CN111224103A - Preparation method of metal ion-doped high-rate mesoporous lithium iron phosphate cathode material - Google Patents
Preparation method of metal ion-doped high-rate mesoporous lithium iron phosphate cathode material Download PDFInfo
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- CN111224103A CN111224103A CN202010053634.9A CN202010053634A CN111224103A CN 111224103 A CN111224103 A CN 111224103A CN 202010053634 A CN202010053634 A CN 202010053634A CN 111224103 A CN111224103 A CN 111224103A
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000010406 cathode material Substances 0.000 title claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 title claims description 10
- 239000002184 metal Substances 0.000 title claims description 10
- 239000000463 material Substances 0.000 claims abstract description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 18
- 239000010405 anode material Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000013110 organic ligand Substances 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000007873 sieving Methods 0.000 claims abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229920000428 triblock copolymer Polymers 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229940062993 ferrous oxalate Drugs 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 2
- 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 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 239000012621 metal-organic framework Substances 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000007774 positive electrode material Substances 0.000 description 10
- 238000009792 diffusion process Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 239000002243 precursor Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000013239 manganese-based metal-organic framework Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a preparation method of a metal ion doped high-rate mesoporous lithium iron phosphate anode material, which comprises the following steps: 1) mixing and dissolving an iron source, a phosphorus source, a lithium source, an M metal ion source, an organic ligand and a macromolecular template agent in a solvent, adjusting the pH value to 1-2, and stirring to form a uniform solution; 2) continuously stirring the solution obtained in the step 1) at normal temperature for 1-3 hours, and then heating and stirring at 60-90 ℃ until sol is formed; 3) transferring the sol obtained in the step 2) into a drying oven, and drying and aging at 80-120 ℃ for 12-24 h to obtain xerogel; 4) transferring the xerogel obtained in the step 3) into an atmosphere furnace, and sintering for 5-15 h at 650-750 ℃ under the protection of inert gas; 5) and 4) cooling and sieving the sintered material obtained in the step 4) to obtain the lithium iron phosphate anode material. The lithium iron phosphate cathode material prepared by the sol-gel method has excellent rate performance.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a preparation method of a metal ion doped high-rate mesoporous lithium iron phosphate anode material.
Background
With the continuous development of human society, environmental problems are increasingly prominent, and with the rise of new energy strategies in China, lithium ion batteries are widely applied as clean energy due to the advantages of small size, high energy density, safety, environmental protection and the like since the early development of the last 90 th century.
The lithium iron phosphate serving as the lithium ion battery anode material has the advantages of wide raw material source, low price, good material thermal stability, high voltage platform, long cycle life, no toxicity, no harm, high safety and the like, is separated from a plurality of anode materials, and becomes the first choice of the power type and energy storage type lithium ion secondary battery anode materials at present. However, the lithium iron phosphate positive electrode material still has two significant disadvantages: firstly, the material has low compacted density, which results in low energy density; and the electronic conductivity and the ionic conductivity of the composite material are low, so that the low capacity and the rate capability are poor.
Aiming at poor rate capability of lithium iron phosphate materials caused by low electronic conductivity and ionic conductivity, the current mainstream method is to coat a carbon layer on the surface of material particles to improve the electronic conductivity of the materials and shorten the diffusion path of lithium ions through the nanocrystallization of the particles to improve the ionic conductivity of the materials, but the rate capability still cannot meet the market demand.
Disclosure of Invention
In view of the above, the present invention aims to provide a preparation method of a metal ion-doped high-rate mesoporous lithium iron phosphate cathode material, so as to overcome the defects of the prior art, substantially increase the ionic and electronic conductivities of the material, and improve the rate capability of the material.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a metal ion doped high-rate mesoporous lithium iron phosphate cathode material comprises the following steps:
1) mixing and dissolving an iron source, a phosphorus source, a lithium source, an M metal ion source, an organic ligand and a macromolecular template agent in a solvent, adjusting the pH value to 1-2, and stirring to form a uniform solution; hydrochloric acid can be selected to adjust the pH; when the pH value is too low, sol is not easy to form when the mixture is heated and stirred, and when the pH value is too high, ferric hydroxide or ferric phosphate precipitation is easy to generate when the mixture is stirred at normal temperature.
