德州仪器 (TI) 大学研究伙伴关系计划的财政支持得到了感激的承认。作者还感谢来自德州一所 & M 大学的能源与运输科学实验室、机械工程研究所、在这项工作初期的帮助。

1. 参考电极和分离器的制备
<ol><li>
参考电极制备
	<ol>
<li>
线材制备
		<ol>
<li>切割120毫米长度的 32 AWG (0.202 毫米直径) 漆包线铜线。 注: 每根导线将成为1参考电极并且将使用在1三电极细胞之内。</li>
			<li>把电线的一端放在实验室的印刷机上。轻轻按大约10毫米的导线一端的压力约4兆帕。切断导线尖端的多余导线, 使扁平截面长度为2毫米。 注: 刀尖的平均厚度约为0.1 毫米. 小心不要弯曲扁平的尖端, 因为它可能会疲劳和脱落。</li>
			<li>将电线放在聚四氟乙烯 (聚四氟乙烯) 切割板上。仔细使用手术刀, 以消除扁平导线尖端的外层绝缘。确保拆卸两侧的绝缘;最后的产品应该是一个平坦的, 闪亮的部分暴露铜。</li>
			<li>用实验室秤称量电线。 注: 此质量将使用后, 泥浆已经铸造, 以确定实际数量的活性物质存在于每个参考电极。</li>
			<li>重复步骤 1.1.1.1-1.1.1.5 为典型的批次大小的36线。把电线放在贮器上存放。一个好的选择是把电线绕在一个小玻璃瓶的边缘。</li>
		</ol>
</li>
		<li>
浆料制备
		<ol>
<li>在 N-methyl-2-pyrrolidinone (NMP) 中制备10% 的聚偏氟乙烯 (PVDF) 溶液。<ol>
<li>使用一个小的长方形称重纸, 不锈钢勺子, 和实验室规模, 测量出所需的 PVDF 粉末质量 (0.1 克)。</li>
				<li>将 PVDF 粉末从称重纸转移到一个500毫升的塑料瓶中。使用1毫升容量的实验室吸管测量和转移适当质量的 NMP 液体 (0.9 克) 到瓶子里。</li>
				<li>在溶液中插入磁性搅拌条;把瓶子放在磁性搅拌板上, 让它永远混合。允许解决方案在第一次使用前至少混合24小时。建议将 PVDF 溶液批量地准备好, 以避免每种泥浆批次都有较小的批次。</li>
			</ol>
</li>
			<li>在称量任何更多的粉末之前, 清洁不锈钢铲, 杵, 和与异丙醇的砂浆, 以避免任何污染。</li>
			<li>使用称重纸、实验室秤和不锈钢铲, 测量出钛酸锂 (Li4Ti5O12) 粉末的适当数量 (0.8 克)。小心地将粉末转移到砂浆和杵上。使用后用异丙醇清洁勺子。</li>
			<li>同样, KS-6 合成石墨和 (0.09 克) 导电添加剂的适当用量 (0.03 克)。小心地将粉末转移到同一个砂浆和杵。用异丙醇清洁勺子。</li>
			<li>轻轻地将三粉末混合在砂浆中, 直到它们均匀分散。研磨粉末混合使用杵, 直到混合物变得均匀。小心地将粉末混合到一个20毫升的一次性混合管。 注: 这将作为一个高剪切搅拌容器, 以确保所有材料均匀分布在泥浆内。</li>
			<li>使用实验室吸管将适量的 NMP (2.2 毫升) 添加到混合管中。添加十六6毫米直径的硅酸盐玻璃混合球和螺丝在帽子上。将混合管放在高剪切混合装置上, 将管子锁定到位, 在最大设置上混合浆料15分钟 (约 6000 rpm)。</li>
			<li>添加0.8 克 PVDF 溶液 (早在步骤1.1.2.1 中制备) 到混合管。继续搅拌泥浆5分钟, 以确保均匀分布的粘合剂。立即将泥浆浇在电线上。如果泥浆的长度超过5分钟, 则在使用前将浆料搅拌15分钟, 以确保均匀的混合物。</li>
		</ol>
</li>
		<li>
参考电极的铸造与干燥
		<ol>
<li>用手蘸露出的铜, 在每个参考电极的尖端, 进入混合浆料。或者, 将浆料从吸管上滴入钢丝尖上。一定要只涂上扁平的, 暴露的铜线部分。</li>
			<li>将铸重导线连接到底座上, 并将浇注端挂起晾干。将铸件重新固定在固定架上, 以避免与任何表面的湿泥浆接触 (请参见图 3a)。在70摄氏度的实验室烤箱中, 将电极干燥至少8小时。</li>
			<li>在干燥后测量参考电极质量, 并估计浆料的干质量 (平均超过100个样品0.1 毫克)。</li>
			<li>将参考电极转移到惰性氩 glovebox 中, 用于电池制造过程。</li>
		</ol>
</li>
	</ol>
</li>
	<li>
阴极和阳极电极的制备
	<ol>
<li>选择要研究的所需电极。 注: 对于这些测试, 预制电极片将用于演示目的。在内部制作的电极或从商业细胞收获的电极也可以使用。</li>
		<li>用空心1.27 厘米 (1/2 英寸) 冲床打出阴极材料圆盘。电极圆盘形状可以根据所需的测试进行机械修改 (请参见图 4)。称量电极, 计算活性物质的百分比。</li>
		<li>重复步骤 1.2. 1-1. 2.2 的阳极材料, 以及所需的额外细胞。将每个电极盘放入一个小玻璃瓶中, 并小心地将瓶子放入惰性氩 glovebox 中, 在电池结构过程中使用它们。</li>
	</ol>
</li>
	<li>
分离器准备
	<ol>
<li>将一张纸 (22.6 厘米 x 28 厘米/8.5 英寸 x 11 英寸) 纵向对折。切约25厘米 x 8.5 厘米的聚丙烯 (PP) 分离器, 并轻轻地把它放在折叠的打印机纸内。 注: 当分离器被手工打出时, 本文提供了一些保护和刚度。</li>
		<li>将纸张和分离三明治放在自我愈合的割垫上。这提供了一个坚实的表面, 并将有助于避免壮志空心冲床。使用空心1.905 厘米 (3/4 英寸) 冲床, 为每个三电极电池冲出一个圆形分隔盘。批量准备分离器, 并将其存放在玻璃瓶中以备以后使用。</li>
		<li>另外, 切开几个小正方形分离器大约5毫米 x 8 毫米;其中一个分隔符将用于每个单元格。把这些放在小玻璃瓶里。将分离器的瓶子转移到惰性氩 glovebox 中, 用于细胞构建过程。</li>
	</ol>
