Pub Date : 2024-07-16DOI: 10.1149/1945-7111/ad63d3
Rupan Das Chakraborty, J. P. Grace, Kiran Kumar Garlapati, S. Martha
Conversion type ternary NiCo2S4, exhibiting high electrical conductivity (~1.25 × 106 S m-1) and high theoretical capacity (703 mAh g-1), has gained interest as an anode material for sodium-ion batteries (SIBs). Despite its potential, NiCo2S4 (NCS) has extensive volume expansion during cycling. This study introduces the NCS-multi-walled carbon nanotube (MWCNT) onto a carbon fiber (CF) electrode (NCS and NCS-MWCNT@CF), developed through electrodeposition, which addresses these limitations. The unique sheet-like morphology of NCS, featuring abundant pores, ensures good access to the electrolyte. Incorporating a three-dimensional conductive CF framework that acts as a free-standing current collector helps prevent the agglomeration of NCS particles and mitigates volume expansion by providing enough buffer space in the layers of the CF matrix. Our findings reveal that NCS on CF electrodes deliver a second cycle capacity of 620 mA g-1 at 30 mA g-1 and retain 72 % capacity after 200 cycles. At 200 mA g-1, the NCS@CF electrodes deliver 378 mAh g-1 in the second cycle with 68% capacity retention in the 200th cycle, whereas NCS-MWCNT@CF delivers 538 mAh g-1 at 200 mA g-1, maintaining 86 % capacity after 100 cycles, making it a potential anode for SIBs.
转化型三元镍钴硅(NiCo2S4)具有高导电性（约 1.25 × 106 S m-1）和高理论容量（703 mAh g-1），作为钠离子电池（SIB）的负极材料已引起人们的兴趣。尽管镍钴锰酸锂 (NCS) 潜力巨大，但在循环过程中会产生大量体积膨胀。本研究介绍了通过电沉积在碳纤维（CF）电极（NCS 和 NCS-MWCNT@CF）上开发的 NCS-多壁碳纳米管（MWCNT），从而解决了这些局限性。NCS 独特的片状形态具有丰富的孔隙，可确保电解质的良好进入。三维导电 CF 框架可充当独立的电流收集器，有助于防止 NCS 颗粒聚集，并通过在 CF 基质层中提供足够的缓冲空间来缓解体积膨胀。我们的研究结果表明，CF 电极上的 NCS 在 30 mA g-1 电流条件下可提供 620 mA g-1 的二次循环容量，并在 200 次循环后保持 72% 的容量。在 200 mA g-1 的条件下，NCS@CF 电极在第二个循环中的容量为 378 mAh g-1，在第 200 个循环中的容量保持率为 68%，而 NCS-MWCNT@CF 在 200 mA g-1 的条件下的容量为 538 mAh g-1，在 100 个循环后的容量保持率为 86%，使其成为 SIB 的潜在阳极。
{"title":"Binderless Electrodeposited NiCo2S4-MWCNT as a Potential Anode Material for Sodium-Ion Batteries","authors":"Rupan Das Chakraborty, J. P. Grace, Kiran Kumar Garlapati, S. Martha","doi":"10.1149/1945-7111/ad63d3","DOIUrl":"https://doi.org/10.1149/1945-7111/ad63d3","url":null,"abstract":"\u0000 Conversion type ternary NiCo2S4, exhibiting high electrical conductivity (~1.25 × 106 S m-1) and high theoretical capacity (703 mAh g-1), has gained interest as an anode material for sodium-ion batteries (SIBs). Despite its potential, NiCo2S4 (NCS) has extensive volume expansion during cycling. This study introduces the NCS-multi-walled carbon nanotube (MWCNT) onto a carbon fiber (CF) electrode (NCS and NCS-MWCNT@CF), developed through electrodeposition, which addresses these limitations. The unique sheet-like morphology of NCS, featuring abundant pores, ensures good access to the electrolyte. Incorporating a three-dimensional conductive CF framework that acts as a free-standing current collector helps prevent the agglomeration of NCS particles and mitigates volume expansion by providing enough buffer space in the layers of the CF matrix. Our findings reveal that NCS on CF electrodes deliver a second cycle capacity of 620 mA g-1 at 30 mA g-1 and retain 72 % capacity after 200 cycles. At 200 mA g-1, the NCS@CF electrodes deliver 378 mAh g-1 in the second cycle with 68% capacity retention in the 200th cycle, whereas NCS-MWCNT@CF delivers 538 mAh g-1 at 200 mA g-1, maintaining 86 % capacity after 100 cycles, making it a potential anode for SIBs.","PeriodicalId":509718,"journal":{"name":"Journal of The Electrochemical Society","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141642241","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-16DOI: 10.1149/1945-7111/ad63cc
Caitlin D. Parke, Kailot C Harris, Xiyue Zhang, Minsung Baek, Chunsheng Wang, P. Albertus
