GB2624493A - Positive electrode material, preparation method therefor, and use thereof - Google Patents
Positive electrode material, preparation method therefor, and use thereof Download PDFInfo
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- GB2624493A GB2624493A GB2310145.4A GB202310145A GB2624493A GB 2624493 A GB2624493 A GB 2624493A GB 202310145 A GB202310145 A GB 202310145A GB 2624493 A GB2624493 A GB 2624493A
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- positive electrode
- electrode material
- manganese
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011572 manganese Substances 0.000 claims abstract description 42
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 39
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000126 substance Substances 0.000 claims abstract description 28
- 239000011248 coating agent Substances 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 239000002344 surface layer Substances 0.000 claims abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 5
- 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 abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 4
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 4
- 150000003624 transition metals Chemical class 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 42
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000012286 potassium permanganate Substances 0.000 claims description 15
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 229940085991 phosphate ion Drugs 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 229910015530 LixMO2 Inorganic materials 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 239000003513 alkali Substances 0.000 description 18
- 230000001351 cycling effect Effects 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000002386 leaching Methods 0.000 description 8
- 239000010452 phosphate Substances 0.000 description 7
- -1 phosphate radical ions Chemical class 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 229910001386 lithium phosphate Inorganic materials 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000007323 disproportionation reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 3
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 3
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid 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
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 1
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- 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
- H01M4/48—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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention discloses a positive electrode material, a preparation method therefor, and a use thereof. The positive electrode material provided in the present invention comprises: a layered positive electrode material having the chemical formula LixMO2 and a coating substance, x ranging from 0.95 to 1.1, and M being a transition metal comprising Mn. The coating substance is disposed on a surface of the layered positive electrode material, and is partially doped in a surface layer of the layered positive electrode material. The coating substance comprises tetravalent manganese, lithium ions, and phosphate ions. The positive electrode material provided in the present invention can effectively inhibit dissolution of manganese from a manganese-containing positive electrode material, thereby improving cycle performance. The present invention also provides a preparation method for the positive electrode material, and a use thereof.
Description
POSITIVE ELECTRODE MATERIAL, METHOD FOR PREPARING THE SAME AND APPLICATION THEREOF
FIELD
[00011 The present application relates to the technical field of secondary batteries, in particular to a positive electrode material, a method for preparing the same and use thereof
BACKGROUND
[00021 Among positive electrode materials of lithium-ion secondary batteries, layered positive electrode materials are an important category, mainly including monomeric materials (lithium cobaltate, lithium nickelate, lithium manganate), binary materials (lithium nickel cobaltate, lithium nickel manganate, lithium cobalt manganate) and ternary materials (lithium nickel cobalt manganate). However, when the Ni content of the above-mentioned layered positive electrode materials exceeds 90% (molar percentage in total transition metals), the surface of the positive electrode materials is prone to generating residual alkali. The surface residual alkali mainly refers to the Li0H, Li2CO3 and other substances on the particle surface of the positive electrode material. The source of the residual alkali mainly comes from the Li not sintered in the sintering reaction, or the residual alkali generated by the decomposition of the material due to high temperature sintering. On the other hand, the residual alkali is generated by the material being left in the air for too long, specifically, when the humidity content in the air is high, the lithium in the lattice tends to migrate to the surface of the positive electrode material and react with the moisture and carbon dioxide in the environment to generate residual alkali.
[00031 The higher the Ni content in the positive electrode material, the harsher the sintering conditions, the more difficult it is to sinter the material to form a specific lithium-to-metal ratio, resulting in more residual alkali in the sintered product. The higher the Ni content, the more obvious the tendency of lithium migration from the lattice to the surface, so relatively speaking, the residual alkali content of high Ni materials is higher compared with other positive electrode materials.
