As one of the fascinating high capacity cathodes, O3‐type layered oxides usually suffer from their intrinsic air sensitivity and sluggish kinetics originating from the spontaneous lattice Na ...extraction during air exposure and high tetrahedral site energy of Na+ diffusion transition state. What is worse, the improvement on the two handicaps is hard to simultaneously realize because of the contradiction between Na containment suggested in air stability mechanism and enhanced Na diffusion mentioned in kinetics strategy. Herein, it is shown that a simple strategy of introducing proper Na vacancies into lattice can simultaneously realize a dual performance improvement. Na vacancies decrease the charge density on transitional metal ions and enhance the antioxidative capability of material, ensuring a stable lattice Na containment for Na0.93Li0.12Ni0.25Fe0.15Mn0.48O2 when exposed to air. Additionally, more Na+ diffusional sites and enlarged Na layer spacing are obtained and result in a significantly decreased energy barrier from ≈1000 to 300 meV and a high rate capability of 70.8% retention at 2000 mA g−1. Remarkably, such a strategy can be easily realized by either pre‐ or post‐treating, which exhibits excellent universality for various O3 materials, implying its enormous potential to promote the commercial application of O3‐type cathodes.
A universal strategy of introducing proper Na vacancies into a crystal lattice is proposed to simultaneously improve air‐stability and kinetics of O3‐type layered oxide cathodes. The dual improvement benefits from the multiple effects of Na vacancies on crystalline and electronic structure, namely, decreased charge density on transition metal ions, enhanced antioxidative capability, decreased Na+ diffusion barrier, and optimized migration path.
The complexity of chemical compounds in lithium‐ion batteries (LIBs) results in great difficulties in the extraction of multiple transition metals, which have similar physicochemical characteristics. ...Here, we propose a novel strategy for selective extraction of nickel, cobalt, and manganese from spent LiNixCoyMn1−x−yO2 (NCM) cathode through the regulation of coordination environment. Depending on adjusting the composition of ligand in transition metal complexes, a tandem leaching and separation system is designed and finally enables nickel, cobalt, and manganese to enrich in the form of NiO, Co3O4, and Mn3O4 with high recovery yields of 99.1 %, 95.1 %, and 95.3 %, respectively. We further confirm that the combination of different transition metals with well‐designed ligands is the key to good selectivity. Through our work, fine‐tuning the coordination environment of metal ions is proved to have great prospects in the battery recycling industry.
The deep eutectic solvent composed of choline chloride and oxalic acid was prepared. After leaching at 120 °C for 10 hours, the nickel oxalate dihydrate and the filtrate containing other metal elements are separated. Then the filtrate is diluted with water to precipitate the cobalt oxalate dihydrate. Finally, manganese compounds were separated by adjusting pH.
Chemical modification of electrode materials by heteroatom dopants is crucial for improving storage performance in rechargeable batteries. Electron configurations of different dopants significantly ...influence the chemical interactions inbetween and the chemical bonding with the host material, yet the underlying mechanism remains unclear. We revealed competitive doping chemistry of Group IIIA elements (boron and aluminum) taking nickel‐rich cathode materials as a model. A notable difference between the atomic radii of B and Al accounts for different spatial configurations of the hybridized orbital in bonding with lattice oxygen. Density functional theory calculations reveal, Al is preferentially bonded to oxygen and vice versa, and shows a much lower diffusion barrier than BIII. In the case of Al‐preoccupation, the bulk diffusion of BIII is hindered. In this way, a B‐rich surface and Al‐rich bulk is formed, which helps to synergistically stabilize the structural evolution and surface chemistry of the cathode.
A model study has been performed on Group IIIA element (boron and aluminum) co‐doped high‐nickel layered oxide cathode materials to understand competitive doping chemistry. A notable difference between the atomic radii of B and Al accounts for different spatial configurations of the hybridized orbital in bonding with lattice oxygen, resulting in the formation of a B‐rich surface and an Al‐rich bulk.
Abstract
The prosperity of the lithium‐ion battery market is dialectically accompanied by the depletion of corresponding resources and the accumulation of spent batteries. It is an urgent priority to ...develop green and efficient battery recycling strategies for helping ease resources and environmental pressures at the current stage. Here, we propose a mild and efficient lithium extracting strategy based on potential controllable redox couples. Active lithium in the spent battery without discharging is extracted using a series of tailored aprotic solutions comprised of polycyclic aromatic hydrocarbons and ethers. This ensures a safe yet efficient recycling process with nearly ≈100 % lithium recovery. We further investigate the Li
+
‐electron concerted redox reactions and the effect of solvation structure on kinetics during the extraction, and broaden the applicability of the Li‐PAHs solution. This work can stimulate new inspiration for designing novel solutions to meet efficient and sustainable demands in recycling batteries.
