CN102838102B - Preparation method of lithium iron phosphate monocrystalline nanorods - Google Patents
Preparation method of lithium iron phosphate monocrystalline nanorods Download PDFInfo
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- CN102838102B CN102838102B CN201210331755.0A CN201210331755A CN102838102B CN 102838102 B CN102838102 B CN 102838102B CN 201210331755 A CN201210331755 A CN 201210331755A CN 102838102 B CN102838102 B CN 102838102B
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- phosphoric acid
- ascorbic acid
- ethylene glycol
- ferrous sulfate
- lifepo4
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- 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
Abstract
The invention relates to a preparation method of lithium iron phosphate monocrystalline nanorods. The method is characterized in that: mixed solvent required by solvothermal reaction is constituted by ethylene glycol and water at volume ratio of 3:1-1:3; and polyethylene glycol is introduced to influence crystal nucleus formation and crystal growth, and realize solvothermal synthesis of lithium iron phosphate monocrystalline nanorods. The preparation method includes dissolving antioxidant ascorbic acid in the mixed solvent of ethylene glycol and water; sequentially dissolving phosphoric acid and ferrous sulfate hexahydrate in the mixed solvent; dropwise adding lithium hydroxide dissolved in ethylene glycol and water into the above solution containing phosphoric acid, ferrous sulfate and ascorbic acid; mixing with appropriate amount of polyethylene glycol; sealing in a reaction kettle system; and performing solvothermal reaction under high temperature 160-240 DEG C and high pressure, to obtain lithium iron phosphate monocrystalline nanorods. The product has stable quality, high purity and good particle dispersivity, which facilitates lithium ion diffusion and improves electrochemical performance of lithium ion battery. The preparation method has the advantages of simple preparation process, easy control, no pollution, low cost, and easy mass production.
Description
Technical field
The present invention relates to a kind of preparation method of LiFePO4 monocrystal nano rod, belong to Inorganic Non-metallic Materials, energy-storage battery Material Field.
Background technology
Lithium ion battery is as a kind of high performance green power supply of filling, in various portable type electronic products and communication tool, be used widely in recent years, and be progressively developed as the electrical source of power of electric automobile, thereby promote it to the future development of safety, environmental protection, low cost and high-energy-density.Wherein, particularly the development of positive electrode is very crucial for new electrode materials.The anode material for lithium-ion batteries of broad research concentrates on the transition metal oxide of lithium as the LiMO of layer structure at present
2the LiMn of (M=Co, Ni, Mn) and spinel structure
2o
4.But they respectively have shortcoming, LICoO as positive electrode
2cost is high, natural resources shortage, and toxicity is large; Lithium nickelate (LiNiO
2) preparation difficulty, poor heat stability; LIMn
2o
4capacity is lower, and cyclical stability especially high-temperature behavior is poor.In order to solve the defect of above material, battery circle has been done large quantity research, above positive electrode is being carried out to various modifications with when improving its performance, and the exploitation of novel anode material is also the emphasis of paying close attention to always.Research is found, LiFePO 4 material operating voltage moderate (3.4V), platform are good, the high 170mAh/g of theoretical capacity, cycle performance is superior, cost is very low, its high-energy-density and high safety performance make it in power lithium-ion battery, have outstanding application prospect, and weak point is that its poorly conductive and lithium ion diffusion velocity is slow, and the microscopic appearance of this and lithium iron phosphate positive material has great associated.At present, academia, is difficult to verify by experiment still in proposing the stage of hypothesis to the concrete mechanism of LiFePO4 removal lithium embedded and process.The lithium iron phosphate positive material of industrialization is at present substantially all that high temperature solid-state method is synthetic, microscopic appearance is spherical, pass through literature query, in laboratory, the LiFePO4 microscopic appearance of preparation is still difficult to regulation and control, concentrate on the bulk of diamond pattern and spherical, (nature. 2009 for the positive electrode of preparing such as people's high temperature solid-state methods such as Kang Byoungwoo, 458, 190.), or LiFePO4 (the ELECTROCHEMISTRY COMMUNICATIONS. 2001 that the people such as Yang SF prepare by hydro thermal method, 3, 505.) be all spherical, below be neither beneficial to the energy density that promotes lithium ion battery, and make to be difficult to realize by observation procedure research positive electrode crystal structure dynamic changes such as original position TEM.
