GB2628441A - Method for preparing lithium ferromanganese phosphate cathode material by spray burning and use thereof - Google Patents
Method for preparing lithium ferromanganese phosphate cathode material by spray burning and use thereof Download PDFInfo
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- GB2628441A GB2628441A GB2309851.0A GB202309851A GB2628441A GB 2628441 A GB2628441 A GB 2628441A GB 202309851 A GB202309851 A GB 202309851A GB 2628441 A GB2628441 A GB 2628441A
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- United Kingdom
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- source
- manganese
- lithium
- iron
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 50
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000007921 spray Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 30
- 229910019142 PO4 Inorganic materials 0.000 title claims description 37
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims description 36
- 239000010452 phosphate Substances 0.000 title claims description 36
- 229910000616 Ferromanganese Inorganic materials 0.000 title claims description 35
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 title claims description 35
- 239000010406 cathode material Substances 0.000 title claims description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000011572 manganese Substances 0.000 claims abstract description 47
- 239000011343 solid material Substances 0.000 claims abstract description 38
- 229910052742 iron Inorganic materials 0.000 claims abstract description 37
- 238000002485 combustion reaction Methods 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 35
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 24
- 239000011574 phosphorus Substances 0.000 claims abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000001694 spray drying Methods 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 229910001868 water Inorganic materials 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 22
- -1 polyoxyethylene lauryl ether Polymers 0.000 claims description 17
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 claims description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 8
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 7
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 7
- UJHSIDUUJPTLDY-UHFFFAOYSA-N (2-nitrophenyl)-phenylmethanone Chemical compound [O-][N+](=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 UJHSIDUUJPTLDY-UHFFFAOYSA-N 0.000 claims description 6
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 6
- ZXDZVVSOWQEMOD-UHFFFAOYSA-N nitric hydrazide Chemical compound NN[N+]([O-])=O ZXDZVVSOWQEMOD-UHFFFAOYSA-N 0.000 claims description 6
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 claims description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- UBYFFBZTJYKVKP-UHFFFAOYSA-J [Mn+4].[O-]P([O-])(=O)OP([O-])([O-])=O Chemical compound [Mn+4].[O-]P([O-])(=O)OP([O-])([O-])=O UBYFFBZTJYKVKP-UHFFFAOYSA-J 0.000 abstract description 9
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 abstract description 6
- 229910000398 iron phosphate Inorganic materials 0.000 abstract description 5
- 239000002244 precipitate Substances 0.000 abstract description 5
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 abstract 2
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 abstract 1
- 239000007774 positive electrode material Substances 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 description 33
- 239000012159 carrier gas Substances 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 11
- 239000007787 solid Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910052493 LiFePO4 Inorganic materials 0.000 description 5
- 229910000668 LiMnPO4 Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229940071125 manganese acetate Drugs 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229930091371 Fructose Natural products 0.000 description 3
- 239000005715 Fructose Substances 0.000 description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 3
- 229930006000 Sucrose Natural products 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000005720 sucrose Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000005536 Jahn Teller effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 2
- BECVLEVEVXAFSH-UHFFFAOYSA-K manganese(3+);phosphate Chemical class [Mn+3].[O-]P([O-])([O-])=O BECVLEVEVXAFSH-UHFFFAOYSA-K 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000011056 performance test Methods 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
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
- H01M4/50—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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Disclosed in the present invention are a method for preparing a lithium manganese iron phosphate positive electrode material by means of spray combustion and the use thereof. The method comprises: mixing and dissolving a manganese source, an iron source and a phosphorus source in an organic solvent to obtain an organic solution containing phosphorus, iron and manganese; then adding a surfactant and a combustion improver; subjecting the resulting mixed solution to spray combustion; mixing the resulting solid material with a lithium source and water, subjecting same to a hydrothermal reaction, further adding a carbon source thereto, and performing spray drying; and calcining same to obtain lithium manganese iron phosphate. In the present invention, the generation of a manganese iron phosphate precipitate is avoided by mixing and dissolving a phosphorus source, a manganese source and an iron source in an organic solvent, and corresponding iron phosphate and manganese pyrophosphate are obtained by means of a spray combustion reaction, such that iron and manganese are more evenly mixed, and the specific capacity and the cycle performance of the material are improved.
