CN109461928B - High-energy-density multi-element positive electrode material and preparation method thereof - Google Patents
High-energy-density multi-element positive electrode material and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000007774 positive electrode material Substances 0.000 title claims description 44
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000011159 matrix material Substances 0.000 claims abstract description 24
- 239000010406 cathode material Substances 0.000 claims abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 239000010405 anode material Substances 0.000 claims abstract description 13
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 239000010416 ion conductor Substances 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 6
- 229910052796 boron Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 239000011572 manganese Substances 0.000 claims description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 239000011247 coating layer Substances 0.000 claims description 20
- 229910009677 Li8ZrO6 Inorganic materials 0.000 claims description 15
- 239000012266 salt solution Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- 238000012216 screening Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 12
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims description 12
- 239000008139 complexing agent Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims description 10
- 159000000002 lithium salts Chemical class 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 229910007822 Li2ZrO3 Inorganic materials 0.000 claims description 9
- 229910010883 Li6Zr2O7 Inorganic materials 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910010565 Li4ZrO4 Inorganic materials 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001556 Li2Si2O5 Inorganic materials 0.000 claims description 2
- 229910007562 Li2SiO3 Inorganic materials 0.000 claims description 2
- 229910007626 Li2SnO3 Inorganic materials 0.000 claims description 2
- 229910007848 Li2TiO3 Inorganic materials 0.000 claims description 2
- 229910010488 Li4TiO4 Inorganic materials 0.000 claims description 2
- 229910010682 Li5AlO4 Inorganic materials 0.000 claims description 2
- 229910010215 LiAl5O8 Inorganic materials 0.000 claims description 2
- 229910010092 LiAlO2 Inorganic materials 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 229910052909 inorganic silicate Inorganic materials 0.000 claims description 2
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 47
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 27
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 24
- 239000010936 titanium Substances 0.000 description 7
- 238000011056 performance test Methods 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 description 3
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 description 3
- WYDJZNNBDSIQFP-UHFFFAOYSA-N [O-2].[Zr+4].[Li+] Chemical compound [O-2].[Zr+4].[Li+] WYDJZNNBDSIQFP-UHFFFAOYSA-N 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 3
- 229940044175 cobalt sulfate Drugs 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229940053662 nickel sulfate Drugs 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- -1 aluminum ion Chemical class 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910017246 Ni0.8Co0.1Mn0.1 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- FYWUVDVZWURZJH-UHFFFAOYSA-E [OH-].[Al+3].[Mn+2].[Co+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-] Chemical compound [OH-].[Al+3].[Mn+2].[Co+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-] FYWUVDVZWURZJH-UHFFFAOYSA-E 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 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 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/50—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
-
- 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
- H01M4/52—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
-
- 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)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a high-energy-density multi-element anode material and a preparation method thereofThe preparation method is that the cathode material is prepared by Li1+a[(Ni x1‑2Co x Mn x ) y1‑M y ]1‑zM′ z O2And Li coated on the surface of the matrix8ZrO6And a lithium ion conductor Li u M″ v O w Wherein a is more than or equal to 0.5 and less than or equal to 0.3, M and M 'are at least one element of La, Cr, Mo, Ca, Fe, Hf, Ti, Zn, Y, Zr, Si, W, Nb, Sm, V, Mg, B and Al, and M' is at least one element of Zr, Ti, Al, Si, Mn and Sn; the total coating amount of the composite oxide is 0.01-3% of the molar amount of the matrix. The anode material has higher energy density and cycling stability, and can be used for lithium ion power batteries. The preparation method of the material has simple process and low cost, and is suitable for large-scale production.
Description
Technical Field
The invention relates to a high-energy-density multi-element anode material and a preparation method thereof, belonging to the technical field of lithium ion batteries.
Background
Along with the improvement of the demands of people on the endurance time of electronic products, the endurance mileage of electric automobiles and the like, the development of high-energy-density lithium ion batteries is an urgent demand of the current market. In the lithium ion battery, the quality of the performance of the positive electrode material determines the performance of the whole battery, wherein the characteristics of high voltage and high specific capacity of the multi-component material are considered to be one of the most promising positive electrode materials of the lithium battery. With the increase of the content of nickel in the multi-component material, the inactive residual lithium on the surface of the multi-component material gradually increases, and the capacity, the multiplying power and other performances of the multi-component material are seriously influenced; the problems of intragranular cracks, material pulverization and the like are easy to occur in the high-voltage charging and discharging process, so that the cycle performance of the material is rapidly reduced. By constructing the lithium ion conductor coating layer on the surface of the material, the interfacial impedance can be effectively reduced, lithium ion channels are increased, side reactions with electrolyte are inhibited, and the electrochemical properties such as capacity, multiplying power, circulation and the like are improved. However, in the previous research and patent reports, the lithium ion conductor as a coating layer usually needs to be synthesized in advance, so that the preparation process is relatively complicated, and the problem that the capacity and rate performance of the material are reduced due to the inactive residual lithium on the surface of the material cannot be solved.
