Boron-doped sodium layered oxide for reversible oxygen redox reaction in Na-ion battery cathodes.

Na-ion cathode materials operating at high voltage with a stable cycling behavior are needed to develop future high-energy Na-ion cells. However, the irreversible oxygen redox reaction at the high-voltage region in sodium layered cathode materials generates structural instability and poor capacity retention upon cycling. Here, we report a doping strategy by incorporating light-weight boron into the cathode active material lattice to decrease the irreversible oxygen oxidation at high voltages (i.e., >4.0 V vs. Na+/Na). The presence of covalent B-O bonds and the negative charges of the oxygen atoms ensures a robust ligand framework for the NaLi1/9Ni2/9Fe2/9Mn4/9O2 cathode material while mitigating the excessive oxidation of oxygen for charge compensation and avoiding irreversible structural changes during cell operation. The B-doped cathode material promotes reversible transition metal redox reaction enabling a room-temperature capacity of 160.5 mAh g-1 at 25 mA g-1 and capacity retention of 82.8% after 200 cycles at 250 mA g-1. A 71.28 mAh single-coated lab-scale Na-ion pouch cell comprising a pre-sodiated hard carbon-based anode and B-doped cathode material is also reported as proof of concept.

P3/O3 Integrated Layered Oxide as High-Power and Long-Life Cathode toward Na-Ion Batteries.

Low-cost and stable sodium-layered oxides (such as P2- and O3-phases) are suggested as highly promising cathode materials for Na-ion batteries (NIBs). Biphasic hybridization, mainly involving P2/O3 and P2/P3 biphases, is typically used to boost their electrochemical performances. Herein, a P3/O3 intergrown layered oxide (Na2/3 Ni1/3 Mn1/3 Ti1/3 O2 ) as high-rate and long-life cathode for NIBs via tuning the amounts of Ti substitution in Na2/3 Ni1/3 Mn2/3- x Tix O2 (x = 0, 1/6, 1/3, 2/3) is demonstrated. The X-ray diffraction (XRD) Rietveld refinement and aberration-corrected scanning transmission electron microscopy show the co-existence of P3 and O3 phases, and density functional theory calculation corroborates the appearance of the anomalous O3 phase at the Ti substitution amount of 1/3. The P3/O3 biphasic cathode delivers an unexpected rate capability (≈88.7% of the initial capacity at a high rate of 5 C) and cycling stability (≈68.7% capacity retention after 2000 cycles at 1 C), superior to those of the sing phases P3-Na2/3 Ni1/3 Mn2/3 O2 , P3-Na2/3 Ni1/3 Mn1/2 Ti1/6 O2 , and O3-Na2/3 Ni1/3 Ti2/3 O2 . The highly reversible structural evolution of the P3/O3 integrated cathode observed by ex situ XRD, ex situ X-ray absorption spectra, and the rapid Na+ diffusion kinetics, underpin the enhancement. These results show the important role of P3/O3 biphasic hybridization in designing and engineering layered oxide cathodes for NIBs.

Insights on Electrochemical Behaviors of Sodium Peroxide as a Sacrificial Cathode Additive for Boosting Energy Density of Na-Ion Battery.

The development of Na-ion full cells (NIFCs) suffers from the issue that the solid electrolyte interphase formation on the carbon anode consumes the limited sodium from cathode and thus incurs the decreased energy density and poor cyclic stability. To address these issues, we herein report that Na2O2 could be used as a sacrificial Na source through spraying its slurry on the surface of cathode, and investigate its stability as well as electrochemical behavior toward NIFCs. The results show that Na2O2 has good chemical and storage stability under a dry atmosphere and has no negative effect on the electrochemical performance of the cathode. Compared with the pristine cathode, the Na2O2-decorated cathode exhibits higher discharge capacity, superior capacity retention, and rate capability in a full cell with a carbon anode. Our cathode Na compensation strategy provides an effective avenue to make up for the irreversible Na+ loss cause by the formation of solid electrolyte interphase on the anode, thereby promoting the electrochemical performance and energy density of NIFCs toward the large-scale application.