</li>
</ol>2. 制备单元的构造
<ol><li>使用一对钳子将导线弯曲成螺旋形 (请参阅图 3b), 准备参考电极。确保最终的螺旋形状将适合在硬币电池的垫片 (大约1.58 厘米直径)。把每个电极螺旋成一个小的重量船, 并把它们放在一边。 注: 额外的线螺旋提供稳定, 也将展开和后来使用的工作单元。</li>
	<li>使用手术刀或刀片清洁锂金属丝带的两面。刮掉任何表面氧化, 直到闪亮的锂显示通过。一定要把锂的两面都清洗干净。在 glovebox 中使用尖锐物体时要格外小心。</li>
	<li>使用空心冲床从清洗过的锂色带中冲出两个1.58 厘米 (5/8 英寸) 的圆盘。</li>
	<li>在0.5 毫米不锈钢垫片的中心放置一盘锂。将锂金属与垫片牢固地压在一起;通常, 拇指按压就足够了。确保锂盘粘在垫片上。</li>
	<li>把硬币盒壳放在一条小重量的小船里。将锂的第二个圆盘装入硬币电池盒内。确保锂的中心和压紧, 使锂坚持到底部的情况下。将几滴电解质 [1.0 M LiPF6在 EC/DEC (1:1 按体积)] 在锂盘上, 在锂的边缘上数滴, 以填补外部缺口。 注: 如果添加的电解质不足, 在分离器和细胞内会出现气泡, 这是不可取的。</li>
	<li>将一个1.905 厘米 (3/4 英寸) 的 PP 分隔符放在润湿的锂盘上。确保分离器完全湿润, 并没有气泡下面被困。将垫片置于所用垫片唇面向上的单元格中;这唇是帽子会坐到的地方。用力按压, 使垫片适合机箱。</li>
	<li>使用一对塑料镊子, 轻轻地把参考电极螺旋到细胞的中心。在参考电极周围添加几滴电解质。将一个小的长方形分隔符放在导线穿过垫片和电池盒的位置上。 注: 该分离器有助于防止电线和金属电池盖之间的短路。</li>
	<li>在参考电极螺旋顶部放置一个1.58 厘米 (5/8 英寸) 的分离器。确保分离器完全湿润, 并没有气泡下面被困。将锂间隔盘放在参考电极的顶部, 将锂涂层侧朝向向下。</li>
	<li>将波浪弹簧放在间隔顶部。确保所有组件都集中在单元格内。用电解质将细胞填充到边缘。当细胞卷曲时, 多余的电解质将被挤出。</li>
	<li>使用塑料镊子, 小心地将电池盖放在组件的顶部。用力压紧, 使瓶盖进入垫片的唇部。弯曲参考电极线, 使其在顶部平坦。这样做是为了确保在压接单元格时导线没有被剪短 (请参见图 2)。</li>
	<li>用塑料镊子小心地将细胞转移到硬币-细胞压接装置中。运输时, 按住单元格以避免任何额外的电解质损失。将硬币电池卷曲到大约5兆帕斯卡 (750 psi)。</li>
	<li>从卷发中取出硬币电池, 然后将暴露的导线从电池顶部向后弯曲。这是为了避免在盖帽和参考电极之间的任何可能的短路。</li>
	<li>从氩 glovebox 中取出已完成的硬币电池。使用异丙醇和无绒布任务雨刷, 仔细清洁细胞外部。注意避免干扰导线或导线离开电池的位置。</li>
	<li>
细胞密封
	<ol>
<li>使用无起毛的雨刷, 小心地烘干硬币细胞。要格外小心, 使电线离开硬币电池的位置变干。</li>
		<li>将等量的树脂和固化剂混合在一起, 形成一种无导电环氧树脂。使用牙签或小型探测装置, 小心地将少量的环氧树脂应用于导线出口硬币电池的位置。这是单元格最有可能泄漏的位置。</li>
		<li>在将硬币电池连接到任何测试设备之前, 允许1小时的环氧树脂干燥。请注意, 它可以采取高达 24 h 为环氧树脂完全固化和硬化。 注: 环氧树脂的用途是密封细胞 (参见图 5), 而不是提供任何机械强度。</li>
	</ol>
</li>
</ol>3. Lithiation 程序
<ol><li>
连接设置
	<ol>
<li>使用手持打火机, 在从细胞中凸出的参考电极线末端烧掉约2厘米的绝缘;这是电线将连接到测试设备。在连接三电极电池进行测试时, 将暴露的导线弯曲回自身以改善连接。</li>
		<li>将一小正方形的电子胶带 (2 厘米 x 2 厘米) 放在硬币电池盒的顶部;这应该防止硬币的顶部和硬币电池持有人之间的任何电接触。将准备单元放置在电池支架中。 注意: 细胞的顶部应该与任何连接绝缘, 细胞的底部应该连接到细胞持有者的负读数。</li>
		<li>使用鳄鱼夹子, 将参考电极连接到电池架上的顶部夹 (正连接)。 注: 该细胞应设置为测试的参考电极作为正极和底部锂盘 (细胞的情况下) 作为负电极。</li>
	</ol>
</li>
	<li>
基准校准电压
	<ol>
<li>计算参考电极的活性材料量。 注: 对于一个典型的电极质量为0.1 毫克和80% 活性物质组成, 这出来到0.08 毫克。</li>
		<li>使用钛酸锂的活性物质质量和理论特定容量20, 确定适当的电流以在 C/16 上充电电池。</li>
		<li>在 C/16 的适当电压范围内多次循环参考电极 (1.25-2.25 V vs锂/锂+);此范围将根据使用中的参考电极而变化。注意在充电和放电过程中应发生的高原电压/参考电压。 注: 对于 Li4Ti5O12电极这个值通常是大约 1.56 V与li/李+。</li>
		<li>记录参考电压及其与之关联的相应单元格。在工作单元中使用此电压后, 校准电极的电位。</li>
		<li>将电池休息24小时, 并监测参考电极电位是否稳定。</li>
		<li>将锂化单元转移到惰性氩气环境中, 用于工作单元结构。避免参考电极与瓶盖或细胞盒之间的任何可能接触;这可能会缩短参考电极并改变其电位。</li>
	</ol>
</li>
</ol>4. 工作单元的建造
<ol><li>把硬币盒壳放在一条小重量的小船里。将阴极盘置于单元格盒的中心。在阴极上放置几滴 DEC 电解质, 并在边缘附近滴几个水滴以填充外部缝隙。</li>
	<li>在电极顶部放置一个1.905 厘米 (3/4 英寸) 的分隔符。确保分离器完全湿润, 并没有气泡下面被困。将垫圈与小唇放置在朝向向上的细胞帽上。用力压紧, 适当地将垫片放入机箱中。将硬币单元格集放到一边, 然后定位锂化准备单元。</li>
