Nucleation and Growth Mode of Solid Electrolyte Interphase in Li-Ion Batteries
锂离子电池中固体电解质间相的成核与生长模式
- Yu-Xing YaoYu-Xing YaoBeijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing 100084, ChinaMore by Yu-Xing Yao
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- Jing WanJing WanKey Laboratory of Molecular Nanostructure and Nanotechnology, Beijing National Laboratory for Molecular Sciences, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, ChinaMore by Jing Wan
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- Ning-Yan LiangNing-Yan LiangBeijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing 100084, ChinaMore by Ning-Yan Liang
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- Chong Yan*Chong Yan*E-mail: yanc@bit.edu.cnAdvanced Research Institute of Multidisciplinary Science, Beijing Institute of Technology, Beijing 100081, ChinaMore by Chong Yan
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- Rui Wen*Rui Wen*E-mail: ruiwen@iccas.ac.cnKey Laboratory of Molecular Nanostructure and Nanotechnology, Beijing National Laboratory for Molecular Sciences, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, ChinaMore by Rui Wen
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- Qiang Zhang*Qiang Zhang*E-mail: zhang-qiang@mails.tsinghua.edu.cnBeijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing 100084, ChinaMore by Qiang Zhang
Abstract 摘要
The solid electrolyte interphase (SEI) is regarded as the most important yet least understood component in Li-ion batteries. Considerable effort has been devoted to unravelling its chemistry, structure, and ion-transport mechanism; however, the nucleation and growth mode of SEI, which underlies all these properties, remains the missing piece. We quantify the growth mode of two representative SEIs on carbonaceous anodes based on classical nucleation theories and in situ atomic force microscopy imaging. The formation of inorganic SEI obeys the mixed 2D/3D growth model and is highly dependent on overpotential, whereby large overpotential favors 2D growth. Organic SEI strictly follows the 2D instantaneous nucleation and growth model regardless of overpotential and enables perfect epitaxial passivation of electrodes. We further demonstrate the use of large current pulses during battery formation to promote 2D inorganic SEI growth and improve capacity retention. These insights offer the potential to tailor desired interphases at the nanoscale for future electrochemical devices.
固体电解质相间层(SEI)被认为是锂离子电池中最重要但最不为人所知的成分。人们已经投入了大量精力来揭示其化学、结构和离子传输机制;然而,作为所有这些特性基础的 SEI 的成核和生长模式仍然是缺失的部分。我们基于经典成核理论和原位原子力显微镜成像,量化了碳质阳极上两种代表性 SEI 的生长模式。无机 SEI 的形成遵循二维/三维混合生长模型,并且高度依赖于过电势,大过电势有利于二维生长。有机 SEI 严格遵循二维瞬时成核和生长模型,与过电位无关,并能实现电极的完美外延钝化。我们进一步展示了在电池形成过程中使用大电流脉冲促进二维无机 SEI 生长和提高容量保持率的方法。这些见解为在纳米尺度上为未来的电化学设备定制所需的相间提供了可能性。
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Introduction 导言
现代锂离子电池(LIB)有别于水性电池(铅酸蓄电池、镍镉电池或镍氢电池)的最显著特点是能够在远远超过电解质阴极极限的极端电极电位下工作。(1-3) 这种电极/电解质界面由固体电解质间相(SEI)在动力学上加以稳定,SEI 是一种 5-50 纳米厚的电子绝缘和离子传导钝化膜,用于保护高还原性阳极。(4)尽管 SEI 的存在微乎其微,但其物理化学特性却对电池性能和安全性产生了深远影响。(5,6)为了解已形成的 SEI 的化学性质、结构和离子传输机制,人们付出了巨大的努力。(7-9)然而,SEI 在新电极表面上的初始成核和生长模式,即上述所有特性的基础,仍然难以捉摸。(10)这些知识对于解释 SEI 形态也至关重要,因为 SEI 形态决定了 SEI 与电极的粘附性和长期循环的稳定性。(11) 要准确量化 SEI 的成核和生长模式,必须将经典模型与现场观测相结合,而据我们所知,目前还没有这种方法。
成核标志着一阶相变的开始,是许多涉及相变的电池反应的共同点,特别是对转换型电极而言。例如,人们使用电化学和光学方法研究了锂核在铜基底上的电沉积和锂 2 S在碳基底上的电沉积,通过量化成核动力学或生长尺寸来指导先进锂金属阳极和硫阴极的合理设计。(12-15)然而,由于以下原因,量化 SEI 的成核和生长模式在技术上具有挑战性。(1) 与块状电极反应不同,SEI 在工作电池中的瞬时形成对容量的贡献微乎其微,因此其电化学信号非常微弱,难以捕捉。(2)经典的成核模型是建立在对单模态恒电位电流-时间瞬态分析的基础上的,在该模型中,成核的速度首先是缓慢的,然后随着电活性面积的增加而加快,最后当生长中心凝聚在一起时,速度又变慢了。(16)然而,以往文献中 SEI 形成的电流瞬态大多是单调递减的,因此无法拟合模型。(17,18) (3) 由于缺乏高空间分辨率的原位表征工具,直接观察纳米级相间演化十分困难。(2) 这些障碍阻碍了对 SEI 成核和生长模式的深入理解。
在这篇论文中,我们通过以下方法克服了这些障碍:(1) 采用高表面积炭黑 (CB) 电极作为放大 SEI 生长的基底;(2) 采用可诱导单模态电流-时间瞬态的弱溶解性电解质 (WSE);(3) 采用原位电化学原子力显微镜 (AFM) 实时监控高取向热解石墨 (HOPG) 电极上的动态 SEI 成核和后续生长。我们首次阐明了无机和有机 SEI 的成核和生长模式与电极过电势的函数关系。
Results and Discussion 结果与讨论
SEI 大致可分为无机相和有机相,前者通常源于无机锂盐的分解,而后者则源于有机溶剂的初始分解。我们选择了由 1.0 M Li 双(氟磺酰)亚胺(LiFSI)在 1,4- 二氧六环(1,4-DX)中组成的 WSE,通过还原 FSI – 阴离子来获得无机 SEI,理由是低极性的 1,4-DX 允许大多数 FSI – 阴离子与锂离子配位,因此有利于它们在阳极/电解质界面上分解。(10,19)产生有机 SEI 层的电解质是通过在 WSE 中加入 0.2 或 0.5 M 碳酸乙烯(EC)配制而成的,分别称为 WSE+0.2 EC 和 WSE+0.5 EC。标准电解质(1.0 M LiPF 6 溶于 EC/dimethyl carbonate (DMC) 混合物中,体积比为 3:7)被用作参考,称为 ECDMC。
选择 CB 作为 SEI 成核和生长的模型电极,是因为 CB 具有石墨结构、高电子传导性和高比面积(64.9 m 2 g –1 ),这使得其不可逆 SEI 容量超过 200 mAh g –1 ( 图 S1)。在 Li | CB 电池的电静电放电过程中,0.75 V 以上的高原区和 0.75 V 以下的斜坡区分别对应于 SEI 生长和锂离子插层(图 1)。对于 WSE,从 1.37 V 到 1.10 V 的长高原表示 LiFSI 分解形成了无机 SEI,包括硫化锂、 3 N锂、氧硫化锂/氧氮化锂、 2 O锂和 LiF,如 X 射线光电子显微镜(XPS,图 S2 所示)所显示的那样。当在 WSE 中加入 EC 时,SEI 高原向下移动到 0.95-0.75 V,与 ECDMC 的高原接近,表明 LiFSI 的还原受到抑制,而 EC 的还原占主导地位。CB 表面的飞行时间二次离子质谱(TOF-SIMS)证实,有机 SEI 碎片(OH – 和 C 2 H – )在 WSE+0.2 EC 中的强度远高于 WSE 中的强度(图 S3),这源于 EC 还原产生的碳酸烷基锂。图 S4 所示的循环伏安 (CV) 曲线与电静态测量结果十分吻合,在图 S4 中,位于 0.88 V 和 0.49 V 的两个不同的阴极峰分别归因于在 WSE 中形成的 LiFSI 衍生的无机 SEI 和在 WSE+0.2 EC 中形成的 EC 衍生的有机 SEI。
由于新相的电结晶速率是过电位的强函数,并直接反映在电流瞬态上,因此采用了恒电位技术来探究 SEI 成核和生长的动力学(图 1b-d)。当 Li | CB 电池保持在 SEI 形成的平衡电位以下时,电流会首先减小,进入主要成核和生长之前的所谓 "孵育期"。孵化期的本质是在克服表面自由能障碍并达到临界核大小之前,随机聚集的微小 SEI 核。(11) 此后,离散的 SEI 核不可逆转地变大、凝聚并钝化整个电极表面,产生单模态电流-时间瞬态。需要注意的是,这种电流峰值只存在于三种 WSE 系统中,在这些系统中,电静电条件下可观察到成核过电位(图 1a)。在未检测到成核过电位的 ECDMC 细胞中,恒电位步进会导致单调递减的电流-时间瞬态,在这种情况下还无法提取动力学参数(图 S5)。我们认为,这就是许多研究未能定量描述 SEI 成核和生长模式的原因。
根据峰值电流(I m )和相应时间(t m )对电流-时间瞬态进行归一化,并与四种经典成核模型进行比较。首先,Scharifker-Hills(SH)模型(包括 3DI 和 3DP)描述了半球形晶核的平面扩散控制三维生长。(20,21) 其次,Bewick-Fleischman-Thirsk(BFT)模型(包括 2DI 和 2DP)模拟圆柱形晶核的二维横向生长。(22-25)这些模型的数学表达式为
LiFSI 衍生的无机 SEI 在 WSE 中的成核和生长遵循 2D/3D 混合生长模式,随着过电势的增加,呈现出从 3DP 到 2DI 的过渡(图 2a)。为了验证这种机制,我们在 WSE 中对 HOPG 电极进行了原位电化学原子力显微镜观察,HOPG 电极具有原子级平坦的台阶和清晰的阶梯边缘,是一个完美的碳质电极模型。图 2b 显示了 HOPG 在开路电位 (OCP) 时的原子力显微镜图像,在从 OCP 到 1.00 V 的阴极扫描过程中,其形貌保持不变(图 S6 显示了从阴极 1.25 V 到 1.00 V 的原子力显微镜图像)。在 1.00 V 时,HOPG 的边缘部位开始出现分散的明亮纳米颗粒(NPs)(图 2c,黄色箭头)并逐渐累积(图 2d),标志着无机 SEI 成核的开始。随着电位维持在 1.00 V,这些孤立的 NP 进一步串联成 NP 链,排列在阶梯边缘,从而保护 HOPG 免受 Li + - 溶剂共渗(图 2e,黄色虚线框;图 2f)。新 NPs 的诞生在一定程度上是渐进的,因为它们会随着时间的推移不断出现,而且大小变化很大。这些 NP 的生长在初始阶段是三维的,半球核的高度从 2.9 ± 0.5 纳米增长到 6.7 ± 0.5 纳米(图 S7)。然而,在从 1.00 V 到 0.73 V 的进一步极化过程中,由于电子隧道障碍,SEI NPs 的最终高度被限制在 6.4-7.3 nm,在此期间只允许二维横向生长(图 S8)。这些结果与从电流-时间瞬态推断出的锂离子无机 SEI 的 2DI/3DP 混合生长模式非常吻合。
相比之下,无论过电位或导电率添加剂的浓度如何,导电率衍生的有机 SEI 都严格遵循 2DI 模型(图 3a,b)。在 WSE+0.2 EC 电解质中,原位电化学原子力显微镜揭示了 HOPG/电解质界面的动态演变。与 OCP 相比,HOPG 表面在阴极 1.11-0.82 V 的电压下没有明显变化(图 3c,d)。这表明,在 WSE+0.2 EC 中,FSI – 的降低受到了抑制,这与电静电和 CV 结果一致(图 1a 和 S4)。这可能是由于在阴极极化的影响下,Li + -EC 复合物优先吸附在电极/电解质界面上。(3) 电解质还原开始于 0.55-0.50 V,所有阶跃边缘瞬间出现的亮线证明了这一点(图 S9)。当电位维持在 0.50 V 时,随着亮线逐渐变粗,膜状有机 SEI 延伸至整个 HOPG 基底面(图 3e-g)。虽然 FSI – 分解产生的少量 NP 同时在边缘成核,但它们的稀疏分布很难对 SEI 的功能做出贡献,因此这种 SEI 仍被认为是 EC 衍生的。与 LiFSI 衍生的 NPs 不同,EC 衍生的 SEI 的厚度几乎保持不变(2.0 ± 0.2 nm),因为 SEI 继续横向生长(图 3h)。图 3i 中的三维原子力显微镜图像显示 SEI 润湿了 HOPG 的平台,并最终扩散到整个表面(图 S10)。这些纳米级观察结果有力地证实了 EC 衍生有机 SEI 的 2DI 成核和生长模式。
