Heteronuclear Binary-Atom-Controlled Cobalt-Based Catalyst for Lithium-Sulfur Batteries

Heteronuclear Binary-Atom-Controlled Cobalt-Based Catalyst for Lithium-Sulfur Batteries | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Heteronuclear Binary-Atom-Controlled Cobalt-Based Catalyst for Lithium-Sulfur Batteries Qiang Liu, Feiyu Wang, Liming Song, Xianwu Li, Yong Xiang, Fan Chen This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8625349/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted 11 You are reading this latest preprint version Abstract This study successfully designed and synthesized a series of cobalt-based catalysts (CoB, CoTiB, and CoCrB) via an ionic modulation strategy, systematically investigating the influence of different metal ions on the catalytic performance of lithium–sulfur batteries and the underlying mechanisms. A low-energy solution-chemical method under alkaline conditions was employed to introduce B, Ti, and Cr elements, using branched-chain cobalt acetate as the cobalt source to construct amorphous/microcrystalline boride materials with high specific surface area and abundant active sites. Structural characterization and theoretical calculations reveal that the introduction of Cr effectively modulates the electronic structure of the material, enhancing its adsorption and catalytic conversion capability toward polysulfides. Electrochemical tests demonstrate that CoCrB exhibits superior reaction kinetics, including low charge-transfer resistance, high polysulfide conversion efficiency, and rapid lithium-ion migration, which is primarily attributed to the orbital-electron synergy between Cr 3+ and Co 2+ . In contrast, CoTiB achieves a better balance between catalytic activity and structural stability, showing excellent reaction reversibility and cycling stability. Long-term cycling and rate performance tests further confirm that CoCrB maintains high capacity retention after 500 cycles at 2 C and delivers favorable rate capability across various current densities. This work clarifies the synergistic enhancement mechanism of heteronuclear diatomic regulation on cobalt-based catalysts, providing new insights and an experimental basis for the design of efficient and stable Li–S battery catalysts through electronic structure modulation. Lithium-sulfur batteries cobalt-based catalysts crystal plane engineering ion synergy Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 1 Introduction Lithium-sulfur (Li-S) batteries are regarded as a key candidate for next-generation high-energy-density energy storage systems due to their exceptionally high theoretical specific capacity (1675 mA h g − 1 ), environmental friendliness, and low cost. 1 , 2 However, their commercialization faces two core challenges: the "shuttle effect" induced by soluble lithium polysulfides (LiPSs) formed during charge-discharge cycles, and the sluggish kinetics of the sulfur reduction reaction (SRR). These issues collectively lead to irreversible active material loss, rapid capacity decay, and poor rate performance, constituting major bottlenecks for industrialisation. 3 – 5 To address these challenges, the design and modification of cathode-side catalysts are paramount. Crystal plane engineering, as a classical surface regulation strategy, has demonstrated potential in enhancing cobalt-based catalyst performance by optimizing catalytic activity through the exposure of specific crystal planes. However, this approach has limitations in precisely regulating electronic structures at the atomic scale. Ion-regulation engineering has emerged as a novel paradigm for rational catalyst design, leveraging its ability to flexibly tailor active site geometry and electronic structure at the atomic/ionic scale. Unlike crystal plane engineering which mainly focuses on macroscopic morphology control, the ion regulation strategy introduces heteronuclear diatoms or multivalent ion to achieve precise trimming of the local coordination environment and electronic structure of the catalyst. This optimizes adsorption strength with LiPSs and accelerates SRR kinetics. The research indicates that ion-engineered catalysts featuring asymmetric geometries and unique electronic distributions expose more intrinsic active sites, significantly lowering reaction energy barriers at key steps and demonstrating outstanding catalytic performance in Li-S batteries. Building upon this, the present study applies ion-tuning engineering to the design of cobalt-based catalysts. By constructing cobalt boride catalysts regulated by heteronuclear diatomic centers (M-CO, M = Ti, Cr), the mechanism of enhancing the catalytic performance of Li-S batteries through ion-scale structure regulation was systematically explored. To address the requirements for anchoring and efficiently converting LiPSs, a series of heteronuclear bimetallic-doped cobalt borides (CoMB) were designed and synthesized. Through comprehensive application of physicochemical characterization and electrochemical testing techniques, we systematically investigated the structure, properties, and adsorption/catalytic conversion behavior of these catalysts towards LiPSs. This revealed the intrinsic mechanism whereby heteronuclear bimetallic synergistic regulation drives enhanced catalytic performance. This work aims to provide novel design concepts and robust experimental evidence for developing highly efficient, stable, and readily synthesized Li-S battery catalysts. 2 Experiment section This study employs a stepwise synthesis strategy to construct heteronuclear bimetallic (M-Co) catalysts featuring asymmetric geometric configurations and unique electron distributions. The core of the synthetic pathway involves: first, completely replacing the anions in the precursor with B to establish an electron-rich boride framework. Subsequently, based on the orbital energy characteristics of Co, either Ti or Cr were introduced for co-doping, thereby precisely regulating the local microenvironment of the active sites at the atomic scale. Throughout this process, the molar ratio of Co to the dopant metal was strictly maintained at 1:1 to facilitate the formation of the heteronuclear bis-atom configuration. 2.1 Synthesis of cobalt precursor Dissolve 0.005 mol of cobalt acetate tetrahydrate ((CH 3 COO) 2 Co·4H 2 O) in 200 mL of anhydrous ethanol. Add 3.5 g of polyvinylpyrrolidone (PVP) as a morphology-controlling agent to induce the formation of uniform, plate-like structures. The mixture was refluxed at 85℃ in an oil bath for 4 h under continuous stirring. After the reaction, the mixture was allowed to cool to room temperature. The precipitate was collected by centrifugation (8000 rpm, 10 min) and washed thrice with anhydrous ethanol to remove residual PVP and by-products. The resulting precipitate was dried overnight in a vacuum oven at 60℃ to yield cobalt precursor powder for subsequent use. 2.2 Synthesis of cobalt-titanium (chromium) hydroxide Add 0.4 mmol of the aforementioned cobalt precursor and 0.4 mmol of either titanium tetrachloride (TiCl 4 ) or hexahydrate chromium trichloride (CrCl 3 ·6H 2 O) to 100 mL of anhydrous ethanol. Sonicate for 30 minutes to ensure thorough dispersion. Meanwhile, dissolve 3.2 mmol sodium hydroxide (NaOH) in 100 mL anhydrous ethanol. Under vigorous stirring, add this solution dropwise to the aforementioned metal salt dispersion. After the addition, the mixture was heated to 85°C under reflux for 4 h. Upon reaction completion, the precipitate was collected by centrifugation and washed several times with anhydrous ethanol until the supernatant was neutral. Finally, vacuum drying at 60℃ yielded cobalt-titanium hydroxide (CoTi-OH) or cobalt-chromium hydroxide (CoCr-OH), respectively. 2.3 Synthesis of cobalt-titanium boride (CoTiB) Disperse 40 mg of dried CoTi-OH powder in 40 mL of anhydrous ethanol. Under an ice-water bath and nitrogen atmosphere protection, rapidly add 50 mg of sodium borohydride (NaBH 4 ). Subsequently, subject the mixture to ultrasonic treatment for 1 h to ensure complete reduction of the precursor by NaBH 4 . Following the reaction, the product was collected by centrifugation and washed alternately three times with anhydrous ethanol and deionized water to remove residual reactants and by-products. The final collected black precipitate was dried in a vacuum oven at 60°C to obtain the target product CoTiB. 2.4 Synthesis of cobalt-chromium boride (CoCrB) The synthesis procedure is identical to that for CoTiB, with the sole modification in step 2.3 being the replacement of the titanium source (TiCl 4 ) with an equimolar amount of chromium source (CrCl 3 ·6H 2 O). 