CN111268664A - Ferromanganese phosphate intermediate, lithium iron manganese phosphate, and methods for producing these - Google Patents
Ferromanganese phosphate intermediate, lithium iron manganese phosphate, and methods for producing these Download PDFInfo
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- CN111268664A CN111268664A CN202010091773.0A CN202010091773A CN111268664A CN 111268664 A CN111268664 A CN 111268664A CN 202010091773 A CN202010091773 A CN 202010091773A CN 111268664 A CN111268664 A CN 111268664A
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- Prior art keywords
- phosphate
- lithium
- hours
- ammonium
- lithium iron
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 10
- 239000010452 phosphate Substances 0.000 title claims abstract description 10
- 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 description 66
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 title abstract description 10
- 229910000616 Ferromanganese Inorganic materials 0.000 title abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 239000002135 nanosheet Substances 0.000 claims abstract description 5
- 239000011572 manganese Substances 0.000 claims description 105
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 96
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 94
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 84
- 229910001868 water Inorganic materials 0.000 claims description 83
- 229910052757 nitrogen Inorganic materials 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 37
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- 229910052799 carbon Inorganic materials 0.000 claims description 30
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 30
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 25
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 24
- 229910052698 phosphorus Inorganic materials 0.000 claims description 24
- 239000011574 phosphorus Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- 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 20
- 229930006000 Sucrose Natural products 0.000 claims description 20
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 20
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 20
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 20
- 239000005720 sucrose Substances 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 19
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 16
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 13
- 239000001103 potassium chloride Substances 0.000 claims description 13
- 235000011164 potassium chloride Nutrition 0.000 claims description 13
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 12
- 239000001099 ammonium carbonate Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 10
- 239000004254 Ammonium phosphate Substances 0.000 claims description 9
- 235000019270 ammonium chloride Nutrition 0.000 claims description 9
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 9
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000012047 saturated solution Substances 0.000 claims description 8
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 7
- 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 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 7
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 7
- 150000001720 carbohydrates Chemical class 0.000 claims description 7
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 7
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 7
- 239000008103 glucose Substances 0.000 claims description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims description 7
- 159000000002 lithium salts Chemical class 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 5
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 5
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
- 229910019500 Mg0.05PO4 Inorganic materials 0.000 claims description 4
- DLRVVLDZNNYCBX-UHFFFAOYSA-N Polydextrose Polymers OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(O)O1 DLRVVLDZNNYCBX-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 239000008101 lactose Substances 0.000 claims description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 2
- 229920001100 Polydextrose Polymers 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 claims description 2
- 229930182830 galactose Natural products 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 239000001259 polydextrose Substances 0.000 claims description 2
- 229940035035 polydextrose Drugs 0.000 claims description 2
- 235000013856 polydextrose Nutrition 0.000 claims description 2
- 229910001631 strontium chloride Inorganic materials 0.000 claims description 2
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims 1
- 150000003841 chloride salts Chemical class 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052744 lithium Inorganic materials 0.000 abstract description 13
- 239000000047 product Substances 0.000 description 72
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 57
- 239000000843 powder Substances 0.000 description 38
- 239000000543 intermediate Substances 0.000 description 36
- 230000001105 regulatory effect Effects 0.000 description 26
- 239000011777 magnesium Substances 0.000 description 20
- 239000002243 precursor Substances 0.000 description 20
- 238000003756 stirring Methods 0.000 description 19
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 16
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 16
- 238000001035 drying Methods 0.000 description 16
- 239000011565 manganese chloride Substances 0.000 description 16
- 235000002867 manganese chloride Nutrition 0.000 description 16
- 229940099607 manganese chloride Drugs 0.000 description 16
- 230000001276 controlling effect Effects 0.000 description 15
- 239000011701 zinc Substances 0.000 description 15
- 239000002244 precipitate Substances 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 239000003153 chemical reaction reagent Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 13
- 239000011790 ferrous sulphate Substances 0.000 description 12
- 235000003891 ferrous sulphate Nutrition 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 11
- 229960001781 ferrous sulfate Drugs 0.000 description 11
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000011575 calcium Substances 0.000 description 9
- 238000001514 detection method Methods 0.000 description 9
- 229960002089 ferrous chloride Drugs 0.000 description 9
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 9
- 150000004685 tetrahydrates Chemical class 0.000 description 9
- OJASMMNWWIJWFK-KUSCCAPHSA-N (3r)-1-[[4-[[(3r)-3-(diethylcarbamoyl)piperidin-1-yl]methyl]phenyl]methyl]-n,n-diethylpiperidine-3-carboxamide;dihydrobromide Chemical compound Br.Br.C1[C@H](C(=O)N(CC)CC)CCCN1CC(C=C1)=CC=C1CN1C[C@H](C(=O)N(CC)CC)CCC1 OJASMMNWWIJWFK-KUSCCAPHSA-N 0.000 description 6
- 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 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 229910052573 porcelain Inorganic materials 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- RAFWXPDQXCSUBB-UHFFFAOYSA-K [O-]P([O-])([O-])=O.N.[Mn+2].[Fe+2] Chemical compound [O-]P([O-])([O-])=O.N.[Mn+2].[Fe+2] RAFWXPDQXCSUBB-UHFFFAOYSA-K 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 3
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- -1 ammonium ions Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 150000004688 heptahydrates Chemical class 0.000 description 2
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 235000011147 magnesium chloride Nutrition 0.000 description 2
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910014985 LiMnxFe1-xPO4 Inorganic materials 0.000 description 1
- 229910014982 LiMnxFe1−xPO4 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 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
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- QHFQAJHNDKBRBO-UHFFFAOYSA-L calcium chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ca+2] QHFQAJHNDKBRBO-UHFFFAOYSA-L 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 235000001055 magnesium Nutrition 0.000 description 1
- 229960002337 magnesium chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 235000016804 zinc Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 description 1
- RNZCSKGULNFAMC-UHFFFAOYSA-L zinc;hydrogen sulfate;hydroxide Chemical compound O.[Zn+2].[O-]S([O-])(=O)=O RNZCSKGULNFAMC-UHFFFAOYSA-L 0.000 description 1
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Abstract
Disclosed are ferromanganese phosphate intermediate, lithium ferromanganese phosphate, and methods for producing the same. The intermediate has the formula: (NH)4)Mn1‑x‑yFexMyPO4·H2O, wherein x is 0.05-0.5 and y is 0-0.2; m is divalent metal and is selected from one or more of Mg, Ca, Co, Mn and Zn; the intermediate has a crystal structure in an orthogonal structure, belongs to a Pmnm (59) space group, and has a two-dimensional nano sheet structure in the appearance.
Description
Technical Field
The invention relates to a manganese iron phosphate intermediate, and lithium manganese iron phosphate formed by adopting the intermediate has improved electrochemical activity and high compaction density. The invention also relates to lithium manganese iron phosphate formed by using the intermediate, a manufacturing method of the intermediate and the lithium manganese iron phosphate, and application of the lithium manganese iron phosphate in a lithium battery.
Technical Field
The lithium ion battery for the vehicle needs high energy density, high power, high safety, long service life and the like, and is one of the development trends of the lithium battery in the future. Among many cathode materials, an olivine-structured transition metal phosphate system represented by lithium iron phosphate has high power, safety, cycle life, and the like, and is widely used in the field of automotive batteries such as electric buses, electric logistics vehicles, start-stop batteries, and the like.
Lithium manganese iron phosphate is a homolog of lithium iron phosphate, but the discharge voltage is higher. Compared with lithium iron phosphate, lithium manganese iron phosphate not only has the characteristics of high power, high safety and long cycle life, but also has the characteristic of high energy density, and is gradually adopted by the battery industry.
Lithium manganese iron phosphate has various manufacturing methods, and one of the manufacturing methods is to form an intermediate of the iron manganese phosphate and then add lithium to the intermediate to obtain the lithium manganese iron phosphate.
CN106981656A discloses a preparation method of a battery-grade ferromanganese phosphate material, which comprises the steps of mixing an iron source, a manganese source, a surfactant and carbon nanotube slurry to obtain slurry A, mixing phosphoric acid and an oxidant to obtain solution B, and further performing induced crystallization, filtration, washing, drying and crushing by means of coprecipitation.
