Defect engineering of air-stable Li5FeO4 towards an ultra-high capacity cathode prelithiation additive.

Antifluorite-type Li5FeO4 (LFO) belongs to a class of promising prelithiation materials for next-generation high-energy lithium-ion batteries. Unfortunately, the incomplete de-lithiation performance and inferior air stability hinder its application. In this work, ultra-high capacity is achieved by selective doping of Zr into the Fe sites (LFO-Zr) of LFO to form a large number of defects. The underlying defect formation mechanism is comprehensively investigated using density functional theory, revealing that such selective site doping not only enlarges the unit cell volume but also induces Li vacancies into the structure, both of which facilitate lithium-ion migration at a high-rate and promote the redox of oxygen anions. As a result, under 0.05 and 1C rates, the capacity of LFO-Zr reaches 805.7 and 624.5 mA h g-1, which are 69.0 and 262.0 mA h g-1 higher than those of LFO, translating to an increase of 9.4% and 73.3%, respectively. In addition, LFO-Zr exhibits excellent electrochemical performance in a humidity of 20%, with a high capacity of 577.6 mA h g-1 maintained. With the LFO-Zr additive, the full cell delivered 193.6 mA h g-1 for the initial cycle at 0.1C. The defect engineering strategy presented in this work delivers insights to promote ultra-high capacity and high-rate performance of air-stable LFO.

Expression of heterosis in photosynthetic traits in F1 generation of sorghum (Sorghum bicolor) hybrids and relationship with yield traits.

Heterosis is a crucial factor in enhancing crop yield, particularly in sorghum (Sorghum bicolor ). This research utilised six sorghum restorer lines, six sorghum sterile lines, and 36 hybrid combinations created through the NCII incomplete double-row hybridisation method. We evaluated the performance of F1 generation hybrids for leaf photosynthesis-related parameters, carbon metabolism-related enzymes, and their correlation with yield traits during the flowering stage. Results showed that hybrid sorghum exhibited significant high-parent heterosis in net photosynthetic rate (P n ), transpiration rate (T r ), stomatal conductance (G s ), apparent leaf meat conductance (AMC), ribulose-1,5-bisphosphate (RuBP) carboxylase, phosphoenolpyruvate (PEP) carboxylase, and sucrose phosphate synthase (SPS). Conversely, inter-cellular carbon dioxide concentration (C i ), instantaneous water uses efficiency (WUE), and sucrose synthase (SuSy) displayed mostly negative heterosis. Traits such as 1000-grain weight (TGW), grain weight per spike (GWPS), and dry matter content (DMC) exhibited significant high-parent heterosis, with TGW reaching the highest value of 82.54%. P n demonstrated positive correlations with T r , C i , G s , RuBP carboxylase, PEP carboxylase, GWPS, TGW, and DMC, suggesting that T r , C i , and G s could aid in identifying high-photosynthesis sorghum varieties. Concurrently, P n could help select carbon-efficient sorghum varieties due to its close relationship with yield. Overall, the F1 generation of sorghum hybrids displayed notable heterosis during anthesis. Combined with field performance, P n at athesis can serve as a valuable indicator for early prediction of the yield potential of the F1 generation of sorghum hybrids and for screening carbon-efficient sorghum varieties.

Sodium compensation: a critical technology for transforming batteries from sodium-starved to sodium-rich systems.

Sodium-ion batteries (SIBs) have attracted wide attention from academia and industry due to the low cost and abundant sodium resources. Despite the rapid industrialization development of SIBs, it still faces problems such as a low initial coulombic efficiency (ICE) leading to a significant decrease in battery energy density (e.g., 20%). Sodium compensation technology (SCT) has emerged as a promising strategy to effectively increase the ICE to 100% and drastically boost battery cycling performance. In this review, we emphasize the importance of SCT in high-performance SIBs and introduce its working principle. The up-to-date advances in different SCTs are underlined in this review. In addition, we elaborate the current merits and demerits of different SCTs. This review also provides insights into possible future research directions in SCT for high-energy SIBs.

Highly efficient ion-transport "polymer-in-ceramic" electrolytes boost stable all-solid-state Li metal batteries.

