Name: focused ion beam fabrication of lipon-based solid-state lithium-ion nanobatteries for in situ testing
Uploaded: 2018-03-07T12:30:00.000+00:00
Duration: 10 min 58 s
Description: Watch this Scientific Journal Video about Focused Ion Beam Fabrication of LiPON-based Solid-state Lithium-ion Nanobatteries for In Situ Testing at JoVE.com

作者承认, 美国能源部, 基础能源科学办公室, 根据奖项编号 DE-SC0002357, 为开发全固态电池和就地的谎言和 TEM 持有人的发展提供资金支持。与国家实验室的合作是可能的, 部分支持东北化学能源储存中心, 能源前沿研究中心, 由美国能源部, 基础能源科学办公室, 根据该奖项数字 DE-SC0001294。这项研究使用了功能性纳米材料中心的资源, 这是美国能源部科学设施办公室, 在布鲁克黑文国家实验室根据合同编号。DE-SC0012704。这项工作是在圣地亚哥纳米技术基础设施 (SDNI) 的一部分进行的, 它是国家纳米技术协调基础设施的成员, 由国家科学基金会 (赠款 ECCS-1542148) 支持。在美国加州大学欧文分校材料研究所 (IMRI) 的部分工作是在空间-时间限制 (CHE-082913) 部分由国家科学基金会化学中心资助的仪器进行的。我们感谢南茜 Dudney, 橡树岭国家实验室为我们提供了薄膜电池。J.L. 承认尤金 Cota-罗伯斯奖学金计划的支持, 并感谢印度塞族, 拉马努金奖学金 (SB/S2/RJN-100/2014)。

