Carbon-Based Composites with Mixed Phosphate-Pyrophosphates with Improved Electrochemical Performance at Elevated Temperature.

Sodium iron phosphate-pyrophosphate, Na4Fe3(PO4)2P2O7 (NFPP) emerges as an excellent cathode material for sodium-ion batteries. Because of lower electronic conductivity, its electrochemical performance depends drastically on the synthesis method. Herein, we provide a simple and unified method for synthesis of composites between NFPP and reduced graphene oxide (rGO) and standard carbon black, designed as electrode materials for both sodium- and lithium-ion batteries. The carbon additives affect only the morphology and textural properties of the composites. The performance of composites in sodium and lithium cells is evaluated at elevated temperatures. It is found that NFPP/rGO outperforms NFPP/C in both Na and Li storage due to its hybrid mechanism of energy storage. In sodium half-cells, NFPP/rGO delivers a reversible capacity of 95 mAh/g at 20 °C and 115 mAh/g at 40 °C with a cycling stability of 95% and 88% at a rate of C/2. In lithium half-cells, the capacity reaches a value of 120 mAh/g at 20 and 40 °C, but the cycling stability becomes worse, especially at 40 °C. The electrochemical performance is discussed on the basis of ex situ XRD and microscopic studies. The good Na storage performance of NFPP/rGO at an elevated temperature represents a first step towards its commercialization.

Dual-Ion Intercalation Chemistry Enabling Hybrid Metal-Ion Batteries.

To outline the role of dual-ion intercalation chemistry to reach sustainable energy storage, the present Review aimed to compare two types of batteries: widely accepted dual-ion batteries based on cationic and anionic co-intercalation versus newly emerged hybrid metal-ion batteries using the co-intercalation of cations only. Among different charge carrier cations, the focus was on the materials able to co-intercalate monovalent ions (such Li+ and Na+ , Li+ and K+ , Na+ and K+ , etc.) or couples of mono- and multivalent ions (Li+ and Mg2+ , Na+ and Mg2+ , Na+ and Zn2+ , H+ and Zn2+ , etc.). Furthermore, the Review was directed on co-intercalation materials composed of environmentally benign and low-cost transition metals (e. g., Mn, Fe, etc.). The effect of the electrolyte on the co-intercalation properties was also discussed. The summarized knowledge on dual-ion energy storage could stimulate further research so that the hybrid metal-ion batteries become feasible in near future.

Iron oxidation to amplify the Na and Li storage capacities of nano-sized maricite NaFePO4.

This study reports an effective approach to improve dramatically the electrochemical performance of nanosized NaFePO4 with a maricite structure, which is commonly considered as electrochemically inactive due to the absence of structural channels for alkaline ion mobility. The approach is based on the complete oxidation under mild conditions (i.e. at low temperatures around 280 °C and traces of oxygen) of the nanosized maricite phase. It is prepared by the phosphate-formate precursor method and is additionally ball-milled with a carbon additive. The oxidation of Fe2+ proceeds at the nanoscale level within the maricite nanoparticles and causes a massive structural transformation of the maricite phase into a monoclinic NASICON phase Na3Fe2(PO4)3 with the preservation of the crystallinity. The oxidized maricite phase exhibits high specific capacities, cycling stability and rate capability when it is used as an electrode in both Na and Li half-cells. The effect of different sodium and lithium electrolytes on the storage performance is investigated as well. It is found that the highest specific capacity (of about 150 mA h g-1) is achieved in Li half-cells using the LiPF6 electrolyte, while in Na half-cells the electrolyte NaFSI/EC:DMC achieves a specific capacity of around 100 mA h g-1. The rate capability is better in Na half-cells than that in Li half-cells. The mechanism of the reversible intercalation/deintercalation of Na+ and Li+ ions is studied by ex situ XRD and TEM analyses. The results show that the maricite is an electrochemically inactive phase, but through manipulation including oxidation or amorphization it becomes an active electrode material.

Storage performance of Mg2+ substituted NaMnPO4 with an olivine structure.