Summary of the invention
The deficiency existing for prior art, the object of the present invention is to provide a kind of technique simple, is easy to the preparation method of the LiFePO4 monocrystal nano rod of control.
The preparation method of LiFePO4 monocrystal nano rod of the present invention, employing be solvent heat synthetic method, comprise the following steps:
1), by ethylene glycol and deionized water 3:1 ~ 1:3 mixing by volume, obtain the mixed solvent of ethylene glycol and water;
2) ascorbic acid is dissolved in to step 1) ethylene glycol and the mixed solvent of water in, be stirred to abundant dissolving, obtain ascorbic acid solution;
3) by the mol ratio of P and Fe, be 1:1, metering takes phosphoric acid and six directions aqueous ferrous sulfate, and phosphoric acid and six directions aqueous ferrous sulfate are dissolved in to step 2) in prepared ascorbic acid solution, ascorbic acid quality and prepared target LiFePO4 mass percent are 10 ~ 30%, the concentration of phosphoric acid and six directions aqueous ferrous sulfate is 0.05 ~ 0.5mol/L, fully stir, obtain the solution that contains phosphoric acid, ferrous sulfate and ascorbic acid;
4) according to step 3) amount of the phosphoric acid that takes, by the mol ratio of Li and P, be 3:1, metering takes lithium hydroxide, and lithium hydroxide is dissolved in to step 1) ethylene glycol and the mixed solvent of water in, the concentration that makes lithium hydroxide is 0.15 ~ 1.5mol/L, fully stirs, and obtains lithium hydroxide solution;
5) under the state stirring, by step 4) lithium hydroxide solution be added drop-wise to step 3) in the prepared solution that contains phosphoric acid, ferrous sulfate and ascorbic acid, form the suspension that contains precipitation;
6) under stirring, polyethylene glycol is added to step 5) suspension in, polyethylene glycol quality and prepared target LiFePO4 mass percent are 10 ~ 100%; Then transfer in autoclave, the mixed solvent prepared by step 1) regulates, and makes its volume account for 2/3 ~ 4/5 of reactor inner bag volume, continues to stir at least 5 minutes, airtight, at 160 ~ 240 ℃, be incubated after 4 ~ 36 hours, be down to room temperature, take out product, filter, with deionized water, absolute ethyl alcohol or acetone, clean successively, at 40 ℃ ~ 100 ℃ temperature, dry, obtain LiFePO4 monocrystal nano rod.
In the present invention, the purity of said phosphoric acid, six directions ferrous sulfate, lithium hydroxide, ascorbic acid, polyethylene glycol, ethylene glycol, absolute ethyl alcohol and acetone is all not less than chemical pure.
The radial dimension of the LiFePO4 monocrystal nano rod that the inventive method is prepared is 50-200 nanometer, and length is 0.5-10 micron.
It is reaction dissolvent that the mixed solvent of ethylene glycol and water is take in the present invention, by the volume ratio of ethylene glycol and water in design mixed solvent, in conjunction with the Surface Modification Effect of polyethylene glycol, coring and growth course in regulation and control heat treatment process, the solvent heat of realizing LiFePO4 monocrystal nano rod is synthetic.Adopt absolute ethyl alcohol and acetone dehydration, and not higher than 100
othe oven dry of C is in order to obtain the LiFePO4 monocrystal nano rod of favorable dispersibility.
