CN115504518A - Positive electrode material precursor, positive electrode material, and preparation method and application of positive electrode material - Google Patents
Positive electrode material precursor, positive electrode material, and preparation method and application of positive electrode material Download PDFInfo
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- CN115504518A CN115504518A CN202211120510.3A CN202211120510A CN115504518A CN 115504518 A CN115504518 A CN 115504518A CN 202211120510 A CN202211120510 A CN 202211120510A CN 115504518 A CN115504518 A CN 115504518A
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- 239000002243 precursor Substances 0.000 title claims abstract description 141
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- 239000013078 crystal Substances 0.000 claims abstract description 27
- 238000000975 co-precipitation Methods 0.000 claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 72
- 239000010406 cathode material Substances 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 43
- 238000005245 sintering Methods 0.000 claims description 40
- 239000002245 particle Substances 0.000 claims description 36
- 239000011572 manganese Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 24
- 229910052759 nickel Inorganic materials 0.000 claims description 24
- 229910017052 cobalt Inorganic materials 0.000 claims description 21
- 239000010941 cobalt Substances 0.000 claims description 21
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 21
- 239000010405 anode material Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 239000000654 additive Substances 0.000 claims description 18
- 230000000996 additive effect Effects 0.000 claims description 18
- 239000012266 salt solution Substances 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 15
- 238000009826 distribution Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 11
- 239000008139 complexing agent Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 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 9
- 239000012716 precipitator Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 60
- 239000000463 material Substances 0.000 description 38
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 33
- 235000011114 ammonium hydroxide Nutrition 0.000 description 33
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 20
- 238000012360 testing method Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 230000007547 defect Effects 0.000 description 11
- 230000014759 maintenance of location Effects 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- 238000011437 continuous method Methods 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000011163 secondary particle Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 4
- 239000011565 manganese chloride Substances 0.000 description 4
- 235000002867 manganese chloride Nutrition 0.000 description 4
- 229940099607 manganese chloride Drugs 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229940053662 nickel sulfate Drugs 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- 230000001351 cycling effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
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- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
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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
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a precursor of a positive electrode material, which is prepared by coprecipitation reaction, wherein the pH of a system is controlled to be 9-12 in the coprecipitation reaction process, and when the coprecipitation reaction reaches balance, the deformation stacking fault rate f of crystals in the system is measured at two time intervals of 4h at random D The difference value of (a) is more than or equal to 0.7 percent, and the deformation stacking fault rate f D ＝0.19FWHM (101) –0.055FWHM (102) –0.5/D (001) Wherein, FWHM (101) Is the full width at half maximum, FWHM, of the (101) diffraction peak (102) Is a (102) diffraction peakHalf peak width of (D) (001) The crystal grain size corresponding to the (001) crystal face. After the precursor of the positive electrode material is prepared into the positive electrode material, the precursor has excellent cycle performance and high initial discharge capacity.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to an anode material precursor, an anode material, and a preparation method and application thereof.
Background
The traditional industrial energy structure faces a new round of adjustment. Among them, the lithium battery industry has become a popular market for new energy industry through years of development. The high-performance anode material is undoubtedly the crown in the whole upstream and downstream industry chain, the performance of the anode material is 60% -70% dependent on the precursor, and the high-performance precursor is undoubtedly the bright pearl which can be brightly and brightly seen on the crown.
At present, a precursor for preparing the lithium ion battery anode material is generally prepared by a coprecipitation method, and nucleation and growth of crystals are mainly controlled by precipitation reaction and complexation reaction in the process. However, the precursor of the cathode material prepared by the existing coprecipitation method has the problems of low first discharge capacity and improved cycle performance after being prepared into the cathode material.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a preparation method of the precursor of the cathode material, and the precursor of the cathode material prepared by the preparation method has excellent cycle performance and higher first discharge capacity after being prepared into the cathode material.
The technical purpose of the invention is realized by the following technical scheme:
the positive electrode material precursor is prepared by coprecipitation reaction, the pH of a system is controlled to be 9-12 in the coprecipitation reaction process, and when the coprecipitation reaction reaches balance, any phase is selectedMeasuring the deformation fault rate f of the crystal in the system at two time intervals of 4h D The difference value of (a) is more than or equal to 0.7 percent, and the deformation fault rate f D ＝0.19FWHM (101) –0.055FWHM (102) –0.5/D (001) Wherein, FWHM (101) Full width at half maximum, FWHM of (101) diffraction peak (102) Is the half-width of the diffraction peak of (102), D (001) The crystal grain size corresponding to the (001) crystal face.
Preferably, when the coprecipitation reaction reaches the equilibrium, the deformation and lamination fault rate f of the crystals in the system is D Is 1 to 10 percent.
Preferably, the particle size distribution span value of the positive electrode material precursor is more than or equal to 1.30, wherein span = (D) 90 -D 10 )/D 50 。
Preferably, the chemical formula of the precursor of the cathode material is Ni x Co y Mn z (OH) 2 (ii) a Wherein x is more than or equal to 0 and less than or equal to 1; y is more than or equal to 0 and less than or equal to 0.9; z is more than or equal to 0 and less than or equal to 0.9, and x + y + z =1.
A preparation method of the precursor of the cathode material comprises the following steps: (1) Mixing a metal salt solution containing nickel, cobalt and manganese, a precipitator, a complexing agent and an alkaline base solution for reaction to obtain a mixed solution, wherein the pH of the system is controlled to be 9-12 in the reaction process, and when the granularity D50 of a precursor crystal obtained by the reaction reaches 1-15 mu m, the pH of the system is adjusted to control the balance of coprecipitation reaction, wherein the adjustment of the pH refers to the adjustment of the pH by 0.02-0.04 or the adjustment of the pH by 0.03-0.06; (2) And (2) carrying out solid-liquid separation on the mixed liquid obtained in the step (1) to obtain a solid, washing, and drying to obtain the precursor of the cathode material.
