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We report the magnitude of the induced magnetic moment in CVD-grown epitaxial and rotated-domain graphene in proximity with a ferromagnetic Ni film, using polarized neutron reflectivity (PNR) and X-ray magnetic circular dichroism (XMCD). The XMCD spectra at the C K-edge confirms the presence of a magnetic signal in the graphene layer and the sum rules give a magnetic moment of up to $\sim\,0.47\,\mu$_B/C atom induced in the graphene layer. For a more precise estimation, we conducted PNR measurements. The PNR results indicate an induced magnetic moment of $\sim$ 0.53 $\mu$_B/C atom at 10 K for rotated graphene and $\sim$ 0.38 $\mu$_B/C atom at 10 K for epitaxial graphene. Additional PNR measurements on graphene grown on a non-magnetic Ni_9Mo_1 substrate, where no magnetic moment in graphene is measured, suggest that the origin of the induced magnetic moment is due to the opening of the graphene's Dirac cone as a result of the strong C pz-3d hybridization., Comment: 21 pages, 7 figures

The reactions of H2, CO2, and CO gas mixtures on the surface of Cu at 200 °C, relevant for industrial methanol synthesis, are investigated using a combination of ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and atmospheric-pressure near edge X-ray absorption fine structure (AtmP-NEXAFS) spectroscopy bridging pressures from 0.1 mbar to 1 bar. We find that the order of gas dosing can critically affect the catalyst chemical state, with the Cu catalyst maintained in a metallic state when H2 is introduced prior to the addition of CO2. Only on increasing the CO2 partial pressure is CuO formation observed that coexists with metallic Cu. When only CO2 is present, the surface oxidizes to Cu2O and CuO, and the subsequent addition of H2 partially reduces the surface to Cu2O without recovering metallic Cu, consistent with a high kinetic barrier to H2 dissociation on Cu2O. The addition of CO to the gas mixture is found to play a key role in removing adsorbed oxygen that otherwise passivates the Cu surface, making metallic Cu surface sites available for CO2 activation and subsequent conversion to CH3OH. These findings are corroborated by mass spectrometry measurements, which show increased H2O formation when H2 is dosed before rather than after CO2. The importance of maintaining metallic Cu sites during the methanol synthesis reaction is thereby highlighted, with the inclusion of CO in the gas feed helping to achieve this even in the absence of ZnO as the catalyst support.

The key charge transfer processes in electrochemical energy storage devices occur at electrode–electrolyte interfaces, which are typically buried, making it challenging to access their interfacial chemistry. In the case of Li-ion batteries, metallic Li electrodes hold promise for increasing energy and power densities and, when used in conjunction with solid electrolytes, the adverse safety implications associated with dendrite formation in organic liquid electrolytes can potentially be overcome. To better understand the stability of solid electrolytes when in contact with alkali metals and the reactions that occur, here we consider the deposition of thin (∼10 nm) alkali metal films onto solid electrolyte surfaces, where the metal is thin enough that X-ray photoelectron spectroscopy can probe the buried electrode–electrolyte interface. We highlight the importance of in situ alkali metal deposition by assessing the contaminant species that are present after glovebox handling and the use of ‘inert’ transfer devices. Consequently, we compare and contrast three available methods for in situ alkali-metal deposition; Li sputter deposition, Li evaporation, and Li plating induced by e− flood-gun irradiation. Studies on both a sulphide solid electrolyte (Li6PS5Cl), and a single-layer graphene probe surface reveal that the more energetic Li deposition methods, such as sputtering, can induce surface damage and interfacial mixing that are not seen with thermal evaporation. This indicates that the appropriate selection of the Li deposition method for in situ studies is required to observe representative behaviour, and the results of previous studies involving energetic deposition may warrant further evaluation.

We combine spatially resolved scanning photoelectron spectroscopy with confocal Raman and optical microscopy to reveal how the oxidation of the buried graphene–Cu interface relates to the Cu crystallographic orientation. We analyze over 100 different graphene covered Cu (high and low index) orientations exposed to air for 2 years. Four general oxidation modes are observed that can be mapped as regions onto the polar plot of Cu surface orientations. These modes are (1) complete, (2) irregular, (3) inhibited, and (4) enhanced wrinkle interface oxidation. We present a comprehensive characterization of these modes, consider the underlying mechanisms, compare air and water mediated oxidation, and discuss this in the context of the diverse prior literature in this area. This understanding incorporates effects from across the wide parameter space of 2D material interface engineering, relevant to key challenges in their emerging applications, ranging from scalable transfer to electronic contacts, encapsulation, and corrosion protection.

The key charge transfer processes in electrochemical energy storage devices occur at electrode-electrolyte interfaces, which are typically buried, making it challenging to access their interfacial chemistry. In the case of Li-ion batteries, metallic Li electrodes hold promise for increasing energy and power densities and, when used in conjunction with solid electrolytes, the adverse safety implications associated with dendrite formation in organic liquid electrolytes can potentially be overcome. To better understand the stability of solid electrolytes when in contact with alkali metals and the reactions that occur, here we consider the deposition of thin (∼10 nm) alkali metal films onto solid electrolyte surfaces, where the metal is thin enough that X-ray photoelectron spectroscopy can probe the buried electrode-electrolyte interface. We highlight the importance of