CN105514422A discloses a precursor, lithium iron manganese phosphate and a preparation method and application thereof. The precursor has a general formula of MnxFe1-x-yMyC2O4·2H2And O, wherein Mn and Fe are divalent, and M is selected from one of magnesium, nickel, zinc, calcium, vanadium and titanium. The preparation method of the precursor comprises the steps of mixing and reacting a water-soluble divalent manganese source, a water-soluble divalent iron source, a water-soluble divalent metal M salt except for manganese salt and ferric salt and a precipitator, and drying to obtain pre-powder; then dispersing the pre-powder in water, adding soluble decomposable ferrous salt, drying, and carrying out heat treatment at 200-500 ℃ under the protection of inert atmosphere to obtain the precursor; the precipitant is oxalic acid and/or water-soluble oxalate. The preparation method of the lithium iron manganese phosphate comprises the steps of mixing the precursor with a water-soluble lithium source, a water-soluble phosphorus source and an organic carbon source, and drying and roasting the obtained mixed product.
CN106865520A discloses a lithium manganese phosphate anode material and a preparation method thereof, wherein the particle size of the material is 0.5-1 μm. The preparation method of the lithium manganese phosphate anode material comprises the following steps: (1) preparing a suspension with solid content of 10-50 wt% from a phosphorus source compound, a manganese source compound, a carbon source compound and a surfactant; (2) carrying out hydrothermal reaction on the suspension under the pressure of 5-15 MPa; (3) after the reaction is finished, filtering, washing and drying at the temperature of 80-120 ℃ to obtain a square manganese phosphate precursor; (4) fully mixing manganese phosphate precursor powder with a lithium source compound, sintering at the high temperature of 700 ℃ for 2-8 hours under the protection of nitrogen atmosphere, and finally naturally cooling to obtain the square lithium manganese phosphate anode material.
CN103887491A reports a preparation method of a positive active material LiMnxFe1-xPO4/C of a lithium ion battery, which comprises the following steps: s1, mixing soluble divalent manganese salt and soluble ferrous salt to form a manganese-iron salt mixture; s2, mixing ferromanganese salt with a complexing precipitator under the protection of inert gas, and performing coprecipitation to prepare MnxFel-xC2O 4.2H2O; s3, washing and drying the precursor; s4, under the protection of inert gas, mixing MnxFe1-xC2O 4.2H2O with soluble lithium salt and phosphate to obtain a precursor solution; s5, reacting the precursor solution in a closed container protected by inert gas to obtain a reactant solution; and S6, adding carbon into the reactant solution, drying to obtain mixture powder, and sintering the mixture powder at high temperature to coat the carbon.
CN105449207A reports the preparation of iron manganese phosphate, which comprises selecting manganese source and iron source to be respectively dissolved in a proper amount of water, respectively adding a proper amount of phosphorus source, then transferring the two mixed solutions into a reaction kettle, and adjusting the pH value of the solution to be less than 2; adding an oxidant and a dispersant, raising the temperature to 50-150 ℃, and reacting for 2-24 hours; washing, filtering and drying the iron phosphate manganese slurry to obtain the final product MnxFe1-xPO4·yH2O, wherein y is 0 or other value. The finished product Mn of the iron phosphate manganese obtained by the inventionXFe1-XPO4·yH2The purity of O (with or without crystal water) is high, the valence states of manganese and iron are positive trivalent, the contents of Mn and Fe are more than 31 percent, the content of P is 18-19 percent, the content of S is less than 0.4 percent, the particle size distribution is uniform, the average particle size is 2.50 mu m, the crystal form is monoclinic, and primary particles are flaky.
CN 106910877B discloses a preparation method of a lithium nickel cobalt aluminate precursor, which comprises the following steps: 1) mixing a nickel salt solution, a cobalt salt solution and an aluminum salt solution according to the molar ratio of Ni to Co to Al of (0.6-0.9) to (0.05-0.3) to (0.01-0.1) to form a first mixed solution; 2) adding the first mixed solution into ammonia water, uniformly stirring, and then adjusting the pH value by using an alkaline solution to form a second mixed solution with the pH value being more than or equal to 12; 3) adding a proper amount of additive into the second mixed solution, uniformly stirring, standing and aging for 10-24h to form precursor colloid; 4) washing the precursor colloid with distilled water, then washing with alcohol liquid, and then centrifuging and concentrating to obtain precursor gel; 5) drying the precursor gel at the temperature of 200-300 ℃ for 4-8h, and then calcining at the temperature of 1100-1600 ℃ for 3-6h to obtain precursor powder.
The main body structure of the precursor, namely the ferromanganese phosphate or the ferromanganese oxalate, has better element distribution uniformity. However: in the preparation process of the manganese iron phosphate precursor, Mn (III) is unstable and has strong oxidizing property, so that Mn with a theoretical stoichiometric ratio is difficult to obtain by a synthetic method1-xFexPO4Materials, or demanding synthesis conditions; and the ferromanganese oxalate has larger gas production, so that the compaction density of the obtained lithium iron manganese phosphate is lower, and the volume energy ratio of the material is reduced.
Accordingly, there is also a need to develop a new intermediate for forming lithium iron manganese phosphate materials with which the formed lithium iron manganese phosphate has improved electrochemical activity.
Disclosure of Invention
It is an object of the present invention to provide a novel intermediate for forming lithium iron manganese phosphate materials with which the formed lithium iron manganese phosphate has improved electrochemical activity.
It is another object of the present invention to provide lithium manganese iron phosphate having improved electroactive properties.
Accordingly, a first aspect of the present invention relates to an intermediate for forming a lithium iron manganese phosphate material having the formula:
(NH4)Mn1-x-yFexMyPO4·H2O，
wherein x is 0.05-0.5 and y is 0-0.2;
m is divalent metal and is selected from one or more of Mg, Ca, Co, Mn and Zn;
the intermediate has a crystal structure in an orthogonal structure, belongs to a Pmnm (59) space group, and has a two-dimensional nano sheet structure in the appearance.
Another aspect of the present invention relates to a method for producing the intermediate described above, comprising:
a) preparing an aqueous solution containing Mn, Fe and M according to the stoichiometric amount to obtain a solution A;
b) synchronously dropwise adding a phosphorus source, a nitrogen source and the liquid A into a reaction kettle, controlling the pH to be between 3.0 and 8.0 in the dropwise adding process, and controlling the temperature to be between room temperature and 90 ℃ to obtain a suspension B, wherein the nitrogen source is selected from ammonia water, ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium nitrate, ammonium dihydrogen phosphate, ammonium monohydrogen phosphate, ammonium phosphate or a mixture of two or more of the ammonium phosphate and the ammonium dihydrogen phosphate in any proportion;
c) optionally aging to give the intermediate.
Another aspect of the invention relates to a lithium iron manganese phosphate having the general formula:
LiaMn1-x-yFexMyPO4/kC
wherein, a is 0.85-1.15, x is 0.05-0.5, and y is 0-0.2;
m is one or more doping elements selected from Mg, Ca, Co, Mn and Zn;
k is the amount of carbon element based on the total weight of other elements in the lithium manganese iron phosphate and is 1-8 wt%;
it is prepared by the following method:
a) preparing an aqueous solution containing Mn, Fe and M according to a chemical formula to obtain a solution A;
b) synchronously dropwise adding a phosphorus source, a nitrogen source and the liquid A into a reaction kettle, controlling the pH to be between 3.0 and 8.0 in the dropwise adding process, and controlling the temperature to be between room temperature and 90 ℃ to obtain a suspension B, wherein the nitrogen source is selected from ammonia water, ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium nitrate, ammonium dihydrogen phosphate, ammonium monohydrogen phosphate, ammonium phosphate or a mixture of two or more of the ammonium phosphate and the ammonium dihydrogen phosphate in any proportion;
c) optionally aging to obtain intermediate (NH)4)Mn1-x-yFexMyPO4·H2O, wherein x is 0.05-0.5 and y is 0-0.2;
d) mixing the intermediate with a molten lithium salt in an inert atmosphere to obtain a lithium iron manganese phosphate material;
e) and mixing the obtained lithium iron manganese phosphate material with a carbohydrate carbon source, and performing heat treatment in an inert atmosphere to obtain the carbon-compounded lithium iron manganese phosphate material.