Further preferably, the pH is continuously adjusted after the particle size D50 of the precursor crystal obtained by the reaction reaches 4-10 μm.
Preferably, in the step (1), the adjusting of the pH means that when the D50 of the precursor crystal is larger than the target particle size by more than 0.3 μm, the pH of the system is adjusted up to 0.02-0.04; when the D50 of the precursor crystal is smaller than the target particle size by more than 0.3 mu m, the pH value of the system is reduced by 0.03-0.06.
Preferably, in the step (1), the total concentration of nickel, cobalt and manganese metal ions in the metal salt solution containing nickel, cobalt and manganese is 1-3mol/L.
Preferably, in the step (1), the molar ratio of nickel element, cobalt element and manganese element in the metal salt solution containing nickel, cobalt and manganese is x: y: z, wherein x is more than or equal to 0 and less than or equal to 1; y is more than or equal to 0 and less than or equal to 0.9; z is more than or equal to 0 and less than or equal to 0.9, and x + y + z =1.
Preferably, in the step (1), the precipitant is at least one of sodium hydroxide solution and potassium hydroxide solution, and the concentration of the precipitant is 2-14mol/L.
Preferably, in the step (1), the complexing agent is ammonia water with a mass fraction of 20%.
Preferably, in the step (1), the alkaline base solution is a mixed solution of sodium hydroxide and ammonia water, the pH of the alkaline base solution is 9 to 12, and the concentration of the ammonia water in the alkaline base solution is 0 to 10g/L.
Preferably, in the step (1), the reaction is performed in a reaction kettle, and the mixing manner is to add the metal salt solution containing nickel, cobalt and manganese, the precipitant and the complexing agent into the alkaline base solution in a concurrent flow manner.
Preferably, in the step (1), after the reaction reaches the equilibrium, the deformation-induced stacking fault rate f of the crystals in the mixed solution is measured at two optional time intervals of 4h D The difference is more than or equal to 0.7 percent.
Preferably, in step (1), the reaction temperature of the reaction is 50-80 ℃.
Preferably, in the step (2), the drying temperature is 90-120 ℃, and the drying time is 30-50h.
A preparation method of a positive electrode material comprises the following steps: and mixing the precursor of the cathode material, a lithium source and an additive, performing primary sintering in an aerobic atmosphere, crushing, mixing with the additive, and performing secondary sintering in the aerobic atmosphere to obtain the cathode material.
Preferably, the lithium source is LiOH or Li 2 CO 3 At least one of (1).
Preferably, the additive is a compound or a combination of compounds containing at least one element of the elements Ni, co, mn, zr, al, mg, ti, sr, W, Y, mo, sb, nb, sn, zn, la, ce, B, and F.
Preferably, the temperature of the primary sintering is 700-1020 ℃, and the sintering time is 28-32h.
Preferably, the temperature of the secondary sintering is 250-750 ℃, and the sintering time is 6-9h.
The cathode material is prepared by the preparation method.
Preferably, the chemical formula of the cathode material is Li 1+a Ni x Co y Mn z M b O 2 @N c Wherein a is more than or equal to 0 and less than or equal to 0.2,0 and less than or equal to B is more than or equal to 0.03,0 and less than or equal to c is more than or equal to 0.04, M and N are at least one of elements of Ni, co, mn, zr, al, mg, ti, sr, W, Y, mo, sb, nb, sn, zn, la, ce, B and F.
The application of the cathode material in the preparation of the lithium ion battery.
The invention has the beneficial effects that:
(1) In the preparation process of the precursor of the cathode material, the pH of the synthesized precursor is controlled to be 9-12, and the pH is continuously adjusted after the granularity reaches the target granularity. The balance of coprecipitation reaction and complexation reaction is controlled by continuously adjusting the pH value, and the growth speed of the crystal is adjusted. The probability of forming defects is high when the crystal grows fast, and ideal crystals without defects can be obtained when the crystal grows slowly. Changing the growth speed of the crystal in different periods by continuously changing the pH of the reaction system so as to obtain a precursor with a gradient defect structure, wherein the growth stacking fault rate f for the structural defect of the precursor D The method is characterized in that the method can be obtained by performing fitting calculation on an XRD (X-ray diffraction) spectrum of a precursor by using X-pert Highscore software, the precursor is subjected to high-temperature lithiation sintering, a gradient defect structure is inherited in the anode material, and the gradient defect structure can release stress generated in the lithium ion de-intercalation process, so that cracking of primary particles and secondary aggregates is reduced, the cycle performance of the anode material is improved, in addition, the gradient defect is in the atomic scale in the material, a new interface cannot be introduced into the gradient defect, new interface impedance cannot be increased, and the electrochemical performance of the material is improved;
(2) In the preparation process of the precursor of the cathode material, the reaction system is at a high pH value, so that high degree of over saturation (supersaturation degree S = [ Me ]) is easily obtained 2+ ][OH - ] 2 /K θ sp,Me(OH)2 ) The nucleation and growth driving force of the crystal are supersaturation, and the nucleation and growth of the crystal are at higher speed under high supersaturation, so that the supersaturation is consumed too fast; because the reaction system is under a high pH value, the balance of precipitation reaction and complex reaction is broken, the precipitation reaction is enhanced, more small particles are generated in a short time, the particle size distribution of the precursor is widened, the wide particle size distribution can effectively improve the packing density among the particles, and the energy density of the anode material is improved, the particle size distribution of the precursor is represented by span value, and span = (D) 90 -D 10 )/D 50 The larger the span value, the broader the particle size distribution of the precursor; as the metal liquid is continuously replenished, the supersaturation degree is increased again, and the reaction process is periodically repeated.
