CN113363493A - Single crystal ternary positive electrode material, preparation method and battery - Google Patents
Single crystal ternary positive electrode material, preparation method and battery Download PDFInfo
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- CN113363493A CN113363493A CN202110713439.9A CN202110713439A CN113363493A CN 113363493 A CN113363493 A CN 113363493A CN 202110713439 A CN202110713439 A CN 202110713439A CN 113363493 A CN113363493 A CN 113363493A
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- 239000013078 crystal Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000007774 positive electrode material Substances 0.000 title claims description 13
- 239000010406 cathode material Substances 0.000 claims abstract description 59
- 239000006258 conductive agent Substances 0.000 claims abstract description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 42
- 238000005245 sintering Methods 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 41
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 31
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000012266 salt solution Substances 0.000 claims description 22
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 20
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 14
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 10
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 8
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 4
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- 229910021318 lanthanum strontium oxide Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 53
- 239000003513 alkali Substances 0.000 abstract description 22
- 230000001276 controlling effect Effects 0.000 abstract description 16
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000011572 manganese Substances 0.000 description 14
- 238000000498 ball milling Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
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- 239000013543 active substance Substances 0.000 description 6
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- 229910021389 graphene Inorganic materials 0.000 description 6
- 239000010416 ion conductor Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
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- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 102100028667 C-type lectin domain family 4 member A Human genes 0.000 description 2
- 101000766908 Homo sapiens C-type lectin domain family 4 member A Proteins 0.000 description 2
- -1 Li/(Ni + Co + Mn) Chemical compound 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 229910018426 Mn0.33(OH)2 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910017124 Ni0.7Co0.15Mn0.15(OH)2 Inorganic materials 0.000 description 2
- 229910017223 Ni0.8Co0.1Mn0.1(OH)2 Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
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- 238000004458 analytical method Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
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- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229940053662 nickel sulfate Drugs 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009469 supplementation Effects 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000011206 ternary composite Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910007822 Li2ZrO3 Inorganic materials 0.000 description 1
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910003327 LiNbO3 Inorganic materials 0.000 description 1
- 229910013467 LiNixCoyMnzO2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
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- 229940011182 cobalt acetate Drugs 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
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- 238000009830 intercalation Methods 0.000 description 1
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- 150000002696 manganese Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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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- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a single crystal ternary cathode material, a preparation method and a battery, wherein the preparation method comprises the following steps: mixing the ternary precursor and a lithium source, and sintering for the first time to obtain a primary sintered product; and mixing the primary sintered product, the conductive agent and the lithium source, and then sintering the mixture for the second time to obtain the single crystal ternary cathode material. According to the invention, the conductivity of the single crystal ternary cathode material is improved and the residual alkali on the surface of the material is reduced by regulating and controlling the addition amount of the conductive agent and the sintering temperature in the secondary sintering process.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and relates to a single crystal ternary cathode material, a preparation method and a battery.
Background
The power battery is the core of the electric automobile, is the only source of the driving energy of the pure electric automobile, and is directly related to the power performance and the service life of the electric automobile and the safety of the electric automobile. The cost of the new energy automobile and the cost of the battery power system occupying the new energy automobile are 30-50%. Since the birth of the electric automobile, the power battery technology has the practical process of the electric automobile. Improving power density, energy density, service life and reducing cost are the core of the research and development of the power battery technology of the electric automobile.
Ternary materials NCM or NCA are widely used in the field of electric vehicles due to their high specific capacity and good cycle and calendar properties. The ternary lithium battery is a lithium battery of which the anode material is a ternary anode material made of nickel cobalt lithium manganate or nickel cobalt lithium aluminate, the ternary composite anode material is prepared from nickel salt, cobalt salt and manganese salt serving as raw materials, the proportion of nickel, cobalt and manganese in the ternary composite anode material can be adjusted according to actual needs, and the lithium battery of which the anode is made of the ternary material has high safety compared with a lithium cobalt battery.
However, during the process of lithium ion desorption/intercalation of ternary materials, especially high nickel ternary materials, the unit cell volume changes greatly, and the internal stress of particles accumulates, causing the particles to generate microcracks, so that the cycle life and the thermal safety of the materials can be reduced. In addition, the residual alkali (lithium carbonate and lithium hydroxide) on the surface of the ternary material can aggravate the side reaction and gas generation with the electrolyte in the use process of the material, and influence the service life and the safety performance of the battery cell. At present, the improvement technology for the microcracks of the ternary material is mainly the regulation and control of the microstructure of the material, such as a core-shell structure, a gradient structure, primary particle emission distribution and the like, and the synthesis process needs to be accurately controlled, so that the production cost is increased. In addition, the single crystallization is a technical route which has low cost and simple process, reduces particle cracks and inhibits side reactions at the interface. Compared with a polycrystalline material, the single crystal has the advantages that no crystal boundary exists in the single crystal, the anti-cracking capability is high, the stress accumulation can be effectively slowed down, the generation of microcracks is inhibited, and therefore the single crystal has more excellent cycle life, calendar life and thermal stability. However, the single crystal ternary material has a large primary particle size (3-5 um) and a long ion diffusion path, so that the power performance is poor, and the application of the single crystal ternary material in a high-power vehicle model is severely limited.
