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The discovery of infinite-layer nickelate superconductors has spurred enormous interest. While the Ni$^{1+}$ cations possess nominally the same 3$d^9$ configuration as Cu$^{2+}$ in cuprates, the electronic structure variances remain elusive. Here, we present a soft x-ray photoemission spectroscopy study on parent and doped infinite-layer Pr-nickelate thin films with a doped perovskite reference. By identifying the Ni character with resonant photoemission and comparison to density functional theory + U (on-site Coulomb repulsion energy) calculations, we estimate U ~5 eV, smaller than the charge transfer energy $\Delta$ ~8 eV, confirming the Mott-Hubbard electronic structure in contrast to charge-transfer cuprates. Near the Fermi level ($E_F$), we observe a signature of occupied rare-earth states in the parent compound, which is consistent with a self-doping picture. Our results demonstrate a correlation between the superconducting transition temperature and the oxygen 2$p$ hybridization near $E_F$ when comparing hole-doped nickelates and cuprates., Comment: 28 pages, 10 figures

A-site deficient Ruddlesden–Popper phases now attract a lot of attention as promising materials for intermediate temperature solid oxide fuel cells' cathodes and oxygen separation membranes. However, controversial information on the A-site deficiency effect on structural, transport and electrochemical properties of these materials apparently requires further studies of such systems. In this work, structural and transport features of (Nd2-xCax)0.975NiO4+δ system were studied. (Nd2-xCax)0.975NiO4+δ (x = 0–0.4) samples were synthesized via a solution-assisted solid state reaction method and characterized by X-ray diffraction. Oxygen transport was studied by the temperature programmed isotope exchange of oxygen with C18O2 in the flow reactor. A high oxygen mobility of materials (D* ~ 10−7 cm2/s at 700 °C) is provided by the cooperative mechanism of oxygen migration involving both regular and highly-mobile interstitial oxygen. As typical for Ruddlesden–Popper phases, doping with Ca leads to increase of total conductivity due to holes' formation and decrease of oxygen mobility due to hampering cooperative mechanism, however, this effect is less pronounced compared to A-site stoichiometric Nd nickelates which can be attributed to oxygen vacancies formation and their participation in cooperative migration as well as to other features of A-site deficiency. High mixed ionic-electronic conductivity of materials makes them promising in using as solid oxide fuel cells’ cathodes and oxygen separation membranes.

One of the main directions for the attainment of high-performance solid oxide electrochemical cells, including those based on proton-conducting electrolytes, consists in the rational engineering of functional materials. Herein, we examine the use of Nd2–xBaxNiO4+δ (NBNx, 0 ≤ x ≤ 0.4) materials as potential oxygen electrodes for protonic ceramic fuel cells (PCFCs) based on conventional Ba(Ce,Zr)O3-electrolytes. A Ba-doping strategy is proposed for Nd2NiO4+δ for reducing chemical interdiffusion of barium-ions from electrolyte to electrode during long-term operation. It is experimentally confirmed that a moderate Ba-content is beneficial in terms of reducing the quantity of impurity phases formed at the NBNx/Ba(Ce,Zr)O3 interface during deliberately-imposed extreme temperature conditions (1250 °C for 20 h). In addition, materials with x = 0.1 and 0.2 exhibit the highest electrical conductivity with no adverse effects on their thermomechanical properties. Thus, when characterising symmetrical cells in wet air conditions, NBN0.1 and NBN0.2 electrodes demonstrates lower polarisation resistances (down to 1.7 Ω cm2 at 700 °C) compared with NBN0, NBN0.3 and NBN0.4 electrodes. Based on these findings, the Ba-doping of nickelates can be recommended as a promising modification for the design of electrodes having good performance and chemical compatibility.

Summary Anisotropies in electronic transportations conventionally originate from the nature of low symmetries in crystal structures and were not anticipated for perovskite oxides with crystal asymmetries much smaller than, e.g., van der Waals or topological crystal. Beyond conventional expectations, here we demonstrate pronounced anisotropies in the inter-band Coulomb repulsion-dominated electronic transportation behaviors in the low-dimensional perovskite family of rare-earth nickelates (ReNiO3). The in-plane orbital entropy associated to the in-plane symmetry of the NiO6 octahedron within ReNiO3 causes intrinsic anisotropies for the gradual orbital transition with temperature to regulate their thermistor transportations. Extrinsically imparting biaxial interfacial strains amplifies the anisotropies in the electronic transportation of ReNiO3. It unveils the overlooked role of orbital directionalities within low-dimensional correlated perovskites that triggers anisotropic transportations despite their higher crystal symmetries, and this introduces new freedoms to regulate their correlated transportations.

