CN106816582A - A kind of iron manganese phosphate for lithium class material and preparation method thereof and cell size and positive pole and lithium battery - Google Patents
A kind of iron manganese phosphate for lithium class material and preparation method thereof and cell size and positive pole and lithium battery Download PDFInfo
- Publication number
- CN106816582A CN106816582A CN201510860701.7A CN201510860701A CN106816582A CN 106816582 A CN106816582 A CN 106816582A CN 201510860701 A CN201510860701 A CN 201510860701A CN 106816582 A CN106816582 A CN 106816582A
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- CN
- China
- Prior art keywords
- manganese phosphate
- lithium iron
- iron manganese
- lithium
- phosphate material
- Prior art date
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- 239000000463 material Substances 0.000 title claims abstract description 246
- 238000002360 preparation method Methods 0.000 title claims abstract description 55
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 30
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 title claims abstract 8
- 150000002641 lithium Chemical class 0.000 title abstract 7
- 239000002245 particle Substances 0.000 claims abstract description 93
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 28
- 239000011572 manganese Substances 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- 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 claims description 209
- 239000002002 slurry Substances 0.000 claims description 95
- 230000001804 emulsifying effect Effects 0.000 claims description 38
- 239000011164 primary particle Substances 0.000 claims description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- 230000006698 induction Effects 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 239000007774 positive electrode material Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 239000011163 secondary particle Substances 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 4
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 20
- 238000011056 performance test Methods 0.000 description 17
- 229910015645 LiMn Inorganic materials 0.000 description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 15
- 238000001694 spray drying Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 230000002829 reductive effect Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 230000009286 beneficial effect Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 7
- 240000001085 Trapa natans Species 0.000 description 7
- 238000005056 compaction Methods 0.000 description 7
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 235000009165 saligot Nutrition 0.000 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 description 6
- 239000008103 glucose Substances 0.000 description 6
- 239000011656 manganese carbonate Substances 0.000 description 6
- 229940093474 manganese carbonate Drugs 0.000 description 6
- 235000006748 manganese carbonate Nutrition 0.000 description 6
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 6
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 6
- 238000003801 milling Methods 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000005955 Ferric phosphate Substances 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 4
- 229940032958 ferric phosphate Drugs 0.000 description 4
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 4
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 4
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 3
- 229930006000 Sucrose Natural products 0.000 description 3
- 238000007600 charging Methods 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 229910000398 iron phosphate Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- 229960004793 sucrose Drugs 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- -1 polyparaphenylene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NRKQBMOGOKEWPX-UHFFFAOYSA-N vanadyl nitrate Chemical compound [O-][N+](=O)O[V](=O)(O[N+]([O-])=O)O[N+]([O-])=O NRKQBMOGOKEWPX-UHFFFAOYSA-N 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910004761 HSV 900 Inorganic materials 0.000 description 1
- 229910004764 HSV900 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- IHWJXGQYRBHUIF-UHFFFAOYSA-N [Ag].[Pt] Chemical compound [Ag].[Pt] IHWJXGQYRBHUIF-UHFFFAOYSA-N 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 1
- IUYLTEAJCNAMJK-UHFFFAOYSA-N cobalt(2+);oxygen(2-) Chemical compound [O-2].[Co+2] IUYLTEAJCNAMJK-UHFFFAOYSA-N 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
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- REKWWOFUJAJBCL-UHFFFAOYSA-L dilithium;hydrogen phosphate Chemical compound [Li+].[Li+].OP([O-])([O-])=O REKWWOFUJAJBCL-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229920005546 furfural resin Polymers 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 description 1
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 1
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000159 nickel phosphate Inorganic materials 0.000 description 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- WIWVNQBYNTWQOW-UHFFFAOYSA-L oxovanadium(2+);diacetate Chemical compound [V+2]=O.CC([O-])=O.CC([O-])=O WIWVNQBYNTWQOW-UHFFFAOYSA-L 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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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- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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Abstract
The invention discloses a kind of iron manganese phosphate for lithium class material and preparation method thereof and positive pole and lithium battery.Wherein, the iron manganese phosphate for lithium class material has LiMnxFe1-x-yMyPO4/ C-structure, wherein 0≤x≤1,0≤y≤1, M is the transition metal in addition to Mn and Fe, the particle diameter D of the iron manganese phosphate for lithium class material50It is 0.5-1.0 μm, D90Be 1.0-5.0 μm, and the iron manganese phosphate for lithium class material cohesive force Cohesive≤1.5kPa.Smaller (the particle diameter D of particle diameter of this iron manganese phosphate for lithium class material50It is 0.5-1.0 μm, D90It is 1.0-5.0 μm), cohesive force is also smaller (Cohesive≤1.5kPa).Be conducive to improving the volume and capacity ratio of lithium battery using the positive electrode prepared by this iron manganese phosphate for lithium class material, and then improve the cruising time of battery.
Description
Technical Field
The invention relates to the field of preparation of anode materials, in particular to a lithium manganese iron phosphate material, a preparation method of the lithium manganese iron phosphate material, battery slurry comprising the lithium manganese iron phosphate material, an anode comprising the lithium manganese iron phosphate material and a lithium battery comprising the anode.
Background
The lithium ion secondary battery is a novel green high-energy rechargeable battery, has the advantages of high voltage, large energy density, good cycle performance, small self-discharge, no memory effect, wide working range and the like, is widely applied to mobile phones, notebook computers, portable electric tools, electronic instruments, weaponry and the like, also has good application prospect in electric automobiles, and has become the key point of competitive research and development of all countries in the world at present. The positive electrode material is an important component of the lithium ion battery, and not only lithium required for reciprocating insertion/extraction in positive and negative lithium insertion compounds but also lithium required for forming an SEI film on the surface of the negative electrode material are required to be provided in the charge and discharge processes of the lithium ion battery, so that research and development of the high-performance positive electrode material are key points in the development of the lithium ion battery.
In the lithium ion battery anode material, the lithium iron manganese phosphate material has the best comprehensive performance, and is considered as an ideal lithium ion secondary power battery anode material. At present, the phosphate material is mainly prepared by a high-temperature solid-phase method, and the high-temperature solid-phase method generally comprises the steps of grinding to form slurry containing primary particles, and then drying and sintering the slurry containing the primary particles to form the lithium iron manganese phosphate material.
In order to further optimize the quality of the phosphate material produced, researchers are constantly improving the processes for producing phosphate materials. For example, chinese patent No. cn201210087676.x discloses a method for preparing high-density spherical lithium iron phosphate, which comprises the following steps: lithium compounds, iron compounds, phosphates, doped metal compounds and carbon black are taken as raw materials and added into a ball mill for wet mixing; spray-drying, and adding N2Pre-burning in a roasting furnace as protective gas; then adding adhesive polyvinyl alcohol to carry out wet mixing again, carrying out spray drying, and placing in a container filled with N2And (4) carrying out secondary roasting by using the roasting furnace as protective gas to prepare and form the lithium iron phosphate material.
In the prior art, although a plurality of preparation methods of the lithium iron manganese phosphate material are provided, a plurality of lithium iron manganese phosphate materials obtained based on different preparation methods are also provided. However, in order to meet the requirements of social development on the endurance time of battery materials or the high-temperature capacity retention rate, further research on the lithium iron manganese phosphate material and the preparation method thereof is needed.
Disclosure of Invention
The invention aims to provide a lithium manganese iron phosphate material, a preparation method thereof, a battery slurry, a positive electrode material and a lithium battery, so as to provide the lithium manganese iron phosphate material with small particle size and low cohesion, further improve the volume specific capacity of the lithium battery comprising the positive electrode material made of the lithium manganese iron phosphate material, and further improve the standby time of the battery.
