CN113292065B - Large-interlayer-spacing monodisperse nano hard carbon material, and synthesis method and application thereof - Google Patents
Large-interlayer-spacing monodisperse nano hard carbon material, and synthesis method and application thereof Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H—ELECTRICITY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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Abstract
Description
技术领域technical field
本发明总体涉及纳米硬碳材料，具体涉及一种大层间距单分散纳米硬碳材料、合成方法及其应用。The present invention generally relates to nanometer hard carbon materials, and in particular relates to a monodisperse nanometer hard carbon material with large interlayer spacing, a synthesis method and applications thereof.
背景技术Background technique
在碳达峰碳中和的战略之下，实现清洁能源太阳能、风能、水能等的有效利用的新型能源***如何构建引发广泛关注。大规模储能技术是实现智能电网***应用及普及所需的核心技术之一，目前以基于锂离子电池的电化学储能技术最受关注。近年来，锂离子电池在动力电池领域，3C领域等应用需求逐渐快速增长，但锂资源在地壳中储量并不丰富，而且中国的锂80％以上需要依赖进口，这非常不利于保障中国的能源安全。此外不丰富的锂资源使得基于锂离子电池的储能***几乎没有降本空间。作为锂离子电池的有效替代和补充，钠离子电池因具有资源丰富，价格低廉的优势是未来智能电网储能技术的重要选择。Under the strategy of carbon peaking and carbon neutrality, how to construct a new energy system that realizes the effective use of clean energy such as solar energy, wind energy, and water energy has attracted widespread attention. Large-scale energy storage technology is one of the core technologies required to realize the application and popularization of smart grid systems. At present, the electrochemical energy storage technology based on lithium-ion batteries is the most concerned. In recent years, the application demand of lithium-ion batteries in the field of power batteries and 3C fields has gradually increased rapidly, but the reserves of lithium resources in the earth's crust are not abundant, and more than 80% of China's lithium needs to be imported, which is very unfavorable to ensure China's energy. Safety. In addition, the lack of abundant lithium resources makes the energy storage system based on lithium-ion batteries almost no room for cost reduction. As an effective replacement and supplement of lithium-ion batteries, sodium-ion batteries are an important choice for future smart grid energy storage technology due to their abundant resources and low price.
钠元素作为与锂同族的元素，与锂有着相似的物理化学性质。与锂离子电池相似，钠离子电池也是由正负极，电解液等关键材料组成。要满足大规模储能应用的需求，合理的钠离子电池应具有高安全、低成本、长寿命等特性，而这些关键材料是决定钠离子电池性能能否达到需求的关键因素，所以对关键材料的研发对推动钠离子电池市场化至关重要。合适的负极材料是发展钠离子电池的关键之一。As an element of the same family as lithium, sodium element has similar physical and chemical properties with lithium. Similar to lithium-ion batteries, sodium-ion batteries are also composed of key materials such as positive and negative electrodes and electrolytes. To meet the needs of large-scale energy storage applications, a reasonable sodium-ion battery should have the characteristics of high safety, low cost, and long life, and these key materials are the key factors that determine whether the performance of the sodium-ion battery can meet the demand. The research and development of Na-ion batteries is crucial to promoting the marketization of sodium-ion batteries. Appropriate anode materials are one of the keys to the development of sodium-ion batteries.
锂离子电池商用化的石墨负极由于在酯基电解液中无法与钠离子形成热力学稳定化合物而无法应用。虽然后来发现醚基电解液中溶剂化钠离子可以共嵌到石墨中贡献容量，但是只有150mAh/g左右的比容量，这非常不利于发展高能量密度的钠离子全电池。硬碳材料由于具有较石墨更大的碳层间距，丰富的微孔和缺陷位点，可以提供丰富的储钠活性位点，能够提供＞300mAh/g的比容量，被认为是最有希望商业化的钠离子电池的负极材料。尤其是基于生物质原材料的硬碳成本低廉，绿色环保，近年来受到了广泛关注。一系列利用橘子皮、香蕉皮以及海藻等生物废弃物作为碳源制备的生物质硬碳被广泛的报道，但是基于这种生物废弃物制备的硬碳材料碳产率非常低(通常低于10％)，而且制备的硬碳状态非常依赖原材料的状态，一致性难以保障，且首周库伦效率往往较低(通常低于60％)，倍率性能和循环寿命通常也较差，难以满足钠离子电池商业化的要求。当前国内尚无或少有商用化的高端硬碳材料供应企业，国外日本个别企业拥有比较高端的硬碳材料，但价格昂贵，且属于特种新能源战略需求材料不允许出口，因此亟需探索其他的一些合成方法简单，一致性可控，成本低廉且储钠性能优异的硬碳材料来满足国内发展钠离子电池的需求。Commercially available graphite anodes for lithium-ion batteries cannot be used due to their inability to form thermodynamically stable compounds with sodium ions in ester-based electrolytes. Although it was later found that solvated sodium ions in ether-based electrolytes can be co-intercalated into graphite to contribute capacity, but only a specific capacity of about 150mAh/g, which is very unfavorable for the development of high-energy-density sodium-ion full batteries. Due to its larger carbon interlayer spacing, abundant micropores and defect sites than graphite, hard carbon materials can provide abundant sodium storage active sites and can provide a specific capacity of >300mAh/g, which is considered to be the most promising commercial material. anode material for sodium-ion batteries. In particular, hard carbon based on biomass raw materials is low-cost, green and environmentally friendly, and has received widespread attention in recent years. A series of biomass hard carbons prepared from biological wastes such as orange peel, banana peel and seaweed have been widely reported, but the carbon yield of hard carbon materials prepared based on this biological waste is very low (usually less than 10%). %), and the state of the prepared hard carbon is very dependent on the state of the raw materials, the consistency is difficult to guarantee, and the coulombic efficiency in the first week is often low (usually lower than 60%), the rate performance and cycle life are usually poor, and it is difficult to meet the sodium ion Requirements for battery commercialization. At present, there are no or few commercial high-end hard carbon material suppliers in China. Some Japanese companies in foreign countries have relatively high-end hard carbon materials, but they are expensive, and materials that are required for special new energy strategies are not allowed to be exported. Therefore, it is urgent to explore other Some of the hard carbon materials with simple synthetic methods, controllable consistency, low cost and excellent sodium storage properties can meet the needs of domestic development of sodium-ion batteries.
