LANGMUIR
·
2024
·
IF 3.7
Xiangnan Li,Xinyu Tang,Ming Ge,Mengdan Zhang,Wenfeng Liu,Xiaojian Liu,Yuantao Cui,Huishuang Zhang,Yanhong Yin,Shuting Yang
Layered transition metal oxides are commonly used as the cathode materials in sodium-ion batteries due to their low cost and easy manufacturing. However, the application is hindered by poor rate performance and complex phase transitions. To address these challenges, a new seven-component high-entropy layered oxide cathode material, O3-NaNi0.25Fe0.15Mn0.3Ti0.1Sn0.05Co0.05Li0.1O2 (HEO) has been developed. The entropy stabilization effect plays a crucial role in improving the performance of electrochemical systems and the stability of structures. The HEO exhibits a specific discharge capacity of 154.1 mA h g–1 at 0.1 C and 94.5 mA h g–1 at 7 C. In-situ and ex-situ XRD results demonstrate that the HEO effectively retards complex phase transitions. This work provides a high-entropy design for the storage materials with a high energy density. Meanwhile, it eliminates industry doubts about the performance of sodium ion layered oxide cathode materials.
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高影响因子
IONICS
·
2024
·
IF 2.4
Liu Liyang,Zhao Xufan,Qi Jiaxing,Abdussalam Abubakar,Zhang Wei,Wang Hongyu,Xu Guobao
Since the concept of hybrid Li/Na-ion batteries (HLNIBs) was proposed, many cathode materials with excellent performance and low cost have been studied. However, in HLNIBs, mixed cationic electrolyte is formed as Na + is extracted from the cathode, resulting in relatively complicated and unstable electrochemical performance, especially for the half-cell test with lithium metal as the anode. It is necessary to consider the tolerance of lithium metal counter electrode to sodium contamination in half-cell test with hybrid-ion electrolyte containing different cations. In this work, we have found that lithium metal electrodes in hybrid-ion electrolyte are unstable and Na + causes significant polarization. The polarization influences over potential and complex interface properties and thus reduces the accuracy of half-cell tests. To solve the problem, lithium difluoro(oxalato)borate (LiDFOB) with excellent film-forming properties was utilized as an additive of symmetrical batteries to form solid electrolyte interface (SEI) film. The adverse effect of Na + on the kinetics of hybrid-ion electrolyte was confirmed by regulating the SEI film on lithium metal electrode. The SEI film exhibits a selective effect on Li + and Na + and inhibits the interfacial transport of Na + , which significantly reduces the overpotential of the batteries and the interface migration impedance and also improves the stability of lithium counter electrode. Lithium metal with stable interfacial properties in the presence of LiDFOB is a reliable counter electrode that resists sodium contamination in half-cell test. Graphical abstract
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Nano Energy
·
2017
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IF 12.343
Qun Huang,Jiatu Liu,Li Zhang,Sheng Xu,Libao Chen,Peng Wang,Douglas G. Ivey,Weifeng Wei
The major hurdle of room temperature sodium-ion batteries (NIBs) for large-scale energy storage applications lies in developing new electrode materials with higher energy/power densities and improved durability. This work presents a novel Na-P3/Li 2 MnO 3 layered composite cathode with an alternating heteroepitaxial nanostructure fabricated by an in-situ composition modulation route. XRD structural refinement, synchrotron XAS and aberration-corrected HAADF-/ABF-STEM were employed to understand the structure evolution accompanying Li substitution. It is revealed that the in-situ formation of Li 2 MnO 3 (Li-O’3) changes the crystallographic and chemical features of the neighboring Na-P3 layered matrix significantly and leads to the alternating Na-P3/Li-O’3 heteroepitaxial nanostructure. This alternating heteroepitaxial nanostructure delivers an extremely high reversible capacity of ~ 210 mAh g −1 between 1.5 and 4.5 V vs. Na/Na + , much improved cycling stability and excellent electrode kinetics . Its enhanced electrochemical performance can be ascribed to the effective suppression of the P3-P3’’ phase transition and subsequent amorphization upon cycling to 4.5 V.
