CN106185862B - A kind of pyrolyzed hard carbon material and application thereof - Google Patents

A kind of pyrolyzed hard carbon material and application thereof Download PDF

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CN106185862B
CN106185862B CN201610505671.2A CN201610505671A CN106185862B CN 106185862 B CN106185862 B CN 106185862B CN 201610505671 A CN201610505671 A CN 201610505671A CN 106185862 B CN106185862 B CN 106185862B
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hard carbon
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corn
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刘品
李云明
胡勇胜
陈立泉
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    • H—ELECTRICITY
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Abstract

本发明公开了一种热解硬碳材料，在一个实施例中，该材料由如下方法制备得到：将废弃生物质干燥处理；在惰性气氛下升温至300℃‑600℃，预碳化1‑5h；在惰性气氛下升温至1000℃‑1600℃，碳化、裂解1‑10h；冷却后即得所述热解碳材料；其中，获得的所述热解硬碳材料为不规则的块状颗粒，颗粒尺寸为1‑20μm，平均粒径为5‑10μm；d002值在0.38‑0.41nm之间，Lc值在1.3‑1.5nm之间,La值在3.7‑4.7nm之间。本发明提供的热解硬碳材料制备简单、原材料资源丰富、成本低廉，是无污染的绿色材料，采用上述材料作为负极活性材料的钠离子二次电池，具有较高的工作电压和能量密度、循环稳定、安全性能好，可以应用于太阳能发电、风力发电、智能电网调峰、分布电站、后备电源或通信基站的大规模储能设备。

The invention discloses a pyrolytic hard carbon material. In one embodiment, the material is prepared by the following method: drying waste biomass; heating up to 300°C-600°C under an inert atmosphere, and pre-carbonizing for 1-5h ; heating up to 1000°C-1600°C under an inert atmosphere, carbonization and cracking for 1-10h; the pyrolysis carbon material is obtained after cooling; wherein, the obtained pyrolysis hard carbon material is irregular block particles, The particle size is 1-20μm, the average particle size is 5-10μm; the d 002 value is between 0.38-0.41nm, the L c value is between 1.3-1.5nm, and the L a value is between 3.7-4.7nm. The pyrolytic hard carbon material provided by the present invention is simple to prepare, rich in raw material resources, low in cost, and is a pollution-free green material. The sodium ion secondary battery using the above material as the negative electrode active material has higher working voltage and energy density, With stable cycle and good safety performance, it can be applied to large-scale energy storage equipment for solar power generation, wind power generation, smart grid peak regulation, distributed power station, backup power supply or communication base station.

Description

一种热解硬碳材料及其用途A kind of pyrolytic hard carbon material and its application

技术领域technical field

本发明涉及材料技术领域，尤其涉及一种热解硬碳材料及其用途。The invention relates to the technical field of materials, in particular to a pyrolysis hard carbon material and its application.

背景技术Background technique

锂离子电池以其高电压，高能量密度和高安全性等优点，使其在便携电子设备领域占据了无可替代的地位，在动力电池领域也迅速崭露头角。与锂离子电池相比，钠离子电池由于钠资源丰富，具有潜在的价格优势，而在大规模储能***有着广阔的应用前景。With its advantages of high voltage, high energy density and high safety, lithium-ion batteries occupy an irreplaceable position in the field of portable electronic devices, and are rapidly emerging in the field of power batteries. Compared with lithium-ion batteries, sodium-ion batteries have a potential price advantage due to abundant sodium resources, and have broad application prospects in large-scale energy storage systems.

目前商业应用的锂离子电池的主要负极材料是石墨材料，对钠离子电池来说，由于热力学原因，钠离子无法在石墨层间实现稳定的可逆脱嵌，因此钠离子电池要寻找其他的新型材料作为负极材料。At present, the main negative electrode material of lithium-ion batteries in commercial application is graphite material. For sodium-ion batteries, due to thermodynamic reasons, sodium ions cannot achieve stable reversible deintercalation between graphite layers, so sodium-ion batteries need to find other new materials. as negative electrode material.

无定形碳按石墨化的难易程度，一般分为软碳(易石墨化碳)和硬碳(难石墨化碳)。其中石油、煤、沥青、聚氯乙烯和蒽等碳化后属于软碳，而且这些前驱物如沥青等成本低廉、产碳率较高；纤维素、糖类、呋喃树脂、酚醛树脂和聚偏二氯乙烯等碳化后属于硬碳。硬碳材料由于其比容量高、储钠电压低等优点成为钠离子二次电池最有应用前景的负极材料。Amorphous carbon is generally divided into soft carbon (easy graphitization carbon) and hard carbon (difficult graphitization carbon) according to the difficulty of graphitization. Among them, petroleum, coal, asphalt, polyvinyl chloride and anthracene belong to soft carbon after carbonization, and these precursors such as asphalt have low cost and high carbon yield; cellulose, sugar, furan resin, phenolic resin and polybias After carbonization, vinyl chloride and the like belong to hard carbon. Due to its high specific capacity and low sodium storage voltage, hard carbon materials have become the most promising anode materials for sodium-ion secondary batteries.

虽然硬碳材料作为钠离子电池具有显著的优点，但是目前生产硬碳材料所用前驱体中碳含量低，其在高温碳化过程中质量损失大，产碳率低，导致硬碳成本较高，制约了其大范围应用。Although hard carbon materials have significant advantages as sodium-ion batteries, the carbon content in the precursors used to produce hard carbon materials is low, and their mass loss is large during high-temperature carbonization, and the carbon production rate is low, resulting in high cost of hard carbon. its wide-ranging application.

本发明采用废弃的生物质为原料，通过简单易操作的工艺制备出一种硬碳材料，不仅实现了废弃生物质的再利用，而且降低了硬碳的生产成本，该材料特别适合作为钠离子二次电池的负极材料。The present invention uses waste biomass as raw material, and prepares a hard carbon material through a simple and easy-to-operate process, which not only realizes the reuse of waste biomass, but also reduces the production cost of hard carbon. This material is especially suitable as a sodium ion Anode materials for secondary batteries.

发明内容Contents of the invention

本发明的目的在于克服现有技术中生产硬碳材料所用前驱体中碳含量低，且在高温碳化过程中质量损失大，产碳率低，导致硬碳材料成本较高、性能不高的问题，为解决上述问题，本发明实施例提供了一种热解硬碳材料和用途。该硬碳材料采用废弃的生物质为原料，通过简单易操作的工艺制备而成，制备方法简单、原材料易得、成本低廉，且所得材料含碳量高、且利用该材料制备的电池性能好，适合于大规模生产。The purpose of the present invention is to overcome the problems of low carbon content in the precursors used in the production of hard carbon materials in the prior art, large mass loss and low carbon production rate in the high-temperature carbonization process, resulting in high cost and low performance of hard carbon materials. In order to solve the above problems, the embodiment of the present invention provides a pyrolytic hard carbon material and its application. The hard carbon material uses waste biomass as a raw material and is prepared through a simple and easy-to-operate process. The preparation method is simple, the raw material is easy to obtain, and the cost is low, and the obtained material has a high carbon content, and the battery prepared by using this material has good performance. , suitable for mass production.