In order to achieve the above object, according to a first aspect of the present invention, there is provided a lithium iron manganese phosphate-based material having LiMnxFe1-x-yMyPO4A structure of/C, wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, M is a transition metal element except Mn and Fe, and the particle size D of the lithium iron manganese phosphate material500.5-1.0 μm, D90Is 1.0-5.0 μm, and the cohesion Cohesive of the lithium iron manganese phosphate material is less than or equal to 1.5 kPa.
According to a second aspect of the present invention, there is provided a preparation method of a lithium iron manganese phosphate material, the preparation method comprising the steps of: grinding and mixing a lithium source, an optional manganese source, an optional iron source, an optional M source, a phosphorus source and a carbon source in proportion to obtain slurry containing primary particles; the slurry containing the primary particles sequentially passes through a first chamber with pressure of P1 and a second chamber with pressure of P2 to obtain refined slurry, wherein P1 is more than or equal to 4000Psi, and P1 is more than 3 times of P2; and sequentially drying and sintering the refined slurry to obtain secondary particles, namely the lithium iron manganese phosphate material.
According to a third aspect of the invention, a lithium iron manganese phosphate material is provided, which is prepared by the preparation method.
According to a fourth aspect of the present invention, a battery slurry is provided, which includes a lithium iron manganese phosphate material and a solvent, where the lithium iron manganese phosphate material is the above-mentioned lithium iron manganese phosphate material of the present invention.
According to a fifth aspect of the present invention, there is provided a positive electrode comprising a current collector and a positive active material layer disposed on the current collector, the positive active material layer comprising the lithium iron manganese phosphate-based material of the present invention.
According to a sixth aspect of the present invention, there is provided a lithium battery having a positive electrode provided therein, the positive electrode being the positive electrode of the present invention.
The lithium iron manganese phosphate material, the preparation method thereof, the battery slurry, the anode material and the lithium battery provided by the invention have the advantages that the particle size of the lithium iron manganese phosphate material is small (the particle size D is small)500.5-1.0 μm, D901.0-5.0 μm), and the Cohesive force is also small (Cohesive is less than or equal to 1.5 kPa). The positive electrode material prepared from the lithium manganese iron phosphate material is beneficial to improving the volume specific capacity of a lithium battery, and further improving the endurance time of the battery.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
fig. 1 shows a 2.00 μm Scanning Electron Microscope (SEM) spectrum of a lithium iron manganese phosphate-based material prepared according to example 1 of the present invention;
fig. 2 shows a 2.00 μm Scanning Electron Microscope (SEM) spectrum of the lithium iron manganese phosphate-based material prepared according to comparative example 1.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
As indicated in the background section, in order to meet the social needs, the specific volume capacity of the battery needs to be further improved, and the standby time of the battery needs to be further prolonged. Therefore, the inventor of the invention provides a novel lithium manganese iron phosphate material, and the lithium manganese iron phosphate material has LiMnxFe1-x-yMyPO4A structure of/C, wherein 0. ltoreq. x.ltoreq.1 (preferably 0.5. ltoreq. x.ltoreq.1), 0. ltoreq. y.ltoreq.1 (preferably 0. ltoreq. y.ltoreq.0.5), M is a transition metal element (preferably M is one or more of Co, Ni, Mg, Zn, V and Ti) other than Mn and Fe, and the particle diameter D of the lithium iron manganese phosphate-based material is500.5-1.0 μm, D90Is 1.0-5.0 μm, and the cohesion Cohesive of the lithium iron manganese phosphate material is less than or equal to 1.5 kPa.
The lithium iron manganese phosphate material has LiMnxFe1-x-yMyPO4The structure of/C means that the alloy has carbon-coated LiMnxFe1-x- yMyPO4The structure of the particles. The lithium iron manganese phosphate material has a small particle size (particle size D)500.5-1.0 μm, D901.0-5.0 μm), and the Cohesive force is also small (Cohesive is less than or equal to 1.5 kPa). The positive electrode is prepared from the lithium manganese iron phosphate material, so that the volume specific capacity of a lithium battery comprising the positive electrode is favorably improved, and the endurance time of the battery is further improved.
In the present invention, among them, the particle diameter D50And D90The volume average particle size is obtained by dispersing powder to be tested in water, then carrying out ultrasonic oscillation, and carrying out particle size test by using a laser particle size analyzer.
In the lithium iron manganese phosphate material, the specific surface area, the compaction density and the magnetic induction intensity of the lithium iron manganese phosphate material are not particularly required, as long as the particle size D of the lithium iron manganese phosphate material500.5-1.0 μm, D90The particle size is 1.0-5.0 mu m, and the volume specific capacity of the lithium manganese iron phosphate material can be correspondingly improved when the cohesion Cohesive is less than or equal to 1.5 kPa. However, in order to further optimize and improve the specific volume capacity or high-temperature capacity retention rate of the lithium battery, the lithium iron manganese phosphate material preferably meets the following requirements:
preferably, the particle size D of the lithium iron manganese phosphate-based material500.5-0.8 μm, D90Is 1.0-3.0 μm, and the cohesion Cohesive of the lithium iron manganese phosphate material is less than or equal to 1.2 kPa. Optimizing the particle size and the cohesion of the lithium iron manganese phosphate material within the range is beneficial to improving the compaction density of the material.
Preferably, the specific surface area S of the lithium iron manganese phosphate material is 12m2/g≤S≤28m2A/g, preferably of 15m2/g≤S≤25m2(ii) in terms of/g. Optimizing the specific surface area of the lithium iron manganese phosphate material within the range is beneficial to improving the surface activity of the material under the condition of not influencing the compaction performance of the material.
Preferably, the compacted density of the lithium iron manganese phosphate material is 2.0g/cm3-2.68g/cm3Preferably 2.2g/cm3-2.55g/cm3. Optimizing the compaction density of the lithium iron manganese phosphate material in the range is beneficial to improving the volume energy density of the lithium battery, and ensuring the pore density of the electrode application and the smoothness of a lithium ion diffusion channel.
Preferably, the magnetic induction intensity of the lithium iron manganese phosphate material is 800-1100ppm, preferably 950-1050 ppm. Optimizing the magnetic induction intensity of the lithium iron manganese phosphate material in the range is beneficial to improving the charge and discharge capacity of the lithium battery. The magnetic induction intensity of the lithium iron manganese phosphate material is tested by adopting a magnetic analyzer MA1040 of a microphone instrument. The testing method comprises the steps of filling lithium iron manganese phosphate material powder into a sample cup (the height of a sample is 12cm), and measuring the magnetic strength of 5 different directions to obtain an average value.
In the lithium iron manganese phosphate material, the content of carbon element in the lithium iron manganese phosphate material is not particularly required, and the conventional amount of carbon in the field can be referred. For example, the content of carbon element in the lithium iron manganese phosphate material is 0.1 to 5 wt% of the total amount of the lithium iron manganese phosphate material, and preferably 0.5 to 3.5 wt% of the total amount of the lithium iron manganese phosphate material. Optimizing the carbon content in the lithium iron manganese phosphate material within the range is beneficial to promoting the material to have relatively good conductivity.
In the prior art, there is no suggestion or expectation about the preparation of the lithium iron manganese phosphate material provided by the present invention, and it may be difficult to prepare the lithium iron manganese phosphate material provided by the present invention by directly adopting the conventional method in the prior art. This may be because:
in the process of forming slurry containing primary particles by grinding through the conventional high-temperature solid phase method, because the grinding and mixing effects are poor, the ball-milled material particles are often large, the requirement of the invention on the particle size of the material is difficult to achieve, and the requirement of the invention on the cohesive force of the material is difficult to achieve
Although the chinese patent No. cn201210087676.x adopts the steps of wet mixing, intermediate pre-sintering and re-wet mixing, the mixing method adopted by the method cannot realize the nano-scale mixing of the raw materials, so that the crushing of the sequential particle sizes obtained by the first wet mixing is irregular, which easily causes the problems of more water caltrops, rough and defective material surfaces, large cohesion among particles, and further causes the problems of poor stacking performance of the corresponding materials and low volume capacity of the battery.
