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2020 , Vol. 8 >Issue 4: 313 - 324

DOI: https://doi.org/10.3969/j.issn.2095-560X.2020.03.009

Progress on Sulfur/Selenium Cathode Materials for Lithium Batteries

  • Biao WANG 1, 2 ,
  • Jin-long HU 1, 3 ,
  • Yi-lun REN 1, 2 ,
  • Ling-zhi ZHANG , †, 1
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  • 1. Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China
  • 2. Nano Science and Technology Institute, University of Science and Technology of China, Suzhou 215123, Jiangsu, China
  • 3. University of Chinese Academy of Sciences, Beijing 100049, China

Received date: 2020-03-16

  Request revised date: 2020-03-19

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版权所有 © 《新能源进展》编辑部
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Abstract

Lithium-sulfur battery has become one of the most potential secondary batteries because of its high energy density, low cost of raw materials. Unfortunately, its practical application has been hindered by serous technical challenges, such as the low conductivity of sulfur, and unsatisfying long-term cycling stability related with the dissolution of intermediate lithium polysulfide (LiPS) into the electrolyte over cycling. Selenium, the main group element of sulfur, has good conductivity and high volume capacity. By combining the advantages of sulfur and selenium, the solid solution of sulfur and selenium (SexSy) has attracted great attention as active material for lithium-sulfur batteries, owing to its enhanced conductivity and high specific capacity of SexSy. However, some problems such as shuttle effect, electrolyte matching and large volume change over cycling still challenge its practical application for SexSy. In this paper, the recent research progress of cathode materials with SexSy for lithium battery was reviewed. The carbon framework materials, metal compounds, metal organic framework materials and heteroatom doping materials were specifically summarized. Some of our recent progresses on the development of cathode materials for lithium-sulfur/selenium batteries were also introduced. At last, some conclusion and prospects for developing high-performance cathode materials for lithium-sulfur/selenium batteries were presented.

Key words： lithium battery; sulfur/selenium cathode; energy density

Cite this article

Biao WANG , Jin-long HU , Yi-lun REN , Ling-zhi ZHANG . Progress on Sulfur/Selenium Cathode Materials for Lithium Batteries[J]. Advances in New and Renewable Energy, 2020 , 8(4) : 313 -324 . DOI: 10.3969/j.issn.2095-560X.2020.03.009

0 引言

随着各种可穿戴设备、电动汽车、可再生能源等的快速发展,现有的电池体系不能满足高能量/功率密度的要求[1,2,3,4,5,6],因此,设计更加合理高效的储能系统成为当下研究的热点。锂硫（Li-S）电池具有高理论比容量（1 675 mA∙h/g）和高理论能量密度（2 600 W∙h/kg）,而且其活性物质硫在地球上储量丰富、价格低廉、无毒无污染,引起了人们的广泛兴趣[7,8,9]。然而,由于S和Li2S的绝缘性,进一步提高Li-S电池的性能以达到令人满意的水平仍然是一个很大的挑战。相比之下,硒作为硫的同主族元素,具有更高的电子导电率和可观的体积容量。然而其能量密度低[10,11,12,13,14],为了平衡S和Se的相反但互补的特性,它们的固溶体（SexSy,例如SeS0.7、Se2S5、Se2S6、SeS2、Se0.06S0.94、Se0.4S0.6）得到人们极大的关注[15,16,17,18,19,20,21]。SexSy同时具备硫和硒的优势,拥有较高的比容量和导电性,因而锂-硫/硒（Li-SexSy）电池被看作是下一代最具前景的二次电池之一。

1 工作原理和面临的挑战

1.1 工作原理

典型的锂-硫/硒电池由SexSy正极、锂负极、隔膜和电解液组成。根据现有的研究结果,不同电解液中SexSy的反应机理不同。在醚基电解液中,放电时,SexSy的还原过程分为四步（图1a）[22,23,24,25]。前两步是S组分与Li反应生成多硫化物,接着反应生成Li2S2和Li2S。后两步是Se组分与Li反应生成多硒化物,然后再生成Li2Se。WEI等[26]发现当SexSy的Se/S比值为2/5和4/5时会产生5个还原峰,这表明反应过程中出现了新的中间相,这些中间相是由SexSy中S—S、Se—S和Se—Se键的裂解和形成而产生的。而对于SeS5,只出现了3个还原峰,这可能是硒的浓度较低导致的结果（图1b）。在充电过程中,Li2Se和Li2S分别被氧化为S82- 和Se82-[27,28,29]。
Fig. 1 Cyclic voltammetry curves of (a) SeS2 and (b) SeS5 in an ether-based electrolyte[22,26]; cyclic voltammetry curves of Se0.94S0.06 (c) and SeS0.7 (d) in a carbonate-based electrolyte[17,30]

