CN1255887C - Method of preparing positive electrode composite material of lithium ion cell contg, ferrous phosphate lithium salt-carbon - Google Patents
Method of preparing positive electrode composite material of lithium ion cell contg, ferrous phosphate lithium salt-carbon Download PDFInfo
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- CN1255887C CN1255887C CNB2004100173825A CN200410017382A CN1255887C CN 1255887 C CN1255887 C CN 1255887C CN B2004100173825 A CNB2004100173825 A CN B2004100173825A CN 200410017382 A CN200410017382 A CN 200410017382A CN 1255887 C CN1255887 C CN 1255887C
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- phosphate
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- lithium salt
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- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 20
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 17
- 229940116007 ferrous phosphate Drugs 0.000 title claims abstract description 9
- 229910000155 iron(II) phosphate Inorganic materials 0.000 title claims abstract description 9
- 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 title claims abstract description 9
- 238000000034 method Methods 0.000 title abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 polyethylene Polymers 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000004743 Polypropylene Substances 0.000 claims abstract description 9
- 229920001155 polypropylene Polymers 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000004698 Polyethylene Substances 0.000 claims abstract description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 6
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 6
- 229920000573 polyethylene Polymers 0.000 claims abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 5
- 239000010452 phosphate Substances 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical group [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 4
- 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
- 238000010438 heat treatment Methods 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 239000004254 Ammonium 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
- 229910052786 argon Inorganic materials 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims 2
- 229910000398 iron phosphate Inorganic materials 0.000 claims 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims 2
- ZTOZIUYGNMLJES-UHFFFAOYSA-K [Li+].[C+4].[Fe+2].[O-]P([O-])([O-])=O Chemical compound [Li+].[C+4].[Fe+2].[O-]P([O-])([O-])=O ZTOZIUYGNMLJES-UHFFFAOYSA-K 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 2
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000000197 pyrolysis Methods 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical class [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 229910013872 LiPF Inorganic materials 0.000 description 4
- 101150058243 Lipf gene Proteins 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 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 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910001947 lithium oxide Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000005955 Ferric phosphate Substances 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940032958 ferric phosphate Drugs 0.000 description 2
- RFGNMWINQUUNKG-UHFFFAOYSA-N iron phosphoric acid Chemical compound [Fe].OP(O)(O)=O RFGNMWINQUUNKG-UHFFFAOYSA-N 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明涉及含磷酸亚铁锂盐-碳的锂离子电池正极复合材料的制备方法，该方法采用一步固相法将一定比例的锂盐、Fe3+化合物和磷酸盐混合均匀，然后将混合物在惰性气氛中热解，热解前加入一定量的聚乙烯或聚丙烯，得到磷酸亚铁基锂盐-碳正极复合材料。该方法不使用较贵的Fe2+原材料，生产工艺简单、安全、成本低，所得正极复合材料纯度高，导电性能得到改善，电化学性能得到很大提高，比容量高，循环性能优良，具有3.4V左右的稳定放电电压平台。由该方法制备出的锂离子电池材料可广泛应用于移动电话、笔记本电脑、小型摄录像机、电动汽车等领域。The present invention relates to the preparation method of lithium ion battery cathode composite material containing ferrous phosphate lithium salt-carbon, this method adopts one-step solid-phase method to mix a certain proportion of lithium salt, Fe3 + compound and phosphate, and then mix the mixture in It is pyrolyzed in an inert atmosphere, and a certain amount of polyethylene or polypropylene is added before pyrolysis to obtain ferrous phosphate-based lithium salt-carbon cathode composite material. The method does not use expensive Fe 2+ raw materials, and the production process is simple, safe, and low in cost. The obtained positive electrode composite material has high purity, improved electrical conductivity, greatly improved electrochemical performance, high specific capacity, and excellent cycle performance. Stable discharge voltage platform around 3.4V. The lithium ion battery material prepared by the method can be widely used in the fields of mobile phones, notebook computers, small video cameras, electric vehicles and the like.
Description
Technical field
The present invention relates to a kind of preparation method of anode composite material of lithium ion battery, particularly a kind of preparation method of ferrous phosphate base lithium salts-carbon composite.
