Modelling high-performing batteries with Mxenes: The case of S-functionalized two-dimensional nitride Mxene electrode

Abstract Recent upsurge in the two-dimensional (2D) materials have established their larger role on energy storage applications. To this end, Mxene represent a new paradigm extending beyond the realm of oft-explored elemental 2D materials beginning with graphene. Here in, we employed first principles modelling based on density functional theory to investigate the role of S-functionalized Nitride Mxenes as anodes for Li/Na ion batteries. To be specific, V2NS2 and Ti2NS2 have been explored with a focus on computing meaningful descriptors to quantify these 2D materials to be optimally performing electrodes. The Li/Na ion adsorption energies are found to be high (>-2 eV) on both the surfaces and associated with significant charge transfer. Interestingly, this ion intercalation can reach up to multilayers which essentially affords higher specific capacity for the substrate. Particularly, these two 2D materials (V2NS2 and Ti2NS2) have been found to be more suitable for Li-ion batteries with estimated theoretical capacities of 299.52 mAh g−1 and 308.28 mAh g−1 respectively. We have also probed the diffusion barriers of ion migration on these two surfaces and these are found to be ultrafast in nature. All these unique features qualify these Mxenes to be potential anode materials for rechargeable batteries and likely to draw imminent attention.

[1]  E. Kaxiras,et al.  Adsorption and diffusion of lithium on layered silicon for Li-ion storage. , 2013, Nano letters.

[2]  G. Kresse,et al.  Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set , 1996 .

[3]  Stefan Grimme,et al.  Semiempirical GGA‐type density functional constructed with a long‐range dispersion correction , 2006, J. Comput. Chem..

[4]  Qiang Sun,et al.  All-carbon-based porous topological semimetal for Li-ion battery anode material , 2017, Proceedings of the National Academy of Sciences.

[5]  Xianfan Xu,et al.  Phosphorene: an unexplored 2D semiconductor with a high hole mobility. , 2014, ACS nano.

[6]  J. Nelson,et al.  Defect chemistry, surface structures, and lithium insertion in anatase TiO2. , 2006, The journal of physical chemistry. B.

[7]  Yury Gogotsi,et al.  2D metal carbides and nitrides (MXenes) for energy storage , 2017 .

[8]  B. George,et al.  Two-Dimensional Titanium Nitride (Ti2N) MXene: Synthesis, Characterization, and Potential Application as Surface-Enhanced Raman Scattering Substrate. , 2017, ACS nano.

[9]  M. Armand,et al.  Issues and challenges facing rechargeable lithium batteries , 2001, Nature.

[10]  R. Ahuja,et al.  Borophane as a Benchmate of Graphene: A Potential 2D Material for Anode of Li and Na-Ion Batteries. , 2017, ACS applied materials & interfaces.

[11]  R. Ahuja,et al.  The curious case of two dimensional Si2BN: A high-capacity battery anode material , 2017 .

[12]  M. Whittingham,et al.  Electrical Energy Storage and Intercalation Chemistry , 1976, Science.

[13]  Donghan Kim,et al.  Sodium‐Ion Batteries , 2013 .

[14]  Wei Kang,et al.  The potential application of phosphorene as an anode material in Li-ion batteries , 2014, 1408.3488.

[15]  Jer-Lai Kuo,et al.  Metallic VS2 Monolayer Polytypes as Potential Sodium-Ion Battery Anode via ab Initio Random Structure Searching. , 2016, ACS applied materials & interfaces.

[16]  V. Presser,et al.  Two‐Dimensional Nanocrystals Produced by Exfoliation of Ti3AlC2 , 2011, Advanced materials.

[17]  A. Hagfeldt,et al.  LI AND NA DIFFUSION IN TIO2 FROM QUANTUM CHEMICAL THEORY VERSUS ELECTROCHEMICAL EXPERIMENT , 1997 .

[18]  Jiajie Zhu,et al.  Silicene for Na-ion battery applications , 2016 .

[19]  Artem R. Oganov,et al.  Synthesis of borophenes: Anisotropic, two-dimensional boron polymorphs , 2015, Science.

