Advanced electrolytes substantially improve the performance of lithium-ion and lithium-metal batteries by extending electrochemical stability windows and stabilizing high-capacity electrodes. Current electrolyte design, however, often treats the electrolyte as a static or isolated medium, overlooking the dynamic interdependencies among ionic transport, interphase formation and redox reactions during charge and discharge. Here we adopt a chemical engineering framework to analyze lithium batteries as process systems. We begin with electrolyte solution thermodynamics to clarify the evolving identities of reactive species across different solvation regimes. We then examine how changes in concentration and electrolyte non-ideality drive interfacial reactivity, guiding the selective formation of inorganic-rich interphase layers. Finally, we revisit mass transport through the lens of the Nernst–Planck equation and introduce dimensionless analysis tools to identify performance-limiting steps across transport and reaction processes. This systems-level approach unifies thermodynamic modeling, interfacial design and transport diagnostics, offering guiding principles for the rational design of high-performance electrolytes. Inspired by analogies between electrochemical cells and chemical reactors, this Perspective explores a process-engineering framework for battery electrolyte design. By connecting electrolyte thermodynamics, interphase chemistry and mass transport across scales, this framework highlights how chemical engineering principles can guide the rational development of next-generation battery electrolytes.

High-capacity anodes are desirable for high-energy lithium-ion batteries but suffer from limited cycle life due to large volume changes during cycling. The LiF-based solid-electrolyte interphase (SEI) has led to prolonged cycling stability. However, current LiF-forming electrolyte designs require anions to enter the Li+ solvation sheath, which inherently reduces the electrolyte's ionic conductivity, limiting both fast-charging and low-temperature performance. Here we develop solvent-bridged electrolytes composed of LiPF6 dissolved in a cosolvent system comprising a bridging cyclic ether that solvates both PF6- and Li+ to form a LiF-rich SEI, and a structural linear ether that governs the electrolyte liquid range. By mitigating direct Li+-anion interactions, the electrolytes maintain high ionic conductivity, enabling stable cycling of micrometre-sized silicon anodes under extreme conditions involving high rates (>4 C), low temperatures (down to -55 °C) and Li plating. Solvent-bridged electrolytes address the intrinsic trade-offs between LiF-rich SEI formation and electrolyte ionic conductivity, offering a promising approach for high-capacity anodes operating under demanding conditions.

Noncovalent interactions are ubiquitous in nature. Although much weaker than covalent bonds, noncovalent interactions are essential for stabilizing structures and enabling functionality across diverse systems, such as DNA and protein. In battery systems, noncovalent interactions occur among cations, anions, solvent molecules, and additives, profoundly influencing thermodynamics, interfacial behaviour, and mass transport. For example, the strength of Li + –solvent interactions directly determines whether solvent co-intercalation occurs and governs the composition and properties of the solid electrolyte interphase (SEI). Deciphering these noncovalent interaction networks is therefore essential for understanding complex reaction mechanisms and offers new strategies for designing next-generation batteries. In our recent work, we used noncovalent chemistry as a framework to re-examine electrolyte component interactions and their influence on battery performances. First, by introducing donor–acceptor noncovalent interactions in the CBPQT-based host–guest complex as redox mediators, we precisely tuned the redox potential of mediators to satisfy the stringent potential requirements for catalyzing polysulfide conversion, thereby accelerating the redox kinetics and enabling high-energy-density lithium–sulfur pouch cells. This study provides a textbook-level illustration of donor–acceptor noncovalent interactions in batteries, offering a clear proof-of-concept of their feasibility on battery engineering, and naturally setting the stage for our subsequent exploration of the more ubiquitous, noncanonical noncovalent interactions in electrolytes [1] . Second, Li + –solvent noncovalent interactions strongly influence the transport behaviour in batteries. During charge and discharge, the directional migration of lithium ions drags solvent molecules via these interactions, forming electro-osmotic solvent flow that leads to local solvent depletion within thick positive electrodes and limits fast-charging capability. To address this, we designed solvent molecules featuring anion–solvent hydrogen bonding to balance cation-induced electro-osmotic drag, suppress solvent depletion, and achieve 4 C fast charging in high-energy-density lithium-ion pouch cells [2] . Furthermore, leveraging differences in Li + –solvent interaction strength among different solvents enables condition-responsive solvent distribution. When two solvents exhibit sufficiently distinct noncovalent interactions with lithium ions, a macroscopic salting-out effect emerges: solvent distribution dynamically adapts to concentration gradients of lithium salts under charging conditions, enriching oxidation-resistant solvents near the positive electrode and reduction-resistant solvents near the negative electrode. This mechanism expands the electrochemical stability window dynamically, reconciling fast charging with high energy density [3] . Overall, our findings highlight the central role of noncovalent chemistry in battery processes and demonstrate its powerful functionality for tuning thermodynamic equilibria, enhancing electrode reaction kinetics, and governing mass transport. This approach opens new avenues for designing high-capacity anodes, high-voltage cathodes, and next-generation batteries that simultaneously deliver fast-charging capability and high energy density. [1] C.-X. Zhao, X.-Y. Li, H. Han, Y. Feng, C. Tang, X. Li, L. Zhang, C. L. Stern, Q. Zhang, J. F. Stoddart, Nat. Chem. Eng. , 2024, 1, 251. [2] C.-X. Zhao, Z. Wang, D. Jacobson, Y. Li, B. Khaykovich, S. Fayfar, L. Zheng, J. LaManna, X. Chen, D. S. Hussey, F. Chen, G. M. Veith, C. Wang, Science , 2025, 390, 745. [3] C.-X. Zhao, Z. Li, B. Chen, F. Chen, C. Wang, Nat. Energy , 2025, 10, 904.

