CN101327922A - Preparation of LiFePO4 - Google Patents
Preparation of LiFePO4 Download PDFInfo
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- CN101327922A CN101327922A CNA2008100630388A CN200810063038A CN101327922A CN 101327922 A CN101327922 A CN 101327922A CN A2008100630388 A CNA2008100630388 A CN A2008100630388A CN 200810063038 A CN200810063038 A CN 200810063038A CN 101327922 A CN101327922 A CN 101327922A
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Abstract
The invention relates to a preparation method of lithium battery material, in particular to a preparation method of LiFePO4 which mainly solves the technical problems existent in the prior art such as the crystal shape of lithium iron phosphate is particle-shape, a post heat treatment is needed during the preparation process, the preparation step is complicated and the preparation cost is high. The invention comprises the following steps: charging a phosphor-containing compound solution and a surfactant into a ferric salt solution for hydrothermal synthesis, wherein the ratio of Fe atom and P atom is 1:1-1.5, the mol ratio of the compound containing Fe atom and the surfactant is 1:1-3; discharging air by introducing inert gas; charging a lithium salt solution inwhich the mol ratio of Fe atom and Li atom is 1:2.5-3.5; heating the mixture solution for hydrothermal treatment by introducing inert gas; drying the product after pumping filtration and washing to obtain flake or cylindrical LiFePO4 crystal.
Description
Technical field
The present invention relates to a kind of preparation method of anode material of lithium battery, especially relate to the preparation method of a kind of LiFePO4.
Background technology
1997, Padhi and Goodenough etc. found that olivine-type LiFePO4 has the embedding of taking off behavior, its spacer is Pnmb, Sauerstoffatom is arranged with a kind of hexagonal closs packing form of dislocation slightly, and phosphorus atom occupies tetrahedral 4c position, and iron atom and lithium atom occupy octahedral 4c and 4a position respectively.If set out with the axial visual angle of b, the FeO6 octahedron couples together with certain angle on the bc plane, and the LiO6 octahedron then is total to the limit along the b direction of principal axis, forms chain.A FeO6 octahedron is total to limits with a PO4 tetrahedron and two LiO6 octahedrons respectively, and a PO4 tetrahedron also is total to the limit with two LiO6 octahedrons simultaneously, and this has just formed the hole that can supply the free embedding of lithium ion to take off.So LiFePO
4Have good electrochemical, discharge platform is very steady, Stability Analysis of Structures in the charge and discharge process, and theoretical capacity is 170mAh/g, with traditional positive electrode material LiMn
2O
4Compare with LiCoO2, it has the following advantages: security is good, and cycle performance is more stable, and cycle life can reach more than 2000 times, and high-temperature behavior is better, and is pollution-free, and environmental friendliness is cheap.
Aspect synthetic method; generally adopt high temperature solid-state method at present; its shortcoming is that the sample thing for preparing is mutually inhomogeneous; the crystal irregular shape, crystalline size is bigger, and particle size distribution is wide; and synthesis temperature is than higher; heat-up time is long, but also the protection of rare gas element will be arranged, and operation is trouble.P.P.Prosini etc. synthesize amorphous LiFePO with the precipitator method
4, when 0.1C discharged, its capacity can reach 164mAh/g.But this method adopts higher LiI reductive agent and the synthesis technique complexity of cost.M.Higuchi etc. adopt the synthetic carbon of microwave method but its synthesis cycle is longer, and size distribution is inhomogeneous.M.StanleyWhittingham adopted soft chemical method to synthesize pure phase LiFePO with tertiary iron phosphate and Lithium Acetate as initiator first in 2002
4, his seminar has selected different reductive agents again for use in building-up process subsequently, is oxidized to Fe3+ to prevent Fe2+ in high-temperature reaction process, and has proved by electro-chemical test and to have adopted the influence of different reductive agents to product chemical property aspect.
