CN102881904A - Method for preparing double-carbon-source coated LiFePO4/C composite anode material through two-step sintering - Google Patents
Method for preparing double-carbon-source coated LiFePO4/C composite anode material through two-step sintering Download PDFInfo
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- CN102881904A CN102881904A CN2012104167993A CN201210416799A CN102881904A CN 102881904 A CN102881904 A CN 102881904A CN 2012104167993 A CN2012104167993 A CN 2012104167993A CN 201210416799 A CN201210416799 A CN 201210416799A CN 102881904 A CN102881904 A CN 102881904A
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Abstract
The invention discloses a method for preparing a double-carbon-source coated LiFePO4/C composite anode material through two-step sintering. A FePO4/PANI precursor is prepared from ferric nitrate, diammonium hydrogen phosphate and aniline in an in situ polymerization method, the precursor, lithium acetate and a carbon source (ascorbic acid) are fully ground after being mixed, a fully ground sample is presintered for 5 hours at the temperature of 200-500 DEG C in a sintering furnace with the atmosphere that argon is used as shielding gas, the sample is taken out after being cooled, the other carbon source (glucose) is added for further grinding, then secondary sintering is carried out for 8-15 hours under the temperature of 600-1000 DEG C, and then the LiFePO4/C composite anode material is obtained. The method disclosed by the invention is easy and convenient, and is low in cost, the electronic conductivity of the material is improved by adding the two carbon sources in two steps, and simultaneously the electrochemical performance of the material is improved.
Description
Technical field
The present invention relates to a kind of LiFePO that two carbon sources coat for preparing
4The two-step method preparation method of/C composite positive pole.
Background technology
China's secondary rechargeable battery industry is stepped into the lithium electricity epoch, owing to chargeable lithium ion battery has natural advantage in environmental protection, also possesses to have extended cycle life, and self-discharge rate is low, memory-less effect etc. advantage.Lithium rechargeable battery is used on various portable type electronic products and the communication tool widely, and very important application prospect is also arranged on electric automobile and energy storage device simultaneously.In recent years, the sales volume of lithium battery is the rapid growth mode always.Senior engineer's lithium electricity industrial research estimates that power lithium-ion battery market and consumption lithium battery market will reach respectively 35,000,000,000 and 75,000,000,000 yuan in 2014.In the composition of lithium ion battery, positive electrode is in occupation of very important position.Than other several anode material for lithium-ion batteries---lithium and cobalt oxides, lithium nickel oxide and lithium manganese oxide, olivine-type LiFePO4 (LiFePO
4) positive electrode has the extensive concern that the advantages such as high theoretical capacity, environmental friendliness, low cost, thermal stability are high, fail safe is good have obtained people because of it, one of lithium ion battery of the another kind energy large-scale production except lithium cobalt oxide as positive electrode material simultaneously, therefore, the olivine-type LiFePO4 has the wide market space.。
The main shortcoming of LiFePO4 is exactly a little less than its conductivity, and overcoming at present the low main method of its electronic conductivity is that carbon coats.Uniformity and carbon-coating thickness thereof that carbon coats can be to LiFePO
4The chemical property of/C material produces greatly impact, so the kind of carbon source, addition and joining day also can be on the impacts of material production different-effect.The present invention adopts in-situ polymerization to synthesize FePO
4/ PANI on the basis of two-step sintering, adopts two-step method to add the synthetic LiFePO of carbon
4/ C composite positive pole, two-step method make synthetic material particle size more even, and two-step method adds more abundant, the more uniform LiFePO of being coated on of formed carbon that carbon further promotes organic substance to decompose in pyroprocess
4Positive electrode surface, therefore prepared LiFePO
4/ C composite positive pole has better chemical property.
Summary of the invention
The purpose of this invention is to provide the LiFePO that a kind of pair of carbon source coats
4The two-step method preparation method of/C composite positive pole.
Concrete steps are:
⑴ in-situ polymerization prepares presoma FePO
4/ PANI: by stoichiometric proportion, respectively with the Fe (NO of 0.0125mol-0.05mol
3)
3Be dissolved in the beaker 1 of the distilled water that 50ml-200ml is housed the (NH of 0.0125mol-0.05mol
4)
2HPO
4Be dissolved in the beaker 2 that 100ml-400ml distilled water is housed, and add 0.5ml-2ml aniline in beaker 2, magnetic agitation dropwise added solution in the beaker 1 in the beaker 2 after 5 minutes, added 0.5ml-2ml NH after dropwising in beaker 2 again
3H
2O regulates the pH value; Magnetic agitation is after 12 hours at normal temperatures, and vacuum filtration, and clean 2-3 time with distilled water is transferred to that drying namely got corresponding FePO in 24 hours in 60 ℃ of baking ovens
4/ PANI presoma.
