WO2014025125A1 - 리튬 금속인산화물의 제조방법 - Google Patents
리튬 금속인산화물의 제조방법 Download PDFInfo
- Publication number
- WO2014025125A1 WO2014025125A1 PCT/KR2013/004162 KR2013004162W WO2014025125A1 WO 2014025125 A1 WO2014025125 A1 WO 2014025125A1 KR 2013004162 W KR2013004162 W KR 2013004162W WO 2014025125 A1 WO2014025125 A1 WO 2014025125A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- phosphate
- iron
- iron phosphate
- particles
- lithium metal
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 55
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 51
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical compound [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 title abstract 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 165
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 129
- 239000002245 particle Substances 0.000 claims abstract description 119
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 62
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 61
- 239000010452 phosphate Substances 0.000 claims abstract description 61
- 238000002156 mixing Methods 0.000 claims abstract description 44
- 239000000243 solution Substances 0.000 claims abstract description 41
- 239000000725 suspension Substances 0.000 claims abstract description 35
- 150000002505 iron Chemical class 0.000 claims abstract description 32
- 239000012266 salt solution Substances 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- 238000010304 firing Methods 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 238000010008 shearing Methods 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 43
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 29
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 14
- 229930006000 Sucrose Natural products 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 14
- 239000005720 sucrose Substances 0.000 claims description 14
- -1 iron (III) halide salt Chemical class 0.000 claims description 11
- 238000011049 filling Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 150000004677 hydrates Chemical class 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- LNOZJRCUHSPCDZ-UHFFFAOYSA-L iron(ii) acetate Chemical compound [Fe+2].CC([O-])=O.CC([O-])=O LNOZJRCUHSPCDZ-UHFFFAOYSA-L 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 claims 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 abstract description 29
- 239000002244 precipitate Substances 0.000 abstract description 7
- 239000010450 olivine Substances 0.000 abstract description 4
- 229910052609 olivine Inorganic materials 0.000 abstract description 4
- 229910015645 LiMn Inorganic materials 0.000 abstract 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 32
- 230000015572 biosynthetic process Effects 0.000 description 27
- 238000003786 synthesis reaction Methods 0.000 description 24
- 229940032958 ferric phosphate Drugs 0.000 description 19
- 239000005955 Ferric phosphate Substances 0.000 description 18
- 239000002904 solvent Substances 0.000 description 17
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 15
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000002002 slurry Substances 0.000 description 9
- 239000011651 chromium Substances 0.000 description 8
- 230000005484 gravity Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 7
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 7
- 235000019838 diammonium phosphate Nutrition 0.000 description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 7
- 239000011812 mixed powder Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 239000005696 Diammonium phosphate Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 5
- 239000005642 Oleic acid Substances 0.000 description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229940116007 ferrous phosphate Drugs 0.000 description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- OIAKUYQUAMNLMV-UHFFFAOYSA-H P(=O)([O-])([O-])[O-].[Fe+2].[Li+].[Al+3].P(=O)([O-])([O-])[O-] Chemical compound P(=O)([O-])([O-])[O-].[Fe+2].[Li+].[Al+3].P(=O)([O-])([O-])[O-] OIAKUYQUAMNLMV-UHFFFAOYSA-H 0.000 description 4
- GWMQLDREFRDWDX-UHFFFAOYSA-H P(=O)([O-])([O-])[O-].[Fe+2].[Li+].[Cr+3].P(=O)([O-])([O-])[O-] Chemical compound P(=O)([O-])([O-])[O-].[Fe+2].[Li+].[Cr+3].P(=O)([O-])([O-])[O-] GWMQLDREFRDWDX-UHFFFAOYSA-H 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 159000000014 iron salts Chemical class 0.000 description 4
- RQKNQWUJROKKEQ-UHFFFAOYSA-K iron(3+);phosphate;hydrate Chemical compound [OH-].[Fe+3].OP([O-])([O-])=O RQKNQWUJROKKEQ-UHFFFAOYSA-K 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 229910010710 LiFePO Inorganic materials 0.000 description 3
- 229910001037 White iron Inorganic materials 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000001939 inductive effect Effects 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 235000014413 iron hydroxide Nutrition 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- 229910016523 CuKa Inorganic materials 0.000 description 1
- 229910016876 Fe(NH4)2(SO4)2 Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 1
- 229910013275 LiMPO Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 238000001016 Ostwald ripening Methods 0.000 description 1
- GBRIBUMIBAOMGB-UHFFFAOYSA-H P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].[Fe+6] Chemical compound P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].[Fe+6] GBRIBUMIBAOMGB-UHFFFAOYSA-H 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001793 charged compounds Polymers 0.000 description 1
- 229960000359 chromic chloride Drugs 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical class Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
- B01J19/0066—Stirrers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1806—Stationary reactors having moving elements inside resulting in a turbulent flow of the reactants, such as in centrifugal-type reactors, or having a high Reynolds-number
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
- B01J6/001—Calcining
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a method for preparing lithium metal phosphate, and more particularly, lithium metal phosphate using iron phosphate (FePO 4 , FP) or metal doped crystalline iron phosphate (MFePO 4 , hereinafter MFP) as a precursor. It relates to a method for producing (LiMPO 4 , hereinafter LMP).