We demonstrate a practical way to identify the presence of a perovskite phase in rare-earth nickelates (RNiO3) using X-ray photoelectron spectroscopy (XPS). By varying the calcination temperature, we prepared RNiO3 powders with different degrees of chemical reaction. We found that perovskite RNiO3 becomes predominant after high-temperature calcination (≥1,000 °C) in X-ray diffraction and XPS (at Ni 3p and O 1s edges) measurements. While the observed spectra at the Ni 3p edge are similar for all powders, a sizable difference was observed in the O 1s-edge spectra depending on the calcination temperature. With the formation of a perovskite phase with a trivalent Ni3+ state, an XPS peak corresponding to oxygen ions in the perovskite lattice distinctly emerges. Our work shows that the Ni3+ state cannot be determined by analyzing the Ni 3p edge solely and rather, the O 1s edge should be simultaneously monitored for explicit identification.

The application of doped lanthanum nickelate type perovskites as Solid Oxide Cell (SOC) materials has proven to be an area of significant study in recent years. These materials, in particular LaNi1-xFexO3, have gained interest due to their apparent resilience to certain degradation effects. There is, therefore, a suggestion in the academic literature that these materials may find application as oxygen electrode materials for future generations of SOC, with lower degradation rates and longer life-times. However, most of the discussion surrounding these materials does not consider the relative performance of such cells with respect to the state-of-the-art. Several commentators have suggested that the popular La‑nickelates are not feasible as replacements for current materials. Clearly, a material with stable but inferior performance is unlikely to offer a realistic alternative to the current crop of cell materials. However, to contradict this, there have also been numerous studies observing how cell performance may be improved via an appropriate tailoring of the electrode architecture. Here, a consideration on the wide body of literature on ABO3-type lanthanum nickelates is provided. This includes an assessment of studies at the fundamental level and with reference to their application in SOC technology. Primarily, this is with reference to LaNi0.6Fe0.4O3 where the literature is most substantial.

Eu doped La2NiO4 powders, with the general formula La2-xEuxNiO4+δ denoted as LENOx (for x = 0, 0.2, 0.4, 0.6 and 0.8), were synthesized via the mechanical milling reaction method. The Eu3+ doping content has a remarkable influence on structural and electrochemical properties. The phase identification and morphology were studied by X-ray diffraction (XRD), Raman spectroscopy, Infrared spectroscopy (IR), A laser size analyzer and scanning electron microscopy (SEM). Lattice parameters were calculated using the Rietveld method. It was observed that the lattice parameter values in LENOx systems varied with the amount of Eu3+. The latter was symmetrically deposited by spin coating on both surfaces of an Ce0.8Sm0.2O1.9 (SDC) electrolyte and studied using AC impedance spectroscopy. The electrochemical properties were studied using two-probe impedance spectroscopy and results showed that the ASR of LENOx was enhanced by the Eu3+ dopant content x. Results also showed that LNEO0.2 had the lowest Area specific resistance (ASR) at 700 °C and it was therefore concluded that doping with the appropriate amount of Eu3+ can further improve the properties of a nickelate cathode.

The search for new electrode materials that can be applied to the solid oxide fuel cell (SOFC) technology is an active field of research. In continuing our studies of Ca-substituted layered nickelates, in this work we investigated Nd2−xCaxNiO4+δ materials synthesized via the solution assistant solid state reaction method to evaluate their prospective usage as cathode materials for the intermediate temperature SOFC. It was found that Ca doping resulted in the temperature decreasing for the Fmmm → I4/mmm transition in Nd2NiO4+δ (NNO) and the tetragonal structure stabilizing at room temperature at x ≥ 0.2 in ambient air. The coefficient of thermal expansion calculated from the linear expansion under heating and cooling was different; however there was a common tendency for it to decrease when the Ca content was increased above 5 mol% (x = 0.1). The dc four-probe measurements revealed an increase in total electrical conductivity with doping. The polarization resistance of the Nd2−xCaxNiO4+δ electrodes in contact with Ce0.8Sm0.2O1.9 depended non-linearly on the Ca content with a moderate maximum at x = 0.1. Ca-doping was found to decrease the interaction of the electrode materials with the electrolyte. It resulted in the polarization resistance of the composite electrodes containing doped materials decreasing compared to the composite electrodes based on Nd2NiO4+δ. The polarization resistance of the Nd1.7Ca0.3NiO4+δ-Ce0.8Sm0.2O1.9 (NCNO3-SDC) electrode formed at 1200 °C is equal to 0.56 Ω cm2 at 700 °C in ambient air and comparable with the resistance of the NNO electrode (0.51 Ω cm2). Due to its superior stability and lower interaction with the electrolyte this electrode composition can be recommended for preferential usage in IT-SOFCs.

