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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.

Although the two active redox centers in Li-rich cathodes, including the anionic and cationic contributions, can enable Li-ion batteries to achieve outstanding specific energy, their behaviors at different current densities have not been clarified. Here, we provide a comparative study of transition metals (TMs) and oxygen redox activities by directly accessing their oxidation states in Li-rich materials operated at very different current rates. Our data reveal that the oxidation of oxygen in the near-surface region is at the same level for electrodes cycled with a wide range of current rates, indicating a reaction gradient of lattice oxygen redox reactions. The oxidation process of lattice oxygen is found to be dynamically compatible with that of the TMs. Combining the results of first principles calculations and complementary experimental findings, we propose a detailed mechanism of structural distortion from octahedral Li to tetrahedral Li and the role of oxygen vacancy in Li+ diffusion. It is found that fast delithiation occurring at high current densities can easily cause local structural transformation, leading to a limited Li+ diffusion rate and consequently suppressing rate capability.

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.

Cation-disordered Li-excess cathodes with oxygen redox reactions are promising candidates for high-energy-density Li ion batteries. Nevertheless, the oxygen redox process that is required for the high capacity often comes with the oxygen loss, which leads to severe capacity degradation and voltage decay. In this work, we have successfully synthesized a series of Li-excess cation-disordered cathodes (Li1.2Mn0.4+xTi0.4-xO2-xFx) (0 ​≤ ​x ​≤ ​0.2) with different fluorine (F) contents. The electrochemical performance results show that the Li1.2Mn0.55Ti0.25O1.85F0.15 (LMTOF0.15) exhibits the highest reversible capacity (275 mAh g-1, under 30 ​mA ​g-1), cyclability, and voltage retentions. The mapping of resonant inelastic X-ray scattering (mRIXS) and differential electrochemical mass spectroscopy (DEMS) results reveal that the fluorination enhances the reversible lattice oxygen redox reaction while suppressing irreversible gas release and surface reactions. The X-ray Absorption Spectroscopy (XAS) during the initial two cycles shows that F-substitution alleviates the reduction of the Mn valence state during the whole (dis)charge processes in the bulk and at the surface of the material, results in higher average discharge voltage. In addition, the introduction of F improves the structural stability and suppresses local lattice distortion of the material. Therefore, LMTOF0.15 is able to cycle with smaller polarization, less interfacial side reaction and Mn dissolution, and therefore results in enhanced cyclability. This work provides a comprehensive understanding of the fluorination effect on the cationic and anionic redox activities in cation-disordered Li-excess cathodes.

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.

Both powerful and unstable, practical lithium metal batteries have remained a difficult challenge for over 50 years. With severe ion depletion gradients in the electrolyte during charging, they rapidly develop porosity, dendrites, and dead Li that cause poor performance and, all too often, spectacular failure. Remarkably, incorporating a small, 100 MHz surface acoustic wave device (SAW) solves this problem. Providing acoustic streaming electrolyte flow during charging, the device enables dense Li plating and avoids porosity and dendrites. SAW-integrated Li cells can operate up to 6 mA cm-2 in a commercial carbonate-based electrolyte; omitting the SAW leads to short circuiting at 2 mA cm-2 . The Li deposition is morphologically dendrite-free and close to theoretical density when cycling with the SAW. With a 245 µm thick Li anode in a full Li||LFP (LiFePO4 ) cell, introducing the SAW increases the uncycled Li from 145 to 225 µm, decreasing Li consumption from 41% to only 8%. A closed-form model is provided to explain the phenomena and serve as a design tool for integrating this chemistry-agnostic approach into batteries whatever the chemistry within.

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.

In this work, we show that the well-known lithium-ion anode material, Li4Ti5O12, exhibits exceptionally high initial capacity of 310 mAh g-1 when it is discharged to 0.01 V. It maintains a reversible capacity of 230 mAh g-1, far exceeding the "theoretical" capacity of 175 mAh g-1 when this anode is lithiated to the composition Li7Ti5O12. Neutron diffraction analyses identify that additional Li reversibly enters into the Li7Ti5O12 to form Li8Ti5O12. density functional theory (DFT) calculations reveal the average potentials of the Li4Ti5O12 to Li7Ti5O12 step and the Li7Ti5O12 to Li8Ti5O12 step are 1.57 and 0.19 V, respectively, which are in excellent agreement with experimental results. Transmission electron microscopy (TEM) studies confirm that the irreversible capacity of Li4Ti5O12 during its first cycle originates from the formation of a solid electrolyte interface (SEI) layer. This work clarifies the fundamental lithiation mechanism of the Li4Ti5O12, when lithiated to 0.01 V vs Li.

Density functional theory is coupled with experiment to explore the ability of substitutional doping to improve oxygen stability in Li-rich layered oxide bulk.

Anisotropic disorder along the c-axis results from static disorder.