Advancements in Manganese-Based Cathode for Sustainable Energy Utilization.

Manganese-based compounds, especially manganese oxides, are one of the most exceptional electrode materials. Specifically, manganese oxides have gained significant interest owing to their unique crystal structures, high theoretical capacity, abundant natural availability and eco-friendly nature. However, as transition metal semiconductors, manganese oxide possess low electrical conductivity, limited rate capacity, and suboptical cycle stability. Thus, combining manganese oxides with carbon or other metallic materials can significantly improve their electrochemical performance. These composites increase active sites and conductivity, thereby improving electrode reaction kinetics, cycle stability, and lifespan of supercapacitors (SCs) and batteries. This paper reviews the latest applications of Mn-based cathodes in SCs and advanced batteries. Moreover, the energy storage mechanisms were also proposed. In this review, the development prospects and challenges for advanced energy storage applications of Mn-based cathodes are summarized.

Enhancement of Li/S Battery Performance by a Modified Reduced Graphene Oxide Carbon Host Decorated with MoO3.

Electrochemical energy storage systems based on sulfur and lithium can theoretically deliver high energy with the further benefit of low cost. However, the working mechanism of this device involves the dissolution of sulfur to high-molecular weight lithium polysulfides (LiPs with general formula Li2Sn, n≥4) in the electrolyte during the discharge process. Therefore, the resulting migration of partially dissociated LiPs by diffusion or under the effect of the electric field to the lithium anode, activates an internal shuttle mechanism, reduces the active material and in general leads to loss of performance and cycling stability. These drawbacks poses challenges to the commercialization of Li/S cells in the short term. In this study, we report on the decoration of reduced graphene oxide with MoO3 particles to enhance interactions with LiPs and retain sulfur at the cathode side. The combination of experiments and density functional theory calculations demonstrated improvements in binding interactions between the cathode and sulfur species, enhancing the cycling stability of the Li/S cells.

Synergistic Effect of CO2 in Accelerating the Galvanic Corrosion of Lithium/Sodium Anodes in Alkali Metal-Carbon Dioxide Batteries.

Rechargeable alkali metal-CO2 batteries, which combine high theoretical energy density and environmentally friendly CO2 fixation ability, have attracted worldwide attention. Unfortunately, their electrochemical performances are usually inferior for practical applications. Aiming to reveal the underlying causes, a combinatorial usage of advanced nondestructive and postmortem characterization tools is used to intensively study the failure mechanisms of Li/Na-CO2 batteries. It is found that a porous interphase layer is formed between the separator and the Li/Na anode during the overvoltage rising and battery performance decaying process. A series of control experiments are designed to identify the underlying mechanisms dictating the observed morphological evolution of Li/Na anodes, and it is found that the CO2 synergist facilitates Li/Na chemical corrosion, the process of which is further promoted by the unwanted galvanic corrosion and the electrochemical cycling conditions. A detailed compositional analysis reveals that the as-formed interphase layers under different conditions are similar in species, with the main differences being their inconsistent quantity. Theoretical calculation results not only suggest an inherent intermolecular affinity between the CO2 and the electrolyte solvent but also provide the most thermodynamically favored CO2 reaction pathways. Based on these results, important implications for the further development of rechargeable alkali metal-CO2 batteries are discussed. The current discoveries not only fundamentally enrich our knowledge of the failure mechanisms of rechargeable alkali metal-CO2 batteries but also provide mechanistic directions for protecting metal anodes to build high-reversible alkali metal-CO2 batteries.

Radical Covalent Organic Frameworks Associated with Liquid Na-K toward Dendrite-Free Alkali Metal Anodes.

Liquid sodium-potassium (Na-K) alloy has the characteristics of high abundance, low redox potential, high capacity, and no dendrites, which has become an ideal alternative material for potassium/sodium metal anodes. However, the high surface tension of liquid sodium potassium alloy at room temperature makes it inconvenient in practical use. Here, the Na-K as reducing agent treats with hydrazone linkages of covalent organic frameworks (COFs) and obtain the carbon-oxygen radical COFs (COR-Tf-DHzDM-COFs). The preparation method solves the problems that the preparation process of the traditional Na-K composite anode is complex and has high cost. The structures of the COR-Tf-DHzDM-COFs are characterized by X-ray diffraction （XRD), fourier transform infrared (FT-IR), electron paramagnetic resonance (EPR), and solid-state NMR measurements. It is the first time that carbon-oxygen radical COFs from bulk COFs are constructed by one-step method and the operation is flexible, convenient, and high rate of quality, which is suitable for big production and widely used. The cycle stability of the composite Na-K anode is improved, which provides a new idea for the design of high-performance liquid metal anode.

Phase Transfer-Mediated Degradation of Ether-Based Localized High-Concentration Electrolytes in Alkali Metal Batteries.

