Lithium–silicon battery

Lithium–silicon batteries are a lithium-ion battery technology that employ a silicon anode and lithium ions as the charge carriers.[1] Silicon has a much larger energy density (25 times as many lithium ions[2]) than graphite. Silicon's large volume change when lithium is inserted is the main obstacle to commercializing this device.[3] Commercial battery anodes may have small amounts of silicon, boosting their performance slightly. The amounts are closely held trade secrets, limited as of 2018 to at most 10% of the anode.[2]

History

The first laboratory experiments with lithium-silicon batteries took place in the late 1990s.[4]

Silicon-graphite composite electrodes

Test sample production of batches of batteries using a silicon-graphite composite electrode were started by Amprius in 2014.[5] The same company claims to have sold several hundred thousand of these batteries as of 2014.[6] In 2016, Stanford University researchers presented a method of encapsulating silicon microparticles in a graphene shell, which confines fractured particles and also acts as a stable solid electrolyte interface layer. These microparticles reached an energy density of 3,300 mAh/g.[7]

Also in 2014, a company called Enevate presented a battery using an unknown monolithic silicon-composite anode with a low cell resistance.[8] These batteries leave 25% of the capacity unused, most likely to reduce degradation.[9] For this technology it was named an Innovation Award Honoree in three categories at 2016's Consumer Electronics Show (CES).[10] Shortly thereafter CES 2016, Sonim Technologies (a company selling rugged mobile phones) would use Enevate's lithium-silicon batteries in its products.[11]

In 2015, Tesla founder Elon Musk claimed that silicon in Model S batteries increased the car’s range by 6%.[2]

As of 2018, products by startups Sila Nanotechnologies, Angstron Materials, Enovix, Enevate, and others were undergoing tests by the battery manufacturers, car companies, and consumer-electronics companies.[2]

China-based Amperex is one of Sila's investors, Sila clients include BMW and Amperex Technology, battery supplier to companies including Apple and Samsung. BMW plans to incorporate Sila technology by 2023 and increase battery-pack capacity by 10-15%.[2]

Enevate produces anodes for vehicle manufacturers and claims to increase electric vehicle range by 30% versus conventional batteries.[2]

Enovix, whose investors include Intel and Qualcomm, is working on anodes that are almost pure silicon. The company claims its batteries would provide 30% to 50% more energy than conventional batteries.[2]

Specific capacity

Specific capacity and volume change for some anode materials (given in their lithiated state).[3][12][13]
Anode material Specific capacity (mAh/g) Volume change
Li 3862 -
LiC
6		 372 10%
Li
13Sn
5		 990 252%
Li
9Al
4		 2235 604%
Li
22Si
5		 4200 320%

A crystalline silicon anode has a theoretical specific capacity of 4200 mAh/g, more than ten times that of anodes such as graphite (372 mAh/g).[3] Each silicon atom can bind up to 4.4 lithium atoms in its fully lithiated state (Li
4.4Si), compared to one lithium atom per 6 carbon atoms for the fully lithiated graphite (LiC
6).[14]

Silicon swelling

The lattice distance between silicon atoms multiplies as it accommodates lithium ions (lithiation), reaching 320% of the original volume.[3] The expansion causes large anisotropic stresses to occur within the electrode material, fracturing and crumbling the silicon material and detachment from the current collector.[15] Prototypical lithium-silicon batteries lose most of their capacity in as little as 10 charge-discharge cycles.[4][16] A solution to the capacity and stability issues posed by the significant volume expansion upon lithiation is critical to the success of silicon anodes.

Silicon nanostructures are one potential solution. Researchers created silicon nanowires on a conductive substrate for an anode, and found that the nanowire morphology creates direct current pathways to help increase power density and decreases disruption from volume change.[17] However, the large volume change of the nanowires can still pose a fading problem.

Other studies examined the potential of silicon nanoparticles. Anodes that use silicon nanoparticles may overcome the price and scale barriers of nanowire batteries, while offering more mechanical stability over cycling compared to other silicon electrodes.[18] Typically, these anodes add carbon as a conductive additive and a binder for increased mechanical stability. However, this geometry does not fully solve the issue of large volume expansion upon lithiation, exposing the battery to increased risk of capacity loss from inaccessible nanoparticles after cycle-induced cracking and stress.

