Name: in situ lithiated reference electrode: four electrode design for in-operando impedance spectroscopy
Uploaded: 2018-09-12T14:00:00.000+00:00
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Description: Watch this Scientific Journal Video about In Situ Lithiated Reference Electrode: Four Electrode Design for In-operando Impedance Spectroscopy at JoVE.com

作者承认美国能源部, 能源效率和可再生能源办公室的财政支持。

1. 剥铜/锡线
<ol><li>热商业获得剥离溶液。<ol>
<li>将商用工业级溶出液倒入不锈钢烧杯 (直径7.6 厘米, 高度8.5 厘米), 从底部到深度约5毫米。把烧杯放到热盘子上。开始加热速度约5°c/分钟。</li>
		<li>将便携式热电偶浸入溶液中, 密切监测溶液的温度坡道, 调整热板的加热速率以保持所需的加热速率。</li>
	</ol>
</li>
	<li>在准备参考线的夹具上设置铜/锡线。<ol>
<li>风一个粗铜线的形式的夹具 (4 厘米宽, 7 厘米长)。安装商用铜/锡 (或纯铜) 线 (25.4 µm 直径), 镀一层薄薄的锡和电子绝缘的聚氨酯涂层) 到夹具, 如图 1a所示。 注意: 这些导线非常细腻, 如果处理粗糙, 可能会断裂。</li>
	</ol>
</li>
	<li>剥离聚合物<ol>
<li>一旦溶出液的温度在热电偶上读数约85摄氏度, 停止加热溶液, 将导线安装夹具浸入溶液中。</li>
		<li>将夹具留在十五年代的解决方案中, 然后在 DI 水中冲洗夹具, 另十五年代清洗吸附在导线上的多余剥离液。</li>
		<li>检查电线的暴露锡 (显示为银色白颜色) 和重复步骤 1.3.2, 直到聚合物完全剥离。 警告:长期暴露的导线到剥离溶液可以蚀刻锡涂层和暴露在下面的红棕色铜线。如果为阻抗谱分析准备了导线, 锡电镀的存在是必要的。</li>
		<li>在 DI 水中冲洗夹具, 室温下干燥 (25 摄氏度)。</li>
		<li>切断在剥离区中部的电线, 以获得两端与暴露锡 (或铜超过多余的剥离电线)。每根导线的大小约为10厘米。</li>
	</ol>
</li>
</ol>2. 参考线准备
<ol><li>要使参考导线接触, 请将导线连接到电线上并焊接接头。<ol>
<li>从一卷电线, 切割件10厘米, 并剥离绝缘盖从两端暴露约2厘米的金属。</li>
		<li>将所述聚合物的一端装入所述绝缘导线的末端, 并焊结以形成导线之间的电接点。</li>
		<li>测量暴露的锡 (或铜) 导线与暴露的电线之间的电阻。 注: 典型电阻值介于6-8 Ω之间。</li>
		<li>将一根导线分别与锡接触, 并将铜暴露成氩气填充的 glovebox, 将其组装成一个单元格。</li>
	</ol>
</li>
	<li>将压扁的锂金属箔装入铜暴露的参考线上<ol>
<li>从 glovebox 内的大箔片中剪下一小块锂金属 (不超过5毫米 x 5 毫米)。 注: 使用专用设备与锂金属接触, 储存在 glovebox 内, 防止交叉污染和随后的电微短路。</li>
		<li>使用用聚合物胶带覆盖的滚筒 (以防止将锂金属粘附到金属辊表面), 在 Ar 下将锂金属片滚到聚四氟乙烯平台上。</li>
		<li>继续滚动, 以达到约25µm 的箔厚度. 使用螺丝量规检查厚度。</li>
		<li>当获得所需的锂金属箔的厚度, 弯曲的箔在中心形成 U 形。将铜外露导线放在弯曲的中间, 使铜与锂金属接触并按下褶皱将铜线封装在两个李层之间。 注意: 在封装铜线时要保持极度警惕, 以确保覆盖所有暴露的尖端。cu 仅用于电子电导, 铜与电解质的接触将导致读取数据中产生错误电压值的混合表面电位。</li>
	</ol>
</li>
</ol>3. 细胞组装和数据采集