Drawings
FIG. 1 is an SEM image of a precursor process sample prepared in example 1 of the present invention and having a reaction time of 80 h;
FIG. 2 is an SEM image of a precursor process sample prepared in example 1 of the present invention and having a reaction time of 84 h;
fig. 3 is an SEM image of the cathode material prepared in example 1 of the present invention;
FIG. 4 is an SEM image of a precursor process sample of a precursor 80h prepared in comparative example 1 of the present invention;
FIG. 5 is an SEM image of a precursor process sample of precursor 84h prepared in comparative example 1 of the present invention;
fig. 6 is a graph comparing the cycle capacity retention rates of the positive electrode materials prepared in example 1 of the present invention and comparative example 1;
FIG. 7 is an X-ray diffraction pattern of the final precursor prepared by the co-precipitation method in example 1 and comparative example 1 of the present invention;
fig. 8 is a graph showing the particle size distribution of the final precursor prepared by the co-precipitation method in example 1 and comparative example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1:
a preparation method of a precursor of a positive electrode material comprises the following steps:
step 1, according to the element molar ratio Ni to Co to Mn =0.70, 0.20, selecting nickel chloride, cobalt chloride and manganese chloride as raw materials, preparing a metal salt solution containing nickel, cobalt and manganese with the total concentration of nickel, cobalt and manganese metal ions being 2.0mol/L, preparing a sodium hydroxide solution with the concentration being 4.5mol/L as a precipitator, and preparing ammonia water with the mass fraction being 20% as a complexing agent;
step 2, adding an alkaline base solution into the reaction kettle until the alkaline base solution overflows a bottom stirring paddle, starting stirring, wherein the alkaline base solution is a mixed solution of sodium hydroxide and ammonia water, the pH value of the alkaline base solution is 11.7, and the concentration of the ammonia water is 8.0g/L;
step 3, adding the metal salt solution containing nickel, cobalt and manganese, the sodium hydroxide solution and ammonia water prepared in the step 1 into a reaction kettle in a concurrent flow manner for reaction, controlling the reaction temperature in the kettle to be 65 ℃, the pH to be 11 and the concentration of the ammonia water to be 8.0g/L, and synthesizing a precursor by adopting a continuous method;
and 4, setting the target granularity D50 of the precursor in the kettle to be 4.0 mu m, and adjusting the pH value of the reaction when the granularity D50 of the precursor in the kettle is detected to be 4.0 +/-0.3 mu m. Specifically, when the D50 is higher than the target particle size by 0.3 mu m, the pH value is adjusted up to 0.02; when the D50 is lower than the target granularity by 0.3 mu m, the pH is reduced by 0.03, and the material is continuously collected;
and 6, drying the precipitate at 120 ℃ for 25h to obtain the precursor of the anode material.
And respectively taking the process samples from 80h to 84h of reaction, and testing (4 h is far lower than the residence time tau of the precursor particles in the reaction kettle, only a small amount of secondary particles are discharged from an overflow port, so that the materials in the kettle are roughly the same batch), wherein the morphology of the precursor is shown in fig. 1 and fig. 2. Obtaining the growth stacking fault rate f of the precursor by adopting X-pert Highscore software fitting D F, measured twice, of 4.7% and 3.3%, respectively D Based on the laser particle size, the difference of (1.4)The calculated span for the instrumental test results was 1.21 and 1.37, respectively.
The precursor of the cathode material is prepared by the preparation method, and the chemical formula of the precursor of the cathode material is Ni 0.70 Co 0.10 Mn 0.20 (OH) 2 。
A preparation method of a positive electrode material comprises the following steps:
(1) The precursor of the cathode material, liOH and an additive ZrO are mixed 2 After being uniformly mixed, the mixture is sintered for one time in an aerobic atmosphere to obtain a primary sintered material, wherein a precursor of the anode material and LiOH are mixed according to the molar ratio of Li/(Ni + Co + Mn) of 1.05, and ZrO 2 In an amount of 3000ppm (as ZrO) 2 The middle Zr accounts for the mass of the precursor), the temperature of the primary sintering is 925 ℃, and the time of the primary sintering is 30h;
(2) Coarsely crushing and finely crushing the calcined material obtained in the step (1), and then mixing with an additive WO 3 And Al 2 O 3 Uniformly mixing, and performing secondary sintering in an aerobic atmosphere to obtain the cathode material, wherein WO 3 And Al 2 O 3 In amounts of 2000ppm and 1000ppm, respectively (in terms of WO) 3 And Al 2 O 3 Wherein W and Al account for the weight of the base material), the temperature of the secondary sintering is 650 ℃, and the time of the secondary sintering is 8h.
The cathode material is prepared by the preparation method, and the chemical formula of the cathode material is Li (Ni) 0.70 Co 0.10 Mn 0.20 ) 0.997 Zr 0.003 O 2 @W 0.00108 Al 0.00366 The SEM image of the positive electrode material is shown in fig. 3.
