CN103187569A - Preparation method for LiFePO4/C contained anode material for lithium ion battery - Google Patents
Preparation method for LiFePO4/C contained anode material for lithium ion battery Download PDFInfo
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- CN103187569A CN103187569A CN2013101094463A CN201310109446A CN103187569A CN 103187569 A CN103187569 A CN 103187569A CN 2013101094463 A CN2013101094463 A CN 2013101094463A CN 201310109446 A CN201310109446 A CN 201310109446A CN 103187569 A CN103187569 A CN 103187569A
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- iron phosphate
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- magnesium
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 12
- 239000010405 anode material Substances 0.000 title claims description 7
- 229910000901 LiFePO4/C Inorganic materials 0.000 title description 8
- 239000000463 material Substances 0.000 claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 20
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 10
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 6
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 6
- 238000000498 ball milling Methods 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 23
- 239000005955 Ferric phosphate Substances 0.000 claims description 19
- 229940032958 ferric phosphate Drugs 0.000 claims description 19
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 19
- 229910052749 magnesium Inorganic materials 0.000 claims description 19
- 239000011777 magnesium Substances 0.000 claims description 19
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 16
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- 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 13
- 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 13
- 239000008103 glucose Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 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
- 239000005720 sucrose Substances 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 150000004032 porphyrins Chemical class 0.000 claims description 4
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- 229910052786 argon Inorganic materials 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 abstract description 16
- -1 organomagnesium metal complex Chemical class 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 abstract description 4
- 239000002002 slurry Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 239000010406 cathode material Substances 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 229910000398 iron phosphate Inorganic materials 0.000 abstract 1
- 239000007774 positive electrode material Substances 0.000 abstract 1
- 238000004886 process control Methods 0.000 abstract 1
- 229910010710 LiFePO Inorganic materials 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 239000002994 raw material Substances 0.000 description 15
- 239000012043 crude product Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 11
- 208000005156 Dehydration Diseases 0.000 description 8
- 230000018044 dehydration Effects 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 238000001694 spray drying Methods 0.000 description 8
- 239000002001 electrolyte material Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 229940062993 ferrous oxalate Drugs 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000003836 solid-state method Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 229960004424 carbon dioxide Drugs 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 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)
- Secondary Cells (AREA)
Abstract
本发明锂离子电池技术领域，具体涉及一种锂离子电池正极材料含碳磷酸铁锂（LiFePO4/C）的制备方法。本发明方法是将磷酸铁、锂盐、碳源化合物及少量有机镁金属配合物按比例混合均匀，加入适量的溶剂进行球磨搅拌成浆状，并烘干形成先驱物，然后在惰性气氛下煅烧得到含碳包覆的磷酸铁锂正极材料。本发明具有制备简单，工艺易控，重复性好等特点。本发明中有机镁金属配合物助剂的加入不但提高了磷酸铁锂材料的振实密度，更是改善了磷酸铁锂材料的导电性，提高了材料在大电流下充放电的性能，使材料更能适用动力电池对磷酸铁锂材料高能量密度及高倍率充放电的应用需求。
The invention relates to the technical field of lithium ion batteries, in particular to a method for preparing carbon-containing lithium iron phosphate (LiFePO 4 /C), a positive electrode material of lithium ion batteries. The method of the present invention is to mix iron phosphate, lithium salt, carbon source compound and a small amount of organomagnesium metal complex uniformly in proportion, add an appropriate amount of solvent, carry out ball milling and stir to form a slurry, and dry to form a precursor, and then calcined in an inert atmosphere A carbon-coated lithium iron phosphate cathode material is obtained. The invention has the characteristics of simple preparation, easy process control, good repeatability and the like. The addition of organic magnesium metal complex additives in the present invention not only improves the tap density of the lithium iron phosphate material, but also improves the conductivity of the lithium iron phosphate material, improves the performance of the material for charging and discharging under high current, and makes the material It is more suitable for the application requirements of power batteries for high energy density and high rate charge and discharge of lithium iron phosphate materials.
Description
Technical field
Technical field of lithium ion of the present invention is specifically related to a kind of anode material for lithium-ion batteries carbon containing LiFePO4 (LiFePO
4/ C) preparation method.
