CN115806281B - Lithium iron manganese phosphate composite material, preparation method thereof and battery - Google Patents
Lithium iron manganese phosphate composite material, preparation method thereof and battery Download PDFInfo
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- CN115806281B CN115806281B CN202211437765.2A CN202211437765A CN115806281B CN 115806281 B CN115806281 B CN 115806281B CN 202211437765 A CN202211437765 A CN 202211437765A CN 115806281 B CN115806281 B CN 115806281B
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- 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 125
- 239000002131 composite material Substances 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 153
- 229910052742 iron Inorganic materials 0.000 claims abstract description 63
- 239000011572 manganese Substances 0.000 claims abstract description 57
- 239000002002 slurry Substances 0.000 claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- 238000002156 mixing Methods 0.000 claims abstract description 41
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 39
- 239000011574 phosphorus Substances 0.000 claims abstract description 39
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 38
- 238000000498 ball milling Methods 0.000 claims abstract description 34
- 239000002243 precursor Substances 0.000 claims abstract description 33
- 238000005245 sintering Methods 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 37
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical group [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 34
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 19
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 17
- 239000002202 Polyethylene glycol Substances 0.000 claims description 15
- 229920002472 Starch Polymers 0.000 claims description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims description 15
- 239000008107 starch Substances 0.000 claims description 15
- 235000019698 starch Nutrition 0.000 claims description 15
- 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 14
- 229930006000 Sucrose Natural products 0.000 claims description 14
- 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 14
- 239000008103 glucose Substances 0.000 claims description 14
- 239000005720 sucrose Substances 0.000 claims description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 13
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910001868 water Inorganic materials 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 10
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims description 10
- 229920000858 Cyclodextrin Polymers 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 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
- 238000001694 spray drying Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000011164 primary particle Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000011978 dissolution method Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 14
- 239000007774 positive electrode material Substances 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 description 25
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 18
- 238000012360 testing method Methods 0.000 description 15
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 6
- 229940071125 manganese acetate Drugs 0.000 description 6
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 6
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 229910000616 Ferromanganese Inorganic materials 0.000 description 3
- 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 3
- 238000006243 chemical reaction Methods 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 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
- 239000002253 acid Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- BZDIAFGKSAYYFC-UHFFFAOYSA-N manganese;hydrate Chemical compound O.[Mn] BZDIAFGKSAYYFC-UHFFFAOYSA-N 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution 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 lithium iron manganese phosphate composite material, a preparation method thereof and a battery, wherein the preparation method comprises the following steps: (1) Mixing an iron source, a phosphorus source and a solvent to obtain a mixed solution; (2) Mixing a manganese source with the mixed solution obtained in the step (1) to obtain pretreated slurry; (3) Mixing a lithium source, a carbon source, a solvent and the pretreatment slurry obtained in the step (2) to obtain a precursor slurry; (4) And (3) drying and sintering the precursor slurry obtained in the step (3) to obtain the lithium iron manganese phosphate composite material. According to the invention, an iron source and a phosphorus source are mixed and completely dissolved to form a solution, then a manganese source is added into the solution, after full ball milling and mixing, iron, manganese and phosphorus elements are uniformly distributed, and the obtained pretreated slurry has fine and uniform particles and no metal component residues, so that the positive electrode material with qualified particle size, morphology and crystal form, high gram capacity and excellent multiplying power performance and cycle performance is prepared.
Description
Technical Field
The invention belongs to the technical field of manufacturing of anode materials, relates to a preparation method of a lithium iron manganese phosphate composite material, and particularly relates to a lithium iron manganese phosphate composite material, a preparation method thereof and a battery.
Background
The positive electrode material of the lithium ion battery is usually used as a lithium ion source in the battery, determines the reversible charge-discharge capacity and the upper limit of the working voltage of the battery, is a key factor for limiting the performance and the cost of the lithium ion battery, and currently, generally adopts a lithium-containing compound with higher electrode potential, such as LiCoO 2 、、LiFePO 4 C or 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 been successfully used as the positive electrode material of the power battery to realize large-scale commercial production due to the advantages of wide raw material sources, low cost, environmental friendliness, good thermal stability, excellent safety performance and the like. However, lithium iron phosphate batteries have been affected by their large number of uses due to their low energy density and other disadvantages.
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 have a certain share in the markets of power batteries and low-cost consumer batteries.
