Structure Regulation and Sodium Storage Performance of Cellulose-Based Hard Carbon

doi:10.12422/j.issn.1006-396X.2024.06.007

Abstract

Abstract:

Cellulose, due to its abundance and propensity to form spherical structures, serves as an exceptional precursor for the synthesis of high-performance hard carbon materials used in sodium-ion batteries. This study explores the interplay between different cellulose types, their structural evolution during hydrothermal spherization, and the subsequent impact on the microcrystalline characteristics and electrochemical performance of the resulting hard carbon for sodium storage. The results observed that the crystallinity of various cellulose precursors-namely natural cellulose, α-cellulose, and microcrystalline cellulose-and their corresponding hard carbons are positively correlated. Among these, hard carbon derived from α-cellulose demonstrated superior attributes, including the highest closed pore volume and a balanced defect density, which contribute to its enhanced sodium storage capacity. Furthermore, the hydrothermal treatment of α-cellulose at 220 °C was optimized to achieve a spherical morphology, which significantly benefited both the capacity and rate performance of the hard carbon. The reversible capacities at current densities of 20 and 2 000 mA/g are 329.4 and 53.9 mA·h/g, respectively.

Key words: Cellulose, Hard carbon, Crystallinity, Spherical morphology, Sodium ion battery

摘要：

纤维素来源丰富，易形成球形结构，是制备高性能储钠硬炭材料的重要前驱体。探究了天然纤维素、甲种纤维素、微晶纤维素等纤维素前驱体的结构及其在水热成球过程中的变化；分析纤维素衍生硬炭的微晶结构与其前驱体电化学储钠性能的关系，并优选了纤维素前驱体。结果表明，纤维素衍生硬炭的结晶度与纤维素前驱体的结晶度呈正相关；甲种纤维素衍生硬炭闭孔体积最大，缺陷密度适中，储钠容量最高，是最佳的纤维素前驱体；在220 ℃的温度下，对甲种纤维素进行水热处理，所得纤维素衍生硬炭呈球形形貌，并且兼具高储钠容量和倍率性能，在20、2 000 mA/g的电流密度下的可逆容量分别为329.4、53.9 mA·h/g。

关键词: 纤维素, 硬炭, 结晶度, 球形形貌, 钠离子电池

CLC Number:

TQ150

Haiyan LIU, Renlu YUAN, Houkun LONG, Qi SHEN, Boyang ZHAO, Xuewei LIU, Huaihe SONG. Structure Regulation and Sodium Storage Performance of Cellulose-Based Hard Carbon[J]. Journal of Petrochemical Universities, 2024, 37(6): 62-73.

刘海燕, 苑仁鲁, 龙厚坤, 沈祺, 赵博洋, 刘学伟, 宋怀河. 纤维素衍生硬炭的结构调控和储钠性能研究[J]. 石油化工高等学校学报, 2024, 37(6): 62-73.

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URL: https://journal.lnpu.edu.cn/syhg/EN/10.12422/j.issn.1006-396X.2024.06.007

https://journal.lnpu.edu.cn/syhg/EN/Y2024/V37/I6/62

Figures/Tables 12

Fig.1 SEM images, XRD patterns and FT-IR spectra of the three celluloses

Table 1 The crystallinity and element contents of the three celluloses

样品	C_XRD/%	C_FT-IR/%	元素质量分数/%
样品	C_XRD/%	C_FT-IR/%	C	O	H
N-Cel	69.7	1.91	42.26	51.17	6.55
M-Cel	89.2	2.15	43.41	50.41	6.16
A-Cel	82.6	1.93	42.25	51.62	6.05

Fig.2 SEM images, XRD patterns and Raman spectra of the three celluloses derived hard carbons

Table 2 Structure parameters of the three cellulose derived hard carbons

样品	d₀₀₂/nm	R	I_D/I_G	比表面积/（cm²·g^-1）	孔体积/（cm³·g^-1）	ρ_true/（g·m^-3）	V_{closed pores}/（cm³·g^-1）
N-Cel-1500	0.385	1.70	1.36	2.00×10⁴	0.000 7	2.09	0.04
M-Cel-1500	0.397	3.26	1.16	1.00×10⁴	0.000 3	1.65	0.16
A-Cel-1500	0.373	2.71	1.18	2.00×10⁴	0.000 8	1.51	0.29

Fig.3 The GCD profiles at 20 mA/g and first GCD profiles of the three celluloses derived hard carbons

Fig.4 Schematic of the preparation process and spheroidization of A-Cel

Fig.5 SEM images and particle size distribution of SEM images of A-Cel-HTx-1500

Fig.6 FT-IR spectra and XRD patterns of A-Cel and A-Cel-HTx

Table 3 Crystallinity and elemental mass fraction of A-Cel at different hydrothermal temperatures

样品	C_XRD/%	元素质量分数/%
样品	C_XRD/%	C	O	H
A-Cel-HT200	79.3	42.44	51.26	6.24
A-Cel-HT220	60.4	67.21	28.33	4.11
A-Cel-HT240		67.90	27.66	4.17

Fig.7 Characterization of the microcrystalline and pore structures of A-Cel-1500 and A-Cel-HTx-1500

Fig.8 Sodium storage performance of A-Cel-1500 and A-Cel-HTx-1500

Fig.9 Electrochemical kinetics analysis of A-Cel-1500 and A-Cel-HT220-1500

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