这项研究由美国海军研究办公室资助。

1. 制造Zn-海绵电极的乳液方法
<ol><li>在 100 mL 玻璃烧杯中加入 2.054 毫升的去离子水。</li>
	<li>在烧饼中加入 4.565 mL 的脱脂。</li>
	<li>搅拌0.1000±0.0003克硫酸钠（SDS），直到溶解。</li>
	<li>用手搅拌0.0050±0.0003克 水溶性 中粘性甲基纤维素（CMC）钠盐5分钟或直到CMC完全溶解。 注意:使用塑料或塑料涂层的搅拌工具。用金属表面的工具搅拌会对由此产生的 Zn 海绵产生不利影响。</li>
	<li>搅拌0.844±0.002克 水溶性 预膨胀的卡盒甲基纤维素树脂。 注:这种类型的水溶性树脂是昂贵的（420公斤=1）6。</li>
	<li>使用装有塑料桨的架空桨搅拌器，在 1，000 rpm 下搅拌该混合物 5 分钟。</li>
	<li>将 50 克 Zn 粉末（平均颗粒大小为 50 μm，含 307 ppm 的双糖和 307 ppm 的钛用于抑制腐蚀）倒入烧杯中，而头顶搅拌器继续以 1，000 rpm 的速度旋转。</li>
	<li>继续搅拌 Zn 糊以相同的速度再搅拌 5 分钟， 1，000 rpm 。</li>
	<li>停止搅拌器，取出烧嘴，在室温下将烧嘴及其内装物在真空中放置5分钟，使混合物过气。</li>
	<li>将 Zn 粘贴成聚丙烯模具（直径为 10 毫米，高度为 ±5 mm），并在露天过夜干燥。模具的形状决定了干燥糊的形式和由此产生的Zn海绵。 注:模具大小和形状可能有所不同。过去的实验5 成功使用直径接近10毫米的圆柱形模具。填充 Zn 粘贴，高度可达 5 mm 或更少。高度越短，所需的干燥时间越短。有关商用模具 的材料表 。。</li>
	<li>小心地从模具中取出干燥的 Zn 糊状物，并将其放入网状外壳中，该套管靠在5、6的氧化铝支架上。 注:例如，通过将穿孔黄铜板弯曲成直径略大于 Zn-海绵电极所需直径的圆柱体来制造网状外壳。弯曲成所需的形状后，用氮化物润滑剂喷洒穿孔金属板。</li>
	<li>将装配件放入管炉（直径为 67 毫米），并带有进出管子的气体端口。 注:使用一个端口（入口端口）将气体输送到炉子中。使用另一个（出口端口）将管炉中的气体排出到烟气罩中。</li>
	<li>将 N2 气体管道送入炉内 30 分钟，速度为 5.7 厘米[最小±1]， 以清除炉内空气。 注:第 1.13 步可以通过将 N2 气体罐与数字控制流量计连接到连接到其中一个入口端口的管子来实现。气体流量计可以手动控制或由计算机控制。</li>
