催化学报 ›› 2026, Vol. 83: 96-131.DOI: 10.1016/S1872-2067(26)64968-6
Aditya Narayan Singha, Kyung-Wan Nama,b,*(
)
收稿日期:2025-09-21
接受日期:2025-12-02
出版日期:2026-04-18
发布日期:2026-03-04
通讯作者:
* 电子信箱: knam@dongguk.edu (K.-W. Nam).
Aditya Narayan Singha, Kyung-Wan Nama,b,*()
Received:2025-09-21
Accepted:2025-12-02
Online:2026-04-18
Published:2026-03-04
Contact:
* E-mail: About author:Kyung-Wan Nam is a Professor in the Department of Energy and Materials Engineering at Dongguk University, Seoul, South Korea, and Director of the BK21 Education Center for Eco-Friendly Emerging Rechargeable Batteries. He received his Ph.D. in Metallurgical Engineering from Yonsei University in 2005 and previously served as a Research Associate and Staff Scientist at Brookhaven National Laboratory from 2006 to 2014. His research focuses on advanced materials for lithium- and sodium-ion batteries, all-solid-state batteries, and supercapacitors, as well as in situ and operando synchrotron X-ray characterization. He has published over 200 peer-reviewed papers, accumulating more than 19,300 citations, with an h-index of 70 (Google Scholar).
摘要：
锂硫(Li-S)电池凭借其超高的理论能量密度(~2600 Wh·kg‒1)、硫天然储量丰富及成本低廉等优势, 已经成为最具潜力的下一代电化学储能技术之一. 然而, 其实际应用仍然受制于以下关键问题: 多硫化物穿梭效应、硫氧化还原动力学迟缓、体积膨胀严重以及循环寿命有限. 本综述对Li-S电池领域的最新研究进展进行了全面且前瞻性的梳理和分析, 重点探讨了超越传统硫宿主材料和电解质的创新策略. 尤其关注单原子催化剂、晶格应变工程、缺陷调控、氧化还原介质辅助转化及高熵MXenes等新兴概念, 这些策略为调控硫电化学过程提供了新的机遇. 此外, 本综述还强调了人工固体电解质界面和电解质优化在稳定锂金属阳极中的作用. 通过整合计算模拟的指导观点与实验中的突破结果, 本综述不仅剖析了Li-S电池所面临的关键挑战的机制起源, 还弥合了实验室演示与可扩展软包电池性能之间的差距. 引入“关键问题概览”框架, 提炼出最紧迫的障碍和相应的调控策略. 最后, 本综述勾勒了将Li-S电池的学术研究转化为商用系统的路线图. 本综述旨在为Li-S电池的实际应用提供技术参考与战略指导.
Aditya Narayan Singh, Kyung-Wan Nam. 实用型锂-硫电池材料的崛起[J]. 催化学报, 2026, 83: 96-131.
Aditya Narayan Singh, Kyung-Wan Nam. The rise of practical lithium-sulfur battery materials[J]. Chinese Journal of Catalysis, 2026, 83: 96-131.
Scheme 1. Overview of the major content discussed in this review.
Fig. 1. Schematic of the charge-discharge process in a typical Li-S cell.
Fig. 2. Schematic of the SRR mechanism during discharge.
Fig. 3. Schematic of the polysulfide shuttle effect in Li-S batteries. Reproduced with permission from Ref. [25]. Copyright 2022, John Wiley and Sons.
Fig. 4. (A) Operando UV-vis spectra of the S42?, and S3?? radicals in DOL: DME and in DMSO. Reproduced with permission from Ref. [32], Copyright 2016, American Chemical Society. Plots showing the impact of solvent selection in regulating the polysulfides precipitations: (B) DN and ε values of general solvents. (C) Anions. (D) Schematic of the impact of high coordination capacity lithium salts and anions. (E) Redox mediators. Reproduced with permission from Ref. [36], Copyright 2024, Elsevier. (F) Plot of onset potential for the reduction of S8 vs. acceptor number (AN). Reproduced with permission from Ref. [26]. Copyright 2018, The Electrochemical Society.
Fig. 5. Schematic of the Li-S battery separator that is CON-modified (A) and CON/CNT-modified (B). (C) Charge-discharge profile of the CON/CNT. (D) Charge-discharge profile for the various separators. (E) Cyclic stability at 0.2 C-rate. (F) DFT configuration for various lengths of S in Li2Sn (n = 1, 2, 4, 6, 8). (G) Calculated binding energies of CON/COC with its interaction with S-species. Reproduced with permission from Ref. [67], Copyright 2023, Wiley-VCH GmbH.
Fig. 6. (A) Schematic of the Fe2O3@CNT cathode coating in the Li-S battery. (B) Comparative rate performance of the CNT-coated and Fe2O3@CNT at various C-rates. (C) Discharge profile of the CNT and Fe2O3@CNT during 0.2 C. Here, QH and QL denote specific discharge capacities during high- and low-voltage plateaus. (D) Comparative profile of the Nyquist plots. Reproduced with permission from Ref. [78], Copyright 2024, Elsevier. (E) Schematic of the passivation effect arising due to slow kinetics. (F) Illustration of the passivation effect due to rapid kinetics. (G) Schematics of the synthesis of the P, Mo-MnO2 electrocatalyst. (H) Rate performances under various modified separators. (I) Charge-discharge profiles for various cathodes at 0.2 C. (J) Cyclic stability at 2 C for 1000 cycles. (K) Gibbs free energy profile for the reduction of S8 to Li2S. Reproduced with permission from Ref. [79], Copyright 2024, Wiley-VCH GmbH.
