CN114715956A - Modified porous nickel-rich cathode material and preparation method thereof - Google Patents
Modified porous nickel-rich cathode material and preparation method thereof Download PDFInfo
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- CN114715956A CN114715956A CN202210474992.6A CN202210474992A CN114715956A CN 114715956 A CN114715956 A CN 114715956A CN 202210474992 A CN202210474992 A CN 202210474992A CN 114715956 A CN114715956 A CN 114715956A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 230
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 108
- 239000010406 cathode material Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 35
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 34
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011572 manganese Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 15
- 239000010941 cobalt Substances 0.000 claims abstract description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000008139 complexing agent Substances 0.000 claims abstract description 11
- 239000012716 precipitator Substances 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 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
- 239000011247 coating layer Substances 0.000 claims description 18
- 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
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 11
- 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
- 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
- 239000007788 liquid Substances 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
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000011236 particulate material Substances 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
- 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
- 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
- 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
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 14
- 238000000576 coating method Methods 0.000 abstract description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 239000010405 anode material Substances 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 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
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 150000002910 rare earth metals Chemical class 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 21
- 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 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 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
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000002994 raw material Substances 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
- 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
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910021311 NaFeO2 Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007664 blowing Methods 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
- 230000001351 cycling effect Effects 0.000 description 1
- 238000006731 degradation reaction 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
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 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
- 238000001000 micrograph Methods 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
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910006525 α-NaFeO2 Inorganic materials 0.000 description 1
- 229910006596 α−NaFeO2 Inorganic materials 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- 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
Abstract
The invention relates to a modified porous nickel-rich cathode material and a preparation method thereof, wherein the method comprises the following steps: (1) the method comprises the following steps of (1) enabling a nickel source, a cobalt source, a manganese source, a precipitator and a complexing agent to be in contact mixing in a solvent, introducing nitrogen into a mixed solution for stirring reaction, and separating a porous precursor 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 carrying out first heat treatment to obtain a porous nickel-rich cathode material; (3) and contacting a cerium source and a lanthanum source with the porous nickel-rich cathode material, and carrying out second heat treatment. The method disclosed by the invention is used for introducing high-flow-rate N during the synthesis of the precursor of the cathode material2A porous structure is introduced for the precursor and the anode material, a buffer space is provided for mutual extrusion of primary particles, and a stress concentration area in the calcining process is reduced; using rare earth elementsThe cerium and the lanthanum are used for coating, doping and co-modifying the nickel-rich anode material, so that the transmission channel of lithium ions is widened, and the rate capability of the material is improved.
Description
Technical Field
The disclosure relates to the field of lithium ion battery materials, in particular to a modified porous nickel-rich cathode material and a preparation method thereof.
Background
With increasingly outstanding environmental problems and energy crisis, lithium ion batteries have been widely used in portable electronic devices and new energy electric vehicles as environmentally friendly and high energy density batteries, but the development of lithium ion battery cathode materials is restricted by cycle stability and safety, which is a problem to be solved urgently.
Disclosure of Invention
The purpose of the disclosure is to provide a modified porous nickel-rich cathode material and a preparation method thereof, and the method improves the structural stability and rate capability of the material.
The first aspect of the present disclosure provides a preparation method of a modified porous nickel-rich cathode material, which includes the following steps:
(1) the method comprises the following steps of (1) enabling a nickel source, a cobalt source, a manganese source, a precipitator and a complexing agent to be in contact mixing in a solvent, introducing nitrogen into a mixed solution for stirring reaction, and separating a porous precursor 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 carrying out first heat treatment to obtain a porous nickel-rich cathode material;
(3) and contacting a cerium source and a lanthanum source with the porous nickel-rich cathode material, and carrying out second heat treatment.
Optionally, in the step (1), the molar ratio of the nickel source to the cobalt source to 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 used in the form of aqueous solutions with the concentration of 2-4 mol/L and 2-6 mol/L respectively, the precipitator is inorganic alkali, and the complexing agent is selected from ammonia water.