	<li>在 30 分钟的清除后，将 N2 气体限制在 2.8 cm+ 最小+1 的恒定速率。</li>
	<li>将炉子在 68 分钟内将温度线性地从 20 升到 369 °C，在 369 °C 保持 5 小时，在 105 分钟内线性地从 369 °C 上升至 584 °C，然后关闭。</li>
	<li>启动炉子程序，而 N2 气体继续流动。</li>
	<li>手动停止N2气体流动后，5小时的温度保持和管道呼吸空气在2.8厘米+最小+1。 注:第 1.17 步可以通过将呼吸空气罐（不是合成空气）与数字控制流量计连接到连接到其他入口端口的管子来实现。</li>
	<li>加热程序停止后，让炉子冷却到室温，而无需主动冷却，但保持呼吸空气流动。</li>
	<li>取出冷却的 Zn 海绵，看到它们和/或将它们砂到所需的尺寸。 注:各种锯具可用于手持旋转锯或垂直带锯。磨蚀性或金刚石叶片是适当的。</li>
</ol>2. 一种基于船的制造Zn海绵电极的方法
<ol><li>在 100 毫升玻璃烧杯中加入 10.5 毫升的去离子水。</li>
	<li>搅拌0.120±0.001克 水溶性 高粘度纤维素胶，也称为卡盒甲基纤维素（CMC）钠盐。 注意:使用塑料或塑料涂层的搅拌工具。用金属表面的工具搅拌会对由此产生的 Zn 海绵产生不利影响。</li>
	<li>漩涡，用手搅拌5分钟或直到CMC溶解。</li>
	<li>搅拌2.400±0.001克玉米淀粉，同时再漩涡2分钟。</li>
	<li>搅拌 120.00 ± 0.01 克 Zn 粉末（平均颗粒大小为 50 μm，含有 307 ppm 的双糖和 307 ppm 的钛，用于抑制腐蚀），同时再涡流 2 分钟。</li>
	<li>将生成的 Zn 粘贴按入所需的模具腔中。 注:模具大小和形状可能有所不同。过去的实验6 成功使用直径接近10毫米的圆柱形模具。填充 Zn 粘贴，高度可达 50 mm 或更少。水性 Zn 糊比乳液 Zn 糊更干燥，因此水性版本可用于制作需要较少干燥时间的较大海绵。高度越短，所需的干燥时间越短。模具需要能够分成两半，因为与乳液 Zn 糊不同，在干燥后，作为液态 Zn 粘贴的最小收缩。无盐黄油可用于润滑模具，然后按压在无色 Zn 糊中，以帮助脱销。 图 1A 显示按照基于水的协议，用 Zn 糊包装的定制模具。 图1B 显示了手工制作的网状套管、带状氧化铝支架，以及由此产生的Zn海绵，使用基于 asous 的方法制造。</li>
	<li>让充满 Zn 糊的模具在 70 °C 的露天在熔炉中干燥过夜。</li>
	<li>遵循乳液方法中描述的相同处理和热处理步骤（1.11/1.19）。</li>
</ol>