CN109244449A discloses a preparation method of a high-conductivity ternary cathode material, which comprises the following steps: the nickel-cobalt-manganese ternary positive electrode material is mixed with imidazoles in an alcohol solventReacting an organic matter with a metal source to form a metal organic framework on the surface of the nickel-cobalt-manganese ternary positive electrode material; wherein the metal source comprises at least one of a metal salt and a metal oxide; sintering the nickel-cobalt-manganese ternary cathode material coated with the metal organic framework in an inert atmosphere to carbonize the metal organic framework to obtain the high-conductivity ternary cathode material; the chemical composition molecular expression of the nickel-cobalt-manganese ternary cathode material is as follows: LiNixCoyMnzO2Wherein x + y + z is 1.
CN109713296A discloses a processing method for improving the conductivity of a high-nickel ternary positive electrode material of a lithium battery, which comprises the following steps: (1) adding foamed nickel into an ethanol solution containing cobalt acetate and manganese acetate, mixing and stirring, and fully adsorbing to obtain an adsorbed product; (2) uniformly mixing the adsorbed product obtained in the step (1) with a strong oxidant and solid alkali, then pre-burning, adding a lithium source after the material is completely solidified, then sintering at high temperature, and cooling after the sintering is finished to obtain a three-dimensional mesh high-nickel ternary cathode material; (3) and (3) placing the three-dimensional mesh high-nickel ternary cathode material obtained in the step (2) into conductive paste, fully soaking, and then curing at low temperature to obtain the high-conductivity high-nickel ternary cathode material, thereby completing the improvement of the conductivity of the high-nickel ternary cathode material of the lithium battery.
CN109728261A discloses a ternary cathode material and a preparation method thereof, wherein the preparation method comprises the following steps: (1) washing with water: adding water to wash the ternary cathode material, adding a graphene oxide solution during washing, and stirring to obtain a washed graphene oxide-coated ternary cathode material; (2) drying: filtering and drying the ternary cathode material coated by the graphene oxide to obtain a dried ternary cathode material coated by the graphene oxide; (3) and (3) sintering: and sintering the dried ternary cathode material coated by the graphene oxide to obtain the ternary cathode material coated by the graphene.
At present, the method for improving the power performance of the single crystal material mainly reduces the primary particle size, but the reduction of the particle size inevitably causes negative effects such as reduction of the stability of the material and reduction of the compaction density of a pole piece. For the residual alkali on the surface of the ternary material, a water washing method is generally adopted, but the production process and the loss of valuable metals are increased, and the material cost is increased. The technical scheme with simple process is developed, the conductivity of the single crystal material is improved, the surface residual alkali is reduced, and the method has important scientific significance and economic value.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a single crystal ternary cathode material, a preparation method and a battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a single crystal ternary cathode material, which comprises the following steps:
mixing the ternary precursor and a lithium source, and sintering for the first time to obtain a primary sintered product;
and mixing the primary sintered product, the conductive agent and the lithium source, and then sintering the mixture for the second time to obtain the single crystal ternary cathode material.
The invention provides a preparation method of a single crystal ternary cathode material, which mainly aims to improve the conductivity of the single crystal ternary cathode material and reduce surface residual alkali, and mainly aims to:
(1) the conductive agent is added in the secondary sintering process, so that the improvement of the conductivity of the single crystal ternary cathode material and the reduction of residual alkali on the surface of the material are realized; (2) supplementing a lithium source again in the secondary sintering process, mainly aiming at ensuring that the conductive agent completely reacts to synthesize the fast ion conductor, and because the residual alkali of a calcined product cannot meet the lithium element amount required by the reaction when the conductive agent is added in a large amount, the lithium source needs to be additionally added for supplementation; however, if the amount of the lithium source is too much, the conductive agent cannot be completely consumed, the excess lithium source exists on the surface layer of the material in the form of residual alkali, and if the amount of the lithium source is too little, the reaction requirement of the conductive agent cannot be met, which affects the quality of the coating layer.
