Name: Zinc-Sponge Battery Electrodes that Suppress Dendrites (Video) | JoVE Journal
Uploaded: 2020-09-29T14:00:00.000+00:00
Duration: 6 min 58 s
Description: Learn a low-cost method for creating rechargeable zinc-sponge electrodes that suppress dendrites in alkaline batteries. This technique enables easy tuning of electrode structure for improved battery performance and scalability.

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5 minutes

This research was funded by the United States Office of Naval Research.

1. An emulsion-based method to create Zn-sponge electrodes
<ol>
	<li>Add 2.054 mL of deionized water to a 100 mL glass beaker.</li>
	<li>Add 4.565 mL of decane to the beaker.</li>
	<li>Stir in 0.1000 &#177; 0.0003 g of sodium dodecyl sulfate (SDS) until dissolved.</li>
	<li>Stir in 0.0050 &#177; 0.0003 g of water-soluble medium viscosity carboxymethyl cellulose (CMC) sodium salt by hand for 5 min or until the CMC is fully dissolved. 
	NOTE: Use plastic or plastic-coated stirring tools. Stirring with tools with a metallic surface can adversely affect resulting Zn sponges.</li>
	<li>Stir in 0.844 &#177; 0.002 g of water-insoluble preswollen carboxymethyl cellulose resin. 
	NOTE: This type of water-insoluble resin is expensive (USD$420 kg&#8211;1)6.</li>
	<li>Stir this mixture at 1,000 rpm for 5 min using an overhead paddle stirrer equipped with a plastic paddle.</li>
	<li>Pour 50 g of Zn powder (average particle size of 50 &#181;m, containing 307 ppm of bismuth and 307 ppm of indium for corrosion suppression) into the beaker while the overhead stirrer continues to spin at 1,000 rpm.</li>
	<li>Continue to stir the Zn paste for an additional 5 min at the same rate, 1,000 rpm.</li>
	<li>Stop the stirrer, remove the beaker, and outgas the mixture by placing the beaker and its contents under vacuum for 5 min in a desiccator at room temperature.</li>
	<li>Portion the Zn paste into polypropylene molds (~10 mm in diameter and ~5 mm in height) and let them dry in open air overnight. The shape of the mold dictates the form of the dried paste and resulting Zn sponges. 
	NOTE: Mold size and shape can vary. Past experiments5 successfully use cylindrical molds with diameters near 10&#160;mm. Fill the Zn paste up to a height of 5 mm or less. The shorter the height, the shorter the required drying time. See Table of Materials for commercially available molds.</li>
	<li>Carefully remove the dried Zn paste preforms from the molds and place them into a mesh casing that rests on a notched alumina holder5,6. 
	NOTE: Fabricate mesh casing, for instance, by bending a perforated-brass sheet into a cylinder with a diameter that is slightly larger than the desired diameter of the Zn-sponge electrode. Spray the perforated-metal sheet with boron-nitride lubricant after bending into a desired shape.</li>
	<li>Place the assembly into a tube furnace (67 mm in diameter) with ports to flow gas in and out of the tube. 
	NOTE: Use one port (the entrance port) to pipe gas into the furnace. Use the other (the exit port) to vent gas out of the tube furnace into a fume hood.</li>
	<li>Pipe N2 gas into the furnace for 30 min at a rate of 5.7&#160;cm&#8729;min&#8211;1 to purge the furnace of air. 
