GB2625624A - Method for preparing tin-based coated positive electrode material precursor, and positive electrode material precursor - Google Patents
Method for preparing tin-based coated positive electrode material precursor, and positive electrode material precursor Download PDFInfo
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- GB2625624A GB2625624A GB2314779.6A GB202314779A GB2625624A GB 2625624 A GB2625624 A GB 2625624A GB 202314779 A GB202314779 A GB 202314779A GB 2625624 A GB2625624 A GB 2625624A
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- 239000002243 precursor Substances 0.000 title claims abstract description 59
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000007774 positive electrode material Substances 0.000 title abstract 7
- 239000000243 solution Substances 0.000 claims abstract description 44
- 239000011259 mixed solution Substances 0.000 claims abstract description 27
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- -1 sulfur ion Chemical class 0.000 claims abstract description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000012265 solid product Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000010406 cathode material Substances 0.000 claims description 80
- 239000011248 coating agent Substances 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 14
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000013508 migration Methods 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 239000011247 coating layer Substances 0.000 description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 8
- 229910052979 sodium sulfide Inorganic materials 0.000 description 8
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 6
- 239000001119 stannous chloride Substances 0.000 description 6
- 235000011150 stannous chloride Nutrition 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 4
- DZXKSFDSPBRJPS-UHFFFAOYSA-N tin(2+);sulfide Chemical compound [S-2].[Sn+2] DZXKSFDSPBRJPS-UHFFFAOYSA-N 0.000 description 4
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 2
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 241000206607 Porphyra umbilicalis Species 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/006—Compounds containing, besides tin, 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
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
- C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
- C01G51/50—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [MnO2]n-, e.g. Li(CoxMn1-x)O2, Li(MyCoxMn1-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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Disclosed in the present invention is a method for preparing a tin-based coated positive electrode material precursor. The method comprises the following steps: (1) mixing a nickel-cobalt-manganese hydroxide with a solution containing a carbonate ion and a sulfur ion; (2) adding a stannous source solution to the mixed solution in step (1), reacting same, and performing solid-liquid separation to obtain a solid product; and (3) soaking the solid product obtained in step (2) in a persulfide solution, performing solid-liquid separation, and then carrying out washing and drying to obtain the positive electrode material precursor. A positive electrode material prepared from the tin-based coated positive electrode material precursor prepared by the preparation method has good conductivity and a good lithium ion migration rate, such that that the positive electrode material is ensured to have relatively good electrochemical performance.
Description
METHOD FOR PREPARING CATHODE MATERIAL PRECURSOR THROUGH
TIN-BASED COATING, AND CATHODE MATERIAL PRECURSOR
TECHNICAL FIELD
100011 The present disclosure belongs to the technical field of lithium battery cathode materials, and particularly relates to a method for preparing a cathode material precursor through tin-based coating, and a cathode material precursor.
BACKGROUND
100021 As a new group of green power supplies, lithium-ion batteries (LIBs) have been widely used in the fields of consumer electronics and new energy vehicles due to their advantages such as high working voltage, long cycling life, lightweight less self-discharge, no memory effect, and high cost performance. As one of the core parts of an LIB, a cathode material determines the performance of the LIB and limits the energy density, power density, and cycling life of the LIB. It is believed that the development of cathode materials determines the development direction of LIBs.
100031 With the rapid development of fields such as electric vehicles and intelligent electronic devices (IEDs), there is an urgent need for lithium batteries with high energy density, long cycling life, and high safety. The use of a cathode with high voltage and high specific capacity is an effective way to improve the energy density of a battery. Layered cathode materials have received extensive attention due to their high theoretical specific capacity, but the application of layered cathode materials at high voltages still faces many challenges, such as structural phase transition at an interface between the cathode material and an electrolyte, transition metal dissolution, oxygen evolution, and continuous oxidative decomposition of an electrolyte, which severely limit the application in lithium batteries with high energy density.
