As a technology that can adjust energy, time, and space, batteries are one of the best ways to optimize energy applications and improve the comprehensive efficiency of energy use. With the increasing demand for energy storage and the wide application of large-scale energy storage systems, batteries with high-energy density and long-cycle life have become a current research focus. However, with the improved battery performance, its safety has become increasingly a concern. Battery accidents are often closely related to the flammable and explosive properties of organic electrolytes, heat accumulation induced by high current charging and discharging, battery monomer structure, and the thermoelectric loop control technology of modules. Nondestructive characterization means are used to accurately analyze the battery performance evolution, such as thermal runaway and life attenuation. These techniques can considerably avoid external interference and conduct insitu detection and analysis of the battery under the real environment and operating conditions to express and monitor the battery service behavior clearly and accurately. Thus, critical information, such as the reaction principle and the health state of the battery, can be derived. Furthermore, preparing electrode materials and designing and grouping battery structures improve the safety and reliability of the battery. Herein, the recently reported battery nondestructive testing, monitoring, and characterization methods are reviewed, including sensor, magnetic resonance, X-ray, neutron scattering, ultrasonic detection, and Raman scattering. These methods help to describe their principles, application methods, and characteristics of information acquisition, making a comprehensive comparison of each characterization technology, especially the mutually supportive relationship of battery data. It provides methods and technical means to deeply explore the relationship between the internal microstructure evolution, electrical performance, and battery safety under different working conditions, which gradually improve the battery efficiency and support the establishment of battery accident warning and life warning mechanisms.
Fig. 3
Schematic of the smart battery design and fabrication. (a) Dendrite formation in a traditional lithium battery where complete penetration of the separator by a lithium dendrite is only detected when the battery fails due to an internal short circuit and VLi-Li drops to zero; (b) In comparison, a lithium battery with a bifunctional separator where the overgrown lithium dendrite penetrates into the separator and makes contact with the conducting copper layer, giving rise to a drop in VCu-Li as warning of impending failure due to an internal short circuit. As well as, the full battery remains safely operational with non-zero potential[11] (NatureCommunications has image copyright)
Fig. 4
