CN115057426B - 一种高倍率和高压实的磷酸锰铁锂的制备方法 - Google Patents
一种高倍率和高压实的磷酸锰铁锂的制备方法 Download PDFInfo
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- CN115057426B CN115057426B CN202210690219.3A CN202210690219A CN115057426B CN 115057426 B CN115057426 B CN 115057426B CN 202210690219 A CN202210690219 A CN 202210690219A CN 115057426 B CN115057426 B CN 115057426B
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- ferrous
- organic acid
- phosphate
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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 37
- 238000005056 compaction Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 53
- 150000007524 organic acids Chemical class 0.000 claims abstract description 46
- 239000000243 solution Substances 0.000 claims abstract description 30
- 239000012266 salt solution Substances 0.000 claims abstract description 21
- JLUGKDWGQPNDGX-UHFFFAOYSA-L azanium;manganese(2+);phosphate Chemical class [NH4+].[Mn+2].[O-]P([O-])([O-])=O JLUGKDWGQPNDGX-UHFFFAOYSA-L 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 15
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 150000002500 ions Chemical class 0.000 claims abstract description 12
- 239000002019 doping agent Substances 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 239000012065 filter cake Substances 0.000 claims abstract description 8
- 238000005096 rolling process Methods 0.000 claims abstract description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- 239000011572 manganese Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- -1 organic acid salt Chemical class 0.000 claims description 13
- 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 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 9
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 235000006708 antioxidants Nutrition 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- 239000005696 Diammonium phosphate Substances 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 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 claims description 2
