CN102897743A - Preparation method of lithium iron phosphate nanometer material - Google Patents
Preparation method of lithium iron phosphate nanometer material Download PDFInfo
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- CN102897743A CN102897743A CN2012104225912A CN201210422591A CN102897743A CN 102897743 A CN102897743 A CN 102897743A CN 2012104225912 A CN2012104225912 A CN 2012104225912A CN 201210422591 A CN201210422591 A CN 201210422591A CN 102897743 A CN102897743 A CN 102897743A
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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
Technical field
The invention belongs to lithium cell anode material of lithium iron phosphate preparations of nanomaterials field, 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], can serve as since the 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 pure extremely low electronic conductivity of iron lithium phosphate self (is 10 under the room temperature
-9～10
-10S/cm) and lithium ion spread coefficient (10
-14～10
-16m
2/ s) [Yamada A, etc, Olivine-type cathodes Achievement s and problems, Journal ofPower Sources, 2003,119-121:232-238.], it is is only discharged and recharged in low range just good chemical property under the condition, and these have seriously hindered LiFePO
4The development of positive electrode material.Carried out a large amount of research for these problem Chinese scholars, the result shows and mainly contains 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 the pure ferric phosphate lithium material: (1) coats the high material of one deck electronic conductivity in the metallic surface, such as carbon black or metal-powder, form 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 the synthesis of nano particle just not lose theoretical specific capacity, and help to weaken polarization, reduce resistance, improve large current discharging capability, can improve simultaneously electronic conductivity and the lithium ion spread coefficient of iron lithium phosphate self, 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 widely interest of researchist.The people such as Lee adopt traditional sol-gel method, and having prepared particle diameter is the pure LiFePO of 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.].It is the pure LiFePO of 20～70nm that a kind of coprecipitation method of the humans such as Zhang Junxi has been prepared grain-size
4Positive electrode material, [Zhang Junxi is 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 helps 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 provides a kind of preparation method of lithium iron phosphate nano material, the method can be controlled the lithium iron phosphate nano granular size that obtains by the method that adds the ferrous phosphate crystal seed, has the advantages such as simple to operation, that 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 the 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 comprises:
(1) preparation ferrous phosphate crystal seed: the Li source compound and the P source compound that under the normal temperature and pressure with mol ratio are 1:1 ~ 3:1 mix with organic solvent, the mol ratio of P source compound and organic solvent is: 0.058:1, mixed solution is stirred 1h under room temperature dissolve reactant wherein fully, above-mentioned mixed solution is mixed with the volume ratio of 19:1 with the ferrous iron source compound aqueous solution of 2mol/L, stir 20min afterwards under nitrogen, room temperature, water-bath is cooled to room temperature behind nitrogen, airtight, 180 ℃ of lower reaction 30min;
(2) be that Li source compound and the P source compound of 1:1 ~ 3:1 mixes in there-necked flask with organic solvent with mol ratio, the mol ratio of P source compound and organic solvent is: 0.058:1, mixed solution is stirred 30min under room temperature, reactant is dissolved fully, the ferrous iron source compound aqueous solution that adds 1 ~ 2mol/L in the above-mentioned mixed solution, the P source compound mol ratio of ferrous iron source compound and adding is 1:1, vacuumize subsequently logical nitrogen, at room temperature stir 10min, in solution, add the crystal seed that is synthesized in the step (1) and stir 5min afterwards;
(3) liquid rotating that obtains of step (2) moves in the autoclave, and at nitrogen, airtight, 160-180 ℃ lower reaction 12h, reaction naturally cools to room temperature after finishing;
(4) product that reaction is obtained washs, centrifugal, vacuum-drying namely obtains final product LiFePO
4
Organic solvent in described step (1) and (2) is ethylene glycol.
Ferrous iron source compound in the described step (1) is ferrous sulfate; Ferrous iron source compound in the 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 that adds in the described step (2) accounts for 0% ~ 10% of reactant mole total amount.
Washing process in the described step (4) is to use first deionized water wash 3 times, uses absolute ethanol washing 3 times again.