(a) Schematic of customized RTD embedded LIB coin cell; (b) RTD embedded polylactic acid spacer and CR2032 cell with internal RTD. Dimension of the RTD embedded spacer was comparable to ordinary CR2032 coin cell spacer, allowing for reliable sensor-electrode contact and cell sealing after assembly[22](ScientificReports has image copyright)
Fig. 6
Schematic diagram and image of FBG sensor attached (a) or implanted (b) on anode electrode of lithium ion battery respectively (c) and (d)[47] (EnergyTechnology has image copyright)
Fig. 8
Schematic of the cell embedded with FBG and corresponding electrochemical performance. (a) The schematic illustration of the structure of FBG and the Li-S pouch cell embedded with FBG; (b) The cycle performance and (c) discharge-charge curves of the Li-S pouch cell embedded with FBG and a normal cell without FBG[23] (EnergyEnvironmentalScience has image copyright)
Fig. 9
The schematic diagram of experimental setup for strain monitoring of anode-free lithium metal batteries[51] (AdvancedScience has image copyright)
Fig. 10
(a) Schematic depiction of the measurement setup with a thin film pouch cell placed in the coil of a NMR device, connected to a battery cycler; (b) Schematic thin film pouch cell; (c)—(f) 7Li-NMR spectra of thin film pouch cells and SEM images of the corresponding electrodes after (c1—f1) and (c2—f2) 8 hours of electrodeposition at 0.5 mA/cm2 containing 1-PF6-C, 1-TFSI-C, 1-TFSI-E and 3-TFSI-E[59] (PhysChemChemPhys has image copyright)
Fig. 12
Noninvasive electron paramagnetic resonance imaging technique monitors changes in lithium deposits inside the battery during charging and discharging[25] (ChemistryofMaterials has image copyright)
Wang等[64]利用原位EPR技术研究锂离子电池中石墨阳极在室温下的锂化/沉积行为。EPR谐振器质量因子、自旋密度和EPR光谱变化分别反映了石墨的电导率、锂化程度和沉积过程。该方法基于微波趋肤深度对整个电池电导率的影响而发生的变化来评估在第1个电位循环形成的SEI膜，得出SEI层膜的形成开始于1.3 V左右。此外对石墨阳极多次锂化/脱锂循环期间EPR自旋密度变化进行定量分析，并将这些数据与同一条件下的电化学测量相关联。研究结果表明，锂金属在石墨负极上的沉积不需要过充电(电位通常≤0 V vs. Li+/Li)。通过光谱模拟得到即使在低扫描速率(0.04 mV/s)下，石墨上的不可逆沉积在约+0.04 V(vs. Li+/Li)开始，长循环期间锂信号的降低证实了碳酸亚乙烯酯(VC)电解质添加剂对锂沉积的抑制，这主要归因于机械柔性和聚合物SEI层具有更高的离子电导率。其研究表明，对于高倍率循环，建议把阳极的安全截止电位限制为+0.05 V，并通过EPR在长循环中的响应进一步证实该提议。
Schellenberger等[67]基于具有两个软X射线透明氮化硅(SiN x )膜窗口的微流体电化学半电池研究硅阳极上的SEI，通过控制气泡形成柔软的X射线透明薄电解质层。在循环过程中形成SEI后，他们使用高强度X射线在入口窗口附近产生气泡并从中推出多余的电解质探测体积，气泡稳定地处于膜之间的中心，留在光束路径中的是一层薄薄的电解质，覆盖着SEI和阳极。通过使用低强度的X射线来避免光束损伤，然后利用透射sXAS在硅薄膜阳极上进行原位SEI研究，而不需要拆解电池。实验结果参考化合物的吸收光谱并进行比较，确定了形成物质并研究了SEI的组成，如乙酸锂、乙烯二碳酸锂或乙烯单碳酸锂、乙酰丙酮锂、氢氧化锂和氟化锂，此外还观察到了醛类物质，这可能是源于多孔SEI膜形态中存在的液体夹杂物。
Fig. 14
Evolution of dendrite growth. (a)—(d) X-ray tomography slices showing the cross-sections of symmetric lithium cells cycled to various stages; (e)—(h) The corresponding 3D reconstructed image[15](NatureMaterials has image copyright)
Fig. 15
(a) 3D visualization of Sn particles at the first lithiation-delithiation process; (b) 3D morphological change of Sn particles at the first sodiation-desodiation cycle; (c) Schematic illustration showing the difference of Sn microstructural change in sodium-ion battery and lithium ion battery[75](NatureCommunications has image copyright)
Fig. 16
(a) Schematic view of conventional X-ray tomography; (b) Schematic of the oblique soft X-ray tomography[80](ElectrochimicaActa has image copyright)
