An Aqueous Dual-Ion Battery Cathode of Mn3 O4 via Reversible Insertion of Nitrate.

We report reversible electrochemical insertion of NO3 - into manganese(II, III) oxide (Mn3 O4 ) as a cathode for aqueous dual-ion batteries. Characterization by TGA, FTIR, EDX, XANES, EXAFS, and EQCM collectively provides unequivocal evidence that reversible oxidative NO3 - insertion takes place inside Mn3 O4 . Ex situ HRTEM and corresponding EDX mapping results suggest that NO3 - insertion de-crystallizes the structure of Mn3 O4 . Kinetic studies reveal fast migration of NO3 - in the Mn3 O4 structure. This finding may open a new direction for novel low-cost aqueous dual-ion batteries.

[1]  Yong‐Mook Kang,et al.  α-MnO2 Nanowire-Anchored Highly Oxidized Cluster as a Catalyst for Li-O2 Batteries: Superior Electrocatalytic Activity and High Functionality. , 2018, Angewandte Chemie.

[2]  M. Winter,et al.  Perspective on Performance, Cost, and Technical Challenges for Practical Dual-Ion Batteries , 2018, Joule.

[3]  Yongbing Tang,et al.  A Review on the Features and Progress of Dual‐Ion Batteries , 2018 .

[4]  F. Pan,et al.  Engineering Fast Ion Conduction and Selective Cation Channels for a High-Rate and High-Voltage Hybrid Aqueous Battery. , 2018, Angewandte Chemie.

[5]  H. Groult,et al.  Electrochemical reactions in fluoride-ion batteries: mechanistic insights from pair distribution function analysis , 2017 .

[6]  Bingan Lu,et al.  Soft Carbon as Anode for High‐Performance Sodium‐Based Dual Ion Full Battery , 2017 .

[7]  Yongbing Tang,et al.  Bubble‐Sheet‐Like Interface Design with an Ultrastable Solid Electrolyte Layer for High‐Performance Dual‐Ion Batteries , 2017, Advanced materials.

[8]  Fan Zhang,et al.  A Novel Potassium‐Ion‐Based Dual‐Ion Battery , 2017, Advanced materials.

[9]  D. Truhlar,et al.  All-Organic Rechargeable Battery with Reversibility Supported by "Water-in-Salt" Electrolyte. , 2017, Chemistry.

[10]  S. Feng,et al.  (EMIm)+(PF6)− Ionic Liquid Unlocks Optimum Energy/Power Density for Architecture of Nanocarbon‐Based Dual‐Ion Battery , 2016 .

[11]  Zelang Jian,et al.  A Hydrocarbon Cathode for Dual-Ion Batteries , 2016 .

[12]  Wenhua Zuo,et al.  Bismuth oxide: a versatile high-capacity electrode material for rechargeable aqueous metal-ion batteries , 2016 .

[13]  M. Winter,et al.  Does Size really Matter? New Insights into the Intercalation Behavior of Anions into a Graphite-Based Positive Electrode for Dual-Ion Batteries , 2016 .

[14]  U. Schubert,et al.  Polymer-Based Organic Batteries. , 2016, Chemical reviews.

[15]  Xiulin Fan,et al.  “Water-in-Salt” electrolytes enable green and safe Li-ion batteries for large scale electric energy storage applications , 2016 .

[16]  P. Moreau,et al.  Reversible anion intercalation in a layered aromatic amine: a high-voltage host structure for organic batteries , 2016 .

[17]  Yunhui Huang,et al.  Routes to High Energy Cathodes of Sodium‐Ion Batteries , 2016 .

[18]  J. Long,et al.  A Dual-Ion Battery Cathode via Oxidative Insertion of Anions in a Metal-Organic Framework. , 2015, Journal of the American Chemical Society.

[19]  P. Cui,et al.  Metal-Organic Frameworks (MOFs) of a Cubic Metal Cluster with Multicentered Mn(I)-Mn(I) Bonds. , 2015, Angewandte Chemie.

[20]  V. Biju,et al.  Mixed valence nanostructured Mn3O4 for supercapacitor applications , 2015, Bulletin of Materials Science.

[21]  Xiulei Ji,et al.  Design of aqueous redox-enhanced electrochemical capacitors with high specific energies and slow self-discharge , 2015, Nature Communications.

[22]  Jun Chen,et al.  Recycling Application of Li—MnO2 Batteries as Rechargeable Lithium—Air Batteries. , 2015 .

[23]  Jun Chen,et al.  Recycling application of Li-MnO₂ batteries as rechargeable lithium-air batteries. , 2015, Angewandte Chemie.

[24]  Chaojiang Niu,et al.  Manganese oxide/carbon yolk-shell nanorod anodes for high capacity lithium batteries. , 2015, Nano letters.

[25]  M. Sathish,et al.  Supercritical fluid processing of nitric acid treated nitrogen doped graphene with enhanced electrochemical supercapacitance , 2014 .

[26]  M. Winter,et al.  Dual-graphite cells based on the reversible intercalation of bis(trifluoromethanesulfonyl)imide anions from an ionic liquid electrolyte , 2014 .

[27]  X. Lou,et al.  Mixed transition-metal oxides: design, synthesis, and energy-related applications. , 2014, Angewandte Chemie.

[28]  Changzhou Yuan,et al.  Gemischte Übergangsmetalloxide: Design, Synthese und energierelevante Anwendungen , 2014 .

