CN100480178C - Particle appearance regulatory lithium iron phosphate preparation method - Google Patents
Particle appearance regulatory lithium iron phosphate preparation method Download PDFInfo
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- CN100480178C CN100480178C CNB2007100006830A CN200710000683A CN100480178C CN 100480178 C CN100480178 C CN 100480178C CN B2007100006830 A CNB2007100006830 A CN B2007100006830A CN 200710000683 A CN200710000683 A CN 200710000683A CN 100480178 C CN100480178 C CN 100480178C
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- 239000002245 particle Substances 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims description 15
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title description 3
- 230000001105 regulatory effect Effects 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000013078 crystal Substances 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- -1 phosphate radical ion Chemical class 0.000 claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 8
- 239000010452 phosphate Substances 0.000 claims abstract description 5
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 229910010710 LiFePO Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229960004756 ethanol Drugs 0.000 claims description 6
- 239000004254 Ammonium phosphate Substances 0.000 claims description 5
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 5
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 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 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- 229920002125 Sokalan® Polymers 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
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229940095064 tartrate Drugs 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 229940116007 ferrous phosphate Drugs 0.000 claims description 2
- 229910000398 iron phosphate Inorganic materials 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
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims description 2
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical group [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 claims description 2
- 150000003016 phosphoric acids Chemical class 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 230000035484 reaction time Effects 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
- 239000000203 mixture Substances 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract 1
- 229910052493 LiFePO4 Inorganic materials 0.000 abstract 1
- 229910001447 ferric ion Inorganic materials 0.000 abstract 1
- 239000003112 inhibitor Substances 0.000 abstract 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000005119 centrifugation Methods 0.000 description 11
- 239000000654 additive Substances 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 9
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 9
- 238000007789 sealing Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 229910019931 (NH4)2Fe(SO4)2 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000186216 Corynebacterium Species 0.000 description 1
- 229910013275 LiMPO Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 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 discloses a modulating method of LiFePO4 particle shape, which comprises the following steps: blending one or more composition with lithium ion, ferric ion and phosphate radical ion; adding solvent and certain quantity of crystal growing inhibitor; proceeding solvent heat reaction under certain temperature; washing; filtering; drying; sintering to improve crystallizing property; obtaining the product with regular shape and size.
Description
Technical field
The present invention relates to the lithium ion battery field, relate in particular to a kind of iron lithium phosphate particulate preparation method.
Technical background
As a kind of novel cathode material for lithium ion battery, LiMPO
4Homologue is LiFePO particularly
4Extensive concern and further investigation (A.K.Padhi, K.S.Nanjundaswarmy, J.B.Goodenough, J.Electrochem.Soc.144 (4) (1997) 1184) have been obtained.LiFePO
4Theoretical capacity with 170mAh/g, actual capacity can surpass 160mAh/g, than commercial LiCoO
2Want high, the about 3.4V of discharge platform compares LiCoO
2Low slightly.But its raw material sources is extensive, and is with low cost, safe, environmentally friendly, is particularly suitable for various high-power electric appliances with power cells such as battery and automobiles.Shortcoming is electric conductivity smaller (～10
-9S/cm), the lithium ion diffusion is poor, and multiplying power discharging property is very poor under the normal temperature.Although by adding easy conductive thing such as carbon black, copper powder, the high temperature pyrolysis carbon coated, carry out the influence that metal ion mixing etc. has been alleviated low conductivity greatly, but still the ion diffusion performance that can not effectively regulate material, thereby can not be fit to the high-power output requirement of power cell such as electric vehicle battery fully.The method of utilization physics and chemistry, the LiFePO of regulation and control different-shape and size
4Particle is a significant problem.We once adopted the method for melting salt to synthesize spheric LiFePO
4Product, its tap density will be greatly enhanced, specific surface area descends simultaneously, safety performance is better, processing characteristics is also very good, be adapted to very much large-scale energy-storage battery and the battery of electric vehicle of energy type (CN200610011378.7), but also have certain distance from the requirement of power-type battery of electric vehicle.The battery of power-type is multiplying power discharging greatly, and this just requires the Unusually narrow particle size distribution of material, regular shape, and size is less.The most suitable employing liquid-phase system of such material such as solvent-thermal method are synthetic.Advantages such as solvent-thermal method comprises hydrothermal method, and it has, and temperature of reaction is low, time weak point, less energy consumption, product good crystallinity, pattern are controlled are used widely in inorganic Nano/micro material synthetic.Although hydrothermal method has been applied to LiFePO
4505), but rarely found synthetic (S.F.Yang, P.Y.Zavalij, M.S.Whittingham.Electrochem.Commun., 3 (9) (2001): to the report of morphology control and adjusting.
