CN115477295A - Method for preparing lithium iron manganese phosphate anode material by spray combustion and application thereof - Google Patents
Method for preparing lithium iron manganese phosphate anode material by spray combustion and application thereof Download PDFInfo
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- CN115477295A CN115477295A CN202211130826.0A CN202211130826A CN115477295A CN 115477295 A CN115477295 A CN 115477295A CN 202211130826 A CN202211130826 A CN 202211130826A CN 115477295 A CN115477295 A CN 115477295A
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- manganese
- iron
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- lithium
- phosphate
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- 238000002485 combustion reaction Methods 0.000 title claims abstract description 58
- 239000007921 spray Substances 0.000 title claims abstract description 33
- 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 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000010405 anode material Substances 0.000 title claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000011572 manganese Substances 0.000 claims abstract description 45
- 229910052742 iron Inorganic materials 0.000 claims abstract description 31
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 28
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 25
- 239000011574 phosphorus Substances 0.000 claims abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000011343 solid material Substances 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 19
- -1 polyoxyethylene lauryl ether Polymers 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 238000001694 spray drying Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 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
- 229940071125 manganese acetate Drugs 0.000 claims description 7
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 7
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- LGROKZMEHJZWDU-UHFFFAOYSA-N n-amino-n-phenylnitramide Chemical compound [O-][N+](=O)N(N)C1=CC=CC=C1 LGROKZMEHJZWDU-UHFFFAOYSA-N 0.000 claims description 6
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 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 4
- KSNGEYQWLMRSIR-UHFFFAOYSA-L 2-hydroxypropanoate;manganese(2+) Chemical compound [Mn+2].CC(O)C([O-])=O.CC(O)C([O-])=O KSNGEYQWLMRSIR-UHFFFAOYSA-L 0.000 claims description 4
- 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
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- 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 8
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 abstract description 5
- 239000002244 precipitate Substances 0.000 abstract description 5
- 239000005955 Ferric phosphate Substances 0.000 abstract description 4
- 229940032958 ferric phosphate Drugs 0.000 abstract description 4
- 229910000399 iron(III) phosphate Inorganic materials 0.000 abstract description 4
- 229910000616 Ferromanganese Inorganic materials 0.000 abstract description 3
- 229910019142 PO4 Inorganic materials 0.000 abstract description 3
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 3
- 239000010452 phosphate Substances 0.000 abstract description 3
- 239000012159 carrier gas Substances 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 238000005507 spraying Methods 0.000 description 12
- 239000010406 cathode material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 4
- 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 description 4
- 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
- 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
- 229960004793 sucrose Drugs 0.000 description 3
- 230000005536 Jahn Teller effect Effects 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229960004887 ferric hydroxide Drugs 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
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 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
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 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
- 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
- 239000011230 binding agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 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
- 239000012212 insulator Substances 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 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
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 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 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal 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
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 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
- 239000005720 sucrose Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- 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
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Crystallography & Structural Chemistry (AREA)
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- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for preparing a lithium manganese iron phosphate anode material by spray combustion and application thereof. According to the invention, the phosphorus source, the manganese source and the iron source are mixed and dissolved by the organic solvent, so that the generation of ferromanganese phosphate precipitate is avoided, and the corresponding ferric phosphate and manganese pyrophosphate are obtained through spray combustion reaction, so that the ferromanganese is mixed more uniformly, and the specific capacity and the cycle performance of the material are improved.
Description
Technical Field
The invention belongs to the technical field of lithium battery anode materials, and particularly relates to a method for preparing a lithium iron manganese phosphate anode material by spray combustion and application thereof.
Background
Compared with a ternary battery, the lithium iron phosphate battery has the advantages of higher safety and lower cost, has the advantages of good thermal stability, long cycle life, environmental friendliness, rich raw material sources and the like, is the most promising power lithium ion battery anode material at present, is gaining favor of more automobile manufacturers, and has continuously improved market share.
However, liFePO 4 The material has a low de-intercalated lithium potential platform (about 3.4V), so that the overall energy density of the battery is reduced, and the development of the battery on electric automobiles is limited. And LiMnPO 4 The working voltage for Li is 4.1V if LiMnPO 4 Can obtain LiFePO 4 Equivalent specific capacity means that the catalyst is equivalent to LiFePO 4 The energy density will be higher by 35% in comparison. Meanwhile, the product is also LiMnPO with low cost of raw materials and environmental protection 4 The advantage of (1). However, liMnPO 4 Has very low conductivity, almost belongs to an insulator, and only LiFePO 4 One thousandth of (a); meanwhile, jahn-Teller effect exists in the redox reaction process, so that the rate performance of the material is poor and the specific discharge capacity is low.
