CN107706417B - A kind of preparation method of spherical carbon anode material for lithium ion battery - Google Patents

A kind of preparation method of spherical carbon anode material for lithium ion battery Download PDF

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CN107706417B
CN107706417B CN201711160144.3A CN201711160144A CN107706417B CN 107706417 B CN107706417 B CN 107706417B CN 201711160144 A CN201711160144 A CN 201711160144A CN 107706417 B CN107706417 B CN 107706417B
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lithium ion
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宋怀河
杨琳
曹瑞雄
马兆昆
恽海顺
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Changzhou Tanda New Material Technology Co ltd
Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Abstract

The invention relates to a preparation method of a spherical carbon negative electrode material of a lithium ion battery. The method comprises the steps of taking starch as a raw material, uniformly mixing the starch with iron powder according to a certain proportion, carrying out stabilization treatment in an air atmosphere at the temperature of 200-250 ℃, then carrying out high-temperature carbonization in an inert atmosphere, and obtaining the spherical carbon negative electrode material through acid washing, water washing, suction filtration and drying. The iron powder is added to separate starch granules from each other, so that the phenomenon that the starch granules are heated unevenly is avoided, the stabilization time is greatly shortened, and the prepared carbon microspheres keep the original shape of the starch granules and have the grain diameter of 2-40 mu m. The method has simple process and low requirement on equipment, and the obtained carbon microspheres have excellent appearance and show excellent electrochemical performance when being used as the cathode material of the lithium ion battery.

Description

一种锂离子电池球形炭负极材料的制备方法A kind of preparation method of spherical carbon anode material for lithium ion battery

技术领域technical field

本发明涉及一种球形炭的制备方法及其在锂离子电池方面的应用,属于锂离子电池负极材料技术领域。The invention relates to a preparation method of spherical carbon and its application in lithium ion batteries, and belongs to the technical field of negative electrode materials of lithium ion batteries.

背景技术Background technique

电子产品在我们的日常生活中扮演着越来越重要的角色,电池市场竞争激烈,锂离子电池因能量密度大,平均输出电压高,循环稳定性好,使用寿命长,体积小,质量轻,无记忆效应,安全可靠等优势,在消费型电子、电动汽车和储能等领域应用广泛。Electronic products play an increasingly important role in our daily life. The battery market is highly competitive. Lithium-ion batteries have high energy density, high average output voltage, good cycle stability, long service life, small size and light weight. It has the advantages of no memory effect, safety and reliability, and is widely used in consumer electronics, electric vehicles and energy storage.

锂离子电池负极材料容量的提高是其能量密度提高的关键之一。炭材料是锂离子电池负极材料的理想选择,目前主要以石墨类材料应用最为广泛。随着锂离子电池应用领域的扩展,对其性能要求不断提高,石墨负极材料的比能量、循环性能及安全性等方面的局限性越来越突出。炭微球具有良好的热稳定性、导热导电性、堆积密度高、表面积体积比低,可以减少SEI膜等副反应所引起的不可逆容量损失,从而利于提高锂离子电池的电化学性能,是研究热点。The improvement of the capacity of anode materials for lithium-ion batteries is one of the keys to the improvement of their energy density. Carbon material is an ideal choice for lithium-ion battery anode material, and currently, graphite-based materials are the most widely used. With the expansion of the application field of lithium-ion batteries, the performance requirements of lithium-ion batteries have been continuously improved, and the limitations of graphite anode materials in terms of specific energy, cycle performance and safety have become more and more prominent. Carbon microspheres have good thermal stability, thermal conductivity, high bulk density, and low surface area-to-volume ratio, which can reduce irreversible capacity loss caused by side reactions such as SEI films, thereby improving the electrochemical performance of lithium-ion batteries. hot spot.

