraction peak intensity of the (003) crystal plane to the diffraction peak intensity of the (104) crystal plane of the single crystal cathode material is 2.45 ⁇ I 003 /I 104 ⁇ 3.05.
- the above-mentioned M is B and at least one selected from Zr, Al, and W, preferably M is a combination of B, Zr, and Al or a combination of B, Zr, Al, and W.
- the cathode material of the embodiment of the present invention compared with the existing nickel-cobalt-manganese-aluminum cathode material, the cathode material is doped with M ions.
- the content of divalent nickel ions can be reduced, thereby reducing the content of nickel from (003 )
- the amount of nickel ions that transition from the crystal plane to the (104) crystal plane reduces the degree of lithium-nickel mixing and stabilizes the crystal structure of the cathode material, thereby increasing the cycle retention and thermal stability of the material, so as to extend the service life of the material and increase Its safety.
- the present invention provides a method for preparing the above-mentioned cathode material. According to an embodiment of the present invention, referring to FIG. 1, the method includes:
- the positive electrode precursor material and the boron source dopant are mixed and then calcined to obtain the calcined product.
- the specific types of the positive electrode precursor material and the boron source dopant are not particularly limited, and those skilled in the art can choose according to actual needs.
- the positive electrode precursor material can be selected from Ni 1-xyz.
- the boron source dopant can be selected from at least one of B 2 O 3 and H 3 BO 3.
- the mass ratio of the positive electrode precursor material to the boron source dopant is not particularly limited, and may be 1:0.001-0.002, for example. The inventor found that the introduction of boron source dopants can increase the internal lattice of the positive electrode precursor material, which makes it easier for lithium salts to enter and form single crystals.
- the specific conditions of pre-sintering are not particularly limited, and those skilled in the art can choose according to actual needs.
- the temperature of pre-sintering can be 900-1000° C., and the time can be 10-15 h.
- the pre-calcined product is mixed with the lithium source and the dopant to obtain the mixed product.
- the specific types of lithium sources and dopants are not particularly limited, and those skilled in the art can choose according to actual needs.
- the lithium source can be selected from at least one of LiOH and Li 2 CO 3 One;
- the dopant may be a substance containing at least one ion source selected from the group consisting of Zr and Al, Ti, Mg, Na, Ca, Nb, Ba, Si, P, W, and Sr.
- the dopant may Selected from Zr(OH) 4 , ZrO 2 , Al 2 O 3 , TiO 2 , Mg(OH) 2 , NaCl, CaCl 2 , Nb 2 O 5 , BaCl 2 , SiO 2 , H 3 PO 3 , WO 3 , SrO At least one of them.
- the mass ratio of the pre-fired product to the lithium source and the dopant is also not particularly limited, for example, it can be 480:260-280:1-10.
- the mixed product is calcined, and the calcined product is washed with water and dried to obtain a dried product.
- the inventor found that the lithium source and dopant are more likely to react with the calcined product, that is, the calcined precursor, to obtain a pure single crystal quaternary cathode material, rather than a single crystal-like material, which can be washed with water. Reduce the residual lithium of the material.
- the specific conditions of calcination are not particularly limited, and those skilled in the art can choose according to actual needs.
- the temperature of calcination can be 830-880°C and the time can be 12-17h.
- the dried product is mixed with an aluminum source coating agent and a boron source coating agent and then subjected to heat treatment to obtain a positive electrode material.
- the inventor found that the dried product is uniformly mixed with the aluminum source coating agent and the boron source coating agent by a dry method, and then heat treated. During the heat treatment process, the boron source acts as a flux to uniformly coat the aluminum source. On the surface of the positive electrode material.
- the specific types of the aluminum source coating agent and the boron source coating agent are not particularly limited, and those skilled in the art can choose according to actual needs.
- the aluminum source coating agent can be selected from Al 2 At least one of O 3 , Al(OH) 3 , and AlF 3 ;
- the boron source coating agent can be selected from at least one of B 2 O 3 and H 3 BO 3 , and it should be noted that in this step
- the specific type of the boron source coating agent may be the same as or different from the boron source dopant in S100, and those skilled in the art can choose according to actual needs.