Drawings
The invention is further described below with reference to the accompanying drawings. In the attached drawings
FIG. 1 is the XRD analysis of the intermediate obtained in example 1;
FIG. 2 is an SEM image of an intermediate produced in example 1;
FIG. 3 is an EDX image under SEM of the intermediate prepared in example 1;
FIG. 4 shows the XRD analysis result of the lithium iron manganese phosphate product in example 1;
FIG. 5 is the SEM analysis result of the lithium iron manganese phosphate product of example 1 (small particles and fibrous substances in the figure, which are conductive carbon materials);
FIG. 6 is the SEM analysis results of the lithium iron manganese phosphate products in examples 1-8;
fig. 7 is a discharge curve of the lithium iron manganese phosphate product of example 5.
Detailed Description
A.Intermediates
The intermediate for forming the lithium iron manganese phosphate material has the following chemical formula:
(NH4)Mn1-x-yFexMyPO4·H2O，
wherein x is 0.05 to 0.5, preferably 0.07 to 0.45, more preferably 0.09 to 0.40, preferably 0.11 to 0.35, most preferably 0.13 to 0.30, and most preferably 0.15 to 0.25;
y is 0 to 0.2, preferably 0.01 to 0.18, more preferably 0.03 to 0.16, preferably 0.05 to 0.14, most preferably 0.07 to 0.12, and most preferably 0.09 to 0.10;
m is divalent metal and is selected from one or more of Mg, Ca, Co, Mn and Zn;
the intermediate has a crystal structure in an orthogonal structure, belongs to a Pmnm (59) space group, and has a two-dimensional nano sheet structure in the appearance.
In one embodiment of the invention, the intermediate is selected from the group consisting of: NH (NH)4Mn0.5Fe0.5PO4·H2O；NH4Mn0.80Fe0.2PO4·H2O；NH4Mn0.875Fe0.125PO4·H2O；NH4Mn0.9Fe0.1PO4·H2O；NH4Mn0.8Fe0.15Mg0.05PO4·H2O；NH4Mn0.8Fe0.15Co0.05PO4·H2O；NH4Mn0.8Fe0.15Ni0.05PO4·H2O；NH4Mn0.7Fe0.15Zn0.15PO4·H2O；NH4Mn0.7Fe0.2Mg0.05Zn0.05PO4·H2O；NH4Mn0.65Fe0.25Co0.05Ni0.05PO4·H2O；NH4Mn0.7Fe0.15Mg0.05Ca0.05Co0.05PO4·H2O；NH4Mn0.85Fe0.05Mg0.1PO4·H2O or a mixture of two or more thereof in any ratio.
The method for producing the intermediate of the present invention comprises:
a) preparing an aqueous solution containing Mn, Fe and M according to the stoichiometric amount to obtain a solution A;
suitable methods for preparing the aqueous solution are not particularly limited, and may be conventional methods known in the art. In one embodiment of the invention, stoichiometric amounts of metal salts of Mn, Fe, and M are placed in water to form an aqueous solution. Suitable metal salts may be their respective sulfates, chlorides, nitrates, acetates or mixtures thereof.
In one embodiment of the present invention, the concentration of liquid A may be in the range of 10g/L to that of the saturated solution, preferably 20-220g/L, more preferably 50-200g/L, still more preferably 80-180g/L, most preferably 100-160g/L, and most preferably 120-140 g/L.
b) Synchronously dropwise adding a phosphorus source, a nitrogen source and the liquid A into a reaction kettle, controlling the pH to be between 3.0 and 8.0 in the dropwise adding process, and controlling the temperature to be between room temperature and 90 ℃ to obtain a suspension B, wherein the nitrogen source is selected from ammonia water, ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium nitrate, ammonium dihydrogen phosphate, ammonium monohydrogen phosphate, ammonium phosphate or a mixture of two or more of the ammonium phosphate and the ammonium dihydrogen phosphate in any proportion;
the method of the invention adopts the steps of synchronously dropwise adding the phosphorus source, the nitrogen source and the liquid A into the reaction kettle, and controlling the pH value to be between 3.0 and 8.0, preferably between 4.0 and 7.5, more preferably between 5.0 and 7.0, and still more preferably between 4.5 and 6.5 in the dropwise adding process. The purpose of the invention is to ensure the formation of the target intermediate throughout the reaction by simultaneous addition and simultaneous pH control.
The acid or base used for controlling pH is not particularly limited and may be an acid or base conventional in the art as long as it does not affect the properties and/or purity of the final intermediate or final product. In one embodiment of the present invention, the acid for controlling pH is selected from sulfuric acid, hydrochloric acid, acetic acid or a mixture thereof, and the base for controlling pH is selected from sodium hydroxide, potassium hydroxide or a mixture thereof.
The source of phosphorus is selected from the group consisting of an aqueous solution of phosphoric acid having a concentration of between 5 and 85% wt, preferably between 15 and 75% wt, more preferably between 25 and 65% wt, a water soluble dihydrogen phosphate salt having a concentration of between 5% wt and a saturated solution, preferably between 10% wt and a saturated solution, a water soluble monohydrogen phosphate salt, a water soluble phosphate salt or a mixture thereof. In one embodiment of the invention, the water-soluble dihydrogen phosphate salt, the water-soluble monohydrogen phosphate salt, and the water-soluble phosphate salt are selected from their respective ammonium, sodium, potassium salts, or mixtures thereof. In one embodiment of the invention, a phosphate system containing ammonium ions is used in place of part or all of the nitrogen source.
The temperature needs to be controlled between room temperature and 90 ℃ in the process of dropwise adding reaction, preferably 30-80 ℃, and more preferably 40-70 ℃.
In one embodiment of the invention, the nitrogen source is selected from one or more of aqueous ammonia at a concentration of between 5 and 28% wt, ammonium chloride, ammonium sulfate, ammonium carbonate and ammonium bicarbonate, ammonium nitrate, ammonium dihydrogen phosphate, ammonium monohydrogen phosphate, ammonium phosphate at a concentration of between 5% wt and saturated solution.
In one embodiment of the invention, phosphate-containing ammonium salts are used in place of some or all of the phosphorus source.
In one embodiment of the present invention, in order to ensure complete incorporation of the metal element into the final intermediate precipitate, the total molar amount P of the phosphorus element and the total molar amount M of the metal element are controlled to be not less than 1, and the total molar amount N of the nitrogen element and the total molar amount M of the metal element are controlled to be not less than 1.
c) Optionally aging to give the intermediate.
The applicable aging method is not particularly limited, and may be a conventional aging method known in the art, for example, stirring is applied during aging. In one embodiment of the invention, the aging time is between 0 and 48 hours, preferably between 0.5 and 40 hours, more preferably between 1 and 24 hours, preferably between 2 and 12 hours.
The method also comprises the steps of carrying out solid-liquid separation, washing and drying on the product obtained by aging. The method of the solid-liquid separation, washing and drying is not particularly limited and may be a method known in the art.
B.Lithium manganese iron phosphate
The invention also relates to lithium manganese iron phosphate, which has the general formula:
LiaMn1-x-yFexMyPO4/kC
wherein the content of the first and second substances,
a is 0.85 to 1.15, preferably 0.88 to 1.12, more preferably 0.90 to 1.10, preferably 0.92 to 0.98, preferably 0.94 to 0.96;
x is 0.05 to 0.5, preferably 0.07 to 0.45, more preferably 0.09 to 0.40, preferably 0.11 to 0.35, most preferably 0.13 to 0.30, and most preferably 0.15 to 0.25;
y is 0 to 0.2, preferably 0.01 to 0.18, more preferably 0.03 to 0.16, preferably 0.05 to 0.14, most preferably 0.07 to 0.12, and most preferably 0.09 to 0.10;
m is one or more doping elements selected from Mg, Ca, Co, Mn and Zn;
k is the amount of carbon element in the range of 1 to 8 wt%, preferably 2 to 7 wt%, more preferably 3 to 6 wt%, preferably 4 to 5 wt%, based on the total weight of other elements in the lithium manganese iron phosphate.
The manufacturing method of the lithium iron manganese phosphate comprises the following steps:
i) preparing an intermediate by the above method;
d) mixing the intermediate with a molten lithium salt in an inert atmosphere to obtain a lithium iron manganese phosphate material;
the inert gas atmosphere is not particularly limited and may be a conventional inert gas atmosphere known in the art, and for example, may be nitrogen, argon, helium or a mixed gas thereof. From the viewpoint of cost, nitrogen is preferred.
