CN1907844A - High density ultrafine composite ferric lithium phosphate anode material and preparation method - Google Patents
High density ultrafine composite ferric lithium phosphate anode material and preparation method Download PDFInfo
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- CN1907844A CN1907844A CNA2006100370413A CN200610037041A CN1907844A CN 1907844 A CN1907844 A CN 1907844A CN A2006100370413 A CNA2006100370413 A CN A2006100370413A CN 200610037041 A CN200610037041 A CN 200610037041A CN 1907844 A CN1907844 A CN 1907844A
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- lithium
- acid
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- high density
- anode material
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- 239000002131 composite material Substances 0.000 title claims abstract description 25
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 title claims description 24
- 239000010405 anode material Substances 0.000 title claims description 23
- 229910001386 lithium phosphate Inorganic materials 0.000 title claims description 20
- 238000002360 preparation method Methods 0.000 title claims description 16
- 239000000203 mixture Substances 0.000 claims abstract description 30
- -1 compound lithium iron phosphate Chemical class 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000007524 organic acids Chemical class 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 239000002482 conductive additive Substances 0.000 claims abstract description 6
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 5
- 239000012467 final product Substances 0.000 claims abstract description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 12
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 8
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 8
- 235000011285 magnesium acetate Nutrition 0.000 claims description 8
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 229940095064 tartrate Drugs 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 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 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 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000011790 ferrous sulphate Substances 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- LNOZJRCUHSPCDZ-UHFFFAOYSA-L iron(ii) acetate Chemical compound [Fe+2].CC([O-])=O.CC([O-])=O LNOZJRCUHSPCDZ-UHFFFAOYSA-L 0.000 claims description 5
- 150000003016 phosphoric acids Chemical class 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims description 4
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 4
- 239000004021 humic acid Substances 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- 239000011654 magnesium acetate Substances 0.000 claims description 4
- 229940069446 magnesium acetate Drugs 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- 239000006259 organic additive Substances 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 5
- 239000010406 cathode material Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 150000002505 iron Chemical class 0.000 abstract description 2
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000002019 doping agent Substances 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 abstract 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910010710 LiFePO Inorganic materials 0.000 description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000009775 high-speed stirring Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- QDZOEBFLNHCSSF-PFFBOGFISA-N (2S)-2-[[(2R)-2-[[(2S)-1-[(2S)-6-amino-2-[[(2S)-1-[(2R)-2-amino-5-carbamimidamidopentanoyl]pyrrolidine-2-carbonyl]amino]hexanoyl]pyrrolidine-2-carbonyl]amino]-3-(1H-indol-3-yl)propanoyl]amino]-N-[(2R)-1-[[(2S)-1-[[(2R)-1-[[(2S)-1-[[(2S)-1-amino-4-methyl-1-oxopentan-2-yl]amino]-4-methyl-1-oxopentan-2-yl]amino]-3-(1H-indol-3-yl)-1-oxopropan-2-yl]amino]-1-oxo-3-phenylpropan-2-yl]amino]-3-(1H-indol-3-yl)-1-oxopropan-2-yl]pentanediamide Chemical compound C([C@@H](C(=O)N[C@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CC(C)C)C(N)=O)NC(=O)[C@@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](CCCCN)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](N)CCCNC(N)=N)C1=CC=CC=C1 QDZOEBFLNHCSSF-PFFBOGFISA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 102100024304 Protachykinin-1 Human genes 0.000 description 1
- 101800003906 Substance P Proteins 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000005406 washing Methods 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
This invention belongs to battery field, which relates to ultra-micro compound lithium iron phosphate cathode material with high density and its fabrication method. Said cathode material is prepared by mixing iron salt, lithium salt and phosphates at a P/Li/Fe ratio of 1-1.1:1-1.1:1-1.1, adding conductive additives containing dopant element and carbon-bearing organic compound, adding organic acid as carrier, adjusting pH, controlling solution temperature in reactor to form sol, separating the sol to obtain nano-precursor and placing it into micorwave oven under protection of inert gas, and obtaining the final product. It is easy to control the chemical component, phase composition and particle size distribution. The conductive additive can be well-distributed. The method also has the advantages of short reaction time, low energy consumption during synthesis process and low cost. The obtained composite has high purity and good compatibility with electrolyte, excellent conductive property and charge and discharge property with large current, and good structure stability,thermal stability and cycle performance.
Description
Affiliated field:
High density ultrafine composite ferric lithium phosphate anode material of the present invention and preparation method belong to field of batteries, particularly relate to a kind of high-density nano level composite ferric lithium phosphate and preparation method of lithium ion anode material.