- the mass ratio of the dried product to the aluminum source coating agent and the boron source coating agent is not particularly limited, and may be 1:0.001-0.003:0.0015-0.007.
- the coating agent is too small, the coating layer cannot be formed (the coating layer here is not a clear physical coating structure, but aluminum and boron are uniformly doped with the elements in the positive electrode material on the surface), and then Can not prevent the side reaction of the material and the electrolyte; too much coating agent will greatly reduce the conductivity of the material, thereby affecting the electrical performance.
- the specific conditions of the heat treatment are not particularly limited, and those skilled in the art can choose according to actual needs.
- the temperature of the heat treatment can be 400-600° C., and the time can be 6-8 hours.
- the amount of boron source and aluminum source used in the last step of coating is very small, it basically does not affect the set dopant content, or the composition and raw material design of the cathode material obtained by the preparation method of this application.
- the element ratio of is basically corresponding.
- a precursor material with more orderly grain size growth direction, greater specific surface area and strength can be obtained .
- the precursor reacts to obtain a pure single-crystal quaternary cathode material instead of a single-crystal material.
- the dried product is packaged with the aluminum source by a dry method.
- the coating agent and the boron source coating agent are uniformly mixed and then subjected to heat treatment.
- the boron source acts as a fluxing agent to uniformly coat the aluminum source on the surface of the positive electrode material to obtain cycle retention and thermal stability.
- a positive electrode material with high life and safety. It should be noted that the characteristics of the above-mentioned positive electrode material are also applicable to the method for preparing the positive electrode material, which will not be repeated here.
- the present invention provides a lithium ion battery.
- the lithium ion battery has the above-mentioned positive electrode material or the positive electrode material prepared by the above-mentioned method for preparing the positive electrode material.
- the lithium ion battery of the embodiment of the present invention because the lithium ion battery has the above-mentioned positive electrode material, and the positive electrode material is doped with M ions to reduce the content of divalent nickel ions, thereby reducing the transition from the (003) crystal plane.
- the amount of nickel ions to the (104) crystal plane reduces the degree of lithium-nickel mixing in the positive electrode material, so that the crystal structure of the positive electrode material is stable, which is beneficial to improve the cycle retention and thermal stability of the lithium ion battery, and prolong the service life of the battery And improve its safety. It should be noted that the characteristics of the above-mentioned positive electrode material or the positive electrode material prepared by the above-mentioned method for preparing the positive electrode material are also applicable to the lithium ion battery, and this will not be repeated.
- the present invention provides an automobile.
- the automobile has the above-mentioned lithium ion battery.
- the automobile of the embodiment of the present invention because the automobile has the above-mentioned lithium-ion battery, the automobile can meet the long-distance requirement under the high cycle retention rate, thermal stability, service life and safety performance of the above-mentioned lithium ion battery , And can significantly reduce potential safety hazards. It should be noted that the features of the lithium-ion battery described above are also applicable to the car, and this will not be repeated here.
- the present invention will be described below with reference to specific embodiments. It should be noted that these embodiments are only descriptive and do not limit the present invention in any way.
- the positive electrode precursor material Ni 0.85 Co 0.08 Mn 0.03 Al 0.04 (OH) 2 and the boron source dopant B 2 O 3 were mixed according to the mass ratio of 1:0.0015, and then calcined at 900°C for 10 hours to obtain the calcined product;
- the pre-calcined product is mixed with lithium source LiOH and dopant Al 2 O 3 in a mass ratio of 480:260:3.84 to obtain a mixed product; the mixed product is calcined at 830°C for 12 hours, and the calcined product is washed and washed with water.
- the dried product After drying, the dried product is obtained; the dried product is mixed with aluminum source coating agent Al 2 O 3 and boron source coating agent B 2 O 3 in a mass ratio of 1:0.0012:0.0015, and then heat treated at 400°C for 6 hours to obtain a positive electrode
- the material is Li 1.05 Ni 0.834 Co 0.079 Mn 0.03 Al 0.04 B 0.008 Al 0.012 .
