CN103187560B - A kind of sulphur carbon composite of imitative animal sclay texture and application thereof - Google Patents
A kind of sulphur carbon composite of imitative animal sclay texture and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 35
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 241001465754 Metazoa Species 0.000 title abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 33
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003763 carbonization Methods 0.000 claims abstract description 10
- 229910052786 argon Inorganic materials 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 239000012620 biological material Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 239000003575 carbonaceous material Substances 0.000 claims description 26
- 229920000742 Cotton Polymers 0.000 claims description 8
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 7
- 239000010406 cathode material Substances 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims 1
- 238000003760 magnetic stirring Methods 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 abstract description 18
- 239000011593 sulfur Substances 0.000 abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 230000014759 maintenance of location Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 238000000227 grinding Methods 0.000 abstract description 2
- 239000005864 Sulphur Substances 0.000 abstract 1
- 238000013019 agitation Methods 0.000 abstract 1
- 239000010405 anode material Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 7
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 241000270295 Serpentes Species 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
Description
（一）技术领域(1) Technical field
本发明涉及一种仿动物鳞片状结构的硫碳复合材料及其作为锂离子电池正极材料的应用。The invention relates to a sulfur-carbon composite material imitating an animal scale structure and its application as a positive electrode material of a lithium ion battery.
（二）背景技术(2) Background technology
锂离子电池是20世纪90年代初出现的新型绿色高能二次电池，已成为世界各国竞相研究开发的重点。正极材料是锂离子电池的一个重要组成部分，目前过渡金属氧化物（LiCoO2）和磷酸盐（LiFePO4）正极材料的最高理论比容量仅为300mAh/g，实际比容量则更低，采用这些正极材料构建的锂离子电池实际比能量约120～200Wh/Kg。为满足动力电池高比能量和高比功率的使用要求，近几年以锂硫电池为代表的新体系备受关注。单质硫的理论比容量为1672mAh/g，锂硫电池理论比能量高达2600Wh/kg，实际比能量可达500～800Wh/Kg。单质硫具有来源丰富、价格便宜、环境友好、电池安全性好等优点，因此，锂硫电池被认为是最具发展前景的绿色高能二次电池，一旦开发成功，在电动汽车等新能源汽车领域具有良好的发展前景。Lithium-ion battery is a new type of green high-energy secondary battery that appeared in the early 1990s, and has become the focus of research and development all over the world. Cathode materials are an important part of lithium-ion batteries. At present, the highest theoretical specific capacity of transition metal oxide (LiCoO 2 ) and phosphate (LiFePO 4 ) cathode materials is only 300mAh/g, and the actual specific capacity is even lower. Using these The actual specific energy of lithium-ion batteries constructed of cathode materials is about 120-200Wh/Kg. In order to meet the high specific energy and high specific power requirements of power batteries, new systems represented by lithium-sulfur batteries have attracted much attention in recent years. The theoretical specific capacity of elemental sulfur is 1672mAh/g, the theoretical specific energy of lithium-sulfur batteries is as high as 2600Wh/kg, and the actual specific energy can reach 500-800Wh/Kg. Elemental sulfur has the advantages of rich sources, cheap price, environmental friendliness, and good battery safety. Therefore, lithium-sulfur batteries are considered to be the most promising green high-energy secondary batteries. Once successfully developed, they will be used in new energy vehicles such as electric vehicles. Has a good development prospect.
目前，科研人员设计的锂硫电池正极结构主要为介孔碳、活性炭、中空碳球、导电聚合物包覆硫等，均是用导电基体包覆硫。以上导电基体合成成本高，得到的电极材料含硫量低，不能满足锂硫电池的大规模应用需求。At present, the positive electrode structures of lithium-sulfur batteries designed by researchers are mainly mesoporous carbon, activated carbon, hollow carbon spheres, conductive polymer-coated sulfur, etc., all of which are coated with conductive matrix sulfur. The synthesis cost of the above conductive matrix is high, and the obtained electrode material has low sulfur content, which cannot meet the large-scale application requirements of lithium-sulfur batteries.