3 Results and discussion 3.1 Catalyst design Figure 1 presents the structural characterization and corresponding theoretical computational energy analysis results for the CoTiB and CoCrB catalysts. Figure 1 a and 1 b present the X-ray diffraction (XRD) patterns for both catalysts, respectively. Under ice bath and nitrogen-protected conditions, the target material was successfully synthesized using NaBH 4 as a strong reducing agent and boron source. The XRD patterns exhibit distinct broadened diffraction peaks at approximately 12° and 36°, indicating significant amorphous characteristics in the synthesized material, consistent with reports employing similar organic precursors. 6 – 8 Although faint diffraction signals attributable to the TiB₂ or CrB₂ (100) planes are observable near ~ 34°, the intensity of the main diffraction peak corresponding to the (101) plane (~ 46°) is notably low. This is mainly due to the low overall crystallinity of the material and the interaction between cobalt and boron ions and organic ligands. Nevertheless, comparison with XRD patterns of CoTiB, and CoCrB synthesized under identical conditions effectively reveals structural differences induced by heteronuclear metal ion doping. To elucidate the doping effects at the atomic scale, computational optimized structural models were constructed (Fig. 1 c, d). These models demonstrate that the introduction of titanium or chromium atoms significantly alters the local coordination environment of the cobalt-boron framework, forming the anticipated heteronuclear diatomic configurations. The properties of the unpaired electrons, closely linked to catalytic activity, were investigated using electron paramagnetic resonance (EPR) spectroscopy (Figure S1 ). EPR signal intensity and line shape exhibited distinct differences among the three catalysts, indicating variations in their unpaired electron concentration and local electronic environment. Among them, CoCrB displayed the strongest EPR signal, revealing the highest unpaired electron density. These electrons serve as active sites for the adsorption and conversion of LiPSs, preliminarily suggesting its potential for superior catalytic activity. To elucidate the mechanisms of the two catalysts in Li-S batteries, we calculated the Gibbs free energy changes for key steps of the SRR via density functional theory (DFT) (Fig. 1 e). Compared to CoTiB, CoCrB exhibits a lower reaction energy barrier (Δ G ) during the conversion of LiS 6 to Li 2 S 4 , indicating superior SRR kinetics. 9 , 10 Fig. 1 f further compares the adsorption energies of different LiPSs (Li 2 S x , x = 1, 2, 4, 6, 8) on both surfaces. Results reveal that CoCrB exhibits stronger adsorption for all Li 2 S x species, with notably more negative adsorption energies for Li 2 S 4 and Li 2 S 2 . This facilitates effective anchoring of LiPSs during cycling, suppresses their shuttling, and promotes subsequent conversion reactions. The aforementioned theoretical calculations demonstrate that chromium incorporation precisely modulates the electronic structure of the catalytic center, concurrently enhancing both LiPSs adsorption capacity and catalytic conversion activity. This provides a theoretical basis for the subsequent differences in electrochemical performance. 3.2 Differences in catalytic activity regulated by different ions To evaluate the electrocatalytic activity of the catalysts, symmetric cells with Li 2 S 6 as the electrolyte were first assembled for cyclic voltammetry (CV) testing (Fig. 2 a, b). The CoB@S electrode exhibited the smallest peak area and highest oxidation peak potential in the CV curve, indicating slower reaction kinetics. 11 – 13 In contrast, both CoTiB@S and CoCrB@S electrodes exhibited significantly enhanced peak currents, confirming that heteronuclear diatomic doping effectively enhances electron transfer capability. Notably, CoTiB@S exhibited the smallest potential difference (Δ E p ) between its oxidation and reduction peaks, reflecting excellent reaction reversibility. Conversely, CoCrB@S required a higher overpotential to drive the reaction, yet its absolute peak current value was marginally higher, suggesting potentially distinct catalytic pathways. Further Tafel analysis (Fig. 2 c, d) provides deeper insights into the electrode process kinetics. CoTiB exhibits the highest peak potential, indicating optimal chemical/electrochemical stability (corrosion resistance) in the electrolyte; conversely, CoCrB demonstrates the highest peak current, signifying its strongest intrinsic catalytic activity towards the Li 2 S 6 redox reaction, capable of significantly lowering the reaction activation energy barrier. This indicates that CoTiB excels in structural stability and reaction reversibility, whereas CoCrB demonstrates superior intrinsic catalytic activity. CV testing of the full cell (Fig. 2 e) further corroborates these trends. The CoCrB-based cell exhibited the strongest current response at the first reduction peak, indicating the highest initial reaction intensity; conversely, the CoTiB-based cell displayed the smallest Δ E p , reaffirming its superior reaction reversibility. 14 – 16 Based on this, it can be inferred that during long-term cycling, CoCrB may offer higher specific capacity due to its greater conversion efficiency, whereas CoTiB may demonstrate superior capacity retention owing to its lower polarization. Initial electrochemical impedance spectroscopy (EIS) testing (Fig. 2 f, conducted prior to cell activation) revealed that the CoCrB electrode exhibited the lowest charge transfer resistance (Rct, approximately 180 Ω), 25–50% lower than other samples. This indicates faster interfacial charge transfer kinetics, laying the foundation for its superior rate performance. Furthermore, wettability of the catalyst surface was evaluated via contact angle measurements (Figure S2). CoCrB exhibited the smallest contact angle, indicating optimal electrolyte affinity. 3.3 Reaction kinetics and lithium ion transport behavior The reaction kinetics and structural stability of the modified cathode were evaluated using constant-current intermittent titration (GITT) (Fig. 3 a). The CoCrB-based cell exhibited the longest total test duration (approximately 125 h), indicating more stable electrochemical behavior during stepwise charge-discharge cycles. 17 , 18 Fig. 3 b–d highlight the voltage response corresponding to the initial portion of the second discharge plateau (Li 2 S 6 decomposition step). Measurements of the activation overpotential (ΔV) for this step reveal values of 135.2 mV for CoCrB, markedly higher than those for CoB (66.1 mV) and CoTiB (45.6 mV). This increased polarization is not detrimental; rather, it indicates that CoCrB significantly accelerates this key rate-limiting step of the SRR, demonstrating its exceptional catalytic capability. Collectively, these results demonstrate that CoCrB not only facilitate es Li + diffusion but also efficiently catalyzes the conversion of Li 2 S 6 to Li 2 S 4 . To quantitatively evaluate the Li + diffusion coefficient ( D Li⁺ ), multi-scan-rate CV tests were conducted (Fig. 4 a, c, e). The linear relationship between the oxidation peak current and the square root of the scan rate for all samples (Fig. 4 b, d, f) confirmed diffusion-step control of the reaction. CoCrB exhibited the highest peak current at all scan rates and yielded the maximum slope value from Tafel equation fitting, corresponding to the highest calculated D Li⁺ value. This quantitatively confirms CoCrB possesses optimal Li + transport kinetics, consistent with GITT analysis conclusions, collectively explaining its outstanding rate performance. 3.4 Electrochemical performance and mechanism validation in full cells Morphological analysis of the cycled lithium metal anode (Fig. 5 a-c) provides direct evidence for suppressed shuttling effects. The anode paired with the CoB cathode exhibited a surface covered with dendrites, cracks, and inert deposits. In contrast, the anodes paired with CoTiB and CoCrB displayed significantly smoother and flatter surfaces, with the CoCrB group exhibiting the least surface damage. This demonstrates that the designed heteronuclear bimetallic catalyst effectively mitigated the shuttle effect by anchoring and transforming LiPSs, which substantially reduced corrosion on the lithium anode and led to a marked enhancement in battery cycle life. The long-term cycling performance of the full cell (at 2 C rate) is shown in Fig. 5 d. The CoCrB based cell achieved the highest initial discharge capacity (850 mA h g − 1 ) due to its superior kinetics. Although capacity decay was slightly faster in the early cycling stage, the decay rate significantly decreased after approximately 300 cycles, ultimately surpassing the capacity retention of CoTiB after 500 cycles. This is because CoCrB has an efficient and continuous catalytic effect, overcoming the cumulative effect of LiPSs accumulation in the middle of the cycle. In contrast, the CoTiB demonstrated its stability advantage through a more gradual decay curve. Rate performance test (Fig. 5 f) further highlights the dynamic advantages of CoCrB. Within the discharge rate range of 0.1℃ to 3℃, CoCrB always maintains the highest reversible capacity. Moreover, when recovering from 3 C to 1 C, it exhibited the highest capacity recovery rate, demonstrating robust structural integrity and rapid charge transport capability. The charge-discharge curve at 0.5 C (Fig. 5 e) reveals that CoCrB not only enhances the capacity of both discharge plateaus, particularly increasing the capacity of the second plateau corresponding to the LiPSs-to-Li 2 S conversion by 40%, but also exhibits significantly red uced voltage polarization at the plateaus. This provides direct evidence of its potent SRR catalytic capability. 