The chemical and electrochemical reactions at the positive electrode–electrolyte interface in Li-ion batteries are hugely influential on cycle life and safety. Ni-rich layered transition metal oxides exhibit higher interfacial reactivity than their lower Ni-content analogues, reacting via mechanisms that are poorly understood. Here, we study the pivotal role of the electrolyte solvent, specifically cyclic ethylene carbonate (EC) and linear ethyl methyl carbonate (EMC), in determining the interfacial reactivity at charged LiNi0.33Mn0.33Co0.33O2(NMC111) and LiNi0.8Mn0.1Co0.1O2(NMC811) cathodes by using both single-solvent model electrolytes and the mixed solvents used in commercial cells. While NMC111 exhibits similar parasitic currents with EC-containing and EC-free electrolytes during high voltage holds in NMC/Li4Ti5O12(LTO) cells, this is not the case for NMC811. Online gas analysis reveals that the solvent-dependent reactivity for Ni-rich cathodes is related to the extent of lattice oxygen release and accompanying electrolyte decomposition, which is higher for EC-containing than EC-free electrolytes. Combined findings from electrochemical impedance spectroscopy (EIS), TEM, solution NMR, ICP, and XPS reveal that the electrolyte solvent has a profound impact on the degradation of the Ni-rich cathode and the electrolyte. Higher lattice oxygen release with EC-containing electrolytes is coupled with higher cathode interfacial impedance, a thicker oxygen-deficient rock-salt surface reconstruction layer, more electrolyte solvent and salt breakdown, and higher amounts of transition metal dissolution. These processes are suppressed in the EC-free electrolyte, highlighting the incompatibility between Ni-rich cathodes and conventional electrolyte solvents. Finally, new mechanistic insights into the chemical oxidation pathways of electrolyte solvents and, critically, the knock-on chemical and electrochemical reactions that further degrade the electrolyte and electrodes curtailing battery lifetime are provided.

Lithium-ion batteries (LIBs) are key to the transition from fossil fuels towards increased use of renewable energy sources, but their cycle-life is limited by degradation processes. We report here detailed ex-situ studies of the interfacial degradation in Ni-rich LiNixMnyCozO2 (NMC) cathode materials cycled vs. graphite. We connect electrochemical signatures of cell degradation with interfacial characterisation with Hard X-ray Photoelectron Spectroscopy (HaXPES), to reveal chemical signatures of different degradation regimes. We then introduce several complementary approaches to performing operando x-ray photoelectron and absorption spectroscopy (XPS/XAS), demonstrating how these can resolve solid-electrolyte interphase (SEI) formation on Li-ion battery anodes.

An electrochemical micro-reactor sealed with a single-layer graphene (SLG) membrane is demonstrated that allows straightforward measurement with established scanning probe microscopies. SLG serves as a working electrode which separates the liquid electrochemical environment from the ambient to enable direct energy-level determination. Kelvin probe force microscopy (KPFM) thereby reveals the shifts in Fermi-level of suspended SLG under electrochemical reaction conditions in aqueous alkaline media. Polymer-free transfer to create suspended SLG minimizes contributions to doping related to any support or contaminants, such that changes in work function (WF) relate predominantly to the electrochemical system under study. These WF changes are rationalized in the context of a simple model of electrochemical gating, providing insight into the interplay between electronic and electrochemical doping (through redox of water) of suspended graphene. Further changes in WF are attributable to the reversible functionalization of graphene during the oxygen evolution reaction. Mechanical changes in the suspended graphene in the form of bulging also occur, which are attributed to electro-wetting of graphene induced by charge-carrier doping.

Silicon monoxide is a promising alternative anode material due to its much higher capacity than graphite, and improved cyclability over other Si anodes. An in-depth analysis of the lithium silicide (Li xSi) phases that form during lithiation/delithiation of SiO is presented here and the results are compared with pure-Si anodes. A series of anode materials is first prepared by heating amorphous silicon monoxide (a-SiO) at different temperatures, X-ray diffraction and 29Si NMR analysis revealing that they comprise small Si domains that are surrounded by amorphous SiO2, the domain size and crystallinity growing with heat treatment. In and ex situ 7Li and 29Si solid-state NMR combined with detailed electrochemical analysis reveals that a characteristic metallic Li xSi phase is formed on lithiating a-SiO with a relatively high Li concentration of x = 3.4-3.5, which is formed/decomposed through a continuous structural evolution involving amorphous phases differing in their degree of Si-Si connectivity. This structural evolution differs from that of pure-Si electrodes where the end member, crystalline Li15Si4, is formed/decomposed through a two-phase reaction. The reaction pathway of SiO depends, however, on the size of the ordered Si domains within the pristine material. When crystalline domains of >3 nm within a SiO2 matrix are present, a phase resembling Li15Si4 forms, albeit at a higher overpotential. The continuous formation/decomposition of amorphous Li xSi phases without the hysteresis and phase change associated with the formation of c-Li15Si4, along with a partially electrochemically active SiO2/lithium silicate buffer layer, are paramount for the good cyclability of a-SiO.

A micro-electrochemical cell is sealed with a polymer-free single-layer graphene (SLG) membrane to monitor the stability of Cu nanoparticles (NPs) attached to SLG, as well as the interfacial electronic interactions between Cu NPs and SLG both in air and in a mildly alkaline aqueous solution under electrochemical control. A combination of techniques, including in-situ Kelvin probe force microscopy (KPFM) and ex-situ electron microscopy, are applied. When Cu NPs are metallic at cathodic potentials, there is a relatively bias-independent offset in the SLG work function due to charge transfer at the Cu-SLG contact. When Cu NPs are oxidized at anodic potentials, on the other hand, the work function of SLG also depends on the applied bias in a quasi-linear fashion due to electrochemical gating, in addition to charge transfer at the CuOx-SLG contact. Furthermore, Cu NPs were found to oxidize and detach from SLG when kept under anodic potentials for a few hours, whereas they remain adhered to SLG at cathodic potentials. This is attributed to water intercalation at the CuO-SLG interface associated with the enhanced hydrophilicity of positively polarized graphene, as supported by the absence of Cu detachment following oxidation by galvanic corrosion in air.

