Boron-doped sodium layered oxide for reversible oxygen redox reaction in Na-ion battery cathodes.
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ABSTRACT:
SUBMITTER: Guo YJ
PROVIDER: S-EPMC8421359 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:Layered Na-based oxides with the general composition of NaxTMO2 (TM: transition metal) have attracted significant attention for their high compositional diversity that provides tunable electrochemical performance for electrodes in sodium-ion batteries. The various compositions bring forward complex structural chemistry that is decisive for the layered stacking structure, Na-ion conductivity, and the redox activity, potentially promising new avenues in functional material properties. In this work, we have explored the maximum Na content in P2-type layered oxides and discovered that the high-content Na in the host enhances the structural stability; moreover, it promotes the oxidation of low-valent cations to their high oxidation states (in this case Ni2+). This can be rationalized by the increased hybridization of the O(2p)-TM(3d-eg*) states, affecting both the local TM environment as well as the interactions between the NaO2 and TMO2 layers. These properties are highly beneficial for the Na storage capabilities as required for cathode materials in sodium-ion batteries. It leads to excellent Na-ion mobility, a large storage capacity (>100 mAh g-1 between 2.0-4.0 V), yet preventing the detrimental sliding of the TMO2 layers (P2-O2 structural transition), as reflected by the ultralong cycle life (3000 (dis)charge cycles demonstrated). These findings expand the horizons of high Na-content P2-type materials, providing new insights of the electronic and structural chemistry for advanced cathode materials.
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Project description:Layered transition metal oxides are the most important cathode materials for Li/Na/K ion batteries. Suppressing undesirable phase transformations during charge-discharge processes is a critical and fundamental challenge towards the rational design of high-performance layered oxide cathodes. Here we report a shale-like NaxMnO2 (S-NMO) electrode that is derived from a simple but effective water-mediated strategy. This strategy expands the Na+ layer spacings of P2-type Na0.67MnO2 and transforms the particles into accordion-like morphology. Therefore, the S-NMO electrode exhibits improved Na+ mobility and near-zero-strain property during charge-discharge processes, which leads to outstanding rate capability (100 mAh g-1 at the operation time of 6 min) and cycling stability (>3000 cycles). In addition, the water-mediated strategy is feasible to other layered sodium oxides and the obtained S-NMO electrode has an excellent tolerance to humidity. This work demonstrates that engineering the spacings of alkali-metal layer is an effective strategy to stabilize the structure of layered transition metal oxides.
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Project description:Sodium-ion batteries are strategically pivotal to achieving large-scale energy storage. Layered oxides, especially manganese-based oxides, are the most popular cathodes due to their high reversible capacity and use of earth-abundant elements. However, less noticed is the fact that the interface of layered cathodes always suffers from atmospheric and electrochemical corrosion, leading to severely diminished electrochemical properties. Herein, we demonstrate an environmentally stable interface via the superficial concentration of titanium, which not only overcomes the above limitations, but also presents unique surface chemical/electrochemical properties. The results show that the atomic-scale interface is composed of spinel-like titanium (III) oxides, enhancing the structural/electrochemical stability and electronic/ionic conductivity. Consequently, the interface-engineered electrode shows excellent cycling performance among all layered manganese-based cathodes, as well as high-energy density. Our findings highlight the significance of a stable interface and, moreover, open opportunities for the design of well-tailored cathode materials for sodium storage.The interface of layered cathodes for sodium ion batteries is subject to atmospheric and electrochemical corrosions. Here, the authors demonstrate an environmentally stable interface via titanium enriched surface reconstruction in a layered manganese-based oxide.
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Project description:The preparation of boron-doped nanocarbon scaffolds with well-defined structures is important for the understanding of the impact of boron doping on their properties and behavior at the molecular level. We recently succeeded in the synthesis of a structurally well-defined nanographene molecule, bearing two boron atoms at the central positions. In this study, the characteristic properties and functions of this boron-doped nanographene were investigated in terms of (1) Lewis acidity, (2) redox properties, and (3) electrode performance in a battery. This boron-doped nanographene was susceptible to chemical adsorption with various Lewis bases, resulting in significant changes in the absorption and fluorescence properties, as well as in the conformation of the honeycomb framework. The two-electron reduction of this boron-doped nanographene produced a dianionic species that showed a substantial biradical character with a triplet ground state. A Li battery electrode, composed of a boron-doped nanographene with small peripheral substituents, displayed a stable performance in the 1.5-4.0 V range with a first discharge capacity of 160 mA h g-1. These results provide important insights into the effect of boron doping on nanocarbon compounds.
