CN115709976B - Modified lithium iron manganese phosphate material, preparation method thereof and battery - Google Patents
Modified lithium iron manganese phosphate material, preparation method thereof and battery Download PDFInfo
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- CN115709976B CN115709976B CN202211429590.0A CN202211429590A CN115709976B CN 115709976 B CN115709976 B CN 115709976B CN 202211429590 A CN202211429590 A CN 202211429590A CN 115709976 B CN115709976 B CN 115709976B
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- 239000000463 material Substances 0.000 title claims abstract description 120
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical class [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 85
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 67
- 238000002156 mixing Methods 0.000 claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 44
- 239000011572 manganese Substances 0.000 claims abstract description 43
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 42
- 229910052742 iron Inorganic materials 0.000 claims abstract description 34
- 239000002002 slurry Substances 0.000 claims abstract description 34
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 31
- 239000002131 composite material Substances 0.000 claims abstract description 25
- 239000003607 modifier Substances 0.000 claims abstract description 25
- 238000005245 sintering Methods 0.000 claims abstract description 23
- 238000000498 ball milling Methods 0.000 claims abstract description 22
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 32
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 30
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 21
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 21
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 19
- 239000012298 atmosphere Substances 0.000 claims description 17
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 16
- 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 claims description 15
- 229930006000 Sucrose Natural products 0.000 claims description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 15
- 239000005720 sucrose Substances 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- 229920002472 Starch Polymers 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000008107 starch Substances 0.000 claims description 14
- 235000019698 starch Nutrition 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910001868 water Inorganic materials 0.000 claims description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 13
- 229910052749 magnesium Inorganic materials 0.000 claims description 13
- 239000011777 magnesium Substances 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- 229910052726 zirconium Inorganic materials 0.000 claims description 13
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 12
- 239000002041 carbon nanotube Substances 0.000 claims description 12
- 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 claims description 11
- 239000002134 carbon nanofiber Substances 0.000 claims description 11
- 239000008103 glucose Substances 0.000 claims description 11
- 229910021389 graphene Inorganic materials 0.000 claims description 11
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- 229910052758 niobium Inorganic materials 0.000 claims description 11
- 239000010955 niobium Substances 0.000 claims description 11
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 10
- 239000000347 magnesium hydroxide Substances 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 229920000858 Cyclodextrin Polymers 0.000 claims description 9
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 9
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 9
- 229940078494 nickel acetate Drugs 0.000 claims description 9
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 9
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 8
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 7
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 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
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 7
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 7
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 238000002715 modification method Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000004090 dissolution Methods 0.000 abstract description 5
- 230000002349 favourable effect Effects 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000011259 mixed solution Substances 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 5
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- -1 metal compound vanadium pentoxide Chemical class 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000009792 diffusion process Methods 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
- 238000004064 recycling Methods 0.000 description 2
- MCPTUMJSKDUTAQ-UHFFFAOYSA-N vanadium;hydrate Chemical compound O.[V] MCPTUMJSKDUTAQ-UHFFFAOYSA-N 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 230000005536 Jahn Teller effect Effects 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910013275 LiMPO Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 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
Abstract
The invention relates to a modified lithium iron manganese phosphate material, a preparation method thereof and a battery, wherein the preparation method comprises the following steps: (1) Mixing an iron source, a manganese source, a phosphorus source, a modifier and a solvent, and ball milling to obtain a pretreated slurry; (2) Mixing a lithium source, a carbon source, a solvent and the obtained pretreatment slurry, drying and sintering to obtain the modified lithium manganese iron phosphate material; the modifier in step (1) comprises a composite carbon source and/or a doped metal compound. According to the invention, the modifier is added in the pretreatment process, so that the modification method for improving the lithium iron manganese phosphate material is provided, the composite carbon source is favorable for forming a conductive network in the synthesis process, the problem of structural damage caused by manganese dissolution in the circulation process is solved by doping the metal compound, the conductivity of the material is improved by the synergistic effect of the composite carbon source and the metal compound, the stability is improved, and the circulation performance is improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, relates to a preparation method of a modified lithium iron manganese phosphate material, and particularly relates to a modified lithium iron manganese phosphate material, a preparation method thereof and a battery.
Background
Positive electrode materials of lithium ion batteries are commonly used as lithium ion sources in batteries to determine reversible charge-discharge capacity and operating voltage of the batteriesThe upper limit, which is a key factor in limiting the performance and cost of lithium ion batteries, is currently generally selected from lithium-containing compounds with higher electrode potential, such as LiCoO 2 、LiNi 1-x-y Co x Mn y O 2 、LiFePO 4 /C、LiMn 2 O 4 Etc. Goodenough et al researchers in 1997 proposed LiMPO 4 The material can be used as the positive electrode material of the lithium ion battery, and the phosphate positive electrode material is widely paid attention to by scientific researchers, liFePO 4 The material has the advantages of wide raw material sources, low cost, environmental friendliness, good thermal stability, excellent safety performance and the like, and has successfully realized large-scale commercial production as a power battery anode material. Meanwhile, lithium iron phosphate batteries have been affected in competition with ternary power batteries because of their low energy density and other drawbacks.
