WO2024082539A1 - Lithium iron manganese phosphate positive electrode material and preparation method therefor and use thereof - Google Patents
Lithium iron manganese phosphate positive electrode material and preparation method therefor and use thereof Download PDFInfo
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- WO2024082539A1 WO2024082539A1 PCT/CN2023/082867 CN2023082867W WO2024082539A1 WO 2024082539 A1 WO2024082539 A1 WO 2024082539A1 CN 2023082867 W CN2023082867 W CN 2023082867W WO 2024082539 A1 WO2024082539 A1 WO 2024082539A1
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- Prior art keywords
- manganese
- iron
- acetylacetonate
- lithium
- positive electrode
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 57
- 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 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000011572 manganese Substances 0.000 claims abstract description 62
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 claims abstract description 38
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 34
- 229910052742 iron Inorganic materials 0.000 claims abstract description 31
- 239000007787 solid Substances 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 16
- 239000011574 phosphorus Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000011261 inert gas Substances 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000001704 evaporation Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims abstract 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 46
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims description 4
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- AQBLLJNPHDIAPN-LNTINUHCSA-K iron(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Fe+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O AQBLLJNPHDIAPN-LNTINUHCSA-K 0.000 description 26
- 239000000047 product Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 238000001694 spray drying Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 8
- JEBAUTBPSKCVJM-UHFFFAOYSA-N [P].[Mn].[Fe] Chemical compound [P].[Mn].[Fe] JEBAUTBPSKCVJM-UHFFFAOYSA-N 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 6
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 5
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000005715 Fructose Substances 0.000 description 4
- 229930091371 Fructose Natural products 0.000 description 4
- 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 4
- 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 4
- 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 4
- 229930006000 Sucrose Natural products 0.000 description 4
- 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 4
- 239000008103 glucose Substances 0.000 description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- ZQZQURFYFJBOCE-FDGPNNRMSA-L manganese(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Mn+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O ZQZQURFYFJBOCE-FDGPNNRMSA-L 0.000 description 4
- 239000005720 sucrose Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910000398 iron phosphate Inorganic materials 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000005536 Jahn Teller effect Effects 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 235000014413 iron hydroxide Nutrition 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
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- MQMHJMFHCMWGNS-UHFFFAOYSA-N phosphanylidynemanganese Chemical compound [Mn]#P MQMHJMFHCMWGNS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 1
- 102100026388 L-amino-acid oxidase Human genes 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000012212 insulator Substances 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
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002244 precipitate 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
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
Definitions
- the present invention belongs to the technical field of lithium battery positive electrode materials, and in particular relates to a lithium manganese iron phosphate positive electrode material and a preparation method and application thereof.
- lithium iron phosphate batteries Compared with ternary batteries, lithium iron phosphate batteries have higher safety and lower cost advantages. They have the advantages of good thermal stability, long cycle life, environmental friendliness, and abundant raw material sources. They are currently the most promising positive electrode material for power lithium-ion batteries. They are gaining favor from more automobile manufacturers and their market share is constantly increasing. Especially in the energy storage market, lithium iron phosphate has broad application prospects.
- LiFePO 4 material has a low lithium insertion and extraction potential platform (about 3.4V), which reduces the overall energy density of the battery and limits its development in electric vehicles.
- the working voltage of LiMnPO 4 to Li is 4.1V. If LiMnPO 4 can obtain a specific capacity equivalent to that of LiFePO 4 , it means that the energy density will be 35% higher than that of LiFePO 4. At the same time, low raw material cost and environmental friendliness are also the advantages of LiMnPO 4.
- LiMnPO 4 the electrical conductivity of LiMnPO 4 is very low, almost an insulator, only one thousandth of LiFePO 4 ; at the same time, there will be a Jahn-Teller effect during the redox reaction, resulting in poor material rate performance and low discharge specific capacity.
- LiMn x Fe (1-x) PO 4 positive electrode material has a high energy density, which can compensate for the shortcomings of LiFePO 4 positive electrode material in this regard, while improving the problem of low rate and discharge specific capacity of LiMnPO 4 positive electrode material, and increasing the possibility of phosphoric acid-based positive electrode material becoming a power lithium-ion battery material.
- the co-precipitation reaction of phosphate and ferrous salt, manganese salt and oxidant has the following problems: since the pH of iron phosphate precipitation is low, while the pH of manganese phosphate precipitation is high, at a higher pH, the reaction of ferrous salt and oxidant will produce iron hydroxide, resulting in high iron hydroxide content, low purity, and low phosphorus content.
- the phosphorus-manganese ratio in the formed divalent manganese phosphate is less than 1, and an additional phosphorus source needs to be supplemented.
- the present invention aims to solve at least one of the technical problems existing in the prior art.
- the present invention provides a lithium iron manganese phosphate positive electrode material and a preparation method and application thereof, which can prepare a lithium iron manganese phosphate positive electrode material with a uniform mixture of iron and manganese, and the positive electrode material has a high specific capacity and cycle performance.
- a method for preparing a lithium iron manganese phosphate positive electrode material comprises the following steps: (1) mixing manganese acetylacetonate, iron acetylacetonate, a phosphorus source and an organic solvent to obtain an organic solution, wherein the manganese in the manganese acetylacetonate is trivalent manganese and the iron in the iron acetylacetonate is trivalent iron; (2) heating the organic solution obtained in step (1) and then evaporating it to obtain a solid gel; (3) mixing a lithium source, a carbon source and water with the solid gel obtained in step (2), drying, calcining under an inert gas, and cooling to obtain the lithium iron manganese phosphate positive electrode material.
- the CAS number of the manganese acetylacetonate is 14284-89-0.
- the CAS number of the ferric acetylacetonate is 14024-18-1.
- the phosphorus source is phosphoric acid.
- the mass concentration of the phosphoric acid is 80%-95%.
- the mass concentration of the phosphoric acid is 85%-95%.
- the organic solvent is at least one of toluene, methanol, n-butanol, glacial acetic acid and ethylene glycol.
- the manganese acetylacetonate, the iron acetylacetonate and the phosphorus source are mixed in a molar ratio of (Fe+Mn) to P of 1:(1-1.1).
- step (1) the manganese acetylacetonate, the iron acetylacetonate and the phosphorus source are mixed in a molar ratio of (Fe+Mn) to P of 1:1.
- the mixing method is to first mix manganese acetylacetonate and iron acetylacetonate to obtain a mixture, then dissolve the mixture in the organic solvent, and then add phosphoric acid dropwise to mix.
- step (1) manganese acetylacetonate and iron acetylacetonate are mixed in a molar ratio of iron to manganese of (0.1-5):1 to obtain a mixture.
- step (1) manganese acetylacetonate and acetyl acetonate are mixed in a molar ratio of iron to manganese of (0.25-4):1. and ferric acetone to obtain a mixture.
- step (1) the mixture is dissolved in the organic solvent at a ratio of (3-15) g/100 g.
- step (1) the mixture is dissolved in the organic solvent at a ratio of (5-10) g/100 g.
- the temperature after heating is 100-150°C.
- step (2) the temperature after heating is 110-140°C.
- the mass of the added water accounts for 10%-45% of the total mass.
- step (3) the mass of the added water accounts for 20%-35% of the total mass.
- the lithium source is at least one of lithium acetate, lithium hydroxide, lithium carbonate and lithium oxalate.
- the carbon source is at least one of glucose, sucrose and fructose.
- the drying method is spray drying.
- the calcination temperature is 500-1000° C. and the calcination time is 5-25 h.
- the calcination temperature is 600-850° C.
- the calcination time is 6-20 h.