Example 2:
a preparation method of a precursor of a positive electrode material comprises the following steps:
step 1, according to the element molar ratio of Ni to Co to Mn =0.65 of 0.07, selecting nickel chloride, cobalt chloride and manganese chloride as raw materials, preparing a metal salt solution containing nickel, cobalt and manganese with the total concentration of nickel, cobalt and manganese metal ions of 2.5mol/L, preparing a sodium hydroxide solution with the concentration of 5.5mol/L as a precipitator, and preparing ammonia water with the mass fraction of 20% as a complexing agent;
step 2, adding an alkaline base solution into the reaction kettle until the alkaline base solution overflows a bottom stirring paddle, starting stirring, wherein the alkaline base solution is a mixed solution of sodium hydroxide and ammonia water, the pH value of the alkaline base solution is 11.9, and the concentration of the ammonia water is 10g/L;
step 3, adding the metal salt solution containing nickel, cobalt and manganese, the sodium hydroxide solution and ammonia water prepared in the step 1 into a reaction kettle in a concurrent flow manner for reaction, controlling the reaction temperature in the kettle to be 60 ℃, the pH to be 11.5 and the concentration of the ammonia water to be 10g/L, and synthesizing a precursor by adopting a continuous method;
and 4, setting the target granularity D50 of the precursor in the kettle to be 4.2 microns, and adjusting the pH value of the reaction when the granularity D50 of the precursor in the kettle is detected to be 4.2 +/-0.3 microns. Specifically, when the D50 is higher than the target particle size by 0.3 mu m, the pH value is adjusted to be 0.04; when the D50 is lower than the target granularity by 0.3 mu m, the pH is adjusted down to 0.06, and the material is continuously collected;
and 6, drying the precipitate at 115 ℃ for 30h to obtain the precursor of the anode material.
And respectively taking process samples for 80h and 84h of reaction progress, and testing (4 h is far lower than the retention time tau of the precursor particles in the reaction kettle, only a small amount of secondary particles are discharged from an overflow port, and therefore the materials in the kettle are approximately the same batch). The growth fault rate f of the precursor is obtained by adopting X-pert Highscore software to fit D F measured twice at 5.9% and 4.4%, respectively D The difference of (a) was 1.5, and the calculated span based on the laser particle sizer test results was 1.11 and 1.40, respectively.
The precursor of the cathode material is prepared by the preparation method, and the chemical formula of the precursor of the cathode material is Ni 0.65 Co 0.07 Mn 0.28 (OH) 2 。
A preparation method of a positive electrode material comprises the following steps:
(1) The precursor of the cathode material, liOH and an additive ZrO are mixed 2 Uniformly mixing with SrO, and sintering in an aerobic atmosphere to obtain a calcined material, wherein the molar ratio of the precursor of the positive electrode material to LiOH is 1.06 according to the molar ratio of Li/(Ni + Co + Mn)Mixed in line, zrO 2 And SrO were added in amounts of 2000ppm and 1500ppm (as ZrO) respectively 2 And Zr and Sr in SrO account for the mass of the precursor), the temperature of the primary sintering is 940 ℃, and the time of the primary sintering is 28h;
(2) Coarsely crushing and finely crushing the calcined material obtained in the step (1), and then mixing the crushed material with an additive Sb 2 O 3 And TiO 2 Uniformly mixing, and performing secondary sintering in an oxygen atmosphere to obtain the cathode material, wherein Sb is 2 O 3 And TiO 2 The amounts of (A) and (B) added were 1500ppm and 2000ppm (as Sb), respectively 2 O 3 And TiO 2 Wherein Sb and Ti account for the weight of the base material), the temperature of the secondary sintering is 550 ℃, and the time of the secondary sintering is 6h.
The cathode material is prepared by the preparation method, and the chemical formula of the cathode material is Li (Ni) 0.65 Co 0.07 Mn 0.28 ) 0.997 Zr 0.002 Sr 0.001 O 2 @Sb 0.00122 Ti 0.00730 。
Example 3:
a preparation method of a precursor of a positive electrode material comprises the following steps:
step 1, according to the element molar ratio of Ni to Co to Mn =0.80 and 0.10, selecting nickel chloride, cobalt chloride and manganese chloride as raw materials, preparing a nickel-cobalt-manganese-containing metal salt solution with the total concentration of nickel-cobalt-manganese metal ions being 1.5mol/L, preparing a sodium hydroxide solution with the concentration being 10mol/L as a precipitator, and preparing ammonia water with the mass fraction being 20% as a complexing agent;
step 2, adding an alkaline base solution into the reaction kettle until the alkaline base solution overflows a bottom stirring paddle, starting stirring, wherein the alkaline base solution is a mixed solution of sodium hydroxide and ammonia water, the pH value of the alkaline base solution is 10.7, and the concentration of the ammonia water is 4g/L;
step 3, adding the metal salt solution containing nickel, cobalt and manganese, the sodium hydroxide solution and ammonia water prepared in the step 1 into a reaction kettle in a concurrent flow manner for reaction, controlling the reaction temperature in the kettle to be 72 ℃, the pH to be 10.7 and the concentration of the ammonia water to be 4g/L, and synthesizing a precursor by adopting a continuous method;
and 4, setting the target granularity D50 of the precursor in the kettle to be 10 microns, and adjusting the pH value of the reaction when the granularity D50 of the precursor in the kettle is detected to be 10 +/-0.3 microns. Specifically, when the D50 is higher than the target granularity by 0.3 mu m, the pH value is adjusted to be 0.03 upwards; when the D50 is lower than the target granularity by 0.3 mu m, the pH is adjusted down to 0.05, and the material is continuously collected;
and 6, drying the precipitate at 90 ℃ for 42h to obtain the precursor of the cathode material.
And respectively taking process samples for 80h and 84h of reaction progress, and testing (4 h is far lower than the retention time tau of the precursor particles in the reaction kettle, only a small amount of secondary particles are discharged from an overflow port, and therefore the materials in the kettle are approximately the same batch). Obtaining the growth stacking fault rate f of the precursor by adopting X-pert Highscore software fitting D F, measured twice, of 3.6% and 2.3%, respectively D The difference of (a) was 1.3, and the calculated span based on the laser particle sizer test results was 1.21 and 1.45, respectively.
