CN117069097A - Preparation method and application of hierarchical pore hard carbon material - Google Patents

Preparation method and application of hierarchical pore hard carbon material Download PDF

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CN117069097A
CN117069097A CN202311033376.8A CN202311033376A CN117069097A CN 117069097 A CN117069097 A CN 117069097A CN 202311033376 A CN202311033376 A CN 202311033376A CN 117069097 A CN117069097 A CN 117069097A
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孙雍荣
谢东
李发勇
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Institute of Biological and Medical Engineering of Guangdong Academy of Sciences
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Abstract

本发明公开了一种多级孔硬碳的制备方法及其应用,以富含纤维素的甘蔗渣为硬碳前驱体,金属纳米颗粒为造孔剂,构筑多级孔硬碳材料,解决了钠离子电池的首圈库伦效率低、循环稳定性差、储钠性能低的问题。

The invention discloses a preparation method and application of hierarchical porous hard carbon. Cellulose-rich sugarcane bagasse is used as the hard carbon precursor and metal nanoparticles are used as pore-forming agents to construct hierarchical porous hard carbon materials, which solves the problem of Sodium-ion batteries have problems such as low first-cycle Coulombic efficiency, poor cycle stability, and low sodium storage performance.

Description

一种多级孔硬碳材料的制备方法与应用Preparation method and application of hierarchical porous hard carbon material

技术领域:Technical areas:

本发明涉及钠离子电池负极材料技术领域,具体涉及一种多级孔硬碳的制备方法与应用。The invention relates to the technical field of negative electrode materials for sodium ion batteries, and in particular to a preparation method and application of hierarchical porous hard carbon.

背景技术:Background technique:

目前安全可靠的新型储能系统的研究变得尤为重要。在新型电化学储能系统中,锂离子电池以其高容量、长循环寿命等优势已被广泛应用于智能电网、电动汽车和移动通讯等领域,然而锂资源在地壳中储量低、分布不均匀、价格昂贵等问题在近年来日益凸显。开发价格低廉、资源储量丰富的新型电化学储能系统显得尤为重要。At present, research on safe and reliable new energy storage systems has become particularly important. In new electrochemical energy storage systems, lithium-ion batteries have been widely used in smart grids, electric vehicles, mobile communications and other fields due to their advantages such as high capacity and long cycle life. However, lithium resources are low in reserves and unevenly distributed in the earth's crust. , high price and other issues have become increasingly prominent in recent years. It is particularly important to develop new electrochemical energy storage systems with low prices and abundant resource reserves.

相比于锂资源的诸多问题,钠资源储量丰富、分布广泛,价格低廉,且在化学元素周期表中其与锂处于同一主族中理化性质接近,因此钠离子电池在储能系统中展现出了广阔的发展空间和应用场景。但与锂离子电池相比,钠离子半径较大,使得钠离子在脱嵌过程中迁移缓慢、体积膨胀严重,因此寻找适宜的电极材料是推动钠离子电池发展的关键。对于钠离子电池来说,正极材料主要以层状氧化物和聚阴离子化合物为主,且正极材料表现了良好的能量密度和循环性。与之匹配的负极材料目前还处于短板,为此开发高性能的负极材料是现阶段钠离子电池的热点和重点。Compared with the many problems of lithium resources, sodium resources are abundant, widely distributed, and cheap. In the periodic table of chemical elements, they are in the same main group as lithium and have similar physical and chemical properties. Therefore, sodium-ion batteries have shown great potential in energy storage systems. It provides a broad development space and application scenarios. However, compared with lithium-ion batteries, the radius of sodium ions is larger, causing sodium ions to migrate slowly and expand seriously during the deintercalation process. Therefore, finding suitable electrode materials is the key to promoting the development of sodium-ion batteries. For sodium-ion batteries, the cathode materials are mainly layered oxides and polyanionic compounds, and the cathode materials show good energy density and cyclability. The matching negative electrode materials are still in a shortcoming, and the development of high-performance negative electrode materials is the hot spot and focus of sodium-ion batteries at this stage.