第一方面，本发明实施例提供了一种热解硬碳材料，由如下方法制备得到：将废弃生物质干燥处理；在惰性气氛下升温至300℃-600℃，预碳化1-5h；在惰性气氛下升温至1000℃-1600℃，碳化、裂解1-10h；冷却后即得所述热解碳材料；其中，In the first aspect, the embodiment of the present invention provides a pyrolytic hard carbon material, which is prepared by the following method: drying waste biomass; heating to 300°C-600°C under an inert atmosphere, and pre-carbonizing for 1-5h; Heat up to 1000°C-1600°C under an inert atmosphere, carbonize and crack for 1-10 hours; after cooling, the pyrolytic carbon material is obtained; wherein,

获得的所述热解硬碳材料为不规则的块状颗粒，颗粒尺寸为1-20μm，平均粒径为5-10μm；d002值在0.38-0.41nm之间，Lc值在1.3-1.5nm之间,La值在3.7-4.7nm之间。The obtained pyrolytic hard carbon material is irregular massive particles with a particle size of 1-20 μm and an average particle size of 5-10 μm; the d 002 value is between 0.38-0.41 nm, and the L c value is between 1.3-1.5 nm, the L a value is between 3.7-4.7nm.

优选地，所述废弃生物质包括玉米瓤、玉米残渣、玉米秆和玉米皮中的一种或多种。Preferably, the waste biomass includes one or more of corn cobs, corn residues, corn stalks and corn husks.

优选地，所述热解硬碳材料的含碳量不低于95％。Preferably, the carbon content of the pyrolytic hard carbon material is not less than 95%.

优选地，，所述材料的表面具有软碳包覆层。Preferably, the surface of the material has a soft carbon coating.

第二方面，本发明提供了一种负极材料，所述负极活性材料包括上述第一方面所述的热解硬碳材料。In a second aspect, the present invention provides a negative electrode material, wherein the negative electrode active material includes the pyrolytic hard carbon material described in the first aspect above.

第三方面，本发明提供了一种钠离子二次电池的负极极片，其特征在于，所述负极极片包括：集流体，涂覆于所述集流体之上的粘结剂和如上述第二方面所述的钠离子二次电池负极材料。In a third aspect, the present invention provides a negative electrode sheet of a sodium ion secondary battery, wherein the negative electrode sheet includes: a current collector, a binder coated on the current collector and the above-mentioned The sodium ion secondary battery negative electrode material described in the second aspect.

第四方面，本发明提供了一种包括上述第三方面所述的负极极片的二次电池。In a fourth aspect, the present invention provides a secondary battery comprising the negative electrode sheet described in the above third aspect.

本发明的目的在于，探求一种采用废弃生物质来制备硬碳的方法。该方法符合当前社会对绿色环保的清洁能源的需求。大量脱离后的玉米瓤和玉米杆经常被直接焚烧，不仅没有实现再利用的价值，也对环境造成了污染。本发明通过将废弃的玉米瓤、玉米杆和玉米残渣再利用，提供了一种工艺简单，成本低廉且适用于中到大规模生产的方法和提供一种应用广泛、特别是在钠离子二次电池中作为负极材料的热解硬碳材料，在电池循环过程中，循环性能稳定。The object of the present invention is to seek a method for preparing hard carbon by using waste biomass. This method meets the current society's demand for green and clean energy. A large number of detached corn cobs and corn stalks are often directly burned, which not only has no value for reuse, but also causes pollution to the environment. The present invention provides a method with simple process, low cost and suitable for medium to large-scale production by reusing discarded corncobs, corn stalks and corn residues, and provides a method with wide application, especially in sodium ion secondary The pyrolytic hard carbon material used as the negative electrode material in the battery has stable cycle performance during the battery cycle.

附图说明Description of drawings

图1为本发明实施例1提供的材料的制备方法；Fig. 1 is the preparation method of the material that the embodiment of the present invention 1 provides;

图2为本发明实施例2提供的硬碳材料的XRD图谱；Fig. 2 is the XRD spectrum of the hard carbon material that the embodiment of the present invention 2 provides;

图3为本发明实施例2提供的硬碳材料的Raman光谱；Fig. 3 is the Raman spectrum of the hard carbon material that the embodiment of the present invention 2 provides;

图4为本发明实施例2提供的硬碳材料的SEM图；Fig. 4 is the SEM picture of the hard carbon material that the embodiment of the present invention 2 provides;

图5为本发明实施例2提供的一种钠离子电池的充放电曲线图；Fig. 5 is a charge-discharge curve diagram of a sodium-ion battery provided in Example 2 of the present invention;

图6为本发明实施例3提供的硬碳材料的XRD图谱；Fig. 6 is the XRD spectrum of the hard carbon material that the embodiment of the present invention 3 provides;

图7为本发明实施例3提供的硬碳材料的Raman光谱；Fig. 7 is the Raman spectrum of the hard carbon material that the embodiment of the present invention 3 provides;

图8为本发明实施例3提供的硬碳材料的SEM图；Fig. 8 is the SEM picture of the hard carbon material that the embodiment of the present invention 3 provides;

图9为本发明实施例3提供的一种钠离子电池的充放电曲线图；Fig. 9 is a charge and discharge curve diagram of a sodium ion battery provided in Example 3 of the present invention;

图10为本发明实施例4提供的硬碳材料的XRD图谱；Fig. 10 is the XRD spectrum of the hard carbon material provided by the embodiment of the present invention 4;

图11为本发明实施例4提供的硬碳材料的Raman光谱；Figure 11 is the Raman spectrum of the hard carbon material provided by Example 4 of the present invention;

图12为本发明实施例4提供的硬碳材料的SEM图；Fig. 12 is the SEM picture of the hard carbon material provided by the embodiment of the present invention 4;

图13为本发明实施例4提供的一种钠离子电池的充放电曲线图；Fig. 13 is a charge and discharge curve diagram of a sodium ion battery provided in Example 4 of the present invention;

图14为本发明实施例5提供的一种钠离子电池的充放电曲线图；Fig. 14 is a charge and discharge curve diagram of a sodium ion battery provided in Example 5 of the present invention;

图15为本发明实施例6提供的硬碳材料的XRD图谱；Figure 15 is the XRD spectrum of the hard carbon material provided by Example 6 of the present invention;

图16为本发明实施例6提供的硬碳材料的Raman光谱；Figure 16 is the Raman spectrum of the hard carbon material provided by Example 6 of the present invention;

图17为本发明实施例6提供的硬碳材料的SEM图；Fig. 17 is the SEM picture of the hard carbon material provided by Example 6 of the present invention;

图18为本发明实施例6提供的一种钠离子电池的充放电曲线图；Fig. 18 is a charge and discharge curve diagram of a sodium ion battery provided in Example 6 of the present invention;

图19为本发明对比例提供的一种钠离子电池的充放电曲线图。Fig. 19 is a charge-discharge curve diagram of a sodium-ion battery provided in a comparative example of the present invention.

具体实施方式Detailed ways

下面通过附图和实施例，对本发明进行进一步的详细说明，但并不意于限制本发明的保护范围。The present invention will be further described in detail through the drawings and examples below, but it is not intended to limit the protection scope of the present invention.

实施例1Example 1

本发明实施例1提供了一种热解硬碳材料，其制备方法如图1所示，包括以下步骤：Embodiment 1 of the present invention provides a kind of pyrolysis hard carbon material, and its preparation method is shown in Figure 1, comprises the following steps:

(1)将废弃生物质进行干燥处理。(1) Dry the waste biomass.

