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JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS · 2023 ·Vol. 34 ·期 10 ·1-12 · IF 2.8

High-temperature solid-phase synthesis of eulyite-type Ba3Yb(PO4)3 as a single host for narrow-band Tb3+ green emission

Zhao Jiaqi,Hu Chen,Fang Jiapeng,Sun Ruyi,Lu Jingyao,Su Shikun,Lei Zonghao,Fang Pengfei,Feng He,Degao Zhong,Teng Bing

In this work, a series of iso-structural eulyite-type Ba 3 Yb(PO 4 ) 3 :Tb 3+ solid solution phosphors were synthesized via high-temperature solid-phase method. The corresponding unit cell structure, luminescence properties, thermal stability, and chromaticity coordinates of the as-obtained phosphors were systematically investigated. The crystal structure of Ba 3 Yb(PO 4 ) 3 :Tb 3+ was refined by GSAS program, which indicates the oxygen ions in Ba 3 Yb(PO 4 ) 3 are disordered at one C3 site, and the oxygen atoms are distributed at two sites. Under 378 nm ultraviolet excitation, the emission peak of Ba 3 Yb(PO 4 ) 3 :Tb 3+ appears in the range of 450–650 nm, and a characteristic green emission peak appears at 542 nm. Moreover, the luminous intensity of the Ba 3 Yb(PO 4 ) 3 :14 at.% Tb 3+ sample at 160 °C is 87.7% at room temperature, and the quantum yield is 55.8%, which reveals good thermal stability. Our results suggest that the Ba 3 Yb(PO 4 ) 3 :Tb 3+ phosphors are promising high-efficiency green light conversion materials for UV-LED applications.

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ELECTROCHIMICA ACTA · 2023 · IF 6.6

Three-dimensional porous Na4MnV(PO4)3 constructed by Aspergillus niger biological template as a high performance cathode for sodium ion batteries

Jiepeng Chen,Yun Huang,Jiapin liu,Chengwei Li,He Zheng,Xi Xu,Lei Fu,Xing Li,Mingshan Wang,Yuanhua Lin,Haijun Cao

The sodium super ion conductor (NASICON) structure materials have attracted extensive attention because of its open three-dimensional crystal network framework and fast sodium ion migration rate. However, the poor electronic conductivity due to the presence of phosphate groups and the consequent high cost have been a barrier to commercialization. In this work, Na 4 MnV(PO 4 ) 3 (NMVP) with three-dimensional porous structure is synthesized in situ using Aspergillus niger as a biological template (noted as NMVP/ANDC). The cell wall of Aspergillus niger is rich in hydroxyl groups , which can adsorb metal ions well, so that NMVP particles can be synthesized on Aspergillus niger without stacking and agglomeration. NMVP grows along Aspergillus niger mycelium has a spongy-like three-dimensional porous network structure, which helps the contact between active materials and electrolyte, reduces the migration distance of sodium ions, and improves the conductivity of active materials. Therefore, NMVP/ANDC has good rate performance and cycle stability. It can provide 109 mAh g −1 at 0.5 C and 79.6% capacity retention after 3000 cycles at 5 C. The biological template method is proposed in this paper opens up a simple way for the preparation of other three-dimensional porous network structural materials.

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APPLIED SURFACE SCIENCE · 2023 · IF 6.7

Stable cycling performance of lituium-doping Na3−xLixV2(PO4)3/C (0 ≤ x ≤ 0.4) cathode materials by Na-site manipulation strategy

