Prabeer Barpanda

Na2.44Mn1.79(SO4)3: a new member of the alluaudite family of insertion compounds for sodium ion batteries

Sodium-ion batteries have been extensively pursued as economic alternatives to lithium-ion batteries. Investigating the polyanion chemistry, alluaudite structured Na2Fe2II(SO4)(3) has been recently discovered as a 3.8 V positive electrode material (Barpanda et al., Nature Commun., 5: 4358, 2014). Registering the highest ever Fe-III/Fe-II redox potential (vs. Na/Na+) and formidable energy density, it has opened up a new polyanion family for sodium batteries. Exploring the alluaudite family, here we report isotypical Na2+2xMn2-xII(SO4)(3) (x = 0.22) as a novel high-voltage cathode material for the first time. Following low-temperature (ca. 350 degrees C) solid-state synthesis, the structure of this new alluaudite compound has been solved adopting a monoclinic framework (s.g. C2/c) showing antiferromagnetic ordering at 3.4 K. Synergising experimental and ab initio DFT investigation, Na2+2xMn2-xII(SO4)(3) has been found to be a potential high-voltage (ca. 4.4 V) cathode material for sodium batteries.

Insight into the limited electrochemical activity of NaVP2O7

Recently, LiVP2O7 has been investigated as a possible high-voltage substitute for Li2FeP2O7. However, its Na-equivalent, NaVP2O7, as an economic replacement for Li2FeP2O7 has not yet been well understood. Here, for the first time, we report the feasibility of NaVP2O7 as a 3.4 V cathode material for Na-ion batteries. Having a theoretical capacity of 108 mA h g−1, it shows an initial discharge capacity of 38.4 mA h g−1 at 1/20C (1C = 108 mA g−1) in the voltage range of 2.5–4.0 V. Our study suggests that part of the sodium ions in the lattice structure exist as structural stabilizers and bring lattice distortion upon desodiation. This study also shows that the title compound, NaVP2O7, suffers from high intrinsic internal resistance, which limits the phase transition kinetics between pristine NaVP2O7 and desodiated Na1−xVP2O7.

Na2M2(SO4)3 (M = Fe, Mn, Co and Ni): towards high-voltage sodium battery applications

Sodium-ion-based batteries have evolved as excellent alternatives to their lithium-ion-based counterparts due to the abundance, uniform geographical distribution and low price of Na resources. In the pursuit of sodium chemistry, recently the alluaudite framework Na2M2(SO4)3 has been unveiled as a high-voltage sodium insertion system. In this context, the framework of density functional theory has been applied to systematically investigate the crystal structure evolution, density of states and charge transfer with sodium ions insertion, and the corresponding average redox potential, for Na2M2(SO4)3 (M = Fe, Mn, Co and Ni). It is shown that full removal of sodium atoms from the Fe-based device is not a favorable process due to the 8% volume shrinkage. The imaginary frequencies obtained in the phonon dispersion also reflect this instability and the possible phase transition. This high volume change has not been observed in the cases of the Co- and Ni-based compounds. This is because the redox reaction assumes a different mechanism for each of the compounds investigated. For the polyanion with Fe, the removal of sodium ions induces a charge reorganization at the Fe centers. For the Mn case, the redox process induces a charge reorganization of the Mn centers with a small participation of the oxygen atoms. The Co and Ni compounds present a distinct trend with the redox reaction occurring with a strong participation of the oxygen sublattice, resulting in a very small volume change upon desodiation. Moreover, the average deintercalation potential for each of the compounds has been computed. The implications of our findings have been discussed both from the scientific perspective and in terms of technological aspects.