<ol><li>在锂离子电池组件之间放置锂金属参照和 Sn 参考线。<ol>
<li>将负极放在夹具中, 使电极的中心从夹具中心稍移。添加400µL 的电解质 (1.2M LiPF6在 Fluoroethylene 碳酸盐 (FEC): 乙基甲基碳酸酯 EMC (5:95 瓦特/瓦)), 以润湿整个电极。</li>
		<li>将一个分离器放在电极顶部, 使用 organophobic 扫, 轻轻地消除分离器和电极之间的滞留气泡。调整分离器的位置, 确保与夹具的同心度完全隔离夹具底座和正极, 避免电池内部短路。 注: 大电极往往会在分离器和电极之间夹住气袋, 因为它们在加入电解质时卷曲。这些气囊需要拆除, 以确保分离器与电极的正确接触。气泡增加了细胞的阻抗, 抑制了离子的转移。</li>
		<li>添加两滴 (约10µL) 的电解质, 一个在2毫米以外的细胞三明治和另一个在中心的电极。将参考导线的 Sn 外露尖端放置在电极的中心和锂金属箔 (封装在铜线上) 上, 使其远离电极。金属与电解液之间的表面张力使导线处于原位。</li>
		<li>放置导线后, 再在锂金属上加一滴 (约10µL) 电解质。</li>
		<li>去除锂箔和分离器之间的额外气泡与聚四氟乙烯扫描。再添加400µL 的电解质。</li>
		<li>将第二个分隔符与第一个分隔符对齐, 以便两个参照线夹在这两个分隔符之间。除去任何额外的气泡。 警告:在放置第二分离器时, 过度的张力会破坏参考线。在细胞内留出多余的导线, 以减少电线中的张力。</li>
		<li>用电解液的400µL 将正极电极润湿。将电极对准第二个分离器顶部的负极。</li>
		<li>小心地将不锈钢垫片置于正极电极上, 以免干扰单元格堆叠对齐。 注意: 由于有活性细胞区的接触减少, 电极不均匀导致电流分布不均, 细胞容量降低。</li>
		<li>将两个不锈钢波浪弹簧放在冰球上, 以适应细胞体积的变化和压力的增强, 确保电极与夹具端子之间的电接触。关闭夹具。由于安装没有密封, 测试是在一个惰性的气氛中的手套箱内进行。</li>
	</ol>
</li>
	<li>记录单个电极电压剖面的锂金属参考线的数据<ol>
<li>将循环仪的辅助参考端子连接到锂金属, 而循环仪的正极和负极端子连接到各自的电极上。 注: 在细胞循环过程中, 循环仪读出正端与 RE Aux1 输出的电位差, 负极和 Aux2 的参考值。当锂金属线连接时, Aux1 和 Aux2 是单个电极对锂金属的电位。</li>
	</ol>
</li>
	<li>Lithiate 锡线原位记录电化学阻抗谱 (EIS)。<ol>
<li>将5µA 的恒流应用于正极和 sn 线之间的6小时, 其上电压截止 4 V 至电化学 lithiate sn。由此形成的锂/锡合金的电位接近于锂金属。断开接线端子, 使导线平衡2小时。 注: 在电路中确保极低电流 (接近 0 A) 以确认 Sn 线的完全 lithiation。</li>
		<li>将循环仪与锂金属连接至循环仪和 Sn 线的辅助端子至循环仪的负端, 确保 Aux2 接近 0 v 的读数。得到了 sn 的锂化相, 表示为 LixSn。</li>
		<li>将循环仪的正、负端子重新连接到电池的各自电极和辅助端子, 以利x锡线。</li>
	</ol>
</li>
	<li>记录 EIS (i) 阴极对阳极, (ii) 阴极对锂化锡线和 (iii) 阳极与锂化锡线。(i) 的阻抗是在 (ii) 和 (iii) 中获得的阻抗之和。恒电位仪由两个端子组成, 用于记录电压和两个电极的电流输出。<ol>
<li>要获得完整的细胞谱, 将电压和电流端子连接到细胞的正负电极上。</li>
		<li>对于正极阻抗, 将电压和电流正极 (也称为工作电极) 连接到正极, 并将负端子 (也称为计数器电极, CE) 连接到 LixSn。参考电极。</li>
		<li>对于负电极阻抗, 将我们的端子连接到负极, 并将 CE 端子连接到 LixSn 参考电极。</li>
		<li>记录 EIS, 提供交流电流或不同的频率, 以循环的电化学情侣之间的小电压振幅 (5 mV), 并绘制阻抗响应作为假想的组成部分与实际的组成部分。</li>
	</ol>
</li>
</ol>

