CN101719548A - Compound lithium iron phosphate used as positive pole material of lithium ion battery and preparation method thereof - Google Patents
Compound lithium iron phosphate used as positive pole material of lithium ion battery and preparation method thereof Download PDFInfo
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- CN101719548A CN101719548A CN200910110478A CN200910110478A CN101719548A CN 101719548 A CN101719548 A CN 101719548A CN 200910110478 A CN200910110478 A CN 200910110478A CN 200910110478 A CN200910110478 A CN 200910110478A CN 101719548 A CN101719548 A CN 101719548A
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- lithium
- ferrous
- phosphoric acid
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- 239000000463 material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 14
- -1 Compound lithium iron phosphate Chemical class 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000011159 matrix material Substances 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 66
- 229910052744 lithium Inorganic materials 0.000 claims description 53
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 51
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 38
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 33
- 238000000498 ball milling Methods 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 239000010405 anode material Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000012467 final product Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011247 coating layer Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
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- 239000004372 Polyvinyl alcohol 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
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- 239000008103 glucose Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- 229930091371 Fructose Natural products 0.000 claims description 4
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- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 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
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
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- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000000428 dust Substances 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 229940062993 ferrous oxalate Drugs 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 4
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 239000010431 corundum Substances 0.000 claims description 2
- 239000005338 frosted glass Substances 0.000 claims description 2
- 230000004927 fusion Effects 0.000 claims description 2
- 235000014413 iron hydroxide Nutrition 0.000 claims description 2
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 4
- 238000000034 method Methods 0.000 abstract description 11
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 4
- 229910021529 ammonia Inorganic materials 0.000 abstract description 3
- 229940116007 ferrous phosphate Drugs 0.000 description 11
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 11
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 11
- 239000010406 cathode material Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 5
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- 230000008901 benefit Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000002253 acid Substances 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
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910006025 NiCoMn Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to compound lithium iron phosphate used as a positive pole material of a lithium ion battery and a preparation method thereof. The compound lithium iron phosphate is a compound material and comprises a lithium iron phosphate matrix and a carbon wrapping layer, wherein the carbon wrapping layer is positioned outside the lithium iron phosphate matrix; the lithium iron phosphate matrix is not dopped with other metal elements; and the wrapping amount of the carbon wrapping layer is 1-10 percent. The compound lithium iron phosphate material is not dopped with other metal elements and accords with the requirement on clean production in the preparation process; the invention only uses lithium dihydrogen phosphate, iron source materials and carbon source materials in the preparation method, has few major materials, easy manufacture procedure control and industrialization without exhausting harmful gas which mainly refers to ammonia, and high discharge capacity of the prepared material and first-time efficiency.
Description
Technical field
The invention belongs to novel energy material field, relate in particular to a kind of ferrous lithium of compound phosphoric acid that is used as anode material for lithium-ion batteries and preparation method thereof.
Background technology
Along with development of human society, the problem of energy crisis and environmental protection becomes increasingly conspicuous.Sony companies in 1991 have at first realized the commercialization of lithium rechargeable battery, and this has promoted the development of electronics industry, information industry, auto industry, energy industry and environmental protection cause to a great extent.Lithium ion battery has been widely used in also becoming redundant electrical power, cordless power tool power supply and hybrid-electric car (HEV), pure electric automobile (EV) power supply of electricity generation systems such as solar energy, wind energy in the mini-plants such as mobile communication equipment, portable computer, video camera, camera.
The anode material of lithium battery of Shi Yonging mainly contains LiCoO in the market
2, LiMn
2O
4, four kinds of NiCoMn ternary material and LiFePO 4s, and former three occupies most market shares, LiFePO 4 has been realized industrialization, but as yet not large-scale application in hybrid electric vehicle and pure electric vehicle.Stratiform cobalt acid lithium because cost an arm and a leg, development and application that shortcomings such as resource scarcity, poor stability hamper power lithium-ion battery always, its range of application also only limits to compact battery.LiMn2O4 is to follow the anode material of lithium battery that develops after the cobalt acid lithium closely, pass through years of researches, material property is greatly improved, but its lower specific capacity, relatively poor cycle performance make its application be subjected to bigger restriction, though research by recent years, cycle performance has obtained certain improvement, but high temperature cyclic performance is not also solved preferably, has limited its application aspect electrokinetic cell especially electric vehicle power sources.Tertiary cathode material had had large development in recent years, but this only is a compromise proposal, can not solve cost, toxicity and the safety issue of lithium battery at all.According to estimates, the demand of anode material for lithium-ion batteries still will increase with fast speeds in recent years.