	<li>
锂化参考电极的提取
	<ol>
<li>在锂化准备单元的顶部应用一小正方形的电子胶带。这有助于防止在拆卸过程中机箱和 cap 之间的短路。</li>
		<li>用薄鼻钳, 牢固地握住准备单元, 用帽面朝上。小心不要用金属钳子把电池剪短。使用端切钳仔细, 但牢牢, 撬开硬币细胞沿边缘。注意不要用金属钳子把电池的顶部和底部剪短。</li>
		<li>一旦大约70% 的细胞被撬开, 用端切钳握住箱子, 用细鼻钳仔细地将细胞盒和瓶盖分开。仔细提取锂化参考电极。丢弃其他单元格组件。</li>
	</ol>
</li>
	<li>用一对钳子, 伸直螺旋形参考电极线, 伸直。重新弯曲导线, 使尖端位于电极的中心, 导线延伸到电池的边缘。切断暴露的绝缘线</li>
	<li>在参考电极上和周围添加几滴电解质。放置一个小的, 长方形的分隔符在上面的电线越过垫片和细胞的情况。这有助于防止短路之间的电线和金属盒和帽。</li>
	<li>在参考电极顶部放置一个1.58 厘米 (5/8 英寸) 的分离器;这有助于防止在参考电极和阳极之间的短路。将准备好的阳极盘放在单元格中参考电极的顶部。注意正确地将阴极的形状与阳极相对准。 注: 参考电极尖端应在中心, 导线应退出矩形间隙。</li>
	<li>小心地将1.0 毫米不锈钢垫片放在阳极上。将波浪弹簧放在间隔顶部。请确保所有组件都集中在单元格中。用电解质将细胞填充到边缘。</li>
	<li>使用塑料镊子, 小心地将电池盖放在组件的顶部。用力按下, 把瓶盖放到垫片的唇上。在卷曲之前, 仔细地将剩余的电线折回电池盖上。这可以防止导线在卷曲过程中被切断。</li>
	<li>用一对塑料镊子小心地将细胞转移到硬币电池压接装置中。当转移细胞时, 保持平坦, 以避免额外的电解质损失。将细胞卷曲至大约5兆帕斯卡 (750 psi)。</li>
	<li>从氩 glovebox 中取出硬币细胞。用异丙醇和无绒布的工作雨刷仔细清洁细胞。</li>
	<li>
细胞密封
	<ol>
<li>使用无起毛的雨刷, 小心地烘干硬币细胞。要格外小心, 使电线离开硬币电池的位置变干。</li>
		<li>将等量的树脂和固化剂混合在一起, 形成一种无导电环氧树脂。使用牙签, 小心地应用少量的环氧树脂的位置, 电线退出硬币电池。这是单元格最有可能泄漏的位置。</li>
		<li>在将硬币电池连接到任何测试设备之前, 允许1小时的环氧树脂干燥。 注: 环氧树脂完全固化硬化可达24小时。然而, 环氧树脂的目的是密封细胞, 而不是提供任何机械强度。</li>
	</ol>
</li>
</ol>5. 电化学测试
<ol><li>
性能和循环
	<ol>
<li>计算阴极和阳极电极的理论容量。<ol>
<li>利用电极盘的总干重, 铝/铜基体的质量, 以及活性材料的重量百分比, 确定每个电极的活性材料的质量。</li>
			<li>通过将活性物质的质量乘以其各自的理论能力, 确定每个电极的容量。使用最极限电极容量 (通常是阴极), 确定整体细胞容量。</li>
		</ol>
</li>
		<li>将电池连接到电化学测量装置, 注意将正功率和正向传感器与阴极、负功率和传感器连接到阳极。通过铜线连接参考电极的引用 (请参见图 6b)。</li>
		<li>通过检查开路电压和电位, 对单元格进行连接并正常工作。使用 lithiation 过程中记录的参考电压校准阴极和阳极电位读数。</li>
		<li>以所需的 C 速率循环整个单元格, 例如 C/10, 同时测量整个电池、阴极和阳极电位。根据需要对其他单元格和 C 速率重复步骤 5.1.1 5.1.4, 具体取决于每个单元格的规格和要求。</li>
	</ol>
</li>
	<li>
电化学阻抗谱
	<ol>
<li>
全细胞阻抗
		<ol>
<li>将单元格连接到 EIS 测量设备。使用以下配置: 正极的正功率和正向传感器, 负极的负功率和负传感器。 注: 参考传感器应连接到阳极。参考电极应保持断开。</li>
			<li>为 EIS 选择恒电位控制, 其振幅为 10 mV。选择 1 mhz 到 1 mhz 的频率范围。收集完整细胞的阻抗。情节和预示的情节, 以分析细胞的反应。 注: 频率范围可能并不总是需要的, 可以修改后收集初步结果。</li>
		</ol>
</li>
		<li>
阴极阻抗
		<ol>
<li>将单元格与 EIS 测量装置连接起来: 正极的正功率和正向传感器, 负极的负功率和负传感器, 以及参照电极通过铜线的参考传感器。</li>
			<li>重复与全细胞阻抗相同的步骤 (步骤 5.2.1.2-5.2.1.3)。</li>
		</ol>
</li>
		<li>
阳极阻抗
		<ol>
<li>将单元格与 EIS 测量装置连接起来: 正极的正功率和正向传感器, 负极的负功率和负传感器, 以及参照电极通过铜线的参考传感器。</li>
			<li>重复与全细胞阻抗相同的步骤 (步骤 5.2.1.2-5.2.1.3)。</li>
		</ol>
</li>
		<li>
阻抗作为电荷状态的函数
		<ol>
<li>根据所需的阻抗测量将单元格连接到 EIS 测量装置: 全电池、阴极或阳极。分别为适当的连接使用步骤5.2.1.1、5.2.2.1 或5.2.3.1。</li>
			<li>在 C/2 上使用恒定电流对电池充电, 直到电池达到上电压限制为止。使用恒定电压控制方法在上限上保持电压, 直到应用电流降至 C/100 以下。细胞现在应该完全充电。</li>
			<li>在 C/2 释放细胞3分钟;细胞现在应该是 90% SOC. 允许细胞休息1小时, 以达到热和电化学平衡条件。</li>
			<li>使用步骤 5.2.1.2 5.2.1.3 中提出的相同步骤收集阻抗。重复步骤5.2.4.3 和5.2.4.4 收集阻抗作为 SOC 的功能。</li>
		</ol>
</li>
	</ol>
</li>
</ol>

