{"title":"Enhancing micro-scale SiOx anode durability: Electro-mechanical strengthening of binder networks via anchoring carbon nanotubes with carboxymethyl cellulose","authors":"","doi":"10.1016/j.jechem.2024.09.037","DOIUrl":"10.1016/j.jechem.2024.09.037","url":null,"abstract":"<div><div>With the increasing prevalence of lithium-ion batteries (LIBs) applications, the demand for high-capacity next-generation materials has also increased. SiO<em><sub>x</sub></em> is currently considered a promising anode material due to its exceptionally high capacity for LIBs. However, the significant volumetric changes of SiO<em><sub>x</sub></em> during cycling and its initial Coulombic efficiency (ICE) complicate its use, whether alone or in combination with graphite materials. In this study, a three-dimensional conductive binder network with high electronic conductivity and robust elasticity for graphite/SiO<em><sub>x</sub></em> blended anodes was proposed by chemically anchoring carbon nanotubes and carboxymethyl cellulose binders using tannic acid as a chemical cross-linker. In addition, a dehydrogenation-based prelithiation strategy employing lithium hydride was utilized to enhance the ICE of SiO<em><sub>x</sub></em>. The combination of these two strategies increased the CE of SiO<em><sub>x</sub></em> from 74% to 87% and effectively mitigated its volume expansion in the graphite/SiO<em><sub>x</sub></em> blended electrode, resulting in an efficient electron-conductive binder network. This led to a remarkable capacity retention of 94% after 30 cycles, even under challenging conditions, with a high capacity of 550 mA h g<sup>−1</sup> and a current density of 4 mA cm<sup>−2</sup>. Furthermore, to validate the feasibility of utilizing prelithiated SiO<em><sub>x</sub></em> anode materials and the conductive binder network in LIBs, a full cell incorporating these materials and a single-crystalline Ni-rich cathode was used. This cell demonstrated a ∼27.3% increase in discharge capacity of the first cycle (∼185.7 mA h g<sup>−1</sup>) and exhibited a cycling stability of 300 cycles. Thus, this study reports a simple, feasible, and insightful method for designing high-performance LIB electrodes.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":null,"pages":null},"PeriodicalIF":13.1,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142530534","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Interface compatibility between sulfide solid electrolytes and Ni-rich oxide cathode materials: factors, modification, perspectives","authors":"","doi":"10.1016/j.jechem.2024.09.039","DOIUrl":"10.1016/j.jechem.2024.09.039","url":null,"abstract":"<div><div>All-solid-state batteries (ASSBs) assembled with sulfide solid electrolytes (SSEs) and nickel (Ni)-rich oxide cathode materials are expected to achieve high energy density and safety, representing potential candidates for the next-generation energy storage systems. However, interfacial issues between SSEs and Ni-rich oxide cathode materials, attributed to space charge layer, interfacial side reactions, and mechanical contact failure, significantly restrict the performances of ASSBs. The interface degradation is closely related to the components of the composite cathode and the process of electrode fabrication. Focusing on the influencing factors of interface compatibility between SSEs and Ni-rich oxide cathode, this article systematically discusses how cathode active materials (CAMs), electrolytes, conductive additives, binders, and electrode fabrication impact the interface compatibility. In addition, the strategies for the compatibility modification are reviewed. Furthermore, the challenges and prospects of intensive research on the degradation and modification of the SSE/Ni-rich cathode material interface are discussed. This review is intended to inspire the development of high-energy-density and high-safety all-solid-state batteries.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":null,"pages":null},"PeriodicalIF":13.1,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142530487","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Improving the reliability of classical molecular dynamics simulations in battery electrolyte design","authors":"","doi":"10.1016/j.jechem.2024.09.038","DOIUrl":"10.1016/j.jechem.2024.09.038","url":null,"abstract":"<div><div>Explorations into new electrolytes have highlighted the critical impact of solvation structure on battery performance. Classical molecular dynamics (CMD) using semi-empirical force fields has become an essential tool for simulating solvation structures. However, mainstream force fields often lack accuracy in describing strong ion-solvent interactions, causing disparities between CMD simulations and experimental observations. Although some empirical methods have been employed in some of the studies to address this issue, their effectiveness