Catalytic role of in-situ formed C-N species for enhanced Li2CO3 decomposition.

Sluggish kinetics of the CO2 reduction/evolution reactions lead to the accumulation of Li2CO3 residuals and thus possible catalyst deactivation, which hinders the long-term cycling stability of Li-CO2 batteries. Apart from catalyst design, constructing a fluorinated solid-electrolyte interphase is a conventional strategy to minimize parasitic reactions and prolong cycle life. However, the catalytic effects of solid-electrolyte interphase components have been overlooked and remain unclear. Herein, we systematically regulate the compositions of solid-electrolyte interphase via tuning electrolyte solvation structures, anion coordination, and binding free energy between Li ion and anion. The cells exhibit distinct improvement in cycling performance with increasing content of C-N species in solid-electrolyte interphase layers. The enhancement originates from a catalytic effect towards accelerating the Li2CO3 formation/decomposition kinetics. Theoretical analysis reveals that C-N species provide strong adsorption sites and promote charge transfer from interface to *CO22- during discharge, and from Li2CO3 to C-N species during charge, thereby building a bidirectional fast-reacting bridge for CO2 reduction/evolution reactions. This finding enables us to design a C-N rich solid-electrolyte interphase via dual-salt electrolytes, improving cycle life of Li-CO2 batteries to twice that using traditional electrolytes. Our work provides an insight into interfacial design by tuning of catalytic properties towards CO2 reduction/evolution reactions.

Structural Distortion in the Wadsley-Roth Niobium Molybdenum Oxide Phase Triggering Extraordinarily Stable Battery Performance.

Wadsley-Roth niobium oxide phases have attracted extensive research interest recently as promising battery anodes. We have synthesized the niobium-molybdenum oxide shear phase (Nb, Mo)13 O33 with superior electrochemical Li-ion storage performance, including an ultralong cycling lifespan of at least 15000 cycles. During electrochemical cycling, a reversible single-phase solid-solution reaction with lithiated intermediate solid solutions is demonstrated using in situ X-ray diffraction, with the valence and short-range structural changes of the electrode probed by in situ Nb and Mo K-edge X-ray absorption spectroscopy. This work reveals that the superior stability of niobium molybdenum oxides is underpinned by changes in octahedral distortion during electrochemical reactions, and we report an in-depth understanding of how this stabilizes the oxide structure during cycling with implications for future long-life battery material design.

Solvent control of water O-H bonds for highly reversible zinc ion batteries.

Aqueous Zn-ion batteries have attracted increasing research interest; however, the development of these batteries has been hindered by several challenges, including dendrite growth, Zn corrosion, cathode material degradation, limited temperature adaptability and electrochemical stability window, which are associated with water activity and the solvation structure of electrolytes. Here we report that water activity is suppressed by increasing the electron density of the water protons through interactions with highly polar dimethylacetamide and trimethyl phosphate molecules. Meanwhile, the Zn corrosion in the hybrid electrolyte is mitigated, and the electrochemical stability window and the operating temperature of the electrolyte are extended. The dimethylacetamide alters the surface energy of Zn, guiding the (002) plane dominated deposition of Zn. Molecular dynamics simulation evidences Zn2+ ions are solvated with fewer water molecules, resulting in lower lattice strain in the NaV3O8·1.5H2O cathode during the insertion of hydrated Zn2+ ions, boosting the lifespan of Zn|| NaV3O8·1.5H2O cell to 3000 cycles.

Revisiting the Role of Discharge Products in Li-CO2 Batteries.

Rechargeable lithium-carbon dioxide (Li-CO2 ) batteries are promising devices for CO2 recycling and energy storage. However, thermodynamically stable and electrically insulating discharge products (DPs) (e.g., Li2 CO3 ) deposited at cathodes require rigorous conditions for completed decomposition, resulting in large recharge polarization and poor battery reversibility. Although progress has been achieved in cathode design and electrolyte optimization, the significance of DPs is generally underestimated. Therefore, it is necessary to revisit the role of DPs in Li-CO2 batteries to boost overall battery performance. Here, a critical and systematic review of DPs in Li-CO2 batteries is reported for the first time. Fundamentals of reactions for formation and decomposition of DPs are appraised; impacts on battery performance including overpotential, capacity, and stability are demonstrated; and the necessity of discharge product management is highlighted. Practical in situ/operando technologies are assessed to characterize reaction intermediates and the corresponding DPs for mechanism investigation. Additionally, achievable control measures to boost the decomposition of DPs are evidenced to provide battery design principles and improve the battery performance. Findings from this work will deepen the understanding of electrochemistry of Li-CO2 batteries and promote practical applications.

