Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences最新文献

{"title":"From salt-in-water to water-in-salt: the emergence of glass-like dynamics and the transference number controversy.","authors":"Hamza Ladib, Tausif Altamash, Johan Jacquemin","doi":"10.1098/rsta.2025.0283","DOIUrl":"https://doi.org/10.1098/rsta.2025.0283","url":null,"abstract":"<p><p>The transition from dilute salt-in-water (SiW) electrolytes to highly concentrated lithium bis(trifluoro methylsulfonyl)imide (LiTFSI) water-in-salt (WiS) systems represents a fundamental shift in the physics of ion transport. We propose that this transition is best understood using concepts from glass physics. In the SiW regime (dilute solutions), ions diffuse largely independently within a water-rich environment, and classical electrolyte theories remain valid. Beyond concentrations ranging from 10 to 15 m (mol kg-1 of water), the liquid undergoes a qualitative reorganization in which the bulky TFSI⁻ anions form a percolating, dynamically crowded matrix that exhibits hallmark signatures of glass-like dynamics, including dynamic heterogeneity and cooperative relaxation, without requiring thermodynamic vitrification. Using molecular-level analysis, we demonstrate that LiTFSI-based water-in-salt electrolytes develop a species-dependent cooperativity hierarchy in which TFSI- becomes increasingly glass-like, while Li⁺ retains comparatively liquid-like mobility. This differential cooperativity offers a mechanistic explanation for the long-standing transference number controversy, reconciling the divergence between nuclear magnetic resonance tracer-frame values and electrochemical solvent-fixed measurements. More broadly, we propose that the SiW-to-WiS crossover can be mapped onto glass-physics order parameters, offering a new research direction for electrolyte design centred on tuning anion-matrix fragility rather than invoking mesoscale phase separation. This article is part of the theme issue 'Electrolytes within the domain of electrochemistry and electrochemical energy storage'.</p>","PeriodicalId":19879,"journal":{"name":"Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences","volume":"384 2330","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149128316","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"综合性期刊","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Advanced electrolytes for low-temperature zinc-ion batteries.","authors":"Ziqi Jiang, Jie Deng, Olivier Fontaine, Xuanze Wang, Yachao Zhu","doi":"10.1098/rsta.2025.0285","DOIUrl":"https://doi.org/10.1098/rsta.2025.0285","url":null,"abstract":"<p><p>Aqueous zinc-ion batteries (ZIBs) are attractive for safe and sustainable energy storage, but their operation in cold environments remains constrained by the temperature sensitivity of water-based electrolytes. When cooled, the strengthening and ordering of the hydrogen-bond (HB) network, together with slowed ion diffusion and altered solvation/desolvation equilibria, can simultaneously reduce conductivity and destabilize electrode interfaces. These coupled effects translate into pronounced polarization, poor zinc plating/stripping reversibility and accelerated performance decay. This mini-review discusses electrolyte advances for low-temperature ZIBs from a physicochemical perspective. We first outline how HB reorganization, Zn2+ solvation structure and ion-solvent interactions collectively govern freezing behaviour, transport kinetics and interfacial reactions. We then survey representative design strategies, including concentration-driven electrolytes, organic co-solvents, eutectic systems and anti-freeze hydrogels, to show how distinct routes can reduce water activity, maintain liquid-like dynamics and promote stable interphases under sub-zero conditions. Finally, we highlight emerging concepts, such as solvation-entropy regulation, chaotropic/kosmotropic ion effects and field- or cycling-induced interphase formation, and discuss the remaining gaps towards transferable design descriptors and practical all-climate zinc batteries. This article is part of the theme issue 'Electrolytes within the domain of electrochemistry and electrochemical energy storage'.</p>","PeriodicalId":19879,"journal":{"name":"Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences","volume":"384 2330","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149128326","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"综合性期刊","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rethinking glyme electrolytes in sodium batteries: from passive solvents to active reaction media.","authors":"Idoia Ruiz de Larramendi, Julen Beitia, Eider Goikolea, Cristina Pozo-Gonzalo, Nagore Ortiz Vitoriano","doi":"10.1098/rsta.2025.0280","DOIUrl":"https://doi.org/10.1098/rsta.2025.0280","url":null,"abstract":"<p><p>Sodium-based batteries are emerging as promising alternatives to lithium technologies owing to the abundance and low cost of sodium. However, their performance is strongly governed by electrolyte chemistry. This perspective examines the role of glyme-based electrolytes in sodium batteries, with particular emphasis on