The precursor of the cathode material is prepared by the preparation method, and the chemical formula of the precursor of the cathode material is Ni 0.80 Co 0.10 Mn 0.10 (OH) 2 。
A preparation method of a positive electrode material comprises the following steps:
(1) Mixing the precursor of the cathode material with LiOH and an additive Y 2 O 3 And La 2 O 3 After being uniformly mixed, the mixture is sintered for one time in an aerobic atmosphere to obtain a primary sintered material, wherein a precursor of the anode material is mixed with LiOH according to the molar ratio of Li/(Ni + Co + Mn) of 1.02, and Y 2 O 3 And La 2 O 3 The amounts of (A) and (B) added were 1500ppm and 2500ppm, respectively (as Y) 2 O 3 And La 2 O 3 The mass of the medium Y and La in the precursor) is 875 ℃, and the time of primary sintering is 32h;
(2) Coarsely crushing and finely crushing the calcined material obtained in the step (1), and then mixing the crushed material with an additive Nb 2 O 5 And CeO 2 Uniformly mixing, and performing secondary sintering in an aerobic atmosphere to obtain the cathode material, wherein Nb is 2 O 5 And CeO 2 Are respectively added in an amount of 1500ppm and 1500ppm (in terms of Nb) 2 O 5 And CeO 2 The Nb and the Ce account for the weight of the base material), the temperature of the secondary sintering is 420 ℃, and the time of the secondary sintering is 7h.
The cathode material is prepared by the preparation method, and the chemical formula of the cathode material is Li (Ni) 0.80 Co 0.10 Mn 0.10 ) 0.997 Y 0.00156 La 0.00164 O 2 @Nb 0.00160 Ce 0.00552 。
Example 4:
a preparation method of a precursor of a positive electrode material comprises the following steps:
step 1, according to the element molar ratio of Ni to Co to Mn =0.95, 0.03, selecting nickel sulfate, cobalt sulfate and manganese sulfate as raw materials, preparing a metal salt solution containing nickel, cobalt and manganese with the total concentration of nickel, cobalt and manganese metal ions being 2mol/L, preparing a sodium hydroxide solution with the concentration being 14.0mol/L as a precipitator, and preparing ammonia water with the mass fraction being 20% as a complexing agent;
step 2, adding an alkaline base solution into the reaction kettle until the alkaline base solution overflows a bottom stirring paddle, starting stirring, wherein the alkaline base solution is a mixed solution of sodium hydroxide and ammonia water, the pH value of the alkaline base solution is 10.8, and the concentration of the ammonia water is 2g/L;
step 3, adding the metal salt solution containing nickel, cobalt and manganese, the sodium hydroxide solution and ammonia water prepared in the step 1 into a reaction kettle in a concurrent flow manner for reaction, controlling the reaction temperature in the kettle to be 50 ℃, the pH to be 10 and the concentration of the ammonia water to be 2g/L, and synthesizing a precursor by adopting a continuous method;
and 4, setting the target granularity D50 of the precursor in the kettle to be 8 microns, and adjusting the pH value of the reaction when the granularity D50 of the precursor in the kettle is detected to be 8 +/-0.3 microns. Specifically, when the D50 is higher than the target particle size by 0.3 mu m, the pH value is adjusted up to 0.03; when the D50 is lower than the target granularity by 0.3 mu m, the pH is adjusted down to 0.04, and the material is continuously collected;
and 6, drying the precipitate at 100 ℃ for 36h to obtain the precursor of the positive electrode material.
Respectively taking the process samples of which the reactions are carried out for 80h and 84h to test (4 h is far lower than the precursor particles)The residence time in the reaction vessel, τ, is such that only a small amount of secondary particles are discharged from the overflow, and thus the vessel contents can be considered to be substantially the same batch). Obtaining the growth stacking fault rate f of the precursor by adopting X-pert Highscore software fitting D 2.6% and 1.9%, respectively, f measured twice D The difference in (b) is 0.7, and the spans calculated based on the laser granulometer test results are 1.09 and 1.48, respectively.
The precursor of the cathode material is prepared by the preparation method, and the chemical formula of the precursor of the cathode material is Ni 0.95 Co 0.02 Mn 0.03 (OH) 2 。
A preparation method of a positive electrode material comprises the following steps:
(1) Mixing the precursor of the cathode material with LiOH and an additive MoO 3 And B 2 O 3 Uniformly mixing, and performing primary sintering in an aerobic atmosphere to obtain a primary sintered material, wherein the anode material precursor and LiOH are mixed according to the molar ratio of Li/(Ni + Co + Mn) of 1.01, and MoO 3 And B 2 O 3 In amounts of 3000ppm and 800ppm (in terms of MoO), respectively 3 And B 2 O 3 The mass of Mo and B in the precursor) is regulated, the temperature of primary sintering is 832 ℃, and the time of primary sintering is 32h;
(2) Coarsely crushing and finely crushing the calcined material obtained in the step (1), and then mixing the crushed material with an additive MgCO 3 Mixing with LiF uniformly, and sintering in an aerobic atmosphere for the second time to obtain the anode material, wherein MgCO 3 And LiF in amounts of 2000ppm and 1000ppm (as MgCO) 3 And Mg and F in LiF account for the weight of the substrate), the temperature of secondary sintering is 300 ℃, and the time of secondary sintering is 9 hours.