- the sol-gel method (Sol-Gel) is a method of preparing a metal alkoxide raw material in a sol state and gelling through condensation reaction, and then drying and heat-treating the LMP, the reaction material used is expensive and based on an organic solvent Since it is a reaction, manufacturing cost is high.
- the present inventors studied a new synthetic method that can solve the above problems, crystalline iron phosphate (FP) or metal-doped crystalline iron phosphate (MFP) prepared by applying a high-gravity level shear force (MFP)
- FP crystalline iron phosphate
- MFP metal-doped crystalline iron phosphate
- structural similarity of precursor and product enables synthesis of crystalline lithium metal phosphate at much lower temperature than amorphous iron phosphate hydrate as precursor, and lower calcination
- the present invention has been found to be able to control the growth of particles at a temperature, thereby reducing process costs.
- the problem to be solved by the present invention is the synthesis of crystalline lithium metal phosphate (LMP) at a low temperature, can control the growth of particles at a low calcination temperature, lithium metal phosphate (which can reduce the process cost) It provides a method for producing LMP).
- LMP crystalline lithium metal phosphate
- It provides a method for producing a lithium metal phosphate comprising the; mixing the iron phosphate with a lithium raw material and calcining.
- the lithium metal phosphate obtained according to the method of the present invention when used as a positive electrode active material for lithium secondary batteries compared to the lithium metal phosphate prepared by the conventional method excellent in battery characteristics and other physical properties.
- FIG. 1 is a schematic diagram of a reactor for preparing amorphous or crystalline iron phosphate used in the production of lithium iron phosphate according to an embodiment of the present invention.
- Figure 3 is a SEM image of the crystalline iron (III) phosphate prepared in accordance with an embodiment of the present invention.
- Figure 4 is a diffraction pattern observed by XRD of lithium iron phosphate prepared from crystalline iron (III) phosphate according to an embodiment of the present invention.
- FIG. 5 is an SEM image of lithium iron phosphate prepared from crystalline iron (III) phosphate according to an embodiment of the present invention.
- Figure 6 is a diffraction pattern observed by XRD of the crystalline iron (II) phosphate prepared according to an embodiment of the present invention.
- FIG. 9 is an SEM image of lithium iron phosphate prepared from crystalline iron (II) phosphate according to an embodiment of the present invention.
- FIG. 10 is a diffraction pattern observed by XRD of lithium chromium iron phosphate prepared from chromium doped crystalline iron phosphate according to an embodiment of the present invention.
- FIG. 11 is an SEM image of lithium chromium iron phosphate prepared from chromium-doped crystalline iron phosphate according to an embodiment of the present invention.
- FIG. 13 is a SEM photograph of lithium aluminum iron phosphate prepared from aluminum-doped crystalline iron phosphate according to an embodiment of the present invention.
- One embodiment of the present invention comprises the steps of mixing the iron salt solution and phosphate solution in the reactor; Applying a shear force to the mixed solution in the reactor during the mixing step to form a suspension containing nano-sized iron phosphate precipitated particles; Obtaining nanosized iron phosphate particles from the suspension; It may be a method of producing a lithium metal phosphate having a structure of the following formula; and mixing and firing the iron phosphate with a lithium raw material.
- LiM n FePO 4 wherein M is selected from the group consisting of Ni, Co, Mn, Cr, Zr, Nb, Cu, V, Ti, Zn, Al, Ga and Mg, n is in the range of 0-1.
- Iron salt solution means that iron salt is dissolved in the solvent, and the solvent is a water solvent, an organic solvent (eg, ethanol), a mixture of water solvent and organic solvent, or a mixture of organic solvents. It may be a mixture.
- the anion of the iron salt solution may include one or more selected from the group consisting of halides, sulphates, nitrates, and acetate.
- Cl - can include at least one selected from the group consisting of -, Br -, SO 4 2- , CH 3 COO -, NO 3 -, OH.
- Iron salts may be compounds comprising at least one anion and at least one cation.
- Iron salts within the positive and negative ions is Fe 2+, Fe 3+, Cl - ions stage (single atom ion), or CH 3 COO, such as -, NO 3 2-, SO 4 2-, OH - like compound Ions (polyatomic ions).
- At least one of the cations in the iron salt may be Fe 3+ or Fe 2+ .
- the iron salt is not particularly limited as long as it can be completely or partially dissolved in a selected solvent, but preferably iron acetate salt, iron halide salt, iron nitrate salt, iron sulphate salt, iron hydroxide salt, hydrates thereof and mixtures thereof Can be selected from.