Ni-rich lithium nickel manganese cobalt (NMC) oxide cathode materials promise Li-ion batteries with increased energy density and lower cost. However, higher Ni content is accompanied by accelerated degradation and thus poor cycle lifetime, with the underlying mechanisms and their relative contributions still poorly understood. Here, we combine electrochemical analysis with surface-sensitive X-ray photoelectron and absorption spectroscopies to observe the interfacial degradation occurring in LiNi

Rechargeable Mg-ion batteries typically suffer from either rapid passivation of the Mg anode or severe corrosion of the current collectors by halogens within the electrolyte, limiting their practical implementation. Here, we demonstrate the broadly applicable strategy of forming an artificial solid electrolyte interphase (a-SEI) layer on Mg to address these challenges. The a-SEI layer is formed by simply soaking Mg foil in a tetraethylene glycol dimethyl ether solution containing LiTFSI and AlCl

Rechargeable Mg-ion batteries typically suffer from either rapid passivation of the Mg anode or severe corrosion of the current collectors by halogens within the electrolyte, limiting their practical implementation. Here, we demonstrate the broadly applicable strategy of forming an artificial solid electrolyte interphase (a-SEI) layer on Mg to address these challenges. The a-SEI layer is formed by simply soaking Mg foil in a tetraethylene glycol dimethyl ether solution containing LiTFSI and AlCl3, with Fourier transform infrared and ultraviolet-visible spectroscopy measurements revealing spontaneous reaction with the Mg foil. The a-SEI is found to mitigate Mg passivation in Mg(TFSI)2/DME electrolytes with symmetric cells exhibiting overpotentials that are 2 V lower compared to when the a-SEI is not present. This approach is extended to Mg(ClO4)2/DME and Mg(TFSI)2/PC electrolytes to achieve reversible Mg plating and stripping, which is not achieved with bare electrodes. The interfacial resistance of the cells with a-SEI protected Mg is found to be two orders of magnitude lower than that with bare Mg in all three of the electrolytes, indicating the formation of an effective Mg-ion transporting interfacial structure. X-ray absorption and photoemission spectroscopy measurements show that the a-SEI contains minimal MgCO3, MgO, Mg(OH)2, and TFSI-, while being rich in MgCl2, MgF2, and MgS, when compared to the passivation layer formed on bare Mg in Mg(TFSI)2/DME.

We find that the use of Au substrate allows fast, self-limited WS2 monolayer growth using a simple sequential exposure pattern of low cost, low toxicity precursors, namely tungsten hexacarbonyl and dimethylsulfide (DMS). We use this model reaction system to fingerprint the technologically important metal organic chemical vapour deposition process by operando X-ray photoelectron spectroscopy (XPS) to address the current lack of understanding of the underlying fundamental growth mechanisms for WS2 and related transition metal dichalcogenides. Au effectively promotes the sulfidation of W with simple organosulfides, enabling WS2 growth with low DMS pressure (1 mbar) and a suppression of carbon contamination of as-grown WS2, which to date has been a major challenge with this precursor chemistry. Full WS2 coverage can be achieved by one exposure cycle of 10 minutes at 700 °C. We discuss our findings in the wider context of previous literature on heterogeneous catalysis, 2D crystal growth, and overlapping process technologies such as atomic layer deposition (ALD) and direct metal conversion, linking to future integrated manufacturing processes for transition metal dichalcogenide layers.

The interface between solid electrolytes and lithium metal electrodes determines the performance of an all-solid-state battery in terms of the ability to demand high power densities and prevent the formation of lithium dendrites. This interface depends strongly on the nature of the solid electrolyte surface in contact with the metallic anode. In the garnet electrolyte/Li system, most papers have focused on the role of current inhomogeneities induced by void formation in the Li metal electrode and the presence of insulating reaction layers following air exposure. However, extended defects in the solid electrolyte induced by chemical and/or structural inhomogeneities can also lead to uneven current distribution, impacting the performance of these systems. In this work, we use complementary surface analysis techniques with varying analysis depths to probe chemical distribution within grains and grain boundaries at the surface and in the bulk of garnet-type electrolytes to explain their electrochemical performance. We show that morphology, post-treatments and storage conditions can greatly affect the surface chemical distribution of grains and grain boundaries. These properties are important to understand since they will dictate the ionic and electronic transport near the interfacial zone between metal and electrolyte which is key to determining chemo-mechanical stability.

Probing the chemistry that occurs at catalyst interfaces under realistic process conditions is key to the rational design of better materials for industrial catalytic reactions. Ambient pressure X-ray photoelectron spectroscopy, has until recently been limited to pressures two orders of magnitude below atmosphere. However, the development of photoelectron transparent membranes based on two-dimensional materials that can maintain large pressure differences and yet have thicknesses approaching or even falling below the inelastic mean free path of photoelectrons, now allows the atmospheric pressure regime and above to be accessed. We introduce here the fundamental principles underlying this membrane-based approach to atmospheric pressure photoelectron spectroscopy, and in this context highlight some of the key design concepts and challenges in performing experiments with this technique. We discuss a number of recent proof-of-concept studies, and highlight the potential of the membrane-based approach for operando characterisation of catalyst interfaces under reaction conditions, as well as some current challenges and limitations in this area.

Fluoroethylene carbonate (FEC) and vinylene carbonate (VC) are widely used as electrolyte additives in lithium ion batteries. Here we analyze the solid electrolyte interphase (SEI) formed on binder-free silicon nanowires (SiNWs) electrodes in pure FEC or VC electrolytes containing 1 M LiPF6 by solid-state nuclear magnetic resonance (ssNMR) with and without dynamic nuclear polarization (DNP) enhancement. We find that the polymeric SEIs formed in pure FEC or VC electrolytes consist mainly of cross-linked polyethylene oxide (PEO) and aliphatic chain functionalities along with additional carbonate and carboxylate species. The formation of branched fragments is further confirmed by 13C-13C correlation NMR experiments. The presence of cross-linked PEO-type polymers in FEC and VC correlates with good capacity retention and high Coulombic efficiencies of the SiNWs. Using 29Si DNP NMR, we are able to probe the interfacial region between SEI and the Si surface for the first time with NMR spectroscopy. Organosiloxanes are identified to form upon cycling, confirming that some of the organic SEI is covalently bonded to the Si surface. We suggest that both the polymeric structure of the SEI and the nature of its adhesion to the redox-active materials are important for electrochemical performance.