图1 （a）SeS2和（b）SeS5在醚基电解液中的循环伏安曲线[22,26];（c）Se0.94S0.06和（d）SeS0.7在碳酸盐基电解液中的循环伏安曲线[17,30]

在碳酸盐基电解液中,放电过程中只有一个还原峰,对应于多硫化物和多硒化物分别转化为Li2S和Li2Se（图1c）[30,31]。氧化峰在第二次充电过程中转移到较高的电压处,并在随后的充电过程中重叠,这是由第一次锂化过程中的体积膨胀引起的。有时会在第一次放电过程中的较高电压处有一个额外的降低峰值,并在随后的放电/充电过程中消失,这对应于SexSy向多硫化物/多硒化物的转换（图1d）[17]。高电压还原峰的消失是由于高阶多硫化物/多硒化物溶解到电解质中的结果[15]。在正极扫描中,只存在一个氧化峰,对应于Li2S转化为多硫化物,Li2Se转化为多硒化物。

1.2 面临的挑战

尽管SexSy基正极材料同时具有硫的高容量和硒的导电性,但Li-SexSy电池的实际应用还存在许多挑战。其中最主要的一部分来自穿梭效应,是由多硫化物/多硒化物溶解于电解液中并扩散到锂负极上,然后在锂负极表面形成Li2Se、绝缘Li2S2和Li2S而引起的。另外,在循环过程中产生的体积变化会严重破坏电池的内部结构。针对上述问题,科研人员对Li-SexSy电池进行了多种改性尝试[32,33,34],本文重点介绍SexSy基复合正极材料的相关进展。

2 正极材料的研究

SexSy正极的改性设计一般是将SexSy与导电基底在纳米尺度下复合,以此减轻循环过程中的材料粉化问题;同时构建高导电、高比表面积的多孔材料来负载更多的活性物质。引入不同孔径的碳材料、金属化合物、金属-有机框架和杂原子掺杂材料等,是提高SexSy电化学性能的有效途径。

2.1 碳材料

由于高导电性,已经有多种碳材料被发现并利用于锂二次电池中。其中,本课题组在锂离子电池硅负极掺杂碳等方面取得了明显的进展[35]。聚3,4-乙烯二氧噻吩/聚苯乙烯磺酸盐 [poly(3,4-ethylenedi-oxythiophene)/poly(styrenesulfonate), PEDOT:PSS] 和纳米级硅材料化合形成碳-硅复合电极[36],显著地提高了硅负极的电导率,并表现了出较为优异的电化学性能。此外,由于碳材料还具有大量的多孔结构和良好的机械强度,本课题组通过软模板聚合的方法合成了硫-硅掺杂的碳纳米线复合结构[37],该材料具有大量的孔隙,形成了稳定的导电网络,有助于快速脱/嵌锂的过程。与硅负极相似,SexSy电极在电池循环过程中存在较大的体积变化和电导率较低的问题,因此研究人员把碳材料改性硅负极的方法借鉴到SexSy正极上。碳材料的引入可以提高活性材料的电导率,但是,过量的碳与活性材料混合则会降低SexSy的负载量,从而影响能量密度[31,38]。适量的碳材料不仅能保持活性材料和导电载体之间的平衡,而且有利于提高正极的寿命和能量密度。
纯SexSy作为正极材料在循环过程中性能不稳定。ZHANG等[29]测量了SeS2在0.5 A/g下的电化学性能,其初始放电容量为850 mA∙h/g,在第10个循环时降到395 mA∙h/g。当把SeS2以49.3%的含量均匀分散在三维连通的介孔碳气凝胶（mesoporous carbon aerogel, MCA）中时,改性后的SeS2在0.5 A/g下经10个循环后的放电容量提高到了601 mA∙h/g。图2为MCA和SeS2@MCA复合材料的高倍扫描电镜图片。这种改进归功于MCA独特的结构,不仅有利于电荷传输,同时提供了孔位用于封装SeS2并捕获多硫/多硒化物中间体以避免活性物质快速损失,使其具有更好的电化学性能。
Fig. 2 High-magnification SEM images of MCA (a) and SeS2@MCA (b) composite[29]