图18
中子和X射线断层扫描的重建图像以及虚拟展开重建后提取的截面示例。在X射线图像中清晰可见的是镍电流收集网，其看起来比Li X MnO2 活性电极材料更亮[27](Nature communication 拥有图片版权)
Fig. 18
Image displays the reconstructed tomograms from neutron and X-ray CT along with examples of sections extracted following virtual unrolling of the reconstructions. Clearly visible in the X-ray images is the nickel current collecting mesh, which appears brighter than the Li X MnO2 active electrode material[27](Naturecommunication has image copyright )
Euser等[28]为了确定锂离子电池的退化机理和失效机制，他们利用原位拉曼光谱监测工况下锂离子电池循环过程中碳酸酯液体电解质的化学反应(图20)。通过从LiNi x Mn y Co1-x-y O2(NMC，x>0.6)-石墨全电池中提取少量电解质{LP57[1.0 mol/L的LiPF6分散于由体积比为3∶7的碳酸乙烯酯(EC)和碳酸甲乙酯(EMC)组成的电解液中]添加了2%的碳酸亚乙烯酯}，利用无硅背景拉曼光谱分析电池在第1个电化学循环期间SEI膜形成过程中的各种电解质化学性质，重复取样以便于实时跟踪电池循环过程中电解质化学变化，此外每次测量完光谱后，再将电解质样品注入电池中。为了进一步追踪锂离子溶剂化动力学，该团队将未含有不同浓度锂盐的电解质进行异位光谱测量，实验结果表明，电解液中锂盐浓度和电极-电解质界面化学能改变碳酸盐类溶剂的溶剂化结构，此外在一个充放电循环中，可从EC的C＝O峰(1782～1817 cm-1)和EMC的C＝O峰(1730～1765 cm-1)的强度比间接跟踪溶剂化环状碳酸盐(Li+—O＝C，EC)和溶剂化线性碳酸盐(Li+—O＝C，EMC)之间的平衡演变。
Hardwick等[92]报道用克尔门控拉曼光谱仪研究LiPF6基碳酸酯电解液中锂离子石墨负极插层结构的变化，追踪完整的电化学锂化和脱锂过程。由于这种电解液在低电位分解会产生具有荧光性质的副产物，使得拉曼散射与荧光发射信号重叠，为此引入能够过滤掉荧光信号的克尔门控光谱仪，即使在高锂化状态(0.5≤x≤1，Li x C6)石墨的拉曼信号也比传统的拉曼显微镜技术清晰度高。实验数据表明石墨带Li0.5C6最初位于1590 cm-1，随着进一步锂化为LiC6，化学位移到1564 cm-1处，再通过数值拟合趋势变化，将此作为石墨负极充电状态(锂化)的函数，提供了一个较为灵敏的监测锂离子电池中石墨负极的高荷电状态的方法。
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... [11](NatureCommunications 拥有图片版权)Schematic of the smart battery design and fabrication. (a) Dendrite formation in a traditional lithium battery where complete penetration of the separator by a lithium dendrite is only detected when the battery fails due to an internal short circuit and <i>V</i><sub>Li-Li </sub>drops to zero; (b) In comparison, a lithium battery with a bifunctional separator where the overgrown lithium dendrite penetrates into the separator and makes contact with the conducting copper layer, giving rise to a drop in <i>V</i><sub>Cu-Li </sub>as warning of impending failure due to an internal short circuit. As well as, the full battery remains safely operational with non-zero potential<sup>[<xref ref-type="bibr" rid="R11">11</xref>]</sup> (<i>Nature</i><i>Communications</i> has image copyright)Fig. 3
... [15](NatureMaterials 拥有图片版权)Evolution of dendrite growth. (a)—(d) X-ray tomography slices showing the cross-sections of symmetric lithium cells cycled to various stages; (e)—(h) The corresponding 3D reconstructed image<sup>[<xref ref-type="bibr" rid="R15">15</xref>]</sup>(<i>Nature</i><i>Materials</i> has image copyright)Fig. 14
... [20](JournalofPowerSources 拥有图片版权)Schematic diagram of ultrasonic monitoring technology and analysis of results<sup>[<xref ref-type="bibr" rid="R20">20</xref>]</sup>(<i>Journal</i><i>of</i><i>Power</i><i>Sources</i> has image copyright)Fig. 19
... [22](ScientificReports 拥有图片版权)(a) Schematic of customized RTD embedded LIB coin cell; (b) RTD embedded polylactic acid spacer and CR2032 cell with internal RTD. Dimension of the RTD embedded spacer was comparable to ordinary CR2032 coin cell spacer, allowing for reliable sensor-electrode contact and cell sealing after assembly<sup>[<xref ref-type="bibr" rid="R22">22</xref>]</sup>(<i>Scientific</i><i>Reports</i> has image copyright)Fig. 4