Li//CFx cells have achieved the highest specific energy of commercial batteries, but new applications requiring higher rates (e.g., C/3) and pulsing (e.g., at 5C/3 rate for 1 min) drive the push for higher energy and power densities. A capacity-contributing electrolyte (CCE) can provide additional capacity at a slightly lower potential than the CFx reaction, increasing cell specific energy. In this work we present a 0D transient model of a primary Li/CFx cell with a CCE composed of both a salt and solvent that provide capacity with a focus on a C/3 rate and pulsing. Novel aspects of our model, in addition to the two CCE reactions, include a variable cathode thickness and porosity (CFx cathode thickness has been measured to expand by >40% at 25°C) and a detailed presentation of the transient evolution of all species and terms that contribute to cell potential (including how salt and solvent reactions affect ionic polarization and the growth of solid-phase product resistances). Our work quantifies the delicate balance of thermodynamic, kinetic, and transport processes and properties that is needed to obtain specific energy enhancements from CCE reactions, and how changing cathode thickness and porosity affect the mechanisms that cause the end of discharge.
{"title":"Modeling a High-Energy, High-Rate Li//CFx Battery with a Capacity-Contributing Electrolyte","authors":"Caitlin D. Parke, Kailot C Harris, Xiyue Zhang, Minsung Baek, Chunsheng Wang, P. Albertus","doi":"10.1149/1945-7111/ad63cc","DOIUrl":"https://doi.org/10.1149/1945-7111/ad63cc","url":null,"abstract":"\u0000 Li//CFx cells have achieved the highest specific energy of commercial batteries, but new applications requiring higher rates (e.g., C/3) and pulsing (e.g., at 5C/3 rate for 1 min) drive the push for higher energy and power densities. A capacity-contributing electrolyte (CCE) can provide additional capacity at a slightly lower potential than the CFx reaction, increasing cell specific energy. In this work we present a 0D transient model of a primary Li/CFx cell with a CCE composed of both a salt and solvent that provide capacity with a focus on a C/3 rate and pulsing. Novel aspects of our model, in addition to the two CCE reactions, include a variable cathode thickness and porosity (CFx cathode thickness has been measured to expand by >40% at 25°C) and a detailed presentation of the transient evolution of all species and terms that contribute to cell potential (including how salt and solvent reactions affect ionic polarization and the growth of solid-phase product resistances). Our work quantifies the delicate balance of thermodynamic, kinetic, and transport processes and properties that is needed to obtain specific energy enhancements from CCE reactions, and how changing cathode thickness and porosity affect the mechanisms that cause the end of discharge.","PeriodicalId":509718,"journal":{"name":"Journal of The Electrochemical Society","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141643906","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-16DOI: 10.1149/1945-7111/ad63ce
Jinwook Rhyu, D. Zhuang, M. Bazant, R. D. Braatz
Diagnostics of lithium-ion batteries are frequently performed in battery management systems for optimized operation of lithium-ion batteries or for second-life usage. However, attempting to extract dominant degradation information requires long rest times between diagnostic pulses, which compete with the need for efficient diagnostics. Here, we design a set of efficient optimal hybrid pulse power characterization (HPPC) diagnostics using model-based design of experiment (DOE) methods, applying knowledge of degradation effects on pulse kinetics and cell properties. We validate that these protocols are effective through minimization of uncertainty, and robust with Markov Chain Monte Carlo (MCMC) simulations. Contrary to traditional HPPC diagnostics which use fixed pulse magnitudes at uniformly distributed state of charges (SOC), we find that well-designed HPPC protocols using our framework outperform traditional protocols in terms of minimizing both parametric uncertainties and diagnostic time. Trade-offs between minimizing parametric uncertainty and total diagnostic time can be made based on different diagnostics needs.