Summary of the invention
The purpose of this invention is to provide a kind of LiFePO
4The preparation method, this method can be regulated and control LiFePO
4The pattern of particulate product and size.Technical scheme of the present invention is to adopt the synthetic LiFePO of solvent thermal reaction low temperature
4During product, regulate and control the pattern and the size of the finished product by adding a certain amount of crystal growth hold back agent.This regulatable regular LiFePO
4The particulate preparation method, concrete steps are as follows:
(1) one or more the compound or the solution that will contain lithium ion, iron ion and phosphate anion mixes, and adds solvent and also adds reasonable opinion product LiFePO
4The crystal growth hold back agent of mass percent (down together) 0.5～50% is transferred in the closed reactor then;
(2) in reactor, carry out solvent thermal reaction;
(3) cooling, with the washing of synthetic head product, filtration, drying obtain LiFePO then
4Particulate product.
Wherein, the mol ratio of Li:Fe:P is preferably 0.97～3.5:0.95～1.05:0.95～1.05 in step (1); The content of Fe is with 0.01～0.5molL in whole reaction system
-1Be advisable.Step (2) solvent thermal reaction temperature is generally 120-250 ℃, and the treatment time is 1-48 hour.The solvent of washing usefulness generally is water and dehydrated alcohol in step (3).
In some cases, for improving crystallinity, step is further calcined product after (3) under nitrogen or inert atmosphere protection.Usually calcining temperature is 250-750 ℃, and the treatment time is 0.5-24 hour, and used shielding gas is nitrogen or argon gas.
Above-mentioned preparation LiFePO
4The compound that contains iron ion be selected from but be not limited to iron ion carbonate, vitriol, phosphoric acid salt, acetate, nitrate, muriate, oxide compound, sulfide, fluorochemical, be preferably vitriol, acetate and muriate; The compound that contains lithium ion is selected from but is not limited to monometallic, phosphoric acid hydrogen two lithiums, lithium hydroxide, is preferably lithium hydroxide; The compound that contains phosphate anion is selected from but is not limited to phosphoric acid, primary ammonium phosphate, Secondary ammonium phosphate, ammonium phosphate, Trilithium phosphate, monometallic, phosphoric acid hydrogen two lithiums, tertiary iron phosphate, ferrous phosphate, ferrous ammonium phosphate, is preferably phosphoric acid, primary ammonium phosphate, Secondary ammonium phosphate and ferrous ammonium phosphate.Solvent is selected from but is not limited to a kind of, two kinds or more of of water, ethanol, ethylene glycol, propyl alcohol, Virahol, propyl carbinol, glycerine, quadrol.The crystal growth hold back agent is selected from but is not limited to graphite, carbon black, sucrose, tartrate, citric acid, polyacrylic acid (PAA), Polyacrylamide, carboxymethyl cellulose and other high molecular polymers.
When product crystal was grown under High Temperature High Pressure, the crystal growth hold back agent can be adsorbed on the specific crystal face, stoped the growth of these crystal faces.The characterization of adsorption and the usage quantity of the effect of additive absorption and the polarity of crystal crystal face, symmetry of crystals, additive, and dissolvant of reaction system character has confidential relation.Additive stops function by crystal face absorption, produces various microcosmic regulating and controlling effects, promotes LiFePO
4Crystal grows into orderly structure by molecular adsorption, self-assembly, directed mode such as additional.The characterization of adsorption of additive and usage quantity have directly determined the pattern of crystal grain, and solvent system is owing to the interaction with additive also can have influence on the particulate pattern.Strong when the additive absorption property, when usage quantity is big, additive molecule just can be adsorbed on the most crystal face, cause crystal along the growth of one dimension direction, form club shaped structure, and these club shaped structures can also be compounded to form multiple structure by the mode of self-assembly; When additive absorption property and usage quantity are medium, then can be adsorbed on some specific crystal faces, form structure such as foliated lamellar, the stratiform etc. of sequential 2 D; A little less than the additive absorption property, usage quantity hour, then LiFePO
4Very little restriction is received in the growth of each crystal face of crystal, can freely grow into the square shape.
