Pub Date : 2024-08-27DOI: 10.1149/1945-7111/ad6eb9
Igor Mele, Klemen Zelič, Marko Firm, Jože Moškon, Miran Gaberšček, Tomaž Katrašnik
Electrochemical impedance spectroscopy (EIS) is essential for non-invasive battery characterization. This paper addresses the challenge of adequate interpretation of EIS spectra, which are often complicated by overlapping internal phenomena occurring on similar time scales. We present, for the first time, a high-fidelity numerical time-domain electrochemical model that can virtually replicate experimental EIS spectra with three superimposed high-frequency semicircles, a transition to the diffusion tail at elevated imaginary values, and a tilted diffusion tail at low frequencies. These advanced features were made possible by extending state-of-the-art porous electrode model with innovative sub-models for the double layer phenomenon at the carbon black/electrolyte and metal Li-anode/electrolyte interfaces, and transport phenomena of charged species through the solid electrolyte interphase at the Li-anode interface. Additionally, we modelled the diffusion tail inclination by introducing representative active particles of varying sizes. Results from custom-made half-cells confirm the model’s ability to decipher EIS spectra more accurately compared to existing models. Moreover, innovative physics-based battery model that is capable of accurately modelling intra-cell phenomena can reveal internal states and physical parameters of batteries using measured EIS spectra. The model, therefore, also enables functionality of an advanced virtual sensor, which is an important diagnostics feature in next-generation battery management systems.
电化学阻抗光谱（EIS）对于非侵入式电池特性分析至关重要。本文探讨了如何充分解释 EIS 光谱的难题，因为在相似的时间尺度上发生的重叠内部现象通常会使 EIS 光谱变得复杂。我们首次提出了一种高保真数值时域电化学模型，该模型可以几乎复制实验 EIS 光谱，其中包括三个叠加的高频半圆、虚值升高时向扩散尾部的过渡以及低频时倾斜的扩散尾部。这些先进特性是通过扩展最先进的多孔电极模型实现的，该模型具有创新的子模型，可用于模拟炭黑/电解质和金属锂阳极/电解质界面的双层现象，以及带电物种通过锂阳极界面上的固体电解质相间层的传输现象。此外，我们还通过引入不同尺寸的代表性活性颗粒来模拟扩散尾部的倾斜度。定制半电池的结果证实，与现有模型相比，该模型能够更准确地解读 EIS 光谱。此外，基于物理学的创新电池模型能够准确模拟电池内部现象，利用测量的 EIS 光谱揭示电池的内部状态和物理参数。因此，该模型还能实现先进虚拟传感器的功能，而这正是下一代电池管理系统的重要诊断功能。
{"title":"Enhanced Porous Electrode Theory Based Electrochemical Model for Higher Fidelity Modelling and Deciphering of the EIS Spectra","authors":"Igor Mele, Klemen Zelič, Marko Firm, Jože Moškon, Miran Gaberšček, Tomaž Katrašnik","doi":"10.1149/1945-7111/ad6eb9","DOIUrl":"https://doi.org/10.1149/1945-7111/ad6eb9","url":null,"abstract":"Electrochemical impedance spectroscopy (EIS) is essential for non-invasive battery characterization. This paper addresses the challenge of adequate interpretation of EIS spectra, which are often complicated by overlapping internal phenomena occurring on similar time scales. We present, for the first time, a high-fidelity numerical time-domain electrochemical model that can virtually replicate experimental EIS spectra with three superimposed high-frequency semicircles, a transition to the diffusion tail at elevated imaginary values, and a tilted diffusion tail at low frequencies. These advanced features were made possible by extending state-of-the-art porous electrode model with innovative sub-models for the double layer phenomenon at the carbon black/electrolyte and metal Li-anode/electrolyte interfaces, and transport phenomena of charged species through the solid electrolyte interphase at the Li-anode interface. Additionally, we modelled the diffusion tail inclination by introducing representative active particles of varying sizes. Results from custom-made half-cells confirm the model’s ability to decipher EIS spectra more accurately compared to existing models. Moreover, innovative physics-based battery model that is capable of accurately modelling intra-cell phenomena can reveal internal states and physical parameters of batteries using measured EIS spectra. The model, therefore, also enables functionality of an advanced virtual sensor, which is an important diagnostics feature in next-generation battery management systems.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"9 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222468","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-27DOI: 10.1149/1945-7111/ad6b46
Samaneh Shahsavarifar, Morteza Rezapour, Mehdi Mehrpooya, Hermann Ehrlich, Teofil Jesionowski, Mohammad Reza Ganjali, Rafael Luque, Mehdi Rahimi-Nasrabadi
Polyoxometalates (POMs) are inorganic nanoclusters that consist of oxygen and transition metals. These nanoclusters serve as excellent precursors for creating electrode materials that contain transition metals. Additionally, the interaction between POMs and carbon substrates produces positive synergistic effects. There has been considerable attention on employing POMs and carbon nanostructures (for example carbon nanotubes, graphene, and mesoporous carbon) in composite materials for diverse purposes including catalysis, transformation, storage of energy, molecular detection, and electrical detection. By combining the reactive nature of POMs with the exceptional electrical properties of carbon nanostructures, highly desirable composite features can be achieved. This review delves into the extensive use of POM/nanocarbon materials for constructing rechargeable lithium-ion batteries, providing an in-depth analysis of the characteristics of POMs and the techniques employed for binding carbon.