The lithium manganese phosphate which is the phosphate positive electrode material is provided with a 4.1V discharge platform, and compared with a 3.4V discharge platform of the lithium iron phosphate, the energy density of the lithium manganese phosphate material is improved by about 20 percent. However, due to the Jahn-Teller effect of Mn, the material structure of the lithium manganese phosphate material is damaged in the circulation process, so that the circulation performance of the material is affected. According to comparison analysis of a large number of documents related to preparation process optimization, surface modification and element doping modification of the lithium manganese phosphate material, the lithium iron phosphate material obtained by substituting the iron element for the manganese element is effectively improved in lithium ion diffusion coefficient and electron conductivity, and the material shows good electrochemical performance, so that the lithium manganese phosphate material is expected to obtain a certain share in the markets of power batteries and low-cost consumer batteries.
However, in the recycling process of the lithium iron manganese phosphate material, the material structure is easy to break, so that the recycling performance of the material is affected. The inherent low lithium ion diffusion coefficient characteristic of the lithium iron manganese phosphate material influences gram capacity exertion, multiplying power performance and the like of the material, so that the battery performance is difficult to meet the indexes of practical application requirements, and the commercialized application process of the lithium iron manganese phosphate material is restricted.
However, the lithium iron manganese phosphate material has performance advantages and prospects over lithium iron phosphate, so that a high-performance lithium iron manganese phosphate composite material modification method is urgently needed, and the performances of material ion conductivity, multiplying power, circulation and the like are improved.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a modified lithium iron manganese phosphate material, a preparation method thereof and a battery.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a modified lithium iron manganese phosphate material, which comprises the following steps:
(1) Mixing an iron source, a manganese source, a phosphorus source, a modifier and a solvent, and ball milling to obtain a pretreated slurry;
(2) Mixing a lithium source, a carbon source, a solvent and the obtained pretreatment slurry, drying and sintering to obtain the modified lithium manganese iron phosphate material;
the modifier in step (1) comprises a composite carbon source and/or a doped metal compound.
According to the invention, the modifier is added in the pretreatment process, so that the modification method for improving the lithium iron manganese phosphate material is provided, and the composite carbon source is favorable for forming a conductive network in the synthesis process, so that the conductivity of the material is improved, the problem of structural damage caused by manganese dissolution in the circulation process is solved by doping the metal compound, the stability is improved, and the circulation performance is improved.
The composite carbon source and/or the doped metal compound serve as a modifier to synergistically improve the effect of the lithium iron manganese phosphate.
As a preferable technical scheme of the invention, the mode of mixing the iron source, the manganese source, the phosphorus source, the modifier and the solvent in the step (1) is as follows:
(a) Mixing an iron source, a phosphorus source and a solvent, and completely dissolving into a mixed solution;
(b) Mixing a manganese source, a modifier and the mixed solution to complete the mixing;
or alternatively, the first and second heat exchangers may be,
(i) Mixing an iron source, a phosphorus source, a modifier and a solvent, and completely dissolving into a mixed solution;
(ii) Mixing a manganese source with the mixed solution to complete the mixing.
The method comprises the steps of completely dissolving an iron source into a phosphoric acid solution, adding a manganese source into the solution, mixing a modifier before a lithium source, fully ball-milling and mixing, and uniformly distributing iron, manganese and phosphorus elements in the pretreated slurry, wherein particles are fine and uniform, and no metal component remains.
Preferably, the iron source in step (1) is any one or a combination of at least two of iron powder, iron sheet or iron ingot, and typical but non-limiting combinations include combinations of iron powder and iron sheet, combinations of iron sheet and iron ingot, combinations of iron powder and iron ingot, or combinations of iron powder, iron sheet and iron ingot, preferably iron powder.
Preferably, the manganese source in step (1) is any one or a combination of at least two of manganese powder, manganese flakes, manganese monoxide, manganese dioxide, manganous oxide or manganese acetate, and typical but non-limiting combinations include combinations of manganese powder and manganese flakes, combinations of manganese flakes and manganese monoxide, combinations of manganese oxide and manganese dioxide, combinations of manganese dioxide and manganous oxide, combinations of manganous oxide and manganese acetate, combinations of manganese powder, manganese flakes and manganese oxide, combinations of manganese flakes, manganese oxide and manganese dioxide, combinations of manganese dioxide, manganese dioxide and manganous oxide, combinations of manganese dioxide, manganous oxide and manganese acetate, combinations of manganese powder, manganese flakes, manganese oxide and manganese dioxide, combinations of manganese dioxide, manganese dioxide and manganous oxide, combinations of manganese oxide, manganese dioxide, manganous oxide and manganese acetate, preferably manganese oxide and/or manganous oxide.
Preferably, the phosphorus source of step (1) comprises phosphoric acid.