图2 MCA（a）和SeS2@MCA（b）复合材料的高倍扫描电镜图像[29]

LI等[39]报道了一种具有聚多巴胺（poly- dopamine, PDA）保护层的高度有序介孔碳骨架（CMK）结构,负载70%的SeS2后用于高性能Li-SeS2电池。制备过程和部分表征分别如图3和图4所示。其中,多孔碳载体不仅为快速氧化还原反应提供了电子传输路径,还有足够的空间用来容纳活性物质和吸附可溶性多硫化物/多硒化物[40,41]。PDA原位聚合在CMK-3/SeS2颗粒表面,成为抑制中间产物溶解的屏障,从而优化循环寿命并提高了活性材料的利用率。通过双重限制策略,CMK-3/SeS2@PDA复合材料在0.2 A/g时表现出大于1 200 mA∙h/g的高放电容量,并在5 A/g的高电流密度下获得530 mA∙h/g的优异放电容量。此外,CMK-3/SeS2@PDA电极具有500次以上的循环寿命,容量衰减率为每圈0.11%。
Fig. 3 Synthetic process of CMK‐3/SeS2@PDA composite[39]

图3 CMK-3/SeS2@PDA复合材料的合成过程[39]

Fig. 4 SEM (a-c) and TEM (d, e) images of CMK-3/SeS2@PDA; (f) EDX spectra comparison of CMK-3/SeS2@PDA and CMK-3/SeS2[39]

图4 （a ~ c）CMK-3/SeS2@PDA的SEM图;（d、e）CMK-3/SeS2@PDA的TEM图;（f）CMK-3/SeS2@PDA和CMK-3/SeS2的EDX图谱[39]

除了上述碳材料,还有许多其他碳材料被用于SexSy宿主,如中空碳纳米立方体[42]、碳纳米管[43]、碳化聚丙烯腈材料[17]等。LI等[19]以Se和S粉为原料,在260℃下制备了非晶S1-xSex/C（x ≤ 0.1）复合材料作为Li-SexSy电池的正极材料。该材料在碳酸盐基电解液中表现出良好的电化学性能。其中S0.94Se0.06/C性能最优,在1 A/g下循环500个周期后容量为910 mA∙h/g,在0.2 A/g下循环100个周期后的容量为1 105 mA∙h/g。本课题组HU等[44]设计了一种双层空心碳球嵌入三维石墨烯结构用于封装Se0.4S0.6,即3DG-DLHC-Se0.4S0.6,其合成工艺如图5所示。3DG-DLHC-Se0.4S0.6作为锂电池的正极材料主要通过3DG和DLHC双重限制多硒化锂和多硫化锂的溶解。此外三维石墨烯与双层空心碳球的结构耦合形成一个有效的三维互连导电网络,用于快速电子/离子输运,同时有足够的空间来缓冲Se0.4S0.6的体积膨胀。
Fig. 5 Synthesis process of 3DG-DLHC-Se0.4S0.6[44]

图5 3DG-DLHC-Se0.4S0.6合成工艺示意图[44]