Fig. 7. (A) Diffusion pathways for Li-ion along V1-H-V2. (B) The obtained energy variations pathways along the optimal pathways. (C) The adsorption energies of LiPS and VS2 on different electrolytes (DOL: 1,3-dioxolane; DME: 1,2-dimethoxythane). Reproduced with permission from Ref. [82]. Copyright 2020, Elsevier. (D) Decomposition energy barrier profile of Li2S on different surface of Sv-VS2 and VI-VS2. (E) Comparison chart of the decomposition barrier of Li2S on numerous surfaces. (F) CI-NEB results obtained for the decomposition energy barrier of Li2S on different surface of Sv-VS2 and VI-VS2. Reproduced with permission from Ref. [89]. Copyright 2023, Elsevier. (G) Schematic showing the synthetic scheme of the Fe-MoS2-C catalyst. (H) Schematic showing the conversion mechanism induced by the Fe-MoS2-C catalyst. Reproduced with permission from Ref. [94]. Copyright 2024, American Chemical Society.
Fig. 8. The decomposition pathways: Pathway 1 during compressive strain (A) and tensile strain (B). (C) Energy barriers of Li2S on the TiC (001) surface. Reproduced with permission from Ref. [104]. Copyright 2024, Elsevier. (D) Periodic table showing elements widely used in MXenes. There are also elements that have not been experimentally confirmed, such as Sc and Mn (bright blue color). A schematic of three typical structures of MXene is also shown below the periodic table. Reproduced with permission from Ref. [105]. Copyright 2019, American Chemical Society. (E) The galvanostatic charge-discharge profile shows lower polarization in B-doped MXene. Cyclic stability at 0.1 C (F) and 1 C (G). Reproduced with permission from Ref. [108]. Copyright 2024, Elsevier.
Fig. 9. (A) Schematic of the synthesized cathode TiN@C. (B) Galvanostatic charge-discharge profile. (C) Cyclic stability test data. (D?D°) SEM image and color of the S-C cathode after battery test. (E?E°) SEM image and color of the S-TiN@C cathode after battery test. Reproduced with permission from Ref. [118]. Copyright 2023, Wiley-VCH GmbH. (F) Schematic of the NCFI@T150 interlayer. (G) XRD patterns of the synthesized cathode materials. (H) The obtained adsorption energies of Li2S6 species on different N-doped carbon materials by DFT calculations. (I) Cyclic stability test at 1 C for 2.5 mg·cm-2 S-loading. (J) Charge-discharge curves at 0.2 C for the NCFI@T150 interlayer. Reproduced with permission from Ref. [119]. Copyright 2024, John Wiley and Sons.
Fig. 10. (A) CV curve of the synthesized cathodes. (B) Cyclic performances. (C) DFT calculations for the S-S of Li2S4 on the surface of the CoP and N-CoP. (D) The obtained Li?S bond length obtained on different surfaces. Reproduced with permission from Ref. [124]. Copyright 2024, Elsevier. (E) The partial density of states (PDOS) of Co d-orbitals. (F) the relaxed Li2S6 adsorbed structures on the surface of CoPx. Reproduced with permission from Ref. [127]. Copyright 2024, Elsevier.
Fig. 11. (A) Schematic of the synthesis of MnM-MIL-100 nanoparticles (where M represents the secondary metal-ion into metal-organic linker). (B) The structure of MnM-MIL-100 and MnNi-MIL-100 and its metal complexes with Li2S6. (C) A comparison of the binding energy of different species. (D) The Nyquist plot of all the synthesized catalysts. Reproduced with permission from Ref. [144]. Copyright ? John Wiley and Sons, 2021. (E) Schematic of 3D crystal shapes of different crystal shapes along with their (hkl) planes. (F) SEM images of the HPC crystal. TEM images of the HPC-S (G) and HBC-0.78-S (H). SEM images of the HBC-3.33 (I), 2.40 (J), 1.21 (K), 0.83 (L), and 0.78 (M). (N) Schematic of the Li-S battery. (O) SEM image of the HPBC crystal. Scale bar in each SEM and TEM image is 3 μm. EDX mapping images of the HPC-S (P) and HBC-0.78-S (Q). Reproduced with permission from Ref. [147]. Copyright 2021, John Wiley and Sons.
Fig. 12. Historical development of SACs for the Li-S battery.
Fig. 13. (A) Comparison chart of delithiation energy barriers for different catalysts. Reproduced with permission from Ref. [163]. Copyright 2019, Elsevier. (B) The adsorption energies calculated from DFT for Li2S and Li2Sm (m = 1, 2, 8) and bond energy of activation of Li?S bond in Li2S on FeN4@G and the (pristine) graphene. All the units are in eV. (C) Activation energy barrier (Ea) of various discharge processes. (D) Long-term cyclic stability of different catalysts. Reproduced with permission from Ref. [155], Copyright 2023, Elsevier. The obtained decomposition energy barrier of Li2S on the surface of C3N4 (E) and C3N4-Fe (F), reproduced with permission from Ref. [156]. Copyright 2025, Elsevier. (G) The calculated reaction energy barrier. Reproduced with permission from Ref. [165]. Copyright 2023, John Wiley and Sons. (H) The Gibbs free energy calculation for SRR obtained for different catalysts. (I) The dissociation energy of Li2S on various paths. (J) Energy profile for various Li-diffusion routes. Reproduced with permission from Ref. [171], Copyright 2024, Elsevier.