	NOTE: Step 1.13 can be achieved by connecting a tank of N2 gas with a digitally controlled flow meter to a tube connected to one of the entrance ports. Gas flow meters can be controlled manually or by a computer.</li>
	<li>Throttle the N2 gas to a constant rate of 2.8 cm&#8729;min&#8211;1 after the 30 min purge.</li>
	<li>Program the furnace to increase temperature linearly from 20 to 369 &#176;C over the course of 68 min, hold at 369 &#176;C for 5 h, rise linearly from 369 to 584 &#176;C over the course of 105 min, and then turn off.</li>
	<li>Start the furnace program while the N2 gas continues to flow.</li>
	<li>Manually stop the N2-gas flow after the 5 h temperature hold and pipe in breathing air at 2.8 cm&#8729;min&#8211;1. 
	NOTE: Step 1.17 can be achieved by connecting a tank of breathing air (not synthetic air) with a digitally controlled flow meter to a tube connected to an additional entrance port.</li>
	<li>Once the heating program stops, let the furnace cool to room temperature without active cooling, but keep the breathing air flowing.</li>
	<li>Remove the cooled Zn sponges and saw them and/or sand them to desired dimensions. 
	NOTE: A variety of sawing tools can be used such as hand-held rotary saws or vertical band saws. Abrasive or diamond blades are appropriate.</li>
</ol>
2. An aqueous-based method to create Zn-sponge electrodes
<ol>
	<li>Add 10.5 mL of deionized water to a 100-mL glass beaker.</li>
	<li>Stir in 0.120 &#177; 0.001 g of water-soluble high-viscosity cellulose gum, also known as carboxymethyl cellulose (CMC) sodium salt. 
	NOTE: Use plastic or plastic-coated stirring tools. Stirring with tools with a metallic surface can adversely affect resulting Zn sponges.</li>
	<li>Vortex and stir this mixture by hand for 5 min or until the CMC is dissolved.</li>
	<li>Stir in 2.400 &#177; 0.001 g of corn starch while vortexing for an additional 2 min.</li>
	<li>Stir in 120.00 &#177; 0.01 g of Zn powder (average particle size of 50 &#181;m, containing 307 ppm of bismuth and 307 ppm of indium for corrosion suppression) while vortexing for an additional 2 min.</li>
	<li>Press the resulting Zn paste into desired mold cavities. 
	NOTE: Mold size and shape can vary. Past experiments6 successfully use cylindrical molds with diameters near 10 mm. Fill the Zn paste up to a height of 50 mm or less. The aqueous Zn paste is dryer than the emulsion Zn paste, so the aqueous version can be used to make larger sponges that require less drying time. The shorter the height, the shorter the required drying time. The mold needs to be able to split in half as the aqueous Zn paste minimally contracts after drying, unlike the emulsion Zn paste. Unsalted butter can be used to lubricate the molds before pressing in the aqueous Zn paste to aid in demolding. Figure 1A shows the custom-machined molds packed with Zn paste following the aqueous-based protocol. Figure 1B shows the hand-made mesh casing, notched alumina holder, and resulting Zn sponge made using the aqueous-based method.</li>
	<li>Leave the Zn-paste-filled molds to dry overnight at 70 &#176;C in open air in a furnace.</li>
	<li>Follow the same handling and heat treatment steps (1.11&#8211;1.19) described for the emulsion-based method.</li>
</ol>