Optionally, in the 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: (1-1.1), the molar ratio of the cerium source, the lanthanum source and the porous nickel-rich cathode material based on the total molar number of nickel-cobalt-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, anhydrous lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate, lithium oxide and lithium nitrate; the cerium source comprises cerium nitrate and/or cerium chloride; the lanthanum source comprises 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 the 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 of 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 with and mixed with the porous nickel-rich cathode material in an organic solvent, and the obtained material is dried and then subjected to the second heat treatment; 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.
The 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, and the modified porous nickel-rich cathode materialThe pore volume of the pores of the electrode material with the pore diameter within the range of 0.1-3 μm is 0.4-0.8 cm3The surface of the modified porous nickel-rich cathode material comprises cerium and lanthanum.
Optionally, the chemical formula of the modified porous nickel-rich cathode material is shown as formula (I): lia(Ni1-x-yCoxMny)1- bMbO2(I), wherein a is more than or equal to 1.0 and less than or equal to 1.1, x is more than or equal to 0.08 and less than or equal to 0.13, y is more than or equal to 0.05 and less 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, b is more than or equal to 0.01 and less than or equal to 0.03, and M comprises cerium and lanthanum.
Optionally, the modified porous nickel-rich cathode material is a particle material, preferably spherical particles or spheroidal particles, the particle size of the particle material is 5-20 μm, the modified porous nickel-rich cathode material comprises an internal porous nickel-rich cathode material and a coating layer coated on the porous nickel-rich cathode material, the coating layer contains cerium and lanthanum, and the thickness of the coating layer is 2-7 nm.
By adopting the technical scheme, the invention provides a preparation method of a modified porous nickel-rich cathode material, and N with high flow rate is introduced into the method when a precursor of the cathode material is synthesized2A porous structure is introduced into the anode material, and in the calcining and circulating processes, the porous structure provides a buffer space for mutual extrusion of primary particles, so that a stress concentration area in the calcining process is reduced, the generation of microcracks and phase change of the material after long-time charge-discharge cycles 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 to carry out coating doping co-modification on the nickel-rich cathode material, so that Li is reduced+/Ni2+Mixed arrangement of (1); the material keeps a good layered structure in the charging and discharging processes, the transmission channel of lithium ions is widened, and the rate capability of the material is improved; and a cerium oxide lanthanum 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 disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:
fig. 1 is a pore size distribution plot of a modified porous nickel-rich cathode material 1 prepared in example 1 of the present disclosure versus a comparative material 1 prepared in comparative example 1;
fig. 2 is an XRD pattern 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;
fig. 3 is a scanning electron micrograph of the modified porous nickel-rich cathode material 1 prepared in example 1 of the present disclosure;
fig. 4 is a transmission electron microscope image of the modified porous nickel-rich cathode material 1 prepared in example 1 of the present disclosure;
FIG. 5 is a scanning electron micrograph of comparative material 1 prepared according to comparative example 1 of the present disclosure;
fig. 6 is a graph of 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 the cycle 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.
Detailed Description
The following detailed description of the embodiments of the disclosure refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The first aspect of the present disclosure provides a preparation method of a modified porous nickel-rich cathode material, including the following steps:
(1) the method comprises the following steps of (1) enabling a nickel source, a cobalt source, a manganese source, a precipitator and a complexing agent to be in contact mixing in a solvent, introducing nitrogen into a mixed solution for stirring reaction, and separating a porous precursor 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 carrying out first heat treatment to obtain a porous nickel-rich cathode material;
(3) and contacting a cerium source and a lanthanum source with the porous nickel-rich cathode material, and carrying out second heat treatment.
In the above embodiment, the present disclosure introduces N at a high flow rate when synthesizing the positive electrode material precursor2A porous structure is introduced into the nickel-rich anode material, the porous structure provides a buffer space for mutual extrusion of primary particles, a stress concentration area in the calcining process is reduced, the generation of microcracks and phase change of the material after long-time charge-discharge circulation is inhibited, and the structural stability of the material is improved; meanwhile, the rare earth elements cerium and lanthanum are adopted to carry out coating, doping and co-modification on the nickel-rich cathode material, so that Li is reduced+/Ni2+The mixed arrangement of the lithium ion battery lead the material to keep a better layered structure in the charging and discharging process, widen the transmission channel of lithium ions, improve the multiplying power performance of the battery and protect the electrode from being corroded by electrolyte.
