CN101567439A - Method for synthesizing nanometer LiFePO4 lithium ion power battery cathode material by ferric iron source - Google Patents
Method for synthesizing nanometer LiFePO4 lithium ion power battery cathode material by ferric iron source Download PDFInfo
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- CN101567439A CN101567439A CNA2009100268137A CN200910026813A CN101567439A CN 101567439 A CN101567439 A CN 101567439A CN A2009100268137 A CNA2009100268137 A CN A2009100268137A CN 200910026813 A CN200910026813 A CN 200910026813A CN 101567439 A CN101567439 A CN 101567439A
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- ferric
- ferric iron
- cathode material
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 17
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 title claims abstract description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 14
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000010406 cathode material Substances 0.000 title claims abstract description 10
- 229910052493 LiFePO4 Inorganic materials 0.000 title abstract description 3
- 230000002194 synthesizing effect Effects 0.000 title abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 238000002485 combustion reaction Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 239000000839 emulsion Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 230000002269 spontaneous effect Effects 0.000 claims abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 239000011574 phosphorus Substances 0.000 claims abstract description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 20
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 229910010710 LiFePO Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- -1 carbon organic compound Chemical class 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical group [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 239000004471 Glycine Substances 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000002671 adjuvant Substances 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical group [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- 239000005955 Ferric phosphate Substances 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 239000006183 anode active material Substances 0.000 claims description 2
- 150000001720 carbohydrates Chemical class 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 229940032958 ferric phosphate Drugs 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical group [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- 239000002243 precursor Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000007599 discharging Methods 0.000 description 4
- 229930006000 Sucrose Natural products 0.000 description 3
- 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 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
- 239000007772 electrode material Substances 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000005720 sucrose Substances 0.000 description 3
- 229910013553 LiNO Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- 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 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940116007 ferrous phosphate Drugs 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- 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 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 238000010792 warming Methods 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 a method for synthesizing a nanometer LiFePO4 lithium ion power battery cathode material by a ferric iron source. The method comprises the steps of: taking lithium source, ferric iron source and phosphorus source compounds as raw materials, performing material mixing according to the stoichiometric proportion of the materials, then adding a certain amount of combustion improver, and dissolving the mixture into water to form a solution or an emulsion with even dispersion; and carrying out spontaneous combustion on the solution or the emulsion to obtain a precursor of the cathode material, and then roasting the prepared precursor under inert atmosphere in a furnace to obtain the cathode material. The method adopts cheap ferric iron source as the raw material, has simple process and reduced cost, also has even particle size and element distribution, can prepare nanometer-grade particles, obviously reduce energy consumption, meet environmental requirement, is suitable for mass production, and greatly accelerates the industrialization process of the cathode material.
Description
Technical field
The present invention relates to a kind of by cheap ferric iron source synthesis nano LiFePO
4The method of lithium ion power battery cathode material belongs to the lithium ion battery material technical field.
Background technology
Lithium ion battery is the latest generation secondary cell that grows up the nineties in 20th century, and the research and development of new type lithium ion electrokinetic cell are current people's active demand, also is of great practical significance to solving global energy problem in short supply.Goodenough in 1997 point out to have the LiFePO of olivine-type structure first
4Can reversibly embed and the removal lithium embedded ion.Consider that it is nontoxic, environmentally friendly, abundant, high, the good cycle of specific capacity in raw material source, LiFePO
4Be considered to become the anode material for lithium-ion batteries of tool potentiality.
LiFePO
4Lithium-ion-power cell has safe discharge potential, stable cycle life during high power discharge, and characteristics such as cost is low, performance is good, environmentally friendly, this has just determined it not only can be applied to our the daily mobile communications tool that contacts, and also may become the electrical source of power of the vehicles that now just developing rapidly.
LiFePO
4Building-up process in source of iron to select be most important, it affects the commercial viability of synthesis condition and synthetic route.Though iron compound is more cheap than the compound of other transition metal, if select relatively costly divalence source of iron, this potential low-cost advantage is just all gone.
Synthetic LiFePO4 method has high temperature solid-state method, hydrothermal synthesis method, coprecipitation and microwave process for synthesizing.Since solid phase method have equipment simple, be easy to advantages such as control process parameters, investment are lower, what realize at present producing in batches also all is solid phase method.