- a lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
- an acetylacetone complex of trivalent manganese and trivalent iron is used in an organic phase to be co-heated with phosphoric acid, and the organic solvent is evaporated to prepare a solid gel.
- phosphorus, iron and manganese are uniformly mixed, which is beneficial to the subsequent preparation of lithium iron manganese phosphate and improves the specific capacity and cycle performance of the material.
- manganese is stably present in a divalent state, resulting in a phosphorus-manganese ratio in the prepared manganese phosphate of less than 1, and the precipitation conditions of iron and manganese in the aqueous phase are different, making it difficult to achieve uniform mixing of iron and manganese.
- the iron and manganese in the generated solid gel are both in a trivalent state combined with phosphate.
- the lithium iron manganese phosphate is subsequently sintered with a lithium source and a carbon source to prepare the lithium iron manganese phosphate, the generation of metal oxides or metal elements is avoided, thereby further improving the specific capacity and cycle performance of the material.
- FIG. 1 is a SEM image of the lithium manganese iron phosphate positive electrode material prepared in Example 1 of the present invention.
- Embodiment 1 is a diagrammatic representation of Embodiment 1:
- a method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
- step (4) The product obtained in step (4) is calcined at 800° C. for 15 h under the protection of an inert gas, and naturally cooled to room temperature to obtain a finished product of lithium manganese iron phosphate positive electrode material.
- a lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above, and its SEM image is shown in FIG1 .
- Embodiment 2 is a diagrammatic representation of Embodiment 1:
- a method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
- step (4) The product obtained in step (4) is calcined at 850° C. for 10 h under the protection of an inert gas, and naturally cooled to room temperature to obtain a finished product of lithium manganese iron phosphate positive electrode material.
- a lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
- Embodiment 3 is a diagrammatic representation of Embodiment 3
- a method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
- step (4) The product obtained in step (4) is calcined at 600° C. for 20 h under the protection of an inert gas, and naturally cooled to room temperature to obtain a finished product of lithium manganese iron phosphate positive electrode material.
- a lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
- Comparative Example 1 (The difference from Example 1 is that it is prepared by aqueous phase coprecipitation)
- a method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
- a lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
- Comparative Example 2 (The difference from Example 2 is that it is prepared by aqueous phase coprecipitation)
- a method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
- a lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
- Comparative Example 3 (The difference from Example 3 is that it is prepared by aqueous phase coprecipitation)
- a method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
- a lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
- Comparative Example 4 (The only difference from Example 1 is that the manganese in manganese acetylacetonate is divalent manganese)
- a method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
- step (4) The product obtained in step (4) is calcined at 800° C. for 15 h under the protection of an inert gas, and naturally cooled to room temperature to obtain a finished product of lithium manganese iron phosphate positive electrode material.
- a lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
- Comparative Example 5 (The only difference from Example 2 is that the manganese in manganese acetylacetonate is divalent manganese)
- a method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
- step (4) The product obtained in step (4) is calcined at 850° C. for 10 h under the protection of an inert gas, and naturally cooled to room temperature to obtain a finished product of lithium manganese iron phosphate positive electrode material.
- a lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
- Comparative Example 6 (The only difference from Example 3 is that the manganese in manganese acetylacetonate is divalent manganese)
- a method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
- step (4) The product obtained in step (4) is calcined at 600° C. for 20 h under the protection of an inert gas, and naturally cooled to room temperature to obtain a finished product of lithium manganese iron phosphate positive electrode material.
- a lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
- the manganese acetylacetonate (CAS No.: 14284-89-0) used in Examples 1-3 is trivalent manganese
- the manganese acetylacetonate (CAS No.: 14024-58-9) used in Comparative Examples 4-6 is divalent manganese
- Comparative Examples 1-3 adopt aqueous phase co-precipitation.
- the amount of precipitate first increases-remains unchanged-and then increases-remains unchanged, that is, due to the different pH values of iron and manganese precipitation, iron phosphate is precipitated first, and then manganese phosphate.
- the lithium iron manganese phosphate positive electrode material obtained in the embodiment and the comparative example, acetylene black as a conductive agent, PVDF as a binder, are mixed at a mass ratio of 8:1:1, and a certain amount of organic solvent NMP is added, and after stirring, it is coated on an aluminum foil to make a positive electrode sheet, and a metal lithium sheet is used for the negative electrode;
- the diaphragm is a Celgard2400 polypropylene porous membrane;
- the solvent in the electrolyte is EC, DMC and EMC at a mass ratio of The solution is composed of 1:1:1, the solute is LiPF 6 , and the concentration of LiPF 6 is 1.0 mol/L; 2023 button cells are assembled in the glove box.
- the battery is tested for charge and discharge cycle performance, and the 0.2C and 1C discharge specific capacities are tested within the cut-off voltage range of 2.0-4.3V; the test electrochemical performance results are shown in Table 2:
- the 0.2C discharge capacity of the lithium manganese iron phosphate positive electrode material prepared by the preparation method of the present application can reach more than 149.3 mAh/g
- the 1C discharge capacity can reach more than 142.4 mAh/g
- the capacity retention rate after 500 cycles at 1C can reach more than 94.06%.
Abstract
Disclosed in the present invention are a lithium iron manganese phosphate positive electrode material and a preparation method therefor and a use thereof. The preparation method comprises the following steps: (1) mixing manganese acetylacetonate, iron acetylacetonate, a phosphorus source and an organic solvent to obtain an organic solution, wherein manganese in manganese acetylacetonate is trivalent manganese, and iron in iron acetylacetonate is trivalent iron; (2) heating the organic solution obtained in step (1) and then evaporating to dryness to obtain a solid gel; and (3) mixing a lithium source, a carbon source, water and the solid gel obtained in step (2), drying, calcining under an inert gas, and cooling to obtain the lithium iron manganese phosphate positive electrode material. According to the method, the lithium iron manganese phosphate positive electrode material in which iron and manganese are uniformly mixed can be prepared, and the positive electrode material has relatively high specific capacity and cycle performance.
Description
本发明属于锂电池正极材料技术领域，特别涉及一种磷酸锰铁锂正极材料及其制备方法和应用。The present invention belongs to the technical field of lithium battery positive electrode materials, and in particular relates to a lithium manganese iron phosphate positive electrode material and a preparation method and application thereof.
磷酸铁锂电池相对于三元电池具备更高的安全性和更低的成本优势，其具备热稳定性好、循环寿命长、环境友好，原料来源丰富等优势，是目前最具应用潜力的动力锂离子电池正极材料，正获得更多汽车厂商的青睐，市场占有率不断提升，尤其在储能市场，磷酸铁锂具有广阔的应用前景。Compared with ternary batteries, lithium iron phosphate batteries have higher safety and lower cost advantages. They have the advantages of good thermal stability, long cycle life, environmental friendliness, and abundant raw material sources. They are currently the most promising positive electrode material for power lithium-ion batteries. They are gaining favor from more automobile manufacturers and their market share is constantly increasing. Especially in the energy storage market, lithium iron phosphate has broad application prospects.
然而，LiFePO4材料由于脱嵌锂电位平台(约3.4V)较低，降低了电池整体的能量密度，限制了其在电动汽车上的发展。而LiMnPO4对Li的工作电压为4.1V，如果LiMnPO4能够获取与LiFePO4相当的比容量，就意味着与LiFePO4相比较将高出35％的能量密度。同时原料成本低、对环境友好也是LiMnPO4的优势。但是，LiMnPO4的电导率很低，几乎属于绝缘体，只有LiFePO4的千分之一；同时在发生氧化还原反应过程中会存在Jahn-Teller效应导致材料倍率性能差以及放电比容量低。However, the LiFePO 4 material has a low lithium insertion and extraction potential platform (about 3.4V), which reduces the overall energy density of the battery and limits its development in electric vehicles. The working voltage of LiMnPO 4 to Li is 4.1V. If LiMnPO 4 can obtain a specific capacity equivalent to that of LiFePO 4 , it means that the energy density will be 35% higher than that of LiFePO 4. At the same time, low raw material cost and environmental friendliness are also the advantages of LiMnPO 4. However, the electrical conductivity of LiMnPO 4 is very low, almost an insulator, only one thousandth of LiFePO 4 ; at the same time, there will be a Jahn-Teller effect during the redox reaction, resulting in poor material rate performance and low discharge specific capacity.