has been limited. Our CMD research, supported by quantum chemical calculations and experimental data, reveals that the solvation structure is influenced not only by the charge model but also by the polarization description. Previous empirical approaches that focused solely on adjusting ion-solvent interaction strengths overlooked the importance of polarization effects. Building on this insight, we propose integrating the Drude polarization model into mainstream force fields and verify its feasibility in carbonate, ether, and nitrile electrolytes. Our experimental results demonstrate that this approach significantly enhances the accuracy of CMD-simulated solvation structures. This work is expected to provide a more reliable CMD method for electrolyte design, shielding researchers from the pitfalls of erroneous simulation outcomes.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":null,"pages":null},"PeriodicalIF":13.1,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142530533","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Unveiling solid-solid contact states in all-solid-state lithium batteries: An electrochemical impedance spectroscopy viewpoint","authors":"","doi":"10.1016/j.jechem.2024.09.035","DOIUrl":"10.1016/j.jechem.2024.09.035","url":null,"abstract":"<div><div>All-solid-state lithium batteries (ASSLBs) are strongly considered as the next-generation energy storage devices for their high energy density and intrinsic safety. The solid-solid contact between lithium metal and solid electrolyte plays a vital role in the performance of working ASSLBs, which is challenging to investigate quantitatively by experimental approach. This work proposed a quantitative model based on the finite element method for electrochemical impedance spectroscopy simulation of different solid-solid contact states in ASSLBs. With the assistance of an equivalent circuit model and distribution of relaxation times, it is discovered that as the number of voids and the sharpness of cracks increase, the contact resistance <em>R</em><sub>c</sub> grows and ultimately dominates the battery impedance. Through accurate fitting, inverse proportional relations between contact resistance <em>R</em><sub>c</sub> and (1 − porosity) as well as crack angle was disclosed. This contribution affords a fresh insight into clarifying solid-solid contact states in ASSLBs.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":null,"pages":null},"PeriodicalIF":13.1,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142530535","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Synergistic enhancement of ion/electron transport by ultrafine nanoparticles and graphene in Li2FeTiO4/C/G nanofibers for symmetric Li-ion batteries","authors":"","doi":"10.1016/j.jechem.2024.09.031","DOIUrl":"10.1016/j.jechem.2024.09.031","url":null,"abstract":"<div><div>Low-cost Fe-based disordered rock salt (DRX) Li<sub>2</sub>FeTiO<sub>4</sub> is capable of providing high capacity (295 mA h g<sup>−1</sup>) by redox activity of cations (Fe<sup>2+</sup>/Fe<sup>4+</sup> and Ti<sup>3+</sup>/Ti<sup>4+</sup>) and anionic oxygen. However, DRX structures lack transport channels for ions and electrons, resulting in sluggish kinetics, poor electrochemical activity, and cyclability. Herein, graphene conductive carbon network permeated Li<sub>2</sub>FeTiO<sub>4</sub> (LFT/C/G) nanofibers are successfully prepared by a facile sol-gel assisted electrospinning method. Ultrafine Li<sub>2</sub>FeTiO<sub>4</sub> nanoparticles (2 nm) and one-dimensional (1D) structure provide abundant active sites and unobstructed diffusion channels, accelerating ion diffusion. In addition, introducing graphene reduces the band gap and Li<sup>+</sup> diffusion barrier and improves the dynamic properties of Li<sub>2</sub>FeTiO<sub>4</sub>, thus achieving a relatively mild interfacial reaction and reversible redox reaction. As expected, the LFT/C/1.0G cathode delivers a remarkable discharge capacity (238.5 mA h g<sup>−1</sup>), high energy density (508.8 Wh kg<sup>−1</sup>), and excellent rate capability (51.2 mA h g<sup>−1</sup> at 1.0 A g<sup>−1</sup>). Besides, the LFT/C/1.0G anode also displays a high capacity (514.5 mA h g<sup>−1</sup> at 500 mA g<sup>−1</sup>) and a remarkable rate capability (243.9 mA h g<sup>−1</sup> at 8 A g<sup>−1</sup>). Moreover, the full batteries based on the LFT/C/1.0G symmetric electrode demonstrate a reversible capacity of 117.0 mA h g<sup>−1</sup> after 100 cycles at 50 mA g<sup>−1</sup>. This study presents useful insights into developing cost-effective DRX cathodes with durable and fast lithium storage.