High-surface-area, nanostructured carbon is widely used for encapsulating sulfur and improving the cyclic stability of Li–S batteries, but the high carbon content and low packing density limit the specific energy that can be achieved. Here we report an approach that does not rely on sulfur encapsulation. We used a low-surface-area, open carbon fibre architecture to control the nucleation and growth of the sulfur species by manipulating the carbon surface chemistry and the solvent properties, such as donor number and Li+ diffusivity. Our approach facilitates the formation of large open spheres and prevents the production of an undesired insulating sulfur-containing film on the carbon surface. This mechanism leads to ~100% sulfur utilization, almost no capacity fading, over 99% coulombic efficiency and high energy density (1,835 Wh kg−1 and 2,317 Wh l−1). This finding offers an alternative approach for designing high-energy and low-cost Li–S batteries through controlling sulfur reaction on low-surface-area carbon.
Subscribe to Journal
Get full journal access for 1 year
only $4.92 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
Bruce, P. G., Freunberger, S. A., Hardwick, L. J. & Tarascon, J.-M. Li–O2 and Li–S batteries with high energy storage. Nat. Mater. 11, 19–29 (2012).
Ji, X., Lee, K. T. & Nazar, L. F. A highly ordered nanostructured carbon–sulphur cathode for lithium–sulphur batteries. Nat. Mater. 8, 500–506 (2009).
Manthiram, A., Chung, S.-H. & Zu, C. Lithium–sulfur batteries: Progress and prospects. Adv. Mater. 27, 1980–2006 (2015).
Eroglu, D., Zavadil, K. R. & Gallagher, K. G. Critical link between materials chemistry and cell-level design for high energy density and low cost lithium–sulfur transportation battery. J. Electrochem. Soc. 162, A982–A990 (2015).
Hagen, M. et al. Lithium–sulfur cells: The gap between the state-of-the-art and the requirements for high energy battery cells. Adv. Energy Mater. 5, 1401986 (2015).
Lv, D. et al. High energy density lithium–sulfur batteries: Challenges of thick sulfur cathodes. Adv. Energy Mater. 5, 1402290 (2015).
Mikhaylik, Y. V. & Akridge, J. R. Polysulfide shuttle study in the Li/S battery system. J. Electrochem. Soc. 151, A1969–A1976 (2004).
Aurbach, D. et al. On the surface chemical aspects of very high energy density, rechargeable Li–sulfur batteries. J. Electrochem. Soc. 156, A694–A702 (2009).
Yang, Y. et al. High-capacity micrometer-sized Li2S particles as cathode materials for advanced rechargeable lithium-ion batteries. J. Am. Chem. Soc. 134, 15387–15394 (2012).
Meini, S., Elazari, R., Rosenman, A., Garsuch, A. & Aurbach, D. The use of redox mediators for enhancing utilization of Li2S cathodes for advanced Li–S battery systems. J. Phys. Chem. Lett. 5, 915–918 (2014).
Schuster, J. et al. Spherical ordered mesoporous carbon nanoparticles with high porosity for lithium–sulfur batteries. Angew. Chem. Int. Edn 51, 3591–3595 (2012).
Zhang, C., Wu, H. B., Yuan, C., Guo, Z. & Lou, X. W. Confining sulfur in double-shelled hollow carbon spheres for lithium–sulfur batteries. Angew. Chem. 124, 9730–9733 (2012).
Cao, Y. et al. Sandwich-type functionalized graphene sheet-sulfur nanocomposite for rechargeable lithium batteries. Phys. Chem. Chem. Phys. 13, 7660–7665 (2011).
Zhou, G. et al. A graphene–pure-sulfur sandwich structure for ultrafast, long-life lithium–sulfur batteries. Adv. Mater. 26, 625–631 (2014).