- the phosphate salt solution refers to a solution in which a solute containing PO 4 3- is dissolved in a solvent, and precipitated particles may be formed or grown when added to the iron salt solution.
- the phosphate solution may be prepared by dissolving a solid salt comprising phosphate in a solvent, and the solvent may comprise water, an organic liquid (eg alcohol) and mixtures thereof.
- Anions of phosphate HPO 4 2-, H 2 PO 4- or PO 4 3- may include at least one selected from the group consisting of a hydrate of the foregoing, and mixtures thereof. However, at least one of the phosphate anion in the PO 4 Can be 3- .
- the iron ions in the iron salt solution and the phosphate ions in the phosphate solution may react to form iron phosphate, and the precipitated iron phosphate particles may be evenly dispersed in the mixed solution to form a suspension. .
- the mixing of the iron salt solution and the phosphate solution may be performed under conditions in which at least one of the nanosize amorphous iron phosphate particles and the crystalline iron phosphate particles is precipitated. That is, when the iron salt solution and the phosphate solution are mixed, nano-size amorphous iron phosphate particles may be precipitated, or nano-size crystalline iron phosphate particles may be precipitated, or nano-size amorphous and crystalline particles may be precipitated together.
- the mixing of the iron salt solution and the phosphate solution may be performed under the conditions in which a precipitate containing iron phosphate is formed. Under these conditions, formation of intermediate iron phosphate species can be prevented.
- Intermediate iron phosphate species may include metal hydroxide oxide compounds formed during the precipitation of iron salts and precipitation solutions. For example, when the pH value of the precipitation solution is greater than 7, the hydroxide ions (OH ⁇ ) are the iron cations (Fe 3+ , Fe 2+ ) of the iron salts (ie, iron chlorides (FeCl 3 , FeCl 2 )) in the solution. It can react immediately with it to form a precipitate.
- Precipitates may be present in combination of hydroxides and oxides rather than a single iron hydroxide or a single iron oxide phase.
- the intermediate species may further react to form a complete iron oxide crystal when heat is applied in the sintering or aging step, or may further form Fe 2 O 3 particles by bubbling air or oxygen.
- it is more preferable that the intermediate species are not formed, and cations (Fe 3+ and Fe 2+ ) react directly with phosphate ions (PO 4 3- ) to form iron phosphate.
- the reactor refers to a region in which the iron salt solution and the phosphate solution react to form iron phosphate, which is described in detail in the molecular level mixing apparatus and the manufacturing system.
- Shearing force is applied to the mixed solution in the reactor during the mixing step to form a suspension containing nano-sized iron phosphate precipitated particles.
- a shear force can be applied to the mixed solution in the reactor during the mixing step.
- the precipitated nano-sized iron phosphate particles may have a relatively narrow particle size distribution.
- the optical narrowness of the particle size distribution can be expressed as a kurtosis ratio.
- the kurtosis ratio may be defined as the average diameter of particles corresponding to 75 mass percent divided by the average diameter of particles corresponding to 25 mass percent. If the kurtosis ratio is large, the particle size distribution curve is wider, and if the kurtosis ratio is small, the particle size distribution curve is narrower and more sharp.
- the particle size distribution can be represented by SediGraph, which shows the cumulative mass percent by particle size.
- Cumulative mass percentage refers to the percentage (mass) of the portion whose particle size is equal to or less than a certain value.
- the average particle size is the precipitated particle size at 50% of SediGraph.
- the kurtosis ratio may be less than three. Preferably less than 2, less than 1.9, less than 1.8, less than 1.7, less than 1.6, or less than 1.5, and even less than 1.3.
- Shear force can be generated by stirring the mixed solution in the reactor with a stirrer, the structure of the reactor and its operation principle and the like will be described later. Applying shear forces can result in fluid flows with Reynolds numbers of 2,000 to 200,000, 5,000 to 150,000 or 8,000 to 100,000. This allows the materials in the reactor to mix well and form an essentially homogeneous mixture.
- the average particle size of the nano-size amorphous or crystalline iron phosphate precipitated particles formed according to the present embodiment may be 1 to 100 nm, preferably 1 to 20 nm, 5 to 30 nm, 5 to 50 nm, 10 to 20 nm. , 10-50 nm, 20-50 nm, 15-30 nm, 10-100 nm, 10-60 nm or 15-20 nm.
- the nano-sized iron phosphate precipitated particles may be amorphous.
- the embodiment may further comprise the step of aging the suspension under conditions in which crystalline iron phosphate particles are formed.
- Aging may refer to a process of maintaining the suspension of the precipitated particles under a specific condition (temperature, pressure, pH, and stirring speed) so that the precipitated particles have an essentially crystalline structure.
- the crystalline structure of the precipitated particles can be formed by rapid nucleation or partial dissolution and recrystallization of the precipitated particles, whereby complete crystallized particles or larger precipitated particles are formed as the particles dissolved on the undissolved particles are recrystallized.
