CN101112979A - Solid-phase method for preparation of high-density spherical-like ferric phosphate lithium - Google Patents
Solid-phase method for preparation of high-density spherical-like ferric phosphate lithium Download PDFInfo
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- CN101112979A CN101112979A CNA2007100289967A CN200710028996A CN101112979A CN 101112979 A CN101112979 A CN 101112979A CN A2007100289967 A CNA2007100289967 A CN A2007100289967A CN 200710028996 A CN200710028996 A CN 200710028996A CN 101112979 A CN101112979 A CN 101112979A
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- Prior art keywords
- lithium
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- solid phase
- iron
- ferric phosphate
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 37
- 239000005955 Ferric phosphate Substances 0.000 title claims description 17
- 229940032958 ferric phosphate Drugs 0.000 title claims description 17
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims description 17
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims description 17
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 title description 3
- 239000000463 material Substances 0.000 claims abstract description 50
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007790 solid phase Substances 0.000 claims abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 150000002739 metals Chemical class 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000001291 vacuum drying Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 7
- 238000001238 wet grinding Methods 0.000 claims description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 5
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 5
- 239000004254 Ammonium phosphate Substances 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000006258 conductive agent Substances 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- LNOZJRCUHSPCDZ-UHFFFAOYSA-L iron(ii) acetate Chemical compound [Fe+2].CC([O-])=O.CC([O-])=O LNOZJRCUHSPCDZ-UHFFFAOYSA-L 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 2
- 229960001708 magnesium carbonate Drugs 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 239000011858 nanopowder Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 229940093916 potassium phosphate Drugs 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract description 15
- 239000013078 crystal Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000004020 conductor Substances 0.000 abstract 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000007599 discharging Methods 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- 229910015645 LiMn Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical class [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- OKTJSMMVPCPJKN-YPZZEJLDSA-N carbon-10 atom Chemical compound [10C] OKTJSMMVPCPJKN-YPZZEJLDSA-N 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a solid phase preparation method of high density spherelike lithium iron phosphate, pertaining to battery field, and comprising the steps that: element molar ratio of iron sources: phosphorus sources: lithium sources is 1:1:1-1.01, and the molar ratio of doped metals is 0.01-0.03, then 0.1 to 10 percent molar ratio of crystal nucleus growth agent is weighted and mixed with deionized water and wet milled for 4 to 8 hours, after being taken out, is dried in a vacuum drying box at 80 to 120 DEG C, and with the protection of nitrogen, is pre-decomposed for 2 to 10 hours under temperature of 250 DEG C to 400 DEG C and then is reacted and synthesized for 18 to 26 hours under 650 to 720 DEG C, then the synthesized products are evenly mixed with 1 to 15 percent conductive materials or organic carbon sources, and covered with carbon for 6 to 16 hours with the protection of 500 to 680 DEG C nitrogen and the temperature is reduced to 80 DEC C or less at a speed of 5 to 10 DEG C per minute, finally, the modified product covered with carbon is taken out. The high density carbon covered spherelike lithium iron phosphate of the invention produced by the solid phase production technique has the highest tap density with 15 to 40 percent improvement based on ordinary solid phase production technique, besides, the ratio between volume and capacity of the material is 15 to 40 percent higher than ordinary materials.
Description
Technical field
The method for preparing solid phase of a kind of high-density spherical-like ferric phosphate lithium of the present invention belongs to field of batteries.Be particularly related to the method for preparing solid phase of the spherical-like ferric phosphate lithium of anode material for lithium-ion batteries.
Background technology
Many advantages such as lithium ion battery has that voltage height, energy density are big, good cycle, self-discharge are little, memory-less effect, operating temperature range are wide, be widely used in mobile telephone, notebook computer, UPS, video camera, various portable power tool, electronic instrument, weaponry etc., also having a good application prospect in electromobile, is that 21st century is to national economy and the significant new high-tech product of people's lives.