Zheng, G., Yang, Y., Cha, J. J., Hong, S. S. & Cui, Y. Hollow Carbon nanofiber-encapsulated sulfur cathodes for high specific capacity rechargeable lithium batteries. Nano Lett. 11, 4462–4467 (2011).
Zheng, G. et al. Amphiphilic surface modification of hollow carbon nanofibers for improved cycle life of lithium sulfur batteries. Nano Lett. 13, 1265–1270 (2013).
Wei Seh, Z. et al. Sulphur–TiO2 yolk–shell nanoarchitecture with internal void space for long-cycle lithium–sulphur batteries. Nat. Commun. 4, 1331 (2013).
Pang, Q., Kundu, D., Cuisinier, M. & Nazar, L. F. Surface-enhanced redox chemistry of polysulphides on a metallic and polar host for lithium-sulphur batteries. Nat. Commun. 5, 4759 (2014).
Xiao, L. et al. A soft approach to encapsulate sulfur: polyaniline nanotubes for lithium-sulfur batteries with long cycle life. Adv. Mater. 24, 1176–1181 (2012).
Chen, H. et al. Rational design of cathode structure for high rate performance lithium–sulfur batteries. Nano Lett. 15, 5443–5448 (2015).
Song, J., Yu, Z., Gordin, M. L. & Wang, D. Advanced sulfur cathode enabled by highly crumpled nitrogen-doped graphene sheets for high-energy-density lithium–sulfur batteries. Nano Lett. 16, 864–870 (2016).
Fan, Q., Liu, W., Weng, Z., Sun, Y. & Wang, H. Ternary hybrid material for high-performance lithium–sulfur battery. J. Am. Chem. Soc. 137, 12946–12953 (2015).
Sun, Q. et al. An aligned and laminated nanostructured carbon hybrid cathode for high-performance lithium–sulfur batteries. Angew. Chem. Int. Edn 54, 10539–10544 (2015).
Manthiram, A., Fu, Y. & Su, Y.-S. Challenges and prospects of lithium–sulfur batteries. Acc. Chem. Res. 46, 1125–1134 (2012).
Yao, H. et al. Improved lithium–sulfur batteries with a conductive coating on the separator to prevent the accumulation of inactive S-related species at the cathode–separator interface. Energy Environ. Sci. 7, 3381–3390 (2014).
Yao, H. et al. Improving lithium–sulphur batteries through spatial control of sulphur species deposition on a hybrid electrode surface. Nat. Commun. 5, 3943 (2014).
Xu, R. et al. Insight into sulfur reactions in Li–S batteries. ACS Appl. Mat. Interfaces 6, 21938–21945 (2014).
Fan, F. Y. et al. Polysulfide flow batteries enabled by percolating nanoscale conductor networks. Nano Lett. 14, 2210–2218 (2014).
Zheng, J. et al. Controlled nucleation and growth process of Li2S2/Li2S in lithium-sulfur batteries. J. Electrochem. Soc. 160, A1992–A1996 (2013).
Aetukuri, N. B. et al. Solvating additives drive solution-mediated electrochemistry and enhance toroid growth in non-aqueous Li–O2 batteries. Nat. Chem. 7, 50–56 (2015).
Gao, X., Chen, Y., Johnson, L. & Bruce, P. G. Promoting solution phase discharge in Li–O2 batteries containing weakly solvating electrolyte solutions. Nat. Mater. 15, 882–888 (2016).
Fan, F. Y., Carter, W. C. & Chiang, Y.-M. Mechanism and kinetics of Li2S precipitation in lithium–sulfur batteries. Adv. Mater. 27, 5203–5209 (2015).
Liu, T. et al. Cycling Li–O2 batteries via LiOH formation and decomposition. Science 350, 530–533 (2015).
Cañas, N. A. et al. Investigations of lithium–sulfur batteries using electrochemical impedance spectroscopy. Electrochim. Acta 97, 42–51 (2013).