自然界有很多动物生有鳞片，如鱼类、蛇类和两栖类动物，其鳞片层层相搭，不仅可防止水分蒸发，也起到隔绝外界物质和皮肤直接接触的作用。有鉴于鳞片的独特作用，本专利首先制备出鳞片状碳材料，然后将硫填充入鳞片状碳材料形成的间隙中。一方面，鳞片状碳材料间隙可以容纳大量硫，提高了含硫量，使得体积比容量大大增加；另一方面，鳞片状碳材料降低了硫与电解液的直接接触面积，提高了活性物质利用率。Many animals in nature have scales, such as fish, snakes and amphibians. The scales are layered together, which not only prevents water from evaporating, but also isolates external substances from direct contact with the skin. In view of the unique function of scales, this patent first prepares scale-like carbon materials, and then fills sulfur into the gaps formed by the scale-like carbon materials. On the one hand, the scale-like carbon material gap can accommodate a large amount of sulfur, increasing the sulfur content, which greatly increases the volume specific capacity; on the other hand, the scale-like carbon material reduces the direct contact area between sulfur and the electrolyte, improving the utilization of active materials. Rate.
（三）发明内容(3) Contents of the invention
本发明第一个目的是提供一种硫碳复合材料，该硫碳复合材料具有仿动物鳞片状结构，具有良好的导电性、高含硫量、高体积比容量以及良好的循环性能和容量保持率。The first object of the present invention is to provide a sulfur-carbon composite material, which has a scale-like structure imitating animals, has good electrical conductivity, high sulfur content, high volume specific capacity, and good cycle performance and capacity retention Rate.
本发明第二个目的是提供所述硫碳复合材料作为锂离子电池正极材料的应用。The second object of the present invention is to provide the application of the sulfur-carbon composite material as the positive electrode material of lithium-ion batteries.
下面具体说明本发明的技术方案。The technical solution of the present invention will be described in detail below.
本发明提供了一种硫碳复合材料，所述硫碳复合材料的制备方法包括如下步骤：The invention provides a sulfur-carbon composite material, and the preparation method of the sulfur-carbon composite material comprises the following steps:
（1）将纤维状中空生物材料在氮气或氩气保护下以5～20℃/min的升温速率升至400～1000℃进行碳化，碳化后冷却、研磨得到鳞片状碳材料；(1) Carbonize the fibrous hollow biological material at a heating rate of 5-20°C/min to 400-1000°C under the protection of nitrogen or argon, and then cool and grind after carbonization to obtain a scaly carbon material;
（2）将步骤（1）所得鳞片状碳材料与单质硫按质量比1：（2～10）分散于溶剂中，磁力搅拌至混合均匀，然后于80～200℃保温1～3小时；(2) Disperse the scaly carbon material obtained in step (1) and elemental sulfur in a solvent at a mass ratio of 1: (2-10), stir magnetically until uniformly mixed, and then keep warm at 80-200°C for 1-3 hours;
（3）冷却后过滤并干燥即得到硫碳复合材料。本发明制得的硫碳复合材料具有仿动物鳞片状结构。(3) After cooling, filter and dry to obtain the sulfur-carbon composite material. The sulfur-carbon composite material prepared by the invention has a scale-like structure imitating animals.
所述步骤（1）中，所述的生物材料为纤维状中空生物材料，优选棉花。升温速率优选为5～18℃/min，更优选为5～10℃/min，最优选为10℃/min；碳化温度优选为400～800℃，更优选为400～600℃，最优选为600℃；碳化时间优选为1～2小时。In the step (1), the biological material is a fibrous hollow biological material, preferably cotton. The heating rate is preferably 5-18°C/min, more preferably 5-10°C/min, most preferably 10°C/min; the carbonization temperature is preferably 400-800°C, more preferably 400-600°C, most preferably 600°C °C; the carbonization time is preferably 1 to 2 hours.
所述步骤（2）中，所述的溶剂能同时分散鳞片状碳材料和单质硫，优选聚乙二醇200。鳞片状碳材料和单质硫的质量比优选为1：2～8，更优选为1:4～6，最优选为1:4。保温温度优选为80～150℃，保温时间优选为1～2小时。In the step (2), the solvent can simultaneously disperse the scaly carbon material and elemental sulfur, preferably polyethylene glycol 200. The mass ratio of the scaly carbon material to the elemental sulfur is preferably 1:2-8, more preferably 1:4-6, and most preferably 1:4. The heat preservation temperature is preferably 80-150°C, and the heat preservation time is preferably 1-2 hours.