100041 In view of the above problems, in the prior art, a coating layer can be formed on a surface of a cathode material precursor to optimize the structural and electrochemical properties of particles, thereby improving the corrosion resistance of a cathode material and reducing a side reaction between a cathode material and an electrolyte. Common coating materials include oxides, fluorides, lithium ion conductors, and the like. A coating layer can separate a cathode material from an electrolyte while reducing the contact resistance among particles to reduce a side reaction between the material and the electrolyte and prevent the corrosion of hydrogen fluoride (HF) resulting from the decomposition of the electrolyte to the cathode material.
[0005] However, coating materials used in the existing methods for preparing a cathode material precursor with a coating layer are mostly oxide materials with low electron conductivity, which will increase the resistivity of a cathode material; and the prepared coating laver on the cathode material precursor is too dense, which will reduce a migration rate of lithium ions and compromise the electrochemical performance of the final cathode material.
SUMMARY
100061 The present disclosure is intended to solve at least one of the technical problems existing in the prior art. In view of this, the present disclosure provides a method for preparing a cathode material precursor through tin-based coating, and a cathode material precursor. A cathode material made from a cathode material precursor prepared by the preparation method has excellent electrical conductivity and lithium ion migration rate, which makes the cathode material have prominent electrochemical performance.
100071 The above technical objective of the present disclosure is achieved by the following technical solutions.
100081 A method for preparing a cathode material precursor through tin-based coating is provided, including the following steps: [0009] (1) mixing a nickel-cobalt-manganese hydroxide with a carbonate and sulfide anion-containing solution to obtain a mixed solution; [0010] (2) adding a stannous source solution to the mixed solution obtained in step (1) to allow a reaction, and conducting solid-liquid separation (SLS) to obtain a solid product; and [0011] (3) soaking the solid product obtained in step (2) in a persulfate solution, conducting SLS to obtain a solid, and washing and drying the solid to obtain the cathode material precursor.
100121 Preferably, in step (1), the nickel-cobalt-manganese hydroxide and the carbonate and sulfide anion-containing solution may be mixed according to a solid-to-liquid ratio (a ratio of a mass of the nickel-cobalt-manganese hydroxide to a volume of the carbonate and sulfide anion-containing solution) of 1 g: (1-5) mL [00131 Preferably, in step (1), a concentration of carbonate anions in the carbonate and sulfide anion-containing solution may be 0.1 mol/L to I 0 mol/L.
100141 Preferably, in step (1), a concentration of sulfide anions in the carbonate and sulfide anion-containing solution may be 0.1 mon to 1 0 mol/L.
100151 Preferably, in step (2), a stannous source in the stannous source solution may be a soluble stannous salt.
100161 Preferably, in step (2), the stannous source in the stannous source solution may be at least one selected from the group consisting of stannous chloride and stannous sulfate.
[0017] Preferably, in step (2), a concentration of stannous cations in the stannous source solution may be 0.01 mol/L to 1 mol/L.
100181 Preferably, in step (2), the stannous source solution may be added dropw se to the mixed solution obtained in step (1).
100191 Preferably, in step (2), the stannous source solution may be added drop se at a rate of mL/h to 50 mL/h 100201 Preferably, in step (2), during the reaction, when a pH of the mixed solution is 8 to 9, the reaction may be stopped and the SLS may be conducted.
100211 Preferably, in step (3), a persulfate in the persulfate solution may be at least one selected from the group consisting of sodium persulfate and ammonium persulfate.
[0022] Preferably, in step (3), a concentration of the persulfate in the persulfate solution may be 0.1 mol/L to 1 mol/L.
[0023] Preferably, in step (3), the solid product and the persulfate solution may be mixed according to a solid-to-liquid ratio of 1 g: (1-5) mL.
100241 Preferably, in step (3), the soaking may be conducted for 1 h to 24 h. 100251 Preferably, in step (3), the solid may be washed first with deionized water and then with ethanol or acetone.
