Challenges and Advances in Rechargeable Batteries for Extreme-Condition Applications.

Rechargeable batteries are widely used as power sources for portable electronics, electric vehicles and smart grids. Their practical performances are, however, largely undermined under extreme conditions, such as in high-altitude drones, ocean exploration and polar expedition. These extreme environmental conditions not only bring new challenges for batteries but also incur unique battery failure mechanisms. To fill in the gap, it is of great importance to understand the battery failure mechanisms under different extreme conditions and figure out the key parameters that limit battery performances. In this review, the authors start by investigating the key challenges from the viewpoints of ionic/charge transfer, material/interface evolution and electrolyte degradation under different extreme conditions. This is followed by different engineering approaches through electrode materials design, electrolyte modification and battery component optimization to enhance practical battery performances. Finally, a short perspective is provided about the future development of rechargeable batteries under extreme conditions.

Phosphorous-Based Heterostructure for the Effective Catalysis of Polysulfide Reactions with Phase Changes in High-Sulfur-Loading Lithium-Sulfur Batteries.

High sulfur loading and long cycle life are the design targets of commercializable lithium-sulfur (Li-S) batteries. The sulfur electrochemical reactions from Li2 S4 to Li2 S, which account for 75% of the battery's theoretical capacity, involve liquid-to-solid and solid-to-solid phase changes in all Li-S battery electrolytes in use today. These are kinetically hindered processes that are exacerbated by a high sulfur loading. In this study, it is observed that an in situ grown bimetallic phosphide/black phosphorus (NiCoP/BP) heterostructure can effectively catalyze the Li2 S4 to Li2 S reactions to increase the sulfur utilization at high sulfur loadings. The NiCoP/BP heterostructure is a good polysulfide adsorber, and the electric field prevailing at the Mott-Schottky junction of the heterostructure can facilitate charge transfer in the Li2 S4 to Li2 S2 liquid-to-solid reaction and Li+ diffusion in the Li2 S2 to Li2 S solid-state reaction. Consequently, a sulfur cathode with the NiCoP/BP catalyst can deliver a specific capacity of 830 mAh g-1 at the sulfur loading of 6 mg cm-2 for 500 cycles at the 0.5 C rate. High sulfur utilization is also possible at a higher sulfur loading of 8 mg cm-2 for 440 cycles at the 1 C rate.

3D π-d Conjugated Coordination Polymer Enabling Ultralong Life Magnesium-Ion Storage.

There has been increasing interests in π-d conjugated coordination polymers (CCPs) for energy storage because of their rapid charge transfer through long-range planar π-d conjugation between ligands and metal centers. Nevertheless, currently reported CCPs for energy storage are mostly based on 1D or 2D structures. There are few 3D CCPs reported to date because of the great challenge in constructing nonplanar coordination geometries, let alone their applications in multivalent ions storage. Herein, a triphenylene-catecholate-based 3D CCP (Mn-HHTP) is successfully synthesized assembled from the multidentate chelating groups of hexahydroxytriphenylene (HHTP) ligands and their isotropic coordination with Mn2+ ions. The 3D conjugated structure of Mn-HHTP enables an exceptional cycle life of >4000 cycles at 0.5 A g-1 for multivalent Mg2+ ion storage, which is far superior to most organic and inorganic electrode materials. Experimental characterizations combined with theoretical calculations indicate that the semiquinone radicals at the HHTP ligands are the electroactive centers for Mg2+ ions storage. The excellent performance of Mn-HHTP opens a new avenue towards the design of 3D CCPs for long-life rechargeable magnesium-ion batteries.

Isolation and functional characteristics of the fungus Hypoxylon spp. Sj18 with biocontrol potential.