Goodenough in 1997 etc. are at patent USA 5,910, propose in 382 the positive electrode of LiFePO4 as new type lithium ion battery, this material has that raw material sources are extensive, free from environmental pollution, security performance is good and the higher advantages such as (170mAh/g) of theoretical capacity, and conductivity is low, the shortcoming of high rate performance difference but exist simultaneously.M.Armand in 1999 etc. publish an article and claim the carbon coating to improve the ferrousphosphate lithium material performance, thereby the research that has promoted ferrousphosphate lithium material is used.
The advantage that ferrousphosphate lithium material has is as follows:
1, safe: LiFePO 4 has solved the security hidden trouble of cobalt acid lithium and LiMn2O4 fully, can consumer's life security not constituted a threat to.
2, stability is high: the capacity stability that voltage platform is stablized (3.4V vs Li/Li+), high-temperature charging is good, and storge quality is good.
3, the long-life: the cycle life of ferrous phosphate lithium battery reaches more than 2000 times.
4, quickly-chargeable: ferrous phosphate lithium battery 10C charging can be charged to more than 80% of capacity in 6 minutes.
5, low price: raw material sources are extensive, cheap, no strategic resource and scarce resource restriction.
6, environmental protection: use advantages of nontoxic raw materials, nontoxic, the unharmful substance discharging of whole process of production cleaning.
Therefore, the large-scale application of lithium iron phosphate cathode material on power lithium-ion battery will be trend of the times.
The preparation method of LiFePO 4 mainly contains solid phase method and liquid phase method at present, wherein solid phase method comprises carbon thermal reduction [Chinese patent 200410003477.1], microwave synthetic [200610065211.9] and mechanical ball milling method etc. again, and liquid phase method has sol-gal process [Chinese patent 200410099216.4], hydro thermal method and coprecipitation [Chinese patent 200410103485.3] etc.It is simple that solid phase method prepares ferrousphosphate lithium material technology, and cost is low, be easy to realize industrialization, but has the deficiency that capacity is lower, multiplying power is relatively poor.The liquid phase method synthesizing lithium ferrous phosphate has that capacity is higher, multiplying power good, material homogeneity is good, increase advantages such as voltage drop is less with multiplying power, but also has preparation condition harshness, complex process, cost height, is difficult to realize the shortcoming of suitability for industrialized production.Wang Deyu etc. are raw material with lithium source, source of iron, phosphate and carbon source material, adopt the ferrousphosphate lithium material of lapping mode preparation, have ammonia to generate [Chinese patent 200410003477.1] in the preparation process
Summary of the invention
First purpose of the present invention is the problems referred to above at existing lithium ferrous phosphate as anode material of lithium ion battery existence, and the ferrous lithium of compound phosphoric acid as anode material for lithium-ion batteries of a kind of material capacity height, good rate capability is provided.
Second purpose of the present invention is to provide the preparation method of the ferrous lithium of compound phosphoric acid of the present invention that a kind of technology is simple, cost is low.
The ferrous lithium of compound phosphoric acid as anode material for lithium-ion batteries of the present invention is a composite material, comprise the carbon coating layer that LiFePO 4 matrix and matrix are outer, described LiFePO 4 matrix does not have other doped with metal elements, and the covering amount of described carbon coating layer is 1-10%.
The preparation raw material of described carbon coating layer adopts the conductive acetylene carbon black, the conductive nano carbon dust, carbon nano-tube, the nano-sized carbon microballoon, gas-phase grown nanometer carbon fibre, sucrose, tartaric acid, glucose, urea, citric acid, acrylic acid, fructose, ascorbic acid, polyethylene glycol, polyvinyl alcohol, glycerol, furane resins, phenolic resins, epoxy resin, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile; butadiene-styrene rubber; one or more in cellulose or the pitch.