钠离子电池负极材料主要分为碳基、金属合金、金属氧化物及其他化合物等。相比于其他材料,碳基材料因具有资源丰富、价格低廉、制备工艺简单等优点,而被认为是最有前景的负极材料。目前碳基材料主要有石墨、软碳、硬碳。然而,石墨类的碳材料因钠离子半径较大,增加了钠离子在石墨层间脱嵌的难度,进而导致性能降低。软碳是指有序度较高的非晶碳材料,且在2800℃以上能够完全石墨化;目前软碳材料的优势在于成本低,首次充放电效率高,但是其克容量较低,主流容量一般在220-240mA h g-1;相比于其他碳材料,硬碳则具备较高的克容量300mA h g-1,但其首圈库伦效率低和长循环稳定差的问题严重阻碍了硬碳在钠离子电池中的应用。Sodium-ion battery anode materials are mainly divided into carbon-based, metal alloys, metal oxides and other compounds. Compared with other materials, carbon-based materials are considered to be the most promising anode materials due to their advantages such as abundant resources, low price, and simple preparation process. At present, carbon-based materials mainly include graphite, soft carbon, and hard carbon. However, graphite-like carbon materials have a large sodium ion radius, which increases the difficulty of sodium ions being deintercalated between graphite layers, resulting in reduced performance. Soft carbon refers to amorphous carbon materials with a high degree of order and can be completely graphitized above 2800°C. Currently, the advantages of soft carbon materials are low cost and high first charge and discharge efficiency, but their gram capacity is low and the mainstream capacity is Generally, it is 220-240mA hg -1 ; compared with other carbon materials, hard carbon has a higher gram capacity of 300mA hg -1 , but its low Coulombic efficiency in the first cycle and poor long-term cycle stability seriously hinder the use of hard carbon. Applications in sodium-ion batteries.

发明内容:Contents of the invention:

本发明的目的是提供一种多级孔硬碳的制备方法及其应用,以富含纤维素的甘蔗渣为硬碳前驱体,金属纳米颗粒为造孔剂,构筑多级孔硬碳材料,并将其应用于钠离子电池中,以解决钠离子电池首圈库伦效率低、循环稳定性差、储钠性能低的问题。The purpose of the present invention is to provide a preparation method and application of hierarchical porous hard carbon. Cellulose-rich sugarcane bagasse is used as the hard carbon precursor and metal nanoparticles are used as pore-forming agents to construct hierarchical porous hard carbon materials. And apply it to sodium-ion batteries to solve the problems of low first-cycle Coulombic efficiency, poor cycle stability, and low sodium storage performance of sodium-ion batteries.

本发明是通过以下技术方案予以实现的:The present invention is realized through the following technical solutions:

一种多级孔硬碳的制备方法,该方法包括以下步骤:A method for preparing hierarchical porous hard carbon, which method includes the following steps:

1)以硝酸铁(Fe(NO3)3)、硝酸钴(Co(NO3)2)、硝酸镍(Ni(NO3)2)等金属盐中的一种作为原料,去离子水为溶剂,超声、搅拌,形成金属离子浓度为0.5wt%~2.0wt%的均一溶液A;1) Use one of metal salts such as iron nitrate (Fe(NO 3 ) 3 ), cobalt nitrate (Co(NO 3 ) 2 ), nickel nitrate (Ni(NO 3 ) 2 ) as the raw material, and deionized water as the solvent , ultrasonic and stir to form a uniform solution A with a metal ion concentration of 0.5wt% to 2.0wt%;