Chinese patent CN107706390A discloses a preparation method of a fast ion conductor and conductive polymer double-modified lithium ion battery multi-element anode material, wherein an oxide or acid reacts with hydroxide to generate a fast ion conductor finished product, and then the resultant is mixed with a ternary material and calcined at high temperature to obtain the fast ion conductor coated multi-element material. The method has complex preparation process and higher required sintering temperature.
Chinese patent CN105789565A discloses Li2ZrO3And Li4ZrO4A preparation method of a lithium-rich manganese-based anode material for a coated lithium ion battery. In the patent, Zr (OC)4H9)4Mixing with a precursor of a positive electrode material, and obtaining ZrO by a hydrothermal method2The coated positive electrode material precursor is mixed with lithium salt and sintered to obtain Li2ZrO3And Li4ZrO4The coated cathode material effectively improves the cycle performance of a sample through the coating of the lithium zirconate. However, the hydrothermal method has low yield and high requirements on equipment, and the organic matter Zr source used in the patent has high cost, so that the method cannot be applied on a large scale.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a nickel-cobalt-manganese multi-element cathode material with high energy density and a preparation method thereof8ZrO6And other lithium ion conductors. Wherein Li8ZrO6The lithium-ion secondary battery is a hexagonal crystal system together with the nickel-cobalt-manganese multi-element positive electrode material, the lithium ions are de-intercalated under the voltage higher than 4.0V, and when two lithium ions are de-intercalated in molecules, the charge-discharge specific capacity can reach 220 mAh/g; other lithium ion conductors in the coating layer can effectively reduce the interface impedance of the battery in the charging and discharging processes and construct a lithium ion channel, and the components in the coating layer can enable the material to have better rate performance and higher energy densityAnd (4) degree.
The invention also provides a preparation method of the metal hydroxide precursor and the anode material, which has the advantages of simple process, easy and stable control of the process, low production cost and suitability for large-scale industrial production.
In order to achieve the purpose, the invention adopts the following technical scheme:
the high-energy-density multi-element cathode material comprises a matrix and a composite oxide coating layer coated on the surface of the matrix; the chemical formula of the matrix is Li1+a[(Ni x1-2Co x Mn x ) y1-M y ]1-zM′ z O2Wherein a is more than or equal to 0.5 and less than or equal to 1.3, and a is more than or equal to 0.05x≤0.3，0≤y≤0.01，0≤z≦ 0.01, the coating layer comprising Li8ZrO6And the chemical formula is Li u M″ v O w Wherein 0 is not more thanu≤8，1≤v≤5，2≤wLess than or equal to 12, M and M 'are at least one element of La, Cr, Mo, Ca, Fe, Hf, Ti, Zn, Y, Zr, Si, W, Nb, Sm, V, Mg, B and Al, M' is at least one element of Zr, Ti, Al, Si, Mn, Sn and W;
the composite oxide coating layer is compact or non-compact; the amount of the coating layer is 0.01-3% of the matrix.
The average particle diameter D of the high-energy-density multi-element cathode material505 to 20 μm.
Preferably, the Li u M″ v O w Is LiAl5O8、LiAlO2、Li5AlO4、Li2SiO3、Li2Si2O5、Li4SiO4、Li2SnO3、Li2TiO3、Li4TiO4、Li4Ti5O12、Li2ZrO3、Li6Zr2O7、Li8ZrO6、Li4ZrO4At least one of (1).
The invention also provides a preparation method of the high-energy-density multi-element cathode material, which comprises the following steps:
(1) dissolving a salt solution of nickel, cobalt, manganese and doping elements to obtain a mixed salt solution of 1-3 mol/L; dissolving sodium hydroxide into an alkali solution with the concentration of 4-10 mol/L; and dissolving ammonia water into a complexing agent solution with the concentration of 2-10 mol/L. Adding the mixed salt solution, the alkali solution and the complexing agent solution into a reaction kettle in a concurrent flow manner for reaction, keeping stirring in the process, controlling the reaction pH value and the reaction temperature, and performing solid-liquid separation, washing, drying and screening on the prepared precursor slurry to obtain spherical nickel-cobalt-manganese hydroxide (Ni) x1-2Co x Mn x ) y1-M y (OH)2；
(2) The (Ni) obtained in the step (1) x1-2Co x Mn x ) y1-M y (OH)2Uniformly mixing with lithium salt and M' oxide, calcining for 4-20 h at 600-1000 ℃ in air or oxygen atmosphere, crushing and screening to obtain the matrix Li of the positive electrode material for the lithium ion battery1+a[(Ni x1-2Co x Mn x ) y1-M y ]1-zM′ z O2；
(3) ZrO 2 is mixed with2Mechanically mixing the oxide of M', the lithium salt and the anode material matrix, then putting the mixture into a muffle furnace, and carrying out heat treatment for 0.5-12 h at the temperature of 450-800 ℃ to obtain the lithium secondary battery anode material8ZrO6And a lithium ion conductor Li u M″ v O w A composite oxide coated multi-element positive electrode material;
a is more than or equal to-0.5 and less than or equal to 1.3, and a is more than or equal to 0.05 and less than or equal to 1.3x≤0.3，0≤y≤0.01，0≤z≤0.01，0≤u≤8，1≤v≤5，2≤wLess than or equal to 12, M and M 'are at least one element of La, Cr, Mo, Ca, Fe, Hf, Ti, Zn, Y, Zr, Si, W, Nb, Sm, V, Mg, B and Al, M' is Zr, Ti, Al,At least one element selected from Si, Mn, Sn and W.
