CN102593428A - Method for preparing cathode material of lithium ion battery - Google Patents
Method for preparing cathode material of lithium ion battery Download PDFInfo
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- CN102593428A CN102593428A CN2011100048153A CN201110004815A CN102593428A CN 102593428 A CN102593428 A CN 102593428A CN 2011100048153 A CN2011100048153 A CN 2011100048153A CN 201110004815 A CN201110004815 A CN 201110004815A CN 102593428 A CN102593428 A CN 102593428A
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Abstract
The invention relates to a method for preparing a cathode material of a lithium ion battery. The method comprises the steps of: dissolving lithium hydrate, phosphoric acid and ferrous sulfate according to the following element molar ratio: Li:P:Fe=3:1:1, by using deionized water respectively, mixing the lithium hydrate and phosphoric acid firstly to form white emulsion, then adding a ferrous sulfate solution to form light green emulsion, uniformly stirring, then adding into a high-pressure reaction kettle, preserving the heat fro 1-12h at the temperature of 180 DEG C to generate lithium iron phosphate, and synthesizing lithium iron phosphate/carbon, namely, the product, by using a carbothermic reduction method with glucose as a carbon source. Compared with the prior art, the method disclosed by the invention is simple and is easy to control and lower in cost, lithium iron phosphate/carbon powder particles obtained according to the method have small average particle size being about 250-400nm and are distributed uniformly, and a battery has a superior performance and has the initial charge/discharge specific capacity being 146.7mAh/g.
Description
Technical field
The present invention relates to a kind of lithium ion battery field, especially relate to a kind of preparation method of anode material for lithium-ion batteries.
Background technology
Along with socioeconomicly develop rapidly, resource and energy worsening shortages, traditional energy bring huge pollution to environment, research and development is efficient, safety, the free of contamination renewable energy resources are imperative.The microelectric technique of develop rapidly simultaneously makes electronic equipment present trend toward miniaturization, and wireless telecommunications and various portable type electronic product have become people's indispensable part of living.Therefore the supply of power supply becomes a problem that urgency is to be solved, and the function of small-sized secondary batteries and characteristic have become the key factor of portable type electronic product market competition advantages such as electricity communication of decision new generation of wireless and notebook computer.On the other hand, in order to eradicate automobile exhaust pollution, development motor vehicle battery system is an important directions of battery development especially.
Lithium ion battery is as the green high-capacity rechargeable battery of a new generation, and with lead acid accumulator, ickel-cadmium cell commonly used, secondary cells such as hydrogen nickel are compared, and has operating voltage height (about 3.6V), discharging and recharging long, specific energy of life-span, big (volumetric specific energy is about 300Wh L
-1), advantages such as discharging voltage balance and memory-less effect, therefore, lithium ion battery can adapt to the requirement of modern science and technology to the small-sized energetic of battery, is one of novel battery technology that development is best at present.
Lithium ion battery mainly comprises several sections such as positive pole, negative pole, electrolyte, adhesive, barrier film and shell.Positive electrode is the important component part of lithium ion battery, and the positive electrode performance has determined the combination property of battery to a great extent, thereby positive electrode research and improvement in performance are one of cores of lithium ion battery development.The anode material for lithium-ion batteries of broad research mainly is a transition metal oxide now, like the LiMO of layer structure
2(M=Co, Ni is Mn) with the LiMn2O4 (LiMn of spinel structure
2O
4); And LiFePO
4Deng polyanion type compound.
LiFePO wherein
4Positive electrode receives extensive concern because of environmental protection, cheap, series of advantages such as theoretical specific capacity is high, stable performance.But little because of existing electron conductivity to hang down with the lithium ion diffusion coefficient, and its practical application is restricted.Main at present through carbon coating or metallic cover, methods such as metal ion mixing and control size are to LiFePO
4Carry out modification.
Summary of the invention
The object of the invention is exactly to provide a kind of preparation method simple for the defective that overcomes above-mentioned prior art existence, control easily, the preparation method of lower-cost anode material for lithium-ion batteries.
