Recent advances in catalytic mechanisms and <italic style="font-style: italic">in situ</italic> characterization of the sulfur reduction reaction in lithium-sulfur batteries

YANG Changheng; ZHANG Huigang; SHEN Zihan; ZHU Qingshan

doi:10.19799/j.cnki.2095-4239.2025.0886

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Recent advances in catalytic mechanisms and in situ characterization of the sulfur reduction reaction in lithium-sulfur batteries

Energy Storage Materials and Devices | 更新时间：2026-05-28

- Recent advances in catalytic mechanisms and in situ characterization of the sulfur reduction reaction in lithium-sulfur batteries
- Energy Storage Science and Technology Vol. 15, Issue 2, Pages: 435-457(2026)
- 作者机构：
  
  1.中国科学院过程工程研究所，北京 100190
  2.中国科学院大学化学工程学院，北京 100049
- 作者简介：
- 基金信息：
- DOI：10.19799/j.cnki.2095-4239.2025.0886
  CLC： TM 911
- Received：09 October 2025，
  
  Revised：2025-11-06，
  
  Published：28 February 2026
- 稿件说明：
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杨昌恒, 张会刚, 沈子涵, 等. 锂硫电池硫还原反应的催化调控机理及原位表征进展[J]. 储能科学与技术, 2026, 15(2): 435-457.

YANG Changheng, ZHANG Huigang, SHEN Zihan, et al. Recent advances in catalytic mechanisms and in situ characterization of the sulfur reduction reaction in lithium-sulfur batteries[J]. Energy Storage Science and Technology, 2026, 15(2): 435-457.
杨昌恒, 张会刚, 沈子涵, 等. 锂硫电池硫还原反应的催化调控机理及原位表征进展[J]. 储能科学与技术, 2026, 15(2): 435-457. DOI： 10.19799/j.cnki.2095-4239.2025.0886.

YANG Changheng, ZHANG Huigang, SHEN Zihan, et al. Recent advances in catalytic mechanisms and in situ characterization of the sulfur reduction reaction in lithium-sulfur batteries[J]. Energy Storage Science and Technology, 2026, 15(2): 435-457. DOI： 10.19799/j.cnki.2095-4239.2025.0886.

摘要

锂硫电池(LSBs)因其高能量密度、低成本和环境友好等优势，在储能等领域展现出广阔的应用前景。然而，循环过程中多硫化物(LiPS)的穿梭效应会导致活性物质的损失和金属锂负极的腐蚀，严重制约LSBs性能提升。因此，构筑能够高效锚定LiPS并加速其氧化还原转化的高活性催化剂，已成为解决该问题的关键途径。围绕这一问题，本文系统梳理了近年来在晶体结构调控、电子结构调控以及原位表征技术方面的进展。在晶体结构调控方面，本文介绍了活性面调控、晶相设计及异质结构构筑等方法，这些策略通过调节活性位点的几何构型与局域配位环境，可增强LiPS的极性吸附并降低关键转化能垒。在电子结构调控方面，本文概述了能带与轨道调控、电子态优化和自旋态调节等方向，重点阐述电子分布、轨道耦合特性与载流子迁移行为对界面反应动力学的影响机制。此外，本文还总结了各类原位表征技术在解析硫物种演化和界面反应机制中的关键作用，强调其在揭示中间体动态变化与催化位点结构重构方面的独特价值。综合来看，晶体结构与电子结构的协同优化对于促进LiPS的吸附-转化过程至关重要，而先进原位技术正不断深化对催化机理的理解，为高性能LSBs的理性设计提供指导。

Abstract

Lithium-sulfur batteries (LSBs) are highly promising for energy storage applic

ations due to their high energy density

low cost

and environmental friendliness. However

the shuttle effect of lithium polysulfides (LiPS) during cycling causes the loss of active materials and corrosion of the lithium metal anode

severely limiting performance improvements. Designing highly efficient catalysts that can strongly anchor LiPS and accelerate their redox conversion has therefore emerged as a key strategy to address this challenge. Motivated by this goal

this review systematically summarizes recent advances in crystal structure engineering

electronic structure modulation

and

in situ

characterization techniques. For crystal structure regulation

strategies such as active-facet modulation

phase engineering

and heterostructure construction are discussed. These approaches optimize the geometric configuration and local coordination environment of active sites

enhancing the polar adsorption of LiPS and reducing key energy barriers during the conversion process. In terms of electronic structure modulation

this review emphasizes band and orbital engineering

electronic state optimization

and spin-state regulation

with a particular focus on how electronic distribution

orbital coupling

and charge-carrier transport collectively influence interfacial reaction kinetics. Furthermore

various

in situ

techniques

including

in situ

XAS

XRD

Raman spectroscopy

TEM

and ATR-FTIR

are summarized for their critical roles in monitoring sulfur-species evolution and elucidating interfacial reaction mechanisms under realistic operating conditions. Overall

the synergistic optimization of crystal and electronic structures is essential for efficient LiPS adsorption and conversion

while advances in

in situ

characterization provide mechanistic insights and valuable guidance for the rational design of high-performance LSBs.

