CN114715956B - Modified porous nickel-rich positive electrode material and preparation method thereof - Google Patents
Modified porous nickel-rich positive electrode material and preparation method thereof Download PDFInfo
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- CN114715956B CN114715956B CN202210474992.6A CN202210474992A CN114715956B CN 114715956 B CN114715956 B CN 114715956B CN 202210474992 A CN202210474992 A CN 202210474992A CN 114715956 B CN114715956 B CN 114715956B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 233
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 111
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims description 12
- 239000000463 material Substances 0.000 claims abstract description 37
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 34
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- 239000011572 manganese Substances 0.000 claims abstract description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 16
- 239000010941 cobalt Substances 0.000 claims abstract description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 239000008139 complexing agent Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000010405 anode material Substances 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 239000012716 precipitator Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 239000010406 cathode material Substances 0.000 claims description 36
- 239000011247 coating layer Substances 0.000 claims description 22
- 238000005245 sintering Methods 0.000 claims description 22
- 239000011148 porous material Substances 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 19
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 14
- 239000012798 spherical particle Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 7
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229910017698 Ni 1-x-y Co Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 3
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 229940071257 lithium acetate Drugs 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229940008015 lithium carbonate Drugs 0.000 claims description 3
- 229940006114 lithium hydroxide anhydrous Drugs 0.000 claims description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 3
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011236 particulate material Substances 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 6
- 238000001354 calcination Methods 0.000 abstract description 5
- 238000001125 extrusion Methods 0.000 abstract description 5
- 239000011164 primary particle Substances 0.000 abstract description 5
- 238000005253 cladding Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 23
- 239000013078 crystal Substances 0.000 description 11
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229910013716 LiNi Inorganic materials 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- -1 cerium ions Chemical class 0.000 description 2
- ONLCZUHLGCEKRZ-UHFFFAOYSA-N cerium(3+) lanthanum(3+) oxygen(2-) Chemical compound [O--].[O--].[O--].[La+3].[Ce+3] ONLCZUHLGCEKRZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical group [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- 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
- H01M4/52—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present disclosure relates to a modified porous nickel-rich positive electrode material and a method for preparing the same, the method comprising: (1) The nickel source, the cobalt source, the manganese source, the precipitator and the complexing agent are contacted and mixed in a solvent, nitrogen is introduced into the mixed solution for stirring reaction, and a porous precursor is separated from a reaction product; the flow rate of the nitrogen is 300-500 mL/min; (2) Mixing a lithium source with the porous precursor and performing first heat treatment to obtain a porous nickel-rich anode material; (3) And contacting a cerium source and a lanthanum source with the porous nickel-rich positive electrode material, and performing second heat treatment. The method of the present disclosure introduces high flow rates of N during synthesis of the positive electrode material precursor 2 A porous structure is introduced for the precursor and the positive electrode material, a buffer space is provided for mutual extrusion of primary particles, and a stress concentration area in the calcination process is reduced; rare earth elements cerium and lanthanum are adopted to carry out cladding doping co-modification on the nickel-rich positive electrode material, so that a lithium ion transmission channel is widened, and the rate capability of the material is improved.
Description
Technical Field
The present disclosure relates to the field of lithium ion battery materials, and in particular, to a modified porous nickel-rich positive electrode material and a preparation method thereof.
Background
With increasingly prominent environmental problems and energy crisis, lithium ion batteries are widely applied to portable electronic equipment and new energy electric vehicles as environmentally friendly and high-energy-density batteries, but the development of positive electrode materials of the lithium ion batteries is limited by the cycle stability and safety, and the problems are needed to be solved currently.
Disclosure of Invention
The invention aims to provide a modified porous nickel-rich positive electrode material and a preparation method thereof, and the method improves the structural stability and the rate capability of the material.
A first aspect of the present disclosure provides a method for preparing a modified porous nickel-rich cathode material, the method comprising the steps of:
(1) The nickel source, the cobalt source, the manganese source, the precipitator and the complexing agent are contacted and mixed in a solvent, nitrogen is introduced into the mixed solution for stirring reaction, and a porous precursor is separated from a reaction product; the flow rate of the nitrogen is 300-500 mL/min;
(2) Mixing a lithium source with the porous precursor and performing first heat treatment to obtain a porous nickel-rich anode material;
(3) And contacting a cerium source and a lanthanum source with the porous nickel-rich positive electrode material, and performing second heat treatment.