"Polymer-in-ceramic" (PIC) electrolytes are widely investigated for all-solid-state batteries (ASSBs) due to their good thermal stability and mechanical performance. However, achieving fast and diversified lithium-ion transport inside the PIC electrolyte and uniform Li+ deposition at the electrolyte/Li anode interface simultaneously remains a challenge. Besides, the effect of ceramic particle size on Li+ transport and Li anodic compatibility is still unclear, which is essential for revealing the enhanced mechanism of the performance for PIC electrolytes. Herein, PIC with moderate ceramic size and contents are prepared and studied to strike a balance between ionic conductivity and anodic compatibility. Through moderate filler-filler interfacial impedance and appropriate surface roughness, a particle size of 17 µm is optimized to facilitate homogeneous Li+ flux on anode and enhance Li+ conductivity of the electrolyte. The PIC electrolyte with ceramic particle size of 17 µm achieves a high lithium ion transference number (0.74) and an ionic conductivity of 4.11 × 10-4 S cm-1 at 60 °C. The Li/PIC/Li symmetric cell can stably cycle for 2800 h at 0.2 mA cm-2 with 0.2 mAh cm-2. Additionally, the Li/PIC/LiFePO4 cell also delivers a superior cycling performance at 0.5C, a high capacity retention of 93.28% after 100 cycles and 83.17% after 200 cycles, respectively.

Effects of dietary forage neutral detergent fiber and rumen degradable starch ratios on chewing activity, ruminal fermentation, ruminal microbes and nutrient digestibility of Hu sheep fed a pelleted total mixed ration.

Pelleted total mixed ration (P-TMR) feeding, which has become a common practice in providing nutrition for fattening sheep, requires careful consideration of the balance between forage neutral detergent fiber (FNDF) and rumen degradable starch (RDS) to maintain proper rumen functions. The present study aimed to investigate the effects of the dietary FNDF/RDS ratio (FRR) on chewing activity, ruminal fermentation, ruminal microbes, and nutrient digestibility in Hu sheep fed a P-TMR diet. This study utilized eight ruminally cannulated male Hu sheep, following a 4 × 4 Latin square design with 31 d each period. Diets consisted of four FRR levels: 1.0 (high FNDF/RDS ratio, HFRR), 0.8 (middle high FNDF/RDS ratio, MHFRR), 0.6 (middle low FNDF/RDS ratio, MLFRR), and 0.4 (low FNDF/RDS ratio, LFRR). Reducing the dietary FRR levels resulted in a linear decrease in ruminal minimum pH and mean pH, while linearly increasing the duration and area of pH below 5.8 and 5.6, as well as the acidosis index. Sheep in the HFRR and MHFRR groups did not experience subacute ruminal acidosis (SARA), whereas sheep in another two groups did. The concentration of total volatile fatty acid and the molar ratios of propionate and valerate, as well as the concentrate of lactate in the rumen linearly increased with reducing dietary FRR, while the molar ratio of acetate and acetate to propionate ratio linearly decreased. The degradability of NDF and ADF for alfalfa hay has a quadratic response with reducing the dietary FRR. The apparent digestibility of dry matter, organic matter, neutral detergent fiber, and acid detergent fiber linearly decreased when the dietary FRR was reduced. In addition, reducing the dietary FRR caused a linear decrease in OTUs, Chao1, and Ace index of ruminal microflora. Reducing FRR in the diet increased the percentage of reads assigned as Firmicutes, but it decreased the percentage of reads assigned as Bacteroidetes in the rumen. At genus level, the percentage of reads assigned as Prevotella, Ruminococcus, Succinivibrio, and Butyrivibrio linearly decreased when the dietary FRR was reduced. The results of this study demonstrate that the dietary FRR of 0.8 is crucial in preventing the onset of SARA and promotes an enhanced richness of ruminal microbes and also improves fiber digestibility, which is a recommended dietary FRR reference when formulating P-TMR diets for sheep.