2) Continuously stirring the solution obtained in the step 1) at normal temperature for 1-3 hours, and then heating and stirring at 60-90 ℃ until sol is formed;
3) transferring the sol obtained in the step 2) into a drying oven, and drying and aging at 80-120 ℃ for 12-24 h to obtain xerogel;
4) transferring the xerogel obtained in the step 3) into an atmosphere furnace, and sintering for 5-15 h at 650-750 ℃ under the protection of inert gas;
5) and 4) cooling and sieving the sintered material obtained in the step 4) to obtain the lithium iron phosphate anode material.
Preferably, in step 1), the iron source includes one or a mixture of two or more of ferric nitrate, ferric chloride, ferric sulfate and ferrous oxalate; the phosphorus source is one or two of phosphoric acid or lithium dihydrogen phosphate; the lithium source is any one or combination of at least two of lithium carbonate, lithium hydroxide, lithium acetate or lithium nitrate; the M metal ion source is one or a mixture of more than two of manganese acetate, manganese chloride, cobalt nitrate and cobalt acetate.
Preferably, in step 1), the organic ligand is dimethyl imidazole or terephthalic acid; the macromolecular template agent comprises one or a mixture of more than two of Cetyl Trimethyl Ammonium Bromide (CTAB), polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) and polyether F127; the solvent is pure water or a mixed solution of the pure water and N, N-dimethylformamide.
Preferably, in the step 1), the mass ratio of the macromolecular template agent to the iron source to the solvent is 1 to (1-5) to (10-40).
Preferably, in the step 1), the molar ratio of Fe, P and Li atoms in the raw materials is 1: 1.01-1.05. When the proportion of iron atoms is too large, the iron atoms are easily reduced into magnetic substances such as ferroferric oxide or iron simple substance and the like during sintering, and when the proportion is too low, the product is impure.
Preferably, the molar ratio of the addition amount of the M metal ions to the Fe atoms in the step 1) is 0.005-0.1: 1.
And 1), complexing the M metal ions with an organic ligand to form a metal organic framework Material (MOFs), and finishing the M metal ions and the preparation of a lithium iron phosphate precursor solution in the same system, so that the process flow is simplified, and the uniformity of the dispersion of the MOFs in the lithium iron phosphate precursor is ensured. MOFs are decomposed into metal oxides and porous carbon at high temperature, can serve as a doping ion source and a coating carbon source, and is poor in conductivity and unobvious in doping due to the fact that the added amount of the material is too small; the material with excessive addition has the advantages of reduced proportion of active substances and excessive doping, and thus, the capacity is low and the cycle stability is reduced.
The macromolecular template agent added in the step 1) is removed in the subsequent sintering, and mesopores and residual carbon are left in the material particles, so that the ionic and electronic conductivity of the material is increased.
The process of drying and aging the sol in the oven to obtain dry gel in the step 3) is beneficial to forming metal organic framework Materials (MOFs) by complexing M metal ions and organic ligands, and is similar to the preparation of the MOFs by a solvothermal method.
Preferably, in step 4), the inert gas is one or a mixture of two or more of nitrogen, argon or helium.
The invention also provides a positive electrode which is prepared by the preparation method.
The invention also provides a lithium ion battery, which comprises the positive electrode material prepared by the preparation method.
Compared with the prior art, the preparation method of the metal ion doped high-rate mesoporous lithium iron phosphate anode material has the following advantages:
(1) according to the preparation method disclosed by the invention, the sol-gel method is adopted, the particle size of the precursor is small when the xerogel is obtained, the grinding process of reducing the particle size such as sand grinding can be omitted, the energy consumption is reduced, the particle size of the primary particle of the finally prepared lithium iron phosphate cathode material is smaller, the diffusion distance of lithium ions is shortened, and the diffusion rate of the lithium ions is improved.