Sodium manganese phospho-olivine, NaMnPO4, is considered to be a higher-voltage alternative to the presently used iron-based electrode material, NaFePO4, for sodium ion batteries. Irrespective of this advantage, the electrochemical performance of NaMnPO4 is still far from what is desired. Herein we provide the first report on the storage performance of NaMnPO4 having a structure modified by Mg2+ substitution. The Mg-substituted phospho-olivines are prepared on the basis of ionic exchange reactions involving the participation of Mg-substituted KMnPO4·H2O dittmarites as structural template. Furthermore, the phosphate particles were covered with a thin layer (up to 5 nm) of activated carbon through ball-milling. The storage performance of phospho-olivines is analyzed in sodium and lithium half-ion cells, as well as in full-ion cells versus bio-mass derived activated carbon and spinel Li4Ti5O12 as anodes. The compatibility of phospho-olivines with electrolytes is assessed by utilization of several types of lithium and sodium carbonate-based solutions. In sodium half-cell, the Mg-substituted phosphate displays a multi-phase mechanism of Na+ intercalation in case when NaTFSI-based electrolyte is used. In lithium half-cell, the high specific capacity and rate capability is achieved for phospho-olivine cycled in LiPF6-based electrolyte. This is a consequence of the occurrence of dual Li+,Na+ intercalation, which encompass nano-sized domains. The utilization of the Mg-substituted phospho-olivine in the full ion cell is demonstrated.

Lithium versus Mono/Polyvalent Ion Intercalation: Hybrid Metal Ion Systems for Energy Storage.

The energy storage by redox intercalation reactions is, nowadays, the most effective rechargeable ion battery. When lithium is used as intercalating agents, the high energy density is achieved at an expense of non-sustainability. The replacement of Li+ with cheaper monovalent ions enables to make greener battery alternatives. The utilization of polyvalent ions instead of Li+ permits to multiplying the battery capacity. Contrary to Li+ , the realization of quick and reversible intercalation of bigger monovalent and of polyvalent ions is a scientific challenge due to kinetic constraints, polarizing ion effects and Coulomb interactions. Herein we provide a vision how to make the intercalation of these ions feasible. The idea is to perform dual intercalation of ions having different charges, radii, preferred coordination and diffusion pathway topology. All these features are demonstrated by the recent knowledge on selective and non-selective intercalation properties of oxides and polyanion compounds with layered and tunnel structures. Based on dual intercalation properties, the fabrication of hybrid metal ion batteries is presented and discussed.

Influence of vanadium concentration and temperature on the preparation of electrochromic thin films of ammonium intercalated vanadium(V) oxide xerogel nanoribbons.

A new and simple chemical method for deposition of thin films of ammonium intercalated V2O5·nH2O xerogels has been designed. The chemical deposition has been performed in aqueous solutions of ammonium metavanadate and acetic acid at temperatures between 50 and 85 °C. Depending on the vanadium concentration and deposition temperature xerogels with different composition have been prepared. The structure, morphology, electrochemical and electrochromic behaviour of the thin films with a composition of (NH4)0.15V2O5·1.3H2O have been examined. The film morphology comprises randomly oriented ribbon-like units (100 nm wide and about 500 nm long) which are composed of aggregated primary smaller particles in the nanoscale region of 50-100 nm. Two relatively stable redox pairs are observed in the cyclic voltammograms which correspond to the two-step electrochromism with colour transformations yellow/green and green/blue. The thin film thickness is found to have strong influence on the transmittance variance as deduced by the optical spectra of the reduced and oxidized states. The best result regarding the transmittance variance of 54% at 400 nm is achieved with thin films with thickness of about 200 nm which makes the prepared films very attractive for application in electrochromic devices.

Facile synthesis of LiMnPO4 olivines with a plate-like morphology from a dittmarite-type KMnPO4·H2O precursor.

Dittmarite-type compound KMnPO(4)·H(2)O was used as a new precursor for the synthesis of nanostructured LiMnPO(4) phospho-olivines with a plate-like morphology at low temperature (about 200 °C) and a short reaction time (90-180 min). The dehydration of KMnPO(4)·H(2)O was studied by DTA and TG analysis. Structural and morphological characterization of both KMnPO(4)·H(2)O and LiMnPO(4) was performed by powder XRD, SEM and TEM analyses. The formation of nanostructured LiMnPO(4) was examined by electron paramagnetic resonance spectroscopy and TEM. It was found that the reaction between KMnPO(4)·H(2)O with the LiCl-LiNO(3) mixture includes a fast ionic exchange of K(+) with Li(+) in the framework of the dittmarite structure, followed by H(2)O release and the formation of the olivine-type structure. The morphology and texture of the dittmarite-type precursor results in a plate-like morphology of LiMnPO(4) with a preferred orientation along the [100] direction. The plate-like morphology of LiMnPO(4) is stable after annealing at 500 °C. The plates are composed of nanocrystallites, with various sizes in the range 10-20 nm. The EPR signal of LiMnPO(4) is due to the exchange-coupled Mn(2+) ions. It was demonstrated that the EPR line-width correlates with the Scherrer crystallite size.