The constant product quality that the inventive method makes, purity is high, and particle dispersion is good, is conducive to lithium ion diffusion, improves the large current density performance of lithium ion battery.Preparation process of the present invention is simple, is easy to control, and pollution-free, cost is low, is easy to large-scale production.
Accompanying drawing explanation
X-ray diffraction (XRD) collection of illustrative plates of the LiFePO4 monocrystal nano rod that Fig. 1 the present invention is synthetic;
Scanning electron microscopy (SEM) photo of the LiFePO4 monocrystal nano rod that Fig. 2 the present invention is synthetic;
High resolution transmission electron microscopy (HRTEM) photo of Fig. 3 LiFePO4 monocrystal nano rod of the present invention;
The charging and discharging curve of the lithium ion battery that the synthetic LiFePO4 monocrystal nano rod of Fig. 4 the present invention is assembled as positive electrode after covering carbon heat treatment.
Embodiment
Below in conjunction with embodiment, further illustrate the present invention.
Example 1
Preparation method comprises the following steps:
1) measure ethylene glycol 20ml and deionized water 20ml, by the mixed solvent of the two mixed preparing ethylene glycol and water.
2) metering takes ascorbic acid 0.1g and is dissolved in step 1) in prepared ethylene glycol and the mixed solvent of water, stir and it was fully dissolved in 30 minutes.
3) by the mol ratio of P and Fe, be 1:1, metering takes phosphoric acid 0.4612g, six directions aqueous ferrous sulfate 1.1121g is dissolved in step 2) in prepared ascorbic acid solution, stir 10 minutes, obtain the solution that contains phosphoric acid, ferrous sulfate and ascorbic acid, ascorbic acid accounts for 15.8% of target LiFePO4 quality, phosphoric acid concentration is 0.1mol/L, and six directions aqueous ferrous sulfate concentration is 0.1mol/L.
4) according to step 3) amount of the phosphoric acid that takes, by the mol ratio of Li and P, be 3:1, metering takes lithium hydroxide 0.5035g, be dissolved in step 1) in prepared ethylene glycol and the mixed solvent of water, stir 30 minutes, join to obtain clarification lithium hydroxide solution, the concentration of lithium hydroxide is 0.3mol/L.
5) under the state stirring, by step 4) prepared lithium hydroxide solution is added drop-wise to step 3) in the prepared solution that contains phosphoric acid, ferrous sulfate and ascorbic acid, form the suspension that contains precipitation.After having mixed, stir 30 minutes.
6) under stirring, 0.0631g polyethylene glycol is added to step 5) in prepared suspension, then transfer in autoclave, the mixed solvent prepared by step 1) regulates, and makes its volume account for 4/5 of reactor inner bag volume, continues to stir 10 minutes.Airtight, at 200 ℃, be incubated 6 hours and heat-treat.Then, be down to room temperature, take out product, filter, with deionized water, acetone, clean successively, at 80 ℃ of temperature, dry, obtain LiFePO4 monocrystal nano rod.
Fig. 1 is shown in by its X-ray diffraction (XRD) collection of illustrative plates, and as seen from the figure, crystalline phase is shown as pure phase, free from admixture, and crystal structure is complete.
Microscopic appearance is single, and physical dimension is comparatively concentrated, is monocrystal nano rod, and radial dimension is 50-100 nanometer, and length is 0.5-5 micron (seeing Fig. 2, Fig. 3).