Description
METHOD FOR PREPARING LITHIUM FERROMANGANESE PHOSPHATE CATHODE MATERIAL BY SPRAY BURNING AND USE THEREOF
TECHNICAL FIELD
The present invention belongs to the technical field of lithium battery cathode materials, and particularly relates to a method for preparing a lithium ferromanganese phosphate cathode material by spray burning and a use thereof
BACKGROUND
Compared with a ternary battery, a lithium iron phosphate battery has the advantages of higher safety and lower cost and the advantages of good thermal stability, long cycle life, environmental friendliness and abundant raw material resources, and is the most potential cathode material for power lithium ion battery at present, thus being favored by more automobile manufacturers, with a continuously increased market share.
However, a LiFePO4 material reduces an overall energy density of the battery due to a lower lithium deintercalation potential platform (about 3.4 V), thus limiting the development thereof in electric vehicles. However, a working voltage of LiMnPO4 for Li is 4.1 V, and if LiMnPO4 can acquire a specific capacity equivalent to that of LiFePO4, it means that the energy density will be 35% higher than that of LiFePO4. Meanwhile, low raw material cost and environmental friendliness are also the advantages of LiMnPO4. However, LiMnPO4 has very low conductivity, almost belonging to an insulator, and the conductivity is only one thousandth of that of LiFePO4. Meanwhile, there may be a Jahn-Teller effect during an oxidation-reduction reaction, leading to a poor rate performance and a low discharge specific capacity of materials.
It can be seen from current research situations that LiMnsFe(1,0PO4 cathode material contains a high energy density, which can compensate for the deficiency of LiFePO4 cathode material in this respect, and improve the problems of low rate and discharge specific capacity of LiMnPO4 cathode material at the same time, thus increasing the possibility of changing a phosphoric acid cathode material into a power lithium-ion battery material.
There are many methods for synthesizing lithium ferromanganese phosphate. At present, LiMn"Fec_")1304 material is prepared by a single high-temperature solid-phase method. However, according to this method, it is difficult to accurately control a ratio of iron to manganese when preparing a precursor, and it is difficult for transition metals to be evenly distributed in a main structure of the material, which may lead to a serious Jahn-Teller effect of Mn3+, thus affecting the cycle and rate performance of the battery. Employing a coprecipitation reaction with a phosphate and a ferrous salt, a manganese salt and an oxidant have the following problems: since an iron phosphate precipitate has a low pH value while a manganese phosphate precipitate has a high pH value, the ferrous salt will react with the oxidant to obtain iron hydroxide at a higher pH value, resulting in high content of ferric hydroxide, low purity of lithium ferromanganese phosphate, and low phosphorus content is.
Therefore, it is necessary to find a method for preparing a lithium ferromanganese phosphate cathode material with high capacity and high cycle performance, which can not only make iron and manganese be evenly mixed at an atomic level, but also make a ratio of phosphorus to iron and manganese reach a theoretical value.
SUMMARY
The present invention aims at solving at least one of the above-mentioned technical problems in the prior art. Therefore, the present invention provides a method for preparing a lithium ferromanganese phosphate cathode material by spray burning and a use thereof. The method can prepare the lithium ferromanganese phosphate cathode material with phosphorus: (iron + manganese) being 1: 1 and uniform mixing of iron and manganese. The material has high specific capacity and cycle performance.