As can be seen from the current state of research, liMn x Fe (1-x) PO 4 The anode material has high energy density and can compensate LiFePO 4 The deficiency of the anode material in this respect is improved and LiMnPO is improved 4 The multiplying power and the specific discharge capacity of the anode material are low, and the possibility that the phosphoric acid anode material is changed into a power lithium ion battery material is improved.
Many synthesis methods of lithium manganese iron phosphate exist, and currently, a single high-temperature solid phase method is used for preparing LiMn x Fe (1-x) PO 4 MaterialHowever, the method is difficult to accurately control the proportion of iron and manganese during precursor preparation, and transition metals are difficult to be uniformly distributed in the main structure of the material, which can cause Mn 3+ The Jahn-Teller effect of the battery is serious, and the cycle and rate performance of the battery are influenced. The coprecipitation reaction of phosphate and ferrous salt, manganese salt and oxidant has the following problems: because the pH of the iron phosphate precipitate is low and the pH of the manganese phosphate precipitate is high, at higher pH, the ferrous salt reacts with the oxidant to obtain ferric hydroxide, resulting in high ferric hydroxide content, low purity, and low phosphorus content.
Therefore, a method for preparing the high-capacity and high-cycle-performance lithium iron manganese phosphate cathode material is needed, wherein the iron and manganese can be uniformly mixed on the atomic layer, and the proportion of phosphorus to iron and manganese can reach a theoretical value.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a method for preparing a lithium iron manganese phosphate positive electrode material by spray combustion and application thereof, wherein the method can be used for preparing phosphorus: (iron + manganese) =1:1, and the iron and manganese are uniformly mixed, and the lithium iron manganese phosphate anode material has high specific capacity and cycle performance.
According to one aspect of the invention, the method for preparing the lithium iron manganese phosphate cathode material by spray combustion comprises the following steps:
s1: 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;
s2: adding a surfactant and a combustion improver into the organic solution to obtain a mixed solution;
s3: carrying out spray combustion 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 an acidic condition, adding a carbon source after the reaction is finished, mixing, and carrying out spray drying to obtain a second solid material;
s5: and calcining the second solid material in an inert atmosphere to obtain the lithium iron manganese phosphate.
In some embodiments of the invention, in step S1, the molar ratio of iron to manganese in the organic solution is (0.25-4): 1, (Fe + Mn): p =1: (1-1.05).
In some embodiments of the invention, in step S1, the manganese source is at least one of manganese acetate or manganese lactate; the iron source is at least one of iron acetate or iron nitrate; the phosphorus source is at least one of diethyl phosphate or triethyl phosphate.
In some embodiments of the invention, in step S1, the organic solvent is at least one of ethanol or glycerol.
In some embodiments of the invention, in step S1, the solid-to-liquid ratio of the mixture of the manganese source, the iron source and the phosphorus source to the organic solvent is (30-50) g/100mL.
In some embodiments of the present invention, in step S2, the organic solution, the surfactant and the combustion improver are used in a ratio of (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 polyoxyethylene nonylphenol ether.
In some embodiments of the present invention, in step S2, the combustion improver is at least one of alkyl nitroanisole, nitrophenylhydrazine, alkoxy nitroaniline or nitrobenzophenone.
In some embodiments of the present invention, in step S3, the temperature of the spray combustion is 550 to 700 ℃, the pore size of the spray head used is 30 to 50 μm, and the pressure of the spray is 0.8 to 1.5MPa. Further, the mixed liquid enters a combustion chamber of the spray combustion device for combustion through carrier gas flow, the carrier gas is air or oxygen, and the carrier gas flow is 100-150L/h.
In some embodiments of the present invention, in step S4, after the first solid material is mixed with the lithium source and water, an acid is added to adjust the pH to 2.5 to 4.0, and then the hydrothermal reaction is performed.
In some embodiments of the present invention, in step S4, the amount of water is 100% to 200% of the total mass of the first solid material and the lithium source solid.
In some embodiments of the present invention, in step S4, the ratio of the first solid material to the lithium source is in a molar ratio (Fe + Mn): li =1: (1.0-1.2).