A fungus with biocontrol potential was isolated from the roots of hickory trees. The strain named sj18 was classified as a member of the genus Hypoxylon (Hypoxylaceae) after multigene phylogenetic analysis (beta-tubulin gene, internal transcribed spacer, 28S large subunit ribosomal RNA gene, and RNA polymerase II subunit gene). The strain grew well on a PDA with an optimum temperature range between 32 and 34 °C. The fungus had obvious inhibitory effects on Botryosphaeria dothidea, Colletotrichum gloeosporioides, and Gibberella moniliformis in fumigation experiments on solid agar plates. In an inoculation experiment of Chinese cabbage, the fungus was also found to have an obvious repellent effect on cabbage caterpillars. In vitro experiments on Petri dishes showed that the fermentation broth of the sj18 strain could kill 100% of Bursaphelenchus xylophilus within 8 h even if the fermentation broth was diluted 8 times. The inoculation test of Arabidopsis thaliana showed that the fungus could promote the lateral root formation of plants and significantly increase their aboveground biomass. Through the analysis of solid phase microextraction (SPME), it was found that the main volatile components of the fermentation products were azulene 65.39% (61.77% + 3.62%), caryophyllene 7.41%, and eucalyptol 6.83% according to the peak area ratio. Therefore, sj18 can be used as a candidate for the further research and development of biocontrol agents.

A novel sunshine duration-based photothermal time model interprets the photosensitivity of flower maturity of pecan cultivars.

Although it is well-known and established that light plays important roles in plant development, up to now, there is no substantial improvements in how to deal with the light factor of spring phenology under natural condition. By monitoring the local meteorologic data and mature dates of two types (male and female) of flower from four pecan cultivars during 9 years, it was found that the complementary pattern of growing degree day and sunshine duration helped to maintain a threshold of driving force related to the maturity of pecan flower during 9 years. A novel photothermal time model based on the linear combination of growing degree day and sunshine duration was then proposed and validated to interpret the variance of mature dates of pecan cultivars. Comparative analysis showed that the new model had made extremely significant improvements to the traditional thermal time model. In addition, this model introduced the conversion coefficient K, which quantified the effect of light on the flowering drive, and revealed the differences of base temperature among cultivars. This was the first time that sunshine duration instead of photoperiod was adopted to develop into a verified model on spring phenological event of tree species. It will help to model the spring phenologies of other tree species more reasonably.

Dual-Band Electrochromic Devices with a Transparent Conductive Capacitive Charge-Balancing Anode.

Dual-band electrochromic devices (DBEDs), which can selectively modulate near-infrared (NIR) and visible (VIS) light transmittance through electrochromism, have gained increasing interest as a building energy saving technology. The technology is strongly dependent on the progress in electrochromic materials. Most current research has focused on the dual-band properties of the cathode materials, leaving the charge-balancing anode materials under-explored by comparison. This is a report of our study on the suitability of tin-doped indium oxide (ITO) nanocrystals (NCs) as a capacitive anode material for DBEDs. The ITO NCs are electrically conductive and VIS light transparent throughout the device operating range. As a result, they would not affect the NIR-selective modulation of the electrochromic device like most other anode materials do. The high surface area and good conductivity of the ITO NCs facilitate the adsorption/desorption of anions; thereby increasing their effectiveness as an ion storage thin film on the anode to balance the cathode charge. The best DBED prototype assembled from an ITO NC anode and a WO3-x cathode showed effective and independent control of VIS light and NIR transmittance with high optical modulation (71.1% at 633 nm, 58.1% at 1200 nm), high coloration efficiency (95 cm2 C-1 at 633 nm, 220 cm2 C-1 at 1200 nm), fast switching speed, good bistability, and cycle stability.

Stepwise Electrocatalysis as a Strategy against Polysulfide Shuttling in Li-S Batteries.

