Lithium–sulfur battery

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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 during discharge; batteries often packaged for 3V

The lithium–sulfur battery (Li–S battery) is a rechargeable battery, notable for its high energy density.[1] By virtue of the low atomic weight of lithium and moderate weight of sulfur, Li–S batteries are relatively light; about the density of water. They were demonstrated on the longest and highest-altitude solar-powered airplane 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 energy densities 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, yet are not commercially available (as of early 2014).[4]

Chemistry[edit]

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

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

Li
2
S → Li
2
S
2
Li
2
S
3
Li
2
S
4
Li
2
S
6
Li
2
S
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 lacks electroconductivity. Sulfur alone is 5×10−30 S cm−1 at 25 °C.[8][clarification needed] 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][10]

One problem with the lithium–sulfur design is that when the sulfur in the cathode absorbs lithium, the Li2S has nearly double the volume of the original sulfur. This causes large mechanical stresses on 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 sulfur surface.[11]

One of the primary shortfalls of most Li–S cells is unwanted reactions with the electrolytes. While S and Li
2
S
are relatively insoluble in most electrolytes, many intermediate polysulfides are not. Dissolving Li
2
S
n
into electrolytes causes irreversible loss of active sulfur.[12] Use of highly reactive lithium as negative electrode causes dissociation of most of the commonly used ether type electrolytes. Use of protective layer in the anode surface has been studied to improve cell safety, i.e. use of Teflon coating showed improvement in the electrolyte stability,[13] LIPON, Li3N also exhibited promising performance.

Safety[edit]

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.[14]

Research[edit]

Research
Anode Cathode Date Source Specific Capacity after cycling Notes
Polyethylene glycol coated, pitted mesoporous carbon 17 May 2009 University of Waterloo[15] 1,110 mAh/g after 20 cycles at a current rate of 168 mA g-1[15] 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[16][17] 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[18][19] 1300 mAh/g after 400 cycles (at 1C) Microwave processing of materials and Laser-printing of electrodes.
Silicon carbon Sulfur 2013 Fraunhofer Institute for Material and Beam Technology IWS]][20] ? after 1,400 cycles
Copolymerized sulfur 2013 University of Arizona[21][22] 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
2013 Stanford University[23][24] 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)[25]

Solid lithium polysulfidophosphate electrolyte. Half the voltage of typical LIBs. Remaining issues include low electrolyte ionic conductivity and brittleness in the ceramic structure.[26][27]
Lithium Sulfur-graphene oxide nanocomposite with styrene-butadiene-carboxymethyl cellulose copolymer binder 2013 Lawrence Berkeley National Laboratory[28] 700 mA·h/g at 1500 cycles (0.05C discharge)

400 mA·h/g at 1500 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)
Graphite-coated Sulfur February 2014 Pacific Northwest National Laboratory 400 cycles Coating prevents polysulfides from destroying the anode.[29]

References[edit]

  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 January 2010. 
  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.; Ahn, J.H.; Ahn, H.J. (November 16–20). "Effects of carbon coating on the electrochemical properties of sulfur cathode for lithium/sulfur cell". Elsevier Science Bv. pp. 548–552. doi:10.1016/j.jpowsour.2008.02.053.  Check date values in: |date= (help)
  10. ^ Choi, Y. J.; Chung, Y. D.; Baek, C. Y.; Kim, K. W.; Ahn, H. J.; Ahn, J. H. (2008). "Effects of carbon coating on the electrochemical properties of sulfur cathode for lithium/sulfur cell". Journal of Power Sources 184 (2): 548. doi:10.1016/j.jpowsour.2008.02.053.  edit
  11. ^ Brian Dodson, "New lithium/sulfur battery doubles energy density of lithium-ion", gizmag, 1 December 2013
  12. ^ Jeong, S.S.; Lim, Y.; ect. (June 18–23). "Electrochemical properties of lithium sulfur cells using PEO polymer electrolytes prepared under three different mixing conditions". Journal of Power Sources (Elsevier Science Bv) 174: 745–750. doi:10.1016/j.jpowsour.2007.06.108.  Check date values in: |date= (help)
  13. ^ 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
  14. ^ Akridge, J.R. (October 2001) "Lithium Sulfur Rechargeable Battery Safety" Battery Power Products & Technology
  15. ^ a b 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
  16. ^ 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. 
  17. ^ Keller, Sarah Jane (October 4, 2011). "Sulfur in hollow nanofibers overcomes challenges of lithium-ion battery design". News (Stanford, CA, USA: Stanford University). Retrieved February 18, 2012. 
  18. ^ Rosenberg, Sarah; Hintennach (1 April 2014). "Laser-printed lithium-sulphur micro-electrodes for Li/S batteries". Russian Journal of Electrochemistry: 327–335. 
  19. ^ Vandenberg, Aurelius; Hintennach (1 April 2014). "A novel design approach for lithium-sulphur batteries". Russian Journal of Electrochemistry: 317–326. 
  20. ^ "Researchers increase lifespan of lithium-sulfur batteries". Gizmag.com. Retrieved 2013-12-04. 
  21. ^ 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.  edit
  22. ^ Radical approach to turn sulfur into polymers
  23. ^ SLAC National Accelerator Laboratory (6 Posts) (2013-01-08). "World-Record Battery Performance Achieved With Egg-Like Nanostructures". CleanTechnica. Retrieved 2013-06-11. 
  24. ^ 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.  edit
  25. ^ http://onlinelibrary.wiley.com/doi/10.1002/anie.201300680/abstract
  26. ^ 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.  edit
  27. ^ "All-solid lithium-sulfur battery stores four times the energy of lithium-ions". Gizmag.com. Retrieved 2013-06-13. 
  28. ^ "New lithium/sulfur battery doubles energy density of lithium-ion". Gizmag.com. Retrieved 2013-12-04. 
  29. ^ Lavars, Nick (February 20, 2014). "Hybrid anode quadruples the lifespan of lithium-sulfur batteries". Retrieved October 2014. 

External links[edit]