[20]  G. Kresse,et al.  From ultrasoft pseudopotentials to the projector augmented-wave method , 1999 .

[21]  Y. Gogotsi,et al.  Ti₃C₂ MXene as a high capacity electrode material for metal (Li, Na, K, Ca) ion batteries. , 2014, ACS applied materials & interfaces.

[22]  Zhong Jin,et al.  Emerging non-lithium ion batteries , 2016 .

[23]  Blöchl,et al.  Projector augmented-wave method. , 1994, Physical review. B, Condensed matter.

[24]  Udo Schwingenschlögl,et al.  S-functionalized MXenes as electrode materials for Li-ion batteries , 2016 .

[25]  S. W. Leeuw,et al.  Diffusion of Li-ions in rutile. An ab initio study , 2003 .

[26]  H. Pang,et al.  MXene–2D layered electrode materials for energy storage , 2018 .

[27]  Shengli Zhang,et al.  Could Borophene Be Used as a Promising Anode Material for High-Performance Lithium Ion Battery? , 2016, ACS applied materials & interfaces.

[28]  Kresse,et al.  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. , 1996, Physical review. B, Condensed matter.

[29]  W. Kang,et al.  Role of Strain and Concentration on the Li Adsorption and Diffusion Properties on Ti2C Layer , 2014 .

[30]  Yi Du,et al.  Silicene: A Promising Anode for Lithium‐Ion Batteries , 2017, Advanced materials.

[31]  Martin Pumera,et al.  Layered transition metal dichalcogenides for electrochemical energy generation and storage , 2014 .

[32]  Jiale Ma,et al.  The S-functionalized Ti3C2 Mxene as a high capacity electrode material for Na-ion batteries: a DFT study. , 2018, Nanoscale.

[33]  Zhen Zhou,et al.  Recent advances in MXene: Preparation, properties, and applications , 2015 .

[34]  Li-zhen Fan,et al.  Two-dimensional Ti3C2 as anode material for Li-ion batteries , 2014 .

[35]  Hui Pan.  Electronic properties and lithium storage capacities of two-dimensional transition-metal nitride monolayers , 2015 .

[36]  A. Hagfeldt,et al.  Li+ Ion Insertion in TiO2 (Anatase). 1. Chronoamperometry on CVD Films and Nanoporous Films , 1997 .

[37]  Gang Zhang,et al.  Ultrafast and directional diffusion of lithium in phosphorene for high-performance lithium-ion battery. , 2015, Nano letters.

[38]  Michael Behringer,et al.  Corrigendum: Application of Blood Flow Restriction to Optimize Exercise Countermeasures for Human Space Flight , 2019, Front. Physiol..

[39]  Yugui Yao,et al.  Borophene as an extremely high capacity electrode material for Li-ion and Na-ion batteries. , 2016, Nanoscale.

[40]  SUPARNA DUTTASINHA,et al.  Van der Waals heterostructures , 2013, Nature.

[41]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[42]  R. Ahuja,et al.  Borophene's tryst with stability: exploring 2D hydrogen boride as an electrode for rechargeable batteries. , 2018, Physical chemistry chemical physics : PCCP.

[43]  Zhongfang Chen,et al.  Metallic VS2 Monolayer: A Promising 2D Anode Material for Lithium Ion Batteries , 2013 .

[44]  S. W. Leeuw,et al.  Open circuit voltage profile for Li-intercalation in rutile and anatase from first principles , 2002 .

[45]  Patrick Vogt,et al.  Silicene: compelling experimental evidence for graphenelike two-dimensional silicon. , 2012, Physical review letters.

[46]  Wolfgang Windl,et al.  Stability and exfoliation of germanane: a germanium graphane analogue. , 2013, ACS nano.

[47]  O. Malyi,et al.  Phosphorene as an anode material for Na-ion batteries: a first-principles study. , 2015, Physical chemistry chemical physics : PCCP.

[48]  A. Benyoussef,et al.  Phosphorene as a promising anode material for lithium-ion batteries: A first-principle study , 2016, 2016 International Renewable and Sustainable Energy Conference (IRSEC).

[49]  Dong Qian,et al.  Epitaxial growth of two-dimensional stanene. , 2015, Nature materials.