- 239000007772 electrode material Substances 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 239000006012 monoammonium phosphate Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims 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 claims 1
- 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 1
- 229930006000 Sucrose Natural products 0.000 claims 1
- 239000008103 glucose Substances 0.000 claims 1
- 229910021389 graphene Inorganic materials 0.000 claims 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims 1
- 239000005720 sucrose Substances 0.000 claims 1
- BOMINLBVYNPVIK-UHFFFAOYSA-N azane;manganese(2+) Chemical compound N.[Mn+2] BOMINLBVYNPVIK-UHFFFAOYSA-N 0.000 abstract description 5
- 239000007791 liquid phase Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- 238000003756 stirring Methods 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 229910000616 Ferromanganese Inorganic materials 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000004254 Ammonium phosphate Substances 0.000 description 5
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 5
- 235000019289 ammonium phosphates Nutrition 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- SPFMQWBKVUQXJV-BTVCFUMJSA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal;hydrate Chemical compound O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O SPFMQWBKVUQXJV-BTVCFUMJSA-N 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 229960000673 dextrose monohydrate Drugs 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910006715 Li—O Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229960001031 glucose Drugs 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 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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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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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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Abstract
本发明公开了一种液相法制备磷酸锰铁锂的方法,包括:将有机酸和/或有机酸盐溶液按摩尔比1.00:0.95‑1.05滴加于含有亚铁离子和亚锰离子的溶液中反应,洗涤抽滤之后得到有机酸亚铁锰铵滤饼;将磷酸铵盐溶液按摩尔比1.00:0.95‑1.00滴加于有机酸亚铁锰铵中反应得到磷酸亚铁锰铵以及有机酸和/或有机酸盐溶液,磷酸亚铁锰铵、碳酸锂、掺杂剂和碳源按摩尔比1.00:0.50‑0.55:0.005‑0.02:0.25‑0.50混合干燥得到前驱体,在160‑250℃的无氧环境下保温,辊压后依次在300‑500℃和600‑800℃的无氧环境下保温,得到高倍率和高压实的磷酸锰铁锂。
Description
技术领域
本发明涉及电池电极材料技术领域,是涉及一种高倍率和高压实的磷酸锰铁锂的制备方法和应用。
背景技术
能源和环境问题日趋严重,石化能源越来越少,在未来将不满足人类的需求,因此寻求新的替代能源是当务之急。近年来,电动车和混合电动车等迅速发展,锂电池作为一种高性能的二次绿色电池有了绝对的优势,主流的便是磷酸锂铁电池,磷酸铁锂(LiFePO4)作为锂离子电池正极材料具有170mAh/g的理论比容量、约3.4V平稳的充放电平台,而且其原料来源广泛,安全性能优异,循环性能良好,但是纯相的LiFePO4的锂离子扩散速率及电子导电率较低,而且其振实密度较低。
磷酸锰锂(LiMnPO4)相对于LiFePO4而言循环稳定性较弱,但是具有使用电压较高(为3.8V),自放电率低,材料成熟,成本低的特点。根据动力电池要求特性可将Fe和Mn两者相结合,兼具两者的优势,采用Mn掺杂的LiFePO4作为锂离子正极材料—磷酸锰铁锂(LiMnxFe1-xPO4),在这种材料中,Mn3+/Mn2+在4.0V左右工作电压位于两者之间,能够实现Li嵌入和脱出,更具有前景的是市场上通用电解液能够在4.0V电压范围内保持稳定不分解,也不会因为电压过低而降低比能量,因此LiMnxFe1-xPO4正极材料成为了人们新的研究热点;但磷酸锰铁锂在实际生产应用中还存在很多问题,如磷酸铁锰锂的橄榄石晶体结构导致离子和电子电导率十分低,较低的离子和电子电导率必然影响材料的倍率性能的发挥,其次就是由于磷酸锰铁锂需要的碳含量更高,导致其压实密度很低,又极大地限制了磷酸锰铁锂正极材料的应用。
发明内容
本发明针对磷酸锰铁锂的倍率和压实密度低的问题,本发明提供一种高倍率和高压实的磷酸锰铁锂的制备方法,通过有机酸或有机酸盐作为合成磷酸亚铁锰铵的调节剂,并且有机酸或有机酸盐可以循环使用,且液相合成的磷酸亚铁锰铵掺杂均匀程度和相关性能有明显的提升;掺杂剂的加入提高了倍率;磷酸锰铁锂前驱体分解时会产生水和气体,导致有气孔产生,辊压便可以使气孔消失,提高压实密度。
本发明的技术方案为:一种高倍率和高压实的磷酸锰铁锂的制备方法,所述方法包括:
将有机酸和/或有机酸盐溶液和含有亚铁离子和亚锰离子的溶液按摩尔比 1.00:(0.95-1.05)混合反应得到有机酸亚铁锰悬浊液,洗涤抽滤之后得到有机酸亚铁锰铵滤饼;
将磷酸铵盐溶液和所述有机酸亚铁锰按摩尔比1.00:(0.95-1.00)混合反应,洗涤抽滤得到磷酸亚铁锰铵以及所述有机酸和/或所述有机酸盐溶液;
将所述磷酸亚铁锰铵、碳酸锂、掺杂剂和碳源按摩尔比1.00:(0.50-0.55):(0.005-0.02):(0.25-0.50)混合,后研磨至0.2μm<粒径<1.0μm,喷雾干燥得到前驱体;
将前驱体在160-250℃的氮气环境下保温2-4小时,冷却至室温,机械辊压后,在300-500℃的氮气环境下保温3-8小时,升温至600-800℃,保温6-12小时,得到高倍率和高压实的磷酸锰铁锂。
本发明的有益效果:
1.采用有机酸或有机酸盐作为调节剂,液相合成磷酸亚铁锰铵避免了杂质相的生成,得到的磷酸亚铁锰铵形貌规一、颗粒细小以及粒径分布均匀和掺杂均匀程度和相关性能有明显的提升。
2.采用本发明公开的方法可以使得有机酸或有机酸盐循环使用,降低制备成本。
3.掺杂剂的加入提高了磷酸锰铁锂的倍率性能,原因是掺杂剂选择的是含有非金属元素的锂源,非金属元素掺杂在O位,降低了Li-O键的键能,稳定了 LiFePO4的内部结构,也为Li+传输提供了更宽的通道。
4.磷酸锰铁锂前驱体分解时会产生水和气体,导致有气孔产生,辊压便可以使气孔消失,提高压实密度。
附图说明
图1为实施例1制备得到的磷酸锰铁锂成品的SEM扫描电镜图(10000倍);
图2为实施例2制备得到的磷酸锰铁锂成品的XRD图。
图3为本申请的工艺流程图。
具体实施方式
本申请实施例本发明针对磷酸锰铁锂的倍率和压实密度低的问题,本发明提供一种高倍率和高压实的磷酸锰铁锂的制备方法,如图3所示,所述方法包括:
S1.将有机酸和/或有机酸盐溶液和含有亚铁离子和亚锰离子的溶液混合反应得到有机酸亚铁锰悬浊液,洗涤抽滤之后得到有机酸亚铁锰滤饼,亚铁离子和亚锰离子的摩尔之和与有机酸或有机酸盐的摩尔之比为1.00:(0.95-1.05);