1. 样品和系统的准备
<ol><li>实现由 Al2O3基板 (500 µm 厚) 组成的完整薄膜电池, 一个金阴极电流收集器 (100-150 nm 厚, 直流溅射), LiCoO2阴极 (2 µm 厚, 射频溅射), LiPON 电解质 (1 µm 厚, rf溅射), 非晶硅阳极 (80 nm 厚, 射频溅射), 铜阳极电流收集器 (100 nm, 直流溅射)16,17。</li>
	<li>在25毫米直径的铝扫描电镜存根上安装一个完整的薄膜电池, 并使用铜带将阴极电流收集器电连接到 SEM 存根, 以最小化充电效果。</li>
	<li>在泵入燃烧室之前, 确认有一个低噪声的电通道存在于铜网格中, 奈米电池将被安装在其中, 将作为阴极的传导通路 (图1)。<ol>
<li>通过屏蔽电馈将阴极引线连接到舞台上, 这是在装有适当连接类型的电子束感应电流 (EBIC) 测量系统中存在的。在内部, 用带有暴露尖端的屏蔽导线将馈连接到舞台上;保护暴露的导线尖端的方法将取决于样品阶段类型, 并且, 在这里, 它由一个未使用的阶段设置螺丝举行到位。</li>
		<li>或者, 根据仪器舞台的接地电路的配置, 使用一条 BNC 电缆将恒电位仪的阴极引线连接到舞台地面,如图1所示。</li>
		<li>使用恒电位仪在恒流模式下进行低电流噪声测试。应用当前要执行的就地循环, 并观察测量电流的精度和精度。 注: 使用1.3.1 中描述的配置, 实现了 1 pa 0.1 pa 的测量电流。</li>
	</ol>
</li>
	<li>同样, 通过使用 BNC 电缆或鳄鱼夹子将恒电位仪的阳极引线与机器人地面连接到探针外部, 从机器人尖端创建导电通路,如图1所示。<ol>
<li>与步骤1.3.3 一样, 在恒流模式下使用恒电位仪进行低电流噪声测试。 注: 使用步骤1.4 中描述的连接, 最小稳定电流达到 10 pa 1 pa, 由于与机器人连接的无屏蔽的理由。</li>
	</ol>
</li>
</ol>2. 奈米电池的解除
<ol><li>在打开电子束和离子束成像之前, 将样品装入 SEM/心室室, 然后泵入系统指定的高真空 (≤10-5毫巴)。</li>
	<li>将电子束聚焦在薄膜电池表面上, 并使用标准的 SEM/eucentric 程序1确定其高度。</li>
	<li>倾斜的样品, 使离子束是正常的电池表面 (这里52°样品倾斜), 并存入1.5 到2µm 厚层的表面上电流收集器的薄膜电池使用离子束电流约 0.3 nA ad 在 25 x 2 µm (图 2) 的区域中驻留 200 ns 的时间。</li>
	<li>将离子束电压设置为30伏, 离子束驻留时间为 100 ns, 用于实验协议的其余部分。</li>
	<li>按照奈米电池软件中的规定, 使用步进模式横断面的铣削选项, 在 Pt 沉积周围暴露该堆积物, 如透射电镜薄板制备 1.选择铣削电流≤2.8 nA。输入一个铣削深度, 延伸至少1µm 在活性薄膜电池下面 (Z = 5 µm 在这种情况下), 横截宽度 (X) 25 µm 和横截高度 (y) 1.5 X Z (这里, Y = 7.5 µm)。之后, 电池横断面暴露, 从 SEM (这里, 电子束是52°从表面正常), 如在图 3中。 注: 实际铣削深度是薄膜电池所依赖的。</li>
	<li>使用光栅软件中提供的横断面清洗程序, 在其中离子束增量地接近被清洗的表面, 用离子束电流≤0.3 nA 来清除重新沉积的材料并清楚地暴露分层结构 (图 3)。</li>
	<li>执行一系列矩形下切 (也称为 J 切割或 U 切口) 在一个阶段倾斜的≤2.8 和光束电流的 nA, 以隔离大多数的奈米电池 2.使下切包括 i) 下矩形 0.5 x 25 µm 低于 Au 电流收集器到 Al2O3基板上, 二) 垂直矩形0.5 µm 宽 (x) 和整个奈米电池厚度 (Y) 和 iii) 垂直矩形0.5 µm 宽 (X), 在铂涂层奈米电池周围的高度小于奈米电池厚度 (Y-2.5 µm),如图 4 a 所示.这三次裁减应以平行方式进行 (同时铣削), 以防止在未切割区域内重新沉积材料。</li>
	<li>旋转示例180°并执行与步骤2.5 相同的水平切边。这将隔离奈米电池的底部和两侧, 但其余的连接区域除外。</li>
	<li>旋转示例180°。将机器人插入控制软件中指定的公园位置, 然后使用软件的 x-y 移动缓慢地将其与奈米电池接触。</li>
	<li>将机器人固定在奈米电池上的 Pt 区域上, 离子束沉积0.5 µm 厚 Pt, 使用30凯文离子束, 电流为 10 pA, 超过 2 x 1 µm 的面积。</li>
	<li>离子磨房奈米电池的剩余的连接的部分与一束电流在 1 nA 附近, 并且垂直地升起奈米电池与机器人(图 4 b).</li>
	<li>用2µm 厚的离子束沉积 Pt 在铜奈米电池上安装, 使用30凯文离子束, 其电流为 0.28 nA, 超过 10 x 5 µm 的面积。</li>
	<li>离子磨掉了机器人和奈米电池之间的连接, 使用30凯文离子束, 其电流为 1 x 1 µm, 深度为2µm, 留下一个独立的部分连接到 Cu 网格 (图5) 1. 注: 铜升降网格为安装奈米电池提供了一个平坦的底座, 并充当舞台与奈米电池之间的传导通路。</li>
</ol>3. 清洁和循环奈米电池
<ol><li>倾斜样品, 使离子束正常的电池表面, 并使用横断面清洗程序 (见步骤 2.4), 以消除重新沉积材料超过5µm 宽部分的奈米电池附近的铜网格, 导致明确的看法, 个别层奈米电池 (图6 a). 注: 从以前的铣削步骤中取出的材料必须从网格安装的奈米电池中除去, 以暴露奈米电池的电化学活性芯并防止短路。</li>
	<li>存入500毫微米厚的谎言-Pt 使用30凯文的电流 0.1 nA 在一个面积 1 x 2 µm, 以创建电接触之间的阴极电流收集器和金属网格, 这是电连接到舞台 (图 6b)。</li>
	<li>将样品倾斜到 0°, 并使用 1 nA 的离子束电流, 使矩形切口3µm 宽和深 (Z ~ 2 µm), 以完全去除阳极电流收集器和电解质, 将阳极与铜网格 (图 6c) 隔离。</li>
	<li>使用横断面清洗过程 (见步骤 2.4), 用离子束电流约 0.1 nA, 将重新沉积的材料移到奈米电池横断面的所有边上, 直到所有各个层都明显可见, 如图6 所示。d。</li>
	<li>将机器人插入到公园位置, 并使用控制软件, 使机器人接触到阳极电流收集器上的 Pt。离子束沉积0.2 µm 厚 Pt 使用30凯文离子束, 电流为 10 pA, 超过 2 x 1 µm 的面积, 以 "焊接" 连接机器人和当前收集器 (图 6d)1。</li>
	<li>在恒电流循环模式下运行恒电位仪。目前使用的参数取决于所制造的奈米电池和所需的 C 速率的最终横截面积, 但一般会按少量 nA 的顺序排列。我们选择电荷和放电电流, 使电流密度按µA/cm2的顺序排列。对于基于 LiCoO2的薄膜电池, 电压范围为2.0 和 4.2 v。</li>
</ol>