Jun Cong,Shao-hua Luo,Peng-yu Li,Xin Yan,Li-xiong Qian,Sheng-xue Yan

Na 3 V 2 (PO 4 ) 3 (NVP) has become a hot material in the research field of sodium-ion batteries (SIBs) as a result of its unique structural advantages. Unfortunately, the poor electronic conductivity and ion diffusion ability fundamentally limit the practical development of NVP. Considering the above defects, a series of Li + doped Na 3−x Li x V 2 (PO 4 ) 3 /C cathode materials for SIBs are synthesized through hydrothermal assisted sol–gel method. The cell volume steadily decline with the raise of Li + doping amount, which is consistent with the usual doping effect. Moreover, with the increase of lithium doping amount, Li + preferentially occupies Na (2) site and then occupies Na (1) site. Through the first principles calculation, it is clear that the introduction of Li + can significantly reinforce the conductivity of the material system and diminish the electron localization phenomenon. The analysis of (1   1   6) crystal plane by TEM shows that Li doping will reduce the interplanar spacing. The change of V valence during the charge–discharge process of Na 2.8 Li 0.2 V 2 (PO 4 ) 3 /C is consistent with that of NVP by V element XANES characterization. There is no conventional phase transition phenomenon in the ex-situ XRD high-voltage charging state. The above facts indicate that lithium doping obtains a stable solid solution NVP. The electrochemical test results show that Na 2.8 Li 0.2 V 2 (PO 4 ) 3 /C can provide an amazing reversible capacity of 116.9 mAh/g (theoretical capacity of 117 mAh/g) and capacity retention rate of 99.82 % after 500 cycles. GITT results show that Li + can significantly increase the Na + diffusion coefficient of the material. Such excellent electrochemical performance is attributed to the fact that the doping of Li + activates the activity of Na + in Na (2) site and improves the reaction efficiency.

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Journal of Materials Chemistry A · 2012 ·Vol. 1 ·期 7 ·2508-2514 · IF 0

A carbon-coated Li3V2(PO4)3 cathode material with an enhanced high-rate capability and long lifespan for lithium-ion batteries

Jing Su,Xing-Long Wu,Jong-Sook Lee,Jaekook Kim,Yu-Guo Guo

A facile sol–gel approach combined with a carbon-coating technique via high-temperature thermally decomposing C2H2 has been developed for the synthesis of a Li3V2(PO4)3/C (LVP/C) cathode material employing the biomass of phytic acid as an eco-friendly phosphorus source. The effects of the carbon-coating on the structural, morphological and electrochemical properties of LVP have been investigated. Compared with pristine LVP, the LVP/C composite presents a higher discharge capacity of 127 mA h g−1 at 0.1 C, better rate capability and long-term cyclability in the voltage range of 3.0–4.3 V. Even at a high charge–discharge rate of 5 C, it can still deliver a reversible capacity of 107 mA h g−1 over 400 cycles without obvious fading, demonstrating great potential as a superior cathode material for lithium-ion batteries.

CAS / MDL: 83-86-3
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ELECTROCHIMICA ACTA · 2024 · IF 5.5

Novel NASICON-type Mn0.5Ti2(PO4)3@F-doped carbon composite with high electrochemical performance as anode materials for potassium-ion batteries

Shaoxiong Liu,Jing Dai,Xuexue Li,Jianjun Xia,Mingyang Xie,Zhifeng Huang,Li Liu

Mn 0.5 Ti 2 (PO 4 ) 3 with a NASICON structural is used as an anode material in potassium-ion batteries due to its abundance of vacancies that can hold potassium ions . This characteristic not only contributes to its excellent stability but also results in a high specific capacity. However, the poor electrical conductivity of the polyanionic type structure limits the material's ability to fully utilize its capacity. In this paper, the conductivity and electrochemical stability of the Mn 0.5 Ti 2 (PO 4 ) 3 anode material are enhanced through composite formation with an F-doped carbon layer. The introduction of F into the carbon matrix creates a large number of vacancy defects and F active sites. The vacancies enhance the transport of potassium ions on the Mn 0.5 Ti 2 (PO 4 ) 3 material's surface, while the active sites exhibit strong electronegativity , improving the absorption of potassium ions. Therefore, the diffusion impedance of potassium ions is significantly reduced, leading to an increased diffusion rate of potassium ions. Attributing to the improved reaction kinetics, the Mn 0.5 Ti 2 (PO 4 ) 3 @F-doped carbon composite demonstrates a high specific capacity of 86 mA h g −1 at 10,000 mA g −1 when used as the anode for potassium-ion batteries. Even more, the specific capacity remains a capacity of 136 mA g −1 after 3000 cycles at 1000 mA h g −1 . This study enhances our comprehension of material design by investigating the alteration of carbon matrix to promote the electrochemical characteristics of materials.