具体地，以废弃生物质作为硬碳前驱体，即以废弃生物质为原料进行制备热解碳材料。优选地，所述废弃生物质可以选择玉米瓤、玉米残渣、玉米秆和玉米皮中的一种或多种。为去除硬碳前驱体中的水份，将硬碳前驱体放进行干燥处理，如，将硬碳前驱体放置在50-120℃的烘箱内烘烤20-30h，去除硬碳前驱体中的水份。需要指出的是，为便于干燥及后续的热处理，在对硬碳前躯体进行干燥处理前，可将硬碳前驱体进行预粉碎。Specifically, waste biomass is used as a hard carbon precursor, that is, waste biomass is used as a raw material to prepare pyrolytic carbon materials. Preferably, the waste biomass can be selected from one or more of corn cobs, corn residues, corn stalks and corn husks. In order to remove the moisture in the hard carbon precursor, dry the hard carbon precursor, for example, place the hard carbon precursor in an oven at 50-120°C for 20-30 hours to remove the moisture in the hard carbon precursor. moisture. It should be pointed out that, in order to facilitate drying and subsequent heat treatment, the hard carbon precursor can be pre-pulverized before drying the hard carbon precursor.

(2)在惰性气氛下升温至300℃-600℃，反应1-5h。(2) Raise the temperature to 300°C-600°C under an inert atmosphere, and react for 1-5h.

具体地，将烘干后的物质装入磁舟中放进管式炉，首先通入惰性气体，优选为氮气，然后慢慢升温至300℃-600℃，在该条件下进行预热，目的是对材料进行预碳化。优选地，在升温过程中以0.5-10℃/min的速率升温。Specifically, put the dried material into a magnetic boat and put it into a tube furnace, first pass in an inert gas, preferably nitrogen, and then slowly raise the temperature to 300°C-600°C, and preheat under this condition, the purpose It is to pre-carbonize the material. Preferably, the temperature is raised at a rate of 0.5-10° C./min during the heating process.

(3)在惰性气氛下升温至1000℃-1600℃，反应1-10h。(3) Raise the temperature to 1000°C-1600°C under an inert atmosphere, and react for 1-10h.

具体地，在预碳化完成后，在管式炉中，慢慢升温至1000℃-1600℃，持续保温1-10h，进行碳化处理，即：使硬碳前驱体发生裂解反应。优选地，在升温过程中以0.5-10℃/min的速率升温。Specifically, after the pre-carbonization is completed, the temperature is slowly raised to 1000°C-1600°C in a tube furnace, and the heat is kept for 1-10h to carry out carbonization treatment, that is, to cause a cracking reaction of the hard carbon precursor. Preferably, the temperature is raised at a rate of 0.5-10° C./min during the heating process.

可选的，为降低材料的表面积，还可以在反应过程加入含有碳氢化合物的气体进行表面包覆，使其表面具有软碳包覆层，优选为甲烷、乙烷、甲苯、乙烯、乙炔和丙炔中的一种或多种。Optionally, in order to reduce the surface area of the material, it is also possible to add gas containing hydrocarbons for surface coating during the reaction, so that the surface has a soft carbon coating, preferably methane, ethane, toluene, ethylene, acetylene and One or more of propyne.

在此过程中硬碳前驱体发生裂解反应，生成硬碳材料。During this process, the hard carbon precursor undergoes a cracking reaction to generate hard carbon materials.

(4)冷却粉碎后，得到所述热解硬碳材料。(4) After cooling and crushing, the pyrolytic hard carbon material is obtained.

具体的，冷却可以采用自然冷却，降至室温后由管式炉中取出，粉碎后即得到所需的硬碳材料。Specifically, natural cooling can be used for cooling, and after cooling down to room temperature, it is taken out from the tube furnace, and the required hard carbon material can be obtained after crushing.

可选的，为了去除硬碳材料中的杂质，在粉碎后，后续还可以增加酸洗步骤。优选地，用于酸洗的液体包括稀盐酸、氢氟酸或其混合物，酸洗过程中，浸泡时间为1-5h。Optionally, in order to remove impurities in the hard carbon material, after crushing, a pickling step may be added subsequently. Preferably, the liquid used for pickling includes dilute hydrochloric acid, hydrofluoric acid or a mixture thereof, and the soaking time is 1-5 hours during the pickling process.

上述获得硬碳材料含碳量不低于95％，具有纳米孔，且为不规则的块状颗粒，颗粒尺寸为1-20μm，平均粒径为5-10μm；d002值在0.38-0.41nm之间，Lc值在1.3-1.5nm之间,La值在3.7-4.7nm之间。。The hard carbon material obtained above has a carbon content of not less than 95%, has nanopores, and is an irregular block particle, the particle size is 1-20 μm, and the average particle size is 5-10 μm; the d 002 value is 0.38-0.41nm Between, the L c value is between 1.3-1.5nm, and the L a value is between 3.7-4.7nm. .

本实施例提供的热解硬碳材料的制备简单，原材料易得、成本低廉，且所得材料含碳量高(不低于95％)，适合于大规模生产。制备采用废弃的生物质作为硬碳前驱体原料，可以提高所得硬碳材料的含碳量。通过改***碳前驱体种类，并调整裂解温度，可以得到不同特征尺寸的颗粒材料，具有不同的电化学性质，从而可根据不同的需求得到最佳性能的硬碳材料，用于钠离子二次电池的负极材料。The pyrolytic hard carbon material provided in this example is easy to prepare, the raw material is readily available, and the cost is low, and the obtained material has a high carbon content (not less than 95%), and is suitable for large-scale production. The preparation uses waste biomass as the raw material of the hard carbon precursor, which can increase the carbon content of the obtained hard carbon material. By changing the type of hard carbon precursor and adjusting the cracking temperature, granular materials with different characteristic sizes can be obtained, which have different electrochemical properties, so that hard carbon materials with the best performance can be obtained according to different requirements, which are used for sodium ion secondary The negative electrode material of the battery.

为更好的理解本发明提供的技术方案，下述以多个具体实例分别说明应用本发明上述实施例1提供的制备方法进行热解硬碳材料制备的具体过程，以及将其应用于钠离子二次电池负极材料和钠离子二次电池的方法及其电池特性。In order to better understand the technical solutions provided by the present invention, the following specific examples illustrate the specific process of applying the preparation method provided in the above-mentioned embodiment 1 of the present invention to prepare pyrolysis hard carbon materials, and apply it to sodium ion Anode materials for secondary batteries and methods for sodium ion secondary batteries and battery characteristics thereof.

实施例2Example 2

热解硬碳材料的制备：把除掉玉米粒的玉米瓤切成宽约1cm的小段，放在烧杯里，置于80℃恒温烘箱里烘烤26h。烘干后放在约5cm*2cm*2cm的瓷舟内，准备用于高温碳化。Preparation of pyrolytic hard carbon material: cut the corn cobs with the corn kernels removed into small pieces about 1 cm wide, put them in a beaker, and bake them in a constant temperature oven at 80°C for 26 hours. After drying, put it in a porcelain boat of about 5cm*2cm*2cm, ready for high-temperature carbonization.