Forage neutral detergent fiber (FNDF) and rumen degradable starch (RDS) are key components of carbohydrates in the diet for ruminants, which would reflect saliva secretion and the acid production potential of feed. However, appropriate FNDF to RDS ratios (FRR) applicable to ruminants under the condition of pelleted total mixed ration (P-TMR) feeding have not been reported. In this study, we investigated the effects of the dietary FRR on chewing activity, ruminal fermentation, ruminal microbial communities, and nutrient digestibility of Hu sheep under P-TMR feeding. The results indicate that reducing dietary FRR levels would induce acidosis in sheep, which negatively affected fiber utilization and ruminal bacterial communities. The FRR of 0.8 was a recommended dietary FRR when formulating a P-TMR diet for fattening sheep, as indicated by decreased ruminal acidosis risk and increased richness of ruminal microbes in the rumen as well as nutrient digestibility.

Carboxylic acid accumulation and secretion contribute to the alkali-stress tolerance of halophyte Leymus chinensis.

Leymus chinensis is a dominant halophytic grass in alkalized grasslands of Northeast China. To explore the alkali-tolerance mechanism of L. chinensis, we applied a widely targeted metabolomic approach to analyze metabolic responses of its root exudates, root tissues and leaves under alkali-stress conditions. L. chinensis extensively secreted organic acids, phenolic acids, free fatty acids and other substances having -COOH or phosphate groups when grown under alkali-stress conditions. The buffering capacity of these secreted substances promoted pH regulation in the rhizosphere during responses to alkali stress. L. chinensis leaves exhibited enhanced accumulations of free fatty acids, lipids, amino acids, organic acids, phenolic acids and alkaloids, which play important roles in maintaining cell membrane stability, regulating osmotic pressure and providing substrates for the alkali-stress responses of roots. The accumulations of numerous flavonoids, saccharides and alcohols were extensively enhanced in the roots of L. chinensis, but rarely enhanced in the leaves, under alkali-stress conditions. Enhanced accumulations of flavonoids, saccharides and alcohols increased the removal of reactive oxygen species and alleviated oxygen damage caused by alkali stress. In this study, we revealed the metabolic response mechanisms of L. chinensis under alkali-stress conditions, emphasizing important roles for the accumulation and secretion of organic acids, amino acids, fatty acids and other substances in alkali tolerance.

Surface structure regulation toward anionic redox activation of Li1.20Mn0.533Ni0.133Co0.133O2 cathodes with high initial coulombic efficiency.

Li-rich layered oxides cathodes (LLOs) as the promising next-generation cathode materials can provide ultrahigh capacity and energy density due to their distinctive anionic redox chemistry. Unfortunately, severe interfacial side reactions, surface structural degradation and sluggish Li+ kinetics have resulted in low initial coulombic efficiency (ICE), capacity decay and poor rate performance, restricting their practical applications for high-energy-density lithium-ion batteries. Herein, Surface structure regulation strategy used as surface modified agent is proposed to activate the anionic redox chemistry via ammonium tungstate treatment. Experimental results showcase that dual coating layer spinel-like structure LiMn2O4 and Li2WO4 have been successfully constructed on the surface of LLOs. The surface spinel-like structure providing 3 D Li+ diffusion channels together with fast-ion conductive layer decrease the interfacial Li+ diffusion barrier and boost the fasting Li+ kinetics. In addition, the in-situ reconstruction layer can further alleviate the interfacial side reactions and reinforce the surface structural stability. As a result, the ICE of modified LLOs can be precisely increased from 74.71 % to 107.42 % with the adjustment of ammonium tungstate usage. Moreover, it delivers a high reversible capacity of 279.5 mAh/g at 0.1 C, as well as excellent rate capability with capacity of 147.2 mAh/g at 5 C. This work provides a significant reference for designing high-energy-density LLOs via surface structure regulation strategy.

Band Structure Engineering Promotes Anionic Redox Reversibility of Cobalt-Free Li-Rich Layered Oxides Cathodes.

