Complete Prevention of Dendrite Formation in Zn Metal Anodes by Means of Pulsed Charging Protocols.

Zn metal as anode in rechargeable batteries, such as Zn/air or Zn/Ni, suffers from poor cyclability. The formation of Zn dendrites upon cycling is the key limiting step. We report a systematic study of the influence of pulsed electroplating protocols on the formation of Zn dendrites and in turn on strategies to completely prevent Zn dendrite formation. Because of the large number of variables in electroplating protocols, a scanning droplet cell technique was adapted as a high-throughput methodology in which a descriptor of the surface roughness can be in situ derived by means of electrochemical impedance spectroscopy. Upon optimizing the electroplating protocol by controlling nucleation, zincate ion depletion, and zincate ion diffusion, scanning electron microscopy and atomic force microscopy confirmed the growth of uniform and homogenous Zn deposits with a complete prevention of dendrite growth. The implementation of pulsed electroplating as the charging protocol for commercially available Ni-Zn batteries leads to substantially prolonged cyclability demonstrating the benefits of pulsed charging in Zn metal-based batteries.

[1]  K. Kordesch,et al.  Triethanolamine as an additive to the anode to improve the rechargeability of alkaline manganese dioxide batteries , 2001 .

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

[3]  Mingyu Wang,et al.  Enhancing the rate and cycling performance of spherical ZnO anode material for advanced zinc-nickel secondary batteries by combined in-situ doping and coating with carbon , 2017 .

[4]  W. Schuhmann,et al.  A Three‐Electrode, Battery‐Type Swagelok Cell for the Evaluation of Secondary Alkaline Batteries: The Case of the Ni–Zn Battery , 2016 .

[5]  C. Koch,et al.  Influence of pulse plating parameters on the synthesis and preferred orientation of nanocrystalline zinc from zinc sulfate electrolytes , 2008 .

[6]  M. Armand,et al.  Building better batteries , 2008, Nature.

[7]  D. Steingart,et al.  An In Situ Synchrotron Study of Zinc Anode Planarization by a Bismuth Additive , 2014 .

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

[9]  S. Mu,et al.  Effect of inhibitors on Zn-dendrite formation for zinc-polyaniline secondary battery , 1998 .

[10]  Jae-Hun Kim,et al.  Metallic anodes for next generation secondary batteries. , 2013, Chemical Society reviews.

[11]  Xizhong Wang,et al.  Dendrite growth in the recharging process of zinc–air batteries , 2015 .

[12]  M. Lohrengel Interface and volume effects in biological cells and electrochemical microcells , 1997 .

[13]  Elton J. Cairns,et al.  The effect of pulse charging on the cycle-life performance of zinc/nickel oxide cells , 1988 .

[14]  Tsung-Shune Chin,et al.  Tetra-alkyl ammonium hydroxides as inhibitors of Zn dendrite in Zn-based secondary batteries , 2007 .

[15]  Stefano Passerini,et al.  An Overview and Future Perspectives of Aluminum Batteries , 2016, Advanced materials.

[16]  J. Mcbreen,et al.  The electrochemistry of metal oxide additives in pasted zinc electrodes , 1981 .

[17]  D. Chin,et al.  Zinc Electrode Morphology in Alkaline Solutions II . Study of Alternating Charging Current Modulation on Pasted Zinc Battery Electrodes , 1982 .

[18]  D. Tuomi The Forming Process in Nickel Positive Electrodes , 1965 .

[19]  Abdelbast Guerfi,et al.  Alkaline aqueous electrolytes for secondary zinc–air batteries: an overview , 2016 .

[20]  A. W. Hassel,et al.  The Scanning Droplet Cell and its Application to Structured Nanometer Oxide Films on Aluminium , 1997 .

[21]  C. Zhang,et al.  Effects of bismuth ion and tetrabutylammonium bromide on the dendritic growth of zinc in alkaline zincate solutions , 2001 .

[22]  J. Cook,et al.  Nonwovens as Separators for Alkaline Batteries An Overview , 2007 .

[23]  R. Penner Brownian Dynamics Simulations of the Growth of Metal Nanocrystal Ensembles on Electrode Surfaces in Solution: 2. The Effect of Deposition Rate on Particle Size Dispersion† , 2001 .

[24]  Hongjie Dai,et al.  Recent advances in zinc-air batteries. , 2014, Chemical Society reviews.

[25]  Sun Tai Kim,et al.  Metal–Air Batteries with High Energy Density: Li–Air versus Zn–Air , 2010 .

[26]  James McBreen,et al.  Bismuth oxide as an additive in pasted zinc electrodes , 1985 .

[27]  E. Barsoukov,et al.  Impedance spectroscopy : theory, experiment, and applications , 2005 .

[28]  K. Blurton,et al.  Controlled Current Deposition of Zinc from Alkaline Solution , 1969 .

[29]  Mark F. Mathias,et al.  Electrochemistry and the Future of the Automobile , 2010 .

[30]  Michael E. Mueller,et al.  Utilization of Hyper-Dendritic Zinc during High Rate Discharge in Alkaline Electrolytes , 2016 .

[31]  Xizhong Wang,et al.  Morphology control of zinc regeneration for zinc–air fuel cell and battery , 2014 .