从目前的研究现状能够看出，LiMnxFe(1-x)PO4正极材料含有高能量密度，可以补偿LiFePO4正极材料在这方面的不足，同时改善LiMnPO4正极材料倍率及放电比容量低的问题，提高磷酸系正极材料变为动力锂离子电池材料的可能性。From the current research status, it can be seen that LiMn x Fe (1-x) PO 4 positive electrode material has a high energy density, which can compensate for the shortcomings of LiFePO 4 positive electrode material in this regard, while improving the problem of low rate and discharge specific capacity of LiMnPO 4 positive electrode material, and increasing the possibility of phosphoric acid-based positive electrode material becoming a power lithium-ion battery material.
磷酸锰铁锂的合成方法有很多，目前使用单一高温固相法制备LiMnxFe(1-x)PO4材料材料，在制备前驱体时很难准确控制铁和锰的配比，过渡金属很难均匀分布于材料主体结构中，会导致Mn3+的Jahn-Teller效应严重，影响电池的循环和倍率性能。而采用磷酸盐与亚铁盐、锰盐与氧化剂共沉淀反应，存在以下问题：由于磷酸铁沉淀的pH较低，而磷酸锰沉淀的pH较高，而在较高的pH下，亚铁盐与氧化剂反应会得到氢氧化铁，导致氢氧化铁的含量高，纯度低，磷含量低。There are many methods for synthesizing lithium manganese iron phosphate. Currently, a single high-temperature solid-phase method is used to prepare LiMn x Fe (1-x) PO 4 material. It is difficult to accurately control the ratio of iron and manganese when preparing the precursor, and it is difficult for the transition metal to be evenly distributed in the main structure of the material, which will lead to a serious Jahn-Teller effect of Mn 3+ , affecting the cycle and rate performance of the battery. The co-precipitation reaction of phosphate and ferrous salt, manganese salt and oxidant has the following problems: since the pH of iron phosphate precipitation is low, while the pH of manganese phosphate precipitation is high, at a higher pH, the reaction of ferrous salt and oxidant will produce iron hydroxide, resulting in high iron hydroxide content, low purity, and low phosphorus content.
同时，由于锰以正二价的稳定形式存在，形成的磷酸二价锰中，磷锰比小于1，需要另外补充磷源。
At the same time, since manganese exists in a stable divalent form, the phosphorus-manganese ratio in the formed divalent manganese phosphate is less than 1, and an additional phosphorus source needs to be supplemented.
因此，需要寻求一种既能够使铁锰达到原子层面的均匀混合，又能使磷与铁锰的比例达到理论值，从而制备得到高容量、高循环性能的磷酸锰铁锂正极材料的方法。Therefore, it is necessary to find a method that can achieve uniform mixing of iron and manganese at the atomic level and make the ratio of phosphorus to iron and manganese reach the theoretical value, so as to prepare a lithium manganese iron phosphate positive electrode material with high capacity and high cycle performance.
发明内容Summary of the invention
本发明旨在至少解决现有技术中存在的技术问题之一。为此，本发明提出一种磷酸锰铁锂正极材料及其制备方法和应用，该方法可制备得到铁锰均匀混合的磷酸锰铁锂正极材料，且该正极材料具有较高的比容量和循环性能。The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention provides a lithium iron manganese phosphate positive electrode material and a preparation method and application thereof, which can prepare a lithium iron manganese phosphate positive electrode material with a uniform mixture of iron and manganese, and the positive electrode material has a high specific capacity and cycle performance.
本发明的上述技术目的是通过以下技术方案得以实现的：The above technical objectives of the present invention are achieved through the following technical solutions:
一种磷酸锰铁锂正极材料的制备方法，包括以下步骤：(1)将乙酰丙酮锰、乙酰丙酮铁、磷源与有机溶剂混合得到有机溶液，其中，所述乙酰丙酮锰中的锰为三价锰，所述乙酰丙酮铁中的铁为三价铁；(2)将步骤(1)得到的有机溶液加热后蒸干，得到固体凝胶；(3)将锂源、碳源、水与步骤(2)得到的固体凝胶混合，干燥、在惰性气体下煅烧，冷却，得到所述磷酸锰铁锂正极材料。A method for preparing a lithium iron manganese phosphate positive electrode material comprises the following steps: (1) mixing manganese acetylacetonate, iron acetylacetonate, a phosphorus source and an organic solvent to obtain an organic solution, wherein the manganese in the manganese acetylacetonate is trivalent manganese and the iron in the iron acetylacetonate is trivalent iron; (2) heating the organic solution obtained in step (1) and then evaporating it to obtain a solid gel; (3) mixing a lithium source, a carbon source and water with the solid gel obtained in step (2), drying, calcining under an inert gas, and cooling to obtain the lithium iron manganese phosphate positive electrode material.
优选的，步骤(1)中，所述乙酰丙酮锰的CAS号为14284-89-0。Preferably, in step (1), the CAS number of the manganese acetylacetonate is 14284-89-0.
优选的，步骤(1)中，所述乙酰丙酮铁的CAS号为14024-18-1。Preferably, in step (1), the CAS number of the ferric acetylacetonate is 14024-18-1.
优选的，步骤(1)中，所述磷源为磷酸。Preferably, in step (1), the phosphorus source is phosphoric acid.
优选的，步骤(1)中，所述磷酸的质量浓度为80％-95％。Preferably, in step (1), the mass concentration of the phosphoric acid is 80%-95%.
进一步优选的，步骤(1)中，所述磷酸的质量浓度为85％-95％。Further preferably, in step (1), the mass concentration of the phosphoric acid is 85%-95%.
优选的，步骤(1)中，所述有机溶剂为甲苯、甲醇、正丁醇、冰乙酸及乙二醇中的至少一种。Preferably, in step (1), the organic solvent is at least one of toluene, methanol, n-butanol, glacial acetic acid and ethylene glycol.
优选的，步骤(1)中，所述乙酰丙酮锰、所述乙酰丙酮铁及所述磷源按照(Fe+Mn)与P的摩尔比为1:(1-1.1)进行混合。Preferably, in step (1), the manganese acetylacetonate, the iron acetylacetonate and the phosphorus source are mixed in a molar ratio of (Fe+Mn) to P of 1:(1-1.1).
进一步优选的，步骤(1)中，所述乙酰丙酮锰、所述乙酰丙酮铁及所述磷源按照(Fe+Mn)与P的摩尔比为1:1进行混合。Further preferably, in step (1), the manganese acetylacetonate, the iron acetylacetonate and the phosphorus source are mixed in a molar ratio of (Fe+Mn) to P of 1:1.
优选的，步骤(1)中，所述的混合的方式为先将乙酰丙酮锰与乙酰丙酮铁混合得到混合物，再将所述混合物溶于所述有机溶剂中，再逐滴加入磷酸混合。Preferably, in step (1), the mixing method is to first mix manganese acetylacetonate and iron acetylacetonate to obtain a mixture, then dissolve the mixture in the organic solvent, and then add phosphoric acid dropwise to mix.
