CN100348478C - Lithium phosphate aggregate, its manufacture method, and manufacture method of lithium/iron/phosphorus-based complex oxide - Google Patents
Lithium phosphate aggregate, its manufacture method, and manufacture method of lithium/iron/phosphorus-based complex oxide Download PDFInfo
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- CN100348478C CN100348478C CNB2004100347371A CN200410034737A CN100348478C CN 100348478 C CN100348478 C CN 100348478C CN B2004100347371 A CNB2004100347371 A CN B2004100347371A CN 200410034737 A CN200410034737 A CN 200410034737A CN 100348478 C CN100348478 C CN 100348478C
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- lithium
- manufacture method
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- lithium phosphate
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Links
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 title claims abstract description 101
- 229910001386 lithium phosphate Inorganic materials 0.000 title claims abstract description 70
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims description 71
- 229910052744 lithium Inorganic materials 0.000 title abstract description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title abstract description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 31
- 229910052742 iron Inorganic materials 0.000 title abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 title abstract description 4
- 239000011574 phosphorus Substances 0.000 title abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 25
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 23
- 239000011164 primary particle Substances 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 19
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 246
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 71
- 239000007864 aqueous solution Substances 0.000 claims description 61
- 239000002131 composite material Substances 0.000 claims description 48
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical class [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 claims description 45
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical class [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 claims description 42
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 36
- 239000003575 carbonaceous material Substances 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 22
- 238000010298 pulverizing process Methods 0.000 claims description 20
- 238000002441 X-ray diffraction Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 229910052791 calcium Inorganic materials 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 238000007670 refining Methods 0.000 claims description 14
- 229910000765 intermetallic Inorganic materials 0.000 claims description 13
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 230000008676 import Effects 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 31
- 239000002245 particle Substances 0.000 abstract description 27
- 239000007774 positive electrode material Substances 0.000 abstract description 21
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 5
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 5
- 239000011147 inorganic material Substances 0.000 abstract description 5
- 229910003480 inorganic solid Inorganic materials 0.000 abstract description 5
- 230000009257 reactivity Effects 0.000 abstract description 5
- 239000007784 solid electrolyte Substances 0.000 abstract description 5
- 229910013275 LiMPO Inorganic materials 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- 239000011572 manganese Substances 0.000 description 31
- 239000011734 sodium Substances 0.000 description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 27
- 239000000047 product Substances 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000002156 mixing Methods 0.000 description 17
- 239000012535 impurity Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 229910052708 sodium Inorganic materials 0.000 description 14
- 229910010710 LiFePO Inorganic materials 0.000 description 13
- 229910019142 PO4 Inorganic materials 0.000 description 13
- 238000011068 loading method Methods 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 13
- 239000010452 phosphate Substances 0.000 description 13
- 235000021317 phosphate Nutrition 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000012528 membrane Substances 0.000 description 12
- 239000003513 alkali Substances 0.000 description 11
- 239000006229 carbon black Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000010304 firing Methods 0.000 description 9
- 229940116007 ferrous phosphate Drugs 0.000 description 8
- 230000005251 gamma ray Effects 0.000 description 8
- 150000002505 iron Chemical class 0.000 description 8
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 238000004611 spectroscopical analysis Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000000108 ultra-filtration Methods 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000002050 diffraction method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000001223 reverse osmosis Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- -1 SPSF Polymers 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000012776 electronic material Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920002492 poly(sulfone) Polymers 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- TWHXWYVOWJCXSI-UHFFFAOYSA-N phosphoric acid;hydrate Chemical compound O.OP(O)(O)=O TWHXWYVOWJCXSI-UHFFFAOYSA-N 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 238000005375 photometry Methods 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910011990 LiFe0.5Mn0.5PO4 Inorganic materials 0.000 description 1
- 229910010586 LiFeO 2 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000004523 agglutinating effect Effects 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229940079938 nitrocellulose Drugs 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 238000004879 turbidimetry Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G07—CHECKING-DEVICES
- G07D—HANDLING OF COINS OR VALUABLE PAPERS, e.g. TESTING, SORTING BY DENOMINATIONS, COUNTING, DISPENSING, CHANGING OR DEPOSITING
- G07D2211/00—Paper-money handling devices
Abstract
The purpose of this invention is to provide a fine and high purity lithium phosphate aggregate useful as a catalyst for manufacturing allyl alcohol, a raw material for manufacturing a functional inorganic material, a raw material of an inorganic solid electrolyte, especially as a raw material for manufacturing LiMPO<SB>4</SB>(M is at least one or more kinds selected among Fe, Mn, Ni, Co and Al) used as a positive electrode active material of a lithium secondary cell and having excellent reactivity and fluidity and further workability such as grinding ; to provide its manufacturing method; and to provide a manufacturing method of a lithium/iron/phosphorus-based complex oxide useful as the positive electrode active material of the lithium secondary cell using the lithium phosphate aggregate. The lithium phosphate aggregate is constituted by forming the aggregate with fine primary particles, and an average particle size of the aggregate is 1-10 [mu]m and the angle of repose is not more than 50[deg.].
Description
Technical field
The present invention relates to the raw material of purposes, the inorganic solid electrolyte of the manufacturing raw material of vinyl carbinol catalyst for producing, functional inorganic material, particularly as the LiMP0 that in the positive active material of lithium secondary battery, uses
4(M represents to be selected from least a above metallic element among Fe, Mn, Ni, Co and the Al.) the manufacturing raw material be useful lithium phosphate condensates, its manufacture method and the manufacture method of using the ithium iron phosphorus series composite oxides of this lithium phosphate condensates.
Background technology
In recent years, progressive rapidly along with the portabilityization of household electrical appliance, wirelessization, lithium-ion secondary cell is practical as the power supply of miniature electric machines such as portable minisize Personal Computer, portable phone, videocorder.About this lithium-ion secondary cell, since people such as water island in 1980 report { " マ テ リ ア Le リ サ one チ Block レ テ イ Application " Vol15, P783-789 (1980) } cobalt acid lithium is useful as the positive active material of lithium-ion secondary cell, research and development progress about cobalt acid lithium is active, up to the present, existing many motions.
But, because Co on earth skewness, be scarce resource, so there is the people developing for example LiNiO
2, LiMn
2O
4, LiFeO
2, LiFePO
4New positive active material Deng the acid of cobalt instead lithium.
LiFePO particularly
4Has volume density greatly to 3.6g/cm
3, noble potential, theoretical capacity that 3.4V takes place be also greatly to the such feature of 170mAh/g.And, except Fe aboundresources and low price, LiFePO
4Each Fe atom contains an electrochemically Li of dedoping under the state in the early stage, so instead the expectation of the positive active material of the new lithium secondary battery of cobalt acid lithium is very big.
Someone has proposed LiFePO
4Or replace the LiFePO of the part of this Fe with other metal
4Lithium secondary battery (for example, with reference to patent documentation 1～6) as positive active material.
As common LiFePO
4Manufacture method, the someone has proposed for example to use the ferrous phosphate salt hydrate and by following reaction formula (1)
Li
3PO
4+Fe
3(PO
4)
2·nH
2O
→3LiFePO
4+nH
2O
Reaction formula (1)
The method of making, use ironic oxalate also pass through following reaction formula (2)
Li
2CO
3+2FeC
2O
4·2H
2O+2(NH
4)
2HPO
4
→2LiFePO
4+4NH
3+5CO
2+5H
2O+2H
2
Reaction formula (2)
The method of making or, use ironic acetate and by following reaction formula (3)
Li
2CO
3+2Fe(CH
3COO)
2+2NH
4H
2PO
4
→2LiFePO
4+4NH
3+CO
2+5H
2O+2CH
3COOH
Reaction formula (3)
The method of making etc.
Wherein, the method (reaction formula (1)) of using Trilithium phosphate and ferrous phosphate salt hydrate is because by product is a water, thus industrial be particularly advantageous.
Manufacture method with regard to this Trilithium phosphate, someone has proposed for example sodium phosphate to be joined the method (for example, with reference to non-patent literature l and patent documentation 7) in the lithium hydroxide aqueous solution or phosphoric acid has been joined method (with reference to non-patent literature 1) in the lithium hydroxide aqueous solution etc.
Wherein, the former method in the lithium hydroxide aqueous solution that sodium phosphate is joined certainly exists the tendency that the sodium content as impurity uprises.In addition, utilize the latter's method in the lithium hydroxide aqueous solution that phosphoric acid is joined, can obtain the low material of foreign matter content.
But, at industrial available Trilithium phosphate, satisfy simultaneously as the prerequisite of the raw material of electronic material, promptly, the Trilithium phosphate of the such condition of the fine particle of purity height, reactivity, flowability and excellent in workability is non-existent.For example, though commercially available have a few Trilithium phosphate of foreign matter content, but it is the median size of primary particle is the above coarse grain of 20 μ m, on aspect other material reactive, have problems, in addition, though commercially available median size is also arranged is the Trilithium phosphate of the following particle coagulation shape of 10 μ m because foreign matter content is many, mobile poor, so have processing ease, and the problem of the blending dispersion difference of other reaction raw materials.