Background technology
Lithium ion battery has the monomer battery voltage height, the energy density height, and memory-less effect, safe in utilization, characteristics such as working temperature is wide have been widely used in mobile phone, notebook computer, electronic instrument, UPS, various portable power tools etc.
Positive electrode material is the important component part of lithium ion battery, and up to now, business-like anode material for lithium-ion batteries still mainly adopts LiCoO
2, LiNiO
2, LiMn
2O
4To LiCoO
2, the problem of existence is cause cobalt acid lithium price higher owing to cobalt resource lacks, and its thermostability is relatively poor and cobalt to problems such as environment are harmful.LiNiO
2The capacity height, but preparation process is difficult relatively, and the material performance is difficult stable, and its safety problem can not be ignored.LiMn
2O
4Low price, safety performance is good, but capacity, cycle performance and high-temperature behavior difference storge quality are relatively poor.In recent years, people are at the anode material for lithium-ion batteries of constantly seeking a new generation.
Iron lithium phosphate (the LiFePO of olivine-type
4) because its raw material sources are extensive, low price, nontoxic, environmentally friendly, not only taken into account LiCoO
2, LiNiO
2And LiMnO
2Advantage, particularly it has outstanding properties such as safety performance is good, good stability, energy density height when the positive electrode material, particularly becomes the preferred material of lithium ion power battery cathode material, is that better condition is created in the Sustainable development of human society.
But, the structures shape of iron lithium phosphate its two obvious two shortcomings, one is that specific conductivity is low; Another is that tap density is low, and this has caused the practical application of pure iron lithium phosphate.At present people have obtained bigger progress by mixing and being coated in the improvement of specific conductivity.And for the preparation of the iron lithium phosphate of high-bulk-density, the LiFePO 4 powder that the spheroidal particle of rule is formed has higher tap density.
At present, method preparing phosphate iron lithium has sol-gel processing, the oxidation reduction process of coprecipitation method, hydrothermal method, the liquid phase of high-temperature solid phase reaction method, liquid phase, the microwave method and the mechanical ball milling method of solid phase.Industrial generally use be solid reaction process, a certain proportion of ferrous salt, lithium salts and phosphoric acid salt is evenly mixed, synthetic LiFePO under protection of inert gas
4The advantage of pyroprocess is easily to realize industrial productionization, but the size distribution of reaction product is inhomogeneous, and pattern is also irregular, is difficult to reach nano level.
In application number is 200410103485.3 patent application; a kind of preparation method of high-density spherical ferric lithium phosphate is disclosed; this method is earlier with the trivalent iron salt aqueous solution, the phosphorus source aqueous solution, alkali aqueous solution reaction synthesizing spherical or class ball shape ferric phosphate presoma; the dry back of washing and lithium source, carbon source, doping metals compound uniform mixing; under inertia or protection of reducing atmosphere, obtained iron lithium phosphate in high-temperature heat treatment 8-48 hour through 600-900 ℃.The iron lithium phosphate median size that this method is prepared is 7-12 μ m, and tap density can reach 2.0-2.2g/cm
3, first discharge specific capacity can reach 140-155mAh/g under the room temperature.
Patent CN1410349 adopts wet chemical method to prepare LiFePO earlier
4Preceding aggressiveness, then the presoma that makes is heat-treated under the protection of inert atmosphere, obtained LiFePO
4Material.
Patent WO02/08555A2 adopts the liquid phase method of co-precipitation, under control suitable substance P H value, makes LiFePO
4Presoma, again presoma roasting in non-oxidizing atmosphere can be made nano level iron phosphate powder, the initial capacity of this material when the 0.5C constant-current discharge can reach more than the 130mAh/g.
Summary of the invention
The objective of the invention is to avoid weak point of the prior art and provide a kind of generated time short, the chemical ingredients of product, phase composition and size-grade distribution are controlled easily, conductive agent distributes more even, cheap, the matrix material purity height that makes, conductivity and high rate during charging-discharging are superior, the LiFePO 4 of anode material Stability Analysis of Structures, thermal stability is good, high density ultrafine composite ferric lithium phosphate anode material that cycle performance is good and preparation method thereof.
The objective of the invention is to reach by following measure, high density ultrafine composite ferric lithium phosphate anode material is by molysite compound, lithium salt compound and the microcosmic salt compound mixed of P: Li: Fe=1-1.1: 1-1.1: 1-1.1 in molar ratio, add doping element compound or carbon containing organic compound more therein as conductive additive, add organic acid as carrier.
