双功能活化制备沥青基硬炭用于钠离子电池负极

doi:10.11949/0438-1157.20240071

摘要/Abstract

摘要：

硬炭作为钠离子电池(SIBs)最具有应用前景的负极材料，其形貌的可控调节和结构优化被广泛研究和关注。以煤沥青为原料，采用柠檬酸钾(C₆H₅K₃O₇·H₂O)作为双功能活化剂：(1)气体分解产物可消耗过量的氢，实现沥青的固态热解，阻碍有序微晶的生成；(2)固态分解产物钾盐进行活化造孔，从而在高温碳化过程中形成丰富的封闭纳米孔。基于此，成功制备了具有高度无序、多孔片状结构的沥青基硬炭材料，并应用于SIBs负极，探究其电化学性能。研究发现，通过调控活化剂用量可以实现沥青基硬炭微观结构的优化，在适宜质量比条件下制备的硬炭(HC-2-1300)首次库仑效率高达81.5%，在0.1 A·g^-1的电流密度下，其可逆比容量为214.2 mAh·g^-1，明显优于直接碳化的样品(DC-1300)。同时，在5 A·g^-1的高电流密度下，HC-2-1300样品仍有116.7 mAh·g^-1的可逆比容量，且在1 A·g^-1电流密度下充放电循环2000圈后，容量保持率达75.1%，显现出优异的倍率性能和循环稳定性，具有广阔的应用前景。

关键词: 钠离子电池, 沥青基硬炭, 双功能活化剂, 电化学性能

Abstract:

As the most promising anode material for sodium-ion batteries (SIBs), hard carbon has been widely studied and focused on its controllable adjustment of morphology and structural optimization. Herein, a novel bifunctional activation strategy was developed to prepare the hard carbon materials with highly disordered structures as anode for SIBs by using coal tar pitch as precursors with the help of potassium citrate monohydrate (C₆H₅K₃O₇·H₂O). It is believed that the C₆H₅K₃O₇·H₂O has a dual role: (1) its gas decomposition products can consume excessive hydrogen and further realize solid pyrolysis of pitch precursors, preventing the formation of ordered microcrystals; (2) the solid decomposition products (potassium salt) act as activating agents to introduce rich closed nanopores into the carbon matrix during high-temperature carbonization. Interestingly, the microstructure of pitch-based hard carbon can be optimized by tuning the amount of activating agents. Furthermore, the electrochemical performance investigations revealed that the as-optimized hard carbon (HC-2-1300) delivers a reversible specific capacity of 214.2 mAh·g^-1 at 0.1 A·g^-1 with an initial coulombic efficiency of as high as 81.5%, which is superior to that of directly carbonized samples (DC-1300). In addition, there is still a high reversible specific capacity of 116.7 mAh·g^-1 at 5 A·g^-1 and good cycling stability with a capacity retention rate of 75.1% over 2000 cycles, highlighting the great potential of pitch-based hard carbon anodes for SIBs.

Key words: sodium-ion batteries, pitch-based hard carbon, bi-functional activating agent, electrochemical performance

中图分类号:

TQ 536.4

吴吉昊, 陈涛, 刘思宇, 刘梦柯, 杨卷. 双功能活化制备沥青基硬炭用于钠离子电池负极[J]. 化工学报, 2024, 75(3): 1019-1027.

Jihao WU, Tao CHEN, Siyu LIU, Mengke LIU, Juan YANG. Preparation of pitch-based hard carbon by bi-functional activation strategy for sodium-ion batteries[J]. CIESC Journal, 2024, 75(3): 1019-1027.

图/表 6

图1 DC-1300 [(a)~(c)]和HC-2-1300 [(d)~(f)]样品的SEM和TEM照片

Fig.1 SEM and TEM images of DC-1300 [(a)—(c)] and HC-2-1300 [(d)—(f)] samples

图2 DC-1300、HC-1-1300、HC-2-1300和HC-4-1300样品的XRD谱图(a)、拉曼光谱(b)、氮气吸附/脱附曲线(c)和孔径分布(d)

Fig.2 XRD patterns (a)， Raman spectra (b)， N2 adsorption/desorption curves (c) and pore size distribution (d) of DC-1300，HC-1-1300，HC-2-1300 and HC-4-1300

表1 不同样品的结构与电化学性能参数

Table 1 Structural and electrochemical parameters of different samples

样品	d₀₀₂/nm	BET表面积/ (m²·g^-1)	孔体积/ (cm³·g^-1)	库仑效率/%
DC-1300	0.345	3.3	0.005	75.6
HC-1-1300	0.376	155.5	0.098	82.2
HC-2-1300	0.372	164.8	0.084	81.5
HC-4-1300	0.370	378.9	0.214	79.4

图3 DC-1300(a)和HC-2-1300(b)样品在扫描速率为0.25 mV·s-1下的CV曲线; DC-1300(c)和HC-2-1300(d)在0.25~5.00 mV·s-1不同扫描速率下的CV曲线以及Ip与v1/2的线性关系

Fig.3 CV curves of DC-1300 (a) and HC-2-1300 (b) at the scan rate of 0.25 mV·s-1; CV curves at different scan rates from 0.25 to 5.00 mV·s-1 and linear relationship between Ipand v1/2 of DC-1300 (c) and HC-2-1300 (d)

图4 DC-1300、HC-1-1300、HC-2-1300和HC-4-1300样品在电流密度为0.1 A·g-1的恒电流充/放电曲线

Fig.4 GCD profiles of DC-1300, HC-1-1300, HC-2-1300 and HC-4-1300 at a current density of 0.1 A·g-1

图5 DC-1300、HC-1-1300、HC-2-1300和HC-4-1300样品在0.1 A·g-1电流密度下的容量分布(a)，倍率性能(b)和在1 A·g-1电流密度的循环性能(c)

Fig.5 The capacity contribution (a)， rate capability (b) at current density of 0.1 A·g-1 and cyclic performance at 1 A·g-1 (c) of DC-1300, HC-1100, HC-1300 and HC-1500

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