Background technology
Chemical cell, for example lithium metal or lithium ion battery are class electrical energy storage devices, comprise current collector, charge storage material, electrolyte, barrier film etc. usually.Lithium metal or lithium ion battery have the current potential height usually, specific capacity is big, specific volume is big, discharge and recharge and wait advantage often, be widely used in fields such as mobile phone, luggable computer, instrument and meter, electric tool, electric motor car, and become gradually main flow once or the secondary chemical cell.
J. B. Goodenough seminar of texas,U.S university in 1997 etc. find LiFePO 4 material (LiFePO first
4) can reversibly embed and deviate from lithium ion.This material non-toxic, environmental friendliness, raw material sources enrich, has cheap, advantage such as capacity is high, good cycle and thermal stability are good, this material becomes desirable power battery anode material, caused the special concern of industrial circle, and many relevant patents have been produced, for example US Patent No. 5910382, US6514640 etc.Yet LiFePO
4Intrinsic conductivity very low, be about 10
-9S/cm is difficult to practicability.
2000, people such as Ravet improved conductivity of electrolyte materials significantly by the carbon coating technology.Wherein adopt carbothermic method to be coated on LiFePO to carbon
4On the crystal boundary, generate network-like electrically conductive graphite (2-3wt%), thereby significantly improve LiFePO
4Conductivity (10
-2S/cm), capacity.The carbon coating technology is by being coated on LiFePO with carbon
4On the crystal boundary, make LiFePO
4Surface conductivity is improved, but its intrinsic conductivity does not increase.
U.S. Valence technology company mixes by vanadium, fluorine and has improved LiFePO
4Conductivity of electrolyte materials.
Conductivity of electrolyte materials has improved significantly by technology such as metal ion mixing, nano-scales in U.S. A123 Systems Inc..Introduce cation impurity as the Li position in the crystal structure of LiFePO4, for example forming, chemical general formula is Li
1-xZ
xMPO
4Material, wherein Z is Ti, Zr, Mg, Ta, W, Nb, Al etc., M is Mn, Nb, Co, Ni, Fe, Cr, V etc., conductivity of electrolyte materials from 10
-9S/cm brings up to 10
-3S/cm.
The main method of preparation LiFePO 4 material comprises high temperature solid-state chemical method, hydrothermal synthesis method etc.It is initial feed that the high temperature solid-state chemical method adopts lithium carbonate, ferrous oxalate, ammonium dihydrogen phosphate etc.; Also can use lithium hydroxide, ferric phosphate is initial feed; Lithium dihydrogen phosphate, iron, iron oxide are initial feed; Be carbon thermal reduction material, carbon source with sucrose, glucose, citric acid, polypropylene, polyethylene, polyvinyl alcohol etc.Above-mentioned raw materials with after the mechanical lapping, drying, is placed in the stove of inert gas shielding, and heating up is heated to about 700 degrees centigrade and keeps being cooled to room temperature after a few hours and namely obtain LiFePO
4/ C material.The advantage of high temperature solid-state method is that technology is simple, easy realization of industrialization, but wayward, the skewness of product particle diameter, pattern is irregular.Hydrothermal synthesis method adopts Na
2HPO
4, FeCl
3, CH3COOLi is raw material, by the synthetic LiFePO of hydro thermal method
4Compare with high temperature solid-state method, the temperature of hydrothermal synthesis method is lower, about 150 degree～200 degree, and the reaction time also only is about 1/5 of solid phase reaction, and can directly obtain LiFePO4, do not need inert gas, product crystal grain is less, thing phase homogeneous, is particularly suitable for the high-multiplying power discharge field, but the Fe inconsistent phenomenon takes place in this kind synthetic method easily in forming olivine structural, influence chemical property, and hydro thermal method needs high temperature high voltage resistant equipment, it is big that the difficulty of suitability for industrialized production is wanted.
Prior art such as US5910382 and US6514640 is in ferric phosphate or other transition metal lithium compound building-up process; normally with lithium carbonate, ferrous oxalate, ammonium di-hydrogen phosphate etc. under nitrogen protection; carbon or carbon monoxide by hydrocarbon (CHn) pyrolysis come the reducing metal ion, form LiFePO
4, remaining carbon is coated on and forms the surface conductance layer on the LiFePO4 crystal.Yet carbon coating layer can only improve the surface conductivity of material, LiFePO
4The conductivity of bulk material does not still improve, and adopts the battery of this material also to be difficult to realize high current charge-discharge.U.S. A123 Systems Inc. is without the carbon coating technology, but improved conductivity of electrolyte materials significantly by the metal ion mixing art, as at LiFePO
4Introduce cation Nb, V impurity in the material, as Li
1-xZxFePO
4(Z is Nb, V etc.), conductivity of electrolyte materials from 10
-9S/cm brings up to 10
-3S/cm.Yet above-mentioned technology still has improved space.
