Abstract
Lithium-ion batteries (LIBs) are widely used in applications ranging from electric vehicles to wearable devices. Before the invention of secondary LIBs, the primary lithium-thionyl chloride (Li-SOCl2) battery was developed in the 1970s using SOCl2 as the catholyte, lithium metal as the anode and amorphous carbon as the cathode1,2,3,4,5,6,7. This battery discharges by lithium oxidation and catholyte reduction to sulfur, sulfur dioxide and lithium chloride, is well known for its high energy density and is widely used in real-world applications; however, it has not been made rechargeable since its invention8,9,10,11,12,13. Here we show that with a highly microporous carbon positive electrode, a starting electrolyte composed of aluminium chloride in SOCl2 with fluoride-based additives, and either sodium or lithium as the negative electrode, we can produce a rechargeable Na/Cl2 or Li/Cl2 battery operating via redox between mainly Cl2/Cl− in the micropores of carbon and Na/Na+ or Li/Li+ redox on the sodium or lithium metal. The reversible Cl2/NaCl or Cl2/LiCl redox in the microporous carbon affords rechargeability at the positive electrode side and the thin alkali-fluoride-doped alkali-chloride solid electrolyte interface stabilizes the negative electrode, both are critical to secondary alkali-metal/Cl2 batteries.
This is a preview of subscription content, access via your institution
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 51 print issues and online access
$199.00 per year
only $3.90 per issue
Buy this article
Purchase on Springer Link
Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
Data availability
The datasets generated during and/or analysed during the current study are available from the corresponding author on reasonable request. Source data are provided with this paper.
References
Venkatasetty, H. V. & Saathoff, D. J. Properties of LiAlCl4–SOCl2 solutions for Li/SOCl2 battery. J. Electrochem. Soc. 128, 773–777 (1981).
Tsaur, K. C. & Pollard, R. Mathematical modeling of the lithium, thionyl chloride static cell: II. Acid electrolyte. J. Electrochem. Soc. 131, 984–990 (1984).
Istone, W. K. & Brodd, R. J. The mechanisms of thionyl chloride reduction at solid electrodes. J. Electrochem. Soc. 131, 2467–2470 (1984).
Gangadharan, R., Namboodiri, P. N. N., Prasad, K. V. & Viswanathan, R. The lithium-thionyl chloride battery—a review. J. Power Sources 4, 1–9 (1979).
Madou, M. J. & Szpak, S. Investigation of SOCl2 reduction by cyclic voltammetry and ac impedance measurements. J. Electrochem. Soc.131, 2471–2475 (1984).
Bedfer, Y., Corset, J., Dhamelincourt, M. C., Wallart, F. & Barbier, P. Raman spectroscopic studies of the structure of electrolytes used in the Li/SOCl2 battery. J. Power Sources 9, 267–272 (1983).
Carter, B. J. et al. Mechanistic studies related to the safety of Li/SOCl2 cells. J. Electrochem. Soc. 525–528 (1985).
Marinčić, N. Materials balance in primary batteries. II. Lithium inorganic batteries at high discharge rates. J. Appl. Electrochem. 6, 51–58 (1976).
Wang, D. et al. The effects of pore size on electrical performance in lithium-thionyl chloride batteries. Front. Mater. 6, 245 (2019).
Klinedinst, K. A. & Domeniconi, M. J. High rate discharge characteristics of Li/SOCl2 cells. J. Electrochem. Soc.127, 539–544 (1980).
Abraham, K. M. & Mank, R. M. Some chemistry in the Li/SOCl2 cell. J. Electrochem. Soc. 127, 2091–2096 (1980).
Spotnitz, R. M., Yeduvaka, G. S., Nagasubramanian, G. & Jungst, R. Modeling self-discharge of Li/SOCl2 cells. J. Power Sources 163, 578–583 (2006).
Morrison, M. M. & Marincic, N. Studies in lithium oxyhalide cells for downhole instrumentation use of lithium tetrachlorogallate electrolyte in Li/SOCl2 cells. J. Power Sources 45, 343–352 (1993).
Sun, H. et al. A safe and non-flammable sodium metal battery based on an ionic liquid electrolyte. Nature Commun. 10, 3302 (2019).