In the preparation process of a plurality of lithium iron manganese phosphate materials, the solid phase method is widely applied to the preparation of lithium iron manganese phosphate anode materials due to the advantages of simple process, less required equipment, easy production, lower cost and the like. The preparation method has a plurality of researches on preparing the lithium iron manganese phosphate material by firstly synthesizing uniform iron manganese precursors, such as ferrous manganese oxalate, ferrous manganese phosphate, ferric manganese oxide and the like, and then mixing and calcining the uniform iron manganese precursors with lithium carbonate and a carbon source, but the preparation method has the problems of synthesizing the uniform iron manganese precursors and complex process flow. The element non-uniformity of the ferro-manganese precursor influences the ion transmission rate, the multiplying power performance, the gram capacity exertion, the circulation reversibility and the like of the material, so that the capacity exertion, the multiplying power performance and the circulation performance of the material are difficult to meet the indexes of practical application requirements, and the commercialized application process of the lithium iron manganese phosphate material is restricted.
Because of the performance advantages and prospects of lithium iron phosphate materials over lithium iron phosphate, there is an urgent need to develop a method suitable for large-scale production of high-performance lithium iron phosphate.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a lithium iron manganese phosphate composite material, a preparation method thereof and a battery, wherein an iron source and a phosphorus source are mixed and completely dissolved to form a solution, then a manganese source is added into the solution, after the solution is fully ball-milled and mixed, iron, manganese and phosphorus elements are uniformly distributed, and the obtained pretreated slurry has fine and uniform particles and no metal component residues, so that the positive electrode material with qualified particle size, morphology and crystal form, high gram capacity and excellent multiplying power performance and cycle performance is prepared.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a lithium iron manganese phosphate composite material, which comprises the following steps:
(1) Mixing an iron source, a phosphorus source and a solvent to obtain a mixed solution;
(2) Mixing a manganese source with the mixed solution obtained in the step (1) to obtain pretreated slurry;
(3) Mixing a lithium source, a carbon source, a solvent and the pretreatment slurry obtained in the step (2) to obtain a precursor slurry;
(4) And (3) drying and sintering the precursor slurry obtained in the step (3) to obtain the lithium iron manganese phosphate composite material.
According to the invention, an iron source and a phosphorus source are mixed and completely dissolved to form a solution, then a manganese source is added into the solution, after full ball milling and mixing, iron, manganese and phosphorus elements are uniformly distributed, and the obtained pretreated slurry has fine and uniform particles and no metal component residues, so that the positive electrode material with qualified particle size, morphology and crystal form, high gram capacity and excellent multiplying power performance and cycle performance is prepared.
Preferably, the iron source of step (1) comprises any one or a combination of at least two of metal iron powder, metal iron sheet or iron ingot, typically but not limited to a combination of metal iron powder and metal iron sheet, a combination of metal iron sheet and iron ingot, a combination of metal iron powder and iron ingot, or a combination of metal iron powder, metal iron sheet and iron ingot, preferably metal iron powder.
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, other non-recited values in the numerical range are equally applicable, and preferably 30 to 40wt%.
Preferably, the solvent of step (1) comprises water.
Preferably, the molar ratio of the iron source to the phosphorus source in the step (1) is 10-40%, for example, 10%, 15%, 20%, 30%, 35% or 40%, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the iron source in the mixed solution of step (1) is completely dissolved.
Preferably, the dissolution means comprises any one or a combination of at least two of stirring at room temperature, stirring at heating, ball milling or ultrasonic treatment, typically but not limited to a combination of stirring at room temperature and stirring at heating, a combination of stirring at heating and ball milling, a combination of ball milling and ultrasonic treatment, a combination of stirring at room temperature, stirring at heating and ball milling, a combination of stirring at heating, ball milling and ultrasonic treatment, or a combination of stirring at room temperature, stirring at heating, ball milling and ultrasonic treatment.
Preferably, the manganese source in step (2) comprises any one or a combination of at least two of metal manganese powder, metal manganese flakes, manganese monoxide, manganese dioxide, manganous oxide or manganese acetate, typically but not limited to combinations comprising metal manganese powder and metal manganese flakes, combinations of metal manganese flakes and manganese monoxide, combinations of manganese monoxide and manganese dioxide, combinations of manganese dioxide and manganous oxide, combinations of manganous oxide and manganese acetate, combinations of metal manganese powder, metal manganese flakes and manganese monoxide, combinations of metal manganese flakes, manganese monoxide and manganese dioxide, combinations of manganese dioxide, manganous oxide and manganese acetate, combinations of metal manganese powder, metal manganese flakes, manganese monoxide and manganese dioxide, combinations of metal manganese flakes, manganese oxide, 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 manganese source, the iron source and the phosphorus source in the step (1) and the step (2) are added in the following proportion:
the molar ratio of (Fe+Mn)/P is 0.95 to 0.99, and may be, for example, 0.95, 0.96, 0.97, 0.98 or 0.99, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable. The Mn/P molar ratio is 0.6 to 0.9, and may be, for example, 0.75, 0.78, 0.8, 0.82 or 0.85, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the mixing in step (2) further comprises dispersing and wet ball milling.