Fig. 14. (A) Plot of S-clusters vs. time showing it follows a zero-order transition. (B) Values of k and normalized k derived on the mass of Co obtained from S-reduction for the Co-SAs/NC and Co-NPs/NC, respectively. (C) Normalized S-k edge XANES spectra of various PSs species (Li2S4, Li2S6, and Li2S8) along with reference molecule. (D) XANES spectra selected at a particular voltage profile. (E) Voltage profile obtained at 0.1 C. (F) Corresponding intensity peak (B at 2,470.9 eV). Reproduced under Creative Commons Attribution Non-Commercial License 4.0 (CC BY-NC) from Ref. [155]. Copyright 2023, The American Association for the Advancement of Science. Energy profile for the NC (G) and Co-N4 (H). (I) Long-term cyclic stability of SA-Co/NGM over other catalyst at 2 C with different separators. Reproduced with permission from Ref. [179]. Copyright 2023, Elsevier.
Fig. 15. (A) HADF-STEM image of Ni-NG material. (B) STEM image with elemental mapping of Ni-NG. (C) DFT calculations showing the Gibbs free energies for SRR. (D) Cycling stability comparison against different separators. Reproduced with permission from Ref. [185]. Copyright 2022, American Chemical Society. (E) A complete energy profile for the discharge process from S8 to Li2S on five different model catalysts. Reproduced with permission from Ref. [186]. Copyright 2021, American Chemical Society.
| Catalyst/ substrate | Synthesis method | Synthesis complexity | SA loading | Scalability | Production cost | Ref. |
|---|---|---|---|---|---|---|
| Li2S@NC: SAFe | pyrolysis, CVD | relatively simpler but requires high temperature and precise control | 5 wt%‒8 wt% | moderate scalability, requires optimization for large-scale production | lower cost but energy-intensive processes increase production cost | [ |
| S@Co-N/G | pyrolysis, CVD, sol-gel | more complex, requires precise precursor control and high energy input | varies (often lower than Fe-based SACs) | challenging scalability due to complex synthesis and high energy requirements | higher cost due to Co's price and synthesis complexity | [ |
| Ni-N5 /HNPC | wet deposition, Pyrolysis | relatively scalable but still needs optimization for long-term stability | 5 wt%‒10 wt% | easier scalability compared to Co and Mo, but uniformity and stability must be ensured | moderate cost (Ni is cheaper than Co and Mo) | [ |
| SV-Co9S8-Mo | high-temperature processes, complex precursor solutions | high synthesis complexity, energy-intensive processes | varies (lower loading compared to others) | least scalable due to high cost and complex synthesis methods | high cost due to Mo's scarcity and complex synthesis | [ |
| S@ZnN4-NC | pyrolysis, sol-gel, CVD | requires high-temperature treatments, precise control for dispersion | 5 wt%‒8 wt% | scalable, but still faces challenges in uniform dispersion and stability | lower cost than Co and Mo, more cost-effective than Co, but energy costs remain | [ |
| Ti@N2C2-C3N, TiSA-NC | pyrolysis | precise control of pyrolysis temperature/atmosphere and dispersion of Ti single atoms | low loading < 5 wt% | scalable, but uniform Ti single-atom dispersion remain challenging. | lower cost than Pt and Ru, but pyrolysis and dispersion control increase energy costs | [ |
| FeSA-NC @CBC | pyrolysis | agglomeration | 5 wt% | scalable, but agglomeration remains a challenge | lower cost than noble metals (Pt, Ru), but pyrolysis energy consumption can increase overall costs | [ |
| SA-Co/NGM | pyrolysis | requires high-temperature pyrolysis, precise grinding and leaching for single-atom Co dispersion | 6.5 wt% | scalable, though uniform single-atom Co dispersion and reproducible separator integration remain challenging | lower cost than noble metals (Pt, Ru), but pyrolysis energy consumption can increase overall costs | [ |
Table 1 Summary of SACs applied to Li-S batteries.