- the amount of Al doping detected by ICP is shown in Table 1, and Figure 2 shows
- Table 1 shows The corrected XRD spectrum of the obtained cathode material shows that the half-width of the (003) diffraction peak at a 2 ⁇ angle of 18.74 degrees, and the half-width of the (003) diffraction peak at a 2 ⁇ angle of 18.74 degrees is the same as
- the ratio of the half-width of the (104) diffraction peak, the ratio of the intensity of the (003) diffraction peak to the intensity of the (104) diffraction peak at the 2 ⁇ angle of 44.4 degrees, the 50-week cycle data at 25°C and the DSC test temperature are shown in the table 2 shown.
- the positive electrode precursor material Ni 0.85 Co 0.08 Mn 0.03 Al 0.04 (OH) 2 and the boron source dopant B 2 O 3 were mixed according to the mass ratio of 1:0.0015, and then calcined at 900°C for 10 hours to obtain the calcined product;
- the pre-calcined product is mixed with lithium source LiOH, dopant Al 2 O 3 , and Zr(OH) 4 at a mass ratio of 480:260:3.84:3.52 to obtain a mixed product; the mixed product is calcined at 830°C for 12h,
- the calcined product is washed with water and dried to obtain a dried product; the dried product is mixed with aluminum source coating agent Al 2 O 3 and boron source coating agent B 2 O 3 according to a mass ratio of 1:0.0012:0.0015.
- the cathode material Li 1.05 Ni 0.829 Co 0.078 Mn 0.03 Al 0.04 B 0.008 Al 0.012 Zr 0.003 is obtained .
- the doping of Al and Zr detected by ICP As shown in Table 1, the half-width of the (003) diffraction peak at a 2 ⁇ angle of 18.74 degrees and the half-width of the (003) diffraction peak at a 2 ⁇ angle of 18.74 degrees and the half-width of the (003) diffraction peak at a 2 ⁇ angle of 18.74 degrees are compared with The ratio of the half-value width of the (104) diffraction peak, the ratio of the intensity of the (003) diffraction peak to the intensity of the (104) diffraction peak near 44.4 degrees, the 50-week cycle data at 25°C and the DSC test temperature are shown in Table 2. .
- the positive electrode precursor material Ni 0.85 Co 0.08 Mn 0.03 Al 0.04 (OH) 2 and the boron source dopant B 2 O 3 were mixed according to the mass ratio of 1:0.0015, and then calcined at 900°C for 10 hours to obtain the calcined product;
- the pre-calcined product is mixed with lithium source LiOH, dopant Al 2 O 3 , and Zr(OH) 4 at a mass ratio of 480:260:3.84:2.24 to obtain a mixed product; the mixed product is calcined at 830°C for 12h,
- the calcined product is washed with water and dried to obtain a dried product; the dried product is mixed with aluminum source coating agent Al 2 O 3 and boron source coating agent B 2 O 3 according to a mass ratio of 1:0.0012:0.0015.
- the cathode material Li 1.05 Ni 0.83 Co 0.078 Mn 0.029 Al 0.04 B 0.008 Al 0.012 Zr 0.002 is obtained .
- the doping of Al and Zr detected by ICP As shown in Table 1, the half-width of the (003) diffraction peak at a 2 ⁇ angle of 18.74 degrees and the half-width of the (003) diffraction peak at a 2 ⁇ angle of 18.74 degrees and the half-width of the (003) diffraction peak at a 2 ⁇ angle of 18.74 degrees are compared with The ratio of the half-value width of the (104) diffraction peak, the ratio of the intensity of the (003) diffraction peak to the intensity of the (104) diffraction peak near 44.4 degrees, the 50-week cycle data at 25°C and the DSC test temperature are shown in Table 2. .
