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First principles and experimental studies of empty Si46 as anode materials for Li-ion batteries

Published online by Cambridge University Press:  17 November 2016

Kwai S. Chan ,
Michael A. Miller ,
Wuwei Liang ,
Carol Ellis-Terrell  and
Candace K. Chan
Kwai S. Chan*
Affiliation:
Department of Materials Engineering, Mechanical Engineering Division, Southwest Research Institute®, San Antonio, TX 78238-5166, USA
Michael A. Miller
Affiliation:
Department of Materials Engineering, Mechanical Engineering Division, Southwest Research Institute®, San Antonio, TX 78238-5166, USA
Wuwei Liang
Affiliation:
Department of Materials Engineering, Mechanical Engineering Division, Southwest Research Institute®, San Antonio, TX 78238-5166, USA
Carol Ellis-Terrell
Affiliation:
Department of Materials Engineering, Mechanical Engineering Division, Southwest Research Institute®, San Antonio, TX 78238-5166, USA
Candace K. Chan
Affiliation:
Materials Science and Engineering, School for Engineering of Matter, Transport and Energy, Arizona State University, Tempe, AZ 85287-8706, USA
*
a) Address all correspondence to this author. e-mail: kchan@swri.edu
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Abstract

The objective of this investigation was to utilize the first-principles molecular dynamics computational approach to investigate the lithiation characteristics of empty silicon clathrates (Si46) for applications as potential anode materials in lithium-ion batteries. The energy of formation, volume expansion, and theoretical capacity were computed for empty silicon clathrates as a function of Li. The theoretical results were compared against experimental data of long-term cyclic tests performed on half-cells using electrodes fabricated from Si46 prepared using a Hofmann-type elimination–oxidation reaction. The comparison revealed that the theoretically predicted capacity (of 791.6 mAh/g) agreed with experimental data (809 mAh/g) that occurred after insertion of 48 Li atoms. The calculations showed that overlithiation beyond 66 Li atoms can cause large volume expansion with a volume strain as high as 120%, which may correlate to experimental observations of decreasing capacities from the maximum at 1030 mAh/g to 553 mA h/g during long-term cycling tests. The finding suggests that overlithiation beyond 66 Li atoms may have caused damage to the cage structure and led to lower reversible capacities.

Keywords

silicon clathratesLi-ion batteryanode materials

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Articles
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Journal of Materials Research , Volume 31 , Issue 23 , 14 December 2016 , pp. 3657 - 3665
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Copyright © Materials Research Society 2016 