Lithium salts comprises a kind of or its mixture of lithium hydroxide, Quilonum Retard, lithium oxalate, lithium fluoride, Trilithium phosphate, Lithium Acetate.
Molysite is soluble ferric iron salt or Iron diacetate, ferrous sulfate or its mixture.
The oxide compound of phosphoric acid salt or phosphorus is NH
4H
2PO
4, (NH
4)
2HPO
4A kind of or its mixture.
Doping element compound is a kind of of magnesium acetate, magnesium hydroxide or its mixture.The carbon containing organic additive is a kind of or its mixture of polypropylene, polyacrylamide, glucose, sucrose, starch, the total weight percent that accounts for raw material 5～20% of the consumption of additive.
Organic acid is a kind of or its mixture of oxalic acid, tartrate, vinylformic acid, citric acid, polyacrylic acid, humic acid, polyvinylpyrrolidone, 2 ethyl hexanoic acid, succsinic acid.
The preparation method of high density ultrafine composite ferric lithium phosphate anode material is by the molysite compound; lithium salt compound and microcosmic salt compound be the mixed of P: Li: Fe=1-1.1: 1-1.1: 1-1.1 in molar ratio; add doping element compound or carbon containing organic compound more therein as conductive additive and uniform mixing; above mixture is mixed in reactor; adding is as the organic acid of carrier; regulate the pH value gradually with lithium hydroxide and ammoniacal liquor then; solution temperature in the controlling reactor is less than or equal to 100 ℃; pH in the controlling reactor is 4.0-9.0; form colloidal sol; and then change into gel precipitation and come out; separation can get the nanometer presoma; in the atmosphere of protection of inert gas, the nanometer presoma is placed in the microwave oven, temperature is set to 600 ℃-800 ℃; time is 5-300 minute, obtains final product.
Lithium salts comprises a kind of or its mixture of lithium hydroxide, Quilonum Retard, lithium oxalate, lithium fluoride, Trilithium phosphate, Lithium Acetate.
Molysite is soluble ferric iron salt or Iron diacetate, ferrous sulfate or its mixture.
The oxide compound of phosphoric acid salt or phosphorus is NH
4H
2PO
4, (NH
4)
2HPO
4A kind of or its mixture.
Doping element compound is a kind of of magnesium acetate, magnesium hydroxide or its mixture.The carbon containing organic additive is a kind of or its mixture of polypropylene, polyacrylamide, glucose, sucrose, starch, the total weight percent that accounts for raw material 5～20% of the consumption of additive.
Organic acid is a kind of or its mixture of oxalic acid, tartrate, vinylformic acid, citric acid, polyacrylic acid, humic acid, polyvinylpyrrolidone, 2 ethyl hexanoic acid, succsinic acid,
The nanometer presoma can be placed in the microwave oven under the inert-free gas protection.
Synthetic with microwave, the material heated time shortens, and favourable crystalline growth prevents segregation.
The present invention has following characteristics:
(1) chemical ingredients of product, phase composition and size-grade distribution are controlled easily;
(2) product is realized mixing easily;
(3) conductive agent distributes more even;
(4) with the synthetic generated time that shortens greatly of microwave;
(5) with the synthetic distribution of controlling the product particle diameter more effectively of microwave;
(6) synthetic materials in lagging material greatly reduces the energy consumption of building-up process.
(7) the synthetic raw material that is adopted is large Chemicals, and is cheap;
(8) the matrix material purity height that makes is just having the charging/discharging voltage platform about 3.4V stably, and better with the electrolytic solution consistency, conductivity and high rate during charging-discharging are superior; This composite positive pole iron lithium phosphate Stability Analysis of Structures, thermal stability is good, and cycle performance is good.
It is between the 500-800nm that this preparation method prepares median size, and tap density can reach 1.5-2.0g/cm
3First discharge specific capacity can reach the high-density nano level composite ferric lithium phosphate of lithium ion anode material of high-bulk-density, height ratio capacity, the pattern rule of 140-150mAh/g under the room temperature, boundless application prospect is arranged, particularly aspect power cell, the composite positive pole iron lithium phosphate of being prepared by this method can be widely used in fields such as mobile telephone, portable notebook, small-sized Video Camera and electromobile.
Description of drawings:
Accompanying drawing 1 is for pressing the first charge-discharge graphic representation of 1 synthetic composite positive pole of embodiment iron lithium phosphate, and voltage range is 2.0-4.2V, and ionogen is LiPF
6, solvent is EC+DMC (volume ratio is 1: 1), with the rate charge-discharge of 0.5C.