According to an aspect of the present invention, a method for preparing a lithium ferromanganese phosphate cathode material by spray burning is provided, comprising the following steps of: Si: mixing and dissolving a manganese source, an iron source and a phosphorus source in an organic solvent to obtain an organic solution containing phosphorous, iron and magnesium; 52: adding a surfactant and a combustion improver into the organic solution to obtain a mixed solution; 53: performing spray burning on the mixed solution to obtain a first solid material; S4: mixing the first solid material with a lithium source and water, carrying out hydrothermal reaction under acidic conditions, adding a carbon source for mixing after the reaction, and carrying out spray drying to obtain a second solid material; and S5: calcining the second solid material in an inert atmosphere to obtain the lithium ferromanganese phosphate.
In some embodiments of the present invention, in step Si, a molar ratio of iron to manganese in the organic solution is (0.25-4): 1, and (Fe + Mn): P = 1: (1-1.05).
In some embodiments of the present invention, in step Sl, the manganese source is at least one of manganous acetate or manganous lactate; the iron source is at least one of ferric acetate or ferric nitrate; and the phosphorus source is at least one of diethyl phosphate or triethyl phosphate.
In some embodiments of the present invention, in step Sl, the organic solvent is at least one of ethanol or glycerine.
In some embodiments of the present invention, in step Si, a solid-to-liquid ratio of a mixed material of the manganese source, iron source and phosphorus source to the organic solvent is (30 to 50) g/100 mL In some embodiments of the present invention, in step S2, a dosage ratio of the organic solution to the surfactant and the combustion improver is (100-200) mL: (0.5-1.0) g: (1.0-2.0) g.
In some embodiments of the present invention, in step S2, the surfactant is at least one of polyoxyethylene lauryl ether or nonylphenol polyoxyelhylene ether.
In some embodiments of the present invention, in step S2, the combustion improver is at least one of alkyl nitroanisole, nitrohydrazine, alkoxynitroaniline or nitrobenzophenone.
In some embodiments of the present invention, in step S3, the spray burning is performed at a temperature of 550°C to 700°C, an aperture of a nozzle used is 30 pm to 50 pm, and a pressure of spray is 0.8 MPa to 1.5 MPa. Further, the mixed solution enters a combustion chamber of a spray burning device for combustion through a carrier gas flow, wherein a carrier gas is air or oxygen, and a carrier gas flow rate is 100 L/h to 150 L/h.
In some embodiments of the present invention, in step S4, after the first solid material is mixed with the lithium source and the water, a pH is adjusted to be 2.5 to 4.0 by adding an acid, and then the hydrothermal reaction is carried out.
In some embodiments of the present invention, in step S4, a dosage of the water s 100% to 200% of a total solid mass of the first solid material and the lithium source.
In some embodiments of the present invention, in step S4, a ratio of the first solid material to the lithium source is that (Fe + Mn): Li = 1: (1.0-1.2).
In some embodiments of the present invention, in step S4, the lithium source is at least one of lithium nitrate, lithium acetate, lithium hydroxide or lithium carbonate.
In some embodiments of the present invention, in step S4, the hydrothermal reaction is carried out at a temperature of 100°C to 120°C. Further, the hydrothermal reaction lasts for 2 hours to 4 hours.
In some embodiments of the present invention, in step S4, a dosage of the carbon source is 0.3 times to 0.5 times of the molecular weight of iron element in the first solid material.
In some embodiments of the present invention, in step S4, the carbon source is at least one of glucose, sucrose or fructose.
In some embodiments of the present invention, in step S5, the calcining is performed at a temperature of 600°C to 850°C. Further, the calcining lasts for 6 hours to 20 hours.
The present invention also provides a use of the method in preparing a lithium ion battery.
According to a preferred embodiment of the present invention, the present invention at least has the following beneficial effects.