Preferably, the oxide of M 'and the oxide particles of M' have an average particle diameter D501-50 nm, and a specific surface area greater than 10m2/g。
Preferably, the oxide of M 'and the oxide of M' are HfO2、TiO2、Y2O3、ZrO2、SiO2、W2O3、Nb2O5、Sm2O3、V2O5、MgO、Al2O3At least one of (1).
Preferably, the reaction pH range in the step (1) is 10-13, and the temperature is 50-70 ℃.
Preferably, the lithium salt in steps (2) and (3) is one or two of lithium carbonate and lithium hydroxide.
Preferably, the lithium salt in the step (2) is added in a molar ratio of Li/(Ni + Co + Mn + M') = 0.95-1.3.
Preferably, the mixing device in the step (3) is one of a ball mill tank, a stirring mill, a coulter mixer, a V-shaped mixer and a high-speed mixer.
Preferably, the heat treatment atmosphere in the step (3) is air or oxygen, the heat treatment temperature is 500-750 ℃, and the time is 4-10 hours.
The invention has the following advantages:
(1) the high-energy-density nickel-cobalt-manganese multi-element cathode material obtained by the invention has better structural stability and excellent cycle performance in the charging and discharging processes.
(2) After the high-energy-density nickel-cobalt-manganese multi-element positive electrode material obtained by the invention is subjected to heat treatment, a coating layer formed on the surface contains Li8ZrO6，Li8ZrO6The lithium ion battery has electrochemical activity of lithium ion deintercalation under the voltage higher than 4.0V, thereby remarkably improving the capacity of the product.
(3) The high-energy-density nickel-cobalt-manganese multi-element cathode material obtained by the invention effectively reduces the content of residual inactive lithium and interface impedance on the surface of cathode material particles through the coating of the composite oxide, and obviously improves the rate capability of the cathode material.
(4) The preparation method has simple process and no pollution. The introduction mode of the doping elements and the coating layer is simple, the dosage is less, and the heat treatment atmosphere has no special requirements.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
Fig. 1 is a scanning electron microscope image of the nickel-cobalt-manganese multi-element cathode material substrate prepared in comparative example 1.
Fig. 2 is a scanning electron microscope image of the high energy density nickel cobalt manganese multi-element cathode material prepared in example 1.
Fig. 3 is an XRD pattern of samples prepared in comparative example 1, example 1 and example 4.
Fig. 4 is a charge and discharge graph of half cells prepared in comparative example 1, example 1 and example 4 at 0.1C.
Fig. 5 is a graph of specific discharge capacity at different rates for half-cells prepared in comparative example 1, example 1 and example 4.
Fig. 6 is a graph of cycle performance at 1C for half cells prepared in comparative example 1, and example 4.
Fig. 7 is a graph of the ac impedance of half cells prepared in comparative example 1, example 1 and example 4.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
Comparative example 1
Dissolving nickel sulfate, cobalt sulfate and manganese sulfate according to the metal molar ratio of 3:1:1 to obtain a mixed salt solution of 2mol/L, and dissolving sodium hydroxide into an alkali solution with the concentration of 8 mol/L; dissolving ammonia water into a complexing agent solution with the concentration of 6 mol/L. And adding 100L of mixed salt solution, alkali solution and complexing agent solution into a reaction kettle in a parallel flow manner for reaction, keeping the stirring speed at 120rpm constant in the process, controlling the pH to be 11.5-11.7 and the temperature to be 60 ℃, keeping the temperature and the stirring speed unchanged when the reaction is finished, continuing stirring for 20min, then carrying out solid-liquid separation and washing on the prepared nickel-cobalt-manganese hydroxide slurry, drying a filter cake at 105 ℃ for 5h, and then screening to obtain the spherical nickel-cobalt-manganese hydroxide.