Large-Scale Synthesis of the Stable Co-Free Layered Oxide Cathode by the Synergetic Contribution of Multielement Chemical Substitution for Practical Sodium-Ion Battery.

The O3-type layered oxide cathodes for sodium-ion batteries (SIBs) are considered as one of the most promising systems to fully meet the requirement for future practical application. However, fatal issues in several respects such as poor air stability, irreversible complex multiphase evolution, inferior cycling lifespan, and poor industrial feasibility are restricting their commercialization development. Here, a stable Co-free O3-type NaNi0.4Cu0.05Mg0.05Mn0.4Ti0.1O2 cathode material with large-scale production could solve these problems for practical SIBs. Owing to the synergetic contribution of the multielement chemical substitution strategy, this novel cathode not only shows excellent air stability and thermal stability as well as a simple phase-transition process but also delivers outstanding battery performance in half-cell and full-cell systems. Meanwhile, various advanced characterization techniques are utilized to accurately decipher the crystalline formation process, atomic arrangement, structural evolution, and inherent effect mechanisms. Surprisingly, apart from restraining the unfavorable multiphase transformation and enhancing air stability, the accurate multielement chemical substitution engineering also shows a pinning effect to alleviate the lattice strains for the high structural reversibility and enlarges the interlayer spacing reasonably to enhance Na+ diffusion, resulting in excellent comprehensive performance. Overall, this study explores the fundamental scientific understandings of multielement chemical substitution strategy and opens up a new field for increasing the practicality to commercialization.

High-Efficiency Cathode Sodium Compensation for Sodium-Ion Batteries.

Sodium-ion batteries have gained much attention for their potential application in large-scale stationary energy storage due to the low cost and abundant sodium sources in the earth. However, the electrochemical performance of sodium-ion full cells (SIFCs) suffers severely from the irreversible consumption of sodium ions of cathode during the solid electrolyte interphase (SEI) formation of hard carbon anode. Here, a high-efficiency cathode sodiation compensation reagent, sodium oxalate (Na2 C2 O4 ), which possesses both a high theoretical capacity of 400 mA h g-1 and a capacity utilization as high as 99%, is proposed. The implementation of Na2 C2 O4 as sacrificial sodium species is successfully realized by decreasing its oxidation potential from 4.41 to 3.97 V through tuning conductive additives with different physicochemical features, and the corresponding mechanism of oxidation potential manipulation is analyzed. Electrochemical results show that in the full cell based on a hard carbon anode and a P2-Na2/3 Ni1/3 Mn1/3 Ti1/3 O2 cathode with Na2 C2 O4 as a sodium reservoir to compensate for sodium loss during SEI formation, the capacity retention is increased from 63% to 85% after 200 cycles and the energy density is improved from 129.2 to 172.6 W h kg-1 . This work can provide a new avenue for accelerating the development of SIFCs.

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Soil samples from four vegetation mini-patches (Artemisia scoparia, Glycyrrhiza uralensis, Sophora alopecuroides, Astragalus melilotoides) in a desert steppe in central Ningxia were collected. Soil physico-chemical properties including soil particle-size distribution, organic matter, pH, EC, total N, total K, total P of three depths were measured. The fractal dimension of particle size distribution characteristics of soils derived from four different vegetation mini-patches and their correlations with soil physico-chemical properties were examined. The results showed that patch vege-tation distribution affected the distribution of soil particle size, with the A. melilotoides mini-patch being the highest (D=2.51) and G. uralensis mini-patch being the lowest (D=2.46). There were significant positive correlation between fractal dimensions and the contents of clay and silt, and nega-tive correlation between fractal dimensions and sand content. Fractal dimensions were positively correlated with pH value and EC, negatively correlated with the contents of soil organic matter and total N, and had no correlation with the contents of soil total K and total P. The patchy vegetation distribution had potential trends of salinization and degradation.