1. According to the present invention, the manganese source, iron source and phosphorus source are dissolved in the organic solvent, so that phosphorus, iron and manganese are evenly mixed, and then subjected to spray burning to generate different iron and manganese phosphates by utilizing the different stabilities of iron and manganese phosphates, wherein iron exists in the form of iron phosphate, and manganese stably exists in the form of manganese pyrophosphate, so as to obtain a mixture of iron phosphate and manganese pyrophosphate, and manganese pyrophosphate in the mixture is further subjected to hydrothermal reaction under acidic conditions, so that manganese pyrophosphate is further subjected to hydrothermal hydrolysis, and manganese pyrophosphate in the precipitate is formed into lithium manganese phosphate in advance, then the carbon source is added, and after spray drying, the lithium ferromanganese phosphate is prepared by sintering. The reaction equation is as follows: spray burning reaction (taking ferric acetate, manganous acetate and triethyl phosphate for
example):
Fe(CR3C00)3+PO4(CELCH2)3+1502->FePO4+12C 02+12H20, and 2Mn(CH3C00)2+2PO4CH3CH2)3+260 2 ->Mn2P20 7+20C 02+2 1H2 0 hydrothermal reaction: H20+2Li++Mn2P207 2L MnPO4+2H+; and sintering reaction: C+Li20+2FePa4 2LiFePai+CO.
2. Because the precipitation environments of iron phosphate and manganese phosphate are different, it is difficult to achieve coprecipitation. In the process of spray burning according to the present invention, firstly, the phosphorus source, manganese source and iron source are mixed and dissolved in the organic solvent to avoid the generation of ferromanganese phosphate precipitate, and then corresponding ferromanganese phosphate and manganese pyrophosphate are obtained through spray burning reaction. On the one hand, the mixing of iron and manganese is more uniform, which is beneficial to the subsequent preparation of the lithium ferromanganese phosphate to improve the specific capacity and cycle performance of the material. On the other hand, (Fe + P = 1: 1 is ensured, which ensures sufficient phosphorus content for the next step of synthesizing the lithium ferromanganese phosphate and avoids the problem of supplementing the phosphorus source.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will be further explained with reference to the accompanying drawings and examples hereinafter, wherein: FIG. 1 is an SEM image of the lithium ferromanganese phosphate prepared in Example 1 of the present invention.
DETAILED DESCRIPTION
The concepts and the technical effects produced of the present invention will be clearly and completely described in conjunction with the examples so as to sufficiently understand the objects, the features and the effects of the present invention. Obviously, the described examples are merely some examples of the present invention, rather than all the examples. All other examples obtained by those skilled in the art without going through any creative effort shall fall within the protection scope of the present invention.
Example 1
This example prepared a lithium ferromanganese phosphate by spray burning, and the specific process was as follows: step I: mixing manganese acetate, ferric acetate and triethyl phosphate according to a molar ratio of iron to manganese of 1: 1 and (Fe + Mn): P = 1: 1, and dissolving the mixture in ethanol according to a ratio of 30 g/100 mL to obtain an organic solution containing phosphorus, iron and manganese; step 2: according to a material ratio of the organic solution: polyoxyethylene lauryl ether: alkyl nitroanisole being 100 mL. 0 5 g' 1 0 g, adding polyoxyethylene lauryl ether and alkyl nitroanisole into the organic solution, and uniformly mixing to obtain a mixed solution; step 3: adding the mixed solution into a spray burning device, and entering a combustion chamber for combustion through a carrier gas flow; wherein a nozzle aperture of the spray burning device was 30 pm, a spray pressure was 1.5 MPa, a carrier gas was oxygen, a carrier gas flow rate was 100 L/h, and a temperature of the combustion chamber was controlled at 550°C; step 4: after the reaction, collecting solid materials in the combustion chamber, mixing the solid materials obtained in step 3 with lithium nitrate according to a molar ratio of (Fe + Mn): Li = 1: (1.0 -1.2), adding deionized water accounting for 100% of the total solid mass, adjusting a pH to 2.5 with nitric acid, and performing a hydrothermal reaction for 4 hours in a closed reaction kettle at a reaction temperature of 120°C; step 5: after the hydrothermal reaction, adding glucose with a molar amount of 0.3 times of the iron element into the reaction kettle, mixing evenly, and then performing spray drying on the mixture to obtain a solid material; and step 6: calcining the solid material obtained in step 5 at 750°C for 14 hours under the protection of inert gas, and naturally cooling to room temperature to obtain a finished product of lithium ferromanganese phosphate cathode material.