| Catalyst/ substrate | Synthesis method | Synthesis complexity | SA loading | Scalability | Production cost | Ref. |
|---|---|---|---|---|---|---|
| Li2S@NC: SAFe | pyrolysis, CVD | relatively simpler but requires high temperature and precise control | 5 wt%‒8 wt% | moderate scalability, requires optimization for large-scale production | lower cost but energy-intensive processes increase production cost | [ |
| S@Co-N/G | pyrolysis, CVD, sol-gel | more complex, requires precise precursor control and high energy input | varies (often lower than Fe-based SACs) | challenging scalability due to complex synthesis and high energy requirements | higher cost due to Co's price and synthesis complexity | [ |
| Ni-N5 /HNPC | wet deposition, Pyrolysis | relatively scalable but still needs optimization for long-term stability | 5 wt%‒10 wt% | easier scalability compared to Co and Mo, but uniformity and stability must be ensured | moderate cost (Ni is cheaper than Co and Mo) | [ |
| SV-Co9S8-Mo | high-temperature processes, complex precursor solutions | high synthesis complexity, energy-intensive processes | varies (lower loading compared to others) | least scalable due to high cost and complex synthesis methods | high cost due to Mo's scarcity and complex synthesis | [ |
| S@ZnN4-NC | pyrolysis, sol-gel, CVD | requires high-temperature treatments, precise control for dispersion | 5 wt%‒8 wt% | scalable, but still faces challenges in uniform dispersion and stability | lower cost than Co and Mo, more cost-effective than Co, but energy costs remain | [ |
| Ti@N2C2-C3N, TiSA-NC | pyrolysis | precise control of pyrolysis temperature/atmosphere and dispersion of Ti single atoms | low loading < 5 wt% | scalable, but uniform Ti single-atom dispersion remain challenging. | lower cost than Pt and Ru, but pyrolysis and dispersion control increase energy costs | [ |
| FeSA-NC @CBC | pyrolysis | agglomeration | 5 wt% | scalable, but agglomeration remains a challenge | lower cost than noble metals (Pt, Ru), but pyrolysis energy consumption can increase overall costs | [ |
| SA-Co/NGM | pyrolysis | requires high-temperature pyrolysis, precise grinding and leaching for single-atom Co dispersion | 6.5 wt% | scalable, though uniform single-atom Co dispersion and reproducible separator integration remain challenging | lower cost than noble metals (Pt, Ru), but pyrolysis energy consumption can increase overall costs | [ |
| Material/ Class | Subclass | Role | Synthesis | Key feature | Areal/ capacity/ Rate | Stability | PS/binding/ mechanism | Cost/ scalability | Ref. |
|---|---|---|---|---|---|---|---|---|---|
| S@CNT (optimized ring-size CNT) | carbon (CNT) | sulfur host cathode | oxidation-controlled CNT; melt-diffusion S loading | selective micropores allow Li+ while blocking LiPS | — | 10 Cyc. | physical confinement + size-selective transport | low cost; scalable CNT processing | [ |
| CON/CNTs | carbon (CON on CNT) | separator modifier/ cathode interface | CON nanosheets wrapped on CNTs; composite fabrication | high conductivity via CNT; chemical adsorption via imide/triazine | 1309 mAh·g−1/ (0.2 C) | >100 Cyc. | polar carbonyl O & triazine units | solution-processable; scalable | [ |
| Fe2O3/rGO/ CNT/S | oxide-carbon hybrid | sulfur host cathode | nano Fe2O3 on rGO/CNT; S infiltration | improved conductivity + LiPS adsorption | 963 mAh·g−1/ 0.5 C | ~79% after 100 Cyc. | polar Fe2O3 chemisorption | Fe oxide low cost; scalable composites | [ |
| Fe2O3@CNT (coating) | oxide-coated CNT | separator/ cathode coating | Fe2O3 deposited on hollow CNT | interwoven CNT; catalytic Fe2O3 | 1273 mAh·g−1/ 0.1 C | 0.067%/Cyc. over 800 cyc. @1 C | lower polarization; faster Li2S formation | low-cost oxide; scalable | [ |
| P,Mo-MnO2 | dual-doped oxide | interlayer/ cathode additive | P & Mo co-doping of MnO2 | reduces S8 → Li2S free energies; boosts kinetics | >1233 mAh·g−1/ 0.2 C | superior at 2 C, long cycling | enhanced nucleation & decomposition of Li2S | doping adds cost; scalable | [ |
| VS2 (monolayer) | sulfide (2D) | sulfur host/ catalytic layer | theoretical & experimental routes | strong LiPS adsorption; fast Li diffusion path | — | — | vdW + charge transfer | hydrothermal/CVD possible | [ |