图 4 展示了这两种代表性 SEI 的成核和生长机制。在 LiFSI 衍生 SEI 的初始成核过程中,无机 NPs 随机散布在石墨边缘(图 4b)。这些 NPs 的生长结合了两种模式:三维生长受限于有限的高度(≈7 nm),在此高度之上禁止电子隧道;二维横向生长则将 NPs 合并在一起。最后,NPs 堆叠成具有强烈空间异质性的粗糙薄膜,松散地附着在石墨边缘(图 4c)。二维生长的比例与施加的过电位呈正相关,因为超高过电位会导致近乎完美的二维生长(图 2a)。另一方面,EC 衍生的有机 SEI 早期成核的特点是阶梯边缘瞬间被丝状结构的一维覆盖(图 4d)。随后的 SEI 生长主要由这种结构向石墨基底面的二维横向延伸促成,并发展成紧贴电极表面的光滑薄膜(图 4e)。这种 SEI 超薄(≈2 nm)、致密且高度均匀,与导电瓷的出色成膜能力相一致,而导电瓷目前几乎是所有商用 LIB 电解液中不可或缺的成分。
一般认为,理想 SEI 的形成应遵循二维生长机制,其本质是一层薄薄的钝化层。即使部分采用三维生长模式,也会诱发粗糙或多孔结构,从而破坏 SEI 的表面均匀性、机械稳定性和电极附着力。为了将 SEI 的成核和生长模式与其电化学特性联系起来,在上述电解质中对石墨 | LiFePO 4 (LFP) 电池进行了评估(图 5)。采用了超稳定 LFP 阴极,因此整个电池的性能主要取决于工作石墨阳极上 SEI 的稳定性。采用 2D/3D SEI 混合生长模式的 WSE 电池在 1.0 C 下循环 300 次后,其初始容量仅保留了 58.9%,这很可能是由于不均匀和脆性 SEI 的失效。相比之下,采用完美 2DI 生长模式的 WSE+0.2 EC 电池的容量保持率达到了 80.6%。这些结果与我们已发表的采用半电池配置的研究成果(19)十分吻合,并进一步表明就 SEI 生长模式而言,二维确实优于三维。先前的分析指出,高过电位有利于无机 SEI 在 WSE 中的二维生长;然而,锂离子电池行业的标准做法规定,在电池形成过程中应使用缓慢的充电速率(0.1 C),WSE 电池就是这种情况。(26)有鉴于此,在对 WSE 电池进行正常充电之前,增加了一个短时间的 4.0 C 高速率脉冲充电,以促进二维 SEI 生长,即 WSE+ 脉冲(图 S11 和 S12)。有趣的是,300 次循环后,WSE+pulse 的容量保持率从 58.9% 提高到 78.2%,接近 WSE+0.2 EC(图 5)。锂离子石墨电池的循环性能进一步证实了这一结果,其中较大的 SEI 形成率与较高的库仑效率(CE)和容量保持率相关(图 S13)。
本研究结果揭示了调节未来锂离子电池界面特性的两个关键方面。(1) 电解质设计。在 WSE+0.2 EC 中,EC 的还原超过了 FSI – 阴离子的还原,即使前者发生在比后者稍低的电位。这可能是 EC 衍生的 SEI 的 2DI 生长模式在电极表面快速传播所致。因此,要最大限度地发挥盐类电解质添加剂的作用,其还原电位必须大大高于有机添加剂。(2) 形成规程。对于使用盐类无机成膜剂的电池,可在电池形成过程中使用大电流脉冲,以促进二维 SEI 生长,从而提高相间质量。
Conclusions 结论
我们根据对时变曲线和原位电化学原子力显微镜成像的模型分析,量化了两种代表性 SEI 的成核和生长模式。LiFSI 衍生的无机 SEI 遵循 2DI/3DP 混合生长模式,其中 2DI 模式的比例与电极过电位呈正相关。无论过电位如何,EC 衍生的有机 SEI 都遵循 2DI 模式,从而实现了电极表面的完美外延钝化。我们进一步证明了在锂离子电池形成过程中使用大电流脉冲促进无机 SEI 的二维生长和提高容量保持率的可行性,尽管人们普遍认为小电流更有利于 SEI 的均匀性。这些发现以前所未有的详细程度揭示了纳米级相间的形成机制,为微调未来电化学设备的界面特性开辟了广阔的前景。
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Experimental section, including electrolytes and electrode materials, in situ electrochemical AFM characterization, electrochemical measurements, and ex situ material characterizations; Supplementary Figures 1–13 (PDF)
实验部分,包括电解质和电极材料、原位电化学 AFM 表征、电化学测量和原位材料表征;补充图 1-13 ( PDF)
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Acknowledgments 致谢
This work was supported by the National Key Research and Development Program (2021YFB2500300), the National Natural Science Foundation of China (22109083, 22005172, and 21825501), Key Research and Development Program of Yunnan Province (202103AA080019), and Tsinghua University Initiative Scientific Research Program.
这项工作得到了国家重点研发计划(2021YFB2500300)、国家自然科学基金(22109083、22005172 和 21825501)、云南省重点研发计划(202103AA080019)和清华大学主动科学研究计划的支持。
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这篇文章引用了 26 篇其他出版物。
- 1Liang, Y.; Yao, Y. Designing Modern Aqueous Batteries. Nat. Rev. Mater. 2023, 8, 109– 122, DOI: 10.1038/s41578-022-00511-3
1Liang, Y.; Yao, Y. Designing Modern Aqueous Batteries.Nat.Rev. Mater.2023, 8, 109- 122, DOI: 10.1038/s41578-022-00511-3 - 2Yao, Y. X.; Yan, C.; Zhang, Q. Emerging Interfacial Chemistry of Graphite Anodes in Lithium-Ion Batteries. Chem. Commun. 2020, 56, 14570– 14584, DOI: 10.1039/D0CC05084AGoogle Scholar 谷歌学者2https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXitVeiur%252FJ&md5=155023addc454132e1c5a0399308b20fEmerging interfacial chemistry of graphite anodes in lithium-ion batteriesYao, Yu-Xing; Yan, Chong; Zhang, QiangChemical Communications (Cambridge, United Kingdom) (2020), 56 (93), 14570-14584CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)A review. Understanding the electrode/electrolyte interfacial chem. is the cornerstone of designing lithium-ion batteries (LIBs) with superior performance. Graphite has been exclusively utilized as the anode material in state-of-the-art LIBs, whose interfacial chem. has a profound impact on battery life and power delivery. However, current understanding of the graphite/electrolyte interface is still incomplete because of its intricate nature, which has driven unremitting explorations and breakthroughs in the past few decades. On the one hand, the applications of emerging exptl. and computational tools have led researchers to re-examine several decades-old problems, such as the underlying mechanism of solid electrolyte interphase (SEI) formation and the co-intercalation mystery. On the other hand, from anion-derived interfacial chem. to artificial interphases, novel interfacial chem. for graphite is being proposed to replace the traditional ethylene carbonate-derived SEI for better performances. By summarizing the latest advances in the emerging interfacial chem. of graphite anodes in LIBs, this review affords a fresh perspective on interface science and engineering towards next-generation energy storage devices.
2Yao,Y. X.;Yan,C.;Zhang,Q.锂离子电池中石墨阳极的新兴界面化学。Chem.Chem.2020, 56, 14570- 14584, doi: 10.1039/d0cc05084a - 3Xu, K. Electrolytes and Interphases in Li-Ion Batteries and Beyond. Chem. Rev. 2014, 114, 11503– 11618, DOI: 10.1021/cr500003wGoogle Scholar 谷歌学者3https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhvVensr3N&md5=5d79be66e09915ece2c476aab47c4224Electrolytes and Interphases in Li-Ion Batteries and BeyondXu, KangChemical Reviews (Washington, DC, United States) (2014), 114 (23), 11503-11618CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review of advances in electrolytes and interphases in lithium-ion batteries.
3Xu, K.锂离子电池中的电解质和相间物及其他。Chem.Rev. 2014, 114, 11503- 11618, DOI: 10.1021/cr500003w - 4Peled, E.; Menkin, S. Review─SEI: Past, Present and Future. J. Electrochem. Soc. 2017, 164, A1703– A1719, DOI: 10.1149/2.1441707jesGoogle Scholar 谷歌学者4https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhtVCitLvN&md5=3a2703b96a3bee6a8036b35db85534a7Review-SEI: Past, Present and FuturePeled, E.; Menkin, S.Journal of the Electrochemical Society (2017), 164 (7), A1703-A1719CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)The Solid-Electrolyte-Interphase (SEI) model for non-aq. alkali-metal batteries constitutes a paradigm change in the understanding of lithium batteries and has thus enabled the development of safer, durable, higher-power and lower-cost lithium batteries for portable and EV applications. Prior to the publication of the SEI model (1979), researchers used the Butler-Volmer equation, in which a direct electron transfer from the electrode to lithium cations in the soln. is assumed. The SEI model proved that this is a mistaken concept and that, in practice, the transfer of electrons from the electrode to the soln. in a lithium battery, must be prevented, since it will result in fast self-discharge of the active materials and poor battery performance. This model provides [E. Peled, in "Lithium Batteries," J.P. Gabano (ed), Academic Press, (1983), E. Peled, J. Electrochem. Soc., 126, 2047 (1979).] new equations for: electrode kinetics (io and b), anode corrosion, SEI resistivity and growth rate and irreversible capacity loss of lithium-ion batteries. This model became a cornerstone in the science and technol. of lithium batteries. This paper reviews the past, present and the future of SEI batteries.