Progress in hydrogen energy and promising directions for its modern development are closely related to design of fuel cells, including solid oxide fuel cells, and solid state membranes for hydrogen, oxygen and synthesis gas production. A necessary condition for fabrication of economically competitive devices in this area is the use of cheap electrode materials combining high electrochemical activity and long-term stability. Ln2NiO4+δ oxides with the Ruddlesden–Popper layered structure possessing a high mixed ion-electron conductivity and moderate values of the coefficients of thermal expansion are promising materials for development of oxygen-conducting membranes and cathodes of intermediate-temperature solid oxide fuel cells. In this paper structural characteristics, electrical conductivity, oxygen mobility and electrochemical properties of Ln2-xCaxNiO4+δ (Ln = La, Pr, Nd; x = 0; 0.3) samples were studied to determine factors, which have the most significant effect on the electrochemical activity of electrodes and their stability. It was found that doping with calcium lead to stabilization of the structure and increased the electrical conductivity of materials. However, addition of calcium decreased the electrochemical activity of electrodes in varying degrees depending on the nature of lanthanide. There is no direct interrelation of such a decrease of activity with either the electrical properties or the interstitial oxygen content. We have revealed correlation of the polarization resistance of electrodes with characteristics of oxygen transfer in the electrode material (self-diffusion coefficient, surface exchange constant). Using the C18O2 SSITKA method, the total oxygen mobility in the doped materials was shown to fall with doping due to a decrease in the content of highly mobile interstitial oxygen and hampering of the cooperative oxygen transport mechanism. In the case of La1.7Ca0.3NiO4+δ, this leads to the appearance of a slow diffusion channel and a substantial decrease in the total diffusion coefficient value which results in a sharp increase in the polarization resistance of the electrodes. This phenomenon is not observed in materials with praseodymium and neodymium. The electrodes based on Pr1.7Ca0.3NiO4+δ and Nd1.7Ca0.3NiO4+δ, developed in this work, have an acceptable level of the electrochemical activity along with a high electrical conductivity and increased stability in comparison with undoped compositions and can be recommended for use as cathodes for intermediate temperature fuel cells.

Ionization energy theory is exploited to predict the changes to atomic polarizability for both anions and cations, the polarization in doped titanates and the energy gap in III–V and II–VI semiconductors. We then extend the above analysis to discuss the physics of metallic and superconducting phases in the recently discovered superconducting nickelates. In doing so, we are able to prove the existence of Ni2+ cations and oxygen vacancy in the metallic normal state of nickelates. We find that the normal state resistivity of the nickelates follows exactly as predicted by the ionization energy theory. Quantitative estimates are also given for the concentrations of Ni2+ and oxygen vacancy in superconducting nickelates.

In this work new RP materials of the La2-xGdxNiO4+δ series were synthesized and their structural features, oxygen stoichiometry and transport properties were studied by X-ray diffraction, TGA, mass relaxation method and oxygen isotope exchange with C18O2 in a flow reactor. According to XRD data, La2-xGdxNiO4+δ (x = 0.0; 0.2; 0.4) are single-phase samples with a tetragonal structure. Doping with Gd resulted only in the insignificant increase of the interstitial oxygen content (δ changes in the range of 0.13–0.15). A high oxygen mobility was demonstrated: at 700 °C Dchem ~ 10−5 cm2/s (mass relaxation data) and self–diffusion coefficient D⁎ ~ 10−8 cm2/s (oxygen isotope exchange data). Such characteristics are determined by the cooperative mechanism of oxygen migration involving both regular and highly-mobile interstitial oxygen. Gd doping, however, resulted in non-uniformity of the oxygen migration routes. To describe this feature, a mathematical model has been developed including a slow exchange between neighboring oxide anions. Oxygen mobility decreases with increasing Gd content.

