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High‐voltage spinel‐type structured LiNi0.5Mn1.5O4 (LNMO) shows promise as a next‐generation high‐energy‐density lithium‐ion battery cathode material, however, capacity decay on extended cycling hinders its widespread adoption, underscoring an urgent need for further development. In this work, we introduce Zn at octahedral 16c crystal sites in LNMO with Fd3‾ ${\bar{3}}$ m space group to improve rate capability and reduce the rapid capacity decay otherwise experienced during extended cycling. The current work resolves the detailed influence of isolated modification at octahedral 16c crystal sites, unveiling the mechanism for these performance improvements. We show that occupation of Zn at previously empty 16c sites prevents the migration of Ni/Mn to adjacent 16c sites, eliminating transformation to a rock‐salt type structured Ni0.25Mn0.75O2 phase above 4.8 V, preventing structure degradation and suppressing voltage polarization. This study provides insights into the fundamental structure‐function relationship of the LNMO battery cathode, pointing to pathways for the crystal structure engineering of materials with superior performance. [ABSTRACT FROM AUTHOR]

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]

Abstract: In situ neutron powder diffraction measurements of a commercial lithium-ion battery reveal perturbations to the phase evolution of the Li x C6 electrode caused by overcharge. Above ∼4.5 V the anode is entirely composed of LiC6. During discharge from the post-overcharged state LiC6 persists to the 90% discharge state, compared with its persistence to the 27% discharge state during conventional cycling. At the completely discharged state the post-overcharged anode is a mixture of LiC12, LiC18, and graphite, while the conventionally cycled anode is composed of graphite alone. The phase evolution of a post-overcharged battery during charge also differs relative to conventional cycling, most noticeably until the 9% state of charge. [Copyright &y& Elsevier]

Abstract: This work uses real-time in situ neutron powder diffraction to study the electrode lattice response and anode phase evolution in a commercial lithium-ion battery. We show that the time-resolved lattice response of the Li x CoO2 cathode and Li x C6 anode under non-equilibrium conditions varies proportionally with the applied current, where higher current results in faster structural change. Higher current also reduces the Li x CoO2 cathode c lattice parameter and the LiC6 quantity that forms at the charged state of the battery, both of which are related to lower battery capacity. At the anode, we find that the Li x C6 phase evolution is current-dependent. [Copyright &y& Elsevier]

Abstract: The structural response to electrochemical cycling of the components within a commercial Li-ion battery (LiCoO2 cathode, graphite anode) is shown through in situ neutron diffraction. Lithuim insertion and extraction is observed in both the cathode and anode. In particular, reversible Li incorporation into both layered and spinel-type LiCoO2 phases that comprise the cathode is shown and each of these components features several phase transitions attributed to Li content and correlated with the state-of-charge of the battery. At the anode, a constant cell voltage correlates with a stable lithiated graphite phase. Transformation to de-lithiated graphite at the discharged state is characterised by a sharp decrease in both structural cell parameters and cell voltage. In the charged state, a two-phase region exists and is composed of the lithiated graphite phase and about 64% LiC6. It is postulated that trapping Li in the solid|electrolyte interface layer results in minimal structural changes to the lithiated graphite anode across the constant cell voltage regions of the electrochemical cycle. [ABSTRACT FROM AUTHOR]

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]

Potassium‐ion batteries (PIBs) are an emerging, affordable, and environmentally friendly alternative to lithium‐ion batteries, with their further development driven by the need for suitably performing electrode materials capable of reversibly accommodating the relatively large K+. Layer‐structured manganese oxides are attractive as electrodes for PIBs, but suffer from structural instability and sluggish kinetics of K+ insertion/extraction, leading to poor rate capability. Herein, cobalt is successfully introduced at the manganese site in the KxMnO2 layered oxide electrode material and it is shown that with only 5% Co, the reversible capacity increases by 30% at 22 mA g‐1 and by 92% at 440 mA g‐1. In operando synchrotron X‐ray diffraction reveals that Co suppresses Jahn–Teller distortion, leading to more isotropic migration pathways for K+ in the interlayer, thus enhancing the ionic diffusion and consequently, rate capability. The detailed analysis reveals that additional phase transitions and larger volume change occur in the Co‐doped material as a result of layer gliding, with these associated with faster capacity decay, despite the overall capacity remaining higher than the pristine material, even after 500 cycles. These results assert the importance of understanding the detailed structural evolution that underpins performance that will inform the strategic design of electrode materials for high‐performance PIBs. [ABSTRACT FROM AUTHOR]

Graphite has been widely used as a negative electrode material in lithium-ion batteries, and recently it has attracted attention for its use in potassium-ion batteries. In this study, the first in situ X-ray diffraction characterisation of a K/graphite electrochemical cell is performed. Various graphite intercalation compounds are found, including the stage three KC36 and stage one KC8 compounds, along with the disappearance of the graphite during the potassiation process. These results show new insights on the non-equilibrium states of potassium-ion intercalation into graphite in K/graphite electrochemical cells. [ABSTRACT FROM AUTHOR]