Stabilizing Cobalt-free Li-rich Layered Oxide Cathodes through Oxygen Lattice Regulation by Two-phase Ru Doping.

The application of Li-rich layered oxides is hindered by their dramatic capacity and voltage decay on cycling. This work comprehensively studies the mechanistic behaviour of cobalt-free Li1.2 Ni0.2 Mn0.6 O2 and demonstrates the positive impact of two-phase Ru doping. A mechanistic transition from the monoclinic to the hexagonal behaviour is found for the structural evolution of Li1.2 Ni0.2 Mn0.6 O2, and the improvement mechanism of Ru doping is understood using the combination of in operando and post-mortem synchrotron analyses. The two-phase Ru doping improves the structural reversibility in the first cycle and restrains structural degradation during cycling by stabilizing oxygen (O2- ) redox and reducing Mn reduction, thus enabling high structural stability, an extraordinarily stable voltage (decay rate <0.45 mV per cycle), and a high capacity-retention rate during long-term cycling. The understanding of the structure-function relationship of Li1.2 Ni0.2 Mn0.6 O2 sheds light on the selective doping strategy and rational materials design for better-performance Li-rich layered oxides.

Introducing 4s-2p Orbital Hybridization to Stabilize Spinel Oxide Cathodes for Lithium-Ion Batteries.

Oxides composed of an oxygen framework and interstitial cations are promising cathode materials for lithium-ion batteries. However, the instability of the oxygen framework under harsh operating conditions results in fast battery capacity decay, due to the weak orbital interactions between cations and oxygen (mainly 3d-2p interaction). Here, a robust and endurable oxygen framework is created by introducing strong 4s-2p orbital hybridization into the structure using LiNi0.5 Mn1.5 O4 oxide as an example. The modified oxide delivers extraordinarily stable battery performance, achieving 71.4 % capacity retention after 2000 cycles at 1 C. This work shows that an orbital-level understanding can be leveraged to engineer high structural stability of the anion oxygen framework of oxides. Moreover, the similarity of the oxygen lattice between oxide electrodes makes this approach extendable to other electrodes, with orbital-focused engineering a new avenue for the fundamental modification of battery materials.

Crystallographic-Site-Specific Structural Engineering Enables Extraordinary Electrochemical Performance of High-Voltage LiNi0.5 Mn1.5 O4 Spinel Cathodes for Lithium-Ion Batteries.

The development of reliable and safe high-energy-density lithium-ion batteries is hindered by the structural instability of cathode materials during cycling, arising as a result of detrimental phase transformations occurring at high operating voltages alongside the loss of active materials induced by transition metal dissolution. Originating from the fundamental structure/function relation of battery materials, the authors purposefully perform crystallographic-site-specific structural engineering on electrode material structure, using the high-voltage LiNi0.5 Mn1.5 O4 (LNMO) cathode as a representative, which directly addresses the root source of structural instability of the Fd 3 ¯ m structure. By employing Sb as a dopant to modify the specific issue-involved 16c and 16d sites simultaneously, the authors successfully transform the detrimental two-phase reaction occurring at high-voltage into a preferential solid-solution reaction and significantly suppress the loss of Mn from the LNMO structure. The modified LNMO material delivers an impressive 99% of its theoretical specific capacity at 1 C, and maintains 87.6% and 72.4% of initial capacity after 1500 and 3000 cycles, respectively. The issue-tracing site-specific structural tailoring demonstrated for this material will facilitate the rapid development of high-energy-density materials for lithium-ion batteries.

Phase Compatible NiFe2O4 Coating Tunes Oxygen Redox in Li-Rich Layered Oxide.

Li-rich layered oxides have attracted intense attention for lithium-ion batteries, as provide substantial capacity from transition metal cation redox simultaneous with reversible oxygen-anion redox. However, unregulated irreversible oxygen-anion redox leads to critical issues such as voltage fade and oxygen release. Here, we report a feasible NiFe2O4 (NFO) surface-coating strategy to turn the nonbonding coordination of surface oxygen into metal-oxygen decoordination. In particular, the surface simplex M-O (M = Ni, Co, Mn from MO6 octahedra) and N-O (N = Ni, Fe from NO6 octahedra) bonds are reconstructed in the form of M-O-N bonds. By applying both in operando and ex situ technologies, we found this heterostructural interface traps surface lattice oxygen, as well as restrains cation migration in Li-rich layered oxide during electrochemical cycling. Therefore, surface lattice oxygen behavior is significantly sustained. More interestingly, we directly observe the surface oxygen redox decouple with cation migration. In addition, the NFO-coating blocks HF produced from electrolyte decomposition, resulting in reducing the dissolution of Mn. With this strategy, higher cycle stability (91.8% at 1 C after 200 cycles) and higher rate capability (109.4 mA g-1 at 1 C) were achieved in this work, compared with pristine Li-rich layered oxide. Our work offers potential for designing electrode materials utilizing oxygen redox chemistry.