CAS / MDL: 24937-79-9
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CERAMICS INTERNATIONAL · 2018 · IF 3.057

Influence of LiBO2 addition on the microstructure and lithium-ion conductivity of Li1+xAlxTi2−x(PO4)3(x = 0.3) ceramic electrolyte

Hainan Bai,Jiulin Hu,Xiaoguang Li,Yusen Duan,Feng Shao,Takahiro Kozawa,Makio Naito,Jingxian Zhang

Concerning the safety problems of conventional Li-ion batteries with liquid electrolytes, it is crucial to develop reliable solid-state electrolytes with high ionic conductivity . Li 1+x Al x Ti 2−x (PO 4 ) 3 (LATP, x = 0.3) is regarded as one of the most promising solid electrolytes due to its high ionic conductivity and excellent chemical stability to humidity. Herein, a new strategy is proposed for improving the sintering behavior and enhancing the ionic conductivity of LATP by using LiBO 2 as the sintering aid via liquid phase sintering . The as-prepared sample LATP with homogeneous microstructure and high relative density of 97.1% was successfully synthesized, yielding high total ionic conductivity of 3.5 × 10 −4   S   cm −1 and low activation energy of 0.39   eV at room temperature. It was found that the addition of LiBO 2 could effectively enhance the densification and increase the ionic conductivity of LATP electrolyte, proving an effective way to synthesis LATP ceramics by a simple and reliable route.

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ACS Applied Materials & Interfaces · 2024 · IF 8.3

Cation/Anion Doping Strategy for Na4MnV(PO4)3 with High Energy Density and Long Cycling Life through Construction by Aspergillus niger

Xudong Wang,Jiepeng Chen,Yun Huang,Jiapin Liu,Lei Fu,Li Liu,Wenping Zeng,Jie Xiao,Xiaoyan Zhang,Xing Li,Mingshan Wang,Yuanhua Lin,Haijun Cao

Na4MnV(PO4)3 (NMVP) has gained attention for its high redox potential, good cycling stability, and competitive price but suffers from poor intrinsic electronic conductivity and Jahn–Teller effect from Mn3+. In this work, cation/anion doping strategy was used for Aspergillus niger-bioderived carbon-coated NMVP (NMVP/AN) to improve the structural stability and electrochemical performance, where Al3+ doping inhibited the dissolution of Mn and enhanced the Mn3+/Mn2+ redox pair activity; besides, F– doping not only weakens the Na2–O bond but also endows the hierarchical and porous structure of NMVP/AN, which led to a more rapid and fluid transfer of Na+. The elaborately designed Na3.9Mn0.9Al0.1V(PO4)3/AN (NMAVP/AN) exhibits 105.9 mA h g–1 at 0.5 C, and the as-prepared Na3.1MnV(PO3.7F0.3)3/AN (NMVPF/AN) delivers 104.1 mA h g–1 at 5 C. Further demonstration of the hard carbon//NMAVP/AN full cell manifests the good potential of Al3+-doped NMVP/AN for practical applications (100.6 mA h g–1 at 1 C). These findings open up the possibility of unlocking the high-performance Na superionic conductor (NASICON).

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RARE METALS · 2025 · IF 11

A Micro-Nano Flower-Like Na3V2(PO4)3@C Constructed by Polar-Driven H-Bond Engineering Toward High-Rate Sodium Storage