4Peled, E.; Menkin, S. Review─SEI:过去、现在和未来。J. Electrochem.Soc. 2017, 164, A1703- A1719, DOI: 10.1149/2.1441707jes - 5Han, B.; Zou, Y.; Xu, G.; Hu, S.; Kang, Y.; Qian, Y.; Wu, J.; Ma, X.; Yao, J.; Li, T.; Zhang, Z.; Meng, H.; Wang, H.; Deng, Y.; Li, J.; Gu, M. Additive Stabilization of SEI on Graphite Observed Using Cryo-Electron Microscopy. Energy Environ. Sci. 2021, 14, 4882– 4889, DOI: 10.1039/D1EE01678DGoogle Scholar 谷歌学者5https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhsVylurjE&md5=d6235f8958226cbed6a7b5d34746bc18Additive stabilization of SEI on graphite observed using cryo-electron microscopyHan, Bing; Zou, Yucheng; Xu, Guiyin; Hu, Shiguang; Kang, Yuanyuan; Qian, Yunxian; Wu, Jing; Ma, Xiaomin; Yao, Jianquan; Li, Tengteng; Zhang, Zhen; Meng, Hong; Wang, Hong; Deng, Yonghong; Li, Ju; Gu, MengEnergy & Environmental Science (2021), 14 (9), 4882-4889CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)Revealing the at. structures of the solid electrolyte interphase (SEI) is challenging due to its sensitivity to electron beam and environmental factors such as moisture and oxygen. Here, we unveiled the at. structures and phase distribution of the fragile solid electrolyte interphase (SEI) on graphite using ultra-low-dosage and aberration-cor. cryo-transmission electron microscopy (cryo-TEM). It is known that propylene carbonate electrolyte can exfoliate a graphite anode and damage its structural integrity. Surprisingly, ethylene carbonate-diethyl carbonate can also damage the surface of the graphite anode by exfoliation even with an initial formation protocol of const.-current charging (0.05C) for three hours and then 0.1C for another 3 h at 45°C: we hypothesize that the exfoliated graphene layers embedded in the SEI enhance local electron channeling, which induces an ever-growing, thick SEI layer with randomly distributed graphene, Li2O, and Li2CO3 nano-crystals. Using the same formation protocol but with 1 wt% vinylene carbonate (VC), tri-Ph phosphate (TPP), or ethylene sulfate (DTD) or 10 wt% monofluoroethylene carbonate (FEC) as the additive is found to cause solid deposition prior to the graphite exfoliation instability, which generates a stable and thin SEI (<90 nm) on the graphite surface which prevents further exfoliation of graphite and rapidly suppresses the decompn. of electrolyte in the later cycles. When using a slower formation protocol including 2 cycles between 3.0 and 4.2 V at a rate of 0.01C at room temp., graphite exfoliation is dramatically reduced, but is still observable initially.
5Han, B.; Zou, Y.; Xu, G.; Hu, S.; Kang, Y.; Qian, Y.; Wu, J.; Ma, X.; Yao, J.; Li, T.; Zhang, Z.; Meng, H.; Wang, H.; Deng, Y.; Li, J.; Gu, M..Additive Stabilization of SEI on Graphite Observed Using Cryo-Electron Microscopy.Energy Environ.2021, 14, 4882- 4889, DOI: 10.1039/D1EE01678D - 6Feng, X.; Ren, D.; He, X.; Ouyang, M. Mitigating Thermal Runaway of Lithium-Ion Batteries. Joule 2020, 4, 743– 770, DOI: 10.1016/j.joule.2020.02.010Google Scholar6https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXnt1Wktbg%253D&md5=e5e0fd46dec59ee89e971a92b03b4894Mitigating Thermal Runaway of Lithium-Ion BatteriesFeng, Xuning; Ren, Dongsheng; He, Xiangming; Ouyang, MinggaoJoule (2020), 4 (4), 743-770CODEN: JOULBR; ISSN:2542-4351. (Cell Press)A review. This paper summarizes the mitigation strategies for the thermal runaway of lithium-ion batteries. The mitigation strategies function at the material level, cell level, and system level. A time-sequence map with states and flows that describe the evolution of the phys. and/or chem. processes has been proposed to interpret the mechanisms, both at the cell level and at the system level. At the cell level, the time-sequence map helps clarify the relationship between thermal runaway and fire. At the system level, the time-sequence map depicts the relationship between the expected thermal runaway propagation and the undesired fire pathway. Mitigation strategies are fulfilled by cutting off a specific transformation flow between the states in the time sequence map. The abuse conditions that may trigger thermal runaway are also summarized for the complete protection of lithium-ion batteries. This perspective provides directions for guaranteeing the safety of lithium-ion batteries for elec. energy storage applications in the future.
- 7Wang, L.; Menakath, A.; Han, F.; Wang, Y.; Zavalij, P. Y.; Gaskell, K. J.; Borodin, O.; Iuga, D.; Brown, S. P.; Wang, C.; Xu, K.; Eichhorn, B. W. Identifying the Components of the Solid-Electrolyte Interphase in Li-Ion Batteries. Nat. Chem. 2019, 11, 789– 796, DOI: 10.1038/s41557-019-0304-zGoogle Scholar7https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhs1alsL7E&md5=f8cd4da5f353732c5f1b7d2f36292667Identifying the components of the solid-electrolyte interphase in Li-ion batteriesWang, Luning; Menakath, Anjali; Han, Fudong; Wang, Yi; Zavalij, Peter Y.; Gaskell, Karen J.; Borodin, Oleg; Iuga, Dinu; Brown, Steven P.; Wang, Chunsheng; Xu, Kang; Eichhorn, Bryan W.Nature Chemistry (2019), 11 (9), 789-796CODEN: NCAHBB; ISSN:1755-4330. (Nature Research)The importance of the solid-electrolyte interphase (SEI) for reversible operation of Li-ion batteries has been well established, but the understanding of its chem. remains incomplete. The current consensus on the identity of the major org. SEI component is that it consists of lithium ethylene di-carbonate (LEDC), which is thought to have high Li-ion cond., but low electronic cond. (to protect the Li/C electrode). Here, we report on the synthesis and structural and spectroscopic characterizations of authentic LEDC and lithium ethylene mono-carbonate (LEMC). Direct comparisons of the SEI grown on graphite anodes suggest that LEMC, instead of LEDC, is likely to be the major SEI component. Single-crystal X-ray diffraction studies on LEMC and lithium Me carbonate (LMC) reveal unusual layered structures and Li+ coordination environments. LEMC has Li+ conductivities of >1 × 10-6 S cm-1, while LEDC is almost an ionic insulator. The complex interconversions and equil. of LMC, LEMC and LEDC in DMSO solns. are also investigated.
- 8Zhou, Y.; Su, M.; Yu, X.; Zhang, Y.; Wang, J. G.; Ren, X.; Cao, R.; Xu, W.; Baer, D. R.; Du, Y.; Borodin, O.; Wang, Y.; Wang, X. L.; Xu, K.; Xu, Z.; Wang, C.; Zhu, Z. Real-Time Mass Spectrometric Characterization of the Solid-Electrolyte Interphase of a Lithium-Ion Battery. Nat. Nanotechnol. 2020, 15, 224– 230, DOI: 10.1038/s41565-019-0618-4Google Scholar8https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXivVeksLs%253D&md5=312cc470aec17d9ea3e196f481fc4fa2Real-time mass spectrometric characterization of the solid-electrolyte interphase of a lithium-ion batteryZhou, Yufan; Su, Mao; Yu, Xiaofei; Zhang, Yanyan; Wang, Jun-Gang; Ren, Xiaodi; Cao, Ruiguo; Xu, Wu; Baer, Donald R.; Du, Yingge; Borodin, Oleg; Wang, Yanting; Wang, Xue-Lin; Xu, Kang; Xu, Zhijie; Wang, Chongmin; Zhu, ZihuaNature Nanotechnology (2020), 15 (3), 224-230CODEN: NNAABX; ISSN:1748-3387. (Nature Research)The solid-electrolyte interphase (SEI) dictates the performance of most batteries, but the understanding of its chem. and structure is limited by the lack of in situ exptl. tools. In this work, a dynamic picture is presented of the SEI formation in lithium-ion batteries using in operando liq. secondary ion mass spectrometry in combination with mol. dynamics simulations. It was found that before any interphasial chem. occurs (during the initial charging), an elec. double layer forms at the electrode/electrolyte interface due to the self-assembly of solvent mols. The formation of the double layer is directed by Li+ and the electrode surface potential. The structure of this double layer predicts the eventual interphasial chem.; in particular, the neg. charged electrode surface repels salt anions from the inner layer and results in an inner SEI that is thin, dense and inorg. in nature. It is this dense layer that is responsible for conducting Li+ and insulating electrons, the main functions of the SEI. An electrolyte-permeable and org.-rich outer layer appears after the formation of the inner layer. In the presence of a highly concd., fluoride-rich electrolyte, the inner SEI layer has an elevated concn. of LiF due to the presence of anions in the double layer. These real-time nanoscale observations will be helpful in engineering better interphases for future batteries.
- 9Jorn, R.; Raguette, L.; Peart, S. Investigating the Mechanism of Lithium Transport at Solid Electrolyte Interphases. J. Phys. Chem. C 2020, 124, 16261– 16270, DOI: 10.1021/acs.jpcc.0c03018Google Scholar9https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhtlKgs7vM&md5=47271d4f0fb51496d92560f64d3086f1Investigating the Mechanism of Lithium Transport at Solid Electrolyte InterphasesJorn, Ryan; Raguette, Lauren; Peart, ShaniyaJournal of Physical Chemistry C (2020), 124 (30), 16261-16270CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)Reactions between carbonate electrolytes and graphite electrodes in lithium-ion storage devices produce a surface film of byproducts known as the solid electrolyte interphase (SEI). Significant progress has been made in assessing the compn. and structure of these interphases; however, their impact on lithium transport during charge and discharge lacks mol. detail. Over the past decade, electrochem. impedance spectroscopy (EIS) has shown that lithium transport is limited by a combination of ion desolvation and ion conduction through the SEI, however which step is rate limiting remains unresolved. In this work, the first step is simulated in this process, i.e., ion desolvation, both into and out of two model SEI's comprised of lithium ethylene dicarbonate (LEDC) and Li2CO3 interfaced with an ethylene carbonate electrolyte. By correlating free-energy changes with solvation structure, it is shown that the path taken for Li+ insertion is a two-step mechanism consisting of overcoming two energy barriers to adsorption and then absorption. The largest measured barrier of the two is 59.2 kJ/mol, within the ests. obtained from EIS measurements. Ion extn. from the LEDC, however, follows a different free-energy profile detd. by the flexibility of the surface groups to extend into the electrolyte. The dependence of extn. from LEDC on the nature of the surface groups, emphasized by comparison with ion extn. from the more rigid Li2CO3 surface, highlights the complex relationship between SEI compn. and lithium transport.