And step two, uniformly mixing the spherical nickel-cobalt-manganese hydroxide obtained in the step one with lithium carbonate, wherein the lithium carbonate is added according to the molar ratio Li/(Ni + Co + Mn) = 1.03. Then calcining the mixture at 850 ℃ for 10 hours, crushing and screening to obtain the average particle diameter D5013 mu m Ni-Co-Mn multi-element anode material matrix Li1.03Ni0.6Co0.2Mn0.2O2. The surface residual lithium titration was carried out, and the result showed that the surface residual lithium content was 0.2% of the matrix.
Step three, ZrO is treated2And the matrix of the cathode material obtained in the step two is prepared according to the proportion of 0.2: and simultaneously putting 100 mass percent of the mixture into a ball-milling mixing tank for dry mixing, then putting the mixture into a muffle furnace for heat treatment, and heating the mixture for 10 hours at 800 ℃ in an oxygen atmosphere to obtain the lithium zirconium oxide coated nickel-cobalt-manganese multi-component material.
As shown in fig. 1, the micro-morphology of the nickel-cobalt-manganese multi-element positive electrode material prepared in the comparative example is spheroidal particles.
As shown in FIG. 3, the XRD pattern of the Ni-Co-Mn multi-component anode material prepared in the comparative example has no other impurity phase peaks except the main phase characteristic peak of the multi-component material, because the surface of the material can be mixed with ZrO2The residual lithium in the reaction is less, the content of the formed lithium zirconium oxide is low, and XRD cannot detect the lithium zirconium oxide.
The material is assembled into a half-cell to be tested for electrochemical performance, the specific discharge capacity of the half-cell is 201.3mAh/g under the multiplying power of 3.0-4.5V and 0.1C, and the energy density is 905.8 Wh/kg.
Comparative example 2
The steps one and two are identical to the preparation steps of the comparative example 1.
Step three, ZrO is treated2Lithium hydroxide and the positive electrode material matrix obtained in the second step are mixed according to the weight ratio of 0.3: 2.2: and simultaneously putting 100 mass percent of the mixture into a high-speed mixer, mixing for 15min at the rotating speed of 800rpm, then putting the mixture into a muffle furnace for heat treatment, heating for 10h at 400 ℃ in air atmosphere, and sieving to obtain the zirconium-coated nickel-cobalt-manganese multi-component material.
Because the heat treatment temperature is lower, the positive electrode material coating layer mainly comprises ZrO2. The material is assembled into a half-cell to be tested for electrochemical performance, the specific discharge capacity of the half-cell is 198.7 mAh/g under the multiplying power of 3.0-4.5V and 0.1C, and the energy density is 894.2 Wh/kg.
Example 1
The steps one and two are identical to the preparation steps of the comparative example 1.
Step three, ZrO is treated2Lithium hydroxide and the positive electrode material matrix obtained in the second step are mixed according to the weight ratio of 0.5: 3.8: 100 mass ratio of the materials are simultaneously put into a high-speed mixer, mixed for 10min at the rotating speed of 1200rpm, then put into a muffle furnace for heat treatment, and heated for 8h at 600 ℃ in air atmosphere to obtain the average particle diameter D 5010 μm, the main component of the coating layer is Li8ZrO6The nickel-cobalt-manganese multi-component material.
As shown in fig. 2, fine coating particles are uniformly adhered to the surface of the secondary particles of the cathode material prepared in this example, and a non-dense coating layer is formed.
As shown in fig. 3, in the XRD spectrum of the ni-co-mn multi-component cathode material prepared in this example, Li is present in addition to the main phase characteristic peak of the multi-component material8ZrO6Indicating the presence of Li on the surface of the material8ZrO6And (4) phase(s).
As shown in FIG. 4, the Ni-Co-Mn multi-element positive electrode material prepared in this embodiment is assembled into a half-cell for electrochemical performance test, which is in the range of 3.0-4.5The specific discharge capacity under V and 0.1C multiplying power is 206.1mAh/g, the energy density is 927.5Wh/kg, and the specific discharge capacity is 11.7Wh/kg higher than that of the sample in the comparative example 1. This is due to Li8ZrO6The lithium-ion battery is a hexagonal system with the nickel-cobalt-manganese multi-element cathode material, and lithium ions are deintercalated under the voltage higher than 4.0V, so that the discharge capacity and the energy density of the material can be remarkably improved.
As shown in fig. 5, the specific discharge capacity of the nickel-cobalt-manganese multi-element positive electrode material prepared in this embodiment at a multiplying power of 3.0-4.5V and 1C is 192.6mAh/g, which is improved by 9.0mAh/g compared with the sample of comparative example 1.
As shown in fig. 6, the nickel-cobalt-manganese multi-element positive electrode material prepared in the embodiment is assembled into a half-cell for electrochemical performance test, and the specific discharge capacity of the half-cell reaches 175.9mAh/g after the half-cell is cycled for 100 weeks under the multiplying power of 3.0-4.5V and 1C, which is increased by 5.9mAh/g compared with that of the half-cell prepared in the comparative example 1.