- Chemical aging may refer to a process of adding a chemical, such as an acid or a base, to the reaction mixture during the aging process to promote the aging process.
- the conditions under which the crystalline iron phosphate particles are formed from the nano-size amorphous iron phosphate particles may include, for example, the following steps (1) (2) (3). (1) while the suspension is constantly stirred, the temperature is gradually raised to heat the precipitated particle suspension (eg, heated at a constant rate from 25 ° C. to about 95 ° C. with constant stirring); (2) maintaining the pH of the suspension in an appropriate range (eg, about pH 3-5 or 2-4) at about 95 ° C. for about 1-5 hours; And (3) cooling the suspension to room temperature (i.e., 25 ° C).
- the heating step (1) may change the saturation amount of the solvent, which may reinforce the recrystallization or cause Ostwald ripening phenomenon, and the precipitated particles grow or recrystallize to form particles having a crystal structure or larger Particles of size can be formed.
- the iron phosphate particles can be obtained from the suspension in which the iron phosphate particles are suspended.
- the iron phosphate particles are obtained by isolating or isolation, which may mean a process associated with removing precipitated particles from the reaction medium. For example, there may be filtration, centrifugation, spray drying, lyophilization or other known methods for removing solids from other liquids.
- separation does not necessarily mean that the precipitated particles are completely removed from the reaction medium.
- separation may include the case where the reaction medium is completely removed from the particles.
- the iron salt solution comprises iron (II or III) acetate salt, iron (II or III) halide salt, iron (II or III) nitrate salt, iron (II or III) sulfate salt, hydrates and mixtures thereof It may include one or more selected from the group consisting of.
- the formed iron phosphate precipitated particles may include iron (ferric or ferrous) phosphate, the ferric or ferrous phosphate may be amorphous iron (ferric or ferrous) phosphate, crystalline iron (ferric or ferrous) phosphate, hydrates thereof and It may include one or more selected from the group consisting of a mixture thereof.
- the iron phosphate may be a metal doped iron phosphate.
- the doped iron phosphate is doped with a dissimilar metal while crystallizing amorphous iron phosphate, and has the following formula:
- M may be selected from the group consisting of Ni, Co, Mn, Cr, Zr, Nb, Cu, V, Ti, Zn, Al, Ga and Mg.
- the molar ratio of [Fe] and [M] is 1-x: x, where x is preferably in the range of 0.01 to 0.05.
- the metal-doped crystalline iron phosphate of Formula II may be prepared by mixing heterogeneous metal salts with amorphous iron phosphate, and crystallizing the amorphous iron phosphate mixed with heterometal salts. Forming the amorphous iron phosphate may be prepared according to methods generally used in the art. For example, the raw material may be prepared by mixing FeCl 3 with (NH 4 ) 2 HPO 4 or NH 4 H 2 PO 4 in a liquid state, followed by reaction. In this case, the [Fe]: [P] molar ratio may be in the range of 1: 0.9 to 1.1, and the volume ratio of the solids to the solvent is preferably 5 to 15%.
- the pH of the reactants it is preferable to adjust the pH of the reactants to 4 to 7, it can be reacted by stirring for 10 to 30 minutes at a temperature of 25 to 70 °C.
- the reactant is preferably washed 2 to 5 times using a reduced pressure filter or centrifuse and then dried.
- the metals added to induce doping include Ni, Co, Mn, Cr, Zr, Nb, Cu, V, Ti, Zn, Al, Ga, and Mg, where [Fe] and [M] Can be mixed such that the molar ratio of 1-x: x, where x is in the range of 0.01 to 0.05.
- the heterometal salt is selected from the group consisting of the following structure, MX 3 (wherein M is Ni, Co, Mn, Cr, Zr, Nb, Cu, V, Ti, Zn, Al, Ga, and Mg); , X is an anion including a halogen).
- MX 3 wherein M is Ni, Co, Mn, Cr, Zr, Nb, Cu, V, Ti, Zn, Al, Ga, and Mg
- X is an anion including a halogen
- the amorphous iron phosphate may be uniformly mixed by mixing in an aqueous solution of a dissimilar metal salt in the form of a slurry.
- the amorphous iron phosphate mixed with the dissimilar metal salt can be crystallized by heating under strong acid.
- a strong acid a thing like phosphoric acid or hydrochloric acid can be added, and it can heat, stirring at 90-100 degreeC for 1 to 6 hours.
- the reaction is terminated when the color of the reactant becomes bright.
- the reactant is preferably washed 2 to 5 times using a reduced pressure filter or centrifugation and then dried.
- the iron phosphate is mixed with a lithium raw material and calcined
- the lithium raw material may be selected from the group consisting of LiOH, Li 2 CO 3 and LiCl, but is not limited thereto.
- the iron phosphate and the lithium raw material is preferably mixed so that the [FP]: [Li] molar ratio is 1: 0.5 to 1.5.