- 10Yan, C.; Jiang, L. L.; Yao, Y. X.; Lu, Y.; Huang, J. Q.; Zhang, Q. Nucleation and Growth Mechanism of Anion-Derived Solid Electrolyte Interphase in Rechargeable Batteries. Angew. Chem., Int. Ed. 2021, 60, 8521– 8525, DOI: 10.1002/anie.202100494Google Scholar10https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXlvV2jurg%253D&md5=b6b7b07f44033198c256c6e2d8c10fafNucleation and Growth Mechanism of Anion-Derived Solid Electrolyte Interphase in Rechargeable BatteriesYan, Chong; Jiang, Li-Li; Yao, Yu-Xing; Lu, Yang; Huang, Jia-Qi; Zhang, QiangAngewandte Chemie, International Edition (2021), 60 (15), 8521-8525CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)Solid electrolyte interphase (SEI) has been widely employed to describe the new phase formed between anode and electrolyte in working batteries. Significant advances have been achieved on the structure and compn. of SEI as well as on the possible ion transport mechanism. However, the nucleation and growth mechanism of SEI catches little attention, which requires the establishment of isothermal electrochem. crystn. theory. Herein we explore the virgin territory of electrochem. crystd. SEI. By using potentiostatic method to regulate the decompn. of anions, an anion-derived SEI forms on graphite surface at at. scale. After fitting the cur-rent-time transients with Laviron theory and Avrami formula, we conclude that the formation of anion-derived interface is surface reaction controlled and obeys the two-dimensional (2D) progressive nucleation and growth model. Atomic force microscope (AFM) images emphasize the conclusion, which reveals the mystery of isothermal electrochem. crystn. of SEI.
- 11Scharifker, B. R.; Mostany, J. Nucleation and Growth of New Phases on Electrode Surfaces. In Developments in Electrochemistry: Science Inspired by Martin Fleischmann; John Wiley & Sons, 2014; pp 65– 75. DOI: 10.1002/9781118694404.ch4 .
- 12Pei, A.; Zheng, G.; Shi, F.; Li, Y.; Cui, Y. Nanoscale Nucleation and Growth of Electrodeposited Lithium Metal. Nano Lett. 2017, 17, 1132– 1139, DOI: 10.1021/acs.nanolett.6b04755Google Scholar12https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXms12htQ%253D%253D&md5=1177f0162e2da0f93e064c9941ee6d48Nanoscale Nucleation and Growth of Electrodeposited Lithium MetalPei, Allen; Zheng, Guangyuan; Shi, Feifei; Li, Yuzhang; Cui, YiNano Letters (2017), 17 (2), 1132-1139CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)Li metal has reemerged as an exciting anode for high energy Li-ion batteries due to its high specific capacity of 3860 mA h g-1 and lowest electrochem. potential of all known materials. However, Li was plagued by the issues of dendrite formation, high chem. reactivity with electrolyte, and infinite relative vol. expansion during plating and stripping, which present safety hazards and low cycling efficiency in batteries with Li metal electrodes. There have been a lot of recent studies on Li metal although little work has focused on the initial nucleation and growth behavior of Li metal, neglecting a crit. fundamental scientific foundation of Li plating. Here, the authors study exptl. the morphol. of Li in the early stages of nucleation and growth on planar Cu electrodes in liq. org. electrolyte. The authors elucidate the dependence of Li nuclei size, shape, and areal d. on current rate, consistent with classical nucleation and growth theory. The nuclei size is proportional to the inverse of overpotential and the no. d. of nuclei is proportional to the cubic power of overpotential. Based on this understanding, the authors propose a strategy to increase the uniformity of electrodeposited Li on the electrode surface.
- 13Biswal, P.; Stalin, S.; Kludze, A.; Choudhury, S.; Archer, L. A. Nucleation and Early Stage Growth of Li Electrodeposits. Nano Lett. 2019, 19, 8191– 8200, DOI: 10.1021/acs.nanolett.9b03548Google Scholar13https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhvVyls7bL&md5=1ef315ba7d464df81166022167da691eNucleation and Early Stage Growth of Li ElectrodepositsBiswal, Prayag; Stalin, Sanjuna; Kludze, Atsu; Choudhury, Snehashis; Archer, Lynden A.Nano Letters (2019), 19 (11), 8191-8200CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)The morphologies that metal electrodeposits form during the earliest stages of electrodeposition are known to play a crit. role in the recharge of electrochem. cells that use metals as anodes. Here, we report results from a combined theor. and exptl. study of the early stage nucleation and growth of electrodeposited Li at liq.-solid interfaces. The spatial characteristics of Li electrodeposits are studied via SEM in tandem with image anal. Comparisons of Li nucleation and growth in multiple electrolytes provide a comprehensive picture of the initial nucleation and growth dynamics. We report that ion diffusion in the bulk electrolyte and through the solid electrolyte interphase (SEI) formed spontaneously on the metal play equally important roles in regulating Li nucleation and growth. We show further that the underlying physics dictating bulk and surface diffusion are similar across a range of electrolyte chemistries and measurement conditions, and that fluorinated electrolytes produce a distinct flattening of Li electrodeposits at low rates. These observations are rationalized using XPS, electrochem. impedance spectroscopy (EIS), and contact angle goniometry to probe the interfacial chem. and dynamics. Our results show that high interfacial energy and high surface ion diffusivity are necessary for uniform Li plating.
- 14Fan, F. Y.; Carter, W. C.; Chiang, Y. M. Mechanism and Kinetics of Li2S Precipitation in Lithium-Sulfur Batteries. Adv. Mater. 2015, 27, 5203– 5209, DOI: 10.1002/adma.201501559Google Scholar14https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhtlSlsrjI&md5=6be65ac077ad8cec86b370200987d8a3Mechanism and Kinetics of Li2S Precipitation in Lithium-Sulfur BatteriesFan, Frank Y.; Carter, W. Craig; Chiang, Yet-MingAdvanced Materials (Weinheim, Germany) (2015), 27 (35), 5203-5209CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)In this paper, we characterize the kinetics and morphol. of Li2S electrodeposited from nonaq. (glyme-based) polysulfide solns. onto carbon fibers and multiwalled carbon nanotubes (MWCNT). Deposition is studied under potentiostatic conditions as a function of overpotential, and galvanostatic conditions as a function of current rate. The deposition mechanism is detd. from a combination of kinetic analyses and direct observations of Li2S morphol. at various stages of deposition by electron microscopy. It is shown that the morphol. of electrodeposited Li2S depends on the nucleation d. and relative rates of nucleation vs. growth, each of which can be manipulated by controlling the overpotential, the characteristics of the substrate, and the choice of solvent. Guidelines for optimizing storage capacity through substrate choice and electrokinetic control are presented.
- 15Li, Z.; Zhou, Y.; Wang, Y.; Lu, Y.-C. Solvent-Mediated Li2S Electrodeposition: A Critical Manipulator in Lithium-Sulfur Batteries. Adv. Energy Mater. 2019, 9, 1802207, DOI: 10.1002/aenm.201802207
- 16Avrami, M. Kinetics of Phase Change. I General Theory. J. Chem. Phys. 1939, 7, 1103– 1112, DOI: 10.1063/1.1750380Google Scholar16https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaH3cXns1Or&md5=480ce56a48273a16bff69815776337f5Kinetics of phase change. I. General theoryAvrami, MelvinJournal of Chemical Physics (1939), 7 (), 1103-12CODEN: JCPSA6; ISSN:0021-9606.The theory of the kinetics of phase change is developed with the experimentally supported assumptions that the new phase is nucleated by germ nuclei which already exist in the old phase, and whose no. can be altered by previous treatment. The d. of germ nuclei diminishes through activation of some of them to become growth nuclei for grains of the new phase, and ingestion of others by these growing grains. The quant. relations between the d. of germ nuclei, growth nuclei, and transformed vol. are derived and expressed in terms of a characteristic time scale for any given substance and process. The geometry and kinetics of a crystal aggregate are studied from this point of view, and it is shown that there is strong evidence of the existence, for any given substance, of an isokinetic range of temps. and concns. in which the characteristic kinetics of phase change remains the same. The detn. of phase reaction kinetics is shown to depend upon the solution of a functional equation of a certain type. Some of the general properties of temp.-time and transformation-time curves, resp., are described and explained.
- 17Antonopoulos, B. K.; Maglia, F.; Schmidt-Stein, F.; Schmidt, J. P.; Hoster, H. E. Formation of the Solid Electrolyte Interphase at Constant Potentials: A Model Study on Highly Oriented Pyrolytic Graphite. Batteries Supercaps 2018, 1, 110– 121, DOI: 10.1002/batt.201800029Google Scholar17https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXjsV2qtbw%253D&md5=b4314cd955c773bd3264affdb7dc5469Formation of the Solid Electrolyte Interphase at Constant Potentials: A Model Study on Highly Oriented Pyrolytic GraphiteAntonopoulos, Byron K.; Maglia, Filippo; Schmidt-Stein, Felix; Schmidt, Jan P.; Hoster, Harry E.Batteries & Supercaps (2018), 1 (3), 110-121CODEN: BSAUBU; ISSN:2566-6223. (Wiley-VCH Verlag GmbH & Co. KGaA)The solid electrolyte interphase (SEI) on graphite anodes is a key enabler for rechargeable lithium-ion batteries (LIBs). It ensures that only Li+ ions and no damaging electrolyte components enter the anode and hinders electrolyte decompn. Its growth should be confined to the initial SEI formation process and stop once the battery is in operation to avoid capacity/power loss. In tech. LIB cells, the SEI is formed at const. current, with the potential of the graphite anode slowly drifting from higher to lower voltages. SEI formation rate, compn., and structure depend on the potential and on the chem. properties of the anode surface. Here, we characterize SEIs formed at const. potentials on the chem. inactive basal plane of highly oriented pyrolytic graphite (HOPG). X-ray photoemission spectroscopy (XPS) detects carbonate species only at lower formation potentials. Cyclic voltammetry (CV) and Electrochem. Impedance Spectroscopy (EIS) with Fc/Fc+ as an electrochem. probe demonstrate how the formation potential influences ion transport and electrochem. kinetics to and at the anode surface, resp. Breaking the EIS data down to a Distribution of Relaxation Times (DRT) reveals distinct kinetics and transport related peaks with varying Arrhenius-type temp. dependencies. We discuss our findings in the context of previous electrochem. studies and existing SEI models and of SEI formation protocols suitable for industry.
- 18Attia, P. M.; Das, S.; Harris, S. J.; Bazant, M. Z.; Chueh, W. C. Electrochemical Kinetics of SEI Growth on Carbon Black: Part I. Experiments. J. Electrochem. Soc. 2019, 166, E97-E106 DOI: 10.1149/2.0231904jesGoogle ScholarThere is no corresponding record for this reference.
- 19Yao, Y. X.; Chen, X.; Yan, C.; Zhang, X. Q.; Cai, W. L.; Huang, J. Q.; Zhang, Q. Regulating Interfacial Chemistry in Lithium-Ion Batteries by a Weakly Solvating Electrolyte. Angew. Chem., Int. Ed. 2021, 60, 4090– 4097, DOI: 10.1002/anie.202011482Google Scholar19https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXitl2ntrzM&md5=fce691c36a536c825ae864dd0f8cdddfRegulating Interfacial Chemistry in Lithium-Ion Batteries by a Weakly Solvating Electrolyte**Yao, Yu-Xing; Chen, Xiang; Yan, Chong; Zhang, Xue-Qiang; Cai, Wen-Long; Huang, Jia-Qi; Zhang, QiangAngewandte Chemie, International Edition (2021), 60 (8), 4090-4097CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)The performance of Li-ion batteries (LIBs) is highly dependent on their interfacial chem., which is regulated by electrolytes. Conventional electrolyte typically contains polar solvents to dissoc. Li salts. Herein we report a weakly solvating electrolyte (WSE) that consists of a pure non-polar solvent, which leads to a peculiar solvation structure where ion pairs and aggregates prevail under a low salt concn. of 1.0 M. Importantly, WSE forms unique anion-derived interphases on graphite electrodes that exhibit fast-charging and long-term cycling characteristics. First-principles calcns. unravel a general principle that the competitive coordination between anions and solvents to Li ions is the origin of different interfacial chemistries. By bridging the gap between soln. thermodn. and interfacial chem. in batteries, this work opens a brand-new way towards precise electrolyte engineering for energy storage devices with desired properties.
