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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 LiNi0.5Mn1.5O4 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. [ABSTRACT FROM AUTHOR]

Spinel LiNi0.5Mn1.5O4 (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 Fd3‾ 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 TiNb2O7 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. [ABSTRACT FROM AUTHOR]

The dissimilar lattice-evolution of the isostructural layered Li(Ni,Co,Al)O2 (NCR) and Li(Ni,Co,Mn)O2 (CGR) cathodes in commercial lithium-ion batteries during overcharging/discharging was examined using operando neutron powder-diffraction. The stacking axis (c parameter) of both cathodes expands on initial lithiation and contracts on further lithiation. Although both the initial increase and later decrease are smaller for the CGR cathode, the overall change between battery charged and discharged states of the c parameter is larger for the CGR (1.29%) than for the NCR cathode (0.33%). We find these differences are correlated to the transition metal to oxygen bond (as measured through the oxygen positional-parameter) which is specific to the different cathode chemistries. Finally, we note the formation of and suggest a model for a LiCx intermediate between graphite and LiC12 in the anode of both batteries. [ABSTRACT FROM PUBLISHER]

Li‐rich layered oxides (LLOs) can deliver almost double the capacity of conventional electrode materials such as LiCoO2 and LiMn2O4; however, voltage fade and capacity degradation are major obstacles to the practical implementation of LLOs in high‐energy lithium‐ion batteries. Herein, hexagonal La0.8Sr0.2MnO3−y (LSM) is used as a protective and phase‐compatible surface layer to stabilize the Li‐rich layered Li1.2Ni0.13Co0.13Mn0.54O2 (LM) cathode material. The LSM is MnOM bonded at the LSM/LM interface and functions by preventing the migration of metal ions in the LM associated with capacity degradation as well as enhancing the electrical transfer and ionic conductivity at the interface. The LSM‐coated LM delivers an enhanced reversible capacity of 202 mAh g−1 at 1 C (260 mA g−1) with excellent cycling stability and rate capability (94% capacity retention after 200 cycles and 144 mAh g−1 at 5 C). This work demonstrates that interfacial bonding between coating and bulk material is a successful strategy for the modification of LLO electrodes for the next‐generation of high‐energy Li‐ion batteries. [ABSTRACT FROM AUTHOR]

The evolution of the 003 reflection of the layered Li(Ni,Co,Mn)O2 (CGR) and Li(Ni,Co,Al)O2 (NCR) cathodes in commercial 18650 lithium-ion batteries during charge/discharge were determined using in situ neutron powder diffraction. The 003 reflection is chosen as it is the stacking axis of the layered structure and shows the largest change during charge/discharge. The comparison between these two cathodes shows that the NCR cathode exhibits an unusual contraction near the charged state and during the potentiostatic step, where the potentiostatic step is recommended by the manufacturer. This feature is not shown to the same degree by the CGR cathode. The behavior is likely related to the compositions of these cathodes, the amount of Li/Ni site mixing and the presence of Al or Mn. [ABSTRACT FROM AUTHOR]

Abstract: In this study, the application of neutron powder diffraction on studying the time-resolved structural evolution of a cell comprised with LiNi0.5Mn1.5O4 cathode and Li4Ti5O12 anode during charge–discharge cycling is demonstrated. As expected, the lattices of the LiNi0.5Mn1.5O4 cathode and the Li4Ti5O12 anode in the cell are found to simultaneously contract during charging and expand during discharging. It is found that for the LiNi0.5Mn1.5O4 cathode a solid-solution reaction is associated with the lattice change and the Ni2+/Ni3+ redox couple between 3.06 and 3.16 V (vs. Li4Ti5O12), and a two-phase reaction between Li x Ni0.5Mn1.5O4 and Ni0.25Mn0.75O2 is corresponding to the Ni3+/Ni4+ redox couple at voltage higher than 3.22 V (vs. Li4Ti5O12) without a corresponding change in lattice. The oxidation states of the metals in the electrodes are determined by tracking the associated change in the oxygen position. In addition, the Ti oxidation state is correlated to the intensity of the Li4Ti5O12 222 reflection at the anode, and the determined oxidation state of the Ni is correlated to the lithium occupancy within the cathode. Furthermore, the small volume changes of the cathode and the anode upon cycling suggest that the cell chemistry is favorable for practical applications. [Copyright &y& Elsevier]

Abstract: In-situ neutron powder diffraction was employed to investigate the structural evolution of the electrode materials in a commercial lithium-ion battery used for electric buses in Taiwan. The battery, containing a vanadium-added LiFePO4 cathode, does not exhibit a delayed phase transition between LiFePO4 (triphylite) and FePO4 (heterosite) suggesting that the delayed phase transition can be suppressed through the use of vanadium-added LiFePO4 cathodes, which also enhances the capacity and prolongs the cycle life of these batteries. Furthermore, we characterize the readily reversible structural change of the anode (Li x C6 where 0 < x ≦ 1) and correlate this to battery voltage. [Copyright &y& Elsevier]

Lithium-ionbatteries are undergoing rapid development to meetthe energy demands of the transportation and renewable energy-generationsectors. The capacity of a lithium-ion battery is dependent on theamount of lithium that can be reversibly incorporated into the cathode.This work directly quantifies the time- and current-dependent lithiumtransfer within a cathode functioning under conventional charge–dischargecycling. We examine Li1+yMn2O4under real working conditions using in situ neutronpowder diffraction and link the atomic-scale structure to the batteryperformance. The lithium location and content, oxygen positional parameter,and lattice parameter of the cathode are measured and linked to thebattery’s charge/discharge characteristics. Lithium insertion(discharge) differs from extraction (charge), a feature that may explainthe relative ease of discharge (compared with charge) of this material.An atomic-scale understanding of cathode functionality, such as revealedhere, will direct improvements in battery performance at both thepractical and the fundamental level. [ABSTRACT FROM AUTHOR]

Lithium-ion batteries power many portable devices and in the future are likely to play a significant role in sustainable-energy systems for transportation and the electrical grid. LiFePO4 is a candidate cathode material for second-generation lithium-ion batteries, bringing a high rate capability to this technology. LiFePO4 functions as a cathode where delithiation occurs via either a solid-solution or a two-phase mechanism, the pathway taken being influenced by sample preparation and electrochemical conditions. The details of the delithiation pathway and the relationship between the two-phase and solid-solution reactions remain controversial. Here we report, using real-time in situ neutron powder diffraction, the simultaneous occurrence of solid-solution and two-phase reactions after deep discharge in nonequilibrium conditions. This work is an example of the experimental investigation of nonequilibrium states in a commercially available LiFePO4 cathode and reveals the concurrent occurrence of and transition between the solid-solution and two-phase reactions. [ABSTRACT FROM AUTHOR]