Deng, Z. et al. Electrochemical impedance spectroscopy study of a lithium/sulfur battery: modeling and analysis of capacity fading. J. Electrochem. Soc. 160, A553–A558 (2013).
Fan, F. Y. & Chiang, Y.-M. Electrodeposition kinetics in Li-S batteries: Effects of low electrolyte/sulfur ratios and deposition surface composition. J. Electrochem. Soc. 164, A917–A922 (2017).
Estevez, L. et al. Tunable oxygen functional groups as electrocatalysts on graphite felt surfaces for all-vanadium flow batteries. ChemSusChem 9, 1455–1461 (2016).
Pang, Q., Liang, X., Kwok, C. Y. & Nazar, L. F. Advances in lithium–sulfur batteries based on multifunctional cathodes and electrolytes. Nat. Energy 1, 16132 (2016).
Cataldo, F. A revision of the Gutmann donor numbers of a series of phosphoramides including TEPA. Eur. Chem. Bull. 4, 92–97 (2015).
Thanh, N. T. K., Maclean, N. & Mahiddine, S. Mechanisms of nucleation and growth of nanoparticles in solution. Chem. Rev. 114, 7610–7630 (2014).
Johnson, L. et al. The role of LiO2 solubility in O2 reduction in aprotic solvents and its consequences for Li–O2 batteries. Nat. Chem. 6, 1091–1099 (2014).
Bijani, S. et al. Study of the Nucleation and growth mechanisms in the electrodeposition of micro- and nanostructured Cu2O thin films. J. Phys. Chem. C 115, 21373–21382 (2011).
Wei, C., Wu, G., Yang, S. & Liu, Q. Electrochemical deposition of layered copper thin films based on the diffusion limited aggregation. Sci. Rep. 6, 34779 (2016).
Abraham, M. J., van der Spoel, D., Lindahl, E., Hess, B. & GROMACS Development Team. GROMACS User Manual version 5.1.2. GROMACS User Manual v.5.1.2 (2016); www.gromacs.org.
Martínez, L., Andrade, R., Birgin, E. G. & Martínez, J. M. Packmol: A package for building initial configurations for molecular dynamics simulations. J. Comput. Chem. 30, 2157–2164 (2009).
Bussi, G., Zykova-Timan, T. & Parrinello, M. Isothermal-isobaric molecular dynamics using stochastic velocity rescaling. J. Chem. Phys. 130, 074101 (2009).
Takeuchi, M. et al. Ion–ion interactions of LiPF6 and LiBF4 in propylene carbonate solutions. J. Mol. Liq. 148, 99–108 (2009).
Rajput, N. N. et al. Elucidating the solvation structure and dynamics of lithium polysulfides resulting from competitive salt and solvent interactions. Chem. Mater. 29, 3375–3379 (2017).
Frisch, M. et al. Gaussian 09 (Gaussian Inc., Wallingford, CT, 2009).
Rajput, N. N., Qu, X., Sa, N., Burrell, A. K. & Persson, K. A. The coupling between stability and ion pair formation in magnesium electrolytes from first-principles quantum mechanics and classical molecular dynamics. J. Am. Chem. Soc. 137, 3411–3420 (2015).
This work was supported as part of the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the US Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES). The SEM images, XPS and NMR measurements were performed at the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the US Department of Energy’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the Department of Energy under Contract DE-AC05-76RLO1830.
The authors declare no competing financial interests.
Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
About this article
Cite this article
Pan, H., Chen, J., Cao, R. et al. Non-encapsulation approach for high-performance Li–S batteries through controlled nucleation and growth. Nat Energy 2, 813–820 (2017). https://doi.org/10.1038/s41560-017-0005-z
Journal of Energy Chemistry (2021)
Energy Storage Materials (2020)
Amorphous TiO2 nanofilm interface coating on mesoporous carbon as efficient sulfur host for Lithium–Sulfur batteries
Electrochimica Acta (2020)
Journal of Materials Chemistry A (2020)