2)在均一溶液A中加入富含纤维素的甘蔗渣,在惰性气体保护下快速搅拌,直至形成均一溶液B;其中,甘蔗渣占总质量的90~98wt%;置于高压反应釜中,并置于程序升温干燥箱中,进行程序升温,反应得到的固体,经离心、洗涤、干燥可得到固体粉末;所述程序升温首先以5℃/min的升温速率升温至120℃~140℃,恒温时间6~12h,然后再以5℃/min的升温速率升温至180℃~200℃,恒温时间6~12h;2) Add cellulose-rich sugarcane bagasse to the uniform solution A, and stir quickly under the protection of inert gas until a uniform solution B is formed; wherein the bagasse accounts for 90-98wt% of the total mass; place it in a high-pressure reaction kettle, And place it in a programmed temperature drying oven, perform programmed temperature rise, and the solid obtained by the reaction can be centrifuged, washed, and dried to obtain solid powder; the programmed temperature rise is first heated to 120°C to 140°C at a heating rate of 5°C/min, The constant temperature time is 6 to 12 hours, and then the temperature is raised to 180°C to 200°C at a heating rate of 5°C/min, and the constant temperature time is 6 to 12 hours;

3)将步骤2)中得到的固体粉末置于管式炉中,在惰性气体的保护下,以5℃/min升温速率升至800~1000℃,恒温2~4h后,自然冷却至室温,得到黑色粉末;3) Place the solid powder obtained in step 2) into a tube furnace, and under the protection of inert gas, raise it to 800-1000°C at a heating rate of 5°C/min. After holding the temperature for 2-4 hours, cool it naturally to room temperature. Black powder is obtained;

4)将步骤3)中得到的黑色粉末浸渍到浓度为0.5~2.0mol L-1的酸液中,浸渍4~6h,以去除金属催化剂,得到具有多级孔结构的硬碳材料。4) Dip the black powder obtained in step 3) into an acid solution with a concentration of 0.5 to 2.0 mol L -1 for 4 to 6 hours to remove the metal catalyst and obtain a hard carbon material with a hierarchical porous structure.

惰性气体为氮气或氩气中的一种。The inert gas is one of nitrogen or argon.

步骤4)酸液为硫酸、盐酸、硝酸中的一种。Step 4) The acid solution is one of sulfuric acid, hydrochloric acid, and nitric acid.

原料以富含纤维素的甘蔗渣为硬碳前驱体,既是生物质,也是废弃物,因此价格低廉且易得到。金属颗粒的加入不仅有助于多级孔的构筑,还可促进甘蔗渣的碳化。得到的多级孔硬碳材料存在着微孔、中孔、大孔等多级孔结构。因具有丰富的孔结构,孔径分布可调等特性,极大提高了钠离子电池的综合性能。The raw material uses cellulose-rich sugarcane bagasse as the hard carbon precursor, which is both biomass and waste, so it is cheap and easy to obtain. The addition of metal particles not only contributes to the construction of multi-level pores, but also promotes the carbonization of sugarcane bagasse. The obtained hierarchical porous hard carbon material has hierarchical pore structures such as micropores, mesopores, and macropores. Due to its rich pore structure and adjustable pore size distribution, it greatly improves the overall performance of sodium-ion batteries.

本发明还保护所述制备方法得到的多级孔硬碳及其应用,主要用作钠离子电池负极材料。The present invention also protects the hierarchical porous hard carbon obtained by the preparation method and its application, which is mainly used as anode material for sodium ion batteries.

本发明还保护一种钠离子电池,以所述制备方法得到的多级孔硬碳为负极,钠片为正极。The invention also protects a sodium ion battery, in which the hierarchical porous hard carbon obtained by the preparation method is used as the negative electrode and the sodium flake is used as the positive electrode.

本发明的有益效果如下:The beneficial effects of the present invention are as follows:

1)本发明以富含纤维素的甘蔗渣为硬碳前驱体,因纤维素独特的大分子多糖结构,有助于硬碳产量的提高和孔径尺寸的可调控,金属纳米颗粒为造孔剂,构筑多级孔硬碳材料,利用程序升温预处理的方式,对金属纳米颗粒的尺寸进行有效调控,以促进多级孔硬碳材料的生成,有效解决了钠离子电池的首圈库伦效率低、循环稳定性差、储钠性能低等问题,有助于推动钠离子电池的商用化进程。1) The present invention uses cellulose-rich sugarcane bagasse as the hard carbon precursor. Due to the unique macromolecular polysaccharide structure of cellulose, it is helpful to increase the yield of hard carbon and control the pore size, and metal nanoparticles are used as pore-forming agents. , constructing hierarchical porous hard carbon materials, using programmed temperature pretreatment to effectively regulate the size of metal nanoparticles to promote the generation of hierarchical porous hard carbon materials, effectively solving the low Coulombic efficiency of the first cycle of sodium-ion batteries , poor cycle stability, and low sodium storage performance, which will help promote the commercialization of sodium-ion batteries.

2)金属颗粒的加入不仅有助于多级孔的构筑,还可促进甘蔗渣的碳化。2) The addition of metal particles not only helps to construct multi-level pores, but also promotes the carbonization of sugarcane bagasse.

3)本发明得到的多级孔硬碳材料存在着微孔、中孔、大孔等多级孔结构。因具有丰富的孔结构与孔径分布的可调控等特性,极大提高了钠离子电池的综合性能。3) The hierarchical porous hard carbon material obtained by the present invention has hierarchical pore structures such as micropores, mesopores, and macropores. Due to its rich pore structure and adjustable pore size distribution, the overall performance of sodium-ion batteries has been greatly improved.

附图说明:Picture description:

图1是对比例1得到的无添加金属盐体系中产生的硬碳的孔径分布图;Figure 1 is a pore size distribution diagram of hard carbon produced in a system without added metal salt obtained in Comparative Example 1;

图2是实施例1得到的以硝酸铁(Fe(NO3)3)盐为造孔剂的硬碳孔径分布图;Figure 2 is a pore size distribution diagram of hard carbon using iron nitrate (Fe(NO 3 ) 3 ) salt as a pore-forming agent obtained in Example 1;

图3是以硝酸铁(Fe(NO3)3)盐为造孔剂的硬碳构筑的钠离子电池性能图。Figure 3 is a performance chart of a sodium-ion battery constructed of hard carbon using iron nitrate (Fe(NO 3 ) 3 ) salt as a pore-forming agent.

具体实施方式:Detailed ways:

以下是对本发明的进一步说明,而不是对本发明的限制。The following is a further description of the present invention, rather than a limitation of the present invention.

实施例1:多级孔硬碳材料的制备Example 1: Preparation of hierarchical porous hard carbon materials

是按以下过程完成:It is completed according to the following process:

(1)以硝酸铁(Fe(NO3)3)为金属盐,去离子水为溶剂,超声、搅拌,直至形成均一溶液A,其中Fe3+的浓度为0.5wt%。(1) Use iron nitrate (Fe(NO 3 ) 3 ) as the metal salt and deionized water as the solvent, sonicate and stir until a uniform solution A is formed, in which the concentration of Fe 3+ is 0.5wt%.

(2)在分散均匀的溶液A中加入一定量富含纤维素的甘蔗渣,在惰性气体氮气保护下快速搅拌,搅拌速度为400rpm,直至形成均一溶液B,其中甘蔗渣占总质量的90wt%;将溶液B置于高压反应釜中,并置于程序升温干燥箱中,首先以5℃/min的升温速率升温至120℃,恒温时间6h,然后再以5℃/min的升温速率升温至180℃,恒温时间6h,得到的固体,经离心、洗涤、干燥得到固体粉末,其中洗涤液为去离子水。(2) Add a certain amount of cellulose-rich bagasse to the uniformly dispersed solution A, and stir rapidly under the protection of inert gas nitrogen at a stirring speed of 400 rpm until a uniform solution B is formed, in which bagasse accounts for 90wt% of the total mass. ; Place solution B in a high-pressure reaction kettle and place it in a programmed temperature drying oven. First, heat it up to 120°C at a heating rate of 5°C/min, hold the temperature for 6 hours, and then heat it up to 120°C at a heating rate of 5°C/min. 180°C, constant temperature for 6 hours, the solid obtained was centrifuged, washed, and dried to obtain solid powder, in which the washing liquid was deionized water.