(2) According to the preparation method, the synthesis of MOFs and the preparation of the lithium iron phosphate precursor are synchronously synthesized in the same solution, so that the uniformity of dispersion is ensured, the operation steps are reduced, and the process flow is simplified.
(3) According to the preparation method, the macromolecular template agent is removed during sintering, and mesopores and partial residual carbon are left in the material particles, the existence of the mesopores can greatly increase the diffusion path of lithium ions, the diffusion rate of the lithium ions is improved, and the residual carbon greatly increases the electronic conductivity of the material.
(4) According to the preparation method, the MOFs material is decomposed into porous carbon and metal oxide at high temperature in an inert atmosphere: the porous carbon enables the lithium ions to shuttle more freely and can coat the particle surface, so that the electronic conductivity of the material is increased; the metal oxide is used as a doped metal ion source, so that the lattice parameter of the lithium iron phosphate is increased, and the lithium ions can be conveniently diffused into the material lattice.
Drawings
Fig. 1 is an SEM image of a lithium iron phosphate positive electrode material obtained by the preparation method of embodiment 1 of the present invention;
fig. 2 is an SEM image of the lithium iron phosphate positive electrode material obtained by the preparation method of embodiment 2 of the present invention;
fig. 3 is a discharge capacity-voltage diagram of lithium iron phosphate positive electrode material obtained by the preparation method of embodiment 1 according to the invention at 10C;
fig. 4 is a discharge capacity-voltage diagram of lithium iron phosphate positive electrode material obtained by the preparation method of embodiment 2 of the present invention at 10C.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
Example 1
In this embodiment, a high-rate lithium iron phosphate positive electrode material is prepared according to the following method steps:
(1) mixing and dissolving 2.50kg of ferric chloride, 0.50kg of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123), 1.57kg of phosphoric acid, 1.16kg of lithium carbonate, 0.1kg of manganese chloride and 0.75kg of terephthalic acid in a mixed solution of 7kg of pure water and 7kg of N, N-dimethyl formamide, adjusting the pH value to 1.5 by using hydrochloric acid, and uniformly stirring;
(2) continuously stirring the solution obtained in the step (1) at normal temperature for 1h, heating and stirring at 80 ℃ until sol is formed, wherein manganese ions are complexed with terephthalic acid to obtain a metal organic framework material Mn-MOFs, and the metal organic framework material Mn-MOFs is uniformly dispersed in the sol;
(3) transferring the sol obtained in the step (2) into a drying oven, and drying and aging for 24h at 100 ℃ to obtain xerogel;
(4) transferring the xerogel obtained in the step (3) into an atmosphere furnace, and sintering for 10h at 700 ℃ under the protection of nitrogen to obtain a sintered material;
(5) cooling the sintered material obtained in the step (4), and then screening the cooled sintered material through a 200-mesh screen to obtain a lithium iron phosphate anode material;
comparative example 1
According to the method and the dosage of the embodiment 1, only an iron source, a phosphorus source, a lithium source and sucrose (sucrose is used as a supplementary carbon source, and the addition amount is 5% of the mass of other raw materials) are added to prepare the obtained lithium iron phosphate cathode material as a comparative example 1.