Preferably, the solid content of the pretreated slurry in the step (2) is 10-60 wt%, for example, 10wt%, 20wt%, 30wt%, 40wt%, 50wt% or 60wt%, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable, preferably 30-40 wt%.
The lithium source in step (3) 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 lithium source in step (3) is added in an amount such that the molar ratio of Li/(fe+mn) is 1.02 to 1.06, for example, 1.02, 1.03, 1.04, 1.05 or 1.06, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the carbon source in step (3) 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.
Preferably, the carbon source in the step (3) is added in an amount of 15-30 g/mol, g/mol represents the mass of the raw material carbon source added correspondingly per mol of the lithium iron manganese phosphate product, and for example, 15g/mol, 18g/mol, 20g/mol, 25g/mol or 30g/mol can be used, but the carbon source is not limited to the listed values, and other non-listed values in the numerical range are equally applicable.
Preferably, the solvent of step (3) comprises water.
Preferably, the mixing in step (3) further comprises dispersing and wet ball milling.
Preferably, the solid content of the precursor slurry in the step (3) is 10-60 wt%, for example, 10wt%, 20wt%, 30wt%, 40wt%, 50wt% or 60wt%, but not limited to the recited values, other non-recited values in the numerical range are equally applicable, and preferably 30-40 wt%.
Preferably, the drying means of step (4) comprises spray drying.
Preferably, the atmosphere of sintering in the step (4) is any one of nitrogen, argon, hydrogen or argon-hydrogen mixture, preferably nitrogen.
Preferably, the sintering temperature in the step (4) is 650 to 800 ℃, for example, 650 ℃, 700 ℃, 720 ℃, 750 ℃, or 800 ℃, but the sintering temperature is not limited to the values listed, and other values not listed in the numerical range are applicable.
Preferably, the sintering time in the step (4) is 4-10 h, for example, may be 4h, 6h, 8h, 9h or 10h, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
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 phosphorus source and a solvent, wherein the molar ratio of the iron source to the phosphorus source is 10-40%, so as to obtain a mixed solution, and completely dissolving the iron source in the mixed solution;
(2) Mixing a manganese source with the mixed solution obtained in the step (1), and performing dispersion and wet ball milling to obtain a pretreated slurry with a solid content of 10-60wt%;
(3) Mixing a lithium source, a carbon source, a solvent and the pretreatment slurry obtained in the step (2), and performing dispersion and wet ball milling to obtain precursor slurry with the solid content of 10-60wt%;
(4) After spray drying the precursor slurry in the step (3), sintering the precursor slurry for 4-10 hours at 650-800 ℃ in any one sintering atmosphere of nitrogen, argon, hydrogen or argon-hydrogen mixed gas to obtain the lithium manganese iron phosphate composite material;
the iron source comprises any one or a combination of at least two of metal iron powder, metal iron sheet or iron ingot;
the phosphorus source comprises phosphoric acid with the concentration of 10-60wt%;
the manganese source comprises any one or a combination of at least two of metal manganese powder, metal manganese sheets, manganese monoxide, manganese dioxide, manganous oxide or manganese acetate;
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 the preparation method provided by the invention, lithium, iron, manganese, phosphorus and carbon elements in the lithium iron phosphate material are respectively derived from a lithium source, an iron source, a manganese source, a phosphorus source and a carbon source, other volatile components difficult to sinter are not introduced into raw materials, and the raw materials are subjected to ball milling, mixing, drying and sintering to obtain the lithium iron phosphate composite material, so that the preparation process is green, efficient and low in cost.
In a second aspect, the present invention provides a lithium iron manganese phosphate composite material, obtained according to the preparation method of the first aspect;
the lithium iron manganese phosphate composite material comprises lithium iron manganese phosphate and a surface-coated carbon layer;
the primary particle morphology of the lithium iron manganese phosphate composite material is similar to a sphere.
Preferably, the primary particles of the lithium manganese iron phosphate composite material have a particle size of 30 to 800nm, for example, 30nm, 100nm, 200nm, 400nm, 600nm or 800nm, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable, preferably 50 to 200nm.
Preferably, the thickness of the carbon layer is 2 to 15nm, for example, 2nm, 5nm, 8nm, 10nm, 12nm or 15nm, but not limited to the values listed, and other values not listed in the numerical range are applicable, preferably 3 to 6nm.