将玉米瓤随瓷舟一起放在管式炉(管长约100cm，直径6cm，以下实施例采用相同的管式炉)中，在氩气保护下，以1℃/min的速率升温至500℃，氩气流量为25mL/min，在500℃预碳化2h，再以5℃/min的速率升温到1300℃，保温2h，之后自然冷却至室温。将已碳化的玉米段取出，在研钵中研磨成粉末，即得到热解硬碳产物。其X射线衍射(XRD)图谱参见图2。从XRD图谱可以得到该硬碳材料的d002＝0.398nm，Lc＝1.39nm。其拉曼光谱参见图3，通过拉曼图谱可以得到该硬碳材料的La＝4.32nm。图4为用扫描电子显微镜(SEM)拍摄的粉末微观图片，从图中可以看出，颗粒尺寸在5-20μm之间。Put the corn cob together with the porcelain boat in a tube furnace (the tube is about 100 cm long and 6 cm in diameter, the same tube furnace is used in the following examples), and under the protection of argon, the temperature is raised to 500 °C at a rate of 1 °C/min , with an argon flow rate of 25mL/min, pre-carbonize at 500°C for 2h, then raise the temperature to 1300°C at a rate of 5°C/min, keep the temperature for 2h, and then cool down to room temperature naturally. The carbonized corn segments are taken out and ground into powder in a mortar to obtain pyrolysis hard carbon products. Its X-ray diffraction (XRD) pattern is shown in Figure 2. From the XRD pattern, it can be obtained that d 002 =0.398nm and Lc=1.39nm of the hard carbon material. Its Raman spectrum is shown in FIG. 3 , and the La=4.32nm of the hard carbon material can be obtained through the Raman spectrum. Figure 4 is a microscopic picture of the powder taken with a scanning electron microscope (SEM). It can be seen from the figure that the particle size is between 5-20 μm.

将上述制备的热解硬碳材料作为电池负极活性材料用于钠离子二次电池的制备。The pyrolytic hard carbon material prepared above is used as the battery negative electrode active material for the preparation of the sodium ion secondary battery.

将上述制备好的热解硬碳材料的粉末与海藻酸钠粘结剂以95：5的质量比混合成均匀的粉末，加入适量去离子水，再研磨一段时间形成均匀的浆料，涂布在作为集流体的铝箔上。得到的极片在常温下静置约3h后，水分挥发干净，将干燥的极片裁成0.8cm*0.8cm的方形薄片，再放入真空烘箱内，在120℃温度下烘8h，得到硬碳负极极片，随即转移到手套箱内备用。Mix the prepared pyrolytic hard carbon material powder and sodium alginate binder at a mass ratio of 95:5 to form a uniform powder, add an appropriate amount of deionized water, grind for a period of time to form a uniform slurry, and coat on aluminum foil as a current collector. After the obtained pole piece was left to stand at room temperature for about 3 hours, the water evaporated completely, and the dried pole piece was cut into square sheets of 0.8cm*0.8cm, then put into a vacuum oven, and baked at 120°C for 8 hours to obtain a hard pole piece. The carbon negative pole piece is then transferred to the glove box for standby.

在充氩手套箱中组装成CR2032扣式实验电池，手套箱中水、氧分压不高于1ppm。以厚约0.3mm，直径为1cm的金属钠片作为对电极，以1mol的NaPF6溶于1L体积比为1:1的碳酸乙烯酯和碳酸二乙酯溶液作为电解液，装配成CR2032扣式电池。对该电池进行电化学充放电测试，所测试的倍率为0.1C，放电截止电压为0.0V，充电截止电压为2.0V。其充放电曲线见图5，首周放电容量约为340mAh/g，首周库仑效率为86.3％，其可逆容量约为300mAh/g，在50周的循环过程中没有明显的容量衰减。其循环曲线有着0.2V以下的平稳的充放电平台，在可逆容量中，0.2V以下的平台部分容量占总容量的72.0％，较高的平台容量对设计以该材料为电极活性物质的电池具有重要的意义。Assemble a CR2032 button-type experimental battery in an argon-filled glove box, and the partial pressure of water and oxygen in the glove box is not higher than 1ppm. With a metal sodium sheet with a thickness of about 0.3mm and a diameter of 1cm as the counter electrode, 1mol of NaPF 6 dissolved in 1L of ethylene carbonate and diethyl carbonate solution with a volume ratio of 1:1 is used as the electrolyte, and assembled into a CR2032 button Battery. Electrochemical charge and discharge tests were carried out on the battery. The tested rate was 0.1C, the discharge cut-off voltage was 0.0V, and the charge cut-off voltage was 2.0V. Its charge-discharge curve is shown in Figure 5. The first-week discharge capacity is about 340mAh/g, the first-week Coulombic efficiency is 86.3%, and its reversible capacity is about 300mAh/g. There is no obvious capacity fading during the 50-cycle cycle. Its cycle curve has a stable charge-discharge platform below 0.2V. In the reversible capacity, the part capacity of the platform below 0.2V accounts for 72.0% of the total capacity. Significance.

实施例3Example 3

热解硬碳材料的制备：把除掉玉米粒的玉米瓤切成宽约1cm的小段，放在烧杯里，置于50℃恒温烘箱里烘干30h。烘干后放在约5cm*2cm*2cm的瓷舟内，准备用于高温碳化。Preparation of pyrolytic hard carbon material: cut the corncobs from which the corn kernels have been removed into small pieces with a width of about 1 cm, put them in a beaker, and dry them in a constant temperature oven at 50°C for 30 hours. After drying, put it in a porcelain boat of about 5cm*2cm*2cm, ready for high-temperature carbonization.

将玉米瓤随瓷舟一起放在管式炉中，在氩气保护下，以1℃/min的速率升温至500℃，氩气流量为25mL/min，在500℃预热2h，再以5℃/min的速率升温到1000℃，保温2h，之后自然冷却至室温。将已碳化的玉米瓤取出，在研钵中研磨成粉末，即得到热解硬碳产物。其X射线衍射(XRD)图谱参见图6。从XRD图谱可以得到该硬碳材料的d002＝0.408nm，Lc＝1.34nm。其拉曼光谱参见图7，通过拉曼图谱可以得到该硬碳材料的La＝4.61nm。图8为用扫描电子显微镜(SEM)拍摄的粉末微观图片，从图中可以看出，颗粒尺寸在10-20μm之间。Put the corn cob together with the porcelain boat in a tube furnace, under the protection of argon, the temperature was raised to 500°C at a rate of 1°C/min, the flow of argon gas was 25mL/min, preheated at 500°C for 2h, and then heated at 500°C for 5 The temperature was raised to 1000°C at a rate of °C/min, kept for 2 hours, and then cooled to room temperature naturally. The carbonized corncobs are taken out and ground into powder in a mortar to obtain pyrolysis hard carbon products. Its X-ray diffraction (XRD) pattern is shown in Figure 6. From the XRD spectrum, it can be obtained that d 002 =0.408nm and L c =1.34nm of the hard carbon material. Its Raman spectrum is shown in Fig. 7, and the Laman of the hard carbon material can be obtained from the Raman spectrum = 4.61nm. Figure 8 is a microscopic picture of the powder taken with a scanning electron microscope (SEM). It can be seen from the figure that the particle size is between 10-20 μm.