<ol>
	<li>Parker, J. F., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Retaining+the+3D+Framework+of+Zinc+Sponge+Anodes+upon+Deep+Discharge+in+Zn-Air+Cells.">Retaining the 3D Framework of Zinc Sponge Anodes upon Deep Discharge in Zn-Air Cells.</a> ACS Applied Materials &amp; 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/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Wiring+zinc+in+three+dimensions+re-writes+battery+performance-dendrite-free+cycling.">Wiring zinc in three dimensions re-writes battery performance-dendrite-free cycling.</a> Energy &amp; Environmental Science. 7, 1117-1124 (2014).</li><li>Parker, J. F., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Rechargeable+nickel-3D+zinc+batteries:+An+energy-dense,+safer+alternative+to+lithium-ion.">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/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Robust+3D+Zn+sponges+enable+high-power,+energy-dense+alkaline+batteries.">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/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Fabricating+architected+zinc+electrodes+with+unprecedented+volumetric+capacity+in+rechargeable+alkaline+cells.">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/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Low-cost+green+synthesis+of+zinc+sponge+for+rechargeable,+sustainable+batteries.">Low-cost green synthesis of zinc sponge for rechargeable, sustainable batteries.</a> Sustainable Energy &amp; Fuels. 4, 3363-3369 (2020).</li><li>Yufit, V., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Operando+Visualization+and+Multi-scale+Tomography+Studies+of+Dendrite+Formation+and+Dissolution+in+Zinc+Batteries.">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://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Metal Foams: A Design Guide. , (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/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Translating+Materials-Level+Performance+into+Device-Relevant+Metrics+for+Zinc-Based+Batteries.">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/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=An+areal-energy+standard+to+validate+air-breathing+electrodes+for+rechargeable+zinc-air+batteries.">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/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Cold+Sintering+as+a+Cost-Effective+Process+to+Manufacture+Porous+Zinc+Electrodes+for+Rechargeable+Zinc-Air+Batteries.">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://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> NPG Asia Materials. 7, 178 (2015).</li><li>Kang, Z., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=3D+Porous+Copper+Skeleton+Supported+Zinc+Anode+toward+High+Capacity+and+Long+Cycle+Life+Zinc+Ion+Batteries.">3D Porous Copper Skeleton Supported Zinc Anode toward High Capacity and Long Cycle Life Zinc Ion Batteries.</a> ACS Sustainable Chemistry &amp; Engineering. 7 (3), 3364-3371 (2019).</li><li>Yu, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ag-Modified+Cu+Foams+as+Three-Dimensional+Andoes+for+Rechargeable+Zinc-Air+Batteries.">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/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Controlled+Electrodeposition+of+Zinc+Oxide+on+Conductive+Meshes+and+Foams+Enabling+Its+Use+as+Secondary+Anode.">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/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Design+Strategy+for+Zinc+Anodes+with+Enhanced+Utilization+and+Retention:+Electrodeposited+Zinc+Oxide+on+Carbon+Mesh+Protected+by+Ionomeric+Layers.">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/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Spatially+homogeneous+copper+foam+as+surface+dendrite-free+host+for+zinc+metal+anode.">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/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Graphene+oxide-modified+zinc+anode+for+rechargeable+aqueous+batteries.">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/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Improving+Cyclability+of+ZnO+Electrodes+through+Microstructural+Design.">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/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Monolithic+Nanoporous+Zn+Anode+for+Rechargeable+Alkaline+Batteries.">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/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Development+of+a+Novel+Zinc/Air+Fuel+Cell+with+a+Zn+Foam+Anode,+a+PVA/KOH+Membrane+and+a+MnO2/SiOC-based+Air+Cathode.">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/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Morphological+evolution+of+Zn-sponge+electrodes+monitored+by+in+situ+X-ray+computed+microtomography.">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/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Do+Zinc+Dendrites+Exist+in+Neutral+Zinc+Batteries:+A+Developed+Electrohealing+Strategy+to+In+Situ+Rescue+In-Service+Batteries.">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/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Hydrogen-Substituted+Graphdiyne+Ion+Tunnels+Directing+Concentration+Redistribution+for+Commercial-Grate+Dendrite-Free+Zinc+Anodes.">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/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Materials+challenges+and+technical+approaches+for+realizing+inexpensive+and+robust+iron-air+batteries+for+large-scale+energy+storage.">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/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Effects+of+Heat+Treatment+on+the+Discharge+Behavior+of+Mg-6wt.%Al-1wt.%Sn+Alloy+as+Anode+for+Magnesium-Air+Batteries.">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/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Suppressing+corrosion+in+primary+aluminum-air+batteries+via+oil+displacement.">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/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=High-Performance+Structural+Batteries.">High-Performance Structural Batteries.</a> Joule. , (2020).</li></ol>