- 20Scharifker, B.; Hills, G. Theoretical and Experimental Studies of Multiple Nucleation. Electrochim. Acta 1983, 28, 879– 889, DOI: 10.1016/0013-4686(83)85163-9Google Scholar20https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL3sXls1Gkurs%253D&md5=1b84c79f4aeb8c6900b5cad5d430fe1aTheoretical and experimental studies of multiple nucleationScharifker, Benjamin; Hill, GrahamElectrochimica Acta (1983), 28 (7), 879-89CODEN: ELCAAV; ISSN:0013-4686.The theory of the potentiostatic current transient for 3-dimensional multiple nucleation with diffusion controlled growth is discussed. Reliable values of nuclear no. densities and nucleation rates are obtained from the anal. of the current max., and good agreement is obtained with exptl. data for nucleation in several electrochem. systems. The termination of the nucleation process by the expansion of diffusion fields is considered, as well as the deviations from randomness obsd. in the distribution of nuclei on the electrode surface.
- 21Hyde, M. E.; Compton, R. G. A Review of the Analysis of Multiple Nucleation with Diffusion Controlled Growth. J. Electroanal. Chem. 2003, 549, 1– 12, DOI: 10.1016/S0022-0728(03)00250-XGoogle Scholar21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXksFKku7Y%253D&md5=9979880541f134c5287c49b26334051eA review of the analysis of multiple nucleation with diffusion controlled growthHyde, Michael E.; Compton, Richard G.Journal of Electroanalytical Chemistry (2003), 549 (), 1-12CODEN: JECHES ISSN:. (Elsevier Science B.V.)A review with refs. is given of the area of electrodeposition of materials via a mechanism of nucleation followed by diffusion controlled growth. A short historical background to the study of nucleation via potentiostatic current transient modeling is provided, followed by an outline of the major methods currently used, with some comments on their relative merits. An overview of the computer simulation of both nucleus distributions and diffusion to growing nuclei is given. Finally, methods, including optical microscopy and SPM, used for studying directly the development of surfaces on which nucleation is occurring are described. A table of some chem. systems to which the theor. models have recently been applied is included.
- 22Bewick, A.; Fleischmann, M.; Thirsk, H. R. Kinetics of the Electrocrystallization of Thin Films of Calomel. Trans. Faraday Soc. 1962, 58, 2200– 2216, DOI: 10.1039/tf9625802200Google Scholar22https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaF3sXntFemug%253D%253D&md5=faad2dbe37b540dc5be5e50498f39ac3Kinetics of the electrocrystallization of thin films of calomelBewick, A.; Fleischmann, M.; Thirsk, H. R.Transactions of the Faraday Society (1962), 58 (), 2200-16CODEN: TFSOA4; ISSN:0014-7672.The formation of calomel on a Hg electrode in HCl starts with the laying down of several monomol. layers, [110] lattice planes, by 2-dimensional growth of 2-dimensional nuclei. The slowest step in the overall mechanism is the incorporation of new material at the edge of the growing patches for which the rate const. at the reversible potential is about 0.005 mole/cm.2 sec.; the nucleation rate const. is about 1010 nuclei/cm.2 sec. The slow incorporation of Cl- involved equil. among that in soln., that adsorbed, and that in lattice. The incorporation of Hg+ was Hg - e .dblharw. Hg+ads and the slow reaction Hg+ads → Hg+lattice.
- 23Fleischmann, M.; Thirsk, H. R. The Growth of Thin Passivating Layers on Metallic Surfaces. J. Electrochem. Soc. 1963, 110, 688, DOI: 10.1149/1.2425851Google Scholar23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaF3sXktl2qtrg%253D&md5=7249a5a02932eb52d75bb525d58b6182Growth of thin passivating layers on metallic surfacesFleischmann, M.; Thirsk, H. R.Journal of the Electrochemical Society (1963), 110 (6), 688-98CODEN: JESOAN; ISSN:0013-4651.The initial stages of passivation were studied by potentiostatic measurements at high frequencies and the results were correlated with electron microscopy and diffraction of the surface films. In favorable cases, passivation can be treated as an example of electrochem. kinetics of crystal growth. Thus, the kinetic equations are derived for: (a) growth of discrete centers at the electrode (e.g., γ-MnO2 on Pt from a soln. contg. MnSO4 and H2SO4, also electrodeposition of α- and β-PbO2 and oxidn. of PbSO4); (b) growth of cylindrical centers from nucleation sites (e.g., oxidn. of Ag2SO4 to AgO); and (c) growth of centers of monomol. heights. The kinetics of the last process can be distinguished from that of adsorption by the current behavior in the initial 0-1000 μsec. This is illustrated by specific adsorption of Cl- on Hg and amalgamated electrodes, which is followed by layer formation, e.g. of TlCl on Tl(Hg), Cd(OH)2 on Cd(Hg), and ZnO on Zn(Hg). For Cd(Hg) in alk. soln. and for Hg in Cl- solns., passivation sets in after a defined no of monolayers have been formed. For Tl(Hg) in Cl- solns., a multimol. layer succeeds the formation of 2 monolayers before the electrode is passivated, while for the case of Zn(Hg) in alk. solns. only a single layer is found.
- 24Fleischmann, M.; Thirsk, H. R. Electrochemical Kinetics of Formation of Monolayers of Solid Phases. Electrochim. Acta 1964, 9, 757– 771, DOI: 10.1016/0013-4686(64)80063-3Google Scholar24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaF2cXkt1eiu70%253D&md5=fba66e64d825a894e107e2a868f931d9Electrochemical kinetics of formation of monolayers of solid phasesFleischmann, M.; Thirsk, H. R.Electrochimica Acta (1964), 9 (6), 757-71CODEN: ELCAAV; ISSN:0013-4686.The mechanisms of crystal growth on electrodes are still a matter for speculation, because of inadequate exptl. data. In cases in which centers could be shown to grow in 2 or 3 dimensions, it was possible to characterize the nature of the nucleation and growth processes of the crystals and to follow the concn. and potential dependence of the rate consts. The formation of the lattice from adsorbed species can be shown to be rate-detg. In most cases of crystal growth, the relative roles of electrochem. deposition, surface diffusion, and lattice formation (and the formation of lattice growth sites) are uncertain. Earlier work (CA 58, 5253a) was done on the electrochem. growth of calomel in chloride solns. under potentiostatic conditions. The successive deposition of unimol. layers of calomel was observed; the kinetics were controlled by the formation, growth, and subsequent overlap of 2-dimensional centers. This mechanism is similar to the classical mechanism of crystal growth except that lattice formation is the rate-detg. step, and that the formation of a large no. of 2-dimensional growth centers is observed. The formation of Cd(OH)2 on Cd amalgam and TlCl on Tl amalgam was studied. A similar pattern of behavior can also be observed in the electrodeposition of metals, in addn. to other oxide and halide systems. The concn. and potential dependence of the rate consts. is discussed, together with some consideration of the kinetics of the sp. adsorption of ions, which precedes the crystal-growth process.
- 25Milchev, A.; Krastev, I. Two-Dimensional Progressive and Instantaneous Nucleation with Overlap: The Case of Multi-Step Electrochemical Reactions. Electrochim. Acta 2011, 56, 2399– 2403, DOI: 10.1016/j.electacta.2010.11.025Google ScholarThere is no corresponding record for this reference.
- 26Zhu, T.; Hu, Q.; Yan, G.; Wang, J.; Wang, Z.; Guo, H.; Li, X.; Peng, W. Manipulating the Composition and Structure of Solid Electrolyte Interphase at Graphite Anode by Adjusting the Formation Condition. Energy Technol. 2019, 7, 1900273, DOI: 10.1002/ente.201900273Google Scholar26https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhs1ymt7rP&md5=1670badab6203be0e8e1dccf690c6db7Manipulating the Composition and Structure of Solid Electrolyte Interphase at Graphite Anode by Adjusting the Formation ConditionZhu, Taohe; Hu, Qiyang; Yan, Guochun; Wang, Jiexi; Wang, Zhixing; Guo, Huajun; Li, Xinhai; Peng, WenjieEnergy Technology (Weinheim, Germany) (2019), 7 (9), n/a1900273CODEN: ETNEFN; ISSN:2194-4296. (Wiley-VCH Verlag GmbH & Co. KGaA)The solid electrolyte interphase (SEI) plays an important role in the comprehensive electrochem. performance of lithium-ion batteries. However, graphite generates a 10% vol. expansion during cycles, resulting in structural cracking of the SEI and further electrolyte decompn. Herein, by adjusting the formation c.d., the compn. and structure of the SEI are regulated to optimize the electrochem. performance of graphite electrodes. The results manifest that the SEI is mainly formed between 1.1 and 1.4 V, and a lower formation c.d. is favorable for forming an excellent SEI at the graphite electrode surface. The SEI formed under such condition possesses more org. lithium salts and less inorg. lithium salts, and it is enwrapped onto the surface of the graphite anode more uniformly as compared with higher formation c.d. Meanwhile, the derived SEI is more stable and thicker, which can effectively stabilize the interface of the electrode/electrolyte to enhance the cyclic stability of graphite anode materials after the formation step, so as to buffer its vol. change during the cycles.
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References
ARTICLE SECTIONSThis article references 26 other publications.
- 1Liang, Y.; Yao, Y. Designing Modern Aqueous Batteries. Nat. Rev. Mater. 2023, 8, 109– 122, DOI: 10.1038/s41578-022-00511-3There is no corresponding record for this reference.
- 2Yao, Y. X.; Yan, C.; Zhang, Q. Emerging Interfacial Chemistry of Graphite Anodes in Lithium-Ion Batteries. Chem. Commun. 2020, 56, 14570– 14584, DOI: 10.1039/D0CC05084A2https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXitVeiur%252FJ&md5=155023addc454132e1c5a0399308b20fEmerging interfacial chemistry of graphite anodes in lithium-ion batteriesYao, Yu-Xing; Yan, Chong; Zhang, QiangChemical Communications (Cambridge, United Kingdom) (2020), 56 (93), 14570-14584CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)A review. Understanding the electrode/electrolyte interfacial chem. is the cornerstone of designing lithium-ion batteries (LIBs) with superior performance. Graphite has been exclusively utilized as the anode material in state-of-the-art LIBs, whose interfacial chem. has a profound impact on battery life and power delivery. However, current understanding of the graphite/electrolyte interface is still incomplete because of its intricate nature, which has driven unremitting explorations and breakthroughs in the past few decades. On the one hand, the applications of emerging exptl. and computational tools have led researchers to re-examine several decades-old problems, such as the underlying mechanism of solid electrolyte interphase (SEI) formation and the co-intercalation mystery. On the other hand, from anion-derived interfacial chem. to artificial interphases, novel interfacial chem. for graphite is being proposed to replace the traditional ethylene carbonate-derived SEI for better performances. By summarizing the latest advances in the emerging interfacial chem. of graphite anodes in LIBs, this review affords a fresh perspective on interface science and engineering towards next-generation energy storage devices.