Optionally, in step (1), the molar ratio of the nickel source, the cobalt source and the manganese source is (0.8-0.85): (0.08-0.13): (0.05-0.1); the solvent is water, the precipitator and the complexing agent are respectively used in the form of aqueous solutions with the concentration of 2-4 mol/L and 2-6 mol/L, the precipitator is inorganic alkali, and the complexing agent is selected from ammonia water.
Optionally, in step (2), the molar ratio of the porous precursor to the lithium source, calculated as the total moles of nickel cobalt manganese elements, is 1: (1-1.1), wherein the molar ratio of the cerium source, the lanthanum source and the porous nickel-rich positive electrode material calculated by the total mole number of nickel, cobalt and manganese elements is (0.009-0.025): (0.001-0.005): (0.97-0.99).
Optionally, the nickel source is a soluble salt of nickel, and the nickel source includes one or more of nickel sulfate, nickel chloride and nickel nitrate; the cobalt source is soluble salt of cobalt, and comprises one or more of cobalt sulfate, cobalt chloride and cobalt nitrate; the manganese source is soluble salt of manganese, and comprises one or more of manganese sulfate, manganese chloride and manganese nitrate; the lithium source comprises one or more of lithium hydroxide monohydrate, lithium hydroxide anhydrous, lithium carbonate, lithium acetate, lithium oxalate, lithium oxide and lithium nitrate; the cerium source comprises cerium nitrate and/or cerium chloride; the lanthanum source includes lanthanum nitrate and/or lanthanum chloride.
Optionally, in the step (1), the nitrogen is introduced below the liquid level of the mixed solution, and the pH of the mixed solution is 10-13; the stirring speed is 600-650 rpm, the reaction temperature is 45-50 ℃ and the reaction time is 12-22 h.
Optionally, in step (2), the first heat treatment includes a first sintering and a second sintering, and the conditions of the first sintering include: the temperature is 400-600 ℃ and the time is 2-8 h; the conditions for the second sintering include: the temperature is 650-950 ℃ and the time is 6-16 h; the first heat treatment and the second heat treatment are both performed under a pure oxygen atmosphere.
Optionally, in the step (3), the cerium source and the lanthanum source are in contact and mixed with the porous nickel-rich cathode material in an organic solvent, and the obtained material is subjected to the second heat treatment after being dried; the organic solvent is ethanol; the conditions of the second heat treatment include: the temperature is 300-700 ℃ and the time is 4-10 h.
A second aspect of the present disclosure provides a modified porous nickel-rich cathode material prepared by the preparation method according to the first aspect of the present disclosure, wherein the pore volume of pores with the pore diameter ranging from 0.1 μm to 3 μm of the modified porous nickel-rich cathode material is 0.4 cm to 0.8cm 3 And/g, wherein the surface of the modified porous nickel-rich positive electrode material comprises cerium element and lanthanum element.
Optionally, the chemical formula of the modified porous nickel-rich positive electrode material is shown as formula (I): li (Li) a (Ni 1-x-y Co x Mn y ) 1- b M b O 2 Wherein a is more than or equal to 1.0 and less than or equal to 1.1,0.08, x is more than or equal to 0.13,0.05 and y is more than or equal to 0.1,0.8 and less than or equal to 1-x-y is more than or equal to 0.85,0.01 and b is more than or equal to 0.03, and M comprises cerium element and lanthanum element.
Optionally, the modified porous nickel-rich positive electrode material is a particle material, preferably spherical particles or spheroid particles, the particle size of the particle material is 5-20 μm, the modified porous nickel-rich positive electrode material comprises an internal porous nickel-rich positive electrode material and a coating layer coated on the porous nickel-rich positive electrode material, the coating layer contains cerium element and lanthanum element, and the thickness of the coating layer is 2-7 nm.
Through the technical scheme, the disclosure provides a preparation method of a modified porous nickel-rich positive electrode material, which is characterized in that high-flow-rate N is introduced during synthesis of a positive electrode material precursor 2 The porous structure is introduced into the positive electrode material, and in the calcining and circulating processes, the porous structure provides a buffer space for the mutual extrusion of primary particles, so that the stress concentration area in the calcining process is reduced, the generation of microcracks and phase changes of the material after long-time charge and discharge circulation is inhibited, and the structural stability of the material and the rate capability of a battery are improved; meanwhile, rare earth elements Ce and La are introduced into the method to carry out cladding doping co-modification on the nickel-rich positive electrode material, so that Li is reduced + /Ni 2+ Is arranged in a mixed row; the material has a better layered structure in the charge and discharge process, widens the transmission channel of lithium ions, and improves the multiplying power performance of the material; and a cerium lanthanum oxide coating layer is formed on the surface of the material, so that the electrode can be protected from being corroded by electrolyte.
