CN102897743B - Preparation method of lithium iron phosphate nanometer material - Google Patents

Preparation method of lithium iron phosphate nanometer material Download PDF

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CN102897743B
CN102897743B CN201210422591.2A CN201210422591A CN102897743B CN 102897743 B CN102897743 B CN 102897743B CN 201210422591 A CN201210422591 A CN 201210422591A CN 102897743 B CN102897743 B CN 102897743B
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iron phosphate
lithium iron
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CN102897743A (en
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周兴平
刘洋
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Donghua University
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Abstract

The invention provides a preparation method of a lithium iron phosphate nanometer material, which comprises the following steps of: (1) preparing a ferrous phosphate seed crystal; (2) mixing a lithium source compound, a phosphorus source compound and an organic solvent together, rapidly stirring for 30 min at room temperature to dissolve completely, adding an aqueous solution of a ferrous source compound, vacuumizing and filling with nitrogen afterwards, stirring for 10 min by magnetic force, and adding the seed crystal synthesized in the step (1) into the solution and stirring; (3) transferring the solution obtained from the step (2) to an autoclave, reacting for 12 h under the conditions of nitrogen, airtightness and 160-180 DEG C afterwards, and naturally cooling to room temperature after the reaction is finished; and (4) centrifuging and washing the product obtained from the reaction, and drying the product in vacuum to obtain the final product. With the method, different sizes of lithium iron phosphate particles can be synthesized by adding the ferrous phosphate seed crystal, the method has the advantages of simplicity and convenience for operation, short preparation time, low temperature requirement and low energy consumption, and mass production can be achieved.

Description

A kind of preparation method of lithium iron phosphate nano material
Technical field
The invention belongs to the preparation field of lithium cell anode material of lithium iron phosphate nano material, particularly a kind of preparation method of lithium iron phosphate nano material.
Background technology
Since the discovery LiFePO 4 materials such as Goodenough can reversibly embed and removal lithium embedded ion [Padhi A K, etc, Phospho-olivines as positive-electrode materials for rechargeable lithiumbatteries, Journal of theElectrochemical Society, 1997,144 (4): 1188-1194],, since can serving as anode material for lithium-ion batteries, lithium iron phosphate positive material has caused numerous concerns.With traditional lithium ion secondary positive source material of lithium cobalt acid LiCoO 2, lithium nickelate LiNiO 2, lithium manganate LiMn 2o 4compare the iron lithium phosphate (LiFePO of olivine structural 4) positive electrode material has relatively high specific storage (170mAh/g), stable operating voltage (3.5V) and cycle life preferably, and its abundant raw material, cheap, thermostability and chemical stability are good, environmentally friendly, the environmental protection energy [the Sylvain F that has development prospect, etc, Comparisonbetween different LiFePO 4synthesis routes and their influence on its physico-chemical properties, Journal of Power Sources, 2003,119-121:252-257; Andersson A S, etc, The source of first-cyclecapacity loss in LiFePO 4, Journal of Power Sources, 2001,97-98:498-502.].
Because the extremely low electronic conductivity of pure iron lithium phosphate self (is 10 under room temperature -9～10 -10and lithium ion spread coefficient (10 S/cm) -14～10 -16m 2/ s) [Yamada A, etc, Olivine-type cathodes Achievement s and problems, Journal ofPower Sources, 2003,119-121:232-238.], make it only discharge and recharge under condition and just have good chemical property in low range, these have seriously hindered LiFePO 4the development of positive electrode material.Carried out a large amount of research for these problem Chinese scholars, result shows to mainly contain 3 kinds of methods [crown, anode material for lithium-ion batteries LiFePO 4preparation and performance study thereof, Shanghai: Fudan University, 2006:14-17; Doeff M M, etc, Optimization of carbon coatings on LiFePO 4, Journal ofPower Sources, 2006,163:180-184.] and can carry out modification to pure ferric phosphate lithium material: (1) is the coated high material of one deck electronic conductivity in metallic surface, as carbon black or metal-powder, forms LiFePO 4/ C or LiFePO 4the matrix material of/M; (2) at LiFePO 4lithium position or iron position doped metal ion, improve the intrinsic conductivity of material; (3) nano-sized particles of synthetic particle diameter, pattern homogeneous, improves the velocity of diffusion of lithium ion.Wherein only have synthesis of nano particle just not lose theoretical specific capacity, and contribute to weaken polarization, reduce resistance, improve large current discharging capability, can improve electronic conductivity and the lithium ion spread coefficient of iron lithium phosphate self simultaneously, the improvement of these performances can effectively promote the chemical property of battery, so the synthetic and preparation of nano ferric phosphate lithium anode material has caused researchist's interest widely.The people such as Lee adopt traditional sol-gel method, the pure LiFePO that to have prepared particle diameter be 50～100nm 4positive electrode material, has good chemical property [Lee S B, etc, Synthesis of LiFePO 4material with improved cycling performance under harsh conditions, Electrochemistry Communications, 2008,10:1219-1221.].The people such as Zhang Junxi have prepared by a kind of coprecipitation method the pure LiFePO that grain-size is 20～70nm 4positive electrode material, [Zhang Junxi, etc., a kind of synthetic LiFePO to have equally good performance 4novel method, investigation of materials journal, 2008,22 (4): 439-443].The lithium iron phosphate nano material of synthetic different size contributes to study the relation between its performance and particle size, can promote further developing of lithium iron phosphate nano material.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of lithium iron phosphate nano material, the lithium iron phosphate nano granular size that the method can obtain by adding the method for ferrous phosphate crystal seed to control, has the advantages such as simple to operation, preparation time is short, temperature requirement is low, energy consumption is low, can produce in a large number; The controlled lithium iron phosphate nano material of size of preparation is laid a good foundation for further studying its performance and size relationship etc.