- 3Xu, K. Electrolytes and Interphases in Li-Ion Batteries and Beyond. Chem. Rev. 2014, 114, 11503– 11618, DOI: 10.1021/cr500003w3https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhvVensr3N&md5=5d79be66e09915ece2c476aab47c4224Electrolytes and Interphases in Li-Ion Batteries and BeyondXu, KangChemical Reviews (Washington, DC, United States) (2014), 114 (23), 11503-11618CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review of advances in electrolytes and interphases in lithium-ion batteries.
- 4Peled, E.; Menkin, S. Review─SEI: Past, Present and Future. J. Electrochem. Soc. 2017, 164, A1703– A1719, DOI: 10.1149/2.1441707jes4https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhtVCitLvN&md5=3a2703b96a3bee6a8036b35db85534a7Review-SEI: Past, Present and FuturePeled, E.; Menkin, S.Journal of the Electrochemical Society (2017), 164 (7), A1703-A1719CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)The Solid-Electrolyte-Interphase (SEI) model for non-aq. alkali-metal batteries constitutes a paradigm change in the understanding of lithium batteries and has thus enabled the development of safer, durable, higher-power and lower-cost lithium batteries for portable and EV applications. Prior to the publication of the SEI model (1979), researchers used the Butler-Volmer equation, in which a direct electron transfer from the electrode to lithium cations in the soln. is assumed. The SEI model proved that this is a mistaken concept and that, in practice, the transfer of electrons from the electrode to the soln. in a lithium battery, must be prevented, since it will result in fast self-discharge of the active materials and poor battery performance. This model provides [E. Peled, in "Lithium Batteries," J.P. Gabano (ed), Academic Press, (1983), E. Peled, J. Electrochem. Soc., 126, 2047 (1979).] new equations for: electrode kinetics (io and b), anode corrosion, SEI resistivity and growth rate and irreversible capacity loss of lithium-ion batteries. This model became a cornerstone in the science and technol. of lithium batteries. This paper reviews the past, present and the future of SEI batteries.
- 5Han, B.; Zou, Y.; Xu, G.; Hu, S.; Kang, Y.; Qian, Y.; Wu, J.; Ma, X.; Yao, J.; Li, T.; Zhang, Z.; Meng, H.; Wang, H.; Deng, Y.; Li, J.; Gu, M. Additive Stabilization of SEI on Graphite Observed Using Cryo-Electron Microscopy. Energy Environ. Sci. 2021, 14, 4882– 4889, DOI: 10.1039/D1EE01678D5https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhsVylurjE&md5=d6235f8958226cbed6a7b5d34746bc18Additive stabilization of SEI on graphite observed using cryo-electron microscopyHan, Bing; Zou, Yucheng; Xu, Guiyin; Hu, Shiguang; Kang, Yuanyuan; Qian, Yunxian; Wu, Jing; Ma, Xiaomin; Yao, Jianquan; Li, Tengteng; Zhang, Zhen; Meng, Hong; Wang, Hong; Deng, Yonghong; Li, Ju; Gu, MengEnergy & Environmental Science (2021), 14 (9), 4882-4889CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)Revealing the at. structures of the solid electrolyte interphase (SEI) is challenging due to its sensitivity to electron beam and environmental factors such as moisture and oxygen. Here, we unveiled the at. structures and phase distribution of the fragile solid electrolyte interphase (SEI) on graphite using ultra-low-dosage and aberration-cor. cryo-transmission electron microscopy (cryo-TEM). It is known that propylene carbonate electrolyte can exfoliate a graphite anode and damage its structural integrity. Surprisingly, ethylene carbonate-diethyl carbonate can also damage the surface of the graphite anode by exfoliation even with an initial formation protocol of const.-current charging (0.05C) for three hours and then 0.1C for another 3 h at 45°C: we hypothesize that the exfoliated graphene layers embedded in the SEI enhance local electron channeling, which induces an ever-growing, thick SEI layer with randomly distributed graphene, Li2O, and Li2CO3 nano-crystals. Using the same formation protocol but with 1 wt% vinylene carbonate (VC), tri-Ph phosphate (TPP), or ethylene sulfate (DTD) or 10 wt% monofluoroethylene carbonate (FEC) as the additive is found to cause solid deposition prior to the graphite exfoliation instability, which generates a stable and thin SEI (<90 nm) on the graphite surface which prevents further exfoliation of graphite and rapidly suppresses the decompn. of electrolyte in the later cycles. When using a slower formation protocol including 2 cycles between 3.0 and 4.2 V at a rate of 0.01C at room temp., graphite exfoliation is dramatically reduced, but is still observable initially.
- 6Feng, X.; Ren, D.; He, X.; Ouyang, M. Mitigating Thermal Runaway of Lithium-Ion Batteries. Joule 2020, 4, 743– 770, DOI: 10.1016/j.joule.2020.02.0106https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXnt1Wktbg%253D&md5=e5e0fd46dec59ee89e971a92b03b4894Mitigating Thermal Runaway of Lithium-Ion BatteriesFeng, Xuning; Ren, Dongsheng; He, Xiangming; Ouyang, MinggaoJoule (2020), 4 (4), 743-770CODEN: JOULBR; ISSN:2542-4351. (Cell Press)A review. This paper summarizes the mitigation strategies for the thermal runaway of lithium-ion batteries. The mitigation strategies function at the material level, cell level, and system level. A time-sequence map with states and flows that describe the evolution of the phys. and/or chem. processes has been proposed to interpret the mechanisms, both at the cell level and at the system level. At the cell level, the time-sequence map helps clarify the relationship between thermal runaway and fire. At the system level, the time-sequence map depicts the relationship between the expected thermal runaway propagation and the undesired fire pathway. Mitigation strategies are fulfilled by cutting off a specific transformation flow between the states in the time sequence map. The abuse conditions that may trigger thermal runaway are also summarized for the complete protection of lithium-ion batteries. This perspective provides directions for guaranteeing the safety of lithium-ion batteries for elec. energy storage applications in the future.
- 7Wang, L.; Menakath, A.; Han, F.; Wang, Y.; Zavalij, P. Y.; Gaskell, K. J.; Borodin, O.; Iuga, D.; Brown, S. P.; Wang, C.; Xu, K.; Eichhorn, B. W. Identifying the Components of the Solid-Electrolyte Interphase in Li-Ion Batteries. Nat. Chem. 2019, 11, 789– 796, DOI: 10.1038/s41557-019-0304-z7https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhs1alsL7E&md5=f8cd4da5f353732c5f1b7d2f36292667Identifying the components of the solid-electrolyte interphase in Li-ion batteriesWang, Luning; Menakath, Anjali; Han, Fudong; Wang, Yi; Zavalij, Peter Y.; Gaskell, Karen J.; Borodin, Oleg; Iuga, Dinu; Brown, Steven P.; Wang, Chunsheng; Xu, Kang; Eichhorn, Bryan W.Nature Chemistry (2019), 11 (9), 789-796CODEN: NCAHBB; ISSN:1755-4330. (Nature Research)The importance of the solid-electrolyte interphase (SEI) for reversible operation of Li-ion batteries has been well established, but the understanding of its chem. remains incomplete. The current consensus on the identity of the major org. SEI component is that it consists of lithium ethylene di-carbonate (LEDC), which is thought to have high Li-ion cond., but low electronic cond. (to protect the Li/C electrode). Here, we report on the synthesis and structural and spectroscopic characterizations of authentic LEDC and lithium ethylene mono-carbonate (LEMC). Direct comparisons of the SEI grown on graphite anodes suggest that LEMC, instead of LEDC, is likely to be the major SEI component. Single-crystal X-ray diffraction studies on LEMC and lithium Me carbonate (LMC) reveal unusual layered structures and Li+ coordination environments. LEMC has Li+ conductivities of >1 × 10-6 S cm-1, while LEDC is almost an ionic insulator. The complex interconversions and equil. of LMC, LEMC and LEDC in DMSO solns. are also investigated.
- 8Zhou, Y.; Su, M.; Yu, X.; Zhang, Y.; Wang, J. G.; Ren, X.; Cao, R.; Xu, W.; Baer, D. R.; Du, Y.; Borodin, O.; Wang, Y.; Wang, X. L.; Xu, K.; Xu, Z.; Wang, C.; Zhu, Z. Real-Time Mass Spectrometric Characterization of the Solid-Electrolyte Interphase of a Lithium-Ion Battery. Nat. Nanotechnol. 2020, 15, 224– 230, DOI: 10.1038/s41565-019-0618-48https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXivVeksLs%253D&md5=312cc470aec17d9ea3e196f481fc4fa2Real-time mass spectrometric characterization of the solid-electrolyte interphase of a lithium-ion batteryZhou, Yufan; Su, Mao; Yu, Xiaofei; Zhang, Yanyan; Wang, Jun-Gang; Ren, Xiaodi; Cao, Ruiguo; Xu, Wu; Baer, Donald R.; Du, Yingge; Borodin, Oleg; Wang, Yanting; Wang, Xue-Lin; Xu, Kang; Xu, Zhijie; Wang, Chongmin; Zhu, ZihuaNature Nanotechnology (2020), 15 (3), 224-230CODEN: NNAABX; ISSN:1748-3387. (Nature Research)The solid-electrolyte interphase (SEI) dictates the performance of most batteries, but the understanding of its chem. and structure is limited by the lack of in situ exptl. tools. In this work, a dynamic picture is presented of the SEI formation in lithium-ion batteries using in operando liq. secondary ion mass spectrometry in combination with mol. dynamics simulations. It was found that before any interphasial chem. occurs (during the initial charging), an elec. double layer forms at the electrode/electrolyte interface due to the self-assembly of solvent mols. The formation of the double layer is directed by Li+ and the electrode surface potential. The structure of this double layer predicts the eventual interphasial chem.; in particular, the neg. charged electrode surface repels salt anions from the inner layer and results in an inner SEI that is thin, dense and inorg. in nature. It is this dense layer that is responsible for conducting Li+ and insulating electrons, the main functions of the SEI. An electrolyte-permeable and org.-rich outer layer appears after the formation of the inner layer. In the presence of a highly concd., fluoride-rich electrolyte, the inner SEI layer has an elevated concn. of LiF due to the presence of anions in the double layer. These real-time nanoscale observations will be helpful in engineering better interphases for future batteries.