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I. Experimental investigation.</a> Journal of Power Sources. 196 (12), 5334-5341 (2011).</li><li>Li, S. E., Wang, B., Peng, H., Hu, X. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=An+electrochemistry-based+impedance+model+for+lithium-ion+batteries.">An electrochemistry-based impedance model for lithium-ion batteries.</a> Journal of Power Sources. 258, 9-18 (2014).</li></ol>

作者没有什么可透露的。

图 2a是全电池的电压剖面图 2b和2c显示对应于正负电极与锂/锂+情侣的电压剖面, 而整个细胞在3和 4.4 v 之间循环。可以看出, 当全细胞扫描在3和 4.4 v 之间时, 正极电极会经历3.65 伏和 4.45 v 之间的电压, 而负极与 0.65 v 和 0.05 v 之间的负电极和李/李分别。在充电过程中, lithiation 和负电极 (与锂/锂+) 的正向...

锂离子电池对高能密度的需求正在推动研究, 以了解限制锂离子电池性能1的基本因素。含有新一代层状过渡金属氧化物阴极、石墨阳极和有机碳酸盐电解质的细胞的高压运行与几种寄生反应2、3有关。其中一些反应消耗了锂离子库存, 并且经常导致细胞4、5、6、7的显著阻抗上升。锂离子的损耗也导致电极表面电位的净转移。在3电极电池设计8、9、10、11中, 对一个完整细胞与参考电极 (RE) 中单个电极的电压变化进行监测。,12,13,14. 有关电压剖面的信息和单个电极上的阻抗变化促进了对 LIB 基本退化机制的更深的理解。传统的3电极电池含有锂金属作为参考电极, 这有助于对每个电极的电化学过程有一个明确的理解。与有机电解质接触的锂金属经过自发的表面改性, 该表面层对 li 的贡献不能量化15。一些3电极的配置, 如 (a) T 模型, (b) 一个微重新定位同工作和反电极的同轴, (c) 有一个硬币电池在反电极背面,等已经提出了前面。这些细胞配置中的大部分都是从细胞夹层中重新定位的, 由于电解质的电导率低, 导致阻抗数据的显著漂移。事实证明, 在整个测量过程中, 一个具有稳定电位的 RE 必须驻扎在三明治的中心, 以确保可靠的阻抗数据。