2.2 金属化合物

含碳基质虽然可以通过物理作用吸附可溶性中间产物,但是利用这种物理吸附方法很难解决活性物质在循环过程中的损失问题。如果增加多硫化物/多硒化物的浓度则会导致中间体不可避免的溶解,电解质的黏度增加,离子扩散速度较慢等一系列不良反应。与含碳基质相比,金属化合物材料在吸附多硫化物/多硒化物的同时还能作为催化剂与中间体结合,提高反应活性,加速多硫化物/多硒化物的氧化还原,有利于实现锂电池的长循环性能。根据对锂离子电池的研究,金属氧化物/硫化物/氮化物等已被用来解决这些问题[45,46,47]。
CHEN等[48]利用螯合竞争诱导聚合策略制备多核-壳（multi-yolk-shell）-Co4N@C（MYS-Co4N@C）纳米盒,大大提高了Li-SeS2电池的整体性能。在这种独特的多核-壳纳米结构中,极性Co4N可以通过强的化学键来限制多硫化物和多硒化物向外扩散,并表现出良好的电催化性能。碳外壳作为一个亚微米大小的反应室,为多硫化物和多硒化物提供空间。此外,高导电性的Co4N核心和碳层可以保证放电/充电过程中电子的平稳传输和活性物质的高利用率。在电流密度为0.2 C时,比较了MYS-Co4N@C/SeS2和C-NBs/SeS2电极的循环性能。在没有极性Co4N核心存在的情况下,C-NBs/SeS2电极的容量严重衰退到600 mA∙h/g以下,100次循环之后,仅保留了初始容量的52%。相比之下,MYS-Co4N@C/SeS2电极具有更高的放电容量,为996 mA∙h/g,100个循环后的容量保持率高达85%。MYS-Co4N@C/SeS2电极的循环稳定性远优于C-NBs/SeS2电极,说明MYS-Co4N@C/SeS2在捕获多硫化物和多硒化物方面的结构优势。此外,在长循环过程中,MYS-Co4N@C/SeS2电极的库仑效率大于99%。结果表明,合理设计的MYS-Co4N@C结构能有效地减缓多硫化物和多硒化物在电解液中的溶解,提高循环寿命。
LI等[49]采用模板法合成了一种中空介孔碳@氮化钛（HMC@TiN）载体,合成路线如图6所示。结果表明HMC/SeS2和HMC@TiN/SeS2均表现出较高的初始放电容量,同时HMC/SeS2的比容量下降更快。这证实了极性材料TiN在提高循环稳定性中的作用[50,51,52]。此外,随着电流密度的增大然后再回到初始值,HMC@TiN/SeS2表现出良好的反应动力学和稳定性。其中第一个循环的放电容量为987 mA∙h/g（0.2 C）,第10、100和200个循环的放电容量分别为923 mA∙h/g、778 mA∙h/g和690 mA∙h/g。从第二次循环开始,库仑效率均在99%以上。即使电流密度从0.1 C增加到4 C（随后又恢复到0.1 C）,放电容量也显示出良好的可逆恢复。
Fig. 6 (a) Process for the synthesis of HMC@TiN; (b) with the TiN shell, dissoluble polysulfide/polyselenide could be effectively confined within the host during cycling; (c) in the bare HMC/SeS2 composite, the intermediates could readily diffuse out of the carbon host during cycling[49]

图6 （a）HMC@TiN的合成方法;（b）利用TiN外壳可以有效地将可溶性多硫化物/多硒化物限制在载体内;（c）在裸露的HMC/SeS2复合材料中,中间产物在循环过程中很容易从碳载体中扩散出去[49]

ZHANG等[53]设计并制备了一种CoS2纳米颗粒修饰的莲藕状碳纤维网络（CoS2@LRC）作为SeS2的载体,用于提高锂储存性能,其合成示意图如图7。该集成电极由三维互连的多通道碳纤维构成,不仅可以容纳大量的SeS2（质量分数为70%）,而且还具有良好的电子和离子运输性能,在0.2 A/g下可获得1 015 mA∙h/g的高容量。此外,碳纤维的内壁和表面都有大量的CoS2颗粒纳米,为限制多硫化物/多硒化物的溶解提供了有效的亲硫位点,从而成功地抑制了穿梭效应,并在0.5 A/g下保持了400次循环的良好循环稳定性。
Fig. 7 (a) Schematic illustration of the synthesis process of CoS2@LRC; (b) proposed advantages of CoS2@LRC/SeS2 over LRC/SeS2[53]

图7 （a）CoS2@LRC的合成过程示意图;（b）CoS2@LRC/SeS2优于LRC/SeS2的原因[53]

2.3 金属-有机框架

金属-有机框架（metal-organic frameworks, MOFs）也被称为多孔配位聚合物,是由有机配体与金属离子或金属团簇通过配位键形成的有机-无机杂化多孔晶态材料[54]。MOFs具有孔隙率大、比表面积大的特点,同时可以通过选择不同长度的有机官能团来调节其孔径。多孔尺寸的调整有利于吸附活性物质和中间产物。除此之外,MOFs还可以提供不饱和金属位点,并通过改变其可变金属中心和有机配体来改变结构和功能。这些不同官能团的组合可以与自由离子形成不同的化学键来约束多硫化物/多硒化物。同时,含金属位点的MOFs也可以作为催化剂来加速反应过程。
HE等[24]合成了一种呈规则菱形十二面体骨架的Co-N-C材料。采用熔融扩散法,SeS2可以被分散到Co-N-C结构中,并且在表面没有残留。这表明MOFs具有良好的结构优势。原位拉曼光谱阐明了Co-N-C/SeS2的电化学反应机理（如图8）。
Fig. 8 (a) C-V curve and contour plot of Raman spectra of the Co-N-C/SeS2 electrode recorded in the initial cathodic scan; (b) selected original Raman spectra, corresponding to (a); (c) CV curves and contour plot of Raman spectra of the Co-N-C/SeS2 electrode recorded in the initial anodic scan; (d) selected original Raman spectra, as corresponding to (c)[24]