Fast charging and low-temperature operation are essential for next-generation energy storage. However, high-energy batteries struggle to meet these demands as existing electrolytes cannot simultaneously deliver fast interfacial kinetics, high ionic conductivity and favourable interphase formation. Prevailing strategies focus on weakening thermodynamic solvation, yet this approach does not directly address the kinetic bottleneck, that is, the desolvation barrier governing interfacial charge transfer. Here we reveal that the desolvation kinetics are dictated by dynamic solvent exchange rather than thermodynamic solvation energy. Guided by this mechanistic insight, we have formulated an electrolyte in which two anions carry distinct anionic potentials: high-anionic-potential anions form contact ion pairs that accelerate solvation-exchange kinetics, while low-anionic-potential anions form solvent-separated ion pairs that sustain high bulk ionic conductivity. The electrolyte enables fast charging and low-temperature operation in high-loading lithium-ion batteries. The design principle was further validated in aqueous aluminium-ion electrochemical systems, underscoring its broader relevance to sustainable, resource-abundant battery chemistries beyond the lithium ion. Together, our findings establish a new electrolyte design paradigm that decouples interfacial and bulk transport properties and expands the design space of battery electrolyte systems.

Fast charging of high-energy batteries is critical for transportation electrification but remains challenging because the rapid rise in cell overpotential easily exceeds electrolytes' fixed electrochemical stability window. Here we design a self-adaptive electrolyte with a dynamically expanding electrochemical stability window that increases in real time during charging, outpacing the rise in overpotential as the charging current intensifies. The self-adaptive electrolyte is a single-phase solution of salt and complementary oxidation- and reduction-resistant solvents at the cloud point composition but can undergo solvent separation to dynamically redistribute solvent components during charging. The oxidation-resistant solvents concentrate at the positive electrode and reduction-resistant solvents accumulate at the negative electrode, broadening the electrolyte stability window in real time during charging. Proof-of-concept experiments validate the versatility of this design in both aqueous zinc-metal and non-aqueous lithium-metal batteries, achieving high Coulombic efficiencies of negative electrodes and enhanced oxidative stability for positive electrodes.

