CN101710615A - Preparation method of composite cathode material of lithium iron phosphate and carbon nano-tubes - Google Patents
Preparation method of composite cathode material of lithium iron phosphate and carbon nano-tubes Download PDFInfo
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- CN101710615A CN101710615A CN200910220007A CN200910220007A CN101710615A CN 101710615 A CN101710615 A CN 101710615A CN 200910220007 A CN200910220007 A CN 200910220007A CN 200910220007 A CN200910220007 A CN 200910220007A CN 101710615 A CN101710615 A CN 101710615A
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Abstract
The invention relates to a preparation method of a composite cathode material of lithium iron phosphate and carbon nano-tubes. The preparation method comprises the following steps of: (1) preparing a precursor by taking citric acid, lithium nitrate, ferric nitrate, and ammonium dihydrogen phosphate as reactants; (2) adding the carbon nano-tubes to the precursor, wherein the mass percentage of the addition the carbon nano-tubes is 1-5 percent relative to the precursor, and thoroughly mixing the carbon nano-tubes with the precursor; (3) heating the mixed liquor of the carbon nano-tubes and the precursor, which treated in the step (2), in a constant temperature water bath with the temperature of 80-90 DEG C till solvent volatilize completely, pre-sintering the dried precursor at 250-350 DEG C for 8-10 hours under nitrogen atmosphere, and preserving the temperature at 700-800 DEG C for 8-10 hours to obtain the composite cathode material of the lithium iron phosphate and the carbon nano-tubes. Since the carbon nano-tubes are added into the sol-gel precursor, on the basis of active particulate carbon cladding provided by a sol-gel method, electric conduction network of carbon is enhanced though using the carbon nano-tubes to improve contacts among particles, thereby improving electrical property of a lithium ion battery.
Description
Technical field
The present invention relates to technical field of lithium ion, is the preparation method of LiFePO4 and carbon/carbon nano tube compound anode material.
Background technology
LiFePO4 LiFePO
4Material has advantages such as cost is low, Environmental compatibility good, specific capacity is higher, good stability with it, become a kind of Postive electrode material of li-ion accumulator that has application potential
[1～4]Pure LiFePO
4Under extremely low charge-discharge magnification (＜C/80), the reversible embedding that just has the Li of 0.6 mole is taken off, and now thinks the reason that pure ferric phosphate lithium conductivity is very low, the lithium ion diffusion velocity is very little more.In order to improve LiFePO
4Performance, the method for modifying of having studied at present mainly contains: lithium position doping high volence metal ion, ultra-fineization and conducting objects compound (comprise surface point is modified, surface coat).Wherein the combination process with carbon is more, the most cheap method that effectively, also is easier to large-scale production of research.The compound effect of carbon mainly contains 3 points: crystal grain thinning, tight contact improve the reducing atmosphere of conductivity, assisted reaction process.Reported multiple carbon raw material as carbon source, as the carbon gel
[5], carbon black
[6], sucrose
[7], cellulose acetate
[9], sugar
[10], glycolic
[11], polypropylene
[12]Deng.
Carbon nano-tube (CNT) with remarkable one-dimentional structure has higher conductivity, can be used to improve positive electrode conductivity.At LiNi
0.7Co
0.3O
2Add an amount of carbon nano-tube in the positive electrode as conductive agent, bigger raising battery capacity.With LiFePO
4Add the composite positive pole of carbon nano-tube in the powder, will improve the conductivity of lithium ion anode material greatly as lithium ion battery.
Summary of the invention
Purpose of the present invention provides the preparation method of a kind of LiFePO4 and carbon/carbon nano tube compound anode material, in the collosol and gel presoma, add carbon nano-tube, provide at sol-gal process on the basis of active particle carbon coating, improve contacting between particle and the particle by carbon nano-tube, strengthen the conductive network of carbon, thereby improved the lithium ion battery electrical property.
