Critical Role of Crystal Water for a Layered Cathode Material in Sodium Ion Batteries

Layered transition metal oxides are considered promising cathodes for sodium ion batteries (SIBs) due to their superior specific capacities. However, they usually suffer from insufficient cycling and rate performance mainly from the structural instability during repeated cycles. We overcome these longstanding challenges by engaging crystal water in the interlayer space of sodium manganese oxide under the Birnessite framework. The crystal water enhances Na ion diffusion both in the crystal host and at the interface, suppresses fatal Mn2+ dissolution, and improves long-term structural stability, leading to excellent performance in rate capability and cycle life. The current study suggests that many hydrated materials can be good candidates for electrode materials of emerging rechargeable batteries that need to deal with the large size or multivalent charge of their carrier ions.

[1]  Haoshen Zhou,et al.  A high-capacity, low-cost layered sodium manganese oxide material as cathode for sodium-ion batteries. , 2014, ChemSusChem.

[2]  Kang Xu,et al.  Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. , 2004, Chemical reviews.

[3]  John T. Vaughey,et al.  Li{sub2}MnO{sub3}-stabilized LiMO{sub2} (M=Mn, Ni, Co) electrodes for high energy lithium-ion batteries , 2007 .

[4]  Y. Sakurai,et al.  Improved cyclability of Na-birnessite partially substituted by cobalt , 2002 .

[5]  Gerbrand Ceder,et al.  Electrochemical Properties of Monoclinic NaNiO2 , 2011 .

[6]  M. Burghammer,et al.  Structure of synthetic K-rich birnessite obtained by high-temperature decomposition of KMnO4. I. two-layer polytype from 800 °C experiment , 2003 .

[7]  Luis Sánchez,et al.  Synthesis and characterization of high-temperature hexagonal P2-Na0.6 MnO2 and its electrochemical behaviour as cathode in sodium cells , 2002 .

[8]  Tetsuro Kobayashi,et al.  High lithium ionic conductivity in the garnet-type oxide Li7−X La3(Zr2−X, NbX)O12 (X = 0–2) , 2011 .

[9]  Shinichi Komaba,et al.  P2-type Na(x)[Fe(1/2)Mn(1/2)]O2 made from earth-abundant elements for rechargeable Na batteries. , 2012, Nature materials.

[10]  J. Pereira‐Ramos,et al.  Birnessite manganese dioxide synthesized via a sol—gel process: a new rechargeable cathodic material for lithium batteries , 1991 .

[11]  Q. Feng,et al.  Structure of synthetic Na-birnessite: Evidence for a triclinic one-layer unit cell , 2002 .

[12]  R. Renuka,et al.  An investigation on layered birnessite type manganese oxides for battery applications , 2000 .

[13]  J. Cabana,et al.  Investigation of cation ordering in triclinic sodium birnessite via 23Na MAS NMR spectroscopy , 2012 .

[14]  Xianzhong Sun,et al.  Rapid hydrothermal synthesis of hierarchical nanostructures assembled from ultrathin birnessite-type MnO2 nanosheets for supercapacitor applications , 2013 .

[15]  J. Pereira‐Ramos,et al.  Doping effects on structure and electrode performance of K-birnessite-type manganese dioxides for rechargeable lithium battery , 2008 .

[16]  Martin Winter,et al.  Toward Na-ion Batteries—Synthesis and Characterization of a Novel High Capacity Na Ion Intercalation Material , 2013 .

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

[18]  Philippe Knauth,et al.  Inorganic solid Li ion conductors: An overview , 2009 .

[19]  M. Whittingham,et al.  Cathodic Behavior of Alkali Manganese Oxides from Permanganate , 1997 .

[20]  D Carlier,et al.  Electrochemical investigation of the P2–NaxCoO2 phase diagram. , 2011, Nature materials.

[21]  T. Ishihara,et al.  Synthesis of mesoporous birnessite-MnO2 composite as a cathode electrode for lithium battery , 2014 .

[22]  A. Hollenkamp,et al.  Cycle stability of birnessite manganese dioxide for electrochemical capacitors , 2010 .

[23]  B. Popov,et al.  Electrochemical synthesis of birnessite-type layered manganese oxides for rechargeable lithium batteries , 2008 .

[24]  Jean-Marie Tarascon,et al.  Synthesis, Structure, and Electrochemical Properties of the Layered Sodium Insertion Cathode Material: NaNi1/3Mn1/3Co1/3O2 , 2012 .

[25]  Michael M. Thackeray,et al.  Improved capacity retention in rechargeable 4 V lithium/lithium- manganese oxide (spinel) cells , 1994 .

[26]  P. Novák,et al.  Electrochemical Insertion of Magnesium in Metal Oxides and Sulfides from Aprotic Electrolytes , 1993 .

[27]  J. Pereira‐Ramos,et al.  Electrochemical sodium insertion into the sol-gel birnessite manganese dioxide , 1993 .

[28]  M. Hirayama,et al.  Synthesis, structure and lithium ionic conductivity of solid solutions of Li10(Ge1−xMx)P2S12 (M = Si, Sn) , 2014 .

[29]  Petr Novák,et al.  Magnesium Insertion Electrodes for Rechargeable Nonaqueous Batteries — A Competitive Alternative to Lithium? , 1999 .

[30]  Shin-ichi Nishimura,et al.  A 3.8-V earth-abundant sodium battery electrode , 2014, Nature Communications.

[31]  Andrea R. Gerson,et al.  Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Sc, Ti, V, Cu and Zn , 2010 .

[32]  S. Komaba,et al.  Enhanced supercapacitive behaviors of birnessite , 2008 .

[33]  C. Delmas,et al.  P2-Na(x)VO2 system as electrodes for batteries and electron-correlated materials. , 2013, Nature materials.

[34]  John B Goodenough,et al.  A superior low-cost cathode for a Na-ion battery. , 2013, Angewandte Chemie.

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

[36]  J. Hanson,et al.  Rietveld refinement of a triclinic structure for synthetic Na-birnessite using synchrotron powder diffraction data , 2002, Powder Diffraction.

[37]  Shin-ichi Nishimura,et al.  High‐Voltage Pyrophosphate Cathodes , 2012 .

[38]  A. Manceau,et al.  Structure of synthetic monoclinic Na-rich birnessite and hexagonal birnessite: I. Results from X-ray diffraction and selected-area electron diffraction , 1997 .

[39]  Kathryn E. Toghill,et al.  A multifunctional 3.5 V iron-based phosphate cathode for rechargeable batteries. , 2007, Nature materials.

[40]  J. Pereira‐Ramos,et al.  Investigation of electrochemical lithium insertion in lamellar ternary oxides of the MxMnOy · zH2O group , 1997 .

[41]  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.