In one embodiment of the present invention, the step of mixing the intermediate with a molten lithium salt comprises mixing the intermediate with a lithium-containing salt, and subsequently heating the mixture under an inert gas atmosphere until the lithium-containing salt melts and is maintained at a temperature.
In one example of the invention, the lithium-containing salt is selected from lithium chloride, sodium chloride, potassium chloride, strontium chloride or a mixture of two or more thereof.
In one embodiment of the present invention, the temperature of the mixture of the intermediate and the lithium-containing salt is raised to 150-.
In one embodiment of the invention, the holding time after melting the lithium-containing salt is 2 to 12 hours, preferably 3 to 11 hours, more preferably 4 to 10 hours, preferably 5 to 9 hours, and preferably 6 to 8 hours.
In one embodiment of the invention, the molar ratio of lithium-containing salt to intermediate in the mixture is greater than 1, preferably greater than 1.1, more preferably greater than 1.2, preferably greater than 1.3, preferably greater than 1.4, for example, a molar ratio of 1.01 to 1.5.
The method also comprises the steps of washing and drying the product after heat preservation by water. The method of washing and drying is not particularly limited and may be a conventional method known in the art. And drying to obtain the lithium iron manganese phosphate material containing the doped metal M.
e) And mixing the obtained lithium iron manganese phosphate material with a carbohydrate carbon source, and performing heat treatment in an inert atmosphere to obtain the carbon-compounded lithium iron manganese phosphate material.
The method for mixing the lithium iron manganese phosphate material with the carbohydrate carbon source is not particularly limited, and may be a conventional method known in the art, such as stirring mixing and the like.
Non-limiting examples of suitable carbohydrate carbon sources are, for example, glucose, sucrose, galactose, lactose, polydextrose, cellulose or mixtures of two or more thereof, preferably glucose, sucrose or mixtures thereof.
The inert gas used for forming the inert atmosphere is not particularly limited and may be a conventional inert gas known in the art. From the viewpoint of cost, nitrogen is preferable.
In one embodiment of the present invention, the temperature of the heat treatment is 450-.
In one embodiment of the invention, the heat treatment is carried out for a period of time of 2 to 15 hours, preferably 3 to 12 hours, preferably 4 to 10 hours, and preferably 5 to 8 hours.
In one embodiment of the present invention, a method for manufacturing a carbon-composite lithium iron manganese phosphate material according to the present invention includes the steps of:
an aqueous solution of manganese sulphate and ferrous sulphate, in stoichiometric proportions, is prepared and is referred to as solution A-1. Using sulfuric acid as a pH regulating reagent, synchronously adding the solution A-1, phosphoric acid and ammonia water into a reaction kettle at the room temperature of +/-5 ℃ under stirring, controlling the pH to be 3.0 +/-0 by regulating the adding speed of the sulfuric acid, and stirring at constant temperature for 24 hours after the addition is finished to finish the reaction;
-filtering the obtained precipitate, washing with deionized water and drying in an oven, and XRD and SEM characterization of the obtained dried product, with the results shown in FIG. 1, FIG. 2, FIG. 3 and FIG. 6 a. XRD detection shows that the manganese phosphate iron ammonium intermediate is a pure-phase manganese phosphate iron ammonium intermediate, SEM shows that the manganese phosphate iron ammonium intermediate is lamellar, and EDX detection results show that the molar ratio of Mn to Fe is close to the charge ratio;
weighing the intermediate, the lithium chloride powder and the sodium chloride powder according to stoichiometric amount, uniformly mixing, placing in a crucible, placing in a tubular furnace protected by nitrogen, heating to 300-;
drying the product after washing, selecting glucose as a carbon source, uniformly mixing the product with the product, placing the mixture in a crucible, placing the crucible in a nitrogen-protected tube furnace, heating to 500-. And obtaining the carbon-compounded lithium manganese iron phosphate. The product was subjected to XRD and SEM characterization, and the results are shown in fig. 4 and 5.
The lithium iron manganese phosphate precursor has a two-dimensional flaky nano structure, is simple to synthesize, has uniform element distribution, does not need harsh reaction conditions, and has high reaction activity;
the manganese lithium iron phosphate prepared by the precursor inherits the morphological characteristics of two-dimensional nano sheets, so that the migration path of lithium ions is shortened, and the electrochemical activity of the material is improved; in addition, because the length and the width of the sheet structure are micron-sized, the lithium iron manganese phosphate prepared by the method has higher compaction density, and the volume energy density of the battery is improved.
Examples
The present invention will be further described with reference to specific examples.
Electrochemical performance test method of lithium manganese iron phosphate
Mixing active substance, conductive agent and binder at weight ratio of 90: 5 with NMP as solvent, and mixing at a ratio of 10mg/cm2The areal density of (a) was coated on one side on an aluminum foil and dried in vacuo. And after the pole piece is rounded, a lithium piece is used as a counter electrode, a solution with the concentration of lithium hexafluorophosphate being 1M and DMC: EC being 3: 1(V/V) is used as an electrolyte, and a PP diaphragm with the thickness of 20 microns is used for isolating the positive electrode and the negative electrode, so that the CR2025 button cell is assembled. The rate test was performed according to the following conditions:
and (3) testing temperature: 23 +/-2 ℃;
voltage range: 2.7-4.5V;
the test flow comprises the following steps:
charging: charging at 150mA/g, and stopping at 1.5mA/g constant voltage after 4.25V;
discharging: after a release of 15mA/g active substance and a cut-off after 2.7V.
Example 1
The contents of manganese sulfate and ferrous sulfate are 10g/L (as MnSO) according to the molar ratio of Mn to Fe being 50 to 504·H2O and FeSO4·7H2O) in a total of 5500mL, and 0.246mol in terms of metal molar amount, and is referred to as "liquid A-1".
30g of 85% industrial phosphoric acid is taken as a phosphorus source (0.26mol), 1M sulfuric acid is taken as a pH regulating reagent, about 33.2g of 26% wt ammonia water is taken as a nitrogen source (0.247mol), liquid A-1, the industrial phosphoric acid and the ammonia water are synchronously added into a reaction kettle at the room temperature of +/-5 ℃ under stirring, and the pH is controlled to be 3.0 +/-0.2 by regulating the adding speed of the sulfuric acid. After the addition is finished, stirring for 24 hours at constant temperature, and finishing the reaction.
The precipitate obtained above was filtered, washed with deionized water, and dried in an oven at 60 ℃ to obtain about 37g of a product, and the dried product was subjected to XRD and SEM characterization, and the results are shown in FIG. 1, FIG. 2, FIG. 3 and FIG. 6 a. XRD detection shows that the NH is pure phase4Mn0.5Fe0.5PO4·H2O, SEM shows that the morphology is lamellar, and the molar ratio of Mn/Fe is close to the charge ratio through EDX detection.
10g of NH are weighed4Mn0.5Fe0.5PO4·H2O (0.0536mol), 10g (0.236mol) of lithium chloride powder and 2g (0.034mol) of sodium chloride powder were mixed uniformly and placed in a 50mL crucibleThe mixture is placed in a 5L/min tubular furnace protected by nitrogen, heated to 400 ℃ and then kept for 4 hours.
The product was washed with water and dried to give about 7.5g of product. Selecting 0.3g of glucose as a carbon source, uniformly mixing the carbon source with the product, placing the mixture in a 50mL crucible, placing the crucible in a 5L/min tubular furnace protected by nitrogen, heating to 650 ℃, and then preserving heat for 3 hours. And obtaining the carbon-compounded lithium manganese iron phosphate.
The product was subjected to XRD and SEM characterization, and the results are shown in fig. 4 and 5.
Example 2
An aqueous solution containing 200g/L of manganese chloride (tetrahydrate) and ferrous chloride (tetrahydrate) was prepared in a molar ratio of Mn to Fe of 80 to 20, and the total amount was 3000mL, and the molar amount of manganese chloride and ferrous chloride was 3.03mol in terms of metal, and the solution was referred to as "liquid A-2".
350g of 85 percent phosphoric acid (3.03mol) is taken as a phosphorus source, 2kg of ammonium sulfate (3.03mol) aqueous solution with the concentration of 20 percent by weight is taken as a nitrogen source, 10M sodium hydroxide is taken as a pH regulating reagent, the solution A-2, the phosphoric acid and the ammonium sulfate solution are synchronously added into a reaction kettle with the temperature range of 70 +/-5 ℃ under stirring, and the pH is controlled to be 5.5 +/-0.2 by regulating the adding speed of the sodium hydroxide. After the addition was completed, the reaction was terminated by maintaining the temperature for 12 hours.