[0026] Preferably, in step (3), the solid may be vacuum-dried at 50°C to 80°C for 2 h to 12 h. 100271 Preferably, a method for preparing a cathode material precursor through tin-based coating may be provided, including the following steps: 100281 Si. preparing a stannous source solution with a stannous cation concentration of 0.01 mol/L to 1 mol/L, where a stannous source in the stannous source solution is at least one selected from the group consisting of stannous chloride and stannous sulfate; 100291 S2. preparing a mixed solution of sodium carbonate and sodium sulfide, where a sodium carbonate concentration is 0.1 mol/L to 1.0 mol/L and a sodium sulfide concentration is 0.1 mol/L to 1.0 rnol/L; [0030] S3. adding a nickel-cobalt-manganese hydroxide to the mixed solution prepared in S2 according to a solid-to-liquid ratio (a ratio of a mass of the nickel-cobalt-manganese hydroxide to a volume of the mixed solution) of 1 g: (1-5) mL: 100311 S4. under continuous stirring at a stirring speed of 200 r/min to 500 rimin, adding the stannous source solution prepared in S1 dropwise to the mixed solution at a rate of 25 mL/h to 50 mL/h: 100321 S5. when it is detected that a pH of the mixed solution is 8 to 9, stopping a reaction and conducting SLS to obtain a wet material; 100331 S6. according to a solid-to-liquid ratio of 1 g: (1-5) mL, soaking the wet material in a 0.1 mol/L to 1 mol/L sodium persulfate/ammonium persulfate solution for 1 h to 24 h: 100341 S7. conducting SLS, and washing a resulting solid first with deionizcd water and then with ethanol or acetone; and [0035] S8. vacuum-drying the washed solid at 50°C to 80°C for 2 h to 12 h to obtain a tin-coated cathode material precursor.
100361 A cathode material precursor prepared by the preparation method described above is provided 100371 A cathode material prepared by mixing and sintering a lithium source and the cathode material precursor described above is provided.
100381 An LIB including the cathode material described above is provided.
[0039] The present disclosure has the following beneficial effects: 100401 (I) in the present disclosure, a nickel-cobalt-manganese hydroxide is mixed with a carbonate and sulfide anion-containing mixed solution and then a stannous source solution is added dropwise to produce a mixed precipitate of stannous hydroxide and stannous sulfide that covers a surface of the precursor (nickel-cobalt-manganese hydroxide); and the coating layer on the surface of the precursor is further dissolved with a persulfate to remove the stannous sulfide in the coating layer, such that a position originally occupied by stannous sulfide in the coating layer of the precursor is vacated and the coating layer becomes loose and porous to obtain a precursor material with a porous coating layer.
[0041] The reaction equations are as follows: after the stannous source solution is added dropwise, stannous cations are hydrolyzed and a stannous sulfide precipitate is produced: Sn2++20F1-=Sn(OH)21 and Sn2--ES2-=SnSI; and the coating layer is further dissolved in the persulfate solution: SnS-1S22-=SnS32' . 100421 (2) The surface of the precursor prepared by this method is coated with a layer of stannous hydroxide. When the precursor is subsequently sintered with a lithium source to prepare a cathode material, the coating layer will be dehydrated and oxidized to generate stannic oxide with high electrical conductivity, which improves the electron conductivity of the cathode material. In addition, the cathode material inherits the morphological characteristics of the precursor, and a coating layer on its surface has a porous structure, which further improves the migration rate of lithium ions, facilitates the intercalation/deintercalation of lithium in the cathode material, prevents a side reaction between the cathode material body and an electrolyte, and improves the cycling performance of the cathode material.
BRIEF DESCRIPTION OF THE DRAWINGS
100431 FIG. I is a scanning electron microscopy (SEM) image of the cathode material precursor prepared in Example 1 of the present disclosure at a magnification of 10,000; and 100441 FIG. 2 is an SEM image of the cathode material precursor prepared in Example 1 of the
present disclosure at a magnification of 100.000.