Example 2
In this embodiment, a high-rate lithium iron phosphate cathode material is prepared according to the following method steps, in comparison with example 1, iron source ferric chloride, a macromolecular template polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123), and M metal ion source manganese chloride are respectively replaced by ferric nitrate, Cetyl Trimethyl Ammonium Bromide (CTAB) and cobalt nitrate, and pure water is used as a solvent:
(1) 2.50kg of ferric nitrate, 0.50kg of cetyltrimethylammonium bromide (CTAB), 1.57kg of phosphoric acid, 1.16kg of lithium carbonate, 0.1kg of cobalt nitrate and 0.75kg of 2-methylimidazole are mixed and dissolved in 14kg of pure water, the pH value is adjusted to 1.5 by using hydrochloric acid, and the mixture is stirred uniformly;
(2) continuously stirring the solution obtained in the step (1) at normal temperature for 1h, heating and stirring at 80 ℃ until sol is formed, wherein metal organic framework materials ZiF-67 obtained by complexing cobalt ions and 2-methylimidazole are uniformly dispersed in the sol;
(3) transferring the sol obtained in the step (2) into a drying oven, and drying and aging for 24h at 100 ℃ to obtain xerogel;
(4) transferring the xerogel obtained in the step (3) into an atmosphere furnace, and sintering for 10h at 700 ℃ under the protection of nitrogen to obtain a sintered material;
(5) cooling the sintered material obtained in the step (4), and then screening the cooled sintered material through a 200-mesh screen to obtain a lithium iron phosphate anode material;
comparative example 2
According to the method and the dosage of the embodiment 2, only an iron source, a phosphorus source, a lithium source and glucose (glucose is used as a supplementary carbon source, and the addition amount is 5% of the mass of other raw materials) are added, and the prepared lithium iron phosphate cathode material is used as a comparative example 2.
The lithium iron phosphate positive electrode materials prepared in the above examples 1, 2 and 2 are respectively mixed with binder polyvinylidene fluoride (PVDF) and conductive agent acetylene black in a mass ratio of 94: 3 to form slurry with a certain viscosity in N-methyl pyrrolidone (NMP), uniformly coated on the surface of an aluminum foil, vacuum-dried and cut into pieces to obtain electrode pieces, the electrode pieces are assembled with a metal lithium piece, a Celgard 2400 membrane, an electrolyte and the like in a glove box filled with argon gas to obtain a button cell, after standing for 8 hours, a rate charge-discharge test is performed on a blue battery test system in a test mode of 0.1C charge/0.1C discharge, 0.3C charge/0.3C discharge, 0.3C charge/0.5C discharge, 0.3C charge/1C discharge, 0.3C charge/2C discharge, 0.3C charge/3C discharge, 0.3C charge/5C discharge, 0.3C charge/10C discharge (1C/g is 150mA/g), wherein the results of the rate test are shown in table 1.
Fig. 1 and 2 are SEM photographs of the lithium iron phosphate positive electrode materials obtained in example 1 and example 2, respectively. As can be seen from the figure, the prepared lithium iron phosphate particles have small particle size of about several hundred nanometers, which is beneficial to shortening the diffusion distance of lithium ions and improving the diffusion rate of the lithium ions; meanwhile, flocculent porous carbon generated by MOFs pyrolysis exists on the surface of the particle, which is beneficial to improving the electronic conductivity of the material.
Fig. 3 and 4 are capacity-voltage graphs of example 1, comparative example 1 and example 2, and comparative example 2 at a discharge rate of 10C, respectively, and it can be seen from the graphs that the discharge plateau voltages of example 1 and example 2 are much higher than those of comparative example 1 and comparative example 2, respectively, which illustrates that the lithium iron phosphate materials prepared in example 1 and example 2 have lower impedance, can bear a charge and discharge current with a larger rate, and release more capacity.
As can be seen from table 1, the capacities of the lithium iron phosphate positive electrode materials prepared by the methods of examples 1 and 2 at the discharge rate of 0.1C are 160.3mAh/g and 159.5mAh/g, respectively, and the capacities at the discharge rate of 10C are still 131.3mAh/g and 130.9mAh/g, 81.91% and 82.07% of the capacity at the discharge rate of 0.1C, respectively; compared with comparative example 1 and comparative example 2 which are not added with MOFs and macromolecular template agents, the discharge specific capacity under 10C is only 90.5mAh/g and 91.1mAh/g respectively, and is only 57.29% and 57.69% of the discharge rate capacity under 0.1C.
