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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]

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]

The steam oxidation resistance of UN and UN-(20 vol%)ZrN fuel pellets is evaluated to enhance understanding of steam corrosion mechanisms in advanced nuclear fuel materials. In situ neutron diffraction shows the modified UN fuel pellets form a (U 0.77 ,Zr 0.23)N solid-solution and the sole crystalline oxidation product detected in bulk is (U 0.77 ,Zr 0.23)O 2. U 2 N 3 is not detected in significant quantities during the steam oxidation of UN or (U 0.77 ,Zr 0.23)N and stable lattice parameters show that hydriding does not take place. Steam oxidation rates, obtained via sequential Rietveld refinement show how (U 0.77 ,Zr 0.23)N has a higher activation energy (79 ± 1 kJmol−1 vs. 50 ± 5 kJmol−1), higher onset temperature (430 °C vs. 400 °C) and slower reaction rates for steam oxidation up to 616 °C, than pure UN. Throughout, both UN and (U 0.77 ,Zr 0.23)N exhibit linear (non-protective) oxidation kinetics, signifying that degradation of the fuel pellets is caused by the evolution of gaseous products at the interface followed by oxide scale spallation. This quantitative and mechanistic understanding of material degradation enables better defined operating regimes and points towards (U,Zr)N solid solutions as a promising strategy for the design of advanced nuclear fuel materials with enhanced steam corrosion resistance. • In situ neutron diffraction measures (U0.77Zr0.23)N and UN steam corrosion. • Rate equations show enhanced steam oxidation resistance for (U0.77Zr0.23)N. • Both (U0.77Zr0.23)N and UN exhibit linear (non-protective) oxidation kinetics. • (U0.77Zr0.23)O2 and UO2 are the only crystalline products detected in bulk. [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]

U 3 Si 2 nuclear fuel is corroded in deuterated steam with in situ neutron diffraction. Density functional theory is coupled with rigorous thermodynamic description of the hydride including gas/solid entropy contributions. H absorbs in the 2 b interstitial site of U 3 Si 2 H x and moves to 8 j for x ≥ 0.5. Hydriding forces lattice expansion and change in a/c ratio linked to site preference. Rietveld refinement tracks the corrosion reactions at 350–500 °C and preference for the 8 j site. Above 375 °C, formation of UO 2 , U 3 Si 5 and USi 3 take place in the grain boundaries and bulk. Hydriding occurs in bulk and precedes other reactions. [Display omitted] • In situ neutron diffraction measures U 3 Si 2 corrosion in deuterated steam. • Rigorous thermodynamic description of hydride using key entropy contributions. • H absorption at 2 b interstitial site of U 3 Si 2 H x , moves to 8 j site for x ≥ 0.5. • From 350 °C, U 3 Si 2 H x fragmented by 1–2% anisotropic lattice expansion. • From 375 °C, UO 2 , U 3 Si 5 and USi 3 form in bulk and in grain boundaries. [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]

Abstract: A simple, surfactant-free assembly process was used to prepare multi-wall carbon nanotube (CNT) buckypapers using a highly efficient purification, sonication, and filtration process. To achieve effective dispersion of CNT into ethanol, a minimum 5-min sonication time was required. Here, we fabricated a buckypaper with pore size of 41±10nm and porosity of 72.9% with a 10-min sonication. The as-prepared buckypaper was used as a membrane for humic acid (HA) removal from water. During purification process, carboxylic and hydroxylic functional groups were introduced onto the CNT surface. The functional groups increased the hydrophilicity of the CNTs and improved the removal efficiency of HA by the buckypaper. The buckypaper prepared from purified CNTs exhibited excellent removal of HA (>93%) and a long lifetime for filtration. [Copyright &y& Elsevier]

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]

Abstract: The structure of the defect pyrochlore NaW2O6+δ ·nH2−z O after ion exchange with K, Rb, Sr or Cs for Na has been investigated using thermal analysis, solid-state nuclear magnetic resonance, laboratory X-ray and neutron diffraction methods. Neutron diffraction studies show that both the A-type cations (Na+, K+, Rb+, and/or Cs+) and the water molecules reside within the channels that form in the 111 direction of the W2O6 framework and that these strongly interact. The analytical results suggest that the water and A-type cations compete for space in the tunnels within the W2O6 pyrochlore framework, with the total number of water molecules and cations being approximately constant in the six samples investigated. The interplay between the cations and water explains the non-linear dependence of the a lattice parameter on the choice of cation. It appears that the ion-exchange capacity of the material will be controlled by the amount of water initially present in the sample. [Copyright &y& Elsevier]