为了解决这些差异, 我们设计了一个包含第四重16的单元格设置。一个超薄的锡镀铜丝夹在电池电极之间, 可以在原位电化学锂化, 形成锂x锡合金。当 Sn 经历 lithiation 时, 参考导线的电压下降, 而一个完全锂化的导线有可能接近 0 V vs。李/李17。锂化组合物具有与锂金属相媲美的潜力, 亚稳态合金在测量的时间段内有利于稳定电位。暴露于电解质中的锂金属易被电解质分解产物形成表面层。通过在电极和锂金属参考之间收集光谱来探测单个电极的阻抗的 EIS 测量由于这些层对阻抗的贡献而不可靠。虽然电解质还原在锂锡表面也不可避免, 但原位锂化参考线具有以下优点: (a) 没有恒定的电解质分解产物, 因为电压总是高于分解电位电解质, 除非锂化, 意味着没有损失的李库存在系统到界面层;(b) 在 Sn 线 lithiation 期间形成的层数在很小的范围内, 对 EIS 数据提供了微不足道的贡献;(c) 由于 Sn 线失去 Li 和导线的电位增加, 形成的产品降解, 导致在每 lithiation 的 lithiation 的新鲜锡线, 从而形成非常薄的界面层, 而不是增加厚度的这些层。以这些合金为参考记录的光谱提供了更准确可靠的电极阻抗数据。我们进行了标准的2032型硬币电池和4电极再电池测试, 以验证我们的设计。这些测试的结果和我们对数据的解释将被用来作为一个代表性的结果来解释我们的协议的有效性。3 - 4 . 4 V 自行车跟随了标准协议 , 包括形成周期、老化周期和周期流阻抗测量在自行车赛期间。硬币细胞测量提供了有关参数的宝贵信息, 如循环寿命, 容量保留, 交流阻抗变化等. 重细胞使监测电压变化和阻抗上升的个别电极。我们对容量衰减和阻抗上升的机械理解可以为电解质系统的发展提供指导, 并了解高压电池运行过程中每个电极的容量损失贡献。
我们的细胞包含Li 1.03 (镍0.5Co0.2锰0.3)0.97O2 (这里被表示作为 NMC532) 基正极, 石墨基负极 (这里被表示为 Gr) 和 1.2 M 解答 LiPF6在 Fluoroethylene 碳酸盐 (FEC): 乙基甲基碳酸酯 (EMC) (5:95 瓦特/瓦) 作为电解质。本研究中使用的电极是阿贡国家实验室的细胞分析、建模和原型 (阵营) 设施中制作的标准电极。正极电极由 NMC532、导电碳添加剂 (C-45) 和聚偏氟乙烯 (PVdF) 粘合剂组成, 重量比为 90:5: 5 在20µm 厚铝电流收集器上。负电极由石墨组成, 与 C-45 混合, 而 PVdF 粘结剂的重量比为 92:2: 6 在10µm 厚铜电流收集器上。从电极层压板上打了5.08 厘米直径的圆盘, 在7.62 厘米内径的夹具上用7.62 厘米的模具打孔。这些电极干燥在120°c 和分离器在75°c 在一个真空烤箱至少 12 h 在细胞汇编之前。夹具设计的示意图表示在图 1中。大的固定装置和电极确保了每单位面积的电流分布的最小不均匀性, 从而提供了阻抗谱中最小的失真。3-4. 4 V 循环遵循一个标准协议, 其中包括两个形成周期的 C/20 率, 100 老化周期以 C/3 率和两个诊断周期在 C/20。所有电池测试均在摄氏30摄氏度进行。用电池循环仪测量电化学循环数据, 利用恒电位仪系统进行电化学阻抗谱 (EIS)。