Sun, H. et al. High-safety and high-energy-density lithium metal batteries in a novel ionic-liquid electrolyte. Adv. Mater. 32, 2001741 (2020).
Zhu, G. et al. Rechargeable aluminum batteries: effects of cations in ionic liquid electrolytes. RSC Adv. 9, 11322–11330 (2019).
Lin, M.-C. et al. An ultrafast rechargeable aluminium-ion battery. Nature 520, 324–328 (2015).
Angell, M. et al. High Coulombic efficiency aluminum-ion battery using an AlCl3-urea ionic liquid analog electrolyte. Proc. Natl Acad. Sci. USA 114, 834–839 (2017).
Pan, C.-J. et al. An operando X-ray diffraction study of chloroaluminate anion-graphite intercalation in aluminum batteries. Proc. Natl Acad. Sci. USA 115, 5670–5675 (2018).
Di Lecce, D., Carbone, L., Gancitano, V. & Hassoun, J. Rechargeable lithium battery using non-flammable electrolyte based on tetraethylene glycol dimethyl ether and olivine cathodes. J. Power Sources 334, 146–153 (2016).
Agostini, M., Xiong, S., Matic, A. & Hassoun, J. Polysulfide-containing glyme-based electrolytes for lithium sulfur battery. Chem. Mater. 27, 4604–4611 (2015).
Cai, K., Song, M.-K., Cairns, E. J. & Zhang, Y. Nanostructured Li2S–C composites as cathode material for high-energy lithium/sulfur batteries. Nano Lett. 12, 6474–6479 (2012).
Angell, M., Zhu, G., Lin, M.-C., Rong, Y. & Dai, H. Ionic liquid analogs of AlCl3 with urea derivatives as electrolytes for aluminum batteries. Adv. Funct. Mater. 30, 1901928 (2020).
Barpanda, P., Oyama, G., Nishimura, S.-i., Chung, S.-C. & Yamada, A. A 3.8-V earth-abundant sodium battery electrode. Nat. Commun. 5, 4358 (2014).
Zhu, C., Kopold, P., van Aken, P. A., Maier, J. & Yu, Y. High power–high energy sodium battery based on threefold interpenetrating network. Adv. Mater. 28, 2409–2416 (2016).
Liu, J. et al. Extension of the Stöber method to the preparation of monodisperse resorcinol–formaldehyde resin polymer and carbon spheres. Angew. Chem. Int. Ed. 50, 5947–5951 (2011).
Tsai, C.-Y., Tai, H.-C., Su, C.-A., Chiang, L.-M. & Li, Y.-Y. Activated microporous carbon nanospheres for use in supercapacitors. ACS Appl. Nano Mater. 3, 10380–10388 (2020).
Gross, S. & Society, E. Proc. Symposium on Battery Design and Optimization (Battery Division, Electrochemical Society, 1979).
Abraham, K. M., Mank, R. M. & Holleck, G. L. Investigations of the Safety of Li/SOCl2 Batteries (1979).
Dey, A. N. Lithium anode film and organic and inorganic electrolyte batteries. Thin Solid Films 43, 131–171 (1977).
Mogensen, M. B. & Hennesø, E. Properties and structure of the LiCl-films on lithium anodes in liquid cathodes. Acta Chim. Slov. 63, 519–534 (2016).
Alvarado, J. et al. Bisalt ether electrolytes: a pathway towards lithium metal batteries with Ni-rich cathodes. Energy Environ. Sci. 12, 780–794 (2019).
Eshetu, G. G. et al. Ultrahigh performance all solid-state lithium sulfur batteries: salt anion’s chemistry-induced anomalous synergistic effect. J. Am. Chem. Soc. 140, 9921–9933 (2018).
Evans, T. I., Nguyen, T. V. & White, R. E. A mathematical model of a lithium/thionyl chloride primary cell. J. Electrochem. Soc. 136, 328–339 (1989).
Gilman, S. The reduction of sulfuryl chloride at teflon-bonded carbon cathodes. J. Electrochem. Soc. 127, 1427–1433 (1980).
