Lithium–sulfur battery

Lithium–sulfur battery
Specific energy 500 W·h/kg demonstrated
Energy density 350 W·h/L
Charge/discharge efficiency C/5 nominal
Cycle durability disputed
Nominal cell voltage cell voltage varies nonlinearly in the range 2.5–1.7 V during discharge; batteries often packaged for 3 V

The lithium–sulfur battery (Li–S battery) is a type of Lithium-ion rechargeable battery, notable for its high energy density.[1] The low atomic weight of lithium and moderate weight of sulfur means that Li–S batteries are relatively light (about the density of water). They were used on the longest and highest-altitude solar-powered aeroplane flight in August 2008.[2]

Lithium–sulfur batteries may succeed lithium-ion cells because of their higher energy density and reduced cost from the use of sulfur.[3] Currently the best Li–S batteries offer specific energies on the order of 500 W·h/kg, significantly better than most lithium-ion batteries which are in the 150 to 200 range. Li–S batteries with up to 1,500 charge and discharge cycles have been demonstrated. As of early 2014, none were commercially available.[4]

Chemistry

Chemical processes in the Li–S cell include lithium dissolution from the anode surface (and incorporation into alkali metal polysulfide salts) during discharge, and reverse lithium plating to the anode while charging.[5] This contrasts with conventional lithium-ion cells, where the lithium ions are intercalated in the anode and cathodes. Each sulfur atom can host two lithium ions. Typically, lithium-ion batteries accommodate only 0.5–0.7 lithium ions per host atom.[6] Consequently, Li-S allows for a much higher lithium storage density. Polysulfides are reduced on the cathode surface in sequence while the cell is discharging:

S
8 → Li
2S
8 → Li
2S
6 → Li
2S
4 → Li
2S
3

Across a porous diffusion separator, sulfur polymers form at the cathode as the cell charges:

Li
2S → Li
2S
2 → Li
2S
3 → Li
2S
4 → Li
2S
6 → Li
2S
8 → S
8

These reactions are analogous to those in the sodium–sulfur battery.

Most use a carbon/sulfur cathode and a lithium anode.[7] Sulfur is very cheap, but has practically no electroconductivity, 5×10−30 S cm−1 at 25 °C.[8] A carbon coating provides the missing electroconductivity. Carbon nanofibers provide an effective electron conduction path and structural integrity, at the disadvantage of higher cost.[9]

One problem with the lithium–sulfur design is that when the sulfur in the cathode absorbs lithium, volume expansion of the LixS compositions happens, and predicted volume expansion of Li2S is nearly 80% of the volume of the original sulfur.[10] This causes large mechanical stresses on the cathode, which is a major cause of rapid degradation. This process reduces the contact between the carbon and the sulfur, and prevents the flow of lithium ions to the carbon surface.[11]

Mechanical properties of the lithiated sulfur compounds are strongly contingent on the lithium content, and with increasing lithium content, the strength of lithiated sulfur compounds improves, although this increment is not linear with lithiation.[12]

One of the primary shortfalls of most Li–S cells is unwanted reactions with the electrolytes. While S and Li
2S are relatively insoluble in most electrolytes, many intermediate polysulfides are not. Dissolving Li
2S
n into electrolytes causes irreversible loss of active sulfur.[13] Use of highly reactive lithium as a negative electrode causes dissociation of most of the commonly used other type electrolytes. Use of a protective layer in the anode surface has been studied to improve cell safety, i.e., using Teflon coating showed improvement in the electrolyte stability,[14] LIPON, Li3N also exhibited promising performance.

Safety

Because of the high potential energy density and the nonlinear discharge and charging response of the cell, a microcontroller and other safety circuitry is sometimes used along with voltage regulators to manage cell operation and prevent rapid discharge.[15]

Research

Research
Anode Cathode Date Source Specific Capacity after cycling Notes
Polyethylene glycol coated, pitted mesoporous carbon 17 May 2009 University of Waterloo[16] 1,110 mAh/g after 20 cycles at a current rate of 168 mA g-1[16] Minimal degradation during charge cycling. To retain polysulfides in the cathode, the surface was functionalized to repel (hydrophobic) polysulfides. In a test using a glyme solvent, a traditional sulfur cathode lost 96% of its sulfur over 30 cycles, while the experimental cathode lost only 25%.
Silicon nanowire Sulfur-coated, disordered carbon nanotubes 2011 Stanford University[17][18] 730mAh/g after 150 cycles (at 0.5C) An electrolyte additive boosted the faraday efficiency from 85% to over 99%.
Silicon nanowire/carbon Sulfur-coated, disordered carbon nanotubes made from carbohydrates 2013 CGS[19][20] 1,300 mAh/g after 400 cycles (at 1C) Microwave processing of materials and laser-printing of electrodes.
Silicon carbon Sulfur 2013Fraunhofer Institute for Material and Beam Technology IWS[21] ? after 1,400 cycles
Copolymerized sulfur 2013University of Arizona[22][23] 823 mAh/g at 100 cycles Uses "inverse vulcanization" on mostly sulfur with a small amount of 1,3-diisopropenylbenzene (DIB) additive
Porous TiO
2-encapsulated sulfur nanoparticles 		2013Stanford University[24][25] 721 mAh/g at 1,000 cycles (0.5C) shell protects the sulfur-lithium intermediate from electrolyte solvent. Each cathode particle is 800 nanometers in diameter. Faraday efficiency of 98.4%.
Sulfur June 2013 Oak Ridge National Laboratory 1200 mA·h/g at 300 cycles at 60 °C (0.1C)