发明内容SUMMARY OF THE INVENTION
本发明的目的是提供一种具有大层间距单分散形貌的纳米硬碳材料的合成方法及其应用。本发明制备的硬碳材料具有平均粒径200nm左右的单分散的球形形貌，较低的比表面积，丰富的微孔，和大的层间距，拥有优异的电化学性能，是一种非常有商业化前景的金属离子电池负极材料。且提供的制备工艺简单，适合规模化生产。The purpose of the present invention is to provide a method for synthesizing a nano-hard carbon material with monodisperse morphology with large interlayer spacing and its application. The hard carbon material prepared by the invention has a monodisperse spherical morphology with an average particle size of about 200 nm, a low specific surface area, abundant micropores, and large interlayer spacing, and has excellent electrochemical performance, which is a very promising A promising metal-ion battery anode material for commercialization. In addition, the provided preparation process is simple and suitable for large-scale production.
根据本发明的第一方面，提供一种具有大层间距单分散形貌的纳米硬碳材料的合成方法，包括以下步骤：According to a first aspect of the present invention, there is provided a method for synthesizing a nano-hard carbon material with monodisperse morphology with large interlayer spacing, comprising the following steps:
(1)将木糖溶解于去离子水，搅拌至均匀，配置浓度为0.3-1.5M的溶液，并将该溶液加热到160～200℃进行脱水缩合反应；(1) Dissolve xylose in deionized water, stir until uniform, configure a solution with a concentration of 0.3-1.5M, and heat the solution to 160-200°C for dehydration condensation reaction;
(2)将步骤(1)得到的材料进行离心清洗，真空干燥；(2) the material obtained in step (1) is subjected to centrifugal cleaning and vacuum drying;
(3)将步骤(2)得到的材料在高温炉中保护气氛下进行高温碳化；温度为900～1500℃，碳化时间为2～5h，升温速率为2～8℃/min；得到大层间距单分散纳米硬碳材料。(3) carbonizing the material obtained in step (2) under a protective atmosphere in a high-temperature furnace; the temperature is 900-1500°C, the carbonization time is 2-5h, and the heating rate is 2-8°C/min; a large interlayer spacing is obtained Monodisperse nano-hard carbon materials.
进一步地，步骤(1)中，搅拌速度为100～1000rpm，搅拌时间为0.2～2h，搅拌温度为20～60℃。Further, in step (1), the stirring speed is 100-1000 rpm, the stirring time is 0.2-2 h, and the stirring temperature is 20-60°C.
进一步地，步骤(1)中脱水缩合反应的反应容器为密封反应釜，溶液填充量约为反应釜内胆容积的70％-80％，依靠高温产生的水蒸汽提供内部的反应压力。Further, in step (1), the reaction vessel of the dehydration condensation reaction is a sealed reaction kettle, and the filling amount of the solution is about 70%-80% of the inner volume of the reaction kettle, and the internal reaction pressure is provided by the water vapor generated by high temperature.
进一步地，步骤(2)中的保护气为氩气或氮气，保护气流速为150～400sccm。Further, the protective gas in step (2) is argon or nitrogen, and the protective gas flow rate is 150-400 sccm.
优选情况下，步骤(1)中脱水缩合反应的加热装置采用微波反应装置。微波反应器可以快速升温至脱水缩合温度有利于增加形核率，形成粒径更小，更均匀的单分散纳米硬碳前驱体，且反应速度极快，可以在0.5～2小时内完成脱水反应，有效节约时间成本。Preferably, the heating device for the dehydration condensation reaction in step (1) adopts a microwave reaction device. The microwave reactor can quickly heat up to the dehydration condensation temperature, which is beneficial to increase the nucleation rate and form a monodisperse nano-hard carbon precursor with smaller particle size and more uniformity, and the reaction speed is extremely fast, and the dehydration reaction can be completed within 0.5 to 2 hours. , effectively saving time and cost.
根据本发明的另一方面，提供采用上述合成方法制备的大层间距单分散纳米硬碳材料以及在金属离子电池负极中的应用。金属离子包括锂、钠、钾、钙、镁、铝等，优选作为钠离子电池负极材料。According to another aspect of the present invention, a monodisperse nano-hard carbon material with large interlayer spacing prepared by the above synthesis method and its application in a negative electrode of a metal ion battery are provided. Metal ions include lithium, sodium, potassium, calcium, magnesium, aluminum, etc., and are preferably used as negative electrode materials for sodium ion batteries.
具体情况下，提供一种钠离子电池，包括根据上述合成方法制备的硬碳负极材料所制备的负极、正极和电解液，其中电解液包含选自NaBF4、NaPF6、NaClO4、NaFSI和NaTFSI的钠盐以及选自碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、乙二醇二甲醚、二乙二醇二甲醚和四乙二醇二甲醚的有机溶剂。Specifically, a sodium-ion battery is provided, comprising a negative electrode, a positive electrode and an electrolyte prepared from the hard carbon negative electrode material prepared according to the above-mentioned synthesis method, wherein the electrolyte contains a material selected from the group consisting of NaBF 4 , NaPF 6 , NaClO 4 , NaFSI and NaTFSI and an organic solvent selected from the group consisting of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
优选情况下，根据本发明的钠离子电池，电解液优选为含有1MNaPF6的碳酸乙烯酯(EC)和碳酸二乙酯(DEC)，其中碳酸乙烯酯(EC)和碳酸二乙酯(DEC)两者体积比为1:1。Preferably, according to the sodium ion battery of the present invention, the electrolyte is preferably ethylene carbonate (EC) and diethyl carbonate (DEC) containing 1M NaPF 6 , wherein ethylene carbonate (EC) and diethyl carbonate (DEC) The volume ratio of the two is 1:1.