Accompanying drawing 2 is for pressing the cycle performance graphic representation of the prepared composite positive pole iron lithium phosphate of embodiment 1, cell making process, discharges and recharges system and voltage range is described as Fig. 1.
Accompanying drawing 3 is for pressing the infrared spectra graphic representation of the prepared composite positive pole iron lithium phosphate of embodiment 1.
Embodiment:
Embodiment 1:
Primary ammonium phosphate, 0.5mol/L Iron diacetate, 0.5mol/L Quilonum Retard, 3.07 gram magnesium acetates with 0.5mol/L, 4.91 the gram polypropylene is mixed, place closed reactor to carry out high-speed stirring 1 hour, toward wherein splashing into oxalic acid, the concentration of oxalic acid is 0.03mol/L then.Stir speed (S.S.) is adjusted to 120r/min, regulates the flow that splashes into ammoniacal liquor, the pH value in the control solution is 9.0.Then the gel-type throw out that obtains is removed solvent being lower than under 100 ℃, with unreacted reaction flush away, separated to get the nanometer presoma then by deionized water; In the atmosphere of protection of inert gas, being placed in the microwave oven 700 ℃, to carry out microwave in insulation reaction 5-300 minute synthetic, finally can get the nano-scale lithium iron phosphate powder.
The chemical property of gained material is measured as follows: 92% positive active material, 3% acetylene black, 5% poly(vinylidene fluoride) binding agent, positive plate is made in evenly mixed back on aluminium foil, be coated in MCMB and make negative pole on the Copper Foil, in the argon gas glove box, be Celgard2300, with the LiPF of 1: 1 NSC 11801 (EC)+methylcarbonate (DMC)+1mol/L with the barrier film
6Be electrolytic solution, be assembled into battery.In the scope of voltage range 2.0-4.2V, discharge and recharge and the cycle performance test experiments.Fig. 1 is a 0.5C rate charge-discharge curve, as can be seen from the figure, and the resulting LiFePO of the present invention
4/ C anode material discharging voltage platform is stable, has higher specific storage, reaches 144.2mAh/g.Fig. 2 recycles the performance curve for what this material was assembled into battery, is similarly the 0.5C discharge, and as seen from the figure, the capacity that recycles 50 primary cells is unattenuated substantially.Fig. 3 is the infrared absorpting light spectra of this material.
Embodiment 2:
With primary ammonium phosphate, the theoretical amount of 0.5mol/L is that 1.2 times 0.5mol/L ferrous sulfate, theoretical amount is that 1.2 times 0.5mol/L Quilonum Retard, 5.06 gram magnesium acetates mix with 6.09 gram sucrose, place closed reactor to carry out high-speed stirring half hour, toward wherein splashing into tartrate, tartaric concentration is 0.03mol/L then.Stir speed (S.S.) is adjusted to 120r/min, regulates the flow that splashes into ammoniacal liquor, the pH value in the control solution is 8.5.Then the gel-type throw out that obtains is removed solvent being lower than under 100 ℃, with unreacted reaction flush away, separated to get the nanometer presoma then by deionized water; In the atmosphere of protection of inert gas, being placed in the microwave oven 650 ℃, to carry out microwave in insulation reaction 5-300 minute synthetic, finally can get the nano-scale lithium iron phosphate powder.
Embodiment 3:
0.5mol/L phosphoric acid, 0.5mol/L iron protoxide, 0.5mol/L lithium hydroxide 5.06 gram magnesium acetates and 7.58 gram polyacrylamides are mixed, place closed reactor to carry out high-speed stirring 2 hours, toward wherein splashing into tartrate, tartaric concentration is 0.03mol/L then.Stir speed (S.S.) is adjusted to 120r/min, regulates the flow that splashes into ammoniacal liquor, the pH value in the control solution is 9.0.Then the gel-type throw out that obtains is removed solvent being lower than under 100 ℃, with unreacted reaction flush away, separated to get the nanometer presoma then by deionized water; In the atmosphere of protection of inert gas, being placed in the microwave oven 750 ℃, to carry out microwave in insulation reaction 5-300 minute synthetic, finally can get the nano-scale lithium iron phosphate powder.