{"title":"Review—Advances in Rechargeable Lithium-Ion Batteries Utilizing Polyoxometalate-Functionalized Nanocarbon Materials","authors":"Samaneh Shahsavarifar, Morteza Rezapour, Mehdi Mehrpooya, Hermann Ehrlich, Teofil Jesionowski, Mohammad Reza Ganjali, Rafael Luque, Mehdi Rahimi-Nasrabadi","doi":"10.1149/1945-7111/ad6b46","DOIUrl":"https://doi.org/10.1149/1945-7111/ad6b46","url":null,"abstract":"Polyoxometalates (POMs) are inorganic nanoclusters that consist of oxygen and transition metals. These nanoclusters serve as excellent precursors for creating electrode materials that contain transition metals. Additionally, the interaction between POMs and carbon substrates produces positive synergistic effects. There has been considerable attention on employing POMs and carbon nanostructures (for example carbon nanotubes, graphene, and mesoporous carbon) in composite materials for diverse purposes including catalysis, transformation, storage of energy, molecular detection, and electrical detection. By combining the reactive nature of POMs with the exceptional electrical properties of carbon nanostructures, highly desirable composite features can be achieved. This review delves into the extensive use of POM/nanocarbon materials for constructing rechargeable lithium-ion batteries, providing an in-depth analysis of the characteristics of POMs and the techniques employed for binding carbon.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"40 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222484","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-26DOI: 10.1149/1945-7111/ad6b48
Eric D. Rus, Eduardo L. Corrêa, Cindi L. Dennis, Thomas P. Moffat
The effects of potential and the presence of B(OH)3 on Pt1-xCox alloy electrodeposition from aqueous chloride-based solutions on Ru substrates was investigated. Films deposited at potentials more reducing than −0.65 V vs SCE were hexagonal close packed and greater than 90% Co (mole basis), and films deposited at potentials more oxidizing than −0.65 V were face centered cubic and showed a monotonic decrease in cobalt content as the potential increased. The composition and structure-potential dependences were not strongly affected by the presence of B(OH)3. Structural change coincided with a distinct knee-like feature in the composition-potential relationship, along with a prominent narrow voltammetric peak associated with Co deposition, possibly related to nucleation and growth of the hcp phase. The presence of B(OH)3 produced a sharp minimum in both Coulombic efficiency and deposition rate at potentials near −0.65 V and almost entirely suppressed the voltammetric feature. This may be associated with a combination of B(OH)3-derived proton reduction and inhibition of metal deposition by adsorbed B(OH)3 or B(OH)3-derived species. The presence of B(OH)3 affected the magnetic behavior of films deposited at potentials more oxidizing than −0.55 V (i.e., those with compositions less than about 40% Co) only weakly, but resulted in generally smaller maximum magnetizations for films deposited at more reducing potentials, and notably a much lower magnetization for films deposited at −0.65 V.