In some embodiments of the 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, the temperature of the hydrothermal reaction in step S4 is 100 to 120 ℃. Further, the time of the hydrothermal reaction is 2-4h.
In some embodiments of the present invention, in step S4, the amount of the carbon source is 0.3 to 0.5 times the molar amount of the iron element in the first solid material.
In some embodiments of the invention, in step S4, the carbon source is at least one of glucose, sucrose or fructose.
In some embodiments of the invention, the temperature of the calcination in step S5 is 600 to 850 ℃. Further, the calcining time is 6-20h.
The invention also provides application of the method in preparation of the lithium ion battery.
According to a preferred embodiment of the present invention, at least the following advantages are provided:
1. the method comprises the steps of dissolving a manganese source, an iron source and a phosphorus source in an organic solvent, uniformly mixing phosphorus, iron and manganese, performing spray combustion, and generating different iron and manganese phosphates by utilizing different stabilities of the iron and manganese phosphates, wherein iron exists in the form of ferric phosphate, and manganese exists stably in the form of manganese pyrophosphate to obtain a mixture of the ferric phosphate and the manganese pyrophosphate, performing hydrothermal reaction under an acidic condition to further perform hydrothermal hydrolysis on the manganese pyrophosphate, forming the manganese pyrophosphate in a precipitate into lithium manganese phosphate in advance, adding a carbon source, performing spray drying, and sintering to obtain the lithium manganese iron phosphate. The reaction equation is as follows:
spray combustion reaction (taking iron acetate, manganese acetate, triethyl phosphate as an example):
Fe(CH 3 COO) 3 +PO 4 (CH 3 CH 2 ) 3 +15O 2 →FePO 4 +12CO 2 +12H 2 O；
2Mn(CH 3 COO) 2 +2PO 4 (CH 3 CH 2 ) 3 +26O 2 →Mn 2 P 2 O 7 +20CO 2 +21H 2 O；
hydrothermal reaction:
H 2 O+2Li + +Mn 2 P 2 O 7 →2LiMnPO 4 +2H + ；
sintering reaction:
C+Li 2 O+2FePO 4 →2LiFePO 4 +CO。
2. according to the invention, in the spray combustion process, firstly, a phosphorus source, a manganese source and an iron source are mixed and dissolved in an organic solvent dissolving mode, so that the generation of ferromanganese phosphate precipitate is avoided, and then, the corresponding ferric phosphate and manganese pyrophosphate are obtained through spray combustion reaction. And on the other hand, P =1:1 is ensured, sufficient phosphorus content is ensured for the next step of synthesizing lithium iron manganese phosphate, and the problem of supplementing a phosphorus source is avoided.
Drawings
The invention is further described with reference to the following figures and examples, in which:
fig. 1 is an SEM image of lithium iron manganese phosphate prepared in example 1 of the present invention.
Detailed Description
The idea of the invention and the resulting technical effects will be clearly and completely described below in connection with the embodiments, so that the objects, features and effects of the invention can be fully understood. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The embodiment prepares the lithium iron manganese phosphate by spray combustion, and the specific process comprises the following steps:
step 1, mixing manganese acetate, iron acetate and triethyl phosphate according to the molar ratio of 1:1 and (Fe + Mn): P =1:1, and dissolving the mixture in ethanol according to the proportion of 30g/100mL to obtain an organic solution of phosphorus, iron and manganese;
step 2, preparing an organic solution according to the material ratio: polyoxyethylene lauryl ether: alkyl nitroanisole =100mL, and 0.5g of;
step 3, adding the mixed solution into a spray combustion device, and feeding the mixed solution into a combustion chamber for combustion through carrier gas flow; the aperture of a spray head of the spraying device is 30 mu m, the spraying pressure is 1.5MPa, the carrier gas is oxygen, the carrier gas flow is 100L/h, and the temperature of a combustion chamber is controlled to be 550 ℃;
step 4, after the reaction is finished, collecting a solid material in the combustion chamber, mixing the solid material obtained in the step 3 with lithium nitrate according to a molar ratio (Fe + Mn): li =1 (1.0-1.2), adding deionized water accounting for 100% of the total mass of the solid, adjusting the pH to 2.5 by using nitric acid, and carrying out hydrothermal reaction in a closed reaction kettle for 4 hours at the reaction temperature of 120 ℃;
step 5, after the hydrothermal reaction is finished, adding glucose with the molar weight of 0.3 time that of the iron element into the reaction kettle, uniformly mixing, and then carrying out spray drying to obtain a solid material;
and 6, calcining the solid material obtained in the step 5 for 14 hours at 750 ℃ under the protection of inert gas, and naturally cooling to room temperature to obtain a finished product of the lithium iron manganese phosphate cathode material.