[patent documentation 1] spy opens flat 9-134724 communique
[patent documentation 2] spy opens flat 9-134725 communique
[patent documentation 3] spy opens flat 11-261394 communique
[patent documentation 4] spy opens the 2001-110414 communique
[patent documentation 5] spy opens the 2001-250555 communique
[patent documentation 6] spy opens the 2000-294238 communique
[patent documentation 7] spy opens clear 64-4251 communique
[non-patent literature 1] with reference to " chemical voluminous dictionary 9 ", altogether uprightly publish, 1993, p.818, the hurdle of Trilithium phosphate.
Summary of the invention
The inventor etc., under this practical situation, further investigate as the method for the useful Trilithium phosphate of the raw material of electronic material obtaining especially, found that, making in the method for Trilithium phosphate by lithium hydroxide aqueous solution and phosphate aqueous solution reaction, the concentration and the temperature of reaction of employed lithium hydroxide aqueous solution in the reaction are set in the specified range, under such condition, react resulting Trilithium phosphate, be high purity and be the fine aggregate that does not have at present, and reactivity and flowability are also excellent, have finished the present invention thus.
That is the LiMPO that, the object of the present invention is to provide the raw material of purposes, the inorganic solid electrolyte of the manufacturing raw material of a kind of vinyl carbinol catalyst for producing, functional inorganic material, particularly uses as the positive active material of lithium secondary battery
4(M represents to be selected from least a above metallic element among Fe, Mn, Ni, Co and the Al.) the manufacturing raw material be that highly purified lithium phosphate condensates, its manufacture method of excellent in workability such as useful fine and reactive, flowability and pulverizing and the positive active material as lithium secondary battery that uses this lithium phosphate condensates are the manufacture method of useful ithium iron phosphorus series composite oxides.
First invention that the present invention wants to provide is a lithium phosphate condensates, it is characterized in that, the median size that fine primary particle forms aggregate, this aggregate is that 1～10 μ m, angle of repose are below 50 degree.
Above-mentioned lithium phosphate condensates, wide being preferably more than 0.2 ° of half value of the diffraction peak of lattice plane (010) face of trying to achieve by X-ray diffraction analysis, and the BET specific surface area is preferably 1～50m
2/ g.In addition, Na content is below the 100ppm, and more preferably, the content of Al, Ca and Si is counted below the 100ppm with total amount.
In addition, second invention that the present invention wants to provide is the manufacture method of lithium phosphate condensates, it is characterized in that, the aqueous solution that contains phosphoric acid is added in the aqueous solution that contains the lithium hydroxide that 4～6 weight % exist with the LiOH form and is reacting below 70 ℃.
The manufacture method of such lithium phosphate condensates contains the import volume of the aqueous solution of phosphoric acid, with respect to lithium hydroxide (LiOH), with phosphoric acid (H
3PO
4) molar ratio computing, be preferably 0.98～1.02.In addition, above-mentioned lithium hydroxide preferably uses secondary filter to contain the refining lithium hydroxide that carries out partial crystallization behind the aqueous solution of lithium hydroxide and obtain.
In addition, the 3rd invention that the present invention wants to provide is the manufacture method of ithium iron phosphorus series composite oxides, it is characterized in that, mix lithium phosphate condensates, ferrous phosphate salt hydrate and the conductive carbon material of (A) above-mentioned first invention or (B) above-mentioned first invention lithium phosphate condensates, ferrous phosphate salt hydrate, contain be selected from Mn, Co, Ni, and Al at least a above metallic compound and the conductive carbon material of metallic element, and fire.
The manufacture method of such ithium iron phosphorus series composite oxides, preferably include: the lithium phosphate condensates that mixes (A) above-mentioned first invention, ferrous phosphate salt hydrate and conductive carbon material or (B) above-mentioned first the invention lithium phosphate condensates, the ferrous phosphate salt hydrate, contain and be selected from Mn, Co, Ni, and at least a above metallic compound of the metallic element among the Al and first operation of conductive carbon material, then, thereby obtain second operation of reacting precursor with the resulting mixture of dry type pulverization process, then, thus fire the 3rd operation that this reacting precursor obtains the ithium iron phosphorus series composite oxides.
In addition, be preferably, after above-mentioned second operation, the operation of resulting reacting precursor being carried out press molding be set.
The median size of the ithium iron phosphorus series composite oxides that generated in addition, is preferably below the 0.5 μ m.
The invention effect
Lithium phosphate condensates of the present invention is the raw material of the purposes that is suitable for vinyl carbinol catalyst for producing, functional inorganic material, inorganic solid electrolyte, particularly is suitable for LiMPO as the positive active material of lithium secondary battery
4(M represents to be selected from least a above metallic element among Fe, Mn, Ni, Co and the Al.) fine and the reactive and excellent in workability such as good fluidity and pulverizing of purposes of manufacturing raw material.In addition, manufacturing method according to the invention can be at industrial this lithium phosphate condensates of advantageously making.In addition, with the ithium iron phosphorus series composite oxides that use lithium phosphate condensates of the present invention to obtain lithium secondary battery, demonstrate near LiFePO as positive active material as making raw material
4The value of theoretical loading capacity.
Description of drawings
Fig. 1 is the Li that obtains with embodiment 1
3PO
4X-ray diffractogram.
Fig. 2 is the Li that obtains with embodiment 1
3PO
4Electron micrograph (10,000 times of multiplying powers).
Embodiment
Below, according to preferred embodiment explaining the present invention.
(lithium phosphate condensates)
Trilithium phosphate of the present invention is that fine primary particle forms the aggregate that aggregate forms.
The primary particle of lithium phosphate condensates of the present invention, the particle diameter of being tried to achieve by the scanning electron microscope photo is below the 1 μ m, be preferably 0.01～1 μ m, in addition, the aggregate of gathering this primary particle, the median size of being tried to achieve by the scanning electron microscope photo be 1～10 μ m, be preferably 1～5 μ m.Lithium phosphate condensates of the present invention is because be the fine particle swarm of the median size of this scope, so reactive excellent.
And, lithium phosphate condensates of the present invention, except the median size with this above-mentioned scope, angle of repose is below 50 degree, is preferably 30～50 degree.Lithium phosphate condensates of the present invention because angle of repose is in this scope, so be the aggregate of particulate, but mobile excellent, handle or with the blending dispersion excellence of other reaction raw materials.
In addition, one of feature of lithium phosphate condensates of the present invention is: use CuK α line as gamma ray source and when carrying out X-ray diffraction analysis, near the half value of diffraction peak (010) face 2 θ=16.8 ° is wide to be more than 0.2 °, is preferably 0.2～0.3 °.Lithium phosphate condensates of the present invention, the half value of the diffraction peak by lattice plane (010) face is wide in this scope, is low, the soft particle swarm of crystallinity, can reach miniaturization by further pulverizing, and processibility is also excellent.
In addition, as other preferred rerum natura of lithium phosphate condensates of the present invention, the BET specific surface area is 1～50m
2/ g, be preferably 15～50m
2/ g, as impurity, Na content be 100ppm following, be preferably 80ppm, the content of Al, Ca and Si is counted below the 100ppm, is preferably below the 80ppm with total amount, at this moment, lithium phosphate condensates of the present invention can be suitable for the manufacturing raw material that electronic material is used, so preferred above-mentioned rerum natura.
Below, the manufacture method of lithium phosphate condensates of the present invention is described.
The manufacture method of lithium phosphate condensates of the present invention, be primarily characterized in that, reacting in the method for making Trilithium phosphate by the aqueous solution that contains lithium hydroxide and the aqueous solution that contains phosphoric acid, the concentration of employed lithium hydroxide aqueous solution is set in the specified range, and, in the specified range field, set temperature of reaction about reaction conditions.
The employed aqueous solution that contains lithium hydroxide in the manufacture method of the present invention, be the aqueous solution that lithium hydroxide is dissolved in water, in the present invention, the aqueous solution that contains this lithium hydroxide is the aqueous solution that contains lithium hydroxide 4～6 weight %, and this is an important condition.In the manufacture method of lithium phosphate condensates of the present invention, the reason that the concentration of lithium hydroxide aqueous solution is set in this scope is: when the concentration less than 4 weight % of lithium hydroxide aqueous solution, strength of solution is low excessively, produces a large amount of waste liquids, thus industrial be disadvantageous, on the other hand, when surpassing 6 weight %, solid-liquid separation, dried Trilithium phosphate solidifies, agglutinating particle is a coarse grain, so inadvisable.
Operable lithium hydroxide, so long as can be at the industrial lithium hydroxide that obtains, just be not particularly limited, it both can be hydrate, it also can be anhydride, but when obtaining highly purified lithium phosphate condensates, the preferred few lithium hydroxide of foreign matter content that uses, particularly because can contain in the lithium hydroxide that industry obtains that Na is more than the 20ppm, Ca is more than the 60ppm, Al is more than the 100ppm, Si is more than the 100ppm, so under the situation of the purposes that is applicable to electronic material, the preferred refining lithium hydroxide of removing these impurity that uses.Preferred these refining lithium hydroxides be by secondary filter contain lithium hydroxide (below, be called " rough lithium hydroxide ") thus the aqueous solution after and carry out the refining lithium hydroxide that partial crystallization has reduced impurity such as Na, Ca, Al, Si.