Most patents are used divalent iron salt, from need carrying out under atmosphere protection at the very start of preparation technology, have increased production cost.For example, CN1772604 proposition lithium salts, divalent iron salt and phosphate, alloy roasting prepare oxygen place doped ferrous phosphate powder for lithium; CN1790782 proposes to prepare with raw material ball milling such as lithium salts, divalent iron salt and phosphate and roasting the method for LiFePO 4.Cause the prepared product of LiFePO 4 synthesis technique all to have the present situation that form is relatively poor, chemical property is not good enough thus, the batch of production is also less.
Summary of the invention
The objective of the invention is to provide a kind of low-cost low energy consumption synthesized high-performance LiFePO
4The new method of lithium ion power battery cathode material.
Technical scheme of the present invention: a kind of ferric iron source synthesis nano LiFePO
4The method of lithium ion power battery cathode material, its concrete steps are: (1) is raw material with lithium source, ferric iron source and P source compound, adds combustion adjuvant, obtains mixed solution or homodisperse emulsion; (2) above-mentioned solution or emulsion are placed baking oven, make its spontaneous combustion, oven temperature is 150 ℃～300 ℃; (3) generate LiFePO according to theory
4With the mass ratio of many carbon organic compound is to carry out proportioning at 5～15: 1, and the presoma that burning is good mixed through ball milling with many carbon organic compound in 0.5～5 hour; (4) again with mixture roasting in inert atmosphere, sintering temperature is 500 ℃～800 ℃, temperature retention time 5～20 hours, and the roasting heating rate is controlled at 2 ℃～10 ℃/minute, makes the nano-scale lithium ion battery anode active material.
The mol ratio of described lithium source, ferric iron source and P source compound consumption is a lithium: iron: phosphorus=0.95～1.05: 1: 1.
Described Li source compound is organic substance or the inorganic lithium salt that contains lithium; Described ferric iron source compound is for containing ferric organic substance or inorganic molysite; Described P source compound is any in ammonium phosphate, ammonium dihydrogen phosphate or the diammonium hydrogen phosphate.
Preferred inorganic lithium salt is lithium nitrate, lithium carbonate or lithium chloride; The excellent organic substance of stating that contains lithium is lithium acetate, lithium alkylide; Preferred inorganic molysite is ferric phosphate, ferric sulfate, iron chloride or ferric nitrate; Preferably containing ferric organic substance is ferric acetate or ironic citrate.
Described combustion adjuvant is at least a kind of in glycine, ammonium nitrate or the urea, and its molar fraction is LiFePO
4In 3～8 times of lithium.
Described many carbon organic compound is carbohydrate, organic acid or polyalcohols compound.
Inert atmosphere in the step (3) is helium, nitrogen or argon gas.
Beneficial effect:
The used raw material of the present invention is common raw material, equipment is simple, synthesising reacting time is compared conventional method and is significantly shortened, the low loss of having avoided Li of sintering temperature, cheap for manufacturing cost, and method for making is simple, meets environmental requirement, products therefrom crystallization degree height, particle are that nanoscale and element are evenly distributed.
Simultaneously, the LiFePO that synthesizes of the present invention
4The carbon that is evenly dispersed is coating, and has improved the electronic conductivity of material greatly, can obtain desirable charge-discharge performance.
Description of drawings
Fig. 1 is the XRD figure of the embodiment of the invention one product.
Fig. 2 sweeps fast cyclic voltammogram for the different multiplying of the embodiment of the invention one product
Fig. 3 is the first charge-discharge figure of the embodiment of the invention two products.
Fig. 4 is the multiplying power comparison diagram of the embodiment of the invention two products.
Fig. 5 sweeps fast cyclic voltammogram for the different multiplying of the embodiment of the invention two products.
Fig. 6 is the voltage platform impedance spectrogram of the embodiment of the invention two products.
Fig. 7 is 50 cycle graphs of 10C multiplying power discharging of the embodiment of the invention two products.
Embodiment
LiFePO
4Synthetic, structural stability test and be assembled into the electrochemical property test of simulated battery with pure Li.
Embodiment one:
At first, with the 0.1mol lithium nitrate, the 0.1mol ferric nitrate, 0.1mol ammonium dihydrogen phosphate (molal quantity * molecular weight can be calculated the weight that needs) is dissolved in the deionized water, adds the glycine of 60g again, and heating is stirred to the formation gel.Again gel is put into 250 ℃ baking oven, made its spontaneous combustion obtain precursor.Again precursor is mixed with sucrose ball milling 30min, with mixture 800 ℃ of roastings of speed 10 hours of 10 ℃/minute in nitrogen atmosphere, promptly obtain needed LiFePO at last
4/ C material.
