KFe(C2O4)F : a fluoro-oxalate cathode material for Li/Na-ion batteries

Funding: The authors want to thank EPSRC (EP/R030472/1) and the Faraday Institution (FIRG018) for their financial support. In addition, AGM wishes to thank the Faraday Institution for financial support and training (Grant number FITG033). The authors also thank EPSRC Light Element Analysis Facility Grant EP/T019298/1 and the EPSRC Strategic Equipment Resource Grant EP/R023751/1.The iron-based polyanionic fluoro-oxalate material, KFe(C2O4)F (KFCF), has been synthesized by hydrothermal methods. This compound shows promising reversible lithium and sodium insertion properties as a cathode material. The material delivered a first-cycle discharge capacity of 120 mAh g-1 at ∼3.3 V (Li+/Li) and 97.4 mAh g-1 at ∼3.0 V (Na+/Na) in LIB and NIB, respectively. Stable cycling performance was observed in both cases. The involvement of reversible Fe2+/Fe3+ redox was confirmed by ex-situ Mössbauer spectroscopy supported by first-principles calculations. This study reveals promising performance from a mixed oxalate-fluoride based polyanionic material thereby opening up further possibilities for materials discovery in the design of new electrode materials.Publisher PDFPeer reviewe

Prussian blue analogues for potassium-ion batteries: insights into the electrochemical mechanisms

A comprehensive description of the electrochemical mechanisms of the Prussian Blue Analogue (PBA) K1.67Mn0.65Fe0.35[Fe(CN)6]0.92\ub70.45H2O is obtained by combining several complementary ex situ and operando physico-chemical characterisation techniques. This particular PBA, which shows very good electrochemical performance as a cathode material in potassium-ion batteries (PIBs), undergoes three successive redox reactions during the (de-)potassiation that are hereby identified by ex situ57Fe M\uf6ssbauer spectroscopy and operando Mn and Fe K-edge X-ray absorption spectroscopy. These reactions come along with notable modifications of the crystal structure, which are followed in real time by operando X-ray diffraction. The correlation of these results, interpreted with the support of chemometric methods, also reveals the limitations of this PBA, probably related to the deactivation of the Mn undergoing extensive reversible Jahn-Teller distortion during cycling as well as possible dissolution in the electrolyte. These results underline that optimisation of the chemical composition of PBAs is a crucial step towards the preparation of reliable and stable PBA-based cathodes for PIBs

Electrochemical Evaluation of Pb, Ag, and Zn Cyanamides/Carbodiimides

PbNCN, Ag2NCN, and ZnNCN were tested as negative electrode materials for Li-ion batteries. A thorough analysis of the electrochemical mechanism by X-ray diffraction and X-ray absorption spectroscopy showed that, unlike transition metal carbodiimides, these compounds react with lithium via a two-step reaction, starting with conversion followed by alloying. The conversion reaction is highly irreversible for the three compounds, whereas the reversibility of the alloying reaction depends on the metal, that is, highly irreversible for PbNCN and Ag2NCN which contain the cyanamide group (NC−N2−) and more reversible for ZnNCN containing carbodiimide (−NCN−). In the case of the more covalent, cyanamide-type PbNCN and Ag2NCN, the conversion reaction occurs at a higher voltage compared to the more ionic, carbodiimide-type ZnNCN, correlated with the nature of bonding in the NCN group and in the phases themselves. Compared to transition metal carbodiimides, these materials show rather low performance, with no improvement in capacity as it would have been expected from the combination of conversion and alloying

K2_2Fe(C2_2O4_4)2_2: An Oxalate Cathode for Li/Na-Ion Batteries Exhibiting a Combination of Multielectron Cation and Anion Redox

The development of multielectron redox-active cathode materials is a top priority for achieving high energy density with long cycle life in the next-generation secondary battery applications. Triggering anion redox activity is regarded as a promising strategy to enhance the energy density of polyanionic cathodes for Li/Na-ion batteries. Herein, K$_2$Fe(C$_2$O$_4$)$_2$ is shown to be a promising new cathode material that combines metal redox activity with oxalate anion (C$_2$O${_4}^{2-}$ redox. This compound reveals specific discharge capacities of 116 and 60 mAh g$^{–1}$ for sodium-ion batterie (NIB) and lithium-ion batterie (LIB) cathode applications, respectively, at a rate of 10 mA g$^{–1}$, with excellent cycling stability. The experimental results are complemented by density functional theory (DFT) calculations of the average atomic charges

Impact of Solution Chemistry on Growth and Structural Features of Mo-Substituted Spinel Iron Oxides

