Selective sodium intercalation into sodium nickel-manganese sulfate for dual Na-Li-ion batteries.

Double sodium transition metal sulfates combine in themselves unique intercalation properties with eco-compatible compositions - a specific feature that makes them attractive electrode materials for lithium and sodium ion batteries. Herein, we examine the intercalation properties of novel double sodium nickel-manganese sulfate, Na2Ni1/2Mn1/2(SO4)2, having a large monoclinic unit cell, through electrochemical and ex situ diffraction and spectroscopic methods. The sulfate salt Na2Ni1/2Mn1/2(SO4)2 is prepared by thermal dehydration of the corresponding hydrate salt Na2Ni1/2Mn1/2(SO4)2·4H2O having a blödite structure. The intercalation reactions on Na2Ni1-xMnx(SO4)2 are studied in two model cells: half-ion cell versus Li metal anode and full-ion cell versus Li4Ti5O12 anode by using lithium (LiPF6 dissolved in EC/DMC) and sodium electrolytes (NaPF6 dissolved in EC:DEC). Based on ex situ XRD and TEM analysis, it is found that sodium intercalation into Na2Ni1/2Mn1/2(SO4)2 takes place via phase separation into the Ni-rich monoclinic phase and Mn-rich alluaudite phase. The redox reactions involving participation of manganese and titanium ions are monitored by ex situ EPR spectroscopy. It has been demonstrated that manganese ions from the sulfate salt are participating in the electrochemical reaction, while the nickel ions remain intact. As a result, a reversible capacity of about 65 mA h g-1 is reached. The selective intercalation properties determine sodium nickel-manganese sulfate as a new electrode material for hybrid lithium-sodium ion batteries that is thought to combine the advantages of individual lithium and sodium batteries.

A fractal-like electrode based on double-wall nanotubes of anatase exhibiting improved electrochemical behaviour in both lithium and sodium batteries.

An anatase nanotube array has been prepared with a special morphology: two concentric walls and a very small central cavity. The method used here to achieve the double-wall structure is a single-step anodization process under a voltage ramp. Thanks to this nanostructure, which is equivalent to a fractal electrode, the electrochemical behaviour is improved, and the specific capacity is higher in both lithium and sodium cells due to pseudocapacitance. The double-wall structure of the nanotube enhances the surface of TiO2 being in contact with the electrolyte solution, thus allowing an easy penetration of the alkali ions into the electrode active material. The occurrence of sodium titanate in the electrode material after electrochemical reaction with sodium is studied by using EPR, HRTEM and NMR experiments.

Correlations between lithium local structure and electrochemistry of layered LiCo(1-2x)Ni(x)Mn(x)O2 oxides: 7Li MAS NMR and EPR studies.

Advanced (7)Li MAS NMR technologies and high frequency EPR are combined to identify structural motifs and their relation to electrochemical properties of layered lithium-cobalt-nickel-manganese oxides LiCo1-2xNixMnxO2 (0 < x ≤ 0.5) used as cathode materials in lithium ion batteries. Structural-chemical shift regularities were established by systematic variation of the ratio of diamagnetic Co(3+) to paramagnetic Ni/Mn ions with variable valences. While EPR allows identifying the oxidation state of transition metal ions inside the layers, (7)Li NMR probes the local structure of Li with respect to transition metal ions located in two adjacent layers. For assignment of the lithium chemical shifts, we examine first magnetically diluted LiCo1-2xNixMnxO2 with x = 0.02, where paramagnetic ions are stabilized only in Mn(4+) and Ni(3+) form. Then the studies are extended towards the intermediate compositions with x = 0.10 and 0.33, containing simultaneously paramagnetic Mn(4+), Ni(3+) and Ni(2+) ions and diamagnetic Co(3+) ions. The benefit of using NMR with ultrafast spinning rates is demonstrated for the end composition LiNi0.5Mn0.5O2 having only paramagnetic Ni(2+) and Mn(2+) ions. The local structure of Li is quantified in respect of the number of Ni(2+) and Mn(4+) neighbors. It has been demonstrated that Ni(2+) and Mn(4+) are non-randomly distributed around Li and their distribution depends on the method of synthesis. The extent of local cationic order and its effect on the electrochemical properties of LiNi0.5Mn0.5O2 are discussed.

Lithium Manganese Sulfates as a New Class of Supercapattery Materials at Elevated Temperatures.