Example 2
This example prepared a lithium ferromanganese phosphate by spray burning, and the specific process was as follows: step 1: mixing manganese acetate, ferric nitrate and triethyl phosphate according to a molar ratio of iron to manganese of 2: 1 and (Fe + Mn): P = 1: 1, and dissolving the mixture in glycerine according to a ratio of 40 g/100 mL to obtain an organic solution containing phosphorus, iron and manganese; step 2: according to a material ratio of the organic solution: nonylphenol polyoxyethylene ether: nitrohydrazine being 150 mL: 0.8 g: 1.5 g, adding nonylphenol polyoxyethylene ether and nitrohydrazine into the organic solution, and uniformly mixing to obtain a mixed solution; step 3: adding the mixed solution into a spray burning device, and entering a combustion chamber for combustion through a carrier gas flow; wherein a nozzle aperture of the spray burning device was 40 nm, a spray pressure was 1.2 MPa, a carrier gas was air, a carrier gas flow rate was 120 L/h, and a temperature of the combustion chamber was controlled at 600°C; step 4: after the reaction, collecting solid materials in the combustion chamber, mixing the solid materials obtained in step 3 with lithium acetate according to a molar ratio of (Fe + Mn): Li = 1: (1.0-1.2), adding deionized water accounting for 150% of the total solid mass, adjusting a pH to 3.0 with nitric acid, and performing a hydrothermal reaction for 3 hours in a closed reaction kettle at a reaction temperature of 110°C; step 5: after the hydrothermal reaction, adding sucrose with a molar amount of 0.4 times of the iron element into the reaction kettle, mixing evenly, and then performing spray drying on the mixture to obtain a solid material; and step 6: calcining the solid material obtained in step 5 at 600°C for 20 hours under the protection of inert gas, and naturally cooling to room temperature to obtain a finished product of lithium ferromanganese phosphate cathode material.
Example 3
This example prepared a lithium ferromanganese phosphate by spray burning, and the specific process was as follows: step 1: mixing manganous lactate, ferric acetate and diethyl phosphate according to a molar ratio that iron to manganese of 4:1 and (Fe + Mn): P = 1: 1, and dissolving the mixture in ethanol according to a ratio of 50 g/100 mL to obtain an organic solution containing phosphorus, iron and 20 manganese; step 2: according to a material ratio of the organic solution: polyoxyethylene lauryl ether: nitrobenzophenone being 200 mL: 1.0 g: 2.0 g, adding polyoxyethylene lauryl ether and nitrobenzophenone into the organic solution, and uniformly mixing to obtain a mixed solution; step 3: adding the mixed solution into a spray burning device, and entering a combustion chamber for combustion through a carrier gas flow; wherein a nozzle aperture of the spray burning device was 50 nm, a spray pressure was 0.8 MPa, a carrier gas was air or oxygen, a carrier gas flow rate was 150 L/h, and a temperature of the combustion chamber was controlled at 700°C; step 4: after the reaction, collecting solid materials in the combustion chamber, mixing the solid materials obtained in step 3 with lithium hydroxide according to a molar ratio of (Fe + Mn): Li =1: (1.0-1.2), adding deionized water accounting for 200% of the total solid mass, adjusting a pH to 4.0 with nitric acid, and performing a hydrothermal reaction for 2 hours in a closed reaction kettle at a reaction temperature of 120°C; step 5: after the hydrothermal reaction, adding fructose with a molar amount of 0.5 times of the iron element into the reaction kettle, mixing evenly, and then performing spray drying on the mixture to obtain a solid material; and step 6: calcining the solid material obtained in step 5 at 850°C for 6 hours under the protection of inert gas, and naturally cooling to room temperature to obtain a finished product of lithium ferromanganese phosphate cathode material.