Membrane proteins govern many important functions in cells via dynamic oligomerization into active complexes. However, analytical methods to study their distribution and functional state in relation to the cellular structure are currently limited. Here, we introduce a technique for studying single-membrane proteins within their native context of the intact plasma membrane. SKBR3 breast cancer cells were grown on silicon microchips with thin silicon nitride windows. The cells were fixed, and the epidermal growth factor receptor ErbB2 was specifically labeled with quantum dot (QD) nanoparticles. For correlative fluorescence- and liquid-phase electron microscopy, we enclosed the liquid samples by chemical vapor deposited (CVD) graphene films. Depending on the local cell thickness, QD labels were imaged with a spatial resolution of 2 nm at a low electron dose. The distribution and stoichiometric assembly of ErbB2 receptors were determined at several different cellular locations, including tunneling nanotubes, where we found higher levels of homodimerization at the connecting sites. This experimental approach is applicable to a wide range of cell lines and membrane proteins and particularly suitable for studies involving both inter- and intracellular heterogeneity in protein distribution and expression.

Efficient injection of charge from metal electrodes into semiconductors is of paramount importance to obtain high performance optoelectronic devices. The quality of the interface between the electrode and the semiconductor must, therefore, be carefully controlled. The case of organic semiconductors presents specific problems: ambient deposition techniques, such as solution processing, restrict the choice of electrodes to those not prone to oxidation, limiting potential applications. Additionally, damage to the semiconductor in sputter coating or high temperature thermal evaporation poses an obstacle to the use of many device-relevant metals as top electrodes in vertical metal–semiconductor–metal structures, making it preferable to use them as bottom electrodes. Here, we propose a possible solution to these problems by implementing graphene-passivated nickel as an air stable bottom electrode in vertical devices comprising organic semiconductors. We use these passivated layers as hole-injecting bottom electrodes, and we show that efficient charge injection can be achieved into standard organic semiconducting polymers, owing to an oxide free nickel/graphene/polymer interface. Crucially, we fabricate our electrodes with low roughness, which, in turn, allows us to produce large area devices (of the order of millimeter squares) without electrical shorts occurring. Our results make these graphene-passivated ferromagnetic electrodes a promising approach for large area organic optoelectronic and spintronic devices. Organic semiconductors serve as a platform for (opto)electronic devices with tunable characteristics by molecular design, enabling versatile device integration, and processing strategies.1 However, ambient processing techniques such as solution processing can facilitate oxidation of metal contacts, resulting in an uncontrolled electronic interface, which is deleterious to performance in semiconductor devices.2,3 New techniques are, therefore, required to control the interface between organic semiconductors and oxidizing metals while maintaining the possibility of solution processing. Graphene has been shown to act as an atomically thin permeation barrier.4–6 Graphene grown via chemical vapor deposition (CVD) directly on the surface of strongly interacting7 catalytic metals, such as Ni, Co, or Fe, acts as a barrier layer to prevent oxidation.8–11 These oxide-free ferromagnetic interfaces have been shown to hold significant benefits within the field of spintronics,12,13 as they enable oxidative fabrication processes, such as solution processing9,10 or atomic layer deposition,14 to be used to fabricate devices with a wider range of relevant materials. One appealing possibility would be to develop graphene-passivated ferromagnets as electrodes9,10 for organic semiconductor spintronics,15–18 where the quality of the electronic interface between the ferromagnetic electrode and the organic semiconductor is of paramount importance.19,20 Another important advantage of an ambient-stable ferromagnetic layer is that it can be used as a bottom electrode in vertical metal-organic semiconductor–metal structures, allowing one to employ techniques such as sputtering to obtain high quality and thickness-controlled metal layers or multi-layers; note that sputtering cannot be used for top-electrodes as it would destroy21 the organic semiconductor. Previous reports using graphene passivated ferromagnets as electrodes for organic semiconductor devices have studied the spin injection properties10 as well as charge injection in lateral organic semiconductor field effect transistors.9 In this work, we investigate few-layer graphene-passivated nickel (Ni/FLG) as a bottom electrode for injection of holes into organic semiconducting polymers in a vertical device structure, demonstrating efficient injection into two standard semiconducting polymers deposited from solution and in air, directly on top of Ni/FLG. Compared to previous reports on graphene-passivated ferromagnetic electrodes, where lithographic techniques had to be used in order to produce micrometer-sized features,8–10,12,14 here, we were able to produce working devices with several orders of magnitude larger active area (4.5 mm2). Our results are, thus, encouraging for the further development of organic optoelectronic and spintronic devices processed from solution under ambient conditions. Nickel was initially sputtered on thermally oxidized silicon wafers, producing films with a thickness of 150 nm. FLG domains were grown on such sputtered Ni films in a custom low-pressure Chemical Vapor Deposition (CVD) reactor (base pressure ∼1 × 10−6 mbar). All substrates were cleaned by sonicating in acetone followed by isopropyl alcohol and blow-dried with a nitrogen gun before loading. Samples were heated to approximately 450 °C using a resistive heater (temperature measurements by a K-type thermocouple) with a rapid ramp rate of 100 °C/min and annealed at ∼1 mbar of H2 for 10 min. This reduces the native oxide prior to graphene growth. After annealing, the H2 flow was stopped and the chamber was evacuated back to approximately base pressure over a period of 5 min. For graphene growth, C2H2 gas was gradually introduced into the reactor via a mass flow controller by incrementally increasing the flow rate over 5 min to achieve a partial pressure of C2H2 of 2.5 × 10−4 mbar. Subsequently, the samples were held at 450 °C in 2.5 × 10−4 mbar of C2H2 for a further 25 min, before rapid cooling (initially ∼300 °C/min) while maintaining the C2H2 flow. All gases were stopped once room temperature had been reached. Upon graphene growth, a roughening of the Ni sputtered on thermally oxidized Si was observed, with an RMS = 67 nm [Fig. 1(a)]. The roughness was found to increase with increasing growth temperature. The roughening of Ni upon graphene growth is explained by grain growth in the sputtered Ni films, occurring at high temperatures during the CVD process: under these conditions, the internal forces in the film are larger than those between the film and the substrate, and diffusion of the film material is appreciable.