Preferably, the carbon content in the lithium iron manganese phosphate composite material is 1.2-5 wt%, for example, may be 1.2wt%, 2wt%, 3wt%, 4wt% or 5wt%, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable, preferably 1.5-3 wt%.
Preferably, the molar ratio of (fe+mn)/P in the lithium manganese iron phosphate composite material is 0.95 to 0.99 in terms of mole number, and may be, for example, 0.95, 0.96, 0.97, 0.98 or 0.99, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the molar ratio of Li/(fe+mn) in the lithium manganese iron phosphate composite material is 1.02 to 1.06, for example, 1.02, 1.03, 1.04, 1.05 or 1.06, in terms of mole number, but the present invention is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the molar ratio of Mn/P in the lithium manganese iron phosphate composite material is 0.6 to 0.9, preferably 0.75 to 0.85, for example, 0.75, 0.78, 0.8, 0.82 or 0.85, in terms of mole, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
In a third aspect, the present invention provides a battery comprising a lithium iron manganese phosphate composite material according to the second aspect.
By the technical scheme, the invention has the following beneficial effects:
(1) According to the invention, an iron source and a phosphorus source are mixed and completely dissolved to form a solution, then a manganese source is added into the solution, after full ball milling and mixing, iron, manganese and phosphorus elements are uniformly distributed, and the obtained pretreated slurry has fine and uniform particles and no metal component residues, so that the positive electrode material with qualified particle size, morphology and crystal form, high gram capacity and excellent multiplying power performance and cycle performance is prepared.
(2) In the preparation method provided by the invention, lithium, iron, manganese, phosphorus and carbon elements in the lithium iron phosphate material are respectively derived from a lithium source, an iron source, a manganese source, a phosphorus source and a carbon source, other volatile components difficult to sinter are not introduced into raw materials, and the raw materials are subjected to ball milling, mixing, drying and sintering to obtain the lithium iron phosphate composite material, so that the preparation process is green, efficient and low in cost.
Drawings
FIG. 1 is a scanning electron microscope image of the lithium iron manganese phosphate composite material provided in example 1.
Description of the embodiments
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 embodiment provides a lithium iron manganese phosphate composite material, wherein primary particles of the lithium iron manganese phosphate composite material are in a similar spherical shape, the particle size is 400nm, and the lithium iron manganese phosphate composite material comprises lithium iron manganese phosphate and a surface-coated carbon layer.
In the lithium manganese iron phosphate, the molar ratio of (Fe+Mn)/P was 0.97, the molar ratio of Li/(Fe+Mn) was 1.04, and the molar ratio of Mn/P was 0.72, in terms of the number of moles.
The thickness of the surface-coated carbon layer is 5nm, and the carbon content in the lithium iron manganese phosphate composite material is 3wt%.
The lithium iron manganese phosphate composite material is prepared by the following method:
(1) Mixing metal iron powder, phosphoric acid and water, and completely dissolving the iron powder by adopting a heating and stirring mode to obtain a mixed solution, wherein the molar ratio of iron to phosphorus is 25%, and the concentration of phosphoric acid is 35wt%;
(2) Mixing manganese oxide with the mixed solution obtained in the step (1), and performing dispersion and wet ball milling to obtain a pretreated slurry with the solid content of 35wt%;
(3) Mixing lithium carbonate, glucose, water and the pretreatment slurry obtained in the step (2), and performing dispersion and wet ball milling to obtain precursor slurry with the solid content of 35wt%;
(4) And (3) performing spray drying on the precursor slurry in the step (3), and sintering for 6 hours at 700 ℃ in nitrogen atmosphere to obtain the lithium iron manganese phosphate composite material, wherein a scanning electron microscope image is shown in figure 1.
Example 2
The embodiment provides a lithium iron manganese phosphate composite material, wherein primary particles of the lithium iron manganese phosphate composite material are in a similar spherical shape, the particle size is 30nm, and the lithium iron manganese phosphate composite material comprises lithium iron manganese phosphate and a surface-coated carbon layer.
In the lithium manganese iron phosphate, the molar ratio of (Fe+Mn)/P was 0.99, the molar ratio of Li/(Fe+Mn) was 1.06, and the molar ratio of Mn/P was 0.89, in terms of the number of moles.
The thickness of the surface-coated carbon layer is 2nm, and the carbon content in the lithium iron manganese phosphate composite material is 1.5wt%.