LiFePO4 monocrystal nano rod is made the chemical property of lithium ion battery:
The LiFePO4 monocrystal nano rod that this example is made is poured in the 20ml deionized water of the ascorbic acid that is dissolved with 0.15g mix and blend into 30 minutes; 80 ℃ are dryly taken out and carry out annealing in process after 12 hours in baking oven; at 600 ℃, nitrogen protective sintering is 6 hours, obtains lithium iron phosphate positive material powder after grinding.By this lithium iron phosphate positive material powder, acetylene black and Kynoar in mass ratio (75:15:10) prepare and fully stir it is uniformly dispersed, the 1-METHYLPYRROLIDONE of take is applied on aluminium foil after solvent furnishing pulpous state, and in vacuum drying chamber, at 100 ℃, after dry 12h, cut-parts become positive plate.Using metal lithium sheet as negative pole, and cel-gard 2000 microporous barriers are as diaphragm, and the LiPF of 1 mol/L (99.9%, solvent is ethylene carbonate and the dimethyl carbonate mixed liquor of volume ratio 1:1) is electrolyte, at water content, is less than 0.1 * 10
-6glove box in successively positive plate, barrier film, negative plate, nickel foam and negative cover are put into anode cover from bottom to top and are compressed and to be made into button cell, and it is carried out to charge-discharge test.The LiFePO4 monocrystal nano rod synthesizing of usining covers the lithium ion battery of assembling as positive electrode after carbon heat treatment, good cycling stability, life-span is long, high rate performance is very excellent, electric current with 170mA/g (current density=1C) carries out charge-discharge test, obtains the excellent capacity of 141 mAh/g.The synthetic LiFePO4 monocrystal nano rod of Fig. 4 the present invention covers the charging and discharging curve of the lithium ion battery of assembling as positive electrode after carbon heat treatment.
Example 2
1) measure ethylene glycol 40ml and deionized water 40ml, by the mixed solvent of the two mixed preparing ethylene glycol and water.
2) metering takes ascorbic acid 0.063g and is dissolved in step 1) in prepared ethylene glycol and the mixed solvent of water, stir and it was fully dissolved in 30 minutes.
3) by the mol ratio of P and Fe, be 1:1, metering takes phosphoric acid 0.4612g, six directions aqueous ferrous sulfate 1.1121g is dissolved in step 2) in prepared ascorbic acid solution, stir 10 minutes, obtain the solution that contains phosphoric acid, ferrous sulfate and ascorbic acid, ascorbic acid accounts for 10% of target LiFePO4 quality, phosphoric acid concentration is 0.05mol/L, and six directions aqueous ferrous sulfate concentration is 0.05mol/L.
4) according to step 3) amount of the phosphoric acid that takes, by the mol ratio of Li and P, be 3:1, metering takes lithium hydroxide 0.5035g, be dissolved in step 1) in prepared ethylene glycol and the mixed solvent of water, stir 30 minutes, join to obtain clarification lithium hydroxide solution, the concentration of lithium hydroxide is 0.15mol/L.
5) under the state stirring, by step 4) prepared lithium hydroxide solution is added drop-wise to step 3) in the prepared solution that contains phosphoric acid, ferrous sulfate and ascorbic acid, form the suspension that contains precipitation.After having mixed, stir 30 minutes.
6) under stirring, 0.316g polyethylene glycol is added to step 5) in prepared suspension, then transfer in autoclave, the mixed solvent prepared by step 1) regulates, and makes its volume account for 4/5 of reactor inner bag volume, continues to stir 10 minutes.Airtight, at 240 ℃, be incubated 6 hours and heat-treat.Then, be down to room temperature, take out product, filter, with deionized water, acetone, clean successively, at 80 ℃ of temperature, dry, obtain LiFePO4 monocrystal nano rod.Radial dimension is 100-200 nanometer, and length is 1-5 micron
Example 3
1) measure ethylene glycol 20ml and deionized water 20ml, by the mixed solvent of the two mixed preparing ethylene glycol and water.
2) metering takes ascorbic acid 0.189g and is dissolved in step 1) in prepared ethylene glycol and the mixed solvent of water, stir and it was fully dissolved in 30 minutes.
3) by the mol ratio of P and Fe, be 1:1, metering takes phosphoric acid 0.4612g, six directions aqueous ferrous sulfate 1.1121g is dissolved in step 2) in prepared ascorbic acid solution, stir 10 minutes, obtain the solution that contains phosphoric acid, ferrous sulfate and ascorbic acid, ascorbic acid accounts for 30% of target LiFePO4 quality, phosphoric acid concentration is 0.1mol/L, and six directions aqueous ferrous sulfate concentration is 0.1mol/L.