The present invention at first utilizes solvent-thermal method to synthesize the ferrous phosphate crystal seed, then in the synthetic precursor of lithium iron phosphate nano material, add crystal seed and control the nano material size of being 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 the size that the ferrous phosphate crystal seed is controlled the lithium iron phosphate nano material that is synthesized, simple to operation, resulting product 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 productions, thereby have good pushing effect for further research and the application of iron lithium phosphate.
Description of drawings
Fig. 1 is technical process of the present invention;
Fig. 2 is the X ray diffracting spectrum of the resulting product of step among the embodiment 1,2,3 (1);
Fig. 3 is the transmission electron microscope picture of the resulting product of step among the embodiment 1,2,3 (1);
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 only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
(1) preparation ferrous phosphate crystal seed: under the normal temperature and pressure with 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 1h reactant is wherein dissolved fully.Above-mentioned mixed solution is added in the flask, add again the FeSO of 1ml 2mol/L
47H
2The O aqueous solution, vacuum nitrogen filling gas afterwards, (v=300rpm) stirs 20min at a high speed under room temperature.Solution in the flask is transferred in the autoclave, seals behind the inflated with nitrogen, water-bath is cooled to room temperature behind 180 ℃ of lower reaction 30min, namely obtains the nanometer ferrousphosphate seed-solution, stay do for subsequent use;
(2) under the normal temperature and pressure with 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 30min under room temperature reactant is dissolved fully, add the FeSO of 1ml 2mol/L in the above-mentioned mixed solution
47H
2The O aqueous solution, FeSO
47H
2The mol ratio of 85% strong phosphoric acid of O and adding is 1:1, vacuumizes subsequently logical nitrogen, at room temperature stirs 10min, adds the crystal seed 0ml that is synthesized in the step (1) and stirs 5min in solution afterwards;
(3) liquid rotating that obtains in the step (2) is moved in the autoclave, seal after passing into nitrogen in the autoclave, make in confined conditions reaction carry out 12h under 180 ℃, reaction naturally cools to room temperature after finishing;
(4) product that reaction is obtained is with the 8000rcf centrifugation, and washs respectively 3 times with deionized water and dehydrated alcohol, then the solid phase that obtains put into vacuum drying oven dry, namely obtains final product LiFePO
4
The XRD figure of the ferrous phosphate crystal seed of step among the embodiment 1,2,3 (1) preparation is seen 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 sees Fig. 3, as seen from the figure, obtained crystal seed major part is the nanoparticle of size about 10nm.The LiFePO of embodiment 1 preparation
4The XRD figure of nano material is seen Fig. 4, contrast JCPDF 81-1173 standard spectrogram, and prepared sample is the olivine structural LiFePO with rhombic system Pnma spacer
4, and the peak type is sharp-pointed, and crystal formation is perfect.The TEM figure of sample sees Fig. 5, can find out, product is the nano particle of diamond platy, and pattern and size distribution are comparatively even, and length distribution is at 170 ~ 200nm, and width is about 80 ~ 100nm.