- Mixing of the crystalline iron phosphate (FP) or metal doped crystalline iron phosphate (MFP) and the lithium raw material may be mixed through a method generally used in the art, for example, dry ball milling or using a mixer. Can be mixed and ground.
- the raw materials are preferably ground to a particle size of about 10nm to 1 ⁇ m.
- the carbon coating material may include sucrose, glucose, escorbic acid or oleic acid, but is not limited thereto.
- the carbon coating material may be included between 20 and 40% by weight of [Li].
- the mixed raw materials may be heat treated at a temperature of 500 to 700 °C. In this case, the heat treatment may be performed for 4 to 12 hours in a 1-5% H 2 / N 2 mixed gas atmosphere.
- the reactor 100 may include a chamber surrounding a closed space.
- the reactor 100 material may be titanium and its alloys.
- the reaction of the iron salt solution with the phosphate solution may occur inside the enclosed space.
- the iron salt solution and the phosphate solution may be supplied to a distributor (not shown) in the reactor 100 through the inflow passages 11 and 12, and the suspension may be discharged from the reactor 100 after the reaction through the outlet passage 13.
- the reactor 100 may include an agitator in the form of a packed bed 30.
- the filling layer 30 may be essentially cylindrical, arranged in a particular structure, and may include a plurality of wire mesh layers having a mesh size of 0.05 mm.
- the filling layer 30 may have a surface area of 100-3000 m 2 / m 3 .
- Filling layer 30 may be in the form of a scroll-shaped cylinder, the cylinder-shaped portion may have a side formed by a plurality of overlapping mesh layer.
- the mesh size may be 0.05-3 mm or 0.1-0.5 mm. Mesh porosity can be at least 90% or 95%.
- the filling layer 30 may have a predetermined structure or may not have a predetermined structure.
- the filling layer 30 may be a wire mesh type made of a relatively inert material such as stainless steel, ordinary metal alloy, titanium metal or plastic.
- the distributor may eject the iron salt solution and the phosphate solution to the inner side of the packed bed 30, and the iron salt solution and the phosphate solution may be mixed and reacted to form a mixture in the packed bed 30 and the reactor 100.
- the filling layer 30 may be mounted to a vertically located rotating shaft. As the shaft and packed bed 30 rotate, a high shear force in the form of centrifugal force may act on the mixture in the reactor 100.
- the magnitude of the centrifugal force acting on the mixture in the packed bed 30 may vary depending on the rotational speed of the shaft and the packed bed 30. The higher the rotational speed of the shaft and packed bed 30, the greater the level of high gravity or shear force acting on the mixture.
- the mixture may move through the packed bed 30 in the radial direction to the outer surface of the packed bed 30.
- the mixture in the packed bed 30 is spread or split under a high gravity field formed by centrifugal force to form a very fine small droplet of yarn or thin film of micrometers to nanometers so that mass transfer between iron salt solution and phosphate solution and Heat transfer may be actively performed. It can also cause intense micro-mixing between the iron salt and phosphate solutions to form a highly homogeneous-saturated solution in a very short time (less than 10 ms). In this process, nano-sized iron phosphate precipitates may be formed.
- the temperature of the reactor, the iron salt solution supply tank (not shown) and the phosphate solution supply tank (not shown) can be controlled using a heating jacket (not shown).
- the temperature may be controlled through a circulation process in which the heated fluid enters through the inlet and exits through the outlet.
- N is the rotation speed (rpm) of the stirrer
- d in is the inner diameter of the stirrer
- d out is the outer diameter.
- High gravity levels can be between 100 and 15,000 m / s 2 , 500 and 2,000 m / s 2 , 1,000 and 5,000 m / s 2, or 800 and 5000 m / s 2 . Due to the use of a strong high gravity level stirrer, the liquids in the reactor can be subjected to strong shear forces as soon as they are injected into the reactor.
- the iron salt solution and the phosphate solution can be injected into the void formed by the vortex.
- the injection speed can be at least 1 m / s, at least 2 m / s, at least 3 m / s, at least 4 m / s or at least 5 m / s.
- the reactor may run in turbulent flow.
- the two solutions can mix faster due to turbulence.
- the blowing flux is preferably 0.1-3000 m 3 / hr, more preferably 0.1-800 m 3 / hr.
- the ejection pressure is preferably 30-3000 kg / cm 2 , more preferably 50-1000 kg / cm 2 .
- Reynolds number Re is preferably 2,000-200,000, more preferably 8,000-100,000. If the Reynolds number is in the above range, high super-saturation can be obtained in a short time because molecular homogeneous chemical homogeneity can be obtained in the reactor before the nucleus is generated. Fine precipitated particles having a uniform particle size distribution can be produced.
- molecular level homogeneity in the reactor can be achieved in a very short time, preventing formation of large intermediate aggregates and formation of intermediate species such as iron hydroxide, hydrous ferric oxides and ferrous oxides or amorphous ferric oxyhydroxide during iron phosphate synthesis.