In a preferred embodiment of the present invention, the mass fraction of the conductive agent is 0.01 to 3 wt%, for example, 0.01 wt%, 0.05 wt%, 0.1 wt%, 1 wt%, 1.2 wt%, 1.4 wt%, 1.6 wt%, 1.8 wt%, 2.0 wt%, 2.2 wt%, 2.4 wt%, 2.6 wt%, 2.8 wt%, or 3.0 wt%, and the mass fraction of the lithium source is 0 to 5 wt% and not 0 wt%, for example, 0.1 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, or 5 wt%, based on 100 wt% of the mass fraction of the primary sintered product, the conductive agent, and the lithium source, in the secondary sintering process, but the mass fraction is not limited to the recited values, and the other values not recited in the range are also applicable.
According to the invention, the improvement of the conductivity of the single crystal ternary cathode material and the reduction of the residual alkali on the surface of the material are realized by regulating and controlling the addition amount of the conductive agent in the secondary sintering process, the addition amount of the conductive agent is limited to be 0.01-3 wt%, and when the addition amount is higher than 3 wt%, on one hand, the content of active substances (capable of storing lithium ions) in the material is reduced, and the conductive agent is not suitable for the exertion of capacity, because the conductive agent coatings are non-electrochemical active substances, the lithium ions can not be stored, and the excessive addition amount can reduce the active substances in the material, so that the lithium removal and insertion capacity of the unit mass of the whole material is reduced; on the other hand, too much conductive agent added amount causes too thick coating layer, which greatly hinders charge transfer between material bulk phase and interface, and is not favorable for the performance of power performance of the material, because the product of high temperature reaction of conductive agent and residual alkali or lithium source is mostly fast ion conductor, which can improve the ion conductivity of the material, but too much coated conductive agent tends to deteriorate the electron conductivity of the material, and the power performance of the positive electrode material is synergistic by the ion conductivity and the electron conductivity. When the addition amount is less than 0.01 wt%, the conductive agent is scattered on the surface of the single crystal particle in a dotted manner, and the dotted coating cannot completely prevent the direct contact between the surface of the material and the electrolyte, so that the risk of side reaction is increased, and although the conductivity is improved, the interface deterioration of the material is aggravated.
In a preferred embodiment of the present invention, the ternary precursor and the lithium source are mixed in a molar ratio of Li/(Ni + Co + Mn) of 1 (1.0 to 1.1), and may be, for example, 1:1.0, 1:1.01, 1:1.02, 1:1.03, 1:1.04, 1:1.05, 1:1.06, 1:1.07, 1:1.08, 1:1.09, or 1:1.1, but not limited to the above-mentioned values, and other values not listed in the above-mentioned values are also applicable.
Preferably, the lithium source comprises one or a combination of at least two of lithium hydroxide, lithium carbonate, lithium chloride, lithium nitrate or lithium sulfate.
In a preferred embodiment of the present invention, the temperature increase rate of the primary sintering is 2 to 10 ℃/min, and may be, for example, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min or 10 ℃/min, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are also applicable.
Preferably, the heating temperature of the primary sintering is 800 to 1100 ℃, for example, 800 ℃, 820 ℃, 840 ℃, 860 ℃, 880 ℃, 900 ℃, 920 ℃, 940 ℃, 960 ℃, 980 ℃, 1000 ℃, 1020 ℃, 1040 ℃, 1060 ℃, 1080 ℃ or 1100 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the heat preservation time of the primary sintering is 7 to 30 hours, for example, 7 hours, 9 hours, 10 hours, 11 hours, 13 hours, 15 hours, 17 hours, 19 hours, 21 hours, 23 hours, 25 hours, 27 hours, 29 hours or 30 hours, but the heat preservation time is not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferred embodiment of the present invention, the conductive agent includes one or a combination of at least two of cobalt hydroxide, cobalt oxide, niobium oxide, zirconium oxide, cerium oxide, lanthanum oxide, strontium oxide, and yttrium oxide, and preferably cobalt oxide, niobium oxide, zirconium oxide, and lanthanum oxide.
The invention selects in particular cobalt oxide, niobium oxide, zirconium oxide or lanthanum oxide as the conductive agent, since these conductive agents can on the one hand form fast ion conductors, such as LiCoO2、LiNbO3、Li2ZrO3、Li7La3Zr2O12Coating the surface layer of the single crystal material can effectively improve the lithium ion conductivity of the single crystal materialThe rate, while side reactions of the electrolyte and the active material can be suppressed; on the other hand, the conductive agents can react with residual alkali on the surface of a calcined product in an oxygen atmosphere, the residual alkali amount of the ternary material can be effectively reduced, and particularly, the conductive agents are applied to high-nickel single crystal ternary, so that the water washing step (mainly used for removing the residual alkali on the surface of the ternary) can be omitted, the manufacturing process of the ternary material is reduced, the yield is improved, and the material cost is reduced.
