For the development of aqueous zinc-ion batteries, exploiting vanadium-based cathode materials with quick kinetics and acceptable cycling stability is crucial. Herein, to achieve these goals, transition metal ions (Zn2+) and organic ions (C5H14ON+ and Ch+) are introduced into layered hydrated V2O5. The intrinsic high conductivity of Ch+ and the oxygen vacancies generated through ion pre-intercalation accelerate the electrical mobility by optimizing the electronic structure. The Zn2+ stabilizes the layered structure and the expanded interlayer spacing improves the ionic diffusivity. The synergistic effect of pre-intercalated Zn2+ and Ch+ results in the (Zn0.1, Ch0.1)V2O4.92·0.56H2O cathode exhibiting a discharge capacity of 473 mAh g−1 at 0.1 A g−1 with a high energy efficiency of 88% and excellent cycling stability with 91% retention after 2000 cycles at 4 A g−1. Ex situ characterizations and density functional theory calculations reveal a reversible intercalation mechanism of Zn2+, and the improved electrochemical kinetics are attributed to the altered electronic conductivity and the reduced binding energy between Zn2+ and host O2−. 

Dual Effects of Metal and Organic Ions Co‐Intercalation Boosting the Kinetics and Stability of Hydrated Vanadate Cathodes for Aqueous Zinc‐Ion Batteries

Aqueous zinc-ion batteries have attracted extensive attention ascribing to affordability, intrinsic safety, and environmental benignity, which have revealed ideal alternative to lithium-ion batteries for large-scale energy storage systems. Nevertheless, the design of aqueous zinc-ion batteries is plagued by obstacles, such as dissolution of cathode materials, dendrites and side reactions of anode, and electrolyte consumption as compared to commercial lithium-ion batteries. In this regard, from the perspective of predominant issues encountered with aqueous zinc-ion batteries, this comprehensive review aims to systematically summarize the design principles and optimization strategies associated with the cathode, anode, electrolyte, and separator. Meanwhile, the impact of design strategies on electrochemistry, and the relationship between issues and strategies are revealed for guiding the rational design of advanced aqueous zinc-ion batteries. Eventually, a series of critical challenges, constructive solutions, and future trends toward cathode, anode, electrolyte and separator are dedicatedly proposed. We envisage that this review would endow researchers a readily accessible means to rapidly acquaint with optimization strategies and design principles for advanced aqueous zinc-ion batteries. 

Optimization Strategies Toward Advanced Aqueous Zinc-ion Batteries: From Facing Key Issues to Viable Solutions

Layered V2O5 is a star cathode material of rechargeable aqueous zinc‐based batteries (RAZBs) owing to the rich redox chemistry of vanadium, which commonly exhibits the 2D ion‐diffusion mechanism through Zn2+ (de)intercalation at edge sites but is plagued by the inert basal planes. Here, hierarchically porous V2O5 nanosheets vertically grown on carbon cloth (V2O5/C) are innovatively prepared, where the porous structure with lattice defects successfully unlocks the V2O5 basal plane to provide additional ion‐diffusion channels and abundant active sites. Thus, highly efficient and ultrafast 3D Li+/Zn2+ co‐insertion/extraction behaviors along both the c‐axis and ab plane of V2O5 are realized for the first time in the formulated 15 m LiTFSI + 1 m Zn(CF3SO3)2 aqueous electrolyte, as elucidated by systematic ex situ analyses, multiple electrochemical measurements, and theoretical computations. As a result, the porous V2O5/C electrode delivers an exceptional high‐rate capability (up to 100 A g−1) and an ultralong cycling durability (15 000 cycles) in RAZBs. Finally, quasi‐solid‐state wearable rechargeable zinc batteries employing the porous V2O5/C cathode demonstrate respectable performance even under severe deformations and low temperatures. This work achieves a conceptual breakthrough represented by an upgrading of the traditional 2D ion transportation in layered cathodes to the more facile 3D diffusion for designing high‐performance battery electrochemistry.