- 9Jorn, R.; Raguette, L.; Peart, S. Investigating the Mechanism of Lithium Transport at Solid Electrolyte Interphases. J. Phys. Chem. C 2020, 124, 16261– 16270, DOI: 10.1021/acs.jpcc.0c030189https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhtlKgs7vM&md5=47271d4f0fb51496d92560f64d3086f1Investigating the Mechanism of Lithium Transport at Solid Electrolyte InterphasesJorn, Ryan; Raguette, Lauren; Peart, ShaniyaJournal of Physical Chemistry C (2020), 124 (30), 16261-16270CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)Reactions between carbonate electrolytes and graphite electrodes in lithium-ion storage devices produce a surface film of byproducts known as the solid electrolyte interphase (SEI). Significant progress has been made in assessing the compn. and structure of these interphases; however, their impact on lithium transport during charge and discharge lacks mol. detail. Over the past decade, electrochem. impedance spectroscopy (EIS) has shown that lithium transport is limited by a combination of ion desolvation and ion conduction through the SEI, however which step is rate limiting remains unresolved. In this work, the first step is simulated in this process, i.e., ion desolvation, both into and out of two model SEI's comprised of lithium ethylene dicarbonate (LEDC) and Li2CO3 interfaced with an ethylene carbonate electrolyte. By correlating free-energy changes with solvation structure, it is shown that the path taken for Li+ insertion is a two-step mechanism consisting of overcoming two energy barriers to adsorption and then absorption. The largest measured barrier of the two is 59.2 kJ/mol, within the ests. obtained from EIS measurements. Ion extn. from the LEDC, however, follows a different free-energy profile detd. by the flexibility of the surface groups to extend into the electrolyte. The dependence of extn. from LEDC on the nature of the surface groups, emphasized by comparison with ion extn. from the more rigid Li2CO3 surface, highlights the complex relationship between SEI compn. and lithium transport.
- 10Yan, C.; Jiang, L. L.; Yao, Y. X.; Lu, Y.; Huang, J. Q.; Zhang, Q. Nucleation and Growth Mechanism of Anion-Derived Solid Electrolyte Interphase in Rechargeable Batteries. Angew. Chem., Int. Ed. 2021, 60, 8521– 8525, DOI: 10.1002/anie.20210049410https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXlvV2jurg%253D&md5=b6b7b07f44033198c256c6e2d8c10fafNucleation and Growth Mechanism of Anion-Derived Solid Electrolyte Interphase in Rechargeable BatteriesYan, Chong; Jiang, Li-Li; Yao, Yu-Xing; Lu, Yang; Huang, Jia-Qi; Zhang, QiangAngewandte Chemie, International Edition (2021), 60 (15), 8521-8525CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)Solid electrolyte interphase (SEI) has been widely employed to describe the new phase formed between anode and electrolyte in working batteries. Significant advances have been achieved on the structure and compn. of SEI as well as on the possible ion transport mechanism. However, the nucleation and growth mechanism of SEI catches little attention, which requires the establishment of isothermal electrochem. crystn. theory. Herein we explore the virgin territory of electrochem. crystd. SEI. By using potentiostatic method to regulate the decompn. of anions, an anion-derived SEI forms on graphite surface at at. scale. After fitting the cur-rent-time transients with Laviron theory and Avrami formula, we conclude that the formation of anion-derived interface is surface reaction controlled and obeys the two-dimensional (2D) progressive nucleation and growth model. Atomic force microscope (AFM) images emphasize the conclusion, which reveals the mystery of isothermal electrochem. crystn. of SEI.
- 11Scharifker, B. R.; Mostany, J. Nucleation and Growth of New Phases on Electrode Surfaces. In Developments in Electrochemistry: Science Inspired by Martin Fleischmann; John Wiley & Sons, 2014; pp 65– 75. DOI: 10.1002/9781118694404.ch4 .There is no corresponding record for this reference.
- 12Pei, A.; Zheng, G.; Shi, F.; Li, Y.; Cui, Y. Nanoscale Nucleation and Growth of Electrodeposited Lithium Metal. Nano Lett. 2017, 17, 1132– 1139, DOI: 10.1021/acs.nanolett.6b0475512https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXms12htQ%253D%253D&md5=1177f0162e2da0f93e064c9941ee6d48Nanoscale Nucleation and Growth of Electrodeposited Lithium MetalPei, Allen; Zheng, Guangyuan; Shi, Feifei; Li, Yuzhang; Cui, YiNano Letters (2017), 17 (2), 1132-1139CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)Li metal has reemerged as an exciting anode for high energy Li-ion batteries due to its high specific capacity of 3860 mA h g-1 and lowest electrochem. potential of all known materials. However, Li was plagued by the issues of dendrite formation, high chem. reactivity with electrolyte, and infinite relative vol. expansion during plating and stripping, which present safety hazards and low cycling efficiency in batteries with Li metal electrodes. There have been a lot of recent studies on Li metal although little work has focused on the initial nucleation and growth behavior of Li metal, neglecting a crit. fundamental scientific foundation of Li plating. Here, the authors study exptl. the morphol. of Li in the early stages of nucleation and growth on planar Cu electrodes in liq. org. electrolyte. The authors elucidate the dependence of Li nuclei size, shape, and areal d. on current rate, consistent with classical nucleation and growth theory. The nuclei size is proportional to the inverse of overpotential and the no. d. of nuclei is proportional to the cubic power of overpotential. Based on this understanding, the authors propose a strategy to increase the uniformity of electrodeposited Li on the electrode surface.
- 13Biswal, P.; Stalin, S.; Kludze, A.; Choudhury, S.; Archer, L. A. Nucleation and Early Stage Growth of Li Electrodeposits. Nano Lett. 2019, 19, 8191– 8200, DOI: 10.1021/acs.nanolett.9b0354813https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhvVyls7bL&md5=1ef315ba7d464df81166022167da691eNucleation and Early Stage Growth of Li ElectrodepositsBiswal, Prayag; Stalin, Sanjuna; Kludze, Atsu; Choudhury, Snehashis; Archer, Lynden A.Nano Letters (2019), 19 (11), 8191-8200CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)The morphologies that metal electrodeposits form during the earliest stages of electrodeposition are known to play a crit. role in the recharge of electrochem. cells that use metals as anodes. Here, we report results from a combined theor. and exptl. study of the early stage nucleation and growth of electrodeposited Li at liq.-solid interfaces. The spatial characteristics of Li electrodeposits are studied via SEM in tandem with image anal. Comparisons of Li nucleation and growth in multiple electrolytes provide a comprehensive picture of the initial nucleation and growth dynamics. We report that ion diffusion in the bulk electrolyte and through the solid electrolyte interphase (SEI) formed spontaneously on the metal play equally important roles in regulating Li nucleation and growth. We show further that the underlying physics dictating bulk and surface diffusion are similar across a range of electrolyte chemistries and measurement conditions, and that fluorinated electrolytes produce a distinct flattening of Li electrodeposits at low rates. These observations are rationalized using XPS, electrochem. impedance spectroscopy (EIS), and contact angle goniometry to probe the interfacial chem. and dynamics. Our results show that high interfacial energy and high surface ion diffusivity are necessary for uniform Li plating.
- 14Fan, F. Y.; Carter, W. C.; Chiang, Y. M. Mechanism and Kinetics of Li2S Precipitation in Lithium-Sulfur Batteries. Adv. Mater. 2015, 27, 5203– 5209, DOI: 10.1002/adma.20150155914https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhtlSlsrjI&md5=6be65ac077ad8cec86b370200987d8a3Mechanism and Kinetics of Li2S Precipitation in Lithium-Sulfur BatteriesFan, Frank Y.; Carter, W. Craig; Chiang, Yet-MingAdvanced Materials (Weinheim, Germany) (2015), 27 (35), 5203-5209CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)In this paper, we characterize the kinetics and morphol. of Li2S electrodeposited from nonaq. (glyme-based) polysulfide solns. onto carbon fibers and multiwalled carbon nanotubes (MWCNT). Deposition is studied under potentiostatic conditions as a function of overpotential, and galvanostatic conditions as a function of current rate. The deposition mechanism is detd. from a combination of kinetic analyses and direct observations of Li2S morphol. at various stages of deposition by electron microscopy. It is shown that the morphol. of electrodeposited Li2S depends on the nucleation d. and relative rates of nucleation vs. growth, each of which can be manipulated by controlling the overpotential, the characteristics of the substrate, and the choice of solvent. Guidelines for optimizing storage capacity through substrate choice and electrokinetic control are presented.
- 15Li, Z.; Zhou, Y.; Wang, Y.; Lu, Y.-C. Solvent-Mediated Li2S Electrodeposition: A Critical Manipulator in Lithium-Sulfur Batteries. Adv. Energy Mater. 2019, 9, 1802207, DOI: 10.1002/aenm.201802207There is no corresponding record for this reference.
- 16Avrami, M. Kinetics of Phase Change. I General Theory. J. Chem. Phys. 1939, 7, 1103– 1112, DOI: 10.1063/1.175038016https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaH3cXns1Or&md5=480ce56a48273a16bff69815776337f5Kinetics of phase change. I. General theoryAvrami, MelvinJournal of Chemical Physics (1939), 7 (), 1103-12CODEN: JCPSA6; ISSN:0021-9606.The theory of the kinetics of phase change is developed with the experimentally supported assumptions that the new phase is nucleated by germ nuclei which already exist in the old phase, and whose no. can be altered by previous treatment. The d. of germ nuclei diminishes through activation of some of them to become growth nuclei for grains of the new phase, and ingestion of others by these growing grains. The quant. relations between the d. of germ nuclei, growth nuclei, and transformed vol. are derived and expressed in terms of a characteristic time scale for any given substance and process. The geometry and kinetics of a crystal aggregate are studied from this point of view, and it is shown that there is strong evidence of the existence, for any given substance, of an isokinetic range of temps. and concns. in which the characteristic kinetics of phase change remains the same. The detn. of phase reaction kinetics is shown to depend upon the solution of a functional equation of a certain type. Some of the general properties of temp.-time and transformation-time curves, resp., are described and explained.
- 17Antonopoulos, B. K.; Maglia, F.; Schmidt-Stein, F.; Schmidt, J. P.; Hoster, H. E. Formation of the Solid Electrolyte Interphase at Constant Potentials: A Model Study on Highly Oriented Pyrolytic Graphite. Batteries Supercaps 2018, 1, 110– 121, DOI: 10.1002/batt.20180002917https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXjsV2qtbw%253D&md5=b4314cd955c773bd3264affdb7dc5469Formation of the Solid Electrolyte Interphase at Constant Potentials: A Model Study on Highly Oriented Pyrolytic GraphiteAntonopoulos, Byron K.; Maglia, Filippo; Schmidt-Stein, Felix; Schmidt, Jan P.; Hoster, Harry E.Batteries & Supercaps (2018), 1 (3), 110-121CODEN: BSAUBU; ISSN:2566-6223. (Wiley-VCH Verlag GmbH & Co. KGaA)The solid electrolyte interphase (SEI) on graphite anodes is a key enabler for rechargeable lithium-ion batteries (LIBs). It ensures that only Li+ ions and no damaging electrolyte components enter the anode and hinders electrolyte decompn. Its growth should be confined to the initial SEI formation process and stop once the battery is in operation to avoid capacity/power loss. In tech. LIB cells, the SEI is formed at const. current, with the potential of the graphite anode slowly drifting from higher to lower voltages. SEI formation rate, compn., and structure depend on the potential and on the chem. properties of the anode surface. Here, we characterize SEIs formed at const. potentials on the chem. inactive basal plane of highly oriented pyrolytic graphite (HOPG). X-ray photoemission spectroscopy (XPS) detects carbonate species only at lower formation potentials. Cyclic voltammetry (CV) and Electrochem. Impedance Spectroscopy (EIS) with Fc/Fc+ as an electrochem. probe demonstrate how the formation potential influences ion transport and electrochem. kinetics to and at the anode surface, resp. Breaking the EIS data down to a Distribution of Relaxation Times (DRT) reveals distinct kinetics and transport related peaks with varying Arrhenius-type temp. dependencies. We discuss our findings in the context of previous electrochem. studies and existing SEI models and of SEI formation protocols suitable for industry.
