Highly reversible zinc metal anode for aqueous batteries

Metallic zinc (Zn) has been regarded as an ideal anode material for aqueous batteries because of its high theoretical capacity (820 mA h g–1), low potential (−0.762 V versus the standard hydrogen electrode), high abundance, low toxicity and intrinsic safety. However, aqueous Zn chemistry persistently suffers from irreversibility issues, as exemplified by its low coulombic efficiency (CE) and dendrite growth during plating/ stripping, and sustained water consumption. In this work, we demonstrate that an aqueous electrolyte based on Zn and lithium salts at high concentrations is a very effective way to address these issues. This unique electrolyte not only enables dendrite-free Zn plating/stripping at nearly 100% CE, but also retains water in the open atmosphere, which makes hermetic cell configurations optional. These merits bring unprecedented flexibility and reversibility to Zn batteries using either LiMn2O4 or O2 cathodes—the former deliver 180 W h kg–1 while retaining 80% capacity for >4,000 cycles, and the latter deliver 300 W h kg–1 (1,000 W h kg–1 based on the cathode) for >200 cycles.Metallic zinc is an ideal anode material for aqueous batteries but suffers from irreversibility issues. An aqueous electrolyte based on Zn and lithium salts using either LiMn2O4 or O2 cathodes now brings unprecedented flexibility and reversibility to Zn batteries.

[1]  K. Persson,et al.  Origin of Electrochemical, Structural, and Transport Properties in Nonaqueous Zinc Electrolytes. , 2016, ACS applied materials & interfaces.

[2]  A. J. Smith,et al.  A High Precision Study of the Coulombic Efficiency of Li-Ion Batteries , 2010 .

[3]  K. Zaghib,et al.  High cycling stability of zinc-anode/conducting polymer rechargeable battery with non-aqueous electrolyte , 2014 .

[4]  Lin Yang,et al.  Flexible High‐Energy Polymer‐Electrolyte‐Based Rechargeable Zinc–Air Batteries , 2015, Advanced materials.

[5]  Lizhi Xiong,et al.  The electrochemical performance improvement of LiMn2O4/Zn based on zinc foil as the current collector and thiourea as an electrolyte additive , 2015 .

[6]  Jing Zhang,et al.  Laminated Cross‐Linked Nanocellulose/Graphene Oxide Electrolyte for Flexible Rechargeable Zinc–Air Batteries , 2016 .

[7]  Xiulin Fan,et al.  “Water‐in‐Salt” Electrolyte Enables High‐Voltage Aqueous Lithium‐Ion Chemistries. , 2016 .

[8]  Pucheng Pei,et al.  Technologies for extending zinc–air battery’s cyclelife: A review , 2014 .

[9]  S. Kheawhom,et al.  Development of a High Energy Density Flexible Zinc-Air Battery , 2016 .

[10]  Xufeng Zhou,et al.  Towards High‐Voltage Aqueous Metal‐Ion Batteries Beyond 1.5 V: The Zinc/Zinc Hexacyanoferrate System , 2015 .

[11]  Pu Chen,et al.  Rechargeable hybrid aqueous batteries , 2012 .

[12]  D. W. Barnum Hydrolysis of cations. Formation constants and standard free energies of formation of hydroxy complexes , 1983 .

[13]  Pengfei Yan,et al.  Reversible aqueous zinc/manganese oxide energy storage from conversion reactions , 2016, Nature Energy.

[14]  Douglas G. Ivey,et al.  Electrochemical behavior of Zn/Zn(II) couples in aprotic ionic liquids based on pyrrolidinium and imidazolium cations and bis(trifluoromethanesulfonyl)imide and dicyanamide anions , 2013 .

[15]  Steven R. Kline,et al.  Reduction and analysis of SANS and USANS data using IGOR Pro , 2006 .

[16]  G. Richmond,et al.  Water at Hydrophobic Surfaces: Weak Hydrogen Bonding and Strong Orientation Effects , 2001, Science.

[17]  Faxing Wang,et al.  An Aqueous Rechargeable Zn//Co3O4 Battery with High Energy Density and Good Cycling Behavior , 2016, Advanced materials.

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

[19]  J. C. Burns,et al.  Predicting and Extending the Lifetime of Li-Ion Batteries , 2013 .

[20]  O. Borodin,et al.  A Density Functional Theory Study of the Structure and Energetics of Zincate Complexes , 2001 .

[21]  William J. Orts,et al.  The 30 m Small-Angle Neutron Scattering Instruments at the National Institute of Standards and Technology , 1998 .

[22]  Maria Forsyth,et al.  Ionic liquid electrolytes as a platform for rechargeable metal-air batteries: a perspective. , 2014, Physical chemistry chemical physics : PCCP.

[23]  Hongjie Dai,et al.  Recent Advances in Zinc—Air Batteries , 2014 .