研究了电位和 B(OH)3 的存在对 Pt1-xCox 合金在 Ru 基底上从氯化物水溶液中电沉积的影响。在相对于 SCE 的还原电位高于 -0.65 V 时沉积的薄膜为六方紧密堆积，钴含量超过 90%（摩尔基）；而在相对于 SCE 的氧化电位高于 -0.65 V 时沉积的薄膜为面中心立方体，并且随着电位的升高，钴含量呈单调下降趋势。结构变化与成分-电位关系中明显的膝状特征以及与钴沉积有关的突出窄伏安峰相吻合，这可能与 hcp 相的成核和生长有关。在电位接近 -0.65 V 时，B(OH)3 的存在会使库仑效率和沉积速率急剧下降，并几乎完全抑制了伏安特性。这可能与 B(OH)3 衍生的质子还原以及吸附的 B(OH)3 或 B(OH)3 衍生物种对金属沉积的抑制作用有关。B(OH)3 的存在对在氧化性比 -0.55 V 更强的电位下沉积的薄膜（即钴含量低于 40% 的薄膜）的磁性行为影响较弱，但对在还原性更强的电位下沉积的薄膜的最大磁化率普遍较小，尤其是在 -0.65 V 下沉积的薄膜的磁化率更低。
{"title":"Influence of Potential and the Presence of Boric Acid on Pt1-xCox Alloy Electrodeposition and Magnetic Properties","authors":"Eric D. Rus, Eduardo L. Corrêa, Cindi L. Dennis, Thomas P. Moffat","doi":"10.1149/1945-7111/ad6b48","DOIUrl":"https://doi.org/10.1149/1945-7111/ad6b48","url":null,"abstract":"The effects of potential and the presence of B(OH)<sub>3</sub> on Pt<sub>1-x</sub>Co<sub>x</sub> alloy electrodeposition from aqueous chloride-based solutions on Ru substrates was investigated. Films deposited at potentials more reducing than −0.65 V vs SCE were hexagonal close packed and greater than 90% Co (mole basis), and films deposited at potentials more oxidizing than −0.65 V were face centered cubic and showed a monotonic decrease in cobalt content as the potential increased. The composition and structure-potential dependences were not strongly affected by the presence of B(OH)<sub>3</sub>. Structural change coincided with a distinct knee-like feature in the composition-potential relationship, along with a prominent narrow voltammetric peak associated with Co deposition, possibly related to nucleation and growth of the hcp phase. The presence of B(OH)<sub>3</sub> produced a sharp minimum in both Coulombic efficiency and deposition rate at potentials near −0.65 V and almost entirely suppressed the voltammetric feature. This may be associated with a combination of B(OH)<sub>3</sub>-derived proton reduction and inhibition of metal deposition by adsorbed B(OH)<sub>3</sub> or B(OH)<sub>3</sub>-derived species. The presence of B(OH)<sub>3</sub> affected the magnetic behavior of films deposited at potentials more oxidizing than −0.55 V (i.e., those with compositions less than about 40% Co) only weakly, but resulted in generally smaller maximum magnetizations for films deposited at more reducing potentials, and notably a much lower magnetization for films deposited at −0.65 V.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"5 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222478","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-23DOI: 10.1149/1945-7111/ad6eb8
Wassila Sefari, Ali Zazoua, Helim Rabiaa, Hafsa Korri-Youssoufi
Bisphenol A is a widely used endocrine disruptor known for its toxicity and prevalence in the environment. It contaminates drinking water, especially when plastic bottles are exposed to Sunlight. Rapid, on-site detection of BPA in drinking water is crucial for protecting human health and the environment. Herein, we developed an electrochemical sensor for detecting and monitoring bisphenol A in water bodies utilizing biobased materials. The device uses a biopolymeric membrane with agarose and gelified green tea tannins (GT/Agar). A sensitive part was made using this natural composite due to its high ability to attach bisphenol A to tannin monomers. Green tea tannins were purified and characterized through HPLC, FTIR, SEM, and AFM. The electrochemical activity of the GT-Agar/Au sensor is also evaluated by electrochemical impedance spectroscopy, cyclic voltammetry, square wave voltammetry and scan rate. Based on its redox signal under the optimal experimental conditions, this sensor has a detection range of 10−16 M to 10−4 M, a limit of detection of 1.52 to 10−17 M and very high selectivity. The proposed sensor successfully determined BPA levels from ultra-trace concentrations in bottled water samples, achieving satisfactory recovery rates. Compared to the results obtained using HPLC, it demonstrates high reliability.