<ol><li>Parker, J. F., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Retaining+the+3D+Framework+of+Zinc+Sponge+Anodes+upon+Deep+Discharge+in+Zn-Air+Cells%5BTitle%5D)+AND+%22ACS+Applied+Materials+%26+Interfaces%22%5BJournal%5D)">Retaining the 3D Framework of Zinc Sponge Anodes upon Deep Discharge in Zn-Air Cells.</a> ACS Applied Materials & Interfaces. 6 (22), 19471-19476 (2014).</li>
<li>Parker, J. F., Chervin, C. N., Nelson, E. S., Rolison, D. R., Long, J. W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Wiring+zinc+in+three+dimensions+re-writes+battery+performance-dendrite-free+cycling%5BTitle%5D)+AND+%22Energy+%26+Environmental+Science%22%5BJournal%5D)">Wiring zinc in three dimensions re-writes battery performance-dendrite-free cycling.</a> Energy & Environmental Science. 7, 1117-1124 (2014).</li>
<li>Parker, J. F., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Rechargeable+nickel-3D+zinc+batteries%3A+An+energy-dense%2C+safer+alternative+to+lithium-ion%5BTitle%5D)+AND+%22Science%22%5BJournal%5D)">Rechargeable nickel-3D zinc batteries: An energy-dense, safer alternative to lithium-ion.</a> Science. 356 (6336), 415-418 (2017).</li>
<li>Ko, J. S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Robust+3D+Zn+sponges+enable+high-power%2C+energy-dense+alkaline+batteries%5BTitle%5D)+AND+%22ACS+Applied+Energy+Materials%22%5BJournal%5D)">Robust 3D Zn sponges enable high-power, energy-dense alkaline batteries.</a> ACS Applied Energy Materials. 2 (1), 212-216 (2018).</li>
<li>Hopkins, B. J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Fabricating+architected+zinc+electrodes+with+unprecedented+volumetric+capacity+in+rechargeable+alkaline+cells%5BTitle%5D)+AND+%22Energy+Storage+Materials%22%5BJournal%5D)">Fabricating architected zinc electrodes with unprecedented volumetric capacity in rechargeable alkaline cells.</a> Energy Storage Materials. 27, 370-376 (2020).</li>
<li>Hopkins, B. J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Low-cost+green+synthesis+of+zinc+sponge+for+rechargeable%2C+sustainable+batteries%5BTitle%5D)+AND+%22Sustainable+Energy+%26+Fuels%22%5BJournal%5D)">Low-cost green synthesis of zinc sponge for rechargeable, sustainable batteries.</a> Sustainable Energy & Fuels. 4, 3363-3369 (2020).</li>
<li>Yufit, V., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Operando+Visualization+and+Multi-scale+Tomography+Studies+of+Dendrite+Formation+and+Dissolution+in+Zinc+Batteries%5BTitle%5D)+AND+%22Joule%22%5BJournal%5D)">Operando Visualization and Multi-scale Tomography Studies of Dendrite Formation and Dissolution in Zinc Batteries.</a> Joule. 3 (2), 485-502 (2019).</li>
<li>Ashby, M. F., et al. <a target="_blank" href="http://scholar.google.com/scholar?hl=en&safe=off&q=author%3aAshby%2C+MF+%22Metal+Foams%3A+A+Design+Guide%22">Metal Foams: A Design Guide</a>. , Butterworth-Heinemann. Oxford. (2000).</li>
<li>Parker, J. F., Ko, J. S., Rolison, D. R., Long, J. W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Translating+Materials-Level+Performance+into+Device-Relevant+Metrics+for+Zinc-Based+Batteries%5BTitle%5D)+AND+%22Joule%22%5BJournal%5D)">Translating Materials-Level Performance into Device-Relevant Metrics for Zinc-Based Batteries.</a> Joule. 2 (12), 2519-2527 (2018).</li>
<li>Hopkins, B. J., Chervin, C. N., Parker, J. F., Long, J. W., Rolison, D. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((An+areal-energy+standard+to+validate+air-breathing+electrodes+for+rechargeable+zinc-air+batteries%5BTitle%5D)+AND+%22Advanced+Energy+Materials%22%5BJournal%5D)">An areal-energy standard to validate air-breathing electrodes for rechargeable zinc-air batteries.</a> Advanced Energy Materials. 10 (30), 2001287(2020).</li>
