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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2025 · IF 9.7

Multiple redox Centers and defect engineering in Fe/Mo dual-doped Na3V2(PO4)3 cathodes for high-performance sodium-ion batteries

Min Xie,Xiaoying Li,Yufan Chen,Xiangyue Liao,Qiaoji Zheng,Heng Zhang,Kwok-Ho Lam,Dunmin Lin

Sodium superionic conductor (NASICON)-type phosphates cathodes have attracted considerable attention due to their high operational voltage and robust three-dimensional (3D) framework; however, the poor intrinsic electronic conductivity and low energy density hinder their broader application. Herein, a novel NASICON-type Na 3 V 1.44 Fe 0.5 Mo 0.06 (PO 4 ) 3 cathode was designed through Fe/Mo dual-doping at the V sites of Na 3 V 2 (PO 4 ) 3 and synthesized via a conventional high-temperature solid-state method. The introduction of Fe 3+ activates the V 4+ /V 5+ redox couple at a high voltage plateau (∼ 4.0 V), while also generates additional Fe 2+ /Fe 3+ and V 4+ /V 5+ redox pairs. Meanwhile, the doing of Mo 6+ creates cation vacancies, effectively modulating the electronic structure of vanadium and promoting ionic transport kinetics. Benefiting from this dual-doping strategy, the Na 3 V 1.44 Fe 0.5 Mo 0.06 (PO 4 ) 3 cathode delivers a high capacity of 123.4 mAh g −1 at 0.2C and an impressive energy density of 406 Wh kg −1 within 2.2–4.2 V. Moreover, it exhibits outstanding cycling stability, presenting a capacity retention of 92 % after 2500 cycles at 30C. This work highlights a viable strategy for advancing high-performance NASICON-type cathodes through complex metal ion doping.

CAS / MDL: 1313-27-5 7803-55-6
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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 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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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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PROGRESS IN SOLID STATE CHEMISTRY · 2026 · IF 9.7

Synergistic boosting of luminescence intensity in Sr3Lu(PO4)3:Cr3+ via B-site substitution and energy transfer toward multifunctional near-infrared applications

Chao Wei,Jingyu Ran,Jie Zhang

The wideband near-infrared (NIR) phosphors for next-generation intelligent NIR light sources are becoming a research hotspot in the field of luminescent materials due to their potential applications in optical sensing, biological imaging, and smart lighting. This study reports a Cr 3+ -activated A 3 B(PO 4 ) 3 -type (Sr 3 Lu(PO 4 ) 3 ), abbreviated as SLP) near-infrared phosphor. Under 466 nm blue light excitation, SLP:Cr 3+ phosphor exhibits a broad near-infrared emission from 700 to 1200 nm with a peak wavelength at 860 nm, a full width at half maximum (FWHM) of 141 nm, and an initial quantum yield of 31.48%. Structural and spectroscopic characterization confirms that Cr 3+ preferentially occupies the octahedral coordination sites of Lu 3+ in the matrix, forming a weak crystal field environment that favors the spin-allowed 4 T 2 → 4 A 2 transition of Cr 3+ , leading to broad near-infrared emission. Additionally, by substituting Y 3+ for the B-site (Lu 3+ site), the luminescent intensity of the material is significantly enhanced, and the quantum yield is increased to 81.53%. Furthermore, the introduction of Yb 3+ constructs a Cr 3+ →Yb 3+ energy transfer system, further optimizing the luminescent performance. Although the phosphor exhibits severe thermal quenching, the packaged near-infrared phosphor-converted light-emitting diodes (NIR pc-LEDs) maintain a low surface temperature of 59.5 °C at 500 mA, ensuring reliable operation. The phosphor also exhibits excellent temperature sensitivity (max relative sensitivity: 3.33%·K −1 ) for fluorescence thermometry. Practical applications including invisible QR code encryption, night vision, biological imaging, and long-distance illumination are demonstrated, showcasing the versatility of the developed NIR pc-LED. This work provides a high-performance NIR phosphor candidate for multi-functional smart light sources.

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Journal of Energy Storage · 2023 · IF 9.4

Insight into the mechanism of Li ion diffusion in fluorine-doped Li1.3Al0.3Ti1.7(PO4)3 as an electrolyte for solid lithium metal batteries

Fusheng Yin,Zhijun Zhang,Yuling Fang,Chunwen Sun

NASICON structured Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP) has attracted widespread attention due to its simple preparation and excellent stability towards water and air. However, there are many problems such as high interfacial resistance between electrolyte and electrodes as well as low ionic conductivity of LATP. In this paper, the effect of F doping on Li ion diffusion channel in electrolyte was investigated in detail by density functional theory (DFT) calculation. The results show that F doping can effectively reduce the formation energy of Li vacancy. Meanwhile, it can also reduce the diffusion energy barrier and induce the high-energy Li ions at 36f site to carry out synergistic diffusion via various ways at the same time. Then, the F-doped LATP electrolyte was prepared successfully. Its ionic conductivity is as high as 0.358 mS cm −1 at room temperature . At the same time, the solid-state lithium metal batteries with F-doped LATP electrolyte shows a high capacity of 136.2 mA h g −1 at 0.5C and excellent cyclability for 200 cycles. These results demonstrate that F doping may be an effective way to improve the performance of LATP electrolyte.