4 Conclusions Based on an ion-regulation strategy, a series of cobalt boride catalysts were successfully designed and synthesized via a low-energy solution process using cobalt acetate as the precursor. By incorporating boron along with titanium or chromium, heteronuclear diatomic catalysts with high specific surface area and abundant active sites were constructed. Systematic investigation revealed distinct modulation effects of different metal ions (Ti 4+ and Cr 3+ ) on the catalytic performance. Theoretical calculations combined with electrochemical analyses demonstrate that the introduction of Cr 3+ optimizes the electronic structure of the catalyst through pronounced orbital electron synergy with Co 2+ . As a result, CoCrB exhibits the lowest charge-transfer resistance, the highest efficiency for adsorbing and converting lithium polysulfides (LiPSs), and the most rapid Li + migration rate, thereby endowing the corresponding battery with the highest specific capacity, excellent rate performance, and outstanding long-term cycling stability. In contrast, the electron-deficient character of Ti 4+ primarily enhances the chemical stability and reaction reversibility of the material, enabling CoTiB to achieve an optimal balance between catalytic activity and structural integrity, which is reflected in its remarkable long-term cycling reversibility. In summary, the ion-regulation strategy yields a clear synergistic enhancement in cobalt-based catalysts: Ti 4+ reinforces the structural stability, whereas Cr 3+ significantly improves the reaction kinetics. This work elucidates the mechanism of performance enhancement driven by heteronuclear bimetallic regulation at the atomic scale and provides valuable theoretical insights as well as a material design framework for developing efficient and stable catalysts for lithium–sulfur batteries through precise electronic structure engineering. Declarations Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Author Contribution Q. Liu: Conceived and designed the core experiments, conducted electrochemical performance tests of lithium-sulfur batteries, and drafted the initial manuscript.F. Wang: Performed material characterization (including XRD and SEM tests) and processed the corresponding data, assisted in optimizing the electrode preparation process.L. Song*: Proposed the research framework and theoretical direction, guided the DFT calculation work, revised and polished the manuscript, and provided financial support for the project.X. Li: Carried out the assembly of lithium-sulfur battery cells and cyclic stability tests, organized and analyzed the experimental data sets.Y. Xiang: Assisted in the theoretical simulation of the material electronic structure, provided technical support for the use of Vaspkit software, and participated in the discussion of research results.F. Chen*: Participated in the design of control experiments, verified the repeatability of key data, reviewed the manuscript for scientific rigor, and coordinated the overall research progress.All authors have read and approved the final version of the manuscript, and agree to the submission of this work to the journal. Acknowledgments This work was supported by the Science and Technology Program of Inner Mongolia Autonomous Region (2025YFHH0167, 2023YFKL0019) and the Key Research and Development Program of Dongguan City (20241201300022). Data Availability All relevant data are within the manuscript and its supplementary materials. References Wang P, Mou H, Wang Y, Song N, Li X, Feng J, Xi B, Xiong S (2025) Niobium Phosphide-Induced Sulfur Cathode Interface with Fast Lithium-Ion Flux Enables Highly Stable Lithium–Sulfur Catalytic Conversion. Angew Chem Int Ed 64(20):e202502255. https://doi.org/10.1002/anie.202502255 Wang T, Wang F, Shi Z, Cui S, Zhang Z, Liu W, Jin Y (2024) Synergistic Effect of In2O3/NC-Co3O4 Interface on Enhancing the Redox Conversion of Polysulfides for High-Performance Li–S Cathode Materials at Low Temperatures. ACS Appl Mater Interfaces 16(24):31158–31170. 10.1021/acsami.4c04733 Xia S, Song J, Zhou Q, Liu L, Ye J, Wang T, Chen Y, Liu Y, Wu Y, van Ree T (2023) A Separator with Double Coatings of Li4Ti5O12 and Conductive Carbon for Li-S Battery of Good Electrochemical Performance. Adv Sci 10(22):2301386. https://doi.org/10.1002/advs.202301386 Xu J, An S, Song X, Cao Y, Wang N, Qiu X, Zhang Y, Chen J, Duan X, Huang J et al (2021) Towards High Performance Li–S Batteries via Sulfonate-Rich COF-Modified Separator. Adv Mater 33(49):2105178. https://doi.org/10.1002/adma.202105178 Yang Q, Cai J, Li G, Gao R, Han Z, Han J, Liu D, Song L, Shi Z, Wang D et al (2024) Chlorine bridge bond-enabled binuclear copper complex for electrocatalyzing lithium–sulfur reactions. Nat Commun 15(1):3231. 10.1038/s41467-024-47565-1 Chen P, Wang T, He D, Shi T, Chen M, Fang K, Lin H, Wang J, Wang C, Pang H (2023) Delocalized Isoelectronic Heterostructured FeCoOxSy Catalysts with Tunable Electron Density for Accelerated Sulfur Redox Kinetics in Li-S batteries. Angew Chem Int Ed 62(47):e202311693. https://doi.org/10.1002/anie.202311693 Li F, Yuan H, Wang Y, Xue Z, He M, Wang J, Wu F, Huang M, Xiang Y, Hu A et al (2025) Tailoring Li-Accelerated Motif Enables Lithium Stabilization and Polysulfide Conversion for Long-Cycling Li–S Batteries. Advanced Functional Materials n/a ( n/a ), e11078. https://doi.org/10.1002/adfm.202511078 Liu S, Zhang J, Yang J, Gao Y, Wang Y, Geng L, Mao W, Guo Y, Wang H, Li J et al (2025) Decelerating and Accelerating Sulfur Reduction Reaction via P-OV-In2O3 Enables High-Performance Li-S Batteries. Small 21(4):2407865. https://doi.org/10.1002/smll.202407865 Zhang H, Zhang M, Liu R, He T, Xiang L, Wu X, Piao Z, Jia Y, Zhang C, Li H et al (2024) Fe3O4-doped mesoporous carbon cathode with a plumber’s nightmare structure for high-performance Li-S batteries. Nat Commun 15(1):5451. 10.1038/s41467-024-49826-5 Zhang W, Chen M, Luo Y, He Y, Liu S, Ye Y, Wang M, Chen Y, Zhu K, Shu H et al (2024) Utilizing 2D layered structure Cu-g-C3N4 electrocatalyst for optimizing polysulfide conversion in wide-temperature Li-S batteries. Chem Eng J 486:150411. https://doi.org/10.1016/j.cej.2024.150411 Jiao X, Hu J, Zuo Y, Qi J, Yan W, Zhang J (2024) Self-recovery catalysts of ZnIn2S4@In2O3 heterostructures with multiple catalytic centers for cascade catalysis in lithium–sulfur battery. Nano Energy 119:109078. https://doi.org/10.1016/j.nanoen.2023.109078 Jin W, Guo Y, Gan T, Shen Z, Zhu X, Zhang P, Zhao Y (2025) Cooperation of Multifunctional Redox Mediator and Separator Modification to Enhance Li-S Batteries Performance under Low Electrolyte/Sulfur Ratios. Angew Chem Int Ed 64(8):e202420544. https://doi.org/10.1002/anie.202420544 Kong Y, Wang L, Mamoor M, Wang B, Qu G, Jing Z, Pang Y, Wang F, Yang X, Wang D et al (2024) Co/Mon Invigorated Bilateral Kinetics Modulation for Advanced Lithium–Sulfur Batteries. Adv Mater 36(13):2310143. https://doi.org/10.1002/adma.202310143 He J, Bhargav A, Yaghoobnejad Asl H, Chen Y, Manthiram A (2020) 1T′-ReS2 Nanosheets In Situ Grown on Carbon Nanotubes as a Highly Efficient Polysulfide Electrocatalyst for Stable Li–S Batteries. Adv Energy Mater 10(23):2001017. https://doi.org/10.1002/aenm.202001017 Li H, Meng R, Ye C, Tadich A, Hua W, Gu Q, Johannessen B, Chen X, Davey K, Qiao S-Z (2024) Developing high-power Li||S batteries via transition metal/carbon nanocomposite electrocatalyst engineering. Nat Nanotechnol 19(6):792–799. 10.1038/s41565-024-01614-4 Li J, Li W, Tian Y, Wang C (2025) Integrated design of polysulfide shuttling and lithium dendrite suppressing framework: In2O3-In2S3 embedded carbon cloth for lithium-sulfur full batteries. Chem Eng J 509:161241. https://doi.org/10.1016/j.cej.2025.161241 Li Y, Zuo Y, Li X, Zhang Y, Ma C, Cheng X, Wang J, Wang J, Lin H, Ling L (2024) Electron delocalization-enhanced sulfur reduction kinetics on an MXene-derived heterostructured electrocatalyst. Nano Res 17(8):7153–7162. 10.1007/s12274-024-6682-6 Lian J, Guo W, Fu Y (2021) Isomeric Organodithiol Additives for Improving Interfacial Chemistry in Rechargeable Li–S Batteries. J Am Chem Soc 143(29):11063–11071. 