<li>Jayasayee, K., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Cold+Sintering+as+a+Cost-Effective+Process+to+Manufacture+Porous+Zinc+Electrodes+for+Rechargeable+Zinc-Air+Batteries%5BTitle%5D)+AND+%22Processes%22%5BJournal%5D)">Cold Sintering as a Cost-Effective Process to Manufacture Porous Zinc Electrodes for Rechargeable Zinc-Air Batteries.</a> Processes. 8 (5), 592(2020).</li>
<li>Chamoun, M., et al. <a target="_blank" href="http://scholar.google.com/scholar?hl=en&safe=off&q=author%3aChamoun%2C+M+%22NPG+Asia+Materials%22">NPG Asia Materials</a>. 7, 178(2015).</li>
<li>Kang, Z., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((3D+Porous+Copper+Skeleton+Supported+Zinc+Anode+toward+High+Capacity+and+Long+Cycle+Life+Zinc+Ion+Batteries%5BTitle%5D)+AND+%22ACS+Sustainable+Chemistry+%26+Engineering%22%5BJournal%5D)">3D Porous Copper Skeleton Supported Zinc Anode toward High Capacity and Long Cycle Life Zinc Ion Batteries.</a> ACS Sustainable Chemistry & Engineering. 7 (3), 3364-3371 (2019).</li>
<li>Yu, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Ag-Modified+Cu+Foams+as+Three-Dimensional+Andoes+for+Rechargeable+Zinc-Air+Batteries%5BTitle%5D)+AND+%22ACS+Applied+Nano+Materials%22%5BJournal%5D)">Ag-Modified Cu Foams as Three-Dimensional Andoes for Rechargeable Zinc-Air Batteries.</a> ACS Applied Nano Materials. 2 (5), 2679-2688 (2019).</li>
<li>Stumpp, M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Controlled+Electrodeposition+of+Zinc+Oxide+on+Conductive+Meshes+and+Foams+Enabling+Its+Use+as+Secondary+Anode%5BTitle%5D)+AND+%22Journal+of+The+Electrochemical+Society%22%5BJournal%5D)">Controlled Electrodeposition of Zinc Oxide on Conductive Meshes and Foams Enabling Its Use as Secondary Anode.</a> Journal of The Electrochemical Society. 165 (10), 461-466 (2018).</li>
<li>Stock, D., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Design+Strategy+for+Zinc+Anodes+with+Enhanced+Utilization+and+Retention%3A+Electrodeposited+Zinc+Oxide+on+Carbon+Mesh+Protected+by+Ionomeric+Layers%5BTitle%5D)+AND+%22ACS+Applied+Energy+Materials%22%5BJournal%5D)">Design Strategy for Zinc Anodes with Enhanced Utilization and Retention: Electrodeposited Zinc Oxide on Carbon Mesh Protected by Ionomeric Layers.</a> ACS Applied Energy Materials. 1 (10), 5579-5588 (2018).</li>
<li>Li, C., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Spatially+homogeneous+copper+foam+as+surface+dendrite-free+host+for+zinc+metal+anode%5BTitle%5D)+AND+%22Chemical+Engineering+Journal%22%5BJournal%5D)">Spatially homogeneous copper foam as surface dendrite-free host for zinc metal anode.</a> Chemical Engineering Journal. 379, 122248(2020).</li>
<li>Zhou, Z., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Graphene+oxide-modified+zinc+anode+for+rechargeable+aqueous+batteries%5BTitle%5D)+AND+%22Chemical+Engineering+Science%22%5BJournal%5D)">Graphene oxide-modified zinc anode for rechargeable aqueous batteries.</a> Chemical Engineering Science. 194, 142-147 (2019).</li>
<li>McDevitt, K. M., Mumm, D. R., Mohraz, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Improving+Cyclability+of+ZnO+Electrodes+through+Microstructural+Design%5BTitle%5D)+AND+%22ACS+Applied+Energy+Materials%22%5BJournal%5D)">Improving Cyclability of ZnO Electrodes through Microstructural Design.</a> ACS Applied Energy Materials. 2 (11), 8107-8117 (2019).</li>