Xu, X. et al. A room-temperature sodium–sulfur battery with high capacity and stable cycling performance. Nat. Commun. 9, 3870 (2018).
Lee, M. et al. High-performance sodium–organic battery by realizing four-sodium storage in disodium rhodizonate. Nat. Energy 2, 861–868 (2017).
Hu, L. et al. Dually decorated Na3V2(PO4)2F3 by carbon and 3D graphene as cathode material for sodium-ion batteries with high energy and power densities. ChemElectroChem 7, 3975–3983 (2020).
Hwang, J.-Y., Kim, J., Yu, T.-Y. & Sun, Y.-K. A new P2-type layered oxide cathode with extremely high energy density for sodium-ion batteries. Adv. Energy Mater. 9, 1803346 (2019).
Liu, X., Ma, W., Lei, X., Zhang, S. & Ding, Y. Rechargeable Na–SO2 battery with ethylenediamine additive in ether-based electrolyte. Adv. Funct. Mater. 30, 2002120 (2020).
Jeong, G. et al. A room-temperature sodium rechargeable battery using an SO2-based nonflammable inorganic liquid catholyte. Sci. Rep. 5, 12827–12827 (2015).
Acknowledgements
This work was supported by a Stanford Bits and Watts Fellowship. Part of this work was performed at the Stanford Nano Shared Facilities (SNSF) supported by the National Science Foundation under award ECCS-2026822.
Author information
Authors and Affiliations
Contributions
G.Z. and H.D. conceived the main idea of the project. G.Z. and X.T. performed the experiments and contributed equally to this work. G.Z. performed the mass spectrometry measurement of species in the battery. H.-C.T., C.-L.H. and Y.-Y.L. prepared the aCNS raw material. H.-C.T. performed the characterizations of aCNS (SEM, TEM, XRD and so on). J.L., C.-S.K., W.-H.H., S.-K.J. and B.-J.H. performed characterizations of electrodes in battery. G.Z. and H.S. performed the LED demo of the Na/Cl2 battery. G.Z., P.L. and M.A. performed X-ray photoelectron spectroscopy measurements. H.C. and M.-C.L. prepared the chemicals used as electrolyte additives and thinner glass fibre separators (60 μm). G.Z. and H.D. prepared the manuscript. All authors participated in experimental data/results analysis and discussion.
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing interests.
Additional information
Peer review information Nature thanks the K. M. Abraham, Jiulin Wang, Jianshe Zhao and the anonymous reviewer(s) for their contribution to the peer review of this work.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Extended data figures and tables
Extended Data Fig. 1 SEM images of aCNS at different battery stages.
a, SEM images of aCNS through the first discharge (from 950 mAh g−1, to 2,100 mAh g−1, and then full discharge) of the Na/Cl2 battery and atomic percentage of C, Na and Cl at these stages measured by SEM/energy dispersive X-ray spectroscopy (EDS) mapping (right bar graph). As discharge continued, more and more NaCl was formed on the aCNS and the discharge stopped when NaCl passivated the aCNS. Some of the NaCl formed was very large in size (tens of micrometres). b, SEM images of aCNS when the Na/Cl2 battery was re-charged to different capacities (375 mAh g−1, 600 mAh g−1, 900 mAh g−1) and the atomic percentage of C, Na and Cl at these stages measured by SEM/EDS mapping (right bar graph). As charging increased, more and more NaCl was removed from the aCNS, exposing the nanospheres underlying the NaCl coating. The active sites of the battery (the sites at which oxidation reactions happened) were in the gaps in the NaCl microcrystal coating that remained intact during battery operations. c, SEM images of aCNS when the Na/Cl2 battery was charged to 900 mAh g−1 then discharged to different capacities (375 mAh g−1, 600 mAh g−1, 900 mAh g−1) and atomic percentage of C, Na and Cl at these stages measured by SEM/EDS mapping (right bar graph). As discharge increased, more and more NaCl formed on the aCNS. When the battery was fully discharged, all the nanospheres were covered and passivated by the NaCl. To take these SEM images, batteries stopping at the designated states were opened inside an argon-filled glovebox and the electrodes were first dried under vacuum, then taken out of the glovebox and transferred into an SEM instrument for the measurements. See Methods for details.