The LiFePO that the inventive method obtains
4Present various regular appearance, even size distribution, and can effectively control according to synthesis condition.Adopt this method, the product of synthesizing submicron and nanometer fast, the reaction times is short, and temperature of reaction is low, and energy waste is few, and simple to operate, and cost is lower.The product particle of preparation presents the shape of rule, and crystal property is good, the specific storage height, and good cycle, high rate performance is good.The product granularity of these regular particles is little, helps Li
+The ionic solid phase diffusion, multiplying power discharging can be widely used in power cell fields such as power tool, electric bicycle and electromobile greatly, is particularly suitable for the high-power drive pond.
Description of drawings
Fig. 1 is the X-ray diffractogram by the prepared LiFePO 4 of embodiment 1.
Fig. 2 is the field emission scanning electron microscope figure by the prepared LiFePO 4 of embodiment 1.
Fig. 3 is the field emission scanning electron microscope figure by the prepared LiFePO 4 of embodiment 2.
Fig. 4 is the field emission scanning electron microscope figure by the prepared LiFePO 4 of embodiment 3.
Fig. 5 is the field emission scanning electron microscope figure by the prepared LiFePO 4 of embodiment 4.
Fig. 6 is the field emission scanning electron microscope figure by the prepared LiFePO 4 of embodiment 6.
Fig. 7 is the field emission scanning electron microscope figure by the prepared LiFePO 4 of embodiment 10.
Fig. 8 is the first charge-discharge figure by the prepared LiFePO 4 of embodiment 1.
Fig. 9 is the cycle diagram by the prepared LiFePO 4 of embodiment 1.
Figure 10 is the multiplying power discharging figure by the prepared LiFePO 4 of embodiment 1.
Figure 11 is by the prepared discharge figure of LiFePO 4 under differing temps of embodiment 1.
Embodiment
For clearer explanation the present invention, enumerate following example, but the present invention is not had any restriction.
Embodiment 1
With 0.3mol LiOHH
2O, 0.1mol FeSO
47H
2O and 0.1mol H
3PO
4Mix, add the 1000ml deionized water dissolving, add 30% sucrose again, transfer to then in the reaction vessel of 1000ml tetrafluoroethylene, 175 ℃ of reactions 5 hours.After the cooling, with deionized water and washing with alcohol, centrifugation, drying.Last in the sealing tube furnace of nitrogen protection in 500 ℃ of pyrolysis 1 hour, obtain the LiFePO 4 particulate product.
The LiFePO 4 product of gained is an olivine structural, adopts Cu target K α radiation, and λ=0.15406nm obtains the X-ray diffraction pattern of this product, as shown in Figure 1.Can see that by field emission scanning electron microscope this LiFePO 4 particle is bar-shaped, be about 1 μ m, wide and high is 0.2-0.4 μ m, as shown in Figure 2.This product charging and discharging curve as shown in Figure 8, voltage range 2.0-4.1V, 25 ℃ of temperature, loading capacity are 145.2mAhg
-1Its cycle diagram as shown in Figure 9, the 0.1C circulation volume remains on 145mAhg
-1, the 0.5C circulation volume remains on 132mAhg
-1Figure 10 has provided its multiplying power discharging curve, at 0.2C, 0.5C, and when 1C, 2C and 4C discharge down, LiFePO
4Capacity is respectively 139.7,132.3, and 119.3,111.6 and 98.18mAhg
-1, kept 0.1C capacity 96.2%, 91.4%, 82.1%, 76.8% and 67.6%, and discharge voltage plateau keeps fine, though only reduced respectively 0.02,0.03,0.10,0.15 and 0.28V. under 8C, discharge, capacity has still kept 57.8mAhg
-1Figure 11 has provided its discharge performance under differing temps.When temperature when room temperature (24 ℃) is brought up to 37 ℃ and 50 ℃, loading capacity is also from 139.7mAhg
-1Brought up to 148.9mAhg
-1And 155.7mAhg
-1
Embodiment 2
With 0.005mol FePO
4With 0.01mol LiOHH
2O mixes, and adds 200mL water/ethanol (1:1/V:V) mixed solvent, adds 50% citric acid again, transfers to then in the reaction vessel of tetrafluoroethylene, 200 ℃ of reactions 5 hours.After the cooling,, in the sealing tube furnace of argon shield,, obtain the LiFePO 4 product in 600 ℃ of calcinings 5 hours with deionized water and washing with alcohol, centrifugation, drying.Product is uniform spindle shape, wide about 0.3-0.6 μ m, and long is 3-5 μ m (see figure 3).