关键词

Keywords

references

BRUCE P G, FREUNBERGER S A, HARDWICK L J, et al. Li-O 2 and Li-S batteries with high energy storage[J ] . Nature Materials, 2011, 11(1): 19-29. DOI: 10.1038/nmat3191.

CHEN Y, WANG T Y, TIAN H J, et al. Advances in lithium-sulfur batteries: From academic research to commercial viability[J]. Advanced Materials, 2021, 33(29): 2003666. DOI: 10.1002/adma.202003666.

CHUNG W J, GRIEBEL J J, KIM E T, et al. The use of elemental sulfur as an alternative feedstock for polymeric materials[J]. Nature Chemistry, 2013, 5(6): 518-524. DOI: 10.1038/nchem.1624.

HAO H C, HUTTER T, BOYCE B L, et al. Review of multifunctional separators: Stabilizing the cathode and the anode for alkali (Li, Na, and K) metal-sulfur and selenium batteries[J]. Chemical Reviews, 2022, 122(9): 8053-8125. DOI: 10.1021/acs.chemrev.1c00838.

ZHOU G M, CHEN H, CUI Y. Formulating energy density for designing practical lithium-sulfur batteries[J]. Nature Energy, 2022, 7(4): 312-319. DOI: 10.1038/s41560-022-01001-0.

BAI Z, WANG Z H, WANG T, et al. Cation-vacancy engineering modulated perovskite oxide for boosting electrocatalytic conversion of polysulfides[J]. Advanced Functional Materials, 2025, 35(14): 2419105. DOI: 10.1002/adfm.202419105.

LIU J B, LI G R, LUO D, et al. Incorporation of heteroatomic Fe activates rapid catalytic behaviors of Co 3 O 4 hollow nanoplates toward advanced lithium-sulfur batteries[J ] . Advanced Functional Materials, 2024, 34(5): 2303357. DOI: 10.1002/adfm.202303357.

MA Z Y, QI Z Q, SONG G H, et al. α-MnO 2 /RuO 2 heterostructure-modified polypropylene separator for high-performance lithium-sulfur battery[J ] . Advanced Functional Materials, 2024, 34(39): 2403101. DOI: 10.1002/adfm.202403101.

TIAN L Y, ZHANG Z, LIU S, et al. High-entropy perovskite oxide nanofibers as efficient bidirectional electrocatalyst of liquid-solid conversion processes in lithium-sulfur batteries[J]. Nano Energy, 2023, 106: 108037. DOI: 10.1016/j.nanoen.2022.108037.

HUANG C, YU J, ZHANG C Y, et al. Electronic spin alignment within homologous NiS 2 /NiSe 2 heterostructures to promote sulfur redox kinetics in lithium-sulfur batteries[J ] . Advanced Materials, 2024, 36(25): 2400810. DOI: 10.1002/adma.202400810.

LAO Z J, HAN Z Y, MA J B, et al. Band structure engineering and orbital orientation control constructing dual active sites for efficient sulfur redox reaction[J]. Advanced Materials, 2024, 36(2): 2309024. DOI: 10.1002/adma.202309024.

LI X, ZUO Y Z, ZHANG Y Z, et al. Controllable sulfurization of MXenes to in-plane multi-heterostructures for efficient sulfur redox kinetics[J]. Advanced Energy Materials, 2024, 14(9): 2303389. DOI: 10.1002/aenm.202303389.

YE X, WU F, XUE Z Y, et al. Accelerated polysulfide conversion by rationally designed NiS 2 -CoS 2 heterostructure in lithium-sulfur batteries[J ] . Advanced Functional Materials, 2025, 35(13): 2417776. DOI: 10.1002/adfm.202417776.

ZHAO C H, HUANG Y, JIANG B, et al. The origin of strain effects on sulfur redox electrocatalyst for lithium sulfur batteries[J]. Advanced Energy Materials, 2024, 14(5): 2302586. DOI: 10.1002/aenm.202302586.

YANG D W, LI M Y, ZHENG X J, et al. Phase engineering of defective copper selenide toward robust lithium-sulfur batteries[J]. ACS Nano, 2022, 16(7): 11102-11114. DOI: 10.1021/acsnano. 2c03788.

ZHAI S J, YE Z, LIU R, et al. Defect strategy-regulated MoSe 2 -modified self-supporting graphene aerogels serving as both cathode and interlayer of lithium-sulfur batteries[J ] . Advanced Functional Materials, 2024, 34(17): 2314379. DOI: 10.1002/adfm. 202314379.

ZHANG C Q, FEI B, YANG D W, et al. Robust lithium-sulfur batteries enabled by highly conductive WSe 2 -based superlattices with tunable interlayer space[J ] . Advanced Functional Materials, 2022, 32(24): 2201322. DOI: 10.1002/adfm.202201322.