| Sv-VS2 vs. VI-VS2 | defect-eng- ineered sulfide | separator coating/ host | S-vacancy and V-self- intercalation | lower Li2S/Li2S6 decomposition barriers for Sv-VS2 | — | 0.043%/cycle over 880 cycles @1 C (Sv-VS2) | defect sites catalyze PS conversion | defect engineering scalable | [ |
| CC@VS2-VO2@Li2S@C | VS2/VO2 heterostructure on carbon cloth | cathode (pre-lithiated) | in situ growth + carbon shell | VO2 anchors LiPS; VS2 converts; CC improves kinetics | 919.8 mAh·g−1/ 588.9 after 500 cycles | 0.072%/cyc. decay | chemisorption (VO2) + catalysis (VS2) | multi-step; moderate | [ |
| Ti3C2Tx/VS2 + CNT | MXene-sulfide composite | sulfur host | Self-assembly; CNT as binder | prevents MXene restacking; strong LiPS adsorption | 1383 mAh·g−1/0.1 C | enhanced cycling | MXene polar surfaces + VS2 | scalable composite | [ |
| Fe-MoS2-C (electron- bridge) | sulfide-carbon heterostructure | sulfur host | CTAB interlayer carbonization; Fe introduction; 700 °C calcination | electron bridge activates basal planes | areal 6.62 mAh·cm−2 | 1000 cycles, 0.056%/cyc. @2 C | S-Fe-C bridge | Fe low cost; scalable | [ |
| Co/CoS2 @NSC | sulfide/metal on N,S‑C | sulfur host | heterostructure on NSC | d-band downshift; strong PS adsorption | 8.25 mAh·cm−2/ S = 8.18 mg·cm−2 | — | polar sites; hybridization | moderate | [ |
| P-CoS2/CNTs | phosphatized CoS2 on CNTs | functional separator | CoS2 core/ Co(PO3)2 shell | grain-boundary defects improve conductivity | 1.75 mAh·cm−2/ 3.6 mg·cm−2 (1000 cycles) | 0.048%/cycle @2 C (1000 cyc.) | Co‒O‒P bonds | scalable coating | [ |
| CoS2-MgS on acetylene black | sulfide heterostructure | separator coating | deposition on carbon black | Co oxidation + Li migration in MgS | 768 mAh·g−1/ (pouch, 80 cycles) | 0.08%/Cyc. over 600 cyc. @5 C | strong PS adsorption + catalysis | scalable; low cost | [ |
| B‑doped MXene (B-MXene) | MXene (B-doped) | sulfur host | B doping; S infiltration | electron-deficient B; lower polarization | — | 71%/0.1 C (150 cyc.)/77% @1 C (500 cyc.) | vacancy/electron deficiency | MXene synthesis moderate | [ |
| HE-MXene TiVNbMoC3 | high-entropy MXene | host & Li anode regulation | HE MXene preparation | atom-relay catalysis; uniform E‑field | 4.92 mAh·cm−2 /0.2 C (100 cycles) | — | cascading trapping of LiPS | complex; emerging | [ |
| HE-MXene/ G@PP | HE-MXene doped graphene on PP | separator modification | composite coating | high conductivity; large active area | — | 0.026%/0.031% per cyc./1/2 C (1200 cyc.) | chemisorption + fast kinetics | Promising scalability | [ |
| TiN@C (ALD-TiN in carbon) | nitride-carbon | sulfur host | ALD TiN (<2 nm) + melt S | lower overcharge; high CE | — | improved CE across rates | TiN polar sites; color test | ALD cost; scalable thin films | [ |
| NCFI@T150 (TiO2/TiN on carbon foam) | TiO2/TiN heterostructure | interlayer | in-situ growth with N-doping | strong Li2S adsorption energies | — | 817→777 mAh·g−1 after 200 cyc./1 C | polar N sites + TiN/TiO2 synergy | scalable foams | [ |
| L-TiN-Cu- CNF | low-crystalline TiN on Cu-CNF | interlayer/host | TiN coating; crystal control | more defect sites; better PS chemisorption | 913 mAh·g−1/2 C | 300 cyc./626 mAh·g−1 | defect-rich TiN | scalable | [ |
| MnNi-MIL-100@S | MOF (multi-metal) | sulfur host | one-pot MIL-100 with Ni; melt-diffusion S | lewis acid-base interactions; deep electrolyte penetration | ~709 mAh·g−1/ (200 cycles) | — | strong binding to Li2S4/Li2S6 | MOF scalable; moderate | [ |
| STAM-1 (Cu(II) MOF) | MOF | S-cathode regulator | Cu-MOF STAM-1 flakes | hydrophobic/hydrophilic domains | initial 452 mAh·g−1/96% after 100 cycles /0.5 C | high retention | encapsulation in pores | scalable solvothermal | [ |
| D-ZIF L (under-coordinated) | MOF derivative | sulfur host | ligand removal to undercoordinate Zn-Co ZIF | reduced steric hindrance; higher conductivity | areal 5.0 mAh·cm−2/5.5 mg·cm−2 | — | exposed metal sites | scalable | [ |
| MIL-96-Al (shape/size tuned) | MOF | sulfur host (HPC/HBC/HPBC) | Co-solvent; modulators; melt‑diffusion | plane-dependent LiPS adsorption; size affects stability | — | — | exposed (101) plane in HBC adsorbs strongly | scalable | [ |
| Li2S@NC: SAFe | Fe SAC | cathode host (Li2S) | PANI-coated carbon + Fe-acetate pyrolysis | lower barrier 0.81 eV vs. 3.4 eV | 588 mAh·g−1/12 C | long life @5 C | strong binding to LiS/Li2Sm | low metal; high T pyrolysis | [ |