优选情况下，根据本发明的钠离子电池，其中负极是将上述硬碳负极材料、乙炔黑和粘结剂(例如海藻酸钠(SA))以质量比8:1:1的比例均匀研磨后与溶剂(例如去离子水)混合后制得负极浆料，并涂覆在铜箔集流体之上制得。Preferably, according to the sodium ion battery of the present invention, the negative electrode is obtained by uniformly grinding the above-mentioned hard carbon negative electrode material, acetylene black and a binder (such as sodium alginate (SA)) in a mass ratio of 8:1:1 The negative electrode slurry is prepared by mixing with a solvent (such as deionized water), and is prepared by coating on the copper foil current collector.
与现有技术相比，本发明具有以下优点和技术效果:Compared with the prior art, the present invention has the following advantages and technical effects:
本发明制备的硬碳材料使用木糖为碳源。木糖是一种由木屑、稻草、玉米芯等富含半纤维素的植物经水解而得的一种五碳糖，所以将木糖作为碳源可以具有非常低的原料成本，有利于降低负极材料成本，从而可以有效的降低电池的成本。本发明中使用的木糖为五碳糖，在加热脱水过程中会脱水生成中间产物呋喃甲醛，呋喃甲醛具有疏水性，所以碳球成核生长过程中倾向于生成单分散的纳米碳球。而蔗糖，葡萄糖等常用原料水热过程中中间产物是羟基甲基糠醛，上面的羟基使其具有亲水性，所以最后水热的产品往往是相互粘连的碳球。单分散的纳米碳球形貌使得表面活性位点利用更充分，钠离子扩散路径更短，有利于钠离子的吸附和扩散，有助于提高比容量。本发明提供的制备方法可以有效控制硬碳的一致性，且碳产率高于20％，远高于报道过的生物质硬碳，合成的硬碳材料具有较大的碳层间距超过0.4nm，远大于石墨和一些报道过的硬碳材料，大层间距能够提供钠离子快速传输和存储的通道和空间；纳米尺度的粒径有利于缩短扩散路径，保证材料在快充时有快速的动力学；纳米尺度的粒径兼具相对较低的比表面积保证了倍率性能的同时又不会引起电解液的过度分解，实现高倍率和高首效兼得；丰富的微孔结构，可提供丰富的钠离子的脱嵌和吸附位点，贡献容量，叠加大层间距的容量贡献实现高的比容量；最后单分散的形貌有利于活性比表面的有效利用，有利于提高比容量和倍率性能。综上，该大层间距单分散的纳米硬碳材料兼具低成本，高比容量，高首效，高倍率性能等优势，具有非常好的商用化前景。The hard carbon material prepared by the present invention uses xylose as a carbon source. Xylose is a five-carbon sugar obtained by hydrolysis of hemicellulose-rich plants such as sawdust, straw, corncob, etc., so using xylose as a carbon source can have very low raw material cost, which is beneficial to reduce the negative electrode Material cost, which can effectively reduce the cost of the battery. The xylose used in the present invention is a five-carbon sugar, which will be dehydrated in the process of heating and dehydration to generate an intermediate product, furancarboxaldehyde, which has hydrophobicity, so it tends to generate monodisperse nano carbon spheres during the nucleation and growth of carbon spheres. The intermediate product in the hydrothermal process of common raw materials such as sucrose and glucose is hydroxymethyl furfural, and the hydroxyl group on it makes it hydrophilic, so the final hydrothermal product is often carbon spheres that adhere to each other. The monodisperse nanocarbon sphere morphology makes the surface active sites more fully utilized, and the sodium ion diffusion path is shorter, which is beneficial to the adsorption and diffusion of sodium ions, and helps to improve the specific capacity. The preparation method provided by the present invention can effectively control the consistency of hard carbon, and the carbon yield is higher than 20%, which is much higher than the reported biomass hard carbon, and the synthesized hard carbon material has a large carbon layer spacing exceeding 0.4nm , much larger than graphite and some reported hard carbon materials, the large interlayer spacing can provide channels and spaces for the rapid transmission and storage of sodium ions; the nano-scale particle size is conducive to shortening the diffusion path and ensuring the material has fast power during fast charging The nano-scale particle size and relatively low specific surface area ensure the rate performance without causing excessive decomposition of the electrolyte, achieving both high rate and high first effect; rich microporous structure can provide rich The deintercalation and adsorption sites of sodium ions contribute to the capacity, and the capacity contribution of the superimposed large interlayer spacing achieves a high specific capacity; the final monodisperse morphology is conducive to the effective use of the active specific surface, and is conducive to improving the specific capacity and rate performance. . In conclusion, the monodispersed nano-hard carbon material with large interlayer spacing has the advantages of low cost, high specific capacity, high first efficiency, and high rate performance, and has a very good commercialization prospect.
附图说明Description of drawings
图1为本发明实施例1制备的大层间距单分散形貌的纳米硬碳材料的SEM图。FIG. 1 is a SEM image of the nano-hard carbon material with large interlayer spacing and monodisperse morphology prepared in Example 1 of the present invention.
图2为本发明实施例1制备的大层间距单分散形貌的纳米硬碳材料的XRD图。2 is an XRD pattern of the nano-hard carbon material with large interlayer spacing and monodisperse morphology prepared in Example 1 of the present invention.
图3为本发明实施例1制备的大层间距单分散形貌的纳米硬碳材料的氮气吸脱附曲线图。3 is a nitrogen adsorption and desorption curve diagram of the nano-hard carbon material with large interlayer spacing and monodisperse morphology prepared in Example 1 of the present invention.
图4为本发明实施例1制备的大层间距单分散形貌的纳米硬碳材料的孔径分布图。4 is a pore size distribution diagram of the nano-hard carbon material with large interlayer spacing and monodisperse morphology prepared in Example 1 of the present invention.
具体实施方式Detailed ways
为了更好的理解本发明，下面通过实施例对本发明进一步说明，实施例只用于解释本发明，并不构成对本发明的限制。For a better understanding of the present invention, the present invention is further described below through examples, which are only used to explain the present invention and do not constitute a limitation to the present invention.