The preparation method of a kind of lithium iron phosphate nano material of the present invention, comprising:
(1) prepare ferrous phosphate crystal seed: the Li source compound that is 1:1 ~ 3:1 by mol ratio under normal temperature and pressure and P source compound mix with organic solvent, the mol ratio of P source compound and organic solvent is: 0.058:1, mixed solution being stirred under room temperature to 1h dissolves reactant wherein completely, above-mentioned mixed solution is mixed with the volume ratio of 19:1 with the ferrous iron source compound aqueous solution of 2mol/L, under nitrogen, room temperature, stir 20min afterwards, nitrogen, airtight, react 30min at 180 ℃ after water-bath be cooled to room temperature;
(2) Li source compound that is 1:1 ~ 3:1 by mol ratio and P source compound mix in there-necked flask with organic solvent, the mol ratio of P source compound and organic solvent is: 0.058:1, mixed solution is stirred to 30min under room temperature, reactant is dissolved completely, to the ferrous iron source compound aqueous solution that adds 1 ~ 2mol/L in above-mentioned mixed solution, ferrous iron source compound is 1:1 with the P source compound mol ratio adding, vacuumize subsequently logical nitrogen, at room temperature stir 10min, in solution, add the crystal seed of synthesized in step (1) and stir 5min afterwards;
(3) liquid rotating that step (2) obtains moves in autoclave, at nitrogen, airtight, 160-180 ℃, reacts 12h, after reaction finishes, naturally cools to room temperature;
(4) product reaction being obtained washs, centrifugal, vacuum-drying, obtains final product LiFePO 4.
Organic solvent in described step (1) and (2) is ethylene glycol.
Ferrous iron source compound in described step (1) is ferrous sulfate; Ferrous iron source compound in described step (2) is ferrous sulfate or iron protochloride.
Li source compound in described step (1) and (2) is lithium hydroxide.
P source compound in described step (1) and (2) is that massfraction is 85% strong phosphoric acid.
Stir speed (S.S.) in described step (1) and (2) is 300rpm.
The amount of the ferrous phosphate crystal seed adding in described step (2) accounts for 0% ~ 10% of reactant mole total amount.
Washing process in described step (4) is first to use deionized water wash 3 times, then uses absolute ethanol washing 3 times.
First the present invention utilizes solvent-thermal method to synthesize ferrous phosphate crystal seed, then in the synthetic precursor of lithium iron phosphate nano material, add crystal seed to control the nano material size of synthesized, present method is simple to operation, preparation time is short, temperature requirement is low, energy consumption is low, can produce in a large number, for the further research of lithium iron phosphate nano material is had laid a good foundation.
beneficial effect
Method utilization of the present invention adds ferrous phosphate crystal seed to control the size of the lithium iron phosphate nano material of synthesized, simple to operation, the product obtaining has good crystalline structure and good size and form and distributes, this homogeneous phase, the lithium iron phosphate nano material that degree of crystallinity is high, particle diameter is even, particle diameter is controlled, specific surface is high have good chemical property, and present method preparation time is short, temperature requirement is low, energy consumption is low, be easy to a large amount of production, thereby there is good pushing effect for further research and the application of iron lithium phosphate.