As shown in fig. 7, the semicircular diameter of the high-frequency part in the nickel-cobalt-manganese multi-element positive electrode material prepared in this example was smaller than that of the positive electrode material prepared in comparative example 1, which indicates that Li8ZrO6The cladding significantly reduces the interfacial resistance of the material.
Example 2
Step one, dissolving nickel sulfate, cobalt sulfate and manganese sulfate according to the metal molar ratio of 2:1:1 to obtain 1.5mol/L mixed salt solution, and mixing aluminum sulfate and sodium hydroxide according to the molar ratio of 1:10 to prepare aluminum solution with the aluminum ion concentration of 0.2 mol/L; dissolving sodium hydroxide into an alkali solution with the concentration of 5 mol/L; dissolving ammonia water into a complexing agent solution with the concentration of 2 mol/L. And (2) adding the mixed salt solution, the aluminum solution, the alkali solution and the complexing agent solution into a reaction kettle in a parallel flow manner for reaction, keeping the stirring speed at 115rpm constant in the process, controlling the pH to be 11.8-12.0 and the temperature to be 55 ℃, keeping the temperature and the stirring speed unchanged when the reaction is finished, continuing stirring for 20min, then carrying out solid-liquid separation and washing on the prepared nickel-cobalt-manganese-aluminum hydroxide slurry, drying the filter cake at 110 ℃ for 3h, and then screening to obtain the spherical nickel-cobalt-manganese-hydroxide material uniformly doped with the aluminum element.
Step two, mixing the spherical nickel-cobalt-manganese hydroxide material with uniformly doped aluminum element obtained in the step one with lithium carbonateAnd (3) uniformly mixing, wherein lithium carbonate is added according to the molar ratio of Li/(Ni + Co + Mn + Al) = 0.95. Sintering the mixture for 8 hours at 900 ℃ in air atmosphere, crushing and screening the mixture to obtain the matrix Li of the positive electrode material for the lithium ion battery0.95(Ni0.5Co0.25Mn0.25)0.995Al0.005O2。
Step three, ZrO is treated2、TiO2Lithium hydroxide and the positive electrode material matrix obtained in the second step are mixed according to the weight ratio of 0.3: 0.2: :1.3: 100 mass ratio of the materials are simultaneously put into a high-speed mixer, mixed for 10min at the rotating speed of 1200rpm, then put into a muffle furnace for heat treatment, and heated for 10h at 500 ℃ in air atmosphere to obtain the average particle diameter D506 μm, the coating layer component contains Li2ZrO3、Li8ZrO6、Li4Ti5O12The nickel-cobalt-manganese multi-component material.
The nickel-cobalt-manganese multi-element positive electrode material prepared in the embodiment is assembled into a half-cell to be tested for electrochemical performance, the specific discharge capacity of the half-cell reaches 180.4mAh/g under the multiplying power of 3.0-4.5V and 0.1C, and the energy density is 811.8 Wh/kg. The capacity retention rate after 80 weeks of circulation under the 1C multiplying power reaches 94.6 percent.
Example 3
Step one, dissolving nickel sulfate, cobalt sulfate and manganese sulfate according to the metal molar ratio of 8:1:1 to obtain a mixed salt solution with the concentration of 2.5mol/L, dissolving sodium hydroxide into an alkali solution with the concentration of 6mol/L, and dissolving ammonia water into a complexing agent solution with the concentration of 6 mol/L. And (2) adding the mixed salt solution, the alkali solution and the complexing agent solution into a reaction kettle in a parallel flow manner for reaction, keeping the stirring rotation speed at 125rpm constant in the process, controlling the pH to be 11.9-12.1 and the temperature to be 65 ℃, keeping the temperature and the stirring rotation speed unchanged when the reaction is finished, continuing stirring for 20min, then carrying out solid-liquid separation and washing on the prepared nickel-cobalt-manganese hydroxide slurry, drying the filter cake at 120 ℃ for 4h, and then screening to obtain the spherical nickel-cobalt-manganese hydroxide material.
And step two, mixing the spherical nickel-cobalt-manganese hydroxide material obtained in the step one with nano alumina powder and nano titanium dioxide powder according to the molar ratio (Ni + Co + Mn) of Al to Ti =99 to 0.4 to 0.6. Will be at the topAnd uniformly mixing the mixture with lithium hydroxide, wherein the lithium hydroxide is added according to the molar ratio of Li/(Ni + Co + Mn + Al + Ti) = 1.25. Sintering the mixture for 16 hours at 750 ℃ in an oxygen atmosphere, and crushing and screening the mixture to obtain a matrix Li of the positive electrode material for the lithium ion battery1.25(Ni0.8Co0.1Mn0.1)0.99Al0.004Ti0.006O2。
Step three, ZrO is treated2Simultaneously putting the lithium hydroxide and the positive electrode material substrate obtained in the step two into a high-speed mixer according to the molar ratio of 0.2:1.4:100, mixing for 15min at the rotating speed of 1000rpm, then putting into a muffle furnace for heat treatment, and heating for 1h at 700 ℃ in an oxygen atmosphere to obtain the average particle diameter D5015 μm, the coating layer containing Li8ZrO6、Li6Zr2O7The composite nickel-cobalt-manganese multi-element material.