Embodiment 2
(1) preparation ferrous phosphate crystal seed: under the normal temperature and pressure with 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 1h reactant is wherein dissolved fully.Above-mentioned mixed solution is added in the flask, add again the FeSO of 1ml 2mol/L
47H
2The O aqueous solution, vacuum nitrogen filling gas afterwards, (v=300rpm) stirs 20min at a high speed under room temperature.Solution in the flask is transferred in the autoclave, seals behind the inflated with nitrogen, water-bath is cooled to room temperature behind 180 ℃ of lower reaction 30min, gets wherein solution for standby;
(2) under the normal temperature and pressure with 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 30min under room temperature reactant is dissolved fully, add the FeSO of 1ml 2mol/L in the above-mentioned mixed solution
47H
2The O aqueous solution, FeSO
47H
2The mol ratio of 85% strong phosphoric acid of O and adding is 1:1, vacuumizes subsequently logical nitrogen, at room temperature stirs 10min, adds the crystal seed 1ml that is synthesized in the step (1) and stirs 5min in solution afterwards;
(3) liquid rotating that obtains in the step (2) is moved in the autoclave, seal after passing into nitrogen in the autoclave, make in confined conditions reaction carry out 12h under 180 ℃, reaction naturally cools to room temperature after finishing;
(4) product that reaction is obtained is with the 8000rcf centrifugation, and washs respectively 3 times with deionized water and dehydrated alcohol, then the solid phase that obtains put into vacuum drying oven dry, namely obtains final product LiFePO
4
TEM figure through the nano material of crystal seed controlling dimension among the embodiment 2 sees Fig. 6, and the nano material (TEM figure sees Fig. 5) that obtains when not adding crystal seed under the same reaction conditions among the embodiment 1 is compared the LiFePO that control obtains through crystal seed
4Nano particle is mainly the rectangle platy shaped particle, and its length distribution is reduced to 80-120nm by 170-200nm, and width then is reduced to 30-70nm by 80-100nm, has illustrated that crystal seed is at LiFePO
4Resultful to its size control during the nano material solvent thermal is synthetic.
Embodiment 3
(1) preparation ferrous phosphate crystal seed: under the normal temperature and pressure with 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 1h reactant is wherein dissolved fully.Above-mentioned mixed solution is added in the flask, add again the FeSO of 1ml 2mol/L
47H
2The O aqueous solution, vacuum nitrogen filling gas afterwards, (v=300rpm) stirs 20min at a high speed under room temperature.Solution in the flask is transferred in the autoclave, seals behind the inflated with nitrogen, water-bath is cooled to room temperature behind 180 ℃ of lower reaction 30min, namely obtains the nanometer ferrousphosphate seed-solution, stay do for subsequent use;
(2) under the normal temperature and pressure with 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 30min under room temperature reactant is dissolved fully, add the FeCl of 2ml1mol/L in the above-mentioned mixed solution
24H
2The O aqueous solution, FeCl
24H
2The mol ratio of 85% strong phosphoric acid of O and adding is 1:1, vacuumizes subsequently logical nitrogen, at room temperature stirs 10min, adds the crystal seed 2ml that is synthesized in the step (1) and stirs 5min in solution afterwards;
(3) liquid rotating that obtains in the step (2) is moved in the autoclave, seal after passing into nitrogen in the autoclave, make in confined conditions reaction carry out 12h under 160 ℃, reaction naturally cools to room temperature after finishing;
(4) product that reaction is obtained is with the centrifugation of 8000rcf rotating speed, and washs respectively 3 times with deionized water and dehydrated alcohol, then the solid phase that obtains put into vacuum drying oven dry, namely obtains final product LiFePO
4
The LiFePO of embodiment 3 preparations
4The XRD figure of nano material is seen Fig. 7, contrast JCPDF 81-1173 standard spectrogram, and prepared sample is the olivine structural LiFePO with rhombic system Pnma spacer
4, and the peak type is sharp-pointed, and crystal formation is perfect, but its peak intensity is than the LiFePO of embodiment 1 gained
4The peak intensity of the XRD figure of nano material is smaller, and resulting nano material size is less than embodiment 1 product as can be known.The infrared spectrum of sample is seen Fig. 8, and we can see LiFePO clearly from curve
4Contained PO in the nano material
4 3-The infrared absorption peak of group.469cm wherein
-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 zone all belong to the antisymmetric stretching vibration pattern of PO.In addition, 1625cm
-1There is the absorption peak of water at the place, and this is because sample does not have complete drying in treating processes or absorbed moisture when exposing in air.