(3)将步骤(2)中得到的固体粉末置于管式炉中,在惰性气体氮气的保护下,以5℃/min升温速率升至1000℃,恒温2h后,自然冷却至室温,即可得到黑色粉末。(3) Place the solid powder obtained in step (2) into a tube furnace, and under the protection of inert gas nitrogen, raise it to 1000°C at a heating rate of 5°C/min. After holding the temperature for 2 hours, cool it naturally to room temperature, that is Black powder is available.

(4)将步骤(3)中得到的黑色粉末浸渍到0.5mol L-1的硫酸酸液中,室温浸渍6h以去除金属催化剂,最后即可得到具有多级孔结构的硬碳材料。其孔径分布图如图2。(4) Dip the black powder obtained in step (3) into 0.5 mol L -1 sulfuric acid solution for 6 hours at room temperature to remove the metal catalyst. Finally, a hard carbon material with a hierarchical pore structure can be obtained. The pore size distribution diagram is shown in Figure 2.

从图2中可以看出,在以硝酸铁(Fe(NO3)3)盐为造孔剂的体系中,硬碳存在着丰富的微孔、中孔和大孔,且孔径体积较大,这种发达的孔径通道,有助于电解液中钠离子的快速传递,同时也有助于钠离子的快速脱嵌。以实施例1得到的硬碳为负极,钠片为正极,构筑了钠离子电池,其比容量如图3所示,从图中可以看出该电池的电压窗口为0~3.0V,比容量为305mA h g-1,拥有较高的电池比容量。As can be seen from Figure 2, in the system using iron nitrate (Fe(NO 3 ) 3 ) salt as the pore-forming agent, hard carbon has abundant micropores, mesopores and macropores, and the pore size is large. This developed pore channel facilitates the rapid transfer of sodium ions in the electrolyte and also facilitates the rapid deintercalation of sodium ions. Using the hard carbon obtained in Example 1 as the negative electrode and the sodium flake as the positive electrode, a sodium ion battery was constructed. Its specific capacity is shown in Figure 3. From the figure, it can be seen that the voltage window of the battery is 0 to 3.0V, and the specific capacity It is 305mA hg -1 and has a high battery specific capacity.

对比例1:Comparative example 1:

参考实施例1,不同之处在于,步骤(1)中没有添加硝酸铁(Fe(NO3)3)。Referring to Example 1, the difference is that iron nitrate (Fe(NO 3 ) 3 ) is not added in step (1).

将富含纤维素的甘蔗渣分散在去离子水中,在惰性气体氮气保护下快速搅拌,搅拌速度为400rpm,直至形成均一溶液B,其中甘蔗渣占总质量的90wt%;将溶液B置于高压反应釜中,并置于程序升温干燥箱中,首先以5℃/min的升温速率升温至120℃,恒温时间6h,然后再以5℃/min的升温速率升温至180℃,恒温时间6h,得到的固体,经离心、洗涤、干燥得到固体粉末,其中洗涤液为去离子水。Disperse the cellulose-rich bagasse in deionized water and stir rapidly under the protection of inert gas nitrogen at a stirring speed of 400 rpm until a uniform solution B is formed, in which bagasse accounts for 90wt% of the total mass; solution B is placed under high pressure Reaction kettle, and placed in a programmed temperature drying oven, first raise the temperature to 120°C at a heating rate of 5°C/min, and hold the temperature for 6 hours, then raise the temperature to 180°C at a heating rate of 5°C/min, and hold the temperature for 6 hours. The obtained solid is centrifuged, washed, and dried to obtain solid powder, in which the washing liquid is deionized water.

(3)将步骤(2)中得到的固体粉末置于管式炉中,在惰性气体氮气的保护下,以5℃/min升温速率升至1000℃,恒温2h后,自然冷却至室温,即可得到黑色粉末。(3) Place the solid powder obtained in step (2) into a tube furnace, and under the protection of inert gas nitrogen, raise it to 1000°C at a heating rate of 5°C/min. After holding the temperature for 2 hours, cool it naturally to room temperature, that is Black powder is available.