Preferably, the concentration of phosphoric acid is 10 to 60wt%, for example, 10wt%, 20wt%, 30wt%, 40wt%, 50wt% or 60wt%, but not limited to the recited values, and other non-recited values within the range of values are equally applicable, preferably 30 to 40wt%.
Preferably, the solvent of step (1) comprises water.
Preferably, the mixing in step (1) further comprises dispersing.
Preferably, the ball milling of step (1) comprises wet ball milling.
Preferably, the rotational speed of the wet ball mill is 240 to 300rpm, for example, 240rpm, 260rpm, 280rpm, 290rpm or 300rpm, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the solid content of the pretreated slurry in step (1) is 10 to 60wt%, for example, 10wt%, 20wt%, 30wt%, 40wt%, 50wt% or 60wt%, but not limited to the recited values, other non-recited values within the range of values are equally applicable, preferably 30 to 40wt%.
Preferably, the lithium source of step (2) comprises any one or a combination of at least two of lithium carbonate, lithium acetate or lithium hydroxide, typically but not limited to a combination of lithium carbonate and lithium acetate, a combination of lithium acetate and lithium hydroxide, a combination of lithium carbonate, lithium acetate and lithium hydroxide, preferably lithium carbonate and/or lithium acetate.
Preferably, the carbon source in step (2) comprises any one or a combination of at least two of glucose, starch, sucrose, polyethylene glycol, polyvinyl alcohol or cyclodextrin, typically but not limited to a combination of glucose and starch, a combination of starch and sucrose, a combination of sucrose and polyethylene glycol, a combination of polyethylene glycol and polyvinyl alcohol, a combination of polyvinyl alcohol and cyclodextrin, a combination of glucose, starch and sucrose, a combination of starch, sucrose and polyethylene glycol, a combination of sucrose, polyethylene glycol and polyvinyl alcohol, a combination of polyethylene glycol, polyvinyl alcohol and cyclodextrin, a combination of glucose, starch, sucrose, polyethylene glycol and polyvinyl alcohol, a combination of sucrose, polyethylene glycol, polyvinyl alcohol and cyclodextrin, a combination of glucose, starch, sucrose, polyethylene glycol and polyvinyl alcohol, a combination of starch, sucrose, polyethylene glycol, polyvinyl alcohol and cyclodextrin, or a combination of glucose, starch, sucrose, polyethylene glycol, polyvinyl alcohol and cyclodextrin, preferably glucose and/or starch.
The carbon source in the preparation method provided by the invention forms a carbon coating layer on the surface of the lithium iron manganese phosphate particles, and the thickness of the carbon coating layer is between 2 and 15 nm.
Preferably, the step (2) further comprises dispersing and wet ball milling after the mixing to obtain precursor slurry.
Preferably, the solid content of the precursor slurry is 10 to 60wt%, for example, 10wt%, 20wt%, 30wt%, 40wt%, 50wt% or 60wt%, but not limited to the recited values, other non-recited values within the range of values are equally applicable, preferably 30 to 40wt%.
Preferably, the drying of step (2) comprises spray drying.
Preferably, the sintering of step (2) is performed under a sintering atmosphere.
Preferably, the sintering atmosphere comprises an inert atmosphere and/or a reducing atmosphere.
Preferably, the inert atmosphere comprises nitrogen and/or argon.
Preferably, the reducing atmosphere comprises hydrogen.
Preferably, the sintering temperature in step (2) is 650 to 800 ℃, and may be 650 ℃, 700 ℃, 720 ℃, 750 ℃, or 800 ℃, for example, but is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the sintering time in the step (2) is 4 to 10 hours, for example, may be 4 hours, 6 hours, 8 hours, 9 hours or 10 hours, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the composite carbon source comprises any one or a combination of at least two of carbon nanotubes, graphene or carbon nanofibers, and typical but non-limiting combinations include combinations of carbon nanotubes and graphene, combinations of graphene and carbon nanofibers, combinations of carbon nanotubes and carbon nanofibers, and combinations of carbon nanotubes, graphene and carbon nanofibers.
Preferably, the metallic element in the metallic compound includes any one or a combination of at least two of vanadium, titanium, magnesium, zirconium, niobium, or nickel, typically but not limited to, a combination of vanadium and titanium, a combination of titanium and magnesium, a combination of magnesium and zirconium, a combination of zirconium and niobium, a combination of niobium and nickel, a combination of vanadium, titanium and magnesium, a combination of titanium, magnesium and zirconium, a combination of magnesium, zirconium and niobium, a combination of zirconium, niobium and nickel, a combination of vanadium, titanium, magnesium and zirconium, a combination of magnesium, zirconium and niobium, a combination of magnesium, zirconium, niobium and nickel, a combination of vanadium, titanium, magnesium, zirconium and niobium, a combination of titanium, magnesium, zirconium, niobium, and nickel, or a combination of vanadium, titanium, magnesium, zirconium, niobium, and nickel.
