A Ternary Composite with Medium Adsorption Confirms Good Reversibility of Li-Se Batteries.

For Li-Se batteries, cathode using carbonaceous hosts to accommodate Se performed modestly, whereas those applying metallic compounds with stronger chemical adsorption exhibited even more rapid capacity decay, the intrinsic reasons for which are still not clear. Herein, it is found that Se tends to precipitate on the surface of the electrode during cycling, and the precipitation speed depends on the polarization degree of the host. A further enhanced adsorption does not certainly generate better electrochemical activity, since hosts with overhigh adsorption ability are hard to desorb polyselenides, leading to catalyst passivation and rapid capacity decay. These findings encourage us to design a ternary anatase/rutile/titanium nitride (aTiO2 /rTiO2 /TiN@C) composite host, integrating good adsorption of TiO2 and rapid electron transport ability of TiN, and introducing rutile to weaken overall adsorption. The aTiO2 /rTiO2 /TiN@C composite with medium adsorption not only avoids rapid loss of active substances in electrolyte but also slows down the precipitation speed of Se. As a result, the aTiO2 /rTiO2 /TiN@C/Se electrode delivered good rate capability(154 mA h g-1 at 20 C) and good cycling stability(a low decay of 0.024% per cycle within 500 cycles at 2 C).

Recent Advances of Pore Structure in Disordered Carbons for Sodium Storage: A Mini Review.

Disordered carbons as the most promising anode materials for sodium ion batteries (SIBs) have attracted much attention, due to the widely-distributed sources and potentially high output voltage when applied in full cells owing to the almost lowest voltage plateau. The complex microstructure makes the sodium storage mechanism of disordered carbons controversial. Recently, many studies show that the plateau region of disordered carbons are closely related to the embedment of sodium ion/semimetal in nanopores. In this regard, the classification, characterization and construction of nanopores are exhaustively discussed in this review. In addition, perspectives about the controllable construction of nanopores are presented in the last section, aiming to catch out more valuable studies include not only the construction of closed pores to enhance capacity but also the design of carbon materials to understand Na storage mechanism.

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.

Self-Template Synthesis of Prussian Blue Analogue Hollow Polyhedrons as Superior Sodium Storage Cathodes.

Prussian blue and its analogues with three-dimensional frame structures have been shown to be of great importance in the research and development of sodium-ion batteries (SIBs). Herein, we develop a simple and convenient self-template method to prepare a hollow-structured Prussian blue analogue (CoFe-PBA). This structure is conducive to buffer the volume changes during ion extraction and insertion processes and shorten the ion diffusion path. When further building a thin polydopamine (PDA) coating, the synthesized CoFe-PBA@PDA exhibits a high discharge capacity of 123.1 mAh g-1 at 0.1 A g-1 with a capacity retention of 71.5% after 500 cycles. Moreover, the capacity retention of CoFe-PBA@PDA after 100 cycles is 14.3% higher than that of the two comparison samples. In addition, the reversible structure of CoFe-PBA@PDA without forming a new phase was verified by in situ X-ray diffraction. This work may provide another design idea or strategy for improving the stability of the PBA cathodes used in SIBs.

Gelation of organic liquid electrolyte to achieve superior sodium-ion full-cells.

The irreversible consumption of active sodium in sodium-ion full-cells (SIFCs) becomes particularly serious due to the existence of unavoidable interface or side reaction, which has become the key to restrict the development of high-performance sodium-ion batteries (SIBs). Interface design and electrolyte optimization have been proved to be effective strategies to improve or solve this problem. In this work, on the basis of traditional organic liquid electrolytes, a novel gel polymer electrolyte with high ionic conductivity (1.13 × 10-3 S cm-1) and wide electrochemical stability window (~4.7 V) was designed and synthesized using bacterial cellulose film as precursor. Compared with the liquid electrolyte, the obtained electrolyte can endow better sodium storage performance in both half- and full-cells. When coupled with sodium hexacyanoferrate cathode and hard carbon anode, a capacity of 94.2 mA h g-1 can be obtained with a capacity retention of 75% after 100 cycles at a current density of 100 mA g-1, while those of with conventional liquid electrolyte can deliver a capacity of 99.0 mA h g-1 but only accompany 58% capacity retention under the same conditions. Significantly, when the current density increases to 800 mA g-1, their capacity difference reaches 23.4 mA h g-1.