<ol>
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Experimental Study of Different Reference Electrode Designs and Their Implications for Half-Cell Impedance Spectra.</a> Journal of the Electrochemical Society. 164 (2), 80-87 (2017).</li><li>Dees, D. W., Jansen, A. N., Abraham, D. 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D., Cui, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Reliable+reference+electrodes+for+lithium-ion+batteries.">Reliable reference electrodes for lithium-ion batteries.</a> Electrochemistry Communications. 31, 141-144 (2013).</li><li>Nakahara, K., Nakajima, R., Matsushima, T., Majima, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Preparation+of+particulate+Li4Ti5O12+having+excellent+characteristics+as+an+electrode+active+material+for+power+storage+cells.">Preparation of particulate Li4Ti5O12 having excellent characteristics as an electrode active material for power storage cells.</a> Journal of Power Sources. 117 (1-2), 131-136 (2003).</li><li>Shi, Y., Wen, L., Li, F., Cheng, H. 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作者没有什么可透露的。

细胞压接压力在制备和工作细胞的成功率上起着重要的作用。如果单元格的压力过大 (> 800 psi), 则参考电极由于在帽和垫片之间的参考导线位置而导致电池盖短路。请注意, 通过此接口的导线是一种要求, 以便将参考电极读数连接到外部测量装置。如果细胞压力过低 (< 700 psi), 细胞可能会有不完全卷曲的问题, 这可能会导致电解质泄漏和空气渗透后, 细胞从惰性氩环境中移除。据发现, 大约 750 psi 是压接电池以避免泄漏或短路问题的最佳压力。为了提供额外的手段, 以防止这些问题与短路的参考线, 在施工过程中的一个重要步骤是额外的方形分离器放置沿垫片, 其中导线越过细胞边界。该分离器提供了一个额外的绝缘层, 有助于防止内部短路。此外, 制备和工作单元可能需要略有不同的压接压力。所述制备单元使用两个比金属箔上的电极铸件厚得多的锂圆盘, 在工作单元中使用。
在制备单元中, 参考电极 lithiation 后, 必须在工作单元中提取并重复使用参考电极。在此过程中, 必须格外小心。一般情况下, 如果参考电极的制备正确, 不应该有任何问题与材料的粘附性的电线扁平的部分。在任何情况下, 应尽量减少参照电极从制备单元中取出并用于工作单元之间的时间量。参考电极不应放置在任何表面上, 或允许在很大的时间外休息。尽量减少导线的操纵是理想的, 因为它避免了可能的疲劳和断裂的电线。
在构造三电极硬币电池的另一个重要考虑是正确地密封细胞。因为导线夹在瓶盖和垫片之间, 所以在电池中可能会出现小的破坏, 从而导致电解质泄漏或空气穿透。如果这种方法不被纠正, 在阻抗测量中可能会出现失真, 而整个细胞可能由于与环境的反应而失败, 特别是在其制造的惰性 glovebox 以外的一段时间内。在细胞的构建过程中, 非导电环氧的使用是至关重要的, 因为它完全封闭了外界环境中的细胞。一个有趣的观察是, 如果细胞没有卷曲到足够高的压力, 环氧树脂将不会正确硬化, 有时会冒泡。这可能是由于电解质被邪恶的和与环氧树脂混合, 或细胞内部压力的升高缓慢泄漏, 并导致气泡形成。请注意, 环氧树脂, 无论是在硬化过程中, 都浸泡在电解质中, 没有明显的迹象表明任何反应被观察到。如果使用得当, 应允许环氧密封单元在 glovebox 内至少干燥1小时, 然后再去除。之后, 环氧在大气环境中会变硬。根据环氧树脂的使用, 它可能需要24小时以上的环氧树脂才能完全固化, 在此过程中, 细胞应允许休息。如果细胞没有密封, 或者密封过程不够, 细胞就会泄漏到环境中。一段时间后, 细胞可能开始改变颜色。在图 5中可以看到一些密封性较差的单元格示例。
在构造三电极硬币单元时, 主电极的形状会对电池的性能产生影响。可以在图 4中看到各种可能的形状。在理想的情况下, 参考电极将被放置在电极的中心。由于参考电极的位置, 可能发生的一些问题涉及细胞内的压力分布不均匀。另一个问题是, 主电极之间的参考电极的存在造成了细胞阻抗的人为增加, 这是因为该引用阻塞了电极区域的一部分。某些配置 (图 44F) 试图通过绘制一个引用可以坐的小区域来减少此问题。问题在于, 这降低了电池容量, 并在制造过程中引入了复杂性。
当将三电极电池连接到电化学测试测量时, 由于所用铜线的小直径, 与参考电极的连接可能非常敏感。注意, 导线直径必须小, 以减少对电池性能的任何影响, 其中之一可能是两个平面电极盘之间的区域堵塞。由于这种连接灵敏度, 使铜线的外露端多次弯曲, 以增加连接面面积。如果未完成此操作, 则参考电极可能看起来短路或出现故障, 实际上该单元格工作正常。
使用三电极硬币电池的一个限制是整个过程是手工完成的。为了产生一致和可靠的结果, 在构造硬币单元时需要一定量的练习。当参考电极、工作电极和/或反电极在细胞内发生意外移位时, 阻抗和电位读数可能会失真或不准确。这对制备细胞来说并不重要, 因为这个细胞的目的仅仅是通过部分 lithiation 来准备参考, 并确定高原电压的值 (通常为 1.565 V 的钛酸锂电极, 用于这程序)。
通过对阳极阻抗畸变的观察, 确定细胞成功的一个好方法。对于不正确密封的电池或电极对准不好的情况, 在采取阳极阻抗时往往会看到电感阻抗回路。当单元格被完全释放时, 这些循环更容易被注意到 (即, 当单元格第一次构造时), 因此可以在单元格的任何循环之前对它们进行测试。在图 9中显示了具有失真呈现的阳极阻抗谱的例子。