The cathode material is prepared by the preparation method, and the chemical formula of the cathode material is Li (Ni) 0.95 Co 0.02 Mn 0.03 ) 0.997 Mo 0.00289 La 0.00053 O 2 @Mg 0.00817 F 0.00368 。
Comparative example 1:
a preparation method of a precursor of a positive electrode material comprises the following steps:
step 1, according to the element molar ratio Ni to Co to Mn =0.70, 0.20, selecting nickel chloride, cobalt chloride and manganese chloride as raw materials, preparing a metal salt solution containing nickel, cobalt and manganese with the total concentration of nickel, cobalt and manganese metal ions being 2.0mol/L, preparing a sodium hydroxide solution with the concentration being 4.5mol/L as a precipitator, and preparing ammonia water with the mass fraction being 20% as a complexing agent;
step 2, adding an alkaline base solution into the reaction kettle until the alkaline base solution overflows a bottom stirring paddle, starting stirring, wherein the alkaline base solution is a mixed solution of sodium hydroxide and ammonia water, the pH value of the alkaline base solution is 10.6, and the concentration of the ammonia water is 4g/L;
step 3, adding the metal salt solution containing nickel, cobalt and manganese, the sodium hydroxide solution and ammonia water prepared in the step 1 into a reaction kettle in a concurrent flow manner for reaction, controlling the reaction temperature in the kettle to be 65 ℃, the pH to be 9.8 and the concentration of the ammonia water to be 4g/L, and synthesizing a precursor by adopting a continuous method;
and 4, setting the target granularity D50 of the precursor in the kettle to be 4.0 mu m, and adjusting the pH value of the reaction when the granularity D50 of the precursor in the kettle is detected to be 4.0 +/-0.3 mu m. Specifically, when the D50 is higher than the target particle size by 0.3 mu m, the pH value is adjusted up to 0.02; when the D50 is lower than the target granularity by 0.3 mu m, the pH is adjusted down to 0.03, and the material is continuously collected;
and 6, drying the precipitate at 120 ℃ for 25 hours to obtain the precursor of the anode material.
And (4) respectively taking the process samples from the 80 th hour and the 84 th hour for the reaction, wherein the residence time of the precursor particles in the reaction kettle is far shorter than tau, only a small amount of secondary particles are discharged from the overflow port, and therefore the materials in the kettle are roughly the same batch), and testing the process samples, wherein the shape of the precursor is shown in fig. 4 and fig. 5. Obtaining the growth stacking fault rate f of the precursor by adopting X-pert Highscore software fitting D F, measured twice, of 3.6% and 3.8%, respectively D The difference of (a) was 0.2, and the calculated span based on the laser particle sizer test results was 1.12 and 1.11, respectively.
The precursor of the cathode material is prepared by the preparation method, and the chemical formula of the precursor of the cathode material is Ni 0.70 Co 0.10 Mn 0.20 (OH) 2 。
A preparation method of a positive electrode material comprises the following steps:
(1) The precursor of the cathode material, liOH and an additive ZrO are mixed 2 After being uniformly mixed, the mixture is sintered for one time in an aerobic atmosphere to obtain a primary sintered material, wherein a precursor of the anode material is mixed with LiOH according to the molar ratio of Li/(Ni + Co + Mn) of 1.05, and ZrO is added 2 In an amount of 3000ppm (as ZrO) 2 The middle Zr accounts for the mass of the precursor), the temperature of the primary sintering is 925 ℃, and the time of the primary sintering is 30h;
(2) Coarsely crushing and finely crushing the calcined material obtained in the step (1), and then mixing with an additive WO 3 And Al 2 O 3 Uniformly mixing, and performing secondary sintering in an aerobic atmosphere to obtain the cathode material, wherein WO 3 And Al 2 O 3 In amounts of 2000ppm and 1000ppm, respectively (in terms of WO) 3 And Al 2 O 3 The medium W and Al account for the weight of the base material), the temperature of the secondary sintering is 650 ℃, and the time of the secondary sintering is 8h.
The cathode material is prepared by the preparation method, and the chemical formula of the cathode material is Li (Ni) 0.70 Co 0.10 Mn 0.20 ) 0.997 Zr 0.003 O 2 @W 0.00108 Al 0.00366 。
Comparative example 2:
a preparation method of a precursor of a positive electrode material comprises the following steps:
step 1, according to the element molar ratio Ni to Co to Mn =0.95, 0.03, selecting nickel sulfate, cobalt sulfate and manganese sulfate as raw materials, preparing a nickel-cobalt-manganese-containing metal salt solution with the total concentration of nickel-cobalt-manganese metal ions of 2mol/L, preparing a sodium hydroxide solution with the concentration of 14mol/L as a precipitator, and preparing ammonia water with the mass fraction of 20% as a complexing agent;
step 2, adding an alkaline base solution into the reaction kettle until the alkaline base solution overflows a bottom stirring paddle, starting stirring, wherein the alkaline base solution is a mixed solution of sodium hydroxide and ammonia water, the pH value of the alkaline base solution is 10, and the concentration of the ammonia water is 1g/L;
step 3, adding the metal salt solution containing nickel, cobalt and manganese, the sodium hydroxide solution and ammonia water prepared in the step 1 into a reaction kettle in a concurrent flow manner for reaction, controlling the reaction temperature in the kettle to be 50 ℃, the pH to be 9.2 and the concentration of the ammonia water to be 1g/L, and synthesizing a precursor by adopting a continuous method;
and 4, setting the target granularity D50 of the precursor in the kettle to be 8 microns, and adjusting the pH value of the reaction when the granularity D50 of the precursor in the kettle is detected to be 8 +/-0.3 microns. Specifically, when the D50 is higher than the target particle size by 0.3 mu m, the pH value is adjusted up to 0.03; when the D50 is lower than the target granularity by 0.3 mu m, the pH is adjusted down to 0.04, and the material is continuously collected;
and 6, drying the precipitate at 100 ℃ for 36h to obtain the precursor of the positive electrode material.