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.

γ-Fe2O3 nanoparticles stabilized by holey reduced graphene oxide as a composite anode for lithium-ion batteries.

Integrating nanoscale active materials on conductive holey reduced graphene oxide (RGO) framework is an effective strategy to synthesize composite electrode materials for advanced lithium-ion batteries. Herein, a composite of γ-Fe2O3 nanoparticles stabilized by the engineered holes on RGO was successfully synthesized by using a facile in-situ etching route, which exhibited high lithium storage performance. The fundamental insight of its enhancement mechanism was discussed. This work offers a newly route to synthesize the composite of holey RGO confined metal oxide nanoparticles for the applications in lithium ion batteries and beyond.

Manipulating irreversible phase transition of NaCrO2 towards an effective sodium compensation additive for superior sodium-ion full cells.

During the first charge process of full cells, a solid electrolyte interphase (SEI) film is formed when the active ion from the cathode is consumed, resulting in irreversible capacity loss. This phenomenon has shown to be more serious in sodium-ion full cells than in lithium-ion full cells. Although many strategies have been employed to alleviate the loss of sodium ions, such as presodiation and construction of an artificial solid electrolyte interface, they are both cumbersome and time-consuming. For the first time, NaCrO2 was used as an effective self-sacrificing sodium compensation additive in sodium-ion full cells due to the irreversible phase transition of NaCrO2 in a high voltage region can deliver an irreversible capacity of up to 230 mAh g-1. Based on this design, sodium-ion full cells coupled with hard carbon as the anode exhibited higher capacity, less polarization, greater energy density, and superior cycle stability than those of a pristine electrode. This is mainly attributed to the removal of sodium ions from NaCrO2, which compensates for the loss of sodium ions consumed during the formation of the SEI film on the anode surface during the first charge process. Overall, this work opens up a new avenue for exploring sodium compensation strategy and contributing to practical application of sodium-ion full cells.

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.

Changes in C:N:P stoichiometry modify N and P conservation strategies of a desert steppe species Glycyrrhiza uralensis.

Numerous studies have concluded that carbon (C):nitrogen (N):phosphorus (P) stoichiometry in both soils and plants tends to be decoupled under global change. We consequently hypothesized that plants will adjust nutrient conservation strategies to balance the altered elemental stoichiometry accordingly. To test our hypothesis, we conducted two pot-cultured experiments (with 8-level water and 6-level N addition treatments) using N-fixing species Glycyrrhiza uralensis Fisch from a desert steppe in northwestern China. We observed that high water availability lowered total N content and the N:P ratio in soils, further promoting both N and P resorption from senescing leaves of G. uralensis. High N addition enhanced soil N availability and the N:P ratio, thereby reducing N resorption, but increasing P resorption of G. uralensis. Comparatively, there were also great changes in senescing leaf C:N:P stoichiometry while no clear changes were observed in either green leaf or root C:N:P stoichiometry of G. uralensis. As expected, the altered C:N:P stoichiometry may, in turn, modify N and P conservation strategies through their close linkages with N and P uptake in green leaves of G. uralensis. This modification may also further exert effects on N and P cycling of the desert steppe.

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.

Improving the Performance of Hard Carbon//Na3V2O2(PO4)2F Sodium-Ion Full Cells by Utilizing the Adsorption Process of Hard Carbon.

Hard carbon has been regarded as a promising anode material for Na-ion batteries. Here, we show, for the first time, the effects of two Na+ uptake/release routes, i.e., adsorption and intercalation processes, on the electrochemical performance of half and full sodium batteries. Various Na+-storage processes are isolated in full cells by controlling the capacity ratio of anode/cathode and the sodiation state of hard carbon anode. Full cells utilizing adsorption region of hard carbon anode show better cycling stability and high rate capability compared to those utilizing intercalation region of hard carbon anode. On the other hand, the intercalation region promises a high working voltage full cell because of the low Na+ intercalation potential. We believe this work is enlightening for the further practical application of hard carbon anode.