In one embodiment of the present disclosure, in the 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), preferably (0.8-0.83): (0.09-0.12): (0.05-0.08); the solvent is water, the precipitator and the complexing agent are used in the form of aqueous solutions with the concentrations of 2-4 mol/L and 2-6 mol/L respectively, the precipitator 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 to the lanthanum source to the porous nickel-rich cathode material based on the total molar 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 raw materials are selected in a preferred ratio for reaction, which is beneficial to improving 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, 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, anhydrous lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate, lithium oxide and lithium nitrate; the cerium source comprises cerium nitrate and/or cerium chloride; the lanthanum source comprises lanthanum nitrate and/or lanthanum chloride. In the above embodiment, by selecting the preferable lithium source, cerium source and lanthanum source, a coating layer including cerium oxide and lanthanum oxide can be formed on the surface of the porous nickel-rich positive electrode material, and the electrode can be protected from the electrolyte.
In one embodiment of the disclosure, 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. In a preferred embodiment, the porous precursor is separated in step (1) by vacuum filtration, washed with deionized water, and dried in a vacuum oven at 80 ℃ for 10 h. In the embodiment, the nitrogen is introduced below the liquid level of the mixed liquid, so that the bubbling effect of the nitrogen can be enhanced, the porosity of the porous precursor is improved, and more buffer spaces are 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 a 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 the conditions of the first sintering include: the temperature is 400-600 ℃, preferably 450-550 ℃, and the time is 2-8 h; the conditions of 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, by selecting the preferred segmental sintering for the first heat treatment, lithium can be continuously diffused into the porous precursor, so as to form a thermodynamically stable porous nickel-rich cathode material, thereby improving the cycle performance and rate performance of the porous nickel-rich cathode material.
In one embodiment of the 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 obtained material is dried and then subjected to the second heat treatment; 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 crushed and sieved prior to mixing with the cerium source and the lanthanum source. In the embodiment, by selecting the preferable second heat treatment, the rare earth elements cerium and lanthanum can be doped and coated on the surface of the porous nickel-rich cathode material, and the doped and coated cerium ions and lanthanum ions form longer Ce-O and La-O bonds, so that a transmission channel of lithium ions is widened, and the rate capability of the battery is improved.
The second aspect of the disclosure provides a modified porous nickel-rich cathode material prepared by the preparation method of the first aspect of the disclosure, wherein the pore volume of pores with pore diameters within the range of 0.1-3 μm of the modified porous nickel-rich cathode material is 0.4-0.8 cm3(ii)/g; the surface of the modified porous nickel-rich cathode material comprises cerium and lanthanum.
The porous modified nickel-rich cathode material provided by the disclosure has a rich porous structure, provides a buffer space for mutual extrusion between primary particles in the calcining and circulating processes, inhibits the generation of microcracks and phase change of the material, and improves the structural stability of the material; rare earth elements Ce and La are introduced to carry out coating doping co-modification on the porous nickel-rich anode material, so that Li is reduced+/Ni2+The mixed arrangement of the components effectively prevents structural degradation and phase change, and improves the safety of the material.
In one embodiment of the present disclosure, the modified porous nickel-rich cathode material has a chemical formula shown in formula (i): lia(Ni1-x-yCoxMny)1-bMbO2(I), wherein a is more than or equal to 1.0 and less than or equal to 1.1, x is more than or equal to 0.08 and less than or equal to 0.13, y is more than or equal to 0.05 and less 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, b is more than or equal to 0.01 and less than or equal to 0.03, and M comprises cerium and lanthanum.
In one embodiment of the disclosure, the modified porous nickel-rich cathode material is a particulate material, such as spherical particles or spheroidal particles, and the particle size of the particulate material is 5-20 μm; the modified porous nickel-rich cathode material comprises an internal porous nickel-rich cathode material and a coating layer coated on the porous nickel-rich cathode material, wherein the coating layer contains cerium and lanthanum, 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, and the electrode can be protected from corrosion of the electrolyte.
The present disclosure is further illustrated by the following examples, but is not to be construed as being limited thereby.