Background technology
Lithium ion battery is the novel green high-power rechargeable battery that occurs early 1990s, has become the emphasis that competitively research and develop countries in the world at present.Positive electrode is an important component part of lithium ion battery, in the lithium ion battery charge and discharge process, not only to be provided in the both positive and negative polarity lithium intercalation compound the needed lithium of back and forth embedding/take off, form the needed lithium of SEI film but also will bear the negative material surface, therefore, research and develop the key point that high performance positive electrode has become the lithium ion battery development.Present research mainly concentrates on the lithium-containing transition metal oxide aspect, and transition metal is mainly cobalt, nickel, manganese.In recent years, based on Fe
3+/ Fe
2+The material of oxidation-reduction pair causes people's very big interest, the LiFePO that particularly has olivine crystal structure
4Become the most promising alternative positive electrode of recent research, compare with other positive electrodes, it has multiple advantages such as safer, more environmental protection, more cheap and suitable height ratio capacity.
Goodenough[A.K.Padhi, K.S.Nanjundaswarmy, J.B.Goodenough, J.Electrochem.Soc., 144 (1997) 1188] research group synthesized a kind of iron content lithium salts LiFePO
4, this material has high theoretical specific capacity (170mAh/g) as anode material for lithium-ion batteries, greater than commercial LiCoO
2Actual discharge specific capacity 140mAh/g, so cause researcher's very big concern.But the conductivity of this material is very poor, can only discharge and recharge under minimum multiplying power under the room temperature, and its preparation needs Fe
2+Do source of iron, price is than Fe
3+Salt is high and need repeatedly heat treatment and grinding, and complicated process of preparation, product purity are not easy control, thereby cost is increased, and these have all limited its application in practical lithium-ion greatly.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing the anode composite material of lithium ion battery of the ferrous lithium salts-carbon of phosphoric acid,, reduce preparation cost, improve product purity, improve the material electric conductivity to simplify preparation technology;
The preparation method of the anode composite material of lithium ion battery of the ferrous lithium salts-carbon of phosphoric acid of the present invention may further comprise the steps:
1) with lithium salts, Fe
3+Compound and phosphate mix in proportion, wherein Li: Fe: the P mol ratio is (0.95-1.1): 1: 1;
2) milled mixtures fully mixes it;
3) in mixture, mix polyethylene or polypropylene; polyethylene or polyacrylic consumption make that the carbon weight percent content is 1-20% in the product; put into tube furnace then; flow velocity be the 5-40 liter/minute inert gas protection under; under 450-900 ℃ of temperature heat treatment 8-50 hour, be cooled to room temperature and get final product.
Said lithium salts can be selected from Li among the present invention
2CO
3, LiOH, lithium oxalate, lithium acetate or lithium phosphate etc., Fe
3+Compound can adopt di-iron trioxide, tri-iron tetroxide or ferric phosphate etc. to contain Fe
3+Compound, phosphate can be selected from ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate or ferric phosphate etc.Said inert gas can be nitrogen or argon gas.High molecular polymer is a hydrocarbon polymer, is advisable with polypropylene.
Usually, reach well-mixed effect, can when grinding, add an amount of alcohol for making mixture.
The present invention adopt one the step solid phase method prepared iron content lithium salts-carbon composite anode active material, the raw material wide material sources that adopted, be easy to get, cheap, the preparation method is simple; The composite material that makes does not contain Co, Ni etc. has the element of bigger pollution to environment, thereby environmentally friendly; This anode composite material purity height is just having the charging/discharging voltage platform about 3.4V stably, and electric conductivity and high rate during charging-discharging are good; This anode composite material Stability Analysis of Structures, thermal stability is good, and cycle performance is good.
The lithium ion battery material of being prepared by this method can be widely used in fields such as mobile phone, notebook computer, small-sized Video Camera, electric automobile.
Description of drawings
Fig. 1 is the crystallogram by the prepared ferrous phosphate base lithium salts-carbon composite of embodiment 1, adopts Rigaku-D/MAX-2550PC type X ray polycrystalline diffractometer (Cu target K
αRay, wavelength X=0.154056nm).