Preferably, the temperature increase rate of the secondary sintering is 4 to 15 ℃/min, for example, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min, 11 ℃/min, 12 ℃/min, 13 ℃/min, 14 ℃/min or 15 ℃/min, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the secondary sintering is performed in an oxygen atmosphere.
Preferably, the heating temperature of the secondary sintering is 600 to 900 ℃, for example, 600 ℃, 620 ℃, 640 ℃, 660 ℃, 680 ℃, 700 ℃, 720 ℃, 740 ℃, 760 ℃, 780 ℃, 800 ℃, 820 ℃, 840 ℃, 860 ℃, 880 ℃, or 900 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
On the basis of controlling the addition amount of the conductive agent, the invention further limits the coating process of secondary sintering, reduces the residual alkali on the surface of the material and simultaneously realizes the improvement of the conductivity of the single crystal material. Particularly, the heating temperature is specially limited and is required to be strictly controlled to be 600-900 ℃, when the sintering temperature exceeds 900 ℃, on one hand, the grain size of a single crystal material is increased, the electrical conductivity of the material is not facilitated, and the power performance is influenced, on the other hand, an element in a conductive agent is diffused into a single crystal phase at an excessively high temperature, so that the surface coating cannot be realized, and the reaction temperature of the conductive agent is excessively high, so that the production of a fast ion conductor cannot be guaranteed; when the sintering temperature is lower than 600 ℃, the reaction between the conductive agent and the residual alkali or the lithium source is insufficient, the quality of a coating layer is poor, and the improvement of the conductivity of the single crystal material cannot be ensured, the surface defects such as micro powder, cracks and the like caused by the crushing of the primary sintered product can be repaired by the secondary sintering, and the fine powder or the cracks in the primary sintered product cannot be re-fused to the bulk phase at an excessively low temperature.
Preferably, the holding time of the secondary sintering is 2 to 15 hours, for example, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours or 15 hours, but the holding time is not limited to the listed values, and other values not listed in the range of the values are also applicable.
As a preferred technical solution of the present invention, the preparation method of the ternary precursor comprises:
preparing mixed salt solution according to the stoichiometric ratio, mixing the mixed salt solution, ammonia water solution and sodium hydroxide solution for reaction to obtain precipitate, and washing and drying the precipitate to obtain the ternary precursor.
Preferably, the molar concentration of the metal ions in the mixed salt solution is 1 to 4mol/L, for example, 1.0mol/L, 1.5mol/L, 2.0mol/L, 2.5mol/L, 3.0mol/L, 3.5mol/L or 4.0mol/L, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the molar concentration of the sodium hydroxide solution is 2 to 6mol/L, and may be, for example, 2.0mol/L, 2.5mol/L, 3.0mol/L, 3.5mol/L, 4.0mol/L, 4.5mol/L, 5.0mol/L, 5.5mol/L, or 6.0mol/L, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the mass concentration of the aqueous ammonia solution is 5 to 20 wt%, and may be, for example, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, or 20 wt%, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the volume ratio of the mixed salt solution, the sodium hydroxide solution and the ammonia water solution is (1-3): 2-6): 0.2-3, and may be, for example, 1:2:0.2, 1:3:1, 2:4:2, 2:5:2, 3:6:3 or 3:5:2, but is not limited to the enumerated values, and other unrecited values within the numerical range are also applicable.
Preferably, the mixed salt solution, the aqueous ammonia solution and the sodium hydroxide solution are mixed and then adjusted to a pH of 8 to 13, for example, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5 or 13.0, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the reaction temperature is 50-80 ℃, for example, 50 ℃, 52 ℃, 54 ℃, 56 ℃, 58 ℃, 60 ℃, 62 ℃, 64 ℃, 66 ℃, 68 ℃, 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃ or 80 ℃, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the stirring rate of the reaction process is 100 to 600r/min, such as 100r/min, 150r/min, 200r/min, 250r/min, 300r/min, 350r/min, 400r/min, 450r/min, 500r/min, 550r/min or 600r/min, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the reaction time is 10 to 20 hours, for example, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours or 20 hours, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the ternary precursor has a D50 value of 3-10 μm, for example, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm, but is not limited to the values recited, and other values not recited within the range of values are equally applicable.
In a second aspect, the invention provides a single crystal ternary cathode material prepared by the method of the first aspect, and the single crystal ternary cathode material comprises single crystal ternary cathode particles and a conductive layer coated on the surfaces of the single crystal ternary cathode particles.
In a preferred embodiment of the present invention, the thickness of the conductive layer is 10 to 500nm, and may be, for example, 10nm, 50nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm or 500nm, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
As a preferable technical scheme, the single crystal ternary cathode material is a high-nickel ternary cathode material.