实施例1Example 1
一种大层间距单分散形貌的纳米硬碳材料的制备方法，包括以下步骤：A preparation method of nano-hard carbon material with large interlayer spacing and monodisperse morphology, comprising the following steps:
(1)将木糖溶解于去离子水，搅拌至均匀，配置浓度为0.73M的溶液，其中搅拌速度为500rpm，搅拌时间为0.5h，搅拌温度为30℃，并将该溶液加热到180℃进行脱水缩合反应24h；(1) Dissolve xylose in deionized water, stir until uniform, configure a solution with a concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, and the stirring temperature is 30°C, and the solution is heated to 180°C Carry out dehydration condensation reaction for 24h;
(2)将步骤(1)得到的材料高速离心清洗，真空干燥，干燥温度60℃，时间24h；(2) high-speed centrifugal cleaning of the material obtained in step (1), vacuum drying, drying temperature 60°C, time 24h;
(3)将步骤(2)得到的材料在高温炉中氩气气氛下进行高温碳化；温度为1200℃，碳化时间为3h，升温速率为5℃/min；氩气流速为200sccm，得到大层间距单分散的纳米硬碳材料。(3) carbonizing the material obtained in step (2) at a high temperature under an argon atmosphere in a high-temperature furnace; the temperature is 1200° C., the carbonization time is 3h, and the heating rate is 5° C./min; the argon gas flow rate is 200sccm to obtain a large layer Pitch monodispersed nanohard carbon materials.
图1为本实施例制备的大层间距单分散的纳米硬碳材料的SEM图，可以看到材料粒径范围160～230nm，具有单分散的特征。FIG. 1 is an SEM image of the monodispersed nano-hard carbon material with large interlayer spacing prepared in this example. It can be seen that the particle size of the material ranges from 160 to 230 nm and has the characteristics of monodispersity.
图2展示了本实施例制备的大层间距单分散的纳米硬碳材料的XRD图，通过布拉格方程可以计算出碳层间距为0.41nm，远大于石墨的碳层间距和一些报道过的硬碳材料，大层间距能够有效容纳钠离子的脱嵌。Figure 2 shows the XRD pattern of the monodisperse nano-hard carbon material with large interlayer spacing prepared in this example. The Bragg equation can calculate the carbon interlayer spacing to be 0.41 nm, which is much larger than that of graphite and some reported hard carbons. materials, the large interlayer spacing can effectively accommodate the deintercalation of sodium ions.
图3为本实施例制备的大层间距单分散的纳米硬碳材料的N2吸脱附曲线图，得到的BET比表面积为292m2/g.较低的比表面积有利于减少电解液在材料表面的分解，从而减少首周不可逆容量。Fig. 3 is the N 2 adsorption and desorption curve diagram of the monodispersed nano-hard carbon material with large interlayer spacing prepared in this example, and the obtained BET specific surface area is 292 m 2 /g. The lower specific surface area is beneficial to reduce the amount of electrolyte in the material decomposition of the surface, thereby reducing the irreversible capacity of the first week.
图4为本实施例制备的大层间距单分散的纳米硬碳材料的孔径分布图，制备的硬碳材料富含微孔，基本不含有介孔，微孔可作为储钠的活性位点，所以丰富的微孔可以提供较高的比容量。Fig. 4 is a pore size distribution diagram of the monodispersed nano-hard carbon material with large interlayer spacing prepared in this example. The prepared hard carbon material is rich in micropores and basically does not contain mesopores, and the micropores can be used as active sites for sodium storage. So abundant micropores can provide higher specific capacity.
实施例2Example 2
一种大层间距单分散的纳米硬碳材料的制备方法，包括以下步骤：A preparation method of a monodispersed nano-hard carbon material with large interlayer spacing, comprising the following steps:
将木糖溶解于去离子水，搅拌至均匀，配置浓度为0.73M的溶液，其中搅拌速度为500rpm，搅拌时间为0.5h，搅拌温度为30℃，并将该溶液加热到190℃进行脱水缩合反应24h；Dissolve xylose in deionized water, stir until uniform, configure a solution with a concentration of 0.73M, wherein the stirring speed is 500 rpm, the stirring time is 0.5 h, and the stirring temperature is 30 ° C, and the solution is heated to 190 ° C for dehydration condensation Reaction 24h;
(2)将步骤(1)得到的材料高速离心清洗，真空干燥，干燥温度60℃，时间24h；(2) high-speed centrifugal cleaning of the material obtained in step (1), vacuum drying, drying temperature 60°C, time 24h;
(3)将步骤(2)得到的材料在高温炉中氩气气氛下进行高温碳化；温度为1200℃，碳化时间为3h，升温速率为5℃/min；氩气流速为200sccm，得到大层间距单分散的纳米硬碳材料。(3) carbonizing the material obtained in step (2) at a high temperature under an argon atmosphere in a high-temperature furnace; the temperature is 1200° C., the carbonization time is 3h, and the heating rate is 5° C./min; the argon gas flow rate is 200sccm to obtain a large layer Pitch monodispersed nanohard carbon materials.
实施例3Example 3
一种大层间距单分散的纳米硬碳材料的制备方法，包括以下步骤：A preparation method of a monodispersed nano-hard carbon material with large interlayer spacing, comprising the following steps:
将木糖溶解于去离子水，搅拌至均匀，配置浓度为0.73M的溶液，其中搅拌速度为500rpm，搅拌时间为0.5h，搅拌温度为30℃，并将该溶液加热到200℃进行脱水缩合反应24h；Dissolve xylose in deionized water, stir until uniform, configure a solution with a concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, and the stirring temperature is 30 °C, and the solution is heated to 200 °C for dehydration condensation Reaction 24h;
(2)将步骤(1)得到的材料高速离心清洗，真空干燥，干燥温度60℃，时间24h；(2) high-speed centrifugal cleaning of the material obtained in step (1), vacuum drying, drying temperature 60°C, time 24h;
(3)将步骤(2)得到的材料在高温炉中氩气气氛下进行高温碳化；温度为1200℃，碳化时间为3h，升温速率为5℃/min；氩气流速为200sccm，得到大层间距单分散的纳米硬碳材料。(3) carbonizing the material obtained in step (2) at a high temperature under an argon atmosphere in a high-temperature furnace; the temperature is 1200° C., the carbonization time is 3h, and the heating rate is 5° C./min; the argon gas flow rate is 200sccm to obtain a large layer Pitch monodispersed nanohard carbon materials.