Preferably, the metal compound includes any one or a combination of at least two of vanadium pentoxide, ammonium metavanadate, titanium dioxide, magnesium hydroxide, magnesium oxide, zirconium hydroxide, niobium pentoxide, niobium hydroxide, or nickel acetate, and typically, but not limited to, a combination of vanadium pentoxide and ammonium metavanadate, a combination of ammonium metavanadate and titanium dioxide, a combination of titanium dioxide and magnesium hydroxide, a combination of magnesium hydroxide and magnesium oxide, a combination of magnesium oxide and zirconium oxide, a combination of zirconium oxide and zirconium hydroxide, a combination of zirconium hydroxide and niobium pentoxide, a combination of niobium pentoxide and niobium hydroxide, a combination of niobium hydroxide and nickel acetate, a combination of vanadium pentoxide, ammonium metavanadate and titanium dioxide, magnesium hydroxide, magnesium oxide, and zirconium oxide, or a combination of magnesium oxide, zirconium hydroxide, niobium pentoxide and niobium hydroxide and nickel acetate.
As a preferred technical scheme of the preparation method according to the first aspect of the present invention, the preparation method comprises the following steps:
(1) Mixing an iron source, a manganese source, a modifier, water and phosphoric acid, dispersing and ball milling by a wet method to obtain a pretreatment slurry with the solid content of 10-60 wt%;
(2) Mixing a lithium source, a carbon source, a solvent and the obtained pretreatment slurry, dispersing and ball milling by a wet method to obtain precursor slurry with the solid content of 10-60 wt%, spray drying the precursor slurry, and sintering at 650-800 ℃ for 4-10 h, wherein the sintering is performed in an inert atmosphere and/or a reducing atmosphere to obtain the modified lithium iron manganese phosphate material;
in the step (1), the iron source is any one or a combination of at least two of iron powder, iron sheets or iron ingots; the manganese source is any one or a combination of at least two of manganese powder, manganese flakes, manganese monoxide, manganese dioxide, manganous oxide or manganese acetate; the modifier comprises a composite carbon source and/or a doped metal compound; the composite carbon source comprises any one or a combination of at least two of carbon nano tubes, graphene or carbon nano fibers; the metal compound comprises any one or a combination of at least two of vanadium pentoxide, ammonium metavanadate, titanium dioxide, magnesium hydroxide, magnesium oxide, zirconium hydroxide, niobium pentoxide, niobium hydroxide or nickel acetate;
in the step (2), the lithium source comprises any one or a combination of at least two of lithium carbonate, lithium acetate or lithium hydroxide; the carbon source comprises any one or a combination of at least two of glucose, starch, sucrose, polyethylene glycol, polyvinyl alcohol or cyclodextrin.
In a second aspect, the invention provides a modified lithium iron manganese phosphate material, which is obtained by the preparation method in the first aspect.
Preferably, the (Fe+Mn)/P in the modified lithium manganese iron phosphate material is 0.95-0.99 in terms of mole, and may be, for example, 0.95, 0.96, 0.97, 0.98 or 0.99, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the Li/(fe+mn) in the modified lithium manganese iron phosphate material is 1.02 to 1.06 in terms of mole, and may be, for example, 1.02, 1.03, 1.04, 1.05 or 1.06, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the Mn/P in the modified lithium manganese iron phosphate material is 0.6 to 0.9 in terms of mole, and may be, for example, 0.6, 0.75, 0.8, 0.85 or 0.9, but is not limited to the recited values, and other non-recited values within the numerical range are equally applicable, preferably 0.75 to 0.85.
Preferably, the carbon content in the modified lithium iron manganese phosphate material is 1.2-5 wt%, for example, 1.2wt%, 2wt%, 3wt%, 4wt% or 5wt%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable, preferably 1.5-3 wt%.
Preferably, the content of the composite carbon in the modified lithium manganese iron phosphate material is 0.3-3 wt%, for example, may be 0.3wt%, 0.5wt%, 1wt%, 2wt% or 3wt%, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the modified lithium manganese iron phosphate material has a doping metal element/P of 0.003 to 0.02 on a molar basis, and may be, for example, 0.003, 0.005, 0.01, 0.015 or 0.02, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
In a third aspect, the present invention provides a battery comprising a modified lithium iron manganese phosphate material according to the second aspect.
By the technical scheme, the invention has the following beneficial effects:
(1) According to the invention, the modifier is added in the pretreatment process, so that the modification method for improving the lithium iron manganese phosphate material is provided, the composite carbon source is favorable for forming a conductive network in the synthesis process, the problem of structural damage caused by manganese dissolution in the circulation process is solved by doping the metal compound, the conductivity of the material is improved by the synergistic effect of the composite carbon source and the metal compound, the stability is improved, and the circulation performance is improved.
(2) According to the invention, the iron source is completely dissolved in the phosphoric acid solution, then the manganese source is added, the modifier is mixed before the lithium source, and after full ball milling and mixing, the iron, manganese and phosphorus elements in the pretreated slurry are uniformly distributed, the particles are fine and uniform, and no metal component remains.