The preparation method of the ferrous lithium of compound phosphoric acid of the invention described above comprises the steps:
(1) be (0.90～1.20) in molar ratio with lithium dihydrogen phosphate, ferrous source material: 1 ratio, add carbon source material and raw material weight 0.5-5 dispersant doubly, ball milling 2～36h is to nanoscale or submicron order;
(2) ball milling disposed slurry drying;
(3) the dry thing of previous step gained is made precursor with ball mill ball milling 1～10h under 100～400rpm rotating speed;
(4) with presoma in non-oxidizing gas helium He, argon Ar, nitrogen N
2Or hydrogen H
2, perhaps nitrogen N
2+ hydrogen H
2Mixed gas protected 200～400 ℃ of following pre-burning 2～12h in tube furnace or box type furnace or rotary furnace or tunnel cave down of=(50～95)+(50～5) (volume ratio) naturally cool to room temperature;
(5) with the pre-imitation frosted glass of previous step gained with ball mill ball milling 1～10h under 100～400rpm rotating speed, or be crushed to the granularity of requirement, then in non-oxidizing gas helium He, argon Ar, nitrogen N with pulverizer
2Or hydrogen H
2, perhaps nitrogen N
2+ hydrogen H
2The mixed gas protected following heating rate with 1-5 ℃/minute of=(50～95)+(50～5) (volume ratio) is warmed up to 500～800 ℃ and constant temperature 8～36h, naturally cools to room temperature;
(6) previous step gained material or is crushed to the granularity of requirement with ball mill ball milling 1～10h under 100～400rpm rotating speed to the granularity that requires with pulverizer;
(7) previous step gained material is carried out mechanical jolt ramming and handles, get final product the ferrous lithium material of compound phosphoric acid.
Described ferrous source material is ferrous oxalate, di-iron trioxide, ferrous acetate, ferric nitrate, iron hydroxide, tri-iron tetroxide, ferrous oxide or ferrous hydroxide.
Described carbon source material is the conductive acetylene carbon black, the conductive nano carbon dust, carbon nano-tube, the nano-sized carbon microballoon, gas-phase grown nanometer carbon fibre, sucrose, tartaric acid, glucose, urea, citric acid, acrylic acid, fructose, ascorbic acid, polyethylene glycol, polyvinyl alcohol, glycerol, furane resins, phenolic resins, epoxy resin, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile; butadiene-styrene rubber; one or more in cellulose or the pitch.
Described dispersant is pure water, ethanol or the mixture of the two.
Described ball mill adopts planetary ball mill, roller ball grinding machine, horizontal ball mill or stirring ball mill, and the balls grinding media is stainless steel, corundum, zirconia or agate.
The drying means of described (2) step slurry is oven dry or expansion drying or a spray drying under 150～350 degree temperature.
Described pulverizer adopts airslide disintegrating mill or mechanical crusher.
Described " granularity of requirement " is to reach nanoscale or submicron order.
It is plain bumper, VC mixer, fusion machine or kneader that the equipment that adopts is handled in described mechanical jolt ramming.The effect that jolt ramming is handled is by mechanical presses, and material mixes repeatedly under the effect of equipment shearing force and disperses, air-out, thereby have the high and finely dispersed characteristics of jolt ramming through the material that jolt ramming is handled.
The present invention prepares the ferrous lithium material of gained compound phosphoric acid and has irregular pattern, and granularity is 0.2～30 μ m, and specific area is 5～45m
2/ g.Adopt the ferrous lithium material of compound phosphoric acid of this method preparation to have good electrochemical, material polarization reduces, and its 1.2C discharges first that capacity is 121.8mAh/g, and efficient is 80.6% first, maximum discharge capacity is 133.7mAh/g, and the capability retention in 50 weeks of circulating is 107.93%.
Technique effect of the present invention is: the ferrous lithium material of compound phosphoric acid of the present invention does not use other doped with metal elements, in preparation process, meet the cleaner production requirement, the present invention only uses lithium dihydrogen phosphate, ferrous source material and carbon source material in preparation process, primary raw material is few, be easy to processing procedure control and industrialization, no pernicious gas-ammonia emission makes the discharge capacity height of material, first the efficient height.
Description of drawings
Fig. 1 is the X-ray diffracting spectrum of the ferrous lithium of compound phosphoric acid of embodiment one preparation.
Fig. 2 is the stereoscan photograph of the ferrous lithium of compound phosphoric acid under 500 times of embodiment one preparation.
Fig. 3 is that the ferrous lithium of compound phosphoric acid of embodiment one preparation is at the first charge-discharge curve between 2.5-3.9V, under the 1.2C multiplying power.
Fig. 4 is that the ferrous lithium of compound phosphoric acid of embodiment one preparation is at the capacity cyclic curve between 2.5-3.9V, under the 1.2C multiplying power.