For achieving the above object, the present invention is achieved through the following technical solutions:
The preparation method of LiFePO4 and carbon/carbon nano tube compound anode material may further comprise the steps:
1) be reactant preparation presoma with citric acid, lithium nitrate, ferric nitrate and ammonium dihydrogen phosphate, detailed process is: citric acid is dissolved in the appropriate amount of deionized water, adds thermal agitation, add the aqueous solution of lithium nitrate, ferric nitrate and monoammonium phosphate successively, solution is dark brown transparence, makes presoma;
2) in presoma, add carbon nano-tube, the mass percent 1-5% of carbon nano-tube addition and presoma, the mixed solution of presoma and carbon nano-tube is added thermal agitation 1-2h, after being cooled to room temperature, ultrasonic 20-40min, move in the vacuum drying chamber and place 10-15h, carbon nano-tube is fully mixed with presoma;
3) through step 2) mixed liquor of processed carbon nanotubes and presoma heats in 80-90 ℃ of water bath with thermostatic control, and is complete until solvent evaporates; Dried presoma is under nitrogen atmosphere, and 250-350 ℃ of pre-burning 8-10h is incubated 8-10h down at 700-800 ℃ again, obtains LiFePO4 and carbon/carbon nano tube compound anode material.
Compared with prior art, the invention has the beneficial effects as follows:
In the collosol and gel presoma, add carbon nano-tube, provide on the basis that active particle carbon coats, improve contacting between particle and the particle, strengthened the conductive network of carbon, thereby improved the lithium ion battery electrical property by carbon nano-tube at sol-gal process.
Description of drawings
Fig. 1 LiFePO
4/ CNT positive electrode XRD spectra;
Fig. 2 CNT-1 sample SEM picture;
Fig. 3 LiFePO
4/ CNT anode composite lithium ion battery variable Rate reversible capability of charging and discharging figure.
Embodiment
The preparation method of LiFePO4 and carbon/carbon nano tube compound anode material may further comprise the steps:
1) impurity in the nanotube mainly contains amorphous carbon, iron etc., therefore need be purified before use: carbon nano-tube is heated in 80 ℃ of following 4M nitric acid about 6h, through ultrasonic, filtration, cleaning repeatedly, be about 5.8 until cleaning fluid pH value;
2) be reactant preparation presoma with citric acid, lithium nitrate, ferric nitrate and ammonium dihydrogen phosphate, detailed process is: citric acid is dissolved in the appropriate amount of deionized water, 80-90 ℃ adds thermal agitation, the aqueous solution that adds lithium nitrate, ferric nitrate and monoammonium phosphate successively, solution is dark brown transparence, makes presoma;
3) get above-mentioned three parts of same presomas, in presoma, add carbon nano-tube, addition is followed successively by 0.25g, 0.1g, 0.05g, make sample CNT-1, CNT-2, CNT-3, the mass percent of carbon nano-tube addition and presoma is respectively 5%, 2%, 1%, and the mixed solution of presoma and carbon nano-tube is added thermal agitation 1-2h, after being cooled to room temperature, ultrasonic 20-40min moves in the vacuum drying chamber and places 10-15h, and carbon nano-tube is fully mixed with presoma;
4) through step 2) mixed liquor of processed carbon nanotubes and presoma heats in 80-90 ℃ of water bath with thermostatic control, and is complete until solvent evaporates; Dried presoma is under nitrogen atmosphere, and 250-350 ℃ of pre-burning 8-10h is incubated 8-10h down at 700-800 ℃ again, obtains LiFePO4 and carbon/carbon nano tube compound anode material.
5) determined the thing phase of end product by X-ray powder diffraction instrument (Rigaku D/max III B), (thermal field emission scan Electronic Speculum LEO-1530) observes its microscopic appearance with scanning electron microscopy.