尽管锂电池的起源可以被任意追溯到过去, 但许多今天发现的锂离子电池的大规模生产和商业化始于二十世纪八十年代。在这个时代开发的许多材料中, 有一个例子是锂钴氧化物 (LiCoO2), 在今天的1中仍然普遍存在。目前许多研究都侧重于发展各种其他金属氧化物结构, 重点放在减少或消除使用钴代替其他较低成本和更环保的金属, 例如锰或镍2。锂离子电池材料不断变化的景观要求有一种有效而准确的方法来表征其性能和安全性。由于任何电池的操作都涉及正负电极的耦合电化学反应, 典型的两电极电池无法独立地表征电极。由于存在退化现象, 性能较差和随后缺乏理解可能会导致危险情况或电池整体性能不佳。以前的研究旨在规范典型的双电极电池的处理技术3。一种改进标准细胞配置缺点的方法是三电极电池。
三电极设置是一种解耦两电极反应的方法, 并为电池操作的基本物理提供了更深入的了解。在三电极装置中, 除了阴极和阳极外, 还引入了参考电极。该参考电极随后用于在操作过程中动态测量阳极和阴极的电位。没有电流通过参考电极, 因此, 它提供了一个奇异的, 理想的稳定, 电压。采用三电极装置, 在操作过程中可同时采集全电池电压、阴极电位和阳极电位。除了潜在的测量, 电极的阻抗贡献可以被描绘成细胞状态的作用的充电4。
三电极设置对于研究锂离子电池的降解现象非常有用, 如电沉积锂金属, 也称为锂电镀。其他组已建议三电极设置5,6,7,8,9,10,11,12, 13但它们经常使用固有不稳定的锂金属作为参考, 包括自定义, 难以装配设置, 从而降低了可靠性。锂电镀发生时, 而不是锂到主电极结构, 锂沉积在表面的结构。这些矿床通常假设一个 (相对) 均匀的金属层 (电镀) 或小树突状结构的形态。电镀可以产生影响, 从造成安全问题, 以阻碍自行车的性能。从现象学的角度来看, 锂电镀是由于锂不能有效地 intercalate 到主电极结构中而产生的。电镀往往发生在低温, 高充电率, 高电极充电状态 (SOC), 或结合这三因素12。低温下, 由于阿伦尼乌斯扩散系数对温度的依赖性, 使电极内部的固态扩散减少。较低的固态扩散导致锂在电极-电解质界面上积聚, 随后再沉积锂。在高充电率下, 出现类似现象。锂试图 intercalate 进入电极结构非常迅速, 但不能, 从而被镀。在更高的 SOC 中, 锂 intercalate 到结构中的平均可用空间较少, 因此在表面上沉积变得更有利。
锂树突是特别重要的, 因为他们所引起的安全问题。如果在细胞内形成树突, 就有可能生长, 刺穿分离器, 导致阳极和阴极之间的内部短路。这内部短可能导致非常高地方温度在易燃的电解质, 经常导致热量失控, 甚至在细胞的爆炸。与枝晶形成有关的另一个问题是活性锂的表面积增加。新沉积的锂将与电解质发生反应, 导致固体电解质相间 (SEI) 的形成, 这将导致容量损失增加, 循环性能较差。
与三电极系统的设计有关的一个问题是选择合适的参考电极。与参考、正极和负极的位置和尺寸有关的物流可以在获取系统的准确结果方面发挥重要作用。一个例子是正负电极在细胞结构过程中的失调和产生的边缘效应可能在参考读数14、15中引入错误。在材料选择方面, 参考电极应具有稳定可靠的电压, 且具有较高的非极化。锂金属是许多研究小组经常使用的参考电极, 它有一个依赖于被动表面薄膜的电位。这可能会产生问题, 因为清洗和老化的锂电极显示不同的电位16。这成为长期老化效应研究的一个问题。通过 Solchenbach 的研究, 通过用锂合金化金并将其作为参考 11, 试图消除一些不稳定问题。其他的研究观察了不同的材料, 包括钛酸锂, 这已经被实验研究, 并显示了一个大的电化学潜在的高原范围约 1.5-1.6 V17 (~ 50% SOC)。这个高原有助于保持一个稳定的潜力, 特别是在发生意外扰动电极的电荷状态。即使在不同的 C 速率和温度下, LTO (包括碳基导电添加剂) 的潜在稳定性也保持不变。18必须强调的是, 参考电极的选择是三电极电池设计中的一个重要步骤。
许多研究小组提出实验性的三电极细胞的设置。杰尔et . 使用了钛酸锂铜线参考电极的薄塑料电池, 研究高温下循环和贮存时阻抗的变化19。McTurk et . 采用一种技术, 即将锂电镀铜线插入商业邮袋单元, 其主要目的是证明无创插入技术的重要性9。Solchenbach et 。使用了改进的接头套管型 T 细胞和金微参考电极 (前面提到) 的阻抗和电位测量。11 Waldmann et 等从商业细胞中收获电极并重建自己的三电极袋细胞, 用于研究锂沉积12。Costard et . 开发了内部实验性的三电极细胞外壳, 以测试不同参考电极材料和配置的有效性13。
这些研究组大多采用纯锂金属作为参考, 这对稳定性和 SEI 的生长有一定的关注, 特别是长期使用。其他问题涉及对现有或商业设置的复杂和耗时的修改。本文提出了一种可靠、经济高效的电化学测试三电极锂离子硬币电池的技术, 如图 1所示。这个三电极安装可以使用标准的硬币电池组件, 铜线, 和钛酸锂基参考电极 (请参见图 2) 来构建。此方法不需要任何专门的设备或详细的修改, 遵循标准的实验室规模的电化学程序和商业供应商的材料。