文献“Non-catalytic CVD preparation of carbon spheres with a specificsize(Carbon,2004,42(4),761-766)”中,作者以甲苯为原料,采用自制的双炉化学气相沉积装置在不添加催化剂的条件下制备球形炭材料。文献“The production of carbonmaterials by hydrothermal carbonization of cellulose Carbon,2009.47(9):2281-2289”中,以纤维素、桉树木屑等为碳源,通过水热法和KOH活化制备炭微球。李永峰等采用煤为原料,改变等离子体的条件制得了炭微球,该制备过程在直流电弧等离子体蒸发实验装置上完成(一种新颖煤基球形炭及其形成机理.大连理工大学学报,2002,42(6):663-668)。文献“Monodispersed hard carbon spherules with uniform nanopores”中以蔗糖为碳源,在190℃密闭条件下脱水,在氩气气氛下进行高温炭化,制备出了比表面积为400m2/g的单分散的炭微球。综上来看,炭微球的很多制备方法对实验条件和设备的要求较高,很大程度的限制了炭微球负极材料的商业化进程,而且制备炭微球的前驱体大多数为不可再生或环境不友好的前驱体。所以简化制备工艺,采用环保的前驱体,提高产率成为炭微球研究的方向。淀粉来源丰富,成本低廉,通过前期的氧化处理,可以制得保持淀粉颗粒原始球形形貌的炭微球材料,不仅降低了成球工艺难度,降低了锂离子电池负极材料的制备成本,而且原料绿色环保可再生,缓解了化石资源短缺的难题。In the document "Non-catalytic CVD preparation of carbon spheres with a specific size (Carbon, 2004, 42(4), 761-766)", the author used toluene as a raw material and used a self-made double-furnace chemical vapor deposition device in a catalyst-free environment. Spherical carbon materials were prepared under the conditions. In the document "The production of carbonmaterials by hydrothermal carbonization of cellulose Carbon, 2009.47(9):2281-2289", carbon microspheres were prepared by hydrothermal method and KOH activation using cellulose, eucalyptus wood chips, etc. as carbon sources. Li Yongfeng et al. used coal as raw material and changed the plasma conditions to prepare carbon microspheres. The preparation process was completed on a DC arc plasma evaporation experimental device (a novel coal-based spherical carbon and its formation mechanism. Journal of Dalian University of Technology, 2002, 42(6):663-668). In the literature "Monodispersed hard carbon spherules with uniform nanopores", sucrose was used as the carbon source, dehydrated at 190 °C in a closed condition, and carbonized at high temperature in an argon atmosphere to prepare monodisperse carbon microparticles with a specific surface area of 400 m 2 /g. ball. In summary, many preparation methods of carbon microspheres have high requirements on experimental conditions and equipment, which greatly limits the commercialization process of carbon microsphere anode materials, and most of the precursors for preparing carbon microspheres are non-renewable. or environmentally unfriendly precursors. Therefore, simplifying the preparation process, using environmentally friendly precursors, and improving the yield have become the research directions of carbon microspheres. Starch is rich in sources and low in cost. Through the early oxidation treatment, carbon microsphere materials that maintain the original spherical shape of starch granules can be obtained, which not only reduces the difficulty of the sphere-forming process, but also reduces the preparation cost of negative electrode materials for lithium ion batteries. Green, environmentally friendly and renewable, alleviating the problem of shortage of fossil resources.