The surge in lithium‐ion batteries has heightened concerns regarding metal resource depletion and the environmental impact of spent batteries. Battery recycling has become paramount globally, but ...conventional techniques, while effective at extracting transition metals like cobalt and nickel from cathodes, often overlook widely used spent LiFePO4 due to its abundant and low‐cost iron content. Direct regeneration, a promising approach for restoring deteriorated cathodes, is hindered by practicality and cost issues despite successful methods like solid‐state sintering. Hence, a smart prelithiation separator based on surface‐engineered sacrificial lithium agents is proposed. Benefiting from the synergistic anionic and cationic redox, the prelithiation separator can intelligently release or intake active lithium via voltage regulation. The staged lithium replenishment strategy was implemented, successfully restoring spent LiFePO4’s capacity to 163.7 mAh g−1 and a doubled life. Simultaneously, the separator can absorb excess active lithium up to approximately 600 mAh g−1 below 2.5 V to prevent over‐lithiation of the cathode This innovative, straightforward, and cost‐effective strategy paves the way for the direct regeneration of spent batteries, expanding the possibilities in the realm of lithium‐ion battery recycling.
A smart lithium compensation strategy by introducing voltage‐responsive prelithiation separator can staged release active lithium, regenerating spent lithium‐ion batteries and extending their life. The separator's ability to absorb excess lithium below operating voltage protects the cathode from electrochemical failure or short circuit, enhancing safety and sustainability.
Light deficiency is a growing abiotic stress in rice production. However, few studies focus on shading effects on grain yield and quality of rice in East China. It is also essential to investigate ...proper nitrogen (N) application strategies that can effectively alleviate the negative impacts of light deficiency on grain yield and quality in rice. A two-year field experiment was conducted to explore the effects of shading (non-shading and shading from heading to maturity) and panicle N application (NDP, decreased panicle N rate; NMP, medium panicle N rate; NIP, increased panicle N rate) treatments on rice yield- and quality-related characteristics. Compared with non-shading, shading resulted in a 9.5–14.8% yield loss (P<0.05), mainly due to lower filled-grain percentage and grain weight. NMP and NIP had higher (P<0.05) grain yield than NDP under non-shading, and no significant difference was observed in rice grain yield among NDP, NMP, and NIP under shading. Compared with NMP and NIP, NDP achieved less yield loss under shading because of the increased filled-grain percentage and grain weight. Shading reduced leaf photosynthetic rate after heading, as well as shoot biomass weight at maturity, shoot biomass accumulation from heading to maturity, and nonstructural carbohydrate (NSC) content in the stem at maturity (P<0.05). The harvest index and NSC remobilization reserve of NDP were increased under shading. Shading decreased (P<0.05) percentages of brown rice, milled rice, head rice, and amylose content while increasing (P<0.05) chalky rice percentage, chalky area, chalky degree, and grain protein. NMP demonstrated a better milling quality under non-shading, while NDP demonstrated under shading. NDP exhibited both lower chalky rice percentage, chalky area, and chalky degree under non-shading and shading, compared with NMP and NIP. NDP under shading decreased amylose content and breakdown but increased grain protein content and setback, contributing to similar overall palatability to non-shading. Our results suggested severe grain yield and quality penalty of rice when subjected to shading after heading. NDP improved NSC remobilization, harvest index, and sink-filling efficiency and alleviated yield loss under shading. Besides, NDP would maintain rice’s milling, appearance, and cooking and eating qualities under shading. Proper N management with a decreased panicle N rate could be adopted to mitigate the negative effects of shading on rice grain yield and quality.
The yield potential of japonica/indica hybrids (JIH) has been achieved over 13.5 t ha−1 in large-scale rice fields, and some physiological traits for yield advantage of JIH over japonica inbred rice ...(JI) and indica hybrid rice (IH) were also identified. To date, little attention has been paid to morphological traits for yield advantage of JIH over JI and IH. For this reason, three JIH, three JI, and three IH were field-grown at East China (Ningbo, Zhejiang Province) in 2015 and 2016. Compared with JI and IH, JIH had 14.3 and 20.8% higher grain yield, respectively, attributed to its more spikelets per panicle and relatively high percentage of filled grains. The advantage in spikelets per panicle of JIH over JI and IH was shown in number of grains on the upper, middle, and lower branches. Compared with JI and IH, JIH had higher leaf area through leaf width and lower leaf angle of upper three leaves, higher leaf area index and leaf area per tiller at heading and maturity stages, higher stem weight per tiller and K and Si concentrations of stem at maturity, higher dry matter weight in leaf, stem, and panicle at heading and maturity stages, and higher biomass accumulation after heading and lower biomass translocation from stem during ripening. Leaf width of upper three leaves were correlated positively, while leaf angle of upper three leaves were correlated negatively with biomass accumulation after heading, stem weight per tiller, and per unit length. Our results indicated that the grain yield advantage of JIH was ascribed mainly to the more spikelets per panicle and relatively high percentage of filled grains. Higher leaf area through leaf width and more erect leaves were associated with improved biomass accumulation and stem weighing during ripening, and were the primary morphological traits underlying higher grain yield of JIH.