{"title":"Optimum Model-Based Design of Diagnostics Experiments (DOE) with Hybrid Pulse Power Characterization (HPPC) for Lithium-Ion Batteries","authors":"Jinwook Rhyu, D. Zhuang, M. Bazant, R. D. Braatz","doi":"10.1149/1945-7111/ad63ce","DOIUrl":"https://doi.org/10.1149/1945-7111/ad63ce","url":null,"abstract":"\u0000 Diagnostics of lithium-ion batteries are frequently performed in battery management systems for optimized operation of lithium-ion batteries or for second-life usage. However, attempting to extract dominant degradation information requires long rest times between diagnostic pulses, which compete with the need for efficient diagnostics. Here, we design a set of efficient optimal hybrid pulse power characterization (HPPC) diagnostics using model-based design of experiment (DOE) methods, applying knowledge of degradation effects on pulse kinetics and cell properties. We validate that these protocols are effective through minimization of uncertainty, and robust with Markov Chain Monte Carlo (MCMC) simulations. Contrary to traditional HPPC diagnostics which use fixed pulse magnitudes at uniformly distributed state of charges (SOC), we find that well-designed HPPC protocols using our framework outperform traditional protocols in terms of minimizing both parametric uncertainties and diagnostic time. Trade-offs between minimizing parametric uncertainty and total diagnostic time can be made based on different diagnostics needs.","PeriodicalId":509718,"journal":{"name":"Journal of The Electrochemical Society","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141643050","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The development of composite electrolytes for all-solid-state batteries is an emerging field, but the creation of predominantly inorganic electrolytes remains challenging. In this study, Li6.25Al0.25La3Zr2O12 (Al-LLZO), a ceramic material selected for its high ionic conductivity (1x104 S.cm-1 at ambient temperature) was shaped by the cold-sintering process (CSP). The organic phase was synthesized by free-radical polymerization of two poly(ethylene oxide) methacrylate derivatives in the presence of lithium bis(trifluoromethanesulfonyl)imide salts (LiTFSI). The polymethacrylate network with dangling poly(ethylene oxide) (PEO) chains was thus obtained. This in-situ polymerization allows the one-pot synthesis of the composite electrolyte during CSP. Remarkably, the ionic conductivity of the CSP pellet varied with the nature of the organic phase, ranging from 1x10−4 to 1x10−5 S.cm-1 for non-grafted and grafted TFSI anion on the PEO-based network, respectively. Additionally, the transport of Li+ remained unaffected by the inorganic material's nature as long as it contained Li species. Furthermore, a significant enhancement of the ionic conductivity was observed in the composite pellet compared to the TFSI grafted network (10−5 to 10−7 S.cm-1, respectively). Electrochemical impedance spectroscopy measurements revealed changes in the Al-LLZOPEO-based polymer interface during CSP with the formation of an interphase, confirmed by a low activation energy value (0.1 eV).