| FeSA-NC @CBC | Fe SAC on N-C aerogel | Binder-free S cathode scaffold | Fe-doped ZIF-8 + bacterial cellulose → pyrolysis | reduced Ea for S8 → Li2Sn & Li2Sn→Li2S | 840 mAh·g−1/1 C | 500 Cyc./ 95% retention | FeN4@G strong LiPS binding | scalable pyrolysis | [ |
| C3N4-Fe @rGO (Fe-N5) | Fe SAC on defective g-C3N4 | sulfur host | absorption-pyrolysis | Lower Li2S decomposition barrier (0.75 eV) | — | — | oversaturated Fe-N5 sites | scalable | [ |
| Channel- FeSAC (ordered) | Fe SAC (ordered channels) | host/ interlayer | templated channels | Ea 15 < 30.8 < 38.2 kJ·mol−1 (channel < bowl < flat) | high areal capacity; long life | — | capture-catalysis microenvironments | — | [ |
| SA-Co/NGM | Co SAC on N-graphene mesh | separator coating/ host | CoZn-ZIF-L → salt‑templated pyrolysis (900 °C) + leach | Co-N4 lowers Li2S decomposition barrier (1.35 eV vs. 2.37) | 649 mAh·g−1/5 C; areal 4.73 mAh·cm−2/6.5 mg·cm−2 | 0.0232%/cycle @2 C (1000 Cyc.) | planar Co-N4 active centers | scalable; pyrolysis | [ |
| CoSA-N-C (15.3 wt% Co) | high-loading Co SAC | sulfur host | salt-template method | lower Li2S decomposition barrier (1.08 eV) | 1574 mAh·g−1/0.05 C | 0.035%/ Cyc. (1000 Cyc. @1 C) | Co-N4 redox centers | — | [ |
| Ni-NG (SAC) | Ni SAC on N-graphene | interlayer | series M-NG study | low SRR Gibbs barrier | 701.8 mAh·g−1/0.5 C (400 cycles) | areal 4.58 mAh·cm−2/3.8 mg·cm−2 | facilitates L-L & L-S steps | moderate | [ |
| Ni-N5/HNPC | Ni SAC in hollow N-porous C | sulfur host | self-templating + pyrolysis | Ni-N5 best among Ni-Nx | 684 mAh·g−1/4 C | — | Ni-N5 active centers | scalable | [ |
| S@ZnN4-NC | Zn SAC on N-CNT arrays | sulfur host | ordered CNT arrays; Zn SAs 8.3 wt% | high site density; fast transport | ~1225 mAh·g−1/S uptake 99% | 500 Cyc./ 0.032%/Cyc. | chemisorption + conversion | lower metal cost; scalable arrays | [ |
| Zn-N/CS (pyridinic N defects) | Zn SAC on carbon sheets | sulfur host | porous carbon with Zn-N4 + pyridinic N | higher d-band center; stronger binding | 1132 mAh·g−1/0.1 C | 72.2% after 800 Cyc./2 C | defect-assisted chemisorption | scalable | [ |
| Zn-Co SA@DNC | dual-metal SAC on double‑shelled CNTs | host/ interlayer | dual SA loading on DNC | synergy lowers barriers; reduces shuttle | 732 mAh·g−1/1 C | 0.034%/ Cyc. (800 Cyc.) | confinement + catalysis | — | [ |
| ZnCoN4O2/ CN | dual-core SA on carbon nanosheets | sulfur host | bulk di-atomic CNS synthesis | lithophilic Zn + sulfurophilic Co | 789.4 mAh·g−1/5 C; 1000 cycles /6 C (0.05%/cycle) | long cycling | faster LiPS conversion & Li+ transport | scalable | [ |
| Mo-N2/C (Mo SAC) | Mo SAC on N-C | interlayer/ host | pyrolysis; N-doped carbon | low barriers ~1.0 eV for key steps | ~744 mAh·g−1/5 C | — | catalyzes bidirectional steps | high Mo cost | [ |
| SV-Co9S8-Mo (Mo SA on S-vacant Co9S8) | SAC on sulfide | sulfur host | anchor Mo on S-vacant Co9S8 | optimized adsorption/desorption balance | 1254 mAh·g−1 /0.2 C; 633/5 C; 821/6.1 mg·cm−2 | — | weaker |ΔEads| for Li2S6 aids kinetics | — | [ |
| V-SACs (pyridinic-N-rich) | V SAC on N-C | host/ interlayer | high-temp; pyridinic-N rich supports | more chemisorption sites; promotes conversion | 921 mAh·g−1/1 C (66% after 500 cyc.) | — | N-defect + V sites | V cheaper than Co/Mo | [ |
Table 2 Comparative analysis of material classes for Li-S batteries.
| Material/ Class | Subclass | Role | Synthesis | Key feature | Areal/ capacity/ Rate | Stability | PS/binding/ mechanism | Cost/ scalability | Ref. |
|---|---|---|---|---|---|---|---|---|---|
| S@CNT (optimized ring-size CNT) | carbon (CNT) | sulfur host cathode | oxidation-controlled CNT; melt-diffusion S loading | selective micropores allow Li+ while blocking LiPS | — | 10 Cyc. | physical confinement + size-selective transport | low cost; scalable CNT processing | [ |
| CON/CNTs | carbon (CON on CNT) | separator modifier/ cathode interface | CON nanosheets wrapped on CNTs; composite fabrication | high conductivity via CNT; chemical adsorption via imide/triazine | 1309 mAh·g−1/ (0.2 C) | >100 Cyc. | polar carbonyl O & triazine units | solution-processable; scalable | [ |
| Fe2O3/rGO/ CNT/S | oxide-carbon hybrid | sulfur host cathode | nano Fe2O3 on rGO/CNT; S infiltration | improved conductivity + LiPS adsorption | 963 mAh·g−1/ 0.5 C | ~79% after 100 Cyc. | polar Fe2O3 chemisorption | Fe oxide low cost; scalable composites | [ |