ZHEN M M, YANG Q H, WANG X Y, et al. Coupling bimetallic selenides with homogeneous mediators synergistically accelerating overall sulfur redox kinetics for high-performances lithium-sulfur batteries[J]. Chemical Engineering Journal, 2024, 496: 153650. DOI: 10.1016/j.cej.2024.153650.

HE J R, BHARGAV A, MANTHIRAM A. In situ grown 1T'-MoTe 2 nanosheets on carbon nanotubes as an efficient electrocatalyst and lithium regulator for stable lithium-sulfur full cells[J ] . Advanced Energy Materials, 2022, 12(1): 2103204. DOI: 10.1002/aenm.202103204.

HUANG C, YU J, LI C H, et al. Combined defect and heterojunction engineering in ZnTe/CoTe 2 @NC sulfur hosts toward robust lithium-sulfur batteries[J ] . Advanced Functional Materials, 2023, 33(46): 2305624. DOI: 10 .1002/adfm.202305624.

LI B, WANG P, YUAN J, et al. Origin of phase engineering CoTe 2 alloy toward kinetics-reinforced and dendrite-free lithium-sulfur batteries[J ] . Advanced Materials, 2024, 36(8): 2309324. DOI: 10.1002/adma.202309324.

CHEN Y Q, ZHANG X D, CHEN Q D, et al. Self-supported tungsten nitride and carbide heterostructures with vanadium doping tandemly catalyze the conversion of polysulfides for lithium-sulfur batteries[J]. Advanced Functional Materials, 2025, 35(1): 2411941. DOI: 10.1002/adfm.202411941.

RAN Q W, LIU J T, LI L, et al. Electronic state-modulated Ni 4 N/Zn 3 N 2 heterogeneous nanosheet arrays toward dendrite-free and kinetic-enhanced Li-S full batteries[J ] . Advanced Functional Materials, 2024, 34(38): 2402872. DOI: 10.1002/adfm.202402872.

YANG S X, JIANG D B, SU Q, et al. In situ constructing a TiO 2 /TiN heterostructure modified carbon interlayer for balancing the surface adsorption and conversion of polysulfides in Li-S batteries[J ] . Advanced Energy Materials, 2024, 14(24): 2470100. DOI: 10.1002/aenm.202470100.

ZHAO Z Q, PAN Y K, YI S, et al. Enhanced electron delocalization within coherent nano-heterocrystal ensembles for optimizing polysulfide conversion in high-energy-density Li-S batteries[J]. Advanced Materials, 2024, 36(13): 2310052. DOI: 10.1002/adma.202310052.

XIA W L, CHEN Y F, HAN M Y, et al. MoC-MoSe 2 heterostructures as multifunctional catalyst toward promoting the stepwise polysulfide conversion for lithium-sulfur batteries[J ] . Advanced Functional Materials, 2024, 34(33): 2400262. DOI: 10.1002/adfm.202400262.

LI J H, WANG Z Y, SHI K X, et al. Nanoreactors encapsulating built-in electric field as a "bridge" for Li-S batteries: Directional migration and rapid conversion of polysulfides[J]. Advanced Energy Materials, 2024, 14(9): 2303546. DOI: 10.1002/aenm.202303546.

WANG Z Y, HUANG W Z, WU H, et al. 3d-orbital high-spin configuration driven from electronic modulation of Fe 3 O 4 /FeP heterostructures empowering efficient electrocatalyst for lithium-sulfur batteries[J ] . Advanced Functional Materials, 2024, 34(49): 2409303. DOI: 10.1002/adfm.202409303.

XIAO R, YU T, YANG S, et al. Non-carbon-dominated catalyst architecture enables double-high-energy-density lithium-sulfur batteries[J]. Advanced Functional Materials, 2024, 34(3): 2308210. DOI: 10.1002/adfm.202308210.

GUO Q Y, WANG C, SHANG J, et al. A freestanding, dissolution- and diffusion-limiting, flexible sulfur electrode enables high specific capacity at high mass loading[J]. Advanced Materials, 2024, 36(25): 2400041. DOI: 10.1002/adma.202400041.

JIA H N, FAN J H, SU P, et al. Cobalt nitride nanoparticles encapsulated in N-doped carbon nanotubes modified separator of Li-S battery achieving the synergistic effect of restriction-adsorption-catalysis of polysulfides[J]. Small, 2024, 20(26): 2311343. DOI: 10.1002/smll.202311343.

WANG B, WANG Y, LAN Y D, et al. Integrated design for discrete sulfur@polymer nanoreactor with tandem connection as lithium-sulfur battery cathodes[J]. Angewandte Chemie International Edition, 2024, 63(31): e202406693. DOI: 10.1002/anie.202406693.

ZUO X T, WANG L F, ZHEN M M, et al. Multifunctional TiN-MXene-Co@CNTs networks as sulfur/lithium host for high-areal-capacity lithium-sulfur batteries[J]. Angewandte Chemie International Edition, 2024, 63(35): e202408026. DOI: 10.1002/anie.202408026.