Designing Novel Sulphate-based Ceramic Materials as Insertion Host Compounds for Secondary Batteries

Rechargeable batteries have propelled the wireless revolution and automobiles market over the past 25 years. Developing better batteries with improved energy density demands unveiling of new cathode ceramic materials with suitable diffusion channels and open framework structure. In this pursuit of achieving higher energy density, one approach is to realize enhanced redox voltage of insertion of ceramic compounds. This can be accomplished by incorporating highly electronegative anions in the cathode ceramics. Building on this idea, recently various sulphate- based compounds have been reported as high voltage cathode materials. The current article highlights the use of sulphate (SO4) based cathodes to realize the highest ever Fe3+/Fe2+ redox potentials in Li-ion batteries (LiFeSO4F fluorosulphate: 3.9 V vs Li/Li+) and Na-ion batteries (Na2Fe2(SO4)3 polysulphate: 3.8 V vs Na/Na+). These sulphate-based cathode ceramic compounds pave way for newer avenues to design better batteries for future applications.

Enabling the Electrochemical Activity in Sodium Iron Metaphosphate [NaFe(PO3)3] Sodium Battery Insertion Material: Structural and Electrochemical Insights

Sodium-ion batteries are widely pursued as an economic alternative to lithium-ion battery technology, where Fe- and Mn-based compounds are particularly attractive owing to their elemental abundance. Pursuing phosphate-based polyanionic chemistry, recently solid-state prepared NaFe(PO3)3 metaphosphate was unveiled as a novel potential sodium insertion material, although it was found to be electrochemically inactive. In the current work, employing energy-savvy solution combustion synthesis, NaFe2+(PO3)3 was produced from low-cost Fe3+ precursors. Owing to the formation of nanoscale carbon-coated product, electrochemical activity was enabled in NaFe(PO3)3 for the first time. In congruence with the first principles density functional theory (DFT) calculations, an Fe3+/Fe2+ redox activity centered at 2.8 V (vs Na/Na+) was observed. Further, the solid-solution metaphosphate family Na(Fe1-xMnx)(PO3)3 (x = 0-1) was prepared for the first time. Their structure and distribution of transition metals (TM = Fe/Mn) was analyzed with synchrotron diffraction, X-ray photoelectron spectroscopy, and Mössbauer spectroscopy. Synergizing experimental and computational tools, NaFe(PO3)3 metaphosphate is presented as an electrochemically active sodium insertion host material.

Cubic Sodium Cobalt Metaphosphate [NaCo(PO3)3] as a Cathode Material for Sodium Ion Batteries

Cubic-framework sodium cobalt-based metaphosphate NaCo(PO3)3 was recently demonstrated to be an attractive Na+ cationic conductor. It can be potentially used in the next-generation rechargeable Na ion batteries. The crystal structure and electrical conductivity were studied and found to have a three-dimensional framework with interconnecting tunnels for Na+ migration ( J. Solid State Electrochem. , 2016 , 20 , 1241 ). This inspired us to study the electrochemical (de)intercalation behavior of Na+ in the NaCo(PO3)3 assuming a cubic Pa3̅ framework. Herein, synergizing experimental and computational tools, we present the first report on the electrochemical activity and Na+ diffusion pathway analysis of cubic NaCo(PO3)3 prepared via conventional solid-state route. The electrochemical analyses reveal NaCo(PO3)3 to be an active sodium insertion material with well-defined reversible Co3+/Co2+ redox activity centered at 3.3 V (vs Na/Na+). Involving a solid-solution redox mechanism, close to 0.7 Na+ per formula unit can be reversibly extracted. This experimental finding is augmented with bond valence site energy (BVSE) modeling to clarify Na+ migration in cubic NaCo(PO3)3. BVSE analyses suggest feasible Na+ migration with moderate energy barrier of 0.68 eV. Cubic NaCo(PO3)3 forms a 3.3 V sodium insertion material.