作为一种优选的方式,滴加过程的流量为0.01-1000升/分钟,滴加结束后,搅拌反应10-30分钟,用质量分数为10%-20%的氨水溶液或酸溶液调节pH值至2.0~3.5,反应30-60分钟,得到的悬浊液进行抽滤,滤饼用等质量去离子水洗涤,洗涤3-5次,转入5-10倍质量的去离子水中,20℃-60℃搅拌加热,转速为300-1000转/分钟,得到所述有机酸亚铁锰盐悬浊液。
具体地,所述含有亚铁离子和亚锰离子的溶液的浓度为1.0-2.5mol/L,其主要由亚铁盐和亚锰盐按摩尔比1.00:(0.25-0.75)溶于溶剂中得到,此处的溶剂为去离子水,亚铁盐和亚锰盐最好是分析纯纯度,并且所述含有亚铁离子和亚锰离子的溶液中还含有抗氧化剂,所述抗氧化剂为抗坏血酸,避免亚铁离子和亚锰离子在制备过程中被空气中的氧气所氧化,抗坏血酸的用量占亚铁盐的量和亚锰盐的量之和的0.1-2.0wt%。
所述含有亚铁离子和亚锰离子的溶液由以下步骤制备得到:将分析纯的亚铁盐和亚锰盐按上述摩尔比加去离子水配制成浓度为1.0-2.5mol/L的亚铁锰溶液,并加入抗坏血酸,20℃-60℃搅拌加热,转速为300-1000转/分钟。
所述亚铁盐选自硫酸亚铁、氯化亚铁以及硝酸亚铁中的至少一种,优选硫酸亚铁;所述亚锰盐选自硫酸亚锰、氯化亚锰以及硝酸亚锰中的至少一种,优选硫酸亚锰。
具体地,所述有机酸和/或有机酸盐溶液的浓度为1.0-10.0mol/L,主要由有机酸和/或有机酸盐溶解于去离子水中得到的溶液;有机酸和/或有机酸盐溶最好是分析纯级别的,所述有机酸选自草酸、柠檬酸以及乙酸中的至少一种,优选草酸;所述有机酸盐选自草酸铵、柠檬酸铵以及乙酸铵中的至少一种,优选草酸铵。
S2.将磷酸铵盐溶液和所述有机酸亚铁锰反应得到磷酸亚铁锰铵以及所述有机酸和/或所述有机酸盐溶液,所述磷酸铵盐与所述有机酸亚铁锰的摩尔之比为1.00:(0.95-1.00)。
作为一种优选的方式,滴加过程的流量为0.01-1000升/分钟,滴加结束后,搅拌反应10-20分钟,用质量分数为10%-20%的氨水溶液调节pH值至5.5-7.0,反应30-60分钟,得到的悬浊液进行抽滤,滤饼用去离子水洗涤抽滤至滤液到达中性,得到所述磷酸亚铁锰铵;
具体地,所述磷酸铵盐溶液的浓度为2.5-5.0mol/L,具体是将分析纯的磷酸铵盐加去离子水和分散剂配制而成,所述分散剂的用量占磷酸铵盐的量的 0.1-1.0wt%,所述分散剂选自乙醇、丙三醇以及聚乙二醇中的至少一种,所述磷酸铵盐选自磷酸二氢铵和/或磷酸氢二铵。
S3.将所述磷酸亚铁锰铵、碳酸锂、掺杂剂和碳源混合,研磨至0.2μm<粒径<1.0μm,喷雾干燥得到前驱体,所述磷酸亚铁锰铵、碳酸锂、掺杂剂和碳源按摩尔比1.00:(0.50-0.55):(0.005-0.02):(0.25-0.50)。
作为一种优选的方式,所述掺杂剂为氟化锂,所述碳源为一水葡萄糖(固含量为30-40%),研磨过程采用球磨机球磨,喷雾过程的温度为120-180℃。
S4.将前驱体在160-250℃的氮气环境下保温2-4小时,冷却至室温,机械辊压后,在300-500℃的氮气环境下保温3-8小时,升温至600-800℃,保温6-12 小时,得到高倍率和高压实的磷酸锰铁锂,本步骤中的氮气环境是氧气含量小于0.01vt%。
本申请通过液相法制备且在制备的过程中加入有机酸/和或有机酸盐。
实施例1
制备磷酸锰铁锂,包括以下步骤:
S1.配置亚铁锰液
将222.4g分析纯七水硫酸亚铁、202.8g的分析纯一水硫酸锰和2.5g抗坏血酸加入到625g去离子水中,在30℃下420转/分钟搅拌溶解,得到所述亚铁锰液;
S2.将180.1g分析纯草酸加入到1000g去离子水中,30℃下搅拌溶解,得到所述有机酸溶液;
S3.把所述草酸溶液滴加至所述铁锰溶液中,反应20分钟后,用质量分数为10%-20%的氨水溶液调节pH=2.0,反应30分钟后,用去离子水洗涤抽滤洗涤三次,加入2000g去离子水,在30℃下420转/分钟搅拌,得到有机酸亚铁锰盐悬浊液,洗涤抽滤之后得到有机酸亚铁锰滤饼;
S4.配制磷酸铵盐溶液
将272.0g分析纯磷酸氢二铵和2.5g乙醇加入到1250g去离子水中,30℃下搅拌溶解,得到所述磷酸铵盐溶液;
S5.合成磷酸亚铁锰铵
将磷酸铵盐溶液滴加至加入水的有机酸亚铁锰铵悬浊液中,反应20分钟后,用质量分数为10%-20%的氨水溶液调节pH=6.0,反应30分钟,用去离子水洗涤抽滤至滤液显中性,得到所述磷酸亚铁锰铵;
S6.制备前驱体
将磷酸亚铁锰铵转移至球磨罐并加入76.1g电池级碳酸锂、91.4一水葡萄糖、2.0g氟化锂、2006.4g锆珠和752.4去离子水,用行星球磨仪球磨至d50=0.43 μm,浆料在180℃喷雾干燥,得到所述前驱体。
S7.预烧