Therefore, for the lithium iron manganese phosphate material provided by the invention, the preparation can be performed by referring to a conventional method in the prior art, but the particle size formed in the preparation process of the lithium iron manganese phosphate material needs to be strictly controlled, and the prepared lithium iron manganese phosphate material needs to be strictly screened so as to obtain the lithium iron manganese phosphate material provided by the invention.
However, in order to simplify the preparation method of the lithium iron manganese phosphate material, the invention also provides a preparation method of the lithium iron manganese phosphate material. The preparation method comprises the following steps: grinding and mixing a lithium source, an optional manganese source, an optional iron source, an optional M source, a phosphorus source and a carbon source according to a proportion to obtain slurry containing primary particles; sequentially passing the slurry containing the primary particles through a first chamber with pressure of P1 and a second chamber with pressure of P2 to obtain refined slurry, wherein P1 is more than or equal to 4000Psi, P1 is more than 3 times of P2, preferably P1 is more than 5 times of P2, and preferably P1 is 5-10 times of P2; and sequentially drying and sintering the refined slurry to obtain secondary particles, namely the lithium iron manganese phosphate material.
According to the preparation method of the lithium iron manganese phosphate material, the slurry containing the primary particles obtained by grinding and mixing sequentially passes through the first chamber and the second chamber with large pressure difference, so that the environmental pressure is suddenly reduced from P1 to P2, and the primary particles are simultaneously subjected to mechanical force effects such as high-speed shearing, high-frequency oscillation, cavitation, convection impact and the like in a narrow area of the second chamber along with the sudden release of the pressure energy, so that a strong cavitation effect similar to an explosion effect is generated. The strong comprehensive action not only makes the water caltrops on the surface of the primary particles round and smooth, but also makes the primary particles subjected to ultra-fine treatment. At the moment, the obtained refined slurry can basically keep the appearance of the original particles after high-temperature sintering, only part of raw materials are melted and sintered, so that the surface is smoother, the interaction force among secondary particles is greatly reduced, and the cohesion of the prepared lithium iron manganese phosphate material is reduced. In addition, the grain size of primary particles is greatly reduced through ultra-fine treatment, so that the particles are not easy to generate local segregation and impurities, trace impurities contained in finished product materials are favorably relatively reduced, and the high-temperature capacity storage rate of corresponding lithium batteries is improved.
In the preparation method of the lithium iron manganese phosphate material provided by the invention, the slurry containing the primary particles sequentially passes through the first chamber (with pressure of P1) and the second chamber (with pressure of P2) with suddenly reduced pressure, wherein P1 is not less than 4000Psi, and P1 is more than 3 times of P2. There is no particular requirement for the pressure of the first chamber and the second chamber, the residence time of the slurry containing the primary particles in the first chamber and the second chamber (the time difference between the time when the material enters the chamber and the time when the material exits the chamber), and the flow rate of the slurry containing the primary particles from the first chamber into the second chamber, and they can be adjusted appropriately according to the actual conditions of the selected apparatus. However, in order to further optimize the physical properties of the prepared lithium iron manganese phosphate material, it is preferable that the parameters in the preparation method further satisfy the following requirements:
preferably, P1 in the preparation method is 4000-28000 Psi; preferably P1 is 10000-25000 Psi; setting the difference Δ P of P1 and P1 and P2 within the above range, particularly preferred range, is advantageous in forming strong cavitation. In practical application, for convenience of selecting usable equipment, the P2 is preferably 800-.
Preferably, the slurry containing primary particles flows from the first chamber into the second chamber at a velocity of 2-20 m/s. Limiting the flow rate of the slurry containing primary particles from the first chamber into the second chamber to the above range has the advantage of efficient processing. The velocity of the above-mentioned primary particle-containing slurry flowing from the first chamber into the second chamber can be adjusted by adjusting the cross-sectional area of the passage (cross-sectional area of a cross-section perpendicular to the direction in which the passage extends) between the first chamber and the second chamber.
In a preferred embodiment of the present invention, in the above preparation method, the first chamber is a homogenizing chamber of a high-pressure homogenizer, and the second chamber is an emulsifying chamber of the high-pressure homogenizer. The invention can adopt the existing high-pressure homogenizer which simultaneously comprises a homogenizing cavity and an emulsifying cavity in the prior art, thereby saving the equipment cost.
The invention firstly proposes that a homogenizer which is provided with a homogenizing cavity and an emulsifying cavity simultaneously is used in the preparation process of the lithium iron manganese phosphate material. The homogenizer is selected to be provided with the homogenizing cavity and the emulsifying cavity at the same time, so that the invention can realize that the slurry containing primary particles sequentially passes through the first cavity and the second cavity with larger pressure difference, the homogenizer does not need to be carried out at high temperature, and the purpose of refining the particle size of the primary particles can be achieved only at normal temperature.
By using the homogenizer with the two chambers of the homogenizing chamber and the emulsifying chamber, after the slurry containing primary particles enters the emulsifying chamber from the homogenizing chamber, a strong cavitation effect similar to an explosion effect is generated in a narrow area formed by the valve core, the valve seat and the impact ring in the emulsifying chamber, and simultaneously, the particle size of the particles in the obtained refined slurry is smaller and the surface water caltrops of the particles are ground to be smoother along with the shearing effect generated by the material passing through a slit between the valve core and the valve seat and the high-speed impact effect generated by the impact of the material and the impact of the material with the impact ring, so that the impurities contained in the prepared lithium iron manganese phosphate material are reduced more favorably, and the cohesion of the lithium iron phosphate material is reduced.
In the preparation method of the lithium iron manganese phosphate material provided by the invention, no special requirement is imposed on the particle size of the primary particles, and the requirement on the particle size of the primary particles in the conventional method in the field can be referred. In a preferred embodiment of the present invention, the primary particles have a particle diameter D50Is 50-200nm, and the secondary particle diameter D500.5-1.0 μm, D90Is 1.0-5.0 μm. The particle size of the primary particles is limited in the range, so that the particles are more uniformly mixed and more fully reacted at a subsequent high temperature, and the particle size of the secondary particles is limited in the range, so that the agglomeration phenomenon among the particles is improved, and the compaction density of the material is increased.
In the preparation method of the lithium iron manganese phosphate material provided by the invention, the raw materials and the mixture ratio of the raw materials do not have special requirements, and the material can be formed into the material with L by referring to the conventional method in the fieldiMnxFe1-x-yMyPO4The raw materials and the raw material proportion adopted by the lithium iron manganese phosphate material with the structure of/C are that x is more than or equal to 0 and less than or equal to 1 (preferably x is more than or equal to 0.5 and less than or equal to 1), and y is more than or equal to 0 and less than or equal to 1 (preferably y is more than or equal to 0 and less than or equal to 0.5). In a preferred embodiment of the present invention, the carbon source is added in an amount of 0.5 to 3.5 wt% of the total amount that may remain in the lithium iron manganese phosphate-based material. As with the conventional method in the field, the carbon source added in the invention can be enriched on the surface of the lithium iron manganese phosphate material in the sintering process, so LiMn is formedxFe1-x-yMyPO4A lithium iron manganese phosphate material with a/C structure, namely a carbon-coated structure. Controlling the amount of the carbon source within the above range is advantageous for ensuring the conductivity of the material and reducing the amount of inactive material.