Additional features and advantages of the present disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the disclosure, and are incorporated in and constitute a part of this specification, illustrate the disclosure and together with the description serve to explain, but do not limit the disclosure. In the drawings:
FIG. 1 is a graph showing pore size distribution of a modified porous nickel-rich cathode material 1 prepared in example 1 and a comparative material 1 prepared in comparative example 1 of the present disclosure;
FIG. 2 is an XRD pattern of a modified porous nickel-rich cathode material 1 prepared in example 1 of the present disclosure and a comparative material 1 prepared in comparative example 1;
FIG. 3 is a scanning electron microscope image of a modified porous nickel-rich cathode material 1 prepared in example 1 of the present disclosure;
FIG. 4 is a transmission electron microscope image of a modified porous nickel-rich cathode material 1 prepared in example 1 of the present disclosure;
FIG. 5 is a scanning electron microscope image of comparative material 1 prepared in comparative example 1 of the present disclosure;
FIG. 6 is a graph of the rate performance of the modified porous nickel-rich cathode material 1 prepared in example 1 of the present disclosure versus the comparative material 1 prepared in comparative example 1;
fig. 7 is a graph of cycle performance of the modified porous nickel-rich cathode material 1 prepared in example 1 of the present disclosure and the comparative material 1 prepared in comparative example 1.
Detailed Description
Specific embodiments of the present disclosure are described in detail below with reference to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure.
A first aspect of the present disclosure provides a method for preparing a modified porous nickel-rich cathode material, the method comprising the steps of:
(1) The nickel source, the cobalt source, the manganese source, the precipitator and the complexing agent are contacted and mixed in a solvent, nitrogen is introduced into the mixed solution for stirring reaction, and a porous precursor is separated from a reaction product; the flow rate of the nitrogen is 300-500 mL/min;
(2) Mixing a lithium source with the porous precursor and performing first heat treatment to obtain a porous nickel-rich anode material;
(3) And contacting a cerium source and a lanthanum source with the porous nickel-rich positive electrode material, and performing second heat treatment.
In the above embodiments, the present disclosure introduces high flow rates of N in synthesizing the positive electrode material precursor 2 A porous structure is introduced into the nickel-rich positive electrode material, the porous structure provides a buffer space for mutual extrusion among primary particles, a stress concentration area in the calcination process is reduced, microcracks and phase changes of the material after long-time charge-discharge circulation are inhibited, and the structural stability of the material is improved; meanwhile, the present disclosure adopts rare earth elements cerium and lanthanum to make nickel-rich positiveCoating doping co-modification is carried out on the electrode material, and Li is reduced + /Ni 2+ The mixed discharge of the lithium ion battery can ensure that the material maintains a better layered structure in the charge and discharge process, widens the transmission channel of lithium ions, improves the rate capability of the battery, and protects the electrode from being corroded by electrolyte.
In one embodiment of the present disclosure, in step (1), the molar ratio of the nickel source, cobalt source and manganese source is (0.8 to 0.85): (0.08-0.13): (0.05 to 0.1), preferably (0.8 to 0.83): (0.09-0.12): (0.05-0.08); the solvent is water, the precipitant and the complexing agent are respectively used in the form of aqueous solutions with the concentration of 2-4 mol/L and 2-6 mol/L, the precipitant is inorganic alkali, such as sodium hydroxide and potassium hydroxide, and the complexing agent is selected from ammonia water.
In one embodiment of the present disclosure, in step (2), the molar ratio of the porous precursor to the lithium source, based on the total moles of nickel cobalt manganese elements, is 1: (1 to 1.1), preferably 1: (1.01-1.05); the molar ratio of the cerium source, the lanthanum source and the porous nickel-rich positive electrode material calculated by the total mole number of nickel, cobalt and manganese elements is (0.009-0.025): (0.001-0.005): (0.97 to 0.99), preferably (0.012 to 0.02): (0.003-0.005): (0.975-0.985). In the above embodiment, the reaction is performed by selecting the raw materials in the preferable ratio, which is advantageous to improve the stability of the porous nickel-rich cathode material.
