CN102544479A - Preparation method of zinc cobaltate array/carbon cloth composite anode material of lithium ion battery - Google Patents
Preparation method of zinc cobaltate array/carbon cloth composite anode material of lithium ion battery Download PDFInfo
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- CN102544479A CN102544479A CN2011104218331A CN201110421833A CN102544479A CN 102544479 A CN102544479 A CN 102544479A CN 2011104218331 A CN2011104218331 A CN 2011104218331A CN 201110421833 A CN201110421833 A CN 201110421833A CN 102544479 A CN102544479 A CN 102544479A
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Abstract
The invention provides a preparation method of electrode material with zinc cobaltate array/carbon cloth composite structure. The preparation method comprises the steps of (1) cleaning a carbon cloth, and placing the carbon cloth in the inner liner of a high-pressure reaction kettle; (2) blending zinc nitrate 1mmol to 4mmol, cobalt nitrate 2mmol to 8mmol, ammonium fluoride 0mmol to 4mmol, and urea 5mmol to 10mmol, and dissolving in deionized water, and transferring to the inner liner of the high-pressure reaction kettle, heating the reaction kettle, cooling naturally to obtain a carbon cloth, on which an array sample grows; and (3) calcining the carbon cloth with the array sample to obtain the zinc cobaltate array/carbon cloth composite material. According to the invention, the method adopts the carbon cloth with good conductivity and low cost as the growth substrate to achieve good contact between the active material and the carbon cloth, thereby facilitating implantation/escape of lithium ion into/from the material and greatly preventing the sample profile from being destroyed during use. In addition, the three-dimensional array has high yield, and has huge advantage when being used as anode of the lithium ion battery, and the novel multi-stage composite structure has high practical value.
Description
Technical field
The invention belongs to energy storage of new generation field, particularly a kind of preparation method who is used for the cobalt acid zinc/carbon cloth composite material of lithium ion battery negative material.
Background technology
Lithium ion battery is current internationally recognized desirable chemical energy source; Have that volume is little, capacitance is big, the voltage advantages of higher; Be widely used in electronic products such as mobile phone, laptop computer, bigger development space will be brought to lithium ion battery in the electric automobile field that enlarges day by day.As everyone knows, it is big that nano material has specific area, and the ions diffusion path is short; Wriggling property strong with characteristics such as plasticity height, the electrode of processing discharges and recharges degree of polarization under big electric current little, the reversible capacity height; Have extended cycle life, suppressed the change in volume that charge and discharge process causes simultaneously.Therefore, the special microstructure and the pattern of combining nano material as intercalation materials of li ions, are expected to improve more effectively the reversible embedding lithium capacity and the cycle life of material with nano material and nano composite material.
Nanometer cobalt acid zinc is mainly used in the lithium ion battery negative material field.Its pattern has fundamental influence to the performance of lithium ion battery.Up to now, be main mainly about the research of cobalt acid zinc with nano particle, nano wire and nanometer sheet, these unordered nanostructures are embedding/are deviating from the process of lithium and are being easy to receive mutual volumetric stress; In addition, because physical dimension is single, exist self-conductive property poor, the ion transfer passage is few, and cycle life is low, problems such as high rate performance difference.So, design a kind of simple path, directly on the good conductive collector, obtaining orderly cobalt acid zinc array structure is pressing for of new type lithium ion battery electrode material future development.
Summary of the invention
The object of the invention is to provide a kind of method for preparing cobalt acid zinc array/carbon cloth negative pole of lithium ion battery with compound structure material.The present invention adopts Hydrothermal Preparation to go out evenly to be grown in the composite construction of the cobalt acid zinc array on carbon cloth surface, can solve effectively the unordered growth of material, electrode material among material self-conductive property difference and the conventional preparation technology combines with substrate insecure, be prone to efflorescence, discharge and recharge that change in volume is big, cyclicity difference and transmission path be than the problem of length.