Xiaolei Wu,Ren Huang,Yibing Zhang,Peng Lv,Suhua Chen,Ying Bai

en The polyanionic compound Na 3 V 2 (PO 4 ) 3 (NVP) has emerged as a competitive cathode material for sodium-ion batteries (SIBs), owing to its high-voltage redox activity (3.4 V vs. the Na + /Na reference couple) and NASICON-type framework that enables superior ionic conductivity. However, the electrochemical performance of NVP is hampered by low intrinsic electronic conductivity, particularly under ultra-fast charging and long-term cycling conditions. Herein, a hierarchical micro-nano flower-like Na 3 V 2 (PO 4 ) 3 with a carbon-coating layer (HF-NVP@C) is synthesized by a facile n-propanol-assisted precipitation method. Theoretical analysis and experimental tests reveal that the polar-driven hydrogen bond engineering, manifested in the distinct molecular interaction between n-propanol and ultrapure water (characterized by a shorter O-H bond length of 1.859 Å and higher binding energy of −0.312 eV compared to methanol and ethanol counterparts), underpins the formation of the unique hierarchical micro-nano flower-like architecture. This hierarchical architecture creates an expanded interfacial area, enhances ionic transport pathways, and increases electrochemically active sites. Furthermore, a glucose-derived carbon coating (∼2 nm in thickness) uniformly adheres to the NVP surface, effectively enhancing its electronic conductivity. Thus, the constructed HF-NVP@C exhibits superior rate capability (68.1 mAh g −1 at 150C) and long-term cycling stability (58.7% capacity retention after 5000 cycles at 1C). This work proposes a viable strategy for designing high-performance polyanionic cathodes using hydrogen bond engineering. 摘要 zh 聚阴离子化合物Na 3 V 2 (PO 4 ) 3 @C(NVP)因其具有高电压氧化还原活性(相对于Na + /Na参比电对为3.4 V)以及能实现优异离子电导率的NASICON型骨架结构,已成为一种具有竞争力的钠离子电池(SIBs)正极材料。然而,由于NVP的本征电子电导率较低,导致其在超快充电和长期循环条件下的电化学性能较差。在本文中,通过一种简便的正丙醇辅助沉淀法合成了具有碳包覆层的分级微-纳花状Na 3 V 2 (PO 4 ) 3 @C(HF-NVP@C)。理论分析和实验测试表明,极性驱动的氢键工程体现在正丙醇与超纯水之间独特的分子相互作用上(其O-H键长为1.859 Å,比甲醇和乙醇对应的键长更短,结合能更高-0.312 eV),是形成这种独特分级微-纳花状结构的基础。这种分级结构扩大了活性材料的面积,增强其离子传输通道,并增加电化学活性位点。此外,葡萄糖衍生的碳涂层(约2 nm厚)均匀地附着在NVP表面,有效提高其电子电导率。因此,构建的HF-NVP@C展现出优异的倍率性能(150C下为68.1 mAh g -1 )和长期循环稳定性(1C下循环5000次后容量保持率为58.7%)。这项工作证明氢键工程设计高性能聚阴离子正极材料策略的可行,同时也为开发高性能钠离子电池正极材料提供了研究基础。

CAS / MDL: 1333-86-4
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JOURNAL OF POWER SOURCES · 2022 · IF 9.794

Superior high-rate and cycle performances of a single-phase ferrous orthophosphate Na1.2Fe4(PO4)3 anode material for lithium-ion batteries

Yilin Ge,Yushan Li,Feng Wang,Xiaoqin Tan,Peng Liu,Dianhui Wang,Wentong Zhou,Qingrong Yao,M.-Sadeeq Balogun (Jie Tang),Dan Huang,Jianqiu Deng

The development of low-cost and eco-friendly electrode materials is crucial for the next-generation rechargeable lithium-ion batteries (LIBs). Herein, the single-phase Na 1.2 Fe 4 (PO 4 ) 3 (NFP) with a monoclinic NaCo 4 (PO 4 ) 3 -type structure is demonstrated to be a suitable anode material for LIBs. The NFP anode exhibits superior high-rate performance, releasing an initial charge capacity of 128.6 mAh g −1 at 10C and a high-capacity retention rate of 86.7% over 1500 cycles. The prominent rate performance and cycling stability of the NFP anode are attributed to the stable single-phase crystal structure and fast Li-ion diffusion verified by galvanostatic intermittent titration technique (GITT). Furthermore, the structure evolution and Li-ion diffusion pathway of the NFP anode are clarified by ex-situ X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and first-principles calculations.