专利CN103647082A在减压条件下,通过低温稳定化、高温炭化制备出硬炭微球负极材料,该方法可避免炭化后炭微球的结块现象,降低硬炭微球的不可逆容量,提高材料的循环稳定性。此方法为了消除炭微球的发泡结块现象,需要长时间(8-100h)低温稳定化处理,使得炭微球的制备时间过长,降低了制备效率。专利CN102364727A将淀粉基硬炭微球与膨胀石墨复合,形成人造的固体空间导电网络结构,改善了硬炭材料的电压滞后现象,提高了材料的首次效率。此方法中炭微球与膨胀石墨复合工艺繁琐,而且增加了材料的制备成本。Patent CN103647082A prepares hard carbon microsphere negative electrode material through low temperature stabilization and high temperature carbonization under reduced pressure. This method can avoid the agglomeration of carbon microspheres after carbonization, reduce the irreversible capacity of hard carbon microspheres, and improve the material's performance. Cyclic Stability. In order to eliminate the foaming and agglomeration phenomenon of carbon microspheres, this method requires a long time (8-100h) of low temperature stabilization treatment, which makes the preparation time of carbon microspheres too long and reduces the preparation efficiency. Patent CN102364727A combines starch-based hard carbon microspheres with expanded graphite to form an artificial solid space conductive network structure, which improves the voltage hysteresis of hard carbon materials and improves the first efficiency of the material. In this method, the composite process of carbon microspheres and expanded graphite is complicated, and the preparation cost of the material is increased.

发明内容SUMMARY OF THE INVENTION

针对现有技术中存在的问题,本发明旨在提供一种以淀粉为前驱体,通过添加铁粉以缩短稳定化时间来制备用于锂离子电池负极的球形炭的方法。In view of the problems in the prior art, the present invention aims to provide a method for preparing spherical carbon for lithium ion battery negative electrode by adding iron powder as a precursor to shorten the stabilization time by using starch as a precursor.

本发明所用的技术方案:一种球形炭的制备方法,具体步骤如下:Technical scheme used in the present invention: a preparation method of spherical carbon, the concrete steps are as follows:

1、将原料淀粉与铁粉按一定比例混合均匀,在200-250℃温度范围内进行加热稳定化预处理;1. Mix the raw starch and iron powder uniformly in a certain proportion, and perform heating stabilization pretreatment in the temperature range of 200-250 °C;

2、将步骤1中稳定化试样置于高温管式炉中,在惰性气氛下于600-1200℃温度范围内进行高温炭化0.5-3h,冷却后得到炭化产物;2. Place the stabilized sample in step 1 in a high-temperature tube furnace, and perform high-temperature carbonization in the temperature range of 600-1200 °C under an inert atmosphere for 0.5-3 hours, and obtain a carbonized product after cooling;

3、将步骤2中的炭化产物酸洗,用去离子水洗,抽滤,烘干,得到锂离子电池球形炭负极材料。3. Pickling the carbonized product in step 2, washing with deionized water, suction filtration, and drying to obtain a spherical carbon negative electrode material for lithium ion batteries.

优选的,所述步骤1中的淀粉原料为马铃薯淀粉、玉米淀粉、小麦淀粉、木薯淀粉、大米淀粉、红薯淀粉、绿豆淀粉中的至少一种。Preferably, the starch raw material in the step 1 is at least one of potato starch, corn starch, wheat starch, tapioca starch, rice starch, sweet potato starch, and mung bean starch.

优选的,所述步骤1中的铁粉为高纯铁粉,粒径为300-1000目。Preferably, the iron powder in the step 1 is high-purity iron powder, and the particle size is 300-1000 mesh.

优选的,所述步骤1中的淀粉与铁粉的混合比例为1:1-100:1。Preferably, the mixing ratio of starch and iron powder in the step 1 is 1:1-100:1.

优选的,所述步骤1中稳定化处理时间为1-12h。Preferably, the stabilization treatment time in the step 1 is 1-12h.

优选的,步骤2中的惰性气氛为高纯氮气。Preferably, the inert atmosphere in step 2 is high-purity nitrogen.

优选的,步骤2中的炭化温度为700-1000℃。Preferably, the carbonization temperature in step 2 is 700-1000°C.

优选的,步骤2中的炭化时间为1-2h。Preferably, the carbonization time in step 2 is 1-2h.

优选的,步骤3中所用的酸为1%稀盐酸。Preferably, the acid used in step 3 is 1% dilute hydrochloric acid.