{"title":"Harnessing Cold Sintering to Fabricate Composite Polymer Electrolytes - A Paradigm Shift in Organic-Inorganic Material Assembly","authors":"Agathe Naboulsi, Thibaut Dussart, Sylvain Franger, Odile Fichet, Giao Nguyen, C. Laberty‐Robert","doi":"10.1149/1945-7111/ad63cd","DOIUrl":"https://doi.org/10.1149/1945-7111/ad63cd","url":null,"abstract":"\u0000 The development of composite electrolytes for all-solid-state batteries is an emerging field, but the creation of predominantly inorganic electrolytes remains challenging. In this study, Li6.25Al0.25La3Zr2O12 (Al-LLZO), a ceramic material selected for its high ionic conductivity (1x104 S.cm-1 at ambient temperature) was shaped by the cold-sintering process (CSP). The organic phase was synthesized by free-radical polymerization of two poly(ethylene oxide) methacrylate derivatives in the presence of lithium bis(trifluoromethanesulfonyl)imide salts (LiTFSI). The polymethacrylate network with dangling poly(ethylene oxide) (PEO) chains was thus obtained. This in-situ polymerization allows the one-pot synthesis of the composite electrolyte during CSP. Remarkably, the ionic conductivity of the CSP pellet varied with the nature of the organic phase, ranging from 1x10−4 to 1x10−5 S.cm-1 for non-grafted and grafted TFSI anion on the PEO-based network, respectively. Additionally, the transport of Li+ remained unaffected by the inorganic material's nature as long as it contained Li species. Furthermore, a significant enhancement of the ionic conductivity was observed in the composite pellet compared to the TFSI grafted network (10−5 to 10−7 S.cm-1, respectively). Electrochemical impedance spectroscopy measurements revealed changes in the Al-LLZOPEO-based polymer interface during CSP with the formation of an interphase, confirmed by a low activation energy value (0.1 eV).","PeriodicalId":509718,"journal":{"name":"Journal of The Electrochemical Society","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141641478","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-16DOI: 10.1149/1945-7111/ad63d1
R. Kapaev, S. Chakrabarty, Ayan Mukherjee, Masato Sonoo, M. Noked
This work presents a mild, fast, and scalable approach for chemical presodiation of Na-ion battery cathodes employing a tunnel-type Na0.44MnO2 (NMO) as a model material to demonstrate its sodiation with sodium-phanazine solutions. After presodiation using this approach, there is an 80% increase in specific capacity and a 66% increase in specific energy of NMO in full cells with hard carbon anodes.
{"title":"Mild and Fast Chemical Presodiation of Na0.44MnO2","authors":"R. Kapaev, S. Chakrabarty, Ayan Mukherjee, Masato Sonoo, M. Noked","doi":"10.1149/1945-7111/ad63d1","DOIUrl":"https://doi.org/10.1149/1945-7111/ad63d1","url":null,"abstract":"\u0000 This work presents a mild, fast, and scalable approach for chemical presodiation of Na-ion battery cathodes employing a tunnel-type Na0.44MnO2 (NMO) as a model material to demonstrate its sodiation with sodium-phanazine solutions. After presodiation using this approach, there is an 80% increase in specific capacity and a 66% increase in specific energy of NMO in full cells with hard carbon anodes.","PeriodicalId":509718,"journal":{"name":"Journal of The Electrochemical Society","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141641582","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-16DOI: 10.1149/1945-7111/ad63d2
Sanil N, Shakila L, Arunkumar V, Kumaresan Radhakrishnan
Alloys of U with Ti are of importance in nuclear industry as fuel for Gen IV fast reactors, hydrogen isotope storage medium for fusion reactors, super conductors, and also as corrosion resistant material for use in various applications. Here, preparation of U2Ti intermetallic compound was investigated by the direct electrochemical reduction of mixed oxide of UO2-TiO2 in LiCl-0.5% Li2O molten salt at 650oC. The mixed oxide pellet of UO2-TiO2 sintered at 1500oC was found to be a mixture of UTi2O6 and UO2 as evidenced by X-ray diffraction (XRD) analysis. Direct electro-lithiothermic reduction of UO2, TiO2, and a mixture of sintered UO2-TiO2 and UTi2O6 coupled with cyclic voltammetry of these oxides in the melt was performed to understand the electro-reduction mechanism. Potentials of reduction of these oxides in the melt, w.r.t Ni/NiO reference electrode, obtained by analysis of CV data of these oxides contained in metallic cavity electrodes and XRD analysis of partially electro-reduced oxides were used to arrive at the electro-reduction mechanism. Results indicate that U2Ti can be prepared conveniently by the electro-lithiothermic reduction of sintered pellet of UO2-TiO2 cathode by constant current electrolysis in a two-electrode cell.