Funder: H2020 Marie Skłodowska-Curie Actions; doi: https://doi.org/10.13039/100010665, Hexagonal boron nitride (h-BN) is well-established as a requisite support, encapsulant and barrier for 2D material technologies, but also recently as an active material for applications ranging from hyperbolic metasurfaces to room temperature single-photon sources. Cost-effective, scalable and high quality growth techniques for h-BN layers are critically required. We utilise widely-available iron foils for the catalytic chemical vapour deposition (CVD) of h BN and report on the significant role of bulk dissolved species in h-BN CVD, and specifically, the balance between dissolved oxygen and carbon. A simple pre-growth conditioning step of the iron foils enables us to tailor an error-tolerant scalable CVD process to give exceptionally large h-BN monolayer domains. We also develop a facile method for the improved transfer of as-grown h-BN away from the iron surface by means of the controlled humidity oxidation and subsequent rapid etching of a thin interfacial iron oxide; thus, avoiding the impurities from the bulk of the foil. We demonstrate wafer-scale (2 inch) production and utilise this h-BN as a protective layer for graphene towards integrated (opto) electronic device fabrication., European Union's Horizon 2020 research and innovation program under Grant Agreement No number 785219. European Union's Horizon 2020 research and innovation program under Grant Agreement No number 796388. the Royal Commission for the Exhibition of 1851. EU Marie Skłodowska-Curie Individual Fellowship (Global) under grant ARTIST (No. 656870). EPSRC (EP/P005152/1, and Doctoral Training Award EP/M508007/1). U.K. Department of Business, Energy and Industrial Strategy (NPL Project Number 121452).

Silicon monoxide is a promising alternative anode material due to its much higher capacity than graphite, and improved cyclability over other Si anodes. An in-depth analysis of the lithium silicide (Li

To improve the energy density in Li-ion batteries, development of cathode materials with higher capacities are required, where much of the current focus is on Ni-rich lithium nickel manganese oxides (NMC). However, higher Nickel content is typically accompanied by accelerated degradation and thus poor cycle life, with undesired reactions at the electrode-electrolyte interfaces strongly implicated. There have been numerous attempts to mitigate this, using various methods including surface coatings, structural doping and advanced synthesis techniques such as core-shell or concentration gradient particles with much lower nickel concentrations at their surface. Designing improved solutions, requires a deeper mechanistic understanding of the underlying interfacial processes involved in degradation and their relative contributions. In this study these reactions are investigated in LiNi0.8Mn0.1Co0.1O2–graphite cells cycled using LP57 electrolyte (1 M LiPF6 in EC:EMC, 3:7) for different number of cycles, providing information about how interfacial degradation proceeds. Electrochemical measurements are combined with post mortem techniques including surface sensitive soft X-ray absorption spectroscopy, and photoelectron spectroscopy measured with different excitation energies. Based on fitted differential voltage analysis (DVA) data from the cells it is shown how the initial capacity fading during the first 300 cycles is almost fully attributable to excessive electrolyte reduction exhibited as SEI thickening, whereas further cycling leads to a larger contribution to capacity fading from loss of active NMC material. The initial capacity fading due to electrolyte reduction can be correlated with more plating of manganese, as compared to nickel, onto the graphite electrode, see figure. However, after 600 cycles both nickel and manganese are found in similar concentrations within the SEI. The changing ratio between the amount of plated nickel and manganese with cycle number indicates that manganese on the NMC surface initially dissolves more easily than the nickel, but as the unstable manganese ions are dissolved more and more nickel will contribute to the transition metal dissolution. The nickel ions in the SEI are also found to change their chemical surrounding as the cycling proceeded, showing that they do not form stable species and are thus likely to contribute to continued breakdown of the SEI. We compare the observed evolution of the SEI that results from cross talk between the NMC and graphite electrodes, to the case where EC-free electrolytes are used and graphite is replaced with Li4Ti5O12 (LTO) such that contributions from electrolyte reduction at the anode are expected to be minimised [1,2]. In addition to the side reactions at the graphite other important side reactions take place on the NMC, some of which are potentially initiated by the graphite electrode [3]. For instance it was found that the Li2CO3 impurities present on the NMC surface decompose throughout the cells’ cycle life rather than just during the initial cycles. Previous studies have shown how Li2CO3 coatings severely decrease the cycle life, and therefore the observations here show that decomposition related to Li2CO3 is a problem that does not disappear during the formation cycling. Instead minimizing the initial Li2CO3 formation is critical. The insights obtained here on the evolution of surface layers coupled with the individual electrochemical degradation of the electrodes will advance the understanding of the Ni-rich NMC’s capacity retention behaviour and inform future efforts to achieve longer cycle lifetimes. [1] Björklund, E., Göttlinger, M., Edström, K., Younesi, R. & Brandell, D. Sulfolane‐Based Ethylene Carbonate‐Free Electrolytes for LiNi0.6Mn0.2Co0.2O2−Li4Ti5O12 Batteries. Batter. Supercaps 3, 201– 207 (2020). [2] Björklund, E., Göttlinger, M., Edström, K., Brandell, D. & Younesi, R. Investigation of Dimethyl Carbonate and Propylene Carbonate Mixtures for LiNi0.6 Mn0.2Co0.2O2-Li4 Ti5 O12 Cells. ChemElectroChem 6, 3429–3436 (2019). [3] Björklund, E., Brandell, D., Hahlin, M., Edström, K. & Younesi, R. How the Negative Electrode Influences Interfacial and Electrochemical Properties of LiNi1/3Co1/3Mn1/3O2 Cathodes in Li-Ion Batteries. J. Electrochem. Soc. 164, A3054–A3059 (2017). Figure 1