优选的，步骤(1)中，按照铁与锰的摩尔比为(0.1-5):1将乙酰丙酮锰与乙酰丙酮铁混合得到混合物。Preferably, in step (1), manganese acetylacetonate and iron acetylacetonate are mixed in a molar ratio of iron to manganese of (0.1-5):1 to obtain a mixture.
进一步优选的，步骤(1)中，按照铁与锰的摩尔比为(0.25-4):1将乙酰丙酮锰与乙酰
丙酮铁混合得到混合物。Further preferably, in step (1), manganese acetylacetonate and acetyl acetonate are mixed in a molar ratio of iron to manganese of (0.25-4):1. and ferric acetone to obtain a mixture.
优选的，步骤(1)中，按照(3-15)g/100g的比例将所述混合物溶于所述有机溶剂中。Preferably, in step (1), the mixture is dissolved in the organic solvent at a ratio of (3-15) g/100 g.
进一步优选的，步骤(1)中，按照(5-10)g/100g的比例将所述混合物溶于所述有机溶剂中。Further preferably, in step (1), the mixture is dissolved in the organic solvent at a ratio of (5-10) g/100 g.
优选的，步骤(2)中，所述加热后的温度为100-150℃。Preferably, in step (2), the temperature after heating is 100-150°C.
进一步优选的，步骤(2)中，所述加热后的温度为110-140℃。Further preferably, in step (2), the temperature after heating is 110-140°C.
优选的，步骤(3)中，按照摩尔比(Fe+Mn):Li:碳源＝1:(1.0-1.5):(0.1-0.5)，将所述固体凝胶与锂源、碳源混合。Preferably, in step (3), the solid gel is mixed with a lithium source and a carbon source according to a molar ratio of (Fe+Mn):Li:carbon source=1:(1.0-1.5):(0.1-0.5).
进一步优选的，步骤(3)中，按照摩尔比(Fe+Mn):Li:碳源＝1:(1.0-1.2):(0.3-0.5)，将所述固体凝胶与锂源、碳源混合。Further preferably, in step (3), the solid gel is mixed with a lithium source and a carbon source according to a molar ratio of (Fe+Mn):Li:carbon source=1:(1.0-1.2):(0.3-0.5).
优选的，步骤(3)中，加入的水的质量占总质量的10％-45％。Preferably, in step (3), the mass of the added water accounts for 10%-45% of the total mass.
进一步优选的，步骤(3)中，加入的水的质量占总质量的20％-35％。Further preferably, in step (3), the mass of the added water accounts for 20%-35% of the total mass.
优选的，步骤(3)中，所述锂源为醋酸锂、氢氧化锂、碳酸锂及草酸锂中的至少一种。Preferably, in step (3), the lithium source is at least one of lithium acetate, lithium hydroxide, lithium carbonate and lithium oxalate.
优选的，步骤(3)中，所述碳源为葡萄糖、蔗糖及果糖中的至少一种。Preferably, in step (3), the carbon source is at least one of glucose, sucrose and fructose.
优选的，步骤(3)中，所述干燥的方式为喷雾干燥。Preferably, in step (3), the drying method is spray drying.
优选的，步骤(3)中，所述煅烧的温度为500-1000℃，煅烧时间为5-25h。Preferably, in step (3), the calcination temperature is 500-1000° C. and the calcination time is 5-25 h.
进一步优选的，步骤(3)中，所述煅烧的温度为600-850℃，煅烧时间为6-20h。Further preferably, in step (3), the calcination temperature is 600-850° C., and the calcination time is 6-20 h.
一种磷酸锰铁锂正极材料，由如上所述的制备方法制备得到。A lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
如上所述的磷酸锰铁锂正极材料在制备锂离子电池中的应用。The application of the lithium iron manganese phosphate positive electrode material as described above in the preparation of lithium ion batteries.
本发明的有益效果是：The beneficial effects of the present invention are:
(1)本发明磷酸锰铁锂正极材料的制备方法中，通过在有机相中，采用三价锰与三价铁的乙酰丙酮络合物，与磷酸进行共热，蒸发有机溶剂制备固体凝胶，一方面，使磷铁锰实现了均匀混合，利于后续制备磷酸锰铁锂，提高材料的比容量和循环性能，而在水相中锰以二价态稳定存在，导致制备的磷酸锰中的磷锰比小于1，且铁与锰在水相中的沉淀条件不同，难以实现铁锰的均匀混合；另一方面，随着有机溶剂的蒸发，形成了磷酸铁、磷酸锰的共晶体，且三价锰仍然稳定存在，实现了(Fe+Mn):P＝1:1，为下一步合成磷酸锰铁锂保证了充足的磷含量，避免了补加磷源的问题。
(1) In the preparation method of the lithium iron manganese phosphate positive electrode material of the present invention, an acetylacetone complex of trivalent manganese and trivalent iron is used in an organic phase to be co-heated with phosphoric acid, and the organic solvent is evaporated to prepare a solid gel. On the one hand, phosphorus, iron and manganese are uniformly mixed, which is beneficial to the subsequent preparation of lithium iron manganese phosphate and improves the specific capacity and cycle performance of the material. In the aqueous phase, manganese is stably present in a divalent state, resulting in a phosphorus-manganese ratio in the prepared manganese phosphate of less than 1, and the precipitation conditions of iron and manganese in the aqueous phase are different, making it difficult to achieve uniform mixing of iron and manganese. On the other hand, as the organic solvent evaporates, a eutectic of iron phosphate and manganese phosphate is formed, and trivalent manganese is still stably present, achieving (Fe+Mn):P=1:1, thereby ensuring sufficient phosphorus content for the next step of synthesizing lithium iron manganese phosphate and avoiding the problem of adding a phosphorus source.
(2)本发明磷酸锰铁锂正极材料的制备方法中，产生的固体凝胶中铁锰均为与磷酸根结合的三价态，后续与锂源、碳源烧结制备磷酸锰铁锂时，避免了金属氧化物或金属单质的产生，进一步提升了材料的比容量和循环性能。(2) In the preparation method of the lithium iron manganese phosphate positive electrode material of the present invention, the iron and manganese in the generated solid gel are both in a trivalent state combined with phosphate. When the lithium iron manganese phosphate is subsequently sintered with a lithium source and a carbon source to prepare the lithium iron manganese phosphate, the generation of metal oxides or metal elements is avoided, thereby further improving the specific capacity and cycle performance of the material.
(3)本发明磷酸锰铁锂正极材料的制备方法中，在有机溶液蒸干阶段，选用与乙酰丙酮锰、乙酰丙酮铁易溶的高沸点有机溶剂，在共热条件下，随着有机溶剂的蒸发，将乙酰丙酮一同带出，或直接升温至乙酰丙酮的沸点，使乙酰丙酮直接挥发，其反应方程式如下：(3) In the preparation method of the lithium manganese iron phosphate positive electrode material of the present invention, in the stage of evaporating the organic solution, a high boiling point organic solvent that is easily soluble in manganese acetylacetonate and iron acetylacetonate is selected, and under co-heating conditions, as the organic solvent evaporates, acetylacetone is taken out together, or the temperature is directly raised to the boiling point of acetylacetone to allow acetylacetone to volatilize directly. The reaction equation is as follows:
Fe(C5H7O2)3+H3PO4→FePO4+3C5H8O2↑Fe(C 5 H 7 O 2 ) 3 +H 3 PO 4 →FePO 4 +3C 5 H 8 O 2 ↑
Mn(C5H7O2)3+H3PO4→MnPO4+3C5H8O2↑Mn(C 5 H 7 O 2 ) 3 +H 3 PO 4 →MnPO 4 +3C 5 H 8 O 2 ↑
图1为本发明实施例1制备得到的磷酸锰铁锂正极材料的SEM图。FIG. 1 is a SEM image of the lithium manganese iron phosphate positive electrode material prepared in Example 1 of the present invention.