[24]  Ji‐Guang Zhang,et al.  Lithium metal anodes for rechargeable batteries , 2014 .

[25]  James W. Evans,et al.  Direct write dispenser printing of a zinc microbattery with an ionic liquid gel electrolyte , 2010 .

[26]  O. Borodin,et al.  Liquid Structure with Nano-Heterogeneity Promotes Cationic Transport in Concentrated Electrolytes. , 2017, ACS Nano.

[27]  D. Ivey,et al.  Rechargeable Zn-air batteries: Progress in electrolyte development and cell configuration advancement , 2015 .

[28]  E. P. Lewis In perspective. , 1972, Nursing outlook.

[29]  Z. Bakenov,et al.  High Performance Zn/LiFePO4 Aqueous Rechargeable Battery for Large Scale Applications , 2015 .

[30]  Rohan Akolkar,et al.  Suppressing Dendrite Growth during Zinc Electrodeposition by PEG-200 Additive , 2013 .

[31]  Linda F. Nazar,et al.  A high-capacity and long-life aqueous rechargeable zinc battery using a metal oxide intercalation cathode , 2016, Nature Energy.

[32]  D. Steingart,et al.  Hyper-dendritic nanoporous zinc foam anodes , 2015 .

[33]  D. Ivey,et al.  The state of water in 1-butly-1-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide and its effect on Zn/Zn(II) redox behavior , 2013 .

[34]  Zhigang Zak Fang,et al.  A lithium–oxygen battery based on lithium superoxide , 2016, Nature.

[35]  Jingde Li,et al.  Pomegranate-Inspired Design of Highly Active and Durable Bifunctional Electrocatalysts for Rechargeable Metal-Air Batteries. , 2016, Angewandte Chemie.

[36]  O. Borodin,et al.  High rate and stable cycling of lithium metal anode , 2015, Nature Communications.

[37]  Min Gyu Kim,et al.  High-performance non-spinel cobalt–manganese mixed oxide-based bifunctional electrocatalysts for rechargeable zinc–air batteries , 2016 .

[38]  Tong Cui,et al.  Dendrite-Free Nanocrystalline Zinc Electrodeposition from an Ionic Liquid Containing Nickel Triflate for Rechargeable Zn-Based Batteries. , 2016, Angewandte Chemie.

[39]  F. La Mantia,et al.  An aqueous zinc-ion battery based on copper hexacyanoferrate. , 2015, ChemSusChem.

[40]  Joseph F. Parker,et al.  Wiring zinc in three dimensions re-writes battery performance—dendrite-free cycling , 2014 .

[41]  Aijun Li,et al.  Self-assembly formation of Bi-functional Co3O4/MnO2-CNTs hybrid catalysts for achieving both high energy/power density and cyclic ability of rechargeable zinc-air battery , 2016, Scientific Reports.

[42]  D. Ivey,et al.  Zn/Zn(II) Redox Kinetics and Zn Deposit Morphology in Water Added Ionic Liquids with Bis(trifluoromethanesulfonyl)imide Anions , 2014 .

[43]  Yunhui Huang,et al.  Hybrid aqueous battery based on Na3V2(PO4)3/C cathode and zinc anode for potential large-scale energy storage , 2016 .

[44]  C. Cramer,et al.  Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions. , 2009, The journal of physical chemistry. B.

[45]  Joseph F. Parker,et al.  Retaining the 3D framework of zinc sponge anodes upon deep discharge in Zn-air cells. , 2014, ACS applied materials & interfaces.

[46]  D. Irish,et al.  Vibrational spectral studies of ion-ion and ion-solvent interactions. III. Zinc nitrate in water/acetonitrile mixtures , 1978 .

[47]  Elizabeth A. Amin,et al.  Zn Coordination Chemistry:  Development of Benchmark Suites for Geometries, Dipole Moments, and Bond Dissociation Energies and Their Use To Test and Validate Density Functionals and Molecular Orbital Theory. , 2008, Journal of chemical theory and computation.

[48]  Joseph F. Parker,et al.  Rechargeable nickel–3D zinc batteries: An energy-dense, safer alternative to lithium-ion , 2017, Science.

[49]  Chenggang Li,et al.  Binary Ion Batteries Operating on the Model of Newton's Cradle , 2012 .

[50]  Zhen Liu,et al.  Dissolution of zinc oxide in a protic ionic liquid with the 1-methylimidazolium cation and electrodeposition of zinc from ZnO/ionic liquid and ZnO/ionic liquid–water mixtures , 2015 .

[51]  D. Irish,et al.  Vibrational spectral studies of ion-ion and ion-solvent interactions. I. Zinc nitrate in water , 1978 .

[52]  Robert C. Wolpert,et al.  A Review of the , 1985 .