阳离子交换树脂基介孔石墨化碳合成与储钠性能

doi:10.11949/0438-1157.20240274

摘要/Abstract

摘要：

利用价格低廉的阳离子交换树脂作为碳源，基于离子交换策略引入铁离子，调控阳离子交换树脂热解过程的石墨化碳结构，并进一步酸刻蚀热解产物中的单质铁和碳化铁，制备了一种介孔石墨化碳，用于钠离子电池负极材料。阳离子交换树脂基介孔石墨化碳相比直接热解所得的树脂基硬碳具有更大的层间距、更少的缺陷结构以及由薄层石墨化碳构成的介孔孔道，可以显著提高碳负极材料在高倍率下的比容量及循环稳定性。将该材料应用于钠离子电池负极材料展示出优异的倍率性能和高倍率下的循环稳定性，在30 A·g^-1的高电流密度下该材料的比容量可达100 mA·h·g^-1，在0.5 A·g^-1的电流密度下循环1000圈后比容量可保持在192 mA·h·g^-1。

关键词: 纳米结构, 热解, 电化学, 钠离子电池, 石墨化碳

Abstract:

Using cheap cation exchange resin as the carbon source, iron ions are introduced based on the ion exchange strategy to regulate the graphitized carbon structure during the pyrolysis process of the cation exchange resin. And further acid etched the elemental iron and iron carbide in the pyrolysis product to prepare a mesoporous graphitized carbon for use as anode material for sodium-ion batteries. The cation exchange resin based graphitic carbon shows larger intergraphene spacing, lower defects and mesoporous tunnels constructed by few graphite layers compared with the hard carbon by direct pyrolysis of resin, which could significantly improve the capacity and cycling stability and carbon anode material at high rates. When applied to anode material in sodium ion battery, this material exhibits excellent rate performance and cycling stability at high rates, showing a specific capacity of 100 mA·h·g^-1 at a high current density of 30 A·g^-1, and a specific capacity of 192 mA·h·g^-1 at a current density of 0.5 A·g^-1 after 1000 cycles.

Key words: nanostructure, pyrolysis, electrochemistry, sodium ion battery, graphitic carbon

中图分类号:

O 646.21

王舒英, 左涛, 石志伟, 范小明, 张卫新. 阳离子交换树脂基介孔石墨化碳合成与储钠性能[J]. 化工学报, 2024, 75(9): 3338-3347.

Shuying WANG, Tao ZUO, Zhiwei SHI, Xiaoming FAN, Weixin ZHANG. Synthesis and sodium ion storage properties of cation exchange resin based mesoporous graphitic carbon[J]. CIESC Journal, 2024, 75(9): 3338-3347.

图/表 6

图1 介孔石墨化碳制备示意图

Fig.1 Schematic illustration of preparation of mesoporous graphitic carbon

图2 不同样品的SEM照片[(a)、(b)];不同样品的EDS mapping图[(c)、(d)]；树脂在0.5 mol·L-1溶液中交换进入及刻蚀出的Fe含量柱状图(e)；样品HCF-700的XRD谱图(f)

Fig.2 SEM images of different samples [(a)， (b)]; EDS mapping results of different samples [(c)， (d)]; histogram of Fe content in ion-exchanged resin and acid-etched resin by thermal treatment (e);XRD patterns of the sample HCF-700 (f)

图3 不同样品的SEM照片[(a)~(c)]、TEM照片[(d)~(f)]和EDS mapping图[(g)、(h)]

Fig.3 SEM images [(a)-(c)]， TEM images [(d)-(f)] and EDS mapping [(g)，(h)] of different samples

图4 不同样品的XRD谱图(a)、XPS全谱图(b)、拉曼光谱图(c)、C 1s XPS光谱图(d)、氮气吸脱附曲线(e)及孔径分布(f)

Fig.4 XRD patterns (a)， XPS survey spectra (b)， Raman spectra (c)， C 1s XPS spectra (d)， N2 adsorption/desorption isotherms (e) and pore size distribution (f) of different samples

图5 HCH-700 (a) 和HC-700 (b) 前3圈的CV曲线；不同样品在电流密度为0.1~30 A·g-1下的倍率性能图 (c)；不同样品在0.5 A·g-1下的长循环图 (d)；HCH-700在10、20 A·g-1下的长循环图 (e)；HCH-700与不同文献中的材料倍率性能对比图（f）；不同循环圈数下HCH-700 (g) 和HC-700 (h) 的EIS图

Fig.5 CV curves for the first 3 cycles of HCH-700 (a) and HC-700 (b); rate performance of different samples at current densities of 0.1—30 A·g-1 (c); long-term stability test of different samples at 0.5 A·g-1 (d); long-term stability test of HCH-700 at 10 and 20 A·g-1 (e); comparison of rate performance of HCH-700 with materials in different references (f); EIS spectra of HCH-700 (g) and HC-700 (h) under different cycle numbers

图6 不同扫描速率下HCH-700 (a) 和HC-700 (b) 的CV曲线；HCH-700 (c) 和HC-700 (d) 的CV峰值电流和扫速之间的线性关系；不同扫描速率下的赝电容占比 (e)；HCH-700和HC-700在30 A·g-1下的实际赝电容 (f)

Fig.6 CV curves of HCH-700 (a) and HC-700 (b) at different scan rates; linear relationship between peak current and scan rate in the CV curve of HCH-700 (c) and HC-700 (d); pseudocapacitance ratio at different scan rates (e); actual pseudocapacity of the HCH-700 and HC-700 under 30 A·g-1 (f)

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