Lithium-sulfur (Li-S) batteries are highly considered as next-generation energy storage techniques. Weakly solvating electrolyte with low lithium polysulfide (LiPS) solvating power promises Li anode protection and improved cycling stability. However, the cathodic LiPS kinetics is inevitably deteriorated, resulting in severe cathodic polarization and limited energy density. Herein, the LiPS kinetic degradation mechanism in weakly solvating electrolytes is disclosed to construct high-energy-density Li-S batteries. Activation polarization instead of concentration or ohmic polarization is identified as the dominant kinetic limitation, which originates from higher charge-transfer activation energy and a changed rate-determining step. To solve the kinetic issue, a titanium nitride (TiN) electrocatalyst is introduced and corresponding Li-S batteries exhibit reduced polarization, prolonged cycling lifespan, and high actual energy density of 381 Wh kg(-1) in 2.5 Ah-level pouch cells. This work clarifies the LiPS reaction mechanism in protective weakly solvating electrolytes and highlights the electrocatalytic regulation strategy toward high-energy-density and long-cycling Li-S batteries.

Despite the fact that noncovalent bonding interactions are ubiquitous, it is primarily those interactions, which are amenable to spectroscopic analysis, that have been well investigated and applied in chemical engineering. New principles and techniques for characterizing noncovalent interactions are required to gain insight into their detailed nature and explore their potential applications. Here we introduce the practice of analytical noncovalent electrochemistry for probing such interactions. The strengths of noncovalent interactions can be determined more accurately by electrochemical means than by relying on spectroscopic measurements. Specifically, electrochemical analyses are capable of recording/identifying minor signals, leading to the discovery of an unexpected 2:1 host–guest complex. Moreover, the proposed technique is capable of probing multiple properties and facilitates the design and screening of active complexes as catalysts. We also demonstrate achieving a high energy density of 495 Wh kg−1 in rechargeable batteries. The analytical procedure provides a fresh perspective for supramolecular science and takes noncovalent chemistry closer to practical applications. Quantifying the strength of noncovalent interactions in supramolecular host–guest systems is key to guiding molecular design for a desired application. Now, a quantitative relationship between noncovalent interactions and electrochemistry is established that provides a new dimension for investigations into noncovalent interactions and enables the control of electrochemical properties in battery engineering.

Zinc–air batteries have been laying in the laboratory for decades of years, enjoying the low-current density galvanostatic cycling test at comfortable room temperatures, almost forgetting their identity as the practical batteries. The best way to revive and reinvigorate zinc–air batteries is through career planning, particularly by analyzing their advantages and disadvantages and identifying their potential applications. This will help to chart a course for the future. Building on its unique advantages of utilizing aqueous electrolyte, being low-cost, and having high environmental adaptability, we have proposed a clear career plan with a focus on wearable devices, extreme temperatures, and marine applications. In this review, we discuss the inherent advantages, current advances, and future direction, intending to remind the battery that the Zn–air battery is intended for practical use to fulfill diverse scenarios.

The unique conversion chemistry of sulfur endows lithium-sulfur batteries with a high theoretical energy density. However, the basic principles of the sulfur conversion chemistry remain unclear. In this work, phase equilibrium analysis is conducted to update the thermodynamic understanding on lithium-sulfur batteries. A ternary phase diagram is plotted following the equilibrium between sulfur, lithium sulfide and dissolved polysulfides. The diagram accurately describes the existing form of different polysulfides and the solid-liquid-solid phase transitions. Quantitative analysis further reveals the stoichiometric ratio of 1.0:4.5 between the two discharge plateaus and identifies the intrinsic insufficient liquid-solid deposition as the main limitation. The relationship between system point and equilibrium potential is established so that the ternary phase diagram can predict the lithium-sulfur thermodynamics at an arbitrary state.

Refreshing the record of the electrocatalytic activity for bifunctional oxygen electrocatalysis is the first priority of developing next -generation rechargeable zinc -air batteries. A Delta E indicator to evaluate the bifunctional electrocatalytic activity has stagnated with a record of Delta E > 0.60 V for decades. Herein, a bifunctional oxygen electrocatalyst is developed to afford an ultrahigh bifunctional electrocatalytic activity of Delta E = 0.57 V and realize high-performance rechargeable zinc -air batteries. Specifically, atomically dispersed Fe -N -C sites and NiFeCe layered double hydroxides are integrated to afford a composite FeNC@LDH electrocatalyst, following the guidance of the data -driven analysis. The FeNC@LDH electrocatalyst demonstrates a record -breaking electrocatalytic activity of Delta E = 0.57 V, far exceeding the state-of-the-art level by ca. 60 mV. Practical ampere -hour -scale zinc -air batteries are constructed with a capacity of 6.4 Ah and cycle under 1.0 A and 1.0 Ah conditions. This work affords a record -breaking bifunctional electrocatalyst for ampere -hour -scale zinc -air batteries in future application scenarios.