A Long Cycle-Life High-Voltage Spinel Lithium-Ion Battery Electrode Achieved by Site-Selective Doping.

Spinel LiNi0.5 Mn1.5 O4 (LNMO) is a promising cathode candidate for the next-generation high energy-density lithium-ion batteries (LIBs). Unfortunately, the application of LNMO is hindered by its poor cycle stability. Now, site-selectively doped LNMO electrode is prepared with exceptional durability. In this work, Mg is selectively doped onto both tetrahedral (8a) and octahedral (16c) sites in the Fd 3 ‾ m structure. This site-selective doping not only suppresses unfavorable two-phase reactions and stabilizes the LNMO structure against structural deformation, but also mitigates the dissolution of Mn during cycling. Mg-doped LNMOs exhibit extraordinarily stable electrochemical performance in both half-cells and prototype full-batteries with novel TiNb2 O7 counter-electrodes. This work pioneers an atomic-doping engineering strategy for electrode materials that could be extended to other energy materials to create high-performance devices.

Understanding Rechargeable Battery Function Using In Operando Neutron Powder Diffraction.

The performance of rechargeable batteries is influenced by the structural and phase changes of components during cycling. Neutron powder diffraction (NPD) provides unique and useful information concerning the structure-function relation of battery components and can be used to study the changes to component phase and structure during battery cycling, known as in operando measurement studies. The development and use of NPD for in operando measurements of batteries is summarized along with detailed experimental approaches that impact the insights gained by these. A summary of the information gained concerning battery function using in operando NPD measurements is provided, including the structural and phase evolution of electrode materials and charge-carrying ion diffusion pathways through these, which are critical to the development of battery technology.

Coupling Topological Insulator SnSb2 Te4 Nanodots with Highly Doped Graphene for High-Rate Energy Storage.

Topological insulators have spurred worldwide interest, but their advantageous properties have scarcely been explored in terms of electrochemical energy storage, and their high-rate capability and long-term cycling stability still remain a significant challenge to harvest. p-Type topological insulator SnSb2 Te4 nanodots anchoring on few-layered graphene (SnSb2 Te4 /G) are synthesized as a stable anode for high-rate lithium-ion batteries and potassium-ion batteries through a ball-milling method. These SnSb2 Te4 /G composite electrodes show ultralong cycle lifespan (478 mAh g-1 at 1 A g-1 after 1000 cycles) and excellent rate capability (remaining 373 mAh g-1 even at 10 A g-1 ) in Li-ion storage owing to the rapid ion transport accelerated by the PN heterojunction, virtual electron highways provided by the conductive topological surface state, and extraordinary pseudocapacitive contribution, whose excellent phase reversibility is confirmed by synchrotron in situ X-ray powder diffraction. Surprisingly, durable lifespan even at practical levels of mass loading (>10 mg cm-2 ) for Li-ion storage and excellent K-ion storage performance are also observed. This work provides new insights for designing high-rate electrode materials by boosting conductive topological surfaces, atomic doping, and the interface interaction.

Heterocarbides Reinforced Electrochemical Energy Storage.

The feasibility of transition metal carbides (TMCs) as promising high-rate electrodes is still hindered by low specific capacity and sluggish charge transfer kinetics. Improving charge transport kinetics motivates research toward directions that would rely on heterostructures. In particular, heterocomposing with carbon-rich TMCs is highly promising for enhancing Li storage. However, due to limited synthesis methods to prepare carbon-rich TMCs, understanding the interfacial interaction effect on the high-rate performance of TMCs is often neglected. In this work, a novel strategy is proposed to construct a binary carbide heteroelectrode, i.e. incorporating the carbon-rich TMC (M=Mo) with its metal-rich TMC nanowires (nws) via an ingenious in situ disproportionation reaction. Results show that the as-prepared MoC-Mo2 C-heteronanowires (hnws) electrode could fully recover its capacity after high-rates testing, and also possesses better lithium accommodation performance. Kinetic analysis verified that both electron and ion transfer in MoC-Mo2 C-hnws are superior to those of its singular counterparts. Such improvements suggest that by taking utilization of the interfacial component interactions of stoichiometry tunable heterocarbides, the electrochemical performance, especially high-rate capability of carbides, could be significantly enhanced.

