Abstract
The abundance of sodium (Na), its low-cost, and low reduction potential provide a lucrative inexpensive, safe, and environmentally benign alternative to lithium ion batteries (LIBs). The significant challenges in advancing sodium ion battery (NIB) technologies lie in finding the better electrode materials. Experimental investigations revealed the real potency of germanium (Ge) as suitable anode materials for NIBs. However, a systematic atomistic study is necessary to understand the fundamental aspects of capacity–voltage correlation, microstructural changes of Ge, as well as diffusion kinetics. We, therefore, performed the Density Functional Theory (DFT) and Ab Initio Molecular Dynamics (AIMD) simulation to investigate the sodiation–desodiation kinetics in germanium–sodium system (Na64Ge64). We analyzed the intercalation potential and capacity correlation for intermediate equilibrium structures and compared our data with the experimental results. Effect of sodiation on inter-atomic distances within Na–Ge system is analyzed by means of Pair Correlation Function (PCF). This provides insight into possible microstructural changes taking place during sodiation of amorphous Ge (a-Ge). We further investigated the diffusivity of sodium in a-Ge electrode material and analyzed the volume expansion trend for Na64Ge64 electrode system. Our computational results provide the fundamental insight into the atomic scale and help experimentalists design Ge-based NIBs for real-life applications.
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References
Whittingham MS (1976) Electrical energy storage and intercalation chemistry. Science 192(4244):1126–1127
Whittingham MS, Thompson AH (1975) Intercalation and lattice expansion in titanium disulfide. J Chem Phys 62(4):1588
Tarascon J-M, Armand M (2011) Issues and challenges facing rechargeable lithium batteries. In: Materials for sustainable energy: a collection of peer-reviewed research and review articles from Nature Publishing Group, World Scientific, pp 171–179
de la Llave E, Borgel V, Park K-J, Hwang J-Y, Sun Y-K, Hartmann P, Chesneau F-F, Aurbach D (2016) Comparison between Na-ion and Li-ion cells: understanding the critical role of the cathodes stability and the anodes pretreatment on the cells behavior. ACS Appl Mater Interfaces 8(3):1867–1875
Böhm H, Beyermann G (1999) ZEBRA batteries, enhanced power by doping. J Power Sources 84(2):270–274
Nithya C, Gopukumar S (2015) Sodium ion batteries: a newer electrochemical storage. Wiley Interdiscip Rev Energy Environ 4(3):253–278
Yabuuchi N, Kubota K, Dahbi M, Komaba S (2014) Research development on sodium-ion batteries. Chem Rev 114(23):11636–11682
Kundu D, Talaie E, Duffort V, Nazar LF (2015) The emerging chemistry of sodium ion batteries for electrochemical energy storage. Angew Chem Int Ed 54(11):3431–3448
Adelhelm P, Hartmann P, Bender CL, Busche M, Eufinger C, Janek J (2015) From lithium to sodium: cell chemistry of room temperature sodium–air and sodium–sulfur batteries. Beilstein J Nanotechnol 2015(6):1016–1055
Stojić M, Kostić D, Stošić B (1986) The behaviour of sodium in Ge, Si and GaAs. Physica B + C 138(1–2):125–128
Delmas C, Fouassier C, Hagenmuller P (1980) Structural classification and properties of the layered oxides. Physica B + C 99(1–4):81–85
Berthelot R, Carlier D, Delmas C (2011) Electrochemical investigation of the P2–NaxCoO2 phase diagram. Nat Mater 10(1):74–80
