Lanthanum-lithium-sodium double chromates as ionic conductors

Lanthanum-lithium-sodium double chromates Li1-xNaxLa(CrO4)2 were prepared and analysed by means of admittance spectroscopy. Their a.c. conductivity parameters are correlated with structural details of high and low temperature forms of pure lanthanum-lithium double chromates. Lithium compounds show the lowest conductivity values and the highest activation energy for ion motion, while the sample Li0.5Na0.5La(CrO4)2 exhibits the highest conductivity 10-5 S cm-1 and the lowest activation energy 0.58 eV.

Multifunctional SA-PProDOT binder for lithium ion batteries

An environmentally benign, highly conductive, and mechanically strong binder system can overcome the dilemma of low conductivity and insufficient mechanical stability of the electrodes to achieve high performance lithium ion batteries (LIBs) at a low cost and in a sustainable way. In this work, the naturally occurring binder sodium alginate (SA) is functionalized with 3,4-propylenedioxythiophene-2,5-dicarboxylic acid (ProDOT) via a one-step esterification reaction in a cyclohexane/dodecyl benzenesulfonic acid (DBSA)/water microemulsion system, resulting in a multifunctional polymer binder, that is, SA-PProDOT. With the synergetic effects of the functional groups (e.g., carboxyl, hydroxyl, and ester groups), the resultant SA-PProDOT polymer not only maintains the outstanding binding capabilities of sodium alginate but also enhances the mechanical integrity and lithium ion diffusion coefficient in the LiFePO4 (LFP) electrode during the operation of the batteries. Because of the conjugated network of the PProDOT and the lithium doping under the battery environment, the SA-PProDOT becomes conductive and matches the conductivity needed for LiFePO4 LIBs. Without the need of conductive additives such as carbon black, the resultant batteries have achieved the theoretical specific capacity of LiFePO4 cathode (ca. 170 mAh/g) at C/10 and ca. 120 mAh/g at 1C for more than 400 cycles.

Two-dimensional tin disulfide nanosheets for enhanced sodium storage

Sodium-ion batteries (SIBs) are considered as complementary alternatives to lithium-ion batteries for grid energy storage due to the abundance of sodium. However, low capacity, poor rate capability, and cycling stability of existing anodes significantly hinder the practical applications of SIBs. Herein, ultrathin two-dimensional SnS2 nanosheets (3-4 nm in thickness) are synthesized via a facile refluxing process toward enhanced sodium storage. The SnS2 nanosheets exhibit a high apparent diffusion coefficient of Na+ and fast sodiation/desodiation reaction kinetics. In half-cells, the nanosheets deliver a high reversible capacity of 733 mAh g-1 at 0.1 A g-1, which still remains up to 435 mAh g-1 at 2 A g-1. The cell has a high capacity retention of 647 mA h g-1 during the 50th cycle at 0.1 A g-1, which is by far the best for SnS2, suggesting that nanosheet morphology is beneficial to improve cycling stability in addition to rate capability. The SnS2 nanosheets also show encouraging performance in a full cell with a Na3V2(PO4)3 cathode. In addition, the sodium storage mechanism is investigated by ex situ XRD coupled with high-resolution TEM. The high specific capacity, good rate capability, and cycling durability suggest that SnS2 nanosheets have great potential working as anodes for high-performance SIBs. © 2015 American Chemical Society.

Potassium phosphate as a reagent for the gravimetric estimation of lithium

Previous attempts for the quantitative estimation of lithium as orthophosphate, employing an alkali metal phosphate, have not been successful. A method, is described for the estimation of lithium as trilithium phosphate from 60% ethyl alcohol solution at 65° to 70° C., employing potassium phosphate reagent, at pH 9.5. The method is applicable in the presence of varying amounts of sodium and/or potassium cations and chloride, sulfate, nitrate, and phosphate anions.

A 3.8-V earth-abundant sodium battery electrode

Rechargeable lithium batteries have ushered the wireless revolution over last two decades and are now matured to enable green automobiles. However, the growing concern on scarcity and large-scale applications of lithium resources have steered effort to realize sustainable sodium-ion batteries, Na and Fe being abundant and low-cost charge carrier and redox centre, respectively. However, their performance is limited owing to low operating voltage and sluggish kinetics. Here we report a hitherto-unknown material with entirely new composition and structure with the first alluaudite-type sulphate framework, Na2Fe2(SO4)(3), registering the highest-ever Fe3+/ Fe2+ redox potential at 3.8V (versus Na, and hence 4.1V versus Li) along with fast rate kinetics. Rare-metal-free Na-ion rechargeable battery system compatible with the present Li-ion battery is now in realistic scope without sacrificing high energy density and high power, and paves way for discovery of new earth-abundant sustainable cathodes for large-scale batteries.

