CN111186828A - 一种掺杂金属磷酸铁锂的制备方法 - Google Patents
一种掺杂金属磷酸铁锂的制备方法 Download PDFInfo
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- iron phosphate
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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 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910052742 iron Inorganic materials 0.000 claims abstract description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 32
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002244 precipitate Substances 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 239000000725 suspension Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- 239000011574 phosphorus Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000000137 annealing Methods 0.000 claims abstract description 6
- 239000010405 anode material Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 5
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- 229940062993 ferrous oxalate Drugs 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- -1 polypropylene Polymers 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229940010514 ammonium ferrous sulfate Drugs 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 2
- 229960001781 ferrous sulfate Drugs 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- ATEAWHILRRXHPW-UHFFFAOYSA-J iron(2+);phosphonato phosphate Chemical compound [Fe+2].[Fe+2].[O-]P([O-])(=O)OP([O-])([O-])=O ATEAWHILRRXHPW-UHFFFAOYSA-J 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 238000004321 preservation Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 13
- 239000010406 cathode material Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 6
- 239000010450 olivine Substances 0.000 description 6
- 229910052609 olivine Inorganic materials 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 230000002687 intercalation Effects 0.000 description 4
- 229910000398 iron phosphate Inorganic materials 0.000 description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 4
- 238000003754 machining Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- XKSGHSJZPRUMJX-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Fe+2].[Co+2].[Li+] Chemical compound P(=O)([O-])([O-])[O-].[Fe+2].[Co+2].[Li+] XKSGHSJZPRUMJX-UHFFFAOYSA-K 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 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
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/36—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
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- 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
- H01M4/626—Metals
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
本发明公开一种掺杂金属磷酸铁锂的制备方法,将铁源和磷源、过氧化氢混合得到絮状沉淀,过滤,冲洗,干燥后得到前躯体;将锂源、还原剂分散至有机溶剂中,再加入前驱体制成悬浮液,悬浮液搅拌后,离心、洗涤、真空干燥得到灰白色沉淀物;灰白色沉淀物与掺杂金属源混匀后退火,得到球状磷酸铁锂正极材料;本发明通过控制原料摩尔比例、烧结温度、保温时间来控制材料结晶程度,使最终产品达到具有较好的倍率性能和循环性能。
Description
技术领域
本发明涉及锂离子电池正极材料领域,具体涉及一种掺杂金属磷酸铁锂的制备方法。
背景技术
随着化石燃料的消耗,带来的环境污染问题愈发严重。在清洁储能设备中,锂离子电池越来越得到重视,正极材料是组成锂离子电池的关键材料,相对于众多得到商业化应用的正极材料,磷酸铁锂具有高容量(170mAh/g)、高放电电压、长循环后容量无明显衰减等优点。就目前磷酸铁锂研究现状,仍存在导电性能差、振实密度低、在低温使用下容量衰减严重等劣势。这些不足阻碍了磷酸铁锂在大倍率下的应用。
目前,国内外研究普遍采用碳包覆或制备纳米尺寸颗粒,增加材料颗粒的比表面积和导电性,通过掺杂金属离子改变磷酸铁锂晶格参数,拓宽锂离子嵌入/脱出通道,从而达到锂离子快速嵌入/脱出,增大材料自身的导电性。但纳米尺寸材料具有较大的比表面积带来的问题是降低了材料的体积能量密度与循环性能,并且在工业化生产中纳米尺寸磷酸铁锂材料具有较差的机械加工性能,从而阻碍了磷酸铁锂正极材料在商业化应用进程。
发明内容
为改善纳米磷酸铁锂在大电流密度下充放电的循环性能及机械加工性能差等缺陷,本申请提供一种掺杂金属且具有较好机械加工性能的磷酸铁锂的制备方法,具体步骤如下:
(1)前驱体的制备:将铁源和磷源加入水中配置成混合溶液,在强力搅拌均匀后加入过氧化氢得到絮状沉淀,搅拌4-12小时后过滤,将沉淀物用去离子水反复冲洗残留杂质,干燥后得到无定型磷酸铁前躯体;
(2)前驱体嵌入锂源:将锂源、还原剂分散至有机溶剂中得到有机溶液,再加入步骤(1)中得到的前驱体制成悬浮液,悬浮液于60-80℃不断搅拌6-12小时后,悬浮液离心、洗涤、真空干燥得到灰白色沉淀物;
(3)将步骤(2)制备的灰白色沉淀物与掺杂金属源混合均匀后,混合物在保护气氛下600~750℃温度环境中退火2-10h,得到橄榄石晶型的掺杂金属磷酸铁锂正极材料。
步骤(1)铁源为焦磷酸亚铁、硫酸亚铁、硫酸亚铁铵、氯化亚铁、草酸亚铁、硝酸亚铁中的一种或几种任意比例混合;磷源为磷酸二氢铵、磷酸氢二铵、磷酸中的一种或几种任意比例混合。
步骤(1)混合溶液中铁和磷的摩尔比为Fe:P=(0.8-1.2):(0.8-1.2);混合溶液中铁元素的浓度为0.1-2mol/L。
步骤(1)过氧化氢按照过氧化氢与铁源中铁元素的摩尔比H2O2:Fe=(0.6-1):1的比例添加。