Li-rich layered oxides cathodes (LLOs) have prevailed as the promising high-energy-density cathode materials due to their distinctive anionic redox chemistry. However, uncontrollable anionic redox process usually leads to structural deterioration and electrochemical degradation. Herein, a Mo/Cl co-doping strategy is proposed to regulate the relative position of energy band for modulating the anionic redox chemistry and strengthening the structural stability of Co-free Li1.16Mn0.56Ni0.28O2 cathodes. The incorporation of Mo with high d state orbit and Cl with low electronegativity can narrow the band energy gap between bonding and antibonding bands via increasing the filled lower-Hubbard band (LHB) and decreasing the non-bonding O 2p energy bands, promoting the anionic redox reversibility. In addition, strong covalent Mo─O and Mn─Cl bonding further increases the covalency of Mn─O band to further stabilize the O2 n- species and enhance the reversible distortion of MnO6 octahedron. The strengthening electronic conductivity, together with the epitaxial structure Li2MoO4 facilitates the fast Li+ kinetics. As a result, the dual doping material exhibits enhanced anionic redox reversibility and suppressed oxygen release with increased cyclic stability and excellent rate performance. This strategy provides some guidance to design high-energy-density LLOs with desirable anionic redox reversibility and stable crystal structure via band structure engineering.

Anion Substitution Strategy toward an Advanced NASICON-Na4Fe3(PO4)2P2O7 Cathode for Sodium-Ion Batteries.

Superior sodium-ion batteries (SIBs) greatly need cathode materials with higher capacity and better durability. Herein, the anion group substitution strategy is proposed to design a cathode material with extraordinary Na+ storage performance, NASICON-Na4Fe3(PO4)1.9(SiO4)0.1P2O7 (NFPP-Si0.1). The experimental and theoretical research revealed that modification in the local structure by anion substitution significantly boosts the ionic/electronic transfer kinetics via optimizing the electronic conductivity and reducing the Na+ diffusion energy barrier. Furthermore, the SiO44- substitution generates a slight expansion of the crystal lattice to broaden the Na+ diffusion channel. Specifically, the custom-designed NFPP-Si0.1 could deliver a high rate capability of 77.6 mAh g-1 at constant 50 C charge-discharge and excellent recyclability of 79.4% retention rate after 7000 cycles at 10 C. Besides, it also possesses outstanding low temperature reversible capacity of 95.5 mAh g-1 at 0.1 C and long-term cyclability of 93.6% capacity retention after 1000 cycles at 5 C in -10 °C. This strategy of heterogeneous and isostructural anion group substitution provides a method for unlocking high-rate and long-life-span mixed polyanionic cathodes.

Harmless pre-lithiation via advantageous surface reconstruction in sacrificial cathode additives for lithium-ion batteries.

Sacrificial cathode additives have emerged as a tempting strategy to compensate the initial capacity loss (ICL) in Li-ion batteries (LIBs) manufacturing. However, the utilization of sacrificial cathode additives inevitably brings residuals, side reactions, and negative impacts in which relevant researches are still in the early stage. In this study, we conduct a systematic investigation on the effects of employing a nickel-based sacrificial additive, Li2Cu0.1Ni0.9O2 (LCNO), and propose a feasible strategy to achieve advantageous surface reconstruction on LCNO. Specifically, we build a Li5AlO4 (LAO) coating layer on the LCNO through dry ball milling and annealing treatment. This process not only consumes surface residual lithium compounds on LCNO but also demonstrates minimal detrimental effects on its performance. The surface reconstructed LCNO (SR-LCNO) reveals mitigated gas generation and suppressed structure degradation under high working voltage (＞4.1 V), thereby causing negligible negative effects on the cycling capability and rate performance of commercial cathode materials. The full cells containing SR-LCNO deliver significantly improved electrochemical properties, with no observed exacerbation of side reactions. This work awakes the awareness of the prudent utilization of sacrificial cathode additives and provides an effective strategy for harmless pre-lithiation via surface reconstructed sacrificial cathode additives.

Effects of low nitrogen on seedling growth, photosynthetic characteristics and antioxidant system of rice varieties with different nitrogen efficiencies.