下面结合具体实施例对本发明做进一步的说明。The present invention will be further described below in conjunction with specific embodiments.
实施例1：Embodiment 1:
一种磷酸锰铁锂正极材料的制备方法，包括如下步骤：A method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
(1)按照摩尔比铁锰比为1:1且(Fe+Mn):P＝1:1，选取乙酰丙酮锰(CAS号：14284-89-0)、乙酰丙酮铁(CAS号：14024-18-1)、质量浓度为90％的磷酸；(1) According to the molar ratio of iron to manganese of 1:1 and (Fe+Mn):P=1:1, manganese acetylacetonate (CAS No.: 14284-89-0), iron acetylacetonate (CAS No.: 14024-18-1), and phosphoric acid with a mass concentration of 90% were selected;
(2)将乙酰丙酮锰、乙酰丙酮铁混合后，按照8g/100g的比例将混合物溶于乙二醇中，并逐滴加入磷酸混合，得到磷铁锰的有机溶液；(2) after mixing manganese acetylacetonate and iron acetylacetonate, dissolving the mixture in ethylene glycol at a ratio of 8 g/100 g, and adding phosphoric acid dropwise to mix, to obtain an organic solution of phosphorus iron manganese;
(3)将有机溶液在140℃下加热、蒸干，得到固体凝胶，并回收得到有机溶剂；(3) heating the organic solution at 140° C. and evaporating to dryness to obtain a solid gel, and recovering the organic solvent;
(4)按照摩尔比(Fe+Mn):Li:碳源＝1:1.1:0.4，将固体凝胶与碳酸锂、葡萄糖混合后，加入总质量25％的去离子水，混合均匀后进行喷雾干燥；(4) mixing the solid gel with lithium carbonate and glucose at a molar ratio of (Fe+Mn):Li:carbon source=1:1.1:0.4, adding 25% of the total mass of deionized water, mixing well, and spray drying;
(5)将步骤(4)所得产物在惰性气体的保护下、800℃煅烧15h，自然冷却至室温，得到磷酸锰铁锂正极材料成品。(5) The product obtained in step (4) is calcined at 800° C. for 15 h under the protection of an inert gas, and naturally cooled to room temperature to obtain a finished product of lithium manganese iron phosphate positive electrode material.
一种磷酸锰铁锂正极材料，由如上所述的制备方法制备得到，其SEM图如图1所示。A lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above, and its SEM image is shown in FIG1 .
实施例2：Embodiment 2:
一种磷酸锰铁锂正极材料的制备方法，包括如下步骤：A method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
(1)按照摩尔比铁锰比为4:1且(Fe+Mn):P＝1:1，选取乙酰丙酮锰(CAS号：14284-89-0)、乙酰丙酮铁(CAS号：14024-18-1)、质量浓度为95％的磷酸；
(1) According to the molar ratio of iron to manganese of 4:1 and (Fe+Mn):P=1:1, manganese acetylacetonate (CAS No.: 14284-89-0), iron acetylacetonate (CAS No.: 14024-18-1), and phosphoric acid with a mass concentration of 95% were selected;
(2)将乙酰丙酮锰、乙酰丙酮铁混合后，按照10g/100g的比例将混合物溶于甲醇中，并逐滴加入磷酸混合，得到磷铁锰的有机溶液；(2) after mixing manganese acetylacetonate and iron acetylacetonate, dissolving the mixture in methanol at a ratio of 10 g/100 g, and adding phosphoric acid dropwise to mix, to obtain an organic solution of phosphorus iron manganese;
(3)将有机溶液在135℃下加热、蒸干，得到固体凝胶，并回收得到有机溶剂；(3) heating the organic solution at 135° C. and evaporating to dryness to obtain a solid gel, and recovering the organic solvent;
(4)按照摩尔比(Fe+Mn):Li:碳源＝1:1.2:0.5，将固体凝胶与氢氧化锂、蔗糖混合后，加入总质量20％的去离子水，混合均匀后进行喷雾干燥；(4) mixing the solid gel with lithium hydroxide and sucrose at a molar ratio of (Fe+Mn):Li:carbon source=1:1.2:0.5, adding 20% of the total mass of deionized water, mixing well, and spray drying;
(5)将步骤(4)所得产物在惰性气体的保护下、850℃煅烧10h，自然冷却至室温，得到磷酸锰铁锂正极材料成品。(5) The product obtained in step (4) is calcined at 850° C. for 10 h under the protection of an inert gas, and naturally cooled to room temperature to obtain a finished product of lithium manganese iron phosphate positive electrode material.
一种磷酸锰铁锂正极材料，由如上所述的制备方法制备得到。A lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
实施例3：Embodiment 3:
一种磷酸锰铁锂正极材料的制备方法，包括如下步骤：A method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
(1)按照摩尔比铁锰比为0.25:1且(Fe+Mn):P＝1:1，选取乙酰丙酮锰(CAS号：14284-89-0)、乙酰丙酮铁(CAS号：14024-18-1)、质量浓度为85％的磷酸；(1) According to the molar ratio of iron to manganese of 0.25:1 and (Fe+Mn):P=1:1, manganese acetylacetonate (CAS No.: 14284-89-0), iron acetylacetonate (CAS No.: 14024-18-1), and phosphoric acid with a mass concentration of 85% were selected;
(2)将乙酰丙酮锰、乙酰丙酮铁混合后，按照5g/100g的比例将混合物溶于正丁醇中，并逐滴加入磷酸混合，得到磷铁锰的有机溶液；(2) after mixing manganese acetylacetonate and iron acetylacetonate, dissolving the mixture in n-butanol at a ratio of 5 g/100 g, and adding phosphoric acid dropwise to mix, to obtain an organic solution of phosphorus iron manganese;
(3)将有机溶液在110℃下加热、蒸干，得到固体凝胶，并回收得到有机溶剂；(3) heating the organic solution at 110° C. and evaporating to dryness to obtain a solid gel, and recovering the organic solvent;
(4)按照摩尔比(Fe+Mn):Li:碳源＝1:1.0:0.3，将固体凝胶与醋酸锂、果糖混合后，加入总质量35％的去离子水，混合均匀后进行喷雾干燥；(4) mixing the solid gel with lithium acetate and fructose in a molar ratio of (Fe+Mn):Li:carbon source=1:1.0:0.3, adding 35% of the total mass of deionized water, mixing well, and spray drying;
(5)将步骤(4)所得产物在惰性气体的保护下、600℃煅烧20h，自然冷却至室温，得到磷酸锰铁锂正极材料成品。(5) The product obtained in step (4) is calcined at 600° C. for 20 h under the protection of an inert gas, and naturally cooled to room temperature to obtain a finished product of lithium manganese iron phosphate positive electrode material.