Embodiment
Embodiment one:
Accurately take by weighing lithium dihydrogen phosphate 110 grams, iron oxide 80.5 grams, glucose 38 grams, add while stirring in the 400ml ethanol, use planetary ball mill ball milling 9 hours (h) under the 220rpm rotating speed then; The slurry that makes is at 200 ℃ of following stirring and dryings; Is that ball-milling medium ball milling 3h under the 290rpm rotating speed makes precursor with above-mentioned dry thing with the zirconia ball with planetary ball mill; In 300 ℃ of following pre-burning 6h of box type furnace, with 400rpm rotating speed ball milling 3h, the heating rate with 5 ℃/minute is warmed up to 700 ℃ and constant temperature 10h to presoma under nitrogen protection then, naturally cools to room temperature with the roller ball grinding machine in the cooling back under nitrogen protection; With above-mentioned burned material planetary ball mill ball milling 3.5h under the 250rpm rotating speed; The gained material is carried out mechanical jolt ramming with plain bumper handles, get final product the ferrous lithium material of compound phosphoric acid.
After the ferrous lithium material of the compound phosphoric acid that embodiment one makes is crossed 200 mesh sieves, do X-ray diffraction, scanning electron microscope analysis and electrochemical property test, the result as shown in Figures 1 to 4.The lithium iron phosphate cathode material granularity d that makes
50=8.15 μ m, specific area are 33.253m
2/ g, tap density is 1.32g/ml.The electrochemical property test of simulated battery carries out on new Weir battery testing system; be used for ferrousphosphate lithium material sample that the positive pole of the button simulated battery of electric performance test makes by embodiment one, conductive agent, binding agent PVdF according to 90: 5: 5 ratio of mass ratio; making solvent with N-methyl pyrrolidone NMP is applied on the Al paper tinsel after evenly; 110 ℃ of dryings are after 10 hours; spreading and punching; in the Braun MBRAUN of argon shield glove box, carry out the simulated battery assembling; with the metal lithium sheet is negative pole; barrier film is Celgard2400, and electrolyte is 1molL
-1LiPF
6/ DMC+DEC+EC (volume ratio is 1: 1: 1) discharges and recharges with the charging and discharging currents density of 1.2C, charging/discharging voltage is 2.5-3.9V, when 3.9V constant current to 0.03mA.The 1.2C that makes lithium ferrous phosphate composite material discharges first that capacity is 121.8mAh/g, and efficient is 80.6% first, and maximum discharge capacity is 133.7mAh/g.
Embodiment two:
Accurately take by weighing lithium dihydrogen phosphate 123 grams, ferrous oxalate 178 grams, polyvinyl alcohol 45 grams, add while stirring in the 345ml pure water, use planetary ball mill ball milling 2h under the 400rpm rotating speed then; The slurry that makes is at 320 ℃ of following wink-dries; Above-mentioned dry thing is made precursor with roller ball grinding machine ball milling 10h under the 100rpm rotating speed; In 210 ℃ of following pre-burning 12h of box type furnace, with 100rpm rotating speed ball milling 3h, the heating rate with 1 ℃/minute is warmed up to 550 ℃ and constant temperature 20h to presoma under nitrogen protection then, naturally cools to room temperature with planetary ball mill in the cooling back under nitrogen protection; With above-mentioned burned material planetary ball mill ball milling 10h under the 100rpm rotating speed; The gained material is carried out mechanical jolt ramming with plain bumper handles, get final product the ferrous lithium material of compound phosphoric acid.
The lithium iron phosphate cathode material granularity d that makes
50=7.50 μ m, specific area are 24.120m
2/ g, tap density is 1.39g/ml.Record material 1.2C and discharge first that capacity is 122.3mAh/g, efficient is 81.3% first.
Embodiment three:
Accurately take by weighing lithium dihydrogen phosphate 126.7 grams, tri-iron tetroxide 89.8 grams, black 15.3 grams of conductive acetylene, add while stirring in 400ml pure water and the ethanol mixed dispersant (volume ratio 50: 50), use planetary ball mill to be ball-milling medium ball milling 34h under the 100rpm rotating speed then with agate ball; The slurry that makes is at 245 ℃ of following stirring and dryings; Above-mentioned dry thing is made precursor with planetary ball mill ball milling 1.2h under the 380rpm rotating speed; Presoma in 390 ℃ of following pre-burning 2.2h of rotary furnace, is warmed up to 800 ℃ and constant temperature 8.5h with 5 ℃/minute heating rate then under nitrogen protection, naturally cool to room temperature; With above-mentioned burned material planetary ball mill ball milling 1.2h under the 390rpm rotating speed; The gained material is carried out mechanical jolt ramming with plain bumper handles, get final product the ferrous lithium material of compound phosphoric acid.