The precipitate obtained above was filtered, washed with deionized water, and dried in a 60 degree oven to yield about 540g of product. SEM shows that the product has a lamellar structure (FIG. 6b), and XRD shows NH as a pure phase4Mn0.80Fe0.2PO4·H2O and a Mn/Fe molar ratio of 4.08: 1 as determined by EDX (Table 1).
10g of NH are weighed4Mn0.80Fe0.2PO4·H2O (0.0538mol), 10g (0.236mol) of lithium chloride powder and 10g (0.013mol) of potassium chloride powder are mixed uniformly, placed in a 100mL porcelain boat, placed in a 5L/min nitrogen-protected tube furnace, heated to 300 ℃ and then kept warm for 24 hours.
The product was washed with water and dried to give about 6.5g of product. Selecting 0.6g of sucrose as a carbon source, uniformly mixing the sucrose with the product, placing the mixture into a 50mL crucible, placing the crucible into a tubular furnace protected by nitrogen at a rate of 3L/min, heating to 500 ℃, and then preserving heat for 12 hours. And obtaining the carbon-compounded lithium manganese iron phosphate.
The material was assembled into a battery and the ultimate compacted density was measured to be 2.47g/cm3The gram capacity is 146mAh, and the average discharge voltage reaches 3.87V.
Example 3
An aqueous solution containing 200g/L of manganese chloride (tetrahydrate) and ferrous chloride (tetrahydrate) was prepared in a molar ratio of Mn to Fe of 7 to 1, and the total amount was 3000mL, and the molar amount of manganese chloride and ferrous chloride was 3.03mol in terms of metal, and the solution was referred to as "liquid A-3".
350g of 85 percent phosphoric acid (3.03mol) is taken as a phosphorus source, 1.2kg of ammonium bicarbonate (3.03mol) aqueous solution with the concentration of 20 percent by weight is taken as a nitrogen source, 1M sodium hydroxide is taken as a pH regulating reagent, the solution A-2, the phosphoric acid and the ammonium bicarbonate solution are synchronously added into a reaction kettle with the temperature range of 70 +/-5 ℃ under stirring, and the pH is controlled to be 5.5 +/-0.2 by regulating the adding speed of the sodium hydroxide. After the addition was completed, the reaction was terminated by maintaining the temperature for 12 hours.
The precipitate obtained above was filtered, washed with deionized water, and dried in an oven at 60 ℃ to give about 530g of the product. SEM shows that the product has a lamellar structure (FIG. 6c), and XRD shows that the NH is pure phase4Mn0.875Fe0.125PO4·H2O and a Mn/Fe molar ratio of 7: 0.99 by EDX (Table 1).
10g of NH are weighed4Mn0.875Fe0.125PO4·H2O (0.0537mol), 10g (0.236mol) of lithium chloride powder and 10g (0.013mol) of potassium chloride powder are mixed uniformly, placed in a 100mL porcelain boat, placed in a 5L/min nitrogen-protected tube furnace, heated to 300 ℃ and then kept warm for 24 hours.
The product was washed with water and dried to give about 6.1g of product. Selecting 0.55g of sucrose as a carbon source, uniformly mixing the sucrose with the product, placing the mixture into a 50mL crucible, placing the crucible into a tubular furnace protected by nitrogen at a rate of 3L/min, heating to 500 ℃, and then preserving heat for 12 hours. And obtaining the carbon-compounded lithium manganese iron phosphate.
The material was assembled into a battery and the ultimate compacted density was measured to be 2.45g/cm3The gram capacity is 141mAh, and the average discharge voltage reaches 3.88V.
Example 4
An aqueous solution containing 200g/L of manganese chloride (tetrahydrate) and ferrous chloride (tetrahydrate) was prepared in a molar ratio of Mn to Fe of 9: 1, and the total amount was 3000mL, and the molar amount of manganese chloride and ferrous chloride was 3.03mol, based on the metal, and the solution was designated as "liquid A-4".
396g of 75 percent phosphoric acid (3.03mol) is taken as a phosphorus source, 540g of ammonium chloride (3.03mol) aqueous solution with the concentration of 30 percent wt is taken as a nitrogen source, sodium hydroxide with the concentration of 10M is taken as a pH regulating reagent, liquid A-2, phosphoric acid and ammonium chloride solution are synchronously added into a reaction kettle with the temperature range of 70 +/-5 ℃ under stirring, and the pH is controlled to be 5.5 +/-0.2 by regulating the adding speed of the sodium hydroxide. After the addition was completed, the reaction was terminated by maintaining the temperature for 12 hours.
The precipitate obtained above was filtered, washed with deionized water, and dried in a 60 degree oven to yield about 540g of product. SEM shows that the resulting product has a lamellar structure (FIG. 6d), and XRD examination shows NH as a pure phase4Mn0.9Fe0.1PO4·H2O and a Mn/Fe molar ratio of 9: 1.1 as determined by EDX (Table 1).
10g of NH are weighed4Mn0.9Fe0.1PO4·H2O (0.0537mol), 10g (0.236mol) of lithium chloride powder and 10g (0.013mol) of potassium chloride powder, which were mixed uniformly, placed in a 100mL porcelain boat, placed in a 5L/min nitrogen-protected tube furnace, heated to 300 ℃ and then held for 24 hours.
The product was washed with water and dried to yield about 6.9g of product. Selecting 0.63g of sucrose as a carbon source, uniformly mixing the sucrose with the product, placing the mixture in a 50mL crucible, placing the crucible in a tubular furnace protected by nitrogen at a rate of 3L/min, heating to 500 ℃, and then preserving heat for 12 hours. And obtaining the carbon-compounded lithium manganese iron phosphate.
The material was assembled into a battery and the ultimate compacted density was measured to be 2.37g/cm3The gram capacity is 135mAh, and the average discharge voltage reaches 3.91V.
Example 5
An aqueous solution containing 150g/L of manganese chloride (tetrahydrate), ferrous sulfate (heptahydrate) and magnesium chloride (hexahydrate) was prepared in a molar ratio of Mn, Fe and Mg of 85: 15: 5, and the total volume was 5000mL, and the molar amount of manganese chloride, ferrous sulfate and magnesium chloride was 3.61mol per mole of metal, and the solution was designated as "liquid A-5".
Using 420g ammonium dihydrogen phosphate as a phosphorus source and a nitrogen source (3.65mol), dissolving in 1000g water, using 10M sodium hydroxide as a pH regulating reagent, stirring, synchronously adding liquid A-5 and ammonium dihydrogen phosphate into a reaction kettle at the temperature of 55 +/-5 ℃, and controlling the pH to be 6.5 +/-0.2 by regulating the adding speed of a sodium hydroxide phase. After the addition, the reaction was terminated by maintaining the temperature for 8 hours.
The precipitate obtained above was filtered, washed with deionized water, and dried in a 60 degree oven to give about 640g of product. SEM shows that the resulting product has a lamellar structure (FIG. 6e), and XRD examination shows NH as a pure phase4Mn0.8Fe0.15Mg0.05PO4·H2O and a Mn/Fe/Mg molar ratio of 81: 13: 6 as determined by EDX (Table 1).
15g of NH are weighed4Mn0.8Fe0.15Mg0.05PO4·H2O (0.081mol), 10g (0.236mol) of lithium chloride powder, 2g (0.034mol) of sodium chloride powder and 2g (0.027mol) of potassium chloride powder are mixed uniformly, placed in a 50mL crucible, placed in a 5L/min tubular furnace protected by nitrogen, heated to 300 ℃ and then kept warm for 12 hours.
The product was washed with water and dried to yield about 12g of product. Selecting 0.5g of sucrose as a carbon source, uniformly mixing the sucrose with the product, placing the mixture into a 50mL crucible, placing the crucible into a 5L/min tubular furnace protected by nitrogen, heating to 600 ℃, and then preserving heat for 8 hours. And obtaining the carbon-compounded lithium manganese iron phosphate.
The material was assembled into a battery and the ultimate compacted density was measured to be 2.51g/cm3The gram capacity is 147 mAh.