Drawings
FIG. 1 is a scanning electron microscope image of the modified lithium iron manganese phosphate material provided in example 1.
Fig. 2 is a scanning electron microscope image of the modified lithium iron manganese phosphate material provided in example 4.
FIG. 3 is a scanning electron microscope image of the modified lithium iron manganese phosphate material provided in example 5.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
Example 1
The present example provides a modified lithium iron manganese phosphate material (fig. 1) in which (fe+mn)/P is 0.97, li/(fe+mn) is 1.04, and Mn/P is 0.75 in terms of molar amount; in the modified lithium iron manganese phosphate material, a carbon coating layer is arranged on the surface of lithium iron manganese phosphate particles, and the carbon content is 3wt%; the modified lithium iron manganese phosphate material is provided with a conductive network of carbon nanotubes, wherein the content of the carbon nanotubes is 1.5wt%; the modified lithium iron manganese phosphate material contains doped metal compound vanadium pentoxide, and the doped metal element/P is 0.01.
The modified lithium iron manganese phosphate material is prepared by the following preparation method:
(1) Mixing iron powder, manganese dioxide, carbon nanotubes, vanadium pentoxide, water and phosphoric acid, dispersing and performing wet ball milling to obtain a pretreatment slurry with the solid content of 35 wt%;
(2) Mixing lithium carbonate, glucose, water and the obtained pretreatment slurry, dispersing and ball-milling by a wet method to obtain precursor slurry with the solid content of 35wt%, spray-drying the precursor slurry, and sintering at 700 ℃ for 7 hours, wherein the sintering is performed under a nitrogen atmosphere to obtain the modified lithium iron manganese phosphate material;
the mixing mode in the step (1) is as follows:
(a) Mixing iron powder, water and phosphoric acid, and completely dissolving into a mixed solution;
(b) Mixing manganese oxide, carbon nanotubes, vanadium pentoxide and the mixed solution to complete the mixing.
Example 2
The embodiment provides a modified lithium iron manganese phosphate material, wherein the molar ratio of (Fe+Mn)/P in the modified lithium iron manganese phosphate material is 0.95, the ratio of Li/(Fe+Mn) is 1.02, and the ratio of Mn/P is 0.6; in the modified lithium iron manganese phosphate material, a carbon coating layer is arranged on the surface of lithium iron manganese phosphate particles, and the carbon content is 1.2wt%; in the modified lithium iron manganese phosphate material, a conductive network of graphene is arranged, and the content of the graphene is 0.3wt%; the modified lithium iron manganese phosphate material contains a doped metal compound magnesium hydroxide, and the doped metal element/P is 0.003.
The modified lithium iron manganese phosphate material is prepared by the following preparation method:
(1) Mixing iron sheets, manganous oxide, graphene, magnesium hydroxide, water and phosphoric acid, dispersing and performing wet ball milling to obtain a pretreatment slurry with the solid content of 10 wt%;
(2) Mixing lithium acetate, starch, water and the obtained pretreated slurry, dispersing and ball milling by a wet method to obtain precursor slurry with the solid content of 10wt%, spray drying the precursor slurry, and sintering at 650 ℃ for 10 hours, wherein the sintering is performed in a hydrogen atmosphere to obtain the modified lithium iron manganese phosphate material;
the mixing mode in the step (1) is as follows:
(a) Mixing iron flakes, water and phosphoric acid, and completely dissolving into a mixed solution;
(b) And mixing the manganous-manganic oxide, the graphene, the magnesium hydroxide and the mixed solution, and completing the mixing.
Example 3
The embodiment provides a modified lithium iron manganese phosphate material, wherein the molar ratio of (Fe+Mn)/P in the modified lithium iron manganese phosphate material is 0.99, the ratio of Li/(Fe+Mn) is 1.06, and the ratio of Mn/P is 0.9; in the modified lithium iron manganese phosphate material, a carbon coating layer is arranged on the surface of lithium iron manganese phosphate particles, and the carbon content is 5wt%; the modified lithium iron manganese phosphate material is provided with a conductive network of carbon nanofibers, wherein the content of the carbon nanofibers is 3wt%; the modified lithium iron manganese phosphate material contains a doped metal compound nickel acetate, and the doped metal element/P is 0.02.
The modified lithium iron manganese phosphate material is prepared by the following preparation method:
(1) Mixing iron ingots, manganese powder, carbon nanofibers, nickel acetate, water and phosphoric acid, dispersing and performing wet ball milling to obtain a pretreatment slurry with the solid content of 60 wt%;
(2) Mixing lithium hydroxide, sucrose, water and the obtained pretreatment slurry, dispersing and ball milling by a wet method to obtain precursor slurry with the solid content of 60wt%, spray drying the precursor slurry, and sintering at 800 ℃ for 4 hours, wherein the sintering is performed under argon to obtain the modified lithium iron manganese phosphate material;
the mixing mode in the step (1) is as follows:
(a) Mixing iron ingot, water and phosphoric acid, and completely dissolving into the mixed solution;
(b) Mixing manganese powder, carbon nanofibers, nickel acetate and the mixed solution to complete the mixing.