One of the key challenges facing Li-ion batteries with Ni-rich layered cathodes is the poor interfacial stability at both electrodes. Several recent reports have investigated the reactivity of the electrolyte at the surface of LiNixMnyCo1-x-yO2 (NMC) as a function of Ni content and electrolyte composition,1,2 but many of the complex processes taking place are not fully understood. In this work, we use a rapid electrochemical-based screening protocol3 to quantify the anodic stability of single-solvent electrolytes and additive-containing electrolyte solutions with respect to the fraction of Ni in the NMC cathode. The current that flows during a high voltage hold at 4.6 V vs Li/Li+ is found to be sensitive to the NMC surface chemistry, the degree of delithiation, and the composition of the electrolyte. Post-test XPS, solution NMR, and online electrochemical mass spectroscopy (OEMS) are combined to study the electrode- and electrolyte-dependent degradation products that are insoluble on the surface of the electrode, soluble in the electrolyte, and released as gas. The insights from quantification of the electrolyte anodic stability and the degradation signatures identified through this work highlight the importance of developing unique solutions to lower the interfacial reactivity of Ni-rich cathodes, which is a critical step to prolong the cycle life of high-energy Li-ion batteries. References Y. Zhang, Y. Katayama, R. Tatara, L. Giordano, Y. Yu, D. Fraggedakis, J. G. Sun, F. Maglia, R. Jung, M. Z. Bazant, Y. Shao-Horn, Energy Environ. Sci., 13, 183, 2020. J. Wandt, A. T. S. Freiberg, A. Ogrodnik, H. A. Gasteiger, Mater. Today, 21, 825, 2018. A. Tornheim, S. E. Trask, Z. Zhang, J. Electrochem. Soc., 163, A1717, 2016.

Hexagonal boron nitride (h-BN) is the only known material aside from graphite with a structure composed of simple, stable, noncorrugated atomically thin layers. While historically used as a lubricant in powder form, h-BN layers have become particularly attractive as an ultimately thin insulator, barrier, or encapsulant. Practically all emerging electronic and photonic device concepts currently rely on h-BN exfoliated from small bulk crystallites, which limits device dimensions and process scalability. We here focus on a systematic understanding of Pt-catalyzed h-BN crystal formation, in order to address this integration challenge for monolayer h-BN via an integrated chemical vapor deposition (CVD) process that enables h-BN crystal domain sizes exceeding 0.5 mm and a merged, continuous layer in a growth time of less than 45 min. The process makes use of commercial, reusable Pt foils and allows a delamination process for easy and clean h-BN layer transfer. We demonstrate sequential pick-up for the assembly of graphene/h-BN heterostructures with atomic layer precision, while minimizing interfacial contamination. The approach can be readily combined with other layered materials and enables the integration of CVD h-BN into high-quality, reliable 2D material device layer stacks.

To realise the widespread implementation of future generations of lithium ion batteries (LIBs) in electric vehicles, significant improvements in the lifetime and power density are required. One of the most important aspects in achieving a long battery lifetime is the formation of an effective solid electrolyte interphase (SEI) layer on the anode. This layer forms mostly within the first few charge/discharge cycles by the decomposition of electrolyte components at the electrode/electrolyte interface. Although the importance of the SEI is well accepted, much dispute remains regarding its chemical composition, thickness, morphology and formation/decomposition mechanisms. This is largely due to a lack of characterisation techniques that can accurately probe the electrode-electrolyte interface with nm-scale surface sensitivity under realistic cycling conditions. As a result, most efforts to characterise the SEI have involved ex situ samples, the preparation of which may alter the SEI layer composition. Therefore, in order to gain the most accurate information, there has been a great drive to perform in situ and operando measurements. Neutron techniques offer several advantages for characterising the processes occurring in LIBs, particularly as the negative scattering length of Lithium gives a high sensitivity to changes in the lithium environment, which is not the case with X-ray techniques. Neutron reflectometry (NR) is one of the few techniques with which the nm-scale structure of buried electrode-electrolyte interfaces in a cell can be observed during electrochemical cycling.1 A number of previous studies have investigated thin film silicon or carbon electrodes, but these have typically been carried out across a limited potential range due to concerns about restructuring due to significant lithiation that could otherwise hinder interpretation of the neutron reflectivity data.2-4 To overcome this limitation we have recently used a nickel working electrode (anode) which, given its zero capacity for lithium insertion, does not alter in structure during electrochemical cycling. Here we directly observe the growth of the SEI layer on a nickel anode as a function of potential (2.00-0.05 V) during the first cycle by using our operando cell developed at ISIS Neutron and Muon Source. During the first lithiation cycle (decreasing potential), we observe the growth of a lithium-rich layer directly in contact with the nickel and another, more organic, layer on top of this lithium-rich layer. We are able to track the evolution of these layers with potential, and characterise their chemical composition using additional X-ray Photoelectron Spectroscopy measurements performed on both cycled nickel and commercial graphite electrodes for comparison. References 1. E. Owejan, J. P. Owejan, S. C. DeCaluwe, and J. A. Dura, Chem. Mater., 2012, 24, 2133−2140. 2. Jerliu, L. Dörrer, E. Hüger, G. Borchardt, R. Steitz, U. Geckle, V. Oberst, M. Bruns, O. Schneiderd and H. Schmidt, Phys. Chem. Chem. Phys., 2013, 15, 7777-7784. 3. M. Veith, M. Doucet, R. L. Sacci, B. Vacaliuc, J. K. Baldwin and J. F. Browning, Sci. Rep., 2017, 7, 6326. 4. Steinhauer, M. Stich, M. Kurniawan, B.-K. Seidlhofer, M. Trapp, A. Bund, N. Wagner, and K. A. Friedrich, ACS Appl. Mater. Interfaces, 2017, 9, 35794−35801.