Nitrogen plays a significant role in influencing various physiological processes in plants, thereby impacting their ability to withstand abiotic stresses. This study used hydroponics to compare the effects of three nitrogen supply levels (1N, 1/2N and 1/4N) on the antioxidant capacity of rice varieties JJ88 (nitrogen efficient) and XN999 (nitrogen inefficient) with different nitrogen use efficiencies. The results show that compared with the XN999 variety, the JJ88 variety has stronger adaptability to low-nitrogen conditions, which is mainly reflected in the relatively small decrease in dry weight and net photosynthetic rate (Pn); In the early stage of low-nitrogen treatment (0-7 d), the [Formula: see text] production rate, hydrogen peroxide (H2O2) and malondialdehyde (MDA) content of JJ88 variety increased relatively slightly, but the superoxide dismutase (SOD), peroxide The activity of enzyme (POD) and catalase (CAT) increased significantly; After low-nitrogen treatment, the ASA-GSH cycle enzyme activity of JJ88 variety was relatively high, and the dehydroascorbate reductase (DHAR) activity after 14 days of low-nitrogen treatment was higher than that of 1N treatment; The content of reduced ascorbic acid (ASA) in non-enzymatic antioxidants was lower than that of 1N treatment after 14 days of low nitrogen treatment; The contents of oxidized dehydroascorbic acid (DHA) and carotenoids (Car) were higher than those of 1N treatment after 21d and 14d of low nitrogen treatment respectively; The contents of reduced glutathione (GSH), oxidized glutathione (GSSG) and proline (Pro) showed a larger upward trend during the entire low-nitrogen treatment period. In summary, the JJ88 rice variety has a strong ability to regulate oxidative stress and osmotic damage under low nitrogen conditions. It can slow down plant damage by regulating antioxidant enzyme activity and antioxidant content. This provides a basis for achieving nitrogen reduction and efficiency improvement in rice and the breeding of nitrogen-efficient varieties.

Molecule Isolation Protective Interface Formed by Planar Additive for Stable Sodium Metal Anodes.

Sodium (Na) metal is an ideal anode for Na-based batteries because of its high specific capacity and low potential. However, interface issues such as side reactions with the electrolyte and uneven deposition severely hinder its practical application. Here, we report a zinc phthalocyanine (ZnPc) electrolyte additive with a planar molecular structure that can form a dense molecular layer when tightly adsorbed on the Na metal anode surface. Such a planar molecular layer can suppress side reactions between the anode and the electrolyte as well as homogenize Na+ flux to reduce dendrite growth. As a result, the molecular isolation interface formed by ZnPc adsorption on the surface of the Na metal anode enhances the interface stability and the cycling performance of the Na metal anode, with the average Coulombic efficiency of the half-cell of 99.95% after 350 stable cycles at 1 mA cm-2 for 1 mAh cm-2. Moreover, the assembled Na||Na3V2(PO4)3 full-cell with this additive delivers excellent stability over 120 cycles, proving the effectiveness of the ZnPc additive in practical application.

Effect of the N,S-Codoped Carbon Layer on the Rate Performance of Air-Stable Lithium Iron Oxide Prelithiation Additives.

Lithium iron oxide (Li5FeO4, LFO) holds great promise in cathode prelithiation additives for lithium-ion batteries. However, it is hard to make full use of the power under high current rates due to its poor air stability and electronic conductivity. The carbon protective layer is an effective approach, and introducing heteroatoms would be beneficial to further improving Li+ kinetics. However, the interplay between the dopants and Li+ is always ignored. Herein, we aim to reveal the interaction among Li+ ions and the defects of carbon layers from nitrogen/sulfur dopants and the corresponding influence on delithiation performances of LFO. It is found that the codoping of nitrogen and sulfur on carbon layers contributes to the boosted capacity and rate capability. The modified SNC@LFO presents a large irreversible capacity (779.3 mAh g-1 at 0.1 C) and excellent rate performance (537.1 mAh g-1 at 1 C), which is up to 16.6 and 64.0%, respectively, compared to LFO.

"Mn-locking" effect by anionic coordination manipulation stabilizing Mn-rich phosphate cathodes.

High-voltage cathodes with high power and stable cyclability are needed for high-performance sodium-ion batteries. However, the low kinetics and inferior capacity retention from structural instability impede the development of Mn-rich phosphate cathodes. Here, we propose light-weight fluorine (F) doping strategy to decrease the energy gap to 0.22 eV from 1.52 eV and trigger a "Mn-locking" effect-to strengthen the adjacent chemical bonding around Mn as confirmed by density functional theory calculations, which ensure the optimized Mn ligand framework, suppressed Mn dissolution, improved structural stability and enhanced electronic conductivity. The combination of in situ and ex situ techniques determine that the F dopant has no influence on the Na+ storage mechanisms. As a result, an outstanding rate performance up to 40C and an improved cycling stability (1000 cycles at 20C) are achieved. This work presents an effective and widely available light-weight anion doping strategy for high-performance polyanionic cathodes.