The concrete operations that obtain this refining lithium hydroxide are that at first, the lithium hydroxide solution of above-mentioned rough lithium hydroxide has been dissolved in modulation.The concentration of the rough lithium hydroxide in the aqueous solution, if below the saturation solubility, just be not particularly limited, but because the solubleness of lithium hydroxide depends on solvent temperature consumingly, so be preferably, for example, under 80 ℃ temperature, make it dissolving, in LiOH, be 1～12 weight %, be preferably 9～12 weight %.
In addition, dissolve the water of rough lithium hydroxide, use and remove Na, K, Ca, Cl, SO by reverse osmosis membrane, ultra filtration filter membrane, ion-exchange membrane etc. at least
4Deng the pure water of ionic impurity, from the viewpoint of sneaking into of the impurity that can prevent to bring, be particularly preferred by institute's dissolved water.In addition, processed water as water flowing in reverse osmosis membrane, ultra filtration filter membrane or ion exchange resin, for example, use the pretreating device that constitutes by aggegation filtration unit and gac etc. handle former water such as process water, town water, river with remove most of outstanding absurd creature and organic water in the former water or, the water handled with the pure water device that makes spent ion exchange resin etc.
As reverse osmosis membrane, can use commercially available film module (module), operational conditions etc. are not particularly limited, can be according to well-established law.Specifically, the molecular weight cut-off of reverse osmosis membrane is 400～100000, be preferably 1000～10000, as material, suitable use is acetate fiber prime system, polyamide-based, crosslinked polyamine system, crosslinked polyethers system, polysulfones, SPSF, polyvinyl alcohol etc. for example.The shape of film can be Any shape such as plate shaped, volution, hollow filate, tubular, pleat shape.
The ultra filtration filter membrane can use commercially available film module, and operational condition etc. are not particularly limited, can be according to well-established law.Specifically, the molecular weight cut-off of ultra filtration filter membrane is 400～100000, is preferably 1000～10000, and as material, suitable use is regenerated cellulose, polyethers sulfonic acid, polysulfones, polyacrylonitrile, polyvinyl alcohol, sintering metal, pottery, carbon etc. for example.The shape of film can be Any shape such as plate shaped, volution, tubular, hollow filate, pleat shape.
Then, secondary filter contains the aqueous solution of the rough lithium hydroxide of above-mentioned synthetic normality, removes the insoluble composition that contains Al, Si impurity composition.
Above-mentioned secondary filter can use filtering materials such as secondary filter film to implement.Operable secondary filter film, can enumerate the gauze strainer with surface filtration effect, depth type filter etc. with self-filtering effect, in the present invention, gauze strainer with surface filtration effect, considering from the viewpoint of can efficient removing insoluble composition well, is particularly preferred.The nominal pore size of secondary filter film is 0.1～1 μ m, be preferably 0.2～0.5 μ m, the material of secondary filter film is not particularly limited, can enumerate organic systems such as pyroxylin (e) cement, cellulose film, cellulose acetate, polyacrylonitrile, polysulfones, polyolefine, polymeric amide, polyimide, polyvinylidene difluoride (PVDF) for example film or, the film of inorganic system such as graphite, pottery, sintered glass.In addition, so long as laboratory scale can be used filtering materials such as PTFE membrane filter.The form of gauze strainer is not particularly limited, and considers but be easy to viewpoint from operability, preferred especially cartridge type.Use commercially available secondary filter device, import in this secondary filter device by rough lithium hydroxide aqueous solution and can implement these secondary filters above-mentioned synthetic normality.This secondary filter operation, also can or add to depress and carry out in decompression, but be not particularly limited, usually, with liquid-feeding pump the rough lithium hydroxide aqueous solution of above-mentioned synthetic normality is 0～100 ℃, is preferably 20～80 ℃, is 1～30mL/min, is preferably 5～15mL/min and imports in the secondary filter device with flow velocity with temperature, at 0.1～0.5MPa, be preferably under the pressure of 0.2～0.3MPa and handle.In addition, by the filter operation that secondary filter is carried out, preferably under the temperature that lithium hydroxide is not separated out, carry out filter operation from the aqueous solution.
Handle by above-mentioned secondary filter, in most cases, obtain making the content of Al, each impurity of Si be reduced to below the 50ppm, be preferably the following lithium hydroxide of 30ppm, in the present invention, for the content that makes Na, Ca, Si, Al further reduces, preferably when handling, above-mentioned secondary filter proceeds the partial crystallization operation.
Concrete partial crystallization operation can be undertaken by following method, that is, make the aqueous solution that method that lithium hydroxide separates out from the aqueous solution that contains the lithium hydroxide that carries out above-mentioned secondary filter or heating contain the lithium hydroxide that carries out above-mentioned secondary filter evaporate the method that a certain amount of moisture is separated out lithium hydroxide by cooling.In the present invention, consider that from the good viewpoint of organic efficiency of refining lithium hydroxide the latter's the method that lithium hydroxide is separated out that heats is particularly preferred.
Heat and make the partial crystallization operation that lithium hydroxide separates out, contain by heating the lithium hydroxide that carries out above-mentioned secondary filter normality the aqueous solution to temperature be more than 80 ℃, be preferably 90～100 ℃ with evaporation except that 10～70 weight % that anhydrate, be preferably 30～60 weight % and implement.In this partial crystallization operation, anhydrate by in this scope, removing, can be removed the refining lithium hydroxide of impurity effectively.In addition, also can under reduced pressure carry out by the partial crystallization operation of this heating.
The refining lithium hydroxide that obtains like this is that the content of Na, Si, Al, each impurity of Ca is lowered to below the 50ppm at least, is preferably the following lithium hydroxide of 20ppm.
The aqueous solution that contains phosphoric acid of the opposing party's reaction raw materials, be the aqueous solution that phosphoric acid is dissolved in water, the concentration that contains the aqueous solution of this phosphoric acid is not particularly limited, but because use contain phosphoric acid 5～50 weight %, when being preferably the aqueous solution of 5～40 weight %, solid-liquid separation, dried Trilithium phosphate can not solidify and obtain the lithium phosphate condensates of stabilised quality, so be particularly preferred.
Operable phosphoric acid so long as at industrial available phosphoric acid, just be not particularly limited, but when obtaining highly purified lithium phosphate condensates, especially preferably uses the few phosphoric acid of foreign matter content.
In addition, dissolve the water of above-mentioned lithium hydroxide and phosphoric acid, use and removed Na, K, Ca, Cl, SO by reverse osmosis membrane, ultra filtration filter membrane, ion-exchange membrane etc. at least
4Deng the pure water of ionic impurity, from the viewpoint of sneaking into of the impurity that can prevent to bring, be particularly preferred by institute's dissolved water.
The manufacture method of lithium phosphate condensates of the present invention is added the phosphate aqueous solution of afore mentioned rules concentration in the lithium hydroxide aqueous solution of afore mentioned rules concentration and is reacted.Usually this reaction is a neutralization reaction and follow heating, and in the manufacture method of Trilithium phosphate of the present invention, keeping that this is reflected at below 70 ℃ also is an essential condition.
In the present invention, temperature of reaction being set in the reason of carrying out in this scope is: when surpassing 70 ℃, the solubleness of Trilithium phosphate rises, and solid-liquid separation, dried Trilithium phosphate solidify, and solidified particle becomes coarse grain, so inadvisable.In addition, in the present invention, this temperature of reaction is below 40 ℃, when being preferably 5～40 ℃ especially, and solid-liquid separation, dried Trilithium phosphate can not solidify, and obtain the lithium phosphate condensates of stabilised quality, so be particularly preferred.
Addition with regard to the aqueous solution that contains phosphoric acid, along with phosphate aqueous solution is imported in the reaction system, the pH value reduces, can make this pH value reach 10.5, but in most cases, import volume with regard to the aqueous solution that contains phosphoric acid, phosphoric acid is 0.98～1.02, is preferably 0.99～1.01 with respect to the mol ratio of lithium hydroxide, being preferably the reaction equivalent especially is 1, not residual from reaction solution unreacted reactant arranged, prevent solid-liquid separation, dried viewpoint of solidifying is considered, is particularly preferred.
Interpolation speed to the aqueous solution that contains phosphoric acid that added is not particularly limited, in order to obtain the material of stabilised quality, so preferably add with certain speed.
Reaction is carried out solid-liquid separation by well-established law after finishing, and reclaims precipitate, and is clean, dry, pulverizes as required, obtains goods.
In addition, the pulverizing of carrying out as required be inferior suitable the carrying out of fragile bonded situation between resulting lithium phosphate condensates is by dry aggregate particle, but the particle of lithium phosphate condensates self has following characteristic.Promptly, it is the aggregate that constitutes by fine primary particle, the primary particle size of being tried to achieve by the scanning electron microscope photo is below the 1 μ m, be preferably 0.01～1 μ m, in addition, the aggregate of this primary particle median size of being tried to achieve by the scanning electron microscope photo is 1～10 μ m, is preferably 1～5 μ m.
The lithium phosphate condensates that obtains like this is except that having above-mentioned particle property, angle of repose be 50 degree following, be preferably 30～50 degree, the preferred CuK α line that uses is as gamma ray source and when carrying out X-ray diffraction analysis, (010) near the half value of the diffraction peak 2 θ=16.8 of face ° is wide is more than 0.2 °, be preferably 0.2～0.3 °, and the BET specific surface area is 1～50m
2/ g, be preferably 15～50m
2/ g.In addition, for impurity, Na content is below the 100ppm, is preferably 80ppm, and the content of Al, Ca and Si is counted below the 100ppm, is preferably below the 80ppm with total amount.