⑵ LiFePO
4/ C composite manufacture: take by weighing 0.0125mol-0.05mol CH by stoichiometric proportion
3COOLi2H
2O is put in the agate mortar, adds the 10ml-20ml absolute ethyl alcohol and dissolves, and the presoma that step (1) is made adds further grinding in the mortar, grinds after 1 hour presoma and CH
3COOLi2H
2The ascorbic acid of the 5%-10% of O quality summation adds together and grinds, and adds simultaneously the 15ml-30ml absolute ethyl alcohol, treats to stop to grind and being transferred to the sintering that carries out next stage in the porcelain boat when batch mixing in the mortar is worn into jelly; Under argon atmosphere, 200 ℃ after-500 ℃ of lower pre-burning 3-5 hours, take out the DEXTROSE ANHYDROUS that adds 0.375g-1.500g and grind, carry out the sintering second time after grinding evenly, after 600 ℃ of-1000 ℃ of lower sintering 8-15 hours, namely get LiFePO
4/ C composite material.
Described Fe (NO
3)
3, (NH
4)
2HPO
4, aniline, NH
3H
2O, CH
3COOLi2H
2It is pure that O and ascorbic acid are analysis.
The present invention prepares the LiFePO4 that carbon coats/C positive electrode with two-step method, and ferric nitrate is source of iron, and diammonium hydrogen phosphate is the phosphorus source, lithium acetate is the lithium source, and ascorbic acid, glucose are carbon source, and cost of material is cheap, and do not produce toxic gas in the preparation process, environment is not polluted.The utilization of two-step sintering method makes the growth of particle in the material sintering process more even, and crystal property is better; The mode that two steps of two carbon sources add makes the more even of carbon coating, and the carbon network coverage gets more comprehensive.The material that the mode that adopts two-step sintering method and two steps to add carbon prepares has higher charge/discharge capacity and good cycle performance.
Description of drawings
Fig. 1 is the XRD figure of the embodiment of the invention 1.
Fig. 2 is the first charge-discharge curve of the embodiment of the invention 1.
Fig. 3 is the cycle life figure of the embodiment of the invention 1.
Embodiment
Embodiment 1:
⑴ in-situ polymerization prepares presoma FePO
4/ PANI: by stoichiometric proportion, respectively with the Fe (NO of 0.025mol
3)
3Be dissolved in the beaker 1 that 100ml distilled water is housed the (NH of 0.025mol
4)
2HPO
4Be dissolved in the beaker 2 that 200ml distilled water is housed, add 1ml aniline in the beaker 2, magnetic agitation dropwise added solution in the beaker 1 in the beaker 2 after 5 minutes, added 1mlNH again in beaker 2 after dropwising
3H
2O regulates the pH value; Magnetic agitation is after 12 hours at normal temperatures, and vacuum filtration, and clean 2 times with distilled water is transferred in 60 ℃ of baking ovens dry 24 hours and namely gets corresponding FePO
4/ PANI presoma.
⑵ LiFePO
4/ C composite manufacture: the CH that takes by weighing respective quality by stoichiometric proportion
3COOLi2H
2O is put in the agate mortar, adds the 15ml absolute ethyl alcohol and dissolves, and the presoma that step (1) is made adds further grinding in the mortar, grinds after 1 hour presoma and CH
3COOLi2H
210% ascorbic acid of O quality summation adds together and grinds, and adds simultaneously the 20ml absolute ethyl alcohol, treats to stop to grind and being transferred to the sintering that carries out next stage in the porcelain boat when batch mixing in the mortar is worn into jelly; Under the argon atmosphere, 350 ℃ of lower pre-burnings were taken out the glucose that adds 0.75g and are ground after 5 hours, carried out the sintering second time after the grinding evenly, namely got LiFePO after 10 hours at 650 ℃ of lower sintering
4/ C composite material.
Described Fe (NO
3)
3, (NH
4)
2HPO
4, aniline, NH
3H
2O, CH
3COOLi2H
2It is pure that O and ascorbic acid are analysis.
X-ray powder diffraction analytical technology (XRD) test result (see figure 1) shows that sample belongs to rhombic system, the Pnmb space group.Prepared sample preparation is become positive plate, then be assembled into CR2025 type button cell.