Embodiment 3
With 0.12mol LiOHH
2O, 0.04mol (NH
4)
2Fe (SO
4)
212H
2O and 0.04mol (NH
4)
2HPO
4Mix, add 400ml water/ethylene glycol (5:1/V:V) mixing solutions, add 4% PAA, transfer to then in the reaction vessel of tetrafluoroethylene, 220 ℃ of reactions 2 hours.After the cooling, with deionized water and washing with alcohol, centrifugation, drying obtains the LiFePO 4 particulate product.Product is a corynebacterium, is about 0.8 μ m, and wide about 0.2 μ m is arranged into the array (see figure 4).Embodiment 4
With 0.02mol LiOHH
2O, 0.01mol LiH
2PO
4With 0.01mol FeAc
2Mix, use the 300ml dissolve with ethanol, add 40% tartrate again, transfer to then in the reaction vessel of tetrafluoroethylene, 250 ℃ of reactions 1 hour.After the cooling, with deionized water and washing with alcohol, centrifugation, drying obtains the LiFePO 4 product.Product is that size 3-5 μ m is spherical, and spheroid is formed (see figure 5) by many stubs.
With 0.05mol LiOHH
2O, 0.025mol LiH
2PO
4With 0.025mol FeAc
2Mix,, add 4% carboxymethyl cellulose again, transfer to then in the reaction vessel of tetrafluoroethylene, 220 ℃ of reactions 6 hours with the dissolving of 500ml butanols.After the cooling, with deionized water and washing with alcohol, centrifugation, drying obtains the LiFePO 4 product.Product is the solid spherical of size 5-7 μ m, and spheroid also is made up of many stubs.
Embodiment 6
With 0.06mol Li
3PO
4With 0.021mol FeCl
2Mix, add 5% polyoxyethylene glycol, mixed solvent (2:1/V:V) 500ml that adds ethanol/ethylene glycol again makees solvent, transfers to then in the reaction vessel of tetrafluoroethylene, 180 ℃ of reactions 24 hours.After the cooling, with deionized water and washing with alcohol, centrifugation, drying.Last in the sealing tube furnace of nitrogen protection in 300 ℃ of calcinings 24 hours, obtain the LiFePO 4 particulate product.Fig. 6 has provided the sem photograph of this product.Particle is a foliated lamellar, is about 1 μ m, wide about 0.2 μ m.
Embodiment 7
With 0.03mol LiOHH
2O, 0.01mol FeSO
47H
2O and 0.01mol H
3PO
4Mix, mixed solvent (3:1/V:V) dissolving with 400ml water/glycerine adds 5% sucrose again, transfers to then in the reaction vessel of 400ml tetrafluoroethylene, 120 ℃ of reactions 48 hours.After the cooling, with deionized water and washing with alcohol, centrifugation, drying.Last in the sealing tube furnace of nitrogen protection in 650 ℃ of pyrolysis 10 hours, obtain the LiFePO 4 particulate product.Product is the synusia shape, and size is 1 * 1 * 0.3 μ m
Embodiment 8
With 0.03mol LiOHH
2O, 0.03mol Fe (SO
4)
27H
2O and 0.03mol (NH
4)
3PO
4Mix, add 600mL water and make solvent, add 2% citric acid again, then 210 ℃ of reactions of airtight reaction vessel 10 hours.After the cooling, with deionized water and washing with alcohol, centrifugation, drying obtains the LiFePO 4 product.Product is a sheet, about 2 * 3 μ m of length and width, the thick 0.2 μ m that is about.