Example 4
This example provides a modified lithium iron manganese phosphate material (fig. 2) that differs from example 1 in that the additive has only a composite carbon source, without the doping metal compound.
Example 5
This example provides a modified lithium iron manganese phosphate material (fig. 3) that differs from example 1 in that the additive has only doped metal compounds and no composite carbon source.
Example 6
This example provides a modified lithium iron manganese phosphate material that differs from example 1 in that the composite carbon content is 0.1wt%.
Example 7
This example provides a modified lithium iron manganese phosphate material that differs from example 1 in that the composite carbon content is 3.5wt%.
Example 8
This example provides a modified lithium iron manganese phosphate material, which differs from example 1 in that the doping metal element/P is 0.002.
Example 9
This example provides a modified lithium iron manganese phosphate material, which differs from example 1 in that the doping metal element/P is 0.035.
Example 10
The present embodiment provides a modified lithium iron manganese phosphate material, which is different from embodiment 1 in that the mixing manner in step (1) is as follows:
(i) Mixing iron powder, carbon nano tubes, vanadium pentoxide, water and phosphoric acid, and completely dissolving into a mixed solution;
(ii) Mixing manganese dioxide and the mixed solution to complete the mixing.
Comparative example 1
This comparative example provides a lithium iron manganese phosphate material that differs from example 1 in the absence of a modifier.
And preparing the modified lithium iron manganese phosphate material into a positive plate, and assembling the button cell according to the standard of GB 31241-2014.
The electrochemical performance is tested, and the test conditions are as follows: the cell was tested for ac impedance using an electrochemical workstation. The electrochemical performance of the button cell was tested using a New Wei/blue electric test system (measuring range I:10mA; measuring range U: 5V). The test voltage interval is 2.5-4.5V, the charge-discharge current is set to be 1C multiplying power by the cycle test, and the cycle is 300 weeks. And after the circulation is finished, detecting the content of the dissolved manganese element to represent the stability of the lithium iron manganese phosphate material.
The test results are shown in table 1 below.
TABLE 1
From table 1 the following conclusions are drawn:
(1) As can be seen from examples 1-3 and 10, the present invention provides a modification method for improving the lithium iron manganese phosphate material by adding a modifier during the pretreatment, wherein the composite carbon source is favorable for forming a conductive network during the synthesis process, and the doped metal compound solves the problem of structural damage caused by dissolution of manganese during the circulation process, and the synergistic effect of the two improves the conductivity, stability and circulation performance of the material.
(2) As is clear from comparison of examples 4 and 5 with example 1, when only the composite carbon source is added, not only is the conductivity reduced, but also the cycle performance is affected, manganese in the material is dissolved after the cycle, the structure of the modified lithium iron manganese phosphate material is destroyed, and the stability is poor; similarly, when only the doping metal compound is added, not only the cycle performance is lowered, but also the conductivity is affected. The modifier provided by the invention improves the electronic capability of the material through synergistic effect, improves the stability and improves the cycle performance.
(3) From a comparison of examples 6-9 with example 1, it is seen that the modified lithium iron manganese phosphate material has inferior properties when the modifier is outside the preferred ranges provided by the present invention.
(4) As can be seen from a comparison of comparative example 1 with example 1, the modified lithium iron manganese phosphate material has poor properties when no modifier is added.
In summary, the modifier is added in the pretreatment process, so that the modification method for improving the lithium iron manganese phosphate material is provided, the composite carbon source is favorable for forming a conductive network in the synthesis process, the doped metal compound solves the problem of structural damage caused by manganese dissolution in the circulation process, and the synergistic effect of the two improves the conductivity, stability and circulation performance of the material.
The detailed structural features of the present invention are described in the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
Claims (29)
1. The preparation method of the modified lithium iron manganese phosphate material is characterized by comprising the following steps of:
(1) Mixing an iron source, a manganese source, a phosphorus source, a modifier and a solvent, and ball milling to obtain a pretreated slurry;
(2) Mixing a lithium source, a carbon source, a solvent and the obtained pretreatment slurry, drying and sintering to obtain the modified lithium manganese iron phosphate material;
the modifier in the step (1) comprises a composite carbon source and a doped metal compound;
wherein the content of composite carbon in the modified lithium iron manganese phosphate material is 0.3-3wt%;
based on the molar weight, the doped metal element/P in the modified lithium iron manganese phosphate material is 0.003-0.02;
the composite carbon source comprises any one or a combination of at least two of carbon nano tubes, graphene or carbon nano fibers;
the metal element in the metal compound comprises any one or a combination of at least two of vanadium, titanium, magnesium, zirconium, niobium or nickel.
2. The method for producing a modified lithium iron manganese phosphate material according to claim 1, wherein the iron source in step (1) is any one or a combination of at least two of iron powder, iron flakes or iron ingots.