The invention provides the preparation method of a kind of cobalt acid zinc array/carbon cloth composite construction electrode material, may further comprise the steps:
(1) cleans charcoal cloth, put into the autoclave liner;
(2) after being dissolved in the deionized water after 1～4mmol zinc nitrate, 2～8mmol cobalt nitrate, 0～4mmol ammonium fluoride and the mixing of 5～10mmol urea, be transferred in the autoclave liner, to the agitated reactor heating, natural cooling obtains the long carbon cloth that array sample is arranged;
(3) there is the carbon cloth calcining of array sample to obtain cobalt acid zinc array/carbon cloth composite material to long.
As optimization, the heating-up temperature of said agitated reactor is 120～180 ℃, heating time 5～10h.
As optimization, 400～500 ℃ of said calcining heats, calcination time 1～5h.
The present invention has following beneficial effect:
1. relatively poor to the used metal collector flexibility in present lithium ion battery field, the shortcoming that cost is higher, the present invention adopts the carbon cloth of good conductivity and cheapness as substrate; Make lithium ion cell electrode at superficial growth cobalt acid zinc; Help making low cost, the high performance lithium ion battery electrode, active material contacts very good with the carbon cloth of being worked out by carbon fiber simultaneously; Be convenient to strengthen electric transmission; Help the embedding of lithium ion in material/deviate from, weakened significantly ubiquity discharge and recharge in the ruined problem of sample topography, the multistage composite structure of this novelty has very high practical value.
2. to be grown in two-dimentional suprabasil nano material array output lower at present many, the problem of reaction process complicacy etc.The present invention adopts first that cobalt acid zinc array is the evenly firm length of hydrothermal reaction condition on the carbon cloth surface, and promptly sample is around growth around the individual carbon fibers, forms three-dimensional multilevel hierarchy, has increased the output of sample under with the homalographic situation greatly.In addition, this material is disposable synthetic, and method is simple, and reaction raw materials is with low cost, and is fast efficient, is beneficial to popularization.
3. adopt the cobalt acid zinc array/carbon cloth composite material of the inventive method preparation to have the specific area higher than particle; Can increase effectively with battery in the contact area of electrolyte; Electrode material is participated in the middle of the electrochemical reaction more fully, so material of the present invention has great advantage as lithium ion battery negative.The present invention simultaneously adopts hydro thermal method quickly synthesized material at a lower temperature, and method is simply effective, helps the promotion and application of the present invention at other metal oxides of preparation.
Description of drawings
Fig. 1 is the scanning electron microscope diagram of pure carbon cloth under 1500 times of amplification conditions;
Fig. 2 is the scanning electron microscope diagram of multistage cobalt acid zinc array/carbon cloth composite construction under 1000 times of amplification conditions;
Fig. 3 is the scanning electron microscope diagram of multistage cobalt acid zinc array/carbon cloth composite structure surface under 10000 times of amplification conditions.
Embodiment
Below through by instance the present invention being described in further detail, but following examples only are illustrative, and protection scope of the present invention does not receive the restriction of these embodiment.
Below in conjunction with concrete embodiment technical scheme of the present invention is further described:
Embodiment 1
With carbon cloth successively at acetone, water, in the ethanol ultrasonic cleaning clean, be cut into unified area (4cm * 2cm), get a slice carbon cloth and put into the autoclave liner after the drying.The 1mmol zinc nitrate; 2mmol cobalt nitrate and 5mmol urea are dissolved in the 35ml deionized water; Be transferred to the autoclave liner of putting into carbon cloth; The drying baker of putting into 120 ℃ to the stubborn good lid of agitated reactor reacts 5h, and reaction naturally cools to room temperature after finishing, and takes out sample and in Muffle furnace, calcines 2h under 400 ℃.But can find out from its electron scanning micrograph and have only a spot of carbon fiber to have neat array to exist that a large amount of carbon fiber surfaces in carbon cloth are not coated by cobalt acid zinc fully.