The composite nickel-cobalt-manganese multi-element positive electrode material prepared in the embodiment is assembled into a half-cell to be subjected to electrochemical performance test, the discharge specific capacity of the half-cell reaches 220.3mAh/g under the multiplying power of 3.0-4.5V and 0.1C, and the energy density is 991.3 Wh/kg.
Example 4
The procedure was consistent with the procedure of comparative example 1.
And step two, mixing the spherical nickel-cobalt-manganese hydroxide material obtained in the step one with nano hafnium oxide powder and nano zirconium oxide powder according to the molar ratio (Ni + Co + Mn) of Hf: Zr =99:0.4: 0.6. And uniformly mixing the mixture with carbonic acid, wherein lithium hydroxide is added according to the molar ratio of Li/(Ni + Co + Mn + Hf + Zr) = 1.03. Sintering the mixture for 16 hours at 750 ℃ in an oxygen atmosphere, and crushing and screening the mixture to obtain a matrix Li of the positive electrode material for the lithium ion battery1.03(Ni0.6Co0.2Mn0.2)0.99Hf0.004Zr0.006O2。
Step three, ZrO is treated2Simultaneously putting the lithium hydroxide and the positive electrode material matrix obtained in the step two into a dry ball-milling mixing tank according to the molar ratio of 1:3:100, ball-milling and mixing for 4 hours at the rotating speed of 100rpm, then putting into a muffle furnace for heat treatment, and heating for 10 hours at 750 ℃ in air atmosphere to obtain the flat anode materialAverage particle diameter D5013 μm, the coating layer contains Li8ZrO6、Li6Zr2O7The nickel-cobalt-manganese multi-component material.
As shown in fig. 3, in the XRD spectrum of the ni-co-mn multi-element cathode material prepared in this example, Li is present in addition to the main phase characteristic peak of the ternary material8ZrO6、Li6Zr2O7、Li2ZrO3Indicating the presence of Li on the surface of the material8ZrO6、Li6Zr2O7、Li2ZrO3And the like.
As shown in fig. 4, the nickel-cobalt-manganese multi-element positive electrode material prepared in this embodiment is assembled into a half-cell for electrochemical performance test, and has a specific discharge capacity of 204.2mAh/g and an energy density of 918.9Wh/kg at a rate of 3.0-4.5V and 0.1C. On the one hand Li8ZrO6The lithium ion deintercalation exists under the voltage higher than 4.0V, so the discharge capacity and the energy density of the material can be improved; li on the other hand6Zr2O7、Li2ZrO3The lithium ion conductor can be used for remarkably reducing the interface impedance in the charging and discharging processes of the battery, reducing the polarization of the material and further improving the discharge capacity.
As shown in fig. 5, the specific discharge capacity of the nickel-cobalt-manganese multi-element positive electrode material prepared in this embodiment at a rate of 3.0-4.5V and 1C is 187.8mAh/g, which is 4.2mAh/g higher than that of the sample of comparative example 1.
As shown in fig. 6, the nickel-cobalt-manganese multi-element positive electrode material prepared in the embodiment is assembled into a half-cell for electrochemical performance test, and the specific discharge capacity of the half-cell reaches 180.6mAh/g after cycling for 100 weeks under the multiplying power of 3.0-4.5V and 1C, which is 10.8 mAh/g higher than that of comparative example 1, and the capacity retention rate is 3.7% higher. The higher heat treatment temperature can lead the surface of the material to generate gradient doping, stabilize the structure of the material and further improve the capacity retention rate of the material.
As shown in fig. 7, the semicircular diameter of the high-frequency part in the nickel-cobalt-manganese multi-element positive electrode material prepared in this example was smaller than that of the positive electrode material prepared in comparative example 1, which indicates that Li8ZrO6、Li6Zr2O7、Li2ZrO3The cladding significantly reduces the interfacial resistance of the material.
The residual lithium content on the surface of the material of the above comparative example was titrated by a potentiometric titrator.
The micro-topography of the materials in the above examples and comparative examples was measured by scanning electron microscopy.
The electrochemical ac impedance of the materials in the above examples and comparative examples was measured by an electrochemical workstation.
The positive electrode active materials in the examples and comparative examples were evaluated for electrical properties by the following methods.