10.1021/jacs.1c04222 Additional Declarations No competing interests reported. Supplementary Files Supporting.docx Cite Share Download PDF Status: Under Review Version 1 posted Editorial decision: Revision requested 07 Feb, 2026 Reviews received at journal 06 Feb, 2026 Reviews received at journal 03 Feb, 2026 Reviewers agreed at journal 29 Jan, 2026 Reviews received at journal 28 Jan, 2026 Reviewers agreed at journal 27 Jan, 2026 Reviewers agreed at journal 27 Jan, 2026 Reviewers invited by journal 27 Jan, 2026 Editor assigned by journal 26 Jan, 2026 Submission checks completed at journal 26 Jan, 2026 First submitted to journal 17 Jan, 2026 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-8625349","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":581700032,"identity":"c4272f09-34f0-470a-a697-92194d7fc998","order_by":0,"name":"Qiang Liu","email":"","orcid":"","institution":"University of Science and Technology Beijing","correspondingAuthor":false,"prefix":"","firstName":"Qiang","middleName":"","lastName":"Liu","suffix":""},{"id":581700033,"identity":"5958675d-7d63-4442-a972-86e58271e2ef","order_by":1,"name":"Feiyu Wang","email":"","orcid":"","institution":"Inner Mongolia North Hauler Joint Stock Co.,Ltd","correspondingAuthor":false,"prefix":"","firstName":"Feiyu","middleName":"","lastName":"Wang","suffix":""},{"id":581700034,"identity":"b73864e5-2139-44a8-a8b0-963a915b6d1e","order_by":2,"name":"Liming Song","email":"","orcid":"","institution":"Inner Mongolia North Hauler Joint Stock Co.,Ltd","correspondingAuthor":false,"prefix":"","firstName":"Liming","middleName":"","lastName":"Song","suffix":""},{"id":581700035,"identity":"330921a0-fd79-4f38-a545-986947642188","order_by":3,"name":"Xianwu Li","email":"","orcid":"","institution":"Inner Mongolia North Hauler Joint Stock Co.,Ltd","correspondingAuthor":false,"prefix":"","firstName":"Xianwu","middleName":"","lastName":"Li","suffix":""},{"id":581700036,"identity":"786056b6-1143-421a-bcce-6756acbe94be","order_by":4,"name":"Yong Xiang","email":"","orcid":"","institution":"University of Electronic Science and Technology of China","correspondingAuthor":false,"prefix":"","firstName":"Yong","middleName":"","lastName":"Xiang","suffix":""},{"id":581700037,"identity":"a0a50d08-3cb6-4a97-a05a-1b1d7f275088","order_by":5,"name":"Fan Chen","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA0ElEQVRIiWNgGAWjYBAC9gYeIFkhIcfP3tj48AMxWngOgLScsTGW7DncbCxBtBbGtrTEDTPS2wR4iNLCfvbg4wK2w4wbJB+2MUgw2MnpNhDSwpOXbDyD5zCzuXRi24MChmRjswMEtNhL8JhJ80gcZrOcndhuIMFwIHEbIS08Ejzmv3kMDvMY3DzYJsFDpBYzZp6ENAmDG4zEauHJMZbmOWBjINmTCAxkAyL8wsN+xvAz7z+J+n724w8ffqiwkyOoBQ0YkKZ8FIyCUTAKRgEOAAC6ND0u5ebrvgAAAABJRU5ErkJggg==","orcid":"","institution":"University of Electronic Science and Technology of China","correspondingAuthor":true,"prefix":"","firstName":"Fan","middleName":"","lastName":"Chen","suffix":""}],"badges":[],"createdAt":"2026-01-17 10:38:53","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-8625349/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-8625349/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":101486449,"identity":"164e9c25-0f89-42bf-bb27-80e45033639c","added_by":"auto","created_at":"2026-01-30 09:13:19","extension":"jpeg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":278399,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eStructural characterization and theoretical energy analysis of CoTiB and CoCrB. \u003c/strong\u003e(a) XRD pattern of CoTiB; (b) XRD pattern of CoCrB; (c) Computationally optimized structural model of CoTiB; (d) Computationally optimized structural model of CoCrB; (e) Gibbs free energy plots for key steps of the sulfur reduction reaction on CoTiB and CoCrB; (f) Comparison of adsorption energies for different Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003ex\u003c/sub\u003e species on CoTiB and CoCrB.\u003c/p\u003e","description":"","filename":"image1.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8625349/v1/39e8b26cac339c928e8b9900.jpeg"},{"id":101486451,"identity":"08363d0a-7a08-4ebc-b8c6-d3ab8a613a34","added_by":"auto","created_at":"2026-01-30 09:13:21","extension":"jpeg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":235829,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eElectrochemical performance characterization of symmetric cells and Li-S full cells.\u003c/strong\u003e(a) CV curves of symmetric cells based on different catalysts; (b) enlarged view of panel (a); (c) forward Tafel scan of symmetric cells; (d) reverse Tafel scan of symmetric cells; (e) CV curves of Li-S full cells; (f) initial Nyquist plots of Li-S full cells.\u003c/p\u003e","description":"","filename":"image2.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8625349/v1/8bb58b8b2e2a8e88f6f4791e.jpeg"},{"id":101486446,"identity":"740c007d-1ef9-409b-8f10-b8bcfbcabdbf","added_by":"auto","created_at":"2026-01-30 09:13:19","extension":"jpeg","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":135676,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eGITT analysis of modified cathodes.\u003c/strong\u003e (a) GITT voltage-time curves for modified cathodes; (b–d) Localized voltage response curves in the Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e decomposition region for CoCrB, CoB, and CoTiB cathodes.\u003c/p\u003e","description":"","filename":"image3.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8625349/v1/3bd5495e74fc1791c90dcaa6.jpeg"},{"id":101486443,"identity":"26502779-04d2-4591-8d16-503cc3cb99de","added_by":"auto","created_at":"2026-01-30 09:13:18","extension":"jpeg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":268050,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eElectrochemical kinetics analysis of the modified CoB, CoTiB, and CoCrB cathodes via multi‑scan‑rate cyclic voltammetry . \u003c/strong\u003e(a, c, e) CV curves at various scan rates for CoB, CoTiB, and CoCrB, respectively; (b, d, f) corresponding Tafel fittings for the oxidation peaks of each material.\u003c/p\u003e","description":"","filename":"image4.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8625349/v1/a01dc5cd72377e9f112aa5c1.jpeg"},{"id":101486475,"identity":"f83ba42f-ed06-427d-9259-660f0a8fdd8d","added_by":"auto","created_at":"2026-01-30 09:13:24","extension":"jpeg","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":389908,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eComprehensive performance of the full cell and morphology of the lithium anode after cycling.\u003c/strong\u003e(a–c) SEM images of the lithium anode paired with CoB, CoCrB, and CoTiB cathodes after 500 cycles at 2 C; (d) Long-term cycling performance at 2 C; (e) Typical charge–discharge curve at 0.5 C; (f) Rate performance test.\u003c/p\u003e","description":"","filename":"image5.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8625349/v1/4d0905df3bb94e1bcc6d4cc5.jpeg"},{"id":101486499,"identity":"9416d576-833c-4a37-be1f-3f0cda12521c","added_by":"auto","created_at":"2026-01-30 09:13:50","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2051019,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8625349/v1/1e5126b1-b67d-4bd2-9221-f7bc0c6b3aec.pdf"},{"id":101486448,"identity":"5bf4d280-c761-4ece-8faf-e7e2b2294ef1","added_by":"auto","created_at":"2026-01-30 09:13:19","extension":"docx","order_by":0,"title":"","display":"","copyAsset":false,"role":"supplement","size":101885,"visible":true,"origin":"","legend":"","description":"","filename":"Supporting.docx","url":"https://assets-eu.researchsquare.com/files/rs-8625349/v1/f36831e5520fb6d4a7bb92e2.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Heteronuclear Binary-Atom-Controlled Cobalt-Based Catalyst for Lithium-Sulfur Batteries","fulltext":[{"header":"1 Introduction","content":"\u003cp\u003eLithium-sulfur (Li-S) batteries are regarded as a key candidate for next-generation high-energy-density energy storage systems due to their exceptionally high theoretical specific capacity (1675 mA h g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e), environmental friendliness, and low cost.\u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e,\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e However, their commercialization faces two core challenges: the \"shuttle effect\" induced by soluble lithium polysulfides (LiPSs) formed during charge-discharge cycles, and the sluggish kinetics of the sulfur reduction reaction (SRR). These issues collectively lead to irreversible active material loss, rapid capacity decay, and poor rate performance, constituting major bottlenecks for industrialisation.