In the preparation method of the lithium iron manganese phosphate material provided by the invention, in the process of grinding and mixing the lithium source, the transition metal source, the phosphorus source and the carbon source according to the proportion, the molar ratio of the lithium source, the manganese source, the iron source and the M source in terms of lithium, the total amount of Mn + Fe + M, and the phosphorus source in terms of phosphorus is (0.95-1.05): 1:1, and mixing.
In the invention, the selection of each raw material is not particularly required, and the conventional materials adopted in the preparation of the lithium iron manganese phosphate material in the field can be referred. Wherein:
lithium sources that may be used include, but are not limited to, one or more of lithium hydroxide, lithium peroxide, lithium oxide, lithium formate, lithium nitrate, lithium carbonate, and lithium iron manganese phosphate.
The phosphorus source that can be used includes, but is not limited to, one or more of phosphoric acid, lithium manganese iron phosphate, lithium monohydrogen phosphate, lithium dihydrogen phosphate, and the corresponding transition metal phosphates.
Iron sources that may be used include, but are not limited to, one or more of ferrous oxide, ferric oxalate, and ferrous acetate.
Manganese sources that may be used include, but are not limited to, one or more of manganese carbonate, manganese phosphate, manganese nitrate, and manganese oxide.
The M source contains one or more compounds selected from the group consisting of Co, Ni, Mg, Zn, V and Ti. Among them, Co-containing compounds that may be used include, but are not limited to, one or more of cobaltosic oxide, cobalt nitrate, cobaltous oxide, cobalt acetate, and cobalt phosphate; ni-containing compounds that may be used include, but are not limited to, one or more of nickel protoxide, nickel oxide, nickel nitrate, nickel acetate, and nickel phosphate; mg-containing compounds that may be used include, but are not limited to, one or more of magnesium oxide, magnesium nitrate, and magnesium acetate; zn-containing compounds that may be used include, but are not limited to, one or more of zinc oxide, zinc nitrate, and zinc acetate; compounds containing V that may be used include, but are not limited to, one or more of vanadia oxide, vanadia pentoxide, vanadia trioxide, vanadyl nitrate, and vanadyl acetate; ti-containing compounds that may be used include, but are not limited to, one or more of titanium dioxide, titanium acetate, and tetrabutyl titanate.
Carbon sources that may be used include, but are not limited to, one or more of triphenylene terpolymers, triphenylene copolymers, phenylanthracene copolymers, polyparaphenylene, soluble starch, polyvinyl alcohol, sucrose, glucose, phenolic resins, furfural resins, artificial graphite, natural graphite, superconducting acetylene black, carbon black, and mesophase carbon globules, or one or more of organic substances that can only have residual carbon by heat treatment in an inert atmosphere.
The process method adopted in the preparation method of the lithium iron manganese phosphate material provided by the invention has no special requirements as long as the corresponding process purpose can be realized. Wherein,
the step of milling and mixing may be carried out by means including, but not limited to, ball milling, sand milling or stirred milling, preferably for a milling time of 1 to 6 hours. In the step of milling and mixing, in order to obtain a slurry containing primary particles, a step of adding a milling liquid including, but not limited to, one or more of deionized water, ethanol, or formaldehyde is further included.
The step of drying the refined slurry may be carried out by a method including, but not limited to, vacuum drying, inert gas protected heating drying, spray drying, freeze drying or flash drying, wherein spray drying is preferred, and the conditions of the spray drying are that the inlet temperature is 200 ℃ to 300 ℃ and the outlet temperature is 95 ℃ to 120 ℃.
In the step of sintering the precursor powder produced by drying, the sintering conditions can refer to the conventional process conditions in the existing method, and the conditions of the sintering treatment in the invention preferably comprise constant-temperature sintering at 650-780 ℃ for 2-20 h. Limiting the sintering conditions within the above range is beneficial to obtaining a more developed crystal form.
Preferably, the invention also provides the lithium iron manganese phosphate material prepared by the preparation method. The lithium iron manganese phosphate material has LiMnxFe1-x-yMyPO4A structure of/C, wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, M is a transition metal element except Mn and Fe, and the particle size D of the lithium iron manganese phosphate material500.5-1.0 μm, D90Is 1.0-5.0 μm, and the cohesion Cohesive of the lithium iron manganese phosphate material is less than or equal to 1.5 kPa.
Preferably, the particle size D of the lithium iron manganese phosphate-based material500.5-0.8 μm, D90Is 1.0-3.0 μm, and the cohesion Cohesive of the lithium iron manganese phosphate material is less than or equal to 1.2 kPa.
Preferably, the specific surface area S of the lithium iron manganese phosphate-based lithium iron manganese phosphate material is 12m2/g≤S≤28m2A/g, preferably of 15m2/g≤S≤25m2/g。
Preferably, the compacted density of the lithium iron manganese phosphate material is 2.0g/cm3-2.68g/cm3Preferably 2.2g/cm3-2.55g/cm3。
Preferably, the magnetic induction intensity of the lithium iron manganese phosphate material is 800-1100ppm, preferably 950-1050 ppm.
Preferably, the content of carbon element in the lithium iron manganese phosphate material is 0.5-3.5 wt% of the total weight of the lithium iron manganese phosphate material.
Preferably, M in the lithium iron manganese phosphate-based material is one or more of Co, Ni, Mg, Zn, V, and Ti.
The lithium iron manganese phosphate material provided by the invention is prepared by the method, and slurry containing primary particles obtained by grinding and mixing sequentially passes through the first chamber and the second chamber with a large pressure difference, so that the environmental pressure is suddenly reduced from P1 to P2, and the primary particles are simultaneously subjected to mechanical force effects such as high-speed shearing, high-frequency oscillation, cavitation, convection impact and the like in a narrow area of the second chamber to generate a strong cavitation effect similar to an explosion effect. Therefore, the surface of the prepared lithium iron manganese phosphate material is smoother, the interaction force among secondary particles is greatly reduced, and the cohesion of the prepared lithium iron manganese phosphate material is reduced. But also reduces the content of impurities in the finished material.
Meanwhile, the invention also provides battery slurry which comprises a lithium manganese iron phosphate material and a solvent, wherein the lithium manganese iron phosphate material is the lithium manganese iron phosphate material. Preferably, the solvent that may be used in the above battery slurry includes, but is not limited to, one or more of water, ethanol, and methanol. The battery slurry also contains a binder and a conductive agent, wherein the raw materials and the use amounts of the binder and the conductive agent can be selected according to the routine selection in the field, for example, the binder can be polyvinylidene fluoride, the conductive agent can be acetylene black, and the weight ratio of the lithium iron manganese phosphate material (positive electrode active material) to the conductive agent and the binder is 80:10: 10.
In the process of preparing the battery slurry, no special requirement is made on the solid content of the battery slurry, and the solid content can be properly selected according to the use requirement of the battery slurry. Generally, the above battery slurry has a solid content of 30 to 60 wt%, preferably 40 to 50 wt%, more preferably 45 to 50 wt%.
In addition, the invention further provides a positive electrode, which comprises a current collector and a positive active material layer arranged on the current collector, wherein the positive active material layer comprises the lithium iron manganese phosphate material. The cathode material provided by the invention is prepared by adopting the battery slurry containing the lithium manganese iron phosphate material, and the cohesion of the lithium manganese iron phosphate material is relatively small, so that the compaction density of the cathode material is favorably improved.
Preferably, the current collector may refer to current collector materials conventionally used in the art, for example, including, but not limited to, silver platinum (Pt), palladium (Pd), aluminum (Al) foil, and the like.