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JOURNAL OF THE AMERICAN CERAMIC SOCIETY
·
2017
·Vol. 100
·期 10
·4412-4424
·
IF 2.841
Jingkun Yuan,Peigang He,Dechang Jia,Jinsong You,Xuzhao Liu,Yao Zhang,Delong Cai,Zhihua Yang,Xiaoming Duan,Shengjin Wang,Yu Zhou
As part of a series of studies, effects of Na + substitution on the thermal evolution of cesium-based geopolymers on heating were studied. A series of sodium-substituted cesium-based geopolymers, Cs (1− x ) Na x GPs (where x =0, 0.1, 0.2, 0.3, and 0.4), were prepared and treated at 1300°C for 2 hours to obtain the corresponding ceramic products. The thermal evolution process was disclosed by virtue of a variety of technical, including TG-DTA, thermal shrinkage, XRD analysis, SEM, and TEM investigation. The results indicated that unheated Cs (1− x ) Na x GPs was not completely amorphous after the substitution of Na + and the crystallinity of Cs (1− x ) Na x GPs gradually increased with the rise of sodium content. Meanwhile, the average particle sizes of Cs (1− x ) Na x GPs also increased evidently with increases in sodium substitution. The final product after heat treatment mainly consisted of pollucite (CsAlSi 2 O 6 ) and amorphous glass phase. The particle size of pollucite grain gradually decreased as more Cs + were replaced maybe owing to the role of Na + in the nucleation process of pollucite. Two forms of Na + present in the final products: A small portion was present in the pollucite grains due to Na + partial occupied the crystallographic sites of Cs + ; and the rest were present in the amorphous glass phase among the pollucite grains. The average coefficient of thermal expansion (CTE) of resulting Cs (1− x ) Na x GPs ceramics increased from 4.80×10 -6 K −1 ( x =0) to 7.26×10 −6 K −1 ( x =0.4) with increases in sodium substitution, which could be due to the amorphous glass phase had a relatively higher CTE than that of pollucite.
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Materials Today Energy
·
2025
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IF 8.6
Xiaoxue Yang,Runming Zeng,Hao Yao,Chunliang Yang,Menglan Lv,Bao Zhang,Lin Fu
The development of thin sodium (Na) metal anodes (e.g., ≤ 40 μm) with favorable electrochemical performance is crucial for the practical implementation of high energy density batteries. However, producing such thin Na foils remains challenging because of metallic Na’s poor processability under conventional mechanical rolling techniques. This study reports the successful fabrication of free-standing Na/Na 2 In (NaIn61) composite foils with tunable thicknesses from 40 to 20 μm. They were successfully fabricated via repeated mechanical rolling, using metallic Na and indium as precursors. In-situ generated Na 2 In particles were uniformly distributed within the Na matrix, and strong interfacial bonding between Na 2 In and Na effectively suppressed dislocation motion during extrusion, thereby significantly enhancing the mechanical processability of the composite foil. Furthermore, Na 2 In reduced the nucleation barrier for Na deposition and stabilized the solid electrolyte interphase, improving Na plating/stripping behavior. A full-cell assembled with a 40 μm-thick NaIn61 composite anode and a NaFe 1/3 Ni 1/3 Mn 1/3 O 2 cathode achieved a high energy density of approximately 172 Wh kg -1 at 0.2 C with a low negative-to-positive capacity ratio of ∼2.0. These findings demonstrate the effectiveness of rational composite design in enabling the production of free-standing, thin Na metal anodes with improved electrochemical performance.
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Journal of Energy Chemistry
·
2025
·
IF 14.9
Ali Hammad,Siyi Zou,Fandi Ning,Ghulam Nabi,Yuzhuo Jiang,Bin Tian,Wentao Huang,Muhammad Rashid,Shiqi Zhao,Xiaochun Zhou
Inorganic materials can solve transportable and on-site hydrolytic hydrogen generation issues. CaH 2 /(Al/Si) composites are preferable due to their notable chemical properties. However, these composites require pretreatments, an inert environment, and long hours of physical ball milling for high homogeneity and synergistic effects. CaH 2 also inhibits the hydrolysis reaction by forming its products on the Al/Si surface, which hinders the direct utilization of composites. This work represents the first investigation of NaH-CaH 2 (Al/Si) fuel composites, which greatly overcome these limitations and can be directly used for on-site hydrogen generation and proton exchange membrane (PEM) fuel cells. The NaH-CaH 2 (Al/Si) fuel composites were prepared by using a straightforward mixing method with variable composition ratios, showing high H 2 yield and fuel cell (FC) performance. NaH addition provides the bridge effect, which opens up a new way to enable efficient hydrolysis and greatly enhances the hydrolysis activity of CaH 2 /(Al/Si) composites. The novel fuel composites (NaH-CaH 2 /Al) have extraordinary FC performance and a 0.42 W/cm 2 peak power density greater than commercial hydrogen generators. It provides high H 2 yield 84.4 % for NaH-CaH 2 /Al and 82 % for NaH-CaH 2 /Si compared to NaOH-CaH 2 (Al/Si), NaCl-CaH 2 (Al/Si), and KCl-CaH 2 (Al/Si) composites. The NaH bridge effect hinders the direct water contact and stops the formation of Ca(OH) 2 around Al/Si, which provides adequate pathways for the CaH 2 (Al/Si) hydrolysis. The impressive capabilities of novel fuel composites are anticipated to offer practical uses in fuel cells, automobile applications, and portable/on-board H 2 generation.