Preferably, the nickel content of the high nickel ternary positive electrode material is greater than or equal to 80 wt%, such as 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, or 95 wt%, but is not limited to the recited values, and other unrecited values within the range are equally applicable.
In a third aspect, the invention provides a battery comprising a positive electrode, a negative electrode and a separator, wherein the single crystal ternary positive electrode material of the second aspect is adopted in the positive electrode.
Compared with the prior art, the invention has the beneficial effects that:
(1) the conductivity of the single crystal ternary cathode material and the residual alkali on the surface of the material are improved by regulating and controlling the addition amount of the conductive agent in the secondary sintering process. The addition amount of the conductive agent is limited to be 0.01-3 wt%, and when the addition amount is higher than 3 wt%, on one hand, the content of active substances (capable of storing lithium ions) of the material is reduced, and the capacity is not favorably exerted, because the conductive agent coatings are all non-electrochemical active substances and can not store lithium ions, and the active substances in the material are reduced due to excessive addition amount, so that the lithium removal and insertion capacity of the whole material per unit mass is reduced; on the other hand, too much conductive agent added amount causes too thick coating layer, which greatly hinders charge transfer between material bulk phase and interface, and is not favorable for the performance of power performance of the material, because the product of high temperature reaction of conductive agent and residual alkali or lithium source is mostly fast ion conductor, which can improve the ion conductivity of the material, but too much coated conductive agent tends to deteriorate the electron conductivity of the material, and the power performance of the positive electrode material is synergistic by the ion conductivity and the electron conductivity. When the addition amount is less than 0.01 wt%, the conductive agent is mostly scattered on the surface of the single crystal particle in a dot form, and the dot coating cannot completely prevent the direct contact between the surface of the material and the electrolyte, so that the risk of side reaction is increased, and although the conductivity is improved, the interface deterioration of the material is aggravated.
(2) Supplementing a lithium source again in the secondary sintering process, mainly aiming at ensuring that the conductive agent completely reacts to synthesize the fast ion conductor, and because the residual alkali of a calcined product cannot meet the lithium element amount required by the reaction when the conductive agent is added in a large amount, the lithium source needs to be additionally added for supplementation; however, if the amount of the lithium source is too much, the conductive agent cannot be completely consumed, the excess lithium source exists on the surface layer of the material in the form of residual alkali, and if the amount of the lithium source is too little, the reaction requirement of the conductive agent cannot be met, which affects the quality of the coating layer.
Drawings
FIG. 1 is an electron micrograph of a calcined product prepared in example 1 of the present invention;
FIG. 2 is an electron micrograph of the single crystal ternary cathode material prepared in example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Example 1
The embodiment provides a preparation method of a single crystal ternary cathode material, which specifically comprises the following steps:
(1) preparing nickel chloride, cobalt chloride and manganese chloride into a mixed salt solution with the concentration of 1mol/L according to the stoichiometric ratio, and simultaneously preparing a 2mol/L sodium hydroxide solution and a 5 wt% ammonia water solution; simultaneously adding the mixed salt solution, the sodium hydroxide solution and the ammonia water solution into a stirrer according to the volume ratio of 1:2:0.2, controlling the pH of the mixed solution to be 8, controlling the reaction temperature to be 50 ℃, the stirring speed to be 600r/min, stirring for 10h, filtering, washing and drying precipitates obtained by reaction in sequence to obtain a precursor Ni0.9Co0.05Mn0.05(OH)2；
(2) Mixing Ni0.9Co0.05Mn0.05(OH)2Mixing and ball-milling the precursor and lithium hydroxide, wherein the proportion of lithium is Li/(Ni + Co + Mn) ═ 1, heating the mixture to 800 ℃ at the heating rate of 2 ℃/min in the atmosphere of oxygen, keeping the temperature for 30h,preparing a primary burned product, and carrying out scanning electron microscope analysis on the primary burned product to obtain an electron microscope photo shown in figure 1;
(3) mixing and ball-milling a calcined product, cobalt oxide and lithium hydroxide, wherein the addition amount of the cobalt oxide is 0.01 wt%, the addition amount of the lithium hydroxide is 0.1 wt%, heating to 700 ℃ at the heating rate of 4 ℃/min in the oxygen atmosphere, and keeping the temperature for 15h to prepare the single crystal ternary cathode material, and carrying out scanning electron microscope analysis on the single crystal ternary cathode material to obtain an electron microscope photo as shown in figure 2.
