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A critical issue in state-of-the-art solid oxide cell stacks is the contacting of the oxygen electrode. The commonly used ceramic contact layers are applied in a green state and cannot be sintered properly, due to compliance limitations arising from other stack components like sealing glasses and steels. The consequence is a low layer and interface strength. A metallic copper manganese foam, which is oxidized under operation conditions into a conductive Cu1+xMn2–xO4 spinel, is presented in this work as a viable contact solution. The foam has been electrochemically tested in a single repeating unit setup for 350 hours of constant operation, followed by dynamic conditions with thermal cycles. After operation, a micro structural analysis using scanning electron microscopy, energy dispersive X-ray spectroscopy and X-ray diffraction was carried out. It was confirmed that after oxidation/operation the manganese solely formed a CuMn-spinel phase, mixed with a CuO phase. A separate Mn-oxide phase was not found. The conductivity and contacting of the foam was sufficient for > 350 h of SOFC operation. With an initial serial resistance comparable to single cell tests using gold foil as contact material and moderate degradation rates, the CuMn foam presented itself as an interesting cathode contact solution.

First order magnetic phase transition materials present a large magnetocaloric effect around the transition temperature, where these materials usually undergo a large volume or structural change. This may lead to some challenges for applications, as the material may break apart during field change, due to high internal stresses. A promising magnetocaloric material is La(Fe, Mn, Si)13Hy, where the transition temperature can be controlled through the Mn amount. In this work we use XRD measurements to evaluate the temperature dependence of the unit cell volume with a varying Mn amount. The system is modelled using the Bean-Rodbell model, which is based on the assumption that the spin-lattice coupling depends linearly on the unit cell volume. This coupling is defined by the model parameter η, where for η > 1 the material undergoes a first order transition and for η ≤ 1 a second order transition. We superimpose a Gaussian distribution of the transition temperature with a standard deviation σT, in order to model the chemical inhomogeneity. Good agreement is obtained between measurements and model with values of η ∼ 1.8 and σ(T) = 1.0 K.

The Li-O-2 battery technology holds the promise to deliver a battery with significantly increased specific energy compared to today's Li-ion batteries. As a cathode support material, reduced graphene oxide has received increasing attention in the Li-O-2 battery community due to the possibility of increased discharge capacity, increased battery cyclability, and decreased, charging, overpotential. In this. article we investigate the effect of water on a thermally, redircedigraphene, oxide cathode in a Li-O-2 battery. Differential electrochemical mass spectrciscnieveals a, decreased electron count for batteries with 1000 ppm water added- to the electrolyte in comparison to dry batteries, indicating additional parasitic electrochemical or chemical processes. A comparable capacity of the wet and dry batteries indicates that the reaction mechanism in the Li-O-2 battery also depends on the 'surface-of-the cathode and not only on addition of water to the electrolyte as demonstrated by the solution-based mechanism In situ synchrotron X-ray diffraction experiment using a new design of a capillary-based Li-O-2 cell with a thermally reduced graphene oxide cathode shows formation of LiOH along with Li2O2.

We use powder X-ray diffraction to evaluate the temperature dependence of the crystalline properties during the magnetic phase transition of La(Fe,Mn,Si)13Hz as a function of the Fe/Mn/Si ratio. Both the paramagnetic and ferromagnetic phases were observed as peak overlaps in the patterns around the Curie temperature (TC) occurring continuously in a temperature range of about 5 K around TC. Using the Williamson-Hall method, we evaluate the strain developing in the crystallites during the transition and find that it is associated with the growth of the paramagnetic phase as the transition occurs. Based on our measurements and microstructure analyses, we propose that cracking during the phase transition is due to or aggravated by the small content of a La-rich phase.

In this work we characterize all-solid-state lithium-sulfur batteries based on nano-confined LiBH4 in mesoporous silica as solid electrolytes. The nano-confined LiBH4 has fast ionic lithium conductivity at room temperature, 0.1 mScm-1, negligible electronic conductivity and its cationic transport number (t+ = 0.96), close to unity, demonstrates a purely cationic conductor. The electrolyte has an excellent stability against lithium metal. The behavior of the batteries is studied by cyclic voltammetry and repeated charge/discharge cycles in galvanostatic conditions. The batteries show very good performance, delivering high capacities versus sulfur mass, typically 1220 mAhg-1 after 40 cycles at moderate temperature (55°C), 0.03 C rates and working voltage of 2 V.