Summary of the invention
The objective of the invention is at above-mentioned present situation, it is abundant, cheap to aim to provide a kind of raw material sources, the synthesis technique simple and feasible, safe and reliable, production cost is low, non-environmental-pollution, product has the anode material for lithium-ion batteries carbon containing LiFePO4 (LiFePO of better chemical property and high-tap density
4/ C) synthetic method.
The synthetic method of anode material for lithium-ion batteries carbon containing LiFePO4 provided by the invention, be with ferric phosphate, lithium salts, carbon-source cpd and organic-magnesium metal complex auxiliary agent in molar ratio 1:0.5:1:0.01 mix, the adding proper amount of solvent is carried out ball milling and is stirred into pulpous state, and oven dry forms precursor, then inert atmosphere " 100 ℃--400 ℃ preheating 1--3 hour; 300 ℃--500 ℃ were dewatered 1--5 hour; 500 ℃--900 ℃ are incubated 4--10 hour, obtain the lithium iron phosphate positive material that carbon containing coats.
Organic-magnesium metal complex auxiliary agent among the present invention not only can improve the conductivity of LiFePO 4 material, improves the performance that material discharges and recharges under big electric current, can also improve the tap density of LiFePO 4 material, thereby improves the energy density of battery.
Among the present invention, described lithium salts is lithium hydroxide, lithium carbonate or lithium acetate.
Among the present invention, described carbon-source cpd is glucose, sucrose, polyethylene glycol or simple substance carbon.
Among the present invention, organic-magnesium metal complex auxiliary agent can be two luxuriant magnesium, oxine magnesium or porphyrin magnesium.
Among the present invention, the consumption of organic-magnesium metal complex auxiliary agent is 0.5% ~ 2% of LiFePO4 molal weight.
Among the present invention, raw material are carried out moistening with solvent, described solvent is a kind of in water, ethanol or the acetone, and adopts mechanical lapping to carry out preliminary treatment.
Among the present invention, the raw material through ball-milling treatment are carried out drying, and preparing described carbon containing LiFePO 4 material by continuous solid state reaction under nitrogen or the inert gas shielding, in not being higher than environment Celsius 900 ℃.
Description of drawings
Fig. 1 is ESEM (SEM) figure by the prepared LiFePO4/C dusty material of embodiment 1.
Fig. 2 is X-ray diffraction (XRD) spectrogram of the prepared LiFePO4/C dusty material of embodiment 1.
Fig. 3 is the charge graph of 10Ah battery under different electric currents that adopts embodiment 1 prepared LiFePO4/C to prepare as positive electrode.
Fig. 4 is the discharge curve of 10Ah battery under different electric currents that adopts embodiment 1 prepared LiFePO4/C to prepare as positive electrode.
Fig. 5 adopts the prepared LiFePO4/C of embodiment 1 to charge and discharge cycle life figure as the 10Ah battery of positive electrode preparation under different electric currents.
Embodiment
In preparing according to LiFePO4/C materials process of the present invention, raw material selection lithium salts, ferric phosphate, carbon-source cpd and organic-magnesium metal complex auxiliary agent also need a spot of solvent and protection nitrogen in addition.Raw material add a small amount of solvent according to the mole proportioning, carry out stirring ball-milling, and spray drying obtains predecessor then.The calciner that predecessor is put into through nitrogen protection carries out preheating, dehydration, roasting, annealing, cooling, pulverizing, obtains target material.