<table><tbody><tr><td>Insulstrip 220</td><td>Ambion Corporation</td><td>081607-1</td><td></td></tr><tr><td>Sodium Hydroxide (23 wt%)</td><td>Ambion Corporation</td><td>1310-73-2</td><td>Contents of Insulstrip 220</td></tr><tr><td>Furfuryl Alcohol (10 wt%)</td><td>Ambion Corporation</td><td>98-00-0</td><td>Contents of Insulstrip 220</td></tr><tr><td>NCM523</td><td>TODA America</td><td>NM4100</td><td></td></tr><tr><td>C-45&amp;nbsp;</td><td>Timcal Inc.</td><td></td><td></td></tr><tr><td>polyvinylidene fluoride (PVdF)</td><td>Sigma Aldrich</td><td>427152</td><td></td></tr><tr><td>Sn over Cu wire</td><td>Kanthal</td><td>MELT # 24633</td><td>Custom ordered</td></tr><tr><td>Battery cycler</td><td>Maccor USA</td><td>Series 2300&amp;nbsp;</td><td></td></tr><tr><td>Potentiostat</td><td>Solartron Analytical</td><td>1470 E</td><td></td></tr></tbody></table>

in situ lithiated reference electrode: four electrode design for in-operando impedance spectroscopy

延长锂离子电池的工作电压会导致这些器件产生更高的能量输出。但是, 高电压可能会触发或加速多个过程, 导致长期性能衰减。考虑到在细胞内发生的物理过程的复杂性, 要充分理解这种性能退化的根本原因, 通常是有挑战性的。这一困难的部分原因是, 电池的任何电化学测量都将返回单元格中所有元件的组合贡献。加入参考电极可以解决问题的一部分, 因为它允许阴极和阳极的电化学反应被单独探测。例如, 阴极所经历的电压范围的变化可以指示全细胞内 cyclable 锂离子池的改变。通过测量每个电极对整体细胞阻抗的贡献, 也可以监测电池中存在的许多 interphases 的结构演化。这种丰富的信息放大了锂离子电池的诊断分析的范围, 为单个细胞组件的优化提供了宝贵的投入。在这项工作中, 我们介绍了能够容纳多个参考电极的测试单元的设计, 并提出了适用于每种特定测量类型的参考电极, 详细说明了装配过程, 以便最大限度地提高实验结果。

图 2是 LiPF6 (FEC) 中的单个电极的电压的典型描述: EMC (5:95 瓦特/瓦) 作为第一和第二个周期中的电解质。图 3显示了在三形成周期和周期寿命老化协议结束后细胞的 EIS 谱。在精确跟踪单个电极的阻抗变化时, 重新 lithiate 以获得 EIS 数据的能力。
<img alt="Figure 1" class="xfigimg" src="/...

Watch this Scientific Journal Video about In Situ Lithiated Reference Electrode: Four Electrode Design for In-operando Impedance Spectroscopy at JoVE.com

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

锂离子电池中的参考电极的加入, 为阐明高电压下的降解机理提供了有价值的信息。在本文中, 我们提出了一个单元设计, 可容纳多个参考电极, 连同组装步骤, 以确保最大的准确性, 获得的电化学测量数据。

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 ...

in-situ-lithiated-reference-electrode-four-electrode-design-for

Research

JoVE Journal

Chemistry

8.7K 次观看.  Argonne National Laboratory. 锂离子电池中的参考电极的加入, 为阐明高电压下的降解机理提供了有价值的信息。在本文中, 我们提出了一个单元设计, 可容纳多个参考电极, 连同组装步骤, 以确保最大的准确性, 获得的电化学测量数据。

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

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. ...

科研

工程学

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 ...

Assessment of Boron Doped Diamond Electrode Quality and Application to In Situ Modification of Local pH by Water Electrolysis

Boron doped diamond (BDD) electrodes have shown considerable promise as an electrode material where many of their reported properties such as extended solvent window, low background currents, corrosion resistance, etc., arise from the catalytically inert nature of the surface. However, if during the growth process, non-diamond-carbon (NDC) becomes incorporated into the electrode matrix, the electrochemical properties will change as the surface becomes more catalytically active. As such it is important that the electrochemist is aware of the quality and resulting key electrochemical properties of the BDD electrode prior to use. This paper describes a series of characterization steps, including Raman microscopy, capacitance, solvent window and redox electrochemistry, to ascertain whether the BDD electrode contains negligible NDC i.e. negligible sp2 carbon. One application is highlighted which takes advantage of the catalytically inert and corrosion resistant nature of an NDC-free surface i.e. stable and quantifiable local proton and hydroxide production due to water electrolysis at a BDD electrode. An approach to measuring the local pH change induced by water electrolysis using iridium oxide coated BDD electrodes is also described in detail.

Assessment of Boron Doped Diamond Electrode Quality and Application to In Situ Modification of Local pH by Water Electrolysis

A protocol is described for the characterization of the key electrochemical parameters of a boron doped diamond (BDD) electrode and subsequent application for in situ pH generation experiments.

掺硼金刚石电极质量和应用，以评估<em&gt;原位</em&gt;本地pH值通过水电改造

Boron doped diamond (BDD) electrodes have shown considerable promise as an electrode material where many of their reported properties such as extended ...