实施例4Example 4
一种大层间距单分散的纳米硬碳材料的制备方法，包括以下步骤：A preparation method of a monodispersed nano-hard carbon material with large interlayer spacing, comprising the following steps:
(1)将木糖溶解于去离子水，搅拌至均匀，配置浓度为0.73M的溶液，其中搅拌速度为500rpm，搅拌时间为0.5h，搅拌温度为30℃，并将该溶液加热到170℃进行脱水缩合反应24h；(1) Dissolve xylose in deionized water, stir until uniform, configure a solution with a concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, and the stirring temperature is 30°C, and the solution is heated to 170°C Carry out dehydration condensation reaction for 24h;
(2)将步骤(1)得到的材料高速离心清洗，真空干燥，干燥温度60℃，时间24h；(2) high-speed centrifugal cleaning of the material obtained in step (1), vacuum drying, drying temperature 60°C, time 24h;
(3)将步骤(2)得到的材料在高温炉中氩气气氛下进行高温碳化；温度为1200℃，碳化时间为3h，升温速率为5℃/min；氩气流速为200sccm，得到大层间距单分散的纳米硬碳材料。(3) carbonizing the material obtained in step (2) at a high temperature under an argon atmosphere in a high-temperature furnace; the temperature is 1200° C., the carbonization time is 3h, and the heating rate is 5° C./min; the argon gas flow rate is 200sccm to obtain a large layer Pitch monodispersed nanohard carbon materials.
实施例5Example 5
一种大层间距单分散的纳米硬碳材料的制备方法，包括以下步骤：A preparation method of a monodispersed nano-hard carbon material with large interlayer spacing, comprising the following steps:
(1)将木糖溶解于去离子水，搅拌至均匀，配置浓度为0.73M的溶液，其中搅拌速度为500rpm，搅拌时间为0.5h，搅拌温度为30℃，并将该溶液加热到160℃进行脱水缩合反应24h；(1) Dissolve xylose in deionized water, stir until uniform, configure a solution with a concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, and the stirring temperature is 30°C, and the solution is heated to 160°C Carry out dehydration condensation reaction for 24h;
(2)将步骤(1)得到的材料高速离心清洗，真空干燥，干燥温度60℃，时间24h；(2) high-speed centrifugal cleaning of the material obtained in step (1), vacuum drying, drying temperature 60°C, time 24h;
(3)将步骤(2)得到的材料在高温炉中氩气气氛下进行高温碳化；温度为1200℃，碳化时间为3h，升温速率为5℃/min；氩气流速为200sccm，得到大层间距单分散的纳米硬碳材料。(3) carbonizing the material obtained in step (2) at a high temperature under an argon atmosphere in a high-temperature furnace; the temperature is 1200° C., the carbonization time is 3h, and the heating rate is 5° C./min; the argon gas flow rate is 200sccm to obtain a large layer Pitch monodispersed nanohard carbon materials.
实施例6Example 6
一种大层间距单分散的纳米硬碳材料的制备方法，包括以下步骤：A preparation method of a monodispersed nano-hard carbon material with large interlayer spacing, comprising the following steps:
(1)将木糖溶解于去离子水，搅拌至均匀，配置浓度为0.73M的溶液，其中搅拌速度为500rpm，搅拌时间为0.5h，搅拌温度为30℃，并将该溶液加热到180℃进行脱水缩合反应24h；(1) Dissolve xylose in deionized water, stir until uniform, configure a solution with a concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, and the stirring temperature is 30°C, and the solution is heated to 180°C Carry out dehydration condensation reaction for 24h;
(2)将步骤(1)得到的材料高速离心清洗，真空干燥，干燥温度60℃，时间24h；(2) high-speed centrifugal cleaning of the material obtained in step (1), vacuum drying, drying temperature 60°C, time 24h;
(3)将步骤(2)得到的材料在高温炉中氩气气氛下进行高温碳化；温度为900℃，碳化时间为3h，升温速率为5℃/min；氩气流速为200sccm，得到大层间距单分散的纳米硬碳材料。(3) carbonizing the material obtained in step (2) at a high temperature under an argon atmosphere in a high-temperature furnace; the temperature is 900°C, the carbonization time is 3h, and the heating rate is 5°C/min; the flow rate of argon is 200sccm to obtain a large layer Pitch monodispersed nanohard carbon materials.
实施例7Example 7
一种大层间距单分散的纳米硬碳材料的制备方法，包括以下步骤：A preparation method of a monodispersed nano-hard carbon material with large interlayer spacing, comprising the following steps:
(1)将木糖溶解于去离子水，搅拌至均匀，配置浓度为0.73M的溶液，其中搅拌速度为500rpm，搅拌时间为0.5h，搅拌温度为30℃，并将该溶液加热到180℃进行脱水缩合反应24h；(1) Dissolve xylose in deionized water, stir until uniform, configure a solution with a concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, and the stirring temperature is 30°C, and the solution is heated to 180°C Carry out dehydration condensation reaction for 24h;
(2)将步骤(1)得到的材料高速离心清洗，真空干燥，干燥温度60℃，时间24h；(2) high-speed centrifugal cleaning of the material obtained in step (1), vacuum drying, drying temperature 60°C, time 24h;
(3)将步骤(2)得到的材料在高温炉中氩气气氛下进行高温碳化；温度为1000℃，碳化时间为3h，升温速率为5℃/min；氩气流速为200sccm，得到大层间距单分散的纳米硬碳材料。(3) carbonizing the material obtained in step (2) at a high temperature under an argon atmosphere in a high-temperature furnace; the temperature is 1000° C., the carbonization time is 3h, and the heating rate is 5° C./min; the argon gas flow rate is 200sccm to obtain a large layer Pitch monodispersed nanohard carbon materials.