Dual-atom catalysts(DACs) afford promising potential for oxygen reduction electrocatalysis due to their high atomic efficiency and high intrinsic activity.However,precise construction of dual-atom sites remains a challenge.In this work,a post-modification strategy is proposed to precisely fabricate DACs for oxygen reduction electrocatalysis.Concretely,a secondary metal precursor is introduced to the primary single-atom sites to introduce direct metal-metal interaction,which ensures the formation of desired atom pair structure during the subsequent pyrolysis process and allows for successful construction of DACs.The as-prepared FeCo-NC DAC exhibits superior oxygen reduction electrocatalytic activity with a half-wave potential of 0,91 V vs.reversible hydrogen electrode.Zn-air batteries equipped with the FeCo-NC DAC demonstrate higher peak power density than those with the Pt/C benchmark.More importantly,this post-modification strategy is demonstrated universal to achieve a variety of dual-atom sites.This work presents an effective synthesis methodology for precise construction of catalytic materials and propels their applications in energy-related devices.

M–N–C catalysts, with their transition metal atoms coordinated to nitrogen/carbon atoms as active sites, are gaining attention for their versatile heterogeneous electrocatalysis. Fabrication of these catalysts can be achieved through either bottom-up chemical synthesis or top-down pyrolysis procedures, where the former offers a well-defined structure and precise synthesis feasibility. This Perspective provides an overview of the history of the technical route dispute between pyrolysis and pyrolysis-free M–N–C catalysts, along with their respective advantages and disadvantages. Additionally, we emphasize the advantages of pyrolysis-free M–N–C catalysts, exemplified by several studies focused on precisely modulating the structure to regulate the activity, as well as the efforts of effectively integrating the active sites. Finally, we discuss the challenges and opportunities of pyrolysis-free M–N–C catalysts, with the aim of maximizing their inherent strengths of precise structure and promoting their industrial applications.

Rechargeable zinc-air batteries have attracted extensive attention as clean, safe, and high-efficient en-ergy storage devices. However, the oxygen redox reactions at cathode are highly sluggish in kinetics and severely limit the actual battery performance. Atomic transition metal sites demonstrate high electro-catalytic activity towards respective oxygen reduction and evolution, while high bifunctional electro-catalytic activity is seldomly achieved. Herein a strategy of composing atomic transition metal sites is proposed to fabricate high active bifunctional oxygen electrocatalysts and high-performance recharge-able zinc-air batteries. Concretely, atomic Fe and Ni sites are composed based on their respective high electrocatalytic activity on oxygen reduction and evolution. The composite electrocatalyst demonstrates high bifunctional electrocatalytic activity (DE = 0.72 V) and exceeds noble-metal-based Pt/C + Ir/C (DE = 0.79 V). Accordingly, rechargeable zinc-air batteries with the composite electrocatalyst realize over 100 stable cycles at 25 mA cm-2. This work affords an effective strategy to fabricate bifunctional oxygen electrocatalysts for high-performance rechargeable zinc-air batteries. (c) 2022 Chinese Society of Particuology and Institute of Process Engineering, Chinese Academy of Sciences. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http:// creativecommons.org/licenses/by-nc-nd/4.0/).