双酚 A 是一种广泛使用的内分泌干扰物，以其毒性和在环境中的普遍存在而闻名。它污染饮用水，尤其是当塑料瓶暴露在阳光下时。快速现场检测饮用水中的双酚 A 对保护人类健康和环境至关重要。在此，我们利用生物基材料开发了一种用于检测和监测水体中双酚 A 的电化学传感器。该装置使用了含有琼脂糖和凝胶绿茶单宁（GT/Agar）的生物高分子膜。由于这种天然复合材料具有很强的将双酚 A 附着在单宁酸单体上的能力，因此使用这种天然复合材料制作了一个敏感部位。对绿茶单宁进行了纯化，并通过 HPLC、傅立叶变换红外光谱、扫描电镜和原子力显微镜对其进行了表征。还通过电化学阻抗谱、循环伏安法、方波伏安法和扫描速率评估了 GT-Agar/Au 传感器的电化学活性。根据其在最佳实验条件下的氧化还原信号，该传感器的检测范围为 10-16 M 至 10-4 M，检测限为 1.52 至 10-17 M，并具有极高的选择性。该传感器成功测定了瓶装水样品中超痕量浓度的双酚 A 含量，回收率令人满意。与使用高效液相色谱法得出的结果相比，它具有很高的可靠性。
{"title":"Bio-Based Materials for Electrochemical Detection of Bisphenol A","authors":"Wassila Sefari, Ali Zazoua, Helim Rabiaa, Hafsa Korri-Youssoufi","doi":"10.1149/1945-7111/ad6eb8","DOIUrl":"https://doi.org/10.1149/1945-7111/ad6eb8","url":null,"abstract":"Bisphenol A is a widely used endocrine disruptor known for its toxicity and prevalence in the environment. It contaminates drinking water, especially when plastic bottles are exposed to Sunlight. Rapid, on-site detection of BPA in drinking water is crucial for protecting human health and the environment. Herein, we developed an electrochemical sensor for detecting and monitoring bisphenol A in water bodies utilizing biobased materials. The device uses a biopolymeric membrane with agarose and gelified green tea tannins (GT/Agar). A sensitive part was made using this natural composite due to its high ability to attach bisphenol A to tannin monomers. Green tea tannins were purified and characterized through HPLC, FTIR, SEM, and AFM. The electrochemical activity of the GT-Agar/Au sensor is also evaluated by electrochemical impedance spectroscopy, cyclic voltammetry, square wave voltammetry and scan rate. Based on its redox signal under the optimal experimental conditions, this sensor has a detection range of 10<sup>−16 </sup>M to 10<sup>−4 </sup>M, a limit of detection of 1.52 to 10<sup>−17 </sup>M and very high selectivity. The proposed sensor successfully determined BPA levels from ultra-trace concentrations in bottled water samples, achieving satisfactory recovery rates. Compared to the results obtained using HPLC, it demonstrates high reliability.<inline-formula>\u0000<inline-graphic xlink:href=\"jesad6eb8-ga.jpg\" xlink:type=\"simple\"></inline-graphic>\u0000</inline-formula>","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"99 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222471","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-08DOI: 10.1149/1945-7111/ad6936
J. Alberto Barreras-Uruchurtu, Nicolas Besnard, Clément Paul, Lauréline Marchal, Samuel Devisme and Bernard Lestriez
We used electrostatic dry spray-coating to fabricate graphite/PVdF anodes. We compared the morphological, mechanical, electrical, and electrochemical properties of electrodes fabricated with three different mixing times of dry electrode components. Quantitative and novel relationships between the PVdF distribution and the electrode properties were obtained. Our investigations suggest that our fabrication methods are viable alternatives for producing electrodes with comparable properties to those fabricated using traditional wet solvent-based methods. Overall, our work provides insights into new and promising methods for fabricating high-quality dry-sprayed electrodes (DSEs) with high mass loadings for use in a variety of electrochemical applications such as electric vehicles.