本发明具体推荐所述的硫碳复合材料按照如下步骤进行：The present invention specifically recommends that the described sulfur-carbon composite material be carried out according to the following steps:
（1）将棉花在氮气或氩气保护下以5～10℃/min的升温速率升至400～600℃碳化1～2小时，然后冷却、研磨得到鳞片状碳材料；(1) Under the protection of nitrogen or argon, the cotton is carbonized at a heating rate of 5-10°C/min to 400-600°C for 1-2 hours, then cooled and ground to obtain a scaly carbon material;
（2）将步骤（1）所得鳞片状碳材料和单质硫按质量比1：4～6分散于聚乙二醇200中，磁力搅拌至混合均匀，然后于80～150℃保温1～2小时；(2) Disperse the scaly carbon material obtained in step (1) and elemental sulfur in polyethylene glycol 200 at a mass ratio of 1:4-6, stir magnetically until evenly mixed, and then keep warm at 80-150°C for 1-2 hours ;
（3）冷却后过滤并干燥即得到硫碳复合材料。(3) After cooling, filter and dry to obtain the sulfur-carbon composite material.
本发明还提供了所述的硫碳复合材料作为锂离子电池正极材料的应用，其中锂离子电池的制备采用常规方法。The present invention also provides the application of the sulfur-carbon composite material as the cathode material of the lithium ion battery, wherein the preparation of the lithium ion battery adopts a conventional method.
本发明与现有技术相比，其有益效果主要体现在：Compared with the prior art, the present invention has beneficial effects mainly reflected in:
（1）本发明采用廉价的纤维状中空生物材料（棉花等）为碳源，其纤维状结构在碳化过程中变脆坍塌，经过研磨后即可得到鳞片状碳材料，所用原材料来源广泛、易得到、价格低廉，易于工业化实施；制备工艺简单，无废水废气排放，因而对环境友好。(1) The present invention uses cheap fibrous hollow biomaterials (cotton, etc.) as the carbon source, and its fibrous structure becomes brittle and collapses during the carbonization process. After grinding, the scale-like carbon material can be obtained. The raw materials used are widely sourced and easily The method is easy to obtain, low in price, and easy to implement industrially; the preparation process is simple, and there is no discharge of waste water and waste gas, so it is friendly to the environment.
（2）本发明制备的硫碳复合材料具有仿动物鳞片状结构，硫紧密填充在鳞片状碳材料形成的间隙中，增加了硫与电子的接触机会，因此具有良好的导电性；由于鳞片状碳材料可形成大量间隙以填充硫，因此材料具有高含硫量；体积一定时，含硫量越高则体积比容量越大，因此材料具有高体积比容量；此外，硫被紧紧束缚在鳞片状碳材料形成的间隙中，此结构有效防止了硫的中间产物-多硫化锂向电解液中的溶解，抑制了穿梭效应，提高了硫的利用率，因此材料具有良好的容量保持率，可作为锂离子电池正极材料广泛应用于能量型锂离子电池等领域。(2) The sulfur-carbon composite material prepared by the present invention has a scale-like structure imitating animals, and sulfur is tightly filled in the gap formed by the scale-like carbon material, which increases the chance of contact between sulfur and electrons, so it has good conductivity; due to the scale-like Carbon materials can form a large number of gaps to fill sulfur, so the material has a high sulfur content; when the volume is constant, the higher the sulfur content, the greater the volume specific capacity, so the material has a high volume specific capacity; in addition, sulfur is tightly bound in In the gap formed by the scale-like carbon material, this structure effectively prevents the dissolution of lithium polysulfide, an intermediate product of sulfur, into the electrolyte, inhibits the shuttle effect, and improves the utilization rate of sulfur, so the material has a good capacity retention rate. It can be widely used as the cathode material of lithium-ion batteries in fields such as energy-type lithium-ion batteries.