Direct Observation of the Evolutionary Process in Room-Temperature Sodium-Sulfur/Selenium Batteries Using operando Light Microscopy.

Understanding the conversion mechanism of active materials in the electrode is essential to guide the design of room-temperature sodium-sulfur/selenium (RT Na-S/Se) batteries. However, there is still some confusion regarding the dissolution and formation of the insulating active particles. Conventional detection methods have difficulty in capturing and presenting the dynamic processes of these microscopic particles in the "black box" battery. In this study, a visualization technique was applied to track and monitor the internal evolution process of RT Na-S/Se batteries, visualizing the dissolution and formation details of insulating solid particles in real time. Supercooled liquid sulfur and spherulites were also observed for the first time in this system. The microstructural evolution mechanism is inferred based on the observation of the dynamic information on microscopic particles. This paper provides insights into the internal workings of RT Na-S and Na-Se batteries, allowing for a more comprehensive and in-depth understanding of their dynamics.

Stabilized Anionic Redox by Rational Structural Design from Surface to Bulk for Long-Life Fast-Charging Li-Rich Oxide Cathodes.

On account of high capacity and high voltage resulting from anionic redox, Li-rich layered oxides (LLOs) have become the most promising cathode candidate for the next-generation high-energy-density lithium-ion batteries (LIBs). Unfortunately, the participation of oxygen anion in charge compensation causes lattice oxygen evolution and accompanying structural degradation, voltage decay, capacity attenuation, low initial columbic efficiency, poor kinetics, and other problems. To resolve these challenges, a rational structural design strategy from surface to bulk by a facile pretreatment method for LLOs is provided to stabilize oxygen redox. On the surface, an integrated structure is constructed to suppress oxygen release, electrolyte attack, and consequent transition metals dissolution, accelerate lithium ions transport on the cathode-electrolyte interface, and alleviate the undesired phase transformation. While in the bulk, B doping into Li and Mn layer tetrahedron is introduced to increase the formation energy of O vacancy and decrease the lithium ions immigration barrier energy, bringing about the high stability of surrounding lattice oxygen and outstanding ions transport ability. Benefiting from the specific structure, the designed material with the enhanced structural integrity and stabilized anionic redox performs an excellent electrochemical performance and fast-charging property..

Transformation and Detection of Soybean Hairy Roots.

Agrobacterium rhizogenes is a soil bacteria with extensive infectivity, which can infect almost all dicotyledonous plants and a few monocotyledonous plants to induce root nodules. This is caused by the root-inducing plasmid, which contains genes responsible for the autonomous growth of root nodules and crown gall base synthesis. Structurally, it is similar to the tumor-inducing plasmid in that it mainly contains the Vir region, the T-DNA region, and the functional region of crown gall base synthesis. Its T-DNA is integrated into the nuclear genome of the plant with the assistance of Vir genes, causing hairy root disease in the host plant and the formation of hairy roots. The roots produced by Agrobacterium rhizogenes-infested plants are characterized by a fast growth rate, high degree of differentiation, physiological, biochemical, and genetic stability, and ease of manipulation and control. In particular, the hairy root system is an efficient and rapid research tool for plants that have no affinity for transformation by Agrobacterium rhizogenes and low transformation efficiency. The establishment of germinating root culture system for the production of secondary metabolites in the original plants through the genetic transformation of natural plants mediated by root-inducing plasmid in Agrobacterium rhizogenes has become a new technology combining plant genetic engineering and cell engineering. It has been widely used in a variety of plants for different molecular purposes, such as pathological analysis, gene function verification, and secondary metabolite research. Chimeric plants obtained by induction of Agrobacterium rhizogenes that can be expressed instantaneously and contemporarily are more rapidly obtained, compared to tissue culture and stably inheritable transgenic strains. In general, transgenic plants can be obtained in approximately one month.

High-Entropy Doping Boosts Ion/Electronic Transport of Na4 Fe3 (PO4 )2 (P2 O7 )/C Cathode for Superior Performance Sodium-Ion Batteries.