一种磷酸锰铁锂正极材料，由如上所述的制备方法制备得到。A lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
对比例1：(与实施例1的区别在于采用水相共沉淀制备)Comparative Example 1: (The difference from Example 1 is that it is prepared by aqueous phase coprecipitation)
一种磷酸锰铁锂正极材料的制备方法，包括如下步骤：A method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
(1)摩尔比铁锰比为1:1，配制金属离子总浓度为1.0mol/L的硝酸铁和硝酸锰的混合溶液；(1) preparing a mixed solution of iron nitrate and manganese nitrate with a total metal ion concentration of 1.0 mol/L in a molar ratio of iron to manganese of 1:1;
(2)向混合溶液中加入质量浓度为90％的磷酸；(2) adding phosphoric acid with a mass concentration of 90% to the mixed solution;
(3)再逐滴加入浓度为1.0mol/L的氢氧化钠溶液，直至混合溶液的pH为6.0；(3) adding a 1.0 mol/L sodium hydroxide solution dropwise until the pH of the mixed solution reaches 6.0;
(4)固液分离，用去离子水洗涤固体料；(4) solid-liquid separation, washing the solid material with deionized water;
(5)将洗涤后的产物，置于400℃下煅烧3h，得到煅烧料；
(5) calcining the washed product at 400° C. for 3 h to obtain a calcined material;
(6)按照摩尔比(Fe+Mn):Li:碳源＝1:1.1:0.4，将煅烧料与碳酸锂、葡萄糖混合后，加入总质量25％的去离子水，混合均匀后进行喷雾干燥；(6) mixing the calcined material with lithium carbonate and glucose in a molar ratio of (Fe+Mn):Li:carbon source=1:1.1:0.4, adding 25% of the total mass of deionized water, mixing well, and spray drying;
(7)在惰性气体的保护下、800℃煅烧15h，自然冷却至室温，得到磷酸锰铁锂正极材料成品。(7) Under the protection of inert gas, calcined at 800° C. for 15 h, and naturally cooled to room temperature to obtain a finished product of lithium manganese iron phosphate positive electrode material.
一种磷酸锰铁锂正极材料，由如上所述的制备方法制备得到。A lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
对比例2：(与实施例2的区别在于采用水相共沉淀制备)Comparative Example 2: (The difference from Example 2 is that it is prepared by aqueous phase coprecipitation)
一种磷酸锰铁锂正极材料的制备方法，包括如下步骤：A method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
(1)摩尔比铁锰比为4:1，配制金属离子总浓度为1.0mol/L的硝酸铁和硝酸锰的混合溶液；(1) preparing a mixed solution of iron nitrate and manganese nitrate with a total metal ion concentration of 1.0 mol/L in a molar ratio of iron to manganese of 4:1;
(2)向混合溶液中加入质量浓度为95％的磷酸；(2) adding phosphoric acid with a mass concentration of 95% to the mixed solution;
(3)再逐滴加入浓度为1.0mol/L的氢氧化钠溶液，直至混合溶液的pH为6.0；(3) adding a 1.0 mol/L sodium hydroxide solution dropwise until the pH of the mixed solution reaches 6.0;
(4)固液分离，用去离子水洗涤固体料；(4) solid-liquid separation, washing the solid material with deionized water;
(5)将洗涤后的产物，置于400℃下煅烧3h，得到煅烧料；(5) calcining the washed product at 400° C. for 3 h to obtain a calcined material;
(6)按照摩尔比(Fe+Mn):Li:碳源＝1:1.2:0.5，将煅烧料与氢氧化锂、蔗糖混合后，加入总质量20％的去离子水，混合均匀后进行喷雾干燥；(6) mixing the calcined material with lithium hydroxide and sucrose in a molar ratio of (Fe+Mn):Li:carbon source=1:1.2:0.5, adding 20% of the total mass of deionized water, mixing well, and spray drying;
(7)在惰性气体的保护下、850℃煅烧10h，自然冷却至室温，得到磷酸锰铁锂正极材料成品。(7) Under the protection of inert gas, calcined at 850° C. for 10 h, and naturally cooled to room temperature to obtain a finished product of lithium manganese iron phosphate positive electrode material.
一种磷酸锰铁锂正极材料，由如上所述的制备方法制备得到。A lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
对比例3：(与实施例3的区别在于采用水相共沉淀制备)Comparative Example 3: (The difference from Example 3 is that it is prepared by aqueous phase coprecipitation)
一种磷酸锰铁锂正极材料的制备方法，包括如下步骤：A method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
(1)摩尔比铁锰比为0.25:1，配制金属离子总浓度为1.0mol/L的硝酸铁和硝酸锰的混合溶液；(1) preparing a mixed solution of iron nitrate and manganese nitrate with a total metal ion concentration of 1.0 mol/L at a molar ratio of iron to manganese of 0.25:1;
(2)向混合溶液中加入质量浓度为85％的磷酸；(2) adding phosphoric acid with a mass concentration of 85% to the mixed solution;
(3)再逐滴加入浓度为1.0mol/L的氢氧化钠溶液，直至混合溶液的pH为6.0；(3) adding a 1.0 mol/L sodium hydroxide solution dropwise until the pH of the mixed solution reaches 6.0;
(4)固液分离，用去离子水洗涤固体料；(4) solid-liquid separation, washing the solid material with deionized water;
(5)将洗涤后的产物，置于400℃下煅烧3h，得到煅烧料；(5) calcining the washed product at 400° C. for 3 h to obtain a calcined material;
(6)按照摩尔比(Fe+Mn):Li:碳源＝1:1.0:0.3，将煅烧料与醋酸锂、果糖混合后，加入总质量35％的去离子水，混合均匀后进行喷雾干燥；
(6) mixing the calcined material with lithium acetate and fructose according to a molar ratio of (Fe+Mn):Li:carbon source=1:1.0:0.3, adding 35% of the total mass of deionized water, mixing well, and spray drying;
(7)在惰性气体的保护下、600℃煅烧20h，自然冷却至室温，得到磷酸锰铁锂正极材料成品。(7) Under the protection of inert gas, calcined at 600° C. for 20 h, and naturally cooled to room temperature to obtain a finished product of lithium manganese iron phosphate positive electrode material.
一种磷酸锰铁锂正极材料，由如上所述的制备方法制备得到。A lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
对比例4：(与实施例1的区别仅在于乙酰丙酮锰中的锰为二价锰)Comparative Example 4: (The only difference from Example 1 is that the manganese in manganese acetylacetonate is divalent manganese)
一种磷酸锰铁锂正极材料的制备方法，包括如下步骤：A method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
(1)按照摩尔比铁锰比为1:1且(Fe+Mn):P＝1:1，选取乙酰丙酮锰(CAS号：14024-58-9)、乙酰丙酮铁(CAS号：14024-18-1)、质量浓度为90％的磷酸；(1) According to the molar ratio of iron to manganese of 1:1 and (Fe+Mn):P=1:1, manganese acetylacetonate (CAS No.: 14024-58-9), iron acetylacetonate (CAS No.: 14024-18-1), and phosphoric acid with a mass concentration of 90% were selected;
(2)将乙酰丙酮锰、乙酰丙酮铁混合后，按照8g/100g的比例将混合物溶于乙二醇中，并逐滴加入磷酸混合，得到磷铁锰的有机溶液；(2) after mixing manganese acetylacetonate and iron acetylacetonate, dissolving the mixture in ethylene glycol at a ratio of 8 g/100 g, and adding phosphoric acid dropwise to mix, to obtain an organic solution of phosphorus iron manganese;
(3)将有机溶液在140℃下加热、蒸干，得到固体凝胶，并回收得到有机溶剂；(3) heating the organic solution at 140° C. and evaporating to dryness to obtain a solid gel, and recovering the organic solvent;
(4)按照摩尔比(Fe+Mn):Li:碳源＝1:1.1:0.4，将固体凝胶与碳酸锂、葡萄糖混合后，加入总质量25％的去离子水，混合均匀后进行喷雾干燥；(4) mixing the solid gel with lithium carbonate and glucose at a molar ratio of (Fe+Mn):Li:carbon source=1:1.1:0.4, adding 25% of the total mass of deionized water, mixing well, and spray drying;
(5)将步骤(4)所得产物在惰性气体的保护下、800℃煅烧15h，自然冷却至室温，得到磷酸锰铁锂正极材料成品。(5) The product obtained in step (4) is calcined at 800° C. for 15 h under the protection of an inert gas, and naturally cooled to room temperature to obtain a finished product of lithium manganese iron phosphate positive electrode material.