The electrochemical properties of the material that is synthesized is estimated by the preparation battery.Experiment selects for use 30 micron aluminum foils as the positive colleeting comb utmost point; Positive electrode is above-mentioned LiFePO4/C material, and this material mixes in 85:10:5 ratio and a small amount of solvent (for example NMP) with conductive carbon black, bonding agent (for example PVDF), makes slurry through vacuum stirring and is coated on the above-mentioned aluminium foil; Coat is made positive plate through vacuumize, roll-in, and the thickness that obtains positive electrode is 100 microns.Select for use 20 micron copper foils as the negative colleeting comb utmost point; Negative material is selected graphite, conductive carbon black, binding agent (for example PVDF) for use, after these negative materials are mixed in 90:5:5 ratio and a small amount of solvent (for example NMP), makes slurry through vacuum stirring and is coated on the above-mentioned Copper Foil; Make negative plate through vacuumize, roll-in, the thickness that makes negative material is 50 microns.The positive and negative electrode sheet (is placed the cavernous insulation diaphragm of 30 micron thickness (for example Celgard 2400) through cutting out in the centre after for example being of a size of 220mm * 180mm).The above positive and negative electrode sheet is separated by porous membrane, pack in the packing of the compound mantle of aluminum plastic with laminating method, inject organic bath (1 mole of LiPF6 organic carbonate fat mixed solvent EC:DEC), draw the positive and negative electrode binding post, through vacuum hotpressing make the 10Ah lithium rechargeable battery (95 * 72 * 25,400g).Fig. 3 for the 10Ah battery constant current formerly of adopting material preparation of the present invention after the charging curve under different multiplying (1C, 5C, 10C) electric current under the constant voltage mode.
Embodiment 1
Raw material such as ferric phosphate, lithium carbonate, glucose and two luxuriant magnesium are carried out chemical purification and mechanical lapping respectively reach nano-scale particle.With purify and porphyrize after ferric phosphate, lithium carbonate, glucose and two luxuriant magnesium mix premixed in the 1:0.5:1:0.01 ratio, add an amount of absolute ethyl alcohol then and in agitating ball mill, mix, obtain predecessor with spray drying then.In 200 ℃ of preheatings 1 hour, 2 hours, 700 ℃ constant temperature of 400 ℃ of dehydrations 6 hours, cool to room temperature obtains crude product to predecessor then, will obtain product LiFePO behind the crude product crushing and classification in nitrogen furnace
4/ C, the performance of material as shown in Table 1.
Table one LiFePO
4The performance of/C positive electrode
Fig. 1 is with the synthetic LiFePO of said method
4The ESEM of/C dusty material (SEM) photo, its result shows that this material is nano particle (about 200nm).Fig. 2 is the LiFePO that is synthesized
4The XRD spectra of/C dusty material, this spectrogram illustrative material has olivine structural.Fig. 3 is the 10Ah battery charging curve of (1C, 5C, 10C) under different current ratios that adopts material preparation of the present invention.Fig. 4 is the 10Ah battery discharge curve of (1C, 5C, 10C) under different current ratios that adopts material preparation of the present invention.Fig. 5 be adopt material preparation of the present invention the 10Ah battery under the different multiplying electric current (1C, 5C, 10C) charge and discharge cycle life attenuation curve figure, adopt the battery of material preparation of the present invention to discharge and recharge 400 circulations shown in the figure under the 1C electric current, capacity is only decayed less than 5%.Above experimental result identity basis LiFePO of the present invention
4/ C material has favorable charge-discharge characteristic, cycle characteristics.But this battery is full of electricity within a short period of time, and the energy heavy-current discharge is adapted at the application on the power series products, for example can be applicable to electric tool, electric automobile etc.
Raw material such as ferric phosphate, lithium carbonate, glucose and oxine magnesium are carried out chemical purification and mechanical lapping respectively reach nano-scale particle.Ferric phosphate, lithium carbonate, glucose and oxine magnesia mixture behind purification and the porphyrize are mixed premixed in the 1:0.5:1:0.01 ratio, add an amount of absolute ethyl alcohol then and in agitating ball mill, mix, obtain predecessor with spray drying then.In 200 ℃ of preheatings 2 hours, 3 hours, 750 ℃ constant temperature of 500 ℃ of dehydrations 8 hours, cool to room temperature obtains crude product to predecessor then, will obtain product LiFePO behind the crude product crushing and classification in nitrogen furnace
4/ C.