Lithium phosphate condensates of the present invention, the particle diameter that is aggregate while aggregate self is fine as described above, and is reactive and mobile excellent, and crystallinity is low, can reach miniaturization by further pulverizing, processibility is also excellent, high purity.Such lithium phosphate condensates, the LiMPO that can be suitable as the raw material of purposes, the inorganic solid electrolyte of the manufacturing raw material of vinyl carbinol catalyst for producing, functional inorganic material for example, particularly uses as the positive active material of lithium secondary battery
4(M represents to be selected from least a above metallic element among Fe, Mn, Co, Ni and the Al.) the manufacturing raw material.
(ithium iron phosphorus series composite oxides)
Below, the manufacture method of ithium iron phosphorus series composite oxides of the present invention is described.
The manufacture method of ithium iron phosphorus series composite oxides of the present invention, it is characterized in that, mix above-mentioned lithium phosphate condensates, ferrous phosphate salt hydrate and conductive carbon material and fire (hereinafter referred to as " manufacture method of A ") or mix above-mentioned lithium phosphate condensates, ferrous phosphate salt hydrate, contain at least a above metallic compound and the conductive carbon material of the metallic element that is selected among Mn, Co, Ni and the Al and fire (hereinafter referred to as " manufacture method of B ").
In the manufacture method of the ithium iron phosphorus series composite oxides of above-mentioned A of the present invention and B, particularly including mixing (A) above-mentioned lithium phosphate condensates, ferrous phosphate salt hydrate and conductive carbon material or (B) above-mentioned lithium phosphate condensates, the ferrous phosphate salt hydrate, contain and be selected from Mn, Co, at least a above metallic compound of the metallic element among Ni and the Al and first operation of conductive carbon material, then, thereby the resulting mixture of pulverization process obtains second operation of reacting precursor, then, thereby fire the 3rd operation that this reacting precursor obtains the ithium iron phosphorus series composite oxides, when using ithium iron phosphorus series composite oxides that above-mentioned operation obtains as the positive active material of lithium secondary battery, can improve loading capacity, so be preferred.
According to the manufacture method of above-mentioned A, can obtain coating as the suitable LiFePO of the positive active material of lithium secondary battery with conductive carbon material
4The ithium iron phosphorus series composite oxides of particle surface, in addition,, can obtain coating LiFe with conductive carbon material according to the manufacture method of above-mentioned B
1-yMe
yPO
4(Me represents to be selected from least a above metallic element among Mn, Co, Ni and the Al.Y represents O＜y＜1) the ithium iron phosphorus series composite oxides of particle surface.
In above-mentioned first operation, operable ferrous phosphate in the manufacture method of above-mentioned A and B so long as industrial available, just be not particularly limited, but if uses following such general formula Fe that uses
3(PO
4)
28H
2The ferrous phosphate salt hydrate that O represents, promptly, the median size of trying to achieve by laser diffractometry is below the 5 μ m, be preferably 1～5 μ m and, use CuK α line to carry out this ferrous phosphate salt hydrate of X-ray diffraction analysis (Fe as gamma ray source
3(PO
4)
28H
2Near the half value of peak (020) face in the time of O), 2 θ=13.1 is wide to be more than 0.20 °, be preferably processibility and reactive excellent ferrous phosphate salt hydrate (Fe such as 0.20～0.40 °, crystallinity are low, pulverizing
3(PO
4)
28H
2O) time, the specific volume that can easily make reacting precursor described later is below the 1.5mL/g, so be particularly preferred.
Ferrous phosphate salt hydrate (Fe with such physical property
3(PO
4)
28H
2O), by alkali being added in the aqueous solution that contains divalent iron salt and phosphoric acid and reacting and to make easily.
As operable divalent iron salt in the manufacture method of ferrous phosphate salt hydrate, can enumerate for example ferrous sulfate, ironic acetate, ironic oxalate etc.They both can be that hydrate also can be an anhydride.Wherein, ferrous sulfate heptahydrate (FeSO
47H
2O), low price and be high purity obtains industrial, easily so be particularly preferred.
In addition, as operable phosphoric acid,, just be not particularly limited if can obtain easily industrial.
In addition,, be not particularly limited, can enumerate for example ammonia, ammoniacal liquor, sodium hydroxide, potassium hydroxide, NaHCO as operable alkali
3, Na
2CO
3, LiOH, K
2CO
3, KHCO
3, Ca (OH)
2Deng organic basess such as mineral alkali or thanomin etc.These alkali can use one or more, wherein, because sodium hydroxide low price and obtain easily industrial, so be particularly preferred.
The divalent iron salt of these raw materials, phosphoric acid and alkali use foreign matter content few, and this is obtaining highly purified ferrous phosphate salt hydrate (Fe
3(PO
4)
28H
2O) on the aspect, be particularly preferred.
As concrete operation, at first, the aqueous solution of modulation dissolving divalent iron salt and phosphoric acid makes phosphoric acid be 0.60～0.75, be preferably 0.65～0.70 with respect to the mol ratio of the iron atom in the divalent iron salt.At this moment, the concentration of the aqueous solution so long as can dissolve divalent iron salt and concentration of phosphoric acid, just is not particularly limited, and counts more than 0.1 mol, is preferably 0.50～1.0 mol with divalent iron salt usually.
Then, alkali is added in this aqueous solution, ferrous phosphate is separated out.The evolution reaction of ferrous phosphate can carry out fast by the interpolation of this alkali.The addition of alkali is 1.8～2.0, is preferably 1.95～2.0 with respect to the mol ratio of divalent iron salt.
Interpolation temperature to this alkali is not particularly limited, and is generally 5～80 ℃, is preferably 15～35 ℃.In addition, the speed of dripping of alkali etc. is not particularly limited, but, preferably slowly imports in the reaction system with certain speed of dripping in order to obtain stay-in-grade material.
After reaction finishes, carry out solid-liquid separation, reclaim precipitate, clean, drying, obtain goods by well-established law.
In addition, just clean, particularly using under the situation of sodium hydroxide as alkali, preferred water is cleaned fully, up to the ferrous phosphate salt hydrate (Fe that separates out
3(PO
4)
28H
2O) the Na content in is below the 1 weight %, is preferably below the 0.8 weight %.
In addition, just dry, when 35 ℃ of less thaies, carrying out drying needs spended time, during above 50 ℃, causes the disengaging of ferrous oxidation and crystal water, so preferably carry out at 35～50 ℃.
Ferrous phosphate salt hydrate (the Fe that obtains like this
3(PO
4)
28H
2O), the median size of trying to achieve by laser diffractometry is below the 5 μ m, be preferably 1～5 μ m, the half value of the diffraction peak of lattice plane (020) face of being tried to achieve by X-ray diffraction analysis is wide to be more than 0.20 °, be preferably 0.20～0.40 °, as preferred rerum natura, Na content as impurity is below the 1 weight %, is preferably below the 0.8 weight %.
Operable conductive carbon material in the manufacture method as above-mentioned A and B, for example can enumerate carbon black class, carbon fibers etc. such as graphite such as natural graphite such as flaky graphite, flaky graphite and amorphous graphite and electrographite, carbon black, acetylene black, graphitized carbon black (Ketjenblack), thermally oxidized black, furnace black, dim, thermal black, they can use one or more.Wherein, because graphitized carbon black is a particulate, obtain easily industrial, so be particularly preferred.
The median size of being tried to achieve by these the electron micrograph of conductive carbon material is below the 1 μ m, be preferably below the 0.1 μ m, when being preferably 0.01～0.1 μ m especially, because can be with high dispersion state attached to LiFePO
4Or LiFe
1-yMe
yPO
4(Me represents to be selected from least a above metallic element among Mn, Co, Ni and the Al.Y represents 0＜y＜1) particle surface, so be preferred.
The operable at least a above metallic compound that contains the metallic element that is selected among Mn, Co, Ni and the Al in the manufacture method as above-mentioned B, can enumerate the oxide compound that contains these metallic elements, oxyhydroxide, nitrate, acetate, carbonate, phosphoric acid salt, organic acid salt etc., rerum natura as these metallic compounds, the median size of trying to achieve by laser diffractometry is below the 10 μ m, be preferably 5 μ m when following, mixing is abundant, reactive good, so be particularly preferred.
In addition, in the manufacture method of ithium iron phosphorus series composite oxides of the present invention, the lithium phosphate condensates of above-mentioned raw materials, ferrous phosphate salt hydrate (Fe
3(PO
4)
28H
2O), conductive carbon material and metallic compound, use highly purifiedly, when particularly using, be preferred as the positive active material of lithium secondary battery.
The operation of first operation is, amount is mixed (A) lithium phosphate condensates, ferrous phosphate salt hydrate and conductive carbon material or (B) lithium phosphate condensates, ferrous phosphate salt hydrate, conductive carbon material and contain at least a above metallic compound of the metallic element that is selected among Mn, Co, Ni and the Al at first, in accordance with regulations.