Infrared and Raman Spectra of Magnesium Ammonium Phosphate Hexahydrate (Struvite) and its Isomorphous Analogues. VIII. Spectra of Protiated and Partially Deuterated Magnesium Rubidium Phosphate Hexahydrate and Magnesium Thallium Phosphate Hexahydrate.

The infrared and Raman spectra of magnesium rubidium phosphate hexahydrate MgRbPO4 • 6H2O and magnesium thallium phosphate hexahydrate, MgTlPO4 • 6H2O were recorded at room temperature (RT) and the boiling temperature of liquid nitrogen (LNT). To facilitate their analysis, also recorded were the spectra of partially deuterated analogues with varying content of deuterium. The effects of deuteration and those of lowering the temperature were the basis of the conclusions drawn regarding the origin of the observed bands which were assigned to vibrations which are predominantly localized in the water molecules (four crystallographically different types of such molecules exist in the structures) and those with PO43- character. It was concluded that in some cases coupling of phosphate and water vibrations is likely to take place. The appearance of the infrared spectra in the O-H stretching regions of the infrared spectra is explained as being the result of an extensive overlap of bands due to components of the fundamental stretching modes of the H2O units with a possible participation of bands due to second-order transitions. A broad band reminiscent of the B band of the well-known ABC trio characteristic of spectra of substances containing strong hydrogen bonds in their structure was found around 2400 cm-1 in the infrared spectra of the two studied compounds.

Vibrational behavior of the phosphates ions in dittmarite-type compounds M'M''PO4.H2O (M'=K+, NH4+; M''=Mn2+, Co2+, Ni2+).

The IR and Raman spectra of the isostructural M'M''PO4.H2O compounds (M'=K+, NH4+; M''=Mn2+, Co2+, Ni2+) are reported and discussed with respect to the normal vibrations of the PO(4)3- ions. The vibrational behavior of PO4(3-) is in agreement with its low site symmetry Cs in the lattices-the symmetric nu1 and nu2 modes are activated in the IR spectra and the degeneration of the asymmetric nu3 and nu4 modes is lifted. A relatively large unit-cell group splitting is observed for nu1 in both the IR and Raman spectra and for nu3 in Raman spectra. It has been established that the mean wavenumbers of the P-O stretches (nuPO) are not affected by the M2+ ions present, but they are lower for the NH4-series than for the K-one (predominant influence of both the smaller repulsion potential and the hydrogen bonds in the NH4-lattices over the influence of the M+-O interactions). The extent of the energetic distortion of the PO(4)3- ions has been estimated based on the spectroscopic data for the site group splitting of the asymmetric modes (Deltanu3 and Deltanu4), the separation between the highest and the lowest wavenumbered P-O stretches (Deltanumax) and the intensity of nu1 in the IR spectra. The data provide an evidence that the PO4(3-) ions in KM''PO4.H2O are more distorted regarding the P-O bond lengths than those in NH4M''PO4.H2O, but their angular distortion is the same in both series. The trends for the energetic distortion of the phosphate ions found from the spectroscopic data correspond to the data for their geometric distortion deduced from the values of the distortion indices DI(PO) and DI(OPO).

Metal-water interactions and hydrogen bonding in dittmarite-type compounds M'M''PO4.H2O (M'=K+, NH4+; M''=Mn2+, Co2+, Ni2+). Correlations of IR spectroscopic and structural data.

The vibrational behavior of the uncoupled nu(OD) modes and of the water librations in dittmarite-type compounds M'M''PO4.H2O (M'=K+, NH4+; M''=Mn2+, Co2+, Ni2+) is analyzed in terms of the influence of two types of metal-water interactions (M+-H2O and M2+-H2O), the hydrogen bonding and the repulsion potential of the lattices. The M+-H2O interaction is found to be the main factor, which influences nuOD. The strong K+-H2O interaction weakens in a higher degree the intramolecular O-H bonds than the corresponding M2+-H2O interactions (M2+=Mn, Co, Ni). As a result nuOD is shifted to lower wavenumbers in the potassium series than in ammonium one, irrespective of the synergetic effect of M2+, the hydrogen bond lengths and the repulsion potential of the lattices. The analysis of the spectroscopic data evidences for the dominating influence of the M2+-H2O interaction on the wagging mode. The blue shift of nuwag strictly follows the increasing synergetic effect of M2+, i.e. nuM'/Mn