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Simple synthesis of highly catalytic carbon-free MnCo2O4@Ni as an oxygen electrode for rechargeable Li-O2 batteries with long-term stability.

ABSTRACT: An effective integrated design with a free standing and carbon-free architecture of spinel MnCo2O4 oxide prepared using facile and cost effective hydrothermal method as the oxygen electrode for the Li-O2 battery, is introduced to avoid the parasitic reactions of carbon and binder with discharge products and reaction intermediates, respectively. The highly porous structure of the electrode allows the electrolyte and oxygen to diffuse effectively into the catalytically active sites and hence improve the cell performance. The amorphous Li2O2 will then precipitate and decompose on the surface of free-standing catalyst nanorods. Electrochemical examination demonstrates that the free-standing electrode without carbon support gives the highest specific capacity and the minimum capacity fading among the rechargeable Li-O2 batteries tested. The Li-O2 cell has demonstrated a cyclability of 119 cycles while maintaining a moderate specific capacity of 1000 mAh g(-1). Furthermore, the synergistic effect of the fast kinetics of electron transport provided by the free-standing structure and the high electro-catalytic activity of the spinel oxide enables excellent performance of the oxygen electrode for Li-O2 cells.

SUBMITTER: Kalubarme RS

PROVIDER: S-EPMC4543937 | biostudies-literature |

REPOSITORIES: biostudies-literature

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P2-Na0.6[Cr0.6Ti0.4]O2 cation-disordered electrode for high-rate symmetric rechargeable sodium-ion batteries.

Project description:Most P2-type layered oxides exhibit Na(+)/vacancy-ordered superstructures because of strong Na(+)-Na(+) interaction in the alkali metal layer and charge ordering in the transition metal layer. These superstructures evidenced by voltage plateaus in the electrochemical curves limit the Na(+) ion transport kinetics and cycle performance in rechargeable batteries. Here we show that such Na(+)/vacancy ordering can be avoided by choosing the transition metal ions with similar ionic radii and different redox potentials, for example, Cr(3+) and Ti(4+). The designed P2-Na(0.6)[Cr(0.6)Ti(0.4)]O2 is completely Na(+)/vacancy-disordered at any sodium content and displays excellent rate capability and long cycle life. A symmetric sodium-ion battery using the same P2-Na(0.6)[Cr(0.6)Ti(0.4)]O2 electrode delivers 75% of the initial capacity at 12C rate. Our contribution demonstrates that the approach of preventing Na(+)/vacancy ordering by breaking charge ordering in the transition metal layer opens a simple way to design disordered electrode materials with high power density and long cycle life.

| S-EPMC4421853 | biostudies-literature

Bifunctional Oxygen Electrocatalyst of Mesoporous Ni/NiO Nanosheets for Flexible Rechargeable Zn-Air Batteries.

Project description:One approach to accelerate the stagnant kinetics of both the oxygen reduction and evolution reactions (ORR/OER) is to develop a rationally designed multiphase nanocomposite, where the functions arising from each of the constituent phases, their interfaces, and the overall structure are properly controlled. Herein, we successfully synthesized an oxygen electrocatalyst consisting of Ni nanoparticles purposely interpenetrated into mesoporous NiO nanosheets (porous Ni/NiO). Benefiting from the contributions of the Ni and NiO phases, the well-established pore channels for charge transport at the interface between the phases, and the enhanced conductivity due to oxygen-deficiency at the pore edges, the porous Ni/NiO nanosheets show a potential of 1.49 V (10 mA cm-2) for the OER and a half-wave potential of 0.76 V for the ORR, outperforming their noble metal counterparts. More significantly, a Zn-air battery employing the porous Ni/NiO nanosheets exhibits an initial charging-discharging voltage gap of 0.83 V (2 mA cm-2), specific capacity of 853 mAh g Zn -1 at 20 mA cm-2, and long-time cycling stability (120 h). In addition, the porous Ni/NiO-based solid-like Zn-air battery shows excellent electrochemical performance and flexibility, illustrating its great potential as a next-generation rechargeable power source for flexible electronics.

| S-EPMC7770935 | biostudies-literature

A Heavily Surface-Doped Polymer with the Bifunctional Catalytic Mechanism in Li-O2 Batteries.