（四）附图说明(4) Description of drawings
图1是鱼类的鳞片图形；Fig. 1 is the scale figure of fish;
图2是实施例1所制备的仿动物鳞片状硫碳复合材料的XRD衍射图；Fig. 2 is the XRD diffractogram of the imitation animal scale-shaped sulfur-carbon composite material prepared in embodiment 1;
图3是实施例1所制备的仿动物鳞片状硫碳复合材料的透射电子显微镜（TEM）照片；3 is a transmission electron microscope (TEM) photo of the animal-like scale-like sulfur-carbon composite material prepared in Example 1;
图4是实施例1所制备的模拟锂离子电池的循环性能图；Fig. 4 is the cycle performance diagram of the simulated lithium-ion battery prepared in embodiment 1;
图5是实施例1所制备的模拟锂离子电池的循环伏安图。5 is a cyclic voltammogram of the simulated lithium-ion battery prepared in Example 1.
（五）具体实施方法(5) Specific implementation methods
下面以具体实施例对本发明的技术方案做进一步说明，但本发明的保护范围不限于此。The technical solutions of the present invention will be further described below with specific examples, but the protection scope of the present invention is not limited thereto.
实施例1Example 1
将3g棉花放入管式炉中，在氮气或氩气的气氛下，以10℃/分钟的升温速率升至600℃并恒温1小时，自然冷却后研磨得到鳞片状碳材料，然后将所得鳞片状碳材料与单质硫按质量比1:4溶于聚乙二醇200中并搅拌至均匀，在100℃下保温2小时，冷却除去溶剂并干燥即得到产物。图2为该材料的XRD衍射图，对照标准卡，为结晶硫，未观察到碳的衍射峰。图3为该材料的透射电镜照片，由图可知产物为仿动物鳞片状结构。Put 3 g of cotton into a tube furnace, raise the temperature up to 600 °C at a rate of 10 °C/min in an atmosphere of nitrogen or argon and keep the temperature constant for 1 hour, cool naturally and grind to obtain a scaly carbon material, and then the obtained scales The carbonaceous material and elemental sulfur are dissolved in polyethylene glycol 200 at a mass ratio of 1:4 and stirred until uniform, kept at 100°C for 2 hours, cooled to remove the solvent and dried to obtain the product. Figure 2 is the XRD diffraction pattern of the material. Compared with the standard card, it is crystalline sulfur, and no diffraction peak of carbon is observed. Figure 3 is a transmission electron micrograph of the material, from which it can be seen that the product is a scale-like structure imitating animals.
用实施例1所制得的仿动物鳞片状硫碳复合材料按下述方法制成电极。Using the animal-like scale-like sulfur-carbon composite material prepared in Example 1, an electrode was made according to the following method.
以80:10:10的质量比分别称取仿动物鳞片状硫碳复合材料:乙炔黑:聚偏四氟乙烯，研磨均匀后制成电极，金属锂片为负极，电解液为1mol/LLiTFSI/DOL–DME(1:1)，聚丙烯微孔薄膜为隔膜，组装成模拟锂离子电池。图4为相应电池在0.25C、1.5–3.0V电压范围内的循环性能曲线，表明所测电池在0.25C有良好的循环性能和容量保持率，可以看出由实施例1制得的仿动物鳞片状硫碳复合材料在0.25C循环100次后的放电容量接近550mAh/g，容量保持率高达93%（图3），循环性能优异。从图5（锂离子电池的循环伏安图）看到，所制备的仿动物鳞片状硫碳复合材料可逆性非常好。Weigh the imitation animal scale-like sulfur-carbon composite material with a mass ratio of 80:10:10: acetylene black: polytetrafluoroethylene, and grind them evenly to make an electrode. The metal lithium sheet is the negative electrode, and the electrolyte is 1mol/LLiTFSI/ DOL–DME (1:1), polypropylene microporous film as a separator, assembled into a simulated lithium-ion battery. Figure 4 is the cycle performance curve of the corresponding battery in the voltage range of 0.25C and 1.5-3.0V, which shows that the measured battery has good cycle performance and capacity retention at 0.25C. It can be seen that the imitation animal prepared in Example 1 The discharge capacity of the scaly sulfur-carbon composite material after 100 cycles at 0.25C is close to 550mAh/g, the capacity retention rate is as high as 93% (Figure 3), and the cycle performance is excellent. It can be seen from Figure 5 (cyclic voltammogram of lithium-ion battery) that the prepared animal-like scale-like sulfur-carbon composite material has very good reversibility.