研究领域: 材料科学 · 电化学 · 储能技术 · 固态电池 · 计算材料科学
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Journal of Materials Chemistry C · 2021 ·Vol. 10 ·期 3 ·994-1002 · IF 7.393

Spectrally tunable and thermally stable near-infrared luminescence in Na3Sc2(PO4)3:Cr3+ phosphors by Ga3+ co-doping for light-emitting diodes

Shihai Miao,Yanjie Liang,Yan Zhang,Dongxun Chen,Shao Yan,Jingwei Liu,Xiao-Jun Wang

Near-infrared (NIR) phosphor-converted light-emitting diodes (LEDs) are becoming an efficient and promising solution for high-power NIR light sources, which have shown a broad range of possible applications in the fields of agriculture, food analysis and biomedical diagnostics. However, there is a long-standing challenge to develop tunable and thermally stable NIR-emitting phosphors as luminescence converters in the design of low-cost, compact and high-efficiency NIR LEDs. Here, we report a tunable broadband NIR photoluminescence in Na3Sc2(PO4)3:Cr3+ phosphors via Ga3+ co-doping and explore their application in NIR LEDs. With the fine-tuning of the doping concentration of Ga3+ ions from 0 to 6%, the NIR luminescence of the obtained phosphor can be tuned from sharp line emission at 694 nm (2E → 4A2 transition of Cr3+) to broadband emission centered at 750 nm (4T2 → 4A2 transition of Cr3+) upon blue light excitation. In the meanwhile, the NIR emission intensity at 100 °C and 150 °C can retain ∼100% and ∼84% of the initial value at room temperature when the Ga3+ content is determined to be 6%, leading to thermally stable broadband NIR emission in the as-synthesized Na3Sc2(PO4)3:Cr3+,Ga3+ phosphors. The NIR LEDs constructed by combining the commercial blue LED chips with the optimized NIR phosphors can generate broadband emission in the wavelength range of 600–1000 nm and deliver ∼4 mW of NIR output power with a power conversion efficiency of 2.6% at a drive current of 60 mA. The potential of the fabricated NIR LEDs as a lighting source for night vision and vein imaging is also demonstrated. The outcomes here highlight promising potential for Na3Sc2(PO4)3:Cr3+,Ga3+ as phosphor-downconverted light emitters in the design of high-power NIR LED devices for practical applications.

研究领域: 材料科学 · 光学材料 · 固态照明 · 光子学 · 半导体器件
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CHEMICAL ENGINEERING JOURNAL · 2019 · IF 8.355

Insights into the Mg storage property and mechanism based on the honeycomb-like structured Na3V2(PO4)3/C/G in anhydrous electrolyte

Jing Zeng,Dongzheng Wu,Xin Wang,Junnan Wu,Jiyang Li,Jing Wang,Jinbao Zhao

The high-voltage cathode material based on the sodium super ionic conductor (NASICON) structured Na 3 V 2 (PO 4 ) 3 (NVP) has been found to be a potential candidate for Mg storage. In this work, to improve its electrochemical performance, we construct honeycomb-like structured NVP/C/G with faster electronic and ionic transport by a convenient and universal spray-drying method for the first time. After electrochemically desodiating two Na from the NVP/C/G (ED-NVP/C/G), the ED-NVP/C/G is tested in highly anhydrous Mg electrolyte, and the insights into its Mg storage property and mechanism are carefully studied. An initial capacity of 87 mAh g −1 with a relatively high average discharge voltage of 2.47 V vs. Mg 2+ /Mg is obtained at 0.1 C. The X-ray diffraction (XRD) results show that the inserted Mg 2+ ions tend to occupy the Na2 (at 18e sites) vacant sites. The investigation of kinetic process by galvanostatic intermittent titration technique (GITT) reveals that the Mg diffusion kinetics is faster during the demagnesiation process. The electrochemical reaction bases on two-phase transition mechanism, and the R ct value shows a positive relationship to the formation of NaV 2 (PO 4 ) 3 phase. Finally, a Mg full cell prototype based on the ED-NVP/C/G cathode with Mg metal anode is built. The rational structure design of NVP/C/G improves the electrochemical performance for Mg storage, and our work also gives new understanding into the Mg storage mechanism in the ED-NVP/C/G structure.

