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Li-rich oxide cathodes are drawing increasing attention as next-generation cathode materials for the development of high-energy-density Li-ion batteries due to their strikingly high capacities. However, transition-metal migration, irreversible structural phase transformations, and the irreversible release of oxygen are responsible for rapid capacity and voltage decay. This study reports a Li-rich cation-ordered rock-salt oxide LixV0.4Ti0.4O2(LVTO, x = 0.97/1.2) with space group Fd3¯ m that delivers a high capacity of over 250 mAh g-1and capacity retention up to 89% after 50 cycles. A comprehensive experimental analysis confirms that the capacity can be attributed to the reversible V3+/V5+multielectron cationic redox reactions and a minor contribution from reversible anionic redox reactions. Importantly, LVTO exhibits nearly zero-strain behavior upon (dis)charge cycling cycles, which is associated with reversible V migration from octahedral to tetrahedral sites. Our results demonstrate that Li-rich rock-salt oxide LVTO could be a promising cobalt-free cathode material for Li-ion batteries.

All-climate temperature operation capability and increased energy density have been recognized as two crucial targets, but they are rarely achieved together in rechargeable lithium (Li) batteries. Herein, we demonstrate an electrolyte system by using monodentate dibutyl ether with both low melting and high boiling points as the sole solvent. Its weak solvation endows an aggregate solvation structure and low solubility toward polysulfide species in a relatively low electrolyte concentration (2 mol L-1). These features were found to be vital in avoiding dendrite growth and enabling Li metal Coulombic efficiencies of 99.0%, 98.2%, and 98.7% at 23 °C, -40 °C, and 50 °C, respectively. Pouch cells employing thin Li metal (50 μm) and high-loading sulfurized polyacrylonitrile (3.3 mAh cm-2) cathodes (negative-to-positive capacity ratio = 2) output 87.5% and 115.9% of their room temperature capacity at -40 °C and 50 °C, respectively. This work provides solvent-based design criteria for a wide temperature range Li-sulfur pouch cells.

3D hosts are promising to extend the cycle life of lithium metal anodes but have rarely been implemented with lean electrolytes thus impacting the practical cell energy density. To overcome this challenge, a 3D host that is lightweight and easy to fabricate with optimum pore size that enables full utilization of its pore volume, essential for lean electrolyte operations, is reported. The host is fabricated by casting a VGCF (vapor-grown carbon fiber)-based slurry loaded with a sparingly soluble rubidium nitrate salt as an additive. The network of fibers generates uniform pores of ≈3 µm in diameter with a porosity of 80%, while the nitrate additive enhances lithiophilicity. This 3D host delivers an average coulombic efficiency of 99.36% at 1 mA cm-2 and 1 mAh cm-2 for over 860 cycles in half-cell tests. Full cells containing an anode with 1.35-fold excess lithium paired with LiNi0.8 Mn0.1 Co0.1 O2 (NMC811) cathodes exhibit capacity retention of 80% over 176 cycles at C/2 under a lean electrolyte condition of 3 g Ah-1 . This work provides a facile and scalable method to advance 3D lithium hosts closer to practical lithium-metal batteries.

Lithium metal batteries (LMBs) hold the promise to pushing cell level energy densities beyond 300 Wh kg-1 while operating at ultra-low temperatures (< -30°C). Batteries capable of both charging and discharging at these temperature extremes are highly desirable due to their inherent reduction of external warming requirements. Here we demonstrate that the local solvation structure of the electrolyte defines the charge-transfer behavior at ultra-low temperature, which is crucial for achieving high Li metal coulombic efficiency (CE) and avoiding dendritic growth. These insights were applied to Li metal full cells, where a high-loading 3.5 mAh cm-2 sulfurized polyacrylonitrile (SPAN) cathode was paired with a one-fold excess Li metal anode. The cell retained 84 % and 76 % of its room temperature capacity when cycled at -40 and -60 °C, respectively, which presented stable performance over 50 cycles. This work provides design criteria for ultra-low temperature LMB electrolytes, and represents a defining step for the performance of low-temperature batteries.

Due to their high specific capacities beyond 250 mA h g-1, lithium-rich oxides have been considered as promising cathodes for the next generation power batteries, bridging the capacity gap between traditional layered-oxide based lithium-ion batteries and future lithium metal batteries such as lithium sulfur and lithium air batteries. However, the practical application of Li-rich oxides has been hindered by formidable challenges. To address these challenges, the understanding of their electrochemical behaviors becomes critical and is expected to offer effective guidance for both materials and cell development. This review aims to provide fundamental insights into the reaction mechanisms, electrochemical challenges and modification strategies of lithium-rich oxides. We first summarize the research history, the pristine structures, and the classification of lithium-rich oxides. Then we review the critical reaction mechanisms that are closely related to their electrochemical features and performances, such as lattice oxygen oxidation, oxygen vacancy formation, transition-metal migration, layered to spinel transitions, 'two-phase mechanism', and lattice evolution. These discussions are coupled with state-of-the-art characterization techniques. As a comparison, the anionic redox reactions of layered sodium transition metal oxides are also discussed. Finally, after a brief overview of the correlation among the aforementioned mechanisms, we provide perspectives on the rational design of lithium-rich oxides with high energy densities and long-term cycling stability. This journal is