With the sample that makes, conductive agent (SuperP), binding agent (PVDF) are pressed mass ratio and are evenly mixed at 85: 8: 7, are coated on the aluminium foil of 10 μ m thickness.All place vacuum drying chamber to dry 12h down for 100 ℃ electrode slice after the punching.With the pure metal lithium sheet is to electrode, and electrolyte adopts 1mol/L LiPF
6, in the glove box of argon shield, be assembled into simulated battery.On the high accuracy battery tester, investigate and charge and discharge the electrode cycle performance.
As shown in Figure 1: synthetic product LiFePO
4Equal and the LiFePO of the position of each diffraction maximum of XRD figure of/C positive electrode and relative intensity
4Standard JCPDS card (83-2092) matches, and shows that product is Pnma (a 62) structure, LiFePO
4Crystallization degree very high.
As shown in Figure 2: synthetic product LiFePO
4/ C positive electrode has invertibity when the Li ion takes off embedding, this material can serve as good electrode material.
Embodiment two:
After ball milling mixed in 2 hours, the speed with 5 ℃/minute in argon atmosphere was warming up to 700 ℃ of roastings 20 hours, promptly obtains needed LiFePO with precursor among the embodiment one and sucrose
4/ C material.The simulated battery preparation is consistent with method among the embodiment one.On the high accuracy battery tester, investigate and charge and discharge the electrode cycle performance.
As shown in Figure 3: synthetic product LiFePO
4/ C positive electrode and Li are assembled into simulated battery, and the 0.1C specific capacitance that discharges first can reach 140mAh/g, and charge and discharge platform is straight, has good embedding lithium performance.
As shown in Figure 4: synthetic product LiFePO
4/ C positive electrode and Li are assembled into simulated battery considerable capacity when big current stabilization discharges and recharges.5C stablizes reversible capability of charging and discharging and reaches 94mAh/g; 10C stablizes reversible capability of charging and discharging and reaches 82mAh/g; The 20C reversible capability of charging and discharging still has 73mAh/g.
As shown in Figure 5: synthetic product LiFePO
4The invertibity of/C positive electrode when the Li ion takes off embedding is splendid.
As shown in Figure 6: synthetic product LiFePO
4It is very little that/C positive electrode and Li are assembled into the overall impedance of simulated battery, is very potential battery material.Solution resistance among the figure under the extremely high frequency is～5 Ω, and high frequency region is made up of the semicircle of two compressions, and this is corresponding to the migration of lithium ion between anodal skin covering of the surface and lithium sheet skin covering of the surface, and the low frequency range correspondence is the diffusion of Li ion in electrode material.
As shown in Figure 7: synthetic product LiFePO
4/ C positive electrode and Li are assembled into simulated battery and show excellent cycle performance in the high current charge-discharge test processs, are to do the good electrode material of electrokinetic cell.50 circulation backs of simulated battery 10C rate charge-discharge specific capacity does not almost reduce.
Embodiment three～embodiment six:
| Raw material | Combustion adjuvant | Many carbon organic compound | Sintering temperature (℃) | Heating rate (℃/min) | |
| Embodiment | LiNO 36.895g+ Fe(CH 3COO) 2·4H 2O24.6g +NH 4H 2PO 4115.02g | Glycine 60g | Sucrose 2.2819g | 600 | 2 |
| Embodiment four | Li 2CO 37.389g +Fe(NO 3) 320.2g +(NH 4) 2HPO 413.206g | Ammonium nitrate 64g | Glucose 18g | 700 | 4 |
| Embodiment five | CH3COOLi·2H 2O10.202g +FeCl 316.2203g +(NH 4) 3PO 414.9087g | Urea 30g | Fructose 18g | 750 | 8 |
| Embodiment six | LiNO 36.895g +FePO 4·4H 2O22.288g | Glycine 45g | Citric acid 3.8428 | 800 | 6 |
Can obtain the LiFePO of correspondence with reference to the method for embodiment one by above experiment parameter
4/ C positive electrode active materials.