Embodiment 4:
0.3mol/L phosphoric acid, 0.3mol/L iron protoxide, 0.3mol/L lithium hydroxide, 4.69 gram magnesium acetates and 5.26 gram glucose are mixed, place closed reactor to carry out high-speed stirring 2 hours, toward wherein splashing into citric acid, the concentration of citric acid is 0.04mol/L then.Stir speed (S.S.) is adjusted to 120r/min, regulates the flow that splashes into ammoniacal liquor, the pH value in the control solution is 7.5.Then the gel-type throw out that obtains is removed solvent being lower than under 100 ℃, with unreacted reaction flush away, separated to get the nanometer presoma then by deionized water; In the atmosphere of protection of inert gas, being placed in the microwave oven 780 ℃, to carry out microwave in insulation reaction 5-300 minute synthetic, finally can get the nano-scale lithium iron phosphate powder.
Claims (10)
1, a kind of preparation method of high density ultrafine composite ferric lithium phosphate anode material, it is characterized in that by the molysite compound, lithium salt compound and microcosmic salt compound be the mixed of P: Li: Fe=1-1.1: 1-1.1: 1-1.1 in molar ratio, add doping element compound or carbon containing organic compound more therein as conductive additive and uniform mixing, above mixture is mixed in reactor, adding is as the organic acid of carrier, regulate the pH value gradually with lithium hydroxide and ammoniacal liquor then, solution temperature in the controlling reactor is less than or equal to 100 ℃, pH in the controlling reactor is 4.0-9.0, form colloidal sol, and then change into gel precipitation and come out, separation can get the nanometer presoma, and the nanometer presoma is placed in the microwave oven, and temperature is set to 600 ℃-800 ℃, time is 5-300 minute, obtains final product.
2, the preparation method of high density ultrafine composite ferric lithium phosphate anode material according to claim 1, it is characterized in that lithium salts comprises a kind of or its mixture of lithium hydroxide, Quilonum Retard, lithium oxalate, lithium fluoride, Trilithium phosphate, Lithium Acetate, molysite is soluble ferric iron salt or Iron diacetate, ferrous sulfate or its mixture, and the oxide compound of phosphoric acid salt or phosphorus is NH
4H
2PO
4, (NH
4)
2HPO
4A kind of or its mixture, doping element compound is a kind of of magnesium acetate, magnesium hydroxide or its mixture.
3, the preparation method of high density ultrafine composite ferric lithium phosphate anode material according to claim 1 is characterized in that organic acid is a kind of or its mixture of oxalic acid, tartrate, vinylformic acid, citric acid, polyacrylic acid, humic acid, polyvinylpyrrolidone, 2 ethyl hexanoic acid, succsinic acid.
4, the preparation method of high density ultrafine composite ferric lithium phosphate anode material according to claim 1 is characterized in that the nanometer presoma is placed in the microwave oven under the atmosphere protection of protection of inert gas.
5, the preparation method of high density ultrafine composite ferric lithium phosphate anode material according to claim 1, it is characterized in that the carbon containing organic additive is a kind of or its mixture of polypropylene, polyacrylamide, glucose, sucrose, starch, the total weight percent that accounts for raw material 5～20% of the consumption of additive.
6, the high density ultrafine composite ferric lithium phosphate anode material made of the preparation method of high density ultrafine composite ferric lithium phosphate anode material according to claim 1.
7, a kind of high density ultrafine composite ferric lithium phosphate anode material, it is characterized in that by molysite compound, lithium salt compound and the microcosmic salt compound mixed of P: Li: Fe=1-1.1: 1-1.1: 1-1.1 in molar ratio, add doping element compound or carbon containing organic compound more therein as conductive additive, add organic acid as carrier.
8, high density ultrafine composite ferric lithium phosphate anode material according to claim 7, it is characterized in that lithium salts comprises a kind of or its mixture of lithium hydroxide, Quilonum Retard, lithium oxalate, lithium fluoride, Trilithium phosphate, Lithium Acetate, molysite is soluble ferric iron salt or Iron diacetate, ferrous sulfate or its mixture, and the oxide compound of phosphoric acid salt or phosphorus is NH
4H
2PO
4, (NH
4)
2HPO
4A kind of or its mixture.
9, high density ultrafine composite ferric lithium phosphate anode material according to claim 7, it is characterized in that doping element compound is a kind of of magnesium acetate, magnesium hydroxide or its mixture, the carbon containing organic additive is a kind of or its mixture of polypropylene, polyacrylamide, glucose, sucrose, starch, the total weight percent that accounts for raw material 5～20% of the consumption of additive.
10, high density ultrafine composite ferric lithium phosphate anode material according to claim 7 is characterized in that organic acid is a kind of or its mixture of oxalic acid, tartrate, vinylformic acid, citric acid, polyacrylic acid, humic acid, polyvinylpyrrolidone, 2 ethyl hexanoic acid, succsinic acid.
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