Voltage decay,i.e., the voltage decrease during electrochemical cycling, has been a decade-long challenge for lithium-ion batteries. This issue not only leads to a substantial loss of energy density, but also raises challenges for the battery management system, hindering the commercial application of high capacity lithium-rich oxide. Here, we show that through a combination of electrochemical conditioning and thermal treatment, Li2MnO3, the parent compound of lithium-rich oxide, which typically displays severe voltage and capacity decay, could be converted into a new phase that essentially suppresses the voltage decay with improved capacity retention and rate performance. By combining atomic-sensitive nuclear magnetic resonance, differential electrochemical mass spectrometry and synchrotron-based resonant inelastic X-ray scattering, we disclose that treatment triggers the formation of three-coexisting phases,i.e., the lithium-rich layered, spinel and defect spinel phases, which enables improved reversibility of the oxygen redox activity and enhanced manganese redox reactions in the initial cycle. Our findings suggest the key role of the local structure in the voltage decay problem and provide insights for material optimizations towards lithium- and manganese-rich cathodes without the voltage decay.

Rechargeable lithium-ion batteries with high energy density that can be safely charged and discharged at high rates are desirable for electrified transportation and other applications1-3. However, the sub-optimal intercalation potentials of current anodes result in a trade-off between energy density, power and safety. Here we report that disordered rock salt4,5 Li3+xV2O5 can be used as a fast-charging anode that can reversibly cycle two lithium ions at an average voltage of about 0.6 volts versus a Li/Li+ reference electrode. The increased potential compared to graphite6,7 reduces the likelihood of lithium metal plating if proper charging controls are used, alleviating a major safety concern (short-circuiting related to Li dendrite growth). In addition, a lithium-ion battery with a disordered rock salt Li3V2O5 anode yields a cell voltage much higher than does a battery using a commercial fast-charging lithium titanate anode or other intercalation anode candidates (Li3VO4 and LiV0.5Ti0.5S2)8,9. Further, disordered rock salt Li3V2O5 can perform over 1,000 charge-discharge cycles with negligible capacity decay and exhibits exceptional rate capability, delivering over 40 per cent of its capacity in 20 seconds. We attribute the low voltage and high rate capability of disordered rock salt Li3V2O5 to a redistributive lithium intercalation mechanism with low energy barriers revealed via ab initio calculations. This low-potential, high-rate intercalation reaction can be used to identify other metal oxide anodes for fast-charging, long-life lithium-ion batteries.

Great focus has recently been placed on anionic redox, to which high capacities of Li-rich layered oxides are attributed. With almost doubled capacity compared with state-of-the-art cathode materials, Li-rich layered oxides still fall short in other performance metrics. Among these, voltage decay upon cycling remains the most hindering obstacle, in which defect electrochemistry plays a critical role. Here, we reveal that the metastable state of cycled Li-rich layered oxide, which stems from structural defects in different dimensions, is responsible for the voltage decay. More importantly, through mild thermal energy, the metastable state can be driven to a stable state, bringing about structural and voltage recovery. However, for the classic layered oxide without reversible anionic redox, thermal energy can only introduce cation disordering, leading to performance deterioration. These insights elucidate that understanding the structure metastability and reversibility is essential for implementing design strategies to improve cycling stability for high-capacity layered oxides.

As a parent compound of Li-rich electrodes, Li2MnO3 exhibits high capacity during the initial charge; however, it suffers notoriously low Coulombic efficiency due to oxygen and surface activities. Here, we successfully optimize the oxygen activities toward reversible oxygen redox reactions by intentionally introducing protons into lithium octahedral vacancies in the Li2MnO3 system with its original structural integrity maintained. Combining structural probes, theoretical calculations, and resonant inelastic X-ray scattering results, a moderate coupling between the introduced protons and lattice oxygen at the oxidized state is revealed, which stabilizes the oxygen activities during charging. Such a coupling leads to an unprecedented initial Coulombic efficiency (99.2%) with a greatly improved discharge capacity of 302 mAh g-1 in the protonated Li2MnO3 electrodes. These findings directly demonstrate an effective concept for controlling oxygen activities in Li-rich systems, which is critical for developing high-energy cathodes in batteries.

Rechargeable lithium metal batteries based on organic electrolytes face challenges of both lithium metal cycling stability and the associated safety issues. Herein, we demonstrate an in situ formed polymer gel electrolyte which enables dendrite-free lithium metal cycling. Moreover, the gel electrolyte goes through further polymerization at elevated temperatures and loses its ionic conductivity, effectively shutting down the battery. When lithium iodide (LiI) is dissolved in vinylene carbonate (VC), LiI induces the polymerization of VC to form poly(vinylene carbonate) (polyVC). The electrolyte then transforms into a polymer gel electrolyte containing VC as the solvent and LiI as the salt. At room temperature, the gel electrolyte enables dendrite-free lithium metal cycling at current densities as high as 5 mA cm-2 for 500 cycles. Furthermore, a Li/Li4Ti5O12 (LTO) cell retains 50% of the initial capacity at the 700th cycle. When the cell is heated to 80 °C, the ionic resistance of the electrolyte increases by a factor of 103, resulting in the shutdown of the cell due to the complete polymerization of VC. The approach of using in situ polymerization to enable stable lithium cycling and to serve as a thermally triggered shutdown mechanism provides a new pathway for fabricating safer lithium metal batteries.