Comparative Example 1 In this comparative example, a lithium ferromanganese phosphate was prepared, which was different from Example 1 in that no hydrothermal reaction was performed, and the specific process was as follows: step 1: mixing manganese acetate, ferric acetate and triethyl phosphate according to a molar ratio of iron to manganese of 1: 1 and (Fe+Mn): P = 1: 1, and dissolving the mixture in ethanol according to a ratio of 30 W100 mL to obtain an organic solution containing phosphorus, iron and manganese; step 2: according to a material ratio of the organic solution: polyoxyethylene lauryl ether: alkyl nitroanisole being 100 mL 0 5 g: 1.0 g, adding polyoxyethylene lauryl ether and alkyl nitroanisole into the organic solution, and uniformly mixing to obtain a mixed solution; step 3: adding the mixed solution into a spray burning device, and entering a combustion chamber for combustion through a carrier gas flow; wherein a nozzle aperture of the spray burning device was 30 a spray pressure was 1.5 MPa, a carrier gas was oxygen, a carrier gas flow rate was 100 L/h, and a temperature of the combustion chamber was controlled at 550°C; step 4: after the reaction, collecting solid materials in the combustion chamber, mixing the solid materials obtained in step 3 with lithium nitrate according to a molar ratio of (Fe+Mn): Li = 1: (1.0-1.2), adding deionized water accounting for 100% of the total solid mass, adding glucose with a molar amount of 0.3 times of the iron element, mixing evenly and then performing spray drying to obtain a solid material; and step 5: calcining the solid material obtained in step 4 at 750°C for 14 hours under the protection of inert gas, and naturally cooling to room temperature to obtain a finished product of lithium ferromanganese phosphate cathode material.
Comparative Example 2 In this comparative example, a lithium ferromanganese phosphate was prepared, which was different from Example 2 in that no hydrothermal reaction was performed, and the specific process was as follows: step 1: mixing manganese acetate, ferric nitrate and triethyl phosphate according to a molar ratio of iron to manganese of 2: 1 and (Fe+Mn): P = 1: 1, and dissolving the mixture in glycerine according to a ratio of 40 g/100 mL to obtain an organic solution containing phosphorus, iron and manganese; step 2: according to a material ratio of the organic solution: nonylphenol polyoxyethylene ether: nitrohydrazine being 150 mL: 0.8 g: 1.5 g, adding nonylphenol polyoxyethylene ether and nitrohydrazine into the organic solution, and uniformly mixing to obtain a mixed solution; step 3: adding the mixed solution into a spray burning device, and entering a combustion chamber for combustion through a carrier gas flow; wherein a nozzle aperture of the spray burning device was 40 pm, a spray pressure was 1.2 MPa, a carrier gas was air, a carrier gas flow rate was 120 L/h, and a temperature of the combustion chamber was controlled at 600°C; step 4: after the reaction, collecting solid materials in the combustion chamber, mixing the solid materials obtained in step 3 with lithium acetate according to a molar ratio of (Fe+Mn): Li = (1.0-1.2), adding deionized water accounting for 150% of the total solid mass, adding sucrose with a molar amount of 0.4 times of the iron element, mixing evenly and then performing spray drying to obtain a solid material; and step 5: calcining the solid material obtained in step 4 at 600°C for 20 hours under the protection of inert gas, and naturally cooling to room temperature to obtain a finished product of lithium ferromanganese phosphate cathode material.