Another nanoparticle approach is to use conducting polymers as both the binder and the additive for nanoparticle batteries. One study examined a three-dimensional conducting polymer and hydrogel network to carry silicon nanoparticles.[19] The framework resulted in a marked improvement in electrode stability, with over 90% capacity retention after 5,000 cycles. However, the potential for inexpensive scale up has not been thoroughly investigated. Other researchers offered another potential solution, utilizing slurry coating techniques – which are currently employed at large scales for electrode production – with a conducting polymer binder.[20] In general, the conducting polymer additive provides both mechanical stabilization and an avenue for conduction, replacing the conventional two-material system of a polymer stabilizer and carbon black particles. The substitution allows both better stabilization and better conduction.

Solid electrolyte interface layer

SEI layer formation on silicon. In green on the left, the normal battery operation, in blue the SEI layer formation. The electrolyte decomposes by reduction.

Another issue is the destabilization of the solid electrolyte interface (SEI) layer consisting of decomposed electrolyte material.[21]

The SEI layer normally forms a layer impenetratable to the electrolyte, which prevents further growth. However, due to the swelling of the silicon, the SEI layer cracks and become porous.[22] Thus, it can thicken. A thick SEI layer results in a higher cell resistance, which decreases cell efficiency.[23][24]

The SEI layer on silicon is composed of reduced electrolyte and lithium.[23] At the operating voltage of the battery, the electrolyte is unstable and decomposes.[21] The consumption of lithium in the formation of the SEI layer further decreases the battery capacity.[24] Limiting growth of the SEI layer is therefore critical for commercial lithium-silicon batteries.