化学

Voltage Biasing, Cyclic Voltammetry, &amp; Electrical Impedance Spectroscopy for Neural Interfaces

Electrical impedance spectroscopy (EIS) and cyclic voltammetry (CV) measure properties of the electrode-tissue interface without additional invasive procedures, and can be used to monitor electrode performance over the long term. EIS measures electrical impedance at multiple frequencies, and increases in impedance indicate increased glial scar formation around the device, while cyclic voltammetry measures the charge carrying capacity of the electrode, and indicates how charge is transferred at different voltage levels. As implanted electrodes age, EIS and CV data change, and electrode sites that previously recorded spiking neurons often exhibit significantly lower efficacy for neural recording. The application of a brief voltage pulse to implanted electrode arrays, known as rejuvenation, can bring back spiking activity on otherwise silent electrode sites for a period of time. Rejuvenation alters EIS and CV, and can be monitored by these complementary methods. Typically, EIS is measured daily as an indication of the tissue response at the electrode site. If spikes are absent in a channel that previously had spikes, then CV is used to determine the charge carrying capacity of the electrode site, and rejuvenation can be applied to improve the interface efficacy. CV and EIS are then repeated to check the changes at the electrode-tissue interface, and neural recordings are collected. The overall goal of rejuvenation is to extend the functional lifetime of implanted arrays.

Voltage Biasing, Cyclic Voltammetry, & Electrical Impedance Spectroscopy for Neural Interfaces

The electrode-tissue interface of neural recording electrodes can be characterized with electrical impedance spectroscopy (EIS) and cyclic voltammetry (CV). Application of voltage biasing changes the electrochemical properties of the electrode-tissue interface and can improve recording capability. Voltage biasing, EIS, CV, and neural recordings are complementary.

偏置电压，循环伏安，神经接口电阻抗光谱

Electrical impedance spectroscopy (EIS) and cyclic voltammetry (CV) measure properties of the electrode-tissue interface without additional invasive ...

神经科学

Electrochemical Impedance Spectroscopy as a Tool for Electrochemical Rate Constant Estimation

Electrochemical impedance spectroscopy (EIS) was used for advanced characterization of organic electroactive compounds along with cyclic voltammetry (CV). In the case of fast reversible electrochemical processes, current is predominantly affected by the rate of diffusion, which is the slowest and limiting stage. EIS is a powerful technique that allows separate analysis of stages of charge transfer that have different AC frequency response. The capability of the method was used to extract the value of charge transfer resistance, which characterizes the rate of charge exchange on the electrode-solution interface. The application of this technique is broad, from biochemistry up to organic electronics. In this work, we are presenting the method of analysis of organic compounds for optoelectronic applications.

Electrochemical impedance spectroscopy (EIS) of species that undergo reversible oxidation or reduction in solution was used for determination of rate constants of oxidation or reduction.

电化学阻抗谱作为电化学速率常数估计的一种工具

Electrochemical impedance spectroscopy (EIS) was used for advanced characterization of organic electroactive compounds along with cyclic voltammetry (CV). ...

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

Solid-state electrolytes are a promising replacement for current organic liquid electrolytes, enabling higher energy densities and improved safety of lithium-ion (Li-ion) batteries. However, a number of setbacks prevent their integration into commercial devices. The main limiting factor is due to nanoscale phenomena occurring at the electrode/electrolyte interfaces, ultimately leading to degradation of battery operation. These key problems are highly challenging to observe and characterize as these batteries contain multiple buried interfaces. One approach for direct observation of interfacial phenomena in thin film batteries is through the fabrication of electrochemically active nanobatteries by a focused ion beam (FIB). As such, a reliable technique to fabricate nanobatteries was developed and demonstrated in recent work. Herein, a detailed protocol with a step-by-step process is presented to enable the reproduction of this nanobattery fabrication process. In particular, this technique was applied to a thin film battery consisting of LiCoO2/LiPON/a-Si, and has further been previously demonstrated by in situ cycling within a transmission electron microscope.

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

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

基于 LiPON 的固态锂离子 Nanobatteries 的聚焦离子束制备方法在原位测试中的研究

Solid-state electrolytes are a promising replacement for current organic liquid electrolytes, enabling higher energy densities and improved safety of ...

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 ...