3. The method for preparing a modified lithium iron manganese phosphate material according to claim 1, wherein the manganese source in the step (1) is any one or a combination of at least two of manganese powder, manganese flakes, manganese monoxide, manganese dioxide, trimanganese tetroxide and manganese acetate.
4. The method of preparing a modified lithium iron manganese phosphate material according to claim 1, wherein the phosphorus source of step (1) comprises phosphoric acid.
5. The method for preparing the modified lithium iron manganese phosphate material according to claim 1, wherein the concentration of phosphoric acid is 10-60wt%.
6. The method of preparing a modified lithium iron manganese phosphate material according to claim 1, wherein the solvent of step (1) comprises water.
7. The method of preparing a modified lithium iron manganese phosphate material according to claim 1, wherein the mixing of step (1) further comprises dispersing.
8. The method of preparing a modified lithium iron manganese phosphate material according to claim 1, wherein the ball milling in step (1) comprises wet ball milling.
9. The method for preparing the modified lithium iron manganese phosphate material according to claim 8, wherein the rotational speed of the wet ball milling is 240-300 rpm.
10. The preparation method of the modified lithium iron manganese phosphate material according to claim 1, wherein the solid content of the pretreatment slurry in the step (1) is 10-60wt%.
11. The method of producing a modified lithium iron manganese phosphate material according to claim 1, wherein the lithium source in step (2) comprises any one or a combination of at least two of lithium carbonate, lithium acetate, and lithium hydroxide.
12. The method of preparing a modified lithium iron manganese phosphate material according to claim 1, wherein the carbon source in step (2) comprises any one or a combination of at least two of glucose, starch, sucrose, polyethylene glycol, polyvinyl alcohol, or cyclodextrin.
13. The method for preparing a modified lithium iron manganese phosphate material according to claim 1, wherein the mixing in the step (2) further comprises dispersing and wet ball milling to obtain a precursor slurry.
14. The method for preparing a modified lithium iron manganese phosphate material according to claim 13, wherein the solid content of the precursor slurry is 10-60wt%.
15. The method of preparing a modified lithium iron manganese phosphate material according to claim 1, wherein the drying of step (2) comprises spray drying.
16. The method for producing a modified lithium iron manganese phosphate material according to claim 1, wherein the sintering in step (2) is performed under a sintering atmosphere.
17. The method of producing a modified lithium iron manganese phosphate material according to claim 16, wherein the sintering atmosphere comprises an inert atmosphere and/or a reducing atmosphere.
18. The method of preparing a modified lithium iron manganese phosphate material according to claim 17, wherein the inert atmosphere comprises nitrogen and/or argon.
19. The method of preparing a modified lithium iron manganese phosphate material according to claim 17, wherein the reducing atmosphere comprises hydrogen.
20. The method for preparing a modified lithium iron manganese phosphate material according to claim 1, wherein the sintering temperature in the step (2) is 650-800 ℃.
21. The method for preparing the modified lithium iron manganese phosphate material according to claim 1, wherein the sintering time in the step (2) is 4-10 hours.
22. The method for producing a modified lithium iron manganese phosphate material according to claim 1, wherein the metal compound comprises any one or a combination of at least two of vanadium pentoxide, ammonium metavanadate, titanium dioxide, magnesium hydroxide, magnesium oxide, zirconium hydroxide, niobium pentoxide, niobium hydroxide, and nickel acetate.
23. The method for preparing the modified lithium iron manganese phosphate material according to claim 1, wherein the preparation method comprises the following steps:
(1) Mixing an iron source, a manganese source, a modifier, water and phosphoric acid, dispersing and performing wet ball milling to obtain a pretreated slurry with the solid content of 10-60wt%;
(2) Mixing a lithium source, a carbon source, a solvent and the obtained pretreatment slurry, dispersing and ball milling by a wet method to obtain precursor slurry with the solid content of 10-60wt%, spray drying the precursor slurry, and sintering at 650-800 ℃ for 4-10 hours, wherein the sintering is performed in an inert atmosphere and/or a reducing atmosphere to obtain the modified lithium iron manganese phosphate material;
in the step (1), the iron source is any one or a combination of at least two of iron powder, iron sheets or iron ingots; the manganese source is any one or a combination of at least two of manganese powder, manganese flakes, manganese monoxide, manganese dioxide, manganous oxide or manganese acetate; the modifier comprises a composite carbon source and a doped metal compound; the composite carbon source comprises any one or a combination of at least two of carbon nano tubes, graphene or carbon nano fibers; the metal compound comprises any one or a combination of at least two of vanadium pentoxide, ammonium metavanadate, titanium dioxide, magnesium hydroxide, magnesium oxide, zirconium hydroxide, niobium pentoxide, niobium hydroxide or nickel acetate;
in the step (2), the lithium source comprises any one or a combination of at least two of lithium carbonate, lithium acetate or lithium hydroxide; the carbon source comprises any one or a combination of at least two of glucose, starch, sucrose, polyethylene glycol, polyvinyl alcohol or cyclodextrin.