In the manufacture method of above-mentioned A, the cooperation ratio of lithium phosphate condensates and ferrous phosphate salt hydrate, mol ratio (Li/Fe) with Fe atom in the ferrous phosphate salt hydrate and the Li atom in the lithium phosphate condensates is expressed as 0.9～1.1, is preferably at 1.00～1.05 o'clock, from obtaining LiFePO
4Monophasic viewpoint considers, is preferred, when this mol ratio less than 0.9 and when surpassing 1.1, owing to remaining unreacting material is arranged, so be worthless.
In addition, in the manufacture method of above-mentioned B, the cooperation ratio of at least a above metallic compound of the metallic element that lithium phosphate condensates, ferrous phosphate salt hydrate and containing is selected among Mn, Co, Ni and the Al, as the Fe atom in the ferrous phosphate salt hydrate, Li atom in the lithium phosphate condensates and the mol ratio of the metallic element (Me) in the metallic compound, in Li/ (Fe+Me), be 0.9～1.1, be preferably at 1.00～1.05 o'clock, from obtaining LiFe
1-yMe
yPO
4Monophasic viewpoint is considered, is particularly preferred.
In addition, with regard to conductive carbon material, with fire before compare, after firing, the amount of the C atom that is contained in the conductive carbon material has the tendency that reduces some, the use level of conductive carbon material, with respect to the total amount of lithium phosphate condensates and ferrous phosphate salt hydrate or lithium phosphate condensates and ferrous phosphate salt hydrate and metallic compound, be 0.08～15.5 weight %, be preferably 3.8～9.5 weight %, at this moment, the covering amount of conductive carbon material uses the C atom with respect to LiFePO
4Or LiFe
1-yMe
yPO
4(Me represents to be selected from least a above metallic element among Mn, Co, Ni and the Al.Y represents 0＜y＜0) content represent, be 0.1～20 weight %, be preferably 5～12 weight %.When the use level less than 0.08 weight % of this conductive carbon material, can not give the ithium iron phosphorus series composite oxides sufficient electroconductibility, so in the lithium secondary battery of resulting ithium iron phosphorus series composite oxides as positive active material, internal resistance rises, on the other hand, when surpassing 15.5 weight %, opposite, the loading capacity of unit weight or volume reduces, so inadvisable.
In addition, in first operation,, preferably use mixing machine to carry out thorough mixing, in advance each raw material is mixed equably with dry type in order to implement second operation described later.
Second operation be in the manufacture of above-mentioned A and B, for have better reactivity, use pulverizer with the mixture of dry type thorough mixing and these raw materials of pulverization process, obtain the operation of reacting precursor.
At this, so-called above-mentioned reacting precursor is meant, fire in the back contain (A) thus lithium phosphate condensates, ferrous phosphate salt hydrate and conductive carbon material or (B) lithium phosphate condensates, ferrous phosphate salt hydrate, conductive carbon material and contain before the mixture of at least a above metallic compound of the metallic element that is selected among Mn, Co, Ni and the Al, for improve reactivity, when making each raw material high dispersing, the grain spacing that makes each stock yard is from the approaching material that has improved the contact area of each raw material as much as possible.
In the present invention, mixture after this pulverization process, its specific volume is below the 1.5mL/g, when being preferably 1.0～1.4mL/g, do not exist in and carry out the grain that sintering causes under 500～700 ℃ the firing temperature and grow up, in X-ray diffraction analysis, obtain conductive carbon material is coated on LiFePO equably
4Or LiFe
1-yMe
yPO
4(Me represents to be selected from least a above metallic element among Mn, Co, Ni and the Al.Y represents 0＜y＜1) the ithium iron phosphorus series composite oxides of monophasic particle surface, so preferably with the mixture of the specific volume of this scope as reacting precursor.
In addition, the so-called specific volume among the present invention be based on the apparent density of JIS-K-5101 record or apparent specific volume method, by tip-tap (tap) method with sample 10g pack in the graduated cylinder of 50mL, volume is left standstill afterwards, reads in tip-tap for 500 times, the data of trying to achieve by following formula.
[formula 1]
Specific volume (mL/g)=V/F
(in the formula, F: quality (g), the V of the sample of handling in the expression receiver: the capacity (mL) of the sample after the expression tip-tap.)
And, in the manufacture method of ithium iron phosphorus series composite oxides of the present invention, above-mentioned reacting precursor, except that specific volume is in this scope, when the ferrous phosphate salt hydrate of the raw material that is contained in this reacting precursor is close to amorphous state, even grow into purpose under situation about firing under 500～700 ℃ the low temperature with what suppress particle diameter, reaction is also carried out fully, obtains LiFePO
4Or LiFe
1-yMe
yPO
4(Me represents to be selected from least a above metallic element among Mn, Co, Ni and the Al.Y represents 0＜y＜1) single-phase, so be particularly preferred.
As operable pulverizer, the preferred pulverizer that uses with powerful shearing force, as pulverizer, preferably use roating sphere shredder, oscillating mill, star lapping machine, vehicle mixer grinder etc. with so powerful shearing force.This pulverizer is that pulverizing vehicles such as ball, pearl are put in the container, mainly the pulverizer of pulverizing by vectorial shearing, rubbing effect.As such device, can utilize commercially available device.
When granular vectorial particle diameter was 1～25mm, pulverizing can be carried out fully, so be preferred.The ceramic bead that this granular vectorial material is zirconium white, aluminum oxide, hardness height, abrasion performance and can prevent the metallic pollution of material are so be particularly preferred.
In addition, with regard to above-mentioned granular vehicle, preferably granular vehicle is accommodated in the container, in order suitably to manage flow vectorial shearing force and frictional force with spatial volume 50～90%, the operating condition of adjusting pulverizer aptly carries out pulverization process, and this is preferred.
In addition, in the manufacture method of ithium iron phosphorus series composite oxides of the present invention, as required, remove beyond the above-mentioned pulverization process, this reacting precursor is carried out press molding to be handled, when further improving the contact area of each raw material, can further improve the loading capacity and the cycle characteristics of lithium secondary battery.Being shaped, difference is not particularly limited pressure with the difference of pressing machine, Intake Quantity etc., is generally 5～200MPa.Compression molding press can suitably use Ingot pressing machine, briquetting press, roller type press etc., so long as the device that can suppress just is not particularly limited.
Then, in the 3rd operation, fire the reacting precursor that in second operation, obtains.
Firing temperature is 500～700 ℃, is preferably 550～650 ℃.In the present invention, by making this firing temperature in this scope,, can improve loading capacity and charging cycle characteristic with the lithium secondary battery of resulting ithium iron phosphorus series composite oxides as positive active material.During 500 ℃ of firing temperature less thaies,,, on the other hand, when surpassing 700 ℃, cause the particle growth owing to produce sintering, so inadvisable so remaining have a unreacting material because reaction fully do not carry out.
Firing time is 2～20 hours, is preferably 5～10 hours.
Fire and can carry out in any environment in inertness atmosphere surroundings such as nitrogen, argon or in the reducing gas environment such as hydrogen, carbon monoxide, be not particularly limited, the security aspect during from operation is considered, preferably carries out in nitrogen, argon gas body.In addition, these are fired as required and also can carry out several times.
After firing, suitably cool off, pulverize as required or classification, obtain coating LiFePO equably with conductive carbon material
4Or LiFe
1-yMe
yPO
4(Me represents to be selected from least a above metallic element among Mn, Co, Ni and the Al.Y represents 0＜y＜1) the ithium iron phosphorus series composite oxides of particle surface.In addition, in order to prevent the oxidation of Fe and Me element, preferably carry out in the cooling becoming inertness atmosphere surrounding gases such as nitrogen, argon or reducing environment gases such as hydrogen, carbon monoxide in the reaction system.In addition, the pulverizing of carrying out as required, being adapted at firing the ithium iron phosphorus series composite oxides that obtain is inferior carrying out of situation of fragile bonded cake mass, but according to ithium iron phosphorus series composite oxides of the present invention manufacture method preferred embodiment, the particle of ithium iron phosphorus series composite oxides self has following specific median size, BET specific surface area.That is, the median size that resulting ithium iron phosphorus series composite oxides are tried to achieve by the scanning electron microscope photo is below the 0.5 μ m, is preferably 0.05～0.5 μ m, and the BET specific surface area is 10～100m
2/ g, be preferably 30～70m
2/ g.
The ithium iron phosphorus series composite oxides of the present invention that obtain like this can be suitable as by positive pole, negative pole, dividing plate and contain the positive active material of the lithium secondary battery that the nonaqueous electrolyte of lithium salts constitutes.
In addition, during as positive active material, its form also can be that median size is that the median size that the following primary particle set of the above 0.5 μ m of 0.05 μ m forms is the following primary particle aggregates of the above 75 μ m of 1 μ m with these ithium iron phosphorus series composite oxides.And, in the above-mentioned aggregate, be preferably, more than 70% of cumulative volume, preferred be that particle diameter is below the above 20 μ m of 1 μ m more than 80%.In addition, when these ithium iron phosphorus series composite oxides are pulverized in atmosphere etc., owing to contain the above moisture of 3000ppm in the resulting ithium iron phosphorus series composite oxides, so before the positive active material use, implement operations such as vacuum-drying, the moisture content of these ithium iron phosphorus series composite oxides is below the 2000ppm, is preferably below the 1500ppm.