Comparative Example 3 In this comparative example, a lithium ferromanganese phosphate was prepared, which was different from Example 3 in that no hydrothermal reaction was performed, and the specific process was as follows: step 1: mixing manganese acetate, ferric acetate and a phosphorus source being diethyl phosphate according to a molar ratio of iron to manganese of 4: 1 and (Fe+Mn): P = 1: 1, and dissolving the mixture in ethanol according to a ratio of 50 g/100 mL to obtain an organic solution of phosphorus, iron and manganese; step 2: according to a material ratio of the organic solution: polyoxyethylene lauryl ether: nitrobenzophenone being 200 mL-10 g: 2.0 g, adding polyoxyethylene lauryl ether and nitrobenzophenone into the organic solution, and uniformly mixing to obtain a mixed solution; step 3: adding the mixed solution into a spray burning device, and entering a combustion chamber for combustion through a carrier gas flow; wherein a nozzle aperture of the spray burning device was 50 jun, a spray pressure was 0.8 MPa, a carrier gas was air or oxygen, a carrier gas flow rate was 150 L/h, and a temperature of the combustion chamber was controlled at 700°C; step 4: after the reaction, collecting solid materials in the combustion chamber, mixing the solid materials obtained in step 3 with lithium hydroxide according to a molar ratio of (Fe+Mn): Li = 1: (1.0-1.2), adding deionized water accounting for 200% of the total solid mass, adding fructose with a molar amount of 0.5 times of the iron element, mixing evenly and then performing spray drying to obtain a solid material; and step 5: calcining the solid material obtained in step 4 at 850°C for 6 hours under the protection of inert gas, and naturally cooling to room temperature to obtain a finished product of lithium ferromanganese phosphate cathode material.
Test Example
The lithium ferromanganese phosphate obtained in the examples and comparative examples as a cathode materials, acetylene black as a conductive agent and PVDF as an adhesive were mixed according to a mass ratio of 8: 1: 1, and added with a certain amount of organic solvent NMP, and the mixture was stirred and then coated on an aluminum foil to prepare a positive plate. In this process, it was found that a slurry prepared from the lithium ferromanganese phosphate cathode materials obtained in the comparative examples was mostly jelly-like and difficult to coat. It was speculated that there was too much residual lithium, so that it was difficult to further sinter manganese pyrophosphate and the lithium source to prepare the lithium ferromanganese phosphate cathode material. Contents of residual lithium in the examples and comparative examples were detected. Results were shown in Table L A2023 button cell comprising the above positive plate, a negative electrode made of a lithium metal plate, a diaphragm made of Celgard2400 polypropylene porous membrane, an electrolyte comprising a solvent consisting of EC, DMC and EMC in a mass ratio of L 1: 1 and a solute of LiPF6 with a concentration of 1.0 mol/L was assembled in a glove box. A charge-discharge cycle performance of the battery was tested, and specific discharge capacities at 0.1 C and 1 C were tested in a cut-off voltage range of 2.2 V to 4.3 V. Results of the electrochemical performance test were shown in Table 1.
Table 1 Contents of residual lithium and electrochemical performances of lithium ferromanganese phosphate Total content of Residual Residual Discharge Discharge Capacity residual lithium LiOH Li2CO3 capacity of capacity of retention rate of (wt%) (vt%) (wiyo 0.1 C mAhig 1 C mAh/g 600 cycles at 1 C Example I 0.13 0.09 0.04 165.9 140.4 92.3% Example 2 0.14 0.08 0.06 165.4 141.1 93.1% Example 3 0.16 0.08 0.08 165.1 140.6 92.6% Comparative 8.36 5.63 2.73 86.5 64.7 73.2%
Example 1
Comparative 5.23 3.53 1.70 104.4 83.3 77.6%
Example 2
Comparative 3.87 2.46 1.41 122.5 101.6 82.4%
Example 3
It could be seen from Table 1 that the specific capac'ties of the comparative examples were all very low, because manganese pyrophosphate was not subjected to the hydrothermal reaction and was not successfully converted into lithium manganese phosphate by spray drying with the lithium source, so that qualified lithium ferromanganese phosphate could not be prepared.