\u003csup\u003e\u003cspan additionalcitationids=\"CR4\" citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eTo address these challenges, the design and modification of cathode-side catalysts are paramount. Crystal plane engineering, as a classical surface regulation strategy, has demonstrated potential in enhancing cobalt-based catalyst performance by optimizing catalytic activity through the exposure of specific crystal planes. However, this approach has limitations in precisely regulating electronic structures at the atomic scale. Ion-regulation engineering has emerged as a novel paradigm for rational catalyst design, leveraging its ability to flexibly tailor active site geometry and electronic structure at the atomic/ionic scale. Unlike crystal plane engineering which mainly focuses on macroscopic morphology control, the ion regulation strategy introduces heteronuclear diatoms or multivalent ion to achieve precise trimming of the local coordination environment and electronic structure of the catalyst. This optimizes adsorption strength with LiPSs and accelerates SRR kinetics. The research indicates that ion-engineered catalysts featuring asymmetric geometries and unique electronic distributions expose more intrinsic active sites, significantly lowering reaction energy barriers at key steps and demonstrating outstanding catalytic performance in Li-S batteries.\u003c/p\u003e \u003cp\u003eBuilding upon this, the present study applies ion-tuning engineering to the design of cobalt-based catalysts. By constructing cobalt boride catalysts regulated by heteronuclear diatomic centers (M-CO, M\u0026thinsp;=\u0026thinsp;Ti, Cr), the mechanism of enhancing the catalytic performance of Li-S batteries through ion-scale structure regulation was systematically explored. To address the requirements for anchoring and efficiently converting LiPSs, a series of heteronuclear bimetallic-doped cobalt borides (CoMB) were designed and synthesized. Through comprehensive application of physicochemical characterization and electrochemical testing techniques, we systematically investigated the structure, properties, and adsorption/catalytic conversion behavior of these catalysts towards LiPSs. This revealed the intrinsic mechanism whereby heteronuclear bimetallic synergistic regulation drives enhanced catalytic performance. This work aims to provide novel design concepts and robust experimental evidence for developing highly efficient, stable, and readily synthesized Li-S battery catalysts.\u003c/p\u003e"},{"header":"2 Experiment section","content":"\u003cp\u003eThis study employs a stepwise synthesis strategy to construct heteronuclear bimetallic (M-Co) catalysts featuring asymmetric geometric configurations and unique electron distributions. The core of the synthetic pathway involves: first, completely replacing the anions in the precursor with B to establish an electron-rich boride framework. Subsequently, based on the orbital energy characteristics of Co, either Ti or Cr were introduced for co-doping, thereby precisely regulating the local microenvironment of the active sites at the atomic scale. Throughout this process, the molar ratio of Co to the dopant metal was strictly maintained at 1:1 to facilitate the formation of the heteronuclear bis-atom configuration.\u003c/p\u003e \u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1 Synthesis of cobalt precursor\u003c/h2\u003e \u003cp\u003eDissolve 0.005 mol of cobalt acetate tetrahydrate ((CH\u003csub\u003e3\u003c/sub\u003eCOO)\u003csub\u003e2\u003c/sub\u003eCo\u0026middot;4H\u003csub\u003e2\u003c/sub\u003eO) in 200 mL of anhydrous ethanol. Add 3.5 g of polyvinylpyrrolidone (PVP) as a morphology-controlling agent to induce the formation of uniform, plate-like structures. The mixture was refluxed at 85℃ in an oil bath for 4 h under continuous stirring. After the reaction, the mixture was allowed to cool to room temperature. The precipitate was collected by centrifugation (8000 rpm, 10 min) and washed thrice with anhydrous ethanol to remove residual PVP and by-products. The resulting precipitate was dried overnight in a vacuum oven at 60℃ to yield cobalt precursor powder for subsequent use.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2 Synthesis of cobalt-titanium (chromium) hydroxide\u003c/h2\u003e \u003cp\u003eAdd 0.4 mmol of the aforementioned cobalt precursor and 0.4 mmol of either titanium tetrachloride (TiCl\u003csub\u003e4\u003c/sub\u003e) or hexahydrate chromium trichloride (CrCl\u003csub\u003e3\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO) to 100 mL of anhydrous ethanol. Sonicate for 30 minutes to ensure thorough dispersion. Meanwhile, dissolve 3.2 mmol sodium hydroxide (NaOH) in 100 mL anhydrous ethanol. Under vigorous stirring, add this solution dropwise to the aforementioned metal salt dispersion. After the addition, the mixture was heated to 85\u0026deg;C under reflux for 4 h. Upon reaction completion, the precipitate was collected by centrifugation and washed several times with anhydrous ethanol until the supernatant was neutral. Finally, vacuum drying at 60℃ yielded cobalt-titanium hydroxide (CoTi-OH) or cobalt-chromium hydroxide (CoCr-OH), respectively.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3 Synthesis of cobalt-titanium boride (CoTiB)\u003c/h2\u003e \u003cp\u003eDisperse 40 mg of dried CoTi-OH powder in 40 mL of anhydrous ethanol. Under an ice-water bath and nitrogen atmosphere protection, rapidly add 50 mg of sodium borohydride (NaBH\u003csub\u003e4\u003c/sub\u003e). Subsequently, subject the mixture to ultrasonic treatment for 1 h to ensure complete reduction of the precursor by NaBH\u003csub\u003e4\u003c/sub\u003e. Following the reaction, the product was collected by centrifugation and washed alternately three times with anhydrous ethanol and deionized water to remove residual reactants and by-products. The final collected black precipitate was dried in a vacuum oven at 60\u0026deg;C to obtain the target product CoTiB.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e2.4 Synthesis of cobalt-chromium boride (CoCrB)\u003c/h2\u003e \u003cp\u003eThe synthesis procedure is identical to that for CoTiB, with the sole modification in step 2.3 being the replacement of the titanium source (TiCl\u003csub\u003e4\u003c/sub\u003e) with an equimolar amount of chromium source (CrCl\u003csub\u003e3\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO).\u003c/p\u003e \u003c/div\u003e"},{"header":"3 Results and discussion","content":"\u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003e3.1 Catalyst design\u003c/h2\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e presents the structural characterization and corresponding theoretical computational energy analysis results for the CoTiB and CoCrB catalysts. Figure\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea and \u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb present the X-ray diffraction (XRD) patterns for both catalysts, respectively. Under ice bath and nitrogen-protected conditions, the target material was successfully synthesized using NaBH\u003csub\u003e4\u003c/sub\u003e as a strong reducing agent and boron source. The XRD patterns exhibit distinct broadened diffraction peaks at approximately 12\u0026deg; and 36\u0026deg;, indicating significant amorphous characteristics in the synthesized material, consistent with reports employing similar organic precursors.\u003csup\u003e\u003cspan additionalcitationids=\"CR7\" citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u003c/sup\u003e Although faint diffraction signals attributable to the TiB₂ or CrB₂ (100) planes are observable near ~\u0026thinsp;34\u0026deg;, the intensity of the main diffraction peak corresponding to the (101) plane (~\u0026thinsp;46\u0026deg;) is notably low. This is mainly due to the low overall crystallinity of the material and the interaction between cobalt and boron ions and organic ligands. Nevertheless, comparison with XRD patterns of CoTiB, and CoCrB synthesized under identical conditions effectively reveals structural differences induced by heteronuclear metal ion doping.\u003c/p\u003e \u003cp\u003eTo elucidate the doping effects at the atomic scale, computational optimized structural models were constructed (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ec, d). These models demonstrate that the introduction of titanium or chromium atoms significantly alters the local coordination environment of the cobalt-boron framework, forming the anticipated heteronuclear diatomic configurations. The properties of the unpaired electrons, closely linked to catalytic activity, were investigated using electron paramagnetic resonance (EPR) spectroscopy (Figure \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e). EPR signal intensity and line shape exhibited distinct differences among the three catalysts, indicating variations in their unpaired electron concentration and local electronic environment. Among them, CoCrB displayed the strongest EPR signal, revealing the highest unpaired electron density. These electrons serve as active sites for the adsorption and conversion of LiPSs, preliminarily suggesting its potential for superior catalytic activity.