- the positive electrode precursor material Ni 0.85 Co 0.08 Mn 0.03 Al 0.04 (OH) 2 and the boron source dopant B 2 O 3 were mixed according to the mass ratio of 1:0.0018, and then calcined at 930°C for 12 hours to obtain the calcined product;
- the calcined product is mixed with lithium source LiOH, dopant Al 2 O 3 , Zr(OH) 4 , WO 3 in a mass ratio of 480:270:3.84:3.52:0.416 to obtain a mixed product;
- the mixed product is at 850 Calcined at °C for 14h, and washed and dried the calcined product to obtain the dried product;
- the quality of the positive electrode material is used as the benchmark and obtained by ICP.
- the doping amounts of Al, Zr and W are shown in Table 1.
- Figure 3 shows the corrected XRD spectrum of the cathode material obtained.
- the cathode material has a half of the (003) diffraction peak at a 2 ⁇ angle of 18.74 degrees.
- the ratio of the diffraction peak intensities, the 50-week cycle data at 25°C and the DSC test temperature are shown in Table 2.
- the positive electrode precursor material Ni 0.85 Co 0.08 Mn 0.03 Al 0.04 (OH) 2 and the boron source dopant B 2 O 3 were mixed according to the mass ratio of 1:0.0018, and then calcined at 930°C for 12 hours to obtain the calcined product;
- the calcined product is mixed with lithium source LiOH, dopant Al 2 O 3 , Zr(OH) 4 , WO 3 according to the mass ratio of 480:270:3.84:3.52:0.832 to obtain the mixed product;
- the mixed product is at 850 Calcined at °C for 14h, and washed and dried the calcined product to obtain the dried product;
- the quality of the positive electrode material is used as the reference, and the result is obtained by ICP.
- the doping amounts of Al, Zr and W are shown in Table 1.
- the half-width of the (003) diffraction peak at a 2 ⁇ angle of 18.74 degrees and a (003) diffraction peak at a 2 ⁇ angle of 18.74 degrees are shown in Table 1.
- the ratio of the half-width of the peak to the half-width of the (104) diffraction peak at a 2 ⁇ angle of 44.4 degrees, the ratio of the intensity of the (003) diffraction peak to the intensity of the (104) diffraction peak, the 50-cycle cycle data at 25°C, and The DSC test temperature is shown in Table 2.
- the positive electrode precursor material Ni 0.85 Co 0.08 Mn 0.03 Al 0.04 (OH) 2 and the boron source dopant B 2 O 3 were mixed according to the mass ratio of 1:0.0018, and then calcined at 930°C for 12 hours to obtain the calcined product;
- the calcined product is mixed with lithium source LiOH, dopant Al 2 O 3 , Zr(OH) 4 , WO 3 in a mass ratio of 480:270:6.5:3.52:0.416 to obtain a mixed product;
- the mixed product is at 850 Calcined at °C for 14h, and washed and dried the calcined product to obtain the dried product;
- FIG. 1 shows the quality of the positive electrode material.
- the doping amounts of Al, Zr and W are shown in Table 1.
- Figure 4 shows the corrected XRD spectrum of the positive electrode material.
- the positive electrode material has a half of the (003) diffraction peak at a 2 ⁇ angle of 18.74 degrees.
- Table 2 shows the ratio of the diffraction peak intensities, the 50-week cycle data at 25°C and the DSC test temperature.
- the positive electrode precursor material Ni 0.85 Co 0.08 Mn 0.03 Al 0.04 (OH) 2 and the boron source dopant B 2 O 3 were mixed according to the mass ratio of 1:0.002, and then calcined at 980°C for 14 hours to obtain the calcined product;
- the calcined product is mixed with lithium source LiOH, dopant Al 2 O 3 , Zr(OH) 4 , WO 3 in a mass ratio of 480:280:7:3.52:0.416 to obtain a mixed product;
- the mixed product is at 880 Calcined at °C for 16h, and washed and dried the calcined product to obtain the dried product;
- the quality of the positive electrode material is used as the benchmark and obtained by ICP detection
- the doping amounts of Al, Zr and W are shown in Table 1.