Na-O2 systems, where the electrolyte actively participates in electrochemical reactions. The effect of glyme chain length, sodium salt identity and salt concentration on the shape of Na⁺ solvation structures, ion pairing, mass transport, superoxide solubility and solid-electrolyte interphase formation are discussed. These interrelated effects control oxygen reduction and evolution kinetics, discharge product formation and long-term reversibility, highlighting the limitations of classical electrolyte descriptors based solely on conductivity or viscosity. The analysis shows that optimal electrolyte performance in Na-O2 batteries arises from a balance between solvation stability, transport properties and interfacial chemistry rather than from maximizing isolated bulk parameters. Comparisons with sodium-ion batteries further emphasize the broader relevance of coordination chemistry and desolvation processes. Finally, this perspective argues for a redefinition of what constitutes a 'good solvent' in reactive battery systems, integrating molecular-level solvation, interfacial reactivity, safety and sustainability considerations. Such an approach is essential for advancing efficient, durable and environmentally responsible sodium-based energy storage technologies. This article is part of the theme issue 'Electrolytes within the domain of electrochemistry and electrochemical energy storage'.</p>","PeriodicalId":19879,"journal":{"name":"Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences","volume":"384 2330","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149128301","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"综合性期刊","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The dependence of inter-phase lithium exchange on salt content in hybrid polymer-ceramic solid composite electrolytes.","authors":"Gabrielle Foran, Julien Mimeault, Marc Bertrand, Cédric Barcha, Steeve Rousselot, David Lepage, Arnaud Prébé, Mickael Dollé","doi":"10.1098/rsta.2025.0282","DOIUrl":"https://doi.org/10.1098/rsta.2025.0282","url":null,"abstract":"<p><p>Hybrid polymer-ceramic solid composite electrolytes have been proposed as a means of circumventing common pitfalls that are associated with either polymer (lower ionic conductivity and low mechanical strength) or ceramic (large interfacial resistance with electrodes, brittle) electrolytes. Despite this premise, significant uncertainty remains as to whether both phases participate in ion conduction and whether interactions between phases cause electrolyte degradation via surface reactions, interfacial resistance or corrosion. In this work, a solid composite electrolyte comprising poly(ethylene) oxide (PEO) and Li1.5Al0.5Ge1.5(PO4)3 (LAGP) was prepared for the purpose of evaluating lithium exchange between the polymer and ceramic phases of the electrolyte material. The PEO phase contained either lithium bis(oxalato)borate (LiBOB), lithium tri(fluoromethanesulfonyl)imide or a mixture of the two salts. 6Li-enriched LAGP and LiBOB were prepared such that 6Li NMR could be used to detect and quantify lithium exchange between the ceramic and the polymer phases following electrochemical polarization of the samples. The 6Li NMR study revealed that lithium-lithium chemical exchange between the polymer and ceramic phases in PEO-LAGP was dependent on which lithium salts were present in the polymer phase. Chemical exchange between the polymer and ceramic phases was linked to decreased ionic conductivity. This article is part of the theme issue 'Electrolytes within the domain of electrochemistry and electrochemical energy storage'.</p>","PeriodicalId":19879,"journal":{"name":"Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences","volume":"384 2330","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149128243","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"综合性期刊","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Inorganic-supported polymer electrolytes for better rechargeable batteries.","authors":"Jiaxun Yang, Xingxing Wang, Wenfang Feng, Gebrekidan Gebresilassie Eshetu, Egbert Figgemeier, Zhibin Zhou, Michel Armand, Heng Zhang","doi":"10.1098/rsta.2025.0276","DOIUrl":"https://doi.org/10.1098/rsta.2025.0276","url":null,"abstract":"<p><p>Inorganic-supported polymer electrolytes (iPEs) harmonize the characteristics of both organic polymers and inorganic components, thus bringing tremendous possibilities in improving the performance of polymer-based rechargeable batteries. Stemming from simple blending of inorganic particles, the iPE families have been conceptually expanded from non-ion-conducting (inactive) to ion-conducting (active) inorganic particles, from physical mixing to chemical modifications and high-order architecting. In this perspective, we provide a brief recap on the historical reflections on iPEs and highlight the opportunities by bridging two families of materials for electrolyte and battery optimization. We succinctly capture the fundamental properties of metal salts and inorganic components, then dive into the synergies between these two components with organic polymers. Furthermore, we put forward the critical impact of surface modifications of inorganic phases and expound intriguing high-order architecting approaches for improving the electrochemical properties of iPEs and their batteries. Finally, we discuss the possible directions to optimize the chemical structures of iPEs towards future battery technologies. This article is part of the theme issue 'Electrolytes within the domain of electrochemistry and electrochemical energy storage'.