Positive electrode material is the important component part of lithium ion battery.At present, the maximum positive electrode material of research is LiCoO
2, LiMn
2O
4And LiFePO
4Deng.But LiCoO
2Be the positive electrode material of unique large-scale commercial, the research comparative maturity, high comprehensive performance, but cost an arm and a leg, capacity is lower, and toxicity is bigger, particularly has the problem of certain safety performance.Spinel LiMn
2O
4Cost is low, and security is good, but cycle performance especially high temperature cyclic performance is poor, certain dissolubility is arranged in electrolytic solution, storge quality is poor.Iron lithium phosphate (LiFePO with quadrature olivine structural
4) positive electrode material becomes new research focus both at home and abroad gradually.Preliminary study shows: LiFePO
4Not only has LiCoO
2And LiMn
2O
4Advantage, and have that cost is low, high temperature performance good, have extended cycle life, operating voltage moderate (3.4V), platform identity be good, voltage pole steadily (can match in excellence or beauty), theoretical capacity big (170mAh/g), Stability Analysis of Structures, safety performance with voltage stabilized source splendid (O and P are with the strong covalent bond mortise, making material be difficult to analyse oxygen decomposes), volume-diminished when high-temperature behavior and good cycle, charging, volume effect when cooperating with carbon negative pole material is good, good with most of electrolyte system consistencies, and storge quality is good; Nontoxic, be real green material.But there are two significant disadvantages in iron lithium phosphate, the one, and specific conductivity is low, causes high-rate charge-discharge capability poor, and actual specific capacity is low: the 2nd, tap density is low, causes volume and capacity ratio low.These two shortcomings have hindered the practical application of this material.
At present, the synthesizing iron lithium phosphate material is about to lithium source, phosphorus source, source of iron ground and mixed together mainly by high-temperature solid phase reaction method, and calcination at high temperature is synthetic.In the ground and mixed process, mix foreign metal compound or carbon source, improve the electroconductibility of material.There is significant disadvantages in this method, and the one, foreign metal compound that mixes or carbon source are failed with lithium source, phosphorus source, source of iron is full and uniform mixes, and fails to reach abundant adulterated effect, and the electroconductibility of material is improved not obvious.The 2nd, even synthetic powder body material conduction makes moderate progress, but tap density is low, and general tap density only is 1.0-1.25g/cm
3, than cobalt acid lithium (general tap density 2.2-2.59g/cm
3Anti-, the high 2.8-2.99g/cm that reaches
3) much lower, low tap density makes that the volume and capacity ratio of iron lithium phosphate is lower much than the sour lithium material of cobalt, has no advantage and can say, has hindered the practical application development of this material.
Synthesizing iron lithium phosphate material another kind method is: presoma adopts wet method synthetic.As CN03102665.6 wet chemical method for preparing iron lithium phosphate, the preparation method of CN200510002012.9 high-density spherical ferric lithium phosphate and iron manganese phosphate for lithium, the preparation methods of CN200610065212.3 high-density spherical ferric lithium phosphate etc. are to adopt the synthetic presoma of wet method.Its advantage is the tap density that has improved LiFePO 4 material, generally can arrive 1.8--2.2g/cm3, but Wet-process phosphoric acid (WPPA) iron lithium material equipment requirements height, technology controlling and process requires high, and wastewater treatment capacity is bigger, is not suitable for producing in batches and commercially producing.
Summary of the invention
The objective of the invention is to avoid weak point of the prior art and a kind of specific conductivity height is provided, charge-discharge performance is good, the tap density height, volume and capacity ratio is big, electroconductibility is improved obviously, presoma adopts process for solid phase synthesis, iron lithium phosphate is easily synthetic, crystal morphology, grain size are identical, improved the conductivity of iron lithium phosphate, and improved the overcharging of LiFePO 4 material, cross and put performance, be suitable for the method for preparing solid phase of a kind of high-density spherical-like ferric phosphate lithium of producing in batches and commercially producing.
The objective of the invention is to realize by following measure:
The method for preparing solid phase of a kind of high-density spherical-like ferric phosphate lithium provided by the invention is the pulp ball milling---drying---and synthetic refinement---is covered the carbon screening---, and packing comprises following each step:
1, with element mol ratio source of iron: phosphorus source: lithium source=1: 1: 1-1.01, take by weighing source of iron, phosphorus source, lithium source, the mol ratio of doping metals and ferro element is 0.01-0.03, take by weighing the nucleus growth agent of the weight percent 0.1-10% of source of iron, phosphorus source and lithium source gross weight again, mix with deionized water, carried out wet-milling 4-8 hour, and after the taking-up, in 80-120 ℃ vacuum drying oven, carried out drying.
2, dry good material under nitrogen protection, at 250 ℃ of-400 ℃ of following predecomposition 2-10 hours, cools to below 80 ℃ then synthetic 18-26 hour of 650-720 ℃ of reaction, and with per minute 4-8 ℃ speed, and synthetic good product is taken out.
