EES batteries最新文献

{"title":"A fluorine-free electrolyte for calcium metal batteries.","authors":"Andrii Kachmar, Robert Markowski, Taniya Purkait, Darsi Rambabu, Petru Apostol, Da Tie, Roy Heyns, Jan Fransaer, Koen Binnemans, Alexandre Ponrouch, Alexandru Vlad","doi":"10.1039/d5eb00162e","DOIUrl":"10.1039/d5eb00162e","url":null,"abstract":"<p><p>Calcium metal batteries (CMBs) have emerged as a promising alternative to lithium(Li)-based technologies due to calcium's (Ca) low reduction potential, high volumetric capacity, and abundance. However, challenges such as poor Ca²⁺ transport across passivation layers and limited electrolyte compatibility hinder practical implementation. Here, we report a fluorine-free electrolyte formulation based on calcium bis(methanesulfonimide) (Ca(MSI)₂) in dimethylacetamide (DMAc). This system offers a safer, more sustainable, and environmentally benign alternative to conventional fluorinated electrolytes. Comparative physicochemical and electrochemical evaluations with the benchmark Ca(TFSI)₂/DMAc electrolyte reveal that Ca(MSI)₂ enables stable calcium plating/stripping over 1600 hours with lower overpotential and improved rate performance. In fact, spectroscopic analyses confirm the formation of a more uniform, fluorine-free interphase that supports better Ca²⁺ transport throughout the passivation layer. These findings highlight the potential of fluorine-free salts for enabling reversible room temperature calcium metal cycling and advance the development of safer, high-performance multivalent batteries.</p>","PeriodicalId":520508,"journal":{"name":"EES batteries","volume":" ","pages":"138-146"},"PeriodicalIF":0.0,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12679347/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145703789","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Revisiting potassium intercalation in graphite: an <i>operando</i> characterisation and computational approach.","authors":"Zhenyu Guo, Kang Wang, Yuanzhu Zhao, Gang Cheng, Yichen Huang, Connor Wright, Zonghao Shen, Hossein Yadegari, Jinglin Jiang, Fei Xie, Kaitian Zheng, Cecilia Mattevi, Carla Molteni, Peter D Haynes, Mary P Ryan, Maria-Magdalena Titirici","doi":"10.1039/d5eb00184f","DOIUrl":"10.1039/d5eb00184f","url":null,"abstract":"<p><p>Potassium-ion batteries (KIBs) with graphite anodes are emerging as a highly promising \"beyond lithium\" technology driven by battery demands, potassium's abundant reserves and the inherent similarities in intercalation chemistry to lithium-ion systems. Despite this potential, a understanding of potassium intercalation into graphite, particularly concerning early intercalation stages and the in-plane ordering of K⁺ within graphite intercalation compounds (GICs), lacks sufficient elucidation. Herein, we employed a multi-modal, <i>operando</i> characterisation approach to elucidate the correlation of electrochemical potassiation and structural evolution in graphite, hence unravelling the specific mechanisms of K-ion storage. <i>Operando</i> electrochemical dilatometry precisely quantifies the macroscopic volume expansion of a graphite electrode during potassiation. Meanwhile, <i>operando</i> synchrotron X-ray diffraction (XRD) records ordered phase transitions during early-stage intercalation, detailing the formation of distinct GIC phases. Furthermore, Raman spectroscopy and density-functional theory (DFT) reveal the in-plane ordering of K⁺ within the graphite gallery and stacking modes. <i>Operando</i> optical microscope and UV-vis spectroscopy together provide insights into the changing optical properties, linking these changes to different GICs and electronic structural changes. This comprehensive study offers fundamental mechanistic insights into K-ion storage in graphite, paving the way for the rational design of high-performance KIB anodes.</p>","PeriodicalId":520508,"journal":{"name":"EES batteries","volume":" ","pages":"163-175"},"PeriodicalIF":0.0,"publicationDate":"2025-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12670375/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145673404","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Spray-dried hard carbon-Sn composites for energy-dense Na-ion batteries.","authors":"Giovanni Gammaitoni, Gihoon Cha, Rajkumar Reddy Kolan, Silke Christiansen, François Fauth, Matteo Bianchini","doi":"10.1039/d5eb00188a","DOIUrl":"10.1039/d5eb00188a","url":null,"abstract":"<p><p>Sustainability and availability of raw materials, besides the usual performance-related metrics, have become