In one embodiment of the present disclosure, the nickel source is a soluble salt of nickel, the nickel source including one or more of nickel sulfate, nickel chloride, and nickel nitrate; the cobalt source is soluble salt of cobalt, and comprises one or more of cobalt sulfate, cobalt chloride and cobalt nitrate; the manganese source is soluble salt of manganese, and comprises one or more of manganese sulfate, manganese chloride and manganese nitrate; the lithium source comprises one or more of lithium hydroxide monohydrate, lithium hydroxide anhydrous, lithium carbonate, lithium acetate, lithium oxalate, lithium oxide and lithium nitrate; the cerium source comprises cerium nitrate and/or cerium chloride; the lanthanum source includes lanthanum nitrate and/or lanthanum chloride. In the above embodiment, by selecting a preferred lithium source, cerium source and lanthanum source, a coating layer containing cerium oxide and lanthanum oxide can be formed on the surface of the porous nickel-rich cathode material, so that the electrode can be protected from corrosion by the electrolyte.
In one embodiment of the disclosure, in the step (1), the nitrogen is introduced below the liquid surface of the mixed solution, and the pH of the mixed solution is 10-13; the stirring speed is 600-650 rpm, the reaction temperature is 45-50 ℃ and the reaction time is 12-22 h. In a preferred embodiment, the porous precursor is separated in step (1) by vacuum filtration, the separated porous precursor is washed with deionized water, and dried in a vacuum oven at 80 ℃ for 10 hours. In the embodiment, the bubbling effect of the nitrogen can be enhanced by introducing the nitrogen below the liquid level of the mixed liquid, the porosity of the porous precursor is improved, and more buffer space is provided for mutual extrusion of primary particles; by selecting the preferable stirring treatment and reaction time, the raw materials can be fully dispersed and reacted, and the introduction of the porous structure is facilitated.
In one embodiment of the present disclosure, in step (2), the first heat treatment includes a first sintering and a second sintering, and conditions of the first sintering include: the temperature is 400-600 ℃, preferably 450-550 ℃ and the time is 2-8 h; the conditions for the second sintering include: the temperature is 650-950 ℃, preferably 750-850 ℃ and the time is 6-16 h; the first heat treatment and the second heat treatment are both performed under a pure oxygen atmosphere. In the above embodiment, the preferred sectional sintering is selected to perform the first heat treatment, so that the lithium source is continuously diffused into the porous precursor to form the porous nickel-rich positive electrode material with relatively stable thermodynamics, and the cycle performance and the rate capability of the porous nickel-rich positive electrode material are improved.
In one embodiment of the present disclosure, in step (3), the cerium source and the lanthanum source are mixed in contact with the porous nickel-rich cathode material in an organic solvent, and the resultant material is subjected to the second heat treatment after being dried; the organic solvent is ethanol; the conditions of the second heat treatment include: the temperature is 300-700 ℃ and the time is 4-10 h; in a preferred embodiment, the porous nickel-rich cathode material is mixed with the cerium source and the lanthanum source after being crushed and sieved. In the above embodiment, by selecting the preferred second heat treatment, rare earth elements cerium and lanthanum are doped and coated on the surface of the porous nickel-rich cathode material, cerium ions and lanthanum ions after doping and coating form longer Ce-O and La-O bonds, the transmission channel of lithium ions is widened, and the rate capability of the battery is improved.
A second aspect of the present disclosure provides a modified porous nickel-rich cathode material prepared by the preparation method according to the first aspect of the present disclosure, wherein the pore volume of pores with the pore diameter ranging from 0.1 μm to 3 μm of the modified porous nickel-rich cathode material is 0.4 cm to 0.8cm 3 /g; the surface of the modified porous nickel-rich positive electrode material contains cerium element and lanthanum element.
The porous modified nickel-rich positive electrode material provided by the disclosure has a rich porous structure, provides a buffer space for mutual extrusion of primary particles in the calcining and circulating processes, inhibits generation of microcracks and phase changes of the material, and improves structural stability of the material; rare earth elements Ce and La are introduced to carry out cladding doping co-modification on the porous nickel-rich positive electrode material, so that Li is reduced + /Ni 2+ Effectively preventing structural degradation and phase change and improving the safety of the material.
