CN102544479B - 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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- CN102544479B CN102544479B CN2011104218331A CN201110421833A CN102544479B CN 102544479 B CN102544479 B CN 102544479B CN 2011104218331 A CN2011104218331 A CN 2011104218331A CN 201110421833 A CN201110421833 A CN 201110421833A CN 102544479 B CN102544479 B CN 102544479B
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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 cobalt acid zinc for lithium ion battery negative material/carbon cloth composite manufacture method.
Background technology
Lithium ion battery is current internationally recognized desirable chemical energy source, have that volume is little, capacitance is large, the voltage advantages of higher, be widely used in the electronic products such as mobile phone, laptop computer, larger development space will be brought to lithium ion battery in the electric automobile field of expanding day.As everyone knows, it is large that nano material has specific area, and the ion the evolving path is short, strong and the plasticity high of wriggling property, the electrode of making discharges and recharges degree of polarization under large electric current little, and reversible capacity is high, have extended cycle life, suppressed simultaneously the change in volume that charge and discharge process causes.Therefore, special microstructure and the pattern of combining nano material as intercalation materials of li ions, are expected to more effectively improve Reversible lithium insertion 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 vital impact to the performance of lithium ion battery.Up to now, mainly take nano particle, nano wire and nanometer sheet as main, these unordered nanostructures are embedding/are deviating from the process of lithium and are being easy to be subject to mutual volumetric stress about the research of cobalt acid zinc; In addition, because physical dimension is single, exist self-conductive poor, the problems such as the ion transfer passage is few, and cycle life is low, and high rate performance is poor.So, design a kind of simple path, directly the good conductive collector obtain ordered cobalt acid zinc array structure be the future development of new type lithium ion battery electrode material in the urgent need to.
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 composite construction of the cobalt acid zinc array that the present invention adopts hydro thermal method to prepare evenly to be grown in the carbon cloth surface, can effectively solve the unordered growth of material among the poor and conventional preparation technology of material self-conductive, electrode material be combined with substrate insecure, easy efflorescence, discharge and recharge the problem that change in volume is large, cyclicity is poor and transmission path is grown.
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, reactor is heated, naturally 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 described reactor is 120～180 ℃, heating time 5～10h.
As optimization, 400～500 ℃ of described calcining heats, calcination time 1～5h.
The present invention has following beneficial effect:
1. relatively poor for 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, be conducive to make low-cost, the high performance lithium ion battery electrode, it is very good that the while active material contacts with the carbon cloth of being worked out by carbon fiber, be convenient to strengthen electric transmission, be conducive to the embedding of lithium ion in material/deviate from, significantly weakened ubiquity and discharged and recharged the destroyed problem of middle 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 complexity etc.The present invention adopts hydrothermal reaction condition first that cobalt acid zinc array is evenly firmly long on the carbon cloth surface, and namely sample is around growth around the individual carbon fibers, forms the three-dimensional multistage structure, has increased greatly the output of sample in the homalographic situation.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. the sour zinc array of the cobalt that adopts the inventive method to prepare/carbon cloth composite material has the specific area higher than particle, can effectively increase 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.Simultaneously the present invention adopts at a lower temperature quickly synthesized material of hydro thermal method, and method is simply effective, is conducive to the present invention in the promotion and application of 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 by by example the present invention being described in further detail, but following examples only are illustrative, and protection scope of the present invention is not subjected to the restriction of these embodiment.
Below in conjunction with specific 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 that the stubborn good lid of reactor is put into 120 ℃ reacts 5h, reaction naturally cools to room temperature after finishing, and takes out sample and 400 ℃ of lower calcining 2h in Muffle furnace.But can find out from its electron scanning micrograph and only have a small amount of carbon fiber to have neat array to exist that a large amount of carbon fiber surfaces in carbon cloth are not coated fully by cobalt acid zinc.
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, be transferred to the autoclave liner of putting into carbon cloth, the drying baker that the stubborn good lid of reactor is put into 120 ℃ reacts 5h, reaction naturally cools to room temperature after finishing, and is long at the 400 ℃ of lower calcining 2h in Muffle furnace of the sample on the carbon cloth.Obtain the cobalt acid zinc nano-wire array of very uniform sequential length on carbon cloth.Comparative example 1 as can be known, it is larger on the impact of reaction system to add ammonium fluoride, 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 longly on the carbon cloth has cobalt acid zinc array to amplify 1000 times scanning electron microscope diagram spectrum, 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, be transferred to the autoclave liner of putting into carbon cloth, the drying baker that the stubborn good lid of reactor is put into 120 ℃ reacts 5h, reaction naturally cools to room temperature after finishing, and is long at the 500 ℃ of lower calcining 2h in Muffle furnace of the sample on the carbon cloth, 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 example 2, but array and unlike product arrays in the middle of the example 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 that the stubborn good lid of reactor is put into 120 ℃ reacts 5h, reaction naturally cools to room temperature after finishing, long at the 400 ℃ of lower calcining 2h in Muffle furnace of the sample on the carbon cloth, also can obtain the cobalt acid zinc array of very uniform sequential length on carbon cloth in the similar embodiment 2, embodiment 4 is on the basis of embodiment 2, 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, be transferred to the autoclave liner of putting into carbon cloth, the drying baker that the stubborn good lid of reactor is put into 150 ℃ reacts 8h, reaction naturally cools to room temperature after finishing, and is long at the 450 ℃ of lower calcining 1h in Muffle furnace of the sample on the carbon cloth, 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, be transferred to the autoclave liner of putting into carbon cloth, the drying baker that the stubborn good lid of reactor is put into 180 ℃ reacts 10h, reaction naturally cools to room temperature after finishing, and is long at the 500 ℃ of lower calcining 5h in Muffle furnace of the sample on the carbon cloth, 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 to implement 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 protection of the invention.
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, reactor is heated, naturally 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 negative pole of lithium ion battery with compound structure material to long.
2. preparation method according to claim 1 is characterized in that, the heating-up temperature of described reactor is 120～180 ℃, heating time 5～10h.
3. preparation method according to claim 1 is characterized in that, 400～500 ℃ of described calcining heats, calcination time 1～5h.
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| CN103325998B (en) * | 2013-05-15 | 2016-01-20 | 同济大学 | Flexible nano SnO 2/ Si complex lithium ion battery cathode material and preparation method thereof |
| CN103420431B (en) * | 2013-07-31 | 2014-10-08 | 上海理工大学 | Preparation method ofzinc cobaltatenanometer material doped with zinc oxide |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| CN114149787B (en) * | 2021-10-09 | 2023-07-04 | 东风汽车集团股份有限公司 | Ice-repellent agent for fuel cell, microporous layer slurry and GDL, and method for preparing same |
| 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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| 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 |
| 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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| KR100907486B1 (en) * | 2008-06-30 | 2009-07-13 | 한국과학기술연구원 | 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| 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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