International audience; We report on the integration of atomically thin 2D insulating hexagonal boron nitride (h-BN) tunnel barriers into magnetic tunnel junctions (2D-MTJs) by fabricating two illustrative systems (Co/h-BN/Co and Co/h-BN/Fe) and by discussing h-BN potential for metallic spin filtering. The h-BN is directly grown by chemical vapor deposition on prepatterned Co and Fe stripes. Spin-transport measurements reveal tunnel magneto-resistances in these h-BN-based MTJs as high as 12% for Co/h-BN/h-BN/Co and 50% for Co/h-BN/Fe. We analyze the spin polarizations of h-BN/Co and h-BN/Fe interfaces extracted from experimental spin signals in light of spin filtering at hybrid chemisorbed/ physisorbed h-BN, with support of ab initio calculations. These experiments illustrate the strong potential of h-BN for MTJs and are expected to ignite further investigations of 2D materials for large signal spin devices.

We systematically dope monolayer graphene with different concentrations of nitric acid over a range of temperatures, and analyze the variation of sheet resistance after vacuum annealing up to 300 degrees C. The optimized HNO3 doping conditions yield sheet resistances as low as 180 Omega sq.(-1), which is significantly more stable under vacuum annealing than previously reported values. Raman and photoemission spectroscopy suggest that this stable graphene doping occurs by a bi-modal mechanism. Under mild conditions the dopants are weakly bonded to graphene, but at high acid temperatures and concentrations, the doping is higher and more stable upon post-doping annealing, without causing significant lattice damage. This work shows that large, stable hole concentrations can be induced by transfer doping in graphene.

Elektrochemisch gewachsenes Cobalt auf Graphen weist außergewöhnliche Katalysatoreigenschaften für die Sauerstoffentwicklungsreaktion (OER) auf und bietet die Möglichkeit, die Morphologie und die chemischen Eigenschaften während der Abscheidung zu kontrollieren. Es gibt allerdings noch kein ausreichendes Verständnis der atomaren Struktur dieses Hybridmaterials. Um die elektronische Struktur von Co/Graphen aufzuklären, haben wir eine Durchflusszelle entwickelt, die durch eine Graphenmembran abgeschlossen wird und elektronische und chemische Informationen über die aktiven Oberflächen unter atmosphärischem Druck und in der Gegenwart von flüssigen Elektrolyten unter Verwendung von Röntgenphotoelektronenspektroskopie (XPS) liefert. Wir konnten zeigen, dass Cobalt an Graphen über Carbonyl-ähnliche Spezies bindet, d. h. Co(CO)x , und so die Reduktion von Co3+ zu Co2+ fördert, das als aktives Zentrum des Katalysators vermutet wird.

Atmospheric pressure X-ray spectroscopy techniques based on soft X-ray excitation can provide powerful interface-sensitive chemical information about a solid surface immersed in a gas or liquid environment. However, X-ray illumination of such dense phases can lead to the generation of considerable quantities of radical species by radiolysis. Soft X-ray absorption measurements of Cu films in both air and aqueous alkali halide solutions reveal that this can cause significant evolution of the Cu oxidation state. In air and NaOH (0.1 M) solutions, the Cu is oxidized toward CuO, while the addition of small amounts of CH3OH to the solution leads to reduction toward Cu2O. For Ni films in NaHCO3 solutions, the oxidation state of the surface is found to remain stable under X-ray illumination and can be electrochemically cycled between a reduced and oxidized state. We provide a consistent explanation for this behavior based on the products of X-ray-induced radiolysis in these different environments and highlight a number of general approaches that can mitigate radiolysis effects when performing operando X-ray measurements.

The direct chemical vapour deposition of freestanding graphene gyroids with controlled sub-60 nm unit cell sizes is demonstrated. Three-dimensional (3D) nickel templates were fabricated through electrodeposition into a selectively voided triblock terpolymer. The high temperature instability of sub-micron unit cell structures was effectively addressed through the early introduction of the car- bon precursor, which stabilizes the metallized gyroidal templates. The as-grown graphene gyroids are self-supporting and can be transferred onto a variety of substrates. Furthermore, they represent the smallest free standing periodic graphene 3D structures yet produced with a pore size of tens of nm, as analysed by electron microscopy and optical spectroscopy. We discuss generality of our methodology for the synthesis of other types of nanoscale, 3D graphene assemblies, and the trans- ferability of this approach to other 2D materials.

Shale gas extraction (SGE) and, more precisely, hydraulic fracturing, also known as fracking, has a propensity to court controversy wherever it is proposed. Many processes within SGE are essentially civil engineering processes and while numerous studies into the efficacy of SGE exist, answers to ethical and societal questions relating to safety, health and environmental sustainability remain unanswered. Recently, the UK Department of Energy and Climate Change announced its intention to support studies that encourage the development of innovative technologies for safe and responsible exploitation of the UK's shale gas resources. This paper explores the current state of knowledge regarding safety, health and wellbeing in the SGE industry, and presents the case for a detailed multi-disciplinary value-engineering study to develop pre-drill assessments and to provide ongoing monitoring tools that will assure public authorities, market operators and citizens that best-practice environmental, safety and sustainability approaches are available and feasible.