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Project description:ConspectusLithium-ion batteries (LIBs) are ubiquitous in all modern portable electronic devices such as mobile phones and laptops as well as for powering hybrid electric vehicles and other large-scale devices. Sodium-ion batteries (NIBs), which possess a similar cell configuration and working mechanism, have already been proven as ideal alternatives for large-scale energy storage systems. The advantages of NIBs are as follows. First, sodium resources are abundantly distributed in the earth's crust. Second, high-performance NIB cathode materials can be fabricated by using solely inexpensive and noncritical transition metals such as manganese and iron, which further reduces the cost of the required raw materials. Recently, the unprecedented demand for lithium and other critical minerals has driven the cost of these primary raw materials (which are utilized in LIBs) to a historic high and thus triggered the commercialization of NIBs.Sodium layered transition metal oxides (NaxTMO2, TM = transition metal/s), such as Mn-based sodium layered oxides, represent an important family of cathode materials with the potential to reduce costs, increase energy density and cycling stability, and improve the safety of NIBs for large-scale energy storage. However, these layered oxides face several key challenges, including irreversible phase transformations during cycling, poor air stability, complex charge-compensation mechanisms, and relatively high cost of the full cell compared to LiFePO4-based LIBs. Our work has focused on the techno-economic analysis, the degradation mechanism of NaxTMO2 upon cycling and air exposure, and the development of effective strategies to improve their electrochemical performances and air stability. Correlating structure-performance relationships and establishing general design strategies of NaxTMO2 must be considered for the commercialization of NIBs.In this Account, we discuss the recent progress in the development of air-stable, electrochemically stable, and cost-effective NaxTMO2. The favorable redox-active cations for NaxTMO2 are emphasized in terms of abundance, cost, supply, and energy density. Different working mechanisms related to NaxTMO2 are summarized, including the electrochemical reversibility, the main structural transformations during the charge and discharge processes, and the charge-compensation mechanisms that accompany the (de)intercalation of Na+ ions, followed by discussions to improve the stability toward ambient air and upon cycling. Then the techno-economics are presented, with an emphasis on cathodes with different chemical compositions, cost breakdown of battery packs, and Na deficiency, factors that are critical to the large-scale implementation. Finally, this Account concludes with an overview of the remaining challenges and new opportunities concerning the practical applications of NaxTMO2, with an emphasis on the cost, large-scale fabrication capability, and electrochemical performance.
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Project description:While organic batteries have attracted great attention due to their high theoretical capacities, high-voltage organic active materials (> 4 V vs Li/Li+ ) remain unexplored. Here, density functional theory calculations are combined with cyclic voltammetry measurements to investigate the electrochemistry of croconic acid (CA) for use as a lithium-ion battery cathode material in both dimethyl sulfoxide and γ-butyrolactone (GBL) electrolytes. DFT calculations demonstrate that CA dilitium salt (CA-Li2 ) has two enolate groups that undergo redox reactions above 4.0 V and a material-level theoretical energy density of 1949 Wh kg-1 for storing four lithium ions in GBL-exceeding the value of both conventional inorganic and known organic cathode materials. Cyclic-voltammetry measurements reveal a highly reversible redox reaction by the enolate group at ≈4 V in both electrolytes. Battery-performance tests of CA as lithium-ion battery cathode in GBL show two discharge voltage plateaus at 3.9 and 3.1 V, and a discharge capacity of 102.2 mAh g-1 with no capacity loss after five cycles. With the higher discharge voltages compared to the known, state-of-the-art organic small molecules, CA promises to be a prime cathode-material candidate for future high-energy-density lithium-ion organic batteries.
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Project description:The conventional P2-type cathode material Na0.67Ni0.33Mn0.67O2 suffers from an irreversible P2-O2 phase transition and serious capacity fading during cycling. Here, we successfully carry out magnesium and calcium ion doping into the transition-metal layers (TM layers) and the alkali-metal layers (AM layers), respectively, of Na0.67Ni0.33Mn0.67O2. Both Mg and Ca doping can reduce O-type stacking in the high-voltage region, leading to enhanced cycling endurance, however, this is associated with a decrease in capacity. The results of density functional theory (DFT) studies reveal that the introduction of Mg2+ and Ca2+ make high-voltage reactions (oxygen redox and Ni4+/Ni3+ redox reactions) less accessible. Thanks to the synergetic effect of co-doping with Mg2+ and Ca2+ ions, the adverse effects on high-voltage reactions involving Ni-O bonding are limited, and the structural stability is further enhanced. The finally obtained P2-type Na0.62Ca0.025Ni0.28Mg0.05Mn0.67O2 exhibits a satisfactory initial energy density of 468.2 W h kg-1 and good capacity retention of 83% after 100 cycles at 50 mA g-1 within the voltage range of 2.2-4.35 V. This work deepens our understanding of the specific effects of Mg2+ and Ca2+ dopants and provides a stability-enhancing strategy utilizing abundant alkaline earth elements.
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Project description:This paper reports on a unique reversible reducing and oxidizing (redox) property of Co(III) in Co-doped amorphous SiO2/γ-Al2O3 composites. The Fenton reaction during the H2O2-catalyzed sol-gel synthesis utilized in this study lead to the partial formation of Co(III) in addition to Co(II) within the composites. High-resolution transmission electron microscopy (HRTEM) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) analyses for the composite powder sample with a composition of Al:Si:Co = 85:10:5 showed the amorphous state of the Co-doped SiO2 that modified γ-Al2O3 nanocrystalline surfaces. In situ X-ray absorption fine structure (XAFS) spectroscopic analysis suggested reversible redox reactions of Co species in the composite powder sample during heat-treatment under H2 at 500 °C followed by subsequent cooling to RT under Ar. Further analyses by in situ IR spectroscopy combined with cyclic temperature programmed reduction/desorption (TPR/TPD) measurements and X-ray photoelectron spectroscopic (XPS) analysis revealed that the alternating Co(III)/(II) redox reactions were associated with OH formation (hydrogenation)-deformation (dehydrogenation) of the amorphous aluminosilicate matrix formed in situ at the SiO2/γ-Al2O3 hetero interface, and the redox reactions were governed by the H2 partial pressure at 250-500 °C. As a result, a supported mesoporous γ-Al2O3/Co-doped amorphous SiO2/mesoporous γ-Al2O3 three-layered composite membrane exhibited an H2-triggered chemical valve property: mesopores under H2 flow (open) and micropores under He flow (closure) at 300-500 °C.
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