- the precipitate may consist mainly of iron phosphate.
- d is the diameter of the pipe (or distributor) for supplying the reaction solution to the molecular level mixer
- u is the flow rate of the liquid
- ⁇ is the density of the liquid
- ⁇ is the viscosity of the liquid
- the flow rate is determined by the flux. Pressure is required to maintain the blowout flux.
- the diameter, flux, pressure and Reynolds number of the dispenser are related to each other.
- the present invention can be implemented in various aspects as follows.
- Nanosize iron phosphate particles were prepared using the system shown in FIG. 1.
- the high gravity level of the packed bed 30 was 1579 m / s 2 , the injection speed of the two solutions was set to 5 m / s.
- the residence time in the molecular level mixing apparatus was 20 s.
- the suspension, suspended in yellow precipitate, was collected in the product tank, ammonium hydroxide solution (5.82 wt%) was added and stirred for 15 minutes under atmospheric conditions. After separation and washing through centrifugation, it was dried for 16 hours at 70 °C to prepare amorphous iron (ferric) phosphate nanoparticles.
- the crystalline iron phosphate was mixed and ground by inducing LiOH and sucrose together.
- the crystalline iron phosphate and LiOH were mixed so that the [FP]: [Li] molar ratio was 1: 1, and the ratio of sucrose was 30% of the weight of [Li].
- the mixed powders were heat-treated at a temperature of 650 ° C. for 10 hours under a 3% H 2 / N 2 mixed gas atmosphere to synthesize lithium iron phosphate.
- the crystalline iron phosphate was mixed together with LiOH and sucrose, which was dry ball milled for 16 hours.
- the crystalline iron phosphate and LiOH were mixed so that the [FP]: [Li] molar ratio was 1: 1, and the ratio of sucrose was 30% of the weight of [Li].
- the mixed powders were heat-treated at a temperature of 660 ° C. for 8 hours under a 3% H 2 / N 2 mixed gas atmosphere to synthesize lithium iron phosphate.
- Crystalline iron (75 ml of a solution of 0.32 mol / l (NH 3 ) 2 HPO 4 and 8.75 g of ammonium hydroxide solution (5.82 wt% as NH 3 ) were premixed, filtered and stored in a tank.
- ferric) phosphate particles were prepared in the same manner as in Example 1.
- Ferric phosphate particles have an average particle size of 33.4 nm and a kurtosis ratio of 1.39. According to the XRD diffraction pattern, it can be confirmed that ferric phosphate was formed by crystallization on meta-strengite I.
- the crystalline iron phosphate was mixed together with lithium carbonate and oleic acid, which was ground in a home mixer for 20 minutes.
- the crystalline iron phosphate and lithium carbonate were mixed so that the [FP]: [Li] molar ratio was 1: 1, and the ratio of oleic acid was mixed so as to be 30% of the weight of [Li].
- the mixed powders were heat-treated at a temperature of 650 ° C. for 8 hours under a 3% H 2 / N 2 mixed gas atmosphere to synthesize lithium iron phosphate.
- the crystalline ferric phosphate particles were mixed except that 75 mL of a 3 mL solution of 75 mL H 3 PO 4 and 7.7 g of ammonium hydroxide solution (25 wt% as NH 3 ) were premixed, filtered and stored in a tank. Prepared by the same method as in Example 1.
- Ferric phosphate particles have an average particle size of 38.7 nm and a degree of ratio of 1.42.
- the XRD diffraction pattern shows that ferric phosphate is formed by crystallization on meta-strengite I.
- the crystalline ferric phosphate particles were prepared in the same manner as in Example 1, except that a mixed solution of pH 9.87 was prepared by bubbling ammonia gas into 75 ml of a 75 ml H 3 PO 4 solution having a concentration of 3 wt%. Prepared. The mixed solution was previously filtered and stored in a tank. Ferric phosphate particles have an average particle size of 35.9 nm and a steepness ratio of 1.46. According to the XRD diffraction pattern, it can be confirmed that ferric phosphate was formed by crystallization on meta-strengite I.
- Lithium iron phosphate was synthesized in the same manner as in Example 1.
- Lithium iron phosphate (LiFePO) 4 Lithium iron phosphate (LiFePO) 4
- Lithium iron phosphate (LiFePO) 4 Lithium iron phosphate (LiFePO) 4
- Lithium carbonate (Li 2 CO 3 ), diammonium phosphate (NH 4 HPO 4 ), and glucose were mixed together with the crystalline iron (II) phosphate (Fe 3 (PO 4 ) 2 .8H 2 O) to 30 Pure water was added to%, followed by beads milling for 1 hour.
- the mixed slurry was dried with a spray dryer and heat-treated at a temperature of 680 ° C. for 10 hours in a 3% H 2 / N 2 mixed gas atmosphere to synthesize lithium iron phosphate.