本发明具有原料来源丰富,成本低,制备流程简单,无污染等特点。通过在淀粉中添加铁粉进行稳定化处理,将淀粉颗粒相互隔开,在同样的稳定化温度下,可以避免淀粉颗粒间的融并、淀粉颗粒因相互堆积而受热不均匀的现象,大大缩短了淀粉的前期稳定化时间,节约资源,使得制备效率得以提升。The invention has the characteristics of abundant raw material sources, low cost, simple preparation process, no pollution and the like. By adding iron powder to the starch for stabilization treatment, the starch granules are separated from each other. At the same stabilization temperature, the fusion of starch granules and the uneven heating of starch granules due to mutual accumulation can be avoided. The pre-stabilization time of starch is shortened, resources are saved, and the preparation efficiency is improved.

通过添加铁粉将淀粉颗粒相互隔开,进行稳定化或炭化处理,淀粉颗粒受热均匀,提高了所制备样品的一致性。操作工艺简单,对设备要求低,易于大规模制备生产。本发明制备的淀粉基炭微球球形形貌佳,用于锂离子电池负极材料表现出优异的循环稳定性与倍率性能。By adding iron powder to separate the starch granules from each other, for stabilization or carbonization treatment, the starch granules are heated evenly, which improves the consistency of the prepared samples. The operation process is simple, the equipment requirements are low, and the large-scale preparation and production are easy. The starch-based carbon microspheres prepared by the invention have good spherical morphology, and show excellent cycle stability and rate performance when used as negative electrode materials for lithium ion batteries.

附图说明Description of drawings

图1为本发明所用原料马铃薯淀粉的扫描电子显微镜(SEM)图。Fig. 1 is the scanning electron microscope (SEM) picture of the raw material potato starch used in the present invention.

图2为本发明实施例1制备的淀粉基炭微球负极材料的扫描电子显微镜图。2 is a scanning electron microscope image of the starch-based carbon microsphere negative electrode material prepared in Example 1 of the present invention.

图3为本发明对比例1制备的淀粉基炭微球负极材料的扫描电子显微镜图。3 is a scanning electron microscope image of the starch-based carbon microsphere negative electrode material prepared in Comparative Example 1 of the present invention.

图4为实施例1制备的炭微球负极材料在50mA/g电流密度下的循环性能曲线。4 is a cycle performance curve of the carbon microsphere negative electrode material prepared in Example 1 at a current density of 50 mA/g.

图5为实施例1制备的炭微球负极材料在0.05-2A/g电流密度下的倍率性能曲线。5 is a rate performance curve of the carbon microsphere negative electrode material prepared in Example 1 at a current density of 0.05-2 A/g.

具体实施方式Detailed ways

下面以实施例的方式对本发明做进一步的说明,但不构成对本发明的限制。The present invention will be further described below by way of examples, but it does not constitute a limitation of the present invention.

实施例1Example 1

将10g马铃薯淀粉与10g铁粉充分搅拌混合,将混合物放入马弗炉中,在空气气氛下,以5℃/min的升温速率升至230℃保温8h,进行稳定化处理,随后将稳定化样放入炭化炉中,在氮气气氛下,以1.5℃/min的升温速率升温至700℃保持1h。将炭化物置于烧杯中,加1%稀盐酸处理,然后用去离子水洗涤数次,抽滤,烘干,得到马铃薯淀粉基炭微球,其粒径范围为5.5-32.6μm。10g potato starch and 10g iron powder were fully stirred and mixed, and the mixture was put into a muffle furnace. The sample was placed in a carbonization furnace, and in a nitrogen atmosphere, the temperature was raised to 700 °C at a heating rate of 1.5 °C/min for 1 h. The carbonized material is placed in a beaker, treated with 1% dilute hydrochloric acid, washed with deionized water for several times, suction filtered, and dried to obtain potato starch-based carbon microspheres with a particle size range of 5.5-32.6 μm.