{"title":"Facile Synthesis of U2Ti Intermetallic by Direct Electrochemical Reduction of UO2-TiO2 Composite in LiCl-Li2O Melt","authors":"Sanil N, Shakila L, Arunkumar V, Kumaresan Radhakrishnan","doi":"10.1149/1945-7111/ad63d2","DOIUrl":"https://doi.org/10.1149/1945-7111/ad63d2","url":null,"abstract":"\u0000 Alloys of U with Ti are of importance in nuclear industry as fuel for Gen IV fast reactors, hydrogen isotope storage medium for fusion reactors, super conductors, and also as corrosion resistant material for use in various applications. Here, preparation of U2Ti intermetallic compound was investigated by the direct electrochemical reduction of mixed oxide of UO2-TiO2 in LiCl-0.5% Li2O molten salt at 650oC. The mixed oxide pellet of UO2-TiO2 sintered at 1500oC was found to be a mixture of UTi2O6 and UO2 as evidenced by X-ray diffraction (XRD) analysis. Direct electro-lithiothermic reduction of UO2, TiO2, and a mixture of sintered UO2-TiO2 and UTi2O6 coupled with cyclic voltammetry of these oxides in the melt was performed to understand the electro-reduction mechanism. Potentials of reduction of these oxides in the melt, w.r.t Ni/NiO reference electrode, obtained by analysis of CV data of these oxides contained in metallic cavity electrodes and XRD analysis of partially electro-reduced oxides were used to arrive at the electro-reduction mechanism. Results indicate that U2Ti can be prepared conveniently by the electro-lithiothermic reduction of sintered pellet of UO2-TiO2 cathode by constant current electrolysis in a two-electrode cell.","PeriodicalId":509718,"journal":{"name":"Journal of The Electrochemical Society","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141642235","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-16DOI: 10.1149/1945-7111/ad63cf
M. F. Ernst, Vivian Meier, Matthias Kornherr, H. Gasteiger
In this work, ≈25 µm thin titanium microporous layers (MPLs) with ≈2 µm small pores and low surface roughness were coated and sintered on top of ≈260 µm thick commercial titanium-powder-sinter sheets with ≈16 µm pores, maintaining a porosity of ≈40% in both layers. Serving as porous transport layers (PTLs) on the anode side in proton exchange membrane water electrolyzers (PEMWEs), these pore-graded, two-layer sheets (“PTL/MPL”) are compared to single-layer PTLs in single-cell PEMWEs. The PTL/MPL samples prepared here give a 3-6 mΩ cm² lower high-frequency resistance (HFR) compared to the as-received single-layer PTL, which is attributed to a partial reduction of the TiO2 surface passivation layer during the MPL sintering process. For ≈1 µm thin anodes with an iridium loading of ≈0.2 mgIr cm-2, the use of an MPL leads to a ≈24 mV improvement in HFR-free cell voltage at 6 A cm-2. As no such benefit is observed for ≈9 µm thick anodes with ≈2.0 mgIr cm 2, mass transport resistances within the PTL/MPL play a minor role. Possible reasons for the higher catalyst utilization in ultra-thin electrodes when using an MPL are discussed. Furthermore, an MPL provides superior mechanical membrane support, which is particularly relevant for thin membrane
{"title":"Preparation and Performance Evaluation of Microporous Transport Layers for Proton Exchange Membrane (PEM) Water Electrolyzer Anodes","authors":"M. F. Ernst, Vivian Meier, Matthias Kornherr, H. Gasteiger","doi":"10.1149/1945-7111/ad63cf","DOIUrl":"https://doi.org/10.1149/1945-7111/ad63cf","url":null,"abstract":"\u0000 In this work, ≈25 µm thin titanium microporous layers (MPLs) with ≈2 µm small pores and low surface roughness were coated and sintered on top of ≈260 µm thick commercial titanium-powder-sinter sheets with ≈16 µm pores, maintaining a porosity of ≈40% in both layers. Serving as porous transport layers (PTLs) on the anode side in proton exchange membrane water electrolyzers (PEMWEs), these pore-graded, two-layer sheets (“PTL/MPL”) are compared to single-layer PTLs in single-cell PEMWEs. The PTL/MPL samples prepared here give a 3-6 mΩ cm² lower high-frequency resistance (HFR) compared to the as-received single-layer PTL, which is attributed to a partial reduction of the TiO2 surface passivation layer during the MPL sintering process. For ≈1 µm thin anodes with an iridium loading of ≈0.2 mgIr cm-2, the use of an MPL leads to a ≈24 mV improvement in HFR-free cell voltage at 6 A cm-2. As no such benefit is observed for ≈9 µm thick anodes with ≈2.0 mgIr cm 2, mass transport resistances within the PTL/MPL play a minor role. Possible reasons for the higher catalyst utilization in ultra-thin electrodes when using an MPL are discussed. Furthermore, an MPL provides superior mechanical membrane support, which is particularly relevant for thin membrane","PeriodicalId":509718,"journal":{"name":"Journal of The Electrochemical Society","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141642694","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-16DOI: 10.1149/1945-7111/ad63d0