crucial aspects for the development of new battery technologies to complement the existing successful Li-ion batteries. Sodium-ion batteries (SIBs) are at the forefront in this respect; however, the development of electrode materials achieving the expected performances is a challenge. Hard carbons (HC) are the most used anode material for SIBs, but poor gravimetric and volumetric capacities have limited the development of energy-dense SIBs. High-density and high-capacity metals that can react with sodium through formation/alloying reactions represent a possible solution, but the huge volume expansion during electrochemical cycling limits their utilization. In this work we explore the synthesis and characterization of sustainable hard carbon-Sn composites as anode materials for Na-ion batteries, with the aim of increasing HC performance without suffering the side effects of Sn volume expansion. Starting from conventional HC synthesis we propose a water-based continuous-flow spray-drying process to prepare our composites, resulting in an increase in HC's gravimetric and volumetric performances, including better long cycling stability. By using a set of analytical tools, we reveal the different physicochemical properties of our composites as a function of the starting cellulose precursors. The amount of Sn in the composites has been carefully evaluated through several techniques and lies at ≈15 or ≈25 wt% depending on the Sn content used for the synthesis. The activation of Sn during electrochemical discharge has been confirmed by <i>operando</i> synchrotron XRD, and the results show the appearance of sodiated Sn phases forming in kinetically driven reactions that do not fully adhere to the expected thermodynamic phase diagram. The electrochemical testing of our materials, carried out using conventional carbonate-based electrolytes, demonstrates excellent performances, with one composite demonstrating 301 mAh g^-1 of capacity after 100 cycles (94% retention). Noteworthy is that the volumetric energy density is also significantly improved. Finally, by synthesizing several HC-Sn composites using alternative methods we demonstrate how spray drying leads to superior performances, especially in terms of capacity retention. Our work establishes the feasibility of spray drying as a scalable and sustainable synthesis route to prepare high-performance negative electrode composites for Na-ion batteries.</p>","PeriodicalId":520508,"journal":{"name":"EES batteries","volume":" ","pages":"1596-1611"},"PeriodicalIF":0.0,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12541904/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145357561","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Lithium solvation and anion-dominated domain structure in water-in-salt electrolytes.","authors":"Timothy S Groves, Kieran J Agg, Shurui Miao, Thomas F Headen, Tristan G A Youngs, Gregory N Smith, Susan Perkin, James E Hallett","doi":"10.1039/d5eb00105f","DOIUrl":"10.1039/d5eb00105f","url":null,"abstract":"<p><p>Water-in-Salt (WiS) electrolytes are an emerging class of high concentration aqueous electrolytes with large electrochemical stability windows, making them attractive as green alternatives in next-generation electrochemical energy storage devices. Recent work has highlighted the existence of water-rich and anion-rich domains in WiS electrolytes, but the extent, morphology and importance of these domains are still disputed. Here, we present neutron total scattering measurements of the archetypal WiS, lithium bis(trifluoromethanesulfonyl)imide, and use empirical potential structure refinement to match the structure of a simulated system to the experimental data for two technologically relevant concentrations, revealing ion solvation, geometric isomerism and long-range structures in unprecedented detail. Our analysis of the modelled WiS electrolyte suggests that water domains are small and isolated and points to a system dominated by percolating, anion-rich domains that assemble through the association of hydrophobic regions, extending throughout the entire system. This structural insight places restrictions on feasible transport mechanisms in WiSs and, more generally, will aid in the understanding of the structure and behaviour of WiS electrolytes, with implications for the design and manufacture of WiS-containing devices.