- the half-width of the (003) diffraction peak at a 2 ⁇ angle of 18.74 degrees and a (003) diffraction peak at a 2 ⁇ angle of 18.74 degrees are shown in Table 1.
- the DSC test temperature is shown in Table 2.
- the positive electrode precursor material Ni 0.85 Co 0.08 Mn 0.03 Al 0.04 (OH) 2 and the boron source dopant B 2 O 3 were mixed according to the mass ratio of 1:0.002, and then calcined at 980°C for 14 hours to obtain the calcined product;
- the calcined product is mixed with lithium source LiOH, dopant Al 2 O 3 , Zr(OH) 4 , WO 3 in a mass ratio of 480:280:7.5:3.52:0.416 to obtain a mixed product;
- the mixed product is at 880 Calcined at °C for 16h, and washed and dried the calcined product to obtain the dried product;
- Figure 5 shows the corrected positive electrode material XRD spectra, based on the quality of the cathode material, the doping amounts of Al, Zr, and W obtained by ICP are shown in Table 1.
- the cathode material has half of the (003) diffraction peak at a 2 ⁇ angle of 18.74 degrees.
- the ratio of the diffraction peak intensities, the 50-week cycle data at 25°C and the DSC test temperature are shown in Table 2.
- the positive electrode precursor material Ni 0.85 Co 0.08 Mn 0.03 Al 0.04 (OH) 2 and the boron source dopant B 2 O 3 were mixed according to the mass ratio of 1:0.002, and then calcined at 980°C for 14 hours to obtain the calcined product;
- the calcined product is mixed with lithium source LiOH, dopant Al 2 O 3 , Zr(OH) 4 , WO 3 at a mass ratio of 480:280:8:3.52:0.416 to obtain a mixed product;
- the mixed product is at 880 Calcined at °C for 16h, and washed and dried the calcined product to obtain the dried product;
- the quality of the positive electrode material is used as the benchmark and obtained by ICP.
- the doping amounts of Al, Zr and W are shown in Table 1.
- Figure 6 shows the corrected XRD spectrum of the cathode material obtained.
- the cathode material has a half of the (003) diffraction peak at a 2 ⁇ angle of 18.74 degrees.
- the ratio of the diffraction peak intensities, the 50-week cycle data at 25°C and the DSC test temperature are shown in Table 2.
- the positive electrode precursor material Ni 0.85 Co 0.07 Mn 0.04 Al 0.04 (OH) 2 and the boron source dopant B 2 O 3 were mixed according to the mass ratio of 1:0.002, and then calcined at 980°C for 14 hours to obtain the calcined product;
- the calcined product is mixed with lithium source LiOH, dopant Al 2 O 3 , Zr(OH) 4 , WO 3 in a mass ratio of 480:280:7:3.52:0.416 to obtain a mixed product;
- the mixed product is at 880 Calcined at °C for 16h, and washed and dried the calcined product to obtain the dried product;
- the quality of the cathode material is used as a benchmark and obtained by ICP detection
- the doping amounts of Al, Zr and W are shown in Table 1.
- the half-width of the (003) diffraction peak at a 2 ⁇ angle of 18.74 degrees and a (003) diffraction peak at a 2 ⁇ angle of 18.74 degrees are shown in Table 1.
- the ratio of the half-width of the peak to the half-width of the (104) diffraction peak at a 2 ⁇ angle of 44.4 degrees, the ratio of the intensity of the (003) diffraction peak to the intensity of the (104) diffraction peak, the 50-cycle cycle data at 25°C, and The DSC test temperature is shown in Table 2.
- the positive electrode precursor material Ni 0.82 Co 0.08 Mn 0.06 Al 0.04 (OH) 2 and the boron source dopant B 2 O 3 were mixed in a mass ratio of 1:0.002 and then calcined at 980°C for 14 hours to obtain the calcined product;
- the calcined product is mixed with lithium source LiOH, dopant Al 2 O 3 , Zr(OH) 4 , WO 3 in a mass ratio of 480:285:8:3.52:1.248 to obtain a mixed product;
- the mixed product is at 880 Calcined at °C for 16h, and washed and dried the calcined product to obtain the dried product;
- the ICP test obtains the result
- the doping amounts of Al, Zr and W are shown in Table 1.