\u003c/p\u003e \u003cp\u003eTo elucidate the mechanisms of the two catalysts in Li-S batteries, we calculated the Gibbs free energy changes for key steps of the SRR via density functional theory (DFT) (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ee). Compared to CoTiB, CoCrB exhibits a lower reaction energy barrier (Δ\u003cem\u003eG\u003c/em\u003e) during the conversion of LiS\u003csub\u003e6\u003c/sub\u003e to Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e4\u003c/sub\u003e, indicating superior SRR kinetics.\u003csup\u003e\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e,\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e\u003c/sup\u003e Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ef further compares the adsorption energies of different LiPSs (Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003ex\u003c/sub\u003e, x\u0026thinsp;=\u0026thinsp;1, 2, 4, 6, 8) on both surfaces. Results reveal that CoCrB exhibits stronger adsorption for all Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003ex\u003c/sub\u003e species, with notably more negative adsorption energies for Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e4\u003c/sub\u003e and Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e2\u003c/sub\u003e. This facilitates effective anchoring of LiPSs during cycling, suppresses their shuttling, and promotes subsequent conversion reactions. The aforementioned theoretical calculations demonstrate that chromium incorporation precisely modulates the electronic structure of the catalytic center, concurrently enhancing both LiPSs adsorption capacity and catalytic conversion activity. This provides a theoretical basis for the subsequent differences in electrochemical performance.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003e3.2 Differences in catalytic activity regulated by different ions\u003c/h2\u003e \u003cp\u003eTo evaluate the electrocatalytic activity of the catalysts, symmetric cells with Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e as the electrolyte were first assembled for cyclic voltammetry (CV) testing (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea, b). The CoB@S electrode exhibited the smallest peak area and highest oxidation peak potential in the CV curve, indicating slower reaction kinetics.\u003csup\u003e\u003cspan additionalcitationids=\"CR12\" citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u003c/sup\u003e In contrast, both CoTiB@S and CoCrB@S electrodes exhibited significantly enhanced peak currents, confirming that heteronuclear diatomic doping effectively enhances electron transfer capability. Notably, CoTiB@S exhibited the smallest potential difference (Δ\u003cem\u003eE\u003c/em\u003e\u003csub\u003e\u003cem\u003ep\u003c/em\u003e\u003c/sub\u003e) between its oxidation and reduction peaks, reflecting excellent reaction reversibility. Conversely, CoCrB@S required a higher overpotential to drive the reaction, yet its absolute peak current value was marginally higher, suggesting potentially distinct catalytic pathways.\u003c/p\u003e \u003cp\u003eFurther Tafel analysis (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec, d) provides deeper insights into the electrode process kinetics. CoTiB exhibits the highest peak potential, indicating optimal chemical/electrochemical stability (corrosion resistance) in the electrolyte; conversely, CoCrB demonstrates the highest peak current, signifying its strongest intrinsic catalytic activity towards the Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e redox reaction, capable of significantly lowering the reaction activation energy barrier. This indicates that CoTiB excels in structural stability and reaction reversibility, whereas CoCrB demonstrates superior intrinsic catalytic activity.\u003c/p\u003e \u003cp\u003eCV testing of the full cell (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ee) further corroborates these trends. The CoCrB-based cell exhibited the strongest current response at the first reduction peak, indicating the highest initial reaction intensity; conversely, the CoTiB-based cell displayed the smallest Δ\u003cem\u003eE\u003c/em\u003e\u003csub\u003e\u003cem\u003ep\u003c/em\u003e\u003c/sub\u003e, reaffirming its superior reaction reversibility.\u003csup\u003e\u003cspan additionalcitationids=\"CR15\" citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u003c/sup\u003e Based on this, it can be inferred that during long-term cycling, CoCrB may offer higher specific capacity due to its greater conversion efficiency, whereas CoTiB may demonstrate superior capacity retention owing to its lower polarization.\u003c/p\u003e \u003cp\u003eInitial electrochemical impedance spectroscopy (EIS) testing (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ef, conducted prior to cell activation) revealed that the CoCrB electrode exhibited the lowest charge transfer resistance (Rct, approximately 180 Ω), 25\u0026ndash;50% lower than other samples. This indicates faster interfacial charge transfer kinetics, laying the foundation for its superior rate performance. Furthermore, wettability of the catalyst surface was evaluated via contact angle measurements (Figure S2). CoCrB exhibited the smallest contact angle, indicating optimal electrolyte affinity.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003e3.3 Reaction kinetics and lithium ion transport behavior\u003c/h2\u003e \u003cp\u003eThe reaction kinetics and structural stability of the modified cathode were evaluated using constant-current intermittent titration (GITT) (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea). The CoCrB-based cell exhibited the longest total test duration (approximately 125 h), indicating more stable electrochemical behavior during stepwise charge-discharge cycles.\u003csup\u003e\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e,\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u003c/sup\u003e Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb\u0026ndash;d highlight the voltage response corresponding to the initial portion of the second discharge plateau (Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e decomposition step). Measurements of the activation overpotential (ΔV) for this step reveal values of 135.2 mV for CoCrB, markedly higher than those for CoB (66.1 mV) and CoTiB (45.6 mV). This increased polarization is not detrimental; rather, it indicates that CoCrB significantly accelerates this key rate-limiting step of the SRR, demonstrating its exceptional catalytic capability. Collectively, these results demonstrate that CoCrB not only facilitate es Li\u003csup\u003e+\u003c/sup\u003e diffusion but also efficiently catalyzes the conversion of Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e6\u003c/sub\u003e to Li\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e4\u003c/sub\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eTo quantitatively evaluate the Li\u003csup\u003e+\u003c/sup\u003e diffusion coefficient (\u003cem\u003eD\u003c/em\u003e\u003csub\u003e\u003cem\u003eLi⁺\u003c/em\u003e\u003c/sub\u003e), multi-scan-rate CV tests were conducted (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea, c, e). The linear relationship between the oxidation peak current and the square root of the scan rate for all samples (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb, d, f) confirmed diffusion-step control of the reaction. CoCrB exhibited the highest peak current at all scan rates and yielded the maximum slope value from Tafel equation fitting, corresponding to the highest calculated \u003cem\u003eD\u003c/em\u003e\u003csub\u003e\u003cem\u003eLi⁺\u003c/em\u003e\u003c/sub\u003e value. This quantitatively confirms CoCrB possesses optimal Li\u003csup\u003e+\u003c/sup\u003e transport kinetics, consistent with GITT analysis conclusions, collectively explaining its outstanding rate performance.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003e3.4 Electrochemical performance and mechanism validation in full cells\u003c/h2\u003e \u003cp\u003eMorphological analysis of the cycled lithium metal anode (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ea-c) provides direct evidence for suppressed shuttling effects. The anode paired with the CoB cathode exhibited a surface covered with dendrites, cracks, and inert deposits. In contrast, the anodes paired with CoTiB and CoCrB displayed significantly smoother and flatter surfaces, with the CoCrB group exhibiting the least surface damage. This demonstrates that the designed heteronuclear bimetallic catalyst effectively mitigated the shuttle effect by anchoring and transforming LiPSs, which substantially reduced corrosion on the lithium anode and led to a marked enhancement in battery cycle life.