Project description:The application of conducting polymers (CPs) in energy storage systems is greatly limited by insufficient reversibility and stability. Here, we successfully incorporated functionalized dopants (Fe(CN)63- [FCN] and PO43- ions) in CPs matrixes to achieve a preferable electrochemical performance. A stable cation inserting/expulsing behavior of surface-doped polycarbazole (PCz) is demonstrated in our work, where doping levels and semiconductor properties of PCz are effectively controlled to adjust their redox properties and stability. With carbon nanotube (CNT) films as the substrate, the CNT/PCz:FCN composite is initially adopted as a free-standing catalytic electrode in Li-O2 cells. The molecule-level dispersed FCN dopants on the surface can work as bifunctional redox mediators on the charge-discharge process. Thus, this composite can not only achieve a low charge plateau of 3.62 V and a regular growth of capacities from 1,800 to 4,800 mAh/gCNT, but also maintain the most of charge voltages under 4.0 V for 150 cycles.

| S-EPMC6489138 | biostudies-literature

Exclusive Solution Discharge in Li–O2 Batteries?

Project description:Capacity, rate performance,

| S-EPMC9469202 | biostudies-literature

Quantitatively analyzing the failure processes of rechargeable Li metal batteries

Project description:Description Advanced spectroscopy methods quantitatively elucidate the failure process of lithium metal batteries. Practical use of lithium (Li) metal for high–energy density lithium metal batteries has been prevented by the continuous formation of Li dendrites, electrochemically isolated Li metal, and the irreversible formation of solid electrolyte interphases (SEIs). Differentiating and quantifying these inactive Li species are key to understand the failure mode. Here, using operando nuclear magnetic resonance (NMR) spectroscopy together with ex situ titration gas chromatography (TGC) and mass spectrometry titration (MST) techniques, we established a solid foundation for quantifying the evolution of dead Li metal and SEI separately. The existence of LiH is identified, which causes deviation in the quantification results of dead Li metal obtained by these three techniques. The formation of inactive Li under various operating conditions has been studied quantitatively, which revealed a general “two-stage” failure process for the Li metal. The combined techniques presented here establish a benchmark to unravel the complex failure mechanism of Li metal.

| S-EPMC8580315 | biostudies-literature

Analysis of Minerals as Electrode Materials for Ca-based Rechargeable Batteries.

Project description:Rechargeable lithium-ion batteries dominate the consumer electronics and electric vehicle markets. However, concerns on Li availability have prompted the development of alternative high energy density electrochemical energy storage systems. Rechargeable batteries based on a Ca metal anode can exhibit advantages in terms of energy density, safety and cost. The development of rechargeable Ca metal batteries requires the identification of suitable high specific energy cathode materials. This work focuses on Ca-bearing minerals because they represent stable and abundant compounds. Suitable minerals should contain a transition metal able of being reversibly reduced and oxidized, which points to several major classes of silicates and carbonates: olivine (CaFeSiO4; kirschsteinite), pyroxene (CaFe/MnSi2O6; hedenbergite and johannsenite, respectively), garnet (Ca3Fe/Cr2Si3O12; andradite and uvarovite, respectively), amphibole (Ca2Fe5Si8O22(OH)2; ferroactinolite) and double carbonates (CaMn(CO3)2; kutnahorite and CaFe(CO3)2; ankerite). This work discusses their electrode characteristics based on crystal chemistry analysis and density functional theory (DFT) calculations. The results indicate that upon Ca deintercalation, compounds such as pyroxene, garnet and double carbonate minerals could display high theoretical energy densities (ranging from 780 to 1500?Wh/kg) with moderate structural modifications. As a downside, DFT calculations indicate a hampered Ca mobility in their crystal structures. The overall analysis then disregards olivine, garnet, pyroxene, amphibole and double carbonates as structural types for future Ca-cathode materials design.

| S-EPMC6609692 | biostudies-literature

Mesoporous Carbons from Polysaccharides and Their Use in Li-O2 Batteries.

Project description:Previous studies have demonstrated that the mesoporosity of carbon material obtained by the Starbon® process from starch-formed by amylose and amylopectin can be tuned by controlling this ratio (the higher the amylose, the higher the mesoporosity). This study shows that starch type can also be an important parameter to control this mesoporosity. Carbons with controlled mesoporosity (Vmeso from 0.1-0.7 cm3/g) have been produced by the pre-mixing of different starches using an ionic liquid (IL) followed by a modified Starbon® process. The results show that the use of starch from corn and maize (commercially available Hylon VII with maize, respectively) is the better combination to increase the mesopore volume. Moreover, "low-cost" mesoporous carbons have been obtained by the direct carbonization of the pre-treated starch mixtures with the IL. In all cases, the IL can be recovered and reused, as demonstrated by its recycling up to three times. Furthermore, and as a comparison, chitosan has been also used as a precursor to obtain N-doped mesoporous carbons (5.5 wt% N) with moderate mesoporosity (Vmeso = 0.43 cm3/g). The different mesoporous carbons have been tested as cathode components in Li-O2 batteries and it is shown that a higher carbon mesoporosity, produced from starch precursor, or the N-doping, produced from chitosan precursor, increase the final battery cell performance (specific capacity and cycling).

| S-EPMC7602621 | biostudies-literature

Nanosponge-Based Composite Gel Polymer Electrolyte for Safer Li-O2 Batteries.