DETAILED DESCRIPTION
100451 The present disclosure is further described below with reference to specific examples.
100461 Example 1:
100471 A method for preparing a cathode material precursor through tin-based coating was provided, including the following steps: 100481 Si. a stannous chloride solution with a concentration of 0.5 mol/L was prepared [0049] S2. a mixed solution of sodium carbonate and sodium sulfide was prepared, where a sodium carbonate concentration was 0.5 mol/L and a sodium sulfide concentration was 0.5 mol/L; [0050] S3. a nickel-cobalt-manganese hydroxide (molecular formula: Nio.62Mno.2C00.18(OH)2) was added to the mixed solution prepared in 52 according to a solid-to-liquid ratio of 1 g: 3 mL1 100511 S4. under continuous stirring at a stirring speed of 300 r/min, the stannous chloride solution prepared in Si was added dropwise to the mixed solution at a rate of 35 mL/11; 100521 Si. when it was detected that a pH of the mixed solution was 8 to 9, a reaction was stopped and SLS was conducted to obtain a wet material; 100531 S6. according to a solid-to-liquid ratio of 1 g: 3 mL, the wet material was soaked in a 0.5 mol/L sodium persulfate/ammonium persulfate solution for 12 h; 100541 S7. SLS was conducted, and a resulting solid was washed first with de on zed water and then with ethanol; and 100551 S8. the washed solid was vacuum-dried at 65°C for 7 h to obtain a tin-coated cathode material precursor.
100561 A cathode material precursor through tin-based coating prepared by the above preparation method was provided. An SEM image of the cathode material precursor at a magnification of 10,000 was shown in FIG. 1, and an SEM image of the cathode material precursor at a magnification of 100,000 was shown in FIG. 2.
[0057] Example 2:
100581 A method for preparing a cathode material precursor through tin-based coating was provided, including the following steps: 100591 SI. a stannous chloride solution with a concentration of 0.01 mol/L was prepared 100601 S2. a mixed solution of sodium carbonate and sodium sulfide was prepared, where a sodium carbonate concentration was 0.1 mol/L and a sodium sulfide concentration was 0.1 mol/L; 100611 S3. a nickel-cobalt-manganese hydroxide (molecular formula: Nio.62Mno.2Coo.is(OH)2) was added to the mixed solution prepared in 52 according to a solid-to-liquid ratio of 1 g: 1 mL, 100621 S4. under continuous stirring at a stirring speed of 200 r/min, the stannous chloride solution prepared in Si was added dropwise to the mixed solution at a rate of 25 mL/h: [0063] S5. when it was detected that a pH of the mixed solution was 8 to 9, a reaction was stopped and SLS was conducted to obtain a wet material; [0064] 56. according to a solid-to-liquid ratio of 1 g: 1 mL, the wet material was soaked in a 0.1 mol/L sodium persulfate/ammonium persulfate solution for 111; 100651 57. SLS was conducted, and a resulting solid was washed first with deionized water and then with ethanol; and [0066] S8. the washed solid was vacuum-dried at 50°C for 12 h to obtain a tin-coated cathode material precursor.
100671 A cathode material precursor through tin-based coating prepared by the above preparation method was provided.
100681 Example 3:
100691 A method for preparing a cathode material precursor through tin-based coating was provided, including the following steps: [0070] SI. a stannous sulfate solution with a concentration of 1 mol/L was prepared; [0071] S2. a mixed solution of sodium carbonate and sodium sulfide was prepared, where a sodium carbonate concentration was 1.0 mol/L and a sodium sulfide concentration was 1.0 mol/L; [0072] S3. a nickel-cobalt-manganese hydroxide (molecular formula: Ni0.85Mno.08Co0.07(OH)2) was added to the mixed solution prepared in S2 according to a solid-to-liquid ratio of 1 g: 5 mL; [0073] S4. under continuous stirring at a stirring speed of 500 r/min, the stannous sulfate solution prepared in Si was added dropwise to the mixed solution at a rate of 50 mL/h; [0074] S5. when it was detected that a pH of the mixed solution was 8 to 9, a reaction was stopped mid SLS was conducted to obtain a wet material; 100751 56. according to a solid-to-liquid ratio of I g: 5 mL, the wet material was soaked in a I mol/L sodium persulfate/ammonium persulfate solution for 24 h; 100761 S7. SLS was conducted, and a resulting solid was washed first with deionized water and then with acetone; and [0077] S8. the washed solid was vacuum-dried at 80°C for 2 h to obtain a tin-coated cathode material precursor.