Example 2
The embodiment prepares the lithium iron manganese phosphate by spray combustion, and the specific process comprises the following steps:
step 1, mixing manganese acetate, ferric nitrate and triethyl phosphate according to the molar ratio of 2:1 and (Fe + Mn): P =1:1, and dissolving the mixture in glycerol according to the proportion of 40g/100mL to obtain an organic solution of phosphorus, iron and manganese;
step 2, preparing an organic solution according to the material ratio: polyoxyethylene nonyl phenyl ether: the preparation method comprises the following steps of (1) adding nonylphenol polyoxyethylene ether and nitrophenylhydrazine into an organic solution, wherein the nitrophenylhydrazine = 150mL;
step 3, adding the mixed solution into a spray combustion device, and enabling the mixed solution to enter a combustion chamber for combustion through carrier gas flow; the aperture of a spray head of the spraying device is 40 mu m, the spraying pressure is 1.2MPa, the carrier gas is air, the carrier gas flow is 120L/h, and the temperature of a combustion chamber is controlled to be 600 ℃;
step 4, after the reaction is finished, collecting a solid material in the combustion chamber, mixing the solid material obtained in the step 3 with lithium acetate according to a molar ratio (Fe + Mn): li =1 (1.0-1.2), adding deionized water accounting for 150% of the total mass of the solid, adjusting the pH to 3.0 by using nitric acid, and carrying out hydrothermal reaction in a closed reaction kettle for 3 hours at the reaction temperature of 110 ℃;
step 5, after the hydrothermal reaction is finished, adding cane sugar with the molar weight of 0.4 time of that of the iron element into the reaction kettle, uniformly mixing, and then carrying out spray drying to obtain a solid material;
and 6, calcining the solid material obtained in the step 5 for 20 hours at the temperature of 600 ℃ under the protection of inert gas, and naturally cooling to room temperature to obtain a finished product of the lithium iron manganese phosphate cathode material.
Example 3
In this embodiment, a lithium iron manganese phosphate is prepared by spray combustion, and the specific process is as follows:
step 1, mixing manganese lactate, iron acetate and phosphorus source diethyl phosphate according to the molar ratio of iron to manganese 4:1 and the molar ratio of (Fe + Mn) P =1:1, and dissolving the mixture in ethanol according to the ratio of 50g/100mL to obtain an organic solution of phosphorus, iron and manganese;
step 2, preparing an organic solution according to the material ratio: polyoxyethylene lauryl ether: 1.0g of nitrobenzophenone =200mL, and 2.0g of;
step 3, adding the mixed solution into a spray combustion device, and feeding the mixed solution into a combustion chamber for combustion through carrier gas flow; the aperture of a nozzle of the spraying device is 50 mu m, the spraying pressure is 0.8MPa, the carrier gas is air or oxygen, the carrier gas flow is 150L/h, and the temperature of a combustion chamber is controlled to be 700 ℃;
step 4, after the reaction is finished, collecting solid materials in the combustion chamber, mixing the solid materials obtained in the step 3 with lithium hydroxide according to a molar ratio (Fe + Mn): li =1 (1.0-1.2), adding deionized water accounting for 200% of the total mass of the solid materials, adjusting the pH to 4.0 by using nitric acid, and carrying out hydrothermal reaction in a closed reaction kettle for 2 hours at the reaction temperature of 120 ℃;
step 5, after the hydrothermal reaction is finished, adding fructose with the molar weight 0.5 times that of the iron element into the reaction kettle, uniformly mixing, and then carrying out spray drying to obtain a solid material;
and 6, calcining the solid material obtained in the step 5 for 6 hours at 850 ℃ under the protection of inert gas, and naturally cooling to room temperature to obtain a finished product of the lithium iron manganese phosphate cathode material.