Localized high-concentration electrolytes (LHCEs) have attracted interest in alkali metal batteries due to the advantages of forming stable solid-electrolyte interphases (SEIs) on anodes and good chemical/electrochemical stability. Herein, a new degradation mechanism is revealed for ether-based LHCEs that questions their compatibility with alkali metal anodes (Li, Na, and K). Specifically, the ether solvent reacts with alkali metals to generate solvated electrons (es - ) that attack hydrofluoroether co-solvents to form a series of byproducts. The ether solvent essentially acts as a phase-transfer reagent that continuously transfers electrons from solid-phase metals into the solution phase, thus inhibiting the formation of stable SEI and leading to continuous alkali metal corrosion. Switching to an ester-based solvating solvent or intercalation anodes such as graphite or molybdenum disulfide has been shown to avoid such a degradation mechanism due to the absence of es - .

Revealing the Solid-State Electrolyte Interfacial Stability Model with Na-K Liquid Alloy.

In this work, the Na-K liquid alloy with a charge selective interfacial layer is developed to achieve an impressively long cycling life with small overpotential on a sodium super-ionic conductor solid-state electrolyte (NASICON SSE). With this unique multi-cation system as the platform, we further propose a unique model that contains a chemical decomposition domain and a kinetic decomposition domain for the interfacial stability model. Based on this model, two charge selection mechanisms are proposed with dynamic chemical kinetic equilibrium and electrochemical kinetics as the manners of control, respectively, and both are validated by the electrochemical measurements with microscopic and spectroscopic characterizations. This study provides an effective design for high-energy-density solid-state battery with alkali Na-K anode, but also presents a novel approach to understand the interfacial chemical processes that could inspire and guide future designs.

Nanoscale interface engineering of inorganic Solid-State electrolytes for High-Performance alkali metal batteries.

All-solid-state metal batteries (ASSMBs) have been regarded as the ideal candidate for the next-generation high-energy storage system due to their ultrahigh specific capacity and the lowest redox potential. However, the uncontrollable chemical reactivity during cycling which directly determines the growth behaviour of metal dendrites, the low coulombic efficiency and the safety concerns severely limit their real-world applications.. Crystallographic optimization based on solid-state electrolytes (SSEs) provides an atomic-scale and fundamental solution for the inhibition of dendrite growth in metal anodes, which has attracted widespread attentions. From this perspective, we summarize the recent advance of the crystallographic optimization for various classes of solid-state electrolytes. We highlight the recent experimental findings of crystallographic optimization for a new generation of all-solid-state batteries, including lithium-ion batteries, sodium-ion batteries, magnesium-ion batteries, with the aim of providing a deeper understanding of the crystallographic reactions in ASSMBs. The challenges and prospects for the future design and engineering of crystallographic optimization of SSEs are discussed, providing ideas for further research into crystallographic optimization to improve the performance of rechargeable batteries.

TMDs beyond MoS2 for Electrochemical Energy Storage.

Atomically thin sheets of two-dimensional (2D) transition metal dichalcogenides (TMDs) have attracted interest as high capacity electrode materials for electrochemical energy storage devices owing to their unique properties (high surface area, high strength and modulus, faster ion diffusion, and so on), which arise from their layered morphology and diversified chemistry. Nevertheless, low electronic conductivity, poor cycling stability, large structural changes during metal-ion insertion/extraction along with high cost of manufacture are challenges that require further research in order for TMDs to find use in commercial batteries and supercapacitors. Here, a systematic review of cutting-edge research focused on TMD materials beyond the widely studied molybdenum disulfide or MoS2 electrode is reported. Accordingly, a critical overview of the recent progress concerning synthesis methods, physicochemical and electrochemical properties is given. Trends and opportunities that may contribute to state-of-the-art research are also discussed.

New Insights into the Electrochemistry Superiority of Liquid Na-K Alloy in Metal Batteries.

The significant issues with alkali metal batteries arise from their poor electrochemical properties and safety problems, limiting their applications. Herein, TiO2 nanoparticles embedded into N-doped porous carbon truncated ocatahedra (TiO2 ⊂NPCTO) are engineered as a cathode material with different metal anodes, including solid Na or K and liquid Na-K alloy. Electrochemical performance and kinetics are systematically analyzed, with the aim to determine detailed electrochemistry. By using a galvanostatic intermittent titration technique, TiO2 ⊂NPCTO/NaK shows faster diffusion of metal ions in insertion and extraction processes than that of Na-ions and K-ions in solid Na and K. The lower reaction resistance of liquid Na-K alloy electrode is also examined. The higher b-value of TiO2 ⊂NPCTO/NaK confirms that the reaction kinetics are promoted by the surface-induced capacitive behavior, favorable for high rate performance. This superiority highly pertains to the distinct liquid-liquid junction between the electrolyte and electrode, and the prohibition of metal dendrite growth, substantiated by symmetric cell testing, which provides a robust and homogeneous interface more stable than the traditional solid-liquid one. Hence, the liquid Na-K alloy-based battery exhibits to better cyclablity with higher capacity, rate capability, and initial coulombic efficiency than solid Na and K batteries.

High-Rate Nanostructured Pyrite Cathodes Enabled by Fluorinated Surface and Compact Grain Stacking via Sulfuration of Ionic Liquid Coated Fluorides.