LAN Y D, WANG Y W, WANG Y, et al. Chip-inspired design of high-performance lithium-sulfur batteries by integrating monodisperse sulfur nanoreactors on graphene[J]. ACS Nano, 2024, 18(24): 15638-15650. DOI: 10.1021/acsnano.4c01264.

XIAN B C, SHEN S H, YANG T Q, et al. Roller-like spore carbon sphere-orientated graphene fibers prepared via rheological engineering for lithium sulfur batteries[J ] . ACS Nano, 2024, 18(40): 27451-27464. DOI: 10.1021/acsnano.4c07864.

ZHOU F Y, MENG Y H, WANG T, et al. Strutted graphene foam loading sulfur for high-rate long-lifetime Li-S batteries[J]. Nano Energy, 2024, 127: 109755. DOI: 10.1016/j.nanoen.2024.109755.

CHENG Z B, CHEN Y Y, LIAN J, et al. Interface engineering of MOF nanosheets for accelerated redox kinetics in lithium-sulfur batteries[J]. Angewandte Chemie International Edition, 2025, 64(11): e202421726. DOI: 10.1002/anie.202421726.

JIANG Y J, CHEN T Y, CHEN J L, et al. Heterostructured bimetallic MOF-on-MOF architectures for efficient oxygen evolution reaction[J]. Advanced Materials, 2024, 36(8): 2306910. DOI: 10.1002/adma.202306910.

WANG J Y, ZHANG X M, WANG X B, et al. Activation of MOF catalysts with low steric hindrance via undercoordination chemistry for efficient polysulfide conversion in lithium-sulfur battery[J ] . Advanced Energy Materials, 2024, 14(37): 2402072. DOI: 10.1002/aenm.202402072.

YANG P, QIANG J, CHEN J Q, et al. A versatile metal-organic-framework pillared interlayer design for high-capacity and long-life lithium-sulfur batteries[J]. Angewandte Chemie International Edition, 2025, 64(2): e202414770. DOI: 10.1002/anie.202414770.

ZHOU L Y, PAN H W, YIN G J, et al. Tailoring the function of battery separators via the design of MOF coatings[J ] . Advanced Functional Materials, 2024, 34(23): 2314246. DOI: 10.1002/adfm. 202314246.

JIANG B, TIAN D, QIU Y, et al. High-index faceted nanocrystals as highly efficient bifunctional electrocatalysts for high-performance lithium-sulfur batteries[J]. Nano-Micro Letters, 2021, 14(1): 40. DOI: 10.1007/s40820-021-00769-2.

LIU K F, FENG J R, GUO J, et al. (1-10) facet-dominated TiB 2 nanosheets with high exposure of dual-atom-sites for enhanced polysulfide conversion in Li-S batteries[J ] . Advanced Functional Materials, 2024, 34(17): 2314657. DOI: 10.1002/adfm.202314657.

XIAO R J, LUO D, WANG J Y, et al. Oxidation states regulation of cobalt active sites through crystal surface engineering for enhanced polysulfide conversion in lithium-sulfur batteries[J]. Advanced Science, 2022, 9(31): 2202352. DOI: 10.1002/advs.2022 02352.

JIANG B, QIU Y, TIAN D, et al. Crystal facet engineering induced active tin dioxide nanocatalysts for highly stable lithium-sulfur batteries[J]. Advanced Energy Materials, 2021, 11(48): 2102995. DOI: 10.1002/aenm.202102995.

WU Z, LIU M L, HE W F, et al. Unveiling the autocatalytic growth of Li 2 S crystals at the solid-liquid interface in lithium-sulfur batteries[J ] . Nature Communications, 2024, 15: 9535. DOI: 10.1038/s41467-024-53797-y.

JIN M J, SUN G W, WANG Y T, et al. Boosting charge transport and catalytic performance in MoS 2 by Zn 2+ intercalation engineering for lithium-sulfur batteries[J ] . ACS Nano, 2024, 18(3): 2017-2029. DOI: 10.1021/acsnano.3c08395.

ZHANG J P, XIE Z R, XI W, et al. 3D printing of tungstate anion modulated 1T-MoS 2 composite cathodes for high-performance lithium-sulfur batteries[J ] . Advanced Energy Materials, 2024, 14(39): 2401792. DOI: 10.1002/aenm.202401792.

HE Y Q, XIONG D F, LUO Y X, et al. Phase reconstruction-assisted electron-Li + reservoirs enable high-performance Li-S battery operation across wide temperature range[J ] . Advanced Functional Materials, 2025, 35(1): 2410899. DOI: 10.1002/adfm. 202410899.

LI H J, XI K, YANG C, et al. Defect-triggered phase transition energizes the defects in non-stoichiometric molybdenum sulfide for catalyzing polysulfide conversion in lithium sulfur batteries[J]. Chemical Engineering Journal, 2025, 515: 163513. DOI: 10.1016/j.cej.2025.163513.