1, Experimental cell assembling and electro-chemical test
Anode pole piece is by 75% active material, the acetylene black of (16,15,12) %, and 8% Kynoar (PVDF) is formed.Adding N-methyl pyrrolidone is modulated into the slip of certain flowability, scrapes the skill in using a kitchen knife in cookery and is coated on equably on the aluminium foil, 80 ℃ of oven dry, rolls film then on roll squeezer, so that the smooth densification of pole piece is smooth.Smooth being positioned over also born in 80～100 ℃ of vacuum drying chambers with weight, and vacuum heat is whole to be made a few hours.The pole piece film of handling well is washed into 1cm
2The disk of size, as backup electrode, electrolyte adopts 1M LiPF
6EC: DMC (1: 1) (MERCK company) mixed liquor; Barrier film adopts Celgard 2400; Metal lithium sheet is packaged into CR2032 type button cell as negative pole in the glove box of argon gas atmosphere.With the cycle charge discharge electrical testing that carries out battery on the LAND 2001A tester, constant current charge-discharge mode, voltage range are 2.5V to 4.2V, and charge and discharge mode charges and discharge for the constant current variable Rate, and probe temperature is a room temperature.
2, the crystal structure analysis of LiFePO4/CNT composite positive pole powder
Determine LiFePO by x-ray powder diffraction instrument
4The thing phase of/CNT composite positive pole.Carbon nano tube-doped LiFePO
4Three kinds of sample CNT-1 of/CNT composite positive pole, 2,3 all are shown as LiFePO through XRD analysis
4Pure phase, and crystallinity is better.Be illustrated in figure 1 as the XRD spectra of CNT-2 after 700 ℃ of heat treatment.
3, LiFePO
4The microscopic appearance analysis of/CNT pre-sintered sample
LiFePO after 700 ℃ of heat treatment
4The SEM image of/CNT sample as shown in Figure 2.The sample particle size is comparatively even, and all about hundreds of nanometers to 1 micron, particle diameter is less.Simultaneously can see LiFePO
4Carbon nano-tube is distributed between the active particle in the/CNT sample.The particle that carbon nano-tube is incited somebody to action in positive electrode links to each other with particle, provides additional conductive path between the carbon coated pellet for originally having, and can further improve the conductance of sample.Because the density of carbon nano-tube is less, therefore, adds minute quantity and just can produce more rich conductive path.
4, the carbon structure parameter is to the influence of LiFePO4/carbon composite anode capacity characteristic
To with LiFePO
4/ CNT composite material be anodal lithium ion battery successively at C/5, C/2, C carries out the electric performance test of constant current cycle charge-discharge under 2C and the 3C speed.Three curves of Fig. 3 have been represented the reversible capacity of three kinds of samples respectively, and under low charge-discharge velocity (C/5), the CNT-2 sample has reached 135mAh/g, and the CNT-1 sample reaches 120mAh/g.The less CNT-3 sample reversible capacity of content of carbon nanotubes is significantly less than sample CNT-1,2, has only 105mAh/g under low rate.But the capacity of three kinds of samples is all along with decay has inevitably taken place in the increase of charge-discharge velocity.This mainly is because the dispersion of carbon nano-tube in presoma is also limited, can not guarantee the higher uniformity in the process of presoma solvent evaporates, and the winding of carbon nano-tube has taken place in some position, is unfavorable for the raising of composite positive pole conductivity.
5, conclusion
1) is carbon source and chelating agent with the citric acid, prepared LiFePO by sol-gel process
4/ CNT anode composite powder body material.
2) by the method for adding carbon nano-tube the positive electrode conductive path is improved.Capacity can reach 135mAh/g under low rate, and capacity remains on 110mAh/g under the 1C charge-discharge velocity, and capacity remains on 80mAh/g during 2C.And along with the increase of content of carbon nanotubes, the capacity of lithium ion battery also increases.