... [23](EnergyEnvironmentalScience 拥有图片版权)Schematic of the cell embedded with FBG and corresponding electrochemical performance. (a) The schematic illustration of the structure of FBG and the Li-S pouch cell embedded with FBG; (b) The cycle performance and (c) discharge-charge curves of the Li-S pouch cell embedded with FBG and a normal cell without FBG<sup>[<xref ref-type="bibr" rid="R23">23</xref>]</sup> (<i>Energy</i><i>Environmental</i><i>Science</i> has image copyright)Fig. 8
... [24](Nature 拥有图片版权)Schematics of the two <i>in</i><i>situ</i> NMR setups<sup>[<xref ref-type="bibr" rid="R24">24</xref>] </sup>(<i>Nature</i> has image copyright)Fig. 111.2.2 电子顺磁共振技术
... Euser等[28]为了确定锂离子电池的退化机理和失效机制，他们利用原位拉曼光谱监测工况下锂离子电池循环过程中碳酸酯液体电解质的化学反应(图20).通过从LiNi x Mn y Co1-x-y O2(NMC，x>0.6)-石墨全电池中提取少量电解质{LP57[1.0 mol/L的LiPF6分散于由体积比为3∶7的碳酸乙烯酯(EC)和碳酸甲乙酯(EMC)组成的电解液中]添加了2%的碳酸亚乙烯酯}，利用无硅背景拉曼光谱分析电池在第1个电化学循环期间SEI膜形成过程中的各种电解质化学性质，重复取样以便于实时跟踪电池循环过程中电解质化学变化，此外每次测量完光谱后，再将电解质样品注入电池中.为了进一步追踪锂离子溶剂化动力学，该团队将未含有不同浓度锂盐的电解质进行异位光谱测量，实验结果表明，电解液中锂盐浓度和电极-电解质界面化学能改变碳酸盐类溶剂的溶剂化结构，此外在一个充放电循环中，可从EC的C＝O峰(1782～1817 cm-1)和EMC的C＝O峰(1730～1765 cm-1)的强度比间接跟踪溶剂化环状碳酸盐(Li+—O＝C，EC)和溶剂化线性碳酸盐(Li+—O＝C，EMC)之间的平衡演变.
... [25](ChemistryofMaterials 拥有图片版权)Noninvasive electron paramagnetic resonance imaging technique monitors changes in lithium deposits inside the battery during charging and discharging<sup>[<xref ref-type="bibr" rid="R25">25</xref>]</sup> (<i>Chemistry</i><i>of</i><i>Materials</i> has image copyright)Fig. 12
... [26](NatureCommunications 拥有图片版权)The schematic depiction of experimental setup of the <i>in</i><i>situ</i> cell for simultaneous<sup>[<xref ref-type="bibr" rid="R26">26</xref>]</sup>(<i>Nature</i><i>Communications</i> has image copyright)Fig. 13
... [27](Nature communication 拥有图片版权)Image displays the reconstructed tomograms from neutron and X-ray CT along with examples of sections extracted following virtual unrolling of the reconstructions. Clearly visible in the X-ray images is the nickel current collecting mesh, which appears brighter than the Li <i><sub>X</sub></i> MnO<sub>2</sub> active electrode material<sup>[<xref ref-type="bibr" rid="R27">27</xref>]</sup>(<i>Nature</i><i>communication</i> has image copyright )Fig. 18
Possible schemes of CO<sub>2</sub>, CH<sub>4</sub>, and C<sub>2</sub>H<sub>4 </sub>evolution in graphite/NMC532 batteries<sup>[<xref ref-type="bibr" rid="R42">42</xref>]</sup> (<i>Journal</i><i>of</i><i>Energy</i><i>Chemistry</i> has image copyright)Fig. 51.1.3 气体传感器
... Jin等[43]首次提出了一种利用H2气体捕集技术检测微米级锂枝晶的方法，用于早期安全预警.这种方法依赖于锂金属和常见电极聚合物黏结剂之间的自发反应产生H2，如聚偏二氟乙烯(PVDF)或苯乙烯丁二烯橡胶(SBR)和羧甲基纤维素(CMC)等.当H2气体通过阀从电池单体中释放出来时，H2气体传感器可以立即捕获到，作为锂金属形成的有效异常指标，进行早期安全预警，所提出的技术在不改变商业锂离子电池结构的情况下工作，并且与现有的电池管理系统兼容.该团队通过对磷酸铁锂-石墨电池组的安全预警实验，表明即使有其他电池组遮挡，也能在早期检测到H2，并且H2在CO、CO2、HCl、HF和SO2气体中最先被捕获，且捕获时间比烟雾早639 s、比火灾早769 s. ...