LIU W, LUO C, ZHANG S W, et al. Cobalt-doping of molybdenum disulfide for enhanced catalytic polysulfide conversion in lithium-sulfur batteries[J]. ACS Nano, 2021, 15(4): 7491-7499. DOI: 10.1021/acsnano.1c00896.

LIN H B, ZHANG S L, ZHANG T R, et al. Simultaneous cobalt and phosphorous doping of MoS 2 for improved catalytic perform ance on polysulfide conversion in lithium-sulfur batteries[J ] . Advanced Energy Materials, 2019, 9(38): 1902096. DOI: 10.1002/aenm.201902096.

SONG N, MA J Z, LIANG Y Z, et al. Phase and orbital engineering effectuating efficient adsorption and catalysis toward high-energy lithium-sulfur batteries[J]. Advanced Materials, 2025, 37(18): e2420588. DOI: 10.1002/adma.202420588.

WANG X Y, CHEN L, YU Y J, et al. Tuning p-band centers and interfacial built-In electric field of heterostructure catalysts to expedite bidirectional sulfur redox for high-performance Li-S batteries[J]. Advanced Functional Materials, 2024, 34(41): 2406290. DOI: 10.1002/adfm.202406290.

DONG Y Y, ZHANG H K, CAI D, et al. Dynamic stereo-conformation of catalyst-In-cavity biomimetic enzymes enable high-sulfur-utilization and lean-electrolyte lithium-sulfur batteries[J]. Advanced Functional Materials, 2024, 34(41): 2406455. DOI: 10.1002/adfm.202406455.

WU K, LU G D, HUANG B, et al. Entropy-driven highly chaotic MXene-based heterostructures as an efficient sulfur redox electrocatalysts for Li-S battery[J]. Advanced Functional Materials, 2024, 34(45): 2404976. DOI: 10.1002/adfm.202404976.

WU X P, XIE R J, CAI D P, et al. Engineering defect-rich bimetallic telluride with dense heterointerfaces for high-performance lithium-sulfur batteries[J]. Advanced Functional Materials, 2024, 34(26): 2315012. DOI: 10.1002/adfm.202315012.

WANG H M, YUAN H, WANG W W, et al. Accelerating sulfur redox kinetics by electronic modulation and drifting effects of pre-lithiation electrocatalysts[J]. Advanced Materials, 2024, 36(8): 2307741. DOI: 10.1002/adma.202307741.

JIAO X C, HU J, ZUO Y Z, et al. Self-recovery catalysts of ZnIn 2 S 4 @In 2 O 3 heterostructures with multiple catalytic centers for cascade catalysis in lithium-sulfur battery[J ] . Nano Energy, 2024, 119: 109078. DOI: 10.1016/j.nanoen.2023.109078.

JIN C Q, ZHAI P B, TANG J L, et al. Ultrathin NiO/Ni 3 S 2 heterostructure as electrocatalyst for accelerated polysulfide conversion in lithium-sulfur batteries[J ] . Energy & Environmental Materials, 2023, 6(6): e12491. DOI: 10.1002/eem2.12491.

LI Y N, DENG Y R, YANG J L, et al. Bidirectional catalyst with robust lithiophilicity and sulfiphilicity for advanced lithium-sulfur battery[J]. Advanced Functional Materials, 2023, 33(44): 2302267. DOI: 10.1002/adfm.202302267.

HUANG Z M, ZHU Y X, KONG Y, et al. Efficient synergism of chemisorption and wackenroder reaction via heterostructured La 2 O 3 -Ti 3 C 2 T x -embedded carbon nanofiber for high-energy lithium-sulfur pouch cells[J ] . Advanced Functional Materials, 2023, 33(36): 2303422. DOI: 10.1002/adfm.202303422.

NGUYEN V P, PARK J S, SHIM H C, et al. Accelerated sulfur evolution reactions by TiS 2 /TiO 2 @MXene host for high-volumetric-energy-density lithium-sulfur batteries[J ] . Advanced Functional Materials, 2023, 33(35): 2303503. DOI: 10.1002/adfm.202303503.

ZHANG X F, WANG T Z, LI Y L, et al. Design of Janus heterostructures embedded in carbon nanofibers via heterointerface and structural engineering for rapid polysulfide conversion[J ] . Advanced Functional Materials, 2025, 35(13): 2418022. DOI: 10.1002/adfm.202418022.

MA Y Y, ZHANG L, LIU S J, et al. An electron-coupled co-ZrO 2 nanodot heterojunction electrocatalyst with lewis acid-base site pairs enables high redox reaction kinetics of Li-S batteries[J ] . ACS Nano, 2024, 18(32): 21480-21490. DOI: 10.1021/acsnano. 4c06270.

KONG Y Y, WANG L, MAMOOR M, et al. Co/MoN invigorated bilateral kinetics modulation for advanced lithium-sulfur batteries[J]. Advanced Materials, 2024, 36(13): 2310143. DOI: 10.1002/adma.202310143.

