Evolution of Local Structural Ordering and Chemical Distribution upon Delithiation of a Rock Salt–Structured Li1.3Ta0.3Mn0.4O2 Cathode

Lithium‐rich disordered rock‐salt oxides have attracted great interest owing to their promising performance as Li‐ion battery cathodes. While experimental and theoretical efforts are critical in advancing this class of materials, a fundamental understanding of key property changes upon Li extraction is largely missing. In the present study, single‐crystal synthesis of a new disordered rock‐salt cathode material, Li_1.3Ta_0.3Mn_0.4O₂ (LTMO), and its use as a model compound to investigate Li concentration–driven evolution of local cationic ordering, charge compensation, and chemical distribution are reported. Through the combined use of 2D and 3D X‐ray nanotomography, it is shown that Li removal accompanied by oxygen oxidation is correlated with the development of morphological defects such as particle cracking. Chemical heterogeneity, quantified by subparticle level distribution of Mn valence state, is minimal during Mn redox, which drastically increases upon the formation of cracks during oxygen redox. Density functional theory and bond valence sum mismatch calculations reveal the presence of local short‐range ordering in the pristine oxide, which gradually disappears along with the extraction of Li. The study suggests that with cycling the transformation into true cation–disordered state can be expected, which likely impacts the voltage profile and obtainable energy density of the oxide cathodes.     

Classical, phenomenological analysis of the kinetics of reactions at the gas-exposed surface of mixed ionic electronic conductors

The kinetics of reactions occurring at the gas-exposed surfaces of charged mixed ionic electronic conductors (MIECs) are examined from theoretical first principles. Analysis based on the classical electrochemical potential-transition state theory model reveals that the nature of the reactions is electrochemical in general. However, the influence of the surface potential on the reaction rate is opposite for adsorption and incorporation reactions. Two-dimensional finite volume models of an MIEC as working electrode in a half-cell configuration are presented. The results for a simple, two-step reduction process show that the effect of the surface potential on the rate of reactions is minimal for incorporation-limited reactions but more influential for adsorption-limited reactions. An erratum to this article is available at .     

Progress of Phosphate-based Polyanion Cathodes for Aqueous Rechargeable Zinc Batteries

Aqueous rechargeable zinc batteries (ARZBs) are recently prevailing devices that utilize the abundant Zn resources and the merits of aqueous electrolytes to become a competitive alternative for large-scale energy storage. Benefiting from the unique inductive effect and flexible structure, the past five years have experienced a diversiform of phosphate-based polyanion materials that are used as cathodes in ARZBs. In this review, the most recent advances in the Zn²⁺ storage mechanisms and electrolyte optimization of the phosphate-based cathodes of ARZBs, which mainly focus on vanadium/iron-based phosphates and their derivatives are presented. Furthermore, in addition to significant progress on polyanion phosphate-based cathode materials, the design strategies both for electrode materials and compatible electrolytes are also elaborated to improve the energy density and extend the cycling life of aqueous Zn/polyanion batteries.     

Metal Ions versus Protons: Tracking of Charge-Carrier Insertion into a Cathode Oxide in Aqueous Rechargeable Batteries

Protons in aqueous electrolytes can perform as an additional type of charge carrier for insertion/extraction in addition to the primary carrier cations in aqueous rechargeable batteries. Despite many diverse claims regarding the effect of protons, mutually conflicting experimental results and their interpretations without direct evidence have been reported over the last decade. Systematic examinations and analyses are thus imperative to clarify the conditions of proton insertion in aqueous rechargeable batteries. Utilizing V₂O₅ as a model cathode and beaker-type cells with a sufficient amount of ZnSO₄ aqueous electrolytes in this work, it is demonstrated that protons are inserted into the cathode prior to Zn-ions in low-pH conditions (pH ≤ 3.0). In stark contrast, the influence of protons on the discharge voltage and capacity is insignificant, when either the pH becomes higher (pH ≥ 4.0) or the electrolyte volume is considerably low in coin-type cells. Similar behavior of pH-dependent proton insertion is also verified in Na–, Mg–, and Al-ion electrolytes. Providing a resolution to the controversy regarding proton insertion, the present study emphasizes that the influence of protons substantially varies depending on the pH and relative volume of electrolytes in aqueous batteries.     

Recent Advances in Mn-Rich Layered Materials for Sodium-Ion Batteries

Branded with low cost and a high degree of safety, with an ambitious aim of substituting lithium-ion batteries in many fields, sodium-ion batteries have received fervid attention in recent years after being dormant for decades. Layered materials are a major focus of study owing to the extensive experience already gained in lithium-ion batteries, and the pursuit of a Mn-rich composition is critical to reduce the cost while retaining the performance. This review provides a timely update of the recent progress of Mn-rich layered materials for sodium-ion batteries based on the understandings of the phase forming principles, structure transformation upon cycling and charge compensation mechanisms and discusses potential ambiguities in the pursuit of high-performance materials.     