</p>","PeriodicalId":19879,"journal":{"name":"Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences","volume":"384 2330","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149128291","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"综合性期刊","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Protic and aprotic bis(oxalato)borate based ionic liquids as electrolytes for electrical double layer capacitors.","authors":"Zhong Zheng, Andrea Balducci","doi":"10.1098/rsta.2025.0277","DOIUrl":"https://doi.org/10.1098/rsta.2025.0277","url":null,"abstract":"<p><p>In this study, we report about the synthesis of two fluorine-free ionic liquids (ILs), the protic 1-methylimidazolium bis(oxalato)borate (1-MimBOB) and the aprotic 1-butyl-2,3-dimethylimidazolium bis(oxalato)borate (BDMimBOB) and about their use as electrolytes for electric double-layer capacitors (EDLCs). We showed that the electrolytes 1.5 M 1-MimBOB in water and 1.5 M BDMimBOB in acetonitrile exhibited good solubility, high ionic conductivity and high thermal stability. EDLC containing protic IL can operate at 1.2 V, while those containing the organic electrolyte can operate at 2.9 V. EDLCs containing these electrolytes display ideal capacitive behaviour, excellent rate capability and promising capacitance retention after 200 hours of floating at their maximum operating voltage. The devices also achieved energy densities up to 23.3 Wh kg⁻¹, highlighting BOB-based ILs as sustainable, fluorine-free electrolytes for next-generation high-performance EDLCs. This article is part of the theme issue 'Electrolytes within the domain of electrochemistry and electrochemical energy storage'.</p>","PeriodicalId":19879,"journal":{"name":"Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences","volume":"384 2330","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149128237","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"综合性期刊","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ca and Mg batteries: tuning interphase and electrolyte stability through cation solvation structure.","authors":"Deyana S Tchitchekova, Tjaša Pavčnik, Alexandre Ponrouch","doi":"10.1098/rsta.2025.0279","DOIUrl":"https://doi.org/10.1098/rsta.2025.0279","url":null,"abstract":"<p><p>High-voltage rechargeable batteries require precise control over thermodynamic and kinetic factors to prevent electrolyte decomposition at both electrodes, thereby ensuring stable operation and minimizing degradation. Organic electrolytes offer a wider electrochemical stability window than aqueous ones but are typically limited to approximately 3 V. To enable high-voltage operation and long cycle life, the formation of stable passivation layers or interphases is essential. These interphases form through the precipitation of insoluble electrolyte decomposition products, driven by the collective behaviour of electrolyte components under battery conditions, where the cation solvation structure plays a crucial role in determining decomposition pathways. At the electrode-electrolyte interface, steep potential gradients and altered solvation environments further influence interphase formation and decomposition mechanisms. This perspective examines the relationship between cation solvation structure and interphase composition, particularly for divalent cations (Ca²⁺ and Mg²⁺), and highlights key areas for improvement in experimental protocols, electrolyte purity, and interphase characterization. Addressing these challenges will enhance both battery performance and the reliability and reproducibility of data in this emerging field. This article is part of the theme issue 'Electrolytes within the domain of electrochemistry and electrochemical energy storage'.</p>","PeriodicalId":19879,"journal":{"name":"Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences","volume":"384 2330","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149128323","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"综合性期刊","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Preface.","authors":"Michael Dee, Margot Kuitems, Mathew Owens, Benjamin Pope","doi":"10.1098/rsta.2025.0266","DOIUrl":"https://doi.org/10.1098/rsta.2025.0266","url":null,"abstract":"","PeriodicalId":19879,"journal":{"name":"Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences","volume":"384 2329","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148920757","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"综合性期刊","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Replicating measurements to quantify smaller perturbations in tree-ring 14C records.","authors":"David Frank, Nicolas Brehm, Charlotte Pearson, Alex Bayliss, Kurt Nicolussi, Joe