Yuya Sakka, Mao Matsumoto, H. Yamashige, Akihisa Takeuchi, M. Uesugi, K. Uesugi, Chengchao Zhong, Keiji Shimoda, Ken'ichi Okazaki, Yuki Orikasa
Si anodes in all-solid-state batteries are expected to achieve high energy density and durability because large volume changes in Si can be mechanically suppressed by the hardness of solid electrolytes. However, the effects of volume changes on the mechanical interface between Si and solid electrolytes during charge/discharge reactions have not been investigated. In this study, operando X-ray computed tomography was used to determine the microstructure of an all-solid-state battery comprising Si active materials and a solid sulfide electrolyte, Li10GeP2S12, during charge/discharge reactions. To evaluate the volume expansion/contraction effects on the charge/discharge properties, the tortuosity of the ion conduction path and the contact area fraction between Si and the solid electrolyte during the charge/discharge reactions were quantitatively estimated. Shell-shaped voids around the Si particles were observed after Si shrinkage owing to the plastic deformation of the solid electrolyte. This characteristic resulted in poor charge/discharge efficiency and incomplete delithiation in the battery. These results will facilitate the design optimization of Si composite electrodes, which will be highly beneficial to the development of effective all-solid-state batteries.
{"title":"Investigating Plastic Deformation Between Silicon and Solid Electrolyte in All-Solid-State Batteries Using Operando X-ray Tomography","authors":"Yuya Sakka, Mao Matsumoto, H. Yamashige, Akihisa Takeuchi, M. Uesugi, K. Uesugi, Chengchao Zhong, Keiji Shimoda, Ken'ichi Okazaki, Yuki Orikasa","doi":"10.1149/1945-7111/ad63d0","DOIUrl":"https://doi.org/10.1149/1945-7111/ad63d0","url":null,"abstract":"\u0000 Si anodes in all-solid-state batteries are expected to achieve high energy density and durability because large volume changes in Si can be mechanically suppressed by the hardness of solid electrolytes. However, the effects of volume changes on the mechanical interface between Si and solid electrolytes during charge/discharge reactions have not been investigated. In this study, operando X-ray computed tomography was used to determine the microstructure of an all-solid-state battery comprising Si active materials and a solid sulfide electrolyte, Li10GeP2S12, during charge/discharge reactions. To evaluate the volume expansion/contraction effects on the charge/discharge properties, the tortuosity of the ion conduction path and the contact area fraction between Si and the solid electrolyte during the charge/discharge reactions were quantitatively estimated. Shell-shaped voids around the Si particles were observed after Si shrinkage owing to the plastic deformation of the solid electrolyte. This characteristic resulted in poor charge/discharge efficiency and incomplete delithiation in the battery. These results will facilitate the design optimization of Si composite electrodes, which will be highly beneficial to the development of effective all-solid-state batteries.","PeriodicalId":509718,"journal":{"name":"Journal of The Electrochemical Society","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141641556","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-15DOI: 10.1149/1945-7111/ad6377
Tianjiao Zhu, Xiaoqian Hao, Yongan Cao, Yuqian Li, Wenju Wang
The application of lithium-sulfur (Li-S) batteries is impeded by the significant polysulfide shuttling phenomenon. Developing suitable anchoring material is an effective way to restrain this behavior. In this work, the anchoring performance of lithium polysulfide (LiPSs) on defective single-wall carbon nanotubes (DSWNT) is investigated by density functional theory. The results demonstrate that the DSWNT with three carbon vacancies (DSWNT-3) has the highest forming capacity and the strongest adsorption capacity, indicating it has the best anchoring effect of LiPSs. As the anchoring material of the cathode, DSWNT-3 has greater energy than solvent molecules to inhibit the dissolution of long-chain polysulfides. In general, DSWNT-3 demonstrates notable efficacy as an anchoring material for Li-S batteries, which establishes a theoretical foundation for exploring the anchoring characteristics of defects and their application in the cathode of Li-S batteries.