将所述前驱体放入管式炉中,通入氮气,在180℃保温3小时,自然冷却降温后,机械辊压,压片密度为2.20g/cm3。
S8.二次烧结
将所述预烧磷酸锰铁锂放入管式炉中,通入氮气,在300℃的氮气环境下保温8小时,升温至600℃,保温12小时,自然冷却降温后,气流粉碎,300 目过筛,得到磷酸锰铁锂成品,其SEM扫描电镜图如图1所示,由图1可知,得到了球形化颗粒且粒径分布区间在0.8-7.0μm的磷酸锰铁锂。
实施例2
制备磷酸锰铁锂,包括以下步骤:
S1.配置亚铁锰液
将111.2g分析纯七水硫酸亚铁、270.4g的分析纯一水硫酸锰和2.5g抗坏血酸加入到625g去离子水中,在40℃下400转/分钟搅拌溶解,得到所述亚铁锰液;
S2.将180.1g分析纯草酸加入到1000g去离子水中,40℃下搅拌溶解,得到所述有机酸溶液;
S3.把所述草酸溶液滴加至所述铁锰溶液中,反应20分钟后,用质量分数为10%-20%的氨水溶液调节pH=2.5,反应30分钟后,用去离子水洗涤抽滤洗涤三次,加入2000g去离子水,在40℃下420转/分钟搅拌,得到有机酸亚铁锰盐悬浊液,洗涤抽滤之后得到有机酸亚铁锰滤饼;
S4.配制磷酸铵盐溶液
将272.0g分析纯磷酸氢二铵和2.5g乙醇加入到1250g去离子水中,40℃下搅拌溶解,得到所述磷酸铵盐溶液;
S5.合成磷酸亚铁锰铵
将磷酸铵盐溶液滴加至加入水的有机酸亚铁锰铵悬浊液中,反应20分钟后,用质量分数为10%-20%的氨水溶液调节pH=6.0,反应30分钟,用去离子水洗涤抽滤至滤液显中性,得到所述磷酸亚铁锰铵;
S6.制备前驱体
将磷酸亚铁锰铵转移至球磨罐并加入76.1g电池级碳酸锂、71.4g一水葡萄糖、1.8g氟化锂、2006.4g锆珠和752.4去离子水,用行星球磨仪球磨至d50=0.36 μm,浆料在180℃喷雾干燥,得到所述前驱体。
S7.预烧
将所述前驱体放入管式炉中,通入氮气,在250℃保温4小时,自然冷却降温后,机械辊压,压片密度为2.20g/cm3。
S8.二次烧结
将所述预烧磷酸锰铁锂放入管式炉中,通入氮气,在500℃的氮气环境下保温5小时,升温至800℃,保温6小时,自然冷却降温后,气流粉碎,300目过筛,得到磷酸锰铁锂成品,其XRD图如图2所示,由图2可知,该成品为磷酸锰铁锂,且结晶度为90%。
最后应说明的是:以上所述仅为本发明的优选实施例而已,并不用于限制本发明的保护范围。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (5)
1.一种高倍率和高压实的磷酸锰铁锂的制备方法,其特征在于,所述方法包括:
将有机酸和/或有机酸盐溶液和含有亚铁离子和亚锰离子的溶液按摩尔比 1 .00:(0.95-1 .05)混合反应得到有机酸亚铁锰悬浊液,洗涤抽滤之后得到有机酸亚铁锰滤饼;所述有机酸选自草酸、柠檬酸以及乙酸中的至少一种;所述有机酸盐选自草酸铵、柠檬酸铵以及乙酸铵中的至少一种;
将磷酸铵盐溶液和所述有机酸亚铁锰按摩尔比1 .00:(0 .95-1 .00)混合反应,洗涤抽滤得到磷酸亚铁锰铵以及所述有机酸和/或所述有机酸盐溶液;
将所述磷酸亚铁锰铵、碳酸锂、掺杂剂和碳源按摩尔比1 .00:(0 .50-0 .55):(0.005-0 .02):(0 .25-0 .50)混合,后研磨至0 .2μm<粒径<1 .0μm,喷雾干燥得到前驱体,所述掺杂剂为氯化锂、硫化锂以及氟化锂中的至少一种,所述碳源为葡萄糖、蔗糖以及石墨烯中的至少一种;
将前驱体在160-250℃的氮气环境下保温2-4小时,冷却至室温,机械辊压后,得到的压片密度为2 .10-2 .50g/cm3,在300-500℃的氮气环境下保温3-8小时,升温至600-800℃,保温6-12小时,得到高倍率和高压实的磷酸锰铁锂。
2.根据权利要求1所述的高倍率和高压实的磷酸锰铁锂的制备方法,其特征在于,所述含有亚铁离子和亚锰离子的溶液主要由亚铁盐和亚锰盐按摩尔比1 .00:(0 .25-0 .75)溶于溶剂中得到;所述亚铁盐选自硫酸亚铁、氯化亚铁以及硝酸亚铁中的至少一种;所述亚锰盐选自硫酸亚锰、氯化亚锰以及硝酸亚锰中的至少一种,所述含有亚铁离子和亚锰离子的溶液中还包括质量为所述亚铁盐和所述亚锰盐质量之和的0 .1-2 .0%的抗氧化剂,所述抗氧化剂为抗坏血酸。
3.根据权利要求1所述的高倍率和高压实的磷酸锰铁锂的制备方法,其特征在于,所述磷酸铵盐溶液中磷酸铵盐选自磷酸二氢铵和/或磷酸氢二铵;所述磷酸铵盐溶液还包括分散剂;所述分散剂选自乙醇、丙三醇以及聚乙二醇中的至少一种。
4.一种如权利要求1-3任一项所述的方法制备得到的磷酸锰铁锂。
5.一种权利要求4所述的磷酸锰铁锂在作为电池电极材料中的应用。
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