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References

REFERENCES

Wen, C.J. and Huggins, R.A.: Chemical diffusion in intermediate phases in the lithium–silicon system. J. Solid State Chem. 37, 271 (1981).Google Scholar
Timmons, A. and Dahn, J.R.: Isotropic volume expansion of particles of amorphous metallic alloys in composite negative electrodes for Li-ion batteries. J. Electrochem. Soc. 154, A444 (2007).Google Scholar
Graetz, J., Ahn, C.C., Yazami, R., and Fultz, B.: Highly reversible lithium storage in nanostructured silicon. Electrochem. Solid-State Lett. 6(9), A194 (2003).Google Scholar
Takamura, T., Ohara, S., Uehara, M., Suzuki, J., and Sekine, K.: A vacuum deposited Si film having a Li extraction capacity over 2000 mA h/g with a long cycle life. J. Power Sources 129, 96 (2004).Google Scholar
Kim, H., Han, B., Choo, J., and Cho, J.: Three-dimensional porous silicon particles for use in high-performance lithium secondary batteries. Angew. Chem., Int. Ed. 47, 1 (2008).Google Scholar
Green, M., Fielder, E., Scrosati, B., Wachtler, M., and Moreno, J.S.: Structured silicon anodes for lithium battery applications. Electrochem. Solid-State Lett. 6(5), A75 (2003).Google Scholar
Chan, C.K., Peng, H., Liu, G., McIlwrath, K., Zhang, X.F., Huggins, R.A., and Cui, Y.: High performance lithium battery anodes using silicon nanowires. Nat. Nanotechnol. 3, 31 (2008).Google Scholar
Cui, L-F., Ruffo, R., Chan, C.K., Peng, H., and Cui, Y.: Crystalline–amorphous core–shell silicon nanowires for high capacity and high current battery electrodes. Nano Lett. 9, 491 (2009).Google Scholar
Lewis, R.B., Timmons, A., Mar, R.E., and Dahn, J.R.: In situ AFM measurements of the expansion and contraction of amorphous Sn–Co–C films reacting with lithium. J. Electrochem. Soc. 154(3), A213 (2007).Google Scholar
Timmons, A. and Dahn, J.R.: In situ optical observations of particle motion in alloy negative electrodes for Li-ion batteries. J. Electrochem. Soc. 153, A1206 (2006).Google Scholar
Beattie, S.D., Larcher, D., Morcrette, M., Simon, B., and Tarascon, J-M.: Si electrodes for Li-ion batteries—A new way to look at an old problem. J. Electrochem. Soc. 155(2), A158 (2008).Google Scholar
Sethuraman, V.A., Chon, M.J., Shimshak, M., Srinivasan, V., and Guduru, P.R.: In situ measurements of stress evolution in silicon thin films during electrochemical lithiation and delithiation. J. Power Sources 195, 5062 (2010).CrossRefGoogle Scholar
Eom, J.Y., Park, J.W., Kwon, H.S., and Rajendran, S.: Electrochemical insertion of lithium into multiwalled carbon nanotube/silicon composites produced by ballmilling. J. Electrochem. Soc. 153(9), A1678 (2006).Google Scholar
Zhang, Y., Zhang, X.G., Zhang, H.L., Zhao, Z.G., Li, F., Liu, C., and Cheng, H.M.: Composite anode material of silicon/graphite/carbon nanotubes for Li-ion batteries. Electrochim. Acta 51, 4994 (2006).Google Scholar
Zhang, Y., Zhao, Z.G., Zhang, X.G., Zhang, H.L., Li, F., Liu, C., and Cheng, H.M.: Pyrolytic carbon-coated silicon/carbon nanotube composites: Promising application for Li-ion batteries. Int. J. Nanomanuf. 2(1/2), 4 (2008).Google Scholar
Ryu, J.H., Kim, J.W., Sung, Y-E., and Oh, S.M.: Failure modes of silicon powder negative electrode in lithium secondary batteries. Electrochem. Solid-State Lett. 7(10), A306 (2004).Google Scholar
Huggins, R.A. and Nix, W.D.: Decrepitation model for capacity loss during cycling of alloys in rechargeable electrochemical systems. Ionics 6, 57 (2000).Google Scholar
Wu, H., Chan, G., Choi, J.W., Ryu, I., Yao, Y., McDowell, M.T., Lee, S.W., Jackson, A., Yang, Y., Hu, L., and Cui, Y.: Stable cycling of double-walled silicon nanotube battery anodes through solid-electrolyte interphase control. Nat. Nanotechnol. 7(5), 310 (2012).Google Scholar