Multiple Anionic Transition-Metal Oxycarbide for Better Lithium Storage and Facilitated Multielectron Reactions.

As an important class of multielectron reaction materials, the applications of transition-metal oxides (TMOs) are impeded by volume expansion and poor electrochemical activity. To address these intrinsic limitations, the renewal of TMOs inspires research on incorporating an advanced interface layer with multiple anionic characteristics, which may add functionality to support properties inaccessible to a single-anion TMO electrode. Herein, a transition-metal oxycarbide (TMOC, M = Mo) with more than one anionic species was prepared as an interface layer on a corresponding oxide. A multiple anionic TMOC possesses advantages of structural stability, abundant active sites, and elevated metal cation valence states. Such merits mitigate volume changes and enhance multielectron reactions significantly. The TMOC nanocomposite has a well-maintained capacity after 1000 cycles at 2 A·g-1 and fully resumed rate performance. In situ synchrotron X-ray powder diffraction (SXRPD) analysis unveils negligible volume expansions occurring upon oxycarbide layer coupling, with lattice spacing variation less than 1% during cycling. The lithium storage mechanism is further inspected by combined analysis of kinetics, SXRPD, and first-principles calculations. Superior to TMO, multielectron reactions of the TMOC electrode have been boosted due to easier rupture of the metal-oxygen bond. Such improvements underscore the importance of incorporating an oxycarbide configuration as a strategy to expand applications of TMOs.

Fe3O4-Decorated Porous Graphene Interlayer for High-Performance Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries are seriously restrained by the shuttling effect of intermediary products and their further reduction on the anode surface. Considerable researches have been devoted to overcoming these issues by introducing carbon-based materials as the sulfur host or interlayer in the Li-S systems. Herein, we constructed a multifunctional interlayer on a separator by inserting Fe3O4 nanoparticles (NPs) in a porous graphene (PG) film to immobilize polysulfides effectively. The porous structure of graphene was optimized by controlling the oxidation conditions for facilitating ion transfer. The polar Fe3O4 NPs were employed to trap sulfur species via strong chemical interaction. By exploiting the PG-Fe3O4 interlayer with optimal porous structure and component, the Li-S battery delivered a superior cycling performance and rate capability. The reversible discharge capacity could be maintained at 732 mAh g-1 after 500 cycles and 356 mAh g-1 after total 2000 cycles at 1 C with a final capacity retention of 49%. Moreover, a capacity of 589 mAh g-1 could also be maintained even at 2 C rate.

Suppressing Self-Discharge and Shuttle Effect of Lithium-Sulfur Batteries with V2 O5 -Decorated Carbon Nanofiber Interlayer.

V2 O5 decorated carbon nanofibers (CNFs) are prepared and used as a multifunctional interlayer for a lithium-sulfur (Li-S) battery. V2 O5 anchored on CNFs can not only suppress the shuttle effect of polysulfide by the strong adsorption and redox reaction, but also work as a high-potential dam to restrain the self-discharge behavior in the battery. As a result, Li-S batteries with a high capacity and long cycling life can be stored and rested for a long time without obvious capacity fading.

Breathable and Wearable Energy Storage Based on Highly Flexible Paper Electrodes.

Breathable and wearable energy storage is achieved based on an innovative design solution. Carbon nanotube/MnO2 -decorated air-laid paper electrodes, with outstanding flexibility and good electrochemical performances, are prepared. They are then assembled into solid-state supercapacitors. By making through-holes on the supercapacitors, breathable and flexible supercapacitors are successfully fabricated.

Ultrafine TiO2 Decorated Carbon Nanofibers as Multifunctional Interlayer for High-Performance Lithium-Sulfur Battery.

Although lithium-sulfur (Li-S) batteries deliver high specific energy densities, lots of intrinsic and fatal obstacles still restrict their practical application. Electrospun carbon nanofibers (CNFs) decorated with ultrafine TiO2 nanoparticles (CNF-T) were prepared and used as a multifunctional interlayer to suppress the volume expansion and shuttle effect of Li-S battery. With this strategy, the CNF network with abundant space and superior conductivity can accommodate and recycle the dissolved polysulfides for the bare sulfur cathode. Meanwhile, the ultrafine TiO2 nanoparticles on CNFs work as anchoring points to capture the polysulfides with the strong interaction, making the battery perform with remarkable and stable electrochemical properties. As a result, the Li-S battery with the CNF-T interlayer delivers an initial reversible capacity of 935 mA h g(-1) at 1 C with a capacity retention of 74.2% after 500 cycles. It is believed that this simple, low-cost and scalable method will definitely bring a novel perspective on the practical utilization of Li-S batteries.