实施例2Example 2
将3g棉花放入管式炉中，在氮气或氩气的气氛下，以10℃/分钟的升温速率升至400℃并恒温1小时，自然冷却后研磨得到鳞片状碳材料，然后将所得鳞片状碳材料与单质硫按1:4溶于聚乙二醇200中并搅拌至均匀，在100℃下保温2小时，冷却后过滤并干燥即得到产物。Put 3g of cotton into a tube furnace, raise the temperature to 400°C at a rate of 10°C/min in an atmosphere of nitrogen or argon and keep the temperature constant for 1 hour, cool naturally and grind to obtain a scaly carbon material, and then the obtained scale The carbonaceous material and elemental sulfur were dissolved in polyethylene glycol 200 at a ratio of 1:4 and stirred until uniform, kept at 100°C for 2 hours, cooled, filtered and dried to obtain the product.
用所制得的仿动物鳞片状硫碳复合材料按实施例1的方法制成电极，组装成模拟锂离子电池，0.25C循环100次后的放电容量接近495mAh/g，容量保持率达80%，循环性能、可逆性能良好。The prepared animal-like scale-like sulfur-carbon composite material is used to make electrodes according to the method in Example 1, and assembled into a simulated lithium-ion battery. After 100 cycles at 0.25C, the discharge capacity is close to 495mAh/g, and the capacity retention rate reaches 80%. , Good cycle performance and reversible performance.
实施例3Example 3
将3g棉花放入管式炉中，在氮气或氩气的气氛下，以10℃/分钟的升温速率升至600℃并恒温1小时，自然冷却后研磨得到鳞片状碳材料，然后将所得鳞片状碳材料与单质硫按质量比1:6溶于聚乙二醇200中并搅拌至均匀，在100℃下保温2小时，冷却后过滤并干燥即得到产物。Put 3g of cotton into a tube furnace, raise the temperature to 600°C at a rate of 10°C/min in an atmosphere of nitrogen or argon, and keep the temperature constant for 1 hour. After natural cooling, grind to obtain a scaly carbon material, and then the obtained scales The carbonaceous material and elemental sulfur are dissolved in polyethylene glycol 200 at a mass ratio of 1:6 and stirred until uniform, kept at 100°C for 2 hours, cooled, filtered and dried to obtain the product.
用所制得的仿动物鳞片状硫碳复合材料按实施例1的方法制成电极，组装成模拟锂离子电池，0.25C循环100次后的放电容量接近472mAh/g，容量保持率达73%，循环性能、可逆性能良好。The prepared animal scale-like sulfur-carbon composite material is used to make electrodes according to the method of Example 1, and assembled into a simulated lithium-ion battery. After 100 cycles at 0.25C, the discharge capacity is close to 472mAh/g, and the capacity retention rate reaches 73%. , Good cycle performance and reversible performance.
实施例4Example 4
将3g棉花放入管式炉中，在氮气或氩气的气氛下，以5℃/分钟的升温速率升至600℃并恒温1小时，自然冷却后研磨得到鳞片状碳材料，然后将所得鳞片状碳材料与单质硫按质量比1:6溶于聚乙二醇200中并搅拌至均匀，在100℃下保温2小时，冷却后过滤并干燥即得到产物。Put 3g of cotton into a tube furnace, raise the temperature to 600°C at a rate of 5°C/min and keep the temperature constant for 1 hour under the atmosphere of nitrogen or argon, cool naturally and grind to obtain a scaly carbon material, and then the obtained scale The carbonaceous material and elemental sulfur are dissolved in polyethylene glycol 200 at a mass ratio of 1:6 and stirred until uniform, kept at 100°C for 2 hours, cooled, filtered and dried to obtain the product.
用所制得的仿动物鳞片状硫碳复合材料按实施例1的方法制成电极，组装成模拟锂离子电池，0.25C循环100次后的放电容量接近403mAh/g，容量保持率达62%。The prepared animal-like scale-like sulfur-carbon composite material is used to make electrodes according to the method of Example 1, and assembled into a simulated lithium-ion battery. After 100 cycles at 0.25C, the discharge capacity is close to 403mAh/g, and the capacity retention rate reaches 62%. .
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