Accompanying drawing explanation
Fig. 1 is technical process of the present invention;
Fig. 2 is the X ray diffracting spectrum of the product that in embodiment 1,2,3, step (1) obtains;
Fig. 3 is the transmission electron microscope picture of the product that in embodiment 1,2,3, step (1) obtains;
Fig. 4 is the X ray diffracting spectrum of embodiment 1 gained final product;
Fig. 5 is the transmission electron microscope picture of embodiment 1 gained final product;
Fig. 6 is the transmission electron microscope picture of embodiment 2 gained final products.
Fig. 7 is the X ray diffracting spectrum of embodiment 3 gained final products;
Fig. 8 is the infrared spectrum of embodiment 3 gained final products;
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
(1) prepare ferrous phosphate crystal seed: under normal temperature and pressure by 0.2266g LiOHH 2o and 0.137ml strong phosphoric acid are mixed with 19ml ethylene glycol, mixed solution high speed (v=300rpm) under room temperature is stirred to 1h reactant is wherein dissolved completely.Above-mentioned mixed solution is added in flask, then add the FeSO of 1ml 2mol/L 47H 2the O aqueous solution, vacuum nitrogen filling gas afterwards, under room temperature, (v=300rpm) stirs 20min at a high speed.Solution in flask is transferred in autoclave, after inflated with nitrogen, seals, at 180 ℃, react 30min after water-bath be cooled to room temperature, obtain nanometer ferrousphosphate seed-solution, stay do for subsequent use;
(2) under normal temperature and pressure by 0.2266g LiOHH 2the strong phosphoric acid of O and 0.137ml 85% is mixed in there-necked flask with 19ml ethylene glycol, 85% strong phosphoric acid and the mol ratio of ethylene glycol are: 0.058:1, mixed solution is stirred under room temperature to 30min reactant is dissolved completely, to the FeSO that adds 1ml 2mol/L in above-mentioned mixed solution 47H 2the O aqueous solution, FeSO 47H 2o is 1:1 with the mol ratio of 85% the strong phosphoric acid adding, and vacuumizes subsequently logical nitrogen, at room temperature stirs 10min, adds the crystal seed 0ml of synthesized in step (1) and stirs 5min afterwards in solution;
(3) liquid rotating obtaining in step (2) is moved in autoclave, after passing into nitrogen in autoclave, seal, make in confined conditions reaction at 180 ℃, carry out 12h, after reaction finishes, naturally cool to room temperature;
(4) product reaction being obtained is with 8000rcf centrifugation, and washs respectively 3 times with deionized water and dehydrated alcohol, then the solid phase obtaining put into vacuum drying oven dry, obtains final product LiFePO 4.
The XRD figure of the ferrous phosphate crystal seed that in embodiment 1,2,3 prepared by step (1) is shown in Fig. 2, contrast JCPDF 30-0662 standard spectrogram, and prepared sample is Fe 3(PO 4) 28H 2o, the TEM figure of this crystal seed is shown in Fig. 3, as seen from the figure, obtained crystal seed major part is the nanoparticle of size in 10nm left and right.LiFePO prepared by embodiment 1 4the XRD figure of nano material is shown in Fig. 4, contrast JCPDF 81-1173 standard spectrogram, and prepared sample is the olivine structural LiFePO with rhombic system Pnma spacer 4, and peak type is sharp-pointed, and crystal formation is more perfect.The TEM figure of sample is shown in Fig. 5, can find out, and the nano particle that product is diamond platy, pattern and size distribution are comparatively even, and length distribution is at 170 ~ 200nm, and width is about 80 ~ 100nm.
Embodiment 2
(1) prepare ferrous phosphate crystal seed: under normal temperature and pressure by 0.2266g LiOHH 2o and 0.137ml strong phosphoric acid are mixed with 19ml ethylene glycol, mixed solution high speed (v=300rpm) under room temperature is stirred to 1h reactant is wherein dissolved completely.Above-mentioned mixed solution is added in flask, then add the FeSO of 1ml 2mol/L 47H 2the O aqueous solution, vacuum nitrogen filling gas afterwards, under room temperature, (v=300rpm) stirs 20min at a high speed.Solution in flask is transferred in autoclave, after inflated with nitrogen, seals, at 180 ℃, react 30min after water-bath be cooled to room temperature, get wherein solution for standby;
(2) under normal temperature and pressure by 0.2266g LiOHH 2the strong phosphoric acid of O and 0.137ml 85% is mixed in there-necked flask with 19ml ethylene glycol, 85% strong phosphoric acid and the mol ratio of ethylene glycol are: 0.058:1, mixed solution is stirred under room temperature to 30min reactant is dissolved completely, to the FeSO that adds 1ml 2mol/L in above-mentioned mixed solution 47H 2the O aqueous solution, FeSO 47H 2o is 1:1 with the mol ratio of 85% the strong phosphoric acid adding, and vacuumizes subsequently logical nitrogen, at room temperature stirs 10min, adds the crystal seed 1ml of synthesized in step (1) and stirs 5min afterwards in solution;
(3) liquid rotating obtaining in step (2) is moved in autoclave, after passing into nitrogen in autoclave, seal, make in confined conditions reaction at 180 ℃, carry out 12h, after reaction finishes, naturally cool to room temperature;
(4) product reaction being obtained is with 8000rcf centrifugation, and washs respectively 3 times with deionized water and dehydrated alcohol, then the solid phase obtaining put into vacuum drying oven dry, obtains final product LiFePO 4.