4) according to step 3) amount of the phosphoric acid that takes, by the mol ratio of Li and P, be 3:1, metering takes lithium hydroxide 0.5035g, be dissolved in step 1) in prepared ethylene glycol and the mixed solvent of water, stir 30 minutes, join to obtain clarification lithium hydroxide solution, the concentration of lithium hydroxide is 0.3mol/L.
5) under the state stirring, by step 4) prepared lithium hydroxide solution is added drop-wise to step 3) in the prepared solution that contains phosphoric acid, ferrous sulfate and ascorbic acid, form the suspension that contains precipitation.After having mixed, stir 30 minutes.
6) under stirring, 0.631g polyethylene glycol is added to step 5) in prepared suspension, then transfer in autoclave, the mixed solvent prepared by step 1) regulates, and makes its volume account for 4/5 of reactor inner bag volume, continues to stir 10 minutes.Airtight, at 160 ℃, be incubated 36 hours and heat-treat.Then, be down to room temperature, take out product, filter, clean successively with deionized water, acetone, at 80 ℃ of temperature, dry, obtain LiFePO4 monocrystal nano rod, radial dimension is 100-200 nanometer, and length is 5-10 micron.
Example 4
1) measure ethylene glycol 20ml and deionized water 20ml, by the mixed solvent of the two mixed preparing ethylene glycol and water.
2) metering takes ascorbic acid 0.5g and is dissolved in step 1) in prepared ethylene glycol and the mixed solvent of water, stir and it was fully dissolved in 30 minutes.
3) by the mol ratio of P and Fe, be 1:1, metering takes phosphoric acid 2.306g, six directions aqueous ferrous sulfate 5.5605g is dissolved in step 2) in prepared ascorbic acid solution, stir 10 minutes, obtain the solution that contains phosphoric acid, ferrous sulfate and ascorbic acid, ascorbic acid accounts for 15.8% of target LiFePO4 quality, phosphoric acid concentration is 0.5mol/L, and six directions aqueous ferrous sulfate concentration is 0.5mol/L.
4) according to step 3) amount of the phosphoric acid that takes, by the mol ratio of Li and P, be 3:1, metering takes lithium hydroxide 2.5175g, be dissolved in step 1) in prepared ethylene glycol and the mixed solvent of water, stir 30 minutes, join to obtain clarification lithium hydroxide solution, the concentration of lithium hydroxide is 1.5mol/L.
5) under the state stirring, by step 4) prepared lithium hydroxide solution is added drop-wise to step 3) in the prepared solution that contains phosphoric acid, ferrous sulfate and ascorbic acid, form the suspension that contains precipitation.After having mixed, stir 30 minutes.
6) under stirring, 0.0631g polyethylene glycol is added to step 5) in prepared suspension, then transfer in autoclave, the mixed solvent prepared by step 1) regulates, and makes its volume account for 2/3 of reactor inner bag volume, continues to stir 10 minutes.Airtight, at 200 ℃, be incubated 24 hours and heat-treat.Then, be down to room temperature, take out product, filter, clean successively with deionized water, acetone, at 80 ℃ of temperature, dry, obtain LiFePO4 monocrystal nano rod, radial dimension is 50-100 nanometer, and length is 2-8 micron.