It is to strengthen LiFePO that carbon coats
4The method that the electroconductibility aspect is very feasible, John R.Owem seminar adopts conventional solid-state method to prepare LiFePO
4Sample is introduced sucrose solution, be evaporated to colloidal sol after, the LiFePO that carbon coats is prepared in high-temperature calcination
4Test result shows, discharge under the C/3.5 multiplying power through the sample after coating, its first loading capacity can reach 158mAh/g, the colloidal sol that L.F.Nazar seminar obtains with Resorcinol and formaldehyde is introduced carbon source, obtains the LiFePO4 sample that carbon coats after high-temperature calcination, under the 5C multiplying power, discharge, capacity is near 120mAh/g, after 800 circulations, and the decay less than 8% of capacity.Akira Kuwahara etc. introduces tensio-active agent and acetylene black simultaneously in hydro-thermal synthetic process, through follow-up calcining, obtain the LiFePO that carbon coats equally
4, the lithium cell of its sample assembling is under low range, and the first charge-discharge capacity can reach 133mAh/g.
Doping is at LiFePO
4Li position or Fe position introduce other metals, change the microcosmic electronic structure of material, thereby increase its electronic conductivity, Y.M.Chiang chose different metal pair LiFePO in 2002
4Fe position and Li position mix simultaneously, prepared a series of samples, by the test shows of electrochemistry aspect, doped metal ion can make the electronic conductivity of material improve 108 times.
At present, LiFePO
4Industrialization become the problem that everybody pays close attention to, it is to cost that reduces lithium ion battery and the security that improves lithium ion battery, enlarge the lithium ion battery industry, promote lithium ion battery to maximize, superpowerization has great importance, and make lithium ion battery at medium-and-large-sized accumulation power supply, the application of aspects such as electromobile becomes possibility.Chinese patent discloses a kind of method (publication number: CN 101047242A) of preparing equal dispersion ferric phosphate lithium nano crystal by hydrothermal synthetis, it is in the presence of tensio-active agent, with soluble ferrite, lithium salts and phosphoric acid is raw material direct synthesizing nanocrystalline lithium iron phosphate under hydrothermal condition, tensio-active agent is cetyl trimethylammonium bromide or polyoxyethylene glycol, the dosage of tensio-active agent is 0.01～0.3mol/L, soluble ferrite, lithium salts and phosphoric acid are by the stoichiometric ratio batching, and its total concn is 0.1～3.0mol/L of reaction system; Also add precipitation agent in building-up process, precipitation agent is selected from ammoniacal liquor, carbon ammonium or urea, and the precipitation agent add-on is 0.1～1.0mol/L; Lithium salts is lithium hydroxide or Quilonum Retard, and ferrous salt is ferrous sulfate or ferrous ammonium sulphate; The concrete operations step of its method is: (1) is under 35～40 ℃ of temperature; tensio-active agent is added deionized water in the autoclave; be stirred to dissolving fully; the concentration of aqueous solution of tensio-active agent is 0.5～3%wt; (2) soluble ferrite and phosphoric acid are prepared burden by stoichiometric ratio; use water dissolution; make the solution that concentration is 20～30%wt; join in the reactor of above-mentioned steps (1); (3) under constantly stirring; the lithium salts that in the reactor of step (2), adds stoichiometric ratio; pH is 7.0～9.0; compactedness 70～80%; seal still and vigorous stirring then; (4) 40～100 ℃ of reactions of the temperature of control reactor are 5～10 hours; again 150～200 ℃ of hydro-thermal reactions 5～14 hours; cool to room temperature then; (5) to the reaction product of step (4) with distilled water wash 2～3 times; filtering separation, resulting solids are dried down for 40～50 ℃ under the nitrogen protection condition; 80～100 ℃ of dryings 1～2 hour; 200 ℃ of dryings 1～2 hour are warming up to 600～700 ℃ of roastings 5～10 hours with 5 ℃/minute temperature rise rate then, and obtaining equal particle diameter is the equal dispersive LiFePO of 0.2～0.5 μ m
4/ C matrix material.But the crystal shape of the iron lithium phosphate for preparing in this way is a particle shape, and preparation process must be carried out postheat treatment, and step is comparatively complicated, and preparation cost is higher.