Metal-polysulfide batteries are attracting broad attention as conversion reaction systems of high theoretical energy density and low cost. However, their further applications are hindered by the low loading of active species, excess conductive additive, and loose (nanostructured) electrode networkss. Herein, we propose that compact grain stacking and surface fluorination are two crucial factors for achieving high-rate and long-life pyrite (FeS2) cathodes enabled by sulfurating ionic liquid wrapped open-framework fluorides. Both of the factors can accelerate the Li- and Na-driven transport across the pyrite-electrolyte interface and conversion propagation between adjacent grains. Such an electrode design enables a highly reversible capacity of 425 mAh/g after 1000 cycles at 1 C for Li storage and 450 mAh/g after 1200 cycles at 2 C for Na storage, even under a high loading of pyrite grains and ultrathin carbon coating (<2 nm). Its cathode energy density can reach to 800 and 350 Wh/kg for Li and Na cells, respectively, under a high power density of 10000 W/kg. The cross-linkage between ionic liquid and fluoride precursors appears to be a solution to the reinforcement of surface fluorination.

Exploring Self-Healing Liquid Na-K Alloy for Dendrite-Free Electrochemical Energy Storage.

The development of high-performance dendrite-free liquid-metal anodes at room temperature is of great importance for the advancement of alkali metal batteries. Herein an intriguing self-healing liquid dendrite-free Na-K alloy, fabricated by a facile room-temperature alloying process, aiming for application in potassium-ion batteries is reported. Through extensive investigation, its self-healing characteristics are rooted upon a thin solid K2 O layer (KOL) coated on the liquid Na-K alloy. The KOL not only acts as a protective layer to prevent the Na-K alloy from making contact with the electrolyte, but also greatly improves the wetting capability and adhesion between the liquid alloy and the carbon matrix (e.g., carbon fiber cloth (CFC)) to form a stable interface. Consequently, the as-prepared CFC/KOL@Na-K alloy anode exhibits prominent electrochemical performance with smaller hysteresis (less than 0.3 V beyond 140 cycles at 0.4 mA cm-2 ), better capacity retention, and higher Coulombic efficiency than the CFC/bare Na-K alloy counterpart. When coupled with a potassium Prussian blue (PPB) cathode, the full cell manifests higher capability retention and improved cycling stability. This research deepens the understanding of self-healing Na-K alloys and opens a new way to achieve high-performance dendrite-free alkali metal anodes for application in rechargeable batteries.

Dual Carbon-Confined SnO2 Hollow Nanospheres Enabling High Performance for the Reversible Storage of Alkali Metal Ions.

To explore a universal electrode material for the high-performance electrochemical storage of Li+, Na+, and K+ ions remains a big challenge. Herein, we propose a "trinity" strategy to coat the SnO2 hollow nanospheres using the dual carbon layer from the polydopamine-derived nitrogen-doped carbon and graphene. Thereinto, hollow structures with sufficient void space could buffer the volume expansion, whereas dual carbon-confined strategy could not only elastically prevent the aggregation of nanoparticle and ensure the structural integrity but also immensely improve the conductivity and endow high rate properties. Benefiting from the effective strategy and specific structure, the dual carbon-confined SnO2 hollow nanosphere (denoted as G@C@SnO2) can serve as the universal host material for alkali metal ions and enable their rapid and reversible storage. As expected, the resulting G@C@SnO2 as a universal anode material shows reversible alkali-metal-ion storage with high performance. We believe this that strategy could pave the way for constructing other metal-oxide-based dual carbon-confined high-performance materials for the future energy storage applications.

Ion-Solvent Complexes Promote Gas Evolution from Electrolytes on a Sodium Metal Anode.

Lithium and sodium metal batteries are considered as promising next-generation energy storage devices due to their ultrahigh energy densities. The high reactivity of alkali metal toward organic solvents and salts results in side reactions, which further lead to undesirable electrolyte depletion, cell failure, and evolution of flammable gas. Herein, first-principles calculations and in situ optical microscopy are used to study the mechanism of organic electrolyte decomposition and gas evolution on a sodium metal anode. Once complexed with sodium ions, solvent molecules show a reduced LUMO, which facilitates the electrolyte decomposition and gas evolution. Such a general mechanism is also applicable to lithium and other metal anodes. We uncover the critical role of ion-solvent complexation for the stability of alkali metal anodes, reveal the mechanism of electrolyte gassing, and provide a mechanistic guidance to electrolyte and lithium/sodium anode design for safe rechargeable batteries.

Liquid K-Na Alloy Anode Enables Dendrite-Free Potassium Batteries.

A K-Na liquid alloy allows a dendrite-free high-capacity anode; its immiscibility with an organic liquid electrolyte offers a liquid-liquid anode-electrolyte interface. Working with a sodiated Na2 MnFe(CN)6 cathode, the working cation becomes K+ to give a potassium battery of long cycle life with an acceptable capacity at high charge/discharge rates.