800 mA·h/g at 300 cycles at 60 °C (1C)[26]

 Solid lithium polysulfidophosphate electrolyte. Half the voltage of typical LIBs. Remaining issues include low electrolyte ionic conductivity and brittleness in the ceramic structure.[27][28]
Lithium Sulfur-graphene oxide nanocomposite with styrene-butadiene-carboxymethyl cellulose copolymer binder 2013 Lawrence Berkeley National Laboratory[29] 700 mA·h/g at 1,500 cycles (0.05C discharge)

400 mA·h/g at 1,500 cycles (0.5C charge/ 1C discharge)

 Voltage between about 1.7 and 2.5 volts, depending on charge state. Lithium bis(trifluoromethanesulfonyl)imide) dissolved in a mixture of nmethyl-(n-butyl) pyrrolidinium bis(trifluoromethanesulfonyl)-imide (PYR14TFSI), 1,3-dioxolane (DOL), dimethoxyethane (DME) with 1 M lithium bis-(trifluoromethylsulfonyl)imide (LiTFSI), and lithium nitrate (LiNO
3). High porosity polypropylene separator. Specific energy is 500 Wh/kg (initial) and 250 Wh/kg at 1,500 cycles (C=1.0)
Lithiated graphite Sulfur February 2014 Pacific Northwest National Laboratory 400 cycles Coating prevents polysulfides from destroying the anode.[30]
Lithiated graphene Sulfur/Lithium-sulfide passivation layer 2014 OXIS Energy[31][32] 240 mA·h/g (1000 cycles)

25 A·h/cell

 Passivation layer prevents sulfur loss
Lithium sulfur batteries Carbon nanotube/Sulfur 2014 Tsinghua University [33] 15.1 mA·h cm −2 at a sulfur loading of 17.3 mgS cm−2 A free-standing CNT–S paper electrode with a high areal sulfur-loading was fabricated, in which short MWCNTs served as the short-range electrical conductive network and super-long CNTs acted as both the long-range conductive network and intercrossed binders.
Glass-coated sulfur with mildly reduced graphene oxide for structural support 2015 University of California, Riverside[34] 700 mA h g−1 (50 cycles)[35] Glass coating prevents lithium polysulfides from permanently migrating to an electrode

Commercialization

So far very few companies, if any have been able to commercialize the technology on an industrial scale as of October 2015. Some companies however, such as Tucson, Arizona based Sion Power have partnered with others such as Airbus Defense and Space in order to test their lithium sulfur battery technology. Airbus Defense and Space successfully launched their prototype High Altitude Pseudo-Satellite (HAPS) aircraft which was powered by solar energy during the day and by such lithium sulfur batteries at night in real life conditions during an 11-day flight. The batteries used in the test flight utilized Sion Power's high specific energy Li-S cells which provide 350 Wh/kg[36] Sion claims to be in the process of volume manufacturing with availability by end of 2017.[37]

Other companies, such as British firm OXIS Energy, have also developed prototype lithium sulfur batteries which are currently operating in small scale, commercial, test applications. As of June 2015, OXIS Energy planned to sell its energy storage batteries from 2016.[38][39] Together with Imperial College London and Cranfield University, OXIS Energy has published equivalent-circuit-network models for its cells.[40]

Sony, which also commercialized the first lithium-ion battery, plans to introduce lithium–sulfur batteries to the market in 2020.[41]