In the following examples, the raw materials used are all commercial products unless otherwise specified.
In the following examples, the specific test methods are as follows:
the thickness of the coating layer is measured by a transmission electron microscope with the model number of FEI Tecnai G-20;
the testing method of the average pore diameter is mercury intrusion instrument, and the instrument model is Kangta Poremaster;
the particle size and SEM test method is a scanning electron microscope, and the instrument model is Hitachi SU 8000;
the XRD test method is X-ray diffractometer with X' Pert PRO type powder X-ray diffractometer of PANalytical company;
the test method of the electrochemical cycle performance is a blue test system, and the model of the instrument is CT 3001A.
Example 1
(1) According to the weight ratio of Ni: co: mn ═ 0.82: 0.10: NiSO is accurately weighed according to the molar ratio of 0.084Crystal, CoSO4Crystal and MnSO4Dissolving the crystal in deionized water, preparing feed liquid with the concentration of 2mol/L, respectively preparing 2mol/L NaOH solution and ammonia water as a precipitator and a complexing agent, adding the solutions into a continuously stirred reaction tank, and controlling the reaction temperature at 48 ℃; n is a radical of2The flow rate was 320mL/min, and N was added2Introducing into the liquid to generate bubbles continuously at a stirring speed of600rpm, the pH value is kept at about 11, and the reaction is continuously carried out for 22 h; vacuum filtering to separate precipitate, washing with deionized water, and drying in vacuum oven at 80 deg.C for 10 hr to obtain porous precursor Ni0.82Co0.1Mn0.08(OH)2；
(2) According to (Ni + Co + Mn): li-1: 1.02 mol ratio accurately weighing Ni0.82Co0.1Mn0.08(OH)2And LiOH. H2And O, uniformly mixing the two, and performing first heat treatment under pure oxygen atmosphere: performing first sintering at 520 ℃ for 5h, then heating to 780 ℃ for second sintering for 10h, cooling to room temperature, crushing and sieving to obtain the porous nickel-rich cathode material Li1.02Ni0.82Co0.1Mn0.08O2；
(3) According to the Ce: la: (Ni + Co + Mn) ═ 0.017: 0.003: the molar ratio of 0.98 accurately weighs cerium nitrate crystal, lanthanum nitrate crystal and Li1.02Ni0.82Co0.1Mn0.08O2Dissolving cerium nitrate crystals and lanthanum nitrate crystals in ethanol, uniformly mixing the solution with the weighed porous nickel-rich cathode material, drying for 3h at 80 ℃ in a vacuum oven, and performing second heat treatment under pure oxygen atmosphere: sintering for 6h at 600 ℃, and sieving to obtain the modified porous nickel-rich cathode material 1 with the chemical structural formula of LiNi0.804Co0.098Mn0.078Ce0.017La0.003O2The nickel-rich anode material is spherical particles, the particle size is 8-12 mu m, the interior of the nickel-rich anode material is porous, the surface of the nickel-rich anode material is a coating layer containing cerium and lanthanum, the thickness of the coating layer is 5.6nm, and pore distribution, XRD (X-ray diffraction), SEM (scanning Electron microscope) and TEM (transmission electron microscope) tests are carried out on the nickel-rich anode material, and the results are shown in figures 1-4.
As can be seen from FIG. 1, the pores of the modified porous nickel-rich cathode material in the range of 0.1-3 μm are significantly increased, which indicates that a porous structure is introduced, wherein the pore volume of the pores with the pore diameter in the range of 0.1-3 μm is 0.56cm3The,/g, is favorable to inhibiting the material from generating microcrack and phase change, improve the structural stability of the material;
as can be seen from FIG. 2, after the porous nickel-rich cathode material is introduced with the rare earth elements of cerium and lanthanum, the products are obviously oxidized with cerium and oxygenThe diffraction peak of lanthanum oxide and other diffraction peaks still correspond to alpha-NaFeO2The 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 cathode 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 coating layer on the surface includes cerium lanthanum oxide and lanthanum oxide, which can protect an electrode from corrosion of an electrolyte, thereby improving rate performance and cycle stability of a battery.