Sodium-Rich Ferric Pyrophosphate Cathode for Stationary Room-Temperature Sodium-Ion Batteries.

In this article, carbon-coated Na3.64Fe2.18(P2O7)2 nanoparticles (∼10 nm) were successfully synthesized via a facile sol-gel method and employed as cathode materials for sodium-ion batteries. The results show that the carbon-coated Na3.64Fe2.18(P2O7)2 cathode delivers a high reversible capacity of 99 mAh g-1 at 0.2 C, outstanding cycling life retention of 96%, and high Coulomb efficiency of almost 100% even after 1000 cycles at 10 C. Furthermore, the electrochemical performances of full batteries consisting of carbon-coated Na3.64Fe2.18(P2O7)2 nanoparticles as the cathode and commercialized hard carbon as the anode are tested. The full batteries exhibit a reversible capacity of 86 mAh g-1 at 0.5 C and capacity retention of 80% after 100 cycles. Therefore, the above-mentioned cathode is a potential candidate for developing inexpensive sodium-ion batteries in large-scale energy storage with long life.

Electrospun graphene-wrapped Na6.24Fe4.88(P2O7)4 nanofibers as a high-performance cathode for sodium-ion batteries.

Na6.24Fe4.88(P2O7)4 is one of the intensively investigated polyanionic compounds and has shown high rate discharge capacity, but its relatively low electronic conductivity hampers the high performance of the batteries. Herein for the first time we report new graphene wrapped Na6.24Fe4.88(P2O7)4 composite nanofibers (NFPO@C@rGO) made from electrospinning for cathodes of SIBs to achieve an even higher performance with a highly stable discharge capacity of ∼99 mA h g-1 at a current density of 40 mA g-1 after 320 cycles, which is 1.6 times higher than that of the pristine Na6.24Fe4.88(P2O7)4 (NFPO@C) composite. In particular, the NFPO@C@rGO composite cathode exhibits an even higher discharge rate capacity of ∼53.9 mA h g-1 at a current density of 1280 mA g-1 (11C) than that of ∼40 mA h g-1 at a current density of 1100 mA g-1 (9.4C) for the reported best high discharge rate performance of NFPO. The superior cycling and high rate capability are attributed to the unique spinning vein fiber based porous structure offering a good intimate contact between NFPO@C and graphene for great electronic conductivity, fast ionic transport, a large reaction surface and a strong solid structure preventing collapse during cycling, thus achieving a high rate discharge performance and high cycling stability.

Porous carbon derived from Sunflower as a host matrix for ultra-stable lithium-selenium battery.

A novel porous carbon material using the spongy tissue of sunflower as raw material is reported for the first time. The obtained porous carbon has an extremely high surface area of 2493.0m2g-1, which is beneficial to focus on encapsulating selenium in it and have an inhibiting effect about diffusion of polyselenides over the charge/discharge processes used as the host matrix for Li-Se battery. The porous carbon/Se composite electrode with 63wt% selenium delivers a high specific capacitance of 319mAhg-1 of the initial capacity, and maintains 290mAhg-1, representing an extremely high capacity retention of 90.9% after 840 cycles with the rate of 1C.

Fabrication of WS2-nanoflowers@rGO composite as an anode material for enhanced electrode performance in lithium-ion batteries.

In this paper, we descried a simple method to fabricate three-dimensional (3D) composite materials, WS2-nanoflowers @ reduced graphene oxide (WS2-NF@rGO), in which rGO crossed-link the isolated WS2-NF to construct a 3D conductive network and provided protection against the volume changes of WS2 during electrochemical processes simultaneously. This unique structure of the WS2-NF@rGO composite could not only promote both ion and electron diffusion, but also enhance the electrode stability, thus obtaining a high-capacity and long-cycle anode material for lithium-ion batteries. As a result, the WS2-NF@rGO exhibited a reversible capacity of 730mAhg-1 after 150 cycles at 100mAg-1 and maintained a capacity of higher than 260mAhg-1 at 2Ag-1, thus exhibiting great potential as an anode material for lithium storage.