Example 2
The embodiment provides a preparation method of a single crystal ternary cathode material, which specifically comprises the following steps:
(1) preparing nickel nitrate, cobalt nitrate and manganese nitrate into a mixed salt solution with the concentration of 1.5mol/L according to the stoichiometric ratio, and simultaneously preparing a 3mol/L sodium hydroxide solution and an 8 wt% ammonia water solution; simultaneously adding the mixed salt solution, the sodium hydroxide solution and the ammonia water solution into a stirrer according to the volume ratio of 1.5:3:1, controlling the pH of the mixed solution to be 9, controlling the reaction temperature to be 55 ℃, the stirring speed to be 500r/min, stirring for 12h, filtering, washing and drying precipitates obtained by reaction in sequence to obtain a precursor Ni0.7Co0.15Mn0.15(OH)2；
(2) Mixing Ni0.7Co0.15Mn0.15(OH)2Mixing and ball-milling the precursor and lithium carbonate, wherein the proportion of lithium is Li/(Ni + Co + Mn) is 1.04, heating the mixture to 850 ℃ at the heating rate of 4 ℃/min in the oxygen atmosphere, and keeping the temperature for 25h to prepare a primary sintered product;
(3) and mixing and ball-milling the primary sintered product, niobium oxide and lithium carbonate, wherein the addition amount of the niobium oxide is 1 wt%, the addition amount of the lithium carbonate is 1 wt%, heating to 650 ℃ at the heating rate of 6 ℃/min in the oxygen atmosphere, and keeping the temperature for 13h to prepare the single crystal ternary cathode material.
Example 3
The embodiment provides a preparation method of a single crystal ternary cathode material, which specifically comprises the following steps:
(1) preparing nickel sulfate, cobalt sulfate and manganese sulfate into a mixed salt solution with the concentration of 4mol/L according to the stoichiometric ratio, and simultaneously preparing a sodium hydroxide solution with the concentration of 4mol/L and an ammonia water solution with the concentration of 10 wt%; simultaneously adding the mixed salt solution, the sodium hydroxide solution and the ammonia water solution into a stirrer according to the volume ratio of 2:4:1, controlling the pH of the mixed solution to be 13, controlling the reaction temperature to be 70 ℃, the stirring speed to be 300r/min, stirring for 15h, filtering, washing and drying precipitates obtained by reaction in sequence to obtain a precursor Ni0.65Co0.1Mn0.35(OH)2；
(2) Mixing Ni0.65Co0.1Mn0.35(OH)2Mixing and ball-milling the precursor and lithium chloride, wherein the proportion of lithium is Li/(Ni + Co + Mn) is 1.03, heating the mixture to 900 ℃ at the heating rate of 5 ℃/min in the oxygen atmosphere, and keeping the temperature for 20h to prepare a calcined product;
(3) and (2) mixing and ball-milling the calcined product, zirconia and lithium chloride, wherein the addition amount of the zirconia is 1.5 wt%, the addition amount of the lithium chloride is 1.5 wt%, heating to 720 ℃ at the heating rate of 8 ℃/min in the oxygen atmosphere, and keeping the temperature for 10h to prepare the single crystal ternary cathode material.
Example 4
The embodiment provides a preparation method of a single crystal ternary cathode material, which specifically comprises the following steps:
(1) preparing nickel sulfate, cobalt chloride and manganese sulfate into a mixed salt solution with the concentration of 2mol/L according to the stoichiometric ratio, and simultaneously preparing a 3.5mol/L sodium hydroxide solution and a 12 wt% ammonia water solution; simultaneously adding the mixed salt solution, the sodium hydroxide solution and the ammonia water solution into a stirrer according to the volume ratio of 2:4:1.5, controlling the pH of the mixed solution to be 10, controlling the reaction temperature to be 60 ℃, the stirring speed to be 400r/min, stirring for 16h, filtering, washing and drying precipitates obtained by reaction in sequence to obtain a precursor Ni0.6Co0.1Mn0.3(OH)2；
(2) Mixing Ni0.6Co0.1Mn0.3(OH)2Mixing and ball-milling the precursor and lithium nitrate, wherein the proportion of lithium, namely Li/(Ni + Co + Mn), is 1.05, heating the mixture to 950 ℃ at the heating rate of 6 ℃/min in the oxygen atmosphere, and keeping the temperature for 15h to prepare a calcined product;
(3) and mixing and ball-milling the primary sintered product, niobium oxide and lithium nitrate, wherein the addition amount of the niobium oxide is 2 wt%, the addition amount of the lithium nitrate is 2 wt%, heating to 800 ℃ at the heating rate of 10 ℃/min in the oxygen atmosphere, and keeping the temperature for 8h to prepare the single crystal ternary cathode material.