Project description:Li-O2 batteries represent a promising rechargeable battery candidate to answer the energy challenges our world is facing, thanks to their ultrahigh theoretical energy density. However, the poor cycling stability of the Li-O2 system and, overall, important safety issues due to the formation of Li dendrites, combined with the use of organic liquid electrolytes and O2 cross-over, inhibit their practical applications. As a solution to these various issues, we propose a composite gel polymer electrolyte consisting of a highly cross-linked polymer matrix, containing a dextrin-based nanosponge and activated with a liquid electrolyte. The polymer matrix, easily obtained by thermally activated one pot free radical polymerization in bulk, allows to limit dendrite nucleation and growth thanks to its cross-linked structure. At the same time, the nanosponge limits the O2 cross-over and avoids the formation of crystalline domains in the polymer matrix, which, combined with the liquid electrolyte, allows a good ionic conductivity at room temperature. Such a composite gel polymer electrolyte, tested in a cell containing Li metal as anode and a simple commercial gas diffusion layer, without any catalyst, as cathode demonstrates a full capacity of 5.05 mAh cm-2 as well as improved reversibility upon cycling, compared to a cell containing liquid electrolyte.

| S-EPMC8156716 | biostudies-literature

Boosting High-Rate Li-S Batteries by an MOF-Derived Catalytic Electrode with a Layer-by-Layer Structure.

Project description:Rechargeable high-energy lithium-sulfur batteries suffer from rapid capacity decay and poor rate capability due to intrinsically intermediate polysulfides' shuttle effect and sluggish redox kinetics. To tackle these problems simultaneously, a layer-by-layer electrode structure is designed, each layer of which consists of ultrafine CoS2-nanoparticle-embedded porous carbon evenly grown on both sides of reduced graphene oxide (rGO). The CoS2 nanoparticles derived from metal-organic frameworks (MOFs) have an average size of ≈10 nm and can facilitate the conversion between Li2S6 and Li2S2/Li2S in the liquid electrolyte by a catalytic effect, leading to improved polysulfide redox kinetics. In addition, the interconnected conductive frameworks with hierarchical pore structure afford fast ion and electron transport and provide sufficient space to confine polysulfides. As a result, the layer-by-layer electrodes exhibit good rate capabilities with 1180.7 and 700 mAh g-1 at 1.0 and 5.0 C, respectively, and maintain an impressive cycling stability with a low capacity decay of 0.033% per cycle within ultralong 1000 cycles at 5.0 C. Even with a high sulfur loading of 3.0 mg cm-2, the electrodes still show high rate performance and stable cycling stability over 300 cycles.

| S-EPMC6702624 | biostudies-literature

Poor Cycling Performance of Rechargeable Lithium-Oxygen Batteries under Lean-Electrolyte and High-Areal-Capacity Conditions: Role of Carbon Electrode Decomposition.

Project description:There is growing demand for practical implementation of lithium-oxygen batteries (LOBs) due to their superior potential for achieving higher energy density than that of conventional lithium-ion batteries. Although recent studies demonstrate the stable operation of 500 Wh kg-1 -class LOBs, their cycle life remains fancy. For further improving the cycle performance of LOBs, the complicated chemical degradation mechanism in LOBs must be elucidated. In particular, the quantitative contribution of each cell component to degradation phenomenon in LOBs under lean-electrolyte and high-areal-capacity conditions should be clarified. In the present study, the mass balance of the positive-electrode reaction in a LOB under lean-electrolyte and high-areal-capacity conditions is quantitatively evaluated. The results reveal carbon electrode decomposition to be the critical factor that prevents the prolonged cycling of the LOB. Notably, the carbon electrode decomposition occur during charging at voltages higher than 3.8 V through the electrochemical decomposition of solid-state side products. The findings of this study highlight the significance of improving the stability of the carbon electrode and/or forming Li2 O2 , which can decompose at voltages lower than 3.8 V, to realize high-energy-density LOBs with long cycle life.

| S-EPMC10460881 | biostudies-literature

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