{"title":"Effect of PVdF Distribution on Properties and Performance of Dry Spray-Coated Graphite Electrodes for Lithium-Ion Batteries for Electric Vehicle Applications","authors":"J. Alberto Barreras-Uruchurtu, Nicolas Besnard, Clément Paul, Lauréline Marchal, Samuel Devisme and Bernard Lestriez","doi":"10.1149/1945-7111/ad6936","DOIUrl":"https://doi.org/10.1149/1945-7111/ad6936","url":null,"abstract":"We used electrostatic dry spray-coating to fabricate graphite/PVdF anodes. We compared the morphological, mechanical, electrical, and electrochemical properties of electrodes fabricated with three different mixing times of dry electrode components. Quantitative and novel relationships between the PVdF distribution and the electrode properties were obtained. Our investigations suggest that our fabrication methods are viable alternatives for producing electrodes with comparable properties to those fabricated using traditional wet solvent-based methods. Overall, our work provides insights into new and promising methods for fabricating high-quality dry-sprayed electrodes (DSEs) with high mass loadings for use in a variety of electrochemical applications such as electric vehicles.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"10 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141942905","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-08DOI: 10.1149/1945-7111/ad68e4
Macgregor F. Macintosh, Mohsen Shakouri and M. N. Obrovac
Substitutional Li[Ni0.6Mn0.2Co0.2]O2 oxides (known as NMC622) were made by all-dry synthesis with Fe and Ti substituting Co and Mn, respectively. The substitutions were performed in three series, Fe substitution for Co, Ti substitution for Mn, and Fe and Ti co-substitution for Co and Mn, according to the formula Li(Ni0.6Mn0.2−yCo0.2−xFexTiy)O2. The resulting oxides were evaluated as cathode materials for Li-ion batteries. Fe-substitution for Co resulted in increased intersite mixing, resulting in increased polarization and capacity fade. Ti-substitution for Mn also resulted in increased intersite mixing, but the mixing was due to Ti3+ in the Li-layer. As a result, Ti-substituted NMCs had improved capacity retention and reduced polarization. These effects were independent of each other, so that Ti could partially offset the negative aspects of Fe-substitution. Additionally, layered Mn-free Li(Ni0.6Ti0.2Co0.2)O2 (NTC622) was produced as an endmember of this series for the first time with low intersite mixing and superior electrochemical performance in comparison to previous reports. These results demonstrate benefits of all-dry Ti-substitution in NMC and the all-dry synthesis method as an avenue towards new cathode composition discovery.
用全干法合成法制备了取代型 Li[Ni0.6Mn0.2Co0.2]O2 氧化物（又称 NMC622），其中 Fe 和 Ti 分别取代了 Co 和 Mn。按照 Li（Ni0.6Mn0.2-yCo0.2-xFexTiy）O2 的公式，分别用 Fe 替代 Co、Ti 替代 Mn 以及 Fe 和 Ti 共同替代 Co 和 Mn 三个系列进行了替代。所得氧化物被评估为锂离子电池的阴极材料。用 Fe 替代 Co 增加了位点间的混合，从而增加了极化和容量衰减。用钛代替锰也会导致晶间混合增加，但这种混合是由于锂层中的 Ti3+ 造成的。因此，以钛替代锰的 NMC 提高了容量保持率并降低了极化。这些影响是相互独立的，因此钛可以部分抵消铁取代的负面影响。此外，作为该系列的末端成员，首次制备出了层状无锰 Li（Ni0.6Ti0.2Co0.2）O2（NTC622），与之前的报告相比，它具有较低的位间混合和优异的电化学性能。这些结果表明了全干法钛替代在 NMC 中的优势，以及全干法合成方法是发现新阴极成分的一种途径。
{"title":"Isovalent Co-Substitution of Iron and Titanium into Single-Crystal NMC622","authors":"Macgregor F. Macintosh, Mohsen Shakouri and M. N. Obrovac","doi":"10.1149/1945-7111/ad68e4","DOIUrl":"https://doi.org/10.1149/1945-7111/ad68e4","url":null,"abstract":"Substitutional Li[Ni0.6Mn0.2Co0.2]O2 oxides (known as NMC622) were made by all-dry synthesis with Fe and Ti substituting Co and Mn, respectively. The substitutions were performed in three series, Fe substitution for Co, Ti substitution for Mn, and Fe and Ti co-substitution for Co and Mn, according to the formula Li(Ni0.6Mn0.2−yCo0.2−xFexTiy)O2. The resulting oxides were evaluated as cathode materials for Li-ion batteries. Fe-substitution for Co resulted in increased intersite mixing, resulting in increased polarization and capacity fade. Ti-substitution for Mn also resulted in increased intersite mixing, but the mixing was due to Ti3+ in the Li-layer. As a result, Ti-substituted NMCs had improved capacity retention and reduced polarization. These effects were independent of each other, so that Ti could partially offset the negative aspects of Fe-substitution. Additionally, layered Mn-free Li(Ni0.6Ti0.2Co0.2)O2 (NTC622) was produced as an endmember of this series for the first time with low intersite mixing and superior electrochemical performance in comparison to previous reports. These results demonstrate benefits of all-dry Ti-substitution in NMC and the all-dry synthesis method as an avenue towards new cathode composition discovery.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"373 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141942901","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-07DOI: 10.1149/1945-7111/ad6939