The perovskite nickelates RNiO$_3$ (R: rare-earth) have been studied as potential multiferroic compounds. A certain degree of charge disproportionation in the Ni ions has been confirmed by high resolution synchrotron power diffraction: instead of the nominal Ni$^{3+}$ valence, they can have the mixed-valence state Ni$^{(3-\delta)+}$ and Ni$^{(3+\delta)+}$, though agreement has not been reached on the precise value of $\delta$ (e.g. for NdNiO$_3$, $\delta=0.0$ and $\delta=0.29$ were reported). Also, the magnetic ground state is not yet clear: collinear and non-collinear Ni-O magnetic structures have been proposed to explain neutron diffraction and soft X-ray resonant sccattering results in these compounds, and more recently a canted antiferromagnetic spin arrangement was proposed on the basis of magnetic susceptibility measurements. This scenario is reminiscent of the situation in the half-doped manganites. In order to gain insight into the ground state of these compounds, we studied the magnetic excitations of some of the different phases proposed, using a localized spin model for a simplified spin chain which could describe these compounds. We first analize the stability of the collinear, orthogonal, and intermediate phases in the classical case. We then explore the quantum ground state indirectly, calculating the spin excitations obtained for each phase, using the Holstein-Primakoff transformation and the linear spin-wave approximation. For the collinear and orthogonal ($\theta=\pi/2$) phases, we predict differences in the magnon spectrum which would allow to distinguish between them in future inelastic neutron scattering experiments.

Pr2NiO4+δ oxide with a layered Ruddlesden–Popper structure is a promising material for SOFC cathodes and oxygen separation membranes due to a high oxygen mobility provided by the cooperative mechanism of oxygen migration involving both interstitial oxygen species and apical oxygen of the NiO6 octahedra. Doping by Ca improves thermodynamic stability and increases electronic conductivity of Pr2 − xCaxNiO4+δ, but decreases oxygen mobility due to decreasing the oxygen excess and appearing of 1–2 additional slow diffusion channels at x ≥ 0.4, probably, due to hampering of cooperative mechanism of migration. However, atomic-scale features of these materials determining oxygen migration require further studies. In this work characteristics of oxygen diffusion in Pr2 − xCaxNiO4+δ (x = 0–0.6) are compared with results of the surface analysis by X-ray photoelectron spectroscopy and modeling of the interstitial oxygen migration by the plane-wave density functional theory calculations. According to the X-ray photoelectron spectroscopy data, the surface is enriched by Pr for undoped sample and by Ca for doped ones. The O1s peak at ~531 eV corresponding to a weakly bound form of surface oxygen located at Pr cations disappears at ~500 °C. Migration of interstitial oxygen was modeled for a I4/mmm phase of Pr2NiO4+δ. The interstitial oxygen anion repulses the apical one in the NiO6 octahedra pushing it into the tetrahedral site between Pr cations. The calculated activation barrier of this migration is equal to 0.585 eV, which reasonably agrees with the experimental value of 0.83 eV obtained by the oxygen isotope exchange method. At the same time, for the model compound Ca2NiO4+δ, obtained by isomorphic substitution of Pr by Ca in Pr2NiO4+δ, calculations implied formation of the peroxide ion comprised of interstitial and lattice oxygen species not revealed in the case of incomplete substitution (up to PrCaNiO4+δ composition). Hence, calculations in the framework of the plane-wave density functional theory provide a realistic estimation of specificity of oxygen migration features in Pr2NiO4+δ doped by alkaline-earth metals. © 2019 Elsevier B.V. Russian Science Foundation, RSF: 16-13-00112 Support by Russian Science Foundation (Project 16-13-00112 ) is gratefully acknowledged.

We propose that the superconductivity recently observed in Nd$_{0.8}$Sr$_{0.2}$NiO$_2$ with critical temperature in the range $9$ K to $15$ K results from the same charge carriers and the same mechanism that we have proposed give rise to superconductivity in both hole-doped and electron-doped cuprates: pairing of hole carriers in oxygen $p\pi$ orbitals, driven by a correlated hopping term in the effective Hamiltonian that lowers the kinetic energy, as described by the theory of hole superconductivity. We predict a large increase in $T_c$ with compressive epitaxial strain., Comment: 4 pages, 4 figures

The rare-earth chain nickelates R 2 BaNiO5 ( R = Nd , Sm, Eu, Gd, Dy, Ho, Er, and Tm) were studied by means of the spectroscopic Er probe. The magnetic ordering was registered and the splitting of the ground-state Kramers doublet of Er3+ as a function of temperature was measured for all the compounds studied. This information was used to analyze a possible orientation of ordered magnetic moments of the nickel ions. The magnetic structures found for R = Ho , Dy, Nd, Gd, Tm, and Er are in good agreement with literature data, those for R = Sm and Eu are predicted for the first time.