将上述制备得到的热解硬碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例3。所测试的倍率为0.1C，放电截止电压为0.0V，充电截止电压为2.0V。其充放电曲线见图9，首周放电容量约340mAg/g，首周库仑效率76.5％，其可逆容量约为230mAh/g，在50周的循环过程中没有明显的容量衰减。其循环曲线在0.2V以下有首平稳的充放电平台，在可逆容量中，平台部分容量比例为57.9％。The pyrolytic hard carbon material prepared above was used as the active material of the negative electrode material of the battery for the preparation of the sodium ion battery, and electrochemical charge and discharge tests were performed. Its preparation process and testing method are the same as in Example 3. The tested rate is 0.1C, the discharge cut-off voltage is 0.0V, and the charge cut-off voltage is 2.0V. Its charge-discharge curve is shown in Figure 9. The first-week discharge capacity is about 340mAg/g, the first-week coulombic efficiency is 76.5%, and its reversible capacity is about 230mAh/g. There is no obvious capacity fading during the 50-week cycle. Its cycle curve has the first stable charging and discharging platform below 0.2V, and in the reversible capacity, the proportion of the platform part capacity is 57.9%.

实施例4Example 4

热解硬碳材料的制备：把除掉玉米粒的玉米瓤切成宽约1cm的小段，放在烧杯里，置于80℃恒温烘箱里烘干26h。烘干后放在约5cm*2cm*2cm的瓷舟内，准备用于高温碳化。Preparation of pyrolytic hard carbon material: cut the corncobs from which the corn kernels have been removed into small pieces with a width of about 1 cm, put them in a beaker, and dry them in a constant temperature oven at 80°C for 26 hours. After drying, put it in a porcelain boat of about 5cm*2cm*2cm, ready for high-temperature carbonization.

将玉米瓤随瓷舟一起放在管式炉中，在氩气保护下，以1℃/min的速率升温至500℃，氩气流量为25mL/min，在500℃预热2h，再以5℃/min的速率升温到1600℃，保温2h，之后自然冷却至室温。将已碳化的玉米瓤取出，在研钵中研磨成粉末，即得到热解硬碳产物。其X射线衍射(XRD)图谱参见图10。从XRD图谱可以得到该硬碳材料的d002＝0.389nm，Lc＝1.47nm。其拉曼光谱参见图11，通过拉曼图谱可以得到该硬碳材料的La＝3.75nm。图12为用扫描电子显微镜(SEM)拍摄的粉末微观图片，从图中可以看出，颗粒尺寸在10-20μm之间。Put the corn cob together with the porcelain boat in a tube furnace, under the protection of argon, the temperature was raised to 500°C at a rate of 1°C/min, the flow of argon gas was 25mL/min, preheated at 500°C for 2h, and then heated at 500°C for 5 The temperature was raised to 1600°C at a rate of °C/min, kept for 2 hours, and then cooled to room temperature naturally. The carbonized corncobs are taken out and ground into powder in a mortar to obtain pyrolysis hard carbon products. Its X-ray diffraction (XRD) pattern is shown in Figure 10. From the XRD spectrum, it can be obtained that d 002 =0.389nm and L c =1.47nm of the hard carbon material. Its Raman spectrum is shown in FIG. 11 , and the Laman spectrum of the hard carbon material can be obtained as L a =3.75nm. Figure 12 is a microscopic picture of the powder taken with a scanning electron microscope (SEM). It can be seen from the figure that the particle size is between 10-20 μm.

将上述制备得到的热解硬碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例3。所测试的倍率为0.1C，放电截止电压为0.0V，充电截止电压为2.0V。其充放电曲线见图13，首周放电容量约320mAg/g，首周库仑效率87.0％，其可逆容量约为270mAh/g，在50周的循环过程中没有明显的容量衰减。其循环曲线在0.2V以下有首平稳的充放电平台，在可逆容量中，平台部分容量比例为81.1％。The pyrolytic hard carbon material prepared above was used as the active material of the negative electrode material of the battery for the preparation of the sodium ion battery, and electrochemical charge and discharge tests were performed. Its preparation process and testing method are the same as in Example 3. The tested rate is 0.1C, the discharge cut-off voltage is 0.0V, and the charge cut-off voltage is 2.0V. Its charge-discharge curve is shown in Figure 13. The first-week discharge capacity is about 320mAg/g, the first-week coulombic efficiency is 87.0%, and its reversible capacity is about 270mAh/g. There is no obvious capacity fading during the 50-week cycle. Its cycle curve has the first stable charging and discharging platform below 0.2V, and in the reversible capacity, the proportion of the platform part capacity is 81.1%.

实施例5Example 5

热解硬碳材料的制备过程同实施例2。The preparation process of the pyrolytic hard carbon material is the same as in Example 2.

将上述制备得到的热解硬碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例1。所测试的倍率为0.2C，放电截止电压为0.0V，充电截止电压为2.0V。其充放电曲线见图14，其可逆容量约为280mAh/g，在2倍于原来电池的循环倍率下，组装的电池虽然容量有所降低，但仍保持较高的循环稳定性。The pyrolytic hard carbon material prepared above was used as the active material of the negative electrode material of the battery for the preparation of the sodium ion battery, and electrochemical charge and discharge tests were performed. Its preparation process and test method are the same as in Example 1. The tested rate is 0.2C, the discharge cut-off voltage is 0.0V, and the charge cut-off voltage is 2.0V. Its charge-discharge curve is shown in Figure 14, and its reversible capacity is about 280mAh/g. At a cycle rate twice that of the original battery, although the capacity of the assembled battery is reduced, it still maintains high cycle stability.

实施例6Example 6

热解硬碳材料的制备：把榨汁后剩下的玉米渣放在烧杯里，置于100℃恒温烘箱里烘干24h。取出后，称取约1g玉米渣，放在约5cm*2cm*2cm的瓷舟内，准备用于高温碳化。Preparation of pyrolytic hard carbon material: Put the remaining corn dregs in a beaker after squeezing the juice, and dry it in a constant temperature oven at 100°C for 24 hours. After taking it out, weigh about 1g of corn dregs and put it in a porcelain boat of about 5cm*2cm*2cm, ready for high-temperature carbonization.

将该产物随瓷舟一起放在管式炉中，在氩气保护下，以1℃/min的速率升温至500℃，氩气流量为25mL/min，在500℃预热2h，再以5℃/min的速率升温到1300℃，保温2h，之后自然冷却至室温。将已碳化的玉米渣取出，在研钵中研磨成粉末，即得到热解硬碳产物。其X射线衍射(XRD)图谱参见图15。其拉曼光谱参见图16。图17为用扫描电子显微镜(SEM)拍摄的粉末微观图片，从图中可以看出，颗粒尺寸在10μm左右。Put the product together with the ceramic boat in a tube furnace, under the protection of argon, the temperature was raised to 500°C at a rate of 1°C/min, the flow rate of argon gas was 25mL/min, preheated at 500°C for 2h, and then heated for 5 The temperature was raised to 1300°C at a rate of °C/min, kept for 2 hours, and then cooled to room temperature naturally. The carbonized corn dregs are taken out and ground into powder in a mortar to obtain pyrolysis hard carbon products. See Figure 15 for its X-ray diffraction (XRD) pattern. Its Raman spectrum is shown in Figure 16. Figure 17 is a microscopic picture of the powder taken with a scanning electron microscope (SEM). It can be seen from the figure that the particle size is about 10 μm.

将上述制备得到的热解硬碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例2。所测试的倍率为0.1C，放电截止电压为0.0V，充电截止电压为2.0V。其充放电曲线见图18，其可逆容量约为270mAh/g，循环性能较好。The pyrolytic hard carbon material prepared above was used as the active material of the negative electrode material of the battery for the preparation of the sodium ion battery, and electrochemical charge and discharge tests were performed. Its preparation process and testing method are the same as in Example 2. The tested rate is 0.1C, the discharge cut-off voltage is 0.0V, and the charge cut-off voltage is 2.0V. Its charge and discharge curve is shown in Figure 18, its reversible capacity is about 270mAh/g, and its cycle performance is good.