See also

References

  1. ↑ Nazri, Gholam-Abbas; Pistoia, Gianfranco, eds. (2004). Lithium Batteries - Science and Technology. Kluwer Academic Publishers. p. 259. ISBN 1-4020-7628-2.
  2. 1 2 3 4 5 6 7 Mims, Christopher (2018-03-18). "The Battery Boost We've Been Waiting for Is Only a Few Years Out". Wall Street Journal. ISSN 0099-9660. Retrieved 2018-03-18.
  3. 1 2 3 4 Mukhopadhyay, Amartya; Sheldon, Brian W. (2014). "Deformation and stress in electrode materials for Li-ion batteries". Progress in Materials Science. 63: 58–116. doi:10.1016/j.pmatsci.2014.02.001.
  4. 1 2 Bourderau, S; Brousse, T; Schleich, D.M (1999). "Amorphous silicon as a possible anode material for Li-ion batteries". Journal of Power Sources. 81–82: 233–236. doi:10.1016/S0378-7753(99)00194-9.
  5. ↑ St. John, Jeff (2014-01-06). "Amprius Gets $30M Boost for Silicon-Based Lithium-Ion Batteries". Greentechmedia. Retrieved 2015-07-21.
  6. ↑ Bullis, Kevin (10 January 2014). "Startup Gets $30 Million to Bring High-Energy Silicon Batteries to Market". MIT Technology Review.
  7. ↑ Li, Yuzhang; Yan, Kai; Lee, Hyun-Wook; Lu, Zhenda; Liu, Nian; Cui, Yi (2016). "Growth of conformal graphene cages on micrometre-sized silicon particles as stable battery anodes". Nature Energy. 1 (2): 15029. doi:10.1038/nenergy.2015.29. ISSN 2058-7546.
  8. ↑ "Enevate Announces HD-Energy® Technology for Li-ion Batteries". 9 December 2014.
  9. ↑ Demerjian, Charlie (26 January 2016). "Enevate introduces a Silicon-Lithium-Ion battery".
  10. ↑ "Enevate Named as CES 2016 Innovation Awards Honoree in Multiple Categories". 12 February 2016.
  11. ↑ "Sonim picks Enevate batteries for ultra-rugged smartphones". 17 February 2016.
  12. ↑ Besenhard, J.; Daniel, C., eds. (2011). Handbook of Battery Materials. Wiley-VCH.
  13. ↑ Nazri, Gholam-Abbas; Pistoia, Gianfranco, eds. (2004). Lithium Batteries - Science and Technology. Kluwer Academic Publishers. p. 117. ISBN 1-4020-7628-2.
  14. ↑ Tarascon, J.M.; Armand, M. (2001). "Issues and challenges facing rechargeable lithium batteries". Nature. 414 (6861): 359–67. doi:10.1038/35104644. PMID 11713543.
  15. ↑ Berla, Lucas A.; Lee, Seok Woo; Ryu, Ill; Cui, Yi; Nix, William D. (2014). "Robustness of amorphous silicon during the initial lithiation/delithiation cycle". Journal of Power Sources. 258: 253–259. doi:10.1016/j.jpowsour.2014.02.032.
  16. ↑ Jung, H (2003). "Amorphous silicon anode for lithium-ion rechargeable batteries". Journal of Power Sources. 115 (2): 346–351. doi:10.1016/S0378-7753(02)00707-3.
  17. ↑ Chan, Candace K.; Peng, Hailin; Liu, Gao; McIlwrath, Kevin; Zhang, Xiao Feng; Huggins, Robert A.; Cui, Yi (Jan 2008). "High-performance lithium battery anodes using silicon nanowires". Nature Nanotechnology. 3 (1): 31–35. doi:10.1038/nnano.2007.411. PMID 18654447.
  18. ↑ Ge, Mingyuan; Rong, Jiepeng; Fang, Xin; Zhang, Anyi; Lu, Yunhao; Zhou, Chongwu (2013-02-06). "Scalable preparation of porous silicon nanoparticles and their application for lithium-ion battery anodes". Nano Research. 6 (3): 174–181. doi:10.1007/s12274-013-0293-y. ISSN 1998-0124.
  19. ↑ Wu, Hui; Yu, Guihua; Pan, Lijia; Liu, Nian; McDowell, Matthew T.; Bao, Zhenan; Cui, Yi (2013-06-04). "Stable Li-ion battery anodes by in-situ polymerization of conducting hydrogel to conformally coat silicon nanoparticles". Nature Communications. 4: 1943. doi:10.1038/ncomms2941. ISSN 2041-1723. PMID 23733138.
  20. ↑ Higgins, Thomas M.; Park, Sang-Hoon; King, Paul J.; Zhang, Chuanfang (John); McEvoy, Niall; Berner, Nina C.; Daly, Dermot; Shmeliov, Aleksey; Khan, Umar (2016-03-22). "A Commercial Conducting Polymer as Both Binder and Conductive Additive for Silicon Nanoparticle-Based Lithium-Ion Battery Negative Electrodes". ACS Nano. 10 (3): 3702–3713. doi:10.1021/acsnano.6b00218. ISSN 1936-0851.
  21. 1 2 Chan, Candace K.; Ruffo, Riccardo; Hong, Seung Sae; Cui, Yi (2009). "Surface chemistry and morphology of the solid electrolyte interphase on silicon nanowire lithium-ion battery anodes". Journal of Power Sources. 189 (2): 1132–1140. doi:10.1016/j.jpowsour.2009.01.007. ISSN 0378-7753.
  22. ↑ Fong, Rosamaría (1990). "Studies of Lithium Intercalation into Carbons Using Nonaqueous Electrochemical Cells". Journal of The Electrochemical Society. 137 (7): 2009. doi:10.1149/1.2086855. ISSN 0013-4651.
  23. 1 2 Ruffo, Riccardo; Hong, Seung Sae; Chan, Candace K.; Huggins, Robert A.; Cui, Yi (2009). "Impedance Analysis of Silicon Nanowire Lithium Ion Battery Anodes". The Journal of Physical Chemistry C. 113 (26): 11390–11398. doi:10.1021/jp901594g. ISSN 1932-7447.
  24. 1 2 Oumellal, Y.; Delpuech, N.; Mazouzi, D.; Dupré, N.; Gaubicher, J.; Moreau, P.; Soudan, P.; Lestriez, B.; Guyomard, D. (2011). "The failure mechanism of nano-sized Si-based negative electrodes for lithium ion batteries". Journal of Materials Chemistry. 21 (17): 6201. doi:10.1039/c1jm10213c. ISSN 0959-9428.
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