References

  1. ↑ Zhang, Sheng S. "Liquid electrolyte lithium/sulfur battery: Fundamental chemistry, problems, and solutions" Journal of Power Sources 2013, vol. 231, 153-162. doi:10.1016/j.jpowsour.2012.12.102
  2. ↑ Amos, J. (24 August 2008) "Solar plane makes record flight" BBC News
  3. ↑ Arumugam Manthiram, Yongzhu Fu, Yu-Sheng Su "Challenges and Prospects of Lithium–Sulfur Batteries" Acc. Chem. Res., 2013, volume 46, pp 1125–1134. doi:10.1021/ar300179v
  4. ↑ "New lithium/sulfur battery doubles energy density of lithium-ion". Gizmag.com. Retrieved 2014-02-18.
  5. ↑ Tudron, F.B., Akridge, J.R., and Puglisi, V.J. (2004) "Lithium-Sulfur Rechargeable Batteries: Characteristics, State of Development, and Applicability to Powering Portable Electronics" (Tucson, AZ: Sion Power)
  6. ↑ Bullis, Kevin (May 22, 2009). "Revisiting Lithium-Sulfur Batteries". Technology Review. Retrieved August 12, 2016.
  7. ↑ Choi, Y.J.; Kim, K.W. (2008). "Improvement of cycle property of sulfur electrode for lithium/sulfur battery". Journal of Alloys and Compounds. Elsevier Science Sa. 449: 313–316. doi:10.1016/j.jallcom.2006.02.098.
  8. ↑ J.A. Dean, ed. (1985). Lange's Handbook of Chemistry (third ed.). New York: McGraw-Hill. pp. 3–5.
  9. ↑ Choi, Y. J.; Chung, Y. D.; Baek, C. Y.; Kim, K. W.; Ahn, J. H. (March 4, 2008). "Effects of carbon coating on the electrochemical properties of sulfur cathode for lithium/sulfur cell". J. Power Sources. Elsevier. 184 (2): 548–552. doi:10.1016/j.jpowsour.2008.02.053. Retrieved August 12, 2016.
  10. ↑ Islam, Md Mahbubul; Ostadhossein, Alireza; Borodin, Oleg; Yeates, A. Todd; Tipton, William W.; Hennig, Richard G.; Kumar, Nitin; Duin, Adri C. T. van. "ReaxFF molecular dynamics simulations on lithiated sulfur cathode materials". Phys. Chem. Chem. Phys. 17 (5): 3383–3393. doi:10.1039/c4cp04532g.
  11. ↑ Brian Dodson, "New lithium/sulfur battery doubles energy density of lithium-ion", gizmag, 1 December 2013
  12. ↑ Islam et al.,ReaxFF molecular dynamics simulations on lithiated sulfur cathode materials, Phys.Chem.Chem.Phys.,2015, 17, 3383, DOI:10.1039/C4CP04532G
  13. ↑ Jeong, S. S.; Lim, Y.; Choi, Y. T.; Kim, K. W.; Ahn, H. J.; Cho, K. K. (2006). "Electrochemical properties of lithium sulfur cells using PEO polymer electrolytes prepared under three different mixing conditions". J. Power Sources. Elsevier. 174 (2): 745–750. doi:10.1016/j.jpowsour.2007.06.108.
  14. ↑ Islam, Md Mahbubul, Vyacheslav S. Bryantsev, and Adri CT van Duin. "ReaxFF Reactive Force Field Simulations on the Influence of Teflon on Electrolyte Decomposition during Li/SWCNT Anode Discharge in Lithium-Sulfur Batteries." Journal of The Electrochemical Society 161.8 (2014): E3009-E3014. doi:10.1149/2.005408jes
  15. ↑ Akridge, J.R. (October 2001) "Lithium Sulfur Rechargeable Battery Safety" Battery Power Products & Technology
  16. 1 2 Xiulei Ji, Kyu Tae Lee, and Linda F. Nazar. (17 May 2009)"A highly ordered nanostructured carbon-sulphur cathode for lithium-sulphur batteries." Nature Materials
  17. ↑ Guangyuan, Zheng; Yuan Yang; Judy J. Cha; Seung Sae Hong; Yi Cui (14 September 2011). "Hollow Carbon Nanofiber-Encapsulated Sulfur Cathodes for High Specific Capacity Rechargeable Lithium Batteries". Nano Letters: 4462–4467. Bibcode:2011NanoL..11.4462Z. doi:10.1021/nl2027684.
  18. ↑ Keller, Sarah Jane (October 4, 2011). "Sulfur in hollow nanofibers overcomes challenges of lithium-ion battery design". Stanford News. Stanford University. Retrieved February 18, 2012.
  19. ↑ Rosenberg, Sarah; Hintennach (1 April 2014). "Laser-printed lithium-sulphur micro-electrodes for Li/S batteries". Russian Journal of Electrochemistry: 327–335.
  20. ↑ Vandenberg, Aurelius; Hintennach (1 April 2014). "A novel design approach for lithium-sulphur batteries". Russian Journal of Electrochemistry: 317–326.