Rodney LaFollette and Michael D. Eskra
It is often observed that some runaway Li-ion cells with layered cathode materials become much hotter internally than existing thermal runaway models predict. Further, metals originally in the positive active material (such as Co, Ni, and Mn) are often found in cells whose temperatures became very high. It has been postulated that the formation of metals can be attributed to reduction of rock salt species (MO, where M is the metal), or the reaction of lithiated active material (LiMO2) with CO2. We propose an alternate process for formation of metals that also results in very high cell temperatures, namely thermite reactions between the Al positive electrode current collector and the positive active material. These reactions are highly exothermic, in contrast with the reactions of MO and LiMO2 mentioned. In this paper the thermodynamics of thermite reactions are presented. Incorporating thermite reactions in runaway models will likely improve temperature prediction of Li-ion cells in thermal runaway.
人们经常发现，一些采用层状阴极材料的失控锂离子电池的内部温度比现有热失控模型预测的温度要高得多。此外，在温度变得非常高的电池中，经常会发现原本存在于正极活性材料中的金属（如钴、镍和锰）。据推测，金属的形成可归因于岩盐物种（MO，其中 M 为金属）的还原，或锂化活性材料（LiMO2）与二氧化碳的反应。我们提出了另一种金属形成过程，它也会导致极高的电池温度，即铝正极集流器与正极活性材料之间的热反应。这些反应的放热程度很高，与上述 MO 和 LiMO2 反应形成鲜明对比。本文介绍了热释电反应的热力学。将热亚硝酸盐反应纳入失控模型可能会改善热失控锂离子电池的温度预测。
{"title":"The Possible Role of Thermite Reactions in Thermal Runaway of Li-ion Cells with Layered Cathodes","authors":"Rodney LaFollette and Michael D. Eskra","doi":"10.1149/1945-7111/ad6939","DOIUrl":"https://doi.org/10.1149/1945-7111/ad6939","url":null,"abstract":"It is often observed that some runaway Li-ion cells with layered cathode materials become much hotter internally than existing thermal runaway models predict. Further, metals originally in the positive active material (such as Co, Ni, and Mn) are often found in cells whose temperatures became very high. It has been postulated that the formation of metals can be attributed to reduction of rock salt species (MO, where M is the metal), or the reaction of lithiated active material (LiMO2) with CO2. We propose an alternate process for formation of metals that also results in very high cell temperatures, namely thermite reactions between the Al positive electrode current collector and the positive active material. These reactions are highly exothermic, in contrast with the reactions of MO and LiMO2 mentioned. In this paper the thermodynamics of thermite reactions are presented. Incorporating thermite reactions in runaway models will likely improve temperature prediction of Li-ion cells in thermal runaway.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"26 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141942904","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-07DOI: 10.1149/1945-7111/ad6938
Wolfgang G. Bessler
Capacity and internal resistance are key properties of batteries determining energy content and power capability. We present a novel algorithm for estimating the absolute values of capacity and internal resistance from voltage and current data. The algorithm is based on voltage-controlled models. Experimentally-measured voltage is used as an input variable to an equivalent circuit model. The simulation gives current as output, which is compared to the experimentally-measured current. We show that capacity loss and resistance increase lead to characteristic fingerprints in the current output of the simulation. In order to exploit these fingerprints, a theory is developed for calculating capacity and resistance from the difference between simulated and measured current. The findings are cast into an algorithm for operando diagnosis of batteries operated with arbitrary load profiles. The algorithm is demonstrated using cycling data from lithium-ion pouch cells operated on full cycles, shallow cycles, and dynamic cycles typical for electric vehicles. Capacity and internal resistance of a “fresh” cell was estimated with high accuracy (mean absolute errors of 0.9% and 1.8%, respectively). For an “aged” cell, the algorithm required adaptation of the model’s open-circuit voltage curve to obtain high accuracies. Highlights Operando diagnosis of capacity and internal resistance of rechargeable batteries. Novel algorithm developed, validated and demonstrated. Use of voltage-controlled models: Voltage as input, current as output. High accuracy achieved for dynamic operation of an NMC-LMO/graphite pouch cell.