100041 During the cycling process of manganese-containing positive electrode materials, Mn(III) generates disproportionation reaction to form Mn(IV) and Mn(II). In addition, with the increase of Ni content, manganese (especially Mn(11)) of the layered positive electrode materials tends to leach during the cycling process, migrate and precipitate at the negative electrode, thus destroying the negative electrode SET film: and with the leaching of manganese, the lattice of the layered positive electrode materials is destroyed, which may lead to the fragmentation of the positive electrode particles, which further affects the cycling performance of the positive electrode material.
[0005] In summary, it is important to provide a positive electrode material that can effectively inhibit the leaching of manganese, improve the cycling performance, and reduce the content of the residual alkali to a certain extent.
SUMMARY
[0006] The present application is aimed to solve at least one of the technical problems existing in the prior art. To this end, the present application provides a positive electrode material, which can effectively inhibit the leaching of manganese in manganese-containing positive electrode materials and reduce the content of the residual alkali to a certain extent.
[0007] The present application further provides a method for preparing the above positive electrode material.
[0008] The present application further provides use of the above positive electrode material.
[0009] According to a first aspect of the present application, a positive electrode material is provided, which comprises: a layered positive electrode material having a chemical formula Li,M02, where x ranges from 0.95 to 1.1 and M is a transition metal, including Mn; and a coating substance, which being partially provided on a surface of the layered positive electrode material and partially doped in a surface layer of the layered positive electrode material; where the coating substance comprises a tetravalent manganese, a lithium ion and a phosphate ion.
[0010] The positive electrode material according to the embodiments of the present application has at least the following beneficial effects.
[0011] (1) When the manganese-containing layered positive electrode material is charged and discharged, the internal Mn(III) (trivalent manganese) tends to generate disproportionation reaction to form Mn(II) and Mn(IV), and the former is easy to leach out of the lattice of the layered positive electrode material.
[0012] In the positive electrode material according to the present application, the surface layer of the layered positive electrode material is doped with tetravalent manganese (equivalent to the formation of a tetravalent manganese enriched surface layer), thereby inhibiting the disproportionation of Mn(III) in the layered positive electrode material, which in turn inhibits the generation and the leaching of Mn(II), and ultimately improves the cycling performance of the obtained positive electrode material.
[0013] (2) Lithium ions and phosphate radical ions in the coating substance may be compounded to form lithium phosphate, which can effectively improve the multiplicative performance of the obtained positive electrode material as a fast ion conductor.
[0014] (3) In the coating substance, the phosphate radical may also fix and protect the tetravalent manganese in the manganese dioxide and inhibit the leaching of manganese from the coating substance.
[0015] (4) The coating substance provided on the surface of the layered positive electrode material blocks the contact between the layered positive electrode material and the outside world to a certain extent, which can reduce the generation of the residual alkali and improve the comprehensive performance of the obtained positive electrode material.
[0016] According to some embodiments of the present application, in Li"MO,, M further includes Ni.
[0017] According to some embodiments of the present application, a molar percentage of Ni to M in LixM02 is 75%. -3 -
[00181 According to some preferred embodiments of the present application, the molar percentage of Ni to M in Li"M02 is 80 to 99%.
[0019] According to some preferred embodiments of the present application, the molar percentage of Ni to M in Li"M02 is 90 to 95%.
[0020] At this Ni content, the positive electrode material provided by conventional technology usually comprises a high content of residual alkali and has poor further cycling performance. The present application can effectively improve the cycling performance of the obtained positive electrode material through the design of structure and materiaL [0021] According to some embod ments of the present application, in Li"M02, M further includes Co. [0022] According to some embodiments of the present application, in Li"M02, M is Ni, Co and Mn.
[0023] According to some embodiments of the present application, in Li"MO-i, M is Ni, Co and Mn, and the molar ratio of Ni, Co and Mn is ( I to I 9):1: I. [0024] According to some embodiments of the present application, the tetravalent manganese is present in a form including manganese dioxide in the coating substance.