Extended Data Fig. 2 EIS of Na/Cl2 battery with acidic 4 M AlCl3 in SOCl2 + 2 wt% NaFSI + 2 wt% NaTFSI as the electrolyte through its first discharge and re-charging and first discharge curve of Na/Cl2 battery using neutral 4 M AlCl3 + 4 M NaCl in SOCl2 as the electrolyte.
a, Impedance measurements at six points along the curve of first discharge of the battery when acidic 4 M AlCl3 in SOCl2 + 2 wt% NaFSI + 2 wt% NaTFSI was used as the electrolyte. b, Charging curve of the Na/Cl2 battery when the charging capacity was 500 mAh g−1. Each spike along the curve was a point at which battery charging was stopped for EIS measurements and then allowed to continue to charge. c, Impedance measurements of the Na/Cl2 battery at different charging capacities tracing the charging curve in b. As charging started, the impedance of the battery rapidly decreased due to removal of NaCl in the coating layer on the positive electrode. d, First discharge curve of Na/Cl2 battery when neutral 4 M AlCl3 + 4 M NaCl in SOCl2 was used as the electrolyte. Only one discharge plateau was observed in neutral electrolyte case.
Extended Data Fig. 3 Cycling performance of Na/Cl2 battery at different capacities.
a, Cycling performance of a Na/Cl2 battery at 500 mAh g−1 (150 mA g−1). The battery was kept at open circuit in a discharged state for two weeks. We found that simply aging the battery in the discharged state for days could improve the battery’s cycle life, probably due to the slower formation of a more uniform SEI layer on the electrode. The loading of aCNS was about 4.5 mg cm−2. b, Na/Cl2 battery cycling at 1,200 mAh g−1. The electrolyte was 4 M AlCl3 in SOCl2 + 1 wt% NaFSI + 1 wt% NaTFSI. c, Na/Cl2 battery cycling at 1,200 mAh g−1. The electrolyte was 4 M AlCl3 in SOCl2 + 2 wt% NaFSI + 2 wt% NaTFSI. Both of the batteries in b, c were first cycling at 500 mAh g−1 (150 mA g−1) for 15 cycles and the cycling capacity was gradually increased to 1,200 mAh g−1 with 150 mA g−1 and 100 mA g−1 currents. The loading of both batteries was about 2.6 mg cm−2. d, Cycling performance of Na/Cl2 battery as the charging current increased from 0.3 C (150 mA g−1) up to 3.9 C (1,950 mA/g−1) with 0.3 C (150 mA g−1) increased for every five cycles. The discharge current was kept at 0.3 C (150 mA g−1). The loading of aCNS was about 3 mg cm2. e, Cycling performance of Na/Cl2 battery at 1,200 mAh g−1 with charging current increased to 0.5 C (600 mA g−1) and discharging current kept at 0.08 C (100 mA g−1). Cycles 1–3: 0.0625 C (75 mA g−1), cycles 4 and 5: 0.08 C (100 mA g−1) for battery stabilization. The loading of the battery was about 3 mg cm−2. f, Typical charge–discharge curves of Na/Cl2 battery at 1,200 mAh g−1. Black curve: 0.5 C (600 mA g−1) charging, 0.08 C (100 mA g−1) discharging. Red curve: 0.08 C (100 mA g−1) charging and discharging. Only a slight increase in overpotential (about 182 mV at 0.08 C versus about 298 mV at 0.5 C) was observed. The loading of the battery was about 3 mg cm−2.
Extended Data Fig. 4 SEM images of aCNS after charging to 1,860 mAh g−1.
Left image: the nanospheres in aCNS were readily observed as NaCl depositing on the surface of aCNS were oxidized. Middle and right images: NaCl microcrystals that were either loosely deposited on top of the nanospheres clusters (not inside the nanospheres, middle image) or deposited in the gaps between the aCNS clusters (right image) were not oxidizable, and could not contribute to the battery’s rechargeable capacity. Middle and right images have different magnifications.