International audienceThe effect of crystallizing solution chemistry on the chemistry of subsequently as-grown materials was investigated for Mo-substituted iron oxides prepared by thermally activated co-precipitation. In the presence of Mo ions, we find that varying the oxidation state of the iron precursor from Fe(II) to Fe(III) causes a progressive loss of atomic long-range order with the stabilization of 2–4 nm particles for the sample prepared with Fe(III). The oxidation state of the Fe precursor also affects the distribution of Fe and Mo cations within the spinel structure. Increasing the Fe precursor oxidation state gives decreased Fe-ion occupation and increased Mo-ion occupation of tetrahedral sites, as revealed by the extended X-ray absorption fine structure. The stabilization of Mo within tetrahedral sites appears to be unexpected, considering the octahedral preferred coordination number of Mo(VI). The analysis of the atomic structure of the sample prepared with Fe(III) indicates a local ordering of vacancies and that the occupation of tetrahedral sites by Mo induces a contraction of the interatomic distances within the polyhedra as compared to Fe atoms. Moreover, the occupancy of Mo into the thermodynamic site preference of a Mo dopant in Fe2O3 assessed by density functional theory calculations points to a stronger preference for Mo substitution at octahedral sites. Hence, we suggest that the synthetized compound is thermodynamically metastable, that is, kinetically trapped. Such a state is suggested to be a consequence of the tetrahedral site occupation by Mo ions. The population of these sites, known to be reactive sites enabling particle growth, is concomitant with the stabilization of very small particles. We confirmed our hypothesis by using a blank experiment without Mo ions, further supporting the impact of tetrahedral Mo ions on the growth of iron oxide nanoparticles. Our findings provide new insights into the relationships between the Fe-chemistry of the crystallizing solution and the structural features of the as-grown Mo-substituted Fe-oxide materials

Impact of Solution Chemistry on Growth and Structural Features of Mo-Substituted Spinel Iron Oxides

The effect of crystallizing solution chemistry on the chemistry of subsequently as-grown materials was investigated for Mo-substituted iron oxides prepared by thermally activated co-precipitation. In the presence of Mo ions, we find that varying the oxidation state of the iron precursor from Fe(II) to Fe(III) causes a progressive loss of atomic long-range order with the stabilization of 2-4 nm particles for the sample prepared with Fe(III). The oxidation state of the Fe precursor also affects the distribution of Fe and Mo cations within the spinel structure. Increasing the Fe precursor oxidation state gives decreased Fe-ion occupation and increased Mo-ion occupation of tetrahedral sites, as revealed by the extended X-ray absorption fine structure. The stabilization of Mo within tetrahedral sites appears to be unexpected, considering the octahedral preferred coordination number of Mo(VI). The analysis of the atomic structure of the sample prepared with Fe(III) indicates a local ordering of vacancies and that the occupation of tetrahedral sites by Mo induces a contraction of the interatomic distances within the polyhedra as compared to Fe atoms. Moreover, the occupancy of Mo into the thermodynamic site preference of a Mo dopant in Fe2O3 assessed by density functional theory calculations points to a stronger preference for Mo substitution at octahedral sites. Hence, we suggest that the synthetized compound is thermodynamically metastable, that is, kinetically trapped. Such a state is suggested to be a consequence of the tetrahedral site occupation by Mo ions. The population of these sites, known to be reactive sites enabling particle growth, is concomitant with the stabilization of very small particles. We confirmed our hypothesis by using a blank experiment without Mo ions, further supporting the impact of tetrahedral Mo ions on the growth of iron oxide nanoparticles. Our findings provide new insights into the relationships between the Fe-chemistry of the crystallizing solution and the structural features of the as-grown Mo-substituted Fe-oxide materials. </p

Kako se ribe mrijeste?

We have reinvestigated the polyanionic compound Na₂Fe₂(C₂O₄)₃·2H₂O, previously reported to be electrochemically inactive in lithium-ion batteries (LIBs), as a positive electrode for sodium-ion batteries (NIBs). The present study demonstrates that it is capable of delivering a reversible capacity close to its theoretical value (117 mA h g^–1) with three redox plateaus at 2.9, 3.3, and 3.6 V versus Na/Na⁺ in the potential range 1.7–4.2 V. The obtained energy density of 326 W h kg^–1 is among the highest of all reported polyanionic cathodes in NIBs. The origin of the electrochemical activity can be traced back to the electronic structure of the compound and the low migration energy barrier of the alkali ion observed in first-principles density-functional theory calculations