Earth‐Abundant Alkali Iron Phosphates (AFePO4) as Efficient Electrocatalysts for the Oxygen Reduction Reaction in Alkaline Solution

Water‐splitting systems are essential for clean energy production. The oxygen reduction reaction (ORR) is a key reaction involved in water splitting, which requires a catalyst. The current work explores the possible application of sodium and potassium iron phosphates (AFePO4, A=Na and K) as electrocatalysts for ORR activity. These earth‐abundant iron phosphates were synthesized by the solution combustion synthesis (SCS) technique by using ascorbic acid both as fuel and reducing agent for Fe. The crystal structure was analyzed by Rietveld refinement. The formation of carbon coating was identified by thermogravimetric analysis and Raman spectroscopy. Electrocatalytic properties of AFePO4 were investigated in alkali electrolytes for the first time by using linear sweep voltammetry with a rotating disk electrode (RDE). The ORR activities of these alkali iron phosphates are comparable to that of the Pt/C system. The Tafel slope and electron transfer number of the alkali iron phosphates were calculated. The ORR activity of NaFePO4 was found to be better than KFePO4 and FePO4. This work demonstrates alkali iron phosphates as alternate cost‐effective, novel electrocatalysts for productive ORR activity in alkaline solution.

In-situ deposition of sodium titanate thin film as anode for sodium-ion micro-batteries developed by pulsed laser deposition

Sodium-ion thin-film micro-batteries form a niche sector of energy storage devices. Sodium titanate, Na2Ti6O13 (NTO) thin films were deposited by pulsed laser deposition (PLD) using solid-state synthesized polycrystalline Na2Ti6O13 compound. The phase-purity and crystallinity of NTO in bulk and thin-film forms were confirmed by Rietveld refinement. Electron microscopy and atomic force microscopy revealed the formation of uniform ∼100 nm thin film with roughness of ∼4 nm consisting of homogeneous nanoscale grains. These PLD-deposited NTO thin-films, when tested in Na-half cell architecture, delivered a near theoretical reversible capacity close to 42 mA h g-1 involving Ti4+/Ti3+ redox activity along with good cycling stability and rate kinetics. Na2Ti6O13 can work as an efficient and safe anode in designing sodium-ion thin-film micro-batteries.

Mechanistic study of Na-ion diffusion and small polaron formation in Kröhnkite Na2Fe(SO4)2·2H2O based cathode materials

Krohnkite-type Na2Fe(SO4)2·2H2O mineral is a sustainable and promising polyanionic cathode that has been experimentally found to offer a high redox potential (3.25 V vs. Na/Na+) along with fast-ion diffusion and high reversibility. Owing to the structural complexity, Na+ diffusion was assumed to occur along a convoluted channel along the b-axis. However, theoretical work related to this material still appears missing to support that statement. In this work, DFT+U calculations have been performed with the primary aim to unveil the Na+ diffusion mechanism in this material. The electronic structure and charge transfer are also envisaged to reveal evidence of Fe2+/3+ redox reaction and a vital role of structural H2O. Based on formation energies of this material with varied Na concentration, a calculated voltage profile is determined to show two voltage plateaus at 4.81 and 3.51 V, corresponding to experimental results. Nudged elastic band calculation reveals that Na+ diffusion is primarily occuring in the [01] direction with a moderate ionic mobility due to the structural distortion induced during migration, suggesting the possibility of defect-assisted diffusion. Intriguingly, the formation of small hole polarons is first observed, and could play a key role in the electronic conduction of this material.

Alluaudite class of high voltage sodium insertion materials: An interplay of polymorphism and magnetism

The research and development with sodium ion batteries has geared up manifold in last one decade, owing to their abundance, non-toxicity, uniform geographical distribution and electrochemical performance complimentary to lithium counterpart. This research often leads to various novel material discoveries such as Na2Fe2(SO4)3 sodium insertion material, which has recently registered the highest-ever Fe3+/Fe2+ redox potential (3.8 V vs. Na) having excellent cyclability and rate kinetics. This basically belongs to a family of materials-Alluaudites Na2M2(SO4)3 (M: Fe, Mn, Co, Ni). Such cathode insertion compounds are basically functional materials, involving redox active 3d transition metals that are often magnetic in nature. We have investigated the magnetic structure and properties of - Alluaudites Na2M2(SO4)3. These alluaudite shows wide structural diversity and polymorphism. Employing various experimental methods involving diffraction, magnetic susceptibility, Mossbauer spectroscopy and low temperature neu...