Ultrafast 3D Hybrid‐Ion Transport in Porous V2O5 Cathodes for Superior‐Rate Rechargeable Aqueous Zinc Batteries

Review of vanadium-based oxide cathodes as aqueous zinc-ion batteries

The demand for energy storage is growing, and the disadvantages of lithium-ion batteries are being explored to overcome them. Accordingly, aqueous zinc-ion batteries (ZIBs) are developing very rapidly, owing to their high safety, environmental friendliness, high abundance of resources, and high cost performance. Over the last decade, ZIBs have made remarkable progress through extensive efforts in the field of electrode materials and through fundamental understanding of non-electrode components, such as solid-electrolyte interphase, electrolytes, separators, binders, and current collectors. In particular, the breakthrough in using separators on non-electrode elements should not be overlooked as such separators have proven key to conferring ZIBs with high energy and power density. In this Review, recent progress in the development of separators in ZIBs is comprehensively summarized based on their functions and roles in ZIBs, including the modification of conventional separators and the development of novel separators. Finally, the prospects and future challenges of separators are also discussed to facilitate ZIBs development.

Improved Strategies for Separators in Zinc-Ion Batteries.

Aqueous zinc–ion batteries (ZIBs) have been promptly developed as a competitive and promising system for future large‐scale energy storage. In recent years, vanadium (V)‐based compounds, with diversity of valences and high electrochemical‐activity, have been widely studied as cathodes for aqueous ZIBs because of their rich reserves and high theoretical capacity. However, the stubborn issues including low conductivity and sluggish kinetics, plague their smooth application in aqueous ZIBs. Among various countermeasures, defect engineering is believed as an effective method to alleviate the above limitations. This review highlights the challenges of different V‐based cathode materials (e.g., vanadium oxides and vanadates) and summarizes the advances in defect engineering strategies including types and effects of the defects, designed strategies, and characterization techniques for high‐energy ZIBs. Finally, several sound prospects in this fervent field are also rationally proposed for fundamental research and practical application.

Advances on Defect Engineering of Vanadium‐Based Compounds for High‐Energy Aqueous Zinc–Ion Batteries

Stoichiometric ratios of carbon (C), nitrogen (N), and phosphorus (P) are considered indicators of nutrient status and ultimate ecosystem health. A detailed investigation of these elements in the leaves, branches, forest layer vegetation and soil, depending on stand age, was carried out. We investigated the effects of stand age (9-, 18-, 28-, and 48-year) on the aboveground plant parts (leaf, branch, herb, shrub, plant litter) and belowground pools (soil, roots) of P. massoniana plantations. The CNP stoichiometry of trees was affected by stand age. Mean N content in the aboveground parts in the nine-yr stand was greater than the other stands (18-, 28-, 48-yr), which decreased with increasing stand age. As stands aged, the nutrient demands of the plantations increased as well as their N:P ratios in soil. C content in the soil ranged from 30 to 105, the total N was 0.06 to 1.6, and the total P content ranged from 3.3–6.4 g kg−1. Soil C, N and P contents were greatly influenced by both stand age and soil depth, because surface soil sequester C and N more actively compared to deeper horizons, and more nutrients are released to the topsoil by the plant litter layer. Similarly, the ratios of other layers had a similar pattern as CNP because more nutrients were taken up by the plantations, decreasing nutrient supply in the deeper soil horizons. The green leaves N:P ratios (16) indicate limited growth of P. massoniana, as the range for global nutrient limitation for woody plants oscillated between 14–16, indicating N and P limitation. Young stands were observed to have greater P content and P resorption efficiency (56.9%–67.3%), with lower C:P and N:P ratios (704.4; 14.8). We conclude that with stand development, the nutrient demands of the plantations also increase, and soil N:P stoichiometry shows that these improve soil quality.