实施例7Example 7

热解硬碳材料的制备：把榨汁后剩下的玉米渣放在烧杯里，置于120℃恒温烘箱里烘干20h。取出后，称取约1g玉米渣，放在约5cm*2cm*2cm的瓷舟内，准备用于高温碳化。Preparation of pyrolysis hard carbon material: put the remaining corn dregs in a beaker after squeezing the juice, and dry it in a constant temperature oven at 120°C for 20 hours. After taking it out, weigh about 1g of corn dregs and put it in a porcelain boat of about 5cm*2cm*2cm, ready for high-temperature carbonization.

将该产物随瓷舟一起放在管式炉中，在氩气保护下，以1℃/min的速率升温至500℃，氩气流量为25mL/min，在500℃预热2h，再以5℃/min的速率升温到1000℃，保温2h，之后自然冷却至室温。将已碳化的玉米渣取出，在研钵中研磨成粉末，即得到热解硬碳产物。Put the product together with the ceramic boat in a tube furnace, under the protection of argon, the temperature was raised to 500°C at a rate of 1°C/min, the flow rate of argon gas was 25mL/min, preheated at 500°C for 2h, and then heated for 5 The temperature was raised to 1000°C at a rate of °C/min, kept for 2 hours, and then cooled to room temperature naturally. The carbonized corn dregs are taken out and ground into powder in a mortar to obtain pyrolysis hard carbon products.

将上述制备得到的热解硬碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例2。所测试的倍率为0.1C，放电截止电压为0.0V，充电截止电压为2.0V。结果见下表1(为了方便对比，将实施例3-7的测试结果也一并放在表1中)。The pyrolytic hard carbon material prepared above was used as the active material of the negative electrode material of the battery for the preparation of the sodium ion battery, and electrochemical charge and discharge tests were performed. Its preparation process and testing method are the same as in Example 2. The tested rate is 0.1C, the discharge cut-off voltage is 0.0V, and the charge cut-off voltage is 2.0V. The results are shown in Table 1 below (for convenience of comparison, the test results of Examples 3-7 are also placed in Table 1).

实施例8Example 8

热解硬碳材料的制备：把榨汁后剩下的玉米渣放在烧杯里，置于80℃恒温烘箱里烘干26h。取出后，称取约1g玉米渣，放在约5cm*2cm*2cm的瓷舟内，准备用于高温碳化。Preparation of pyrolytic hard carbon material: put the remaining corn dregs in a beaker after squeezing the juice, and dry it in a constant temperature oven at 80°C for 26 hours. After taking it out, weigh about 1g of corn dregs and put it in a porcelain boat of about 5cm*2cm*2cm, ready for high-temperature carbonization.

将该产物随瓷舟一起放在管式炉中，在氩气保护下，以1℃/min的速率升温至500℃，氩气流量为25mL/min，在500℃预热2h，再以5℃/min的速率升温到1600℃，保温2h，之后自然冷却至室温。将已碳化的玉米渣取出，在研钵中研磨成粉末，即得到热解硬碳产物。Put the product together with the ceramic boat in a tube furnace, under the protection of argon, the temperature was raised to 500°C at a rate of 1°C/min, the flow rate of argon gas was 25mL/min, preheated at 500°C for 2h, and then heated for 5 The temperature was raised to 1600°C at a rate of °C/min, kept for 2 hours, and then cooled to room temperature naturally. The carbonized corn dregs are taken out and ground into powder in a mortar to obtain pyrolysis hard carbon products.

将上述制备得到的热解硬碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例2。所测试的倍率为0.1C，放电截止电压为0.0V，充电截止电压为2.0V。结果见下表1。The pyrolytic hard carbon material prepared above was used as the active material of the negative electrode material of the battery for the preparation of the sodium ion battery, and electrochemical charge and discharge tests were performed. Its preparation process and testing method are the same as in Example 2. The tested rate is 0.1C, the discharge cut-off voltage is 0.0V, and the charge cut-off voltage is 2.0V. The results are shown in Table 1 below.

实施例9Example 9

热解硬碳材料的制备：把玉米杆洗干净，去除杂质，切成约1cm厚的小段后，放在烧杯中置于80℃恒温烘箱里烘干26h。烘干后放在约5cm*2cm*2cm的瓷舟内，准备用于高温碳化。Preparation of pyrolytic hard carbon material: Wash corn stalks, remove impurities, cut into small pieces about 1 cm thick, put them in a beaker and dry them in a constant temperature oven at 80°C for 26 hours. After drying, put it in a porcelain boat of about 5cm*2cm*2cm, ready for high-temperature carbonization.

将该产物随瓷舟一起放在管式炉中，在氩气保护下，以1℃/min的速率升温至500℃，氩气流量为25mL/min，在500℃预热2h，再以5℃/min的速率升温到1300℃，保温2h，之后自然冷却至室温。将已碳化的玉米杆取出，在研钵中研磨成粉末，即得到热解硬碳产物。Put the product together with the ceramic boat in a tube furnace, under the protection of argon, the temperature was raised to 500°C at a rate of 1°C/min, the flow rate of argon gas was 25mL/min, preheated at 500°C for 2h, and then heated for 5 The temperature was raised to 1300°C at a rate of °C/min, kept for 2 hours, and then cooled to room temperature naturally. The carbonized corn stalks are taken out and ground into powder in a mortar to obtain pyrolysis hard carbon products.

将上述制备得到的热解硬碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例2。所测试的倍率为0.1C，放电截止电压为0.0V，充电截止电压为2.0V。结果见下表1。The pyrolytic hard carbon material prepared above was used as the active material of the negative electrode material of the battery for the preparation of the sodium ion battery, and electrochemical charge and discharge tests were performed. Its preparation process and testing method are the same as in Example 2. The tested rate is 0.1C, the discharge cut-off voltage is 0.0V, and the charge cut-off voltage is 2.0V. The results are shown in Table 1 below.

实施例10Example 10

热解硬碳材料的制备：把玉米杆洗干净，去除杂质，切成约1cm厚的小段后，放在烧杯中置于80℃恒温烘箱里烘干26h。烘干后放在约5cm*2cm*2cm的瓷舟内，准备用于高温碳化。Preparation of pyrolytic hard carbon material: Wash corn stalks, remove impurities, cut into small pieces about 1 cm thick, put them in a beaker and dry them in a constant temperature oven at 80°C for 26 hours. After drying, put it in a porcelain boat of about 5cm*2cm*2cm, ready for high-temperature carbonization.

将该产物随瓷舟一起放在管式炉中，在氩气保护下，以1℃/min的速率升温至500℃，氩气流量为25mL/min，在500℃预热2h，再以5℃/min的速率升温到1000℃，保温2h，之后自然冷却至室温。将已碳化的玉米杆取出，在研钵中研磨成粉末，即得到热解硬碳产物。Put the product together with the ceramic boat in a tube furnace, under the protection of argon, the temperature was raised to 500°C at a rate of 1°C/min, the flow rate of argon gas was 25mL/min, preheated at 500°C for 2h, and then heated for 5 The temperature was raised to 1000°C at a rate of °C/min, kept for 2 hours, and then cooled to room temperature naturally. The carbonized corn stalks are taken out and ground into powder in a mortar to obtain pyrolysis hard carbon products.