In addition, the ithium iron phosphorus series composite oxides that obtain with manufacture method of the present invention, can with known other lithium-cobalt system composite oxides, lithium nickel composite oxide or lithium manganese system complex oxide and usefulness, the security that can further improve the lithium secondary battery that uses present lithium-cobalt system composite oxides, lithium nickel composite oxide or lithium manganese system complex oxide.At this moment, to and the rerum natura of lithium-cobalt system composite oxides, lithium nickel composite oxide or the lithium manganese system complex oxide of usefulness etc. be not particularly limited, but be preferably, median size be 1～20 μ m following, be preferably 1～15 μ m, more preferably 2～10 μ m, the BET specific surface area is 0.1～2.0m
2/ g, be preferably 0.2～1.5m
2/ g, 0.3～1.0m more preferably
2/ g.
[embodiment]
Below, explain the present invention by embodiment, but the present invention is not limited to this.
＜lithium hydroxide 〉
In addition, in an embodiment of the present invention, use the lithium hydroxide of commercially available lithium hydroxide one salt hydrate having been implemented following purification operations.
Foreign matter content in this commercially available lithium hydroxide sample is as shown in table 1.
In addition, this impurity level is the value of trying to achieve by ICP mass analysis and turbidimetry.
[table 1]
Table 1
| The content of LiOH (weight %) | 56.8 |
| Na content (ppm) | 22 |
| Ca content (ppm) | 60 |
| Al content (ppm) | 120 |
| Si content (ppm) | 110 |
Above-mentioned rough lithium hydroxide one salt hydrate 1062g is dissolved among the pure water 5000g modulation aqueous solution under 50 ℃.In addition, pure water is a pure water of handling the water of handling with the Water Purifiers with ion exchange resin with ultra-filtration filters module (Xu Huaxuegongyeshe system, molecular weight cut-off 6000), and employed pure water also is the pure water that carries out with the same processing of this pure water among the refining and embodiment of following lithium hydroxide.
Then, under 40 ℃, dissolved the aqueous solution of above-mentioned synthetic rough lithium hydroxide by the PTFE system membrane filter filtration of 0.5 μ m with the aperture.
Take the filtered liquid after a part is filtered, under reduced pressure carry out drying, the foreign matter content in the lithium hydroxide sample that obtains is as shown in table 2.
[table 2]
Table 2
| The content of LiOH (weight %) | 56.8 |
| Na content (ppm) | 21 |
| Ca content (ppm) | 55 |
| Al content (ppm) | 20 |
| Si content (ppm) | 1O |
Then, be warmed to 95 ℃, while under reduced pressure keep the partial crystallization that moisture carries out 4 hours here.In addition, the moisture of recovery is 3300g.After the cooling, carry out solid-liquid separation, reclaim the lithium hydroxide of separating out, then, under reduced pressure carry out the lithium hydroxide (LiOHH that drying obtains by well-established law
2O) foreign matter content in the sample is as shown in table 3.
[table 3]
Table 3
| The content of LiOH (weight %) | 56.8 |
| Na content (ppm) | 2.6 |
| Ca content (ppm) | 7.1 |
| Al content (ppm) | 2.2 |
| Si content (ppm) | 7.3 |
Embodiment 1
In reactor, one salt hydrate 126g is dissolved in the pure water with above-mentioned refining lithium hydroxide, modulation 1500g, 4.8 weight % lithium hydroxide aqueous solutions (pH value 11.6).
Then, to contain phosphoric acid (Japanese chemical industry society system below 40 ℃ while the temperature of keeping reaction system, the high purity product) the phosphate aqueous solution 1000g of 9.8 weight %, with in 83mL/ minute speed, about 12 minutes these reaction vessels that all drip of cost, make Trilithium phosphate separate out (pH value 10.5).
Then, filter, reclaim Trilithium phosphate.
Then, descended the dry Trilithium phosphates that reclaimed 20 hours, obtain dry product 110 ℃ of temperature.With the resulting dry product of X-ray diffraction analysis, consequently consistent with JCPDS card number (25-1030) diffraction pattern, be Li so confirm this dry product
3PO
4
Resulting Li
3PO
4Each rerum natura as shown in table 5.In addition, reaction conditions is as shown in table 4.
In addition, use CuK α line to carry out the resulting Li of X-ray diffraction analysis as gamma ray source
3PO
4, the half value of measuring near diffraction peak (010) face in 2 θ=16.8 is wide, and its result is as shown in table 5.In addition, resulting Li
3PO
4X-ray diffractogram as shown in Figure 1.
In addition, the content of Na, Ca, Al, Si is tried to achieve by the ICP optical spectroscopy.In addition, the particle diameter of primary particle and primary particle aggregate is tried to achieve by scanning electron microscope.In addition, this scanning electron microscope photo as shown in Figure 2.
Embodiment 2
In reactor, one salt hydrate 126g is dissolved in the pure water with above-mentioned refining lithium hydroxide, modulation 1500g, 4.8 weight % lithium hydroxide aqueous solutions (pH value 11.6).
Then, to contain phosphoric acid (Japanese chemical industry society system below 40 ℃ while the temperature of keeping reaction system, the high purity product) the phosphate aqueous solution 262g of 38 weight %, with in 83mL/ minute speed, about 3 minutes 30 seconds these reaction vessels that all drip of cost, make Trilithium phosphate separate out (pH value 10.5).
Then, filter, reclaim Trilithium phosphate.
Then, descended the dry Trilithium phosphates that reclaimed 23 hours, obtain dry product 48 ℃ of temperature.With the resulting dry product of X-ray diffraction analysis, consequently consistent with JCPDS card number 25-1030 diffraction pattern, be Li so confirm this dry product
3PO
4
Resulting Li
3PO
4Each rerum natura as shown in table 5.In addition, reaction conditions is as shown in table 4.
In addition, use CuK α line to carry out the resulting Li of X-ray diffraction analysis as gamma ray source
3PO
4, the half value of measuring near diffraction peak (010) face in 2 θ=16.8 is wide, and its result is as shown in table 5.
In addition, the particle diameter of the content of Na, Ca, Al, Si, primary particle and primary particle aggregate is tried to achieve similarly to Example 1.
Embodiment 3
In reactor, one salt hydrate 126g is dissolved in the pure water with above-mentioned refining lithium hydroxide, modulation 1500g, 4.8 weight % lithium hydroxide aqueous solutions (pH value 11.6).Then, to contain phosphoric acid (Japanese chemical industry society system below 70 ℃ while the temperature of keeping reaction system, the high purity product) the phosphate aqueous solution 980g of 9.8 weight %, with in 83mL/ minute speed, about 12 minutes these reaction vessels that all drip of cost, make Trilithium phosphate separate out (pH value 10.5).
Then, filter, reclaim Trilithium phosphate.
Then, descended the dry Trilithium phosphates that reclaimed 20 hours, obtain dry product 110 ℃ of temperature.With the resulting dry product of X-ray diffraction analysis, consequently consistent with JCPDS card number 25-1030 diffraction pattern, be Li so confirm this dry product
3PO
4
Resulting Li
3PO
4Each rerum natura as shown in table 5.In addition, reaction conditions is as shown in table 4.
In addition, use CuK α line to carry out the resulting Li of X-ray diffraction analysis as gamma ray source
3PO
4, the half value of measuring near diffraction peak (010) face in 2 θ=16.8 is wide, and its result is as shown in table 4.
In addition, the particle diameter of the content of Na, Ca, Al, Si, primary particle and primary particle aggregate is tried to achieve similarly to Example 1.
Comparative example 1
In reactor, one salt hydrate 126g is dissolved in the pure water with above-mentioned refining lithium hydroxide, modulation 800g, 9 weight % lithium hydroxide aqueous solutions (pH value 12.1).
Then, to contain phosphoric acid (Japanese chemical industry society system below 40 ℃ while the temperature of keeping reaction system, the high purity product) the phosphate aqueous solution 1000g of 9.8 weight %, with in 83mL/ minute speed, about 12 minutes these reaction vessels that all drip of cost, make Trilithium phosphate separate out (pH value 10.5).
Then, filter, reclaim Trilithium phosphate.
Then, descended the dry Trilithium phosphates that reclaimed 20 hours, obtain dry product 110 ℃ of temperature.With the resulting dry product of X-ray diffraction analysis, consequently consistent with JCPDS card number 25-1030 diffraction pattern, be Li so confirm this dry product
3PO
4
Resulting Li
3PO
4Each rerum natura as shown in table 5.In addition, reaction conditions is as shown in table 4.
In addition, use CuK α line to carry out the resulting Li of X-ray diffraction analysis as gamma ray source
3PO
4, the half value of measuring near diffraction peak (010) face in 2 θ=16.8 is wide, and its result is as shown in table 5.
In addition, the particle diameter of the content of Na, Ca, Al, Si, primary particle and primary particle aggregate is tried to achieve similarly to Example 1.
Comparative example 2～3
For each rerum natura of two kinds of more commercially available Trilithium phosphates, close and remember in table 5.