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Vegetation patch is one of the most basic characteristics of natural grazing grassland. To explore the effects of vegetation patch on soil microbial community, the changes of soil microbial biomass and community structure under four different vegetation patches in Ningxia desert steppe were quantified using phospholipid fatty acid (PLFA) analysis. The results showed that: 1) Soil microbial groups were abundant in vegetation patches, with the highest bacterial content, low fungal and actinomycete content, and the Gram-positive bacteria content being higher than that of Gram-negative bacteria in the patches of the four plant communities; 2) The total soil microbial biomass of Glycyrrhiza uralensis patch was significantly higher than that of Artemisia scoparia, Sophora alopecuroides, and Astragalus melilotoides patches; 3) Total PLFAs, Gram-positive bacteria, Gram-negative bacteria, fungi, anaerobic bacteria and fungi/bacteria were significantly positively correlated with soil organic C, and significantly negatively correlated with soil pH, indicating that soil organic C and pH were important factors affecting the growth and development of soil microorganisms in desert steppe.

Nonaqueous Sodium-Ion Full Cells: Status, Strategies, and Prospects.

With ever-increasing efforts focused on basic research of sodium-ion batteries (SIBs) and growing energy demand, sodium-ion full cells (SIFCs), as unique bridging technology between sodium-ion half-cells (SIHCs) and commercial batteries, have attracted more and more interest and attention. To promote the development of SIFCs in a better way, it is essential to gain a systematic and profound insight into their key issues and research status. This Review mainly focuses on the interface issues, major challenges, and recent progresses in SIFCs based on diversified electrolytes (i.e., nonaqueous liquid electrolytes, quasi-solid-state electrolytes, and all-solid-state electrolytes) and summarizes the modification strategies to improve their electrochemical performance, including interface modification, cathode/anode matching, capacity ratio, electrolyte optimization, and sodium compensation. Outlooks and perspectives on the future research directions to build better SIFCs are also provided.

Exposing {010} Active Facets by Multiple-Layer Oriented Stacking Nanosheets for High-Performance Capacitive Sodium-Ion Oxide Cathode.

As one of the most promising cathodes for rechargeable sodium-ion batteries (SIBs), O3-type layered transition metal oxides commonly suffer from inevitably complicated phase transitions and sluggish kinetics. Here, a Na[Li0.05 Ni0.3 Mn0.5 Cu0.1 Mg0.05 ]O2 cathode material with the exposed {010} active facets by multiple-layer oriented stacking nanosheets is presented. Owing to reasonable geometrical structure design and chemical substitution, the electrode delivers outstanding rate performance (71.8 mAh g-1 and 16.9 kW kg-1 at 50C), remarkable cycling stability (91.9% capacity retention after 600 cycles at 5C), and excellent compatibility with hard carbon anode. Based on the combined analyses of cyclic voltammograms, ex situ X-ray absorption spectroscopy, and operando X-ray diffraction, the reaction mechanisms behind the superior electrochemical performance are clearly articulated. Surprisingly, Ni2+ /Ni3+ and Cu2+ /Cu3+ redox couples are simultaneously involved in the charge compensation with a highly reversible O3-P3 phase transition during charge/discharge process and the Na+ storage is governed by a capacitive mechanism via quantitative kinetics analysis. This optimal bifunctional regulation strategy may offer new insights into the rational design of high-performance cathode materials for SIBs.

Exploration of Na(2.65)Ti(3.35)Fe(0.65)O9 as anode materials for Na-ion batteries.

Na(2.65)Ti(3.35)Fe(0.65)O9 rods were prepared by a simple solid-state route and coated with carbon to enhance their electronic conductivity. For the first time, Na(2.65)Ti(3.35)Fe(0.65)O9 was explored as an anode material for Na-ion batteries to deliver a discharge capacity of 137.5 mA h g(-1) at a current rate of 40 mA g(-1). The charge/discharge capacity of a carbon-coated sample increased by 46.3% to achieve 201.1 mA h g(-1).