- the half-width of the (003) diffraction peak at a 2 ⁇ angle of 18.74 degrees and a (003) diffraction peak at a 2 ⁇ angle of 18.74 degrees are shown in Table 1.
- the DSC test temperature is shown in Table 2.
- the positive electrode precursor material Ni 0.85 Co 0.08 Mn 0.03 Al 0.04 (OH) 2 and the boron source dopant B 2 O 3 were mixed according to the mass ratio of 1:0.0015, and then calcined at 900°C for 10 hours to obtain the calcined product;
- the pre-calcined product is mixed with the lithium source LiOH according to the mass ratio of 150:94 to obtain the mixed product;
- the mixed product is calcined at 830°C for 12 hours, and the calcined product is washed and dried to obtain the dried product;
- the product is mixed with aluminum source coating agent Al 2 O 3 and boron source coating agent B 2 O 3 in a mass ratio of 1:0.0012:0.0015, and then heat treated at 400°C for 6 hours to obtain cathode material Li 1.05 Ni 0.835 Co 0.079 Mn 0.03 Al 0.04 B 0.008 Al 0.006 .
- Figure 7 shows the corrected XRD spectrum of the obtained positive electrode material.
- the ratio of the half-width of the peak to the half-width of the (104) diffraction peak at a 2 ⁇ angle of 44.4 degrees, the ratio of the intensity of the (003) diffraction peak to the intensity of the (104) diffraction peak, the 50-cycle cycle data at 25°C and its The DSC test temperature is shown in Table 2.
- the amount of Al doping is determined as follows: ICP is used to detect the amount of doped B and Al content of the product after pre-sintering; the Al content of the product after drying is measured by ICP, the difference between the two Al content is Al The amount of doping.
- the measured doping amount in the table exceeds the designed doping amount because the positive electrode precursor material originally contains very small amounts of doping elements.
- the positive electrode material synthesized in the embodiment of the present invention is doped with M ions and coated with B, and can obtain a positive electrode material with a high cycle retention rate and a high DSC temperature, that is, a long cycle, thermal Positive electrode material with good stability.
- the half-value width of the (003) diffraction peak is 0.0550-0.0800 by co-doping in an appropriate proportion in Examples 1-11, and the half-value width of the (104) diffraction peak is the same as the (003) diffraction peak.
- the ratio of the half-width of the peak is 1.4500-1.6000, and the ratio of the diffraction peak intensity of I 003 to I 104 is 2.45 ⁇ I 003 /I 104 ⁇ 3.00. Furthermore, the 50-week cycle (25°C) test data in Table 2 also proves that the positive electrode material obtained in Examples 1-11 has a long cycle life and high thermal stability.