- 18Attia, P. M.; Das, S.; Harris, S. J.; Bazant, M. Z.; Chueh, W. C. Electrochemical Kinetics of SEI Growth on Carbon Black: Part I. Experiments. J. Electrochem. Soc. 2019, 166, E97-E106 DOI: 10.1149/2.0231904jesThere is no corresponding record for this reference.
- 19Yao, Y. X.; Chen, X.; Yan, C.; Zhang, X. Q.; Cai, W. L.; Huang, J. Q.; Zhang, Q. Regulating Interfacial Chemistry in Lithium-Ion Batteries by a Weakly Solvating Electrolyte. Angew. Chem., Int. Ed. 2021, 60, 4090– 4097, DOI: 10.1002/anie.20201148219https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXitl2ntrzM&md5=fce691c36a536c825ae864dd0f8cdddfRegulating Interfacial Chemistry in Lithium-Ion Batteries by a Weakly Solvating Electrolyte**Yao, Yu-Xing; Chen, Xiang; Yan, Chong; Zhang, Xue-Qiang; Cai, Wen-Long; Huang, Jia-Qi; Zhang, QiangAngewandte Chemie, International Edition (2021), 60 (8), 4090-4097CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)The performance of Li-ion batteries (LIBs) is highly dependent on their interfacial chem., which is regulated by electrolytes. Conventional electrolyte typically contains polar solvents to dissoc. Li salts. Herein we report a weakly solvating electrolyte (WSE) that consists of a pure non-polar solvent, which leads to a peculiar solvation structure where ion pairs and aggregates prevail under a low salt concn. of 1.0 M. Importantly, WSE forms unique anion-derived interphases on graphite electrodes that exhibit fast-charging and long-term cycling characteristics. First-principles calcns. unravel a general principle that the competitive coordination between anions and solvents to Li ions is the origin of different interfacial chemistries. By bridging the gap between soln. thermodn. and interfacial chem. in batteries, this work opens a brand-new way towards precise electrolyte engineering for energy storage devices with desired properties.
- 20Scharifker, B.; Hills, G. Theoretical and Experimental Studies of Multiple Nucleation. Electrochim. Acta 1983, 28, 879– 889, DOI: 10.1016/0013-4686(83)85163-920https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL3sXls1Gkurs%253D&md5=1b84c79f4aeb8c6900b5cad5d430fe1aTheoretical and experimental studies of multiple nucleationScharifker, Benjamin; Hill, GrahamElectrochimica Acta (1983), 28 (7), 879-89CODEN: ELCAAV; ISSN:0013-4686.The theory of the potentiostatic current transient for 3-dimensional multiple nucleation with diffusion controlled growth is discussed. Reliable values of nuclear no. densities and nucleation rates are obtained from the anal. of the current max., and good agreement is obtained with exptl. data for nucleation in several electrochem. systems. The termination of the nucleation process by the expansion of diffusion fields is considered, as well as the deviations from randomness obsd. in the distribution of nuclei on the electrode surface.
- 21Hyde, M. E.; Compton, R. G. A Review of the Analysis of Multiple Nucleation with Diffusion Controlled Growth. J. Electroanal. Chem. 2003, 549, 1– 12, DOI: 10.1016/S0022-0728(03)00250-X21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXksFKku7Y%253D&md5=9979880541f134c5287c49b26334051eA review of the analysis of multiple nucleation with diffusion controlled growthHyde, Michael E.; Compton, Richard G.Journal of Electroanalytical Chemistry (2003), 549 (), 1-12CODEN: JECHES ISSN:. (Elsevier Science B.V.)A review with refs. is given of the area of electrodeposition of materials via a mechanism of nucleation followed by diffusion controlled growth. A short historical background to the study of nucleation via potentiostatic current transient modeling is provided, followed by an outline of the major methods currently used, with some comments on their relative merits. An overview of the computer simulation of both nucleus distributions and diffusion to growing nuclei is given. Finally, methods, including optical microscopy and SPM, used for studying directly the development of surfaces on which nucleation is occurring are described. A table of some chem. systems to which the theor. models have recently been applied is included.
- 22Bewick, A.; Fleischmann, M.; Thirsk, H. R. Kinetics of the Electrocrystallization of Thin Films of Calomel. Trans. Faraday Soc. 1962, 58, 2200– 2216, DOI: 10.1039/tf962580220022https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaF3sXntFemug%253D%253D&md5=faad2dbe37b540dc5be5e50498f39ac3Kinetics of the electrocrystallization of thin films of calomelBewick, A.; Fleischmann, M.; Thirsk, H. R.Transactions of the Faraday Society (1962), 58 (), 2200-16CODEN: TFSOA4; ISSN:0014-7672.The formation of calomel on a Hg electrode in HCl starts with the laying down of several monomol. layers, [110] lattice planes, by 2-dimensional growth of 2-dimensional nuclei. The slowest step in the overall mechanism is the incorporation of new material at the edge of the growing patches for which the rate const. at the reversible potential is about 0.005 mole/cm.2 sec.; the nucleation rate const. is about 1010 nuclei/cm.2 sec. The slow incorporation of Cl- involved equil. among that in soln., that adsorbed, and that in lattice. The incorporation of Hg+ was Hg - e .dblharw. Hg+ads and the slow reaction Hg+ads → Hg+lattice.
- 23Fleischmann, M.; Thirsk, H. R. The Growth of Thin Passivating Layers on Metallic Surfaces. J. Electrochem. Soc. 1963, 110, 688, DOI: 10.1149/1.242585123https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaF3sXktl2qtrg%253D&md5=7249a5a02932eb52d75bb525d58b6182Growth of thin passivating layers on metallic surfacesFleischmann, M.; Thirsk, H. R.Journal of the Electrochemical Society (1963), 110 (6), 688-98CODEN: JESOAN; ISSN:0013-4651.The initial stages of passivation were studied by potentiostatic measurements at high frequencies and the results were correlated with electron microscopy and diffraction of the surface films. In favorable cases, passivation can be treated as an example of electrochem. kinetics of crystal growth. Thus, the kinetic equations are derived for: (a) growth of discrete centers at the electrode (e.g., γ-MnO2 on Pt from a soln. contg. MnSO4 and H2SO4, also electrodeposition of α- and β-PbO2 and oxidn. of PbSO4); (b) growth of cylindrical centers from nucleation sites (e.g., oxidn. of Ag2SO4 to AgO); and (c) growth of centers of monomol. heights. The kinetics of the last process can be distinguished from that of adsorption by the current behavior in the initial 0-1000 μsec. This is illustrated by specific adsorption of Cl- on Hg and amalgamated electrodes, which is followed by layer formation, e.g. of TlCl on Tl(Hg), Cd(OH)2 on Cd(Hg), and ZnO on Zn(Hg). For Cd(Hg) in alk. soln. and for Hg in Cl- solns., passivation sets in after a defined no of monolayers have been formed. For Tl(Hg) in Cl- solns., a multimol. layer succeeds the formation of 2 monolayers before the electrode is passivated, while for the case of Zn(Hg) in alk. solns. only a single layer is found.
- 24Fleischmann, M.; Thirsk, H. R. Electrochemical Kinetics of Formation of Monolayers of Solid Phases. Electrochim. Acta 1964, 9, 757– 771, DOI: 10.1016/0013-4686(64)80063-324https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaF2cXkt1eiu70%253D&md5=fba66e64d825a894e107e2a868f931d9Electrochemical kinetics of formation of monolayers of solid phasesFleischmann, M.; Thirsk, H. R.Electrochimica Acta (1964), 9 (6), 757-71CODEN: ELCAAV; ISSN:0013-4686.The mechanisms of crystal growth on electrodes are still a matter for speculation, because of inadequate exptl. data. In cases in which centers could be shown to grow in 2 or 3 dimensions, it was possible to characterize the nature of the nucleation and growth processes of the crystals and to follow the concn. and potential dependence of the rate consts. The formation of the lattice from adsorbed species can be shown to be rate-detg. In most cases of crystal growth, the relative roles of electrochem. deposition, surface diffusion, and lattice formation (and the formation of lattice growth sites) are uncertain. Earlier work (CA 58, 5253a) was done on the electrochem. growth of calomel in chloride solns. under potentiostatic conditions. The successive deposition of unimol. layers of calomel was observed; the kinetics were controlled by the formation, growth, and subsequent overlap of 2-dimensional centers. This mechanism is similar to the classical mechanism of crystal growth except that lattice formation is the rate-detg. step, and that the formation of a large no. of 2-dimensional growth centers is observed. The formation of Cd(OH)2 on Cd amalgam and TlCl on Tl amalgam was studied. A similar pattern of behavior can also be observed in the electrodeposition of metals, in addn. to other oxide and halide systems. The concn. and potential dependence of the rate consts. is discussed, together with some consideration of the kinetics of the sp. adsorption of ions, which precedes the crystal-growth process.
- 25Milchev, A.; Krastev, I. Two-Dimensional Progressive and Instantaneous Nucleation with Overlap: The Case of Multi-Step Electrochemical Reactions. Electrochim. Acta 2011, 56, 2399– 2403, DOI: 10.1016/j.electacta.2010.11.025There is no corresponding record for this reference.
- 26Zhu, T.; Hu, Q.; Yan, G.; Wang, J.; Wang, Z.; Guo, H.; Li, X.; Peng, W. Manipulating the Composition and Structure of Solid Electrolyte Interphase at Graphite Anode by Adjusting the Formation Condition. Energy Technol. 2019, 7, 1900273, DOI: 10.1002/ente.20190027326https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhs1ymt7rP&md5=1670badab6203be0e8e1dccf690c6db7Manipulating the Composition and Structure of Solid Electrolyte Interphase at Graphite Anode by Adjusting the Formation ConditionZhu, Taohe; Hu, Qiyang; Yan, Guochun; Wang, Jiexi; Wang, Zhixing; Guo, Huajun; Li, Xinhai; Peng, WenjieEnergy Technology (Weinheim, Germany) (2019), 7 (9), n/a1900273CODEN: ETNEFN; ISSN:2194-4296. (Wiley-VCH Verlag GmbH & Co. KGaA)The solid electrolyte interphase (SEI) plays an important role in the comprehensive electrochem. performance of lithium-ion batteries. However, graphite generates a 10% vol. expansion during cycles, resulting in structural cracking of the SEI and further electrolyte decompn. Herein, by adjusting the formation c.d., the compn. and structure of the SEI are regulated to optimize the electrochem. performance of graphite electrodes. The results manifest that the SEI is mainly formed between 1.1 and 1.4 V, and a lower formation c.d. is favorable for forming an excellent SEI at the graphite electrode surface. The SEI formed under such condition possesses more org. lithium salts and less inorg. lithium salts, and it is enwrapped onto the surface of the graphite anode more uniformly as compared with higher formation c.d. Meanwhile, the derived SEI is more stable and thicker, which can effectively stabilize the interface of the electrode/electrolyte to enhance the cyclic stability of graphite anode materials after the formation step, so as to buffer its vol. change during the cycles.
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Experimental section, including electrolytes and electrode materials, in situ electrochemical AFM characterization, electrochemical measurements, and ex situ material characterizations; Supplementary Figures 1–13 (PDF)
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