步骤(2)锂源为碳酸锂、氢氧化锂、乙酸锂、硝酸锂中一种或几种任意比例混合。
步骤(2)还原剂为酒石酸和/或抗坏血酸。
步骤(2)有机溶剂为甲醇、乙醇、丙醇、异丙醇、聚丙烯醇、正丁醇、聚乙二醇、聚乙烯吡咯烷酮、丙酮中一种或几种任意比例混合。
步骤(2)锂源与还原剂的摩尔比为1:(0.5-2),有机溶液中锂源的浓度为0.1mol-1mol/L,步骤(1)铁源中的铁和步骤(2)锂源中锂的摩尔比为Fe: Li=(0.8-1.2):(0.8-1.2)。
步骤(3)灰白色沉淀物与掺杂金属源按照步骤(1)铁源中的铁元素与掺杂金属的摩尔比为Fe:A=1:(0.04-0.08)的比例混合,A为掺杂金属,掺杂金属源为活性金属单质、活泼类金属单质、金属氧化物、金属合金化合物、金属盐中一种或两种以上,优选为镁单质、铝单质、钒单质、锰单质、钴单质、锌单质、铬单质、镍单质、铝氧化物、钴氧化物、锰氧化物、镧系中金属单质及镧系中金属单质氧化物中的一种或几种任意比例混合。
步骤(3)保护气氛为氮气、氩气、氢气、一氧化碳、二氧化碳、氩氢混合气中至少一种气氛。
本发明通过控制原料比例来控制掺杂量等参数,再通过烧结温度、保温时间来控制材料结晶程度,使最终产品达到比较高的倍率性能,制备的磷酸铁锂正极材料具有较高的体积能量密度和循环性能,较好的机械加工性能和倍率性能,使用电站储能及动力电池正极材料。
本发明在于掺杂过程简单,效果明显,最终形貌仍保持前驱体形貌,尺寸及形貌未发生变化,且原料易得;烧结温度低,保温时间短,制备材料所消耗能源较少。
附图说明
图1为本发明实施例1的掺杂金属磷酸铁锂正极材料的SEM图及EDS图;
图2为本发明实施例1的掺杂金属磷酸铁锂正极材料在不同电流密度下充放电性能曲线;
图3为本发明实施例1和对比例1制备得到的正极材料的循环性能。
具体实施方式
以下将配合附图和实施例来详细说明本申请的实施方式,本申请如何应用技术手段来解决技术问题并达成技术功效的实现过程能充分理解并据以实施。
实施例1
一种掺杂金属磷酸铁锂的制备方法,具体步骤如下:
(1)前驱体的制备:将铁源(硫酸亚铁、硝酸亚铁质量比1:1混合)和磷源(磷酸二氢铵、磷酸氢二铵质量比1:1混合)加入水中配置成混合溶液,混合溶液中铁元素的浓度为0.1mol/L,铁和磷的摩尔比为Fe:P=1:1,混合溶液在强力搅拌均匀后加入过氧化氢得到絮状沉淀,过氧化氢与铁源中铁元素的摩尔比H2O2:Fe=0.6:1,搅拌4小时后过滤,将沉淀物用去离子水反复冲洗残留杂质,干燥后得到无定型磷酸铁前躯体;
(2)前驱体嵌入锂源:将锂源(碳酸锂、氢氧化锂质量比1:0.5混合)、还原剂抗坏血酸分散至有机溶剂乙醇中得到有机溶液,锂源与还原剂的摩尔比为1:0.5,有机溶液中锂源的浓度为0.1mol/L,再加入步骤(2)中得到的前驱体制成悬浮液,步骤(1)铁源中的铁和步骤(2)锂源中锂的摩尔比为Fe: Li=1:1,悬浮液于60℃不断搅拌12小时后,悬浮液离心,去离子水洗涤,真空干燥得到灰白色沉淀物;
(3)将步骤(2)制备的灰白色沉淀物与掺杂金属源氧化钴按摩尔比Fe:Co=1:0.05混合均匀后,混合物在氮气气氛下600℃温度环境中退火10h,得到橄榄石晶型的掺杂钴离子的磷酸铁锂正极材料。
对比例1
其他步骤同实施例1,步骤(3)不掺杂掺杂金属源氧化钴,直接将步骤(2)制备的灰白色沉淀物在氮气气氛下600℃温度环境中退火10h,得到不掺杂的磷酸铁锂正极材料。
图1为实施例1制备得到的橄榄石晶型的掺杂钴离子磷酸铁锂正极材料的SEM图和EDS图,从图中可以看出颗粒呈类球形分布,D50为500nm,EDS能谱图显示Co元素存在。
图2为实施例1制备得到的橄榄石晶型的球状磷酸铁锂正极材料充放电性能曲线,图3为实施例1和对比例1制备得到的正极材料的循环性能,从图中可以看出实施例1制备出的掺杂金属钴磷酸铁锂具有较好的比容量和循环性能,在2C电流密度下,对比例1未掺杂金属的磷酸铁锂容量衰减严重。
实施例2
一种掺杂金属磷酸铁锂的制备方法,具体步骤如下:
(1)前驱体的制备:将铁源(氯化亚铁)和磷源(磷酸氢二铵)加入水中配置成混合溶液,混合溶液中铁元素的浓度为1mol/L,铁和磷的摩尔比为Fe:P=0.8:1.2,混合溶液在强力搅拌均匀后加入过氧化氢得到絮状沉淀,过氧化氢与铁源中铁元素的摩尔比H2O2:Fe=0.8:1,搅拌8小时后过滤,将沉淀物用去离子水反复冲洗残留杂质,干燥后得到无定型磷酸铁前驱体;