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ADVANCED FUNCTIONAL MATERIALS
·
2024
·Vol. 34
·期 21
·2314954
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IF 18.5
Shuixin Xia,Wenxuan Fan,Zhen Hou,Chenrui Li,Zongyan Jiang,Junhe Yang,Jianfeng Mao,Shiyou Zheng
The practical application of sodium (Na) metal anode has been seriously hindered by the uncontrolled Na dendrite growth and severe volume expansion inducing short battery lifespan and safety concerns. Here, highly sodiophilic and ultrafine ZnS-modified carbon fibers have been rationally constructed as a scaffold to obviate these drawbacks. The in situ generated Na 2 S-reinforced fast ion transport interphase and the effective space confinement synergistically facilitate the fast sodium ion interfacial transfer and the homogeneous and dendrite-free Na deposition, thus enabling high-rate and dendrite-free Na metal anode. The modified Na metal demonstrates ultrahigh rate capability (15 mA cm −2 ) and ultralong cycling life (5300 cycles). Moreover, the Na|Na 3 V 2 (PO 4 ) 3 (NVP) cell delivers ultrahigh rate capability (80 C) and extraordinarily ultralong lifespan cycling durability (2980 cycles). The Na|NVP pouch cell also exhibits an extraordinarily ultralong-term cycle life of over 1070 cycles with an extremely low capacity decay rate of 0.0088% per cycle at 10 C. This work provides a facile and efficient strategy to propel the Na metal anode towards practicability.
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JOURNAL OF CHEMICAL AND ENGINEERING DATA
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2024
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IF 2
Jie Li,Huan Zhou,Jie Yang,Cunbing Xu,Sifan Wang,Yifan Li,Jiangbo Chen
The solid–liquid phase equilibria of the Li+, Na+, Ca2+//Cl––H2O quaternary system at 298.15 and 323.15 K are studied via the isothermal solubility phase equilibrium method. The solubility data and liquid properties of density and pH are obtained. The phase diagrams of the quaternary systems, including the water free diagram, the water diagram, and the dry salt diagram, are plotted to show the phase regions, water content, and salting-in effect. NaCl occupies the largest phase region at both 298.15 and 323.15 K. One double salt LiCl·CaCl2·5H2O occurs at 298.15 K and builds up two invariant points; one incommensurate invariant point saturated by (NaCl, LiCl·H2O, LiCl·CaCl2·5H2O) and one commensurate invariant point saturated by (NaCl, CaCl2·4H2O, LiCl·CaCl2·5H2O), but at 323.15 K, no double salt forms. The salting-in effect that happened in ternary systems still occurs in the quaternary Li+, Na+, Ca2+// Cl––H2O system at both temperatures. NaCl saturated concentration increases with LiCl and CaCl2 contents and results in a very high total salt content at commensurate invariant points, e.g., they are 56.92 and 60.62% at 298.15 and 323.15 K, respectively.
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Journal of Materials Chemistry A
·
2024
·
IF 10.7
Xinyu Li,Sheng Dai,Qinlong Chen,Hongyan Mao,Huilin Pan
The air stability of electrode materials is a crucial factor for their practical application in rechargeable batteries. Na4Fe3(PO4)2P2O7 (NFPP) is a cathode material for sodium-ion batteries that has garnered increasing attention for long-life stationary energy storage. However, there is limited understanding regarding the air stability of NFPP. Here, we systematically investigated the chemical and structural stability and degradation mechanism of NFPP upon heating in ambient air. It is revealed that the extraction of Na+, Fe2+, and PO43− ions from NFPP is induced by moisture in ambient air, resulting in the formation of a composite amorphous phase and Na3PO4 small crystalline clusters on the NFPP surface. In addition, we observed a gradual enrichment of crystalline Na3PO4 through X-ray diffraction analysis during prolonged air exposure. The degraded NFPP leads to significantly reduced capacity and enlarged charge and discharge polarization. We demonstrate that optimal re-calcination under an inert atmosphere can effectively restore the mildly deteriorated NFPP material in terms of both structure and electrochemical performance. This research provides valuable insights for practical applications of polyanion cathodes in sodium-ion batteries.