<table border="0" cellpadding="0" cellspacing="0" style="width:1225px;" width="1224">
	<colgroup>
		<col />
		<col />
		<col />
		<col />
	</colgroup>
	<tbody>
		<tr height="21">
			<td height="21" style="height:21px;width:351px;">Agate Mortar and Pestle</td>
			<td style="width:163px;">VWR</td>
			<td style="width:147px;">89037-492</td>
			<td style="width:565px;">5 in diameter</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:351px;">Die Set</td>
			<td style="width:163px;">Mayhew</td>
			<td style="width:147px;">66000</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:351px;">Laboratory Press</td>
			<td style="width:163px;">MTI</td>
			<td style="width:147px;">YLJ-12</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:351px;">Analytical Scale</td>
			<td style="width:163px;">Ohaus</td>
			<td style="width:147px;">Adventurer AX</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:351px;">High-Shear Mixing Device</td>
			<td style="width:163px;">IKA</td>
			<td style="width:147px;">3645000</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:351px;">Argon-filled Glovebox</td>
			<td style="width:163px;">MBraun</td>
			<td style="width:147px;">LABstar</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:351px;">Hydraulic Crimper</td>
			<td style="width:163px;">MTI</td>
			<td style="width:147px;">MSK-110</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:351px;">Battery Cycler</td>
			<td style="width:163px;">Arbin Instruments</td>
			<td style="width:147px;">BT2000</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:351px;">Potentiostat/Galvanostat/EIS</td>
			<td style="width:163px;">Bio-Logic</td>
			<td style="width:147px;">VMP3</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:351px;">Vacuum Oven and Pump</td>
			<td style="width:163px;">MTI</td>
			<td style="width:147px;">-</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:351px;">Copper Wire</td>
			<td style="width:163px;">Remington</td>
			<td style="width:147px;">PN155</td>
			<td>32 AWG</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:351px;">Glass Balls</td>
			<td style="width:163px;">McMasterr-Carr</td>
			<td style="width:147px;">8996K25</td>
			<td>6 mm borosilicate glass balls</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:351px;">Stirring Tube</td>
			<td style="width:163px;">IKA</td>
			<td style="width:147px;">3703000</td>
			<td>20 ml</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:351px;">Celgard 2500 Separator</td>
			<td style="width:163px;">MTI</td>
			<td style="width:147px;">EQ-bsf-0025-60C</td>
			<td>25 &#956;m thick; Polypropylene</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:351px;">Stainless Steel CR2032 Coin Cell Kit</td>
			<td style="width:163px;">Pred Materials</td>
			<td style="width:147px;"></td>
			<td>Coin cell kit includes: case, cap, PP gasket</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:351px;">Stainless Steel Spacer</td>
			<td style="width:163px;">Pred Materials</td>
			<td style="width:147px;"></td>
			<td>15.5 mm diameter &#215; 0.5 mm thickness</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:351px;">Stainless Steel Wave Spring</td>
			<td style="width:163px;">Pred Materials</td>
			<td style="width:147px;"></td>
			<td>15.0 mm diameter &#215; 1.4 mm height</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:351px;">Li-ion Battery Anode - Graphite</td>
			<td style="width:163px;">MTI</td>
			<td>bc-cf-241-ss-005</td>
			<td>Cu Foil Single Side Coated by CMS Graphite (241mm L x 200mm W x 50&#956;m Thickness)</td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;width:351px;">Li-ion Battery Cathode - LiCoO2</td>
			<td style="width:163px;">MTI</td>
			<td>bc-af-241co-ss-55</td>
			<td>Al Foil Single Side Coated by LiCoO2 (241mm L x 200mm W x 55&#956;m Thickness)</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:351px;">Polyvinylidene Difluoride (PVDF)</td>
			<td style="width:163px;">Kynar</td>
			<td style="width:147px;">Flex 2801</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:351px;">N-Methyl-2-Pyrrolidinone Anhydrous (NMP), 99.5%</td>
			<td style="width:163px;">Sigma Aldrich</td>
			<td style="width:147px;">328634</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:351px;">CNERGY Super C-65</td>
			<td style="width:163px;">Timcal</td>
			<td style="width:147px;"></td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;width:351px;">Electrolyte (1.0 M LiPF6 in EC/DEC, 1:1 by vol.)</td>
			<td style="width:163px;">BASF</td>
			<td style="width:147px;">50316366</td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;width:351px;">Lithium Titanate (Li4Ti5O12)</td>
			<td style="width:163px;">Sigma Aldrich</td>
			<td style="width:147px;">702277</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:351px;">KS6 Synthetic Graphite</td>
			<td style="width:163px;">Timcal</td>
			<td style="width:147px;"></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:351px;">Lithium Metal Ribbon</td>
			<td style="width:163px;">Sigma Aldrich</td>
			<td style="width:147px;">320080</td>
			<td>0.75 mm thickness</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:351px;">Epoxy Multipurpose</td>
			<td style="width:163px;">Loctite</td>
			<td style="width:147px;"></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:351px;">Electrical Tape</td>
			<td style="width:163px;">Scotch 3M Super 88&#160;</td>
			<td style="width:147px;"></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:351px;">Isopropyl Alcohol (IPA), ACS reagent, &#8805;99.5%</td>
			<td style="width:163px;">Sigma Aldrich</td>
			<td style="width:147px;">190764</td>
			<td></td>
		</tr>
	</tbody>
</table>

three-electrode coin cell preparation and electrodeposition analytics for lithium-ion batteries

锂离子电池在高能量和电力应用中得到应用, 例如在电动和混合动力汽车中, 监测降解和随后的安全问题变得越来越重要。在锂离子电池的设置中, 在正负端的电压测量内在地包括阴极和阳极的影响, 耦合和总和的总电池性能。因此, 监测与特定电极相关的降解方面的能力是极其困难的, 因为电极是从根本上耦合的。三电极安装可以克服这个问题。通过引入第三 (参考) 电极, 可以解耦各电极的影响, 并可独立测量电化学性能。参考电极 (RE) 必须有一个稳定的电位, 然后可以根据已知的参考, 例如, 锂金属进行校准。三电极电池可用于运行电化学测试, 如循环, 循环伏安, 电化学阻抗谱 (EIS)。三电极细胞 EIS 测量可以阐明单个电极阻抗对全细胞的贡献。此外, 监测阳极电位允许检测电沉积由于锂电镀, 这可能会引起安全问题。这对于电动汽车中锂离子电池的快速充电尤为重要。为了监测和表征电化学电池的安全和降解方面, 三电极的设置可以证明是无价的。本文旨在为采用2032元电池体系结构构建三电极硬币电池装置提供指导, 该系统易于生产, 可靠性高, 成本效益高。