Example 5
The embodiment provides a preparation method of a single crystal ternary cathode material, which specifically comprises the following steps:
(1) preparing nickel nitrate, cobalt chloride and manganese nitrate into a mixed salt solution with the concentration of 2.5mol/L according to the stoichiometric ratio, and simultaneously preparing a 5mol/L sodium hydroxide solution and a 15 wt% ammonia water solution; simultaneously adding the mixed salt solution, the sodium hydroxide solution and the ammonia water solution into a stirrer according to the volume ratio of 3:5:2, controlling the pH of the mixed solution to be 11, controlling the reaction temperature to be 65 ℃, the stirring speed to be 200r/min, stirring for 18h, filtering, washing and drying precipitates obtained by reaction in sequence to obtain a precursor Ni0.8Co0.1Mn0.1(OH)2；
(2) Mixing Ni0.8Co0.1Mn0.1(OH)2Mixing and ball-milling the precursor and lithium hydroxide, wherein the proportion of lithium is Li/(Ni + Co + Mn) is 1.08, heating the mixture to 1000 ℃ at the heating rate of 8 ℃/min under the oxygen atmosphere, and keeping the temperature for 12h to prepare a calcined product;
(3) and mixing and ball-milling the primary sintered product, niobium oxide and lithium hydroxide, wherein the addition amount of the niobium oxide is 2.5 wt%, and the addition amount of the lithium hydroxide is 2.5 wt%, heating to 850 ℃ at the heating rate of 13 ℃/min in the oxygen atmosphere, and keeping the temperature for 5h to prepare the single crystal ternary cathode material.
Example 6
The embodiment provides a preparation method of a single crystal ternary cathode material, which specifically comprises the following steps:
(1) preparing nickel chloride, cobalt nitrate and manganese chloride into a mixed salt solution with the concentration of 3mol/L according to the stoichiometric ratio, and simultaneously preparing a 6mol/L sodium hydroxide solution and a 20 wt% ammonia water solution; simultaneously adding the mixed salt solution, the sodium hydroxide solution and the ammonia water solution into a stirrer according to the volume ratio of 3:6:3, controlling the pH of the mixed solution to be 13, controlling the reaction temperature to be 80 ℃, the stirring speed to be 100r/min, stirring for 20h, filtering, washing and drying precipitates obtained by reaction in sequence to obtain a precursor Ni0.55Co0.12Mn0.33(OH)2；
(2) Mixing Ni0.55Co0.12Mn0.33(OH)2Mixing and ball-milling the precursor and lithium sulfate, wherein the proportion of lithium Li/(Ni + Co + Mn) is 1.1, heating the mixture to 1100 ℃ at the heating rate of 10 ℃/min in the oxygen atmosphere, and keeping the temperature for 7h to prepare a calcined product;
(3) and (3) mixing and ball-milling the primary sintered product, niobium oxide and lithium sulfate, wherein the addition amount of niobium oxide is 3 wt%, the addition amount of lithium sulfate is 3 wt%, heating to 900 ℃ at the heating rate of 15 ℃/min in the oxygen atmosphere, and keeping the temperature for 2h to prepare the single crystal ternary cathode material.
Example 7
The embodiment provides a preparation method of a single-crystal ternary cathode material, which is different from the preparation method of the embodiment 1 in that: the heating temperature in the step (3) is 550 ℃, and other operation steps and process parameters are completely the same as those in the step (1).
Example 8
The embodiment provides a preparation method of a single-crystal ternary cathode material, which is different from the preparation method of the embodiment 1 in that: the heating temperature in the step (3) is 950 ℃, and other operation steps and process parameters are completely the same as those in the step (1).
Comparative example 1
The comparative example provides a preparation method of a single crystal ternary cathode material, which is different from the preparation method of example 1 in that: the addition amount of the cobalt oxide in the step (3) is 0.005 wt%, and other operation steps and process parameters are completely the same as those in the step 1.
Comparative example 2
The comparative example provides a preparation method of a single crystal ternary cathode material, which is different from the preparation method of example 1 in that: the niobium oxide was added in an amount of 3.5 wt% in step (3), and the other operation steps and process parameters were exactly the same as in the above 1.
The surface residual alkali content of the single crystal ternary cathode materials prepared in examples 1 to 8 and comparative examples 1 to 2 was measured, and the measurement results are shown in table 1 below.
The single crystal ternary positive electrode materials prepared in the examples 1-8 and the comparative examples 1-2 are assembled into the button cell, and the assembling method of the button cell comprises the following steps: adopting EC/DMC electrolyte, mixing the lithium hexafluorophosphate with the content of 1.0mol/L, mixing the positive electrode material with SP (carbon black conductive agent), CNT (carbon nano tube) and PVDF (polyvinylidene fluoride), wherein the mass ratio of the positive electrode material to the SP, the CNT and the PVDF is 90:4.5:0.5:5, pulping and stirring for 6 hours by using NMP (N-methyl pyrrolidone) as a solvent, and assembling to obtain the button cell.