100781 A cathode material precursor through tin-based coating prepared by the above preparation method was provided.
[0079] Test Example
[0080] The nickel-cobalt-manganese hydroxides used in Examples 1 to 3 were taken as Comparative Examples I to 3, respectively. The cathode material precursors through tin-based coating obtained in Examples 1 to 3 and the nickel-cobalt-manganese hydroxides in Examples 1 to 3 were each mixed with lithium hydroxide according to a Li/(Ni+Co+Mn) molar ratio of 1.04, and a resulting mixture was heated to 750°C and kept at the temperature for 10 h in an oxygen-atmosphere furnace, then furnace-cooled, crushed, and sieved to obtain a corresponding cathode material. Each cathode material was subjected to an electrical conduction performance test, and test results were shown in Table 1: 100811 Table 1 Electrical conduction nerfonnance test results of cathode materials Electrical conductivity (s/cm) Bulk resistivity (Q*cm) Example I 346* 10-2 36.1 Example 2 -I 73* l02 38.9 Example 3 3,98* 102 34.3 Comparative Example 1 2.88* i0 358.6 Comparative Example 2 2.84* 10-3 359.3 Comparative Example 3 2.86* 10-3 358.8 100821 it can be seen from Table I that the cathode material made from the cathode material precursor through tin-based coating of the present disclosure has excellent electrical conduction performance, with an electrical conductivity of less than 3.98 * 10-2 s/cm and a bulk resistivity of less than 343 Q*cm. Moreover, it can be seen from the comparison between Example 1 and Comparative Example 1, the comparison between Example 2 and Comparative Example 2, and the comparison between Example 3 and Comparative Example 3 that the electrical conduction performance of the cathode material made from the tin-coated cathode material precursor of the present disclosure is far superior to the electrical conduction performance of the cathode material made from the cathode material precursor without tin coating.
[0083] Each cathode material, acetylene black (as a conductive agent), and polyvinylidene fluoride (PVDF) (as a binder) were weighed and mixed in a ratio of 92:4:4. then a specified amount of an organic solvent N-methylpyn-olidone (NMP) was added, and a resulting mixture was stirred and coated on an aluminum foil to obtain a positive electrode sheet and then with a metal lithium sheet as a negative electrode, an LIB was assembled in an argon-filled glove box. A charge-discharge test was conducted at room temperature and a current of 3.6 A. during which the initial efficiency (%), specific discharge capacity at 0.1 C, specific discharge capacity at 1 C, and cycling retention after 300 cycles (%) were detennined. Test results were shown in Table 2, 00841 Table 2 Electrochemical nerfonnance test results of batteries Initial Specific Specific Capacity efficiency discharge discharge retention after capacity at 0.1 C capacity at 1 C 300 cycles at 0.1 (%) (in A 11 1g) (mAh/g) C (%) Example I 92.6 192.1 178.4 92.3 Example 2 92.3 192.6 178.8 90.1 Example 3 93.1 214.3 194.1 91.2 Comparative 86.5 190.2 171.2 85.3
Example 1
Comparative 86.8 190.2 171.1 85.2
Example 2
Comparative 87.1 210.6 189.3 82.1
Example 3
[0085] It can be seen from Table 2 that the battery assembled by the cathode material made from the cathode material precursor through tin-based coating of the present disclosure has excellent electrochemical perfonnance, with an initial efficiency of 92.3% or higher, a specific discharge capacity of 192.1 mAh/ g or higher at 0.1 C. a specific discharge capacity of 178.4 mAh/g or higher at 1 C, and a capacity retention of 90.1% or higher after 300 cycles at 0.1 C. Moreover, it can be seen from the comparison between Example I and Comparative Example 1, the comparison between Example 2 and Comparative Example 2, and the comparison between Example 3 and Comparative Example 3 that the electrochemical performance of the battery assembled by the cathode material made from the tin-coated cathode material precursor of the present disclosure is far superior to the electrochemical performance of the battery assembled by the cathode material made from the cathode material precursor without tin-based coating.
100861 The above examples are preferred implementations of the present disclosure. However, the implementations of the present disclosure are not limited by the above examples. Any change, modification, substitution, combination, and simplification made without departing from the spiritual essence and principle of the present disclosure should be an equivalent replacement manner, and all are included in the protection scope of the present disclosure.