Embodiment 3
Raw material such as ferric phosphate, lithium carbonate, glucose and porphyrin magnesium are carried out chemical purification and mechanical lapping respectively reach nano-scale particle.With purify and porphyrize after ferric phosphate, lithium carbonate, glucose and porphyrin magnesium mix premixed in the 1:0.5:1:0.01 ratio, add an amount of absolute ethyl alcohol then and in agitating ball mill, mix, obtain predecessor with spray drying then.Predecessor in nitrogen furnace in 350 ℃ of preheatings 2 hours, 3 hours, 750 ℃ constant temperature of 400 ℃ of dehydrations 9 hours, cool to room temperature obtains crude product then, will obtain product LiFePO behind the crude product crushing and classification
4/ C.
Raw material such as ferric phosphate, lithium carbonate, sucrose and two luxuriant magnesium are carried out chemical purification and mechanical lapping respectively reach nano-scale particle.With purify and porphyrize after ferric phosphate, lithium carbonate, sucrose and two luxuriant magnesium mix premixed in the 1:0.5:1.2:0.01 ratio, add an amount of absolute ethyl alcohol then and in agitating ball mill, mix, obtain predecessor with spray drying then.In 300 ℃ of preheatings 2 hours, 4 hours, 680 ℃ constant temperature of 450 ℃ of dehydrations 8 hours, cool to room temperature obtains crude product to predecessor then, will obtain product LiFePO behind the crude product crushing and classification in nitrogen furnace
4/ C.
Embodiment 5
Raw material such as ferric phosphate, lithium carbonate, polyethylene glycol and two luxuriant magnesium are carried out chemical purification and mechanical lapping respectively reach nano-scale particle.With purify and porphyrize after ferric phosphate, lithium carbonate, polyethylene glycol and two luxuriant magnesium mix premixed in the 1:0.5:1.5:0.01 ratio, add an amount of absolute ethyl alcohol then and in agitating ball mill, mix, obtain predecessor with spray drying then.In 250 ℃ of preheatings 2 hours, 3 hours, 650 ℃ constant temperature of 350 ℃ of dehydrations 8 hours, cool to room temperature obtains crude product to predecessor then, will obtain product LiFePO behind the crude product crushing and classification in nitrogen furnace
4/ C.
Raw material such as ferric phosphate, lithium hydroxide, glucose and two luxuriant magnesium are carried out chemical purification and mechanical lapping respectively reach nano-scale particle.With purify and porphyrize after ferric phosphate, lithium hydroxide, glucose and two luxuriant magnesium mix premixed in the 1:1.05:1:0.01 ratio, add an amount of absolute ethyl alcohol then and in agitating ball mill, mix, obtain predecessor with spray drying then.In 400 ℃ of preheatings 1 hour, 3 hours, 800 ℃ constant temperature of 500 ℃ of dehydrations 6 hours, cool to room temperature obtains crude product to predecessor then, will obtain product LiFePO behind the crude product crushing and classification in nitrogen furnace
4/ C.
Raw material such as ferric phosphate, lithium carbonate, glucose and two luxuriant magnesium are carried out chemical purification and mechanical lapping respectively reach nano-scale particle.With purify and porphyrize after ferric phosphate, lithium carbonate, glucose and two luxuriant magnesium mix premixed in the 1:0.5:1:0.01 ratio, add proper amount of deionized water then and in agitating ball mill, mix, obtain predecessor with spray drying then.In 300 ℃ of preheatings 2 hours, 4 hours, 820 ℃ constant temperature of 450 ℃ of dehydrations 8 hours, cool to room temperature obtains crude product to predecessor then, will obtain product LiFePO behind the crude product crushing and classification in nitrogen furnace
4/ C.
It should be appreciated by those skilled in the art that abovely only to be described at the preferred embodiments of the present invention, under the situation of the scope that does not break away from spirit of the present invention and claim, can carry out variations and modifications.
Claims (7)
1. anode material for lithium-ion batteries carbon containing method preparing phosphate iron lithium, it is characterized in that, with ferric phosphate, lithium salts, carbon-source cpd and organic-magnesium metal complex auxiliary agent in molar ratio 1:0.5:1:0.01 mix, the adding proper amount of solvent is carried out ball milling and is stirred into pulpous state, and oven dry forms precursor, then inert atmosphere " 100 ℃--400 ℃ preheating 1--3 hour; 300 ℃--500 ℃ were dewatered 1--5 hour; 500 ℃--900 ℃ are incubated 4--10 hour, obtain the lithium iron phosphate positive material that carbon containing coats.