<li>Wang, C., Zhu, G., Liu, P., Chen, Q. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Monolithic+Nanoporous+Zn+Anode+for+Rechargeable+Alkaline+Batteries%5BTitle%5D)+AND+%22ACS+Nano%22%5BJournal%5D)">Monolithic Nanoporous Zn Anode for Rechargeable Alkaline Batteries.</a> ACS Nano. 14 (2), 2404-2411 (2020).</li>
<li>Drillet, J. F., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Development+of+a+Novel+Zinc%2FAir+Fuel+Cell+with+a+Zn+Foam+Anode%2C+a+PVA%2FKOH+Membrane+and+a+MnO2%2FSiOC-based+Air+Cathode%5BTitle%5D)+AND+%22ECS+Transactions%22%5BJournal%5D)">Development of a Novel Zinc/Air Fuel Cell with a Zn Foam Anode, a PVA/KOH Membrane and a MnO2/SiOC-based Air Cathode.</a> ECS Transactions. 28, 13-24 (2010).</li>
<li>Bozzini, B., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Morphological+evolution+of+Zn-sponge+electrodes+monitored+by+in+situ+X-ray+computed+microtomography%5BTitle%5D)+AND+%22ACS+Applied+Energy+Materials%22%5BJournal%5D)">Morphological evolution of Zn-sponge electrodes monitored by in situ X-ray computed microtomography.</a> ACS Applied Energy Materials. , (2020).</li>
<li>Yang, Q., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Do+Zinc+Dendrites+Exist+in+Neutral+Zinc+Batteries%3A+A+Developed+Electrohealing+Strategy+to+In+Situ+Rescue+In-Service+Batteries%5BTitle%5D)+AND+%22Advanced+Materials%22%5BJournal%5D)">Do Zinc Dendrites Exist in Neutral Zinc Batteries: A Developed Electrohealing Strategy to In Situ Rescue In-Service Batteries.</a> Advanced Materials. 31, 1903778(2019).</li>
<li>Yang, Q., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Hydrogen-Substituted+Graphdiyne+Ion+Tunnels+Directing+Concentration+Redistribution+for+Commercial-Grate+Dendrite-Free+Zinc+Anodes%5BTitle%5D)+AND+%22Advanced+Materials%22%5BJournal%5D)">Hydrogen-Substituted Graphdiyne Ion Tunnels Directing Concentration Redistribution for Commercial-Grate Dendrite-Free Zinc Anodes.</a> Advanced Materials. 32, 2001755(2020).</li>
<li>Narayanan, S. R., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Materials+challenges+and+technical+approaches+for+realizing+inexpensive+and+robust+iron-air+batteries+for+large-scale+energy+storage%5BTitle%5D)+AND+%22Solid+State+Ionics%22%5BJournal%5D)">Materials challenges and technical approaches for realizing inexpensive and robust iron-air batteries for large-scale energy storage.</a> Solid State Ionics. 216, 105-109 (2012).</li>
<li>Xiong, H., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Effects+of+Heat+Treatment+on+the+Discharge+Behavior+of+Mg-6wt.%25Al-1wt.%25Sn+Alloy+as+Anode+for+Magnesium-Air+Batteries%5BTitle%5D)+AND+%22Journal+of+Materials+Engineering+and+Performance%22%5BJournal%5D)">Effects of Heat Treatment on the Discharge Behavior of Mg-6wt.%Al-1wt.%Sn Alloy as Anode for Magnesium-Air Batteries.</a> Journal of Materials Engineering and Performance. 26, 2901-2911 (2017).</li>
<li>Hopkins, B. J., Shao-Horn, Y., Hart, D. P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((Suppressing+corrosion+in+primary+aluminum-air+batteries+via+oil+displacement%5BTitle%5D)+AND+%22Science%22%5BJournal%5D)">Suppressing corrosion in primary aluminum-air batteries via oil displacement.</a> Science. 362, 658-661 (2018).</li>
<li>Hopkins, B. J., Long, J. W., Rolison, D. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/pubmed?term=((High-Performance+Structural+Batteries%5BTitle%5D)+AND+%22Joule%22%5BJournal%5D)">High-Performance Structural Batteries.</a> Joule. , (2020).</li>
</ol>