Concrete operations are as follows: according to active material: acetylene black (C): the respectively weighing of PVDF=80:10:10 ratio, at first with an amount of NMP(N-N-methyl-2-2-pyrrolidone N-) add in the mortar, again with the poly-inclined to one side tetrafluoroethene of load weighted PVDF() add and wherein grind, dissolve rear adding acetylene black fully and active material grinds together until PVDF, to be mixed relatively evenly after, roll into the thin slice of even thickness at aluminium foil with simple and easy applicator, place 120 ℃ of vacuum drying chambers after 4 hours, with its circular pole piece that is washed into diameter 14mm, the quality of each pole piece is between 2mg-4mg.Take metal lithium sheet as negative pole, the Celgard2300 microporous polypropylene membrane is barrier film, uses lmol/LiPF
6/ E C+DMC+EMC (l:l:l volume ratio) is electrolyte, is lower than 5% in relative humidity, oxygen forces down and be assembled into CR2025 type button cell in the glove box that is full of argon gas of 10ppm, then puts vacuum drying chamber after 12 hours, can carry out charge-discharge test.Charging voltage 2.5V-4.2V, charge-discharge magnification are 0.2C, and its first discharge specific capacity is 156.7mAh/g, and efficiency for charge-discharge is 98%, and the first charge-discharge curve is seen Fig. 2.Sample discharge and recharge 10 later cycle performances as shown in Figure 3.
Embodiment 2:
⑴ in-situ polymerization prepares presoma FePO
4/ PANI: by stoichiometric proportion, respectively with the Fe (NO of 0.025mol
3)
3Be dissolved in the beaker 1 that 100ml distilled water is housed the (NH of 0.025mol
4)
2HPO
4Be dissolved in the beaker 2 that 200ml distilled water is housed, add 1ml aniline in beaker 2, magnetic agitation dropwise added solution in the beaker 1 in the beaker 2 after 5 minutes, added 1mlNH again in beaker 2 after dropwising
3H
2O regulates pH value; Magnetic agitation is after 12 hours at normal temperatures, and vacuum filtration, and clean 3 times with distilled water is transferred in 60 ℃ of baking ovens dry 24 hours and namely gets corresponding FePO
4/ PANI presoma.
⑵ LiFePO
4/ C composite manufacture: the CH that takes by weighing respective quality by stoichiometric proportion
3COOLi2H
2O is put in the agate mortar, adds the 15ml absolute ethyl alcohol and dissolves, and the presoma that step (1) is made adds further grinding in the mortar, grinds after 1 hour presoma and CH
3COOLi2H
210% ascorbic acid of O quality summation adds together and grinds, and adds simultaneously the 20ml absolute ethyl alcohol, treats to stop to grind and being transferred to the sintering that carries out next stage in the porcelain boat when batch mixing in the mortar is worn into jelly; Under the argon atmosphere,, take out the glucose that adds 0.375g and grind after 5 hours 350 ℃ of pre-burnings, carry out the sintering second time after the grinding evenly, namely get LiFePO after 10 hours at 700 ℃ of lower sintering
4/ C composite material.
Described Fe (NO
3)
3, (NH
4)
2HPO
4, aniline, NH
3H
2O, CH
3COOLi2H
2It is pure that O and ascorbic acid are analysis.
X-ray powder diffraction analytical technology (XRD) test result (see figure 1) shows that sample belongs to rhombic system, the Pnmb space group.Prepared sample preparation is become positive plate, then be assembled into CR2025 type button cell.
Concrete operations are as follows: according to active material: acetylene black (C): the respectively weighing of PVDF=80:10:10 ratio, at first with an amount of NMP(N-N-methyl-2-2-pyrrolidone N-) add in the mortar, again with the poly-inclined to one side tetrafluoroethene of load weighted PVDF() add and wherein grind, dissolve rear adding acetylene black fully and active material grinds together until PVDF, to be mixed relatively evenly after, roll into the thin slice of even thickness at aluminium foil with simple and easy applicator, place 120 ℃ of vacuum drying chambers after 4 hours, with its circular pole piece that is washed into diameter 14mm, the quality of each pole piece is between 2mg-4mg.Take metal lithium sheet as negative pole, the Celgard2300 microporous polypropylene membrane is barrier film, uses lmol/LiPF
6/ E C+DMC+EMC (l:l:l volume ratio) is electrolyte, be lower than 5% in relative humidity, oxygen forces down and be assembled into CR2025 type button cell in the glove box that is full of argon gas of 10ppm, place vacuum drying chamber after 12 hours until battery, can carry out charge-discharge test.Charging voltage 2.5V-4.2V, charge-discharge magnification are 0.2C, its first discharge capacity be 147.6mAh/g, first charge-discharge still can reach 136.7mAh/g when efficiency for charge-discharge was 91.7%, 0.5C, sample has preferably charge-discharge performance.