Claims (10)
- CLAIMS: 1. A method for preparing a cathode material precursor through tin-based coating, comprising the following steps: (1) mixing a nickel-cobalt-manganese hydroxide with a carbonate and sulfide anion-containing solution to obtain a mixed solution; (2) adding a stannous source solution to the mixed solution obtained in step (1) to allow a reaction, and conducting solid-liquid separation (SLS) to obtain a solid product; and (3) soaking the solid product obtained in step (2) in a persulfate solution, conducting SLS to obtain a solid, and washing and drying the solid to obtain the cathode material precursor.
- 2. The method for preparing the cathode material precursor through tin-based coating according to claim 1, wherein in step (1), when mixing, a ratio of a mass of the nickel-cobalt-manganese hydroxide to a volume of the carbonate and sulfide anion-containing solution is 1 g: (1-5) mL.
- 3. The method for preparing the cathode material precursor through tin-based coating according to claim 1, wherein in step (1), a concentration of sulfide anions in the carbonate and sulfide anion-containing solution is 0.1 mol/L to 1.0 mol/L.
- 4. The method for preparing the cathode material precursor through tin-based coating according to claim 1, wherein in step (2), a concentration of stannous cations in the stannous source solution is 0.01 mol/L to 1 mol/L.
- 5. The method for preparing the cathode material precursor through tin-based coating according to claim 1, wherein in step (2), the stannous source solution is added dropwise to the mixed solution obtained in step ( I).
- 6. The method for preparing the cathode material precursor through tin-based coating according to claim 1, wherein in step (2), during the reaction, when a pH of the mixed solution is 8 to 9. the reaction is stopped and the SLS is conducted.
- 7. The method for preparing the cathode material precursor through tin-based coating according to claim 1, wherein in step (3). a concentration of a persulfate salt in the persulfate solution is 0.1 mol/L to 1 mol/L.
- S. The method for preparing the cathode material precursor through tin-based coating according to claim 1, wherein in step (3), when mixing, a ratio of a mass of the solid product to a volume of the persulfate solution is 1 g: (1-5) mL.
- 9. A cathode material precursor prepared by the method according to any one of claims 1 to
- 10. A cathode material prepared by mixing and sintering a lithium source and the cathode material precursor according to claim 9.
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| PCT/CN2023/074953 WO2023207249A1 (en) | 2022-04-24 | 2023-02-08 | Method for preparing tin-based coated positive electrode material precursor, and positive electrode material precursor |
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| JP2009076279A (en) * | 2007-09-19 | 2009-04-09 | Toyota Motor Corp | Manufacturing method of positive active material |
| CN101796671A (en) * | 2007-09-04 | 2010-08-04 | 丰田自动车株式会社 | Metal oxide-coated positive electrode active material, lithium secondary battery, and manufacture method therefor |
| CN113929152A (en) * | 2020-07-14 | 2022-01-14 | 恒大新能源技术(深圳)有限公司 | Composite material precursor, composite material, preparation method of composite material and positive plate |
| CN113928152A (en) * | 2021-11-04 | 2022-01-14 | 深圳供电局有限公司 | Electric automobile fills electric pile structure |
| CN114229884A (en) * | 2021-10-28 | 2022-03-25 | 广东邦普循环科技有限公司 | Metal sulfide sodium ion battery cathode material and preparation method thereof |
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| CN101796671A (en) * | 2007-09-04 | 2010-08-04 | 丰田自动车株式会社 | Metal oxide-coated positive electrode active material, lithium secondary battery, and manufacture method therefor |
| JP2009076279A (en) * | 2007-09-19 | 2009-04-09 | Toyota Motor Corp | Manufacturing method of positive active material |
| CN113929152A (en) * | 2020-07-14 | 2022-01-14 | 恒大新能源技术(深圳)有限公司 | Composite material precursor, composite material, preparation method of composite material and positive plate |
| CN114229884A (en) * | 2021-10-28 | 2022-03-25 | 广东邦普循环科技有限公司 | Metal sulfide sodium ion battery cathode material and preparation method thereof |
| CN113928152A (en) * | 2021-11-04 | 2022-01-14 | 深圳供电局有限公司 | Electric automobile fills electric pile structure |
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