{"title":"Capacity and Resistance Diagnosis of Batteries with Voltage-Controlled Models","authors":"Wolfgang G. Bessler","doi":"10.1149/1945-7111/ad6938","DOIUrl":"https://doi.org/10.1149/1945-7111/ad6938","url":null,"abstract":"Capacity and internal resistance are key properties of batteries determining energy content and power capability. We present a novel algorithm for estimating the absolute values of capacity and internal resistance from voltage and current data. The algorithm is based on voltage-controlled models. Experimentally-measured voltage is used as an input variable to an equivalent circuit model. The simulation gives current as output, which is compared to the experimentally-measured current. We show that capacity loss and resistance increase lead to characteristic fingerprints in the current output of the simulation. In order to exploit these fingerprints, a theory is developed for calculating capacity and resistance from the difference between simulated and measured current. The findings are cast into an algorithm for operando diagnosis of batteries operated with arbitrary load profiles. The algorithm is demonstrated using cycling data from lithium-ion pouch cells operated on full cycles, shallow cycles, and dynamic cycles typical for electric vehicles. Capacity and internal resistance of a “fresh” cell was estimated with high accuracy (mean absolute errors of 0.9% and 1.8%, respectively). For an “aged” cell, the algorithm required adaptation of the model’s open-circuit voltage curve to obtain high accuracies. Highlights Operando diagnosis of capacity and internal resistance of rechargeable batteries. Novel algorithm developed, validated and demonstrated. Use of voltage-controlled models: Voltage as input, current as output. High accuracy achieved for dynamic operation of an NMC-LMO/graphite pouch cell.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"16 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141942902","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-07DOI: 10.1149/1945-7111/ad68a9
Julian Knorr, Jiahao Li, Maximilian Schamel, Thomas Kufner, Alexander Adam and Michael A. Danzer
The energy density of lithium-ion batteries can be improved by adding silicon as a secondary active anode material alongside graphite. However, accurate state estimation of batteries with blend electrodes requires detailed knowledge of the interplay between the active materials during lithiation. Challenges arise from the current split between the active materials and the overlap of their working potentials. This study examines the lithiation behavior of blend anodes using a setup consisting of a pure graphite and a pure SiOx half-cell connected in parallel. The setup allows for current measurements of both active materials, the determination of the state of lithiation throughout the entire charging process and measurements of balancing effects between the active materials during relaxation periods. Analysis of the behavior at increased charge rates results in greater SiOx lithiation after similar charge throughput indicating better kinetics for SiOx compared to graphite. A Doyle-Fuller-Newman model of a blend anode is used to further investigate the experimental findings on the lithiation behavior and transfer them to blend electrodes. Simulation-based variations of the silicon content show that an increased SiOx content in blend anodes leads to improved rate capability.