最后得到的硬碳材料孔径分布图如图1.The final pore size distribution diagram of the hard carbon material is shown in Figure 1.

从图1中可以看出,无添加金属盐体系中产生的硬碳存在着微孔、中孔和大孔,其中微孔和中孔体积相对较小。As can be seen from Figure 1, the hard carbon produced in the system without added metal salts has micropores, mesopores and macropores, and the volumes of micropores and mesopores are relatively small.

实施例1和对比例1对比可知,金属颗粒的加入不仅有助于多级孔的构筑,还可促进甘蔗渣的碳化。Comparing Example 1 and Comparative Example 1, it can be seen that the addition of metal particles not only contributes to the construction of multi-level pores, but also promotes the carbonization of sugarcane bagasse.

实施例2:Example 2:

参考实施例1,不同之处在于,步骤(1)中硝酸铁(Fe(NO3)3)替换为硝酸钴(Co(NO3)2)。Referring to Example 1, the difference is that in step (1), iron nitrate (Fe(NO 3 ) 3 ) is replaced by cobalt nitrate (Co(NO 3 ) 2 ).

实施例3:Example 3:

参考实施例1,不同之处在于,步骤(2)的程序升温程序为首先以5℃/min的升温速率升温至140℃,恒温时间6h,然后再以5℃/min的升温速率升温至200℃,恒温时间6h。Referring to Example 1, the difference is that the programmed temperature rise program of step (2) is to first raise the temperature to 140°C at a heating rate of 5°C/min, hold the temperature for 6 hours, and then raise the temperature to 200°C at a heating rate of 5°C/min. ℃, constant temperature time 6h.

实施例4:Example 4:

参考实施例1,不同之处在于,步骤(3)为:将步骤(2)中得到的固体粉末置于管式炉中,在惰性气体氮气的保护下,以5℃/min升温速率升至800℃,恒温2h后,自然冷却至室温,即可得到黑色粉末。Referring to Example 1, the difference is that step (3) is: the solid powder obtained in step (2) is placed in a tube furnace, and under the protection of inert gas nitrogen, the temperature is raised to 5°C/min at a heating rate of 5°C/min. 800℃, constant temperature for 2 hours, then naturally cooled to room temperature, black powder can be obtained.

Claims (6)