We report the growth of carbon nanotubes on tetrahedral-amorphous carbon using a Fe-Cu catalyst system at temperatures

A bimetallic CoCu alloy thin-film catalyst is developed that enables the growth of uniform, high-quality graphene at 750 °C in 3 min by chemical vapour deposition. The growth outcome is found to vary significantly as the Cu concentration is varied, with ∼1 at% Cu added to Co yielding complete coverage single-layer graphene growth for the conditions used. The suppression of multilayer formation is attributable to Cu decoration of high reactivity sites on the Co surface which otherwise serve as preferential nucleation sites for multilayer graphene. X-ray photoemission spectroscopy shows that Co and Cu form an alloy at high temperatures, which has a drastically lower carbon solubility, as determined by using the calculated Co-Cu-C ternary phase diagram. Raman spectroscopy confirms the high quality (ID/IG < 0.05) and spatial uniformity of the single-layer graphene. The rational design of a bimetallic catalyst highlights the potential of catalyst alloying for producing two-dimensional materials with tailored properties.

We report the growth of vertically-aligned nanotube forests, of up to 0.2 mm in height, on an 85:15 sp 2 : sp 3 carbon support with Fe catalyst. This is achieved by purely-thermal chemical vapour deposition with the catalyst pretreated in inert environments. Pretreating the catalyst in a reducing atmosphere causes catalyst diffusion into the support and the growth of defective tubes. Other sp 2 : sp 3 compositions, including graphite, tetrahedral amorphous carbon, and pure diamond, also lead to the growth of defective carbon morphologies. These results pave the way towards controlled growth of forests on carbon fibres. It could give rise to applications in enhanced fuel cell electrodes and better hierarchical carbon fibre-nanotube composites.

Intercalation of oxygen at the interface of graphene grown by chemical vapour deposition and its polycrystalline copper catalyst can have a strong impact on the electronic, chemical and structural properties of both the graphene and the Cu. This can affect the oxidation resistance of the metal as well as subsequent graphene transfer. Here, we show, using near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS), X-ray absorption near edge spectroscopy (XANES), energy dispersive X-ray spectroscopy (EDX) and (environmental) scanning electron microscopy (ESEM) that both the oxygen intercalation and de-intercalation are kinetically driven and can be clearly distinguished from carbon etching. The obtained results reveal that a charge transfer between as grown graphene and Cu can be annulled by intercalating oxygen creating quasi-free-standing graphene. This effect is found to be reversible on vacuum annealing proceeding via graphene grain boundaries and defects within the graphene but not without loss of graphene by oxidative etching for repeated (de-)intercalation cycles.

Complementary in situ X-ray photoelectron spectroscopy (XPS), X-ray diffractometry, and environmental scanning electron microscopy are used to fingerprint the entire graphene chemical vapor deposition process on technologically important polycrystalline Cu catalysts to address the current lack of understanding of the underlying fundamental growth mechanisms and catalyst interactions. Graphene forms directly on metallic Cu during the high-temperature hydrocarbon exposure, whereby an upshift in the binding energies of the corresponding C1s XPS core level signatures is indicative of coupling between the Cu catalyst and the growing graphene. Minor carbon uptake into Cu can under certain conditions manifest itself as carbon precipitation upon cooling. Postgrowth, ambient air exposure even at room temperature decouples the graphene from Cu by (reversible) oxygen intercalation. The importance of these dynamic interactions is discussed for graphene growth, processing, and device integration.

Ambient-pressure X-ray photoelectron spectroscopy (APXPS) and high-pressure scanning tunneling microscopy (HPSTM) were used to study the structure and chemistry of model Cu(100) and Cu(111) catalyst surfaces in the adsorption and dissociation of CO2. It was found that the (100) face is more active in dissociating CO2 than the (111) face. Atomic oxygen formed after the dissociation of CO2 poisons the surface by blocking further adsorption of CO2. This "self-poisoning" mechanism explains the need to mix CO into the industrial feed for methanol production from CO2, as it scavenges the chemisorbed O. The HPSTM images show that the (100) surface breaks up into nanoclusters in the presence of CO2 at 20 Torr and above, producing active kink and step sites. If the surface is precovered with atomic oxygen, no such nanoclustering occurs.

Atmospheric pressure X-ray photoelectron spectroscopy (XPS) is demonstrated using single-layer graphene membranes as photoelectron-transparent barriers that sustain pressure differences in excess of 6 orders of magnitude. The graphene serves as a support for catalyst nanoparticles under atmospheric pressure reaction conditions (up to 1.5 bar), where XPS allows the oxidation state of Cu nanoparticles and gas phase species to be simultaneously probed. We thereby observe that the Cu(2+) oxidation state is stable in O2 (1 bar) but is spontaneously reduced under vacuum. We further demonstrate the detection of various gas-phase species (Ar, CO, CO2, N2, O2) in the pressure range 10-1500 mbar including species with low photoionization cross sections (He, H2). Pressure-dependent changes in the apparent binding energies of gas-phase species are observed, attributable to changes in work function of the metal-coated grids supporting the graphene. We expect atmospheric pressure XPS based on this graphene membrane approach to be a valuable tool for studying nanoparticle catalysis.

We report on the integration of atomically thin 2D insulating hexagonal boron nitride (h-BN) tunnel barriers into Co/h-BN/Fe magnetic tunnel junctions (MTJs). The h-BN monolayer is directly grown by chemical vapor deposition on Fe. The Conductive Tip Atomic Force Microscopy (CT-AFM) measurements reveal the homogeneity of the tunnel behavior of our h-BN layers. As expected for tunneling, the resistance depends exponentially on the number of h-BN layers. The h-BN monolayer properties are also characterized through integration into complete MTJ devices. A Tunnel Magnetoresistance of up to 6% is observed for a MTJ based on a single atomically thin h-BN layer.