The lithium iron manganese phosphate composite material is prepared by the following method:
(1) Mixing a metal iron sheet, phosphoric acid and water, and completely dissolving the metal iron sheet by adopting ultrasonic treatment to obtain a mixed solution, wherein the molar ratio of iron to phosphorus is 10%, and the concentration of phosphoric acid is 10wt%;
(2) Mixing the manganous-manganic oxide with the mixed solution obtained in the step (1), and performing dispersion and wet ball milling to obtain a pretreated slurry with the solid content of 10wt%;
(3) Mixing lithium acetate, starch, water and the pretreatment slurry obtained in the step (2), and performing dispersion and wet ball milling to obtain precursor slurry with the solid content of 10wt%;
(4) And (3) performing spray drying on the precursor slurry in the step (3), and sintering for 10 hours at 650 ℃ in an argon atmosphere to obtain the lithium iron manganese phosphate composite material.
Example 3
The embodiment provides a lithium iron manganese phosphate composite material, wherein primary particles of the lithium iron manganese phosphate composite material are in a similar spherical shape, the particle size is 800nm, and the lithium iron manganese phosphate composite material comprises lithium iron manganese phosphate and a surface-coated carbon layer.
In the lithium manganese iron phosphate, the molar ratio of (Fe+Mn)/P was 0.95, the molar ratio of Li/(Fe+Mn) was 1.02, and the molar ratio of Mn/P was 0.55, in terms of number of moles.
The thickness of the surface-coated carbon layer is 10nm, and the carbon content in the lithium iron manganese phosphate composite material is 5wt%.
The lithium iron manganese phosphate composite material is prepared by the following method:
(1) Mixing an iron ingot, phosphoric acid and water, and completely dissolving the iron ingot by ball milling to obtain a mixed solution, wherein the molar ratio of an iron source to a phosphorus source is 40%, and the concentration of the phosphoric acid is 60wt%;
(2) Mixing manganese acetate with the mixed solution obtained in the step (1), and performing dispersion and wet ball milling to obtain a pretreated slurry with a solid content of 60wt%;
(3) Mixing lithium hydroxide, polyethylene glycol, water and the pretreatment slurry obtained in the step (2), and performing dispersion and wet ball milling to obtain precursor slurry with the solid content of 60wt%;
(4) And (3) performing spray drying on the precursor slurry in the step (3), and sintering for 4 hours at 800 ℃ in a hydrogen atmosphere to obtain the lithium iron manganese phosphate composite material.
Example 4
The present example provides a lithium iron manganese phosphate composite material, which differs from example 1 in that step (2) of the preparation method is not ball milled.
Example 5
This example provides a lithium iron manganese phosphate composite material, which differs from example 1 in that the metallic iron powder described in step (1) is replaced with an equimolar amount of ferric sulfate.
Example 6
This example provides a lithium iron manganese phosphate composite material that differs from example 1 in that the manganese monoxide described in step (2) is replaced with an equimolar amount of manganese sulfate.
Example 7
This example provides a lithium iron manganese phosphate composite material, which differs from example 1 in that the lithium carbonate described in step (3) is replaced with an equimolar amount of lithium sulfate.
Example 8
This example provides a lithium iron manganese phosphate composite material differing from example 1 in that the carbon source is added in an amount of 10g/mol, and the carbon content in the lithium iron manganese phosphate composite material is 1wt%.
Example 9
This example provides a lithium iron manganese phosphate composite material differing from example 1 in that the carbon source is added in an amount of 35g/mol, and the carbon content in the lithium iron manganese phosphate composite material is 6wt%.
Comparative example 1
This comparative example provides a lithium iron manganese phosphate composite material, and the rest of the steps are the same as in example 1, except that the metal iron powder mixed in step (1) is replaced with manganese monoxide and the manganese monoxide mixed in step (2) is replaced with metal iron powder in the preparation method.
Comparative example 2
This comparative example provides a lithium iron manganese phosphate composite material, which differs from example 1 in that: the lithium iron manganese phosphate composite material is prepared by the following method:
(1) Mixing metal iron powder, manganese monoxide, phosphoric acid and water, dispersing and ball milling by a wet method to obtain a pretreatment slurry with the solid content of 35wt%; wherein, the mole ratio of iron and phosphorus is 25%, and the concentration of phosphoric acid is 35wt%;
(2) Mixing lithium carbonate, glucose, water and the pretreatment slurry obtained in the step (1), and performing dispersion and wet ball milling to obtain precursor slurry with the solid content of 35wt%;
(3) And (3) performing spray drying on the precursor slurry in the step (2), and sintering for 6 hours at 700 ℃ in a nitrogen atmosphere to obtain the lithium iron manganese phosphate composite material.
Comparative example 3
This comparative example provides a lithium iron manganese phosphate composite material, which differs from example 1 in that: the lithium iron manganese phosphate composite material is prepared from a raw material of ferromanganese phosphate.