图8 （a）首次正极扫描记录的Co-N-C/SeS2电极拉曼光谱的CV曲线和轮廓图;（b）选定的拉曼光谱,与（a）对应;（c）初始负极扫描记录的Co-N-C/SeS2电极拉曼光谱的CV曲线和轮廓图;（d）选定的原始拉曼光谱,与（c）对应[24]

在Co-N-C的影响下,多硫化物/多硒化物在放电过程中完全转变为了Li2S和Li2Se,随后在充电过程中被氧化成SeS2。此外,X射线光电子能谱（X-ray photoelectron spectroscopy, XPS）分析（如图9）进一步证明了MOFs与中间产物之间的强化学作用,由此发现金属离子和活性材料的光谱都向更高的结合能方向移动,这意味着存在强化学相互作用。而且,图10c中168 ~ 172 eV处出现的新峰证实了硫代硫酸盐和聚硫代硫酸盐的形成,这表明长链多硫化物/多硒化物转变为了短链[55]。得益于其独特的结构和丰富的微孔和中孔,高导电的Co-N-C基质为电子转移和离子扩散提供了高效的通道,并为负载SeS2纳米颗粒提供了足够的空间,减少了多硫化物/多硒化物在电解液中的溶解以及充放电循环中的体积变化。此外,均匀分布在Co-N-C复合材料中的钴纳米粒子不仅通过强烈的化学相互作用固定了多硫化物/多硒化物,而且有利于放电/充电过程中的催化作用。这些优点使Co-N-C/SeS2复合阴极在SeS2负载量高达66.5%（质量分数）条件下也能提供1 165.1 mA∙h/g的可逆容量。
Fig. 9 High-resolution XPS spectra[24]: S 2p spectra of Li2S6 (a) and Co-N-C/Li2S6 (b); Co 2p spectra of Co-N-C (c) and Co-N-C/Li2S6 (d)

图9 高分辨XPS谱图[24]：Li2S6（a）和Co-N-C/Li2S6（b）的S 2p谱图;Co-N-C（c）和Co-N-C/Li2S6（d）的Co 2p谱图

Fig. 10 Cycling performance (a) and coulombic efficiency (b) of SenS8-n/NMC (n = 1-3) at 250 mA/g; (c) rate performances of SenS8-n/NMC (n = 1-3) at different current densities; (d) EIS of SenS8-n/NMC (n = 1-3) before the first cycle; (e) long-term cycling performance of Se2S6/NMC at 250 mA/g[16]

图10 SenS8-n/NMC（n = 1 ~ 3）在250 mA/g时的循环性能（a）和库仑效率（b）;（c）不同电流密度下SenS8-n/NMC（n = 1 ~ 3）的速率性能;（d）第一次循环前SenS8-n/NMC （n = 1 ~ 3）的EIS;（e）SenS8-n/NMC在250 mA/g时的长循环性能[16]

MOFs对可溶性中间产物有较强限制作用,可抑制穿梭效应,其与多硫化物/多硒化物之间的吸附能大于纯碳材料与多硫化物/多硒化物之间的吸附能。与纯碳载体和金属化合物载体相比,MOFs以其独特的结构,结合碳材料和金属化合物材料的优点,缓解了锂电池固有的问题,提高了锂电池性能。