SUN L, XU H N, XIE J, et al. D-band center modulation of metallic co-incorporated Co 7 Fe 3 alloy heterostructure for regulating polysulfides in highly efficient lithium-sulfur batteries[J ] . Advanced Functional Materials, 2025, 35(10): 2416826. DOI: 10.1002/adfm.2024168 26.

ZHAO C C, LIU Y X, HUO F, et al. Synergistic catalysts for lithium-sulfur batteries: Ni single atom and MoC nanoclusters composites[J]. Angewandte Chemie International Edition, 2025, 64(19): e202502177. DOI: 10.1002/anie.202502177.

YAN R, ZHAO Z Y, ZHU R, et al. Alveoli-inspired carbon cathodes with interconnected porous structure and asymmetric coordinated vanadium sites for superior Li-S batteries[J]. Angewandte Chemie International Edition, 2024, 63(25): e202404019. DOI: 10.1002/anie.202404019.

ZUO X T, ZHEN M M, LIU D P, et al. Hollow and porous N-doped carbon framework as lithium-sulfur battery interlayer for accelerating polysulfide redox kinetics[J]. Advanced Functional Materials, 2024, 34(44): 2405486. DOI: 10.1002/adfm.202405486.

LIU B, WANG J, LI Z P, et al. Multiwall carbon nanotube-hyperbranched polymaleimide core-shell nanowires with hierarchical porous and polar structure as sulfur host for sustainable lithium-sulfur batteries[J]. Nano Energy, 2024, 126: 109611. DOI: 10.1016/j.nanoen.2024.109611.

MA H W, YU Z S, LI H C, et al. Tandem carbon hollow spheres with tailored inner structure as sulfur immobilization for superior lithium-sulfur batteries[J]. Advanced Functional Materials, 2024, 34(12): 2310301. DOI: 10.1002/adfm.202310301.

HAMMER B, NØRSKOV J K. Theoretical surface science and catalysis-calculations and concepts//Impact of surface science on catalysis[M]. Amsterdam: Elsevier, 2000: 71-129. DOI:10.1016/s0360-0564(02)45013-4.

SHEN Z H, CAO M Q, ZHANG Z L, et al. Efficient Ni 2 Co 4 P 3 nanowires catalysts enhance ultrahigh-loading lithium-sulfur conversion in a microreactor-like battery[J ] . Advanced Functional Materials, 2020, 30(3): 1906661. DOI: 10.1002/adfm.201906661.

SHEN Z H, JIN X, TIAN J M, et al. Cation-doped ZnS catalysts for polysulfide conversion in lithium-sulfur batteries[J]. Nature Catalysis, 2022, 5(6): 555-563. DOI: 10.1038/s41929-022-00804-4.

SUN Y F, WANG J Y, SHANG T X, et al. Counting d-orbital vacancies of transition-metal catalysts for the sulfur reduction reaction[J]. Angewandte Chemie International Edition, 2023, 62(46): e202306791. DOI: 10.1002/anie.202306791.

ZHANG Y, YU T, XIAO R, et al. The role of long-range interactions between high-entropy single-atoms in catalyzing sulfur conversion reactions[J]. Advanced Materials, 2025, 37(10): 2570081. DOI: 10.1002/adma.202570081.

ZHOU J B, LIU X J, ZHU L Q, et al. Deciphering the modulation essence of p bands in co-based compounds on Li-S chemistry[J]. Joule, 2018, 2(12): 2681-2693. DOI: 10.1016/j.joule.2018.08.010.

HUA W X, SHANG T X, LI H, et al. Optimizing the p charge of S in p-block metal sulfides for sulfur reduction electrocatalysis[J]. Nature Catalysis, 2023, 6(2): 174-184. DOI: 10.1038/s41929-023-00912-9.

GUO M, GU S N, ZHOU R, et al. Flexible and binder free electrode with d-p band center manipulated MoTe 2 nanosheets towards high energy lithium-sulfur batteries[J ] . Chemical Engineering Journal, 2024, 484: 149500. DOI: 10.1016/j.cej. 2024.149500.

KIM S, LIM W G, JUNG H, et al. Protective catalytic layer powering activity and stability of electrocatalyst for high-energy lithium-sulfur pouch cell[J]. Nature Communications, 2025, 16: 1649. DOI: 10.1038/s41467-025-56606-2.

SHEN J D, XU X J, LIU J, et al. Unraveling the catalytic activity of Fe-based compounds toward Li 2 S x in Li-S chemical system from d-p bands[J ] . Advanced Energy Materials, 2021, 11(26): 2100673. DOI: 10.1002/aenm.202100673.

YANG Q, WEI X J, CAO X, et al. Unveiling the synergistic catalysis essence of trimetallic Fe-Co-Ni phosphides for lithium-sulfur chemistry[J]. Chemical Engineering Journal, 2023, 452: 139638. DOI: 10.1016/j.cej.2022.139638.