将所得炭微球用作锂离子电池负极材料组装电池,测试其循环性能、倍率性能。测试条件为:25℃,电流密度0.05-2A/g,电压范围0.01-3V。The obtained carbon microspheres were used as negative electrode materials for lithium ion batteries to assemble batteries, and their cycle performance and rate performance were tested. The test conditions are: 25°C, current density 0.05-2A/g, voltage range 0.01-3V.

如附图5所示,所得炭微球用作锂离子电池负极材料,在50mA/g的电流密度下,可逆比容量为323.2mAh/g。在2A/g电流密度下,可逆比容量为82.7mAh/g。循环性能优异,当电流密度回归50mA/g时,可逆比容量达到336.3mAh/g。As shown in FIG. 5 , the obtained carbon microspheres were used as negative electrode materials for lithium-ion batteries, and at a current density of 50 mA/g, the reversible specific capacity was 323.2 mAh/g. At a current density of 2 A/g, the reversible specific capacity was 82.7 mAh/g. The cycle performance is excellent. When the current density returns to 50 mA/g, the reversible specific capacity reaches 336.3 mAh/g.

实施例2Example 2

将10g马铃薯淀粉与0.1g铁粉充分搅拌混合,将混合物放入马弗炉中,在空气气氛下,以5℃/min的升温速率升至230℃保温8h,进行稳定化处理,随后将稳定化样放入炭化炉中,在氮气气氛下,以1.5℃/min的升温速率升温至700℃保持1h。将炭化物置于烧杯中,加1%稀盐酸处理,然后用去离子水洗涤数次,抽滤,烘干,得到马铃薯淀粉基炭微球,其粒径范围为6.0-30.66μm。将所得炭材料组装电池并进行电化学性能测试,电流密度为50mAh/g下,首次放电比容量为645.6mAh/g,可逆比容量为350.5mAh/g,循环50次后的容量保持率为70%。10g potato starch and 0.1g iron powder were fully stirred and mixed, the mixture was put into a muffle furnace, and in an air atmosphere, the temperature was raised to 230°C at a heating rate of 5°C/min for 8 hours, and then stabilized. The chemical samples were placed in a carbonization furnace, and in a nitrogen atmosphere, the temperature was raised to 700 °C at a heating rate of 1.5 °C/min for 1 h. The carbonized material is placed in a beaker, treated with 1% dilute hydrochloric acid, washed with deionized water for several times, suction filtered, and dried to obtain potato starch-based carbon microspheres with a particle size range of 6.0-30.66 μm. The obtained carbon material was assembled into a battery and tested for electrochemical performance. At a current density of 50mAh/g, the first discharge specific capacity was 645.6mAh/g, the reversible specific capacity was 350.5mAh/g, and the capacity retention rate after 50 cycles was 70. %.

实施例3Example 3

将10g马铃薯淀粉与1g铁粉充分搅拌混合,将混合物放入马弗炉中,在空气气氛下,以5℃/min的升温速率升至230℃保温8h,进行稳定化处理,随后将稳定化样放入炭化炉中,在氮气气氛下,以1.5℃/min的升温速率升温至700℃保持1h。将炭化物置于烧杯中,加1%稀盐酸处理,然后用去离子水洗涤数次,抽滤,烘干,得到马铃薯淀粉基炭微球。其粒径范围为3.9-28.13μm。10g of potato starch and 1g of iron powder were fully stirred and mixed, and the mixture was put into a muffle furnace. The sample was placed in a carbonization furnace, and in a nitrogen atmosphere, the temperature was raised to 700 °C at a heating rate of 1.5 °C/min for 1 h. The carbonized product was placed in a beaker, treated with 1% dilute hydrochloric acid, washed several times with deionized water, suction filtered, and dried to obtain potato starch-based carbon microspheres. Its particle size range is 3.9-28.13 μm.