J.F.P., D.R.R., and J.W.L. hold patents related to zinc electrodes: US Patents no. 9802254, 10008711,&#160;10720635, and 10763500, EU Patent no 2926395, and China Patent no. 104813521.

Modifications and troubleshooting associated with these protocols include filling the freshly mixed Zn paste into a mold cavity. Care should be taken to avoid air pockets. Unwanted voids can be decreased by tapping the mold after filling or while filling. Because the aqueous Zn paste is dry, pressure can be applied directly to the Zn paste to push out air pockets while filling up the mold cavity.
A limitation of the methods is that Zn-sponge pore structure is disordered, but the Zn and porogen...

The purpose of the reported fabrication methods is to create zinc (Zn) sponge electrodes that suppress dendrite formation and shape change. Historically, these problems have limited the cycle life of Zn batteries. Zinc-sponge electrodes have resolved these issues, enabling Zn batteries with longer cycle lives1,2,3,4,5,6. The sponge structure suppresses dendrite formation and shape change because (1) the fused Zn framework electrically wires the entire volume of the sponge; (2) the pores hold zincate near the Zn-sponge surface; and (3) the sponge has a high surface area that decreases local current density below values identified to sprout dendrites in alkaline electrolytes7. However, if sponge surface area is too high, substantial corrosion occurs5. If the sponge pores are too large, the sponge will have a low volumetric capacity5. Also, if the sponge pores are too small, the Zn electrode will have insufficient electrolyte to access Zn during discharge, resulting in low power and capacity5,6.
The rationale behind the reported fabrication methods is to create Zn sponges with appropriate sponge porosities and pore diameters. Experimentally, we find that Zn sponges with porosities from 50 to 70% and pore diameters near 10&#160;&#181;m cycle well in full-cell batteries and display low corrosion rates5. We note that existing methods to manufacture commercial metal foams fail to achieve similar morphologies on these length scales8, so the reported fabrication methods are needed.
The advantages of the methods reported here over alternatives are characterized by fine control of sponge features and by the ability to fabricate large, dense Zn sponges with technologically relevant areal-capacity values5,6,9,10. Alternative methods to create Zn foams may be unable to create comparable 10 &#181;m pores with sponge porosities near 50%. Such alternatives may, however, require less energy to fabricate because they avoid high-temperature processing steps. Alternative processes include the following strategies: cold sintering Zn particles11, depositing Zn on three-dimensional host structures12,13,14,15,16,17, cutting Zn foil into two-dimensional foams18, and creating Zn foams via spinodal decomposition19 or percolation dissolution20.
The context of the reported methods in the wider body of the published literature is primarily established by work from Drillet et al.21. They adapted methods of fabricating porous ceramics to create one of the earliest reported three-dimensional, albeit fragile, Zn foams for batteries. These authors, however, failed to demonstrate rechargeability, likely because of the poor connectivity between the Zn particles. Prior to rechargeable Zn-sponge electrodes, the best alternative to a Zn foil electrode was a Zn-powder electrode, wherein Zn powder is mixed with a gel electrolyte. Zinc-powder electrodes are commercially used in primary alkaline batteries (Zn&#8211;MnO2) but have poor rechargeability because Zn particles become passivated by Zn oxide (ZnO), which can increase local current density that spurs dendrite growth3,22. We note that there are other dendrite-suppression strategies that do not involve foam or sponge architectures23,24.
The reported Zn-sponge fabrication methods require a tube furnace, sources of air and nitrogen gas (N2), and a fume hood. All steps can be performed at a lab desk without environmental control, but exhaust from the tube furnace during heat treatment should be piped to a fume hood. Resulting electrodes are appropriate for those interested in creating rechargeable Zn electrodes capable of high areal capacity (&#62; 10 mAh cmgeo&#8211;2)6.
The first reported fabrication method is an emulsion-based route to create Zn-sponge electrodes. The second, is an aqueous-based route. An advantage of the emulsion route is its ability to create Zn paste that, when dried, is easy to demold from a mold cavity. A disadvantage is its reliance on expensive materials. For the aqueous route, sponge preforms can be challenging to demold, but this process uses inexpensive and abundant materials.
Both methods involve mixing Zn particles with a porogen and viscosity-enhancing agent. The resulting mixture is heated under N2 and then breathing air (not synthetic air). During heating under N2, the Zn particles anneal and the porogen decomposes; under breathing air, the annealed Zn particles fuse and the porogen burns out. These processes yield metal foams or sponges. The mechanical and electrochemical properties of the Zn sponges can be tuned by varying Zn-to-porogen mass ratio, heating time under N2 and air, and size and shape of the Zn and porogen particles.