The object of the invention can be realized through following technical scheme:
A kind of preparation method of anode material for lithium-ion batteries is characterized in that, this method may further comprise the steps: with lithium hydroxide; Phosphoric acid; Ferrous sulfate is used deionized water dissolving respectively, and lithium hydroxide solution and phosphoric acid solution are mixed the formation white emulsion earlier, adds copperas solution then and forms the light green emulsion; Be placed in the autoclave fast after stirring; The control temperature is that 180 ℃ of insulation reaction 2-12h generate ferric lithium phosphate precursor, and through after suction filtration, washing, the drying ferric lithium phosphate precursor being immersed in the glucose solution, the presoma that will flood glucose again was in 100 ℃ of vacuumizes 24 hours; The oven dry back obtains battery anode material of lithium iron phosphate/carbon through the carbon of carbothermic method coating 15-25wt%.
Li in the described autoclave: P: the Fe mol ratio is 3: 1: 1.
The compactedness of described autoclave is 50v/v%.
In the described glucose solution, the quality of contained glucose is the 15-25% of LiFePO4.
Described carbothermic method is divided into two-section calcining, and at first controlling temperature is 350 ℃ of calcinings 5 hours, and controlling temperature then is 700 ℃ of calcinings 12 hours, and two-section calcining all adopts nitrogen protection.
Compared with prior art, the electrode material that the present invention can synthesis nano LiFePO4/carbon, the preparation method is simple; Control easily, cost is lower, and the LiFePO4 that obtains thus/toner body particle average grain diameter is tiny; Be approximately 250-400nm; Even particle distribution, battery performance is superior, and the first charge-discharge specific capacity is 146.7mAh/g.
Description of drawings
Fig. 1 is field emission scanning electron microscope (FESEM) figure of embodiment 1 sample;
Fig. 2 is embodiment 1 a sample X ray diffracting spectrum (XRD);
Fig. 3 is the N of embodiment 1 sample
2Adsorption isotherm and BJH graph of pore diameter distribution;
Fig. 4 is the first constant current charge-discharge curve of embodiment 7 under 0.1C.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is elaborated.
With lithium hydroxide, phosphoric acid is the ferrous sulfate raw material, and by Li: P: the Fe mol ratio is stoichiometric proportion weighing in 3: 1: 1.The lithium hydroxide of 3.78g is dissolved in the 20mL deionized water, adds the H of 10mL again
3PO
4Mix with LiOH solution, after stirring a few minutes, add 20mL ferrous sulfate (8.34g) solution at last and mix, change in the hydrothermal reaction kettle of 100mL, compactedness is 50v/v%.Agitated reactor is placed baking oven, with 3 ℃ of min
-1Heating rate be warming up to 180 ℃ of reaction 2h from room temperature and take out, naturally cool to room temperature, be filtered to neutrality with deionized water wash.Gained light green color product obtains the LiFePO 4 powder of 250-400nm behind 100 ℃ of oven dry 12h, uniform particles, and its SEM collection of illustrative plates is as shown in Figure 1.Hydro-thermal synthetic material LiFePO4 is mixed through infusion process than 20wt.% by certain mass with glucose, and solvent is deionized water and absolute ethyl alcohol, after 100 ℃ of oven dry, places tube furnace, at N
2Under the protection, with 10 ℃ of min
-1Heating rate be warmed up to 350 ℃ earlier, constant temperature 5h, cooling back is taken out and is ground.Then with 10 ℃ of min
-1Heating rate be warmed up to 600 ℃ respectively, 700 ℃, 800 ℃, insulation obtains LiFePO behind the 12h
4/ C carbon clad composite material, its XRD figure spectrum and products therefrom N2 adsorption isotherm and pore structure distribute respectively like Fig. 2 and as shown in Figure 3, and its XRD figure spectrum is gentle with standard diagram, according to the criteria for classification LiFePO of IUPAC to adsorption isotherm
4/ C composite material shows as the II type isothermal adsorption curve of non-hole or large pore material; Wherein adsorption isotherm delay winding shows as H3 delay ring.