Most issues with Li-S batteries are caused by the slowness of the multielectron sulfur electrochemical reaction resulting in the loss of sulfur as soluble polysulfides to the electrolyte and the redox shuttling of polysulfides between the cathode and anode during battery charge and discharge. The acceleration of the polysulfide conversion reaction to their end products via electrocatalysis has the appeal of a root-cause solution. However, the polysulfide electrocatalysts developed to date have rarely considered polysulfide conversion as a multistep reaction and, as such, were not optimized to target specific steps in the overall S8 ↔ Li2Sn ↔ Li2S conversion. The targeting approach is however beneficial, as it can be used to design multicatalyst systems to reduce as many rate-limiting steps in the overall catalysis as effectively possible. This article demonstrates the concept and implementation of stepwise electrocatalysis in polysulfide conversion, using Fe-N and Co-N co-doped carbons to selectively catalyze the long-chain polysulfide conversion (S8 ↔ Li2S4) and the short-chain polysulfide conversion reactions (Li2S4 ↔ Li2S), respectively. The two electrocatalysts were deployed in the sulfur cathode as a dual layer, using an ordered spatial separation to synergize their catalytic effects. A sulfur electrode designed as such could utilize ∼90% of the sulfur theoretical specific capacity and support a high areal capacity of ∼8.3 mAh cm-2 and a low electrolyte/sulfur ratio of 5 µL mg-1.

Effect of a fungus, Hypoxylon spp., on endophytes in the roots of Asparagus.

The fungal isolate Hypoxylon spp. (Sj18) was isolated from the root of pecan. It might have effects on the plant's stress tolerance and endophytic community. Inoculation experiments were carried out on the roots of Asparagus with normal and inactivated Sj18, and the diversity and community structure of endophytes in the root of inoculated Asparagus were studied. It was found that Sj18 fungi affected the endophytic community of Asparagus roots. From being a low-abundance genus, the salt-tolerant bacterium Halomonas became the dominant genus. In order to verify that Sj18 can improve salt tolerance, Arabidopsis thaliana was inoculated with Sj18 in a salt tolerance test. The result showed that A. thaliana grew better in a high salt environment after inoculation with Sj18. Sj18 changed the microbe diversity, community composition and structure of endophytes in the roots of Asparagus, which increased the bacterial diversity. A total of 16 phyla and 184 genera of bacteria were detected. However, the diversity of fungi decreased.

A Cathode-Integrated Sulfur-Deficient Co9S8 Catalytic Interlayer for the Reutilization of "Lost" Polysulfides in Lithium-Sulfur Batteries.

Lithium-sulfur batteries, with their high theoretical energy density and the low material cost of sulfur, are highly promising as a post-lithium ion battery contender. Their current performance is however compromised by sulfur loss and polysulfide shuttle to result in low energy efficiency and poor cycle stability. Herein, a catalytic material (Co9S8- x/CNT, nanoparticles with a metallic Co9S8 core and a sulfur-deficient shell on a CNT support) was applied as an interlayer on the sulfur cathode to retain migratory polysulfides and promote their reutilization. The Co9S8- x/CNT catalyst is highly effective for the conversion of polysulfides to insoluble end products (S or Li2S/Li2S2), and its deployment as a cathode-integrated interlayer was able to retain the polysulfides in the cathode for reuse. The accumulation of polysulfides in the electrolyte and the polysulfide shuttle were significantly reduced as a result. Consequently, a host-free sulfur cathode with the Co9S8- x/CNT interlayer had a low capacity fade rate of 0.049% per cycle for 1000 cycles at a 0.3C rate, a significant improvement of the capacity fade rate without it (0.28% per cycle for 200 cycles). The results here provide not only direct evidence for the contributions of sulfur deficiencies on the catalytic activity of Co9S8 in polysulfide conversion reactions but also the methodology on how the catalyst should be deployed in a Li-S battery for the best catalytic outcome.

Rational Synthesis and Assembly of Ni3S4 Nanorods for Enhanced Electrochemical Sodium-Ion Storage.