In this work we study the structural degradation of a laboratory Li-ion battery LiFePO4/Carbon Black (LFP/CB) cathode by various electron microscopy techniques including low kV Focused Ion Beam (FIB)/Scanning Electron Microscopy (SEM) 3D tomography. Several changes are observed in FIB/SEM images of fresh and degraded cathodes, including cracks in the LFP particles, secondary disconnected particles, and agglomeration of CB. Low voltage (1 kV) SEM images show that the CB agglomerates have a different brightness than the fresh CB, due to charging effects. This suggests that the electronic conductivity of the CB agglomerates is low compared to that of the fresh CB particles. HRTEM analysis shows that fresh CB particles are quasi crystalline, whereas the LFP/CB interface in the degraded electrode shows amorphous carbon surrounding the LFP particles. The presence of the amorphous carbon is known to impede the electronic conductivity and thereby decreasing percolation in the cathode and reducing the electrode capacity.

Transmission electron microscopy (TEM) has been used intensively in investigating battery materials, e.g. to obtain phase maps of partially (dis)charged (lithium) iron phosphate (LFP/FP), which is one of the most promising cathode material for next generation lithium ion (Li-ion) batteries. Due to the weak interaction between Li atoms and fast electrons, mapping of the Li distribution is not straightforward. In this work, we revisited the issue of TEM measurements of Li distribution maps for LFP/FP. Different TEM techniques, including spectroscopic techniques (energy filtered (EF)TEM in the energy range from low-loss to core loss) and a STEM diffraction technique (automated crystal orientation mapping (ACOM)), were applied to map the lithiation of the same location in the same sample. This enabled a direct comparison of the results. The maps obtained by all methods showed excellent agreement with each other. Because of the strong difference in the imaging mechanisms, it proves the reliability of both the spectroscopic and STEM diffraction phase mapping. A comprehensive comparison of all methods is given in terms of information content, dose level, acquisition time and signal quality. The latter three are crucial for the design of in situ experiments with beam sensitive Li-ion battery materials. Furthermore, we demonstrated the power of STEM diffraction (ACOM-STEM) providing additional crystallographic information, which can be analyzed to gain a deeper understanding of the LFP/FP interface properties such as statistical information on phase boundary orientation and misorientation between domains.

Reduced graphene oxide (rGO) has shown great promise as an air-cathode for Li–air batteries with high capacity. In this article we demonstrate how the oxidation time of graphene oxide (GO) affects the ratio of different functional groups and how trends of these in GO are extended to chemically and thermally reduced GO. We investigate how differences in functional groups and synthesis may affect the performance of Li–O2 batteries. The oxidation timescale of the GO was varied between 30min and 3days before reduction. Powder X-ray diffraction, micro-Raman, FE-SEM, BET analysis, and XPS were used to characterize the GO’s and rGO’s. Selected samples of GO and rGO were analyzed by solid state 13C MAS NMR. These methods highlighted the difference between the two types of rGO’s, and XPS indicated how the chemical trends in GO are extended to rGO. A comparison between XPS and 13C MAS NMR showed that both techniques can enhance the structural understanding of rGO. Different rGO cathodes were tested in Li–O2 batteries which revealed a difference in overpotentials and discharge capacities for the different rGO’s. We report the highest Li–O2 battery discharge capacity recorded of approximately 60,000mAh/gcarbon achieved with a thermally reduced GO cathode.

For Li-air batteries to reach their full potential as energy storage system, a complete understanding of the conditions and reactions in the battery during operation is needed. To follow the reactions in situ a capillary-based Li-O2 battery has been developed for synchrotron-based in situ X-ray powder diffraction (XRPD). In this article, we present the results for the analysis of 1st and 2nd deep discharge and charge for a cathode being cycled between 2 and 4.6 V. The crystalline precipitation of Li2O2 only is observed in the capillary battery. However, there are indications of side reactions. The Li2O2 diffraction peaks grow with the same rate during charge and the development of the full width at half maximum (FWHM) is hkl dependent. The difference in the FWHM of the 100 and the 102 reflections indicate anisotropic morphology of the Li2O2 crystallites or defects along the c-axis. The effect of constant exposure of X-ray radiation to the electrolyte and cathode during charge of the battery was also investigated. X-ray exposure during charge leads to changes in the development of the intensity and the FWHM of the Li2O2 diffraction peaks. The X-ray diffraction results are supported by ex situ X-ray photoelectron spectroscopy (XPS) of discharged cathodes to illuminate non-crystalline deposited materials.