Summary of the invention
The purpose of this invention is to provide a kind of LiFePO
4The preparation method, it mainly is that the crystal shape that solves the existing in prior technology iron lithium phosphate is a particle shape, preparation process must be carried out postheat treatment, step is comparatively complicated, the technical problem that preparation cost is more high.
Above-mentioned technical problem of the present invention is mainly solved by following technical proposals:
A kind of LiFePO of the present invention
4The preparation method, it is characterized in that:
A. adding P contained compound solution, tensio-active agent carry out hydro-thermal and synthesize in iron salt solutions; Wherein iron salt solutions is FeSO
4Or Fe
3(PO4)
2, P contained compound is H
3PO
4Or Fe
3(PO4)
2Or Li
3PO
4Or LiH
2PO
4, tensio-active agent is PEG or CTAB or amino dodecane; The mol ratio of Fe atom and P atom is 1: 1～1.5, and containing the compound of Fe atom and the mol ratio of tensio-active agent is 1: 1～3;
B. feed protection of inert gas, then exhausted air;
C. add lithium salt solution, lithium salt solution is LiOH or Li
2CO
3Or Li
3PO
4Or LiH
2PO
4, the mol ratio of Fe atom and Li atom is 1: 2.5～3.5;
D. feed protection of inert gas, pH value is controlled to be 4.0～10.0, heats up to carry out hydrothermal treatment consists;
E. suction filtration, the oven dry of washing back, getting crystal is the LiFePO of sheet or column
4Finished product.
Tensio-active agent and initiator source are introduced simultaneously, and it is more regular to prepare pattern, the particle materials with smaller.Tensio-active agent also can be used as carbon source and introduces.It is excessive that lithium salts need not in reaction process, saved material cost.Choose molysite and other metallic salts of solubility,, directly be dissolved in the high-temperature high-pressure reaction kettle and react according to different proportionings, because the salt difference of selecting for use, therefore proportioning also can regulate.
All choose soluble metal salt among the step a as initiator, can effectively guarantee the abundant contact reacts between the metal, prevent in conventional solid-state method owing to the problem of mixing the inhomogeneous aspects such as proportioning change that cause.Feeding non-oxidizing gas in the steps d is in order to get rid of the dissolved oxygen in the aqueous solution, can effectively to prevent Fe
2+Oxidation, the adding of reductive agent can further guarantee the reducing environment under High Temperature High Pressure in the preparation process.
For anode material for lithium-ion batteries, its pattern, granular size all is the determinative of its chemical property, the adding of promoting agent can reduce the internal resistance between the ion in step a, the microscopic appearance of control product.And the different surfaces promoting agent, the solvation effect difference, also different with the mating reaction between the metal ion, so also different to the regulating and controlling effect of product microscopic appearance.Therefore, present method can prepare the chemical property better products by the regulation and control to microscopic appearance.
As preferably, described step a adds carbon and coats carbon source in iron salt solutions, and carbon coats the wherein a kind of or combination that carbon source is sucrose, glucose, citric acid, urea, dodecyl bromination ammonia, carbon nanotube; Carbon carbon coated source quality accounts for 1～5% of iron salt solutions quality.
As preferably, described step a adds in iron salt solutions and mixes atom M, and M is Mg or Mn or Co, mixes atom M quality and accounts for 1～5% of iron salt solutions quality.
As preferably, described rare gas element is nitrogen, argon gas, ammonia.Rare gas element also can be other non-oxidizing gas.
As preferably, the hydrothermal treatment consists temperature in the described steps d is 120～220 ℃.
As preferably, the hydrothermal treatment consists time in the described steps d is 60～480min.
As preferably, the bake out temperature among the described step e is 400～600 ℃.
As preferably, the time of the feeding protection of inert gas among described step b and the d is 5～15min.
Therefore, the present invention has the LiFePO for preparing
4Be shaped as column or sheet, excellent property, cheap, can carry out postheat treatment as required in the synthesis technique, characteristics such as step is comparatively simple.