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我们没有什么可透露的。

正如我们的结果所证明的, 所描述的技术产生的电化学活性 nanobatteries 从一个更大的薄膜电池。通过 galvanostatically 偏置奈米电池, 这种技术已启用了前置和原位茎/鳗鱼的特征. 这使得对与电化学电荷相关的定量化学现象进行空前高分辨率的表征。然而, 为了实现这些结果, 必须克服一些具体的障碍。
在开始处理之前, 应进行恒定电流测试, 以确保奈米电池的阴极和阳极有低噪声的电通路。阴极侧测试可以执行与室通气。在奈米电池制造前, 将正极端子连接起来, 就像执行实验 (通过真空馈或舞台地面), 负极端子直接连接到舞台上。请注意, 如果使用触摸报警器作为舞台连接, 仪器的触控报警能力可能会被禁用, 只有在不需要进一步倾斜的情况下才会进行连接。然而, 这里的测试将要求系统在真空下, 电流将通过机器人和舞台电路。机器人可以电粘附铂到铜网格为恒定的电流噪声测试。如果当前解决问题持续存在, 请与供应商联系, 以了解如何将舞台与系统地面脱钩的信息。
为了使这种技术起作用, 使用所提供的离子束规格来最小化对固体电解质 LiPON 的损伤是至关重要的。LiPON 是高度敏感的长期暴露于 (i) 潮湿的大气条件, (ii) 电子束, 和 (iii) 离子束。因此, 固态奈米电池制造过程要求尽量减少暴露在所有三的这些条件。应绝对减少对大气条件的前期和后加工接触。描述的就地的循环过程被开发为一个解决方案, 以尽量减少这种暴露。在制造过程中, 电子束成像应受到限制, 因为它损害了固体电解质。同样, 离子束成像也应限于避免电解质和其它活性成分的降解。具体的铣削文件和时间是基于在特定试剂、设备和制造商的材料/设备表中列出的设备;这可能是不同的谎言仪器, 并可能需要修改时, 使用其他仪器。
在奈米电池的所有参数中, 最关键的考虑是使用低光束电流和停留时间来最小化损坏 14.每当需要时, 成像是用电子在低像素停留时间和离子束在较低的光束电流 (通常在 pA) 和低停留时间 (100 ns)。大部分时间, 高停留时间电子束成像产生可见变化的 LiPON 电解质。图 7a显示未损坏的 LiPON, 并且通过电子束进一步成像会导致 LiPON 层的损坏, 如图 7b所示。这种损害是不可逆转的, 导致对比变化, 并将使奈米电池电化学不活跃。
此外, 对于电化学循环, 必须适当地注意使阴极电流收集器和网格之间的电接触正确 (图 6b)。保持与阳极的机器人接触同样重要 (图 6);如图 8a中所示, 在150s 周围, 电化学数据中的尖峰对应于与阳极的振动诱发的接触问题。考虑到机器人阳极接触的不稳定性可能, 通过限制奈米电池容量来最小化原位测试时间, 从而减少充电时间. 
如果电压剖面与薄膜电池不一致, 则重复清洗过程, 因为可能会出现一些重新沉积导致短路问题 (图 10)。特别是阳极隔离步骤是重新沉积材料的一个很大的来源。这种清洗程序减少了奈米电池截面, 因此应相应地修正电流密度。据指出, 离子束损伤不能完全避免, 它被限制在几 nm 之间的最大25毫微米到表面, 计算从离子散射模拟 SRIM 程序30凯文 Ga+到电极材料18。低能耗处理可以在很大程度上减少19的损坏。这里演示的这个过程是独一无二的, 在纳米器件的制造、操作和原位测试中, 都是由 "颤-SEM" 双光束系统启用的. 可以将该过程扩展到任何其他电池化学和其他纳米器件。
值得注意的是, 本协议中提供的具体参数可能不能直接传递给交替的电化学系统。在高扫描速率下, LiPON 被确定对离子束的热效应敏感。然而, 其他电解质可能受到其他敏感性。同样, 尽管本协议中测试的材料系统在 Ga+离子铣削后表现出良好的电化学, 但其他材料系统可能更容易受到离子落伍和注入的影响。因此, 对于替代材料系统, 可能需要更多地探索参数空间。更敏感的材料, 如硫化物可能在离子磨后表现不佳, 虽然这一领域的研究主要是未开发的先进的表征技术。实际上, 这些参数将转化为最感兴趣的物质系统, 因为现代固体电解质一般是结晶性的, 比 LiPON 更健壮。尽管有这些潜在的限制, 该技术将应用于新材料系统, 提供了发现交替界面现象的潜力, 最终揭示了阻抗机制。这项技术的一个自然的后续行动是观察电化学循环在 TEM。这是在本协议中描述的系统上执行的, 并在这些接口上发现了以前看不见的行为。这项技术将使观测的交替形式的阻抗。