The preparation process flow of the lithium iron manganese phosphate composite material is as follows:
(1) Mixing lithium carbonate, glucose, water and ferromanganese phosphate, dispersing and ball milling by a wet method to obtain precursor slurry with the solid content of 35wt%;
(2) And (3) performing spray drying on the precursor slurry in the step (1), and sintering for 6 hours at 700 ℃ in a nitrogen atmosphere to obtain the lithium iron manganese phosphate composite material.
Comparative example 4
This comparative example provides a lithium iron manganese phosphate composite material, which differs from example 1 in that: the lithium iron manganese phosphate composite material is prepared by adopting a liquid phase synthesis method.
The preparation process flow of the lithium iron manganese phosphate composite material is as follows:
(1) After the raw materials are dissolved, the elements are uniformly mixed, and the nanocrystallization of the product is realized through a series of physicochemical reactions, so that a precursor is prepared;
(2) And (3) uniformly coating a layer of conductive carbon on the surface of the precursor prepared in the step (1) by adopting a solid-phase sintering process, so as to realize carbon coating of the product.
And (3) assembling the obtained lithium iron manganese phosphate composite material into a button type lithium ion battery according to GB 31241-2014, and testing.
Test conditions: 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).
Test voltage interval is 2.5-4.5V, gram capacity test: setting charge-discharge current to be 0.1C multiplying power;
and (3) cyclic test: setting charge and discharge current as 1C multiplying power, circulating for 300 weeks, and calculating capacity retention rate;
multiplying power test: the discharge capacity percentage of 1C discharge specific capacity to 0.1C discharge specific capacity was compared.
The test results are shown in table 1 below.
TABLE 1
And assembling the obtained lithium iron manganese phosphate composite material into a 5Ah soft package lithium ion battery according to GB 31241-2014, and testing.
Test conditions: the voltage interval is 2.5-4.5V.
Gram capacity test: setting charge-discharge current to be 0.1C multiplying power;
and (3) cyclic test: setting charge and discharge current as 1C multiplying power, circulating for 300 weeks, and calculating capacity retention rate;
multiplying power test: the discharge capacity percentage of 1C discharge specific capacity to 0.1C discharge specific capacity was compared.
The test results are shown in table 2 below.
TABLE 2
From table 1, the following conclusions can be drawn:
(1) According to the embodiment 1-3, the lithium iron phosphate composite material obtained by the preparation method provided by the invention has the advantages of qualified particle size, morphology and crystal form, high gram capacity of the material and excellent rate capability and cycle performance.
(2) As can be seen from a comparison between example 4 and example 1, in the preparation method provided by the invention, by optimizing the mixing sequence and performing full ball milling, phosphorus, manganese and iron elements are uniformly distributed in the material, so that particles in the pretreatment slurry are fine and uniform, no metal component remains, and further the positive electrode material with high gram capacity and excellent rate capability and cycle performance is obtained.
(3) As can be seen from the comparison of examples 5-7 and example 1, the lithium, iron, manganese, phosphorus and carbon elements in the material are respectively derived from a lithium source, an iron source, a manganese source, a phosphorus source and a carbon source, other difficultly sintered volatile components are not introduced into the raw materials, the raw materials are subjected to ball milling, mixing, drying and sintering to obtain the lithium iron manganese phosphate composite material, the preparation process is green, efficient and low in cost, and when the lithium iron manganese phosphate composite material is replaced by other raw materials, impurities are introduced in the preparation process to influence the performance of the lithium iron manganese phosphate composite material.
(4) As can be seen from comparison of comparative examples 1 and 2 with example 1, in the preparation method, the mixing sequence of completely dissolving the iron source and the phosphoric acid solution, and then adding the manganese source into the solution is that due to the complete reaction of the iron powder and the phosphoric acid and the influence of the dissolution characteristics of the manganese source and the acid solution, the uniform distribution condition of iron, manganese and phosphorus elements in the precursor is improved, and in the button cell and soft package battery test, the gram capacity of the material is exerted well, the metal impurity residues are less, the safety risk of the soft package is reduced, and the material with qualified particle size, morphology and crystal form, high gram capacity, excellent multiplying power performance and cycle performance is obtained.
(5) As can be seen from comparison of comparative examples 3 and 4 with example 1, the preparation method provided by the invention adopts the process of controlling the raw material addition sequence and performing ball milling reaction step by step, and compared with the conventional manganese iron phosphate or manganese iron phosphate precursor in the prior art, the preparation method improves the distribution of iron, manganese and phosphorus elements in the material, thereby obtaining the material with qualified particle size, morphology and crystal form, high gram capacity and excellent rate performance and cycle performance.