[0025] According to a second aspect embodiment of the present application, a method for preparing the positive electrode material is provided, which comprises: mixing the layered positive electrode material with an phosphoric acid aqueous solution, adding an alkaline potassium permanganate solution and a divalent manganese precursor to the obtained mixed system in sequence; and after reaction, drying and calcining a solid product.
[0026] The mechanism of the described preparation method is as follows.
[0027] A certain amount of residual alkali is present on the surffice of the layered positive electrode material, in the process of mixing with the phosphoric acid aqueous solution, on the one hand, the phosphoric acid aqueous solution reacts with the residual alkali to reduce the -4 -content of the residual alkali; on the other hand, the lithium in the residual alkali can react with the phosphate radical to produce precipitated lithium phosphate, which is deposited on the surface of the layered positive electrode material; on another hand, the acidity of phosphoric acid will also destroy the surface structure of the layered positive electrode material to a certain extent, leaving defects on the surface of the layered positive electrode material and increasing the specific surface area of the layered positive electrode material.
100281 Alkaline potassium permanganate is reacted with a divalent manganese precursor to produce manganese dioxide precipitate attached to the surface of the layered positive electrode material.
[0029] During calcination, manganese dioxide and lithium phosphate are doped on the shallow surface of the layered positive electrode material.
[0030] The preparation method according to the embodiments of the present application has at least the following beneficial effects.
[0031] (1) During calcination, defect locations formed on the surface of the layered positive electrode material etched by phosphoric acid are more likely to deposit manganese dioxide, and are also more likely to serve as a pathway for the formation of shallow surface doping of the coating substance such as tetravalent manganese. Thus, the steps of the present application are cooperated with each other to make it easier tor the coating substance to enter the lattice, forming shallow surface doping, and then playing the role in improving the comprehensive performance of the obtained positive electrode material.
[0032] (2) The phosphoric acid aqueous solution is used to treat the layered positive electrode material, the lithium in the residual alkali can be transformed into lithium phosphate, i.e., the lithium loss brought about by traditional acid and alkali washing is avoided, thus avoiding the capacity loss of the positive electrode material and improving the capacity of the positive electrode material to a certain extent.
[0033] (3) In the preparation method, if the divalent manganese precursor is added first and then alkaline potassium permanganate is added, the divalent manganese tends to react with phosphate radical to form manganese phosphate precipitation, and the chance of forming _ s _ tetravalent manganese decreases. The present application limits the order of adding materials to fmther ensure the consistency and high quality of the performance of the obtained positive electrode material.
100341 (4) In the positive electrode material prepared according to the preparation method, the surface layer is doped with the coating substance, which is equivalent to forming a manganese enrich surface layer, inhibiting the leaching of manganese in the positive electrode material and improving the cycling performance of the obtained positive electrode material.
[00351 According to some embodiments of the present application, the phosphoric acid aqueous solution has a concentration of lwt% to 5wt%.
[0036] According to some embodiments of the present application, a solid-liquid ratio of the layered positive electrode material and the phosphoric acid aqueous solution is 0.5g/m1 to [0037] According to some embodiments of the present application, the duration of the mixing is 5min to 30min [0038] According to some embodiments of the present application, the mass ratio of the solute the potassium permanganate and the layered positive electrode material in the alkaline potassium permanganate is (4 to 16)g:500g.
[0039] According to some preferred embodiments of the present application, the mass ratio of the solute potassium permanganate and the layered positive electrode material in the alkaline potassium permanganate is (7.8 to 8.1)g:500g.
[0040] According to some embodiments of the present application, the alkaline potassium permanganate solution has a pH of 7 to 13.
[0041] According to some preferred embodiments of the present application, the alkaline potassium permanganate solution has a pH of about 12.
[0042] According to some embodiments of the present application, the alkaline potassium permanganate solution has a concentration of 0.1mol/L to 2 mon.
[0043] According to some embodiments of the present application, the alkaline potassium permanganate solution has a concentration of about lmol/L.