聚焦离子束 (心室) 主要用于透射电镜 (TEM) 标本制备和电路编辑1,2。在过去的两年中, 纳米加工使用了很大的进展, 重点是半导体材料 3.尽管其对科学进步的重要性, 但仍然存在的主要问题, 包括表面损坏, 重新沉积, 和优先溅射由于高电流密度4,5。在 TEM 标本的制备过程中, 已经有好几篇关于对大块材料产生损伤的文章, 并提出了一些减少此种损坏的方法6,7,8,9。然而, 由多个具有不同功能的层组成的活动设备的谎言制作仍然是有限的。
对于固态设备, 特别是在能量存储领域, 接口起着至关重要的作用, 而固-固界面通常被看作是阻抗10的主要来源。由于在单个设备中存在多个接口, 因此这些接口的特征特别难以描述, 因为它们的埋藏性质和数据卷积相结合。完全固态 nanobatteries 的制备对于探测和理解这些界面的动态特性是至关重要的, 这最终会影响电池的电化学过程。基于锂磷氮化 (LiPON) 的薄膜电池在两年前被证明, 目前商业化的是11。虽然从薄膜电池中进行电化学活性 nanobatteries 的制作是至关重要的, 可以对接口进行就地评估, 但大多数试图利用 nanobatteries 制造的使用不保留电化学活动, 因为短路12。在就地循环中的初始尝试只细化了奈米电池的一小部分, 以观察电子全息13的锂分布.
最近的工作证明了电化学活性 nanobatteries 的成功的谎言制作, 这既启用了前原位和原位扫描透射电子显微镜 (茎) 和电子能量损耗光谱学 (鳗鱼) 界面现象的特征14,15。重要的谎言制造参数, 有助于保持电化学活动已表明 Santhanagopalan et 等。14, 本手稿中介绍了详细的协议。这个过程是基于一个模型 LiCoO2/LiPON/Si 电池, 但最终将使探索进一步的薄膜电池化学。