Electrochemical Roughening of Thin-Film Platinum Macro and Microelectrodes

This protocol demonstrates a method for electrochemical roughening of thin-film platinum electrodes without preferential dissolution at grain boundaries of the metal. Using this method, a crack free, thin-film macroelectrode surface with up to 40 times increase in active surface area was obtained. The roughening is easy to do in a standard electrochemical characterization laboratory and incudes the application of voltage pulses followed by extended application of a reductive voltage in a perchloric acid solution. The protocol includes the chemical and electrochemical preparation of both a macroscale (1.2 mm diameter) and microscale (20 &#181;m diameter) platinum disc electrode surface, roughening the electrode surface and characterizing the effects of surface roughening on electrode active surface area. This electrochemical characterization includes cyclic voltammetry and impedance spectroscopy and is demonstrated for both the macroelectrodes and the microelectrodes. Roughening increases electrode active surface area, decreases electrode impedance, increases platinum charge injection limits to those of titanium nitride electrodes of same geometry and improves substrates for adhesion of electrochemically deposited films.

This protocol demonstrates a method for electrochemical roughening of thin-film platinum electrodes without preferential dissolution at grain boundaries. The electrochemical techniques of cyclic voltammetry and impedance spectroscopy are demonstrated to characterize these electrode surfaces.

薄膜铂金宏观和微电极的电化学粗加工

This protocol demonstrates a method for electrochemical roughening of thin-film platinum electrodes without preferential dissolution at grain boundaries ...

A Method for Systematic Electrochemical and Electrophysiological Evaluation of Neural Recording Electrodes

New materials and designs for neural implants are typically tested separately, with a demonstration of performance but without reference to other implant characteristics.&#160;This precludes a rational selection of a particular implant as optimal for a particular application and the development of new materials based on the most critical performance parameters.&#160;This article develops a protocol for in vitro and in vivo testing of neural recording electrodes.&#160;Recommended parameters for electrochemical and electrophysiological testing are documented with the key steps and potential issues discussed.&#160;This method eliminates or reduces the impact of many systematic errors present in simpler in vivo testing paradigms, especially variations in electrode/neuron distance and between animal models.&#160;The result is a strong correlation between the critical in vitro and in vivo responses, such as impedance and signal-to-noise ratio.&#160;This protocol can easily be adapted to test other electrode materials and designs.&#160;The in vitro techniques can be expanded to any other nondestructive method to determine further important performance indicators.&#160;The principles used for the surgical approach in the auditory pathway can also be modified to other neural regions or tissue.

Different electrode coatings affect neural recording performance through changes to electrochemical, chemical and mechanical properties. Comparison of electrodes in vitro is relatively simple, however comparison of in vivo response is typically complicated by variations in electrode/neuron distance and between animals. This article provides a robust method to compare neural recording electrodes.

对于系统电化学神经记录电极和电生理评价方法

New materials and designs for neural implants are typically tested separately, with a demonstration of performance but without reference to other implant ...

A Salt-Templated Synthesis Method for Porous Platinum-based Macrobeams and Macrotubes

The synthesis of high surface area porous noble metal nanomaterials generally relies on time consuming coalescence of pre-formed nanoparticles, followed by rinsing and supercritical drying steps, often resulting in mechanically fragile materials. Here, a method to synthesize nanostructured porous platinum-based macrotubes and macrobeams with a square cross section from insoluble salt needle templates is presented. The combination of oppositely charged platinum, palladium, and copper square planar ions results in the rapid formation of insoluble salt needles. Depending on the stoichiometric ratio of metal ions present in the salt-template and the choice of chemical reducing agent, either macrotubes or macrobeams form with a porous nanostructure comprised of either fused nanoparticles or nanofibrils. Elemental composition of the macrotubes and macrobeams, determined with x-ray diffractometry and x-ray photoelectron spectroscopy, is controlled by the stoichiometric ratio of metal ions present in the salt-template. Macrotubes and macrobeams may be pressed into free standing films, and the electrochemically active surface area is determined with electrochemical impedance spectroscopy and cyclic voltammetry. This synthesis method demonstrates a simple, relatively fast approach to achieve high-surface area platinum-based macrotubes and macrobeams with tunable nanostructure and elemental composition that may be pressed into free-standing films with no required binding materials.

A synthesis method to obtain porous platinum-based macrotubes and macrobeams with a square cross section through chemical reduction of insoluble salt-needle templates is presented.

多孔铂基微波和宏管的盐模板合成方法

The synthesis of high surface area porous noble metal nanomaterials generally relies on time consuming coalescence of pre-formed nanoparticles, followed ...