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":null,"pages":null},"PeriodicalIF":13.1,"publicationDate":"2024-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142531068","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Nickel-copper alloying arrays realizing efficient co-electrosynthesis of adipic acid and hydrogen","authors":"","doi":"10.1016/j.jechem.2024.09.033","DOIUrl":"10.1016/j.jechem.2024.09.033","url":null,"abstract":"<div><div>Constructing electrocatalytic overall reaction technology to couple the electrosynthesis of adipic acid with energy-saving hydrogen production is of significant for sustainable energy systems. However, the development of highly-active bifunctional electrocatalysts remains a challenge. Herein, 3D hierarchical nickel-copper alloying arrays with dendritic morphology are manufactured by a simple electrodeposition process, standing for the excellent bifunctional electrocatalyst towards the co-production of adipic acid and H<sub>2</sub> from cyclohexanone and water. The membrane-free flow electrolyzer of Cu<sub>0.81</sub>Ni<sub>0.19</sub>/NF shows the superior electrooxidation performance of ketone-alcohol (KA) oil with high faradaic efficiencies of over 90% for adipic acid and H<sub>2</sub>, robust stability over 200 h as well as a high yield of 0.6 mmol h<sup>−1</sup> for adipic acid at 100 mA cm<sup>−2</sup>. In-situ spectroscopy indicates the Cu<sub>0.81</sub>Ni<sub>0.19</sub> alloy contributes to forming more active NiOOH species to involve in the conversion of cyclohexanone to adipic acid, while the proposed reaction pathway undergoes the 2-hydroxycyclohexanone and 2,7-oxepanedione intermediates. Moreover, the theoretical calculations confirm that the optimal electronic interaction, boosted reaction kinetics as well as improved adsorption free energy of reaction intermediates, synergistically endows Cu<sub>0.81</sub>Ni<sub>0.19</sub> alloy with superior bifunctional performance.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":null,"pages":null},"PeriodicalIF":13.1,"publicationDate":"2024-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142530536","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Functional ternary salt construction enabling an in-situ Li3N/LiF-enriched interface for ultra-stable all-solid-state lithium metal batteries","authors":"","doi":"10.1016/j.jechem.2024.09.034","DOIUrl":"10.1016/j.jechem.2024.09.034","url":null,"abstract":"<div><div>Poly(ethylene oxide)-based polymer all-solid-state lithium metal batteries (ASSLBs) have received widespread attention due to their low cost, good process ability, and high energy density. Nevertheless, the growth of Li dendrites within polymer solid-state electrolytes damages the reversibility of Li anodes and still impedes their widespread application. One efficient strategy is to construct a superior solid electrolyte interface. Herein, a stable interface enriched with Li<sub>3</sub>N and LiF is in-situ formed between Li anode and a ternary salt electrolyte. This ternary salt electrolyte is innovatively designed by introducing lithium bis(trifluoromethane sulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), and LiNO<sub>3</sub> to poly(ethylene oxide) matrix. Surface characterization indicates that LiNO<sub>3</sub> and LiFSI contribute to forming a Li<sub>3</sub>N-LiF-enriched interface and meanwhile LiTFSI ensures excellent conductivity. Theoretically, among various Li compound components, Li<sub>3</sub>N has high ionic conductivity, which is beneficial for reducing overpotential, while LiF has high interfacial energy which can enhance nucleation energy and suppress the formation of Li dendrites. The experimental results show that ASSLBs coupled with LiFePO<sub>4</sub> cathode display extremely excellent cycle stability approximately 2200 cycles at 2 C, with a final and corresponding discharge specific capacity of 96.7 mA h g<sup>−1</sup>. Additionally, a schematic illustration of the working mechanism for the Li<sub>3</sub>N-LiF interface is proposed.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":null,"pages":null},"PeriodicalIF":13.1,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142530540","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Feature selection strategy optimization for lithium-ion battery state of health estimation under impedance uncertainties","authors":"","doi":"10.1016/j.jechem.2024.09.032","DOIUrl":"10.1016/j.jechem.2024.09.032","url":null,"abstract":"<div><div>Battery health evaluation and management are vital for the long-term reliability and optimal performance of lithium-ion batteries in electric vehicles. Electrochemical impedance spectroscopy (EIS) offers valuable insights into battery degradation analysis and modeling. However, previous studies have not adequately addressed the impedance uncertainties, particularly during battery operating conditions, which can substantially impact the robustness and accuracy of state of health (SOH) estimation. Motivated by this, this paper proposes a comprehensive feature optimization scheme that integrates impedance validity assessment with correlation analysis. By utilizing metrics such as impedance residuals and correlation coefficients, the proposed method effectively filters out invalid and insignificant impedance data, thereby enhancing the reliability of the input features. Subsequently, the extreme gradient boosting (XGBoost) modeling framework is constructed for estimating the battery degradation trajectories. The XGBoost model incorporates a diverse range of hyperparameters, optimized by a genetic algorithm to improve its adaptability and generalization performance. Experimental validation confirms the effectiveness of the proposed feature optimization scheme, demonstrating the superior estimation performance of the proposed method in comparison with four baseline techniques.