\u003c/p\u003e \u003cp\u003eThe long-term cycling performance of the full cell (at 2 C rate) is shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ed. The CoCrB based cell achieved the highest initial discharge capacity (850 mA h g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) due to its superior kinetics. Although capacity decay was slightly faster in the early cycling stage, the decay rate significantly decreased after approximately 300 cycles, ultimately surpassing the capacity retention of CoTiB after 500 cycles. This is because CoCrB has an efficient and continuous catalytic effect, overcoming the cumulative effect of LiPSs accumulation in the middle of the cycle. In contrast, the CoTiB demonstrated its stability advantage through a more gradual decay curve.\u003c/p\u003e \u003cp\u003eRate performance test (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ef) further highlights the dynamic advantages of CoCrB. Within the discharge rate range of 0.1℃ to 3℃, CoCrB always maintains the highest reversible capacity. Moreover, when recovering from 3 C to 1 C, it exhibited the highest capacity recovery rate, demonstrating robust structural integrity and rapid charge transport capability. The charge-discharge curve at 0.5 C (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ee) reveals that CoCrB not only enhances the capacity of both discharge plateaus, particularly increasing the capacity of the second plateau corresponding to the LiPSs-to-Li\u003csub\u003e2\u003c/sub\u003eS conversion by 40%, but also exhibits significantly red uced voltage polarization at the plateaus. This provides direct evidence of its potent SRR catalytic capability.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e"},{"header":"4 Conclusions","content":"\u003cp\u003eBased on an ion-regulation strategy, a series of cobalt boride catalysts were successfully designed and synthesized via a low-energy solution process using cobalt acetate as the precursor. By incorporating boron along with titanium or chromium, heteronuclear diatomic catalysts with high specific surface area and abundant active sites were constructed. Systematic investigation revealed distinct modulation effects of different metal ions (Ti\u003csup\u003e4+\u003c/sup\u003e and Cr\u003csup\u003e3+\u003c/sup\u003e) on the catalytic performance. Theoretical calculations combined with electrochemical analyses demonstrate that the introduction of Cr\u003csup\u003e3+\u003c/sup\u003e optimizes the electronic structure of the catalyst through pronounced orbital electron synergy with Co\u003csup\u003e2+\u003c/sup\u003e. As a result, CoCrB exhibits the lowest charge-transfer resistance, the highest efficiency for adsorbing and converting lithium polysulfides (LiPSs), and the most rapid Li\u003csup\u003e+\u003c/sup\u003e migration rate, thereby endowing the corresponding battery with the highest specific capacity, excellent rate performance, and outstanding long-term cycling stability. In contrast, the electron-deficient character of Ti\u003csup\u003e4+\u003c/sup\u003e primarily enhances the chemical stability and reaction reversibility of the material, enabling CoTiB to achieve an optimal balance between catalytic activity and structural integrity, which is reflected in its remarkable long-term cycling reversibility.\u003c/p\u003e \u003cp\u003eIn summary, the ion-regulation strategy yields a clear synergistic enhancement in cobalt-based catalysts: Ti\u003csup\u003e4+\u003c/sup\u003e reinforces the structural stability, whereas Cr\u003csup\u003e3+\u003c/sup\u003e significantly improves the reaction kinetics. This work elucidates the mechanism of performance enhancement driven by heteronuclear bimetallic regulation at the atomic scale and provides valuable theoretical insights as well as a material design framework for developing efficient and stable catalysts for lithium\u0026ndash;sulfur batteries through precise electronic structure engineering.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eDeclaration of Competing Interest\u003c/h2\u003e \u003cp\u003eThe authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.\u003c/p\u003e\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eQ. Liu: Conceived and designed the core experiments, conducted electrochemical performance tests of lithium-sulfur batteries, and drafted the initial manuscript.F. Wang: Performed material characterization (including XRD and SEM tests) and processed the corresponding data, assisted in optimizing the electrode preparation process.L. Song*: Proposed the research framework and theoretical direction, guided the DFT calculation work, revised and polished the manuscript, and provided financial support for the project.X. Li: Carried out the assembly of lithium-sulfur battery cells and cyclic stability tests, organized and analyzed the experimental data sets.Y. Xiang: Assisted in the theoretical simulation of the material electronic structure, provided technical support for the use of Vaspkit software, and participated in the discussion of research results.F. Chen*: Participated in the design of control experiments, verified the repeatability of key data, reviewed the manuscript for scientific rigor, and coordinated the overall research progress.All authors have read and approved the final version of the manuscript, and agree to the submission of this work to the journal.\u003c/p\u003e\u003ch2\u003eAcknowledgments\u003c/h2\u003e \u003cp\u003eThis work was supported by the Science and Technology Program of Inner Mongolia Autonomous Region (2025YFHH0167, 2023YFKL0019) and the Key Research and Development Program of Dongguan City (20241201300022).\u003c/p\u003e\u003ch2\u003eData Availability\u003c/h2\u003e\u003cp\u003eAll relevant data are within the manuscript and its supplementary materials.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eWang P, Mou H, Wang Y, Song N, Li X, Feng J, Xi B, Xiong S (2025) Niobium Phosphide-Induced Sulfur Cathode Interface with Fast Lithium-Ion Flux Enables Highly Stable Lithium\u0026ndash;Sulfur Catalytic Conversion. Angew Chem Int Ed 64(20):e202502255. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1002/anie.202502255\u003c/span\u003e\u003cspan address=\"10.1002/anie.202502255\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWang T, Wang F, Shi Z, Cui S, Zhang Z, Liu W, Jin Y (2024) Synergistic Effect of In2O3/NC-Co3O4 Interface on Enhancing the Redox Conversion of Polysulfides for High-Performance Li\u0026ndash;S Cathode Materials at Low Temperatures. ACS Appl Mater Interfaces 16(24):31158\u0026ndash;31170. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003e10.1021/acsami.4c04733\u003c/span\u003e\u003cspan address=\"10.1021/acsami.4c04733\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eXia S, Song J, Zhou Q, Liu L, Ye J, Wang T, Chen Y, Liu Y, Wu Y, van Ree T (2023) A Separator with Double Coatings of Li4Ti5O12 and Conductive Carbon for Li-S Battery of Good Electrochemical Performance. Adv Sci 10(22):2301386. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1002/advs.202301386\u003c/span\u003e\u003cspan address=\"10.1002/advs.202301386\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eXu J, An S, Song X, Cao Y, Wang N, Qiu X, Zhang Y, Chen J, Duan X, Huang J et al (2021) Towards High Performance Li\u0026ndash;S Batteries via Sulfonate-Rich COF-Modified Separator. Adv Mater 33(49):2105178. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1002/adma.202105178\u003c/span\u003e\u003cspan address=\"10.1002/adma.202105178\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eYang Q, Cai J, Li G, Gao R, Han Z, Han J, Liu D, Song L, Shi Z, Wang D et al (2024) Chlorine bridge bond-enabled binuclear copper complex for electrocatalyzing lithium\u0026ndash;sulfur reactions. Nat Commun 15(1):3231. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003e10.1038/s41467-024-47565-1\u003c/span\u003e\u003cspan address=\"10.1038/s41467-024-47565-1\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eChen P, Wang T, He D, Shi T, Chen M, Fang K, Lin H, Wang J, Wang C, Pang H (2023) Delocalized Isoelectronic Heterostructured FeCoOxSy Catalysts with Tunable Electron Density for Accelerated Sulfur Redox Kinetics in Li-S batteries. Angew Chem Int Ed 62(47):e202311693. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1002/anie.202311693\u003c/span\u003e\u003cspan address=\"10.1002/anie.202311693\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLi F, Yuan H, Wang Y, Xue Z, He M, Wang J, Wu F, Huang M, Xiang Y, Hu A et al (2025) Tailoring Li-Accelerated Motif Enables Lithium Stabilization and Polysulfide Conversion for Long-Cycling Li\u0026ndash;S Batteries. \u003cem\u003eAdvanced Functional Materials n/a\u003c/em\u003e (\u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003en/a\u003c/span\u003e\u003cspan address=\"http://n/a\" targettype=\"URL\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e), e11078. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1002/adfm.202511078\u003c/span\u003e\u003cspan address=\"10.1002/adfm.202511078\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLiu S, Zhang J, Yang J, Gao Y, Wang Y, Geng L, Mao W, Guo Y, Wang H, Li J et al (2025) Decelerating and Accelerating Sulfur Reduction Reaction via P-OV-In2O3 Enables High-Performance Li-S Batteries. Small 21(4):2407865. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1002/smll.202407865\u003c/span\u003e\u003cspan address=\"10.1002/smll.202407865\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZhang H, Zhang M, Liu R, He T, Xiang L, Wu X, Piao Z, Jia Y, Zhang C, Li H et al (2024) Fe3O4-doped mesoporous carbon cathode with a plumber\u0026rsquo;s nightmare structure for high-performance Li-S batteries. Nat Commun 15(1):5451. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003e10.1038/s41467-024-49826-5\u003c/span\u003e\u003cspan address=\"10.1038/s41467-024-49826-5\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZhang W, Chen M, Luo Y, He Y, Liu S, Ye Y, Wang M, Chen Y, Zhu K, Shu H et al (2024) Utilizing 2D layered structure Cu-g-C3N4 electrocatalyst for optimizing polysulfide conversion in wide-temperature Li-S batteries. Chem Eng J 486:150411. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.cej.2024.150411\u003c/span\u003e\u003cspan address=\"10.1016/j.cej.2024.150411\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJiao X, Hu J, Zuo Y, Qi J, Yan W, Zhang J (2024) Self-recovery catalysts of ZnIn2S4@In2O3 heterostructures with multiple catalytic centers for cascade catalysis in lithium\u0026ndash;sulfur battery. Nano Energy 119:109078. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.nanoen.2023.109078\u003c/span\u003e\u003cspan address=\"10.1016/j.nanoen.2023.109078\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJin W, Guo Y, Gan T, Shen Z, Zhu X, Zhang P, Zhao Y (2025) Cooperation of Multifunctional Redox Mediator and Separator Modification to Enhance Li-S Batteries Performance under Low Electrolyte/Sulfur Ratios. Angew Chem Int Ed 64(8):e202420544. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1002/anie.202420544\u003c/span\u003e\u003cspan address=\"10.1002/anie.202420544\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKong Y, Wang L, Mamoor M, Wang B, Qu G, Jing Z, Pang Y, Wang F, Yang X, Wang D et al (2024) Co/Mon Invigorated Bilateral Kinetics Modulation for Advanced Lithium\u0026ndash;Sulfur Batteries. Adv Mater 36(13):2310143. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1002/adma.202310143\u003c/span\u003e\u003cspan address=\"10.1002/adma.202310143\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHe J, Bhargav A, Yaghoobnejad Asl H, Chen Y, Manthiram A (2020) 1T\u0026prime;-ReS2 Nanosheets In Situ Grown on Carbon Nanotubes as a Highly Efficient Polysulfide Electrocatalyst for Stable Li\u0026ndash;S Batteries. Adv Energy Mater 10(23):2001017. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1002/aenm.202001017\u003c/span\u003e\u003cspan address=\"10.1002/aenm.202001017\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLi H, Meng R, Ye C, Tadich A, Hua W, Gu Q, Johannessen B, Chen X, Davey K, Qiao S-Z (2024) Developing high-power Li||S batteries via transition metal/carbon nanocomposite electrocatalyst engineering. Nat Nanotechnol 19(6):792\u0026ndash;799. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003e10.1038/s41565-024-01614-4\u003c/span\u003e\u003cspan address=\"10.1038/s41565-024-01614-4\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLi J, Li W, Tian Y, Wang C (2025) Integrated design of polysulfide shuttling and lithium dendrite suppressing framework: In2O3-In2S3 embedded carbon cloth for lithium-sulfur full batteries. Chem Eng J 509:161241. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.cej.2025.161241\u003c/span\u003e\u003cspan address=\"10.1016/j.cej.2025.161241\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLi Y, Zuo Y, Li X, Zhang Y, Ma C, Cheng X, Wang J, Wang J, Lin H, Ling L (2024) Electron delocalization-enhanced sulfur reduction kinetics on an MXene-derived heterostructured electrocatalyst. Nano Res 17(8):7153\u0026ndash;7162. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003e10.1007/s12274-024-6682-6\u003c/span\u003e\u003cspan address=\"10.1007/s12274-024-6682-6\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLian J, Guo W, Fu Y (2021) Isomeric Organodithiol Additives for Improving Interfacial Chemistry in Rechargeable Li\u0026ndash;S Batteries. J Am Chem Soc 143(29):11063\u0026ndash;11071. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003e10.1021/jacs.1c04222\u003c/span\u003e\u003cspan address=\"10.1021/jacs.1c04222\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"ionics","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"","sideBox":" Learn more about [Ionics](https://www.springer.com/journal/11581) ","snPcode":"11581","submissionUrl":"https://mc.manuscriptcentral.com/ionics","title":"Ionics","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Lithium-sulfur batteries, cobalt-based catalysts, crystal plane engineering, ion synergy","lastPublishedDoi":"10.21203/rs.3.rs-8625349/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8625349/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThis study successfully designed and synthesized a series of cobalt-based catalysts (CoB, CoTiB, and CoCrB) via an ionic modulation strategy, systematically investigating the influence of different metal ions on the catalytic performance of lithium\u0026ndash;sulfur batteries and the underlying mechanisms. A low-energy solution-chemical method under alkaline conditions was employed to introduce B, Ti, and Cr elements, using branched-chain cobalt acetate as the cobalt source to construct amorphous/microcrystalline boride materials with high specific surface area and abundant active sites. Structural characterization and theoretical calculations reveal that the introduction of Cr effectively modulates the electronic structure of the material, enhancing its adsorption and catalytic conversion capability toward polysulfides. Electrochemical tests demonstrate that CoCrB exhibits superior reaction kinetics, including low charge-transfer resistance, high polysulfide conversion efficiency, and rapid lithium-ion migration, which is primarily attributed to the orbital-electron synergy between Cr\u003csup\u003e3+\u003c/sup\u003e and Co\u003csup\u003e2+\u003c/sup\u003e. In contrast, CoTiB achieves a better balance between catalytic activity and structural stability, showing excellent reaction reversibility and cycling stability. Long-term cycling and rate performance tests further confirm that CoCrB maintains high capacity retention after 500 cycles at 2 C and delivers favorable rate capability across various current densities. This work clarifies the synergistic enhancement mechanism of heteronuclear diatomic regulation on cobalt-based catalysts, providing new insights and an experimental basis for the design of efficient and stable Li\u0026ndash;S battery catalysts through electronic structure modulation.\u003c/p\u003e","manuscriptTitle":"Heteronuclear Binary-Atom-Controlled Cobalt-Based Catalyst for Lithium-Sulfur Batteries","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-01-30 09:11:47","doi":"10.21203/rs.3.rs-8625349/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2026-02-07T11:57:06+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-02-06T06:09:11+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-02-04T02:46:53+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"143251539391500163435765807516385940853","date":"2026-01-30T01:14:20+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-01-28T10:04:54+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"334498253401028186782072142717551450345","date":"2026-01-28T03:39:22+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"310629396821924665035052735891791747549","date":"2026-01-28T02:58:40+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2026-01-27T22:27:49+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2026-01-27T02:36:15+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2026-01-27T02:34:59+00:00","index":"","fulltext":""},{"type":"submitted","content":"Ionics","date":"2026-01-17T10:29:25+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"ionics","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"","sideBox":" Learn more about [Ionics](https://www.springer.com/journal/11581) ","snPcode":"11581","submissionUrl":"https://mc.manuscriptcentral.com/ionics","title":"Ionics","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"a7010412-49aa-4d7d-b9bc-c926cc8b960b","owner":[],"postedDate":"January 30th, 2026","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[],"tags":[],"updatedAt":"2026-04-09T16:09:48+00:00","versionOfRecord":[],"versionCreatedAt":"2026-01-30 09:11:47","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-8625349","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-8625349","identity":"rs-8625349","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}