Air-Stable Li2S Cathode for Quasi-Solid-State Anode-Free Batteries with High Volumetric Energy

Anode-free batteries can maximize the energy density but their development is hindered by a lack of Li-rich cathodes for compensating the irreversible Li loss. Li₂S cathode is particularly appealing to this desire due to 2.6–4.7 folds more Li content and 4.2–6.8 times higher capacity than conventional intercalation cathodes. But its practical application is hindered by poor stability against moisture attacking in the air. Herein, a facile expendable polymer sheathing strategy toward air-stable Li₂S cathodes with high capacities for developing high-performance quasi-solid-state anode-free batteries without risk of cell leakage is reported. Tight protection by dense polymer barrier dramatically prolongs the lifetime of Li₂S cathode by 2,000 times at least in the air. Such air-stable Li₂S cathode allows for high compatibility of anode-free battery production with commercial schemes. More attractively, the polymer protective layer can in situ transform to multifunctional gel polymer electrolyte for releasing ionic pathways and enhancing cell performance by inhibiting LiPS loss and smoothing Li plating. With air-stable Li₂S cathode, the quasi-solid-state anode-free cells are assembled in ambient environment to deliver superb volumetric energy density of 1093 Wh L⁻¹. This study may shed new light to push the commercialization of high-energy and reliable anode-free batteries forward.     

An Intrinsically Nonflammable Electrolyte for Prominent-Safety Lithium Metal Batteries with High Energy Density and Cycling Stability

Nex-generation high-energy-density storage battery, assembled with lithium (Li)-metal anode and nickel-rich cathode, puts forward urgent demand for advanced electrolytes that simultaneously possess high security, wide electrochemical window, and good compatibility with electrode materials. Herein an intrinsically nonflammable electrolyte is designed by using 1 M lithium difluoro(oxalato)borate (LiDFOB) in triethyl phosphate (TEP) and N-methyl-N-propyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide [Pyr₁₃][TFSI] ionic liquid (IL) solvents. The introduction of IL can bring plentiful organic cations and anions, which provides a cation shielding effect and regulates the Li⁺ solvation structure with plentiful Li⁺-DFOB⁻ and Li⁺-TFSI⁻ complexes. The unique Li⁺ solvation structure can induce stable anion-derived electrolyte/electrode interphases, which effectively inhibit Li dendrite growth and suppress side reactions between TEP and electrodes. Therefore, the LiNi_0.9Co_0.05Mn_0.05O₂ (NCM90)/Li coin cell with this electrolyte can deliver stable cycling even under 4.5 V and 60 °C. Moreover, a Li-metal battery with thick NCM90 cathode (≈ 15 mg cm⁻²) and thin Li-metal anode (≈ 50 µm) (N/P ≈ 3), also reveals stable cycling performance under 4.4 V. And a 2.2 Ah NCM90/Li pouch cell can simultaneously possess prominent safety with stably passing the nail penetration test, and high gravimetric energy density of 470 Wh kg⁻¹ at 4.4 V.     

固体氧化物电解池直接电解CO2的研究进展

固体氧化物电解池是一种高效、环境友好型的能量转换器件,可以直接将电能转化为化学能. 本文介绍了近年来作者课题组在固体氧化物电解池直接用于CO₂还原的研究进展,并以阴极材料为主着重讨论了金属陶瓷电极和混合导电型钙钛矿氧化物电极的研究工作,最后展望了未来固体氧化物电解池直接电解CO₂的研究思路和方向.     

A Trip to Oz and a Peak Behind the Curtain of Magnesium Batteries

The introduction of the Li‐ion battery has revolutionized the electronics industry due to its high energy density. Magnesium batteries may have the potential to exceed the energy densities of Li‐ion batteries. Herein, the major advancements in magnesium electrochemistry and the challenges that must be overcome to realize a practical magnesium battery are discussed. So too are the controversial realities of current magnesium battery research and their implications.     

Atomic Insights into the Enhanced Surface Stability in High Voltage Cathode Materials by Ultrathin Coating

Surface properties of electrode materials play a critical role in the function of batteries. Therefore, surface modifications, such as coatings, have been widely used to improve battery performance. Understanding how these coatings function to improve battery performance is crucial for both scientific research and applications. In this study the electrochemical performance of coated and uncoated LiNi_0.5Mn_1.5O₄ (LNMO) electrodes is correlated with ensemble‐averaged soft X‐ray absorption spectroscopy (XAS) and spatially resolved scanning transmission electron microscopy‐electron energy loss spectroscopy (STEM‐EELS) to illustrate the mechanism of how ultrathin layer Al₂O₃ coatings improve the cycle life of LiNi_0.5Mn_1.5O₄. Mn²⁺ evolution on the surface is clearly observed in the uncoated sample, which results from the reaction between the electrolytic solution and the surfaces of LiNi_0.5Mn_1.5O₄ particles, and also possibly atomic structure reconstructions and oxygen loss from the surface region in LiNi_0.5Mn_1.5O₄. The coating effectively suppresses Mn²⁺ evolution and improves the battery performance by decelerating the impedance buildup from the surface passivation. This study demonstrates the importance of combining ensemble‐averaged techniques (e.g., XAS) with localized techniques (e.g., STEM‐EELS), as the latter may yield unrepresentative information due to the limited number of studied particles, and sheds light on the design of future coating processes and materials.