1.一种多级孔硬碳的制备方法,其特征在于,该方法包括以下步骤:1. A method for preparing hierarchical porous hard carbon, characterized in that the method includes the following steps: 1)以硝酸铁、硝酸钴、硝酸镍中的一种作为原料,去离子水为溶剂,超声、搅拌,形成金属离子浓度为0.5wt%~2.0wt%的均一溶液A;1) Using one of iron nitrate, cobalt nitrate, and nickel nitrate as raw material, deionized water as solvent, ultrasonic and stirring to form a uniform solution A with a metal ion concentration of 0.5wt% to 2.0wt%; 2)在均一溶液A中加入富含纤维素的甘蔗渣,在惰性气体保护下快速搅拌,直至形成均一溶液B;其中,甘蔗渣占总质量的90~98wt%;置于高压反应釜中,并置于程序升温干燥箱中,进行程序升温,反应得到的固体,经离心、洗涤、干燥可得到固体粉末;所述程序升温首先以5℃/min的升温速率升温至120℃~140℃,恒温时间6~12h,然后再以5℃/min的升温速率升温至180℃~200℃,恒温时间6~12h;2) Add cellulose-rich sugarcane bagasse to the uniform solution A, and stir quickly under the protection of inert gas until a uniform solution B is formed; wherein the bagasse accounts for 90-98wt% of the total mass; place it in a high-pressure reaction kettle, And place it in a programmed temperature drying oven, perform programmed temperature rise, and the solid obtained by the reaction can be centrifuged, washed, and dried to obtain solid powder; the programmed temperature rise is first heated to 120°C to 140°C at a heating rate of 5°C/min, The constant temperature time is 6 to 12 hours, and then the temperature is raised to 180°C to 200°C at a heating rate of 5°C/min, and the constant temperature time is 6 to 12 hours; 3)将步骤2)中得到的固体粉末置于管式炉中,在惰性气体的保护下,以5℃/min升温速率升至800~1000℃,恒温2~4h后,自然冷却至室温,得到黑色粉末;3) Place the solid powder obtained in step 2) into a tube furnace, and under the protection of inert gas, raise it to 800-1000°C at a heating rate of 5°C/min. After holding the temperature for 2-4 hours, cool it naturally to room temperature. Black powder is obtained; 4)将步骤3)中得到的黑色粉末浸渍到浓度为0.5~2.0mol L-1的酸液中,浸渍4~6h得到具有多级孔结构的硬碳材料。4) Dip the black powder obtained in step 3) into an acid solution with a concentration of 0.5 to 2.0 mol L -1 , and immerse for 4 to 6 hours to obtain a hard carbon material with a hierarchical pore structure. 2.根据权利要求1所述的制备方法,其特征在于,惰性气体为氮气或氩气中的一种。2. The preparation method according to claim 1, characterized in that the inert gas is one of nitrogen or argon. 3.根据权利要求1所述的制备方法,其特征在于,步骤4)酸液为硫酸、盐酸、硝酸中的一种。3. The preparation method according to claim 1, characterized in that the acid liquid in step 4) is one of sulfuric acid, hydrochloric acid and nitric acid. 4.如权利要求1所述制备方法得到的多级孔硬碳。4. The hierarchical porous hard carbon obtained by the preparation method according to claim 1. 5.如权利要求1所述制备方法得到的多级孔硬碳的应用,其特征在于,用作钠离子电池负极材料。5. Application of the hierarchical porous hard carbon obtained by the preparation method according to claim 1, characterized in that it is used as a negative electrode material for sodium ion batteries. 6.一种钠离子电池,以权利要求1所述制备方法得到的多级孔硬碳为负极,钠片为正极。6. A sodium ion battery, using the hierarchical porous hard carbon obtained by the preparation method of claim 1 as the negative electrode, and the sodium sheet as the positive electrode.
CN202311033376.8A 2023-08-16 2023-08-16 Preparation method and application of hierarchical pore hard carbon material Pending CN117069097A (en)

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Publication number Priority date Publication date Assignee Title
CN108059144A (en) * 2017-12-11 2018-05-22 桂林电子科技大学 Hard carbon prepared by a kind of biomass waste material bagasse and its preparation method and application
CN112794324A (en) * 2019-11-14 2021-05-14 华南理工大学 A kind of high mesoporosity lignin hierarchical porous carbon material and its preparation method and application
CN113735095A (en) * 2021-08-06 2021-12-03 深圳市德方纳米科技股份有限公司 Porous hard carbon material and preparation method and application thereof
CN115124025A (en) * 2022-08-16 2022-09-30 中国石油大学(华东) A kind of hard carbon material, its preparation method and application in sodium ion battery
CN116199223A (en) * 2023-03-24 2023-06-02 河北省科学院能源研究所 Preparation method of hard porous carbon for sodium ion battery
WO2023109660A1 (en) * 2021-12-15 2023-06-22 深圳先进技术研究院 Hard carbon negative electrode material for sodium-ion battery and preparation method therefor

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108059144A (en) * 2017-12-11 2018-05-22 桂林电子科技大学 Hard carbon prepared by a kind of biomass waste material bagasse and its preparation method and application
CN112794324A (en) * 2019-11-14 2021-05-14 华南理工大学 A kind of high mesoporosity lignin hierarchical porous carbon material and its preparation method and application
CN113735095A (en) * 2021-08-06 2021-12-03 深圳市德方纳米科技股份有限公司 Porous hard carbon material and preparation method and application thereof
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