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.

Synthesis, and crystal and electronic structure of sodium metal phosphate for use as a hybrid capacitor in non-aqueous electrolyte

Energy storage devices based on sodium have been considered as an alternative to traditional lithium based systems because of the natural abundance, cost effectiveness and low environmental impact of sodium. Their synthesis, and crystal and electronic properties have been discussed, because of the importance of electronic conductivity in supercapacitors for high rate applications. The density of states of a mixed sodium transition metal phosphate (maricite, NaMn1/3Co1/3Ni1/3PO4) has been determined with the ab initio generalized gradient approximation (GGA)+Hubbard term (U) method. The computed results for the mixed maricite are compared with the band gap of the parent NaFePO4 and the electrochemical experimental results are in good agreement. A mixed sodium transition metal phosphate served as an active electrode material for a hybrid supercapacitor. The hybrid device (maricite versus carbon) in a nonaqueous electrolyte shows redox peaks in the cyclic voltammograms and asymmetric profiles in the charge-discharge curves while exhibiting a specific capacitance of 40 F g(-1) and these processes are found to be quasi-reversible. After long term cycling, the device exhibits excellent capacity retention (95%) and coulombic efficiency (92%). The presence of carbon and the nanocomposite morphology, identified through X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) studies, ensures the high rate capability while offering possibilities to develop new cathode materials for sodium hybrid devices.

Pursuit of Sustainable Iron-Based Sodium Battery Cathodes: Two Case Studies

Rechargeable batteries have been the torchbearer electrochemical energy storage devices empowering small-scale electronic gadgets to large-scale grid storage. Complementing the lithium-ion technology, sodium-ion batteries have emerged as viable economic alternatives in applications unrestricted by volume/weight. What is the best performance limit for new-age Na-ion batteries? This mission has unravelled suites of oxides and polyanionic positive insertion (cathode) compounds in the quest to realize high energy density. Economically and ecologically, iron-based cathodes are ideal for mass-scale dissemination of sodium batteries. This Perspective captures the progress of Fe-containing earth-abundant sodium battery cathodes with two best examples: (i) an oxide system delivering the highest capacity (similar to 200 mA h/g) and (ii) a polyanionic system showing the highest redox potential (3.8 V). Both develop very high energy density with commercial promise for large-scale applications. Here, the structural and electrochemical properties of these two cathodes are compared and contrasted to describe two alternate strategies to achieve the same goal, i.e., improved energy density in Fe-based sodium battery cathodes.

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.

Photoionization of 1s electron and corresponding shake-up process in ground and excited lithium atoms

The cross sections of the 18 electron photoionization and corresponding shake-up processes for Li atoms in the ground state 1s(2)2s and excited states 1s(2)2p, 1s(2)3p, 1s(2)3p and 1s(2)3d are calculated using the multi-configuration Dirac-Fock method. The latest experimental photoelectron spectrum at hv = 100 eV [Cubaynes D et al. Phys. Rev. Lett. 99 (2007) 213004] has been reproduced by the present theoretical investigation excellently. The relative intensity of the shake-up satellites shows that the effects of correlation and relaxation become more important for the higher excited states of the lithium atom, which are explained very well by the spatial overlap of the initial and final state wavefunctions. In addition, strong dependence of the cross section on the atomic orbitals of the valence electrons are found, especially near the threshold.

High capacity carbon based electrodes for lithium/oxygen batteries

Porous carbon aerogels are prepared by polycondensation of resorcinol (R) and formaldehyde (F)catalyzed by sodium carbonate (C) followed by carbonization of the resultant aerogels at 800? in an inert atmosphere. The porous texture of the carbons has been adjusted by the change of the molar ratio of resorcinol to catalyst (R/C) in the gel precursors in the range of 100 to 500. The porous structure of the aerogels and carbon aerogels are characterized by N2 adsorption-desorption measurements at 77 K. It is found that total pore volume and average pore diameter of the carbons increase with increase in the R/C ratio of the gel precursors.The prepared carbon aerogels are used as active materials in fabrication of composite carbon electrodes. The electrochemical performance of the electrodes has been tested by using them as cathodes in a Li/O2 cell. Through the galvanostatic charge/discharge measurements, it is found that with an increase of R/C ratio, the specific capacity of the Li/O2 cell fabricated from the carbon aerogels increases from 716 to 2077 charge/discharge cycles indicate that the carbon samples possess excellent stability on cycling.