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JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
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IF 9.4
Zi-hui Ma,Tao Yang,Yan Song,Xiao-dong Tian,Zheng-yang Liu,Xiang-jie Gong,Zhan-jun Liu
Hyper cross-linked polymers (HCPs), as a key precursor of hard carbon (HC) anode materials, stand out because of their capacity for molecular-scale structural design and comparatively straightforward preparation techniques, which are not seen in other porous materials synthesized procedure. A novel synthesis method of HCPs is developed in this paper, which is through the incorporation of functional macromolecules , the structural control and heteroatom doping of the product has been achieved, thus augmenting its electrochemical performance in batteries. In this work, carbonized tetraphenylporphyrin zinc (TPP-Zn) doped HCP-based hard carbon (CTHCP) with stable structure was prepared by Friedel-Crafts reaction and carbonization by using naphthalene and trace TPP-Zn as monomers, dimethoxybenzene (DMB) as crosslinking agent and FeCl 3 as catalyst. The introduction of TPP-Zn, a functional macromolecule with unique two-dimensional structure, realized the pore structure regulation and N doping of the raw carbonized HCP-based hard carbon (CHCP). The results showed that CTHCP had higher mesoporous volume, N content and wider layer spacing than CHCP. In addition, CTHCP anode exhibited excellent Li + /Na + storage performance, initial reversible capacity, rate performance and long cycle life. More amount of N -containing (N-5) active sites and mesoporous content in CTHCP anode was the main reason for the improvement of Na + storage effect. While the increased interlayer spacing had a greater effect on the lithium storage capacity. This study uncovered the design rules of HC anode materials suitable for Li + /Na + batteries and provided a new idea for the preparation of high-performance HC anode materials.
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高影响因子
Journal of Materials Chemistry A
·
2025
·
IF 9.5
Wenwen Yin,Jiawei Ma,Yanyan Li,Qing Cheng,Bernt Johannessen,Fangxi Xie,Mingmei Wu
Exploiting bifunctional and highly efficient electrocatalysts that can facilitate the reversible formation and decomposition of discharge products is crucial for rechargeable Na-air batteries (SABs). However, restricted by scaling relations, air cathodes based on single metal systems usually exhibit inferior activity and fail to achieve a stable and long cycle life of Na-air batteries. Dual single-atom catalysts (DACs) with two metal sites can circumvent the scaling relations and endow the single-atom catalysts with superior activity. Herein, we present a hollow carbon microsphere loaded with Ni and Fe single atoms (Ni-HCMs-Fe) as a demonstration of DAC air cathodes for SABs. Notably, Na-air batteries with Ni-HCMs-Fe as an air cathode can achieve a low overpotential gap of 530 mV, a high specific capacity of 5382.9 mAh g−1, and an ultralong cycle life of over 450 cycles (1800 hours) with NaO2 as the main discharge product. Due to the different adsorption energies between oxygenated intermediates and Ni/Fe sites, the Ni-HCMs-Fe catalysts can break through the scaling relations and display optimized binding ability towards intermediates, thus boosting the reversible formation and decomposition of NaO2 in SABs. This work pioneers the use of DACs in SABs, paving the way for their practical applications.
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APPLIED CATALYSIS B-ENVIRONMENTAL
·
2022
·
IF 24.319
Xi-xi Sun,Ruichen Li,Zhiwei Yang,Nan Zhang,Chao Wu,Junhua Li,Yulin Chen,Qiang Chen,Jing Zhang,Hongjian Yan,Xiang Lv,Jiagang Wu
The strategy of modulating polarization rotation of potassium sodium-niobate ((K 0.5 Na 0.5 )NbO 3 , KNN) lead-free piezoelectric materials was reported to boost piezoelectric properties and resultant piezocatalytic activities. The effectiveness of modulating polarization rotation was proved by degrading Rhodamine B (RhB) using three KNN-based samples with different phase structures (i.e., orthorhombic (O) phase, orthorhombic-tetragonal (O-T) coexistence phase, and rhombohedral-orthorhombic-tetragonal (R-O-T) coexistence phase). Poled samples with the R-O-T coexistence phase show a reaction rate constant of 0.091 min −1 owing to the easiest polarization rotation, 2.12 times more than that of poled O-phase featured samples with the most difficult polarization rotation. Enhanced piezocatalytic activities primarily originate from the easier polarization rotation and improved carrier concentration, accompanied by the trace of the mechano-charge generation. Therefore, modulating polarization rotation effectively boosts piezocatalysis of KNN-based materials, promising for harnessing natural energy and disease treatment.
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