J.F.P.、D.R.R.和J.W.L.拥有与锌电极有关的专利:美国专利第9802254、10008711、10720635和10763500、欧盟专利无2926395、中国专利104813521。

与这些协议相关的修改和故障排除包括将新混合的 Zn 糊填充到模具腔中。应小心避免气囊。填充后或灌装时点击模具可减少不需要的空隙。由于水性 Zn 糊是干燥的，因此可以直接施加压力到 Zn 糊中，以在填充模具腔的同时推出气囊。
方法的一个局限性是Zn-海绵毛孔结构紊乱，但Zn和波源粒子大小可用于改变孔隙形态。使用添加剂制造可以制造出更有序、可能更坚固、更轻的...

报告的制造方法的目的是制造锌（Zn）海绵电极，抑制树突的形成和形状的变化。从历史上看，这些问题限制了Zn电池的循环寿命。锌海绵电极解决了这些问题，使Zn电池的循环寿命更长，1，2，3，4，5，6。海绵结构抑制树突的形成和形状的变化，因为（1） 融合的Zn框架电导海绵的整个体积:（2） 孔隙在Zn-海绵表面附近持有锌酸盐:和（3）海绵有一个高表面积，降低局部电流密度低于价值确定发芽树突在碱性电解质7。但是，如果海绵表面积过高，则会发生大量腐蚀。如果海绵毛孔太大，海绵的体积容量将很低。此外，如果海绵孔隙过小，Zn电极在放电过程中电解质将不足以进入Zn，导致功率和容量低5，6。
报告制造方法背后的理由是制造具有适当海绵孔隙和孔径的Zn海绵。实验中，我们发现Zn海绵的孔隙在50%到70%之间，孔径接近10μm的周期在全电池中，并显示低腐蚀率5。我们注意到，现有的商业金属泡沫制造方法未能在这些长度尺度8上达到类似的形态，因此需要报告的制造方法。
这里报告的方法比替代品的优势是，海绵特征的精细控制，并能够制造大型，密集的Zn海绵与技术相关的是容量值5，6，9，10。创建 Zn 泡沫的替代方法可能无法创建具有海绵孔隙接近 50% 的可比 10 μm 毛孔。然而，这种替代品可能需要更少的能量来制造，因为它们避免了高温处理步骤。替代过程包括以下策略:冷烧结Zn粒子11，将Zn沉积在三维宿主结构12，13，14，15，16，17，切割Zn箔成二维泡沫18，并通过脊柱分解19或渗透溶解20产生Zn泡沫。
所报告的方法在更广泛的出版的文献中是主要由钻头等人的作品建立的。他们采用了制造多孔陶瓷的方法，为电池制造了最早报道的三维（尽管很脆弱）Zn泡沫之一。然而，这些作者未能证明可充电性，可能是因为Zn粒子之间的连接性差。在可充电的 Zn-海绵电极之前，Zn 箔电极的最佳替代品是 Zn 粉末电极，其中 Zn 粉末与凝胶电解质混合。锌粉电极在原石碱性电池（Zn-MnO2）中用于商业用途，但充电性差，因为Zn粒子由Zn氧化物（ZnO）钝化，这可以增加局部电流密度，刺激树突生长3，22。我们注意到，还有其他树突抑制策略，不涉及泡沫或海绵结构23，24。
据报道，Zn-海绵的制造方法需要一个管炉，空气和氮气的来源（N2）和烟罩。所有步骤都可以在没有环境控制的情况下在实验室办公桌前执行，但在热处理过程中管炉的排气应管道输送到烟气罩。由此产生的电极适合那些有兴趣创建可充电的Zn电极能够高正位容量（>10毫安厘米地球+2）6。
第一个报告的制造方法是一种基于乳液的路线，以创建Zn-海绵电极。第二，是一条基于阿苏的路线。乳液路线的一个优点是它能够创建 Zn 糊状体，当干燥时，很容易从模具腔中脱下。缺点是它依赖昂贵的材料。对于海绵路线，海绵预制件可能具有挑战性，但这个过程使用廉价和丰富的材料。
这两种方法都涉及将 Zn 颗粒与粥原和粘度增强剂混合。产生的混合物在N2 下加热，然后呼吸空气（不是合成空气）。在N2下加热时，Zn颗粒退火和粥原分解:在呼吸空气下，退火的Zn颗粒熔断，粥原燃烧。这些工艺产生金属泡沫或海绵。Zn 海绵的机械和电化学特性可以通过不同的 Zn-porogen 质量比、N2 下的加热时间和空气以及 Zn 和聚源颗粒的大小和形状来调整。