</p>","PeriodicalId":520508,"journal":{"name":"EES batteries","volume":" ","pages":"1797-1808"},"PeriodicalIF":0.0,"publicationDate":"2025-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12372462/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144985792","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"High-performance anode-less all-solid-state batteries enabled by multisite nucleation and an elastic network.","authors":"Jihoon Oh, Yeeun Sohn, Jang Wook Choi","doi":"10.1039/d5eb00050e","DOIUrl":"10.1039/d5eb00050e","url":null,"abstract":"<p><p>Anode-less all-solid-state batteries (ALASSBs) represent a promising energy storage platform for various upcoming green mobility applications, as they offer superior energy density, manufacturing feasibility, and enhanced safety. However, their practical implementation is hindered by the formation of heterogeneous lithium (Li) deposits during repeated cycling, particularly at ambient temperatures. In this study, we introduce a novel multi-seed strategy that integrates strategically distributed nucleation sites with a highly elastic and adhesive polymer matrix. The incorporation of multiple lithiophilic metallic seeds with a range of lithiation potentials promotes uniform Li deposition by facilitating diversified lithiation pathways. Simultaneously, the elastic polymer network enables stress dissipation across the protection layer, thereby effectively mitigating mechanical degradation. Even at room temperature (25 °C), the resulting anode-less full-cell retained 70% of its capacity after 100 cycles at a current density of 0.5C (1C = 2 mA cm^-2). This study conveys a useful design principle for protective layers in ALASSBs: the advantageous synergistic effect created by combining multiple lithiophilic seeds with enlarged nucleation pathways and a stress-releasing elastic binder.</p>","PeriodicalId":520508,"journal":{"name":"EES batteries","volume":" ","pages":"566-575"},"PeriodicalIF":0.0,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12004216/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144045599","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Probing the electrochemical behaviour of lithium imide as an electrolyte for solid-state batteries.","authors":"Jeremy P Lowen, Teresa Insinna, Tharigopala V Beatriceveena, Mark P Stockham, Bo Dong, Sarah J Day, Clare P Grey, Emma Kendrick, Peter R Slater, Paul A Anderson, Joshua W Makepeace","doi":"10.1039/d5eb00058k","DOIUrl":"10.1039/d5eb00058k","url":null,"abstract":"<p><p>All-solid-state batteries utilising a Li-metal anode have long promised to be the next-generation of high-performance energy storage device, with a step-change in energy density, cycling stability and cell safety touted as potential advantages compared to conventional Li-ion battery cells. A key to enabling this technology is the development of solid-state electrolytes with the elusive combination of high ionic conductivity, wide electrochemical stability and the ability to form a conductive and stable interface with Li metal. Presently, oxide and sulfide-based materials, particularly garnet and argyrodite-type structures, have proved most promising for this application. However, these still suffer from a number of challenges, including resistive lithium metal interfaces, poor lithium dendrite suppression (at high current density) and low voltage stability. Here we report the first application of lithium imide, an antifluorite-structured material, as a solid electrolyte in a Li-metal battery. Low-temperature synthesis of lithium imide produces promising Li-ion conductivity, reaching >1 mS cm^-1 at 30 °C using a modest post-synthetic mechanochemical treatment, as well as displaying at least 5 V stability <i>vs.</i> Li⁺/Li. <i>In situ</i> electrochemical operation of lithium imide with Li-metal electrodes reveals an apparent 1000-fold increase in its measured conductivity, whilst appearing to remain an electronic insulator. It is postulated that stoichiometry variation at the grain boundary may contribute to this conductivity improvement. Furthermore, the material is shown to possess impressive resistance to hard shorting under high current density conditions (70 mA cm^-2) as well as the ability to operate in Li-metal battery cells. These results not only highlight the promising performance of lithium imide, but also its potential to be the basis for a new family of antifluorite based solid electrolytes.</p>","PeriodicalId":520508,"journal":{"name":"EES batteries","volume":" ","pages":"527-540"},"PeriodicalIF":0.0,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12001454/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144036111","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}