[table 4]
Table 4
| The concentration of LiOH in the lithium hydroxide aqueous solution (weight %) | Concentration of phosphoric acid in the phosphate aqueous solution (weight %) | Temperature of reaction (℃) | |
| Embodiment 1 | 4.8 | 9.8 | 35～38 |
| Embodiment 2 | 4.8 | 38 | 35～38 |
| Embodiment 3 | 4.8 | 9.8 | 65～68 |
| Comparative example 1 | 9 | 9.8 | 35～38 |
[table 5]
Table 5
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| The particle diameter of primary particle (μ m) | 0.1～0.3 | 0.1～0.3 | 0.1～0.3 | 0.1～0.3 | 0.1～0.3 | 0.1～0.3 |
| The median size of primary particle aggregate (μ m) | 3 | 3 | 5 | 15 | 6 | 23 |
| Angle of repose (degree) | 43.6 | 44.8 | 44.9 | 51.2 | 52.1 | 44.8 |
| Half value wide (°) | 0.254 | 0.339 | 0.292 | 0.372 | 0.235 | 0.141 |
| BET specific surface area (m 2/g) | 17.25 | 37.21 | 26.32 | 47.34 | 20.59 | 1.09 |
| Purity (%) | 95.0 | 94.7 | 95.1 | 95.3 | 97.0 | 95.4 |
| The content of Na (ppm) | 47 | 87 | 31 | 28 | 3000 | 30 |
| The content of Al (ppm) | 7 | 7 | 6 | 6 | 10 | 6 |
| The content of Si (ppm) | 13 | 24 | 12 | 12 | 50 | 13 |
| The content of Ca (ppm) | 12 | 20 | 8 | 9 | N.D. | 10 |
| The content of Mg (ppm) | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. |
| The content of K (ppm) | 17 | 7 | 9 | 11 | 190 | 10 |
| The content of Ti (ppm) | 2 | 2 | 2 | 2 | N.D. | 2 |
| The content of Mn (ppm) | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. |
| The content of Zn (ppm) | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. |
| The content of Cr (ppm) | 5 | 5 | 5 | 5 | N.D. | 5 |
| The content of Ni (ppm) | N.D. | N.D. | N.D. | N.D. | 10 | N.D. |
| The content of Cu (ppm) | N.D. | N.D. | N.D. | N.D. | N.D. | N.D. |
| The content of Co (ppm) | 40 | N.D. | 6 | N.D. | N.D. | N.D. |
Notes) " N.D. " expression in the table 5 detects below the boundary 1ppm.
Synthesizing of＜ithium iron phosphorus series composite oxides 〉
Synthesis example 1: ferrous phosphate salt hydrate synthetic
To contain Na:13ppm, Ti:1200ppm, Mn:3900ppm, Zn:96ppm, Co:29ppm, Cr:4ppm, the following ferrous sulfate heptahydrate (FeSO of Ni:18ppm, Cu:1ppm
47H
2O) 907g (3 moles) and 75% phosphoric acid (H
3PO
4) 261g (2 moles) is dissolved in the 3L water, makes mixing solutions (17 ℃ of temperature, pH value 1.6).With in 83mL/ minute speed, about 18 minutes these mixing solutionss that drip of cost, make ferrous phosphate separate out (31 ℃ of temperature, pH value 6.7) 16% sodium hydroxide (NaOH) aqueous solution 1500mL (6 moles).
Then, filter, reclaim ferrous phosphate, water 4.5L cleans the ferrous phosphate of this recovery meticulously.
Then, the ferrous phosphate after 50 ℃ of dry down cleaning of temperature 23 hours obtains dry product 490g.With the resulting dry product of X-ray diffraction analysis, consequently consistent with JCPDS card number 30-662 diffraction pattern, be Fe so confirm this dry product
3(PO
4)
28H
2O (yield is 98%).
Resulting Fe
3(PO
4)
28H
2Each rerum natura of O is as shown in table 6.
In addition, use CuK α line to carry out the resulting Fe of X-ray diffraction analysis as gamma ray source
3(PO
4)
28H
2O, the half value of having measured near diffraction peak (020) face 2 θ=13.1 ° is wide.
In addition, the content of Na, Si, Al, Ca, Ti, Mn, Zn, Cr, Ni, Cu, Co is tried to achieve by the ICP optical spectroscopy.In addition, SO
4Content converts to the S atomic percent measurement result of utilizing the ICP optical spectroscopy to obtain and to try to achieve, and tries to achieve the P content of this dry product by absorption photometry.In addition, median size is tried to achieve by laser diffractometry.
[table 6]
Table 6
| The rerum natura of ferrous phosphate salt hydrate | |
| P content (weight %) | 12.2 |
| Median size (μ m) | 2.3 |
| (020) half value of face wide (°) | 0.34 |
| Na content (ppm) | 2170 |
| Si content (ppm) | N.D. |
| Al content (ppm) | 40 |
| Ca content (ppm) | N.D. |
| SO 4Content (ppm) | 3910 |
| Ti content (ppm) | 2350 |
| Mn content (ppm) | 6220 |
| Zn content (ppm) | 180 |
| Co content (ppm) | 30 |
| Cr content (ppm) | 10 |
| Ni content (ppm) | 3 |
| Cu content (ppm) | 5 |
Notes) " N.D. " expression in the table 6 detects below the boundary 1ppm.
Synthesis example 2: manganous phosphate synthetic
With manganous sulfate monohydrate (MnSO
4H
2O) 1352g (8 moles) and 75% phosphoric acid (H
3PO
4) 697g (5.3 moles) is dissolved in the 25L water, makes mixing solutions (pH value 1.3).With in 161mL/ minute speed, about 100 minutes these mixing solutionss that drip of cost, make manganous phosphate separate out (pH value 6.5) 4% sodium hydroxide (NaOH) aqueous solution 16L (16 moles).
Then, filter, reclaim manganous phosphate, water 40L cleans the manganous phosphate of this recovery meticulously.
Then, the manganous phosphate after 50 ℃ of dry down cleaning of temperature 23 hours obtains dry product 1241g.With the resulting dry product of X-ray diffraction analysis, consequently since with the data of document (RUSS.J.Inorg.Chem.23,341,1978) record and face at interval and diffracted intensity consistent, and Mn content is 34.8 weight %, PO
4Content is 40.2 weight %, is Mn so confirm this dry product
3(PO
4)
26H
2O (yield is 98%).
Resulting Mn
3(PO
4)
26H
2Each rerum natura of O is as shown in table 7.
In addition, the content of Na, Si, Al, Ca, Ti, Mn, Zn, Cr, Ni, Cu, Co is tried to achieve by the ICP optical spectroscopy.In addition, SO
4Content converts to the S atomic percent measurement result of utilizing the ICP optical spectroscopy to obtain and to try to achieve, and tries to achieve the P content of this dry product by absorption photometry.In addition, median size is tried to achieve by laser diffractometry.
[table 7]
Table 7
| The rerum natura of manganous phosphate salt hydrate | |
| P content (weight %) | 40.2 |
| Mn content (weight %) | 34.8 |
| Median size (μ m) | 4.9 |
| Na content (ppm) | 1410 |
| Si content (ppm) | N.D. |
| Al content (ppm) | N.D. |
| Ca content (ppm) | N.D. |
| SO 4Content (ppm) | 2470 |
| Ti content (ppm) | N.D. |
| Zn content (ppm) | 80 |
| Co content (ppm) | 130 |
| Cr content (ppm) | 10 |
| Ni content (ppm) | 190 |
| Cu content (ppm) | 1 |
Notes) " N.D. " expression in the table 7 detects below the boundary 1ppm.
Embodiment 4
Utilize lithium phosphate condensates 11.9g that the mixing machine thorough mixing obtains and synthetic ferrous phosphate hydrated salt crystal (Fe in synthesis example 1 in embodiment 1
3(PO
4)
28H
2O) 50.2g and particle diameter are graphitized carbon black (ケ Star チ エ Application Block ラ Star Network イ Application one Na シ ヨ Na Le society system, the trade(brand)name ECP) 5.0g of 0.05 μ m.Then, use this mixture of oscillating mill pulverization process, obtain reacting precursor.
In addition, to pulverize the specific volume of product be that sample 10g is encased in the graduated cylinder of 50mL, is placed on the DUAL AUTOTAP device that ュ ア サ ア イ オ ニ Network ス (strain) makes, reads volume after rapping 500 times and try to achieve by following formula to oscillating mill.
[formula 2]
Specific volume (mL/g)=V/F
(in the formula, F: the quality (g) of the sample of handling in the expression receiver, V: the capacity (mL) of back sample is rapped in expression)
In addition, the operating condition of oscillating mill is as follows.
Vibration number: 1000Hz
Treatment time: 3 minutes
The Intake Quantity of raw material: 12g
The main rerum natura of resulting reacting precursor is as shown in table 8.
Then, utilize manual press that the exert pressure of 10g reacting precursor with 44MPa is shaped.Then, under nitrogen environment, 600 ℃, fire resulting pulverizing product 5 hours, after the cooling, pulverize, obtained coating the LiFePO of graphitized carbon black
4The resulting LiFePO that coats graphitized carbon black
4Main rerum natura as shown in table 9.