ZHAO Z X, YI Z L, DUAN Y R, et al. Regulating the d-p band center of FeP/Fe 2 P heterostructure host with built-in electric field enabled efficient bidirectional electrocatalyst toward advanced lithium-sulfur batteries[J ] . Chemical Engineering Journal, 2023, 463: 142397. DOI: 10.1016/j.cej.2023.142397.

SHEN J D, XU X J, LIU J, et al. Mechanistic understanding of metal phosphide host for sulfur cathode in high-energy-density lithium-sulfur batteries[J]. ACS Nano, 2019, 13(8): 8986-8996. DOI: 10.1021/acsnano.9b02903.

SUN R, BAI Y, BAI Z, et al. Phosphorus vacancies as effective polysulfide promoter for high-energy-density lithium-sulfur batteries[J]. Advanced Energy Materials, 2022, 12(12): 2102739. DOI: 10.1002/aenm.202102739.

TIAN S H, LIU G, XU S X, et al. Deposition mode design of Li 2 S: Transmitted orbital overlap strategy in highly stable lithium-sulfur battery[J ] . Advanced Functional Materials, 2024, 34(3): 2309437. DOI: 10.1002/adfm.202309437.

YOU T Q, SUN H Y, HUA W X, et al. Insights into co-catalytic single-atom-support interactions for boosting sulfur reduction electrocatalysis[J]. Angewandte Chemie International Edition, 2025, 64(16): e202425144. DOI: 10.1002/anie.202425144.

LI M, LIU H, LI H F, et al. Electron-deficient cobalt centers realized by rational p-π conjugation regulation for high-performance Li-S batteries[J]. Angewandte Chemie International Edition, 2025, 64(22): e202503174. DOI: 10.1002/anie.202503174.

YU J, HUANG C, USOLTSEV O, et al. Promoting polysulfide redox reactions through electronic spin manipulation[J]. ACS Nano, 2024, 18(29): 19268-19282. DOI: 10.1021/acsnano.4c05278.

ZHOU F, GONG Z Q, WANG R H, et al. Band structure and spin-state-induced electronic configuration regulation for efficient sulfur redox reaction[J]. Advanced Functional Materials, 2025, 35(12): 2417730. DOI: 10.1002/adfm.202417730.

ZHANG C Y, UNIVERSITY L, et al. Metal doping activation of anion-mediated electron transfer in catalytic reactions[J]. Journal of the American Chemical Society, 2025, 147(8): 7070-7082. DOI: 10.1021/jacs.4c18236.

LI Q, MA Z P, LIU M, et al. High spin-state modulation of catalytic centers by weak ligand field for promoting sulfur redox reaction in lithium-sulfur batteries[J]. Angewandte Chemie International Edition, 2025, 64(4): e202416176. DOI: 10.1002/anie.202416176.

LV Q L, SUN Y J, LI B, et al. Metal-organic frameworks with axial cobalt-oxygen coordination modulate polysulfide redox for lithium-sulfur batteries[J]. Advanced Energy Materials, 2025, 15(5): 2403223. DOI: 10.1002/aenm.202403223.

CHEN W J, YU Y, DU Y, et al. A click chemistry strategy toward spin-polarized transition-metal single site catalysts for dynamic probing of sulfur redox electrocatalysis[J]. Advanced Materials, 2024, 36(45): 2409369. DOI: 10.1002/adma.202409369.

CHANTLER C T, BUNKER G, D'ANGELO P, et al. X-ray absorption spectroscopy[J]. Nature Reviews Methods Primers, 2024, 4: 89. DOI: 10.1038/s43586-024-00366-8.

WANG M Y, ÁRNADÓTTIR L, XU Z J, et al. In situ X-ray absorption spectroscopy studies of nanoscale electrocatalysts[J ] . Nano-Micro Letters, 2019, 11(1): 47. DOI: 10.1007/s40820-019-0277-x.

XU W X, LANG S Y, WANG K Y, et al. Fundamental mechanistic insights into the catalytic reactions of Li-S redox by Co single-atom electrocatalysts via operando methods[J ] . Science Advances, 2023, 9(33): eadi5108. DOI: 10.1126/sciadv.adi5108.

CAI G L, LV H F, ZHANG G K, et al. A volcano correlation between catalytic activity for sulfur reduction reaction and Fe atom count in metal center[J]. Journal of the American Chemical Society, 2024, 146(19): 13055-13065. DOI: 10.1021/jacs.3c14312.

YU L H, ZHANG H, WANG L P, et al. Catalytically altering the redox pathway of sulfur in propylene carbonate electrolyte using dual-nitrogen/oxygen-containing carbon[J]. Chinese Journal of Catalysis, 2024, 63: 224-233. DOI: 10.1016/S1872-2067(24)60096-3.

STANJEK H, HÄUSLER W. Basics of X-ray diffraction[J]. Hyperfine Interactions, 2004, 154(1): 107-119. DOI:10.1023/B: HYPE.0000032028.60546.38.