Shiva K, Singh P, Zhou W, Goodenough JB (2016) NaFe2PO4(SO4)2: a potential cathode for a Na-ion battery. Energy Environ Sci 9(10):3103–3106
Xu J, Lee DH, Meng YS (2013) Recent advances in sodium intercalation positive electrode materials for sodium ion batteries. Funct Mater Lett 6(01):1330001–1330007
Okamoto Y (2013) Density functional theory calculations of alkali metal (Li, Na, and K) graphite intercalation compounds. J Phys Chem C 118(1):16–19
Balogun M-S, Luo Y, Qiu W, Liu P, Tong Y (2016) A review of carbon materials and their composites with alloy metals for sodium ion battery anodes. Carbon 98:162–178
Chevrier V, Ceder G (2011) Challenges for Na-ion negative electrodes. J Electrochem Soc 158(9):A1011–A1014
Jache B, Adelhelm P (2014) Use of graphite as a highly reversible electrode with superior cycle life for sodium-ion batteries by making use of co-intercalation phenomena. Angew Chem Int Ed 53(38):10169–10173
Wen Y, He K, Zhu Y, Han F, Xu Y, Matsuda I, Ishii Y, Cumings J, Wang C (2014) Expanded graphite as superior anode for sodium-ion batteries. Nat Commun 5:4033-1–4033-10
Mei Y, Huang Y, Hu X (2016) Nanostructured Ti-based anode materials for Na-ion batteries. J Mater Chem A 4(31):12001–12013
Legrain F, Malyi O, Manzhos S (2015) Insertion energetics of lithium, sodium, and magnesium in crystalline and amorphous titanium dioxide: a comparative first-principles study. J Power Sources 278:197–202
Li W, Zhou M, Li H, Wang K, Cheng S, Jiang K (2015) A high performance sulfur-doped disordered carbon anode for sodium ion batteries. Energy Environ Sci 8(10):2916–2921
Klein F, Jache B, Bhide A, Adelhelm P (2013) Conversion reactions for sodium-ion batteries. Phys Chem Chem Phys 15(38):15876–15887
Mortazavi M, Ye Q, Birbilis N, Medhekar NV (2015) High capacity group-15 alloy anodes for Na-ion batteries: electrochemical and mechanical insights. J Power Sources 285:29–36
Mortazavi M, Deng J, Shenoy VB, Medhekar NV (2013) Elastic softening of alloy negative electrodes for Na-ion batteries. J Power Sources 225:207–214
Stevens D, Dahn J (2000) An in situ small-angle X-ray scattering study of sodium insertion into a nanoporous carbon anode material within an operating electrochemical cell. J Electrochem Soc 147(12):4428–4431
Wang Y-X, Chou S-L, Liu H-K, Dou S-X (2013) Reduced graphene oxide with superior cycling stability and rate capability for sodium storage. Carbon 57:202–208
Li D, Zhang L, Chen H, Wang J, Ding L-X, Wang S, Ashman PJ, Wang H (2016) Graphene-based nitrogen-doped carbon sandwich nanosheets: a new capacitive process controlled anode material for high-performance sodium-ion batteries. J Mater Chem A 4(22):8630–8635
Usui H, Yoshioka S, Wasada K, Shimizu M, Sakaguchi H (2015) Nb-doped rutile TiO2: a potential anode material for Na-ion battery. ACS Appl Mater Interfaces 7(12):6567–6573
Umebayashi T, Yamaki T, Itoh H, Asai K (2002) Band gap narrowing of titanium dioxide by sulfur doping. Appl Phys Lett 81(3):454–456
Fu S, Ni J, Xu Y, Zhang Q, Li L (2016) Hydrogenation driven conductive Na2Ti3O7 nanoarrays as robust binder-free anodes for Sodium-ion batteries. Nano Lett 16(7):4544–4551
Li H, Fei H, Liu X, Yang J, Wei M (2015) In situ synthesis of Na2 Ti7 O15 nanotubes on a Ti net substrate as a high performance anode for Na-ion batteries. Chem Commun 51(45):9298–9300
Jung SC, Jung DS, Choi JW, Han Y-K (2014) Atom-level understanding of the sodiation process in silicon anode material. J Phys Chem Lett 5(7):1283–1288