In one embodiment of the present disclosure, the modified porous nickel-rich positive electrode material has a chemical formula as shown in formula (i): li (Li) a (Ni 1-x-y Co x Mn y ) 1-b M b O 2 Wherein a is more than or equal to 1.0 and less than or equal to 1.1,0.08, x is more than or equal to 0.13,0.05 and y is more than or equal to 0.1,0.8 and less than or equal to 1-x-y is more than or equal to 0.85,0.01 and b is more than or equal to 0.03, and M comprises cerium element and lanthanum element.
In one embodiment of the present disclosure, the modified porous nickel-rich cathode material is a particulate material, such as spherical particles or spheroidal particles, having a particle size of 5 to 20 μm; the modified porous nickel-rich positive electrode material comprises an internal porous nickel-rich positive electrode material and a coating layer coated on the porous nickel-rich positive electrode material, wherein the coating layer contains cerium element and lanthanum element, and the thickness of the coating layer is 2-7 nm. In the above embodiment, the surface of the modified porous nickel-rich cathode material is a coating layer containing cerium oxide and lanthanum oxide, so that the electrode can be protected from corrosion by the electrolyte.
The present disclosure is further illustrated by the following examples, but the present disclosure is not limited thereby.
In the following examples, all materials used, unless otherwise specified, were commercially available products.
In the following examples, specific test methods are as follows:
the thickness of the coating layer is tested by a transmission electron microscope, and the model of the instrument is FEI Tecnai G-20;
the testing method of the average pore diameter is a mercury porosimeter, and the instrument model is Kang Da porosimter;
the particle size and SEM test method is a scanning electron microscope, and the instrument model is Hitachi SU8000;
the XRD testing method is an X-ray diffractometer, and the instrument model is an X' Pert PRO powder X-ray diffractometer of PANalytical company;
the electrochemical cycle performance test method is a blue electric test system, and the instrument model is CT3001A.
Example 1
(1) According to Ni: co: mn=0.82: 0.10:0.08 molar ratio of accurately weighing NiSO 4 Crystals, coSO 4 Crystal and MnSO 4 The crystal is dissolved in deionized water, the concentration of the prepared feed liquid is 2mol/L, 2mol/L NaOH solution and ammonia water are respectively prepared as a precipitator and a complexing agent, the solutions are added into a continuously stirred reaction tank, and the reaction temperature is controlled at 48 ℃; n (N) 2 The flow rate is 320mL/min, N is added 2 Introducing the mixture below the surface of the liquid, continuously generating bubbles, stirring at 600rpm, keeping the pH value at about 11, and continuously reacting for 22 hours; separating precipitate by vacuum filtration, washing with deionized water, and drying in a vacuum oven at 80deg.C for 10 hr to obtain porous precursor Ni 0.82 Co 0.1 Mn 0.08 (OH) 2 ；
(2) According to (ni+co+mn): li=1: 1.02 molar ratio of accurately weighing Ni 0.82 Co 0.1 Mn 0.08 (OH) 2 And LiOH.H 2 O, uniformly mixing the two, and performing first heat treatment in pure oxygen atmosphere: the first sintering is carried out for 5h at 520 ℃, and then the temperature is raised to 78 DEGPerforming second sintering at 0 ℃ for 10 hours, cooling to room temperature, crushing and sieving to obtain the porous nickel-rich anode material Li 1.02 Ni 0.82 Co 0.1 Mn 0.08 O 2 ；
(3) According to Ce: la: (ni+co+mn) =0.017: 0.003:0.98 molar ratio of cerium nitrate crystal, lanthanum nitrate crystal and Li 1.02 Ni 0.82 Co 0.1 Mn 0.08 O 2 Dissolving cerium nitrate crystals and lanthanum nitrate crystals in ethanol, uniformly mixing the solution with the weighed porous nickel-rich cathode material, drying in a vacuum oven at 80 ℃ for 3 hours, and performing second heat treatment in pure oxygen atmosphere: sintering at 600 ℃ for 6 hours, sieving to obtain the modified porous nickel-rich anode material 1, wherein the chemical structural formula of the modified porous nickel-rich anode material is LiNi 0.804 Co 0.098 Mn 0.078 Ce 0.017 La 0.003 O 2 Spherical particles with the particle size of 8-12 mu m, a porous nickel-rich positive electrode material inside, and a coating layer containing cerium element and lanthanum element on the surface, wherein the thickness of the coating layer is 5.6nm, and the results of pore distribution, XRD, SEM and TEM tests are shown in figures 1-4.
