碳负载硒掺杂硫化钴在锂硫电池中的性能研究

doi:10.11949/0438-1157.20241336

摘要/Abstract

摘要：

阴离子掺杂诱导空位工程可以有效调节过渡金属硫化物的电子结构，从而提高其对锂硫电池中多硫化锂（LiPSs）的吸附及硫的利用率。以羰基化煤沥青基多孔碳（DCC）为Co纳米粒子的载体，经过一步高温硫化、硒化，将Co纳米粒子转化为具有S空位的Se掺杂CoS₂（CoSe _x S _y @DCC）催化剂。制备的CoSe₅S₂@DCC具有丰富的孔结构和S空位，可有效地提高其对LiPSs的吸附能力，并加速了硫转化的反应动力学。电化学测试结果表明，负载S后的CoSe₅S₂@DCC/S正极具有较好的倍率性能（在0.1 C下其比容量为1120 mAh·g^-1；在5 C下比容量为488.5 mAh·g^-1）、循环稳定性（在5 C的电流密度下，经2000次循环后可维持400.3 mAh·g^-1的比容量，库仑效率接近100%）和快的离子扩散性能。这一工作对利用阴离子掺杂诱导空位工程以提高锂硫电池用催化剂催化活性的研究具有重要的参考价值。

关键词: 空位工程, 羰基化煤沥青, 锂硫电池, 吸附, 动力学, 催化剂活化

Abstract:

Anion-doping-induced vacancy engineering effectively regulates the electronic structure of transition metal sulfides, thereby improving their adsorption and sulfur utilization efficiency for lithium polysulfide (LiPSs) in lithium-sulfur batteries (LSBs). Herein, diketone coal tar pitch-based porous carbon (DCC) with Co nanoparticles was prepared, and then Co nanoparticles were converted into Se-doping CoS₂ with S vacancy catalyst(CoSe _x S _y @DCC) via one-step high-temperature sulfurization and selenization processes. The obtained CoSe₅S₂@DCC has abundant pores and S vacancies, effectively improving the adsorption capacity to LiPSs and accelerating the reaction kinetics of sulfur conversion. The electrochemical test results indicate that the CoSe₅S₂@DCC/S cathode after S being loaded exhibits good rate performance (with a specific capacity of 1120 mAh·g^-1 at 0.1 C and 488.5 mAh·g^-1 at 5 C), cycling stability (maintaining a specific capacity of 400.3 mAh·g^-1 after 2000 cycles at 5 C, with a coulombic efficiency of 100%) and fast ion diffusion. This work has important reference value for the study of using anion doping to induce vacancy engineering to improve the catalytic activity of catalysts for lithium-sulfur batteries.

Key words: vacancy engineering, diketone coal tar pitch, lithium-sulfur battery, adsorption, kinetics, catalyst activation

中图分类号:

O 646

何军, 李勇, 赵楠, 何孝军. 碳负载硒掺杂硫化钴在锂硫电池中的性能研究[J]. 化工学报, 2025, 76(6): 2995-3008.

Jun HE, Yong LI, Nan ZHAO, Xiaojun HE. Study on the properties of carbon with Se doping cobalt sulfide in lithium-sulfur batteries[J]. CIESC Journal, 2025, 76(6): 2995-3008.

图/表 10

图1 CoSe x S y @DCC正极材料合成示意图

Fig.1 Schematic illustration to prepare CoSe x S y @DCC cathode material

表1 DCTP的元素含量

Table 1 Element content of DCTP

样品	含量(M_ad)/%（质量分数）
样品	C	H	O	N	S
DCTP	77.84	3.42	17.34	0.82	0.58

图2 DCC [(a)、(b)], Co@DCC [(c)、(d)], CoSe@DCC [(e)、(f)], CoSe5S2@DCC [(g)、(h)]和CoSe2S5@DCC [(i)、(j)]的FESEM图；CoSe5S2@DCC的FESEM图及其对应的EDS映射[(k)~(m)]

Fig.2 FESEM images of DCC [(a),(b)], Co@DCC [(c),(d)], CoSe@DCC [(e),(f)], CoSe5S2@DCC [(g),(h)], and CoSe2S5@DCC [(i),(j)] CoSe5S2@DCC and the corresponding EDS mapping[(k)—(m)]

图3 Co@DCC的TEM和HRTEM图[(a)~(c)]；Co@DCC和相应的EDS mapping图(d)；CoSe@DCC的TEM和HRTEM图[(e)~(g)]；CoSe@DCC和相应的EDS mapping图(h)；CoSe5S2@DCC的TEM和HRTEM [(i)~(l)]；空位(m)和晶体畸变图(n)；CoSe5S2@DCC和相应的EDS mapping图(o)

Fig.3 TEM and HRTEM images of Co@DCC [(a)~(c)]; Co@DCC and the corresponding EDS mapping (d); TEM and HRTEM images of CoSe@DCC [(e)~(g)]; CoSe@DCC and the corresponding EDS mapping (h); TEM and HRTEM images of CoSe5S2@DCC [(i)~(l)]; Vacancy sites (m); Lattice distortion (n); CoSe5S2@DCC and the corresponding EDS mapping (o)

