The Effects of Vanadium Substitution on One-dimensional Tunnel Structures of Cryptomelane: Combined TEM and DFT Study

Abstract Rational design of energy storage materials requires mechanistic understanding which relies on atomic scale characterization of structure and defects. Here we utilize vanadium (V)-substituted one-dimensional cryptomelane as a model material to study structural features critical to electrochemical reversibility of the cathode in lithium-ion batteries. We found the substitution of manganese (Mn) atoms in the tunnel wall with V enhances structural uniformity in the parent KMn8O16 material by inhibiting formation of irregular (2 × 3 and 2 × 1) manganese oxide tunnel structures. Upon lithiation, both transmission electron microscopy (TEM) and density functional theory (DFT) reveal significant structural evolution, eventually resulting in phase separation and formation of highly reduced manganese oxide. During this process, Mn4+ accepts electrons donated by intercalated Li, while the V4+ substituent is not electrochemically reduced but acts to stabilize the tunnel framework structure. As a result, the V substituted material shows higher operating voltage and improved electrochemical reversibility. Our results highlight the benefits of V-substitution in cryptomelane, and the significance of integrating characterization with simulation for understanding and developing design principles for lithium ion battery materials.

[1]  Alexander B. Brady,et al.  Transition Metal Substitution of Hollandite α-MnO2: Enhanced Potential and Structural Stability on Lithiation from First-Principles Calculation , 2019, The Journal of Physical Chemistry C.

[2]  H. Xin,et al.  Atomic-level tunnel engineering of todorokite MnO2 for precise evaluation of lithium storage mechanisms by in situ transmission electron microscopy , 2019, Nano Energy.

[3]  P. Ajayan,et al.  Direct Cation Exchange in Monolayer MoS_{2} via Recombination-Enhanced Migration. , 2019, Physical review letters.

[4]  Bryan W. Byles,et al.  Ordering Heterogeneity of [MnO6] Octahedra in Tunnel-Structured MnO2 and Its Influence on Ion Storage , 2019, Joule.

[5]  P. Ajayan,et al.  Rhenium‐Doped and Stabilized MoS2 Atomic Layers with Basal‐Plane Catalytic Activity , 2018, Advanced materials.

[6]  M. Hybertsen,et al.  Atomic Scale Account of the Surface Effect on Ionic Transport in Silver Hollandite , 2018, Chemistry of Materials.

[7]  Christopher S. Johnson,et al.  The quest for manganese-rich electrodes for lithium batteries: strategic design and electrochemical behavior , 2018 .

[8]  Ji‐Guang Zhang,et al.  Tailoring grain boundary structures and chemistry of Ni-rich layered cathodes for enhanced cycle stability of lithium-ion batteries , 2018, Nature Energy.

[9]  G. Ceder,et al.  Revealing and Rationalizing the Rich Polytypism of Todorokite MnO2. , 2018, Journal of the American Chemical Society.

[10]  S. Jiang,et al.  Atomically Dispersed Transition Metals on Carbon Nanotubes with Ultrahigh Loading for Selective Electrochemical Carbon Dioxide Reduction , 2018, Advanced materials.

[11]  K. Zaghib,et al.  Layered oxides-LiNi 1/3 Co 1/3 Mn 1/3 O 2 as anode electrode for symmetric rechargeable lithium-ion batteries , 2018 .

[12]  Lisa M. Housel,et al.  Investigation of α-MnO2 Tunneled Structures as Model Cation Hosts for Energy Storage. , 2018, Accounts of chemical research.

[13]  Christian Masquelier,et al.  Atomic-Scale Influence of Grain Boundaries on Li-Ion Conduction in Solid Electrolytes for All-Solid-State Batteries. , 2018, Journal of the American Chemical Society.

[14]  Alexander B. Brady,et al.  Unveiling the Structural Evolution of Ag1.2Mn8O16 under Coulombically Controlled (De)Lithiation , 2018 .

[15]  A. Marschilok,et al.  Lithiation Mechanism of Tunnel‐Structured MnO2 Electrode Investigated by In Situ Transmission Electron Microscopy , 2017, Advanced materials.

[16]  Ping Liu,et al.  A first principles study of spinel ZnFe2O4 for electrode materials in lithium-ion batteries. , 2017, Physical chemistry chemical physics : PCCP.