实施例8Example 8
一种大层间距单分散的纳米硬碳材料的制备方法，包括以下步骤：A preparation method of a monodispersed nano-hard carbon material with large interlayer spacing, comprising the following steps:
(1)将木糖溶解于去离子水，搅拌至均匀，配置浓度为0.73M的溶液，其中搅拌速度为500rpm，搅拌时间为0.5h，搅拌温度为30℃，并将该溶液加热到180℃进行脱水缩合反应24h；(1) Dissolve xylose in deionized water, stir until uniform, configure a solution with a concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, and the stirring temperature is 30°C, and the solution is heated to 180°C Carry out dehydration condensation reaction for 24h;
(2)将步骤(1)得到的材料高速离心清洗，真空干燥，干燥温度60℃，时间24h；(2) high-speed centrifugal cleaning of the material obtained in step (1), vacuum drying, drying temperature 60°C, time 24h;
(3)将步骤(2)得到的材料在高温炉中氩气气氛下进行高温碳化；温度为1100℃，碳化时间为3h，升温速率为5℃/min；氩气流速为200sccm，得到大层间距单分散的纳米硬碳材料。(3) carbonizing the material obtained in step (2) at a high temperature under an argon atmosphere in a high-temperature furnace; the temperature is 1100° C., the carbonization time is 3h, and the heating rate is 5° C./min; the argon gas flow rate is 200sccm to obtain a large layer Pitch monodispersed nanohard carbon materials.
实施例9Example 9
一种大层间距单分散的纳米硬碳材料的制备方法，包括以下步骤：A preparation method of a monodispersed nano-hard carbon material with large interlayer spacing, comprising the following steps:
(1)将木糖溶解于去离子水，搅拌至均匀，配置浓度为0.73M的溶液，其中搅拌速度为500rpm，搅拌时间为0.5h，搅拌温度为30℃，并将该溶液加热到180℃进行脱水缩合反应24h；(1) Dissolve xylose in deionized water, stir until uniform, configure a solution with a concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, and the stirring temperature is 30°C, and the solution is heated to 180°C Carry out dehydration condensation reaction for 24h;
(2)将步骤(1)得到的材料高速离心清洗，真空干燥，干燥温度60℃，时间24h；(2) high-speed centrifugal cleaning of the material obtained in step (1), vacuum drying, drying temperature 60°C, time 24h;
(3)将步骤(2)得到的材料在高温炉中氩气气氛下进行高温碳化；温度为1300℃，碳化时间为3h，升温速率为5℃/min；氩气流速为200sccm，得到大层间距单分散的纳米硬碳材料。(3) carbonizing the material obtained in step (2) at a high temperature in an argon atmosphere in a high-temperature furnace; the temperature is 1300°C, the carbonization time is 3h, and the heating rate is 5°C/min; the argon gas flow rate is 200sccm to obtain a large layer Pitch monodispersed nanohard carbon materials.
实施例10Example 10
一种大层间距单分散的纳米硬碳材料的制备方法，包括以下步骤：A preparation method of a monodispersed nano-hard carbon material with large interlayer spacing, comprising the following steps:
(1)将木糖溶解于去离子水，搅拌至均匀，配置浓度为0.73M的溶液，其中搅拌速度为500rpm，搅拌时间为0.5h，搅拌温度为30℃，并将该溶液加热到180℃进行脱水缩合反应24h；(1) Dissolve xylose in deionized water, stir until uniform, configure a solution with a concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, and the stirring temperature is 30°C, and the solution is heated to 180°C Carry out dehydration condensation reaction for 24h;
(2)将步骤(1)得到的材料高速离心清洗，真空干燥，干燥温度60℃，时间24h；(2) high-speed centrifugal cleaning of the material obtained in step (1), vacuum drying, drying temperature 60°C, time 24h;
(3)将步骤(2)得到的材料在高温炉中氩气气氛下进行高温碳化；温度为1400℃，碳化时间为3h，升温速率为5℃/min；氩气流速为200sccm，得到大层间距单分散的纳米硬碳材料。(3) carbonizing the material obtained in step (2) at a high temperature under an argon atmosphere in a high-temperature furnace; the temperature is 1400°C, the carbonization time is 3h, and the heating rate is 5°C/min; the flow rate of argon is 200sccm to obtain a large layer Pitch monodispersed nanohard carbon materials.
实施例11Example 11
一种大层间距单分散的纳米硬碳材料的制备方法，包括以下步骤：A preparation method of a monodispersed nano-hard carbon material with large interlayer spacing, comprising the following steps:
(1)将木糖溶解于去离子水，搅拌至均匀，配置浓度为0.73M的溶液，其中搅拌速度为500rpm，搅拌时间为0.5h，搅拌温度为30℃，并将该溶液加热到180℃进行脱水缩合反应24h；(1) Dissolve xylose in deionized water, stir until uniform, configure a solution with a concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, and the stirring temperature is 30°C, and the solution is heated to 180°C Carry out dehydration condensation reaction for 24h;
(2)将步骤(1)得到的材料高速离心清洗，真空干燥，干燥温度60℃，时间24h；(2) high-speed centrifugal cleaning of the material obtained in step (1), vacuum drying, drying temperature 60°C, time 24h;
(3)将步骤(2)得到的材料在高温炉中氩气气氛下进行高温碳化；温度为1500℃，碳化时间为3h，升温速率为5℃/min；氩气流速为200sccm，得到大层间距单分散的纳米硬碳材料。(3) carbonizing the material obtained in step (2) at a high temperature under an argon atmosphere in a high-temperature furnace; the temperature is 1500°C, the carbonization time is 3h, and the heating rate is 5°C/min; the argon gas flow rate is 200sccm to obtain a large layer Pitch monodispersed nanohard carbon materials.