<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

我们报告了两种方法来制造锌海绵电极，以抑制树突的形成和可充电锌电池的形状变化。这两种方法的特点是创建由锌颗粒、有机粥原和粘度增强剂制成的糊糊，这些粘稠性增强剂在惰性气体下加热，然后在空气中加热。在惰性气体加热过程中，锌颗粒一起退火，波源分解:在空气中，锌熔断和残余有机物燃烧，产生开放细胞金属泡沫或海绵。我们通过不同的锌与孢子质量比、惰性气体和空气下的加热时间以及锌和粥原颗粒的大小和形状来调整锌海绵的机械和电化学特性。报告方法的一个优点是它们能够微调锌海绵结构。锌和粥原颗粒的选定大小和形状影响孔隙结构的形态。一个限制是，由此产生的海绵有紊乱的孔隙结构，导致低体积锌（<30%）的机械强度低。这些锌海绵电极的应用包括用于电网存储、个人电子产品、电动汽车和电力航空的电池。用户可以期望锌海绵电极以技术相关速率循环高达 40% 的放电深度，并且无需形成分离器穿孔树突。

由此产生的，完全热处理，乳液为基础的Zn海绵有2.8克+厘米+3的密度，而水性海绵接近3.3克+厘米+3。在空气加热过程中，Zn 表面形成一层 ZnO，厚度应为 0.5°1.0 μm（使用扫描电子显微镜观察）5。产生的海绵中的固体应该是72%Zn（乳液版本）或78%Zn（水文版本），其余的为ZnO（X射线衍射测量）6。两种海绵的孔隙应接近50%，孔径分布以10μm为中心，?...

Watch this Scientific Journal Video about Zinc-Sponge Battery Electrodes that Suppress Dendrites at JoVE.com

Zinc-Sponge Battery Electrodes that Suppress Dendrites

报告协议的目标是制造可充电的锌海绵电极，以抑制锌电池（如镍锌或锌空气）的树突和形状变化。

抑制登德里特的锌海绵电池电极

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

4.3K 次观看.  U.S. Naval Research Laboratory, Washington, DC, 20375, United States. 报告协议的目标是制造可充电的锌海绵电极，以抑制锌电池（如镍锌或锌空气）的树突和形状变化。

视频: Zinc-Sponge Battery Electrodes that Suppress Dendrites

Construction and Testing of Coin Cells of Lithium Ion Batteries

Rechargeable lithium ion batteries have wide applications in electronics, where customers always demand more capacity and longer lifetime. Lithium ion batteries have also been considered to be used in electric and hybrid vehicles1 or even electrical grid stabilization systems2. All these applications simulate a dramatic increase in the research and development of battery materials3-7, including new materials3,8, doping9, nanostructuring10-13, coatings or surface modifications14-17 and novel binders18. Consequently, an increasing number of physicists, chemists and materials scientists have recently ventured into this area. Coin cells are widely used in research laboratories to test new battery materials; even for the research and development that target large-scale and high-power applications, small coin cells are often used to test the capacities and rate capabilities of new materials in the initial stage. 
 In 2010, we started a National Science Foundation (NSF) sponsored research project to investigate the surface adsorption and disordering in battery materials (grant no. DMR-1006515). In the initial stage of this project, we have struggled to learn the techniques of assembling and testing coin cells, which cannot be achieved without numerous help of other researchers in other universities (through frequent calls, email exchanges and two site visits). Thus, we feel that it is beneficial to document, by both text and video, a protocol of assembling and testing a coin cell, which will help other new researchers in this field. This effort represents the "Broader Impact" activities of our NSF project, and it will also help to educate and inspire students.
In this video article, we document a protocol to assemble a CR2032 coin cell with a LiCoO2 working electrode, a Li counter electrode, and (the mostly commonly used) polyvinylidene fluoride (PVDF) binder. To ensure new learners to readily repeat the protocol, we keep the protocol as specific and explicit as we can. However, it is important to note that in specific research and development work, many parameters adopted here can be varied. First, one can make coin cells of different sizes and test the working electrode against a counter electrode other than Li. Second, the amounts of C black and binder added into the working electrodes are often varied to suit the particular purpose of research; for example, large amounts of C black or even inert powder were added to the working electrode to test the "intrinsic" performance of cathode materials14. Third, better binders (other than PVDF) have also developed and used18. Finally, other types of electrolytes (instead of LiPF6) can also be used; in fact, certain high-voltage electrode materials will require the uses of special electrolytes7.