Embodiment 2
The cleaning way among the embodiment 1 is adopted in the cleaning of carbon cloth.The 1mmol zinc nitrate; The 2mmol cobalt nitrate; 2mmol ammonium fluoride and 5mmol urea are dissolved in the 35ml deionized water, are transferred to the autoclave liner of putting into carbon cloth, and the drying baker of putting into the stubborn good lid of agitated reactor 120 ℃ reacts 5h; Reaction naturally cools to room temperature after finishing, and length is calcined 2h at the sample on the carbon cloth under 400 ℃ in Muffle furnace.Obtain the cobalt acid zinc nano-wire array of very uniform sequential length on carbon cloth.Comparative example 1 can know that the adding ammonium fluoride is bigger to the influence of reaction system, and fluorine ion has promoted sample in the suprabasil growth of carbon cloth.Fig. 1 can see that for amplifying the electron scanning micrograph of 1500 times pure carbon cloth it is to be worked out by many carbon fibers, and the surface is very smooth, and every carbon fiber diameter probably is about 10 μ m.Fig. 2 has cobalt acid zinc array to amplify 1000 times scanning electron microscope diagram spectrum for long on the carbon cloth, from then on can find out carbon fiber surface about a lot of 10 μ m one deck cobalt acid zinc array in good order of having grown uniformly among the figure.Fig. 3 is the electron scanning micrograph of 10000 times of amplifications, and the diameter that can see every nano wire in the array is 50nm～120nm, length 4 μ m～6 μ m.
Embodiment 3
The cleaning of carbon cloth is fully according to the cleaning way among the embodiment 1.The 1mmol zinc nitrate; The 2mmol cobalt nitrate, 2mmol ammonium fluoride and 5mmol urea are dissolved in the 35ml deionized water, are transferred to the autoclave liner of putting into carbon cloth; The drying baker of putting into 120 ℃ to the stubborn good lid of agitated reactor reacts 5h; Reaction naturally cools to room temperature after finishing, and length is calcined 2h at the sample on the carbon cloth under 500 ℃ in Muffle furnace, obtains final cobalt acid zinc product.Calcining heat in this scheme is adjusted to 500 ℃; Other all do not do change; Also can obtain the cobalt acid zinc nano-wire array on carbon cloth of very uniform sequential length in the similar instance 2, but array and unlike product arrays in the middle of the instance 2 near 90 degree, but the angle of array has diminished.
Embodiment 4
The cleaning of carbon cloth is fully according to the cleaning way among the embodiment 1.The 2mmol zinc nitrate, the 4mmol cobalt nitrate, 2mmol ammonium fluoride and 5mmol urea are dissolved in the 35ml deionized water; Be transferred to the autoclave liner of putting into carbon cloth, the drying baker of putting into the stubborn good lid of agitated reactor 120 ℃ reacts 5h, and reaction naturally cools to room temperature after finishing; Length is calcined 2h at the sample on the carbon cloth under 400 ℃ in Muffle furnace; Also can obtain the cobalt acid zinc array on carbon cloth of very uniform sequential length in the similar embodiment 2, embodiment 4 is on the basis of embodiment 2, and the amount of zinc nitrate and cobalt nitrate has been strengthened one times; The obvious chap of nanowire size, and coating layer has been thickeied some.
Embodiment 5
The cleaning of carbon cloth is fully according to the cleaning way among the embodiment 1.The 4mmol zinc nitrate; The 8mmol cobalt nitrate, 4mmol ammonium fluoride and 8mmol urea are dissolved in the 60ml deionized water, are transferred to the autoclave liner of putting into carbon cloth; The drying baker of putting into 150 ℃ to the stubborn good lid of agitated reactor reacts 8h; Reaction naturally cools to room temperature after finishing, and length is calcined 1h at the sample on the carbon cloth under 450 ℃ in Muffle furnace, also can obtain the cobalt acid zinc array of very uniform sequential length on carbon cloth in the similar embodiment 4.
Embodiment 6
The cleaning of carbon cloth is fully according to the cleaning way among the embodiment 1.The 4mmol zinc nitrate; The 8mmol cobalt nitrate, 4mmol ammonium fluoride and 10mmol urea are dissolved in the 60ml deionized water, are transferred to the autoclave liner of putting into carbon cloth; The drying baker of putting into 180 ℃ to the stubborn good lid of agitated reactor reacts 10h; Reaction naturally cools to room temperature after finishing, and length is calcined 5h at the sample on the carbon cloth under 500 ℃ in Muffle furnace, also can obtain the cobalt acid zinc array in the similar embodiment 5.