Example 2
The method of example 1 is used, with the only difference that: n is a radical of2The flow rate is 420mL/min, and the modified porous nickel-rich cathode material 2 with the chemical structural formula of LiNi is obtained0.804Co0.098Mn0.078Ce0.017La0.003O2The coating is spherical particles with a particle size of 7-13 μm and a coating thickness of 3-7 nm.
Example 3
The method of example 1 is used, with the only difference that: according to Ce: la: (Ni + Co + Mn) ═ 0.007: 0.006: the molar ratio of 0.987 accurately weighs cerium nitrate crystal, lanthanum nitrate crystal and Li1.02Ni0.82Co0.1Mn0.08O2Obtaining a modified porous nickel-rich cathode material 3 with the chemical structural formula of Li1.007Ni0.809Co0.099Mn0.079Ce0.007La0.006O2The coating is spherical particles with a particle size of 8-13 μm and a coating thickness of 2-7 nm.
Example 4
The method of example 1 is used, with the only difference that: first heat treatment of step (2)The treatment process comprises the following steps: sintering at 580 ℃ for 5h, then heating to 730 ℃ and sintering for 10h to obtain the modified porous nickel-rich cathode material 4 with the chemical structural formula of LiNi0.804Co0.09 8Mn0.078Ce0.017La0.003O2The coating is spherical particles with a particle size of 6-11 μm and a coating thickness of 2-6 nm.
Example 5
The method of example 1 is used, with the only difference that: step (2) adopts a one-step sintering method, the temperature is raised to 780 ℃ and the sintering is carried out for 10 hours, so as to obtain the modified porous nickel-rich cathode material 5, the chemical structural formula of which is LiNi0.804Co0.098Mn0.078Ce0.017La0.003O2The spherical particles have a particle size of 7 to 12 μm and a coating layer thickness of 3 to 7 nm.
Comparative example 1
The method of example 1 is used, with the only difference that: n is a radical of hydrogen2The flow rate is 80mL/min, cerium nitrate crystals and lanthanum nitrate crystals are not introduced, and Li obtained in the step (2)1.02Ni0.82Co0.1Mn0.08O2Namely, the comparative material 1 is spherical particles with the particle size of 7-13 μm, and the results of pore distribution, XRD and SEM tests are shown in figures 1, 2 and 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 0.21cm3(ii) a significantly lower pore volume than 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 α -NaFeO2The R-3m space group of the structure shows that the material has a good layered structure;
as can be seen from FIG. 5, comparative material 1 prepared in comparative example 1 was spherical particles having a particle size of 7 to 13 μm.
Comparative example 2
The method of example 1 is used, with the only difference that: n is a radical of2The flow rate was 80mL/min to obtain comparative material 2, whose chemical formula is LiNi0.804Co0.098Mn0.078Ce0.017La0.003O2In the shape ofSpherical particles with a particle size of 8-13 μm and a coating thickness of 2-6 nm.
Comparative example 3
The method of example 1 is used, with the only difference that: n is a radical of2The flow rate was 600mL/min to obtain a comparative material 3 having the chemical formula LiNi0.804Co0.098Mn0.078Ce0.017La0.003O2The coating is spherical particles with a particle size of 8-14 μm and a coating thickness of 2-8 nm.
Test example
Electrochemical performance was tested as follows: the materials prepared by the examples and the comparative examples, the conductive agent acetylene black and the binder PVDF 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 90 ℃ by blowing air, tabletting the aluminum foil by using a tablet machine after complete drying, then punching the tabletted pole piece into a circular electrode piece with the diameter of 14mm, and drying for 2 hours at 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 of lithium is added-1The LiPF6/EC + DEC + DMC (volume ratio is 1: 1: 1) is used as an electrolyte to assemble the button cell. And (3) carrying out charge and discharge tests on the assembled battery above a blue test, wherein the temperature is 25 +/-1 ℃, and the test voltage range is 3.0-4.3V.