The pyrolysis of MOFs dopes metal ions of the lithium iron phosphate anode material and coats porous carbon, and the mesoporous and residual carbon formed in the material particles are removed by the macromolecular template agent, so that the multiplying power performance of the lithium iron phosphate anode material is greatly improved.
TABLE 1 comparison of Rate Properties
The applicant states that the present invention is illustrated by the above examples to show the detailed methods and process flows of the present invention, but the present invention is not limited to the above detailed methods and process flows, i.e. it is not meant that the present invention must rely on the above detailed methods and process flows to be practiced. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (9)
1. A preparation method of a metal ion doped high-rate mesoporous lithium iron phosphate cathode material is characterized by comprising the following steps:
1) mixing and dissolving an iron source, a phosphorus source, a lithium source, an M metal ion source, an organic ligand and a macromolecular template agent in a solvent, adjusting the pH value to 1-2, and stirring to form a uniform solution;
2) continuously stirring the solution obtained in the step 1) at normal temperature for 1-3 hours, and then heating and stirring at 60-90 ℃ until sol is formed;
3) transferring the sol obtained in the step 2) into a drying oven, and drying and aging at 80-120 ℃ for 12-24 h to obtain xerogel;
4) transferring the xerogel obtained in the step 3) into an atmosphere furnace, and sintering for 5-15 h at 650-750 ℃ under the protection of inert gas;
5) and 4) cooling and sieving the sintered material obtained in the step 4) to obtain the lithium iron phosphate anode material.
2. The preparation method of the metal ion-doped high-rate mesoporous lithium iron phosphate cathode material according to claim 1, characterized in that: in the step 1), the iron source comprises one or a mixture of more than two of ferric nitrate, ferric chloride, ferric sulfate and ferrous oxalate; the phosphorus source is one or two of phosphoric acid or lithium dihydrogen phosphate; the lithium source is any one or combination of at least two of lithium carbonate, lithium hydroxide, lithium acetate or lithium nitrate; the M metal ion source is one or a mixture of more than two of manganese acetate, manganese chloride, cobalt nitrate and cobalt acetate.
3. The preparation method of the metal ion-doped high-rate mesoporous lithium iron phosphate cathode material according to claim 1, characterized in that: in the step 1), the organic ligand is dimethyl imidazole or terephthalic acid; the macromolecular template agent comprises one or a mixture of more than two of Cetyl Trimethyl Ammonium Bromide (CTAB), polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) and polyether F127; the solvent is pure water or a mixed solution of the pure water and N, N-dimethylformamide.
4. The preparation method of the metal ion-doped high-rate mesoporous lithium iron phosphate cathode material according to claim 1, characterized in that: in the step 1), the mass ratio of the macromolecular template agent to the iron source to the solvent is 1 to (1-5) to (10-40).
5. The preparation method of the metal ion-doped high-rate mesoporous lithium iron phosphate cathode material according to claim 1, characterized in that: in the step 1), the molar ratio of Fe to P to Li atoms in the raw materials is 1: 1.01-1.05.
6. The preparation method of the metal ion-doped high-rate mesoporous lithium iron phosphate cathode material according to claim 1, characterized in that: the molar ratio of the addition amount of the M metal ions to the Fe atoms in the step 1) is 0.005-0.1: 1.
7. The preparation method of the metal ion-doped high-rate mesoporous lithium iron phosphate cathode material according to claim 1, characterized in that: in the step 4), the inert gas is one or a mixture of more than two of nitrogen, argon or helium.
8. A positive electrode characterized in that: the preparation method of any one of claims 1 to 7 is used for obtaining the cathode material.
9. A lithium ion battery, characterized by: the preparation method of any one of claims 1 to 7 is used for obtaining the cathode material.
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