[0044] According to some embodiments of the present application, the molar ratio of the alkaline potassium permanganate and the divalent manganese precursor is (0.8 to 1.2): I. [0045] According to some embodiments of the present application, the divalent manganese 5 precursor includes at least one of manganese hydroxide, manganese sulfate and manganese chloride.
[0046] According to some preferred embodiments of the present application, the divalent manganese precursor is selected from manganese hydroxide. The impurity components introduced by the divalent manganese precursor may thus be avoided as much as possible.
[0047] According to some embodiments of the present application, the duration of the reaction is 0.5h to 211; preferably, the method of the reaction is a standing reaction.
[0048] According to some embodiments of the present application, the drying is performed at a temperature of 80°C to 200°C.
[0049] According to some embodiments of the present application, the duration of the drying is 4h to 20h.
[0050] According to some embodiments of the present application, the duration of the drying is 8h to 1(1h.
[0051] According to some embodiments of the present application, the calcination is performed at a temperature of 450°C to 550°C.
[0052] According to some embodiments of the present application, the duration of the calcination is lih to 8h.
[0053] According to some embodiments of the present application, the calcination is performed under an oxygen atmosphere.
[0054] According to a third aspect embodiment of the present application, a secondary //5 battery is provided, and the raw material for preparing the secondary battery comprises the above positive electrode material.
[0055] The secondary battery according to the embodiments of the present application has at least the following beneficial effects.
[0056] Since the secondary battery uses all the technical solutions of the positive electrode material of the above embodiments, it has at least all the beneficial effects brought about by the technical solutions of the above embodiments.
[111057] Other features and advantages of the present application will be set forth in the subsequent specification and, in part, will become apparent from the specification or will be understood by implementing the present application.
BRIEF DESCRIPTION OF THE DRAWINGS
[0058] The above and/or additional aspects and advantages of the present application will become apparent and easily understood from the description of the examples in conjunction with the following accompanying drawings.
[0059] Figure 1 shows the scanning electron microscope image of the positive electrode material according to the first example of the present application; and [0060] Figure 2 shows the scanning electron microscope image of the positive electrode material according to the first example of the present application.
DETAILED DESCRIPTION
[0061] The examples of the present application will be described in detail below, and schematic examples are shown in the accompanying drawings, wherein the same or similar designations from beginning to end indicate the same or similar components or components having the same or similar functions. The examples described below by reference to the accompanying drawings are exemplary and are intended only to explain the present application and are not to be construed as limiting the present application.
Example 1
[0062] A positive electrode material was prepared in this example, and the process was as -8 -follows.
[00631 Si. 500g of LiNio9Co0.o5MIl0.0502 was immersed in phosphoric acid aqueous solution with a mass fraction of 5% and a volume of 500m1 for soaking for 5min.
[00641 S2. 50rri1 of Imola-alkaline potassium permanganate (pH=12) and 5g of manganese hydroxide were sequentially added to the mixture obtained in step Si. After stirring evenly the reaction was allowed to stand for 0.51i. The manganese dioxide generated by the reaction was precipitated on the surface of EiNio9Coo osMno o500.
[00651 S3. The product obtained in step S2 was subjected to solid-liquid separation, and the resulting solid was placed in a drying oven and dried at 80°C for 8h.
[00661 S4. The product obtained from step S3 was transferred to a muffle furnace and calcined under oxygen atmosphere with a sintering temperature of 450°C and a time of 8h.
[00671 The SEM images of the positive electrode material obtained in this example are shown in Figures 1 to 2. The results showed that there were certain pits on the surface of the positive electrode material, and there was a coating substance deposited in the pits as well as on the surface. This indicates that the coating substance had been successfully deposited on the surface of the layered positive electrode material.
Example 2
[00681 A positive electrode material was prepared in this example, specifically differing from Example 1 in that 1110 in step Sl, the mass concentration of phosphoric acid aqueous solution was 1%.