Claims (1)
1. LiFePO that two carbon sources coat
4The two-step method preparation method of/C composite positive pole is characterized in that concrete steps are:
⑴ in-situ polymerization prepares presoma FePO
4/ PANI: by stoichiometric proportion, respectively with the Fe (NO of 0.0125mol-0.05mol
3)
3Be dissolved in the beaker 1 of the distilled water that 50ml-200ml is housed the (NH of 0.0125mol-0.05mol
4)
2HPO
4Be dissolved in the beaker 2 that 100ml-400ml distilled water is housed, and add 0.5ml-2ml aniline in beaker 2, magnetic agitation dropwise added solution in the beaker 1 in the beaker 2 after 5 minutes, added 0.5ml-2ml NH after dropwising in beaker 2 again
3H
2O regulates the pH value; Magnetic agitation is after 12 hours at normal temperatures, and vacuum filtration, and clean 2-3 time with distilled water is transferred to that drying namely got corresponding FePO in 24 hours in 60 ℃ of baking ovens
4/ PANI presoma;
⑵ LiFePO
4/ C composite manufacture: take by weighing 0.0125mol-0.05mol CH by stoichiometric proportion
3COOLi2H
2O is put in the agate mortar, adds the 10ml-20ml absolute ethyl alcohol and dissolves, and the presoma that step (1) is made adds further grinding in the mortar, grinds after 1 hour presoma and CH
3COOLi2H
2The ascorbic acid of the 5%-10% of O quality summation adds together and grinds, and adds simultaneously the 15ml-30ml absolute ethyl alcohol, treats to stop to grind and being transferred to the sintering that carries out next stage in the porcelain boat when batch mixing in the mortar is worn into jelly; Under argon atmosphere, 200 ℃ after-500 ℃ of lower pre-burning 3-5 hours, take out the DEXTROSE ANHYDROUS that adds 0.375g-1.500g and grind, carry out the sintering second time after grinding evenly, after 600 ℃ of-1000 ℃ of lower sintering 8-15 hours, namely get LiFePO
4/ C composite material;
Described Fe (NO
3)
3, (NH
4)
2HPO
4, aniline, NH
3H
2O, CH
3COOLi2H
2It is pure that O and ascorbic acid are analysis.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106654219A (en) * | 2017-01-12 | 2017-05-10 | 吉林大学 | Ion exchange assisted preparation method of LiFePO4/C nano composite material |
| CN107204461A (en) * | 2017-05-27 | 2017-09-26 | 广东烛光新能源科技有限公司 | A kind of anode material for lithium-ion batteries and preparation method thereof |
| CN109192953A (en) * | 2018-09-07 | 2019-01-11 | 桑顿新能源科技有限公司 | A kind of high magnification spherical LiFePO 4 carbon composite anode material and preparation method thereof |
| CN109638282A (en) * | 2018-12-19 | 2019-04-16 | 中科廊坊过程工程研究院 | A kind of cladded type lithium iron phosphate positive material and its preparation method and application |
| CN112615005A (en) * | 2020-12-17 | 2021-04-06 | 桂林理工大学 | Method for preparing lithium iron phosphate anode composite material with good electrochemical performance based on waste bagasse |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106654219A (en) * | 2017-01-12 | 2017-05-10 | 吉林大学 | Ion exchange assisted preparation method of LiFePO4/C nano composite material |
| CN107204461A (en) * | 2017-05-27 | 2017-09-26 | 广东烛光新能源科技有限公司 | A kind of anode material for lithium-ion batteries and preparation method thereof |
| CN107204461B (en) * | 2017-05-27 | 2019-11-05 | 广东烛光新能源科技有限公司 | A kind of anode material for lithium-ion batteries and preparation method thereof |
| CN109192953A (en) * | 2018-09-07 | 2019-01-11 | 桑顿新能源科技有限公司 | A kind of high magnification spherical LiFePO 4 carbon composite anode material and preparation method thereof |
| CN109192953B (en) * | 2018-09-07 | 2021-08-17 | 桑顿新能源科技(长沙)有限公司 | High-rate spherical lithium iron phosphate carbon composite cathode material and preparation method thereof |
| CN109638282A (en) * | 2018-12-19 | 2019-04-16 | 中科廊坊过程工程研究院 | A kind of cladded type lithium iron phosphate positive material and its preparation method and application |
| CN109638282B (en) * | 2018-12-19 | 2021-08-06 | 中科廊坊过程工程研究院 | Coated lithium iron phosphate cathode material and preparation method and application thereof |
| CN112615005A (en) * | 2020-12-17 | 2021-04-06 | 桂林理工大学 | Method for preparing lithium iron phosphate anode composite material with good electrochemical performance based on waste bagasse |
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