将上述制备得到的热解硬碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例2。所测试的倍率为0.1C，放电截止电压为0.0V，充电截止电压为2.0V。结果见下表1。The pyrolytic hard carbon material prepared above was used as the active material of the negative electrode material of the battery for the preparation of the sodium ion battery, and electrochemical charge and discharge tests were performed. Its preparation process and test method are the same as in Example 2. The tested rate is 0.1C, the discharge cut-off voltage is 0.0V, and the charge cut-off voltage is 2.0V. The results are shown in Table 1 below.

实施例11Example 11

热解硬碳材料的制备：把玉米杆洗干净，去除杂质，切成约1cm厚的小段后，放在烧杯中置于60℃恒温烘箱里烘干28h。烘干后放在约5cm*2cm*2cm的瓷舟内，准备用于高温碳化。Preparation of pyrolytic hard carbon material: Wash corn stalks to remove impurities, cut into small pieces about 1 cm thick, put them in a beaker and dry them in a constant temperature oven at 60°C for 28 hours. After drying, put it in a porcelain boat of about 5cm*2cm*2cm, ready for high-temperature carbonization.

将该产物随瓷舟一起放在管式炉中，在氩气保护下，以1℃/min的速率升温至500℃，氩气流量为25mL/min，在500℃预热2h，再以5℃/min的速率升温到1600℃，保温2h，之后自然冷却至室温。将已碳化的玉米杆取出，在研钵中研磨成粉末，即得到热解硬碳产物。Put the product together with the ceramic boat in a tube furnace, under the protection of argon, the temperature was raised to 500°C at a rate of 1°C/min, the flow rate of argon gas was 25mL/min, preheated at 500°C for 2h, and then heated for 5 The temperature was raised to 1600°C at a rate of °C/min, kept for 2 hours, and then cooled to room temperature naturally. The carbonized corn stalks are taken out and ground into powder in a mortar to obtain pyrolysis hard carbon products.

将上述制备得到的热解硬碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例2。所测试的倍率为0.1C，放电截止电压为0.0V，充电截止电压为2.0V。结果见下表1。The pyrolytic hard carbon material prepared above was used as the active material of the negative electrode material of the battery for the preparation of the sodium ion battery, and electrochemical charge and discharge tests were performed. Its preparation process and test method are the same as in Example 2. The tested rate is 0.1C, the discharge cut-off voltage is 0.0V, and the charge cut-off voltage is 2.0V. The results are shown in Table 1 below.

实施例12Example 12

热解硬碳材料的制备：把玉米皮洗干净，去除杂质，切成小于1cm*1cm的碎片后，放在烧杯中置于90℃恒温烘箱里烘干22h。烘干后放在约5cm*2cm*2cm的瓷舟内，准备用于高温碳化。Preparation of pyrolytic hard carbon material: Wash corn husks, remove impurities, cut into pieces smaller than 1cm*1cm, put them in a beaker and dry them in a constant temperature oven at 90°C for 22 hours. After drying, put it in a porcelain boat of about 5cm*2cm*2cm, ready for high-temperature carbonization.

将该产物随瓷舟一起放在管式炉中，在氩气保护下，以1℃/min的速率升温至500℃，氩气流量为25mL/min，在500℃预热2h，再以5℃/min的速率升温到1300℃，保温2h，之后自然冷却至室温。将已碳化的玉米皮取出，在研钵中研磨成粉末，即得到热解硬碳产物。Put the product together with the ceramic boat in a tube furnace, under the protection of argon, the temperature was raised to 500°C at a rate of 1°C/min, the flow rate of argon gas was 25mL/min, preheated at 500°C for 2h, and then heated for 5 The temperature was raised to 1300°C at a rate of °C/min, kept for 2 hours, and then cooled to room temperature naturally. The carbonized corn husks are taken out and ground into powder in a mortar to obtain pyrolysis hard carbon products.

将上述制备得到的热解硬碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例2。所测试的倍率为0.1C，放电截止电压为0.0V，充电截止电压为2.0V。结果见下表1。The pyrolytic hard carbon material prepared above was used as the active material of the negative electrode material of the battery for the preparation of the sodium ion battery, and electrochemical charge and discharge tests were performed. Its preparation process and test method are the same as in Example 2. The tested rate is 0.1C, the discharge cut-off voltage is 0.0V, and the charge cut-off voltage is 2.0V. The results are shown in Table 1 below.

实施例13Example 13

热解硬碳材料的制备：把玉米皮洗干净，去除杂质，切成小于1cm*1cm的碎片后，放在烧杯中置于80℃恒温烘箱里烘干26h。烘干后放在约5cm*2cm*2cm的瓷舟内，准备用于高温碳化。Preparation of pyrolytic hard carbon material: Wash corn husks, remove impurities, cut into pieces smaller than 1cm*1cm, put them in a beaker and dry them in a constant temperature oven at 80°C for 26 hours. After drying, put it in a porcelain boat of about 5cm*2cm*2cm, ready for high-temperature carbonization.

将该产物随瓷舟一起放在管式炉中，在氩气保护下，以1℃/min的速率升温至500℃，氩气流量为25mL/min，在500℃预热2h，再以5℃/min的速率升温到1000℃，保温2h，之后自然冷却至室温。将已碳化的玉米皮取出，在研钵中研磨成粉末，即得到热解硬碳产物。Put the product together with the ceramic boat in a tube furnace, under the protection of argon, the temperature was raised to 500°C at a rate of 1°C/min, the flow rate of argon gas was 25mL/min, preheated at 500°C for 2h, and then heated for 5 The temperature was raised to 1000°C at a rate of °C/min, kept for 2 hours, and then cooled to room temperature naturally. The carbonized corn husks are taken out and ground into powder in a mortar to obtain pyrolysis hard carbon products.

将上述制备得到的热解硬碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例2。所测试的倍率为0.1C，放电截止电压为0.0V，充电截止电压为2.0V。结果见下表1。The pyrolytic hard carbon material prepared above was used as the active material of the negative electrode material of the battery for the preparation of the sodium ion battery, and electrochemical charge and discharge tests were performed. Its preparation process and test method are the same as in Example 2. The tested rate is 0.1C, the discharge cut-off voltage is 0.0V, and the charge cut-off voltage is 2.0V. The results are shown in Table 1 below.

实施例14Example 14

热解硬碳材料的制备：把玉米皮洗干净，去除杂质，切成小于1cm*1cm的碎片后，放在烧杯中置于70℃恒温烘箱里烘干27h。烘干后放在约5cm*2cm*2cm的瓷舟内，准备用于高温碳化。Preparation of pyrolytic hard carbon material: Wash corn husks, remove impurities, cut into pieces smaller than 1cm*1cm, put them in a beaker and dry them in a constant temperature oven at 70°C for 27 hours. After drying, put it in a porcelain boat of about 5cm*2cm*2cm, ready for high-temperature carbonization.