The present invention not only is confined to above-mentioned embodiment; Persons skilled in the art are according to content disclosed by the invention; Can adopt other multiple embodiment embodiment of the present invention, therefore, every employing project organization of the present invention and thinking; Do some simple designs that change or change, all fall into the scope of the present invention's protection.
Claims (3)
1. the preparation method of cobalt acid zinc array/carbon cloth composite construction electrode material may further comprise the steps:
(1) cleans charcoal cloth, put into the autoclave liner;
(2) after being dissolved in the deionized water after 1～4mmol zinc nitrate, 2～8mmol cobalt nitrate, 0～4mmol ammonium fluoride and the mixing of 5～10mmol urea, be transferred in the autoclave liner, to the agitated reactor heating, natural cooling obtains the long carbon cloth that array sample is arranged;
(3) there is the carbon cloth calcining of array sample to obtain cobalt acid zinc array/carbon cloth composite material to long.
2. preparation method according to claim 1 is characterized in that, the heating-up temperature of said agitated reactor is 120～180 ℃, heating time 5～10h.
3. preparation method according to claim 1 is characterized in that, 400～500 ℃ of said calcining heats, calcination time 1～5h.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103325998A (en) * | 2013-05-15 | 2013-09-25 | 同济大学 | Flexible nano SnO2/Si composite lithium ion battery negative-electrode material and preparation method thereof |
| CN103420431A (en) * | 2013-07-31 | 2013-12-04 | 上海理工大学 | Preparation method ofzinc cobaltatenanometer material doped with zinc oxide |
| CN103956483A (en) * | 2014-04-30 | 2014-07-30 | 新疆维吾尔自治区产品质量监督检验研究院 | Preparation method and application of zinc cobaltate/nickel oxide core-shell nanowire array |
| CN104616900A (en) * | 2015-01-23 | 2015-05-13 | 三峡大学 | Cobalt-nickel metal sulfide, preparation method and application thereof |
| CN105720270A (en) * | 2016-02-02 | 2016-06-29 | 陕西科技大学 | Preparation method of flexible anode material beta-ZnMoO4 for lithium-ion battery |
| CN106340403A (en) * | 2016-09-30 | 2017-01-18 | 江苏大学 | Preparation method and purpose of zinc cobaltate nano wire or nanometer band electrode material |
| CN106410203A (en) * | 2016-11-11 | 2017-02-15 | 南京理工大学 | Method for preparing spherical zinc cobaltate/carbon composite material by using metal alkoxide as precursor |
| CN107634206A (en) * | 2017-09-15 | 2018-01-26 | 江苏科技大学 | A kind of lithium ion battery flexibility negative material and preparation method thereof |
| CN108539183A (en) * | 2018-05-14 | 2018-09-14 | 山东玉皇新能源科技有限公司 | Lithium titanate composite material and preparation method thereof and lithium ion battery negative material and lithium ion battery |
| CN110224128A (en) * | 2019-06-21 | 2019-09-10 | 南京农业大学 | Cobalt acid zinc nano-array material of a kind of PVA pyrolysis carbon coated and preparation method thereof, application |
| CN114149787A (en) * | 2021-10-09 | 2022-03-08 | 东风汽车集团股份有限公司 | Anti-ice hydrophobic agent for fuel cell, microporous layer slurry and GDL and preparation method thereof |
| CN114525551A (en) * | 2022-03-24 | 2022-05-24 | 湖南祯晟炭素实业有限公司 | Preparation method of carbon composite material for aluminum electrolysis cell cathode integrated molding |
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| CN101465416A (en) * | 2008-12-31 | 2009-06-24 | 大连海事大学 | High specific capacity composite electrode pole piece for lithium ion battery |
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| CN102270761A (en) * | 2010-06-03 | 2011-12-07 | 上海空间电源研究所 | Method for making integrated flexible organic free radical electrode |