实施例12Example 12
一种大层间距单分散的纳米硬碳材料的制备方法，包括以下步骤：A preparation method of a monodispersed nano-hard carbon material with large interlayer spacing, comprising the following steps:
(1)将木糖溶解于去离子水，搅拌至均匀，配置浓度为0.73M的溶液，其中搅拌速度为500rpm，搅拌时间为0.5h，搅拌温度为30℃，并将该溶液采用微波加热到180℃进行脱水缩合反应0.5h；(1) Dissolve xylose in deionized water, stir until uniform, configure a solution with a concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, and the stirring temperature is 30°C, and the solution is heated to The dehydration condensation reaction was carried out at 180°C for 0.5h;
(2)将步骤(1)得到的材料高速离心清洗，真空干燥，干燥温度60℃，时间24h；(2) high-speed centrifugal cleaning of the material obtained in step (1), vacuum drying, drying temperature 60°C, time 24h;
(3)将步骤(2)得到的材料在高温炉中氩气气氛下进行高温碳化；温度为1400℃，碳化时间为3h，升温速率为5℃/min；氩气流速为200sccm，得到大层间距单分散的纳米硬碳材料。(3) carbonizing the material obtained in step (2) at a high temperature under an argon atmosphere in a high-temperature furnace; the temperature is 1400°C, the carbonization time is 3h, and the heating rate is 5°C/min; the flow rate of argon is 200sccm to obtain a large layer Pitch monodispersed nanohard carbon materials.
实施例13Example 13
一种大层间距单分散的纳米硬碳材料的制备方法，包括以下步骤：A preparation method of a monodispersed nano-hard carbon material with large interlayer spacing, comprising the following steps:
(1)将木糖溶解于去离子水，搅拌至均匀，配置浓度为0.73M的溶液，其中搅拌速度为500rpm，搅拌时间为0.5h，搅拌温度为30℃，并将该溶液采用微波加热到180℃进行脱水缩合反应1h；(1) Dissolve xylose in deionized water, stir until uniform, configure a solution with a concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, and the stirring temperature is 30°C, and the solution is heated to The dehydration condensation reaction was carried out at 180°C for 1h;
(2)将步骤(1)得到的材料高速离心清洗，真空干燥，干燥温度60℃，时间24h；(2) high-speed centrifugal cleaning of the material obtained in step (1), vacuum drying, drying temperature 60°C, time 24h;
(3)将步骤(2)得到的材料在高温炉中氩气气氛下进行高温碳化；温度为1400℃，碳化时间为3h，升温速率为5℃/min；氩气流速为200sccm，得到大层间距单分散的纳米硬碳材料。(3) carbonizing the material obtained in step (2) at a high temperature under an argon atmosphere in a high-temperature furnace; the temperature is 1400°C, the carbonization time is 3h, and the heating rate is 5°C/min; the flow rate of argon is 200sccm to obtain a large layer Pitch monodispersed nanohard carbon materials.
实施例14Example 14
一种大层间距单分散的纳米硬碳材料的制备方法，包括以下步骤：A preparation method of a monodispersed nano-hard carbon material with large interlayer spacing, comprising the following steps:
(1)将木糖溶解于去离子水，搅拌至均匀，配置浓度为0.73M的溶液，其中搅拌速度为500rpm，搅拌时间为0.5h，搅拌温度为30℃，并将该溶液采用微波加热到180℃进行脱水缩合反应2h；(1) Dissolve xylose in deionized water, stir until uniform, configure a solution with a concentration of 0.73M, wherein the stirring speed is 500rpm, the stirring time is 0.5h, and the stirring temperature is 30°C, and the solution is heated to The dehydration condensation reaction was carried out at 180°C for 2h;
(2)将步骤(1)得到的材料高速离心清洗，真空干燥，干燥温度60℃，时间24h；(2) high-speed centrifugal cleaning of the material obtained in step (1), vacuum drying, drying temperature 60°C, time 24h;
(3)将步骤(2)得到的材料在高温炉中氩气气氛下进行高温碳化；温度为1400℃，碳化时间为3h，升温速率为5℃/min；氩气流速为200sccm，得到大层间距单分散的纳米硬碳材料。(3) carbonizing the material obtained in step (2) at a high temperature under an argon atmosphere in a high-temperature furnace; the temperature is 1400°C, the carbonization time is 3h, and the heating rate is 5°C/min; the flow rate of argon is 200sccm to obtain a large layer Pitch monodispersed nanohard carbon materials.
试验例Test example
钠离子电池组装和电化学性能测试Na-ion battery assembly and electrochemical performance testing
(1)采用涂片法将实施例1制得的硬碳粉末材料、乙炔黑、粘结剂海藻酸钠(SA)以质量比8:1:1的比例均匀的与溶剂去离子水混合，1200r/min速度磁力搅拌12小时，制得负极浆料，涂覆在铜箔集流体之上，并放入真空干燥箱中100℃下干燥24h；再经过辊压，剪裁得到硬碳负极极片。(1) The hard carbon powder material, acetylene black and binder sodium alginate (SA) prepared in Example 1 were uniformly mixed with solvent deionized water in a mass ratio of 8:1:1 by smear method , 1200r/min speed magnetic stirring for 12 hours, the negative electrode slurry was prepared, coated on the copper foil current collector, and placed in a vacuum drying box for drying at 100 ° C for 24 hours; then rolled and cut to obtain a hard carbon negative electrode piece.
(2)选取部分切好的均匀完整的极片，使用精密天平称量，并计算活性材料的质量((m总-m铜)*0.8)；以钠片作对电极和参比电极，在氩气氛围下的手套箱中，按正确的操作步骤与正极壳、负极壳、玻璃纤维隔膜、钠片(直径12mm*厚度为1mm)、电解液一起组装成CR2025型纽扣电池。所用的电解液为溶解有1M NaPF6的碳酸乙烯酯(EC)和碳酸二乙酯(DEC)(两者体积比为1:1)的混合液，使用扣式电池封口机对组装好的电池进行密封，从手套箱取出，常温下静置4小时。(2) Select some of the cut uniform and complete pole pieces, weigh them with a precision balance, and calculate the mass of the active material ((mtotal-mcopper)*0.8); use sodium pieces as the counter electrode and reference electrode, in argon In the glove box under the atmosphere, assemble the CR2025 button battery together with the positive electrode case, the negative electrode case, the glass fiber separator, the sodium sheet (diameter 12mm*thickness 1mm) and the electrolyte according to the correct operation steps. The electrolyte used is a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) (the volume ratio of the two is 1:1) dissolved with 1M NaPF 6 , and the assembled battery is sealed by a button battery sealer. It was sealed, taken out from the glove box, and allowed to stand at room temperature for 4 hours.