Description of drawings
Accompanying drawing 1 is the x-ray diffraction pattern of product, and wherein, a is embodiment 1, and b is embodiment 2, and c is embodiment 3;
Accompanying drawing 2 is stereoscan photograph figure of embodiment 1 product;
Accompanying drawing 3 is stereoscan photograph figure of embodiment 3 products;
Accompanying drawing 4 is cyclic voltammetry curves of embodiment 1 product;
Accompanying drawing 5 is the discharge curve first of product, and a is embodiment 1, and b is embodiment 2, and c is embodiment 3.
Embodiment
Below by embodiment, and in conjunction with the accompanying drawings, technical scheme of the present invention is described in further detail.
Embodiment 1: a kind of LiFePO of this example
4The preparation method, the steps include:
A. adding P contained compound solution, tensio-active agent, carbon in the 10ml iron salt solutions coats carbon source to carry out hydro-thermal synthetic; Wherein iron salt solutions is FeSO
4, P contained compound is H
3PO
4, tensio-active agent is PEG, it is sucrose that carbon coats carbon source; The mol ratio of Fe atom and P atom is 1: 1, and the mol ratio of Fe atom and tensio-active agent is 1: 1, and sucrose is 5% of FeSO4 quality.
B. feed nitrogen 10min, then exhausted air;
C. add the 10ml lithium salt solution, lithium salt solution is LiOH, and the mol ratio of Fe atom and Li atom is 1: 2.5;
D. feed nitrogen 10min, pH value is controlled to be 9.0, is warming up to 180 ℃ and carries out hydrothermal treatment consists 360min;
E. suction filtration, the oven dry of washing back, the crystal that gets pure phase is the LiFePO of sheet or column
4Finished product.
The X ray diffracting data of present embodiment product is seen a among Fig. 1.
The scanning electron microscope picture of present embodiment product is seen Fig. 2, is sheet.
The cyclic voltammogram of present embodiment product is seen Fig. 4, and along with the increase of the scanning number of turns, peak current increases gradually, illustrates that the product of this Hydrothermal Preparation has electrochemical reversibility preferably.
The discharge curve first of present embodiment product is seen a among Fig. 5, and discharge platform is all at 3.4V, and capacity is respectively 110mAhg
-1, 120mAhg
-1, 50mAhg
-1Different conditions is described except that pattern being had the tangible regulation and control, its chemical property also has corresponding change, and this example has further been illustrated the Modulatory character of this hydrothermal method to product, and the effect aspect the optimization synthesis technique.
Embodiment 2: a kind of LiFePO of this example
4The preparation method, its mol ratio of Fe atom and P atom in step a is 1: 1.2, all the other steps are identical with embodiment 1 method.
Products therefrom after x-ray diffraction technique is analyzed, also be that pure phase is pure, and degree of crystallinity LiFePO preferably
4Sample, scanning electron microscope is compared no change with embodiment 1, and electrochemical behavior shows its loading capacity rising first.
The X ray diffracting data of present embodiment product is seen the b among Fig. 1.
The discharge curve first of present embodiment is seen the b among Fig. 5.
Embodiment 3: a kind of LiFePO of this example
4The preparation method, its mol ratio of Fe atom and P atom in step a is 1: 1.4, all the other steps are identical with embodiment 1 method.
Products therefrom X-ray diffraction data and embodiment 1, embodiment 2 indistinctions, scanning electron microscope are compared with embodiment 1 obviously and are changed to column by on chip, and electrochemical data demonstration product loading capacity first has tangible decay than embodiment 1 and comparative example 1.
The scanning electron microscope picture of present embodiment is seen Fig. 3, is column, and the LiFePO that uses preparation method's preparation of the present invention is described
4Sample has Modulatory character to the product pattern under different conditions.
Present embodiment discharge curve is first seen c among Fig. 5.