2.4 杂原子掺杂材料

杂原子掺杂是将基底材料功能化的另一种手段。最常用的掺杂基质是多孔碳材料。每一种杂原子掺杂剂都能够通过独特的机理发挥作用,因此对碳材料进行二元或多元共掺杂可以通过协同效应进一步提高碳纳米材料的性能。
氮在元素周期表中与碳相邻,因其原子大小和碳很接近,可以较容易地取代碳材料中碳原子。同时,与碳原子相比,氮掺杂原子具有更高的电子亲合力,这使得氮掺杂原子很容易改变碳材料中的原子结构和电子排列,进而使碳纳米材料中电荷的离域化、自旋密度的变化以及更接近费米能级的态密度的增加。这些优化进一步使碳材料具有n型导电性,增强了材料的电子输运特性,不仅有利于多硫化物/多硒化物的化学吸附,而且提高了化学活性,加速了化学反应过程等[56]。SUN等[16]通过简单的熔融扩散法,将SenS8-n（n = 1 ~ 3）分子均匀地限制在氮掺杂的介孔碳（nitrogen-doped mesoporous carbons, NCMs）中,制备了SenS8-n/NMC复合材料。其电化学性能如图10。其中Se2S6/NMC作为正极材料具有优异的循环稳定性,初始库仑效率高达96.5%,100次循环后的可逆容量为883 mA∙h/g,200次循环后的可逆容量为780 mA∙h/g。
本课题组成功合成了一种硫掺杂三维介孔碳（ISMC）与SeS2复合的正极材料SeS2@ISMC[18],其部分表征如图11。扫描和透射电镜测试结果表明,SeS2均匀地分散于ISMC丰富的介孔结构中,其中SeS2的质量占比为55%,在0.5 A/g下循环200次后的可逆容量为486 mA∙h/g,在4 A/g下可以达到465 mA∙h/g。SeS2@ISMC正极材料表现出良好电化学性能的原因可总结为三点：①三维网络结构限制了多硫化物/多硒化物的溶解;②互连的SeS2@ISMC网络结构提高了离子和电子的传输;③硫原子的掺杂大大地提高了碳基底的导电性。
Fig. 11 SEM images of ISMC (a) and SeS2@ISMC (b); (c) cycling performance and coulombic efficiency of SeS2@MC and SeS2@ISMC at 500 mA/g; (d) rate capabilities of SeS2@ISMC[18]

图11 ISMC（a）和SeS2@ISMC（b）的SEM图;（c）SeS2@MC和SeS2@ISMC在500 mA/g下的循环性能和库伦效率图;（d）SeS2@ISMC倍率性能图[18]

除氮原子和硫原子外,还有氧、磷等多种原子被用作掺杂原子[57,58,59,60],MOFs可以算是杂原子掺杂材料的一种类型,可以增强吸附多硫化物/多硒化物的物理化学作用。即杂原子掺杂可以进一步增强宿主材料的功能,提高整个反应环境的导电性。

3 结论与展望

近年来,SexSy由于兼具S和Se的优势而备受关注。使用多孔碳材料、金属化合物、MOFs或杂原子掺杂材料有助于多硫化物/多硒化物的物理和化学吸附,从而进一步限制多硫化物/多硒化物的溶解和扩散。此外,具有内部空间的宿主材料的独特结构可以容纳活性材料和缓解材料的体积膨胀。本文综述了Li-SexSy电池正极材料的设计与优化以及反应机理与电解液的关系,为Li-SexSy电池的设计提供了参考。部分电池的性能如表1所示。为了进一步开发轻质、体积小、能量密度高、循环寿命长的可充电电池,科研人员不仅要关注正极材料的设计,也要考虑到电池的隔膜、电解液和负极等其他部分。随着研究的不断深入,高体积能量密度的SexSy将在未来的可充电电池中得到有效的开发和应用。
Table 1 Different hosts load SexSy composite cathodes

表1 不同载体负载SexSy复合正极

Meterial Initial capacity / (mA∙h/g) C-rate Cycle number Cycling stability / % Ref.
SeS2@ISMC 858.0 0.5 A/g 200 56.6 [18]
S0.94Se0.06/C 1 755 0.2 A/g 200 61.4 [19]
Co-N-C/SeS2 1 153.5 0.2 C 200 84.1 [24]
Se2S5/MCM 1 150.6 1 C 100 60.6 [26]
SeS2@MCA 846.0 0.5 A/g 10 71.0 [29]
CMK-3/SeS2@PDA 1 234.0 0.2 A/g 150 63.5 [38]
SeS2/HMCNCs 986.3 0.2 A/g 100 82.3 [41
3DG-DLHC-Se0.4S0.6 667.0 1 A/g 500 54.9 [44]
MYS-Co4N@C/SeS2 909.0 0.5 C 300 73.6 [47]
HMC@TiN/SeS2 987.0 0.2 C 50 85.1 [48]
CoS2@LRC/SeS2 1 015.0 0.2 A/g 100 73.4 [52]

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