Fig. 2 is that voltage range 2.5-4.2V, electrolyte are 1mol/L LiPF by the prepared simulation lithium ion battery charging and discharging curve figure of embodiment 1
6/ EC-DMC (1: 1), charge-discharge magnification are 0.1C, and measuring temperature is 30 ℃ ± 0.5 ℃.
Fig. 3 is that voltage range 2.5-4.2V, electrolyte are 1mol/L LiPF by the prepared discharge curve of simulation lithium ion battery under different charge-discharge magnifications of embodiment 1
6/ EC-DMC (1: 1), charge-discharge magnification is respectively 0.1C, 0.2C, 0.5C, and measuring temperature is 30 ℃ ± 0.5 ℃.
Fig. 4 is that voltage range 2.5-4.2V, electrolyte are 1mol/L LiPF by the cycle performance figure of the prepared simulation lithium ion battery of embodiment 1
6/ EC-DMC (1: 1), charge-discharge magnification are 0.2C, and measuring temperature is 30 ℃ ± 0.5 ℃.
Embodiment
0.5 moles of hydrogen lithia and 0.5 mole of phosphoric acid iron are mixed, put into the nylon jar, and adding 80ml alcohol, after mixing 2 hours on the ball mill, this mixture is mixed 14 gram polypropylene put into tube furnace, under 5 liters/minute blanket of nitrogen, rise to 700 ℃ with 5 ℃/minute speed, and under this temperature constant 10 hours, be cooled to room temperature then.
Record that the carbon weight percent content is 2.5% in the gained composite material, its XRD spectra is seen Fig. 1, and the reference standard card is the intact olivine-type LiFePO of crystal formation
4, and do not observe the diffraction maximum of carbon.
Composite material with embodiment 1 gained is made electrode as follows.
Take by weighing the composite material of embodiment 1 gained respectively with 80: 10: 10 mass ratioes: carbon black: polytetrafluoroethylene, make electrode after grinding evenly, being equipped with pour lithium slice is negative pole, to be dissolved in the 1.0mol/L LiPF in ethyl carbonate+dimethyl carbonate (volume ratio 1: 1) mixed solvent
6Be electrolyte, the polypropylene microporous membrane is a barrier film, is assembled into the simulation lithium ion battery.Fig. 2 presses the 0.1C multiplying power at the first charge-discharge curve of 4.2V-2.5V during by voltage for respective battery, shows that the battery of surveying has the platform of charging/discharging voltage stably about 3.4V, and the reversible specific capacity that can calculate embodiment 1 composite material is 164mAh/g.Fig. 3 is the discharge curve of respective battery under different charge-discharge magnifications.In the discharge-rate scope of 0.1C-0.5C, the reversible capacity of positive electrode active materials is between between+the 145-164mAh/g.Fig. 4 is the cycle performance of respective battery under the 0.2C multiplying power.Wherein, specific capacity is with LiFePO
4Mass Calculation, but not LiFePO
4The quality of-carbon complex is identical therewith in following examples.
Embodiment 2:
The ammonium dihydrogen phosphate of 0.5 moles of hydrogen lithia, 0.25 mole di-iron trioxide and 0.5 mole mixed and put into the nylon jar, add 80ml alcohol, after fully mixing 2 hours on the ball mill, this mixture is mixed 20 gram polypropylene put into tube furnace, under 5 liters/minute blanket of nitrogen, rise to 700 ℃ with 5 ℃/minute speed, and under this temperature constant 20 hours, be cooled to room temperature then.The carbon weight percent content that records the gained composite material is 4.6%, and equally the method by embodiment 1 prepares electrode slice, is assembled into behind the battery with the 0.2C rate charge-discharge, and the mensuration reversible capacity is 157mAh/g.