Carbon black (CB) additives commonly used to increase the electrical conductivity of electrodes in Li-ion batteries are generally believed to be electrochemically inert additives in cathodes. Decomposition of electrolyte in the surface region of CB in Li-ion cells at high voltages up to 4.9 V is here studied using electrochemical measurements as well as structural and surface characterizations. LiPF6 and LiClO4 dissolved in ethylene carbonate:diethylene carbonate (1:1) were used as the electrolyte to study irreversible charge capacity of CB cathodes when cycled between 4.9 V and 2.5 V. Synchrotron-based soft X-ray photoelectron spectroscopy (SOXPES) results revealed spontaneous partial decomposition of the electrolytes on the CB electrode, without applying external current or voltage. Depth profile analysis of the electrolyte/cathode interphase indicated that the concentration of decomposed species is highest at the outermost surface of the CB. It is concluded that carboxylate and carbonate bonds (originating from solvent decomposition) and LiF (when LiPF6 was used) take part in the formation of the decomposed species. Electrochemical impedance spectroscopy measurements and transmission electron microscopy results, however, did not show formation of a dense surface layer on CB particles.

Ionic liquids (ILs) have been proposed as promising solvents for Li-air battery electrolytes. Here, several ILs have been investigated using differential electrochemical mass spectrometry (DEMS) to investigate the electrochemical stability in a Li-O-2 system, by means of quantitative determination of the rechargeability (GER/ORR), and thereby the Coulombic efficiency of discharge and charge. None of the IL-based electrolytes are found to behave as needed for a functional Li-O-2 battery but perform better than commonly used organic solvents. Also the extent of rechargeability/reversibility has been found to be strongly dependent on the choice of IL cation and anion as well as various impurities.

Possible changes in the oxidation state of the oxygen ion in the lithium iron phosphate Li3Fe2(PO4)3 at high voltages in lithium-ion (Li-ion) batteries are studied using experimental and computational analysis. Results obtained from synchrotron-based hard X-ray photoelectron spectroscopy and density functional theory (DFT) show that the oxidation state of O2− ions is altered to higher oxidation states (Oδ−, δ<2) upon charging Li3Fe2(PO4)3 to 4.7 V.

Reduced graphene oxide (rGO) has shown great promise as an air-cathode for Li-air batteries with high capacity. In this article we demonstrate how the oxidation time of graphene oxide (GO) affects the ratio of different functional groups and how trends of these in GO are extended to chemically and thermally reduced GO. We investigate how differences in functional groups and synthesis may affect the performance of Li-O-2 batteries. The oxidation timescale of the GO was varied between 30 min and 3 days before reduction. Powder Xray diffraction, micro-Raman, FE-SEM, BET analysis, and XPS were used to characterize the GO's and rGO's. Selected samples of GO and rGO were analyzed by solid state C-13 MAS NMR. These methods highlighted the difference between the two types of rGO's, and XPS indicated how the chemical trends in GO are extended to rGO. A comparison between XPS and C-13 MAS NMR showed that both techniques can enhance the structural understanding of rGO. Different rGO cathodes were tested in Li-O-2 batteries which revealed a difference in overpotentials and discharge capacities for the different rGO's. We report the highest Li-O-2 battery discharge capacity recorded of approximately 60,000 mAh/gcarbon achieved with a thermally reduced GO cathode. (C) 2015 Elsevier Ltd. All rights reserved.

LiBH4–Ca(BH4)2 composites were prepared by ball milling. Their crystal structures and phase composition were investigated using synchrotron X-ray diffraction and Rietveld refinement, and their ionic conductivity was measured using impedance spectroscopy. The materials were found to form a physical mixture. The composites were composed of α-Ca(BH4)2, γ-Ca(BH4)2 and orthorhombic LiBH4, and the relative phase quantities of the Ca(BH4)2 polymorphs varied significantly with LiBH4 content. The formation of small amounts of orthorhombic CaH2 and cubic CaH2 in a CaF2-like structure was observed upon heat treatment. Concurrent formation of elemental boron may also occur. The ionic conductivity of the composites was measured using impedance spectroscopy, and was found to be lower than that of ball milled LiBH4. Electronic band structure calculations indicate that cubic CaH2 with hydrogen defects is electronically conducting. Its formation along with the possible precipitation of boron therefore has an effect on the measured conductivity of the LiBH4–Ca(BH4)2 composites and may increase the risk of an internal short-circuit in the cells.

Dimethyl sulfoxide (DMSO) and acetonitrile (MeCN) have recently been highlighted as promising electrolyte solvents for Li-O2 batteries. Possible reactions between these two solvents and Li2O2 are here discussed using X-ray photoelectron spectroscopy to analyze surface of the Li2O2 powder after direct contact with the solvents for different times of exposure. The results indicated that Li2O2 decomposes DMSO solvents, whereas no indication of degradation of MeCN by Li2O2 was observed.