Comparative example 1
The comparative example prepares a lithium manganese iron phosphate, and the difference with the example 1 is that hydrothermal reaction is not carried out, and the specific process is as follows:
step 1, mixing manganese acetate, iron acetate and triethyl phosphate according to the molar ratio of iron to manganese of 1:1 and (Fe + Mn): P =1:1, and dissolving the mixture into ethanol according to the proportion of 30g/100mL to obtain an organic solution of phosphorus, iron and manganese;
step 2, preparing an organic solution according to the material ratio: polyoxyethylene lauryl ether: alkyl nitroanisole =100mL, and 0.5g of;
step 3, adding the mixed solution into a spray combustion device, and feeding the mixed solution into a combustion chamber for combustion through carrier gas flow; the aperture of a spray head of the spraying device is 30 mu m, the spraying pressure is 1.5MPa, the carrier gas is oxygen, the carrier gas flow is 100L/h, and the temperature of a combustion chamber is controlled to be 550 ℃;
step 4, after the reaction is finished, collecting a solid material in the combustion chamber, mixing the solid material obtained in the step 3 with lithium nitrate according to a molar ratio (Fe + Mn): li =1 (1.0-1.2), adding deionized water accounting for 100% of the total mass of the solid, adding glucose accounting for 0.3 time of the molar weight of the iron element, uniformly mixing, and performing spray drying to obtain a solid material;
and 5, calcining the solid material obtained in the step 4 for 14 hours at 750 ℃ under the protection of inert gas, and naturally cooling to room temperature to obtain a finished product of the lithium iron manganese phosphate cathode material.
Comparative example 2
The comparative example prepares lithium manganese iron phosphate, and the difference with the example 2 is that hydrothermal reaction is not carried out, and the specific process is as follows:
step 1, mixing manganese acetate, ferric nitrate and triethyl phosphate according to the molar ratio of iron to manganese of 2:1 and (Fe + Mn): P =1:1, and dissolving the mixture into glycerol according to the proportion of 40g/100mL to obtain an organic solution of phosphorus, iron and manganese;
step 2, preparing an organic solution according to the material ratio: polyoxyethylene nonyl phenyl ether: the preparation method comprises the following steps of (1) adding nonylphenol polyoxyethylene ether and nitrophenylhydrazine into an organic solution, wherein the nitrophenylhydrazine = 150mL;
step 3, adding the mixed solution into a spray combustion device, and feeding the mixed solution into a combustion chamber for combustion through carrier gas flow; the aperture of a nozzle of the spraying device is 40 mu m, the spraying pressure is 1.2MPa, the carrier gas is air, the carrier gas flow is 120L/h, and the temperature of a combustion chamber is controlled to be 600 ℃;
step 4, after the reaction is finished, collecting the solid material in the combustion chamber, mixing the solid material obtained in the step 3 with lithium acetate according to a molar ratio (Fe + Mn): li =1 (1.0-1.2), adding deionized water accounting for 150% of the total mass of the solid, adding cane sugar accounting for 0.4 time of the molar weight of the iron element, uniformly mixing, and performing spray drying to obtain the solid material;
and 5, calcining the solid material obtained in the step 4 for 20 hours at the temperature of 600 ℃ under the protection of inert gas, and naturally cooling to room temperature to obtain a finished product of the lithium iron manganese phosphate cathode material.
Comparative example 3
The comparative example prepares lithium manganese iron phosphate, and the difference with the example 3 is that hydrothermal reaction is not carried out, and the specific process is as follows:
step 1, mixing manganese lactate, iron acetate and phosphorus source diethyl phosphate according to the molar ratio of iron to manganese 4:1 and the molar ratio of (Fe + Mn) P =1:1, and dissolving the mixture in ethanol according to the ratio of 50g/100mL to obtain an organic solution of phosphorus, iron and manganese;
step 2, preparing an organic solution according to the material ratio: polyoxyethylene lauryl ether: 1.0g of nitrobenzophenone =200mL, and 2.0g of;
step 3, adding the mixed solution into a spray combustion device, and feeding the mixed solution into a combustion chamber for combustion through carrier gas flow; the aperture of a nozzle of the spraying device is 50 mu m, the spraying pressure is 0.8MPa, the carrier gas is air or oxygen, the flow rate of the carrier gas is 150L/h, and the temperature of a combustion chamber is controlled to be 700 ℃;
step 4, after the reaction is finished, collecting solid materials in the combustion chamber, mixing the solid materials obtained in the step 3 with lithium hydroxide according to a molar ratio (Fe + Mn): li =1 (1.0-1.2), adding deionized water accounting for 200% of the total mass of the solid materials, adding fructose accounting for 0.5 time of the molar weight of the iron element, uniformly mixing, and performing spray drying to obtain solid materials;
and 5, calcining the solid material obtained in the step 4 for 6 hours at 850 ℃ under the protection of inert gas, and naturally cooling to room temperature to obtain a finished product of the lithium iron manganese phosphate cathode material.