Example 6
An aqueous solution containing 150g/L of manganese chloride (tetrahydrate), ferrous sulfate (heptahydrate) and cobalt sulfate (heptahydrate) was prepared in a molar ratio of Mn, Fe and Co of 85: 15: 5, and the total volume was 5000mL, and the molar amount of manganese chloride, ferrous sulfate and cobalt sulfate was 3.54mol per mole of metal, and the solution was designated as "liquid A-6".
Using 420g ammonium dihydrogen phosphate as a phosphorus source and a nitrogen source (3.65mol), dissolving in 1000g water, using 10M sodium hydroxide as a pH regulating reagent, stirring, synchronously adding liquid A-6 and ammonium dihydrogen phosphate into a reaction kettle at the temperature of 55 +/-5 ℃, and controlling the pH to be 6.5 +/-0.2 by regulating the adding speed of a sodium hydroxide phase. After the addition, the reaction was terminated by maintaining the temperature for 8 hours.
The precipitate obtained above was filtered, washed with deionized water, and dried in a 60-degree oven to give about 630g of the product. SEM shows that the product has a lamellar structure (FIG. 6f), and XRD shows that the NH is pure phase4Mn0.8Fe0.15Co0.05PO4·H2O and a Mn/Fe/Co molar ratio of 80/13/6 (Table 1) as determined by EDX.
15g of NH are weighed4Mn0.8Fe0.15Co0.05PO4·H2O (0.081mol), 10g (0.236mol) of lithium chloride powder, 2g (0.034mol) of sodium chloride powder and 2g (0.027mol) of potassium chloride powder are mixed uniformly, placed in a 50mL crucible, placed in a 5L/min tubular furnace protected by nitrogen, heated to 300 ℃ and then kept warm for 12 hours.
The product was washed with water and dried to give about 12.1g of product. Selecting 0.5g of sucrose as a carbon source, uniformly mixing the sucrose with the product, placing the mixture into a 50mL crucible, placing the crucible into a 5L/min tubular furnace protected by nitrogen, heating to 600 ℃, and then preserving heat for 8 hours. And obtaining the carbon-compounded lithium manganese iron phosphate.
The material was assembled into a battery and the ultimate compacted density was measured to be 2.42g/cm3The gram capacity is 151 mAh.
Example 7
An aqueous solution containing 150g/L of manganese chloride (tetrahydrate), ferrous sulfate (heptahydrate) and nickel sulfate (hexahydrate) was prepared in a molar ratio of Mn, Fe and Ni of 85: 15: 5, and the total volume was 5000mL, and the molar amount of manganese chloride, ferrous sulfate and nickel sulfate was 3.55mol per mole of metal, and the solution was designated as "liquid A-7".
Using 420g ammonium dihydrogen phosphate as a phosphorus source and a nitrogen source (3.65mol), dissolving in 1000g water, using 10M sodium hydroxide as a pH regulating reagent, stirring, synchronously adding liquid A-7 and ammonium dihydrogen phosphate into a reaction kettle at the temperature of 55 +/-5 ℃, and controlling the pH to be 5 +/-0.2 by regulating the adding speed of a sodium hydroxide phase. After the addition, the reaction was terminated by maintaining the temperature for 8 hours.
The precipitate obtained above was filtered, washed with deionized water, and dried in a 60 degree oven to yield about 620g of product. SEM shows that the resulting product has a lamellar structure (FIG. 6g) and XRD examination shows NH as a pure phase4Mn0.8Fe0.15Ni0.05PO4·H2O and a Mn/Fe/Ni molar ratio of 81/15/4 (Table 1) as determined by EDX.
15g of NH are weighed4Mn0.8Fe0.15Ni0.05PO4·H2O (0.081mol), 10g (0.236mol) of lithium chloride powder, 2g (0.034mol) of sodium chloride powder and 2g (0.027mol) of potassium chloride powder are mixed uniformly, placed in a 50mL crucible, placed in a 5L/min tubular furnace protected by nitrogen, heated to 300 ℃ and then kept warm for 12 hours.
The product was washed with water and dried to yield about 12.5g of product. Selecting 0.5g of sucrose as a carbon source, uniformly mixing the sucrose with the product, placing the mixture into a 50mL crucible, placing the crucible into a 5L/min tubular furnace protected by nitrogen, heating to 600 ℃, and then preserving heat for 8 hours. And obtaining the carbon-compounded lithium manganese iron phosphate.
The material was assembled into a battery and the ultimate compacted density was measured to be 2.42g/cm3The gram capacity is 144 mAh.
Example 8
An aqueous solution containing 150g/L of manganese chloride (tetrahydrate), ferrous sulfate (heptahydrate) and zinc sulfate (monohydrate) was prepared in a molar ratio of Mn, Fe and Zn of 70: 15, and the total volume was 5000mL, and the molar amount of manganese chloride, ferrous sulfate and zinc sulfate was 3.84mol per mole of metal, and the solution was designated as "liquid A-8".
450g of ammonium dihydrogen phosphate is taken as a phosphorus source and a nitrogen source (3.9mol), the ammonium dihydrogen phosphate is dissolved in 1000g of water, sodium hydroxide with the concentration of 10M is taken as a pH regulating reagent, liquid A-8 and the ammonium dihydrogen phosphate are synchronously added into a reaction kettle with the temperature of 55 +/-5 ℃ under stirring, and the pH is controlled to be 6 +/-0.2 by regulating the adding speed of a sodium hydroxide phase. After the addition, the reaction was terminated by maintaining the temperature for 8 hours.
The precipitate obtained above was filtered and then deionizedWater washed and dried in a 60 degree oven to yield about 640g of product. SEM shows that the obtained product has a lamellar structure (FIG. 6h), and XRD detection shows that the product is pure-phase NH4Mn0.7Fe0.15Zn0.15PO4·H2O and a Mn/Fe/Zn molar ratio of 72/12/16 (Table 1) as determined by EDX.
15g of NH are weighed4Mn0.7Fe0.15Zn0.15PO4·H2O (0.080mol), 10g (0.236mol) of lithium chloride powder, 2g (0.034mol) of sodium chloride powder and 2g (0.027mol) of potassium chloride powder are uniformly mixed, placed in a 50mL crucible, placed in a 5L/min nitrogen-protected tube furnace, heated to 300 ℃, and then kept warm for 12 hours.
The product was washed with water and dried to give about 11g of product. Selecting 0.5g of sucrose as a carbon source, uniformly mixing the sucrose with the product, placing the mixture into a 50mL crucible, placing the crucible into a 5L/min tubular furnace protected by nitrogen, heating to 600 ℃, and then preserving heat for 8 hours. And obtaining the carbon-compounded lithium manganese iron phosphate.
The material was assembled into a battery and the ultimate compacted density was measured to be 2.35g/cm3The gram capacity is 131 mAh.
Example 9
An aqueous solution of 86g/L of manganese chloride (tetrahydrate), ferrous sulfate (heptahydrate), magnesium chloride (hexahydrate) and zinc acetate (dihydrate) is prepared according to the molar ratio of Mn, Fe, Mg and Zn of 70: 20: 5, the total volume of the aqueous solution is 5000mL, the molar amount of the metal is 2.00mol, and the solution is marked as liquid A-9.
230g of ammonium dihydrogen phosphate is taken as a phosphorus source and a nitrogen source (2mol), dissolved in 800g of water, potassium hydroxide with the concentration of 2M is taken as a pH regulating reagent, liquid A-9 and the ammonium dihydrogen phosphate are synchronously added into a reaction kettle with the temperature of 45 +/-5 ℃ under stirring, and the pH is controlled to be 4.5 +/-0.2 by regulating the adding speed of a potassium hydroxide phase. After the addition was completed, the reaction was terminated by maintaining the temperature for 12 hours.
The precipitate obtained above was filtered, washed with deionized water, and dried in an oven at 60 ℃ to give about 340g of the product. XRD detection shows that the NH is pure phase4Mn0.7Fe0.2Mg0.05Zn0.05PO4·H2O, SEM showed the morphology to be lamellar.
The product was washed with water and dried to obtain about 1g of NH weighed out in an amount of 15g4Mn0.7Fe0.2Mg0.05Zn0.05PO4·H2O (0.081mol), 10g (0.236mol) of lithium chloride powder, 2g (0.034mol) of sodium chloride powder and 2g (0.027mol) of potassium chloride powder are mixed uniformly, placed in a 50mL crucible, placed in a 5L/min tubular furnace protected by nitrogen, heated to 300 ℃ and then kept warm for 12 hours.