三电极电池的电压和电位剖面的典型结果可以在图 7中看到。在一个理想的设置, 全细胞电压应该是相同的, 从一个双电极电池生产使用相同的电极夫妇。这是确定插入参考电极是否修改单元性能的一种方法。如果两个和三电极的全电池性能之间有显著的差异 (对于相同的工作和计数器电极), 那么可以假定插入参考电极修改了细胞的行为, 结果是不再有意义。
在充电过程中, 锂从阴极向阳极电极移动。当锂从阴极显微组织中除去时, 其对 li/锂+的电位就会增加。相反发生与阳极, 因为结构是不断填充锂。在放电过程中, 出现反向情况。这些电位的变化反映在三电极电位剖面中, 可以在图 7中看到。
三电极电池设置的一个强大的结果是检测锂电镀的开始。图 8显示了一个硬币电池快速充电过程中阳极电位剖面的例子。从图中放大的部分可以看出, 阳极电位在 CC 充电过程结束时达到负值。这表明电池中存在锂电镀。使用标准双电极设置时, 无法进行此测量。
三电极安装的阻抗结果显示在图 9中。典型的阻抗响应包括三个特征区域: 高频半圆、中频半圆和低频扩散尾。该地块的 Re (Z) 截距、半圆的半径和扩散尾的斜率可以用来描述细胞内发生的重要电化学现象。
另一个强大的使用三电极工具是阻抗特性的功能的电荷状态。这种阻抗可以与各种降解现象相关, 包括电沉积锂。图 10显示了一个用于单个硬币电池的完整电池、阴极和阳极的阻抗谱的示例。随着细胞 SOC 的变化, 阻抗的变化可以用来表征电极阻抗的个体贡献。对于阳极, 阻抗可以与各种降解现象相关, 包括 SEI 层的生长和锂的电镀和枝晶的形成。失真的阻抗测量包括电感回路 (请参见图 11) 可以与两个不同的因素相关联。电池的密封不良以及电解质泄漏 (请参见图 5) 可以诱发感应阻抗响应。电极形状和参考电极尖端的位置 (参见图 4) 也可以在阻抗响应21上诱发感应回路。
单个电极电位的行为可以用来提供分析, 这在传统的双电极设置中是不可用的。例如, 在电位剖面中的高原区域可以表示电极结构中的相变。这些相变可以通过附加电化学测试 (如循环伏安法) 得到证实。此外, 阳极电位的值可以与其他方法一起使用, 以确定锂电镀, 一旦阳极电位达到低于 0.0 V vs锂/锂+的值时, 就会发生这种情况。
<img alt="Figure 1" class="xfigimg" src="/files/ftp_upload/57735/57735fig1.jpg"> 图 1.内部三电极单元格设置.(a) 此面板显示已完成的三电极硬币单元格的照片。(b) 此面板显示内部单元格组件的分解视图。<a href="/files/ftp_upload/57735/57735fig1large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>
<img alt="Figure 2" class="xfigimg" src="/files/ftp_upload/57735/57735fig2.jpg"> 图 2.三电极硬币电池, 显示参考电极的入口点以及内部布局.请注意, 在这个数字中, cap 是透明的, 波形弹簧 (未显示) 位于顶部间隔的上方。<a href="/files/ftp_upload/57735/57735fig2large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>
<img alt="Figure 3" class="xfigimg" src="/files/ftp_upload/57735/57735fig3.jpg"> 图 3.参考电极配置.(a) 此面板显示了一个参考电极批次, 该批处理贴在持有者元素 (例如, 清洁玻璃容器) 上, 其涂层端被挂起晾干。以下面板显示与 (b) 对应的参考电极配置, 即在电极铸造到导线上后立即出现的情况 (c) 在准备单元中的使用, 以及 (d) 在工作单元中的使用。面板不被绘制成刻度。<a href="/files/ftp_upload/57735/57735fig3large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>
<img alt="Figure 4" class="xfigimg" src="/files/ftp_upload/57735/57735fig4.jpg"> 图 4.各种电极, 可用于建造三电极硬币细胞。这些面板显示 () 一个螺旋形状,(b) 一个中心引用 (c) 一个小孔形状, (d) 一侧的比萨饼切片形状, (e), 和 (f) 一侧带有一个小型圆形切口。<a href="/files/ftp_upload/57735/57735fig4large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>
<img alt="Figure 5" class="xfigimg" src="/files/ftp_upload/57735/57735fig5.jpg"> 图 5.不正确密封的三电极硬币电池, 表明泄漏和电解质与环境的反应.在这种情况下, 建议将电池从支架上取出, 因为电解液会生锈电子端子。<a href="/files/ftp_upload/57735/57735fig5large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>
<img alt="Figure 6" class="xfigimg" src="/files/ftp_upload/57735/57735fig6.jpg"> 图 6。与电化学测试机的连接以测量阻抗。连接配置显示为(a) 一个完整单元格 (zF), (b) 一个阴极 (zC) 和 (c) 阳极 (za)。三电极电池的性能和循环可以使用面板 (b) 中显示的阴极连接进行。<a href="/files/ftp_upload/57735/57735fig6large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>
<img alt="Figure 7" class="xfigimg" src="/files/ftp_upload/57735/57735fig7.jpg"> 图 7.电压测量.这些面板显示了阳极、阴极和全电池 (两个和三电极电池) 的电压测量 (a) 恒定电流, 恒压 (CCCV) 充电在 C/10 和 (b) 恒电流 (CC) 放电在 C/10。<a href="/files/ftp_upload/57735/57735fig7large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>
<img alt="Figure 8" class="xfigimg" src="/files/ftp_upload/57735/57735fig8.jpg"> 图 8.负极电位在快速充电期间.这个面板显示了一个负极电位发生在快速充电 (1 c 速率) 的三电极硬币电池, 表明可能存在的锂电镀。<a href="/files/ftp_upload/57735/57735fig8large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>
<img alt="Figure 9" class="xfigimg" src="/files/ftp_upload/57735/57735fig9.jpg"> 图 9.阻抗响应.这些面板显示阻抗响应, 从使用一个完整的电池, 阴极, 阳极的频率响应分析仪, 显示 (a) 一个完整的频率范围和 (b) 低频范围。<a href="/files/ftp_upload/57735/57735fig9large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>
<img alt="Figure 10" class="xfigimg" src="/files/ftp_upload/57735/57735fig10.jpg"> 图 10.EIS这些面板显示了对应于 (a) 的全电池、(b) 阴极和 (c) 阳极测量三电极硬币电池作为 SOC 功能的电化学阻抗谱.<a href="/files/ftp_upload/57735/57735fig10large.jpg" target="_blank">请单击此处查看更大的此数字的版本.</a>
<img alt="Figure 11" class="xfigimg" src="/files/ftp_upload/57735/57735fig11.jpg"> 图 11.阳极阻抗畸变。此图显示了测量三电极硬币电池的阳极阻抗失真, 这可能是由于单元内部的参考电极不正确或在导线的出口位置附近的硬币电池密封不当造成的。<a href="/files/ftp_upload/57735/57735fig11large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>

Watch this Scientific Journal Video about Three-electrode Coin Cell Preparation and Electrodeposition Analytics for Lithium-ion Batteries at JoVE.com

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

三电极电池是研究锂离子电池电化学的有用的。这样的电化学设置允许与阴极和阳极相关的现象被分离和独立检查。在这里, 我们提出了建设和使用一个三电极硬币电池的指南, 重点是锂电镀分析。

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 ...

three-electrode-coin-cell-preparation-electrodeposition-analytics-for

Nanyang Technological University

Research

JoVE Journal

Engineering

36.3K 次观看.  Texas A&M University. 三电极电池是研究锂离子电池电化学的有用的。这样的电化学设置允许与阴极和阳极相关的现象被分离和独立检查。在这里, 我们提出了建设和使用一个三电极硬币电池的指南, 重点是锂电镀分析。

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

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

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. ...