<table><tbody><tr><td>Biologic SP-200 Potentiostat</td><td>Biologic Science Instruments</td><td>SP-200</td><td>Ultra Low Current&amp;nbsp; Option needed for pA current resolution</td></tr><tr><td>FEI Scios DualBeam FIB/SEM</td><td>FEI</td><td></td><td>Current noise improves with a shielded stage feedthrough</td></tr><tr><td>SEM Stub: Large &amp;Oslash;25.4mm x 9.5mm pin height</td><td>Ted Pella</td><td>16144</td><td>Or equivalent</td></tr><tr><td>PELCO Colloidal Silver Paste, Conductive</td><td>Ted Pella, Inc.</td><td>16032</td><td>Or equivalent</td></tr><tr><td>PELCO&amp;reg;&amp;nbsp;FIB Lift-Out TEM Grids</td><td>Ted Pella</td><td>10GC04</td><td>Or equivalent</td></tr></tbody></table>

focused ion beam fabrication of lipon-based solid-state lithium-ion nanobatteries for in situ testing

固态电解质是目前有机液体电解质的一个有希望的替代品, 能够提高能量密度, 提高锂离子电池的安全性。然而, 许多挫折阻碍了它们融入商业设备。主要限制因素是由于在电极/电解质界面上发生的纳米尺度现象, 最终导致电池运行的退化。这些关键问题是非常具有挑战性的观察和特点, 因为这些电池包含多个埋入接口。一种直接观察薄膜电池界面现象的方法是通过聚焦离子束 (nanobatteries) 制备电化学活性的。因此, 在最近的工作中开发并展示了一种可靠的制造 nanobatteries 的技术。在此, 提出了一个分步过程的详细协议, 以使这个奈米电池的制作过程得以重现。特别是, 该技术被应用于由 LiCoO2/LiPON/Si 组成的薄膜电池, 并在透射电子显微镜中进一步证明了原位循环。