一种磷酸锰铁锂正极材料，由如上所述的制备方法制备得到。A lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
对比例5：(与实施例2的区别仅在于乙酰丙酮锰中的锰为二价锰)Comparative Example 5: (The only difference from Example 2 is that the manganese in manganese acetylacetonate is divalent manganese)
一种磷酸锰铁锂正极材料的制备方法，包括如下步骤：A method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
(1)按照摩尔比铁锰比为4:1且(Fe+Mn):P＝1:1，选取乙酰丙酮锰(CAS号：14024-58-9)、乙酰丙酮铁(CAS号：14024-18-1)、质量浓度为95％的磷酸；(1) According to the molar ratio of iron to manganese of 4:1 and (Fe+Mn):P=1:1, manganese acetylacetonate (CAS No.: 14024-58-9), iron acetylacetonate (CAS No.: 14024-18-1), and phosphoric acid with a mass concentration of 95% were selected;
(2)将乙酰丙酮锰、乙酰丙酮铁混合后，按照10g/100g的比例将混合物溶于甲醇中，并逐滴加入磷酸混合，得到磷铁锰的有机溶液；(2) after mixing manganese acetylacetonate and iron acetylacetonate, dissolving the mixture in methanol at a ratio of 10 g/100 g, and adding phosphoric acid dropwise to mix, to obtain an organic solution of phosphorus iron manganese;
(3)将有机溶液在135℃下加热、蒸干，得到固体凝胶，并回收得到有机溶剂；(3) heating the organic solution at 135° C. and evaporating to dryness to obtain a solid gel, and recovering the organic solvent;
(4)按照摩尔比(Fe+Mn):Li:碳源＝1:1.2:0.5，将固体凝胶与氢氧化锂、蔗糖混合后，加入总质量20％的去离子水，混合均匀后进行喷雾干燥；(4) mixing the solid gel with lithium hydroxide and sucrose at a molar ratio of (Fe+Mn):Li:carbon source=1:1.2:0.5, adding 20% of the total mass of deionized water, mixing well, and spray drying;
(5)将步骤(4)所得产物在惰性气体的保护下、850℃煅烧10h，自然冷却至室温，得到磷酸锰铁锂正极材料成品。(5) The product obtained in step (4) is calcined at 850° C. for 10 h under the protection of an inert gas, and naturally cooled to room temperature to obtain a finished product of lithium manganese iron phosphate positive electrode material.
一种磷酸锰铁锂正极材料，由如上所述的制备方法制备得到。A lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
对比例6：(与实施例3的区别仅在于乙酰丙酮锰中的锰为二价锰)
Comparative Example 6: (The only difference from Example 3 is that the manganese in manganese acetylacetonate is divalent manganese)
一种磷酸锰铁锂正极材料的制备方法，包括如下步骤：A method for preparing a lithium manganese iron phosphate positive electrode material comprises the following steps:
(1)按照摩尔比铁锰比为0.25:1且(Fe+Mn):P＝1:1，选取乙酰丙酮锰(CAS号：14024-58-9)、乙酰丙酮铁(CAS号：14024-18-1)、质量浓度为85％的磷酸；(1) According to the molar ratio of iron to manganese of 0.25:1 and (Fe+Mn):P=1:1, manganese acetylacetonate (CAS No.: 14024-58-9), iron acetylacetonate (CAS No.: 14024-18-1), and phosphoric acid with a mass concentration of 85% were selected;
(2)将乙酰丙酮锰、乙酰丙酮铁混合后，按照5g/100g的比例将混合物溶于正丁醇中，并逐滴加入磷酸混合，得到磷铁锰的有机溶液；(2) after mixing manganese acetylacetonate and iron acetylacetonate, dissolving the mixture in n-butanol at a ratio of 5 g/100 g, and adding phosphoric acid dropwise to mix, to obtain an organic solution of phosphorus iron manganese;
(3)将有机溶液在110℃下加热、蒸干，得到固体凝胶，并回收得到有机溶剂；(3) heating the organic solution at 110° C. and evaporating to dryness to obtain a solid gel, and recovering the organic solvent;
(4)按照摩尔比(Fe+Mn):Li:碳源＝1:1.0:0.3，将固体凝胶与醋酸锂、果糖混合后，加入总质量35％的去离子水，混合均匀后进行喷雾干燥；(4) mixing the solid gel with lithium acetate and fructose in a molar ratio of (Fe+Mn):Li:carbon source=1:1.0:0.3, adding 35% of the total mass of deionized water, mixing well, and spray drying;
(5)将步骤(4)所得产物在惰性气体的保护下、600℃煅烧20h，自然冷却至室温，得到磷酸锰铁锂正极材料成品。(5) The product obtained in step (4) is calcined at 600° C. for 20 h under the protection of an inert gas, and naturally cooled to room temperature to obtain a finished product of lithium manganese iron phosphate positive electrode material.
一种磷酸锰铁锂正极材料，由如上所述的制备方法制备得到。A lithium manganese iron phosphate positive electrode material is prepared by the preparation method as described above.
其中，实施例1-3采用的乙酰丙酮锰(CAS号：14284-89-0)为三价锰，对比例4-6采用的乙酰丙酮锰(CAS号：14024-58-9)为二价锰；对比例1-3采用水相共沉淀，沉淀过程中，随着混合溶液pH的增加，沉淀物料量先增加——保持不变——再增加——保持不变，即铁锰沉淀pH不同导致，先沉淀的为磷酸铁，而后再是磷酸锰。Among them, the manganese acetylacetonate (CAS No.: 14284-89-0) used in Examples 1-3 is trivalent manganese, and the manganese acetylacetonate (CAS No.: 14024-58-9) used in Comparative Examples 4-6 is divalent manganese; Comparative Examples 1-3 adopt aqueous phase co-precipitation. During the precipitation process, as the pH of the mixed solution increases, the amount of precipitate first increases-remains unchanged-and then increases-remains unchanged, that is, due to the different pH values of iron and manganese precipitation, iron phosphate is precipitated first, and then manganese phosphate.
对实施例和对比例所得产物进行ICP(电感耦合等离子体光谱仪)检测铁锰磷的元素摩尔比，结果如表1所示：The products obtained in the examples and comparative examples were subjected to ICP (inductively coupled plasma spectrometer) to detect the molar ratio of iron, manganese and phosphorus. The results are shown in Table 1:
表1：产物中铁锰磷的元素摩尔比
Table 1: Molar ratio of iron, manganese and phosphorus in the product
Table 1: Molar ratio of iron, manganese and phosphorus in the product
试验例：Test example:
以实施例和对比例得到的磷酸锰铁锂正极材料，乙炔黑为导电剂，PVDF为粘结剂，按质量比8:1:1进行混合，并加入一定量的有机溶剂NMP，搅拌后涂覆于铝箔上制成正极片，负极采用金属锂片；隔膜为Celgard2400聚丙烯多孔膜；电解液中溶剂为EC、DMC和EMC按质量比
1:1:1组成的溶液，溶质为LiPF6，LiPF6的浓度为1.0mol/L；在手套箱内组装2023型扣式电池。对电池进行充放电循环性能测试，在截止电压2.0-4.3V范围内，测试0.2C、1C放电比容量；测试电化学性能结果如表2所示：The lithium iron manganese phosphate positive electrode material obtained in the embodiment and the comparative example, acetylene black as a conductive agent, PVDF as a binder, are mixed at a mass ratio of 8:1:1, and a certain amount of organic solvent NMP is added, and after stirring, it is coated on an aluminum foil to make a positive electrode sheet, and a metal lithium sheet is used for the negative electrode; the diaphragm is a Celgard2400 polypropylene porous membrane; the solvent in the electrolyte is EC, DMC and EMC at a mass ratio of The solution is composed of 1:1:1, the solute is LiPF 6 , and the concentration of LiPF 6 is 1.0 mol/L; 2023 button cells are assembled in the glove box. The battery is tested for charge and discharge cycle performance, and the 0.2C and 1C discharge specific capacities are tested within the cut-off voltage range of 2.0-4.3V; the test electrochemical performance results are shown in Table 2:
表2：电化学性能测试结果
Table 2: Electrochemical performance test results
Table 2: Electrochemical performance test results
由表2可知，本申请的制备方法制备得到的磷酸锰铁锂正极材料的0.2C放电容量能达到149.3mAh/g以上，1C放电容量能达到142.4mAh/g以上，1C循环500次容量保持率能达到94.06％以上。As can be seen from Table 2, the 0.2C discharge capacity of the lithium manganese iron phosphate positive electrode material prepared by the preparation method of the present application can reach more than 149.3 mAh/g, the 1C discharge capacity can reach more than 142.4 mAh/g, and the capacity retention rate after 500 cycles at 1C can reach more than 94.06%.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.