Wu, H. and Cu, Y.: Designing nanostructured Si anodes for high energy lithium ion batteries. Nano Today 7(5), 414 (2012).Google Scholar
Aydinol, M.K. and Ceder, G.: First-principles prediction of insertion potentials in Li–Mn for secondary Li batteries. J. Electrochem. Soc. 144(11), 3832 (1997).Google Scholar
Kubota, Y., Escano, M.C.S., Nakanishi, H., and Kasai, H.: Crystal and electronic structure of Li15Si4 . J. Appl. Phys. 102, 053704 (2007).Google Scholar
Chevrier, V.L., Zwanziger, J.W., and Dahn, J.R.: First principles studies of silicon as a negative electrode materials for lithium-ion batteries. Can. J. Phys. 87, 625 (2009).Google Scholar
Chevrier, V.L. and Dahn, J.R.: First principles model of amorphous silicon lithiation. J. Electrochem. Soc. 156(6), A454 (2009).Google Scholar
Chevrier, V.L. and Dahn, J.R.: First principles studies of disordered lithiated silicon. J. Electrochem. Soc. 157(4), A392 (2010).Google Scholar
Zhang, Q., Zhang, W., Wan, W., Cui, Y., and Wang, E.: Lithium insertion in silicon nanowires: An ab initio study. Nano Lett. 10, 3243 (2010).Google Scholar
Chan, K.S. and Miller, M.A.: Anodes—Synthesis and characterization of silicon clathrates for anode applications in lithium-ion batteries. Energy Storage R&D, FY2014 Final Report, Southwest Research Institute (2014).Google Scholar
Li, Y., Raghavan, R., Wagner, N.A., Davidowski, S.K., Baggetto, L., Zhao, R., Cheng, Q., Yarger, J.L., Veith, G.M., Ellis-Terrell, C., Miller, M.A., Chan, K.S., and Chan, C.K.: Type I clathrates as novel silicon anodes: An electrochemical and structural investigation. Adv. Sci. 2, 1500057 (2015). doi: 10.1002/advs.201500057.Google Scholar
Peng, X., Wei, Q., Li, Y., and Chan, C.K.: First-principles study of lithiation of Type I Ba-doped silicon clathrates. J. Phys. Chem. C 119(51), 28247 (2015). doi: 10.1021/acs.jpcc.5b07523.Google Scholar
Adams, G.B., O'Keeffe, M., Kemkov, A.A., Sankey, O.F., and Huang, Y-M.: Wide-band-gap Si in open four-fold-coordinated clathrate structures. Phys. Rev. B: Condens. Matter Mater. Phys. 49, 8084 (1994).CrossRefGoogle Scholar
San-Miguel, A. and Toulemonde, P.: High-pressure properties of group IV clathrates. High Pressure Res. 25, 159 (2005).CrossRefGoogle Scholar
Mélinon, P., Kéghélian, P., Perez, A., Champagnon, B., Guyot, Y., Saviot, L., Reny, E., Cros, C., Pouchard, M., and Dianoux, A.J.: Phonon density of states of silicon clathrates: Characteristic width narrowing effect with respect to the diamond phase. Phys. Rev. B: Condens. Matter Mater. Phys. 59, 10099 (1999).Google Scholar
CPMD, Version 3.13, IBM Corp 1990-2008, MPI für Festkörperforschung Stuttgart, 1997–2001, http://www.cpmd.org.Google Scholar
Car, R. and Parrinello, M.: Unified approach for molecular dynamics and density functional theory. Phys. Rev. Lett. 55(22), 2471 (1985).Google Scholar
Guloy, A.M., Ramlau, R., Tang, Z., Schnelle, W., Baitinger, M., and Grin, Y.: A guest-free germanium clathrate. Nature, 443, 320 (2006). doi: 10.1038/nature05145.Google Scholar
Chan, K.S., Miller, M.A., Ellis-Terrell, C., and Chan, C.K.: Synthesis and characterization of empty silicon clathrates for anode applications in Li-ion batteries. In Proceedings of 2016 MRS Spring Meeting, March 28-April 1, 2016, Phoenix, AZ. MRS Advance, CJO 2016, doi: 10.1557/adv.2016.434.Google Scholar
Li, J. and Dahn, J.R.: An in-situ x-ray diffraction study of the reaction of Li with crystalline Si. J. Electrochem. Soc. 154, A156 (2007).CrossRefGoogle Scholar
Langer, T., Dupke, S., Trill, H., Passerini, S., Eckert, H., Pöttgen, R., and Winter, M.: Electrochemical lithiation of silicon clathrate-II. J. Electrochem. Soc. 159, A1318 (2012).Google Scholar
Wagner, N.A., Raghavan, R., Zhao, R., Wei, Q., Peng, X., and Chan, C.K.: Electrochemical cycling of sodium-filled silicon clathrate. ChemElectroChem, 1(2), 347 (2014).CrossRefGoogle Scholar