Giacalone, Urs Ramsperger, Marcus Christl, Lukas Wacker","doi":"10.1098/rsta.2025.0256","DOIUrl":"https://doi.org/10.1098/rsta.2025.0256","url":null,"abstract":"<p><p>Rapid increases in cosmogenic isotopes in tree-ring and ice core records point to rare, extreme perturbations in the Heliosphere over the past millennia. Identifying additional radiocarbon spikes-so-called Miyake events-and replicating or refuting published candidate events have since become an international priority. Yet, at present there are large gaps, both in magnitude and understanding, between more frequent and lower-energy events identified in space-age measurements and larger rare events identified over the past 15 ka from palaeo archives. Here, we generate additional annually-resolved radiocarbon data for a few short intervals between 3-4 ka before present (BP, i.e. 1950 CE), where initial radiocarbon data suggest either an increase in radiocarbon production or alternatively significant noise arising from the scale of error on the radiocarbon measurement continuum. By performing multiple high-precision radiocarbon measurements per analysed tree-ring year on the same cellulose samples, we reduce uncertainties and thus increase the sensitivity for detecting potential events. In addition to refining the structure of radiocarbon time-series during the Holocene, our findings contribute to the identification and characterization of a likely Miyake-type event in approximately 3481 BP/1532 BCE, and suggest further work is needed to either confirm or refute possible events at approximately 3763 BP/1814 BCE (moderate confidence) and approximately 3060 BP/1111 BCE (low confidence). Initial carbon cycle modelling of these event candidates suggests that they are two times smaller than any other of the Miyake events identified and confirmed in paleoenvironmental data. We also discuss sources of variability and uncertainty in the tree-ring radiocarbon measurement continuum. Using conventional dendrochronological statistics on radiocarbon time-series, we show that dramatic increases in replication (50-100x) would allow datasets to capture 95% of the theoretical variance in the inter-annual to medium frequency domains and, thereby, advance quantification of solar, geomagnetic and carbon cycle variation in Holocene tree-ring records, such as potentially distinguishing high versus low amplitude Schwabe solar cycles over the past millennia. This calls for a big-science approach-more typical for the space sciences-to produce and analyse such high-precision paleoenvironmental records. This article is part of the Theo Murphy meeting issue 'Radiocarbon and cosmic radiation events'.</p>","PeriodicalId":19879,"journal":{"name":"Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences","volume":"384 2329","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148920782","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"综合性期刊","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ultra-high-precision measurements of carbon-14 and its application for space weather and space climate research.","authors":"Hiroko Miyahara, Fuyuki Tokanai, Toru Moriya, Mirei Takeyama, Hirohisa Sakurai, Kazuho Horiuchi, Motonari Ohyama, Hideyuki Hotta, Fusa Miyake, Ryuho Kataoka, Kazuaki Yamamoto","doi":"10.1098/rsta.2025.0260","DOIUrl":"https://doi.org/10.1098/rsta.2025.0260","url":null,"abstract":"<p><p>This paper reviews recent progress in high-precision carbon-14 measurements in tree rings and their importance for accurately reconstructing past solar activity cycles as well as extreme solar and galactic cosmic-ray events. While measurements with conventional precision of accelerator mass spectrometry have provided valuable insights into long-term solar variability and have contributed to the discovery of candidates for extremely intense solar proton events in the past, their limited precision often blurs short-term signals. High-precision analyses, on the other hand, enable us not only to resolve the 11-year solar cycle more clearly, but also to disentangle transient cosmic-ray events, including candidates for extreme solar proton events, from the background solar cycle modulation. Without achieving such precision, transient signals may be smeared into the cycle variability, leading to uncertainties in the reconstruction of solar cycle properties themselves. Moreover, improved precision dramatically increases the number of detectable transient events, opening a new window into the occurrence frequency and intensity distribution. By reviewing our recent high-precision datasets alongside related archives, we demonstrate how this methodological advance enhances our understanding of both the cyclic and sporadic components of solar activity. This article is part of the Theo Murphy meeting issue 'Radiocarbon and cosmic radiation events'.</p>","PeriodicalId":19879,"journal":{"name":"Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences","volume":"384 2329","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148920788","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"综合性期刊","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}