Embodiment 9
With 0.03mol LiAc2H
2O, 0.03mol Fe
3(PO
4)
22H
2O and 0.03mol (NH
4)
3PO
4Mix, add mixed solvent (4:1/V:V) 200ml of entry and quadrol, add 20% carbon black, 190 ℃ of reactions 24 hours.After the cooling, with deionized water and washing with alcohol, centrifugation, drying.Last in the sealing tube furnace of nitrogen protection in 600 ℃ of calcinings 2 hours, obtain the LiFePO 4 sandwich-like product.
With 0.1mol LiOHH
2O, 0.1mol FeSO
47H
2O and 0.1mol LiH
2PO
4Mix, add mixed solvent (3:1/V:V) 1000ml of entry/Virahol, add 20% graphite again, transfer to then in the reaction vessel of tetrafluoroethylene, 170 ℃ of reactions 24 hours.After the cooling, with deionized water and washing with alcohol, centrifugation, drying.Last in the sealing tube furnace of nitrogen protection in 400 ℃ of calcinings 5 hours, obtain the LiFePO 4 particulate product.Fig. 7 has provided the sem photograph of product.Particle is the square shape, is of a size of 0.5 * 0.5 * 0.4 μ m.
Embodiment 11
With 0.01molLiOHH
2O and 0.01mol NH
4FePO
4Mix, add the mixed solvent 500ml of entry/ethanol/quadrol (3:3:1/V:V:V), add 0.5% polyacrylamide, transfer to then in the reaction vessel of tetrafluoroethylene, 160 ℃ of reactions 18 hours.After the cooling, with deionized water and washing with alcohol, centrifugation, drying, last in the sealing tube furnace of nitrogen protection in 750 ℃ of calcinings 0.5 hour, obtain pain phosphorus ferrous silicate lithium particulate product.
Claims (8)
1, a kind of LiFePO
4The particulate preparation method comprises the steps:
(1) multiple compound or the solution that contains lithium ion, iron ion and phosphate anion is mixed, add solvent and add reasonable opinion product LiFePO
4The crystal growth hold back agent of mass percent 0.5～50%, transfer in the closed reactor then, wherein said solvent is selected from one or more in water, ethanol, ethylene glycol, propyl alcohol, Virahol, propyl carbinol, glycerine and the quadrol, and described crystal growth hold back agent is selected from a kind of in graphite, carbon black, sucrose, tartrate, citric acid, polyacrylic acid, Polyacrylamide and the carboxymethyl cellulose;
(2) in reactor, carry out solvent thermal reaction;
(3) cooling with synthetic head product washing, is filtered, drying then, obtains having the regular LiFePO of certain pattern
4Particle.
2, preparation method as claimed in claim 1 is characterized in that, the described compound that contains iron ion is selected from carbonate, vitriol, phosphoric acid salt, acetate, nitrate, muriate, fluorochemical, oxide compound and the sulfide of Fe.
3, preparation method as claimed in claim 1 is characterized in that, the described compound that contains lithium ion is selected from monometallic, phosphoric acid hydrogen two lithiums and lithium hydroxide.
4, preparation method as claimed in claim 1, it is characterized in that the described compound that contains phosphate anion is selected from: phosphoric acid, primary ammonium phosphate, Secondary ammonium phosphate, ammonium phosphate, Trilithium phosphate, monometallic, phosphoric acid hydrogen two lithiums, tertiary iron phosphate, ferrous phosphate and ferrous ammonium phosphate.
As the described preparation method of arbitrary claim in the claim 1～4, it is characterized in that 5, the mol ratio of Li:Fe:P is 0.97～3.5:0.95～1.05:0.95～1.05 in the described step (1), the content of Fe is 0.01～0.5molL in the whole reaction system
-1
6, preparation method as claimed in claim 1 is characterized in that, the temperature of described step (2) solvent thermal reaction is 120-250 ℃, and the reaction times is 1-48 hour.
7, preparation method as claimed in claim 1 is characterized in that, the solvent of washing usefulness is water and dehydrated alcohol in the step (3).
8, preparation method as claimed in claim 1 is characterized in that, after described step (3) product is further calcined under nitrogen or inert atmosphere protection, and calcining temperature is 250-750 ℃, and the time is 0.5-24 hour.
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