Claims (11)
1. the preparation method of a lithium iron phosphate nano material comprises:
(1) preparation ferrous phosphate crystal seed: the Li source compound and the P source compound that under the normal temperature and pressure with mol ratio are 1:1 ~ 3:1 mix with organic solvent, the mol ratio of P source compound and organic solvent is: 0.058:1, stir 1h with mixed solution reactant wherein dissolved fully 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, stir 20min afterwards under nitrogen, room temperature, water-bath is cooled to room temperature behind nitrogen, airtight, 180 ℃ of lower reaction 30min;
(2) be that Li source compound and the P source compound of 1:1 ~ 3:1 mixes in there-necked flask with organic solvent with mol ratio, the mol ratio of P source compound and organic solvent is: 0.058:1, mixed solution is stirred 30min under room temperature, reactant is dissolved fully, the ferrous iron source compound aqueous solution that adds 1 ~ 2mol/L in the above-mentioned mixed solution, the P source compound mol ratio of ferrous iron source compound and adding is 1:1, vacuumize subsequently logical nitrogen, at room temperature stir 10min, in solution, add the crystal seed that is synthesized in the step (1) and stir 5min afterwards;
(3) liquid rotating that obtains of step (2) moves in the autoclave, and at nitrogen, airtight, 160-180 ℃ lower reaction 12h, reaction naturally cools to room temperature after finishing;
(4) product that reaction is obtained washs, centrifugal, vacuum-drying namely 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: with the size of 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, it is characterized in that: the ferrous phosphate crystal seed that described step (1) is produced is that the crystal seed that adds in the described step (2) is the heterogeneous crystal seed different from the final product iron lithium phosphate, is called the xenogenesis crystalline substance.
4. the preparation method of a kind of lithium iron phosphate nano material according to claim 1, it is characterized in that: the organic solvent in described step (1) and (2) is ethylene glycol.
5. the preparation method of a kind of lithium iron phosphate nano material according to claim 1, it is characterized in that: the ferrous iron source compound in the described step (1) is ferrous sulfate.
6. the preparation method of a kind of lithium iron phosphate nano material according to claim 1, it is characterized in that: the Li source compound in described step (1) and (2) is lithium hydroxide.
7. the preparation method of a kind of lithium iron phosphate nano material according to claim 1, it is characterized in that: the P source compound in described step (1) and (2) is that massfraction is 85% strong phosphoric acid.
8. the preparation method of a kind of lithium iron phosphate nano material according to claim 1, it is characterized in that: the stir speed (S.S.) in described step (1) and (2) is 300rpm.
9. the preparation method of a kind of lithium iron phosphate nano material according to claim 1, it is characterized in that: the ferrous iron source compound in the described step (2) is ferrous sulfate or iron protochloride.
10. the preparation method of a kind of lithium iron phosphate nano material according to claim 1, it is characterized in that: the amount of the crystal seed that adds in the described step (2) accounts for 0% ~ 10% of reactant mole total amount.
11. the preparation method of a kind of lithium iron phosphate nano material according to claim 1 is characterized in that: the washing process in the described step (4) is to use first deionized water wash 3 times, uses absolute ethanol washing 3 times again.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104520236A (en) * | 2012-08-10 | 2015-04-15 | 三星精密化学株式会社 | Method for preparing lithium metal phosphor oxide |
| 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 |
| CN107369827A (en) * | 2017-08-09 | 2017-11-21 | 湖南工业大学 | A kind of preparation method of phosphoric acid vanadium lithium/carbon composite anode material of flower-like structure |
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| CN104520236A (en) * | 2012-08-10 | 2015-04-15 | 三星精密化学株式会社 | Method for preparing lithium metal phosphor oxide |
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| 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 |
| CN107369827A (en) * | 2017-08-09 | 2017-11-21 | 湖南工业大学 | A kind of preparation method of phosphoric acid vanadium lithium/carbon composite anode material of flower-like structure |
| 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 |
| CN107706379A (en) * | 2017-09-27 | 2018-02-16 | 郴州博太超细石墨股份有限公司 | A kind of preparation method of phosphoric acid vanadium lithium/graphene/carbon composite positive pole |
| CN107706380A (en) * | 2017-09-27 | 2018-02-16 | 郴州博太超细石墨股份有限公司 | A kind of method that phosphoric acid vanadium lithium/grapheme composite positive electrode material is prepared in Metal Substrate |
| 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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