一个具有代表性的固态锂离子奈米电池制造过程在参考图1-7 的协议中逐步显示出来。
图 8显示了原位测试两个制造的电池的电化学充电配置文件。两个配置文件清楚地显示一个 3.6 V 高原对应于 LiCoO2-Si 全细胞化学和氧化 co3 + → co4 +。Cell-1 (图 8a) 以较低电流密度 (50 µA/cm2) 进行测试, 将电荷容量限制为12.5 µAh/cm2。Cell-2 (图 8b) 在更高电流密度 (1.25 毫安/cm2) 中显示一个充电配置文件, 该值由 4.2 v 的上截止电压限制.记录的容量约为105µAh/厘米2, 接近 Cell-2 的理论容量 (110-120 µAh/cm2)。nanobatteries 的第一放电容量很差, 而随后的循环容量 (电荷和放电) 由于第一个周期的不可逆转性而受到限制。nanobatteries 的放电过程仍未优化, 但是, 在图 9中, 在电流密度为60µA/厘米2的情况下, 有代表性的电荷放电剖面。充电容量被限制了到30分钟, 并且放电被限制了到 2 V, 并且明显地可逆转是大约35%。虽然可逆性比文献14中报告的要好得多, 但需要进一步优化。
如果电压剖面不符合薄膜电池化学, 这可能是由于光束损坏或短路的重新沉积材料。图 10显示的电压配置文件与短路电压是恒定的, 并与应用电流成正比。离子束图像证实了沿边缘重新沉积的材料。机器人必须移除, 并需要进一步的横断面清洗步骤, 以清除此材料。这种清洗程序减少了奈米电池截面, 因此应相应地修正电流密度。
<img alt="Figure 1" class="xfigimg" src="/files/ftp_upload/56259/56259fig1.jpg"> 图 1: 电气连接示意图.恒电位仪通过外部连接连接到奈米电池: 1) 恒电位仪的负端到机器人针的断开接地;2) 阴极侧对电屏蔽真空馈或直接连接到舞台地面如触摸报警电路 (显示)。内部连接是在机器人和阳极之间, 在阴极和舞台之间通过一个铜 TEM 提升网格之间进行的。<a href="//cloudflare-jove-com.bdigitaluss.remotexs.co/files/ftp_upload/56259/56259fig1large.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/56259/56259fig2.jpg"> 图 2: Pt 沉积.薄膜电池表面沉积铂保护帽的 SEM 图像, 以避免损坏并使其接触.<a href="//cloudflare-jove-com.bdigitaluss.remotexs.co/files/ftp_upload/56259/56259fig2large.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/56259/56259fig3.jpg"> 图 3: 奈米电池剖面。在(a) 52°横断面视图和(b)和奈米电池上视图的横截切割后的扫描电镜图像。<a href="//cloudflare-jove-com.bdigitaluss.remotexs.co/files/ftp_upload/56259/56259fig3large.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/56259/56259fig4.jpg"> 图 4: 奈米电池 liftout 。(a)的离子束图像在机器人的情况下, 带下切口的薄板和(b)解除隔离的奈米电池。<a href="//cloudflare-jove-com.bdigitaluss.remotexs.co/files/ftp_upload/56259/56259fig4large.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/56259/56259fig5.jpg"> 图 5: 奈米电池安装。(a)离子束和(b)将提升的奈米电池焊接到铜 TEM 网格的扫描电镜图像。<a href="//cloudflare-jove-com.bdigitaluss.remotexs.co/files/ftp_upload/56259/56259fig5large.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/56259/56259fig6.jpg"> 图 6:奈米电池清洗。(a)的离子束图像清洗其中一个奈米电池剖面, (b ) 通过 Pt 沉积电连接栅格和阴极电流收集器, (c ) 切割以隔离 TEM 网格中的阳极, (d ) 清洗横断面的前, 后, 两侧, 以消除所有重新沉积材料。最后的接触是对阳极使用机器人的偏置.<a href="//cloudflare-jove-com.bdigitaluss.remotexs.co/files/ftp_upload/56259/56259fig6large.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/56259/56259fig7.jpg"> 图 7:奈米电池损坏。扫描电镜图像的奈米电池剖面与(a ) 未损坏的 LiPON 层和(b ) 成像, 在更高的放大诱导损伤的 LiPON 层所指示的圆圈.高停留时间电子束成像在 LiPON 电解质中产生可见的变化。<a href="//cloudflare-jove-com.bdigitaluss.remotexs.co/files/ftp_upload/56259/56259fig7large.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/56259/56259fig8.jpg"> 图 8:奈米电池充电数据。在不同电流密度下制备的奈米电池电化学充电剖面与(a ) 容量限制为12.5 µAh/cm 2 和 (b ) 电压限制为 4.2 V 截止。<a href="//cloudflare-jove-com.bdigitaluss.remotexs.co/files/ftp_upload/56259/56259fig8large.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/56259/56259fig9.jpg"> 图 9: 奈米电池循环配置文件。在电流密度为60µA/厘米2的情况下, 奈米电池电化学充电和放电配置文件。<a href="//cloudflare-jove-com.bdigitaluss.remotexs.co/files/ftp_upload/56259/56259fig9large.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/56259/56259fig10.jpg"> 图 10: 短路奈米电池。(a)未正确清洗的奈米电池的电压剖面, 导致从重新沉积材料中短路, 而(b ) 横截面离子束图像。<a href="//cloudflare-jove-com.bdigitaluss.remotexs.co/files/ftp_upload/56259/56259fig10large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>

Watch this Scientific Journal Video about Focused Ion Beam Fabrication of LiPON-based Solid-state Lithium-ion Nanobatteries for In Situ Testing at JoVE.com

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

提出了一种利用聚焦离子束制备电化学活性 LiPON 的固态锂离子 nanobatteries 的协议。

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 ...

focused-ion-beam-fabrication-lipon-based-solid-state-lithium-ion

Universidad San Sebastian

Research

JoVE Journal

Engineering

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

10.1K 次观看.  University of California San Diego. 提出了一种利用聚焦离子束制备电化学活性 LiPON 的固态锂离子 nanobatteries 的协议。

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

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. ...

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 ...

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 ...

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

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 ...