Claims (1)
1. the preparation method of LiFePO4 and carbon/carbon nano tube compound anode material is characterized in that, may further comprise the steps:
1) be reactant preparation presoma with citric acid, lithium nitrate, ferric nitrate and ammonium dihydrogen phosphate, detailed process is: citric acid is dissolved in the appropriate amount of deionized water, adds thermal agitation, add the aqueous solution of lithium nitrate, ferric nitrate and monoammonium phosphate successively, solution is dark brown transparence, makes presoma;
2) in presoma, add carbon nano-tube, the mass percent 1-5% of carbon nano-tube addition and presoma, the mixed solution of presoma and carbon nano-tube is added thermal agitation 1-2h, after being cooled to room temperature, ultrasonic 20-40min, move in the vacuum drying chamber and place 10-15h, carbon nano-tube is fully mixed with presoma;
3) through step 2) mixed liquor of processed carbon nanotubes and presoma heats in 80-90 ℃ of water bath with thermostatic control, and is complete until solvent evaporates; Dried presoma is under nitrogen atmosphere, and 250-350 ℃ of pre-burning 8-10h is incubated 8-10h down at 700-800 ℃ again, obtains LiFePO4 and carbon/carbon nano tube compound anode material.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102169992A (en) * | 2011-03-31 | 2011-08-31 | 江苏乐能电池股份有限公司 | Lithium ferric phosphate (LiFePO4) / carbon nano tube net composite positive electrode material and preparation method thereof |
| CN102324494A (en) * | 2010-07-20 | 2012-01-18 | 上海大象能源科技有限公司 | Lithium iron phosphate / nano-powder tube oxide composite cathode material and preparation method thereof |
| CN102437334A (en) * | 2011-11-23 | 2012-05-02 | 陕西科技大学 | Microwave hydrothermal synthesizing method for carbon nanotube/LiFePO4 lithium ion battery anode material |
| CN102569796A (en) * | 2012-01-17 | 2012-07-11 | 东南大学 | Preparation method of lithium iron phosphate/carbon nanotube composite material |
| CN102945965A (en) * | 2012-11-27 | 2013-02-27 | 广东中科信泰新能源有限公司 | Preparing method of porous carbon embedding type lithium ion battery anode material |
| CN103219518A (en) * | 2013-04-24 | 2013-07-24 | 湖北大学 | Preparation method of carbon-coated lithium iron phosphate material by using carbon black as carbon source |
| 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 |
| CN104716320A (en) * | 2015-03-10 | 2015-06-17 | 中国科学院过程工程研究所 | Composite-coated lithium iron phosphate, preparation method of composite-coated lithium iron phosphate, and lithium ion battery |
| CN106531985A (en) * | 2016-10-12 | 2017-03-22 | 深圳市沃特玛电池有限公司 | Preparation method of carbon nanobelt coated lithium iron phosphate material |
| CN109786693A (en) * | 2018-12-28 | 2019-05-21 | 沈阳国科金能科技有限公司 | A kind of preparation method of carbon nanotube composite lithium iron phosphate cathode material |
| CN110323434A (en) * | 2019-07-11 | 2019-10-11 | 江苏力泰锂能科技有限公司 | Prepare iron manganese phosphate for lithium-carbon composite method and iron manganese phosphate for lithium-carbon composite |
| CN111900374A (en) * | 2020-08-06 | 2020-11-06 | 福建东方醒狮新能源有限公司 | High energy density quick charging type lithium ion power battery |
| CN113991072A (en) * | 2021-09-14 | 2022-01-28 | 陕西创普斯新能源科技有限公司 | Carbon nanotube/lithium iron phosphate composite material and preparation method and application thereof |
| CN115020681A (en) * | 2022-07-14 | 2022-09-06 | 江苏众钠能源科技有限公司 | Carbon-coated sodium ferric sulfate cathode material and preparation method thereof |