The lithium iron phosphate cathode material granularity d that makes
50=6.72 μ m, specific area are 22.123m
2/ g, tap density is 1.42g/ml.Record material 1.2C and discharge first that capacity is 121.7mAh/g, efficient is 82.2% first.
Embodiment four:
Accurately take by weighing lithium dihydrogen phosphate 120 grams, ferrous oxalate 177 grams, pitch 20 grams, adding while stirring contains in the 350ml water of 5% quality ethanol, uses stirring ball mill ball milling 25h under the 150rpm rotating speed then; The slurry that makes is 330 ℃ of following spray dryings; Above-mentioned dry thing is made precursor with roller ball grinding machine ball milling 8h under the 150rpm rotating speed; Presoma in 280 ℃ of following pre-burning 8h of rotary furnace, is warmed up to 650 ℃ and constant temperature 16h with 3 ℃/minute heating rate then under the nitrogen and hydrogen mixture protection that contains 8% hydrogen, naturally cool to room temperature; Above-mentioned burned material is crushed to the granularity of requirement with airslide disintegrating mill; The gained material is carried out mechanical jolt ramming with plain bumper handles, get final product the ferrous lithium material of compound phosphoric acid.
The lithium iron phosphate cathode material granularity d that makes
50=6.13 μ m, specific area are 23.454m
2/ g, tap density is 1.48g/ml.Record material 1.2C and discharge first that capacity is 122.5mAh/g, efficient is 80.2% first.
Embodiment five:
Accurately take by weighing lithium dihydrogen phosphate 124 grams, iron oxide 89 grams, sucrose 24 grams, add while stirring in the mixed dispersant (volume ratio 85: 15) of 360ml pure water and ethanol, use planetary ball mill to be ball-milling medium ball milling 20h under the 300rpm rotating speed then with zirconia ball; The slurry that makes is at 200 ℃ of following stirring and dryings; Above-mentioned dry thing is made precursor with planetary ball mill ball milling 6h under the 200rpm rotating speed; Presoma in 290 ℃ of following pre-burning 4h of box type furnace, is warmed up to 620 ℃ and constant temperature 18h with 3 ℃/minute heating rate then under argon shield, naturally cool to room temperature; Above-mentioned burned material is crushed to the granularity of requirement with airslide disintegrating mill; The gained material is carried out jolt ramming with plain bumper handles, get final product the ferrous lithium material of compound phosphoric acid.
The lithium iron phosphate cathode material granularity d that makes
50=5.92 μ m, specific area are 29.135m
2/ g, tap density is 1.44g/ml.Record material 1.2C and discharge first that capacity is 122.3mAh/g, efficient is 81.6% first.
Embodiment six:
Accurately take by weighing lithium dihydrogen phosphate 125 grams, iron oxide 90 grams, acrylic acid 28 grams, add while stirring in the 360ml pure water, use planetary ball mill ball milling 13h under the 220rpm rotating speed then; The slurry that makes is 250 ℃ of following spray dryings; Is that ball-milling medium ball milling 4h under the 250rpm rotating speed makes precursor with above-mentioned dry thing with the zirconia ball with planetary ball mill; Presoma in 290 ℃ of following pre-burning 7h of box type furnace, is warmed up to 750 ℃ and constant temperature 12h with 3 ℃/minute heating rate then under argon shield, naturally cool to room temperature; Above-mentioned burned material is pulverized with mechanical crusher; The gained material is carried out jolt ramming with plain bumper handles, get final product the ferrous lithium material of compound phosphoric acid.
The lithium iron phosphate cathode material granularity d that makes
50=6.10 μ m, specific area are 25.376m
2/ g, tap density is 1.49g/ml, and 1.2C discharges first that capacity is 123.1mAh/g, and efficient is 81.5% first.
Claims (10)
1. ferrous lithium of compound phosphoric acid as anode material for lithium-ion batteries, it is characterized in that: the ferrous lithium of described compound phosphoric acid comprises LiFePO 4 matrix and the outer carbon coating layer of matrix, described LiFePO 4 matrix does not have other doped with metal elements, and the covering amount of described carbon coating layer is 1-10%.