<table><tbody><tr><td>Corn starch</td><td>Argo</td><td>Not applicable</td><td>This acts as a porogen and viscosity-enhancing agent.</td></tr><tr><td>Decane</td><td>MilliporeSigma</td><td>D901</td><td></td></tr><tr><td>Medium viscosity water-soluble carboxymethyl cellulose (CMC) sodium salt</td><td>MilliporeSigma</td><td>C4888-500G</td><td>This CMC acts primarily as a viscosity-enhancing agent.</td></tr><tr><td>Overhead stirrer</td><td>Caframo Lab Solutions</td><td>BDC3030</td><td></td></tr><tr><td>Small cylindrical models for Zn sponges</td><td>VWR</td><td>66014-358</td><td>The caps of the vials can be used as molds.</td></tr><tr><td>Sodium dodecyl sulfate</td><td>MilliporeSigma</td><td>436143</td><td></td></tr><tr><td>Water-insoluble IonSep CMC 52 preswollen carboxymethyl cellulose resin</td><td>BIOpHORETICS</td><td>B45019.01</td><td>This CMC acts as a porogen and viscosity-enhancing agent.</td></tr><tr><td>Zn powder</td><td>EverZinc</td><td>Custom order</td><td></td></tr></tbody></table>

zinc-sponge battery electrodes that suppress dendrites

Zinc-Sponge Battery Electrodes that Suppress Dendrites

We report two methods to create zinc-sponge electrodes that suppress dendrite formation and shape change for rechargeable zinc batteries. Both methods are characterized by creating a paste made of zinc particles, organic porogen, and viscosity-enhancing agent that is heated under an inert gas and then air. During heating under the inert gas, the zinc particles anneal together, and the porogen decomposes; under air, the zinc fuses and residual organic burns out, yielding an open-cell metal foam or sponge. We tune the mechanical and electrochemical properties of the zinc sponges by varying zinc-to-porogen mass ratio, heating time under inert gas and air, and size and shape of the zinc and porogen particles. An advantage of the reported methods is their ability to finely tune zinc-sponge architecture. The selected size and shape of the zinc and porogen particles influence the morphology of the pore structure. A limitation is that resulting sponges have disordered pore structures that result in low mechanical strength at low volume fractions of zinc (&#60;30%). Applications for these zinc-sponge electrodes include batteries for grid-storage, personal electronics, electric vehicles, and electric aviation. Users can expect zinc-sponge electrodes to cycle up to 40% depth of discharge at technologically relevant rates and areal capacities without the formation of separator-piercing dendrites.

Resulting, fully heat-treated, emulsion-based Zn sponges have densities of 2.8 g∙cm–3 while aqueous-based sponges approach 3.3 g∙cm–3. During heating under air, a layer of ZnO forms on the Zn surfaces, which should have a thickness of 0.5–1.0 µm (observed using scanning electron microscopy)5. The solid in the resulting sponges should be 72% Zn (emulsion version) or 78% Zn (aqueous version) with the remainder being ZnO (measured by X-ray diffraction)6. ...

The goal of the reported protocols is to create rechargeable zinc-sponge electrodes that suppress dendrites and shape change in zinc batteries, such as nickel&#8211;zinc or zinc&#8211;air.