| Fe2O3@CNT (coating) | oxide-coated CNT | separator/ cathode coating | Fe2O3 deposited on hollow CNT | interwoven CNT; catalytic Fe2O3 | 1273 mAh·g−1/ 0.1 C | 0.067%/Cyc. over 800 cyc. @1 C | lower polarization; faster Li2S formation | low-cost oxide; scalable | [ |
| P,Mo-MnO2 | dual-doped oxide | interlayer/ cathode additive | P & Mo co-doping of MnO2 | reduces S8 → Li2S free energies; boosts kinetics | >1233 mAh·g−1/ 0.2 C | superior at 2 C, long cycling | enhanced nucleation & decomposition of Li2S | doping adds cost; scalable | [ |
| VS2 (monolayer) | sulfide (2D) | sulfur host/ catalytic layer | theoretical & experimental routes | strong LiPS adsorption; fast Li diffusion path | — | — | vdW + charge transfer | hydrothermal/CVD possible | [ |
| Sv-VS2 vs. VI-VS2 | defect-eng- ineered sulfide | separator coating/ host | S-vacancy and V-self- intercalation | lower Li2S/Li2S6 decomposition barriers for Sv-VS2 | — | 0.043%/cycle over 880 cycles @1 C (Sv-VS2) | defect sites catalyze PS conversion | defect engineering scalable | [ |
| CC@VS2-VO2@Li2S@C | VS2/VO2 heterostructure on carbon cloth | cathode (pre-lithiated) | in situ growth + carbon shell | VO2 anchors LiPS; VS2 converts; CC improves kinetics | 919.8 mAh·g−1/ 588.9 after 500 cycles | 0.072%/cyc. decay | chemisorption (VO2) + catalysis (VS2) | multi-step; moderate | [ |
| Ti3C2Tx/VS2 + CNT | MXene-sulfide composite | sulfur host | Self-assembly; CNT as binder | prevents MXene restacking; strong LiPS adsorption | 1383 mAh·g−1/0.1 C | enhanced cycling | MXene polar surfaces + VS2 | scalable composite | [ |
| Fe-MoS2-C (electron- bridge) | sulfide-carbon heterostructure | sulfur host | CTAB interlayer carbonization; Fe introduction; 700 °C calcination | electron bridge activates basal planes | areal 6.62 mAh·cm−2 | 1000 cycles, 0.056%/cyc. @2 C | S-Fe-C bridge | Fe low cost; scalable | [ |
| Co/CoS2 @NSC | sulfide/metal on N,S‑C | sulfur host | heterostructure on NSC | d-band downshift; strong PS adsorption | 8.25 mAh·cm−2/ S = 8.18 mg·cm−2 | — | polar sites; hybridization | moderate | [ |
| P-CoS2/CNTs | phosphatized CoS2 on CNTs | functional separator | CoS2 core/ Co(PO3)2 shell | grain-boundary defects improve conductivity | 1.75 mAh·cm−2/ 3.6 mg·cm−2 (1000 cycles) | 0.048%/cycle @2 C (1000 cyc.) | Co‒O‒P bonds | scalable coating | [ |
| CoS2-MgS on acetylene black | sulfide heterostructure | separator coating | deposition on carbon black | Co oxidation + Li migration in MgS | 768 mAh·g−1/ (pouch, 80 cycles) | 0.08%/Cyc. over 600 cyc. @5 C | strong PS adsorption + catalysis | scalable; low cost | [ |
| B‑doped MXene (B-MXene) | MXene (B-doped) | sulfur host | B doping; S infiltration | electron-deficient B; lower polarization | — | 71%/0.1 C (150 cyc.)/77% @1 C (500 cyc.) | vacancy/electron deficiency | MXene synthesis moderate | [ |
| HE-MXene TiVNbMoC3 | high-entropy MXene | host & Li anode regulation | HE MXene preparation | atom-relay catalysis; uniform E‑field | 4.92 mAh·cm−2 /0.2 C (100 cycles) | — | cascading trapping of LiPS | complex; emerging | [ |
| HE-MXene/ G@PP | HE-MXene doped graphene on PP | separator modification | composite coating | high conductivity; large active area | — | 0.026%/0.031% per cyc./1/2 C (1200 cyc.) | chemisorption + fast kinetics | Promising scalability | [ |
| TiN@C (ALD-TiN in carbon) | nitride-carbon | sulfur host | ALD TiN (<2 nm) + melt S | lower overcharge; high CE | — | improved CE across rates | TiN polar sites; color test | ALD cost; scalable thin films | [ |
| NCFI@T150 (TiO2/TiN on carbon foam) | TiO2/TiN heterostructure | interlayer | in-situ growth with N-doping | strong Li2S adsorption energies | — | 817→777 mAh·g−1 after 200 cyc./1 C | polar N sites + TiN/TiO2 synergy | scalable foams | [ |
| L-TiN-Cu- CNF | low-crystalline TiN on Cu-CNF | interlayer/host | TiN coating; crystal control | more defect sites; better PS chemisorption | 913 mAh·g−1/2 C | 300 cyc./626 mAh·g−1 | defect-rich TiN | scalable | [ |
| MnNi-MIL-100@S | MOF (multi-metal) | sulfur host | one-pot MIL-100 with Ni; melt-diffusion S | lewis acid-base interactions; deep electrolyte penetration | ~709 mAh·g−1/ (200 cycles) | — | strong binding to Li2S4/Li2S6 | MOF scalable; moderate | [ |
| STAM-1 (Cu(II) MOF) | MOF | S-cathode regulator | Cu-MOF STAM-1 flakes | hydrophobic/hydrophilic domains | initial 452 mAh·g−1/96% after 100 cycles /0.5 C | high retention | encapsulation in pores | scalable solvothermal | [ |