Abel PR, Lin Y-M, de Souza T, Chou C-Y, Gupta A, Goodenough JB, Hwang GS, Heller A, Mullins CB (2013) Nanocolumnar germanium thin films as a high-rate sodium-ion battery anode material. J Phys Chem C 117(37):18885–18890
Komaba S, Matsuura Y, Ishikawa T, Yabuuchi N, Murata W, Kuze S (2012) Redox reaction of Sn-polyacrylate electrodes in aprotic Na cell. Electrochem Commun 21:65–68
Li Z, Ding J, Mitlin D (2015) Tin and tin compounds for sodium ion battery anodes: phase transformations and performance. Acc Chem Res 48(6):1657–1665
Baggetto L, Ganesh P, Meisner RP, Unocic RR, Jumas J-C, Bridges CA, Veith GM (2013) Characterization of sodium ion electrochemical reaction with tin anodes: experiment and theory. J Power Sources 234:48–59
Malyi OI, Tan TL, Manzhos S (2013) A comparative computational study of structures, diffusion, and dopant interactions between Li and Na insertion into Si. Appl Phys Express 6(2):027301-1–027301-3
Kulish VV, Malyi OI, Ng M-F, Chen Z, Manzhos S, Wu P (2014) Controlling Na diffusion by rational design of Si-based layered architectures. Phys Chem Chem Phys 16(9):4260–4267
Baggetto L, Keum JK, Browning JF, Veith GM (2013) Germanium as negative electrode material for sodium-ion batteries. Electrochem Commun 34:41–44
Kresse G, Furthmüller J (1996) Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B 54(16):11169–11186
Blöchl PE (1994) Projector augmented-wave method. Phys Rev B 50(24):17953–17979
Kresse G, Joubert D (1999) From ultrasoft pseudopotentials to the projector augmented-wave method. Phys Rev B 59(3):1758–1775
Johari P, Qi Y, Shenoy VB (2011) The mixing mechanism during lithiation of Si negative electrode in Li-ion batteries: an ab initio molecular dynamics study. Nano Lett 11(12):5494–5500
Farbod B, Cui K, Kalisvaart WP, Kupsta M, Zahiri B, Kohandehghan A, Lotfabad EM, Li Z, Luber EJ, Mitlin D (2014) Anodes for sodium ion batteries based on tin–germanium–antimony alloys. ACS Nano 8(5):4415–4429
Jung SC, Kim H-J, Kang Y-J, Han Y-K (2016) Advantages of Ge anode for Na-ion batteries: Ge versus Si and Sn. J Alloy Compd 688:158–163
Hwang J-Y, Myung S-T, Sun Y-K (2017) Sodium-ion batteries: present and future. Chem Soc Rev 46(12):3529–3614
Grigorovici R, Mǎnǎilǎ R (1969) Short-range order in amorphous germanium. J Non-Cryst Solids 1(5):371–387
Panchmatia PM, Armstrong AR, Bruce PG, Islam MS (2014) Lithium-ion diffusion mechanisms in the battery anode material Li1+xV1−xO2. Phys Chem Chem Phys 16(39):21114–21118
Acknowledgements
DD acknowledges NJIT for the faculty start-up package. We thank Prof. Siva Nadimpalli of NJIT for his suggestion throughout the project. We are grateful to the High-Performance Computing (HPC) facilities managed by Academic and Research Computing Systems (ARCS) in the Department of Information Services and Technology (IST) of the New Jersey Institute of Technology (NJIT). Some computations were performed on Kong.njit.edu HPC cluster, managed by ARCS. We acknowledge the support of the Extreme Science and Engineering Discovery Environment (XSEDE) for providing us their computational facilities (Start-Up Allocation—DMR170065 and Research Allocation—DMR180013). Most of these calculations were performed in XSEDE SDSC COMET Cluster.
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Sharma, V., Ghatak, K. & Datta, D. Amorphous germanium as a promising anode material for sodium ion batteries: a first principle study. J Mater Sci 53, 14423–14434 (2018). https://doi.org/10.1007/s10853-018-2661-1
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DOI: https://doi.org/10.1007/s10853-018-2661-1