- the mixed powders were heat-treated at a temperature of 650 ° C. for 8 hours under a 3% H 2 / N 2 mixed gas atmosphere to synthesize lithium iron phosphate.
- the chromium-doped crystalline iron phosphate was mixed together with LiOH and sucrose, which was dry ball milled for 16 hours.
- the chromium-doped crystalline iron phosphate and LiOH were mixed so that the molar ratio was 1: 1, and the ratio of sucrose was 30% of the weight of [Li].
- the mixed powders were heat treated at a temperature of 660 ° C. for 3 hours under a 3% H 2 / N 2 mixed gas atmosphere to synthesize lithium chromium iron phosphate.
- the aluminum doped crystalline iron phosphate prepared above was mixed and ground by inducing lithium carbonate and glucose together.
- the aluminum-doped crystalline iron phosphate and lithium carbonate were mixed so that the molar ratio is 1: 1, and the glucose ratio was mixed so that 30% of the weight of [Li].
- the mixed powders were heat-treated at a temperature of 650 ° C. for 10 hours under a 3% H 2 / N 2 mixed gas atmosphere to synthesize lithium aluminum iron phosphate.
- Li 2 CO 3 , FeC 2 O 4 , (NH 4 ) 2 HPO 4 and sucrose were placed in water and ball milled for 16 hours.
- acetone, ethanol, isopropanol may be used as the solvent.
- Li 2 CO 3 , FeC 2 O 4 , (NH 4 ) 2 HPO 4 mix so that the [Li]: [Fe]: [P] molar ratio is 1: 1: 1, and the sucrose is [Li] weight.
- the mixture was mixed to 30% of the amount. At this time, the volume ratio of the solid to the solvent was 30%.
- the mixture was heat-treated at 750 ° C. for 8 hours under a 3% H 2 / N 2 reducing gas atmosphere to synthesize lithium iron phosphate.
- Amorphous iron phosphate hydrate (Amorphous FePO 4 2H 2 O) was mixed with LiOH and sucrose and dry ball milled for 16 hours.
- the [FP]: [Li] molar ratio was mixed to be 1: 1
- the sucrose was mixed to be 30% of the weight of [Li].
- the mixture was heat-treated at 800 ° C. for 8 hours under a 3% H 2 / N 2 reducing gas atmosphere to synthesize lithium iron phosphate.
- Example 1 XRD diffraction patterns and SEM observations of the crystalline iron phosphate used as a raw material in Example 1 and the lithium iron phosphate prepared therefrom are shown in FIGS. 4 and 5.
- Figure 4 shows that the XRD diffraction pattern of the lithium iron phosphate prepared by the method of the present invention that the nanoparticles form a crystalline olivine (Olivine) structure.
- the ratio of active material: conductive agent (carbon black): binder (PVdF) was 85: 5: 10wt. % Was added to NMP (N-methylpyrrolidone) solvent and mixed to prepare a slurry. Subsequently, an aluminum plate was placed on the glass plate sterilized with alcohol or acetone, and the mixed slurry was evenly applied with a doctor blade to a thickness of 20 to 25 ⁇ m. The solvent was removed by drying in an oven (about 90-100 ° C.) for 8 hours.
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Abstract
Description
Claims (22)
- 철염 용액과 인산염 용액을 반응기에서 혼합하는 단계;상기 혼합 단계 중 상기 반응기 내의 혼합용액에 전단력을 인가하여, 나노사이즈 철인산염 석출입자를 함유하는 서스펜션을 형성하는 단계;상기 서스펜션으로부터 나노사이즈 철인산염 입자를 수득하는 단계; 및상기 철인산염을 리튬 원료와 혼합하고 소성하는 단계;를 포함하는 하기 식의 구조를 갖는 리튬 금속인산화물의 제조방법:식 ILiMnFePO4여기서, M은 Ni, Co, Mn, Cr, Zr, Nb, Cu, V, Ti, Zn, Al, Ga 및 Mg으로 이루어진 군으로부터 선택되고, n은 0 내지 1의 범위이다.
- 제1항에 있어서,상기 철염 용액은 iron(Ⅲ) acetate salt, iron(Ⅲ) halide salt, iron(Ⅲ) nitrate salt, iron(Ⅲ) sulfate salt, 이들의 수화물 및 혼합물로 이루어진 그룹으로부터 선택된 1종 이상을 포함하는 리튬 금속인산화물의 제조방법.
- 제1항에 있어서,iron(Ⅱ) acetate salt, iron(Ⅱ) halide salt, iron(Ⅱ) nitrate salt, iron(Ⅱ) sulfate salt, iron(Ⅱ) hydroxide, 이들의 수화물 및 혼합물로 이루어진 그룹에서 선택된 1종 이상을 포함하는 리튬 금속인산화물의 제조방법.
- 제1항에 있어서,상기 전단력을 인가하는 단계는 상기 혼합용액을 교반기로 교반하는 단계를 포함하는 리튬 금속인산화물의 제조방법.