Nanoscale Characterization of Liquid-Solid Interfaces by Coupling Cryo-Focused Ion Beam Milling with Scanning Electron Microscopy and Spectroscopy

Physical and chemical processes at solid-liquid interfaces play a crucial role in many natural and technological phenomena, including catalysis, solar energy and fuel generation, and electrochemical energy storage. Nanoscale characterization of such interfaces has recently been achieved using cryogenic electron microscopy, thereby providing a new path to advancing our fundamental understanding of interface processes.
This contribution provides a practical guide to mapping the structure and chemistry of solid-liquid interfaces in materials and devices using an integrated cryogenic electron microscopy approach. In this approach, we pair cryogenic sample preparation which allows stabilization of solid-liquid interfaces with cryogenic focused ion beam (cryo-FIB) milling to create cross-sections through these complex buried structures. Cryogenic scanning electron microscopy (cryo-SEM) techniques performed in a dual-beam FIB/SEM enable direct imaging as well as chemical mapping at the nanoscale. We discuss practical challenges, strategies to overcome them, as well as protocols for obtaining optimal results. While we focus in our discussion on interfaces in energy storage devices, the methods outlined are broadly applicable to a range of fields where solid-liquid interface play a key role.

Cryogenic Focused Ion Beam (FIB) and Scanning Electron Microscopy (SEM) techniques can provide key insights into the chemistry and morphology of intact solid-liquid interfaces. Methods for preparing high quality Energy Dispersive X-ray (EDX) spectroscopic maps of such interfaces are detailed, with a focus on energy storage devices.

通过冷冻聚焦离子束铣削与扫描电子显微镜和光谱学耦合，对液固界面进行纳米级表征

Physical and chemical processes at solid-liquid interfaces play a crucial role in many natural and technological phenomena, including catalysis, solar ...

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

With the ever-increasing use of Li-ion batteries, especially due to their adoption in electric vehicles, their safety is in prime focus. Thus, the all-solid-state batteries (ASSBs) that use solid electrolytes instead of liquid electrolytes, which reduce the risk of flammability, have been the center stage of battery research for the last few years. However, in the ASSB, the ion transportation through the solid-solid electrolyte-electrode interface poses a challenge due to contact and chemical/electrochemical stability issues. Applying a suitable coating around the electrode and/or electrolyte particles offers a convenient solution, leading to better performance. For this, researchers are screening potential electronic/ionic conductive and nonconductive coatings to find the best coatings with suitable thickness for long-term chemical, electrochemical, and mechanical stability. Operando transmission electron microscopy (TEM) couples high spatial resolution with high temporal resolution to allow visualization of dynamic processes, and thus is an ideal tool to evaluate electrode/electrolyte coatings via studying (de)lithiation at a single particle level in real-time. However, the accumulated electron dose during a typical high-resolution in situ work may affect the electrochemical pathways, evaluation of which can be time-consuming. The current protocol presents an alternative procedure in which the potential coatings are applied on Si nanoparticles and are subjected to (de)lithiation during operando TEM experiments. The high volume changes of Si nanoparticles during (de)lithiation allow monitoring of the coating behavior at a relatively low magnification. Thus, the whole process is very electron-dose efficient and offers quick screening of potential coatings.

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

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

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

摘要

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此视频中的章节

钮扣电池锂离子电池的建设和测试

正极材料的同步辐射技术锂离子和钠离子电池表征

原位中子衍射用特制的锂离子电池

锂离子纽扣电池的非水电极加工和施工

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

原位锂化参考电极: 四原位阻抗谱的电极设计

锂离子电池三电极硬币电池制备及电沉积分析

锂离子电池材料用石墨烯液位的制备

通过冷冻聚焦离子束铣削与扫描电子显微镜和光谱学耦合，对液固界面进行纳米级表征

使用原位透射电子显微镜筛选全固态电池涂层

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

摘要

探索更多视频

此视频中的章节

钮扣电池锂离子电池的建设和测试

正极材料的同步辐射技术锂离子和钠离子电池表征

原位中子衍射用特制的锂离子电池

锂离子纽扣电池的非水电极加工和施工

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

原位锂化参考电极: 四原位阻抗谱的电极设计

锂离子电池三电极硬币电池制备及电沉积分析

锂离子电池材料用石墨烯液位的制备

通过冷冻聚焦离子束铣削与扫描电子显微镜和光谱学耦合，对液固界面进行纳米级表征

使用 原位 透射电子显微镜筛选全固态电池涂层

使用原位透射电子显微镜筛选全固态电池涂层