24. A modified lithium iron manganese phosphate material, characterized in that it is obtained by the preparation method according to any one of claims 1 to 23.
25. The modified lithium iron manganese phosphate material according to claim 24, wherein (fe+mn)/P is 0.95 to 0.99 in terms of molar amount.
26. The modified lithium iron manganese phosphate material according to claim 24, wherein Li/(fe+mn) in the modified lithium iron manganese phosphate material is 1.02 to 1.06 on a molar basis.
27. The modified lithium iron manganese phosphate material according to claim 24, wherein the Mn/P in the modified lithium iron manganese phosphate material is 0.6 to 0.9 in terms of molar amount.
28. The modified lithium iron manganese phosphate material of claim 24, wherein the carbon content of the modified lithium iron manganese phosphate material is 1.2-5 wt%.
29. A battery comprising the modified lithium iron manganese phosphate material of any one of claims 24-28.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102610819A (en) * | 2012-04-05 | 2012-07-25 | 宁波力邦新能源科技有限公司 | Preparing method of high-activity material |
| CN102769131A (en) * | 2012-05-10 | 2012-11-07 | 浙江瓦力新能源科技有限公司 | Method for preparing manganese phosphate lithium / carbon composite material |
| CN107706403A (en) * | 2017-11-20 | 2018-02-16 | 中国科学院过程工程研究所 | A kind of complex carbon material and the modified electrode material and lithium ion battery using its preparation |
| CN108172794A (en) * | 2017-12-27 | 2018-06-15 | 中科廊坊过程工程研究院 | A kind of composite positive pole and its preparation method and application |
| CN109103452A (en) * | 2018-08-28 | 2018-12-28 | 重庆大学 | The preparation method of nano lithium iron manganese anode composite material |
| CN109650367A (en) * | 2018-10-11 | 2019-04-19 | 广东光华科技股份有限公司 | Iron manganese phosphate for lithium and preparation method thereof |
| CN113571705A (en) * | 2021-06-30 | 2021-10-29 | 清华大学 | Cathode material, preparation method thereof and lithium ion battery |
| WO2021253714A1 (en) * | 2020-06-15 | 2021-12-23 | 宁波锋成先进能源材料研究院有限公司 | Carbon/titanium phosphate composite material and preparation method therefor and use thereof |
| CN113929073A (en) * | 2021-10-14 | 2022-01-14 | 湖北万润新能源科技股份有限公司 | Preparation method of lithium iron manganese phosphate cathode material |
| CN115231541A (en) * | 2022-06-27 | 2022-10-25 | 广东邦普循环科技有限公司 | Preparation method and application of lithium iron manganese phosphate |
-
2022
- 2022-11-15 CN CN202211429590.0A patent/CN115709976B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102610819A (en) * | 2012-04-05 | 2012-07-25 | 宁波力邦新能源科技有限公司 | Preparing method of high-activity material |
| CN102769131A (en) * | 2012-05-10 | 2012-11-07 | 浙江瓦力新能源科技有限公司 | Method for preparing manganese phosphate lithium / carbon composite material |
| CN107706403A (en) * | 2017-11-20 | 2018-02-16 | 中国科学院过程工程研究所 | A kind of complex carbon material and the modified electrode material and lithium ion battery using its preparation |
| CN108172794A (en) * | 2017-12-27 | 2018-06-15 | 中科廊坊过程工程研究院 | A kind of composite positive pole and its preparation method and application |
| CN109103452A (en) * | 2018-08-28 | 2018-12-28 | 重庆大学 | The preparation method of nano lithium iron manganese anode composite material |
| CN109650367A (en) * | 2018-10-11 | 2019-04-19 | 广东光华科技股份有限公司 | Iron manganese phosphate for lithium and preparation method thereof |
| WO2021253714A1 (en) * | 2020-06-15 | 2021-12-23 | 宁波锋成先进能源材料研究院有限公司 | Carbon/titanium phosphate composite material and preparation method therefor and use thereof |
| CN113571705A (en) * | 2021-06-30 | 2021-10-29 | 清华大学 | Cathode material, preparation method thereof and lithium ion battery |
| CN113929073A (en) * | 2021-10-14 | 2022-01-14 | 湖北万润新能源科技股份有限公司 | Preparation method of lithium iron manganese phosphate cathode material |
| CN115231541A (en) * | 2022-06-27 | 2022-10-25 | 广东邦普循环科技有限公司 | Preparation method and application of lithium iron manganese phosphate |
Non-Patent Citations (2)
| Title |
|---|
| Engineering hierarchical structure and surface of Na4MnV(PO4)3 for ultrafast sodium storage by a scalable ball milling approach;Zhu, L et al.;《NANO ENERGY》;全文 * |
| 改性磷酸铁锂的制备工艺与低温电化学性能研究;陈均青;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;全文 * |
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