It is widely reported that japonica/indica hybrids (JIH) have superior grain yield over other main varietal groups such as indica hybrids (IH) under sufficient resource inputs. To date, little ...attention has been paid to yield performance of JIH under input-reduced practices, and whether JIH could have better grain yield performance over IH under input-reduced practices. In this study, three JIH varieties and three IH varieties were compared in grain yield and their related morpho-physiological traits under two cultivation modes, i.e., conventional high-yielding method (CHYM) and double reductions in nitrogen rate and planting density (DRNP). Our results showed that JIH had 8.3 and 13.3% higher grain yield over IH under CHYM and DRNP, respectively. The superior grain yield of JIH over IH under DRNP was mainly attributed to larger sink size and improved sink filling efficiency. Three main morpho-physiological traits were concluded for better yield performance of JIH over IH under DRNP. Firstly, JIH had the reduced unproductive tillers growth, indicated by a higher percentage of productive tillers and the percentage of effective leaf area index (LAI) to total LAI at heading stage. Secondly, a synergistic increase in biomass accumulation and harvest index were achieved of JIH, supported by higher biomass accumulation and leaf area duration during the main growth periods, and improved non-structural carbohydrate (NSC) remobilization after heading. Thirdly, JIH had an improved canopy structure, showing as higher leaf area of upper three leaves and lower light extinction coefficient. Our results suggested that improved morpho-physiological traits of JIH could lead to better grain yield performance over IH under input-reduced practices.
Late-maturity type of Yongyou japonica/indica hybrids series （LMYS） have shown great yield potential, and are being widely planted in the lower reaches of Yangtze River, China. Knowledge about ...suitable growing zone and evaluation of yield advantage is of practicall importance for LMYS in this region. Fifteen LMYS, two high-yielding inbred japonica check varieties （CK-J） and two high-yielding hybrid indica check varieties （CK-I） were grown at Xinghua （119.57°E, 33.05°N） of Lixiahe region, Yangzhou （119.25°E, 32.30°N）of Yanjiang region, Changshu （120.46°E, 31.41°N）of Taihu Lake region, and Ningbo （121.31°E, 29.45°N） of Ningshao Plain in 2013 and 2014. The results showed that maturity dates of the 15 were later than the secure maturity date at Xinghua and 6, 14 and 15 LMYS were mature before the secure maturity date at Yangzhou, Changshu and Ningbo, respectively. One variety was identified as high-yielding variety among LMYS （HYYS） at Yangzhou, 8 HYYS in 201：3 and 9 HYYS in 2014 at Changshu, 9 HYYS at Ningbo. HYYS here referred to the variety among LMYS that was mature before the secure maturity date and had at least 8% higher grain yield than both CK-J and CK-I at each experimental site. Grain yield of HYYS at each experimental site was about 12.0 t ha-1 or higher, and was significantly higher than CK varieties. High yield of HYYS was mainly attributed to larger sink size due to more spikelets per panicle. Plant height of HYYS was about 140 cm, and was significantly higher than check varieties. Significant positive correlations were recorded between duration from heading to maturity stage and grain yield, and also between whole growth periods and grain yield. HYYS had obvious advantage over check varieties in biomass accumulation and leaf area duration from heading to maturity stage. Comprehensive consideration about safe matudty and yield performance of LMYS at each experimental site, Taihu Lake region （representative site Changshu） and Ningshao Plain （representative site Ningbo） were thought suitable growing zones for LMYS in the lower reaches of Yangtze River. The main factors underlying high yield ofHYYS were larger sink size, higher plant height, longer duration from heading to maturity stage and whole growth periods, and higher biomass accumulation and leaf area duration during grain filling stage.
financed by the Special Program of Super Rice of Ministry of Agriculture, China （02318802013231）;the National Public Services Sectors （Agricultural） Research Projects, Ministry of Agriculture, China ...（201303102）;the Great Technology Project of Ningbo, China （2013C11001）
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