In addition, the invention further provides a lithium battery, wherein a positive electrode is arranged in the lithium battery, and the positive electrode material is the positive electrode. According to the lithium battery provided by the invention, the positive electrode is prepared by adopting the battery slurry containing the lithium iron manganese phosphate material, and the volume energy density of the positive electrode is relatively improved.
The carbon-coated lithium manganese iron phosphate material, the preparation method thereof, the battery slurry and the lithium battery, and the beneficial effects thereof will be further described below by combining specific examples and comparative examples.
The high-pressure homogenizer referred to in the following examples and comparative examples is the german APV high-pressure homogenizer APV 2000.
The test items and test methods referred to in the following examples and comparative examples are as follows:
cohesion: the test was carried out using a FT4 multifunction powder tester manufactured by Dachang Huajia (Freeman Technology Co.), under the test conditions of three pretreatments, an application pressure of 9KPa, and a rotation speed of a paddle of 18 DEG/min
Particle size: and (3) performing ultrasonic dispersion for 10 minutes by adopting a particle size tester of a micro-nano in the Jinan and using deionized water as a dispersing agent.
Specific surface area: the method is characterized in that a gold-Ept V-Sorb2800 device is adopted for testing, and a static method is adopted for pretreating and drying a lithium iron manganese phosphate material sample for 2 hours at the temperature of 150 ℃.
Compacting density: 80 parts by weight of a lithium manganese iron phosphate material sample of the invention: 10 parts by weight of acetylene black (commercially available from Termitial under the name SuperP): 10 parts by weight of PVDF (a product of PVDF HSV900, commercially available from Akema (Normal maturing) fluorine chemical Co., Ltd.) was used as a battery paste, the battery paste was dried at 80 ℃ for 2 hours, the dried battery paste was ground and passed through a 400-mesh screen, 0.3 g of the battery paste was weighed and pressed under 2MPa, the thickness was measured, the volume was calculated from the thickness, and the compaction density was calculated based on the thickness.
Magnetic induction intensity: the test was performed using a microphone instrument magnetic analyzer MA 1040. The testing method comprises the steps of filling lithium iron manganese phosphate material powder into a sample cup (the height of a sample is 12cm), and measuring the magnetic strength of 5 different directions to obtain an average value.
Examples 1 to 12
The lithium iron manganese phosphate material and the preparation method thereof of the present invention will be described.
Example 1
(1) Lithium iron manganese phosphate material (LiMn)0.5Fe0.5PO4The preparation method of the/C) comprises the following steps:
0.5mol of phosphoric acid (the concentration is 85 wt%) is weighed and dissolved in 1L of deionized water, 57.47 g of manganese carbonate, 75.41 g of iron phosphate and 19.3 g of glucose (2.5 wt% can be remained) are weighed and respectively added into the phosphoric acid solution slowly to obtain a solution A; 41.9 g of lithium hydroxide monohydrate was weighed out and dissolved in 1L of deionized water. And adding a lithium hydroxide aqueous solution into the solution A under the condition of stirring to obtain a mixed solution B.
The mixed solution B was added to a ball mill and ground at 300rpm for 2 hours to obtain slurry C containing primary particles (particle diameter: 2.8 μm). Adding the slurry C into a high-pressure homogenizer, and sequentially passing through a homogenizing cavity and an emulsifying cavity in the high-pressure homogenizer, wherein the pressure in the homogenizing cavity is 15000Psi, the slurry C flows into the emulsifying cavity at the speed of 10m/s, and the pressure in the emulsifying cavity is 2000Psi, so as to obtain refined slurry D; and (3) spray-drying the refined slurry D, then heating to 700 ℃ in a nitrogen atmosphere, keeping the temperature constant for 10 hours, and then cooling to room temperature to obtain the carbon-coated lithium manganese iron phosphate material.
(2) Scanning spectrum of electron microscope for lithium manganese iron phosphate material
As shown in fig. 1, fig. 1 is a Scanning Electron Microscope (SEM) atlas of the prepared lithium iron manganese phosphate material at 2.00 μm, and it can be seen from the atlas that the particle size distribution is relatively uniform, the water caltrops of the particles are smaller, and the sphericity is relatively better.
(3) Performance test result of lithium manganese iron phosphate material
The particle size D of the lithium iron manganese phosphate material50Has a particle diameter D of 0.65 μm901.8 μm and a specific surface area of 21.5m2(ii) g, compacted density of 2.53g/cm3(ii) a The Cohesive force Cohesive was 0.84kPa, and the magnetic induction was 980 ppm.
Example 2
(1) Lithium manganese iron phosphate (LiMn)0.5Fe0.5PO4The preparation method of the material comprises the following steps: with reference to example 1, the difference is that:
the mixed solution B was added to a ball mill and ground at 300rpm for 1.5 hours to obtain slurry C containing primary particles (particle diameter: 3.2 μm). Adding the slurry C into a high-pressure homogenizer, and sequentially passing through a homogenizing cavity and an emulsifying cavity in the high-pressure homogenizer, wherein the pressure in the homogenizing cavity is 10000Psi, the slurry C flows into the emulsifying cavity at the speed of 7m/s, and the pressure in the emulsifying cavity is 1000Psi, so as to obtain refined slurry D; and (3) spray-drying the refined slurry D, heating to 780 ℃ in a nitrogen atmosphere, keeping the temperature constant for 5 hours, and then cooling to room temperature to obtain the lithium iron manganese phosphate material.
(2) Property and performance test and result of lithium manganese iron phosphate material
The lithium manganese iron phosphate materialParticle diameter D of the material50Has a particle diameter D of 0.78 μm902.1 μm, a specific surface area of 20.7m2(g) the compacted density is 2.52g/cm3(ii) a The Cohesive force Cohesive was 0.92kPa, and the magnetic induction was 1010 ppm.
Example 3
(1) Lithium iron manganese phosphate material (LiMn)0.5Fe0.5PO4The preparation method of the/C) comprises the following steps: with reference to example 1, the difference is that:
the mixed solution B was added to a ball mill and ground at a rotation speed of 300rmp for 2.5 hours to obtain a slurry C containing primary particles (particle diameter: 2.5 μm). Adding the slurry C into a high-pressure homogenizer, and sequentially passing through a homogenizing cavity and an emulsifying cavity in the high-pressure homogenizer, wherein the pressure in the homogenizing cavity is 25000Psi, the slurry C flows into the emulsifying cavity at the speed of 14m/s, and the pressure in the emulsifying cavity is 3000Psi, so as to obtain refined slurry D; and (3) spray-drying the refined slurry D, heating to 650 ℃ in a nitrogen atmosphere, keeping the temperature constant for 20 hours, and then cooling to room temperature to obtain the lithium iron manganese phosphate material.
(2) Performance test result of lithium iron manganese phosphate material
The particle size D of the lithium iron manganese phosphate material50Has a particle diameter D of 0.58 μm901.4 μm, a specific surface area of 22.6m2(ii) g, compacted density of 2.51g/cm3(ii) a The Cohesive force Cohesive was 0.74kPa, and the magnetic induction was 956 ppm.
Example 4
(1) Lithium iron manganese phosphate material (LiMn)0.5Fe0.5PO4The preparation method of the/C) comprises the following steps: with reference to example 1, the difference is that:
adding the mixed solution B into a ball mill, and grinding for 3.5h at the rotating speed of 200 rpm to obtain slurry C containing primary particles (the particle size is 2.6 um). Adding the slurry C into a high-pressure homogenizer, and sequentially passing through a homogenizing cavity and an emulsifying cavity in the high-pressure homogenizer, wherein the pressure range in the homogenizing cavity is 20000Psi, the slurry C flows into the emulsifying cavity at the speed of 14m/s, and the pressure range of the emulsifying cavity is 4000Psi, so as to obtain refined slurry D; and (3) spray-drying the refined slurry D, heating to 680 ℃ in a nitrogen atmosphere, keeping the temperature for 12 hours, and then cooling to room temperature to obtain the lithium iron manganese phosphate material.