To make supercapattery devices feasible, there is an urgent need to find electrode materials that exhibit a hybrid mechanism of energy storage. Herein, we provide a first report on the capability of lithium manganese sulfates to be used as supercapattery materials at elevated temperatures. Two compositions are studied: monoclinic Li2Mn(SO4)2 and orthorhombic Li2Mn2(SO4)3, which are prepared by a freeze-drying method followed by heat treatment at 500 °C. The electrochemical performance of sulfate electrodes is evaluated in lithium-ion cells using two types of electrolytes: conventional carbonate-based electrolytes and ionic liquid IL ones. The electrochemical measurements are carried out in the temperature range of 20-60 °C. The stability of sulfate electrodes after cycling is monitored by in-situ Raman spectroscopy and ex-situ XRD and TEM analysis. It is found that sulfate salts store Li+ by a hybrid mechanism that depends on the kind of electrolyte used and the recording temperature. Li2Mn(SO4)2 outperforms Li2Mn2(SO4)3 and displays excellent electrochemical properties at elevated temperatures: at 60 °C, the energy density reaches 280 Wh/kg at a power density of 11,000 W/kg. During cell cycling, there is a transformation of the Li-rich salt, Li2Mn(SO4)2, into a defective Li-poor one, Li2Mn2(SO4)3, which appears to be responsible for the improved storage properties. The data reveals that Li2Mn(SO4)2 is a prospective candidate for supercapacitor electrode materials at elevated temperatures.

Lithium storage mechanisms and effect of partial cobalt substitution in manganese carbonate electrodes.

A promising group of inorganic salts recently emerged for the negative electrode of advanced lithium-ion batteries. Manganese carbonate combines low weight and significant lithium storage properties. Electron paramagnetic resonance (EPR) and magnetic measurements are used to study the environment of manganese ions during cycling in lithium test cells. To observe reversible lithium storage into manganese carbonate, preparation by a reverse micelles method is used. The resulting nanostructuration favors a capacitive lithium storage mechanism in manganese carbonate with good rate performance. Partial substitution of cobalt by manganese improves cycling efficiency at high rates.

Oxygen-Storage Materials to Stabilize the Oxygen Redox Activity of Three-Layered Sodium Transition Metal Oxides.

To double the energy density of lithium- and sodium-ion batteries there is a need to activate simultaneously cationic and anionic redox reactions at the intercalation-type electrodes. In contrast to the cationic redox activity, the oxygen redox activity enforces an enhancement in the surface reactivity of the oxides leading to their poor reversibility and cycling stability. Herein, we propose a new concept to stabilize oxygen redox activity by using oxygen-storage materials as an efficient buffer supplying and receiving oxygen during alkali ion intercalation. As a proof-of-concept, the study is focused on CeO2 as a modifier of sodium nickel-manganese oxide with a three-layer sequence, P3-Na2/3Ni1/2Mn1/2O2. The CeO2-modified P3-Na2/3Ni1/2Mn1/2O2 displays a drastic increase in the reversible capacity following the order Na+ intercalation < Li+ intercalation < Li+,Na+ cointercalation.

Hybrid Li/Na Ion Batteries: Temperature-Induced Reactivity of Three-Layered Oxide (P3-Na2/3Ni1/3Mg1/6Mn1/2O2) Toward Lithium Ionic Liquid Electrolytes.

Hybrid metal ion batteries are perceived as competitive alternatives to lithium ion batteries because they provide better balance between energy/power density, battery cost, and environmental requirements. However, their cycling stability and high-temperature storage performance are still far from the desired. Herein, we first examine the temperature-induced reactivity of three-layered oxide, P3-Na2/3Ni1/3Mg1/6Mn1/2O2, toward lithium ionic liquid electrolyte upon cycling in hybrid Li/Na ion cells. Through ex situ X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses, the structural and surface changes in P3-Na2/3Ni1/3Mg1/6Mn1/2O2 are monitored and discussed. Understanding the relevant changes occurring during dual Li+ and Na+ intercalation into P3-Na2/3Ni1/3Mg1/6Mn1/2O2 is of crucial importance to enhance the overall performance of hybrid Li/Na ion batteries at elevated temperatures.

Layered P3-NaxCo1/3Ni1/3Mn1/3O2 versus Spinel Li4Ti5O12 as a Positive and a Negative Electrode in a Full Sodium-Lithium Cell.

The development of lithium and sodium ion batteries without using lithium and sodium metal as anodes gives the impetus for elaboration of low-cost and environmentally friendly energy storage devices. In this contribution we demonstrate the design and construction of a new type of hybrid sodium-lithium ion cell by using unique electrode combination (Li4Ti5O12 spinel as a negative electrode and layered Na3/4Co1/3Ni1/3Mn1/3O2 as a positive electrode) and conventional lithium electrolyte (LiPF6 salt dissolved in EC/DMC). The cell operates at an average potential of 2.35 V by delivering a reversible capacity of about 100 mAh/g. The mechanism of the electrochemical reaction in the full sodium-lithium ion cell is studied by means of postmortem analysis, as well as ex situ X-ray diffraction analysis, HR-TEM, and electron paramagnetic resonance spectroscopy (EPR). The changes in the surface composition of electrodes are examined by ex situ X-ray photoelectron spectroscopy (XPS).