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":null,"pages":null},"PeriodicalIF":13.1,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142530528","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Atomically precise M-N-C electrocatalysts for oxygen reduction: Effects of inter-site distance, metal–metal interaction, coordination environment, and spin states","authors":"","doi":"10.1016/j.jechem.2024.08.068","DOIUrl":"10.1016/j.jechem.2024.08.068","url":null,"abstract":"<div><div>Inspired by molecular catalysts, researchers developed atomically precise nitrogen-coordinated single or dual metal sites imbedded in graphitized carbon (M-N-C) to fully utilize metallic sites for O<sub>2</sub> activation. These catalysts performed remarkably well in the electrocatalytic oxygen reduction reaction (ORR) due to their distinct coordination and electrical structures. Nonetheless, their maximum efficacy in practical applications has yet to be achieved. This agenda identifies tailoring the coordination environment, spin states, intersite distance, and metal–metal interaction as innovative approaches to regulate the ORR performance of these catalysts. However, it is necessary to undertake a precise assessment of these methodologies and the knowledge obtained to be implemented in the design of future M-N-C catalysts for ORR. Therefore, this review aims to analyze recent progress in M-N-C ORR catalysts, emphasizing their innovative engineering with aspects such as alteration in intersite distance, metal–metal interaction, coordination environment, and spin states. Additionally, we critically discuss how to logically monitor the atomic structure, local coordination, spin, and electronic states of M-N-C catalysts to modulate their ORR activity. We have also highlighted the challenges associated with M-N-C catalysts and proposed suggestions for their future design and fabrication.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":null,"pages":null},"PeriodicalIF":13.1,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142530532","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Boosting bidirectional sulfur conversion enabled by introducing boron-doped atoms and phosphorus vacancies in Ni2P for lithium-sulfur batteries","authors":"","doi":"10.1016/j.jechem.2024.09.027","DOIUrl":"10.1016/j.jechem.2024.09.027","url":null,"abstract":"<div><div>Lithium-sulfur (Li-S) batteries have gained great attention due to the high theoretical energy density and low cost, yet their further commercialization has been obstructed by the notorious shuttle effect and sluggish redox dynamics. Herein, we supply a strategy to optimize the electron structure of Ni<sub>2</sub>P by concurrently introducing B-doped atoms and P vacancies in Ni<sub>2</sub>P (V<sub>p</sub>-B-Ni<sub>2</sub>P), thereby enhancing the bidirectional sulfur conversion. The study indicates that the simultaneous introduction of B-doped atoms and P vacancies in Ni<sub>2</sub>P causes the redistribution of electron around Ni atoms, bringing about the upward shift of <em>d</em>-band center of Ni atoms and effective <em>d</em>-<em>p</em> orbital hybridization between Ni atoms and sulfur species, thus strengthening the chemical anchoring for lithium polysulfides (LiPSs) as well as expediting the bidirectional conversion kinetics of sulfur species. Meanwhile, theoretical calculations reveal that the incorporation of B-doped atoms and P vacancies in Ni<sub>2</sub>P selectively promotes Li<sub>2</sub>S dissolution and nucleation processes. Thus, the Li-S batteries with V<sub>p</sub>-B-Ni<sub>2</sub>P-separators present outstanding rate ability of 777 mA h g<sup>−1</sup> at 5 C and high areal capacity of 8.03 mA h cm<sup>−2</sup> under E/S of 5 μL mg<sup>−1</sup> and sulfur loading of 7.20 mg cm<sup>−2</sup>. This work elucidates that introducing heteroatom and vacancy in metal phosphide collaboratively regulates the electron structure to accelerate bidirectional sulfur conversion.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":null,"pages":null},"PeriodicalIF":13.1,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142415977","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}