The examples of the present invention are described in detail with reference to the drawings above, but the present invention is not limited to the above examples, and various changes may also be made within the knowledge scope of those ordinary skilled in the art without departing from the purpose of the present invention. In addition, in case of no conflict, the examples in the present invention and the features in the examples may be combined with each other.
Claims (10)
- CLAIMS1. A method for preparing a lithium ferromanganese phosphate cathode material by spray burning, comprising the following steps of: Si: mixing and dissolving a manganese source, an iron source and a phosphorus source in an organic solvent to obtain an organic solution containing phosphorous, iron and magnesium; S2: adding a surfactant and a combustion improver into the organic solution to obtain a mixed solution; S3: performing spray burning on the mixed solution to obtain a first solid material; S4: mixing the first solid material with a lithium source and water, carrying out hydrothermal reaction under acidic conditions, adding a carbon source for mixing after the reaction, and carrying out spray drying to obtain a second solid material; and S5: calcining the second solid material in an inert atmosphere to obtain the lithium ferromanganese phosphate.
- 2. The method according to claim 1, wherein in step Si, the manganese source is at least one of manganous acetate or manganous lactate; the iron source is at least one of ferric acetate or ferric nitrate; and the phosphorus source is at least one of diethyl phosphate or triethyl phosphate.
- 3. The method according to claim 1, wherein in step Sl, a solid-to-liquid ratio of a mixed material of the manganese source, iron source and phosphorus source to the organic solvent is (30 to 50) g/100 mL.
- 4. The method according to claim 1, wherein in step S2, a dosage ratio of the organic solution, the surfactant and the combustion improver is (100-200) mL: (0.5-1.0) g: (1.0-2.0) g.
- 5. The method according to claim 1, wherein in step S2, the surfactant is at least one of polyoxyethylene lauryl ether or nonylphenol polyoxyethylene ether.
- 6. The method according to claim 1, wherein in step S2, the combustion improver is at least one of alkyl nitroanisole, nitrohydrazine, alkoxynitroaniline or nitrobenzophenone.
- 7. The method according to claim 1, wherein in step S3, the spray burning is performed at a -1 -temperature of 550°C to 700°C, an aperture of a nozzle used is 30 pm to 50 pm, and a pressure of the spray is 0.8 MPa to 1.5 MPa.
- 8. The method according to claim 1, wherein in step S4, after the first solid material is mixed with the lithium source and the water, a pH is adjusted to be 2.5 to 4.0 by adding an acid, and then the hydrothermal reaction is carried out.
- 9. The method according to claim 1, wherein in step S4, the hydrothermal reaction is carried out at a temperature of 100°C to 120°C.
- 10. Use of the method according to any one of claims 1 to 9 in preparing a lithium ion battery.
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| PCT/CN2023/077682 WO2024055516A1 (en) | 2022-09-16 | 2023-02-22 | Method for preparing lithium manganese iron phosphate positive electrode material by means of spray combustion and use thereof |
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| US20170040596A1 (en) * | 2014-04-29 | 2017-02-09 | Jiangsu Huadong Institute Of Li-Ion Battery Co., Ltd. | Methods for making lithium manganese phosphate and lithium manganese phosphate/carbon composite material |
| CN113582151A (en) * | 2021-07-28 | 2021-11-02 | 段镇忠 | Lithium ferric manganese phosphate cathode material and preparation method and application thereof |
| CN115477295A (en) * | 2022-09-16 | 2022-12-16 | 广东邦普循环科技有限公司 | Method for preparing lithium iron manganese phosphate anode material by spray combustion and application thereof |
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- 2023-02-22 GB GB2309851.0A patent/GB2628441A/en active Pending
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| US20170040596A1 (en) * | 2014-04-29 | 2017-02-09 | Jiangsu Huadong Institute Of Li-Ion Battery Co., Ltd. | Methods for making lithium manganese phosphate and lithium manganese phosphate/carbon composite material |
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