实施例4Example 4

将10g马铃薯淀粉与1g铁粉充分搅拌混合,将混合物放入马弗炉中,在空气气氛下,以5℃/min的升温速率升至230℃保温12h,进行稳定化处理,随后将稳定化样放入炭化炉中,在氮气气氛下,以1.5℃/min的升温速率升温至700℃保持1h。将炭化物置于烧杯中,加1%稀盐酸处理,然后用去离子水洗涤数次,抽滤,烘干,得到马铃薯淀粉基炭微球。10g potato starch and 1g iron powder were fully stirred and mixed, and the mixture was put into a muffle furnace. The sample was placed in a carbonization furnace, and in a nitrogen atmosphere, the temperature was raised to 700 °C at a heating rate of 1.5 °C/min for 1 h. The carbonized product was placed in a beaker, treated with 1% dilute hydrochloric acid, washed several times with deionized water, suction filtered, and dried to obtain potato starch-based carbon microspheres.

实施例5Example 5

将10g马铃薯淀粉与1g铁粉充分搅拌混合,将混合物放入马弗炉中,在空气气氛下,以5℃/min的升温速率升至230℃保温2h,进行稳定化处理,随后将稳定化样放入炭化炉中,在氮气气氛下,以1.5℃/min的升温速率升温至700℃保持1h。将炭化物置于烧杯中,加1%稀盐酸处理,然后用去离子水洗涤数次,抽滤,烘干,得到马铃薯淀粉基炭微球。10g potato starch and 1g iron powder are fully stirred and mixed, and the mixture is put into a muffle furnace. The sample was placed in a carbonization furnace, and in a nitrogen atmosphere, the temperature was raised to 700 °C at a heating rate of 1.5 °C/min for 1 h. The carbonized product was placed in a beaker, treated with 1% dilute hydrochloric acid, washed several times with deionized water, suction filtered, and dried to obtain potato starch-based carbon microspheres.

实施例6Example 6

将10g马铃薯淀粉与1g铁粉充分搅拌混合,将混合物放入马弗炉中,在空气气氛下,以5℃/min的升温速率升至230℃保温8h,进行稳定化处理,随后将稳定化样放入炭化炉中,在氮气气氛下,以1.5℃/min的升温速率升温至1000℃保持1h。将炭化物置于烧杯中,加1%稀盐酸处理,然后用去离子水洗涤数次,抽滤,烘干,得到马铃薯淀粉基炭微球。其粒径范围为6-32μm。10g of potato starch and 1g of iron powder were fully stirred and mixed, and the mixture was put into a muffle furnace. The sample was placed in a carbonization furnace, and in a nitrogen atmosphere, the temperature was raised to 1000 °C at a heating rate of 1.5 °C/min for 1 h. The carbonized product was placed in a beaker, treated with 1% dilute hydrochloric acid, washed several times with deionized water, suction filtered, and dried to obtain potato starch-based carbon microspheres. Its particle size range is 6-32 μm.

实施例7Example 7

将10g玉米淀粉与10g铁粉充分搅拌混合,将混合物放入马弗炉中,在空气气氛下,以5℃/min的升温速率升至230℃保温8h,进行稳定化处理,随后将稳定化样放入炭化炉中,在氮气气氛下,以1.5℃/min的升温速率升温至700℃保持1h。将炭化物置于烧杯中,加1%稀盐酸处理,然后用去离子水洗涤数次,抽滤,烘干,得到玉米淀粉基炭材料。10g cornstarch and 10g iron powder are fully stirred and mixed, and the mixture is put into a muffle furnace. The sample was placed in a carbonization furnace, and in a nitrogen atmosphere, the temperature was raised to 700 °C at a heating rate of 1.5 °C/min for 1 h. The carbonized material is placed in a beaker, treated with 1% dilute hydrochloric acid, washed several times with deionized water, suction filtered, and dried to obtain a cornstarch-based carbon material.