3, synthetic good product again with conductive agent or the organic carbon source uniform mixing of weight percent 1-15%, under 500-680 ℃ of nitrogen protection, cover carbon 6-16 hour, and cool to below 80 ℃ with per minute 5-10 ℃ speed, will cover the good modified product of carbon and take out.Obtain high-density, high-performance class spheric iron lithium phosphate product.
Described source of iron is that iron protochloride, Iron nitrate, ferrous sulfate, Ferrox, Iron diacetate, sulfuric acid two ammoniums are ferrous, one or more the mixture of ammonium sulfate in ferrous.
Described phosphorus source is one or more the mixture in ammonium phosphate, primary ammonium phosphate, Secondary ammonium phosphate, potassiumphosphate, potassium primary phosphate, dipotassium hydrogen phosphate, the phosphoric acid.
Described lithium source is one or more the mixture in Lithium Acetate, lithium chloride, Lithium Sulphate, lithium nitrate, Quilonum Retard, the lithium hydroxide.
Described doping metals is one or more a mixture of the compound of Mg, Ti, Cr, Al, Sr, the used compound of described doping metals is one or more the mixture in magnesium nitrate, magnesium oxide, sal epsom, magnesiumcarbonate, Titanium Nitrate, titanium oxide, lithium titanate, zirconium white, zirconium nitrate, manganous carbonate, manganese oxide, manganous sulfate, the manganous nitrate, and consumption is doping metals/iron=0.01-0.03 mol ratio.
Described nucleus growth agent is one or more the mixture in nano-silver powder, copper nanoparticle, carbon nano powder, ultrafine titanium oxide powder, the aluminum oxide powder.
Described organic carbon source is one or more the mixture in sucrose, starch, the glucose, and the consumption mass ratio is sucrose, starch or glucose/iron lithium phosphate=0.5-15%.
Described conductive agent is one or more the mixture in graphite, acetylene black, the organic carbon source.
Raw material of the present invention mixes employing deionized water wet-grinding technology and relative device, and raw material mixes the employing deionized water, and water consumption is the 15-25% of the weight of dried raw material, has avoided employing organic solvent wet-grinding technology and relative device to bring like this and has produced unsafe phenomenon.
Drying of the present invention is to adopt inflated with nitrogen protection vacuum-drying, and temperature is controlled at 80-120 ℃.
The present invention has added the agent of weight percent 0.1-10% nucleus growth before synthetic, make synthetic LiFePO 4 material consistent appearance, and size distribution is even.
The present invention adopts earlier syntheticly covers carbon again, has avoided synthesizing, covering one step of carbon and has finished technology and cause the low shortcoming of tap density.
The present invention has added metallic compound before synthetic, mol ratio is: doping metals/iron=0.01-0.03 makes LiFePO 4 material that excellent conducting performance not only be arranged, and the high performance performance that overcharges, puts is excessively arranged.
The present invention adopts liquid process to produce the highdensity carbon spherical-like ferric phosphate lithium product that covers, tap density is the highest, reach 1.55-1.75g/ml, (1.0-1.3) improved 15-40% on the basis of general solid phase production technique, and the volume and capacity ratio of this material has improved 15-40% than general material.
The present invention improves the tap density and the volume and capacity ratio of material, and by importing the nucleus growth agent, covering carbon and doped metal ion, improves the conductivity of material.The product that the present invention produced: loose density reaches 0.6-0.7g/cm3; Tap density reaches 1.55-1.75g/cm3; Conductivity reaches 5 * 10 near the level of cobalt acid lithium
-3Scm
-1The quality of materials specific storage can reach 125-145mAh/g (0.2C charges and discharge).
The difference of the spherical high-density high-performance iron phosphate lithium solid phase production technique of class provided by the invention and other production technique is:
1, adopts deionized water to carry out wet-milling, and, avoided material in drying process, the generation of security incident without organic reagent.
2, this technology presoma adopts process for solid phase synthesis, has avoided in the synthetic presoma process of wet method, and equipment is huge, the deficiency that wastewater treatment capacity is big.
3, can control industrial scale and reaction atmosphere well; The while material is heated very even, temperature of charge consistence height.
4, the earlier synthetic technology of carbon restoration again of the present invention can overcome LiFePO 4 material poorly conductive, shortcoming that tap density is low well.