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| WO2010002084A1 (en) * | 2008-06-30 | 2010-01-07 | Korea Institute Of Science And Technology | Anode for secondary battery having negative active material with multi-component metal oxide nanofiber web structure and secondary battery using the same, and fabrication method of negative active material for secondary battery |
| CN101465416A (en) * | 2008-12-31 | 2009-06-24 | 大连海事大学 | High specific capacity composite electrode pole piece for lithium ion battery |
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103325998A (en) * | 2013-05-15 | 2013-09-25 | 同济大学 | Flexible nano SnO2/Si composite lithium ion battery negative-electrode material and preparation method thereof |
| CN103420431A (en) * | 2013-07-31 | 2013-12-04 | 上海理工大学 | Preparation method ofzinc cobaltatenanometer material doped with zinc oxide |
| CN103420431B (en) * | 2013-07-31 | 2014-10-08 | 上海理工大学 | Preparation method ofzinc cobaltatenanometer material doped with zinc oxide |
| CN103956483A (en) * | 2014-04-30 | 2014-07-30 | 新疆维吾尔自治区产品质量监督检验研究院 | Preparation method and application of zinc cobaltate/nickel oxide core-shell nanowire array |
| CN103956483B (en) * | 2014-04-30 | 2016-01-13 | 新疆维吾尔自治区产品质量监督检验研究院 | The preparation method and application of cobalt acid zinc/nickel oxide core-shell nano linear array |
| CN104616900B (en) * | 2015-01-23 | 2017-11-10 | 三峡大学 | A kind of cobalt nickel bimetal sulfide, preparation method and applications |
| CN104616900A (en) * | 2015-01-23 | 2015-05-13 | 三峡大学 | Cobalt-nickel metal sulfide, preparation method and application thereof |
| CN105720270A (en) * | 2016-02-02 | 2016-06-29 | 陕西科技大学 | Preparation method of flexible anode material beta-ZnMoO4 for lithium-ion battery |
| CN106340403A (en) * | 2016-09-30 | 2017-01-18 | 江苏大学 | Preparation method and purpose of zinc cobaltate nano wire or nanometer band electrode material |
| CN106410203A (en) * | 2016-11-11 | 2017-02-15 | 南京理工大学 | Method for preparing spherical zinc cobaltate/carbon composite material by using metal alkoxide as precursor |
| CN106410203B (en) * | 2016-11-11 | 2019-07-12 | 南京理工大学 | A method of using metal alkoxide as precursor preparation spherical shape cobalt acid zinc/carbon composite |
| CN107634206A (en) * | 2017-09-15 | 2018-01-26 | 江苏科技大学 | A kind of lithium ion battery flexibility negative material and preparation method thereof |
| CN107634206B (en) * | 2017-09-15 | 2020-06-05 | 江苏科技大学 | Flexible negative electrode material of lithium ion battery and preparation method thereof |
| CN108539183A (en) * | 2018-05-14 | 2018-09-14 | 山东玉皇新能源科技有限公司 | Lithium titanate composite material and preparation method thereof and lithium ion battery negative material and lithium ion battery |
| CN108539183B (en) * | 2018-05-14 | 2020-09-25 | 山东玉皇新能源科技有限公司 | Lithium titanate composite material and preparation method thereof, lithium ion battery cathode material and lithium ion battery |
| CN110224128A (en) * | 2019-06-21 | 2019-09-10 | 南京农业大学 | Cobalt acid zinc nano-array material of a kind of PVA pyrolysis carbon coated and preparation method thereof, application |
| CN114149787A (en) * | 2021-10-09 | 2022-03-08 | 东风汽车集团股份有限公司 | Anti-ice hydrophobic agent for fuel cell, microporous layer slurry and GDL and preparation method thereof |
| CN114525551A (en) * | 2022-03-24 | 2022-05-24 | 湖南祯晟炭素实业有限公司 | Preparation method of carbon composite material for aluminum electrolysis cell cathode integrated molding |
| CN114525551B (en) * | 2022-03-24 | 2022-10-11 | 湖南祯晟炭素实业有限公司 | Preparation method of carbon composite material for aluminum electrolysis cell cathode integrated molding |
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