图4 DCC、Co@DCC、CoSe@DCC、CoSe5S2@DCC和CoSe2S5@DCC的XRD谱图(a)、Raman谱图(b)、N2吸脱附等温线(c)、孔径分布曲线(d)、XPS谱图(e)；CoSe5S2@DCC的C 1s(f)、Co 2p(g)、Se 3d(h)和S 2p(i)高分辨光谱

Fig.4 XRD patterns (a), Raman spectra (b), Nitrogen adsorption/desorption isotherms (c), pore size distribution curves (d) and XPS spectra (e) of DCC, Co@DCC, CoSe@DCC, CoSe5S2@DCC, and CoSe2S5@DCC; High resolution XPS spectra of C 1s(f), Co 2p (g), Se 3d (h), and S 2p (i) for CoSe5S2@DCC

表2 DCC、Co@DCC、CoSe@DCC、CoSe5S2@DCC和CoSe2S5@DCC的比表面积及孔结构参数

Table 2 Specific surface area and pore structure parameters of DCC， Co@DCC， CoSe@DCC， CoSe5S2 @DCC， and CoSe2S5@DCC

Samples	D_ap/Å	S_BET/ (m²·g^-1)	S_mic/ (m²·g^-1)	V_t/ (cm³·g^-1)	V_mic/(cm³·g^-1)
DCC	25.26	2817.56	857.18	1.54	0.44
Co@DCC	17.12	1252.67	1074.4	0.53	0.42
CoSe₃@DCC	22.16	205.84	21.26	0.111	0.004
CoSe₅S₂@DCC	20.98	449.03	67.88	0.232	0.022
CoSe₂S₅@DCC	19.66	1575.1	754.0	0.765	0.3

图5 不同样品在Li2S6溶液中吸附并静置12 h后的照片(a)和上清液的紫外可见吸收光谱(b)

Fig.5 Photographs of various samples after adsorption and settling in Li2S6 solution after 12 h (a) and UV-vis spectrum of supnatant (b)

图6 DCC (a)、Co@DCC/S (b)、CoSe@DCC/S (c)、CoSe5S2@DCC/S (d)和CoSe2S5@DCC/S (e)的TGA曲线

Fig.6 TGA curves of DCC/S (a), Co@DCC/S (b), CoSe@DCC/S (c), CoSe5S2@DCC/S (d), and CoSe2S5@DCC/S (e)

图7 0.1C下DCC/S、Co@DCC/S、CoSe@DCC/S、CoSe5S2@DCC/S、CoSe2S5@DCC/S基电池的GCD曲线(a)；各电极电池在0.1~5C下的倍率性能比较(b)；CoSe5S2@DCC/S电池在0.1~5C下的GCD曲线(c)；0.1 mV·s-1时DCC/S、Co@DCC/S、CoSe@DCC/S、CoSe5S2@DCC/S、CoSe2S5@DCC/S的初始CV曲线(d)；基于CoSe5S2@DCC/S电池在0.1~2 mV·s-1下的CV曲线(e)；氧化峰A：不同正极的峰值电流与扫描速率的平方根的关系(f)；根据Randles-Sevcik方程从CV氧化还原峰计算Li+扩散系数(g)；各正极的Nyquist图(h)；1C时的循环稳定性(i)；5C时的长周期循环测试(j)；CoSe5S2@DCC/S电池在5C下第1、50、100、300、500、1000、1500、2000次循环的GCD曲线(k)

Fig.7 GCD curves of DCC/S, Co@DCC/S, CoSe@DCC/S, CoSe5S2@DCC/S, and CoSe2S5@DCC/S cells at 0.1C (a); Rate performance comparison at 0.1 to 5C of all cells (b); GCD curves of the CoSe5S2@DCC/S cell at 0.1—5C (c); The initial CV curves of DCC/S, Co@DCC/S, CoSe@DCC/S, CoSe5S2@DCC/S, and CoSe2S5@DCC/S at 0.1 mV·s-1 (d); CV curves of cells based on CoSe5S2@DCC/S electrodes at 0.1—2 mV·s-1 (e); Oxidation A peak: current vs. square root of scan rate for different cathodes (f); Li+ diffusion coefficient calculated from the CV redox peaks according to the Randles-Sevcik equation (g); Nyquist plot for each cathode (h); Cycle stability at 1C (i); Long cycle test at 5C (j); GCD curves of the CoSe5S2@DCC/S cell at the cycle of 1, 50, 100, 300, 500, 1000, 1500, and 2000 at 5C (k)

图8 DCC/S (a)、Co@DCC/S (b)、CoSe@DCC/S (c)和CoSe2S5@DCC/S (d)基电池在0.1~2 mV·s-1扫描速率下的CV曲线；还原峰B：不同正极的峰值电流与扫描速率的平方根的关系(e)；还原峰C：不同正极的峰值电流与扫描速率的平方根的关系(f)

Fig.8 CV curves of cells based on DCC/S (a), Co@DCC/S (b), CoSe@DCC/S (c), and CoSe2S5@DCC/S (d) electrodes at scan rates in the range 0.1—2 mV·s-1; Reduction B peak: current vs square root of scan rate for different cathodes (e); Reduction C peak: current vs square root of scan rate for different cathodes (f)

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