Example 3
1100691 A positive electrode material was prepared in this example, specifically differing from Example 1 in that in step 54, the sintering was performed at a temperature of 550°C and the sintering time 1115 was 6h.
Contrast example 1
[0070] A positive electrode material was prepared in this contrast example, specifically differing from Example I in that in step Si, the phosphoric acid aqueous solution was replaced with an oxalic acid aqueous solution of equal concentration.
Contrast example 2
[0071] A positive electrode material was prepared in this contrast example, specifically differing from Example I in that (1) in step Si, the phosphoric acid aqueous solution was replaced with water of equal volume; and (2) step S2 was not included.
Contrast example 3
[0072] A positive electrode material was prepared in this contrast example, specifically differing from Example 1 in that in step Sl, the phosphoric acid aqueous solution was replaced with water of equal volume. 15 Contrast example 4 A positive electrode material was prepared in this contrast example, specifically differing from Example 1 in that step S2 was not included. Test example I00731 In the present test example, button cells were prepared using the positive electrode materials obtained from Examples 1-3 and Contrast examples 1-4 as the positive electrode active materials, and the electrochemical performance of the button cells were tested. Specifically as the following: [0074] N-methylpyn-olidone was used as a solvent, the positive electrode material, acetylene black and PVDF were mixed evenly in the mass ratio of 9.2: 0.5: 0.3 to form a slurry, and then the slurry was coated on aluminum foil, dried by blast at 80°C for 8h and then vacuum dried at 120°C for 12h to obtain the positive electrode.
[0075] The cells were assembled in a glove box under the protection of argon gas. A lithium metal plate was used as the negative electrode, a polypropylene film was used as a separating membrane, 1M LiPF6-EC/DMC (1:1, v/v) was used as an electrolyte, and 2032 type button cell case was used.
[0076] The resulting button cells were tested for electrochemical performance at 25°C, current 0.1C, and voltage in a range of 3.0V to 4.5V.
[0077] The test results are shown in Table 1.
Table I Electrochemical performance data of the button cells corresponding to the positive electrode materials obtained from Examples 1-3 and Contrast examples 1-4 discharge capacity after the discharge capacity after cycle io[) rate for first week 100 cycles 100 weeks mAh/g mAh/g Example 1 200.2 183.1 91.5% Example 2 202.7 180.2 88.9% Example 3 203.3 179.7 88.4% Contrast example 1 195.1 156.5 80.2% Contrast example 2 206.3 159.4 77.2% Contrast example 3 2012 170.3 814% Contrast example 4 195.4 130.6 66.8% [0078] From the results in Table 1, it can be seen that the positive electrode material prepared by the method according to the present application can maintain a better cycling pertiftmance on the basis of ensuring the discharge gram specific capacity after the first week due to the shallow doping of the coating substance and the synergistic effect between manganese and phosphate radical in the coating substance (Examples I -3).
[0079] From the comparison between Example 1 and Example 2, it can be seen that if the concentration of phosphate was reduced, the surface defects formed on the surface of LiNio9C000sMno0500 were reduced, and the corresponding loss of lithium was reduced, thus having a slightly higher gram capacity; however, the effect of the coating substance for shallow doping was reduced, and the manganese content of the manganese enrich layer formed was reduced, and the cycling performance became worse.
[0089] From the comparison between Example I and Example 3, it can be seen that higher calcination temperature might lose cycling performance to some extent; the present application can significantly reduce the temperature required to form shallow doping by the surface defects formed by phosphoric acid, thus improving the cycling pertbrmance of the obtained positive electrode material to some extent.
[0081] From the comparison between Example 1 and Contrast example 1, it can be seen that if phosphoric acid was replaced with oxalic acid, the structure of the positive electrode material was severely damaged due to the excessive acidity of oxalic acid, and the capacity and cycling pertbrmance were lost.