The electrochemical performance of the button cell prepared in the above way is tested under the conditions that the charging voltage is 3.0-4.3V and the current is 0.1C, the DCIR value is the internal resistance value of the cell measured by normal-temperature pulse 5C discharge for 10s under 50% SOC, and the test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the conductive coating agent is introduced in the process of the second sintering, so that the conductivity of the material can be effectively improved, and the residual alkali can be effectively reduced, and the comparison of comparative examples 1 and 2 and example 1 shows that the conductive coating agent reduces the DCIR value of the battery from 200 omega to within 100 omega, reduces the residual lithium carbonate of the material from 2700ppm to 1600ppm, and reduces the residual lithium hydroxide from 3000ppm to 2000 ppm.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The preparation method of the single crystal ternary cathode material is characterized by comprising the following steps of:
mixing the ternary precursor and a lithium source, and sintering for the first time to obtain a primary sintered product;
and mixing the primary sintered product, the conductive agent and the lithium source, and then sintering the mixture for the second time to obtain the single crystal ternary cathode material.
2. The method according to claim 1, wherein the mass fraction of the conductive agent is 0.01 to 3 wt% and the mass fraction of the lithium source is 0 to 5 wt% and is not 0 wt% based on 100 wt% of the mass fractions of the primary sintered product, the conductive agent, and the lithium source in the secondary sintering process.
3. The method according to claim 1 or 2, wherein the ternary precursor and the lithium source are mixed in a molar ratio of Li/(Ni + Co + Mn) of 1 (1.0-1.1);
preferably, the lithium source comprises one or a combination of at least two of lithium hydroxide, lithium carbonate, lithium chloride, lithium nitrate or lithium sulfate.
4. The method according to any one of claims 1 to 3, wherein the temperature rise rate of the primary sintering is 2 to 10 ℃/min;
preferably, the heating temperature of the primary sintering is 800-1100 ℃;
preferably, the heat preservation time of the primary sintering is 7-30 h.
5. A method according to any one of claims 1 to 4, wherein the conductive agent comprises one or a combination of at least two of cobalt hydroxide, cobalt oxide, niobium oxide, zirconium oxide, cerium oxide, lanthanum oxide, strontium oxide or yttrium oxide, preferably cobalt oxide, niobium oxide, zirconium oxide or lanthanum oxide;
preferably, the temperature rise rate of the secondary sintering is 4-15 ℃/min;
preferably, the secondary sintering is performed in an oxygen atmosphere;
preferably, the heating temperature of the secondary sintering is 600-900 ℃;
preferably, the heat preservation time of the secondary sintering is 2-15 h.
6. The method according to any one of claims 1 to 5, wherein the method for preparing the ternary precursor comprises:
preparing a mixed salt solution according to a stoichiometric ratio, mixing the mixed salt solution, an ammonia water solution and a sodium hydroxide solution for reaction to obtain a precipitate, and washing and drying the precipitate to obtain the ternary precursor;
preferably, the molar concentration of metal ions in the mixed salt solution is 1-4 mol/L;
preferably, the molar concentration of the sodium hydroxide solution is 2-6 mol/L;
preferably, the mass concentration of the ammonia water solution is 5-20 wt%;
preferably, the volume ratio of the mixed salt solution to the sodium hydroxide solution to the ammonia water solution is (1-3) to (2-6) to (0.2-3);
preferably, the mixed salt solution, the ammonia water solution and the sodium hydroxide solution are mixed and then the pH value is adjusted to 8-13;
preferably, the reaction temperature is 50-80 ℃;
preferably, the stirring speed in the reaction process is 100-600 r/min;
preferably, the reaction time is 10-20 h;
preferably, D50 of the ternary precursor is 3-10 μm.
7. The single crystal ternary cathode material prepared by the method of any one of claims 1 to 6, wherein the single crystal ternary cathode material comprises single crystal ternary cathode particles and a conductive layer coated on the surfaces of the single crystal ternary cathode particles.
8. A single crystal ternary cathode material according to claim 7, wherein the thickness of the conductive layer is 10 to 500 nm.
9. The single crystal ternary cathode material according to claim 7 or 8, wherein the single crystal ternary cathode material is a high nickel ternary cathode material;
preferably, the nickel content of the high-nickel ternary cathode material is more than or equal to 80 wt%.
10. A battery comprising a positive electrode, a negative electrode and a separator, wherein the single crystal ternary positive electrode material according to any one of claims 7 to 9 is used in the positive electrode.
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