Atomic Fe in N-doped carbon (FeNC) electrocatalysts for oxygen (O2) reduction at the cathode of proton exchange membrane fuel cells (PEMFCs) are the most promising alternative to platinum-group-metal catalysts. Despite recent progress on atomic FeNC O2 reduction, their controlled synthesis and stability for practical applications remains challenging. A two-step synthesis approach has recently led to significant advances in terms of Fe-loading and mass activity; however, the Fe utilisation remains low owing to the difficulty of building scaffolds with sufficient porosity that electrochemically exposes the active sites. Herein, we addressed this issue by coordinating Fe in a highly porous nitrogen doped carbon support (~3295 m2 g-1), prepared by pyrolysis of inexpensive 2,4,6-triaminopyrimidine and a Mg2+ salt active site template and porogen. Upon Fe coordination, a high electrochemical active site density of 2.54×10^19 sites gFeNC-1 and a record 52% FeNx electrochemical utilisation based on in situ nitrite stripping was achieved. The Fe single atoms are characterised pre- and post-electrochemical accelerated stress testing by aberration-corrected high-angle annular dark field scanning transmission electron microscopy, showing no Fe clustering. Moreover, ex situ X-ray absorption spectroscopy and low-temperature Mössbauer spectroscopy suggest the presence of penta-coordinated Fe sites, which were further studied by density functional theory calculations.

Open AccessRenewablesRESEARCH ARTICLES23 Jan 2023Low-Temperature Working Feasibility of Zinc-Air Batteries with Noble-Metal-Free Electrocatalysts Chang-Xin Zhao, Jia-Ning Liu, Nan Yao, Xiaoyuan Zeng, Aibing Chen, Peng Dong, Yingjie Zhang, Xinzhi Ma, Cheng Tang, Bo-Quan Li and Qiang Zhang Chang-Xin Zhao Google Scholar More articles by this author , Jia-Ning Liu Google Scholar More articles by this author , Nan Yao Google Scholar More articles by this author , Xiaoyuan Zeng Google Scholar More articles by this author , Aibing Chen Google Scholar More articles by this author , Peng Dong Google Scholar More articles by this author , Yingjie Zhang Google Scholar More articles by this author , Xinzhi Ma Google Scholar More articles by this author , Cheng Tang Google Scholar More articles by this author , Bo-Quan Li Google Scholar More articles by this author and Qiang Zhang Google Scholar More articles by this author https://doi.org/10.31635/renewables.023.202300026 SectionsSupplemental MaterialAboutPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Expanding the application scenario for rechargeable batteries is the key to the terminal utilization of renewable energy. Enabling zinc-air batteries at low temperatures is drawing increasing attention, yet the low-temperature working feasibility of zinc-air batteries with noble-metal-free electrocatalysts remains indistinct. In this contribution, the low-temperature performances of zinc-air batteries with noble-metal-free electrocatalysts are comprehensively investigated. Armed with a representative noble-metal-free bifunctional oxygen electrocatalyst, the zinc-air batteries demonstrate satisfactory yet relatively declined performance at low temperatures, compared with that at room temperatures. The reduced electrolyte conductivity is identified as one of the limiting factors for the reduced low-temperature performances. Furthermore, electrolyte engineering via regulating the solvation structure is performed on the zinc-air batteries with noble-metal-free electrocatalysts, where a promoted low-temperature performance is achieved. This work reveals the compatibility between noble-metal-free electrocatalysts and low-temperature feasibility/low-temperature performance enhancement strategies for zinc-air batteries and affords new opportunities to satisfy low-cost and efficient energy storage at harsh working conditions. Download figure Download PowerPoint Next article FiguresReferencesRelatedDetails Issue AssignmentNot Yet AssignedSupporting Information Copyright & Permissions© 2023 Chinese Chemical Society Downloaded 0 times PDF downloadLoading ...

Lithium–sulfur (Li–S) batteries promise ultrahigh theoretical energy density and attract great attention as next‐generation energy storage devices. However, the sluggish sulfur redox kinetics severely restricts the practical performances of Li–S batteries. Introducing electrocatalysts can accelerate the sulfur redox kinetics and enhance the discharge capacity and rate performances, where advanced electrocatalysts are required for better performance promotion. Herein, a Fe–Co‐based dual‐atom catalyst (DAC) is adopted to accelerate the sulfur redox kinetics and construct high‐performance Li–S batteries. The unique structure of the dual‐atom site allows synergistic effect between the adjacent metal atoms, thus enhancing the interactions with lithium polysulfides and promoting the sulfur redox kinetics over the single‐atom counterparts. As a result, Li–S batteries with DAC afford a high discharge capacity of 1034.6 mAh g −1 at 0.1 C and excellent rate performances of 728.0 mAh g −1 at 4.0 C. The introduction of DAC demonstrates the promising potential of applying advanced materials for constructing high‐performance Li–S batteries.