| D-ZIF L (under-coordinated) | MOF derivative | sulfur host | ligand removal to undercoordinate Zn-Co ZIF | reduced steric hindrance; higher conductivity | areal 5.0 mAh·cm−2/5.5 mg·cm−2 | — | exposed metal sites | scalable | [ |
| MIL-96-Al (shape/size tuned) | MOF | sulfur host (HPC/HBC/HPBC) | Co-solvent; modulators; melt‑diffusion | plane-dependent LiPS adsorption; size affects stability | — | — | exposed (101) plane in HBC adsorbs strongly | scalable | [ |
| Li2S@NC: SAFe | Fe SAC | cathode host (Li2S) | PANI-coated carbon + Fe-acetate pyrolysis | lower barrier 0.81 eV vs. 3.4 eV | 588 mAh·g−1/12 C | long life @5 C | strong binding to LiS/Li2Sm | low metal; high T pyrolysis | [ |
| FeSA-NC @CBC | Fe SAC on N-C aerogel | Binder-free S cathode scaffold | Fe-doped ZIF-8 + bacterial cellulose → pyrolysis | reduced Ea for S8 → Li2Sn & Li2Sn→Li2S | 840 mAh·g−1/1 C | 500 Cyc./ 95% retention | FeN4@G strong LiPS binding | scalable pyrolysis | [ |
| C3N4-Fe @rGO (Fe-N5) | Fe SAC on defective g-C3N4 | sulfur host | absorption-pyrolysis | Lower Li2S decomposition barrier (0.75 eV) | — | — | oversaturated Fe-N5 sites | scalable | [ |
| Channel- FeSAC (ordered) | Fe SAC (ordered channels) | host/ interlayer | templated channels | Ea 15 < 30.8 < 38.2 kJ·mol−1 (channel < bowl < flat) | high areal capacity; long life | — | capture-catalysis microenvironments | — | [ |
| SA-Co/NGM | Co SAC on N-graphene mesh | separator coating/ host | CoZn-ZIF-L → salt‑templated pyrolysis (900 °C) + leach | Co-N4 lowers Li2S decomposition barrier (1.35 eV vs. 2.37) | 649 mAh·g−1/5 C; areal 4.73 mAh·cm−2/6.5 mg·cm−2 | 0.0232%/cycle @2 C (1000 Cyc.) | planar Co-N4 active centers | scalable; pyrolysis | [ |
| CoSA-N-C (15.3 wt% Co) | high-loading Co SAC | sulfur host | salt-template method | lower Li2S decomposition barrier (1.08 eV) | 1574 mAh·g−1/0.05 C | 0.035%/ Cyc. (1000 Cyc. @1 C) | Co-N4 redox centers | — | [ |
| Ni-NG (SAC) | Ni SAC on N-graphene | interlayer | series M-NG study | low SRR Gibbs barrier | 701.8 mAh·g−1/0.5 C (400 cycles) | areal 4.58 mAh·cm−2/3.8 mg·cm−2 | facilitates L-L & L-S steps | moderate | [ |
| Ni-N5/HNPC | Ni SAC in hollow N-porous C | sulfur host | self-templating + pyrolysis | Ni-N5 best among Ni-Nx | 684 mAh·g−1/4 C | — | Ni-N5 active centers | scalable | [ |
| S@ZnN4-NC | Zn SAC on N-CNT arrays | sulfur host | ordered CNT arrays; Zn SAs 8.3 wt% | high site density; fast transport | ~1225 mAh·g−1/S uptake 99% | 500 Cyc./ 0.032%/Cyc. | chemisorption + conversion | lower metal cost; scalable arrays | [ |
| Zn-N/CS (pyridinic N defects) | Zn SAC on carbon sheets | sulfur host | porous carbon with Zn-N4 + pyridinic N | higher d-band center; stronger binding | 1132 mAh·g−1/0.1 C | 72.2% after 800 Cyc./2 C | defect-assisted chemisorption | scalable | [ |
| Zn-Co SA@DNC | dual-metal SAC on double‑shelled CNTs | host/ interlayer | dual SA loading on DNC | synergy lowers barriers; reduces shuttle | 732 mAh·g−1/1 C | 0.034%/ Cyc. (800 Cyc.) | confinement + catalysis | — | [ |
| ZnCoN4O2/ CN | dual-core SA on carbon nanosheets | sulfur host | bulk di-atomic CNS synthesis | lithophilic Zn + sulfurophilic Co | 789.4 mAh·g−1/5 C; 1000 cycles /6 C (0.05%/cycle) | long cycling | faster LiPS conversion & Li+ transport | scalable | [ |
| Mo-N2/C (Mo SAC) | Mo SAC on N-C | interlayer/ host | pyrolysis; N-doped carbon | low barriers ~1.0 eV for key steps | ~744 mAh·g−1/5 C | — | catalyzes bidirectional steps | high Mo cost | [ |
| SV-Co9S8-Mo (Mo SA on S-vacant Co9S8) | SAC on sulfide | sulfur host | anchor Mo on S-vacant Co9S8 | optimized adsorption/desorption balance | 1254 mAh·g−1 /0.2 C; 633/5 C; 821/6.1 mg·cm−2 | — | weaker |ΔEads| for Li2S6 aids kinetics | — | [ |
| V-SACs (pyridinic-N-rich) | V SAC on N-C | host/ interlayer | high-temp; pyridinic-N rich supports | more chemisorption sites; promotes conversion | 921 mAh·g−1/1 C (66% after 500 cyc.) | — | N-defect + V sites | V cheaper than Co/Mo | [ |
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| [2] | 刘小妮, 刘晓斌, 李彩霞, 杨波, 王磊. 缺陷工程在金属基电池中的研究进展[J]. 催化学报, 2023, 45(2): 27-87. |
| [3] | 曾攀, 袁程, 刘根林, 郜杰昌, 李彦光, 张亮. 调控电催化剂电子结构促进锂硫电池多硫化物催化转化的研究进展[J]. 催化学报, 2022, 43(12): 2946-2965. |
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