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Pub Date : 2024-07-15DOI: 10.1149/1945-7111/ad6376
Ankit Verma, Maxwell C. Schulze, Andrew M. Colclasure, Marco-Tulio F. Rodrigues, S. Trask, Krzysztof Pupek, Daniel P Abraham
Silicon-based lithium-ion batteries exhibit severe time-based degradation resulting in poor calendar lives. This has been identified as the major impediment towards commercialization with cycle life considered a solved issue through nanosizing and protective coatings allowing over 1000 cycles of life to be achieved. In this work, rapid screening of sixteen electrolytes for calendar life extension of Si-rich systems (70 wt% Si) is performed using the voltage hold (V-hold) protocol. V-hold significantly shortens the testing duration over the traditional open circuit voltage reference performance test allowing us to screen electrolytes within a span of two months. We find a novel ethylene carbonate (EC) free electrolyte formulation containing lithium hexafluorophosphate (LiPF6) salt, and binary solvent mix of fluoroethylene carbonate, ethyl methyl carbonate that extends calendar life of Si cells as compared to conventional EC based electrolyte. Our coupled experimental-theoretical analysis framework provides a decoupling of the parasitic currents during V-hold, allowing us to extrapolate the capacity loss to predict semiquantitative calendar lifetimes. Subsequently, cycle aging and oxidative stability tests of the EC free system also show enhanced performance over baseline electrolyte.
硅基锂离子电池表现出严重的时基降解，导致日历寿命较短。这已被认为是商业化的主要障碍，通过纳米化和保护涂层，循环寿命可达到 1000 次以上。在这项工作中，使用电压保持（V-hold）协议对十六种电解质进行了快速筛选，以延长富硅系统（70 wt% Si）的日历寿命。与传统的开路电压参考性能测试相比，电压保持大大缩短了测试时间，使我们能够在两个月的时间内筛选出电解质。我们发现了一种新型无碳酸乙烯酯（EC）电解质配方，其中含有六氟磷酸锂（LiPF6）盐以及氟乙烯碳酸酯和乙基甲基碳酸酯的二元混合溶剂，与传统的基于 EC 的电解质相比，它能延长硅电池的日历寿命。我们的实验-理论耦合分析框架提供了 V 保持期间寄生电流的解耦，使我们能够推断容量损失，从而预测半定量的日历寿命。随后，对不含导电率的系统进行的循环老化和氧化稳定性测试也表明，其性能比基线电解液有所提高。
{"title":"Significant Improvements to Si Calendar Lifetime Using Rapid Electrolyte Screening via Potentiostatic Holds","authors":"Ankit Verma, Maxwell C. Schulze, Andrew M. Colclasure, Marco-Tulio F. Rodrigues, S. Trask, Krzysztof Pupek, Daniel P Abraham","doi":"10.1149/1945-7111/ad6376","DOIUrl":"https://doi.org/10.1149/1945-7111/ad6376","url":null,"abstract":"\u0000 Silicon-based lithium-ion batteries exhibit severe time-based degradation resulting in poor calendar lives. This has been identified as the major impediment towards commercialization with cycle life considered a solved issue through nanosizing and protective coatings allowing over 1000 cycles of life to be achieved. In this work, rapid screening of sixteen electrolytes for calendar life extension of Si-rich systems (70 wt% Si) is performed using the voltage hold (V-hold) protocol. V-hold significantly shortens the testing duration over the traditional open circuit voltage reference performance test allowing us to screen electrolytes within a span of two months. We find a novel ethylene carbonate (EC) free electrolyte formulation containing lithium hexafluorophosphate (LiPF6) salt, and binary solvent mix of fluoroethylene carbonate, ethyl methyl carbonate that extends calendar life of Si cells as compared to conventional EC based electrolyte. Our coupled experimental-theoretical analysis framework provides a decoupling of the parasitic currents during V-hold, allowing us to extrapolate the capacity loss to predict semiquantitative calendar lifetimes. Subsequently, cycle aging and oxidative stability tests of the EC free system also show enhanced performance over baseline electrolyte.","PeriodicalId":509718,"journal":{"name":"Journal of The Electrochemical Society","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141649382","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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