High-intensity ultrasonication as a way to prepare graphene/amorphous iron oxyhydroxide hybrid electrode with high capacity in lithium battery.

The preparation of graphene/iron oxyhydroxide hybrid electrode material with very homogeneous distribution and close contact of graphene and amorphous iron oxyhydroxide nanoparticles has been achieved by using high-intensity ultrasonication. Due to the negative charge of the graphene surface, iron ions are attracted toward the surface of dispersed graphene, according to the zeta potential measurements. The anchoring of the FeO(OH) particles to the graphene layers has been revealed by using mainly TEM, XPS and EPR. TEM observations show that the size of the iron oxide particles is about 4 nm. The ultrasonication treatment is the key parameter to achieve small particle size in these graphene/iron oxyhydroxide hybrid materials. The electrochemical behavior of composite graphene/amorphous iron oxyhydroxide prepared by using high-intensity ultrasonication is outstanding in terms of gravimetric capacity and cycling stability, particularly when metallic foam is used as both the substrate and current collector. The XRD-amorphous character of iron oxyhydroxide in the hybrid electrode material and the small particle size contribute to achieve the improved electrochemical performance.

P3-Type Layered Sodium-Deficient Nickel-Manganese Oxides: A Flexible Structural Matrix for Reversible Sodium and Lithium Intercalation.

Sodium-deficient nickel-manganese oxides exhibit a layered structure, which is flexible enough to acquire different layer stacking. The effect of layer stacking on the intercalation properties of P3-Nax Ni0.5 Mn0.5 O2 (x=0.50, 0.67) and P2-Na2/3 Ni1/3 Mn2/3 O2 , for use as cathodes in sodium- and lithium-ion batteries, is examined. For P3-Na0.67 Ni0.5 Mn0.5 O2 , a large trigonal superstructure with 2√3 a×2√3 a×2 c is observed, whereas for P2-Na2/3 Ni1/3 Mn2/3 O2 there is a superstructure with reduced lattice parameters. In sodium cells, P3 and P2 phases intercalate sodium reversibly at a well-expressed voltage plateau. Preservation of the P3-type structure during sodium intercalation determines improving cycling stability of the P3 phase within an extended potential range, in comparison with that for the P2 phase, for which a P2-O2 phase transformation has been found. Between 2.0 and 4.0 V, P3 and P2 phases display an excellent rate capability. In lithium cells, the P3 phase intercalates lithium, accompanied by a P3-O3 structural transformation. The in situ generated O3 phase, containing lithium and sodium simultaneously, determines the specific voltage profile of P3-Nax Ni0.5 Mn0.5 O2 . The P2 phase does not display any reversible lithium intercalation. The P3 phase demonstrates a higher capacity at lower rates in lithium cells, whereas in sodium cells P3-Nax Ni0.5 Mn0.5 O2 operates better at higher rates. These findings reveal the unique ability of sodium-deficient nickel-manganese oxides with a P3-type structure for application as low-cost electrode materials in both sodium- and lithium-ion batteries.

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.

Local structure of Mn4+ and Fe3+ spin probes in layered LiAlO2 oxide by modelling of zero-field splitting parameters.

The zero-field splitting parameters (ZFS) of Mn(4+) and Fe(3+) ions in LiAlO(2) with a layered structure are analyzed experimentally and theoretically by using high-frequency electron paramagnetic resonance spectroscopy, Neuman superposition model (NSM), DFT and multiconfigurational calculations. The interpretation of ZFS is based on the comparison of the experimentally determined values with the calculated ones. This approach allows assessing the performance of different methods for computation of ZFS of Fe(3+) and Mn(4+) in layered oxide matrices. DFT and multiconfigurational calculations are used to analyze the effect of oxygen, aluminium, and lithium neighbours on ZFS of Fe(3+) and Mn(4+). These calculations are based on a cluster comprising Fe(3+) or Mn(4+) ions in a trigonally compressed octahedron with 6 metal ions (Al(3+) or Co(3+)) as first metal neighbours and 6 O(2-) and 2 Li(+) (above and below the layer) as second neighbours. A satisfactory agreement with the experimental data is achieved when the local structure of Mn(4+) and Fe(3+) deviates from the trigonal host-site geometry. The local structure of Fe(3+) comprises an axial distortion, while trigonal environment with reduced extent of distortion appears around Mn(4+).