/pdf/ecological-stoichiometry-in-pinus-massoniana-l-plantation-28rtefdj.pdf

Ecological Stoichiometry in Pinus massoniana L. Plantation: Increasing Nutrient Limitation in a 48-Year Chronosequence

Conversion-type cathodes for aqueous zinc ion batteries (ZIBs) can provide flat plateau slop and stable output potential, compared to general intercalation-type cathodes. The high volumetric capacity and stable output potential of Te make it a promising cathode for ZIBs, but sluggish kinetics and large volume change hinder its further application. To address these issues, we revisit fully-zinced ZnTe and construct ZnTe/rGO composites as the new conversion-type cathode. The electrode undergoes a solid-to-solid conversion reaction and shows a stable output potential with ultra-flat discharge plateau slop of 0.09 V (Ah g-1)-1. When ZnTe is de-zinced and transformed to Te during charge process, it has a volume shrinkage which generates empty space in graphene matrix for latter volume expansion of Te. The graphene matrix also improves conductivity and reaction kinetics of the cathode. Due to the combination of pre-zincation of ZnTe, graphene matrix and the elimination of "shuttle effects" process, ZnTe/rGO electrode exhibits a high and stable capacity of 186 mAh g-1 at 500 mA g-1 after 300 cycling, with almost no decay after initial 10 cycles.

ZnTe/rGO composite as the Fully-Zinced Conversion-Type Cathodes for Aqueous Zinc Ion Batteries.

Forest inventory data (FID) are important resources for understanding the dynamics of forest carbon cycling at regional and global scales. Developing carbon storage growth models and analyzing the difference and climate effect on carbon sequestration capacity have a great importance in practice, which can provide a decision-making basis for promoting high-quality development of forestry and implementing the carbon emission peak and carbon neutralization strategy. Based on the carbon storage dataset of 2680 sample plots from the ninth national forest inventory (NFI) of China, the carbon storage growth models and climate-sensitive variable-parameter carbon storage growth models for three major coniferous plantations (Larix spp., Pinus massoniana, and Pinus tabuliformis) were developed by using weighted nonlinear regression method. The effects of two climate factors (mean annual temperature (MAT) and mean annual precipitation (MAP)) on carbon storage growth and carbon sequestration capacity were analyzed and compared. The mean prediction error (MPE) of carbon storage growth models for three major coniferous plantations was less than 5%, and total relative error (TRE) was approximately less than 2% for self- and cross- validation. The maximum current annual increment of carbon storage for P. massoniana, Larix, and P. tabuliformis was 2.29, 1.89, and 1.19 t/(ha·a), respectively, and their corresponding age of inflection point was 9a, 14a, and 30a, respectively. The maximum average increment of carbon storage for P. massoniana, Larix, and P. tabuliformis was 1.85, 1.50, and 0.94 t/(ha·a), respectively, and their corresponding age of quantitative maturity was 16a, 24a, and 53a, respectively. The maximum average increment of carbon storage for the P. massoniana and Larix plantations was approximately 1.97 and 1.60 times, respectively, that of P. tabuliformis plantation. The average increment of carbon storage for the P. massoniana and Larix plantations reduced approximately by 4.5% and 3.8%, respectively, when the MAT decreases by 1 °C. The average increment of carbon storage for the Larix and P.tabuliformis plantations decreased by approximately 6.5% and 3.6%, respectively, when the MAP decreases by 100 mm. Our findings suggest that: the carbon sequestration capacity is from highest to lowest in the P. massoniana, Larix, and P. tabuliformis forests. MAT and MAP have different effects on the carbon growth process and carbon sequestration capacity of these plantations. The greatest impact on carbon sequestration capacity was detected in the Larix plantation, followed by the P. massoniana and P. tabuliformis plantations. It is essential to coordinate regional development and employ scientific management strategies to fully develop the maximum carbon sequestration capacity in terms of plantations in China. In the present study, we estimate the carbon storage in major coniferous plantations in China and describe a useful methodology for estimating forest carbon storage at regional and global levels.

/pdf/effect-of-climate-on-carbon-storage-growth-models-for-three-3syl5ur8.pdf

Effect of Climate on Carbon Storage Growth Models for Three Major Coniferous Plantations in China Based on National Forest Inventory Data

Visiting Znte as the Fully-Zinced Conversion-Type Cathodes for Aqueous Zinc Ion Batteries

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