Fe-based mixed phosphate cathodes for Na-ion batteries usually possess weak rate capacity and cycle stability challenges resulting from sluggish diffusion kinetics and poor conductivity under the relatively low preparation temperature. Here, the excellent sodium storage capability of this system is obtained by introducing the high-entropy doping to enhance the electronic and ionic conductivity. As designed high-entropy doping Na4 Fe2.85 (Ni,Co,Mn,Cu,Mg)0.03 (PO4 )2 P2 O7 (NFPP-HE) cathode can release 122 mAh g-1 at 0.1 C, even 85 mAh g-1 at ultrahigh rate of 50 C, and keep a high retention of 82.3% after 1500 cycles at 10 C. Besides, the cathode also exhibits outstanding fast charge capacity in terms of the cyclability and capacity with 105 mAh g-1 at 5 C/1 C, corresponding 94.3% retention after 500 cycles. The combination of in situ X-ray diffraction, density functional theory, conductive-atomic force microscopy, and galvanostatic intermittent titration technique tests reveal that the reversible structure evolution with optimized Na+ migration path and energy barrier boost the Na+ kinetics and improve the interfacial electronic transfer, thus improving performance.

In Situ Polymerized Flame Retardant Gel Electrolyte for High-Performance and Safety-Enhanced Lithium Metal Batteries.

A flame retardant gel electrolyte (FRGE) is deemed as one of the most promising electrolytes to relieve the problems of safety hazards and interfacial incompatibility of Li metal batteries. Herein, a novel solvent triethyl 2-fluoro-2-phosphonoacetate (TFPA) with outstanding flame retardancy is introduced in the polymer skeleton synthesized by in situ polymerization of the monomer polyethylene glycol dimethacrylate (PEGDMA) and the cross-linker pentaerythritol tetraacrylate (PETEA). The FRGE exhibits superb interfacial compatibility with Li metal anodes and inhibits uncontrolled Li dendrite growth. This can be ascribed to the restriction of free phosphate molecules by the polymer skeleton, thus realizing a stable cycling performance over 500 h at 1 mA cm-2 and 1 mAh cm-2 in the Li||Li symmetric cell. In addition, the high ionic conductivity (3.15 mS cm-1) and Li+ transference number (0.47) of the FRGE further enhance the electrochemical performance of the correspondent battery. As a result, the LiFePO4|FRGE|Li cell exhibits excellent long-term cycling life with a capacity retention of 94.6% after 700 cycles. This work points to a new pathway for the practical development of high-safety and high-energy-density Li metal-based batteries.

Integrating surface structure via triphenyl phosphate treatment to stabilize Li-rich Mn-based cathode materials.

Li-rich Mn-based layered oxides (LLOs) have emerged as one of the most promising cathode materials for the next-generation lithium-ion batteries (LIBs) because of their high energy density, high specific capacity, and environmental friendliness. These materials, however, have drawbacks such as capacity degradation, low initial coulombic efficiency (ICE), voltage decay, and poor rate performance due to irreversible oxygen release and structural deterioration during cycling. Herein, we present a facile method of triphenyl phosphate (TPP) surface treatment to create an integrated surface structure on LLOs that includes oxygen vacancies, Li3PO4, and carbon. When used for LIBs, the treated LLOs show an increased initial coulombic efficiency (ICE) of 83.6% and capacity retention of 84.2% at 1C after 200 cycles. It is suggested that the enhanced performance of the treated LLOs can be attributed to the synergetic functions of each component in the integrated surface, such as the oxygen vacancy and Li3PO4 being able to inhibit the evolution of oxygen and accelerate the transport of lithium ions, while the carbon layer can restrain undesirable interfacial side reactions and reduce the dissolution of transition metals. Furthermore, electrochemical impedance spectroscopy (EIS) and galvanostatic intermittent titration technique (GITT) prove an enhanced kinetic property of the treated LLOs cathode, and ex-situ X-ray diffractometer shows a suppressed structural transformation of TPP-treated LLOs during the battery reaction. This study provides an effective strategy for constructing an integrated surface structure on LLOs to achieve high-energy cathode materials in LIBs.