A protocol to construct and test coin cells of lithium ion batteries is described. The specific procedures of making a working electrode, preparing a counter electrode, assembling a cell inside a glovebox and testing the cell are presented.

钮扣电池锂离子电池的建设和测试

Rechargeable lithium ion batteries have wide applications in electronics, where customers always demand more capacity and longer lifetime.  Lithium ion ...

科研

工程学

Fabrication of VB2/Air Cells for Electrochemical Testing

A technique to investigate the properties and performance of new multi-electron metal/air battery systems is proposed and presented. A method for synthesizing nanoscopic VB2 is presented as well as step-by-step procedure for applying a zirconium oxide coating to the VB2 particles for stabilization upon discharge. The process for disassembling existing zinc/air cells is shown, in addition construction of the new working electrode to replace the conventional zinc/air cell anode with a the nanoscopic VB2 anode. Finally, discharge of the completed VB2/air battery is reported. We show that using the zinc/air cell as a test bed is useful to provide a consistent configuration to study the performance of the high-energy high capacity nanoscopic VB2 anode.

Fabrication of VB2/Air Cells for Electrochemical Testing

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.

VB制作<sub&gt; 2</sub&gt; /空气电池电化学测试

A technique to investigate the properties and performance of new multi-electron metal/air battery systems is proposed and presented. A method for ...

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

Intercalation compounds such as transition metal oxides or phosphates are the most commonly used electrode materials in Li-ion and Na-ion batteries. During insertion or removal of alkali metal ions, the redox states of transition metals in the compounds change and structural transformations such as phase transitions and/or lattice parameter increases or decreases occur. These behaviors in turn determine important characteristics of the batteries such as the potential profiles, rate capabilities, and cycle lives. The extremely bright and tunable x-rays produced by synchrotron radiation allow rapid acquisition of high-resolution data that provide information about these processes. Transformations in the bulk materials, such as phase transitions, can be directly observed using X-ray diffraction (XRD), while X-ray absorption spectroscopy (XAS) gives information about the local electronic and geometric structures (e.g.&#160;changes in redox states and bond lengths). In situ experiments carried out on operating cells are particularly useful because they allow direct correlation between the electrochemical and structural properties of the materials. These experiments are time-consuming and can be challenging to design due to the reactivity and air-sensitivity of the alkali metal anodes used in the half-cell configurations, and/or the possibility of signal interference from other cell components and hardware. For these reasons, it is appropriate to carry out ex situ experiments (e.g.&#160;on electrodes harvested from partially charged or cycled cells) in some cases. Here, we present detailed protocols for the preparation of both ex situ and in situ samples for experiments involving synchrotron radiation and demonstrate how these experiments are done.

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 devices

正极材料的同步辐射技术锂离子和钠离子电池表征

Intercalation compounds such as transition metal oxides or phosphates are the most commonly used electrode materials in Li-ion and Na-ion batteries. ...

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

Li-ion batteries are widely used in portable electronic devices and are considered as promising candidates for higher-energy applications such as electric vehicles.1,2 However, many challenges, such as energy density and battery lifetimes, need to be overcome before this particular battery technology can be widely implemented in such applications.3 This research is challenging, and we outline a method to address these challenges using in situ NPD to probe the crystal structure of electrodes undergoing electrochemical cycling (charge/discharge) in a battery. NPD data help determine the underlying structural mechanism responsible for a range of electrode properties, and this information can direct the development of better electrodes and batteries.
We briefly review six types of battery designs custom-made for NPD experiments and detail the method to construct the &#8216;roll-over&#8217; cell that we have successfully used on the high-intensity NPD instrument, WOMBAT, at the Australian Nuclear Science and Technology Organisation (ANSTO). The design considerations and materials used for cell construction are discussed in conjunction with aspects of the actual in situ NPD experiment and initial directions are presented on how to analyze such complex in situ data.