Test results show that the 5.0C specific discharge capacity of the modified porous nickel-rich cathode material prepared by the preparation method of the embodiment 1-5 is higher, and the capacity retention rate is better after 100 cycles under the condition of 1.0C; comparative examples 1-3 the capacity retention rate of the obtained positive electrode material is lower after 100 cycles under the condition of 1.0C without adopting the preparation method disclosed by the disclosure; by comparison, the modified porous nickel-rich cathode material prepared by the method disclosed by the embodiments 1-5 has better cycling stability and higher rate capability.
Comparing the data of example 1 and example 3, it can be seen that the molar ratio of the cerium source and the lanthanum source to the porous nickel-rich cathode material based on the total moles of nickel, cobalt and manganese elements preferred in the present disclosure in example 1 is (0.009-0.025): (0.001-0.005): (0.97-0.99), the prepared modified porous nickel-rich cathode material is high in first-time specific discharge capacity, and good in rate capability; as can be seen from comparison of the data in example 1 and example 5, in example 1, when the preferred embodiment of the present disclosure, in which the first heat treatment includes the first sintering and the second sintering, is adopted, the obtained modified porous nickel-rich cathode material has better structural stability, better capacity retention rate after 100 cycles, and better cycle stability.
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.
Claims (10)
1. A preparation method of a modified porous nickel-rich cathode material is characterized by comprising the following steps:
(1) the method comprises the following steps of (1) enabling a nickel source, a cobalt source, a manganese source, a precipitator and a complexing agent to be in contact mixing in a solvent, introducing nitrogen into a mixed solution for stirring reaction, and separating a porous precursor 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 carrying out first heat treatment to obtain a porous nickel-rich cathode material;
(3) and contacting a cerium source and a lanthanum source with the porous nickel-rich cathode material, and carrying out second heat treatment.
2. The method according to claim 1, wherein in the step (1), the molar ratio of the nickel source to the cobalt source to 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 used in the form of aqueous solutions with the concentrations of 2-4 mol/L and 2-6 mol/L respectively, 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 based on the total moles of nickel-cobalt-manganese elements is 1: (1-1.1), the molar ratio of the cerium source, the lanthanum source and the porous nickel-rich cathode material based on the total molar number of nickel-cobalt-manganese elements is (0.009-0.025): (0.001-0.005): (0.97-0.99).
4. The preparation 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, anhydrous lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate, lithium oxide and lithium nitrate; the cerium source comprises cerium nitrate and/or cerium chloride; the lanthanum source comprises lanthanum nitrate and/or lanthanum chloride.
5. The preparation method according to claim 1, wherein in the step (1), the nitrogen gas is introduced below the liquid level of the mixed solution, and 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 production method according to claim 1, wherein in the 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 of 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 preparation method according to claim 1, wherein in the step (3), the cerium source and the lanthanum source are contacted and mixed with the porous nickel-rich cathode material in an organic solvent, and the obtained material is dried and then subjected to the second heat treatment; 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 cathode material prepared by the preparation method of any one of claims 1 to 7, wherein the pore volume of pores with the pore diameter of 0.1 to 3 μm of the modified porous nickel-rich cathode material is 0.4 to 0.8cm3(ii)/g; the surface of the modified porous nickel-rich cathode material comprises cerium and lanthanum.
9. The modified porous nickel-rich cathode material as claimed in claim 8, wherein the chemical formula of the modified porous nickel-rich cathode material is shown as formula (I);
Lia(Ni1-x-yCoxMny)1-bMbO2 (Ⅰ)，
wherein a is more than or equal to 1.0 and less than or equal to 1.1, x is more than or equal to 0.08 and less than or equal to 0.13, y is more than or equal to 0.05 and less than or equal to 0.1, 0.8 and less than or equal to 1-x-y and less than or equal to 0.85, b is more than or equal to 0.01 and less than or equal to 0.03, and M comprises cerium and lanthanum.
10. The modified porous nickel-rich cathode material according to claim 8, wherein the modified porous nickel-rich cathode material is a particulate material, preferably spherical particles or quasi-spherical particles, and the particle size of the particulate material is 5-20 μm; the modified porous nickel-rich cathode material comprises an internal porous nickel-rich cathode material and a coating layer coated on the porous nickel-rich cathode material, wherein the coating layer contains cerium and lanthanum, and the thickness of the coating layer is 2-7 nm.
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