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- 2009-11-19 CN CN200910220007A patent/CN101710615A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324494A (en) * | 2010-07-20 | 2012-01-18 | 上海大象能源科技有限公司 | Lithium iron phosphate / nano-powder tube oxide composite cathode material and preparation method thereof |
| CN102169992A (en) * | 2011-03-31 | 2011-08-31 | 江苏乐能电池股份有限公司 | Lithium ferric phosphate (LiFePO4) / carbon nano tube net composite positive electrode material and preparation method thereof |
| CN102437334A (en) * | 2011-11-23 | 2012-05-02 | 陕西科技大学 | Microwave hydrothermal synthesizing method for carbon nanotube/LiFePO4 lithium ion battery anode material |
| CN102569796A (en) * | 2012-01-17 | 2012-07-11 | 东南大学 | Preparation method of lithium iron phosphate/carbon nanotube composite material |
| CN102945965A (en) * | 2012-11-27 | 2013-02-27 | 广东中科信泰新能源有限公司 | Preparing method of porous carbon embedding type lithium ion battery anode material |
| CN103219518A (en) * | 2013-04-24 | 2013-07-24 | 湖北大学 | Preparation method of carbon-coated lithium iron phosphate material by using carbon black as carbon source |
| 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 |
| CN104716320A (en) * | 2015-03-10 | 2015-06-17 | 中国科学院过程工程研究所 | Composite-coated lithium iron phosphate, preparation method of composite-coated lithium iron phosphate, and lithium ion battery |
| US10243211B2 (en) | 2015-03-10 | 2019-03-26 | Institute Of Process Engineering, Chinese Academy Of Sciences | Composite-coated lithium iron phosphate and preparation method therefor, and lithium ion battery |
| CN104716320B (en) * | 2015-03-10 | 2017-06-16 | 中国科学院过程工程研究所 | A kind of LiFePO4 of composite cladding, its preparation method and lithium ion battery |
| CN106531985B (en) * | 2016-10-12 | 2018-07-24 | 深圳市沃特玛电池有限公司 | A kind of preparation method of carbon nanobelts coated LiFePO 4 for lithium ion batteries material |
| CN106531985A (en) * | 2016-10-12 | 2017-03-22 | 深圳市沃特玛电池有限公司 | Preparation method of carbon nanobelt coated lithium iron phosphate material |
| CN109786693A (en) * | 2018-12-28 | 2019-05-21 | 沈阳国科金能科技有限公司 | A kind of preparation method of carbon nanotube composite lithium iron phosphate cathode material |
| CN110323434A (en) * | 2019-07-11 | 2019-10-11 | 江苏力泰锂能科技有限公司 | Prepare iron manganese phosphate for lithium-carbon composite method and iron manganese phosphate for lithium-carbon composite |
| CN110323434B (en) * | 2019-07-11 | 2022-07-22 | 江苏力泰锂能科技有限公司 | Method for preparing lithium iron manganese phosphate-carbon composite material and lithium iron manganese phosphate-carbon composite material |
| CN111900374A (en) * | 2020-08-06 | 2020-11-06 | 福建东方醒狮新能源有限公司 | High energy density quick charging type lithium ion power battery |
| CN113991072A (en) * | 2021-09-14 | 2022-01-28 | 陕西创普斯新能源科技有限公司 | Carbon nanotube/lithium iron phosphate composite material and preparation method and application thereof |
| CN113991072B (en) * | 2021-09-14 | 2024-01-12 | 陕西创普斯新能源科技有限公司 | Carbon nano tube/lithium iron phosphate composite material and preparation method and application thereof |
| CN115020681A (en) * | 2022-07-14 | 2022-09-06 | 江苏众钠能源科技有限公司 | Carbon-coated sodium ferric sulfate cathode material and preparation method thereof |
| CN115020681B (en) * | 2022-07-14 | 2024-05-07 | 江苏众钠能源科技有限公司 | Carbon-coated sodium ferric sulfate positive electrode material and preparation method thereof |
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Open date: 20100519 |