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

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.

原位中子衍射用特制的锂离子电池

Li-ion batteries are widely used in portable electronic devices and are considered as promising candidates for higher-energy applications such as electric ...

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

Imaging morphological changes that occur during the lifetime of rechargeable batteries is necessary to understand how these devices fail. Since the advent of lithium-ion batteries, researchers have known that the lithium metal anode has the highest theoretical energy density of any anode material. However, rechargeable batteries containing a lithium metal anode are not widely used in consumer products because the growth of lithium dendrites from the anode upon charging of the battery causes premature cell failure by short circuit. Lithium dendrites can also form in commercial lithium-ion batteries with graphite anodes if they are improperly charged. We demonstrate that lithium dendrite growth can be studied using synchrotron-based hard X-ray microtomography. This non-destructive imaging technique allows researchers to study the growth of lithium dendrites, in addition to other morphological changes inside batteries, and subsequently develop methods to extend battery life.

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.

电池的使用同步为基础的硬X射线微断层故障分析

Imaging morphological changes that occur during the lifetime of rechargeable batteries is necessary to understand how these devices fail. Since the advent ...

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

Research into new and improved materials to be utilized in lithium-ion batteries (LIB) necessitates an experimental counterpart to any computational analysis. Testing of lithium-ion batteries in an academic setting has taken on several forms, but at the most basic level lies the coin cell construction. In traditional LIB electrode preparation, a multi-phase slurry composed of active material, binder, and conductive additive is cast out onto a substrate. An electrode disc can then be punched from the dried sheet and used in the construction of a coin cell for electrochemical evaluation. Utilization of the potential of the active material in a battery is critically dependent on the microstructure of the electrode, as an appropriate distribution of the primary components are crucial to ensuring optimal electrical conductivity, porosity, and tortuosity, such that electrochemical and transport interaction is optimized. Processing steps ranging from the combination of dry powder, wet mixing, and drying can all critically affect multi-phase interactions that influence the microstructure formation. Electrochemical probing necessitates the construction of electrodes and coin cells with the utmost care and precision. This paper aims at providing a step-by-step guide of non-aqueous electrode processing and coin cell construction for lithium-ion batteries within an academic setting and with emphasis on deciphering the influence of drying and calendaring.

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.

锂离子纽扣电池的非水电极加工和施工

Research into new and improved materials to be utilized in lithium-ion batteries (LIB) necessitates an experimental counterpart to any computational ...

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

Extending operating voltage of Li-ion batteries results in higher energy output from these devices. High voltages, however, may trigger or accelerate multiple processes responsible for long-term performance decay. Given the complexity of physical processes occurring inside the cell, it is often challenging to achieve a full understanding of the root causes of this performance degradation. This difficulty arises in part from the fact that any electrochemical measurement of a battery will return the combined contributions of all components in the cell. Incorporation of a reference electrode can solve part of the problem, as it allows the electrochemical reactions of the cathode and the anode to be individually probed. A variation in the voltage range experienced by the cathode, for example, can indicate alterations in the pool of cyclable lithium ions in the full-cell. The structural evolution of the many interphases existing in the battery can also be monitored, by measuring the contributions of each electrode to the overall cell impedance. Such wealth of information amplifies the reach of diagnostic analysis in Li-ion batteries and provides valuable input to the optimization of individual cell components. In this work, we introduce the design of a test cell able to accommodate multiple reference electrodes, and present reference electrodes that are appropriate for each specific type of measurement, detailing the assembly process in order to maximize the accuracy of the experimental results.

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.

原位锂化参考电极: 四原位阻抗谱的电极设计

Extending operating voltage of Li-ion batteries results in higher energy output from these devices. High voltages, however, may trigger or accelerate ...