Even though advocated as the potential low-cost alternatives to current lithium-ion technology, the practical viability of sodium-ion batteries remains illusive and depends on the development of high-performance electrode materials. Very few candidates available at present can simultaneously meet the requirements on capacity, rate capability, and cycle life. Herein, we report a high-temperature solution method to prepare Ni3S4 nanorods with uniform sizes. These colloidal nanorods readily self-assemble side by side and form microsized superstructures, which unfortunately negates the nanoscale feature of individual nanorods. To this end, we further introduce two-dimensional graphene nanosheets as the spacer to interrupt nanorod self-assembly. Resultant composite presents a marked advantage toward electrochemical storage of Na+ ions. We demonstrate that in half-cells it exhibits large reversible specific capacity in excess of 600 mAh/g, high rate capability with >300 mAh/g retained at 4 A/g, and great cycle life at different current rates. This anode material can also be combined with the NASICON-type Na3V2(PO4)3 cathode in full cells to enable large capacity and good cyclability.

Amorphous MoS3 as the sulfur-equivalent cathode material for room-temperature Li-S and Na-S batteries.

Many problems associated with Li-S and Na-S batteries essentially root in the generation of their soluble polysulfide intermediates. While conventional wisdom mainly focuses on trapping polysulfides at the cathode using various functional materials, few strategies are available at present to fully resolve or circumvent this long-standing issue. In this study, we propose the concept of sulfur-equivalent cathode materials, and demonstrate the great potential of amorphous MoS3 as such a material for room-temperature Li-S and Na-S batteries. In Li-S batteries, MoS3 exhibits sulfur-like behavior with large reversible specific capacity, excellent cycle life, and the possibility to achieve high areal capacity. Most remarkably, it is also fully cyclable in the carbonate electrolyte under a relatively high temperature of 55 °C. MoS3 can also be used as the cathode material of even more challenging Na-S batteries to enable decent capacity and good cycle life. Operando X-ray absorption spectroscopy (XAS) experiments are carried out to track the structural evolution of MoS3 It largely preserves its chain-like structure during repetitive battery cycling without generating any free polysulfide intermediates.

Hierarchical VS2 Nanosheet Assemblies: A Universal Host Material for the Reversible Storage of Alkali Metal Ions.

Reversible electrochemical storage of alkali metal ions is the basis of many secondary batteries. Over years, various electrode materials are developed and optimized for a specific type of alkali metal ions (Li+ , Na+ , or K+ ), yet there are very few (if not none) candidates that can serve as a universal host material for all of them. Herein, a facile solvothermal method is developed to prepare VS2 nanosheet assemblies. Individual nanosheets are featured with a few atomic layer thickness, and they are hierarchically arranged with minimized stacking. Electrochemical measurements show that VS2 nanosheet assemblies enable the rapid and durable storage of Li+ , Na+ , or K+ ions. Most remarkably, the large reversible specific capacity and great cycling stability observed for both Na+ and K+ are extraordinary and superior to most existing electrode materials. The experimental results of this study are further supported by density functional theory calculations showing that the layered structure of VS2 has large adsorption energy and low diffusion barriers for the intercalation of alkali metal ions.

Improved Sodium-Ion Storage Performance of Ultrasmall Iron Selenide Nanoparticles.

Sodium-ion batteries are potential low-cost alternatives to current lithium-ion technology, yet their performances still fall short of expectation due to the lack of suitable electrode materials with large capacity, long-term cycling stability, and high-rate performance. In this work, we demonstrated that ultrasmall (∼5 nm) iron selenide (FeSe2) nanoparticles exhibited a remarkable activity for sodium-ion storage. They were prepared from a high-temperature solution method with a narrow size distribution and high yield and could be readily redispersed in nonpolar organic solvents. In ether-based electrolyte, FeSe2 nanoparticles exhibited a large specific capacity of ∼500 mAh/g (close to the theoretical limit), high rate capability with ∼250 mAh/g retained at 10 A/g, and excellent cycling stability at both low and high current rates by virtue of their advantageous nanosizing effect. Full sodium-ion batteries were also constructed from coupling FeSe2 with NASICON-type Na3V2(PO4)3 cathode and demonstrated impressive capacity and cycle ability.