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Abstract
Description
Claims (12)
- 一种正极材料,其特征在于,其通式为Li aNi 1-x-y-zCo xMn yAl zM bO 2,其中,1.04≤a≤1.08、0.04≤x≤0.08、0.025≤y≤0.06、0.03≤z≤0.09、0.015≤b≤0.06,M为B和选自Zr和Al、Ti、Mg、Na、Ca、Nb、Ba、Si、P、W、Sr中的至少之一。
- 根据权利要求1所述的正极材料,其特征在于,0.028≤y≤0.06,优选0.04≤y≤0.06;优选1.04≤a≤1.05,优选0.075≤x≤0.08;优选0.03≤z≤0.04;优选0.02≤b≤0.05。
- 根据权利要求1或2所述的正极材料,其特征在于,所述b的取值范围为0.02≤b≤0.03。
- 根据权利要求1或2所述的正极材料,其特征在于,所述正极材料具有与LiCoO 2类似的α-NaFeO 2型层状结构,且所述正极材料的晶型归属为六方晶系的R-3m空间群。
- 根据权利要求1或2所述的正极材料,其特征在于,所述正极材料在(003)晶面2θ角为18.74度附近,优选所述正极材料在(003)晶面2θ角为18.74±0.2度,且所述正极材料在(003)晶面的衍射峰的半峰宽为0.0550-0.0700。
- 根据权利要求5所述的正极材料,其特征在于,所述正极材料在(104)晶面2θ角为44.4度附近,优选所述正极材料在(104)晶面2θ角为44.4±0.2度,所述正极材料在(003)晶面衍射峰的半峰宽与在(104)晶面衍射峰的半峰宽的比值为1.45-1.6。
- 根据权利要求6所述的正极材料,其特征在于,所述正极材料的(003)晶面的衍射峰强度和(104)晶面的衍射峰强度的比值为2.45≤I 003/I 104≤3.05。
- 根据权利要求1或2所述的正极材料,其特征在于,所述M为B和选自Zr和Al、W中的至少之一,优选M为B、Zr、Al的组合或B、Zr、Al、W的组合。
- 一种制备权利要求1-8中任一项所述的正极材料的方法,其特征在于,包括:将正极前驱体材料与硼源掺杂剂混合后进行预烧;将所述预烧后产物与锂源、其它掺杂剂混合,所述其它掺杂剂为包含选自Zr和Al、Ti、Mg、Na、Ca、Nb、Ba、Si、P、W、Sr中的至少之一离子源的物质;将所述混合后产物进行煅烧,并将煅烧后产物进行水洗和干燥;将所述干燥后产物与铝源包覆剂、硼源包覆剂混合后进行热处理,以便得到所述正极材料。
- 根据权利要求9所述的方法,其特征在于,所述正极前驱体材料选自Ni 1-x-y-zCo xMn yAl z(OH) 2、Ni 1-x-y-zCo xMn yAl zCO 3中的至少之一,其中0.04≤x≤0.08、0.04≤y≤0.06、0.03≤z≤0.09;优选0.03≤y≤0.06,进一步优选0.04≤y≤0.06;优选地,所述硼源掺杂剂和所述硼源包覆剂分别独立地选自B 2O 3、H 3BO 3中的至少之一;优选地,所述正极前驱体材料与所述硼源掺杂剂的质量比为1:0.001-0.002;优选地,所述预烧的温度为900-1000℃,时间为10-15h;优选地,所述预烧后产物与所述锂源、所述其它掺杂剂的质量比为480:260-280:1-10;优选地,所述锂源选自LiOH、Li 2CO 3中的至少之一;优选地,所述其它掺杂剂选自Zr(OH) 4、ZrO 2、Al 2O 3、TiO 2、Mg(OH) 2、NaCl、CaCl 2、Nb 2O 5、BaCl 2、SiO 2、H 3PO 3、WO 3、SrO中的至少之一;优选地,所述煅烧的温度为830-880℃,时间为12-17h;优选地,所述干燥后产物与所述铝源包覆剂、所述硼源包覆剂的质量比为1:0.001-0.003:0.0015-0.007;优选地,所述铝源包覆剂选自Al 2O 3、Al(OH) 3、AlF 3中的至少之一;优选地,所述热处理的温度为400-600℃,时间为6-8h。
- 一种锂离子电池,包括正极材料,其特征在于,所述正极材料为权利要求1-8中任一项所述的正极材料。
- 一种汽车,所述汽车具有锂离子电池,其特征在于,所述锂离子电池为权利要求11所述的锂离子电池。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2022528258A JP7486580B2 (ja) | 2019-12-18 | 2020-12-07 | 正極材料およびその製造方法と使用 |
US17/766,227 US20240055591A1 (en) | 2019-12-18 | 2020-12-07 | Cathode electrode material and preparation method and application thereof |
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WO2024070822A1 (ja) * | 2022-09-29 | 2024-04-04 | 株式会社村田製作所 | 二次電池用正極活物質、二次電池用正極および二次電池 |
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