Claims (7)
1, a kind of ferric iron source synthesis nano LiFePO
4The method of lithium ion power battery cathode material, its concrete steps are: (1) is raw material with lithium source, ferric iron source and P source compound, adds combustion adjuvant, obtains mixed solution or homodisperse emulsion; (2) above-mentioned solution or emulsion are placed baking oven, make its spontaneous combustion, oven temperature is 150 ℃～300 ℃; (3) generate LiFePO according to theory
4With the mass ratio of many carbon organic compound is to carry out proportioning at 5～15: 1, and the presoma that burning is good mixed through ball milling with many carbon organic compound in 0.5～5 hour; (4) again with mixture roasting in inert atmosphere, sintering temperature is 500 ℃～800 ℃, temperature retention time 5～20 hours, and the roasting heating rate is controlled at 2 ℃～10 ℃/minute, makes the nano-scale lithium ion battery anode active material.
2, method according to claim 1, the mol ratio that it is characterized in that described lithium source, ferric iron source and P source compound consumption is a lithium: iron: phosphorus=0.95～1.05: 1: 1.
3, method according to claim 1 is characterized in that described Li source compound is organic substance or the inorganic lithium salt that contains lithium; Described ferric iron source compound is for containing ferric organic substance or inorganic molysite; Described P source compound is any in ammonium phosphate, ammonium dihydrogen phosphate or the diammonium hydrogen phosphate.
4, method according to claim 3 is characterized in that described inorganic lithium salt is lithium nitrate, lithium carbonate or lithium chloride; The described organic substance that contains lithium is lithium acetate, lithium alkylide; Described inorganic molysite is ferric phosphate, ferric sulfate, iron chloride or ferric nitrate; It is described that to contain ferric organic substance be ferric acetate or ironic citrate.
5, method according to claim 1 is characterized in that described combustion adjuvant is at least a kind of in glycine, ammonium nitrate or the urea, and its molar fraction is LiFePO
4In 3～8 times of lithium.
6, method according to claim 1 is characterized in that described many carbon organic compound is carbohydrate, organic acid or polyalcohols compound.
7, method according to claim 1 is characterized in that the inert atmosphere in the step (3) is helium, nitrogen or argon gas.
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| CN102024945A (en) * | 2010-11-05 | 2011-04-20 | 华南理工大学 | Method for preparing carbon-coated lithium iron phosphate anode material of lithium ion battery |
| CN102725225A (en) * | 2010-01-14 | 2012-10-10 | 杰富意化学株式会社 | Method for producing lithium iron phosphate |
| CN103035882A (en) * | 2011-10-10 | 2013-04-10 | 成都理工大学 | Method for synthesizing Li3V2(PO4)3/C by using glycine-nitrate combustion method |
| CN103956489A (en) * | 2014-04-22 | 2014-07-30 | 上海大学 | Method for preparing lithium iron phosphate electrode material by using twice carbon adding technology based on liquid phase mixing material |
| CN104157874A (en) * | 2014-08-25 | 2014-11-19 | 兰州理工大学 | Preparation method of nanometer cathode material LiFePO4 |
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| JP4491946B2 (en) * | 2000-09-29 | 2010-06-30 | ソニー株式会社 | Method for producing positive electrode active material and method for producing non-aqueous electrolyte battery |
| CN100420075C (en) * | 2005-12-22 | 2008-09-17 | 上海交通大学 | Method for preparing lithium ion battery anode material lithium ion phosphate |
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| CN102725225A (en) * | 2010-01-14 | 2012-10-10 | 杰富意化学株式会社 | Method for producing lithium iron phosphate |
| CN102725225B (en) * | 2010-01-14 | 2015-04-15 | 杰富意化学株式会社 | Method for producing lithium iron phosphate |
| CN102024945A (en) * | 2010-11-05 | 2011-04-20 | 华南理工大学 | Method for preparing carbon-coated lithium iron phosphate anode material of lithium ion battery |
| CN103035882A (en) * | 2011-10-10 | 2013-04-10 | 成都理工大学 | Method for synthesizing Li3V2(PO4)3/C by using glycine-nitrate combustion method |
| CN103956489A (en) * | 2014-04-22 | 2014-07-30 | 上海大学 | Method for preparing lithium iron phosphate electrode material by using twice carbon adding technology based on liquid phase mixing material |
| CN104157874A (en) * | 2014-08-25 | 2014-11-19 | 兰州理工大学 | Preparation method of nanometer cathode material LiFePO4 |
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