Coordination engineering for single-atom sites has drawn increasing attention, yet its chemical synthesis remains a tough issue, especially for tailorable coordination structures. Herein, a molecular recognition strategy is proposed to fabricate single-atom sites with regulable local coordination structures. Specifically, a heteroatom-containing ligand serves as the guest molecule to induce coordination interaction with the metal-containing host, precisely settling the heteroatoms into the local structure of single-atom sites. As a proof of concept, thiophene is selected as the guest molecule, and sulfur atoms are successfully introduced into the local coordination structure of iron single-atom sites. Ultrahigh oxygen reduction electrocatalytic activity is achieved with a half-wave potential of 0.93 V versus reversible hydrogen electrode. Furthermore, the strategy possesses excellent universality towards diversified types of single-atom sites. This work makes breakthroughs in the fabrication of single-atom sites and affords new opportunities in structural regulation at the atomic level.

Single-atom catalysts exhibit promising electrocatalytic activity, a trait that can be further enhanced through the introduction of heteroatom doping within the carbon skeleton. Nonetheless, the intricate relationship between the doping positions and activity remains incompletely elucidated. This contribution sheds light on an inductive effect of single-atom sites, showcasing that the activity of the oxygen reduction reaction (ORR) can be augmented by reducing the spatial gap between the doped heteroatom and the single-atom sites. Drawing inspiration from this inductive effect, we propose a synthesis strategy involving ligand modification aimed at precisely adjusting the distance between dopants and single-atom sites. This precise synthesis leads to optimized electrocatalytic activity for the ORR. The resultant electrocatalyst, characterized by Fe-N3P1 single-atom sites, demonstrates remarkable ORR activity, thus exhibiting great potential in zinc-air batteries and fuel cells.

The electrochemical CO2 reduction reaction (CO2RR) to value-added chemicals with renewable electricity is a promising method to decarbonise parts of the chemical industry. Recently, single metal atoms in nitrogen-doped carbon (MNC) have emerged as potential electrocatalysts for CO2RR to CO with high activity and faradaic efficiency, although the reaction limitation for CO2RR to CO is unclear. To understand the comparison of intrinsic activity of different MNCs, we synthesized two catalysts through a decoupled two-step synthesis approach of high temperature pyrolysis and low temperature metalation (Fe or Ni). The highly meso-porous structure resulted in the highest reported electrochemical active site utilisation based on in situ nitrite stripping; up to 59±6% for NiNC. Ex-situ X-ray absorption spectroscopy confirmed the penta-coordinated nature of the active sites. The catalysts are amongst the most active in the literature for CO2 reduction to CO. Our density functional theory calculations (DFT) show that their binding to the reaction intermediates approximates to that of Au surfaces. However, we find that the TOFs of the most active catalysts for CO evolution converge, suggesting a fundamental ceiling to the catalytic rates.

Lithium–sulfur (Li–S) batteries are deemed as future energy storage devices due to ultrahigh theoretical energy density. Cathodic polysulfide electrocatalysts have been widely investigated to promote sluggish sulfur redox kinetics. Probing the surface structure of electrocatalysts is vital to understanding the mechanism of polysulfide electrocatalysis. In this work, we for the first time identify surface gelation on disulfide electrocatalysts. Concretely, the Lewis acid sites on disulfides trigger the ring-opening polymerization of the dioxolane solvent to generate a surface gel layer, covering disulfides and reducing the electrocatalytic activity. Accordingly, a Lewis base triethylamine (TEA) is introduced as a competitive inhibitor. Consequently, Li–S batteries with disulfide electrocatalysts and TEA afford high specific capacity and improved rate responses. This work affords new insights on the actual surface structure of electrocatalysts in Li–S batteries.