We report two methods to create zinc-sponge electrodes that suppress dendrite formation and shape change for rechargeable zinc batteries. Both methods are ...

zinc-sponge-battery-electrodes-that-suppress-dendrites

Research

JoVE Journal

Chemistry

A protocol is presented to study multi-electron metal/air battery systems by using previous technology developed for the zinc/air cell. Electrochemical testing is then performed on fabricated batteries to evaluate performance.

Fabrication of VB2/Air Cells for Electrochemical Testing

We describe the use of synchrotron X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) techniques to probe details of intercalation/deintercalation processes in electrode materials for Li-ion and Na-ion batteries. Both in situ and ex situ experiments are used to understand structural behavior relevant to the operation of...

Characterization of Electrode Materials for Lithium Ion and Sodium Ion Batteries Using Synchrotron Radiation Techniques

We describe the design and construction of an electrochemical cell for the examination of electrode materials using in situ neutron powder diffraction (NPD). We briefly comment on alternate in situ NPD cell designs and discuss methods for the analysis of the corresponding in situ NPD data produced using this cell.

In Situ Neutron Powder Diffraction Using Custom-made Lithium-ion Batteries

Synchrotron-based hard X-ray microtomography is used to image the electrochemical growth of dendrites from a lithium metal electrode through a solid polymer electrolyte membrane.

Failure Analysis of Batteries Using Synchrotron-based Hard X-ray Microtomography

Non-aqueous electrode processing is central to the construction of coin cells and the evaluation of new electrode chemistries for lithium-ion batteries. A step-by-step guide to the basic practices needed as an electrochemical engineer working with batteries in an academic experimental setting is furnished.

Non-aqueous Electrode Processing and Construction of Lithium-ion Coin Cells

A protocol for the fabrication of electrochemically active LiPON-based solid-state lithium-ion nanobatteries using a focused ion beam is presented.

Focused Ion Beam Fabrication of LiPON-based Solid-state Lithium-ion Nanobatteries for In Situ Testing

The incorporation of reference electrodes in a Li-ion battery provides valuable information to elucidate degradation mechanisms at high voltages. In this article, we present a cell design that accommodates multiple reference electrodes, along with the assembly steps to assure maximum accuracy of the data obtained in electrochemical measurements.

In Situ Lithiated Reference Electrode: Four Electrode Design for In-operando Impedance Spectroscopy

Three-electrode cells are useful in studying the electrochemistry of lithium-ion batteries. Such an electrochemical setup allows the phenomena associated with the cathode and anode to be decoupled and examined independently. Here, we present a guide for construction and use of a three-electrode coin cell with emphasis on lithium plating analytics.

Three-electrode Coin Cell Preparation and Electrodeposition Analytics for Lithium-ion Batteries

A protocol for the construction of a soluble lead flow battery with an extended lifespan, in which sodium acetate is supplied in the methanesulfonic electrolyte as an additive, is presented.

Extending the Lifespan of Soluble Lead Flow Batteries with a Sodium Acetate Additive

Utilizing the volume change of Si nanoparticles during (de)lithiation, the present protocol describes a screening method of potential coatings for all-solid-state batteries using in situ transmission electron microscopy.

Screening of Coatings for an All-Solid-State Battery Using In Situ Transmission Electron Microscopy

Here, we present a simple and low-cost glycerol displacement method based on Archimedes' principle for measuring lead-acid battery electrode porosities. The method demonstrates good reproducibility and is safer than traditional techniques, requiring low-hazard chemicals and equipment. Combining the technique with microstructural analysis by X-ray diffraction provides information on battery electrode properties and degradation.

Archimedes-Based Glycerol Displacement for Electrode Porosity Measurement in Lead-Acid Batteries

Learn a low-cost method for creating rechargeable zinc-sponge electrodes that suppress dendrites in alkaline batteries. This technique enables easy tuning of electrode structure for improved battery performance and scalability.

Zinc-Sponge Battery Electrodes that Suppress Dendrites

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