Preparation and Use of Photocatalytically Active Segmented Ag|ZnO and Coaxial TiO2-Ag Nanowires Made by Templated Electrodeposition

Photocatalytically active nanostructures require a large specific surface area with the presence of many catalytically active sites for the oxidation and reduction half reactions, and fast electron (hole) diffusion and charge separation. Nanowires present suitable architectures to meet these requirements. Axially segmented Ag|ZnO and radially segmented (coaxial) TiO2-Ag nanowires with a diameter of 200 nm and a length of 6-20 &#181;m were made by templated electrodeposition within the pores of polycarbonate track-etched (PCTE) or anodized aluminum oxide (AAO) membranes, respectively. In the photocatalytic experiments, the ZnO and TiO2 phases acted as photoanodes, and Ag as cathode. No external circuit is needed to connect both electrodes, which is a key advantage over conventional photo-electrochemical cells. For making segmented Ag|ZnO nanowires, the Ag salt electrolyte was replaced after formation of the Ag segment to form a ZnO segment attached to the Ag segment. For making coaxial TiO2-Ag nanowires, a TiO2 gel was first formed by the electrochemically induced sol-gel method. Drying and thermal annealing of the as-formed TiO2 gel resulted in the formation of crystalline TiO2 nanotubes. A subsequent Ag electrodeposition step inside the TiO2 nanotubes resulted in formation of coaxial TiO2-Ag nanowires. Due to the combination of an n-type semiconductor (ZnO or TiO2) and a metal (Ag) within the same nanowire, a Schottky barrier was created at the interface between the phases. To demonstrate the photocatalytic activity of these nanowires, the Ag|ZnO nanowires were used in a photocatalytic experiment in which H2 gas was detected upon UV illumination of the nanowires dispersed in a methanol/water mixture. After 17 min&#160;of illumination, approximately 0.2 vol% H2 gas was detected from a suspension of ~0.1 g of Ag|ZnO nanowires in a 50 ml 80 vol% aqueous methanol solution.

Preparation and Use of Photocatalytically Active Segmented Ag|ZnO and Coaxial TiO2-Ag Nanowires Made by Templated Electrodeposition

Procedures are outlined to prepare segmented and coaxial nanowires via templated electrodeposition in nanopores. As examples, segmented nanowires consisting of Ag and ZnO segments, and coaxial nanowires consisting of a TiO2 shell and a Ag core were made. The nanowires were used in photocatalytic hydrogen formation experiments.

制备和使用光催化活性分段银|氧化锌和二氧化钛同轴<sub&gt; 2</sub&gt;银纳米线制成由模板电

Photocatalytically active nanostructures require a large specific surface area with the presence of many catalytically active sites for the oxidation and ...

The Preparation of Electrohydrodynamic Bridges from Polar Dielectric Liquids

Horizontal and vertical liquid bridges are simple and powerful tools for exploring the interaction of high intensity electric fields (8-20 kV/cm) and polar dielectric liquids. These bridges are unique from capillary bridges in that they exhibit extensibility beyond a few millimeters, have complex bi-directional mass transfer patterns, and emit non-Planck infrared radiation. A number of common solvents can form such bridges as well as low conductivity solutions and colloidal suspensions. The macroscopic behavior is governed by electrohydrodynamics and provides a means of studying fluid flow phenomena without the presence of rigid walls. Prior to the onset of a liquid bridge several important phenomena can be observed including advancing meniscus height (electrowetting), bulk fluid circulation (the Sumoto effect), and the ejection of charged droplets (electrospray). The interaction between surface, polarization, and displacement forces can be directly examined by varying applied voltage and bridge length. The electric field, assisted by gravity, stabilizes the liquid bridge against Rayleigh-Plateau instabilities. Construction of basic apparatus for both vertical and horizontal orientation along with operational examples, including thermographic images, for three liquids (e.g., water, DMSO, and glycerol) is presented.

Horizontal and vertical electrohydrodynamic liquid bridges are simple and powerful tools for exploring the interaction of high intensity electric fields and polar dielectric liquids. The construction of basic apparatus and operational examples, including thermographic images, for three liquids (e.g., water, DMSO, and glycerol) is presented.

高压直流电桥从极地介电液的制备

Horizontal and vertical liquid bridges are simple and powerful tools for exploring the interaction of high intensity electric fields (8-20 kV/cm) and ...

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 ...

Synthesis of Ionic Liquid Based Electrolytes, Assembly of Li-ion Batteries, and Measurements of Performance at High Temperature

The chemical instability of the traditional electrolyte remains a safety issue in widely used energy storage devices such as Li-ion batteries. Li-ion batteries for use in devices operating at elevated temperatures require thermally stable and non-flammable electrolytes. Ionic liquids (ILs), which are non-flammable, non-volatile, thermally stable molten salts, are an ideal replacement for flammable and low boiling point organic solvent electrolytes currently used today. We herein describe the procedures to: 1) synthesize mono- and di-phosphonium ionic liquids paired with chloride or bis(trifluoromethane)sulfonimide (TFSI) anions; 2) measure the thermal properties and stability of these ionic liquids by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA); 3) measure the electrochemical properties of the ionic liquids by cyclic voltammetry (CV); 4) prepare electrolytes containing lithium bis(trifluoromethane)sulfonamide; 5) measure the conductivity of the electrolytes as a function of temperature; 6) assemble a coin cell battery with two of the electrolytes along with a Li metal anode and LiCoO2 cathode; and 7) evaluate battery performance at 100 &#176;C. We additionally describe the challenges in execution as well as the insights gained from performing these experiments.

Here, we describe protocols to prepare phosphonium-based ionic liquid and lithium bis(trifluoromethane)sulfonimide salt electrolytes, and assemble a non-flammable and high temperature functioning lithium-ion coin cell battery.

离子液体基电解质的合成，装配锂离子电池，并在高温性能的测量

The chemical instability of the traditional electrolyte remains a safety issue in widely used energy storage devices such as Li-ion batteries. Li-ion ...

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 ...

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 ...