[0082] From the comparison between Example 1 and Contrast example 2, it can be seen that if only ordinary water washing was used, the loss of lithium was less compared with phosphoric acid washing, so the capacity was improved to some extent; however, the cycling performance of the obtained positive electrode material was significantly worse due to no deposition and shallow doping of the coating substance.
[0083] From the comparison between Example 1 and Contrast example 3, it can be seen that if phosphoric acid washing was replaced by water washing, the surface of the positive electrode material cannot form defects during the preparation process due to the absence of phosphate radical in the coating substance, which in turn cannot effectively promote the entry of manganese into the lattice of the positive electrode material and form shallow doping, thus the disproportionation and leaching of manganese in the positive electrode material cannot be inhibited, and the final cycling performance was significantly reduced.
[0084] From the comparison between Example I and Contrast example 4, it can be seen that -12 -if only phosphoric acid washing was used, the coating substance did not comprise manganese and cannot inhibit the leaching of manganese in the positive electrode material, thus, the cycling performance also decreased significantly.
[00851 The examples of the present application are described in detail above in conjunction with the accompanying drawings, but the present application is not limited to the above examples, and various variations can be made within the scope of knowledge possessed by those of ordinary skill in the art to which they belong, without departing from the purpose of the present application.
Claims (10)
- CLAIMSI. A positive electrode material, comprising: a layered positive electrode material having a chemical formula Li,M02, wherein x ranges from 035 to I. I and M is a transition metal, including Mn; and a coating substance, which is partially provided on a surface of the layered positive electrode material and partially doped in a surface layer of the layered positive electrode material; wherein the coating substance comprises a tetravalent manganese, a lithium ion and a phosphate ion.
- 2. The positive electrode material according to claim 1, wherein, in Li"MO, M further comprises Ni; preferably, the molar percentage of Ni to M in Li,M02 is 75%.
- 3. The positive electrode material according to claim I or 2, wherein, in the coating substance, the tetravalent manganese is present in a form including manganese dioxide.
- 4. A method for preparing the positive electrode material according to any one of claims I to 3, comprising: mixing the layered positive electrode material with a phosphoric acid aqueous solution, adding an alkaline potassium permanganate solution and a divalent manganese precursor to the obtained mixed system in sequence; and after reaction, drying and calcining a solid product.
- 5. The preparation method according to claim 4, wherein the concentration of the phosphoric acid aqueous solution is I wt% to 5wt%.
- -14 - 6. The preparation method according to claim 4, wherein a solid-liquid ratio of the layered positive electrode material and the phosphoric acid aqueous solution is 0.5g/ml to Ig/ml.
- 7. The preparation method according to claim 4, wherein a molar ratio of the alkaline potassium permanganate and the divalent manganese precursor is (0.8 to 1.2):1.
- 8. The preparation method according to claim 4, wherein the calcination is performed at a temperature of 450°C to 550°C.
- 9. The preparation method according to claim 4, wherein duration of the calcination is 6h to 8h.
- 10. A secondary battery, wherein a preparation raw material thereof comprises the positive electrode material according to any one of claims 1 to 3.-15 -
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| CN202210750189.0A CN115172686A (en) | 2022-06-29 | 2022-06-29 | Cathode material and preparation method and application thereof |
| PCT/CN2022/118010 WO2024000816A1 (en) | 2022-06-29 | 2022-09-09 | Positive electrode material, preparation method therefor, and use thereof |
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| CN108717971A (en) * | 2018-05-24 | 2018-10-30 | 北京长城华冠汽车科技股份有限公司 | The preparation method of manganese dioxide and the anode modified material coated with manganese dioxide |
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- 2022-09-09 HU HU2400112A patent/HUP2400112A1/en unknown
- 2022-09-09 DE DE112022003304.5T patent/DE112022003304T5/en active Pending
- 2022-09-09 GB GB2310145.4A patent/GB2624493A/en active Pending
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| GB202310145D0 (en) | 2023-08-16 |
| DE112022003304T5 (en) | 2024-04-18 |
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