As can be seen from FIG. 1, the modified porous nickel-rich cathode material has significantly increased pores in the range of 0.1-3 μm, indicating the introduction of a porous structure in which the pore volume of pores having a pore diameter in the range of 0.1-3 μm is 0.56cm 3 And/g, the generation of microcracks and phase change of the material is favorably inhibited, and the structural stability of the material is improved;
as can be seen from FIG. 2, after the rare earth elements cerium and lanthanum are introduced into the porous nickel-rich cathode material, obvious diffraction peaks of cerium oxide and lanthanum oxide appear in the product, and other diffraction peaks still correspond to alpha-NaFeO 2 The R-3m space group of the structure shows that the coated material keeps a good layered structure, and simultaneously shows that cerium and lanthanum are successfully coated on the porous nickel-rich positive electrode material, and stable cerium oxide and lanthanum oxide are formed in the preparation process, so that the consumption and loss of lithium ions can be reduced in the circulation process, and the rate capability and the circulation stability of a battery made of the material are improved;
as can be seen from fig. 3, the modified porous nickel-rich cathode material prepared in example 1 is spherical particles with a particle size of 8-12 μm;
as can be seen from fig. 4, the modified porous nickel-rich cathode material prepared in example 1 includes an internal porous nickel-rich cathode material and a coating layer coated on the porous nickel-rich cathode material, wherein the surface coating layer includes lanthanum cerium oxide and lanthanum oxide, which can protect the electrode from corrosion of the electrolyte, thereby improving the rate performance and cycle stability of the battery.
Example 2
The procedure of example 1 was used, with the only difference that: n (N) 2 The flow rate is 420mL/min, and the modified porous nickel-rich positive electrode material 2 is obtained, and the chemical structural formula of the modified porous nickel-rich positive electrode material is LiNi 0.804 Co 0.098 Mn 0.078 Ce 0.017 La 0.003 O 2 Spherical particles with the particle diameter of 7-13 mu m and the thickness of the coating layer of 3-7 nm.
Example 3
The procedure of example 1 was used, with the only difference that: according to Ce: la: (ni+co+mn) =0.007: 0.006:0.987, and accurately weighing cerium nitrate crystal, lanthanum nitrate crystal and Li 1.02 Ni 0.82 Co 0.1 Mn 0.08 O 2 Obtaining the modified porous nickel-rich positive electrode material 3, the chemical structural formula of which is Li 1.007 Ni 0.809 Co 0.099 Mn 0.079 Ce 0.007 La 0.006 O 2 Spherical particles with the particle diameter of 8-13 mu m and the thickness of the coating layer of 2-7 nm.
Example 4
The procedure of example 1 was used, with the only difference that: the first heat treatment of step (2) includes: sintering for 5h at 580 ℃, then heating to 730 ℃ and sintering for 10h to obtain the modified porous nickel-rich anode material 4, wherein the chemical structural formula of the modified porous nickel-rich anode material is LiNi 0.804 Co 0.09 8 Mn 0.078 Ce 0.017 La 0.003 O 2 Spherical particles with the particle diameter of 6-11 mu m and the thickness of the coating layer of 2-6 nm.
Example 5
The procedure of example 1 was used, with the only difference that: step (2) adopts a one-step sintering method, and the temperature is raised to 780 ℃ for sintering for 10 hours, thus obtaining the modifiedThe chemical structural formula of the porous nickel-rich positive electrode material 5 is LiNi 0.804 Co 0.098 Mn 0.078 Ce 0.017 La 0.003 O 2 Spherical particles with the particle diameter of 7-12 mu m and the thickness of the coating layer of 3-7 nm.