The structural evolution of the “zero-strain” Li4Ti5O12 anode within a functioning Li-ion battery during charge–discharge cycling was studied using in situ neutron powder-diffraction, allowing correlation of the anode structure to the measured charge–discharge profile. While the overall lattice response controls the “zero-strain” property, the oxygen atom is the only variable in the atomic structure and responds to the oxidation state of the titanium, resulting in distortion of the TiO6 octahedron and contributing to the anode's stability upon lithiation/delithiation. Interestingly, the trend of the octahedral distortion on charge–discharge does not reflect that of the lattice parameter, with the latter thought to be influenced by the interplay of lithium location and quantity. Here we report the details of the TiO6 octahedral distortion in terms of the O–Ti–O bond angle that ranges from 83.7(3)° to 85.4(5)°. [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]

The reaction evolution and kinetics of the LiFePO 4 positive electrode material is dependent on the synthesis method and cycling conditions. In operando neutron powder diffraction is used investigate the structure-electrochemistry relationship of the electrode materials in a Valence Technology Inc. 18650 Energy cell (IFR18650EC) containing a graphite negative electrode and a Mg-doped LiFePO 4 (Li(MgFe)PO 4 ) positive electrode. Two cells were studied at ambient (298 K) and elevated (323 K) temperature, and higher temperatures were found to improve reaction kinetics and hence capacity. Rietveld refinement of structural models against the diffraction data revealed information about the nucleation of the lithiated and delithiated phases in the Li(MgFe)PO 4 positive electrode material as a function of each cell's state of charge. Polarisation was indicated by a shift in the potential at which the lithiated and delithiated (MgFe)PO 4 phases nucleate during cycling, the extent of which was found to be linearly proportional to the applied current. This work provides new evidence for polarisation of the positive electrode material in a Li-ion battery system. [ABSTRACT FROM AUTHOR]

Commercial 18650 lithium ion cells containing a blended positive electrode of layered LiNi 0.5 Mn 0.3 Co 0.2 O 2 and spinel Li 1.1 Mn 1.9 O 4 alongside a graphite negative electrode were stored at various depth-of-discharge (DoD) at 60 °C for 1, 2, 4, and 6 months. After storage, the cells were cycled at C/25 at 25 °C between 2.75 and 4.2 V for capacity determination and incremental capacity analysis (ICA). In addition to ICA analysis, the mechanism for capacity fade was investigated by combining the results of neutron powder diffraction under in-situ and operando conditions, in conjunction with post-mortem studies of the electrodes using synchrotron X-ray powder diffraction and inductively-coupled plasma optical emission spectroscopy. Among the cells, those stored at 25% DoD suffered the highest capacity fade due to their higher losses of active Li, NMC, and LMO than cells stored at other DoD. The cells stored at 0% DoD shows second high capacity fade because they exhibit the highest of active LMO and graphite anode among the stored cells and higher losses of active Li and NMC than cells stored at 50% DoD. [ABSTRACT FROM AUTHOR]

Li-rich metal oxides, regarded as a high-voltage composite cathode, is currently one of the hottest positive electrode material for lithium-ion batteries, due to its high-capacity and high-energy performance. The crystallography, phase composition and morphology can be altered by synthesis parameters, which can influence drastically the capacity and cycling performance. In this work, we demonstrate Li 1.207 Ni 0.127 Mn 0.54 Co 0.127 O 2 , obtained by a co-precipitation method, exhibits super-high specific capacity up to 298 mAh g −1 and excellent capacity retention of ∼100% up to 50 cycles. Using neutron powder diffraction and transmission X-ray microscopy, we have found that the cooling-treatments applied after sintering during synthesis are crucially important in controlling the phase composition and morphology of the cathodes, thereby influencing the electrochemical performance. Unique spherical microstructure, larger lattice, and higher content of Li-rich monoclinic component can be achieved in the rapid quenching process, whereas severe particle cracking along with the smaller lattice and lower monoclinic component content is obtained when natural cooling of the furnace is applied. Combined with electrochemical impedance spectra, a plausible mechanism is described for the poorer specific capacity and cycling stability of the composite cathodes. [ABSTRACT FROM AUTHOR]