In addition, the content of Na, Si, Al, Ca, Ti, Mn, Zn, Cr, Ni, Cu, Co is tried to achieve by the ICP optical spectroscopy.In addition, SO
4Content converts to the S atomic percent measurement result of utilizing the ICP optical spectroscopy to obtain and to try to achieve.Median size is tried to achieve by electron micrograph.In addition, utilize full organic body carbon meter (society of Shimadzu Seisakusho Ltd. system, TOC-5000A) to measure the LiFePO that has coated graphitized carbon black
4In the C atom content.
Embodiment 5
Utilize lithium aggregate 5.6g that the mixing machine thorough mixing obtains and synthetic ferrous phosphate salt hydrate (Fe in synthesis example 1 in embodiment 1
3(PO
4)
28H
2O) 11.4g and in synthesis example 2 synthetic manganous phosphate salt hydrate (Mn
3(PO
4)
26H
2O) 10.8g and particle diameter are graphitized carbon black (ケ Star チ エ Application Block ラ Star Network イ Application one Na シ ヨ Na Le society system, the trade(brand)name ECP) 2.3g of 0.1 μ m.Then, use this mixture of oscillating mill pulverization process, obtain reacting precursor.Measure each rerum natura of resulting reacting precursor similarly to Example 4, its result is as shown in table 8.
In addition, the operating condition of oscillating mill is as follows.
Vibration number: 1000Hz
Treatment time: 3 minutes
The Intake Quantity of raw material: 12g
Then, utilize manual press that the exert pressure of 10g reacting precursor with 44MPa is shaped.Then, under nitrogen environment, 600 ℃, fire these press forming product 5 hours, after the cooling, pulverize, obtained coating phosphoric acid (iron-manganese) phosphorus-based complex oxide of graphitized carbon black.Median size, BET specific surface area, Na, Si, Al, Ca, Ti, Mn, Zn, Cr, Ni, Cu, Co, the SO of resulting phosphoric acid (iron-manganese) phosphorus-based complex oxide
4Content, try to achieve with similarly to Example 4 method, its result is as shown in table 9.
[table 8]
Table 8
| Specific volume (mL/g) | |
| Embodiment 4 | 1.22 |
| Embodiment 5 | 1.21 |
[table 9]
Table 9
| Embodiment 4 | Embodiment 5 | |
| Median size (μ m) | 0.2 | 0.2 |
| BET specific surface area (m 2/g) | 56 | 57 |
| C atom content (weight %) | 8.1 | 8.1 |
| Na content (weight %) | 0.25 | 0.23 |
| Si content (weight %) | 0.002 | 0.004 |
| Al content (weight %) | 0.003 | 0.003 |
| Ca content (weight %) | 0.003 | 0.024 |
| SO 4Content (weight %) | 0.16 | 0.19 |
| Ti content (weight %) | 0.12 | 0.08 |
| Mn content (weight %) | 0.6 | 18.0 |
| Zn content (weight %) | 0.016 | 0.011 |
| Co content (weight %) | 0.009 | 0.014 |
| Cr content (weight %) | 0.001 | 0.002 |
| Ni content (weight %) | 0.001 | 0.009 |
| Cu content (weight %) | 0.002 | 0.002 |
Notes) the C atom content in the table 9 is represented with respect to LiFePO
4Or LiFe
0.5Mn
0.5PO
4The amount of C atom.
＜reference example 〉
＜battery performance test 〉
(I) making of lithium secondary battery:
The coating of the above-mentioned such embodiment that makes 4 of vacuum-drying the LiFePO of graphitized carbon black
4, this of being tried to achieve by Karl Fischer method coated the LiFePO of graphitized carbon black
4Moisture content be below the 1500ppm, mix these ithium iron phosphorus series composite oxides 91 weight %, powdered graphite 6 weight %, polyvinylidene difluoride (PVDF) 3 weight % with as anodal agent, they are distributed in the N-N-methyl-2-2-pyrrolidone N-, modulate mixing cream.Carry out drying, pressurization after should mixing cream being coated on the aluminium foil, it is the disk of 15mm that punching out becomes diameter, has obtained positive plate.
Use this positive plate, and use each parts such as dividing plate, negative pole, positive pole, collector plate, mounting appliance, outside terminal, electrolytic solution, make lithium secondary battery.Wherein, negative pole uses metallic lithium foil, and electrolytic solution uses the LiPF with 1 mole
6Be dissolved in the solution in 1 liter of 1: 1 mixed solution of NSC 11801 and Methyl ethyl carbonate.
(II) performance evaluation of battery
At room temperature, make the lithium secondary battery of made carry out work, measured the loading capacity after initial stage loading capacity and the 10 times circulation.In addition, calculate with respect to LiFePO by following formula
4The ratio of theoretical loading capacity (170mAh/g).Its result is as shown in table 10.
[formula 3]
[table 10]
Table 10
| Initial stage loading capacity (mAh/g) | Loading capacity (mAh/g) after 10 times circulates | Ratio (%) with respect to theoretical loading capacity | |
| Embodiment 4 | 160 | 158 | 93 |
According to the result of table 10 as can be known, use the LiFePO that utilizes lithium phosphate condensates of the present invention to make
4As the lithium secondary battery of positive active material, demonstrate and approach LiFePO
4The value of theoretical loading capacity, obtained the lithium secondary battery of high loading capacity.
Claims (11)
1. lithium phosphate condensates is characterized in that: fine primary particle forms aggregate, and the median size of this aggregate is that 1～10 μ m, angle of repose are below 50 degree.
2. lithium phosphate condensates as claimed in claim 1 is characterized in that: the half value of the diffraction peak of lattice plane (010) face of being tried to achieve by X-ray diffraction analysis is wide to be more than 0.2 °.
3. lithium phosphate condensates as claimed in claim 1 or 2 is characterized in that: the BET specific surface area is 1～50m
2/ g.
4. lithium phosphate condensates as claimed in claim 1 or 2 is characterized in that: Na content is below the 100ppm, and the content of Al, Ca and Si is counted below the 100ppm with total amount.
5. the manufacture method of each described lithium phosphate condensates in the claim 1～4 is characterized in that: the aqueous solution that contains phosphoric acid is added to contain lithium hydroxide and count in the aqueous solution of 4～6 weight % with LiOH and reacting below 70 ℃.
6. the manufacture method of lithium phosphate condensates as claimed in claim 5, it is characterized in that: the import volume that contains the aqueous solution of phosphoric acid is that phosphoric acid is 0.98～1.02 with respect to the mol ratio of lithium hydroxide.
7. as the manufacture method of claim 5 or 6 described lithium phosphate condensates, it is characterized in that: described lithium hydroxide, use secondary filter to contain behind the aqueous solution of lithium hydroxide and carry out the refining lithium hydroxide that partial crystallization obtains.
8. the manufacture method of ithium iron phosphorus series composite oxides, it is characterized in that: mix in (A) claim 1～4 each described lithium phosphate condensates, ferrous phosphate salt hydrate and conductive carbon material or (B) each described lithium phosphate condensates, ferrous phosphate salt hydrate in the claim 1～4, contain at least a above metallic compound and the conductive carbon material of the metallic element that is selected among Mn, Co, Ni and the Al, and fire.
9. the manufacture method of ithium iron phosphorus series composite oxides as claimed in claim 8, it is characterized in that: comprising: mix each described lithium phosphate condensates in (A) claim 1～4, ferrous phosphate salt hydrate and conductive carbon material or (B) each described lithium phosphate condensates in the claim 1～4, the ferrous phosphate salt hydrate, contain and be selected from Mn, Co, at least a above metallic compound of the metallic element among Ni and the Al and first operation of conductive carbon material, then, thereby obtain second operation of reacting precursor with the resulting mixture of dry type pulverization process, then, thus fire the 3rd operation that this reacting precursor obtains the ithium iron phosphorus series composite oxides.
10. the manufacture method of ithium iron phosphorus series composite oxides as claimed in claim 9 is characterized in that: after described second operation, the operation of resulting reacting precursor being carried out press molding is set.
11. the manufacture method as the described ithium iron phosphorus series composite oxides of claim 8～10 is characterized in that: the median size of the ithium iron phosphorus series composite oxides that generated is below the 0.5 μ m.
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| JP2003131032 | 2003-05-09 | ||
| JP2004118757A JP4620378B2 (en) | 2003-05-09 | 2004-04-14 | Lithium phosphate aggregate, method for producing the same, and method for producing lithium iron phosphorus composite oxide |
| JP2004118757 | 2004-04-14 |
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| CN106252658A (en) * | 2015-09-30 | 2016-12-21 | 住友大阪水泥股份有限公司 | Electrode for lithium ion secondary battery material and manufacture method thereof |
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| DE102010026828A1 (en) * | 2010-07-12 | 2012-01-12 | Bk Giulini Gmbh | Process for the preparation of lithium dihydrogen phosphate |
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| KR102367354B1 (en) * | 2019-03-28 | 2022-02-24 | 한국생산기술연구원 | Method for purifying waste lithium phosphate and method for manufacturing lithium iron phosphate comprising the same |
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| CN106252658B (en) * | 2015-09-30 | 2019-02-15 | 住友大阪水泥股份有限公司 | Electrode for lithium ion secondary battery material and its manufacturing method |
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| CN1608977A (en) | 2005-04-27 |
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| JP2004359538A (en) | 2004-12-24 |
| JP4620378B2 (en) | 2011-01-26 |
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