Claims (2)
1. a preparation method for LiFePO4 monocrystal nano rod, is characterized in that comprising the following steps:
1), by ethylene glycol and deionized water 3:1 ~ 1:3 mixing by volume, obtain the mixed solvent of ethylene glycol and water;
2) ascorbic acid is dissolved in to step 1) ethylene glycol and the mixed solvent of water in, be stirred to abundant dissolving, obtain ascorbic acid solution;
3) by the mol ratio of P and Fe, be 1:1, metering takes phosphoric acid and six ferrous sulfate hydrates, and phosphoric acid and six ferrous sulfate hydrates are dissolved in to step 2) in prepared ascorbic acid solution, ascorbic acid quality and prepared target LiFePO4 mass percent are 10 ~ 30%, the concentration of phosphoric acid and six ferrous sulfate hydrates is 0.05 ~ 0.5mol/L, fully stir, obtain the solution that contains phosphoric acid, ferrous sulfate and ascorbic acid;
4) according to step 3) amount of the phosphoric acid that takes, by the mol ratio of Li and P, be 3:1, metering takes lithium hydroxide, and lithium hydroxide is dissolved in to step 1) ethylene glycol and the mixed solvent of water in, the concentration that makes lithium hydroxide is 0.15 ~ 1.5mol/L, fully stirs, and obtains lithium hydroxide solution;
5) under the state stirring, by step 4) lithium hydroxide solution be added drop-wise to step 3) in the prepared solution that contains phosphoric acid, ferrous sulfate and ascorbic acid, form the suspension that contains precipitation;
6) under stirring, polyethylene glycol is added to step 5) suspension in, polyethylene glycol quality and prepared target LiFePO4 mass percent are 10 ~ 100%; Then transfer in autoclave, the mixed solvent prepared by step 1) regulates, make its volume account for 2/3 ~ 4/5 of reactor inner bag volume, continue to stir at least 5 minutes, airtight, at 160 ~ 240 ℃, be incubated after 4 ~ 36 hours, be down to room temperature, take out product, filter, with deionized water, absolute ethyl alcohol or acetone, clean successively, at 40 ℃ ~ 100 ℃ temperature, dry, obtain LiFePO4 monocrystal nano rod, the radial dimension of LiFePO4 monocrystal nano rod is 50-200 nanometer, and length is 0.5-10 micron.
2. according to the preparation method of the LiFePO4 monocrystal nano rod described in claim l, it is characterized in that the purity of said phosphoric acid, six ferrous sulfate hydrates, lithium hydroxide, ascorbic acid, polyethylene glycol, ethylene glycol, absolute ethyl alcohol and acetone is all not less than chemical pure.
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| FR3000956B1 (en) * | 2013-01-17 | 2017-12-08 | Commissariat Energie Atomique | PROCESS FOR THE SYNTHESIS OF LIM1-X-Y-ZNYQZFEXPO4 COMPOUND AND ITS USE AS ELECTRODE MATERIAL FOR LITHIUM ACCUMULATOR |
| PL233550B1 (en) | 2014-03-12 | 2019-10-31 | Akademia Gorniczo Hutnicza Im Stanislawa Staszica W Krakowie | Method for obtaining the transition metal crystalline nanometric lithium phosphate |
| CN104183827B (en) * | 2014-08-21 | 2016-08-17 | 浙江大学 | A kind of lithium iron phosphate nano rod and preparation method thereof |
| CN107636204B (en) | 2015-05-30 | 2020-06-23 | 清洁锂公司 | High purity lithium and related products and methods |
| CN106058247B (en) * | 2016-05-31 | 2018-10-19 | 浙江大学 | Monodisperse lithium iron phosphate nanometer rods and its preparation method and application |
| CN106848229B (en) * | 2017-02-03 | 2020-07-03 | 南京邮电大学 | Preparation method of metal organic compound cathode material |
| CN109167060B (en) * | 2018-08-14 | 2022-06-14 | 南京理工大学 | Preparation method of porous lithium iron phosphate electrode material |
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| CN101891181B (en) * | 2010-08-11 | 2012-01-04 | 河北工业大学 | Preparation method of pure-phase high-crystallinity lithium iron phosphate |
| CN102569796A (en) * | 2012-01-17 | 2012-07-11 | 东南大学 | Preparation method of lithium iron phosphate/carbon nanotube composite material |
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