3.7g of product. Selecting 0.7g of sucrose as a carbon source, uniformly mixing the sucrose with the product, placing the mixture into a 50mL crucible, placing the crucible into a 5L/min tubular furnace protected by nitrogen, heating to 600 ℃, and then preserving heat for 8 hours. And obtaining the carbon-compounded lithium manganese iron phosphate.
The material was assembled into a battery and the ultimate compacted density was measured to be 2.4g/cm3The gram capacity was 147mAh, the 0.1C discharge curve of the product, as shown in FIG. 7.
Example 10
An aqueous solution containing 111g/L of manganese chloride (tetrahydrate), ferrous sulfate (heptahydrate), cobalt acetate (tetrahydrate) and nickel chloride (hexahydrate) was prepared in a molar ratio of Mn, Fe, Co and Ni of 65: 25: 5, and the total volume was 3000mL, and the molar amount of metal was 1.50mol, and the solution was designated as solution A-10.
Dissolving 200g of diammonium hydrogen phosphate (1.51mol) as a phosphorus source and a nitrogen source in 500g of water, taking Sanjian with the concentration of 10M as a pH regulating reagent, synchronously adding liquid A-10 and diammonium hydrogen phosphate into a reaction kettle at the temperature of 55-60 ℃ while stirring, and controlling the pH to be 5.5 +/-0.2 by regulating the adding speed of hydrochloric acid. After the addition, the reaction was terminated by maintaining the temperature for 6 hours.
The precipitate obtained above was filtered, washed with deionized water and dried in an oven at 60 ℃ to give about 247g of the product. XRD detection shows pure-phase NH4Mn0.65Fe0.25Co0.05Ni0.05PO4·H2O, SEM showed the morphology to be lamellar.
25g of NH were weighed4Mn0.65Fe0.25Co0.05Ni0.05PO4·H2O (0.134mol), 20g (0.526mol) of lithium chloride powder, 5g (0.085mol) of sodium chloride powder and 5g (0.067mol) of potassium chloride powder are mixed uniformly, placed in a 100mL porcelain boat, placed in a tube furnace protected by nitrogen at 8L/min, heated to 350 ℃ and then kept warm for 18 hours.
The product was washed with water and dried to yield about 17.5g of product. Selecting 1.4g of lactose as a carbon source, uniformly mixing the lactose with the product, placing the mixture in a 50mL crucible, placing the crucible in a tubular furnace protected by nitrogen at 8L/min, heating to 680 ℃, and then preserving the heat for 3 hours. And obtaining the carbon-compounded lithium manganese iron phosphate.
The material was assembled into a battery and the ultimate compacted density was measured to be 2.45g/cm3The gram capacity is 149 mAh.
Example 11
Manganese chloride (tetrahydrate), ferrous chloride (tetrahydrate), magnesium chloride (hexahydrate), calcium chloride (hexahydrate) and cobalt acetate (tetrahydrate) are prepared into aqueous solution with the content of 204g/L according to the molar ratio of Mn to Fe to Mg to Ca to Co of 70 to 15 to 5, the total volume is 5000mL, the molar amount of metal is 5.0mol, and the solution is recorded as liquid A-11.
580g of 85% phosphoric acid (5.03mol) is used as a phosphorus source, 631g of 28% ammonia water (5.05mol) is used as a nitrogen source, 10M sodium hydroxide is used as a pH regulating reagent, liquid A-11, the phosphoric acid and the ammonia water are synchronously added into a reaction kettle at the temperature of 70-75 ℃ under stirring, and the pH is controlled to be 8.0 by regulating the adding speed of the sodium hydroxide relative to the liquid A-1. After the addition, the reaction was terminated by maintaining the temperature for 3 hours.
The precipitate obtained above was filtered, washed with deionized water, and dried in a 60 degree oven to give about 880g of product. XRD detection shows pure-phase NH4Mn0.7Fe0.15Mg0.05Ca0.05Co0.05PO4·H2O, SEM showed the morphology to be lamellar.
20g of NH are weighed4Mn0.7Fe0.15Mg0.05Ca0.05Co0.05PO4·H2O (0.109mol), 20g (0.526mol) of lithium chloride powder and 10g (0.134mol) of potassium chloride powder were mixedAfter the mixture is uniform, the mixture is placed in a porcelain boat of 100mL, placed in a tube furnace protected by nitrogen at the rate of 7L/min, heated to 380 ℃ and then kept for 24 hours.
The product was washed with water and dried to give about 15.1g of product. Selecting 1.0g of cellulose as a carbon source, uniformly mixing the carbon source with the product, placing the mixture in a 50mL crucible, placing the crucible in a 10L/min tubular furnace protected by nitrogen, heating to 700 ℃, and then preserving heat for 2 hours. And obtaining the carbon-compounded lithium manganese iron phosphate.
The material was assembled into a battery and the ultimate compacted density was measured to be 2.55g/cm3The gram capacity is 133 mAh.
Example 12
An aqueous solution (saturated solution) containing 390g/L of manganese chloride (tetrahydrate), ferrous chloride (tetrahydrate) and cobalt acetate (tetrahydrate) was prepared in a molar ratio of Mn, Fe and Mg of 85: 5: 10, and the total volume was 4000mL, and the molar amount of manganese chloride, ferrous chloride and cobalt acetate was 7.72mol per mol of metal, and the solution was designated as liquid A-12.
900g of 85 percent phosphoric acid (7.81mol) is taken as a phosphorus source, 1.7kg of ammonium chloride (8.0mol) aqueous solution with the concentration of 25 percent by weight is taken as a nitrogen source, 10M sodium hydroxide is taken as a pH regulating reagent, liquid A-12, the phosphoric acid and the ammonium chloride are synchronously added into a reaction kettle with the temperature range of 80-90 ℃ under stirring, and the pH is controlled to be 7.5 by regulating the adding speed of the sodium hydroxide relative to the liquid A-1. After the addition, the reaction was terminated by maintaining the temperature for 1 hour.
The precipitate obtained above was filtered, washed with deionized water, and dried in an oven at 60 ℃ to obtain about 1.35kg of the product. XRD detection shows pure-phase NH4Mn0.85Fe0.05Mg0.1PO4·H2O, SEM showed the morphology to be lamellar.
50g of NH are weighed4Mn0.85Fe0.05Mg0.1PO4·H2O (0.273mol), 50g (1.32mol) of lithium chloride powder and 50g (0.67mol) of potassium chloride powder are mixed uniformly, placed in a 300mL porcelain boat, placed in a 10L/min nitrogen-protected tube furnace, heated to 300 ℃ and then kept warm for 24 hours.
The product was washed with water and dried to yield about 39.2g of product. Selecting 6g of glucose as a carbon source, uniformly mixing the carbon source with the product, placing the mixture in a 100mL crucible, placing the crucible in a 10L/min tubular furnace protected by nitrogen, heating to 550 ℃, and then preserving heat for 12 hours. And obtaining the carbon-compounded lithium manganese iron phosphate.
The material was assembled into a battery and the ultimate compacted density was measured to be 2.41g/cm3The gram capacity is 141mAh, and the average discharge voltage reaches 3.89V.
TABLE 1 EDX analysis results of molar ratios of respective elements of examples 1 to 8
| Examples | Element(s) | Ratio of |
| 1 | Mn∶Fe | 1∶1 |
| 2 | Mn∶Fe | 4.08∶1 |
| 3 | Mn∶Fe | 7∶0.99 |
| 4 |
Mn∶ |
9∶1.1 |
| 5 | Mn∶Fe∶Mg | 81∶13∶6 |
| 6 |
Mn∶ |
80∶13∶6 |
| 7 | Mn∶Fe∶Ni | 81∶15∶4 |
| 8 | Mn∶Fe∶Zn | 72∶12∶16 |
Claims (10)
1. An intermediate for forming a lithium iron manganese phosphate material having the formula:
(NH4)Mn1-x-yFexMyPO4·H2O，
wherein x is 0.05-0.5 and y is 0-0.2;
m is divalent metal and is selected from one or more of Mg, Ca, Co, Mn and Zn;
the intermediate has a crystal structure in an orthogonal structure, belongs to a Pmnm (59) space group, and has a two-dimensional nano sheet structure in the appearance.