化学

Elemental-sensitive Detection of the Chemistry in Batteries through Soft X-ray Absorption Spectroscopy and Resonant Inelastic X-ray Scattering

Energy storage has become more and more a limiting factor of today's sustainable energy applications, including electric vehicles and green electric grid based on volatile solar and wind sources. The pressing demand of developing high-performance electrochemical energy storage solutions, i.e., batteries, relies on both fundamental understanding and practical developments from both the academy and industry. The formidable challenge of developing successful battery technology stems from the different requirements for different energy-storage applications. Energy density, power, stability, safety, and cost parameters all have to be balanced in batteries to meet the requirements of different applications. Therefore, multiple battery technologies based on different materials and mechanisms need to be developed and optimized. Incisive tools that could directly probe the chemical reactions in various battery materials are becoming critical to advance the field beyond its conventional trial-and-error approach. Here, we present detailed protocols for soft X-ray absorption spectroscopy (sXAS), soft X-ray emission spectroscopy (sXES), and resonant inelastic X-ray scattering (RIXS) experiments, which are inherently elemental-sensitive probes of the transition-metal 3d and anion 2p states in battery compounds. We provide the details on the experimental techniques and demonstrations revealing the key chemical states in battery materials through these soft X-ray spectroscopy techniques.

Here, we present a protocol for typical experiments of soft X-ray absorption spectroscopy (sXAS) and resonant inelastic X-ray scattering (RIXS) with applications in battery material studies.

软 x 射线吸收光谱和共振非弹性 x 射线散射法检测电池化学成分的元素敏感度

Energy storage has become more and more a limiting factor of today's sustainable energy applications, including electric vehicles and green electric grid ...

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

As lithium-ion batteries find use in high energy and power applications, such as in electric and hybrid-electric vehicles, monitoring the degradation and subsequent safety issues becomes increasingly important. In a Li-ion cell setup, the voltage measurement across the positive and negative terminals inherently includes the effect of the cathode and anode which are coupled and sum to the total cell performance. Accordingly, the ability to monitor the degradation aspects associated with a specific electrode is extremely difficult because the electrodes are fundamentally coupled. A three-electrode setup can overcome this problem. By introducing a third (reference) electrode, the influence of each electrode can be decoupled, and the electrochemical properties can be measured independently. The reference electrode (RE) must have a stable potential that can then be calibrated against a known reference, for example, lithium metal. The three-electrode cell can be used to run electrochemical tests such as cycling, cyclic voltammetry, and electrochemical impedance spectroscopy (EIS). Three-electrode cell EIS measurements can elucidate the contribution of individual electrode impedance to the full cell. In addition, monitoring the anode potential allows the detection of electrodeposition due to lithium plating, which can cause safety concerns. This is especially important for the fast charging of Li-ion batteries in electric vehicles. In order to monitor and characterize the safety and degradation aspects of an electrochemical cell, a three-electrode setup can prove invaluable. This paper aims to provide a guide to constructing a three-electrode coin cell setup using the 2032-coin cell architecture, which is easy to produce, reliable, and cost-effective.

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.

锂离子电池三电极硬币电池制备及电沉积分析

As lithium-ion batteries find use in high energy and power applications, such as in electric and hybrid-electric vehicles, monitoring the degradation and ...

Preparation of Graphene Liquid Cells for the Observation of Lithium-ion Battery Material

In this work, we introduce the preparation of graphene liquid cells (GLCs), encapsulating both electrode materials and organic liquid electrolytes between two graphene sheets, and the facile synthesis of one-dimensional nanostructures using electrospinning. The GLC enables in situ transmission electron microscopy (TEM) for the lithiation dynamics of electrode materials. The in situ GLC-TEM using an electron beam for both imaging and lithiation can utilize not only realistic battery electrolytes, but also the high-resolution imaging of various morphological, phase, and interfacial transitions.

Here, we present a protocol for the fabrication and preparation of a graphene liquid cell for in situ transmission electron microscopy observation, along with a synthesis of electrode materials and electrochemical battery cell tests.

锂离子电池材料用石墨烯液位的制备

In this work, we introduce the preparation of graphene liquid cells (GLCs), encapsulating both electrode materials and organic liquid electrolytes between ...