Comparative example 1
The procedure of example 1 was used, with the only difference that: n (N) 2 The flow rate is 80mL/min, cerium nitrate crystals and lanthanum nitrate crystals are not introduced, and Li obtained in the step (2) is obtained 1.02 Ni 0.82 Co 0.1 Mn 0.08 O 2 Namely, a comparative material 1, which is in the shape of spherical particles with a particle diameter of 7-13 μm, was subjected to pore distribution, XRD and SEM tests, and the results are shown in FIG. 1, FIG. 2 and FIG. 5;
as can be seen from FIG. 1, the pore volume of the pores having a pore diameter in the range of 0.1 to 3 μm is 0.21cm 3 /g, significantly lower than the pore volume of example 1, indicating that example 1 incorporates a porous structure;
as can be seen from FIG. 2, all diffraction peaks of comparative example 1 correspond to alpha-NaFeO 2 R-3m space group of the structure shows that the material has a good lamellar structure;
as can be seen from FIG. 5, the comparative material 1 prepared in comparative example 1 was spherical particles having a particle diameter of 7 to 13. Mu.m.
Comparative example 2
The procedure of example 1 was used, with the only difference that: n (N) 2 The flow rate is 80mL/min, and the comparative material 2 is obtained, and the chemical structural formula of the comparative material is LiNi 0.804 Co 0.098 Mn 0.078 Ce 0.017 La 0.003 O 2 Spherical particles with the particle diameter of 8-13 mu m and the thickness of the coating layer of 2-6 nm.
Comparative example 3
The procedure of example 1 was used, with the only difference that: n (N) 2 The flow rate is 600mL/min, and the comparative material 3 is obtained, and the chemical structural formula of the comparative material is LiNi 0.804 Co 0.098 Mn 0.078 Ce 0.017 La 0.003 O 2 Spherical particles with the particle diameter of 8-14 mu m and the thickness of the coating layer of 2-8 nm.
Test case
The electrochemical performance test was as follows: the materials prepared by the examples and the comparative examples, the conductive agent acetylene black and the binder PVDF are mixed according to the mass ratio of 90:5:5, adding NMP (N-methyl-pyrrolidone) and fully and uniformly mixing to obtain slurry with certain viscosity; uniformly coating the obtained slurry on an aluminum foil, drying for 2 hours at the temperature of 90 ℃ by air blast, tabletting the aluminum foil by a tabletting machine after the drying is completed, punching the tabletting pole piece into a circular electrode piece with the diameter of 14mm, and drying for 2 hours at the temperature of 120 ℃ in a vacuum drying oven; in a glove box protected by argon, a Celgard 2400 membrane is taken as a diaphragm, a metal lithium sheet is taken as a cathode, and 1mol L -1 LiPF6/ec+dec+dmc (volume ratio 1:1:1) as electrolyte, and assembled into a coin cell. And (3) carrying out charge and discharge test on the assembled battery above a blue electric test, wherein the temperature is 25+/-1 ℃, and the test voltage range is 3.0-4.3V.
Test results show that the modified porous nickel-rich positive electrode material prepared by the preparation method of the examples 1-5 has higher discharge specific capacity of 5.0C and better capacity retention rate after 100 cycles under the condition of 1.0C; comparative examples 1 to 3, which did not employ the preparation method of the present disclosure, yielded positive electrode materials having a lower capacity retention after 100 cycles at 1.0C; comparison shows that the modified porous nickel-rich positive electrode materials prepared by the methods disclosed in examples 1-5 have better cycle stability and higher rate capability.
As can be seen from a comparison of the data of example 1 and example 3, the molar ratio of the cerium source, the lanthanum source, and the porous nickel-rich cathode material of example 1, calculated on the total mole number of nickel cobalt manganese elements, which are preferred in the present disclosure, is (0.009-0.025): (0.001-0.005): in the embodiment of (0.97-0.99), the prepared modified porous nickel-rich positive electrode material has higher initial discharge specific capacity and better multiplying power performance; as can be seen from a comparison of the data in example 1 and example 5, in example 1, when the preferred first heat treatment of the present disclosure includes the first sintering and the second sintering, the modified porous nickel-rich positive electrode material has better structural stability, better capacity retention after 100 cycles, and better cycle stability.
The preferred embodiments of the present disclosure have been described in detail above with reference to the accompanying drawings, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the foregoing embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present disclosure does not further describe various possible combinations.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.
Claims (11)
1. The preparation method of the modified porous nickel-rich cathode material is characterized by comprising the following steps of:
(1) The nickel source, the cobalt source, the manganese source, the precipitator and the complexing agent are contacted and mixed in a solvent, nitrogen is introduced into the mixed solution for stirring reaction, and a porous precursor is separated from a reaction product; the nitrogen is introduced below the liquid level of the mixed liquid, and the flow rate of the nitrogen is 300-500 mL/min;
(2) Mixing a lithium source with the porous precursor and performing first heat treatment to obtain a porous nickel-rich anode material;
(3) And contacting a cerium source and a lanthanum source with the porous nickel-rich positive electrode material, and performing second heat treatment.