Assembling the button cell:
firstly, mixing a composite nickel-cobalt-manganese multi-element positive electrode active substance, acetylene black and polyvinylidene fluoride (PVDF) for a non-aqueous electrolyte secondary battery according to a mass ratio of 95: 2.5%, coating the mixture on an aluminum foil, drying the mixture, performing press forming by using 100Mpa pressure to form a positive electrode piece with the diameter of 12mm and the thickness of 120 mu m, and then putting the positive electrode piece into a vacuum drying box to dry for 12 hours at 120 ℃.
The negative electrode uses a Li metal sheet with the diameter of 17mm and the thickness of 1 mm; the separator used was a polyethylene porous film having a thickness of 25 μm; LiPF of 1mol/L is used as electrolyte6And a mixture of Ethylene Carbonate (EC) and diethyl carbonate (DEC) in equal amounts.
Assembling the positive pole piece, the diaphragm, the negative pole piece and the electrolyte into a 2025 type button cell in an Ar gas glove box with the water content and the oxygen content of less than 5ppm, and taking the cell as an unactivated cell.
And (3) placing the button cell for 24 hours after manufacturing, charging the button cell to the cut-off voltage of 4.3V by adopting the current density of 20mA/g after the open-circuit voltage is stable, and charging the button cell to the cut-off current of 0.024mA at the constant voltage of 4.3V. The cell was then discharged to a cut-off voltage of 3.0V at the same current density, and the above procedure was repeated again, and the cell at this time was regarded as an activated cell.
The performance of the button cell was evaluated as follows:
(1) and (3) rate performance test: and (3) using the activated battery at the temperature of 25 ℃, and circularly inspecting the rate performance of the material for 1 time at current densities of 0.1C, 0.2C, 1C, 2C and 5C in a voltage range of 3.0-4.5V.
(2) And (3) testing the cycle performance: and (3) inspecting the cycle performance of the material at the temperature of 25 ℃ and under the current density of 1C in a voltage range of 3.0-4.4V and 3.0-4.5V by using the activated battery.
(3) And (3) testing the alternating current impedance performance: the ac impedance test was performed using an unactivated cell at an amplitude of 5mV over a test frequency range of 0.1Hz to 100 kHz.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. A high energy density multi-element cathode material is characterized in that: comprises a substrate and a composite oxide coating layer coated on the surface of the substrate; the chemical formula of the matrix is Li1+a[(Ni1-2xCoxMnx)1-yMy]1-zM′zO2Wherein-0.5. ltoreq. a.ltoreq.0.3, 0.05. ltoreq. x.ltoreq.0.3, 0. ltoreq. y.ltoreq.0.01, 0. ltoreq. z.ltoreq.0.01, the coating layer contains Li8ZrO6And the chemical formula is LiuM″vOwWherein u is more than or equal to 0 and less than or equal to 8, V is more than or equal to 1 and less than or equal to 5, W is more than or equal to 2 and less than or equal to 12, M and M 'are at least one element of La, Cr, Mo, Ca, Fe, Hf, Ti, Zn, Y, Zr, Si, W, Nb, Sm, V, Mg, B and Al, and M' is at least one element of Zr, Ti, Al, Si, Mn, Sn and W;
the composite oxide coating layer is compact or non-compact; the amount of the coating layer accounts for 0.01-3% of the matrix;
the preparation method of the high-energy-density multi-element cathode material comprises the following steps:
(1) dissolving a salt solution of nickel, cobalt, manganese and doping elements to obtain a mixed salt solution of 1-3 mol/L; dissolving sodium hydroxide into an alkali solution with the concentration of 4-10 mol/L; dissolving ammonia water into a complexing agent solution with the concentration of 2-10 mol/L;
adding the mixed salt solution, the alkali solution and the complexing agent solution into a reaction kettle in a concurrent flow manner for reaction, keeping stirring in the process, controlling the reaction pH value and the reaction temperature, and performing solid-liquid separation, washing, drying and screening on the prepared precursor slurry to obtain spherical nickel-cobalt-manganese hydroxide (Ni)1-2xCoxMnx)1-yMy(OH)2；
(2) The (Ni) obtained in the step (1)1-2xCoxMnx)1-yMy(OH)2Uniformly mixing with lithium salt and M' oxide, calcining for 4-20 h at 600-1000 ℃ in air or oxygen atmosphere, crushing and screening to obtain the matrix Li of the positive electrode material for the lithium ion battery1+a[(Ni1-2xCoxMnx)1-yMy]1-zM′zO2；
(3) ZrO 2 is mixed with2Mechanically mixing the oxide of M', the lithium salt and the anode material matrix, then putting the mixture into a muffle furnace, and carrying out heat treatment for 0.5-12 h at the temperature of 450-800 ℃ to obtain the lithium secondary battery anode material8ZrO6And a lithium ion conductor LiuM″vOwA composite oxide coated multi-element positive electrode material;
a is more than or equal to 0.5 and less than or equal to 1.3, x is more than or equal to 0.05 and less than or equal to 0.3, Y is more than or equal to 0 and less than or equal to 0.01, z is more than or equal to 0 and less than or equal to 8, V is more than or equal to 1 and less than or equal to 5, W is more than or equal to 2 and less than or equal to 12, M and M 'are at least one element of La, Cr, Mo, Ca, Fe, Hf, Ti, Zn, Y, Zr, Si, W, Nb, Sm, V, Mg, B and Al, and M' is at least one element of Zr, Ti, Al, Si, Mn, Sn and W.