{"title":"Active Material Lithiation in Gr/SiOx Blend Anodes at Increased C-Rates","authors":"Julian Knorr, Jiahao Li, Maximilian Schamel, Thomas Kufner, Alexander Adam and Michael A. Danzer","doi":"10.1149/1945-7111/ad68a9","DOIUrl":"https://doi.org/10.1149/1945-7111/ad68a9","url":null,"abstract":"The energy density of lithium-ion batteries can be improved by adding silicon as a secondary active anode material alongside graphite. However, accurate state estimation of batteries with blend electrodes requires detailed knowledge of the interplay between the active materials during lithiation. Challenges arise from the current split between the active materials and the overlap of their working potentials. This study examines the lithiation behavior of blend anodes using a setup consisting of a pure graphite and a pure SiOx half-cell connected in parallel. The setup allows for current measurements of both active materials, the determination of the state of lithiation throughout the entire charging process and measurements of balancing effects between the active materials during relaxation periods. Analysis of the behavior at increased charge rates results in greater SiOx lithiation after similar charge throughput indicating better kinetics for SiOx compared to graphite. A Doyle-Fuller-Newman model of a blend anode is used to further investigate the experimental findings on the lithiation behavior and transfer them to blend electrodes. Simulation-based variations of the silicon content show that an increased SiOx content in blend anodes leads to improved rate capability.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"70 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141942900","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-07DOI: 10.1149/1945-7111/ad68a8
Timon Scharmann, Canel Özcelikman, Do Minh Nguyen, Carina Amata Heck, Christian Wacker, Peter Michalowski, Arno Kwade and Klaus Dröder
All-solid-state batteries (ASSBs), defined through a solid electrolyte, are emerging as a promising solution to address current challenges in energy and power density demands for electromobility. Within the various possible types of solid electrolytes, sulfide-based materials exhibit advantageous high ionic conductivities. However, due to the strong reactivity of sulfides, atmospheric exposure can lead to the formation of toxic hydrogen sulfide and additionally negatively impact the resulting battery performance. Both factors present key challenges for ASSB production, as they necessitate the development of a material-adapted, economically viable and safe process atmosphere. In the present study, the influence of different production atmospheres on sulfide-based solid electrolytes is experimentally investigated. For this purpose, sulfide sheets are exposed to defined atmospheres with dynamic air fluctuations at dew points ranging from −60 °C to 0 °C. The resulting ionic conductivities indicate a dependency on the prevailing dew point and exposure time with a discernible impact on performance even at dew points of −60 °C within atmospheres with constant air circulation. With the acquired results, a detailed and knowledge-based selection and design of dry room production atmospheres for ASSB cell assembly is possible, which is a necessary step for further industrialization.
通过固体电解质定义的全固态电池（ASSB）正在成为一种有前途的解决方案，以应对当前电动汽车在能量和功率密度需求方面的挑战。在各种可能的固态电解质类型中，硫化物基材料具有高离子电导率的优势。然而，由于硫化物具有很强的反应性，暴露在大气中会形成有毒的硫化氢，从而对电池性能产生负面影响。这两个因素都对 ASSB 的生产提出了关键挑战，因为它们要求开发一种与材料相适应、经济上可行且安全的工艺气氛。本研究通过实验研究了不同生产气氛对硫化物固体电解质的影响。为此，硫化片暴露在露点为 -60 °C 至 0 °C 的具有动态空气波动的特定气氛中。结果表明，离子电导率与当时的露点和暴露时间有关，即使在露点为-60 °C、空气循环恒定的环境中，离子电导率也会对性能产生明显影响。有了这些结果，就可以根据知识详细选择和设计用于 ASSB 电池组装的干燥室生产环境，这是进一步工业化的必要步骤。
{"title":"Atmospheric Influences on Li6PS5Cl Separators and the Resulting Ionic Conductivity for All-Solid-State Batteries","authors":"Timon Scharmann, Canel Özcelikman, Do Minh Nguyen, Carina Amata Heck, Christian Wacker, Peter Michalowski, Arno Kwade and Klaus Dröder","doi":"10.1149/1945-7111/ad68a8","DOIUrl":"https://doi.org/10.1149/1945-7111/ad68a8","url":null,"abstract":"All-solid-state batteries (ASSBs), defined through a solid electrolyte, are emerging as a promising solution to address current challenges in energy and power density demands for electromobility. Within the various possible types of solid electrolytes, sulfide-based materials exhibit advantageous high ionic conductivities. However, due to the strong reactivity of sulfides, atmospheric exposure can lead to the formation of toxic hydrogen sulfide and additionally negatively impact the resulting battery performance. Both factors present key challenges for ASSB production, as they necessitate the development of a material-adapted, economically viable and safe process atmosphere. In the present study, the influence of different production atmospheres on sulfide-based solid electrolytes is experimentally investigated. For this purpose, sulfide sheets are exposed to defined atmospheres with dynamic air fluctuations at dew points ranging from −60 °C to 0 °C. The resulting ionic conductivities indicate a dependency on the prevailing dew point and exposure time with a discernible impact on performance even at dew points of −60 °C within atmospheres with constant air circulation. With the acquired results, a detailed and knowledge-based selection and design of dry room production atmospheres for ASSB cell assembly is possible, which is a necessary step for further industrialization.","PeriodicalId":17364,"journal":{"name":"Journal of The Electrochemical Society","volume":"70 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141942908","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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