The application of detailed in-situ neutron diffraction studies on lithium ion batteries has been limited in part due to the requirement of expensive deuterated carbonate-based electrolyte. This work presents an in-situ neutron diffraction study of the structural evolution of the Li x (Ni 0.4 Mn 0.4 Co 0.2 )O 2 (NMC442) positive electrode material using a recently-developed low-cost deuterated ethyl acetate-based electrolyte. Rietveld analysis show that the NMC442 c lattice parameter gradually increases until x = 0.47 (4.03 V) and then decreases during the first charge. The decreasing trend of the c lattice parameter with time during the hold at 4.7 V and 4.9 V agrees very well with the change of current. Overall the structural changes appear highly reversible when 4.7 V is used as an upper cutoff voltage, even following a 10 h hold at 4.7 V. However, the electrode/electrolyte changes dramatically when charged and held at 4.9 V. There is a significant drop in background attributed to electrolyte decomposition and an unexpected increase in the a lattice parameter is noted after the 4.9 V hold. Therefore, the electrolyte system used is both beneficial for in-situ neutron diffraction studies and battery performance until 4.7 V, but appears to degrade in combination with the electrode at 4.9 V. By comparison to Li(Ni 0.8 Mn 0.1 Co 0.1 )O 2 (NMC811), the contraction of the c lattice with increasing voltage and decreasing lithium content of the NMC442 is less rapid. The transition metal composition significantly affects the c lattice contraction above 4.0 V. [ABSTRACT FROM AUTHOR]

A low-cost deuterated electrolyte suitable for in situ neutron diffraction measurements of normal and high voltage Li-ion battery electrodes is reported here. Li[Ni 0.4 Mn 0.4 Co 0.2 ]O 2 /graphite (NMC(442)/graphite) pouch cells filled with 1:0.1:2 (molar ratio) of lithium bis(fluorosulfonyl) imide (LiFSi):LiPF 6 : ethyl acetate (EA) and LiFSi:LiPF 6 :deuterated EA (d8-EA) electrolytes were successfully cycled between 2.8 V and 4.7 V at 40°C for 250 h without significant capacity loss, polarization growth, or gas production. The signal-to-noise ratio of neutron powder diffraction patterns taken on NMC(442) powder with a conventional deuterated organic carbonate-based electrolyte and filled with LiFSi:LiPF 6 :d8-EA electrolyte were virtually identical. Out of all the solvents widely available in deuterated form tested in highly-concentrated systems, EA was the only one providing a good balance between cost and charge-discharge capacity retention to 4.7 V. The use of such an electrolyte blend would half the cost of deuterated solvents needed for in situ neutron diffraction measurements of Li-ion batteries compared to conventional deuterated carbonate-based electrolytes. [ABSTRACT FROM AUTHOR]

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]

Abstract: This work presents the first in-situ neutron diffraction study of the MoS2 electrode, undertaken in a custom-built Li-ion battery during discharge. A review of custom-designed cells for in-situ neutron diffraction experiments is presented along with our optimised cell, which we use to show real-time information corresponding to Li-insertion into MoS2 via disappearance of the (103) reflection and increase in the d-spacing of the (002) reflection. The changes in the diffraction patterns begin at the 1.1V plateau and are complete during the 0.5V plateau. Sequential Rietveld-refinement indicates the presence of an intermediate lithiated phase (Li x MoS2) between MoS2 and LiMoS2. We observe the disappearance of all reflections for the MoS2, corresponding to the loss of long-range order, during the 0.5V plateau and no new diffraction peaks appear with further electrochemical cycling. This result is indicative of a transformation from long-range ordered MoS2 to short-range ordered LiMoS2, a result that we confirm using ex-situ synchrotron X-ray and neutron diffraction. [Copyright &y& Elsevier]

[Display omitted] • The effect of site-selective W6+ ion doping on the electrochemical performance of monoclinic TiNb 2 O 7 (TNO) has been investigated for lithium ion battery (LIC). • The ionic substitution of both Ti4+ and Nb5+ ions with W6+ ions in TNO improved the electronic conductivity. • The selective doping of W6+ ions at the Ti4+ site of TNO (W T -TNO) displayed the improved electrochemical activity, and Li+ ion diffusivity. • LIC exhibited a remarkable rate capability (156.2 mA h/g at 20 C) and excellent cycling stability (85.5% of capacity retention ratio after 500 cycles at 6 C). Monoclinic TiNb 2 O 7 (TNO) has recently been reported as a promising anode candidate for next-generation high-energy–density lithium-ion batteries (LIBs). Unfortunately, poor electronic and ionic conductivities have limited its practical application. In this study, we prepared selectively W6+-doped TNO to overcome these drawbacks. We demonstrate herein the effect of site-selective substitution on the electrochemical performance of TNO after selectively doping its Ti4+ and Nb5+ sites with W6+ ions. The W6+ ions were incorporated into the TNO lattice without dramatically altering the lattice parameters. The ionic substitution of both Ti4+ and Nb5+ ions with W6+ ions in TNO improved the electronic conductivity because of partial reduction of the Ti4+ and Nb5+ ions as a result of charge compensation. Compared with the Nb-substituted TNO (i.e., the TNO derivative in which some of the Nb5+ ions had been replaced by W6+ ions), the Ti-substituted TNO displayed superior transfer properties, presumably because of its lower effective mass. As a result, the Ti-substituted TNO had the highest energy storage performance with its reversible capacity reaching 156.2 mA h/g, even at a rate of 20 C. After 500 repetitive cycles at 6 C, 85.5% of the capacity was retained without significant capacity fading. [ABSTRACT FROM AUTHOR]