In summary, the method comprises the steps of firstly mixing an iron source and a phosphorus source to be completely dissolved to form a solution, then adding a manganese source into the solution, fully ball-milling and mixing, uniformly distributing iron, manganese and phosphorus elements, and obtaining the pretreated slurry with fine and uniform particles and no metal component residues, so that the positive electrode material with qualified particle size, morphology and crystal form, high gram capacity and excellent multiplying power performance and cycle performance is prepared.
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 (37)
1. The preparation method of the lithium iron manganese phosphate composite material is characterized by comprising the following steps of:
(1) Mixing an iron source, a phosphorus source and a solvent to obtain a mixed solution, wherein the iron source in the mixed solution is completely dissolved; the iron source is any one or the combination of at least two of metal iron powder, metal iron sheet or iron ingot;
(2) Mixing a manganese source with the mixed solution obtained in the step (1), and performing dispersion and wet ball milling to obtain pretreated slurry; the manganese source is manganese monoxide and/or manganous oxide; the addition ratio of the manganese source, the iron source and the phosphorus source in the step (1) and the step (2) is as follows: the molar ratio of (Fe+Mn)/P is 0.95-0.99, and the molar ratio of Mn/P is 0.6-0.9;
(3) Mixing a lithium source, a carbon source, a solvent and the pretreatment slurry obtained in the step (2) to obtain a precursor slurry; the lithium source comprises any one or a combination of at least two of lithium carbonate, lithium acetate or lithium hydroxide;
(4) And (3) drying and sintering the precursor slurry obtained in the step (3) to obtain the lithium iron manganese phosphate composite material.
2. The method for preparing a lithium iron manganese phosphate composite material according to claim 1, wherein the iron source in the step (1) is metal iron powder.
3. The method of preparing a lithium iron manganese phosphate composite according to claim 1, wherein the phosphorus source of step (1) comprises phosphoric acid.
4. The method for preparing the lithium iron manganese phosphate composite material according to claim 3, wherein the concentration of phosphoric acid is 10-60wt%.
5. The method for preparing a lithium iron manganese phosphate composite material according to claim 4, wherein the concentration of phosphoric acid is 30-40 wt%.
6. The method of preparing a lithium iron manganese phosphate composite according to claim 1, wherein the solvent of step (1) comprises water.
7. The method for preparing a lithium iron manganese phosphate composite material according to claim 1, wherein the molar ratio of the iron source to the phosphorus source in the step (1) is 10-40%.
8. The method for preparing a lithium iron manganese phosphate composite material according to claim 1, wherein the dissolution method comprises any one or a combination of at least two of stirring at normal temperature, heating stirring, ball milling or ultrasonic treatment.
9. The method for preparing a lithium iron manganese phosphate composite material according to claim 1, wherein the solid content of the pretreatment slurry in the step (2) is 10-60wt%.
10. The method for preparing a lithium iron manganese phosphate composite material according to claim 9, wherein the solid content of the pretreatment slurry in the step (2) is 30-40 wt%.
11. The method of preparing a lithium iron manganese phosphate composite according to claim 1, wherein the lithium source in step (3) is lithium carbonate and/or lithium acetate.
12. The method for preparing a lithium iron manganese phosphate composite material according to claim 1, wherein the addition amount of the lithium source in the step (3) satisfies a molar ratio of Li/(fe+mn) of 1.02 to 1.06.
13. The method of preparing a lithium iron manganese phosphate composite according to claim 1, wherein the carbon source of step (3) comprises any one or a combination of at least two of glucose, starch, sucrose, polyethylene glycol, polyvinyl alcohol, or cyclodextrin.
14. The method for preparing a lithium iron manganese phosphate composite according to claim 13, wherein the carbon source in the step (3) is glucose and/or starch.
15. The preparation method of the lithium iron manganese phosphate composite material according to claim 1, wherein the addition amount of the carbon source in the step (3) is 15-30 g/mol, and g/mol represents the mass of the raw material carbon source added correspondingly per mol of lithium iron manganese phosphate product.
16. The method of preparing a lithium iron manganese phosphate composite according to claim 1, wherein the solvent of step (3) comprises water.
17. The method for preparing a lithium iron manganese phosphate composite material according to claim 1, wherein the mixing in step (3) further comprises dispersing and wet ball milling.
18. The method for preparing a lithium iron manganese phosphate composite material according to claim 1, wherein the solid content of the precursor slurry in the step (3) is 10-60wt%.
19. The method for preparing a lithium iron manganese phosphate composite material according to claim 18, wherein the solid content of the precursor slurry in the step (3) is 30-40 wt%.