(2) Property and performance test and result of lithium manganese iron phosphate material
The particle size D of the lithium iron manganese phosphate material50Has a particle diameter D of 0.53 μm901.3 μm, and a specific surface area of 24.3m2(ii) g, compacted density of 2.54g/cm3(ii) a The Cohesive force Cohesive was 0.65kPa, and the magnetic induction was 915 ppm.
Example 5
(1) Lithium iron manganese phosphate material (LiMn)0.5Fe0.5PO4The preparation method of the/C) comprises the following steps: with reference to example 1, the difference is that: and adding the slurry C into a high-pressure homogenizer, and sequentially passing through a homogenizing cavity and an emulsifying cavity in the high-pressure homogenizer, wherein the pressure in the homogenizing cavity is 8000Psi, the slurry C flows into the emulsifying cavity at the speed of 6m/s, and the pressure in the emulsifying cavity is 800Psi, so as to obtain refined slurry D.
(2) Performance test result of lithium iron manganese phosphate material
The particle size D of the lithium iron manganese phosphate material50Has a particle diameter D of 0.82 μm902.5 μm, a specific surface area of 16.3m2(g) the compacted density is 2.42g/cm3(ii) a The Cohesive force Cohesive was 1.12kPa, and the magnetic induction was 1050 ppm.
Example 6
(1) Lithium iron manganese phosphate material (LiMn)0.5Fe0.5PO4The preparation method of the/C) comprises the following steps: with reference to example 1, the difference is that:
and adding the slurry C into a high-pressure homogenizer, and sequentially passing through a homogenizing cavity and an emulsifying cavity in the high-pressure homogenizer, wherein the pressure range in the homogenizing cavity is 4000Psi, the slurry C flows into the emulsifying cavity at the speed of 3m/s, and the pressure range of the emulsifying cavity is 800Psi, so as to obtain refined slurry D.
(2) Property and performance test and result of lithium manganese iron phosphate material
The particle size D of the lithium iron manganese phosphate material50Has a particle diameter D of 0.96 μm902.9 μm, a specific surface area of 12.9m2(g) the compacted density is 2.41g/cm3(ii) a The Cohesive force Cohesive was 1.47kPa, and the magnetic induction was 1098 ppm.
Example 7
(1) Lithium iron manganese phosphate material (LiMn)0.5Fe0.5PO4The preparation method of the/C) comprises the following steps: with reference to example 1, the difference is that:
and adding the slurry C into a high-pressure homogenizer, and sequentially passing through a homogenizing cavity and an emulsifying cavity in the high-pressure homogenizer, wherein the pressure range in the homogenizing cavity is 28000Psi, the slurry C flows into the emulsifying cavity at the speed of 20m/s, and the pressure range of the emulsifying cavity is 2800Psi, so as to obtain refined slurry D.
(2) Property and performance test and result of lithium manganese iron phosphate material
The particle size D of the lithium iron manganese phosphate material50Has a particle diameter D of 0.59 μm901.2 μm, a specific surface area of 26.4m2(ii) g, compacted density of 2.62g/cm3(ii) a The Cohesive force Cohesive was 0.58kPa, and the magnetic induction was 842 ppm.
Example 8
(1) Lithium iron manganese phosphate material (LiMn)0.5Fe0.5PO4The preparation method of the/C) comprises the following steps: with reference to example 1, the difference is that:
and adding the slurry C into a high-pressure homogenizer, and sequentially passing through a homogenizing cavity and an emulsifying cavity in the high-pressure homogenizer, wherein the pressure range in the homogenizing cavity is 28000Psi, the slurry C flows into the emulsifying cavity at the speed of 20m/s, and the pressure range of the emulsifying cavity is 4000Psi, so as to obtain refined slurry D.
(2) Property and performance test and result of lithium manganese iron phosphate material
The particle size D of the lithium iron manganese phosphate material50Has a particle diameter D of 0.52 μm901.1 μm, a specific surface area of 27.6m2(g) the compacted density is 2.67g/cm3(ii) a The Cohesive force Cohesive was 0.51kPa, and the magnetic induction was 815 ppm.
Example 9
(1) Lithium iron manganese phosphate material (LiMn)0.5Fe0.5PO4The preparation method of the/C) comprises the following steps: with reference to example 1, the difference is that:
adding the slurry C into a high-pressure homogenizer, and sequentially passing through a homogenizing cavity and an emulsifying cavity in the high-pressure homogenizer, wherein the pressure range in the homogenizing cavity is 15000Psi, the slurry C flows into the emulsifying cavity at the speed of 11m/s, and the pressure range of the emulsifying cavity is 5000Psi, so as to obtain refined slurry D; and (3) spray-drying the refined slurry D, heating to 700 ℃ in a nitrogen atmosphere, keeping the temperature constant for 10 hours, and then cooling to room temperature to obtain the lithium iron manganese phosphate material.
(2) Property and performance test and result of lithium manganese iron phosphate material
The particle size D of the lithium iron manganese phosphate material50Has a particle diameter D of 0.51 μm900.99 μm, a specific surface area of 29.6m2(g) the compacted density is 2.43g/cm3(ii) a The Cohesive force Cohesive was 0.56kPa, and the magnetic induction was 792 ppm.
Comparative example 1
(1) Lithium iron manganese phosphate material (LiMn)0.5Fe0.5PO4The preparation method of the/C) comprises the following steps: with reference to example 1, the difference is that:
will be mixed withAdding the mixed solution B into a ball mill, and grinding at the rotating speed of 300rmp for 2h to obtain the particle diameter D50Less than 2.8 μm of slurry C. And (3) spray-drying the slurry C, heating to 700 ℃ in a nitrogen atmosphere, keeping the temperature constant for 10 hours, and then cooling to room temperature to obtain the lithium iron manganese phosphate material.
(2) Scanning spectrum of electron microscope for lithium manganese iron phosphate material
As shown in fig. 2, fig. 2 is a Scanning Electron Microscope (SEM) image of the prepared lithium iron manganese phosphate material at 2.00 μm, and it can be seen from the image that the prepared lithium iron manganese phosphate material has a large particle size and clear water caltrops.
(3) Property and performance test and result of lithium manganese iron phosphate material
The particle size D of the lithium iron manganese phosphate material50Has a particle diameter D of 2.5 μm908.5 μm, a specific surface area of 12.3m2(ii) g, compacted density 1.88g/cm3(ii) a The Cohesive force Cohesive was 14.3kPa, and the magnetic induction was 4250 ppm.
Comparative example 2
(1) Lithium iron manganese phosphate material (LiMn)0.5Fe0.5PO4The preparation method of the/C) comprises the following steps: with reference to example 1, the difference is that:
adding the mixed solution B into a ball mill, and grinding at the rotating speed of 400rmp for 2h to obtain the product containing primary particles (particle diameter D)501.8 μm). Adding the slurry C into a high-pressure homogenizer, and sequentially passing through a homogenizing cavity and an emulsifying cavity in the high-pressure homogenizer, wherein the pressure range in the homogenizing cavity is 2000Psi, the slurry C flows into the emulsifying cavity at the speed of 1m/s, and the pressure range of the emulsifying cavity is 200Psi to obtain refined slurry D; and (3) spray-drying the refined slurry D, then heating to 700 ℃ in a nitrogen atmosphere, keeping the temperature constant for 10 hours, and then cooling to room temperature to obtain the lithium iron manganese phosphate material.