And respectively taking process samples for 80h and 84h of reaction progress, and testing (4 h is far lower than the retention time tau of the precursor particles in the reaction kettle, only a small amount of secondary particles are discharged from an overflow port, and therefore the materials in the kettle are approximately the same batch). The growth fault rate f of the precursor is obtained by adopting X-pert Highscore software to fit D F, measured twice, was 0.83% and 0.74%, respectively D The difference of (a) was 0.09, and the calculated span based on the laser particle sizer test results was 1.08 and 1.03, respectively.
The precursor of the cathode material is prepared by the preparation method, and the chemical formula of the precursor of the cathode material is Ni 0.95 Co 0.02 Mn 0.03 (OH) 2 。
A preparation method of a positive electrode material comprises the following steps:
(1) Mixing the precursor of the cathode material with LiOH and an additive MoO 3 And B 2 O 3 After being uniformly mixed, the mixture is sintered for one time in an aerobic atmosphere to obtain a primary sintered material, wherein a positive electrode material precursor and LiOH are mixed according to the molar ratio of Li/(Ni + Co + Mn) of 1.01, and MoO 3 And B 2 O 3 In amounts of 3000ppm and 800ppm (in terms of MoO), respectively 3 And B 2 O 3 The mass of the medium Mo and B in the precursor), the temperature of the primary sintering is 832 ℃, and the temperature of the primary sintering is 32h;
(2) Will be provided withThe calcined material obtained in the step (1) is subjected to coarse crushing and fine crushing and then is mixed with an additive MgCO 3 Mixing with LiF uniformly, and sintering in aerobic atmosphere to obtain the cathode material, wherein MgCO is 3 And LiF in amounts of 2000ppm and 1000ppm (as MgCO) 3 And Mg and F in LiF account for the weight of the substrate), the temperature of the secondary sintering is 300 ℃, and the temperature of the secondary sintering is 9 hours.
The cathode material is prepared by the preparation method, and the chemical formula of the cathode material is Li (Ni) 0.95 Co 0.02 Mn 0.03 ) 0.997 Mo 0.00289 La 0.00053 O 2 @Mg 0.00817 F 0.00368 。
Test example:
the anode materials of the embodiments 1-4 and the comparative examples 1-2 are respectively prepared into button cells for lithium ion battery electrochemical performance test, and the method comprises the following specific steps: the method comprises the steps of taking N-methyl pyrrolidone as a solvent, uniformly mixing a positive electrode active substance, acetylene black and PVDF according to the mass ratio of 8: 1, coating on an aluminum foil, carrying out forced air drying at 80 ℃ for 8h, and carrying out vacuum drying at 120 ℃ for 12h. The battery is assembled in an argon-protected glove box, the negative electrode is a metal lithium sheet, the diaphragm is a polypropylene film, and the electrolyte is 1M LiPF6-EC/DMC (1: 1,v/v). The first discharge capacity and the first efficiency are tested by carrying out the rate discharge at 0.1C under a specific cut-off voltage, and then the cycle capacity retention rate after 100 cycles is recorded by cycling 100 cycles at the rate of 1C under the cut-off voltage which is the same as that in the half cell test, and the test results are shown in Table 1, wherein a comparison graph of the cycle capacity retention rates of the cathode materials prepared in the example 1 and the comparative example 1 is shown in FIG. 6, an X-ray diffraction graph of the precursor finished products prepared by the co-precipitation method in the example 1 and the comparative example 1 is shown in FIG. 7, XRD shows that the main peak positions of the precursors do not obviously shift, but in the example 1, I (101) /I (001) The peak intensity ratio is significantly smaller. Theoretical studies have confirmed I (101) And I (001) The ratio of peak intensities is related to defects in the precursor, I (101) /I (001) The smaller the peak intensity ratio, the more defects in the precursor, thus directly confirming that the precursor can be controlled by changing the process conditions in example 1And forming defects in the body, thereby realizing the controllable preparation of the precursor with the gradient defect structure. The particle size distribution of the final precursor prepared by the co-precipitation method in example 1 and comparative example 1 of the present invention is shown in fig. 8. As can be seen from the figure, the particle size distribution of the precursors in example 1 and comparative example 1 both conform to the characteristic of normal distribution, but the particle size distribution of the precursor in example 1 is more "squat", which indicates that the particle size distribution is wider, while the particle size distribution of the precursor in comparative example 1 is relatively concentrated, and the performance of the precursor on the particle size distribution and the mechanism of process adjustment in the examples realize mutual evidence.
Table 1: results of battery performance testing
As can be seen from Table 1, the precursor of the positive electrode material prepared by the preparation method disclosed by the invention has excellent electrochemical performance after being prepared into the positive electrode material, the 0.1C discharge capacity of the precursor can reach more than 192mAh/g, the first efficiency can reach more than 90.8%, and the circulating capacity retention rate after 100 circles can reach more than 90.1%.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A positive electrode material precursor characterized in that: the positive electrode material precursor is prepared by coprecipitation reaction, the pH of a system is controlled to be 9-12 in the coprecipitation reaction process, and after the coprecipitation reaction reaches balance, the deformation stacking fault rate f of crystals in the system is measured at two time intervals of 4 hours at random D The difference value of (A) is more than or equal to 0.7 percent, theDeformation stacking fault ratio f D ＝0.19FWHM (101) –0.055FWHM (102) –0.5/D (001) Wherein, FWHM (101) Is the full width at half maximum, FWHM, of the (101) diffraction peak (102) Is the half-value width of the (102) diffraction peak, D (001) The crystal grain size corresponding to the (001) crystal plane.
2. The positive electrode material precursor according to claim 1, wherein: when the coprecipitation reaction reaches the equilibrium, the deformation stacking fault rate f of the crystal in the system D 1 to 10 percent.
3. A positive electrode material precursor according to claim 1, characterized in that: the particle size distribution span value of the precursor of the positive electrode material is more than or equal to 1.30.