[17]  A. Marschilok,et al.  Synthesis of cryptomelane type α-MnO2 (KxMn8O16) cathode materials with tunable K+ content: the role of tunnel cation concentration on electrochemistry , 2017 .

[18]  Alexander B. Brady,et al.  Probing the Li Insertion Mechanism of ZnFe2O4 in Li-Ion Batteries: A Combined X-Ray Diffraction, Extended X-Ray Absorption Fine Structure, and Density Functional Theory Study , 2017 .

[19]  Doron Aurbach,et al.  Promise and reality of post-lithium-ion batteries with high energy densities , 2016 .

[20]  Jun Zhou,et al.  2D vanadium doped manganese dioxides nanosheets for pseudocapacitive energy storage. , 2015, Nanoscale.

[21]  Alexander B. Brady,et al.  Structural Defects of Silver Hollandite, Ag(x)Mn8O(y), Nanorods: Dramatic Impact on Electrochemistry. , 2015, ACS nano.

[22]  Kang Xu,et al.  Electrolytes and interphases in Li-ion batteries and beyond. , 2014, Chemical reviews.

[23]  Aimee M. Morey,et al.  Enhancement of Catalytic Activities of Octahedral Molecular Sieve Manganese Oxide for Total and Preferential CO Oxidation through Vanadium Ion Framework Substitution , 2013 .

[24]  Kristin A. Persson,et al.  Commentary: The Materials Project: A materials genome approach to accelerating materials innovation , 2013 .

[25]  A. Marschilok,et al.  Synthetic control of composition and crystallite size of silver hollandite, Ag(x)Mn8O16: impact on electrochemistry. , 2012, ACS applied materials & interfaces.

[26]  Jaephil Cho,et al.  Roles of nanosize in lithium reactive nanomaterials for lithium ion batteries , 2011 .

[27]  L. Laffont,et al.  High resolution electron energy loss spectroscopy of manganese oxides: Application to Mn3O4 nanoparticles , 2010 .

[28]  Min Yu,et al.  Accurate and efficient algorithm for Bader charge integration. , 2010, The Journal of chemical physics.

[29]  Thierry Brousse,et al.  Variation of the MnO2 Birnessite Structure upon Charge/Discharge in an Electrochemical Supercapacitor Electrode in Aqueous Na2SO4 Electrolyte , 2008 .

[30]  S. Suib.  Porous manganese oxide octahedral molecular sieves and octahedral layered materials. , 2008, Accounts of chemical research.

[31]  Itaru Honma,et al.  Nanosize effect on high-rate Li-ion intercalation in LiCoO2 electrode. , 2007, Journal of the American Chemical Society.

[32]  Christopher S. Johnson.  Development and utility of manganese oxides as cathodes in lithium batteries , 2007 .

[33]  M. Whittingham,et al.  Lithium batteries and cathode materials. , 2004, Chemical reviews.

[34]  S. Suib,et al.  Higher valency ion substitution into the manganese oxide framework. , 2004, Journal of the American Chemical Society.

[35]  C. Cesari,et al.  Vanadium valency and hybridization in V-doped hafnia investigated by electron energy loss spectroscopy , 2001 .

[36]  Q. Feng,et al.  Manganese oxide porous crystals , 1999 .

[37]  J. Post,et al.  Manganese oxide minerals: crystal structures and economic and environmental significance. , 1999, Proceedings of the National Academy of Sciences of the United States of America.

[38]  S. Suib,et al.  A Review of Porous Manganese Oxide Materials , 1998 .

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

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

[41]  S. Suib.  A Review of Open Framework Structures , 1996 .

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

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

[44]  H. Monkhorst,et al.  SPECIAL POINTS FOR BRILLOUIN-ZONE INTEGRATIONS , 1976 .

[45]  W. Kohn,et al.  Self-Consistent Equations Including Exchange and Correlation Effects , 1965 .

[46]  A. Marschilok,et al.  Tunnel Structured α-MnO2with Different Tunnel Cations (H+, K+, Ag+) as Cathode Materials in Rechargeable Lithium Batteries: The Role of Tunnel Cation on Electrochemistry , 2017 .

[47]  L. Gu,et al.  Surface structure evolution of cathode materials for Li-ion batteries , 2015 .

[48]  Michael M. Thackeray,et al.  Manganese oxides for lithium batteries , 1997 .

[49]  John Aurie Dean,et al.  Lange's Handbook of Chemistry , 1978 .