2. Intermediate according to claim 1, characterized in that x is between 0.07 and 0.45, preferably between 0.09 and 0.40, preferably between 0.11 and 0.35, most preferably between 0.13 and 0.30, preferably between 0.15 and 0.25; y is from 0.01 to 0.18, preferably from 0.03 to 0.16, preferably from 0.05 to 0.14, particularly preferably from 0.07 to 0.12, particularly preferably from 0.09 to 0.10.
3. The intermediate of claim 1, which is selected from the group consisting of: NH (NH)4Mn0.5Fe0.5PO4·H2O；NH4Mn0.80Fe0.2PO4·H2O；NH4Mn0.875Fe0.125PO4·H2O；NH4Mn0.9Fe0.1PO4·H2O；NH4Mn0.8Fe0.15Mg0.05PO4·H2O；NH4Mn0.8Fe0.15Co0.05PO4·H2O；NH4Mn0.8Fe0.15Ni0.05PO4·H2O；NH4Mn0.7Fe0.15Zn0.15PO4·H2O；NH4Mn0.7Fe0.2Mg0.05Zn0.05PO4·H2O；NH4Mn0.65Fe0.25Co0.05Ni0.05PO4·H2O；NH4Mn0.7Fe0.15Mg0.05Ca0.05Co0.05PO4·H2O；NH4Mn0.85Fe0.05Mg0.1PO4·H2O or a mixture of two or more thereof in any ratio.
4. A method of making the intermediate of any one of claims 1-3, comprising:
a) preparing an aqueous solution containing Mn, Fe and M according to the stoichiometric amount to obtain a solution A;
b) synchronously dropwise adding a phosphorus source, a nitrogen source and the liquid A into a reaction kettle, controlling the pH to be between 3.0 and 8.0 in the dropwise adding process, and controlling the temperature to be between room temperature and 90 ℃ to obtain a suspension B, wherein the nitrogen source is selected from ammonia water, ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium nitrate, ammonium dihydrogen phosphate, ammonium monohydrogen phosphate, ammonium phosphate or a mixture of two or more of the ammonium phosphate and the ammonium dihydrogen phosphate in any proportion;
c) optionally aging to give the intermediate.
5. The method of claim 4, wherein said Mn, Fe, and M are formed from their respective metal salts in water; the metal salts are their respective sulfates, chlorides, nitrates, acetates or mixtures thereof;
the concentration of the liquid A is between 10g/L and the saturated solution, preferably between 20 and 220g/L, more preferably between 50 and 200g/L, preferably between 80 and 180g/L, most preferably between 100 and 160g/L, and preferably between 120 and 140 g/L.
6. A process according to claim 4 or 5, characterized in that the pH during the dropwise addition is controlled between 4.0 and 7.5, preferably between 5.0 and 7.0, more preferably between 4.5 and 6.5;
the phosphorus source is selected from an aqueous solution of phosphoric acid having a concentration of between 5 and 85% wt, preferably between 15 and 75% wt, more preferably between 25 and 65% wt, a water soluble dihydrogen phosphate, a water soluble monohydrogen phosphate, a water soluble phosphate or a mixture thereof having a concentration of between 5% wt and a saturated solution, preferably between 10% wt and a saturated solution.
7. A lithium iron manganese phosphate having the general formula:
LiaMn1-x-yFexMyPO4/kC
wherein, a is 0.85-1.15, x is 0.05-0.5, and y is 0-0.2;
m is one or more doping elements selected from Mg, Ca, Co, Mn and Zn;
k is the amount of carbon element based on the total weight of other elements in the lithium manganese iron phosphate and is 1-8 wt%;
it is prepared by the following method:
i) providing an intermediate as claimed in any one of claims 1 to 3;
ii) mixing the intermediate with a molten lithium salt in an inert atmosphere to obtain a lithium iron manganese phosphate material;
and iii) mixing the obtained lithium iron manganese phosphate material with a carbohydrate carbon source, and performing heat treatment in an inert atmosphere to obtain the carbon-compounded lithium iron manganese phosphate material.
8. The lithium iron manganese phosphate of claim 7, wherein: the lithium salt is selected from lithium chloride, sodium chloride, potassium chloride, strontium chloride or a mixture of two or more of the foregoing;
the carbohydrate carbon source is selected from one or more of glucose, sucrose, galactose, lactose, polydextrose and cellulose, and is preferably glucose or sucrose.
9. The lithium iron manganese phosphate of claim 7 or 8, wherein:
heating the mixture of the intermediate and the lithium salt to 150-450 ℃ under the inert gas atmosphere, preferably to 180-430 ℃, more preferably to 200-400 ℃, preferably to 220-380 ℃, and preferably to 250-350 ℃; keeping the temperature for 2 to 12 hours, preferably 3 to 11 hours, more preferably 4 to 10 hours, preferably 5 to 9 hours, and preferably 6 to 8 hours;
the obtained lithium iron manganese phosphate material is mixed with a carbohydrate carbon source, and then is subjected to heat treatment for 2 to 15 hours, preferably 3 to 12 hours, preferably 4 to 10 hours, and preferably 5 to 8 hours at the temperature of 450-700 ℃, preferably 480-680 ℃, more preferably 550-650 ℃, preferably 580-620 ℃ in an inert atmosphere.
10. Use of lithium iron manganese phosphate according to any one of claims 7 to 9 in a lithium ion battery.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113078308A (en) * | 2021-06-04 | 2021-07-06 | 蜂巢能源科技有限公司 | Cobalt-free and nickel-free positive electrode material, preparation method thereof and battery |
| CN115636402A (en) * | 2022-10-28 | 2023-01-24 | 深圳市德方纳米科技股份有限公司 | Lithium manganese iron phosphate material and preparation method and application thereof |
| CN116835560A (en) * | 2023-08-28 | 2023-10-03 | 合肥国轩高科动力能源有限公司 | Lithium iron manganese phosphate composite material, preparation method thereof and positive electrode plate |
| CN116924377A (en) * | 2023-09-18 | 2023-10-24 | 宁波容百新能源科技股份有限公司 | Ammonium ferromanganese phosphate, lithium ferromanganese phosphate, and preparation methods and applications thereof |
Citations (1)
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| WO2013038517A1 (en) * | 2011-09-14 | 2013-03-21 | 住友金属鉱山株式会社 | Manganese iron magnesium ammonium phosphate, method for producing same, positive electrode active material for lithium secondary batteries using manganese iron magnesium ammonium phosphate, method for producing same, and lithium secondary battery using said positive electrode active material |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2013038517A1 (en) * | 2011-09-14 | 2013-03-21 | 住友金属鉱山株式会社 | Manganese iron magnesium ammonium phosphate, method for producing same, positive electrode active material for lithium secondary batteries using manganese iron magnesium ammonium phosphate, method for producing same, and lithium secondary battery using said positive electrode active material |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113078308A (en) * | 2021-06-04 | 2021-07-06 | 蜂巢能源科技有限公司 | Cobalt-free and nickel-free positive electrode material, preparation method thereof and battery |
| CN115636402A (en) * | 2022-10-28 | 2023-01-24 | 深圳市德方纳米科技股份有限公司 | Lithium manganese iron phosphate material and preparation method and application thereof |
| CN115636402B (en) * | 2022-10-28 | 2024-04-16 | 深圳市德方纳米科技股份有限公司 | Lithium iron manganese phosphate material and preparation method and application thereof |
| CN116835560A (en) * | 2023-08-28 | 2023-10-03 | 合肥国轩高科动力能源有限公司 | Lithium iron manganese phosphate composite material, preparation method thereof and positive electrode plate |
| CN116835560B (en) * | 2023-08-28 | 2024-01-23 | 合肥国轩高科动力能源有限公司 | Lithium iron manganese phosphate composite material, preparation method thereof and positive electrode plate |
| CN116924377A (en) * | 2023-09-18 | 2023-10-24 | 宁波容百新能源科技股份有限公司 | Ammonium ferromanganese phosphate, lithium ferromanganese phosphate, and preparation methods and applications thereof |
| CN116924377B (en) * | 2023-09-18 | 2024-01-02 | 宁波容百新能源科技股份有限公司 | Ammonium ferromanganese phosphate, lithium ferromanganese phosphate, and preparation methods and applications thereof |
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