Test examples
Mixing the lithium iron manganese phosphate positive electrode material obtained in the examples and the comparative examples, acetylene black as a conductive agent and PVDF as a binder according to a mass ratio of 8. In the process, the fact that most of the slurry prepared from the lithium iron manganese phosphate cathode material obtained in the comparative example is jelly-shaped and difficult to coat is found, the residual lithium is guessed to be excessive, manganese pyrophosphate and a lithium source are difficult to further sinter to prepare the lithium iron manganese phosphate cathode material, the residual lithium content of the examples and the comparative examples is detected, and the results are shown in table 1;
a metal lithium sheet is adopted as a negative electrode; the diaphragm is Celgard2400 polypropylene porous membrane; the solvent in the electrolyte is a solution composed of EC, DMC and EMC according to a mass ratio of 1 6 ，LiPF 6 The concentration of (A) is 1.0mol/L; a 2023 button cell battery was assembled in the glove box. The battery is subjected to charge-discharge cycle performance test, and the electricity is cut offTesting the discharge specific capacity of 0.1C and 1C within the voltage range of 2.2-4.3V; the results of testing electrochemical performance are shown in table 1.
TABLE 1 residual lithium content and electrochemical Properties of lithium manganese iron phosphate
As can be seen from table 1, the specific capacities of the comparative examples were all very low, since manganese pyrophosphate did not undergo hydrothermal reaction, and could not be successfully converted into lithium manganese phosphate by spray drying with a lithium source, and qualified lithium iron manganese phosphate could not be prepared.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A method for preparing a lithium iron manganese phosphate anode material by spray combustion is characterized by comprising the following steps:
s1: 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;
s2: adding a surfactant and a combustion improver into the organic solution to obtain a mixed solution;
s3: carrying out spray combustion 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 an acidic condition, adding a carbon source after the reaction is finished, mixing, and carrying out spray drying to obtain a second solid material;
s5: and calcining the second solid material in an inert atmosphere to obtain the lithium iron manganese phosphate.
2. The method according to claim 1, wherein in step S1, the manganese source is at least one of manganese acetate or manganese lactate; the iron source is at least one of iron acetate or iron nitrate; the phosphorus source is at least one of diethyl phosphate or triethyl phosphate.
3. The method according to claim 1, wherein in step S1, the solid-to-liquid ratio of the mixture of the manganese source, the iron source and the phosphorus source to the organic solvent is (30-50) g/100mL.
4. The method according to claim 1, wherein in step S2, the organic solution, the surfactant and the combustion improver are used in a ratio of (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 polyoxyethylene nonylphenol ether.
6. The method according to claim 1, wherein in step S2, the combustion improver is at least one of alkyl nitroanisole, nitrophenylhydrazine, alkoxy nitroaniline or nitrobenzophenone.
7. The method according to claim 1, wherein in step S3, the temperature of the spray combustion is 550-700 ℃, the hole diameter of the spray head used is 30-50 μm, and the pressure of the spray is 0.8-1.5MPa.
8. The method according to claim 1, wherein in step S4, the first solid material is mixed with a lithium source and water, and then the hydrothermal reaction is performed after adding acid to adjust the pH to 2.5-4.0.
9. The method according to claim 1, wherein the temperature of the hydrothermal reaction in step S4 is 100-120 ℃.
10. Use of the method according to any one of claims 1 to 9 for the preparation of 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 |
| FR2306738A FR3139814A1 (en) | 2022-09-16 | 2023-06-27 | METHOD FOR PREPARING LITHIUM FERROMANGANESE PHOSPHATE CATHODE MATERIAL BY SPRAY COMBUSTION, AND USE THEREOF |
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| WO2024055516A1 (en) * | 2022-09-16 | 2024-03-21 | 广东邦普循环科技有限公司 | Method for preparing lithium manganese iron phosphate positive electrode material by means of spray combustion and use thereof |
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| CN113582151B (en) * | 2021-07-28 | 2024-03-22 | 段镇忠 | Lithium iron manganese phosphate anode material and preparation method and application thereof |
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| JP2014093171A (en) * | 2012-11-02 | 2014-05-19 | Hitachi Metals Ltd | Method of producing positive electrode active material for lithium secondary battery and lithium secondary battery, positive electrode for lithium secondary battery and positive electrode active material for lithium secondary battery |
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