4. The positive electrode material precursor according to claim 1, wherein: the chemical formula of the precursor of the anode material is Ni x Co y Mn z (OH) 2 (ii) a Wherein x is more than or equal to 0 and less than or equal to 1; y is more than or equal to 0 and less than or equal to 0.9; z is more than or equal to 0 and less than or equal to 0.9, and x + y + z =1.
5. A method for producing a precursor of a positive electrode material according to any one of claims 1 to 4, characterized by: the method comprises the following steps:
(1) Mixing a metal salt solution containing nickel, cobalt and manganese, a precipitator, a complexing agent and an alkaline base solution for reaction to obtain a mixed solution, controlling the pH of the system to be 9-12 in the reaction process, and adjusting the pH of the system after the granularity D50 of a precursor crystal obtained by the reaction reaches 1-15 mu m to control the balance of coprecipitation reaction;
(2) And (2) carrying out solid-liquid separation on the mixed liquid obtained in the step (1) to obtain a solid, washing, and drying to obtain the precursor of the cathode material.
6. The method for producing a precursor of a positive electrode material according to claim 5, characterized in that: in the step (1), the adjustment of the pH refers to adjusting the pH of the system to be 0.02-0.04 when the D50 of the precursor crystal is larger than the target particle size by more than 0.3 μm; when the D50 of the precursor crystal is smaller than the target particle size by more than 0.3 mu m, the pH value of the system is reduced by 0.03-0.06.
7. A preparation method of a positive electrode material is characterized by comprising the following steps: the method comprises the following steps: the positive electrode material is produced by mixing the positive electrode material precursor according to any one of claims 1 to 4, a lithium source and an additive, primary sintering in an oxygen-containing atmosphere, crushing, mixing with the additive, and secondary sintering in an oxygen-containing atmosphere.
8. The method for producing a positive electrode material according to claim 7, wherein: the additive is a compound or a combination of compounds containing at least one element of Ni, co, mn, zr, al, mg, ti, sr, W, Y, mo, sb, nb, sn, zn, la, ce, B and F elements.
9. A positive electrode material characterized in that: prepared by the preparation method of any one of claims 7 to 8.
10. Use of the positive electrode material of claim 9 in the preparation of a lithium ion battery.
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| PCT/CN2023/077443 WO2024055513A1 (en) | 2022-09-15 | 2023-02-21 | Positive electrode material precursor, positive electrode material, method for preparing same, and use thereof |
| FR2306735A FR3139951A1 (en) | 2022-09-15 | 2023-06-27 | CATHODE MATERIAL PRECURSOR, CATHODE MATERIAL, PREPARATION METHOD AND USE OF CATHODE MATERIAL |
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| CN (1) | CN115504518A (en) |
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| WO2024055513A1 (en) * | 2022-09-15 | 2024-03-21 | 广东邦普循环科技有限公司 | Positive electrode material precursor, positive electrode material, method for preparing same, and use thereof |
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| US20150024207A1 (en) * | 2012-02-21 | 2015-01-22 | Sumitomo Metal Mining Co., Ltd. | Nickel-cobalt-manganese composite hydroxide and method for manufacturing same |
| CN113387399A (en) * | 2021-05-13 | 2021-09-14 | 北京泰丰先行新能源科技有限公司 | High-nickel ternary positive electrode material precursor and preparation method thereof |
| CN114229922A (en) * | 2022-02-21 | 2022-03-25 | 浙江帕瓦新能源股份有限公司 | Nickel-cobalt-manganese ternary precursor, positive electrode material and preparation method |
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| KR101596723B1 (en) * | 2013-04-30 | 2016-02-23 | 한양대학교 산학협력단 | A method of preparing positive active material for lithium battery and positive active material made by the same |
| CN103545504B (en) * | 2013-10-17 | 2016-01-20 | 江西赣锋锂业股份有限公司 | A kind of preparation method of ternary anode material precursor |
| CN112151790B (en) * | 2020-08-26 | 2022-03-08 | 万华化学集团股份有限公司 | High-nickel ternary cathode material precursor, crystal face controllable growth method thereof, ternary cathode material and lithium ion battery |
| CN113582256B (en) * | 2021-09-28 | 2021-12-10 | 金驰能源材料有限公司 | High-nickel single crystal positive electrode material, precursor thereof and preparation method of precursor |
| CN114394631B (en) * | 2021-12-31 | 2023-07-07 | 宜宾光原锂电材料有限公司 | Preparation method of ternary positive electrode material precursor |
| CN114408988B (en) * | 2022-03-31 | 2022-06-24 | 金驰能源材料有限公司 | Ternary positive electrode material precursor and preparation method thereof |
| CN115504518A (en) * | 2022-09-15 | 2022-12-23 | 广东邦普循环科技有限公司 | Positive electrode material precursor, positive electrode material, and preparation method and application of positive electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150024207A1 (en) * | 2012-02-21 | 2015-01-22 | Sumitomo Metal Mining Co., Ltd. | Nickel-cobalt-manganese composite hydroxide and method for manufacturing same |
| CN113387399A (en) * | 2021-05-13 | 2021-09-14 | 北京泰丰先行新能源科技有限公司 | High-nickel ternary positive electrode material precursor and preparation method thereof |
| CN114229922A (en) * | 2022-02-21 | 2022-03-25 | 浙江帕瓦新能源股份有限公司 | Nickel-cobalt-manganese ternary precursor, positive electrode material and preparation method |
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| WO2024055513A1 (en) * | 2022-09-15 | 2024-03-21 | 广东邦普循环科技有限公司 | Positive electrode material precursor, positive electrode material, method for preparing same, and use thereof |
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| WO2024055513A1 (en) | 2024-03-21 |
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