将该产物随瓷舟一起放在管式炉中，在氩气保护下，以1℃/min的速率升温至500℃，氩气流量为25mL/min，在500℃预热2h，再以5℃/min的速率升温到1600℃，保温2h，之后自然冷却至室温。将已碳化的玉米皮取出，在研钵中研磨成粉末，即得到热解硬碳产物。Put the product together with the ceramic boat in a tube furnace, under the protection of argon, the temperature was raised to 500°C at a rate of 1°C/min, the flow rate of argon gas was 25mL/min, preheated at 500°C for 2h, and then heated for 5 The temperature was raised to 1600°C at a rate of °C/min, kept for 2 hours, and then cooled to room temperature naturally. The carbonized corn husks are taken out and ground into powder in a mortar to obtain pyrolysis hard carbon products.

将上述制备得到的热解硬碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例2。所测试的倍率为0.1C，放电截止电压为0.0V，充电截止电压为2.0V。结果见下表1。The pyrolytic hard carbon material prepared above was used as the active material of the negative electrode material of the battery for the preparation of the sodium ion battery, and electrochemical charge and discharge tests were performed. Its preparation process and test method are the same as in Example 2. The tested rate is 0.1C, the discharge cut-off voltage is 0.0V, and the charge cut-off voltage is 2.0V. The results are shown in Table 1 below.

表1不同实施例中制备的材料的相关结构参数和比容量Relevant structural parameters and specific capacity of the material prepared in the different embodiments of table 1

对比例comparative example

硬碳材料的制备：把除掉玉米粒的玉米瓤切成宽约1cm的小段，放在烧杯里，置于80℃恒温烘箱里烘烤24h。烘干后放在约5cm*2cm*2cm的瓷舟内，准备用于高温碳化。Preparation of the hard carbon material: cut the corn cobs with the corn kernels removed into small pieces about 1 cm wide, put them in a beaker, and bake them in a constant temperature oven at 80°C for 24 hours. After drying, put it in a porcelain boat of about 5cm*2cm*2cm, ready for high-temperature carbonization.

将玉米瓤随瓷舟一起放在管式炉(管长约100cm，直径6cm，以下实施例采用相同的管式炉)中，在氩气保护下，以1℃/min的速率升温至500℃，氩气流量为25mL/min，在500℃预碳化2h，再以5℃/min的速率升温到800℃，保温2h，之后自然冷却至室温。将已碳化的玉米段取出，在研钵中研磨成粉末，即得到热解硬碳产物。Put the corn cob together with the porcelain boat in a tube furnace (the tube is about 100 cm long and 6 cm in diameter, the same tube furnace is used in the following examples), and under the protection of argon, the temperature is raised to 500 °C at a rate of 1 °C/min , the flow rate of argon gas is 25mL/min, pre-carbonization at 500°C for 2h, and then the temperature is raised to 800°C at a rate of 5°C/min, kept for 2h, and then naturally cooled to room temperature. The carbonized corn segments are taken out and ground into powder in a mortar to obtain pyrolysis hard carbon products.

将上述制备得到的硬碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例2。所测试的倍率为0.1C，放电截止电压为0.0V，充电截止电压为2.0V。其充放电曲线见图19，首周放电容量约280mAg/g，首周库仑效率70.7％，其可逆容量约为200mAh/g。与实施例3-5相比，该材料的首周库仑效率更低，可逆容量也更低。不同于其他1000℃以上高温热解材料的循环性能，该材料的循环曲线在0.2V以下的部分没有表现出平台，而是呈斜坡状，在可逆容量中，0.2V以下部分容量比例为45.2％。以上数据表明，在较低碳化温度下热解得到的材料其电化学性能无法满足实际电池的性能要求。The hard carbon material prepared above was used as the active material of the negative electrode material of the battery for the preparation of the sodium ion battery, and electrochemical charge and discharge tests were carried out. Its preparation process and test method are the same as in Example 2. The tested rate is 0.1C, the discharge cut-off voltage is 0.0V, and the charge cut-off voltage is 2.0V. Its charge-discharge curve is shown in Figure 19. The discharge capacity in the first week is about 280mAg/g, the coulombic efficiency in the first week is 70.7%, and its reversible capacity is about 200mAh/g. Compared with Examples 3-5, the material has lower first-week Coulombic efficiency and lower reversible capacity. Different from the cycle performance of other high-temperature pyrolysis materials above 1000°C, the part of the cycle curve of this material below 0.2V does not show a plateau, but a slope. In the reversible capacity, the part below 0.2V has a capacity ratio of 45.2%. . The above data show that the electrochemical performance of the material obtained by pyrolysis at a lower carbonization temperature cannot meet the performance requirements of the actual battery.

本发明上述实施例中提供的硬碳材料制备简单、原材料资源丰富、成本低廉，是无污染的绿色材料，可以作为钠离子二次电池的负极活性材料应用于二次电池中。通过与对比例相比较，可以看出，采用本发明实施例提供的热解硬碳材料而获得的钠离子二次电池，具有较高的工作电压和能量密度、循环稳定、安全性能好，明显高于在较低碳化温度下热解得到的材料其电化学性能，可以应用于太阳能发电、风力发电、智能电网调峰、分布电站、后备电源或通信基站的大规模储能设备。The hard carbon material provided in the above embodiments of the present invention is simple to prepare, rich in raw material resources, low in cost, is a non-polluting green material, and can be used as a negative electrode active material of a sodium ion secondary battery in a secondary battery. By comparing with the comparative example, it can be seen that the sodium ion secondary battery obtained by using the pyrolysis hard carbon material provided by the embodiment of the present invention has a higher working voltage and energy density, stable cycle, and good safety performance, obviously Its electrochemical performance is higher than that of materials obtained by pyrolysis at a lower carbonization temperature, and can be applied to large-scale energy storage equipment for solar power generation, wind power generation, smart grid peak regulation, distributed power stations, backup power supplies or communication base stations.

以上所述的具体实施方式，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施方式而已，并不用于限定本发明的保护范围，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The specific embodiments described above have further described the purpose, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above descriptions are only specific embodiments of the present invention and are not intended to limit the scope of the present invention. Protection scope, within the spirit and principles of the present invention, any modification, equivalent replacement, improvement, etc., shall be included in the protection scope of the present invention.

Claims (6)

1. A pyrolytic hard carbon material, which is characterized by being prepared by the following method: drying the waste biomass; heating to 300-600 ℃ under inert atmosphere, and pre-carbonizing for 1-5 h; heating to 1300-1600 ℃ under inert atmosphere, carbonizing, and cracking for 1-10 h; cooling to obtain the pyrolytic carbon material; wherein,
the obtained pyrolytic hard carbon material is irregular blocky particles, the particle size is 1-20 mu m, and the average particle size is 5-10 mu m; d002The value is between 0.38 and 0.41nm, LcValue between 1.3 and 1.5nm, LaThe value is between 3.7 and 4.7nm；
Wherein the waste biomass comprises one or more of corn pulp, corn residue, corn stalks and corn husks.
2. A pyrolytic hard carbon material according to claim 1, characterized in that the carbon content of the pyrolytic hard carbon material is not less than 95%.
3. A pyrolytically hard carbon material as claimed in claim 1, characterised in that the surface of the material has a soft carbon coating.
4. A negative electrode material for a sodium ion secondary battery, characterized in that the negative electrode active material comprises the pyrolytic hard carbon material according to any one of claims 1 to 3.
5. A negative electrode plate of a sodium ion secondary battery, characterized in that the negative electrode plate comprises:
a current collector, a binder coated on the current collector and the negative electrode material of the sodium-ion secondary battery as claimed in claim 4.
6. A secondary battery comprising the negative electrode tab of claim 5.
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