实施例8Example 8

将10g小麦淀粉与10g铁粉充分搅拌混合,将混合物放入马弗炉中,在空气气氛下,以5℃/min的升温速率升至230℃保温8h,进行稳定化处理,随后将稳定化样放入炭化炉中,在氮气气氛下,以1.5℃/min的升温速率升温至700℃保持1h。将炭化物置于烧杯中,加1%稀盐酸处理,然后用去离子水洗涤数次,抽滤,烘干,得到小麦淀粉基炭材料。10g wheat starch and 10g iron powder were fully stirred and mixed, and the mixture was put into a muffle furnace. The sample was placed in a carbonization furnace, and in a nitrogen atmosphere, the temperature was raised to 700 °C at a heating rate of 1.5 °C/min for 1 h. The carbonized material is placed in a beaker, treated with 1% dilute hydrochloric acid, washed several times with deionized water, suction filtered, and dried to obtain a wheat starch-based carbon material.

对比例1Comparative Example 1

将10g马铃薯淀粉放入马弗炉中,在空气气氛下,以5℃/min的升温速率升至230℃保温8h,进行稳定化处理,随后将稳定化样放入炭化炉中,在氮气气氛下,以1.5℃/min的升温速率升温至700℃保持1h,待冷却后得到马铃薯淀粉基炭材料。本例与实施例1相比,将马铃薯淀粉直接稳定化处理,在后期炭化过程中,淀粉颗粒发生融并与粘连现象,未能完全保留马铃薯淀粉颗粒的球形形貌。Put 10 g of potato starch into a muffle furnace, and in an air atmosphere, raise the temperature to 230 °C for 8 h at a heating rate of 5 °C/min for stabilization treatment. At the heating rate of 1.5°C/min, the temperature was raised to 700°C for 1 h, and the potato starch-based carbon material was obtained after cooling. Compared with Example 1, the potato starch was directly stabilized in this example. During the later carbonization process, the starch granules were melted and adhered, and the spherical shape of the potato starch granules could not be completely preserved.

以上已对本发明的部分实施例进行了具体说明,但本发明并不限于上述所述实施例,熟悉本领域的技术人员在不违背本发明精神的前提下可作出等同的变型或替换,这些等同的变型或替换均包含在本申请权利要求所限定的范围内。Some embodiments of the present invention have been specifically described above, but the present invention is not limited to the above-mentioned embodiments. Those skilled in the art can make equivalent modifications or substitutions without departing from the spirit of the present invention. Variations or substitutions of the above are all included within the scope defined by the claims of the present application.

Claims (4)

1. A preparation method of a spherical carbon negative electrode material of a lithium ion battery is provided, the particle diameter of the spherical carbon negative electrode material is 2-40 μm, and the preparation method is characterized by comprising the following steps:
(1) the starch raw material is at least one of potato starch, corn starch, wheat starch, tapioca starch, rice starch and mung bean starch, the starch raw material and iron powder are fully and uniformly mixed according to a certain proportion, and the mixture is subjected to heating stabilization pretreatment for 1-12h within the temperature range of 200-;
(2) placing the stabilized sample in the step (1) in an inert atmosphere, carbonizing at the temperature of 600-1200 ℃ for 0.5-3h, and cooling to obtain a carbonized product;
(3) and (3) pickling the carbide obtained in the step (2), washing with deionized water, performing suction filtration, and drying to obtain the spherical carbon negative electrode material of the lithium ion battery.
2. The preparation method of the spherical carbon negative electrode material of the lithium ion battery according to claim 1, characterized by comprising the following steps: the particle size of the iron powder is 300-1000 meshes.
3. The preparation method of the spherical carbon negative electrode material of the lithium ion battery according to claim 1, characterized by comprising the following steps: the mixing ratio of the starch and the iron powder in the step (1) is 1: 1-500: 1.
4. the preparation method of the spherical carbon negative electrode material of the lithium ion battery according to claim 1, characterized by comprising the following steps:
the acid in the step (3) is 1% dilute hydrochloric acid.
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