Embodiment 5
Embodiment 5 and embodiment 1 are similar, and difference is that hydro-thermal synthetic material LiFePO4 mixes through infusion process than 15wt.% by certain mass with glucose.
Embodiment 7
The simulated battery assembling: positive electrode is the LiFePO that instance 1 synthesizes
4/ C carbon clad composite material, negative pole are metal lithium sheet, and barrier film is the Celgard2700 microporous polypropylene membrane, and electrolyte is lithium hexafluoro phosphate (LiPF in the electrolyte
6), solvent is ethylene carbonate (EC) and dimethyl carbonate (DMC) (volume ratio is 1: 1).In vacuum glove box, be assembled into CR2032 type button cell, on the Land tester, carry out charge-discharge test, the charging/discharging voltage scope is 2.2-3.8V.Constant current charge-discharge figure sees shown in Figure 4, and its first charge-discharge is 146.7mAh/g.
Claims (5)
1. the preparation method of an anode material for lithium-ion batteries is characterized in that, this method may further comprise the steps: with lithium hydroxide; Phosphoric acid; Ferrous sulfate is used deionized water dissolving respectively, and lithium hydroxide solution and phosphoric acid solution are mixed the formation white emulsion earlier, adds copperas solution then and forms the light green emulsion; Be placed in the autoclave fast after stirring; The control temperature is that 180 ℃ of insulation reaction 2-12h generate ferric lithium phosphate precursor, and through after suction filtration, washing, the drying ferric lithium phosphate precursor being immersed in the glucose solution, the presoma that will flood glucose again was in 100 ℃ of vacuumizes 24 hours; The oven dry back obtains battery anode material of lithium iron phosphate/carbon through the carbon of carbothermic method coating 15-25wt%.
2. the preparation method of a kind of anode material for lithium-ion batteries according to claim 1 is characterized in that, Li in the described autoclave: P: the Fe mol ratio is 3: 1: 1.
3. the preparation method of a kind of anode material for lithium-ion batteries according to claim 1 is characterized in that, the compactedness of described autoclave is 50v/v%.
4. the preparation method of a kind of anode material for lithium-ion batteries according to claim 1 is characterized in that, in the described glucose solution, the quality of contained glucose is the 15-25% of LiFePO4.
5. the preparation method of a kind of anode material for lithium-ion batteries according to claim 1; It is characterized in that described carbothermic method is divided into two-section calcining, at first controlling temperature is 350 ℃ of calcinings 5 hours; Controlling temperature then is 700 ℃ of calcinings 12 hours, and two-section calcining all adopts nitrogen protection.
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| CN2011100048153A CN102593428A (en) | 2011-01-11 | 2011-01-11 | Method for preparing cathode material of lithium ion battery |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102867962A (en) * | 2012-09-27 | 2013-01-09 | 北京航空航天大学 | Preparation method of LiFePO4 composite positive electrode material modified by CePO4 |
| CN103337633A (en) * | 2013-07-04 | 2013-10-02 | 哈尔滨工程大学 | In-situ carbon coating preparation method for secondary lithium ion battery cathode material lithium nickel phosphate |
| CN104282886A (en) * | 2014-10-14 | 2015-01-14 | 江苏华东锂电技术研究院有限公司 | Carbon coating method for electrode active material of lithium ion battery |
| CN104733708B (en) * | 2014-10-22 | 2017-06-13 | 长沙理工大学 | Preparation method of lithium nickel cobalt manganese oxide composite material with surface coated with lithium iron phosphate |