2. preparation method according to claim 1, it is characterized in that: described lithium salts is lithium hydroxide, lithium carbonate or lithium acetate.
3. preparation method according to claim 1, it is characterized in that: described carbon-source cpd is glucose, sucrose, polyethylene glycol or simple substance carbon.
4. preparation method according to claim 1, it is characterized in that: described organic-magnesium metal complex auxiliary agent is two luxuriant magnesium, oxine magnesium or porphyrin magnesium.
5. preparation method according to claim 1, it is characterized in that: described solvent is water, ethanol or acetone.
6. method according to claim 1, it is characterized in that: described inert atmosphere is nitrogen or argon gas.
7. according to claim 1 or 3 described preparation methods, it is characterized in that: the consumption of described organic-magnesium metal complex auxiliary agent is 0.5% ~ 2% of LiFePO4 molal weight.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103390750A (en) * | 2013-07-26 | 2013-11-13 | 合肥国轩高科动力能源股份公司 | Method for preparing lithium iron phosphate positive material |
| CN108732499A (en) * | 2017-04-13 | 2018-11-02 | 中国电力科学研究院 | A kind of method and system of detection cycle life of lithium ion battery |
| CN111883751A (en) * | 2020-07-09 | 2020-11-03 | 合肥国轩高科动力能源有限公司 | Lithium iron phosphate composite positive electrode material and preparation method thereof |
| CN113363483A (en) * | 2021-04-27 | 2021-09-07 | 北京当升材料科技股份有限公司 | Olivine-structure positive electrode material, preparation method and application thereof, and lithium ion battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101572305A (en) * | 2009-05-31 | 2009-11-04 | 浙江大学 | Preparation method of LiFePO*/C cathode material with high rate performance |
| CN102347476A (en) * | 2010-08-02 | 2012-02-08 | 中国科学院宁波材料技术与工程研究所 | Lithium iron phosphate/carbon composite anode material prepared by catalytic graphitization method, and preparation method thereof |
-
2013
- 2013-03-31 CN CN2013101094463A patent/CN103187569A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101572305A (en) * | 2009-05-31 | 2009-11-04 | 浙江大学 | Preparation method of LiFePO*/C cathode material with high rate performance |
| CN102347476A (en) * | 2010-08-02 | 2012-02-08 | 中国科学院宁波材料技术与工程研究所 | Lithium iron phosphate/carbon composite anode material prepared by catalytic graphitization method, and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| MATTHEW R. ROBERTS等: ""High-throughput studies of Li1−xMgx/2FePO4 and LiFe1−yMgyPO4 and the effect of carbon coating"", 《JOURNAL OF POWER SOURCES》 * |
| MATTHEW R. ROBERTS等: ""High-throughput studies of Li1−xMgx/2FePO4 and LiFe1−yMgyPO4 and the effect of carbon coating"", 《JOURNAL OF POWER SOURCES》, vol. 179, no. 2, 30 January 2008 (2008-01-30), pages 754 - 762, XP029162802, DOI: doi:10.1016/j.jpowsour.2008.01.034 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103390750A (en) * | 2013-07-26 | 2013-11-13 | 合肥国轩高科动力能源股份公司 | Method for preparing lithium iron phosphate positive material |
| CN103390750B (en) * | 2013-07-26 | 2015-08-05 | 合肥国轩高科动力能源股份公司 | A kind of preparation method of lithium iron phosphate positive material |
| CN108732499A (en) * | 2017-04-13 | 2018-11-02 | 中国电力科学研究院 | A kind of method and system of detection cycle life of lithium ion battery |
| CN108732499B (en) * | 2017-04-13 | 2021-08-27 | 中国电力科学研究院 | Method and system for detecting cycle life of lithium ion battery |
| CN111883751A (en) * | 2020-07-09 | 2020-11-03 | 合肥国轩高科动力能源有限公司 | Lithium iron phosphate composite positive electrode material and preparation method thereof |
| CN111883751B (en) * | 2020-07-09 | 2022-06-07 | 合肥国轩高科动力能源有限公司 | A kind of lithium iron phosphate composite cathode material and preparation method thereof |
| CN113363483A (en) * | 2021-04-27 | 2021-09-07 | 北京当升材料科技股份有限公司 | Olivine-structure positive electrode material, preparation method and application thereof, and lithium ion battery |
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