分别对制得的钠离子电池进行电化学性能测试，测试使用仪器为LAND CT2001A测试仪(武汉市蓝电电子有限公司)测试循环周期设置为500周，具体地：在0.001-2.5V的电压范围和100mA/g的电流密度下，将电池充放电循环500周；检测充放电循环500周后的充电比容量(mAh/g)，并计算充放电循环500周的容量保持率(＝充放电循环500周后充电比容量÷初始的充电比容量×100％)。Electrochemical performance tests were carried out on the prepared sodium-ion batteries respectively. The test instrument was a LAND CT2001A tester (Wuhan Landian Electronics Co., Ltd.), and the test cycle was set to 500 weeks, specifically: in the voltage range of 0.001-2.5V Under the current density of 100 mA/g, the battery was charged and discharged for 500 cycles; the specific charge capacity (mAh/g) after 500 cycles of charge and discharge was detected, and the capacity retention rate of 500 cycles of charge and discharge was calculated (= charge and discharge cycle Charge specific capacity after 500 weeks ÷ initial charge specific capacity × 100%).
实施例1-14所制备的大层间距单分散的纳米硬碳材料，相应的首次充电比容量、500周循环后容量保持率结果如表1所示。Table 1 shows the corresponding specific capacity of the first charge and the capacity retention rate after 500 cycles of the monodispersed nano-hard carbon materials with large interlayer spacing prepared in Examples 1-14.
表1Table 1
将表1中的实施例1与实施例2-5比较可知，脱水反应的温度过高将导致颗粒的平均粒径变大，这是因为高温促进了脱水过程中形核长大过程，然而粒径增大意味着活性比表面积降低，扩散距离增加，这最终会降低硬碳的储钠容量；温度过低会导致脱水过程不能够充分进行，得到的前驱体中氧含量过高，进一步高温碳化过程中过高的氧含量使得层间距过大，结构稳定性变差，从而导致循环稳定性降低，且含氧基团往往会造成不可逆容量导致首周库伦效率降低。通过对比优选出水热温度为180～190℃为合适的水热温度范围，优选180℃为最佳水热温度。Comparing Example 1 with Examples 2-5 in Table 1, it can be seen that the temperature of the dehydration reaction is too high, and the average particle size of the particles will become larger, because the high temperature promotes the nucleation and growth process during the dehydration process. The increase of the diameter means that the active specific surface area decreases and the diffusion distance increases, which will eventually reduce the sodium storage capacity of the hard carbon; if the temperature is too low, the dehydration process will not be fully carried out, and the oxygen content in the obtained precursor will be too high. Excessive oxygen content in the process makes the interlayer spacing too large and the structural stability deteriorates, resulting in reduced cycle stability, and oxygen-containing groups often cause irreversible capacity and reduce the first week Coulombic efficiency. By comparison, the optimum hydrothermal temperature is 180-190°C, and the optimum hydrothermal temperature is preferably 180°C.
将表1中的实施例1与实施例6-11比较可看出碳化温度对制备的大层间距单分散的纳米硬碳材料影响比较明显，碳化温度低会导致含氧基团过多，石墨化程度不足，短程有序微区过小，层间距过大，这会导致电解液分解增多，不可逆容量增加，可逆容量降低，且结构稳定性也会降低。碳化温度高会减少一些缺陷位点，层间距也会有所减小，导致储钠活性位点减少从而导致储钠容量有所降低。通过对比优选出碳化温度为1100～1300℃为合适的碳化温度范围，优选1200℃为最佳碳化温度。Comparing Example 1 in Table 1 with Examples 6-11, it can be seen that the carbonization temperature has an obvious influence on the prepared nano-hard carbon material with large interlayer spacing. Low carbonization temperature will lead to excessive oxygen-containing groups, graphite The degree of chemistry is insufficient, the short-range ordered microdomain is too small, and the interlayer spacing is too large, which will lead to an increase in the decomposition of the electrolyte, an increase in the irreversible capacity, a decrease in the reversible capacity, and a decrease in the structural stability. High carbonization temperature will reduce some defect sites, and the interlayer spacing will also be reduced, resulting in the reduction of sodium storage active sites and the reduction of sodium storage capacity. By comparison, it is preferred that the carbonization temperature is 1100-1300°C as the suitable carbonization temperature range, and the optimum carbonization temperature is preferably 1200°C.
进一步选择微波水热的方法快速制备大层间距单分散硬碳纳米颗粒，将表1中的实施例1与实施例12-14比较可以看出，微波水热可以在0.5～2h内快速完成脱水缩合反应，并且由于微波加热更加均匀，颗粒形核和长大过程一致性更高，得到的产物粒径大小更均匀，这有利于电极的一致性，并且可以进一步增多有效活性比表面，从而进一步优化电化学性能。实施例12-14比较可以看出微波水热时间在1h时效果最佳。The microwave hydrothermal method is further selected to rapidly prepare monodisperse hard carbon nanoparticles with large interlayer spacing. Comparing Example 1 in Table 1 with Examples 12-14, it can be seen that microwave hydrothermal can quickly complete dehydration within 0.5 to 2 hours. Condensation reaction, and because the microwave heating is more uniform, the particle nucleation and growth process are more consistent, and the particle size of the obtained product is more uniform, which is beneficial to the consistency of the electrode, and can further increase the effective active specific surface area, thereby further Optimize electrochemical performance. It can be seen from the comparison of Examples 12-14 that the microwave hydrothermal time is the best when 1h.
综上，选择较佳的水热温度(180～190℃)和碳化温度(1100～1300℃)，能得到粒径均匀且层间距超过0.4nm的大层间距单分散硬碳纳米颗粒，采用该优化结构的硬碳材料作为钠离子电池负极材料表现出最优的综合性能，包括高的比容量，高的首周库伦效率和高的容量保持率等。To sum up, choosing the best hydrothermal temperature (180-190°C) and carbonization temperature (1100-1300°C) can obtain monodisperse hard carbon nanoparticles with uniform particle size and large interlayer spacing exceeding 0.4 nm. The optimized structure of hard carbon material as anode material for Na-ion battery shows the best comprehensive performance, including high specific capacity, high first-week Coulombic efficiency and high capacity retention rate.
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