[29]  Kang Xu,et al.  Dual-graphite chemistry enabled by a high voltage electrolyte , 2014 .

[30]  T. Jaramillo,et al.  In situ X-ray absorption spectroscopy investigation of a bifunctional manganese oxide catalyst with high activity for electrochemical water oxidation and oxygen reduction. , 2013, Journal of the American Chemical Society.

[31]  Bruce Dunn,et al.  High-rate electrochemical energy storage through Li+ intercalation pseudocapacitance. , 2013, Nature materials.

[32]  Haoshen Zhou,et al.  Suppressed Activation Energy for Interfacial Charge Transfer of a Prussian Blue Analog Thin Film Electrode with Hydrated Ions (Li+, Na+, and Mg2+) , 2013 .

[33]  John B Goodenough,et al.  The Li-ion rechargeable battery: a perspective. , 2013, Journal of the American Chemical Society.

[34]  Jun Chen,et al.  Organic Electrode Materials for Rechargeable Lithium Batteries , 2012 .

[35]  L. Nyholm,et al.  Toward Flexible Polymer and Paper‐Based Energy Storage Devices , 2011, Advanced materials.

[36]  H. Dai,et al.  Mn3O4-graphene hybrid as a high-capacity anode material for lithium ion batteries. , 2010, Journal of the American Chemical Society.

[37]  P. He,et al.  Raising the cycling stability of aqueous lithium-ion batteries by eliminating oxygen in the electrolyte. , 2010, Nature chemistry.

[38]  D. Dhawale,et al.  A novel chemical synthesis and characterization of Mn3O4 thin films for supercapacitor application , 2010 .

[39]  J. Goodenough,et al.  Challenges for Rechargeable Li Batteries , 2010 .

[40]  Hiroyuki Nishide,et al.  Emerging N‐Type Redox‐Active Radical Polymer for a Totally Organic Polymer‐Based Rechargeable Battery , 2009 .

[41]  Kenichiroh Koshika,et al.  An ultrafast chargeable polymer electrode based on the combination of nitroxide radical and aqueous electrolyte. , 2009, Chemical communications.

[42]  F. Farges.  Ab initio and experimental pre-edge investigations of the Mn K-edge XANES in oxide-type materials , 2005 .

[43]  Yun‐Hong Zhang,et al.  Drawing out the structural information of the first layer of hydrated ions: ATR-FTIR spectroscopic studies on aqueous NH4NO3, NaNO3, and Mg(NO3)2 solutions. , 2005, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[44]  Jianjun Niu,et al.  Comparative studies of self-discharge by potential decay and float-current measurements at C double-layer capacitor and battery electrodes , 2004 .

[45]  Yoji Sakurai,et al.  Reaction behavior of LiFePO4 as a cathode material for rechargeable lithium batteries , 2002 .

[46]  M. Kantcheva.  Identification, Stability, and Reactivity of NOx Species Adsorbed on Titania-Supported Manganese Catalysts , 2001 .

[47]  J. Dahn,et al.  Energy and Capacity Projections for Practical Dual‐Graphite Cells , 2000 .

[48]  J. Dahn,et al.  Electrochemical Intercalation of PF 6 into Graphite , 2000 .

[49]  S. Ardizzone,et al.  Mn3O4 and γ-MnOOH powders, preparation, phase composition and XPS characterisation , 1998 .

[50]  A. Hagfeldt,et al.  Li+ Ion Insertion in TiO2 (Anatase). 2. Voltammetry on Nanoporous Films , 1997 .

[51]  M. Noel,et al.  Effect of solvents on the intercalation/de-intercalation behaviour of monovalent ionic species from non-aqueous solvents on polypropylene-graphite composite electrode , 1997 .

[52]  P. Novák,et al.  Electrochemically Active Polymers for Rechargeable Batteries. , 1997, Chemical reviews.

[53]  A. Bard,et al.  Observation and Characterization by Scanning Tunneling Microscopy of Structures Generated by Cleaving Highly Oriented Pyrolytic Graphite , 1991 .

[54]  F. Beck,et al.  Reversible electrochemical insertion of anions in poly-p-phenylene from aqueous electrolytes , 1983 .

[55]  P. Nigrey,et al.  Lightweight Rechargeable Storage Batteries Using Polyacetylene, ( CH ) x as the Cathode‐Active Material , 1981 .

[56]  E. R. Nightingale,et al.  PHENOMENOLOGICAL THEORY OF ION SOLVATION. EFFECTIVE RADII OF HYDRATED IONS , 1959 .

[57]  M. Winter,et al.  Influence of Graphite Characteristics on the Electrochemical Intercalation of Bis(trifluoromethanesulfonyl) imide Anions into a Graphite-Based Cathode , 2013 .

[58]  Martin Winter,et al.  Reversible Intercalation of Bis(trifluoromethanesulfonyl)imide Anions from an Ionic Liquid Electrolyte into Graphite for High Performance Dual-Ion Cells , 2012 .

[59]  K. Nam,et al.  In Situ Mn K-edge X-ray Absorption Spectroscopy Studies of Electrodeposited Manganese Oxide Films for Electrochemical Capacitors , 2007 .

[60]  Paul J. Nigrey,et al.  Organic batteries: reversible n- and p- type electrochemical doping of polyacetylene, (CH)x , 1981 .