5, the present invention has imported the nucleus growth agent in the high temperature building-up process, overcome well in the high temperature building-up process, and the synthetic difficulty of iron lithium phosphate, crystal morphology differs, the shortcoming that grain size is different.
6, the present invention imports doping metals in the high temperature building-up process, has not only improved the conductivity of iron lithium phosphate, and has improved overcharging, crossing and put performance of LiFePO 4 material.
Description of drawings
Accompanying drawing 1 material crystals pattern of the present invention.
Accompanying drawing 2 material X-ray powder diffraction collection of illustrative plates of the present invention.
Accompanying drawing 3 materials of the present invention are made the 18650-1200mAh battery, and 1C charges and discharge cycle life.
Accompanying drawing 4 material charging and discharging curves of the present invention.
Accompanying drawing 5 quality of materials specific storagies of the present invention.
Accompanying drawing 6 materials of the present invention are made the 18650-1200mAh battery, and 1C fills 10C puts cycle life.
Embodiment
The invention will be further described below in conjunction with embodiment.
Technology of the present invention comprises following each step:
1, proportioning raw materials: source of iron, phosphorus source, lithium source=1: 1: 1-1.01, the compound of doping metals Mg, Ti, Cr, Al, Sr, metal/iron=0.01-0.03 mol ratio, nucleus growth agent are source of iron, phosphorus source, lithium source element substance weight per-cent 0.1-10%.
2, defibrination: take by weighing deionized water: source of iron, phosphorus source, lithium source element substance weight=0.18～0.22: 1.Mixed 4-8 hour.Take out, under vacuum 80-120 ℃ dry 5-8 hour.
3, synthetic: under nitrogen protection, in synthetic furnace, 250-400 ℃ of predecomposition 2-10 hour, then, under 650-720 ℃, was carried out in synthetic furnace building-up reactions 18-26 hour.After reacting completely, cool to 80 ℃, take out product with the thermograde of per minute 4-8 ℃ speed.
4, cover carbon: in synthetic product, add the organic carbon source of weight percent 1-15%, thorough mixing.Then, cover carbon in covering the carbon stove, covering the carbon temperature is 500--680 ℃, and cools to below 80 ℃ nitrogen protection with per minute 5-10 ℃ speed.
Embodiment one:
Take by weighing 6169 gram Ferroxs, 3992 gram primary ammonium phosphates, 1293 gram Quilonum Retards, 68 gram nano-silver powder nucleus growth agent.Raw material: water=2: 1, wet-milling 4 hours.Vacuum 105-110 ℃ of drying 6 hours.Material under nitrogen protection, 5 ℃ of/minute intensifications, 360 ℃ of predecomposition 10 hours, again 700 ℃ synthetic 16 hours.6-10 ℃/minute cools to 80 ℃, discharging.Add 8% glucose in the material equably, again under nitrogen protection 550 ℃ covered carbon 10 hours.Cool to 80 ℃.Material is carried out ball milling and screening, obtain the iron lithium phosphate crystal powder.The performance of this material is as follows:
Loose density: 0.65g/cm
3
Tap density: 1.64g/cm
3
Ferrous content: 30.89%
Carbon content: 2.81%
Specific surface area: 22.7m
2/ g
D
10 0.70um； D
50 1.90um； D
90 5.79um
The material crystals pattern is seen accompanying drawing 1;
Material X-ray powder diffraction collection of illustrative plates is seen accompanying drawing 2;
Material is made the 18650-1200mAh battery, and 1C charges and discharge cycle life and sees accompanying drawing 3
Embodiment two
Take by weighing 6169 gram Ferroxs, 3992 gram primary ammonium phosphates, 1293 gram Quilonum Retards, 82 gram copper nanoparticle nucleus growth agent.Raw material: water=2: 1, wet-milling 4 hours.Vacuum 105-110 ℃ of drying 6 hours.Material under nitrogen protection, 5 ℃ of/minute intensifications, 360 ℃ of predecomposition 10 hours, again 700 ℃ synthetic 16 hours.6-10 ℃/minute cools to 80 ℃, discharging.Add 10% glucose in the material equably, again under nitrogen protection 550 ℃ covered carbon 10 hours.Cool to 80 ℃.Material is carried out ball milling and screening, obtain the iron lithium phosphate crystal powder.The performance of this material is as follows:
Loose density: 0.67g/cm
3
Tap density: 1.62g/cm
3
Ferrous content: 30.43%
Carbon content: 2.95%
Specific surface area: 23.4m
2/ g
D
10 0.92um； D
50 2.12um； D
90 3.98um
The material charging and discharging curve is seen accompanying drawing 4;