(2)前驱体嵌入锂源:将锂源(乙酸锂)、还原剂酒石酸分散至有机溶剂乙醇中得到有机溶液,锂源与还原剂的摩尔比为1:1,有机溶液中锂源的浓度为0.5mol/L,再加入步骤(2)中得到的前驱体制成悬浮液,步骤(1)铁源中的铁和步骤(2)锂源中锂的摩尔比为Fe: Li=0.8:1.2,悬浮液于70℃不断搅拌10小时后,悬浮液离心,去离子水洗涤,真空干燥得到灰白色沉淀物;
(3)将步骤(2)制备的灰白色沉淀物与掺杂金属源单质钴按摩尔比Fe:Co=1:0.08混合均匀后,混合物在氩气气氛下750℃温度环境中退火2h,得到橄榄石晶型的掺杂金属磷酸铁锂正极材料。
实施例3
一种掺杂金属磷酸铁锂的制备方法,具体步骤如下:
(1)前驱体的制备:将铁源(草酸亚铁)和磷源(磷酸氢二铵)加入水中配置成混合溶液,混合溶液中铁元素的浓度2mol/L,铁和磷的摩尔比为Fe:P=1.2:0.8,混合溶液在强力搅拌均匀后加入过氧化氢得到絮状沉淀,过氧化氢与铁源中铁元素的摩尔比H2O2:Fe=1:1,搅拌12小时后过滤,将沉淀物用去离子水反复冲洗残留杂质,干燥后得到无定型磷酸铁前驱体;
(2)前驱体嵌入锂源:将锂源(硝酸锂)、还原剂抗坏血酸分散至有机溶剂丙醇中得到有机溶液,锂源与还原剂的摩尔比为1:2,有机溶液中锂源的浓度为1mol/L,再加入步骤(2)中得到的前驱体制成悬浮液,步骤(1)铁源中的铁和步骤(2)锂源中锂的摩尔比为Fe: Li=1.2:0.8,悬浮液于80℃不断搅拌6小时后,悬浮液离心,去离子水洗涤,真空干燥得到灰白色沉淀物;
(3)将步骤(2)制备的灰白色沉淀物与掺杂金属源单质镍按摩尔比Fe:Ni=1:0.04混合均匀后,混合物在氮气气氛下650℃温度环境中退火6h,得到橄榄石晶型的掺杂金属磷酸铁锂正极材料。
Claims (10)
1.一种掺杂金属磷酸铁锂的制备方法,其特征在于,具体步骤如下:
(1)将铁源和磷源加入水中配置成混合溶液,搅拌均匀后加入过氧化氢得到絮状沉淀,继续搅拌4-12小时后过滤,沉淀物用去离子水反复冲洗,干燥后得到前躯体;
(2)将锂源、还原剂分散至有机溶剂中得到有机溶液,再加入步骤(1)的前驱体制成悬浮液,悬浮液于60-80℃不断搅拌6-12小时后,离心、洗涤、真空干燥得到灰白色沉淀物;
(3)将步骤(2)的灰白色沉淀物与掺杂金属源混合均匀后,混合物在保护气氛下600~750℃退火2-10h,得到掺杂金属磷酸铁锂正极材料。
2.根据权利要求1所述掺杂金属磷酸铁锂的制备方法,其特征在于,步骤(1)铁源为焦磷酸亚铁、硫酸亚铁、硫酸亚铁铵、氯化亚铁、草酸亚铁、硝酸亚铁中的一种或几种任意比例混合;磷源为磷酸二氢铵、磷酸氢二铵、磷酸中的一种或几种任意比例混合。
3.根据权利要求1所述掺杂金属磷酸铁锂的制备方法,其特征在于,步骤(1)混合溶液中铁和磷的摩尔比为Fe:P=(0.8-1.2):(0.8-1.2);混合溶液中铁的浓度为0.1-2mol/L。
4.根据权利要求1所述掺杂金属磷酸铁锂的制备方法,其特征在于,步骤(1)过氧化氢按照过氧化氢与铁源中铁元素的摩尔比H2O2:Fe=(0.6-1):1的比例添加。
5.根据权利要求1所述掺杂金属磷酸铁锂的制备方法,其特征在于,步骤(2)锂源为碳酸锂、氢氧化锂、乙酸锂、硝酸锂中一种或几种任意比例混合。
6.根据权利要求1所述掺杂金属磷酸铁锂的制备方法,其特征在于,步骤(2)还原剂为酒石酸和/或抗坏血酸。
7.根据权利要求1所述掺杂金属磷酸铁锂的制备方法,其特征在于,步骤(2)有机溶剂为甲醇、乙醇、丙醇、异丙醇、聚丙烯醇、正丁醇、聚乙二醇、聚乙烯吡咯烷酮、丙酮中一种或几种任意比例混合。
8.根据权利要求1所述掺杂金属磷酸铁锂的制备方法,其特征在于,步骤(2)锂源与还原剂的摩尔比为1:(0.5-2),有机溶液中锂源的浓度为0.1mol-1mol/L,步骤(1)铁源中的铁和步骤(2)锂源中锂的摩尔比为Fe: Li=(0.8-1.2):(0.8-1.2)。
9.根据权利要求1所述掺杂金属磷酸铁锂的制备方法,其特征在于,步骤(3)灰白色沉淀物与掺杂金属源按照步骤(1)铁源中的铁元素与掺杂金属的摩尔比为Fe:A=1:(0.04-0.08)的比例混合,A为掺杂金属,掺杂金属源为镁单质、铝单质、钒单质、锰单质、钴单质、锌单质、铬单质、镍单质、铝氧化物、钴氧化物、锰氧化物、镧系金属单质、镧系金属氧化物中的一种或几种任意比例混合。
10.根据权利要求1所述掺杂金属磷酸铁锂的制备方法,其特征在于,步骤(3)保护气氛为氮气、氩气、氢气、一氧化碳、二氧化碳、氩氢混合气中一种或几种任意比例混合的气氛。
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