TEM figure through the nano material of crystal seed controlling dimension in embodiment 2 is shown in Fig. 6, and the nano material (TEM figure is shown in Fig. 5) obtaining when not adding crystal seed under same reaction conditions in embodiment 1 is compared, and passes through the LiFePO that crystal seed control obtains 4nano particle is mainly rectangle platy shaped particle, and its length distribution is reduced to 80-120nm by 170-200nm, and width is reduced to 30-70nm by 80-100nm, has illustrated that crystal seed is at LiFePO 4during nano material solvent thermal is synthetic, be resultful to its size control.
Embodiment 3
(1) prepare ferrous phosphate crystal seed: under normal temperature and pressure by 0.2266g LiOHH 2o and 0.137ml strong phosphoric acid are mixed with 19ml ethylene glycol, mixed solution high speed (v=300rpm) under room temperature is stirred to 1h reactant is wherein dissolved completely.Above-mentioned mixed solution is added in flask, then add the FeSO of 1ml 2mol/L 47H 2the O aqueous solution, vacuum nitrogen filling gas afterwards, under room temperature, (v=300rpm) stirs 20min at a high speed.Solution in flask is transferred in autoclave, after inflated with nitrogen, seals, at 180 ℃, react 30min after water-bath be cooled to room temperature, obtain nanometer ferrousphosphate seed-solution, stay do for subsequent use;
(2) under normal temperature and pressure by 0.2266g LiOHH 2the strong phosphoric acid of O and 0.137ml 85% is mixed in there-necked flask with 19ml ethylene glycol, 85% strong phosphoric acid and the mol ratio of ethylene glycol are: 0.058:1, mixed solution is stirred under room temperature to 30min reactant is dissolved completely, to the FeCl that adds 2ml1mol/L in above-mentioned mixed solution 24H 2the O aqueous solution, FeCl 24H 2o is 1:1 with the mol ratio of 85% the strong phosphoric acid adding, and vacuumizes subsequently logical nitrogen, at room temperature stirs 10min, adds the crystal seed 2ml of synthesized in step (1) and stirs 5min afterwards in solution;
(3) liquid rotating obtaining in step (2) is moved in autoclave, after passing into nitrogen in autoclave, seal, make in confined conditions reaction at 160 ℃, carry out 12h, after reaction finishes, naturally cool to room temperature;
(4) product reaction being obtained is with the centrifugation of 8000rcf rotating speed, and washs respectively 3 times with deionized water and dehydrated alcohol, then the solid phase obtaining put into vacuum drying oven dry, obtains final product LiFePO 4.
LiFePO prepared by embodiment 3 4the XRD figure of nano material is shown in Fig. 7, contrast JCPDF 81-1173 standard spectrogram, and prepared sample is the olivine structural LiFePO with rhombic system Pnma spacer 4, and peak type is sharp-pointed, and crystal formation is more perfect, but its peak intensity is compared with the LiFePO of embodiment 1 gained 4the peak intensity of the XRD figure of nano material is smaller, and known obtained nano material size is less compared with embodiment 1 product.The infrared spectrum of sample is shown in Fig. 8, and from curve, we can see LiFePO clearly 4contained PO in nano material 4 3-the infrared absorption peak of group.Wherein 469cm -1and 503cm -1the absorption peak at place belongs to beam mode or the phosphatic lattice vibration of PO2,552cm -1the absorption peak at place belongs to the symmetric curvature vibration modes of PO2; 585cm -1belong to the unsymmetrically flexural vibration of PO2; 639cm -1belong to the symmetrical stretching vibration pattern of PO2; 967cm -1the absorption peak at place belongs to the symmetrical stretching vibration pattern of PO; 1050 ~ 1140cm -1three absorption peaks in region all belong to the antisymmetric stretching vibration pattern of PO.In addition 1625cm, -1there is the absorption peak of water at place, and this is because sample does not have complete drying in treating processes or absorbed moisture while exposing in air.