Preparation of controlled porosity carbon-aerogels for energy storage in rechargeable lithium oxygen batteries

Porous carbon aerogels are prepared by polycondensation of resorcinol and formaldehyde catalyzed by sodium carbonate followed by carbonization of the resultant aerogels in an inert atmosphere. Pore structure of carbon aerogels is adjusted by changing the molar ratio of resorcinol to catalyst during gel preparation and also pyrolysis under Ar and activation under CO2 atmosphere at different temperatures. The prepared carbons are used as active materials in fabrication of composite carbon electrodes. The electrochemical performance of the electrodes has been tested in a Li/O2 cell. Through the galvanostatic charge/discharge measurements, it is found that the cell performance (i.e. discharge capacity and discharge voltage) depends on the morphology of carbon and a combined effect of pore volume, pore size and surface area of carbon affects the storage capacity. A Li/O2 cell using the carbon with the largest pore volume (2.195cm3/g) and a wide pore size (14.23 nm) showed a specific capacity of 1290mAh g-1.

alphaENaC-mediated lithium absorption promotes nephrogenic diabetes insipidus.

Lithium-induced nephrogenic diabetes insipidus (NDI) is accompanied by polyuria, downregulation of aquaporin 2 (AQP2), and cellular remodeling of the collecting duct (CD). The amiloride-sensitive epithelial sodium channel (ENaC) is a likely candidate for lithium entry. Here, we subjected transgenic mice lacking αENaC specifically in the CD (knockout [KO] mice) and littermate controls to chronic lithium treatment. In contrast to control mice, KO mice did not markedly increase their water intake. Furthermore, KO mice did not demonstrate the polyuria and reduction in urine osmolality induced by lithium treatment in the control mice. Lithium treatment reduced AQP2 protein levels in the cortex/outer medulla and inner medulla (IM) of control mice but only partially reduced AQP2 levels in the IM of KO mice. Furthermore, lithium induced expression of H(+)-ATPase in the IM of control mice but not KO mice. In conclusion, the absence of functional ENaC in the CD protects mice from lithium-induced NDI. These data support the hypothesis that ENaC-mediated lithium entry into the CD principal cells contributes to the pathogenesis of lithium-induced NDI.

Effect of Lithium Nitrate on the Alkali-Silica Reaction Gel

Lithium nitrate has been used to prevent and to mediate the expansion caused by alkali-silica reaction (ASR). However, there is limited information on how it affects the existing reaction products caused by ASR. The aim of the present work is to determine the modifications caused by the LiNO3 treatment on the structure of the gel produced by ASR. ASR gel samples obtained from a concrete dam were exposed to an aqueous solution of lithium nitrate and sodium hydroxide with molar LiNO3/NaOH = 0.74, and the resulting products were analyzed by X-ray diffraction, infrared spectroscopy, and solid-state nuclear magnetic resonance of Si-29, Na-23, and Li-7. The treatment of the gel samples produces significant structural modifications in ASR products. A new amorphous silicate compound incorporating Li+ ions is formed, with an average silicate network that can be described as linear in contrast with the layered structure of the original gel. This elimination of the layered structure after the Li-based treatments may be related to the reduction of the tendency of the gel to expand. Also, several crystalline compounds containing potassium indicate the release of this species from the original ASR gel.

Suppression of bitterness using sodium salts

Bitterness is an ongoing taste problem for both the pharmaceutical and food industries. This paper reports on how salts (NaCI, NaAcetate, NaGluconate, LiCI, KCI) and bitter compounds (urea, quinine-HCI, caffeine, amiloride-HCI, magnesium sulfate, KCI) interact to influence bitter perception. Sodium salts differentially suppress bitterness of these compounds; for example urea bitterness was suppressed by over 70% by sodium salts, while MgSO4 bitterness was not reduced. This study indicated that lithium ions had the same bitter suppressing ability as sodium ions, however the potassium cation had no bitter suppression ability. Changing the anion attached to the sodium did not affect bitter suppression, however, as the anion increased in size, perceived saltiness decreased. This indicates that sodium's mode of action is at the peripheral taste level, rather than a cognitive affect. A second experiment revealed that suppressing bitterness with a sodium salt in a bitter/sweet mixture causes an increase in sweetness. This suggests adding salt to a food matrix will not only increase salt perception, but also potentiate flavor by differential suppression of undesirable tastes such as bitter, while increasing more desirable tastes such as sweet.