... [47](EnergyTechnology 拥有图片版权)Schematic diagram and image of FBG sensor attached (a) or implanted (b) on anode electrode of lithium ion battery respectively (c) and (d)<sup>[<xref ref-type="bibr" rid="R47">47</xref>]</sup> (<i>Energy</i><i>Technology</i> has image copyright)Fig. 6
... [48](Energy&EnvironmentalScience 拥有图片版权)(a) Schematics and spectra of a FBG; (b) Schematics and spectra of a TFBG<sup>[<xref ref-type="bibr" rid="R48">48</xref>]</sup> (<i>Energy</i><i>&</i><i>Environmental</i><i>Science</i> has image copyright)Fig. 7
... [51](AdvancedScience 拥有图片版权)The schematic diagram of experimental setup for strain monitoring of anode-free lithium metal batteries<sup>[<xref ref-type="bibr" rid="R51">51</xref>]</sup> (<i>Advanced</i><i>Science</i> has image copyright)Fig. 9<strong>1.2</strong> 磁共振技术
... [59](PhysChemChemPhys 拥有图片版权)(a) Schematic depiction of the measurement setup with a thin film pouch cell placed in the coil of a NMR device, connected to a battery cycler; (b) Schematic thin film pouch cell; (c)—(f) <sup>7</sup>Li-NMR spectra of thin film pouch cells and SEM images of the corresponding electrodes after (c<sub>1</sub>—f<sub>1</sub>) and (c<sub>2</sub>—f<sub>2</sub>) 8 hours of electrodeposition at 0.5 mA/cm<sup>2</sup> containing 1-PF6-C, 1-TFSI-C, 1-TFSI-E and 3-TFSI-E<sup>[<xref ref-type="bibr" rid="R59">59</xref>]</sup> (<i>Phys</i><i>Chem</i><i>Chem</i><i>Phys</i> has image copyright)Fig. 10
... Schellenberger等[67]基于具有两个软X射线透明氮化硅(SiN x )膜窗口的微流体电化学半电池研究硅阳极上的SEI，通过控制气泡形成柔软的X射线透明薄电解质层.在循环过程中形成SEI后，他们使用高强度X射线在入口窗口附近产生气泡并从中推出多余的电解质探测体积，气泡稳定地处于膜之间的中心，留在光束路径中的是一层薄薄的电解质，覆盖着SEI和阳极.通过使用低强度的X射线来避免光束损伤，然后利用透射sXAS在硅薄膜阳极上进行原位SEI研究，而不需要拆解电池.实验结果参考化合物的吸收光谱并进行比较，确定了形成物质并研究了SEI的组成，如乙酸锂、乙烯二碳酸锂或乙烯单碳酸锂、乙酰丙酮锂、氢氧化锂和氟化锂，此外还观察到了醛类物质，这可能是源于多孔SEI膜形态中存在的液体夹杂物. ...
... [75](NatureCommunications 拥有图片版权)(a) 3D visualization of Sn particles at the first lithiation-delithiation process; (b) 3D morphological change of Sn particles at the first sodiation-desodiation cycle; (c) Schematic illustration showing the difference of Sn microstructural change in sodium-ion battery and lithium ion battery<sup>[<xref ref-type="bibr" rid="R75">75</xref>]</sup>(<i>Nature</i><i>Communications</i> has image copyright)Fig. 15