The quality of materials specific storage is seen accompanying drawing 5;
Material is made the 18650-1200mAh battery, and 1C fills 10C to be put cycle life and see accompanying drawing 6
Claims (10)
1. the method for preparing solid phase of a high-density spherical-like ferric phosphate lithium is characterized in that comprising following each step:
1, with element mol ratio source of iron: phosphorus source: lithium source=1: 1: 1-1.01, take by weighing source of iron, phosphorus source, lithium source, the mol ratio of doping metals and ferro element is 0.01-0.03, take by weighing the nucleus growth agent of the weight percent 0.1-10% of source of iron, phosphorus source and lithium source 3 material gross weight again, mix with deionized water, carried out wet-milling 4-8 hour, after the taking-up, in 80-120 ℃ vacuum drying oven, carry out drying
2, dry good material under nitrogen protection, at 250 ℃ of-400 ℃ of following predecomposition 2-10 hours, cools to below 80 ℃ then synthetic 18-26 hour of 650-720 ℃ of reaction, and with per minute 4-8 ℃ speed, synthetic good product taken out,
3, synthetic good product again with conductive agent or the organic carbon source uniform mixing of weight percent 1-15%, under 500-680 ℃ of nitrogen protection, cover carbon 6-16 hour, and cool to below 80 ℃ with per minute 5-10 ℃ speed, will cover the good modified product of carbon and take out.
2. the method for preparing solid phase of a kind of high-density spherical-like ferric phosphate lithium according to claim 1 is characterized in that described source of iron is that iron protochloride, Iron nitrate, ferrous sulfate, Ferrox, Iron diacetate, sulfuric acid two ammoniums are ferrous, one or more the mixture of ammonium sulfate in ferrous.
3. the method for preparing solid phase of a kind of high-density spherical-like ferric phosphate lithium according to claim 1 is characterized in that described phosphorus source is one or more the mixture in ammonium phosphate, primary ammonium phosphate, phosphoric acid hydrogen two money, potassiumphosphate, potassium primary phosphate, dipotassium hydrogen phosphate, the phosphoric acid.
4. the method for preparing solid phase of a kind of high-density spherical-like ferric phosphate lithium according to claim 1 is characterized in that described lithium source is one or more the mixture in Lithium Acetate, lithium chloride, Lithium Sulphate, lithium nitrate, Quilonum Retard, the lithium hydroxide.
5. the method for preparing solid phase of a kind of high-density spherical-like ferric phosphate lithium according to claim 1 is characterized in that described doping metals is one or more a mixture of the compound of Mg, Ti, Cr, Al, Sr.
6. the method for preparing solid phase of a kind of high-density spherical-like ferric phosphate lithium according to claim 1 is characterized in that described nucleus growth agent is one or more the mixture in nano-silver powder, copper nanoparticle, carbon nano powder, ultrafine titanium oxide powder, the aluminum oxide powder.
7. the method for preparing solid phase of a kind of high-density spherical-like ferric phosphate lithium according to claim 1, it is characterized in that described organic carbon source is one or more the mixture in sucrose, starch, the glucose, the consumption mass ratio is sucrose, starch or glucose/iron lithium phosphate=0.5-15%.
8. the method for preparing solid phase of a kind of high-density spherical-like ferric phosphate lithium according to claim 1 is characterized in that described conductive agent is one or more the mixture in graphite, acetylene black, the organic carbon source.
9. the method for preparing solid phase of a kind of high-density spherical-like ferric phosphate lithium according to claim 1 is characterized in that raw material mixes the employing deionized water, and water consumption is the 15-25% of dried raw material.
10. the method for preparing solid phase of a kind of high-density spherical-like ferric phosphate lithium according to claim 5, the compound that it is characterized in that described doping metals is one or more the mixture in magnesium nitrate, magnesium oxide, sal epsom, magnesiumcarbonate, Titanium Nitrate, titanium oxide, lithium titanate, zirconium white, zirconium nitrate, manganous carbonate, manganese oxide, manganous sulfate, the manganous nitrate, and consumption is doping metals/iron=0.01-0.03 mol ratio.
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