Claims (8)
1. LiFePO
4The preparation method, it is characterized in that:
A. adding P contained compound solution, tensio-active agent carry out hydro-thermal and synthesize in iron salt solutions; Wherein iron salt solutions is FeSO
4Or Fe
3(PO4)
2, P contained compound is H
3PO
4Or Fe
3(PO4)
2Or Li
3PO
4Or LiH
2PO
4, tensio-active agent is PEG or CTAB or amino dodecane; The mol ratio of Fe atom and P atom is 1: 1～1.5, and containing the compound of Fe atom and the mol ratio of tensio-active agent is 1: 1～3;
B. feed protection of inert gas, then exhausted air;
C. add lithium salt solution, lithium salt solution is LiOH or Li
2CO
3Or Li
3PO
4Or LiH
2PO
4, the mol ratio of Fe atom and Li atom is 1: 2.5～3.5;
D. feed protection of inert gas, pH value is controlled to be 4.0～10.0, heats up to carry out hydrothermal treatment consists;
E. suction filtration, the oven dry of washing back, getting crystal is the LiFePO of sheet or column
4Finished product.
2. a kind of LiFePO according to claim 1
4The preparation method, it is characterized in that described step a adds carbon and coats carbon source in iron salt solutions, carbon coats the wherein a kind of or combination that carbon source is sucrose, glucose, citric acid, urea, dodecyl bromination ammonia, carbon nanotube; Carbon carbon coated source quality accounts for 1～5% of iron salt solutions quality.
3. a kind of LiFePO according to claim 1
4The preparation method, it is characterized in that described step a adds the soluble metallic salt of foreign atom M in iron salt solutions, wherein M is Mg or Mn or Co, the quality of institute's doped metal salt accounts for 1～5% of molysite quality.
4. a kind of LiFePO according to claim 1
4The preparation method, it is characterized in that described rare gas element is nitrogen, argon gas, ammonia.
5. a kind of LiFePO according to claim 1
4The preparation method, it is characterized in that the hydrothermal treatment consists temperature in the described steps d is 120～220 ℃.
6. a kind of LiFePO according to claim 1
4The preparation method, it is characterized in that the hydrothermal treatment consists time in the described steps d is 60～480min.
7. a kind of LiFePO according to claim 1
4The preparation method, it is characterized in that the bake out temperature among the described step e is 400～600 ℃.
8. a kind of LiFePO according to claim 1
4The preparation method, the time that it is characterized in that the feeding protection of inert gas among described step b and the d is 5～15min.
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|---|---|---|---|
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| CN101327922B CN101327922B (en) | 2011-07-27 |
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| WO2010094987A1 (en) * | 2009-02-20 | 2010-08-26 | Toyota Jidosha Kabushiki Kaisha | Lithium metal (ii) phosphate crystal material |
| CN101937987A (en) * | 2010-07-30 | 2011-01-05 | 合肥工业大学 | Method for preparing composite anode material LiFePO4/C for lithium ion battery |
| CN101964418A (en) * | 2010-09-28 | 2011-02-02 | 彩虹集团公司 | Method for preparing lithium iron phosphate-doped nano powder for lithium ion battery |
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| CN105036103A (en) * | 2015-08-03 | 2015-11-11 | 山东威能环保电源科技股份有限公司 | Preparation method of cuboid lithium battery anode lithium ferric manganese phosphate material |
| CN105036103B (en) * | 2015-08-03 | 2017-08-01 | 山东威能环保电源科技股份有限公司 | A kind of preparation method of cuboid-type anode material of lithium battery lithium ferric manganese phosphate |
| CN106450298A (en) * | 2016-10-13 | 2017-02-22 | 中南大学 | Preparation method of lithium iron phosphate-lithium vanadium phosphate flaky composite cathode material |
| CN106450298B (en) * | 2016-10-13 | 2020-03-31 | 中南大学 | Preparation method of flaky composite anode material lithium iron phosphate-lithium vanadium phosphate |
| CN107628594A (en) * | 2017-08-22 | 2018-01-26 | 西安建筑科技大学 | A kind of two-dimensional nano piece is assembled into the solvent hot preparation method of the flower-shaped lithium iron phosphate positive materials of 3D |
| CN107628594B (en) * | 2017-08-22 | 2020-01-07 | 西安建筑科技大学 | Solvothermal preparation method of 3D flower-shaped lithium iron phosphate cathode material assembled by two-dimensional nanosheets |
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