  21. ↑ "Researchers increase lifespan of lithium-sulfur batteries". Gizmag.com. Retrieved 2013-12-04.
  22. ↑ Chung, W. J.; Griebel, J. J.; Kim, E. T.; Yoon, H.; Simmonds, A. G.; Ji, H. J.; Dirlam, P. T.; Glass, R. S.; Wie, J. J.; Nguyen, N. A.; Guralnick, B. W.; Park, J.; Somogyi, Á. D.; Theato, P.; MacKay, M. E.; Sung, Y. E.; Char, K.; Pyun, J. (2013). "The use of elemental sulfur as an alternative feedstock for polymeric materials". Nature Chemistry. 5 (6): 518–524. doi:10.1038/nchem.1624. PMID 23695634.
  23. ↑ Radical approach to turn sulfur into polymers
  24. ↑ SLAC National Accelerator Laboratory (6 Posts) (2013-01-08). "World-Record Battery Performance Achieved With Egg-Like Nanostructures". CleanTechnica. Retrieved 2013-06-11.
  25. ↑ Wei Seh, Z.; Li, W.; Cha, J. J.; Zheng, G.; Yang, Y.; McDowell, M. T.; Hsu, P. C.; Cui, Y. (2013). "Sulphur–TiO2 yolk–shell nanoarchitecture with internal void space for long-cycle lithium–sulphur batteries". Nature Communications. 4: 1331. doi:10.1038/ncomms2327. PMID 23299881.
  26. ↑ "Lithium Polysulfidophosphates: A Family of Lithium-Conducting Sulfur-Rich Compounds for Lithium–Sulfur Batteries - Lin - 2013 - Angewandte Chemie International Edition - Wiley Online Library". wiley.com.
  27. ↑ Lin, Z.; Liu, Z.; Fu, W.; Dudney, N. J.; Liang, C. (2013). "Lithium Polysulfidophosphates: A Family of Lithium-Conducting Sulfur-Rich Compounds for Lithium-Sulfur Batteries". Angewandte Chemie International Edition: n/a. doi:10.1002/anie.201300680.
  28. ↑ "All-solid lithium-sulfur battery stores four times the energy of lithium-ions". Gizmag.com. Retrieved 2013-06-13.
  29. ↑ "New lithium/sulfur battery doubles energy density of lithium-ion". Gizmag.com. Retrieved 2013-12-04.
  30. ↑ Lavars, Nick (February 20, 2014). "Hybrid anode quadruples the lifespan of lithium-sulfur batteries". Retrieved August 22, 2016.
  31. ↑ "A whiff of brimstone". Economist. January 3, 2015. Retrieved August 22, 2016.
  32. ↑ "Li-S battery company OXIS Energy reports 300 Wh/kg and 25 Ah cell, predicting 33 Ah by mid-2015, 500 Wh/kg by end of 2018". Green Car Congress. November 12, 2014. Retrieved August 22, 2016.
  33. ↑ Yuan, Zhe; Peng, Hong-Jie; Huang, Jia-Qi; Liu, Xin-Yan; Wang, Dai-Wei; Cheng, Xin-Bing; Zhang, Qiang (2014-10-01). "Hierarchical Free-Standing Carbon-Nanotube Paper Electrodes with Ultrahigh Sulfur-Loading for Lithium–Sulfur Batteries". Advanced Functional Materials. 24 (39): 6105–6112. doi:10.1002/adfm.201401501. ISSN 1616-3028.
  34. ↑ Nealon, Sean (2015-03-03). "Glass coating for improved battery performance". R&D. Retrieved August 22, 2016.
  35. ↑ Nealon, Sean (March 2, 2015). "Glass coating improves battery performance". phys.org. Retrieved August 22, 2016.
  36. ↑ Kopera, J (September 2014) "Sion Power's Lithium-Sulfur Batteries Power High Altitude Pseudo-Satellite Flight" Sion Power Company Press Release
  37. ↑ "Sion Power Delivers Next Generation Battery Performance Through Patented Licerion® Technology". Retrieved 4 October 2016.
  38. ↑ "Anesco and OXIS to Release Lithium Sulfur Battery Storage by 2016" (press release). OXIS Energy. July 14, 2015. Retrieved August 22, 2016.
  39. ↑ "OXIS battery powers driverless vehicle for the UK Government's Smart City Gateway programme" (press release). OXIS Energy. February 22, 2015. Retrieved August 22, 2016.
  40. ↑ Propp, K.; Marinescu, M.; Auger, D. J.; et al. (August 12, 2016). "Multi-temperature state-dependent equivalent circuit discharge model for lithium-sulfur batteries". J. Power Sources. Elsevier. 328: 289–299. doi:10.1016/j.jpowsour.2016.07.090. Retrieved August 12, 2016.
  41. ↑ "Sony battery to offer 40% longer phone life". Nikkei Asian Review. December 17, 2015. Retrieved August 22, 2016.

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