20. The method of preparing a lithium iron manganese phosphate composite according to claim 1, wherein the drying in step (4) comprises spray drying.
21. The method for preparing a lithium iron manganese phosphate composite material according to claim 1, wherein the sintering atmosphere in the step (4) is any one of nitrogen, argon, hydrogen or argon-hydrogen mixture.
22. The method for preparing a lithium iron manganese phosphate composite according to claim 21, wherein the atmosphere for sintering in step (4) is nitrogen.
23. The method for preparing a lithium iron manganese phosphate composite material according to claim 1, wherein the sintering temperature in the step (4) is 650-800 ℃.
24. The method for preparing the lithium iron manganese phosphate composite material according to claim 1, wherein the sintering time in the step (4) is 4-10 hours.
25. The method for preparing the lithium iron manganese phosphate composite material according to claim 1, wherein the preparation method comprises the following steps:
(1) Mixing an iron source, a phosphorus source and a solvent, wherein the molar ratio of the iron source to the phosphorus source is 10-40%, so as to obtain a mixed solution, and completely dissolving the iron source in the mixed solution;
(2) Mixing a manganese source with the mixed solution obtained in the step (1), and performing dispersion and wet ball milling to obtain a pretreated slurry with a solid content of 10-60wt%; the addition ratio of the manganese source, the iron source and the phosphorus source in the step (1) and the step (2) is as follows: the molar ratio of (Fe+Mn)/P is 0.95-0.99, and the molar ratio of Mn/P is 0.6-0.9;
(3) Mixing a lithium source, a carbon source, a solvent and the pretreatment slurry obtained in the step (2), and performing dispersion and wet ball milling to obtain precursor slurry with the solid content of 10-60wt%;
(4) After spray drying the precursor slurry in the step (3), sintering the precursor slurry for 4-10 hours at 650-800 ℃ in any one sintering atmosphere of nitrogen, argon, hydrogen or argon-hydrogen mixed gas to obtain the lithium manganese iron phosphate composite material;
the iron source is any one or the combination of at least two of metal iron powder, metal iron sheet or iron ingot;
the phosphorus source comprises phosphoric acid with the concentration of 10-60wt%;
the manganese source is manganese monoxide and/or manganous oxide;
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.
26. A lithium iron manganese phosphate composite material, characterized in that it is obtained according to the preparation method of any one of claims 1-25;
the lithium iron manganese phosphate composite material comprises lithium iron manganese phosphate and a surface-coated carbon layer;
the primary particle morphology of the lithium iron manganese phosphate composite material is similar to a sphere.
27. The lithium iron manganese phosphate composite material according to claim 26, wherein primary particles of the lithium iron manganese phosphate composite material have a particle size in a range of 30-800 nm.
28. The lithium iron manganese phosphate composite material according to claim 27, wherein primary particles of the lithium iron manganese phosphate composite material have a particle size in a range of 50-200 nm.
29. The lithium iron manganese phosphate composite material according to claim 26, wherein the thickness of the carbon layer is 2-15 nm.
30. The lithium iron manganese phosphate composite material according to claim 29, wherein the carbon layer has a thickness of 3-6 nm.
31. The lithium iron manganese phosphate composite material according to claim 26, wherein the carbon content of the lithium iron manganese phosphate composite material is 1.2-5wt%.
32. The lithium iron manganese phosphate composite material according to claim 31, wherein the carbon content of the lithium iron manganese phosphate composite material is 1.5-3 wt%.
33. The lithium iron manganese phosphate composite material according to claim 26, wherein the molar ratio of (fe+mn)/P in the lithium iron manganese phosphate composite material is 0.95 to 0.99 in terms of moles.
34. The lithium iron manganese phosphate composite material according to claim 33, wherein the molar ratio of Li/(fe+mn) in the lithium iron manganese phosphate composite material is 1.02 to 1.06 in terms of moles.
35. The lithium iron manganese phosphate composite material according to claim 26, wherein the molar ratio of Mn/P in the lithium iron manganese phosphate composite material is 0.6 to 0.9 in terms of moles.
36. The lithium iron manganese phosphate composite material according to claim 35, wherein the molar ratio of Mn/P in the lithium iron manganese phosphate composite material is 0.75 to 0.85 in terms of moles.
37. A battery comprising a lithium iron manganese phosphate composite according to any one of claims 26 to 36.
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| CN115010108A (en) * | 2022-06-15 | 2022-09-06 | 浙江格派钴业新材料有限公司 | Preparation method of high-compaction lithium iron manganese phosphate cathode material for lithium ion battery |
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