(2) Performance test result of lithium iron manganese phosphate material
The particle size D of the lithium iron manganese phosphate material50Has a particle diameter D of 1.5 μm904.2 μm and a specific surface area of 13.8m2(ii) g, compacted density 1.99g/cm3(ii) a The Cohesive force Cohesive was 12.1kPa, and the magnetic induction was 3560 ppm.
Example 10
(1) Lithium iron manganese phosphate material (LiMn)0.3Fe0.7PO4The preparation method of the/C) comprises the following steps: with reference to example 1, the difference is that,
weighing 0.3mol of phosphoric acid (the concentration is 85 wt%), dissolving the phosphoric acid in 1L of deionized water, weighing 34.5 g of manganese carbonate, 105.6 g of ferric phosphate and 22.7 g of glucose, and slowly adding the manganese carbonate, the ferric phosphate and the glucose into a phosphoric acid solution respectively to obtain a solution A; 41.9 g of lithium hydroxide monohydrate was weighed out and dissolved in 1L of deionized water. And adding a lithium hydroxide aqueous solution into the solution A under the condition of stirring to obtain a mixed solution B.
(2) Performance test result of lithium iron manganese phosphate material
The particle size of the lithium iron manganese phosphate material is 0.68 mu m, and the particle size D901.7 μm, a specific surface area of 20.5g/cm3The compacted density is 2.55g/cm3The Cohesive force Cohesive was 0.82kPa, and the magnetic induction intensity was 845 ppm.
Comparative example 3
(1) Lithium iron manganese phosphate material (LiMn)0.3Fe0.7PO4The preparation method of the/C) comprises the following steps: with reference to example 10, the difference is that:
adding the mixed solution B into a ball mill, and grinding for 2h at the rotating speed of 300rmp to obtain slurry C with the particle size of less than 2.9 mu m. And (3) spray-drying the slurry C, heating to 700 ℃ in a nitrogen atmosphere, keeping the temperature constant for 10 hours, and then cooling to room temperature to obtain the lithium iron manganese phosphate material.
(2) Performance test result of lithium iron manganese phosphate material
The particle size D of the lithium iron manganese phosphate material50Is 2.5 μmParticle diameter D909.28 μm, a specific surface area of 14.5m2(g), the compacted density is 2.1g/cm3(ii) a The Cohesive force Cohesive was 19.4kPa, and the magnetic induction was 2890 ppm.
Example 11
(1) Lithium manganese iron phosphate material (LiFePO)4The preparation method of the/C) comprises the following steps: with reference to example 1, the difference is that,
weighing 150.8 g of ferric phosphate and 27.6 g of glucose, and slowly adding the ferric phosphate and the glucose into a phosphoric acid solution respectively to obtain a solution A; 41.9 g of lithium hydroxide monohydrate was weighed out and dissolved in 1L of deionized water. And adding a lithium hydroxide aqueous solution into the solution A under the condition of stirring to obtain a mixed solution B.
(2) Performance test result of lithium iron manganese phosphate material
The particle size of the lithium iron manganese phosphate material is 0.67 mu m, and the particle size D901.6 μm, a specific surface area of 20.8g/cm3And a compacted density of 2.51g/cm3The Cohesive force Cohesive was 0.79kPa, and the magnetic induction intensity was 809 ppm.
Comparative example 4
(1) Lithium manganese iron phosphate material (LiFePO)4The preparation method of the/C) comprises the following steps: with reference to example 11, the difference is that:
adding the mixed solution B into a ball mill, and grinding for 2h at the rotating speed of 300rmp to obtain slurry C with the particle size of less than 2.9 mu m. And (3) spray-drying the slurry C, heating to 700 ℃ in a nitrogen atmosphere, keeping the temperature constant for 10 hours, and then cooling to room temperature to obtain the lithium iron manganese phosphate material.
(2) Performance test result of lithium iron manganese phosphate material
The particle size D of the lithium iron manganese phosphate material50Has a particle diameter D of 2.4 μm905.9 μm and a specific surface area of 11.2m2(ii) g, compacted density of 2.0g/cm3(ii) a Cohesion Cohesive of 2.8kPa, magnetic inductionThe strength was 926.7 ppm.
Example 12
(1) Lithium iron manganese phosphate material (LiMn)0.4Fe0.5Co0.1PO4The preparation method of the/C) comprises the following steps: with reference to example 1, the difference is that:
weighing 0.5mol of phosphoric acid (the concentration is 85 wt%), dissolving the phosphoric acid in 1L of deionized water, weighing 46.0 g of manganese carbonate, 75.4 g of iron phosphate, 11.9 g of cobalt carbonate and 13.4 g of cane sugar (1.6 wt% can be remained at the end), and slowly adding the manganese carbonate, the iron phosphate, the cobalt carbonate and the cane sugar into the phosphoric acid solution respectively to obtain a solution A; 41.9 g of lithium hydroxide monohydrate was weighed out and dissolved in 1L of deionized water. And adding a lithium hydroxide aqueous solution into the solution A under the condition of stirring to obtain a mixed solution B.
(2) Performance test result of lithium iron manganese phosphate material
The particle size of the lithium iron manganese phosphate material is 0.75 mu m, and the particle size D901.9 μm, a specific surface area of 21.6g/cm3The compacted density is 2.55g/cm3The Cohesive force Cohesive was 0.75kPa, and the magnetic induction was 913 ppm.
Comparative example 5
(1) Lithium iron manganese phosphate material (LiMn)0.4Fe0.5Co0.1PO4The preparation method of the/C) comprises the following steps: with reference to example 12, the difference is that:
adding the mixed solution B into a ball mill, and grinding for 2h at the rotating speed of 300rmp to obtain slurry C with the particle size of less than 2.9 mu m. And (3) spray-drying the slurry C, heating to 700 ℃ in a nitrogen atmosphere, keeping the temperature constant for 10 hours, and then cooling to room temperature to obtain the lithium iron manganese phosphate material.
(2) Performance test result of lithium iron manganese phosphate material
The particle size D of the lithium iron manganese phosphate material50Has a particle diameter D of 2.6 μm90Has a specific surface area of 6.7 μmIs 11.7m2(g), the compacted density is 2.2g/cm3(ii) a The Cohesive force Cohesive was 18.9kPa, and the magnetic induction was 9850 ppm.
Testing
(1) Preparation of the positive electrode: the lithium iron manganese phosphate materials prepared in examples 1 to 12 and comparative examples 1 to 5 were used as positive electrode active materials, respectively, the positive electrode active material was mixed with acetylene black and polyvinylidene fluoride (obtained from Qingfeng plastics materials Co., Ltd., Dongguan, under the brand name FR900) in an amount of 80:10:10 by weight in N-methylpyrrolidone (NMP) to form a battery slurry with a solid content of 50 wt%, and the slurry obtained after uniform stirring was coated on a current collector (an aluminum foil with a thickness of 16 μm), and was baked at 100 ℃. + -. 5 ℃ to form a material layer with a thickness of 70 μm, thereby obtaining positive electrode materials S1-S12 and D1-D5.
(2) Preparation of lithium ion monolithic battery: lithium ion monolithic batteries were fabricated by using positive electrodes S1-S12 and D1-D5 prepared from the lithium iron phosphate materials of examples 1-12 and comparative examples 1-5, respectively, in which the negative electrode material was graphite, the separator material was polyvinylidene fluoride (PVDF, a product commercially available from akoma (trade name) fluorine chemical ltd. PVDF HSV 900), and the electrolyte was 1mol/LLiPF6(EC + DMC) (where LiPF6 is lithium hexafluorophosphate, EC is ethylene carbonate, DMC is dimethyl carbonate, and the volume ratio of EC to DMC is 1:1), the batteries produced were designated as T1-T12 and P1-P5, respectively.