The impact of wind-power generation on the planning of regulating reserve

Ovaj članak predstavlja novi pristup za određivanje optimalne raspodjele regulacijskih rezervi (RR) između raspoloživih regulacijskih proizvodnih jedinica. Razvijen je korištenjem evolucijskog algoritma za minimiziranje gubitaka prijenosa i proračuna tokova snaga iterativnom metodom sa korekcijom reaktivne snage za regulaciju napona. Ovaj pristup uključuje uporabu stvarnih operativnih podataka izravno iz dispečerskog centra, kao i dnevne i satne planove potrošnje i proizvodnje iz vjetroelektrana za utvrđivanje potrebne snage za regulaciju frekvencije. Testiranjem predloženog pristupa na studiji slučaja, pokazana je mogućnost primjene na realnim elektroenergetskim sustavima. Dobiveni rezultati ispitivanja sa stvarnim podacima Hrvatskog kontrolnog područja pokazuju znatne uštede u troškovima pomoćnih usluga i uočljiv utjecaj različitih odstupanja proizvodnje od plana svake pojedine vjetroelektrane na optimalnu raspodjelu RR.This paper presents new approach to the optimal distribution of the regulating reserve (RR) in a set of available regulating generation units. It is developed using evolutionary computation for the transmission-loss minimization and power-flow computation by applying the iterative method with a reactive power correction for voltage control. The approach involves the use of actual operating data directly from the network’s dispatch centre as well as daily and hourly plans of wind and load power for determining the RR requirements for the load frequency control (LFC). By testing the proposed approach on a case study, the possibility of implementing it on real power systems is demonstrated. The obtained results of the testing with actual data from the Croatian control area indicate substantial savings in ancillary service costs for the LFC and the considerable impact of different variations from the plan of each individual wind-power plant on the optimal RR distribution

Metal Oxide Clusters on Nitrogen-Doped Carbon are Highly Selective for CO2Electroreduction to CO

The electrochemical reduction of CO2 (eCO2RR) using renewable energy is an effective approach to pursue carbon neutrality. The eCO2RR to CO is indispensable in promoting C-C coupling through bifunctional catalysis and achieving cascade conversion from CO2 to C2+. This work investigates a series of M/N-C (M = Mn, Fe, Co, Ni, Cu, and Zn) catalysts, for which the metal precursor interacted with the nitrogen-doped carbon support (N-C) at room temperature, resulting in the metal being present as (sub)nanosized metal oxide clusters under ex situ conditions, except for Cu/N-C and Zn/N-C. A volcano trend in their activity toward CO as a function of the group of the transition metal is revealed, with Co/N-C exhibiting the highest activity at -0.5 V versus RHE, while Ni/N-C shows both appreciable activity and selectivity. Operando X-ray absorption spectroscopy shows that the majority of Cu atoms in Cu/N-C form Cu0 clusters during eCO2RR, while Mn/, Fe/, Co/, and Ni/N-C catalysts maintain the metal hydroxide structures, with a minor amount of M0 formed in Fe/, Co/, and Ni/N-C. The superior activity of Fe/, Co/, and Ni/N-C is ascribed to the phase contraction and the HCO3- insertion into the layered structure of metal hydroxides. Our work provides a facile synthetic approach toward highly active and selective electrocatalysts to convert CO2 into CO. Coupled with state-of-the-art NiFe-based anodes in a full-cell device, Ni/N-C exhibits >80% Faradaic efficiency toward CO at 100 mA cm-2.The research leading to these results has received funding from the A-LEAF Project, which is funded by the European Union’s H2020 Programme under grant agreement no. 732840. ICN2 and ICIQ acknowledge funding from the FEDER/Ministerio de Ciencia e Innovación, Agencia Estatal de Investigación (projects ENE2017-85087-C3 and RTI2018-095618-B-I00) and the Generalitat de Catalunya (2017 SGR 327 and 2017- SGR-1406) and by the CERCA Programme / Generalitat de Catalunya. ICN2 and ICIQ are supported by the Severo Ochoa program from Spanish MINECO (grants no. SEV-2017-0706 and CEX2019-000925-S)

Stabilizing the Structure of LiCoPO4 Nanocrystals via Addition of Fe3+: Formation of Fe3+ Surface Layer, Creation of Diffusion-Enhancing Vacancies, and Enabling High-Voltage Battery Operation

Factors affecting the cyclability of the Fe-substituted LiCoPO4 (LiCo0.8Fe0.2PO4, LCFP) material were elucidated, including both the structural and electrode/electrolyte stability. Electrochemical characterization of the synthesized LCFP nanoparticles lends clear evidence for improved electrochemical stability of LCP, as well as enhanced rate capability, with Fe3+ substitution. Surface analysis using X-ray photoelectron spectroscopy (XPS) and electron energy loss spectroscopy (EELS) suggest that Fe enrichment on the surface of LCFP occurs through the oxidation of Fe2+ into Fe3+ in the synthesis process. The Fe3+-rich phase on the LCP surface enhances the stability of the delithiated phase, preventing oxidative reactions with electrolytes during high-voltage operation. This surface protection persists as long as the electrochemical reduction of Fe3+ is avoided by ensuring that the full range of operating voltages lie above the Fe3+/Fe2+ redox potential. Our findings may offer new approaches to stabilize the structure of LCP and other high-voltage positive electrodes for use in 5 V-class Li-ion batteries