2. the ferrous lithium of compound phosphoric acid as anode material for lithium-ion batteries according to claim 1 is characterized in that: the raw material of described carbon coating layer adopts the conductive acetylene carbon black, the conductive nano carbon dust, carbon nano-tube, the nano-sized carbon microballoon, gas-phase grown nanometer carbon fibre, sucrose, tartaric acid, glucose, urea, citric acid, acrylic acid, fructose, ascorbic acid, polyethylene glycol, polyvinyl alcohol, glycerol, furane resins, phenolic resins, epoxy resin, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile; butadiene-styrene rubber; one or more in cellulose or the pitch.
3. the preparation method of the ferrous lithium of the described compound phosphoric acid of claim 1 comprises the steps:
(1) be (0.90～1.20) in molar ratio with lithium dihydrogen phosphate, ferrous source material: 1 ratio, add carbon source material and raw material weight 0.5-5 dispersant doubly, ball milling 2～36h is to nanoscale or submicron order;
(2) ball milling disposed slurry drying;
(3) the dry thing of previous step gained is made precursor with ball mill ball milling 1～10h under 100～400rpm rotating speed;
(4) with presoma in non-oxidizing gas helium He, argon Ar, nitrogen N
2Or hydrogen H
2, perhaps nitrogen N
2+ hydrogen H
2Mixed gas protected 200～400 ℃ of following pre-burning 2～12h in tube furnace or box type furnace or rotary furnace or tunnel cave down of=(50～95)+(50～5) (volume ratio) naturally cool to room temperature;
(5) with the pre-imitation frosted glass of previous step gained with ball mill ball milling 1～10h under 100～400rpm rotating speed, or be crushed to the granularity of requirement, then in non-oxidizing gas helium He, argon Ar, nitrogen N with pulverizer
2Or hydrogen H
2, perhaps nitrogen N
2+ hydrogen H
2The mixed gas protected following heating rate with 1-5 ℃/minute of=(50～95)+(50～5) (volume ratio) is warmed up to 500～800 ℃ and constant temperature 8～36h, naturally cools to room temperature;
(6) previous step gained material or is crushed to the granularity of requirement with ball mill ball milling 1～10h under 100～400rpm rotating speed to the granularity that requires with pulverizer;
(7) previous step gained material is carried out mechanical jolt ramming and handles, get final product the ferrous lithium material of compound phosphoric acid.
4. the preparation method of the ferrous lithium of compound phosphoric acid according to claim 3 is characterized in that: described ferrous source material is ferrous oxalate, di-iron trioxide, ferrous acetate, ferric nitrate, iron hydroxide, tri-iron tetroxide, ferrous oxide or ferrous hydroxide.
5. the preparation method of the ferrous lithium of compound phosphoric acid according to claim 3 is characterized in that: described carbon source material is the conductive acetylene carbon black, the conductive nano carbon dust, carbon nano-tube, the nano-sized carbon microballoon, gas-phase grown nanometer carbon fibre, sucrose, tartaric acid, glucose, urea, citric acid, acrylic acid, fructose, ascorbic acid, polyethylene glycol, polyvinyl alcohol, glycerol, furane resins, phenolic resins, epoxy resin, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile; butadiene-styrene rubber; one or more in cellulose or the pitch.
6. the preparation method of the ferrous lithium of compound phosphoric acid according to claim 3 is characterized in that: described dispersant is pure water, ethanol or the mixture of the two.
7. the preparation method of the ferrous lithium of compound phosphoric acid according to claim 3, it is characterized in that: described ball mill adopts planetary ball mill, roller ball grinding machine, horizontal ball mill or stirring ball mill, and the balls grinding media is stainless steel, corundum, zirconia or agate.
8. the preparation method of the ferrous lithium of compound phosphoric acid according to claim 3 is characterized in that: the drying means of described (2) step slurry is oven dry or expansion drying or a spray drying under 150～350 degree temperature.
9. the preparation method of the ferrous lithium of compound phosphoric acid according to claim 3 is characterized in that: described pulverizer adopts airslide disintegrating mill or mechanical crusher.
10. the preparation method of the ferrous lithium of compound phosphoric acid according to claim 3 is characterized in that: it is plain bumper, VC mixer, fusion machine or kneader that the equipment that adopts is handled in described mechanical jolt ramming.
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