Extended Data Fig. 5 Na/Cl2 battery performances when 2 wt% FEC and 2 wt% NaPF6 were used as the electrolyte additives and XPS of Na metal immersing in electrolytes with different additives (2 wt% NaFSI + 2 wt% NaTFSI, 2 wt% NaPF6, and 2 wt% FEC) and after battery cycling.
a, Na/Cl2 battery cycling performance at 500 mAh g−1, 150 mA g−1 when 4 M AlCl3 in SOCl2 + 2 wt% FEC was used as the electrolyte. The battery behaved poorly and died after cycle 9. b, Na/Cl2 battery cycling performance at 1,200 mAh g−1, 100 mA g−1 when 4 M AlCl3 in SOCl2 + 2 wt% NaPF6 was used as the electrolyte. The battery showed worse cycling performance than when 2 wt% NaFSI + 2 wt% NaTFSI was used as the electrolyte additive. c, Atomic percentage of different elements, calculated from XPS survey spectrum, on the Na metal after immersing in 4 M AlCl3 in SOCl2 with different additives (2 wt% NaFSI + 2 wt% NaTFSI, 2 wt% NaPF6 and 2 wt% FEC). d, Cl 2p spectrum of Na metal after immersing in 4 M AlCl3 in SOCl2 with different additives (2 wt% NaPF6 and 2 wt% FEC). e, F 1s spectrum of Na metal after immersing in 4 M AlCl3 in SOCl2 with different additives (2 wt% NaPF6 and 2 wt% FEC). f, S 2p spectrum of Na metal after immersing in 4 M AlCl3 in SOCl2 with different additives (2 wt% NaPF6 and 2 wt% FEC). g, Atomic percentage of different elements, calculated from XPS survey spectrum, on the Na electrode after cycling in batteries using 4 M AlCl3 in SOCl2 with different additives (2 wt% NaFSI + 2 wt% NaTFSI, 2 wt% NaPF6 and 2 wt% FEC) as the electrolyte. h, F 1s spectrum of Na electrode after cycling in batteries using 4 M AlCl3 in SOCl2 with different additives (2 wt% NaPF6 and 2 wt% FEC) as the electrolyte. The batteries using 2 wt% NaFSI + 2 wt% NaTFSI and 2 wt% NaPF6 as the electrolyte additives in g, h were stopped at cycle 21. The battery using 2 wt% FEC as the electrolyte additive was stopped at cycle 9 when the battery died.
Extended Data Fig. 6 Characterizations of Na anode immersed and cycled in 4 M AlCl3 in SOCl2 with and without 2 wt% NaFSI/NaTFSI, and charge–discharge curves of the normal battery versus decayed battery.
a, Atomic percentage of different elements on the Na metal when immersed in 4 M AlCl3 in SOCl2 with and without 2 wt% NaFSI/NaTFSI as additives. b, F 1s spectrum of Na immersed in 4 M AlCl3 in SOCl2 with/without additives. c, S 2p spectrum of Na immersed in 4 M AlCl3 in SOCl2 with/without additives. d, Cl 2p spectrum of Na immersed in 4 M AlCl3 in SOCl2 with/without additives. e, Atomic percentage of different elements on the Na metal after cycling for 21 cycles in Na/Cl2 battery when 4 M AlCl3 in SOCl2 with and without 2 wt% NaFSI/NaTFSI as additives were used as the electrolyte. f, F 1s spectrum of Na cycled in Na/Cl2 battery when 4 M AlCl3 in SOCl2 with/without additives were used as the electrolyte. g, SEM images of Na anode from actual Na/Cl2 battery in charged state (top images) and when lost cycling capability (bottom images). Note that in the case of battery without fluoride additive, the Na anode surface was coated by more densely packed NaCl particles, eventually leading to the loss of re-chargeability. h, Charge–discharge curves of the battery at normal state and after the battery started to decay.
Extended Data Fig. 7 SEM images of Na electrodes after cycling in batteries using 4 M AlCl3 in SOCl2 with different additives (2 wt% NaFSI + 2 wt% NaTFSI, 2 wt% NaPF6, and 2 wt% FEC) as the electrolytes.