Claims (10)
- 一种磷酸锰铁锂正极材料的制备方法，其特征在于：包括以下步骤：A method for preparing a lithium manganese iron phosphate positive electrode material, characterized in that it comprises the following steps:(1)将乙酰丙酮锰、乙酰丙酮铁、磷源与有机溶剂混合得到有机溶液，其中，所述乙酰丙酮锰中的锰为三价锰，所述乙酰丙酮铁中的铁为三价铁；(1) mixing manganese acetylacetonate, ferric acetylacetonate, a phosphorus source and an organic solvent to obtain an organic solution, wherein the manganese in the manganese acetylacetonate is trivalent manganese, and the iron in the ferric acetylacetonate is trivalent iron;(2)将步骤(1)得到的有机溶液加热后蒸干，得到固体凝胶；(2) heating the organic solution obtained in step (1) and evaporating it to dryness to obtain a solid gel;(3)将锂源、碳源、水与步骤(2)得到的固体凝胶混合，干燥、在惰性气体下煅烧，冷却，得到所述磷酸锰铁锂正极材料。(3) Mixing a lithium source, a carbon source, and water with the solid gel obtained in step (2), drying, calcining under an inert gas, and cooling to obtain the lithium manganese iron phosphate positive electrode material.
- 根据权利要求1所述的的制备方法，其特征在于：步骤(1)中，所述磷源为磷酸。The preparation method according to claim 1, characterized in that: in step (1), the phosphorus source is phosphoric acid.
- 根据权利要求1所述的的制备方法，其特征在于：步骤(1)中，所述有机溶剂为甲苯、甲醇、正丁醇、冰乙酸及乙二醇中的至少一种。The preparation method according to claim 1 is characterized in that: in step (1), the organic solvent is at least one of toluene, methanol, n-butanol, glacial acetic acid and ethylene glycol.
- 根据权利要求1所述的的制备方法，其特征在于：步骤(1)中，所述乙酰丙酮锰、所述乙酰丙酮铁及所述磷源按照(Fe+Mn)与P的摩尔比为1:(1-1.1)进行混合。The preparation method according to claim 1 is characterized in that: in step (1), the manganese acetylacetonate, the iron acetylacetonate and the phosphorus source are mixed according to a molar ratio of (Fe+Mn) to P of 1:(1-1.1).
- 根据权利要求2所述的的制备方法，其特征在于：步骤(1)中，所述的混合的方式为先将乙酰丙酮锰与乙酰丙酮铁混合得到混合物，再将所述混合物溶于所述有机溶剂中，再逐滴加入磷酸混合。The preparation method according to claim 2 is characterized in that: in step (1), the mixing method is to first mix manganese acetylacetonate and iron acetylacetonate to obtain a mixture, then dissolve the mixture in the organic solvent, and then add phosphoric acid dropwise to mix.
- 根据权利要求5所述的的制备方法，其特征在于：步骤(1)中，按照铁与锰的摩尔比为(0.1-5):1将乙酰丙酮锰与乙酰丙酮铁混合得到混合物。The preparation method according to claim 5 is characterized in that: in step (1), manganese acetylacetonate and iron acetylacetonate are mixed according to a molar ratio of iron to manganese of (0.1-5):1 to obtain a mixture.
- 根据权利要求5所述的的制备方法，其特征在于：步骤(1)中，按照(3-15)g/100g的比例将所述混合物溶于所述有机溶剂中。The preparation method according to claim 5 is characterized in that: in step (1), the mixture is dissolved in the organic solvent at a ratio of (3-15) g/100 g.
- 根据权利要求1所述的的制备方法，其特征在于：步骤(3)中，按照摩尔比(Fe+Mn):Li:碳源＝1:(1.0-1.2):(0.3-0.5)，将所述固体凝胶与锂源、碳源混合。The preparation method according to claim 1 is characterized in that: in step (3), the solid gel is mixed with a lithium source and a carbon source according to a molar ratio of (Fe+Mn):Li:carbon source=1:(1.0-1.2):(0.3-0.5).
- 一种磷酸锰铁锂正极材料，其特征在于：由权利要求1-8任一项所述的制备方法制备得到。A lithium manganese iron phosphate positive electrode material, characterized in that it is prepared by the preparation method described in any one of claims 1 to 8.
- 权利要求9所述的磷酸锰铁锂正极材料在制备锂离子电池中的应用。 Use of the lithium iron manganese phosphate positive electrode material described in claim 9 in the preparation of lithium ion batteries.
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| CN202211293362.5A CN115893357A (en) | 2022-10-21 | 2022-10-21 | Lithium iron manganese phosphate positive electrode material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103702934A (en) * | 2011-06-27 | 2014-04-02 | 新加坡国立大学 | An approach for manufacturing efficient mesoporous nano-composite positive electrode limn1-xfexpo4 materials |
| WO2015003568A1 (en) * | 2013-07-10 | 2015-01-15 | 江苏华东锂电技术研究院有限公司 | Method for preparing positive electrode active material of lithium ion battery |
| JP2015032345A (en) * | 2013-07-31 | 2015-02-16 | 太平洋セメント株式会社 | Method for manufacturing lithium manganese phosphate positive electrode active material |
| CN104752718A (en) * | 2013-12-27 | 2015-07-01 | 比亚迪股份有限公司 | LiMnxFe1-xPO4 positive electrode active material and preparation method thereof |
| CN115072695A (en) * | 2022-07-07 | 2022-09-20 | 江苏协鑫锂电科技有限公司 | Preparation method of high-capacity lithium manganese iron phosphate material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103702934A (en) * | 2011-06-27 | 2014-04-02 | 新加坡国立大学 | An approach for manufacturing efficient mesoporous nano-composite positive electrode limn1-xfexpo4 materials |
| WO2015003568A1 (en) * | 2013-07-10 | 2015-01-15 | 江苏华东锂电技术研究院有限公司 | Method for preparing positive electrode active material of lithium ion battery |
| JP2015032345A (en) * | 2013-07-31 | 2015-02-16 | 太平洋セメント株式会社 | Method for manufacturing lithium manganese phosphate positive electrode active material |
| CN104752718A (en) * | 2013-12-27 | 2015-07-01 | 比亚迪股份有限公司 | LiMnxFe1-xPO4 positive electrode active material and preparation method thereof |
| CN115072695A (en) * | 2022-07-07 | 2022-09-20 | 江苏协鑫锂电科技有限公司 | Preparation method of high-capacity lithium manganese iron phosphate material |
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