(3) Battery performance testing
Firstly, respectively marking the batteries as T1-T12 and P1-P5, placing the batteries on a test cabinet, firstly carrying out constant-current constant-voltage charging at 0.1C, wherein the charging range is 2.5-4.35V, recording the first discharge capacity of the batteries, and calculating the mass specific capacity and the volume specific capacity of the batteries according to the following formulas;
specific mass capacity ═ first discharge capacity (milliampere-hour) of battery/weight (gram) of positive electrode material
Specific volumetric capacity (mAmph) of the battery/volume (cm) of the positive electrode material3)
Charging and discharging the battery for one week (7 days) under the current of 0.1C, and recording the discharge capacity C0; and fully charging the battery at 0.1 ℃, storing the battery in a 65 ℃ oven at a high temperature for 7 days, taking out the battery, cooling the battery, discharging the battery until the voltage is cut off to 2.5V, and recording the residual capacity C1, wherein the capacity retention ratio of the battery at 65 ℃ for 7 days is (C0/C1) × 100%.
(2) And (3) testing results: as shown in table 1.
TABLE 1
| Test items | T1 | T2 | T3 | T4 | T5 | T6 |
| Specific capacity of mass (milliampere/gram) | 165.3 | 162.6 | 163.3 | 158.3 | 157.2 | 151.0 |
| 418.2 | 409.8 | 410.0 | 402.2 | 380.4 | 363.9 | |
| Capacity retention at 65 ℃ for 7 days (%) | 98.5％ | 98.0％ | 98.3％ | 97.2％ | 97.2％ | 96.8％ |
| Test items | T7 | T8 | T9 | T10 | T11 | T12 |
| Specific capacity of mass (milliampere/gram) | 146.8 | 145.9 | 161.3 | 162.5 | 159.8 | 161.7 |
| 384.6 | 389.6 | 391.8 | 414.4 | 401.1 | 412.3 | |
| Capacity retention at 65 ℃ for 7 days (%) | 97.3％ | 97.4％ | 97.4％ | 97.3％ | 97.4％ | 97.2％ |
| Test items | P1 | P2 | P3 | P4 | P5 |
| Specific capacity of mass (milliampere/gram) | 135.2 | 150.2 | 143.8 | 132.6 | 110.8 | |
| 254.2 | 298.9 | 302.0 | 265.2 | 243.8 | ||
| Capacity retention at 65 degrees 7 days (%) | 90.5％ | 91.9％ | 93.2％ | 87.4％ | 79.3％ |
As can be seen from the data in table 1 and fig. 1 and 2, compared with the lithium iron manganese phosphate material prepared in comparative example 1, the lithium iron manganese phosphate materials prepared in examples 1 to 12 according to the method of the present invention have relatively uniform particle size distribution, smaller water caltrops and relatively better sphericity, smaller particle size and lower cohesion, and can also obtain relatively higher compacted density through reasonable arrangement. Meanwhile, the lithium iron manganese phosphate materials prepared according to embodiments 1 to 12 of the method of the present invention have smaller particle sizes, and the water caltrops on the surfaces of the particles are ground more smoothly, so as to be more favorable for reducing impurities contained in the prepared lithium iron manganese phosphate materials, and further to be favorable for improving the capacity retention rate of the battery at high temperature (7 days at 65 ℃).
The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (18)
1. A lithium iron manganese phosphate material, characterized in that the lithium iron manganese phosphate material has LiMnxFe1-x-yMyPO4A structure of/C, wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, M is a transition metal element except Mn and Fe, and the particle size D of the lithium iron manganese phosphate material500.5-1.0 μm, D90Is 1.0-5.0 μm, and the cohesion Cohesive of the lithium iron manganese phosphate material is less than or equal to 1.5 kPa.
2. Phosphorus according to claim 1A lithium iron manganese phosphate material, wherein the particle diameter D of the lithium iron manganese phosphate material500.5-0.8 μm, D90Is 1.0-3.0 μm, and the cohesion Cohesive of the lithium iron manganese phosphate material is less than or equal to 1.2 kPa.
3. The lithium iron manganese phosphate-based material according to claim 1 or 2, wherein the specific surface area S of the lithium iron manganese phosphate-based material is 12m2/g≤S≤28m2A/g, preferably of 15m2/g≤S≤25m2/g。
4. The lithium iron manganese phosphate-based material according to claim 1 or 2, wherein the compacted density of the lithium iron manganese phosphate-based material is 2.0g/cm3-2.68g/cm3Preferably 2.2g/cm3-2.55g/cm3。
5. The lithium iron manganese phosphate-based material according to claim 1 or 2, wherein the magnetic induction of the lithium iron manganese phosphate-based material is 800-1100ppm, preferably 950-1050 ppm.
6. The lithium iron manganese phosphate-based material according to claim 1 or 2, wherein the content of carbon element in the lithium iron manganese phosphate-based material is 0.5 to 3.5 wt% of the total amount of the lithium iron manganese phosphate-based material.
7. The lithium iron manganese phosphate-based material according to claim 1 or 2, wherein the M is one or more of Co, Ni, Mg, Zn, V, and Ti.
8. The preparation method of the lithium iron manganese phosphate material is characterized by comprising the following steps of:
grinding and mixing a lithium source, an optional manganese source, an optional iron source, an optional M source, a phosphorus source and a carbon source according to a proportion to obtain slurry containing primary particles;
the slurry containing the primary particles sequentially passes through a first chamber with pressure of P1 and a second chamber with pressure of P2 to obtain refined slurry, wherein P1 is more than or equal to 4000Psi, and P1 is more than 3 times of P2;
and sequentially drying and sintering the refined slurry to obtain secondary particles, namely the manganese phosphate iron material.
9. The method according to claim 8, wherein the P1 is 4000-28000 Psi; preferably P1 is 10000-25000 Psi; preferably P1 is 5 times or more greater than P2, preferably P2 is 1000-4000 Psi.
10. The production method according to claim 9, wherein the slurry containing the primary particles flows from the first chamber into the second chamber at a velocity of 2 to 20 m/s.
11. The production method according to any one of claims 8 to 10, wherein the first chamber is a homogenizing chamber of a high-pressure homogenizer, and the second chamber is an emulsifying chamber of the high-pressure homogenizer.
12. The production method according to any one of claims 8 to 10, wherein the primary particles have a particle diameter of 50 to 200nm, and the secondary particles have a particle diameter of 2 to 10 μm.
13. The production method according to any one of claims 8 to 10, wherein the carbon source is added in an amount such that the content of carbon elements finally remaining in the produced lithium iron manganese phosphate-based material is 0.5 to 3.5 wt% based on the total weight of the lithium iron manganese phosphate-based material.
14. The preparation method according to any one of claims 8 to 10, wherein the sintering treatment conditions comprise constant temperature sintering at 780 ℃ for 2-20 h.
15. A lithium iron manganese phosphate-based material, characterized in that the lithium iron manganese phosphate-based material is prepared by the preparation method of any one of claims 8 to 14.
16. A battery paste, characterized in that the battery paste comprises a lithium iron manganese phosphate-based material and a solvent, characterized in that the lithium iron manganese phosphate-based material is the lithium iron manganese phosphate-based material of any one of claims 1 to 7 and 15.
17. A positive electrode comprising a current collector and a positive electrode active material layer provided on the current collector, characterized in that the positive electrode active material layer comprises the lithium iron manganese phosphate-based material according to any one of claims 1 to 7 and 15.
18. A lithium battery having a positive electrode mounted therein, wherein the positive electrode material comprises the positive electrode of claim 17.
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