- 제4항에 있어서,상기 교반기는 밀폐된 쳄버 내에 위치하는 충전층을 포함하고, 상기 충전층은 회전축을 중심으로 회전하는 리튬 금속인산화물의 제조방법.
- 제5항에 있어서,상기 충전층은 실린더 형태이고, 최소한 하나의 메쉬층을 포함하는 리튬 금속인산화물의 제조방법.
- 제1항에 있어서,상기 전단력에 의하여 상기 반응기 내에 레이놀즈 넘버(Reynolds number) 2,000~200,000의 흐름 조건이 형성되는 리튬 금속인산화물의 제조방법.
- 제1항에 있어서,상기 전단력 인가는 나노사이즈 비정질 철인산염 및 결정질 철인산염 입자 중 최소한 하나가 형성되는 조건 하에서 수행되는 리튬 금속인산화물의 제조방법.
- 제1항에 있어서,상기 나노사이즈 철인산염 석출입자는 첨도가 3보다 작은 폭이 좁은 입자사이즈분포(narrow particle size distribution)를 가지는 리튬 금속인산화물의 제조방법.
- 제1항에 있어서,상기 혼합은 철인산염 중간종이 형성되지 않는 조건 하에서 수행되는 리튬 금속인산화물의 제조방법.
- 제1항에 있어서,상기 나노사이즈 철인산염 석출입자는 비정질인 리튬 금속인산화물의 제조방법.
- 제11항에 있어서,결정질 철인산염 입자가 형성되는 조건 하에서 상기 서스펜션을 에이징하는 단계를 더 포함하는 리튬 금속인산화물의 제조방법.
- 제11항에 있어서,상기 나노사이즈 비정질 철인산염 석출입자를 에이징하는 단계를 더 포함하는 리튬 금속인산화물의 제조방법.
- 제13항에 있어서,상기 에이징 단계 중, 나노사이즈 비정질 철인산염 입자를 함유하는 혼합물에 전단력을 인가하고 상기 전단력 및 상기 혼합물 내 조건을 조절하여 결정질 나노사이즈 철인산염 입자를 형성시키는 단계;를 더 포함하는 리튬 금속인산화물의 제조방법.
- 제14항에 있어서,나노사이즈 철인산염 입자를 함유하는 혼합물로부터 결정질 철인산염 입자를 분리하는 단계; 및결정질 철인산염 분말을 형성하기 위하여 결정질 철인산염 입자를 건조하는 단계;를 더 포함하는 리튬 금속인산화물의 제조방법.
- 제1항에 있어서,상기 철인산염은 금속 도핑된 철인산염을 포함하는 리튬 금속인산화물의 제조방법.
- 제16항에 있어서,상기 금속 도핑된 결정질 철인산염은 비결정 철인산염을 결정화시키면서 이종 금속을 도핑시킨 것으로, 다음 식을 갖는 리튬 금속인산화물의 제조방법.식 ⅡMFePO4여기서, M은 Ni, Co, Mn, Cr, Zr, Nb, Cu, V, Ti, Zn, Al, Ga 및 Mg으로 이루어진 군으로부터 선택됨.
- 제17항에 있어서,[Fe]와 [M]의 몰비가 1-x:x이고, 여기서 x는 0.01 내지 0.05 인 리튬 금속인산화물의 제조방법.
- 제1항에 있어서,상기 소성온도는 500℃ 내지 700℃ 인 리튬 금속인산화물의 제조방법.
- 제1항에 있어서,상기 리튬 원료 물질로는 LiOH, Li2CO3 및 LiCl로 이루어진 군에서 선택되는 1종 이상을 포함하는 리튬 금속인산화물의 제조방법.
- 제1항에 있어서,상기 결정질 철인산염 또는 금속도핑된 결정질 철인산염과 리튬 원료 물질은 [FP]:[Li]의 몰비가 1: 0.5~1.5가 되도록 혼합되어지는 리튬 금속인산화물의 제조방법.
- 제1항에 있어서,상기 결정질 철인산염 또는 금속도핑된 결정질 철인산염과 리튬 원료 물질을 혼합하는 단계에서 수크로즈 또는 글루코스로부터 선택되는 카본 코팅 원료물질을 더 포함하는 리튬 금속인산화물의 제조방법.
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KR20140021446A (ko) | 2014-02-20 |
KR101973052B1 (ko) | 2019-04-26 |
JP6316291B2 (ja) | 2018-04-25 |
EP2883838B1 (en) | 2020-09-09 |
JP2015525735A (ja) | 2015-09-07 |
EP2883838A4 (en) | 2016-03-30 |
US20150210546A1 (en) | 2015-07-30 |
CA2878918C (en) | 2020-12-15 |
EP2883838A1 (en) | 2015-06-17 |
CA2878918A1 (en) | 2014-02-13 |
CN109336078A (zh) | 2019-02-15 |
US10752504B2 (en) | 2020-08-25 |
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