| CN108539146A (en) * | 2018-03-15 | 2018-09-14 | 南京国轩电池有限公司 | A kind of lithium ion battery composite cathode material and the preparation method and application thereof |
| CN114873573A (en) * | 2022-04-19 | 2022-08-09 | 江苏理工学院 | NaTi 2 (PO4) 3 @ C micro-nano composite material and preparation method and application thereof |
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| CN1747206A (en) * | 2005-07-15 | 2006-03-15 | 中国科学院上海微系统与信息技术研究所 | Nanometer ferrous phosphate lithium/carbon composite material, method for preparing solid phase and application |
| CN1903707A (en) * | 2006-08-18 | 2007-01-31 | 河南环宇集团有限公司 | Semiwet method of preparing lithium ferrous phosphate and its prepared lithium ferrous phosphate |
| JP2009302067A (en) * | 2009-09-28 | 2009-12-24 | Kri Inc | Iron phosphate lithium, and secondary battery using the same |
| CN101752564A (en) * | 2010-01-20 | 2010-06-23 | 河北工业大学 | Hydrothermal synthesis method of LiFePO4 of anode material of lithium ion battery with one-dimensional nanometer structure |
| CN101800311A (en) * | 2010-02-08 | 2010-08-11 | 北京理工大学 | Method for preparing lithium iron phosphate with high rate discharge by using ultrasonic coprecipitation |
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2011
- 2011-01-11 CN CN2011100048153A patent/CN102593428A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1747206A (en) * | 2005-07-15 | 2006-03-15 | 中国科学院上海微系统与信息技术研究所 | Nanometer ferrous phosphate lithium/carbon composite material, method for preparing solid phase and application |
| CN1903707A (en) * | 2006-08-18 | 2007-01-31 | 河南环宇集团有限公司 | Semiwet method of preparing lithium ferrous phosphate and its prepared lithium ferrous phosphate |
| JP2009302067A (en) * | 2009-09-28 | 2009-12-24 | Kri Inc | Iron phosphate lithium, and secondary battery using the same |
| CN101752564A (en) * | 2010-01-20 | 2010-06-23 | 河北工业大学 | Hydrothermal synthesis method of LiFePO4 of anode material of lithium ion battery with one-dimensional nanometer structure |
| CN101800311A (en) * | 2010-02-08 | 2010-08-11 | 北京理工大学 | Method for preparing lithium iron phosphate with high rate discharge by using ultrasonic coprecipitation |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102867962A (en) * | 2012-09-27 | 2013-01-09 | 北京航空航天大学 | Preparation method of LiFePO4 composite positive electrode material modified by CePO4 |
| CN102867962B (en) * | 2012-09-27 | 2015-05-06 | 北京航空航天大学 | Preparation method of LiFePO4 composite positive electrode material modified by CePO4 |
| CN103337633A (en) * | 2013-07-04 | 2013-10-02 | 哈尔滨工程大学 | In-situ carbon coating preparation method for secondary lithium ion battery cathode material lithium nickel phosphate |
| CN104282886A (en) * | 2014-10-14 | 2015-01-14 | 江苏华东锂电技术研究院有限公司 | Carbon coating method for electrode active material of lithium ion battery |
| CN104282886B (en) * | 2014-10-14 | 2016-10-12 | 江苏华东锂电技术研究院有限公司 | The carbon method for coating of lithium ion battery electrode active material |
| CN104733708B (en) * | 2014-10-22 | 2017-06-13 | 长沙理工大学 | Preparation method of lithium nickel cobalt manganese oxide composite material with surface coated with lithium iron phosphate |
| CN108539146A (en) * | 2018-03-15 | 2018-09-14 | 南京国轩电池有限公司 | A kind of lithium ion battery composite cathode material and the preparation method and application thereof |
| CN114873573A (en) * | 2022-04-19 | 2022-08-09 | 江苏理工学院 | NaTi 2 (PO4) 3 @ C micro-nano composite material and preparation method and application thereof |
| CN114873573B (en) * | 2022-04-19 | 2023-09-22 | 江苏理工学院 | NaTi (sodium silicate) 2 (PO 4 ) 3 @C micro-nano composite material and preparation method and application thereof |
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Application publication date: 20120718 |