Top row: SEM images of Na electrode after cycling in battery using 4 M AlCl3 in SOCl2 + 2 wt% NaFSI + 2 wt% NaTFSI as the electrolyte. The SEI layer contained loosely packed, square-shaped NaCl crystals and abundant voids still present in the SEI (indicated by circles). Middle row: SEM images of Na electrode after cycling in battery using 4 M AlCl3 in SOCl2 + 2 wt% NaPF6 as the electrolyte. The SEI layer contained closely packed, square-shaped NaCl crystals that were grown on top of a uniform layer of NaCl crystals. Such morphology made ions penetrations much less efficient. Bottom row: SEM images of Na electrode after cycling in battery using 4 M AlCl3 in SOCl2 + 2 wt% FEC as the electrolyte. The SEI layer was made of very large NaCl crystals (tens of micrometres in size) packed together. Such morphology made ions penetrations only possible via the small cracks between these crystals and the least efficient. The batteries using 2 wt% NaFSI + 2 wt% NaTFSI and 2 wt% NaPF6 as the electrolyte additives were both stopped at cycle 21. The battery using 2 wt% FEC as the electrolyte additive was stopped at cycle 9 when the battery died.
Extended Data Fig. 8 Na/Cl2 battery cycling performance using less electrolyte (4 M AlCl3 in SOCl2 + 2 wt% NaFSI + 2 wt% NaTFSI) and thinner separators down to 60 μm.
a, Na/Cl2 battery cycling performance at 500 mAh g−1 using 100 μl electrolyte with one layer of QR-100 separator. The loading of the battery was about 5 mg cm−2. b, Na/Cl2 battery cycling performance at 500 mAh g−1 using 75 μl electrolyte with one layer of QR-100 separator. The loading of the battery was about 5 mg cm−2. c, Na/Cl2 battery cycling performance at 500 mAh g−1 using 50 μl electrolyte with one layer of 60-μm glass fibre separator. The loading of the battery was about 5 mg cm−2. d, Charge–discharge curve of Na/Cl2 battery at 500 mAh g−1 using 50 μl electrolyte. e, Na/Cl2 battery cycling performance at 1,200 mAh g−1 using 100 μl electrolyte with one layer of QR-100 separator. The loading of the battery was about 3.6 mg cm−2. f, Charge–discharge curve of Na/Cl2 battery at 1,200 mAh g−1 using 100 μl electrolyte.
Extended Data Fig. 9 Li/Cl2 battery cycling at 500 mAh g−1 with 4 M AlCl3 in SOCl2 + 2 wt% LiFSI + 2 wt% LiTFSI as the electrolyte.
a, Cycling performance of Li/Cl2 battery at 500 mAh g−1 with 150 mA g−1 and 100 mA g−1 currents (the first five cycles were cycling at 150 mA g−1 and starting from cycle 6 the current was 100 mA g−1). The loading of the battery was about 4.5 mg cm−2. b, Typical charge–discharge curve of Li/Cl2 battery at 500 mAh g−1 cycling capacity. The loading of the battery was about 4.5 mg cm−2.
Supplementary information
Supplementary Information
This file contains Supplementary Discussion, Supplementary Figures and Tables, and additional references. The Supplementary Discussion includes discussions related to the main manuscript such as details on mass spectrometry experiments, battery working mechanisms, and effects of different electrolyte additives. The 14 display items – Supplementary Figures 1-12 and Supplementary Tables 1-2 – show data relating to battery performances, battery characterizations, and mass spectrometry experiments.
Rights and permissions
About this article
Cite this article
Zhu, G., Tian, X., Tai, HC. et al. Rechargeable Na/Cl2 and Li/Cl2 batteries. Nature 596, 525–530 (2021). https://doi.org/10.1038/s41586-021-03757-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41586-021-03757-z
This article is cited by
-
A rechargeable Ca/Cl2 battery
Nature Communications (2024)
-
Post lithium-sulfur battery era: challenges and opportunities towards practical application
Science China Chemistry (2024)
-
CO2-mediated organocatalytic chlorine evolution under industrial conditions
Nature (2023)
-
Electrolyte design principles for developing quasi-solid-state rechargeable halide-ion batteries
Nature Communications (2023)
-
Development of rechargeable high-energy hybrid zinc-iodine aqueous batteries exploiting reversible chlorine-based redox reaction
Nature Communications (2023)
Comments
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.