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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2024 · IF 9.4

Construction of SnO2 buffer layer and analysis of its interface modification for Li and Li1.5Al0.5Ge1.5(PO4)3 in solid-state batteries

Jinhong Song,Chen Zhang,Zejian Zheng,Shizhe Huo,Yihan Lin,Fei Yang,Lei Liu

SnO 2 layer between Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) and lithium anode was prepared through simple scratch-coating process to improve interface properties. The physical phase, morphology, and electrochemical properties of Li/SnO 2 /LAGP structure were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and electrochemical analytical methods. It was found that SnO 2 layer effectively improved the interface stability of LAGP and lithium anode. The prepared Li/SnO 2 /LAGP/SnO 2 /Li symmetric cell exhibited a large critical current density of 1.8 mA cm −2 and demonstrated excellent cycling characteristics. The polarization voltages of symmetric cell were 0.1 V and 0.8 V after 1000 h of cycling at current densities of 0.04 mA cm −2 and 0.5 mA cm −2 , respectively. Li/SnO 2 @LAGP/LiFePO 4 solid-state full cells were also assembled, exhibiting a discharge specific capacity of 150 mAh g −1 after 200 cycles at 0.1C with capacity retention rate of 96 %. The good interface properties of Li/SnO 2 /LAGP structure are attributed to the transformation of SnO 2 layer into a buffer layer containing Li 2 O, Sn 0 , and Li x Sn y alloy during cycling process, which effectively inhibits the reduction reaction between LAGP and lithium anode.

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MATERIALS CHEMISTRY AND PHYSICS · 2024 · IF 4.3

NASICON-structure Na3+xMnVxTi1-x(PO4)3/C cathode for sodium-ion battery with excellent cycling performance and high specific capacity

Mingxuan Zong,Yanjiang Zhang,Jianquan Liang,Xinghai Li,Qi Qi,Kangyi Chen,Li Zhao,Changsong Dai

The recently discovered Na 3 MnTi(PO 4 ) 3 cathode material has an extremely high theoretical capacity, but its poor cycling performance makes it challenging to apply. In this work, a series of NASICON-type Na 3+x MnV x Ti 1-x (PO 4 ) 3 /C (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.8, 1) cathode materials were prepared by sol-gel method for sodium-ion batteries. X-ray diffraction (XRD) indicates that vanadium doping has increased the cell spacing within the material and the cell volume. From the results of X-ray photoelectron spectroscopy (XPS) and Energy dispersive X-ray spectroscopy (EDS) mapping images, it is shown that vanadium has been successfully doped into the material. Among them, the Na 3·3 MnV 0·3 Ti 0·7 (PO 4 ) 3 /C delivers an outstanding specific capacity (121.7 mAh g −1 at 0.1C, C = 135 mA g −1 ) and Na 3·4 MnV 0·4 Ti 0·6 (PO 4 ) 3 /C shows an excellent capacity retention (80.88 % after 1500 cycles at 1C). Notably, the coulombic efficiency of both materials during cycling is close to 100 %, indicating that these materials have great practical application value.

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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2025 · IF 9.7

High-entropy doping for high-performance Na3V2(PO4)3@C cathode materials in sodium-ion and hybrid lithium/sodium-ion batteries

Beibei Ma,Yawen Liang,Xiaokai Ma,Wenjie Wang,Chengcheng Miao,Guanqi Yu,Qizhao Wang,Chunyang Xu,Xinwei Cui

The rising demand for cost-effective and safe energy storage systems has ignited strong global interest in advanced cathodes that surpass lithium-ion batteries in practical applications. Herein, we propose a composite material in which five ions, Ti 4+ , Mn 2+ , Fe 2+ , Zr 4+ , and Mo 6+ , are doped into the lattice of Na 3 V 2 (PO 4 ) 3 and a uniform carbon-coating layer is applied to its surface, resulting in the formation of high-entropy doped Na 3 V 2 (PO 4 ) 3 @C materials (HENVP@C). When employed as the cathode material for Sodium-ion batteries (SIBs) and hybrid lithium/sodium-ion batteries (HLSIBs), HENVP@C shows remarkable Li + /Na + storage capabilities. The results of electrochemical performance tests on half-cells reveal that HENVP@C exhibits a high capacity, along with excellent cycle life and stability. High-entropy doping effectively stabilizes the NASICON structure of HENVP@C, enhances ionic conductivity, and optimizes ion diffusion kinetics, particularly improving its dual-ion pseudocapacitive storage capability. In addition, the surface carbon coating improves the electronic conductivity of the material. The insights presented in this work provide new ideas for designing cathode materials for SIBs and HLSIBs.

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