Claims (10)

1. a preparation method for lithium iron phosphate nano material, comprising:
(1) prepare ferrous phosphate crystal seed: the Li source compound that is 1:1～3:1 by mol ratio under normal temperature and pressure and P source compound mix with organic solvent, the mol ratio of P source compound and organic solvent is: 0.058:1 stirs mixed solution 1h reactant is wherein dissolved completely under room temperature; Above-mentioned mixed solution is mixed with the volume ratio of 19:1 with the ferrous iron source compound aqueous solution of 2mol/L, under nitrogen, room temperature, stirs 20min afterwards, nitrogen, airtight, react 30min at 180 ℃ after water-bath be cooled to room temperature;
(2) Li source compound that is 1:1～3:1 by mol ratio and P source compound mix in there-necked flask with organic solvent, the mol ratio of P source compound and organic solvent is: 0.058:1, mixed solution is stirred to 30min under room temperature, reactant is dissolved completely, to the ferrous iron source compound aqueous solution that adds 1～2mol/L in above-mentioned mixed solution, ferrous iron source compound is 1:1 with the P source compound mol ratio adding, vacuumize subsequently logical nitrogen, at room temperature stir 10min, in solution, add the crystal seed of synthesized in step (1) and stir 5min afterwards;
(3) liquid rotating that step (2) obtains moves in autoclave, at nitrogen, airtight, 160-180 ℃, reacts 12h, after reaction finishes, naturally cools to room temperature;
(4) product reaction being obtained washs, centrifugal, vacuum-drying, obtains final product LiFePO 4.
2. the preparation method of a kind of lithium iron phosphate nano material according to claim 1, is characterized in that: the size of using the method control products therefrom that adds crystal seed.
3. the preparation method of a kind of lithium iron phosphate nano material according to claim 1, is characterized in that: the organic solvent in described step (1) and (2) is ethylene glycol.
4. the preparation method of a kind of lithium iron phosphate nano material according to claim 1, is characterized in that: the ferrous iron source compound in described step (1) is ferrous sulfate.
5. the preparation method of a kind of lithium iron phosphate nano material according to claim 1, is characterized in that: the Li source compound in described step (1) and (2) is lithium hydroxide.
6. the preparation method of a kind of lithium iron phosphate nano material according to claim 1, is characterized in that: the P source compound in described step (1) and (2) is that massfraction is 85% strong phosphoric acid.
7. the preparation method of a kind of lithium iron phosphate nano material according to claim 1, is characterized in that: the stir speed (S.S.) in described step (1) and (2) is 300rpm.
8. the preparation method of a kind of lithium iron phosphate nano material according to claim 1, is characterized in that: the ferrous iron source compound in described step (2) is ferrous sulfate or iron protochloride.
9. the preparation method of a kind of lithium iron phosphate nano material according to claim 1, is characterized in that: the amount of the crystal seed adding in described step (2) accounts for 0%～10% of reactant mole total amount.
10. the preparation method of a kind of lithium iron phosphate nano material according to claim 1, is characterized in that: the washing process in described step (4) is first to use deionized water wash 3 times, then uses absolute ethanol washing 3 times.
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KR101973052B1 (en) * 2012-08-10 2019-04-26 삼성에스디아이 주식회사 Method for Preparation of Lithium Metal Phosphate
CN106915734A (en) * 2017-03-03 2017-07-04 沧州凯盛达新能源科技有限公司 The preparation method of ferric lithium phosphate precursor
CN107369827B (en) * 2017-08-09 2020-02-14 湖南工业大学 Preparation method of lithium vanadium phosphate/carbon composite positive electrode material with flower-like structure
CN107706379B (en) * 2017-09-27 2020-06-12 郴州博太超细石墨股份有限公司 Preparation method of lithium vanadium phosphate/graphene/carbon composite cathode material
CN107706380B (en) * 2017-09-27 2020-06-12 郴州博太超细石墨股份有限公司 Method for preparing lithium vanadium phosphate/graphene composite cathode material on metal base
CN107799754A (en) * 2017-10-31 2018-03-13 湖南国盛石墨科技有限公司 A kind of preparation method of fluorophosphoric acid vanadium lithium/fluorinated graphene composite positive pole

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