CONDER J, BOUCHET R, TRABESINGER S, et al. Direct observation of lithium polysulfides in lithium-sulfur batteries using operando X-ray diffraction[J]. Nature Energy, 2017, 2: 17069. DOI: 10.1038/nenergy.2017.69.

LUO L, LI J Y, YAGHOOBNEJAD ASL H, et al. In-situ assembled VS 4 as a polysulfide mediator for high-loading lithium-sulfur batteries[J ] . ACS Energy Letters, 2020, 5(4): 1177-1185. DOI: 10.1021/acsenergylett.0c00292.

CHEN W G, WANG J X, WAN F, et al. Review of optical fibre sensors for electrical equipment characteristic state parameters detection[J]. High Voltage, 2019, 4(4): 271-281. DOI: 10.1049/hve.2019.0157.

GENG P B, WANG L, DU M, et al. MIL-96-Al for Li-S batteries: Shape or size?[J]. Advanced Materials, 2022, 34(4): 2107836. DOI: 10.1002/adma.202107836.

ZHOU R, REN Y Q, LI W X, et al. Rare earth single-atom catalysis for high-performance Li-S full battery with ultrahigh capacity[J]. Angewandte Chemie International Edition, 2024, 63(31): e202405417. DOI: 10.1002/anie.202405417.

NELSON J, MISRA S, YANG Y, et al. In operando X-ray diffraction and transmission X-ray microscopy of lithium sulfur batteries[J]. Journal of the American Chemical Society, 2012, 134(14): 6337-6343. DOI: 10.1021/ja2121926.

WANG B, WANG L, KONG Y Y, et al. Hafnium diboride spherical superstructure born of 5d-metal Hf-MOF-induced p orbital activity of B atom and enhanced kinetics of sulfur cathode reaction[J]. Advanced Energy Materials, 2023, 13(22): 2300590. DOI: 10.1002/aenm.202300590.

LIU R L, WEI Z Y, PENG L L, et al. Establishing reaction networks in the 16-electron sulfur reduction reaction[J]. Nature, 2024, 626(7997): 98-104. DOI: 10.1038/s41586-023-06918-4.

AHMED S S, MESSALI Z, OUAHABI A, et al. Nonparametric denoising methods based on contourlet transform with sharp frequency localization: Application to low exposure time electron microscopy images[J]. Entropy, 2015, 17(5): 3461-3478. DOI: 10.3390/e17053461.

XU Z L, KIM S J, CHANG D, et al. Visualization of regulated nucleation and growth of lithium sulfides for high energy lithium sulfur batteries[J]. Energy & Environmental Science, 2019, 12(10): 3144-3155. DOI: 10.1039/C9EE01338E.

ZHOU S Y, SHI J, LIU S G, et al. Visualizing interfacial collective reaction behaviour of Li-S batteries[J]. Nature, 2023, 621(7977): 75-81. DOI: 10.1038/s41586-023-06326-8.

KLEIN K L, ANDERSON I M, DE JONGE N. Transmission electron microscopy with a liquid flow cell[J]. Journal of Microscopy, 2011, 242(2): 117-123. DOI: 10.1111/j.1365-2818.2010.03484.x.

NOLTE O, GEITNER R, HAGER M D, et al. IR spectroscopy as a method for online electrolyte state assessment in RFBs[J]. Advanced Energy Materials, 2021, 11(28): 2100931. DOI: 10.1002/aenm.202100931.

SAQIB N, OHLHAUSEN G M, PORTER J M. In operando infrared spectroscopy of lithium polysulfides using a novel spectro-electrochemical cell[J]. Journal of Power Sources, 2017, 364: 266-271. DOI: 10.1016/j.jpowsour.2017.08.030.

SAQIB N, SILVA C J, MAUPIN C M, et al. A novel optical diagnostic for in situ measurements of lithium polysulfides in battery electrolytes[J ] . Applied Spectroscopy, 2017, 71(7): 1593-1599.

DILLARD C, SINGH A, KALRA V. Polysulfide speciation and electrolyte interactions in lithium-sulfur batteries with in situ infrared spectroelectrochemistry[J ] . The Journal of Physical Chemistry C, 2018, 122(32): 18195-18203. DOI: 10.1021/acs.jpcc.8b02506.

YANG R L, CHEN Y, PAN Y X, et al. Single-step laser-printed integrated sulfur cathode toward high-performance lithium-sulfur batteries[J]. Nature Communications, 2025, 16: 2386. DOI: 10.1038/s41467-025-57755-0.

HAN Z Y, CHEN A, LI Z J, et al. Machine learning-based design of electrocatalytic materials towards high-energy lithium||sulfur batteries development[J]. Nature Communications, 2024, 15: 8433. DOI: 10.1038/s41467-024-52550-9.

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Recent advances in catalytic mechanisms and in situ characterization of the sulfur reduction reaction in lithium-sulfur batteries

DOI：10.19799/j.cnki.2095-4239.2025.0886

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