2. The high energy density multi-element positive electrode material according to claim 1, wherein: the average particle diameter D of the high-energy-density multi-element cathode material505 to 20 μm.
3. The high energy density multi-element positive electrode material according to claim 1The method is characterized in that: the LiuM″vOwIs LiAl5O8、LiAlO2、Li5AlO4、Li2SiO3、Li2Si2O5、Li4SiO4、Li2SnO3、Li2TiO3、Li4TiO4、Li4Ti5O12、Li2ZrO3、Li6Zr2O7、Li8ZrO6、Li4ZrO4At least one of (1).
4. A preparation method of a high-energy-density multi-element cathode material is characterized by comprising the following steps:
(1) dissolving a salt solution of nickel, cobalt, manganese and doping elements to obtain a mixed salt solution of 1-3 mol/L; dissolving sodium hydroxide into an alkali solution with the concentration of 4-10 mol/L; dissolving ammonia water into a complexing agent solution with the concentration of 2-10 mol/L;
adding the mixed salt solution, the alkali solution and the complexing agent solution into a reaction kettle in a concurrent flow manner for reaction, keeping stirring in the process, controlling the reaction pH value and the reaction temperature, and performing solid-liquid separation, washing, drying and screening on the prepared precursor slurry to obtain spherical nickel-cobalt-manganese hydroxide (Ni)1-2xCoxMnx)1-yMy(OH)2；
(2) The (Ni) obtained in the step (1)1-2xCoxMnx)1-yMy(OH)2Uniformly mixing with lithium salt and M' oxide, calcining for 4-20 h at 600-1000 ℃ in air or oxygen atmosphere, crushing and screening to obtain the matrix Li of the positive electrode material for the lithium ion battery1+a[(Ni1-2xCoxMnx)1-yMy]1-zM′zO2；
(3) ZrO 2 is mixed with2Mechanically mixing the oxide of M', the lithium salt and the anode material matrix, then putting the mixture into a muffle furnace, and heating the mixture at the temperature of 450-800 DEG CLi is prepared for 0.5-12 h8ZrO6And a lithium ion conductor LiuM″vOwA composite oxide coated multi-element positive electrode material;
a is more than or equal to 0.5 and less than or equal to 1.3, x is more than or equal to 0.05 and less than or equal to 0.3, Y is more than or equal to 0 and less than or equal to 0.01, z is more than or equal to 0 and less than or equal to 8, V is more than or equal to 1 and less than or equal to 5, W is more than or equal to 2 and less than or equal to 12, M and M 'are at least one element of La, Cr, Mo, Ca, Fe, Hf, Ti, Zn, Y, Zr, Si, W, Nb, Sm, V, Mg, B and Al, and M' is at least one element of Zr, Ti, Al, Si, Mn, Sn and W.
5. The method for preparing a high energy density multi-element positive electrode material according to claim 4, wherein: the oxide of M 'and the oxide particle of M' have an average particle diameter D501-50 nm, and a specific surface area greater than 10m2/g。
6. The method for preparing a high energy density multi-element positive electrode material according to claim 4, wherein: the oxide of M 'and the oxide of M' are HfO2、TiO2、Y2O3、ZrO2、SiO2、W2O3、Nb2O5、Sm2O3、V2O5、MgO、Al2O3At least one of (1).
7. The method for preparing a high energy density multi-element positive electrode material according to claim 4, wherein: the reaction pH range is 10-13, and the temperature is 50-70 ℃.
8. The method for preparing a high energy density multi-element positive electrode material according to claim 4, wherein: the lithium salt in the step (2) is added in an amount that the molar ratio of Li/(Ni + Co + Mn + M + M') is 0.95-1.3.
9. The method for preparing a high energy density multi-element positive electrode material according to claim 4, wherein: and (3) the heat treatment atmosphere is air or oxygen, the heat treatment temperature is 500-750 ℃, and the time is 4-10 hours.
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| CN111082029B (en) * | 2019-12-31 | 2021-08-03 | 北京当升材料科技股份有限公司 | Lithium-rich manganese-based material and preparation method and application thereof |
| CN111446444B (en) * | 2020-03-03 | 2021-06-15 | 北京当升材料科技股份有限公司 | Lithium-rich manganese-based material and preparation method and application thereof |
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| CN115385393A (en) * | 2022-08-23 | 2022-11-25 | 荆门市格林美新材料有限公司 | Zirconium-doped nickel-cobalt-manganese hydroxide and preparation method and application thereof |
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