2. The method according to claim 1, wherein in the step (1), the molar ratio of the nickel source, the cobalt source and the manganese source is (0.8 to 0.85): (0.08-0.13): (0.05-0.1); the solvent is water, the precipitator and the complexing agent are respectively used in the form of aqueous solutions with the concentration of 2-4 mol/L and 2-6 mol/L, the precipitator is inorganic alkali, and the complexing agent is selected from ammonia water.
3. The method according to claim 1, wherein in the step (2), the molar ratio of the porous precursor to the lithium source, in terms of the total mole number of nickel cobalt manganese elements, is 1: (1-1.1), wherein the molar ratio of the cerium source, the lanthanum source and the porous nickel-rich positive electrode material calculated by the total mole number of nickel, cobalt and manganese elements is (0.009-0.025): (0.001-0.005): (0.97-0.99).
4. The method of claim 1, wherein the nickel source is a soluble salt of nickel, and the nickel source comprises one or more of nickel sulfate, nickel chloride, and nickel nitrate; the cobalt source is soluble salt of cobalt, and comprises one or more of cobalt sulfate, cobalt chloride and cobalt nitrate; the manganese source is soluble salt of manganese, and comprises one or more of manganese sulfate, manganese chloride and manganese nitrate; the lithium source comprises one or more of lithium hydroxide monohydrate, lithium hydroxide anhydrous, lithium carbonate, lithium acetate, lithium oxalate, lithium oxide and lithium nitrate; the cerium source comprises cerium nitrate and/or cerium chloride; the lanthanum source includes lanthanum nitrate and/or lanthanum chloride.
5. The method according to claim 1, wherein in the step (1), the pH of the mixed solution is 10 to 13; the stirring speed is 600-650 rpm, the reaction temperature is 45-50 ℃ and the reaction time is 12-22 h.
6. The method of claim 1, wherein in step (2), the first heat treatment comprises a first sintering and a second sintering, and the conditions of the first sintering comprise: the temperature is 400-600 ℃ and the time is 2-8 h; the conditions for the second sintering include: the temperature is 650-950 ℃ and the time is 6-16 h; the first heat treatment and the second heat treatment are both performed under a pure oxygen atmosphere.
7. The method according to claim 1, wherein in step (3), the cerium source and the lanthanum source are mixed in an organic solvent in contact with the porous nickel-rich cathode material, and the resultant material is subjected to the second heat treatment after being dried; the organic solvent is ethanol;
the conditions of the second heat treatment include: the temperature is 300-700 ℃ and the time is 4-10 h.
8. The modified porous nickel-rich positive electrode material prepared by the preparation method according to any one of claims 1 to 7, wherein the pore volume of pores with the pore diameter ranging from 0.1 μm to 3 μm of the modified porous nickel-rich positive electrode material is 0.4 cm to 0.8cm 3 /g; the surface of the modified porous nickel-rich positive electrode material contains cerium element and lanthanum element.
9. The modified porous nickel-rich cathode material according to claim 8, wherein the modified porous nickel-rich cathode material has a chemical formula shown in formula (i);
Li a (Ni 1-x-y Co x Mn y ) 1-b M b O 2 (Ⅰ)，
wherein a is more than or equal to 1.0 and less than or equal to 1.1,0.08, x is more than or equal to 0.13,0.05, y is more than or equal to 0.1,0.8 and less than or equal to 1-x-y is more than or equal to 0.85,0.01 and b is more than or equal to 0.03, and M comprises cerium element and lanthanum element.
10. The modified porous nickel-rich cathode material according to claim 8, wherein the modified porous nickel-rich cathode material is a particulate material having a particle size of 5-20 μm; the modified porous nickel-rich positive electrode material comprises an internal porous nickel-rich positive electrode material and a coating layer coated on the porous nickel-rich positive electrode material, wherein the coating layer contains cerium element and lanthanum element, and the thickness of the coating layer is 2-7 nm.
11. The modified porous nickel-rich cathode material of claim 10, wherein the modified porous nickel-rich cathode material is a spherical particle or a spheroid-like particle.
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