Embodiment 3:
0.5 moles of hydrogen lithia and 0.5 mole of phosphoric acid iron are mixed, put into the nylon jar, and adding 80ml alcohol, after mixing 1 hour on the ball mill, this mixture is mixed 25 gram polyethylene put into tube furnace, under 5 liters/minute blanket of nitrogen, rise to 500 ℃ with 5 ℃/minute speed, and under this temperature constant 24 hours, be cooled to room temperature then.The carbon weight percent content that records the gained composite material is 3.1%, and prepares electrode slice by the method for embodiment 1, is assembled into behind the battery with the 0.5C rate charge-discharge, and the mensuration reversible capacity is 148mAh/g.
Embodiment 4:
With 0.25 mole of lithium carbonate, 0.25 the di-iron trioxide of mole and 0.5 mole ammonium hydrogen phosphate mix, put into the nylon jar, and add 80ml alcohol, after mixing 1 hour on the ball mill, this mixture is mixed 25 gram polypropylene put into tube furnace, under 5 liters/minute blanket of nitrogen, rise to 600 ℃ with 5 ℃/minute speed, and under this temperature constant 48 hours, be cooled to room temperature then.The carbon weight percent content that records the gained composite material is 7.6%, and prepares electrode slice by the method for embodiment 1, is assembled into behind the battery with the 1C rate charge-discharge, and the mensuration reversible capacity is 125mAh/g.
Claims (5)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100173825A CN1255887C (en) | 2004-03-25 | 2004-03-25 | Method of preparing positive electrode composite material of lithium ion cell contg, ferrous phosphate lithium salt-carbon |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100173825A CN1255887C (en) | 2004-03-25 | 2004-03-25 | Method of preparing positive electrode composite material of lithium ion cell contg, ferrous phosphate lithium salt-carbon |
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| Publication Number | Publication Date |
|---|---|
| CN1564343A CN1564343A (en) | 2005-01-12 |
| CN1255887C true CN1255887C (en) | 2006-05-10 |
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| TWI463727B (en) * | 2009-03-24 | 2014-12-01 | Battery Energy Technology Inc | A synthetic method of lithium-ion battery composite cathode material with olivine structure prepared by polymer carbon source |
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| CN100461506C (en) * | 2005-04-12 | 2009-02-11 | 广州融达电源材料有限公司 | Method for producing lithium battery positive pole material by carbon-covering method |
| CN1332462C (en) * | 2005-11-15 | 2007-08-15 | 厦门大学 | Lithium iron phosphate anode material and its preparing method |
| CN100347081C (en) * | 2005-12-29 | 2007-11-07 | 上海交通大学 | Process for preparing lithium ferrous phosphate coated with carbon |
| CN100404413C (en) * | 2006-03-22 | 2008-07-23 | 浙江大学 | Preparation method of carbon-coated lithium iron phosphate as cathode material for lithium ion battery |
| CN100413781C (en) * | 2006-03-24 | 2008-08-27 | 山东科技大学 | Synthetic method of lithium iron phosphate lithium ion battery cathode material |
| FR2898885B1 (en) * | 2006-03-27 | 2008-05-30 | Commissariat Energie Atomique | COMPOUND BASED ON TITANIUM AND CARBON DISPHOSPHATE, PROCESS FOR THE PREPARATION AND USE AS ACTIVE MATERIAL OF ELECTRODE FOR LITHIUM ACCUMULATOR |
| CN101209821B (en) * | 2006-12-31 | 2010-05-19 | 比亚迪股份有限公司 | Preparation method for lithium ion secondary battery positive pole active substance lithium iron phosphate |
| CN101314463B (en) * | 2007-05-28 | 2011-04-06 | 上海比亚迪有限公司 | Method of producing active compound lithium iron phosphate of lithium ion secondary battery anode |
| CN101572305B (en) * | 2009-05-31 | 2011-08-17 | 浙江大学 | A preparation method of LiFePO4/C cathode material with high rate performance |
| CN101969118A (en) * | 2010-10-13 | 2011-02-09 | 武汉大学 | Method for synthesizing carbon-coated lithium iron phosphate of lithium ion battery cathode material |
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| TWI463727B (en) * | 2009-03-24 | 2014-12-01 | Battery Energy Technology Inc | A synthetic method of lithium-ion battery composite cathode material with olivine structure prepared by polymer carbon source |
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