研究领域: 材料科学 · 电化学 · 能源存储 · 无机化学 · 固态离子学
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ACS Applied Energy Materials · 2025 · IF 5.5

Enhanced High-Rate Capability of Aqueous Lithium Batteries with Multiple Effects of N-Doped Carbon Coating on the LiTi2(PO4)3 Interface

Liwei Liu,Yutong Wang,Chunmeng Zhang,Shaochen Wang,Guoyong Huang

LiTi2(PO4)3 (LTP) is widely recognized as a promising anode material for aqueous lithium-ion batteries due to its stable three-dimensional framework structure and working potential within the aqueous electrolyte potential window. However, the low conductivity of pure-phase LTP poses a significant challenge that must be overcome for its practical application. In this work, N-doped carbon-coated LTP (NC@LTP) composites with a layered flower-like morphology were synthesized via an organic precipitation method. The N-doped carbon layer improved the conductivity and hydrophilicity of the anode and caused carbon defects that facilitated Li+ transport. The initial specific capacity at 10 C was enhanced from 39.4 to 81.5 mAh g–1 after N-doping. The pouch cells retained 92.7% of their capacity after 150 cycles at 1 C and demonstrated excellent safety in abuse tests. In addition, the modification mechanism of the N-doped carbon layer was verified through DFT calculations. This study provides references and ideas for the modification of high-performance aqueous lithium-ion battery electrode materials.

CAS / MDL: 57-13-6
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RARE METALS · 2023 ·Vol. 42 ·期 10 ·3387-3398 · IF 8.8

Flexible and free-standing La0.33Ti2(PO4)3/C nanofibers film as a novel high-performance anode for sodium- and potassium-ion batteries

Dai Jing,Jing Jian,Yang Jian-Ping,Zhang Wen,Liu Shao-Xiong,Wang Qian-Fu,Wen Jia-Xing,Hu Hai,Li Hui-Fang,Liu Li

Na superionic conductor (NASICON)-type La 0.33 Ti 2 (PO 4 ) 3 (LaTP) is firstly proposed as sodium/potassium storage materials. The density functional theory (DFT) calculations show that LaTP has good electronic character and low Na + /K + migration barriers. The flexible La 0.33 Ti 2 (PO 4 ) 3 /C nanofiber film is synthesized via electrostatic spinning and investigated as free-standing electrode applied to sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs) in this work. The low band gap and Na + /K + migration barriers of LaTP, unique morphology, and complete conductive carbon net allow the La 0.33 Ti 2 (PO 4 ) 3 /C nanofibers film to deliver high capacity (296.3 mAh·g −1 for SIBs and 235.8 mAh·g −1 for PIBs), excellent rate performance (142.5 mAh·g −1 for SIBs and 50.5 mAh·g −1 for PIBs at 1.00 A·g −1 ), and superior cyclability above 1000 cycles. The full-cell tests show that the material has a good application prospect, indicating a promising flexible anode material for SIBs and PIBs. Graphical abstract

CAS / MDL: 128-69-8
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Journal of Energy Storage · 2023 · IF 9.4

Towards enhanced structural stability by investigation of the mechanism of K ion doping in Na3V2(PO4)3/C for sodium ion batteries

Jun Cong,Shao-hua Luo,Peng-yu Li,Kun Li,Peng-wei Li,Sheng-xue Yan

Na 3 V 2 (PO 4 ) 3 is particularly suitable as cathode materials for sodium ion batteries (SIBs). Its NASICON structure is not only conducive to the rapid migration of Na + , but also has less volume deformation during Na + deintercalation, and the main frame mechanism remains unchanged. However, owing to its own structure, the electronic conductivity is limited, which limits its practical application. Here, on the basis of carbon coating to enhance the electronic conductivity, the effect of sodium site doping of K + on the structure and properties of Na 3 V 2 (PO 4 ) 3 /C is deeply explored by comparing series Na 3-x K x V 2 (PO 4 ) 3 /C (x = 0, 0.05, 0.1, 0.15, 0.2). The initial discharge capacity of Na 2.9 K 0.1 V 2 (PO 4 ) 3 /C is 107.7 mAh·g −1 in the potential range of 2.5–3.8 V at 0.2C, and the capacity remains 95 % after 300 cycles. The excellent performance of Na 2.9 K 0.1 V 2 (PO 4 ) 3 /C benefits from the large radius of K + as functional support ions, which lightly relieves the deformation pressure of Na + during the deintercalation process, thereby stabilizing the crystal structure. Moreover, the doping of K + plays a critical role in improving the diffusion coefficient of Na + . Density functional theory (DFT) calculations demonstrate that the Na-site doping of K + can enhance the electronic conductivity of the material, which in turn brings excellent electrochemical performance. Prime novelty statement • On the basis of carbon coating, Na 2.9 K 0.1 V 2 (PO 4 ) 3 /C cathode materials with excellent electrochemical performance are obtained by doping K at theNa-site. • The effect of Na-site doping of K + on the structure and properties of Na 3 V 2 (PO 4 ) 3 /C is deeply explored by comparing series Na 3-x K x V 2 (PO 4 ) 3 /C (x = 0, 0.05, 0.1, 0.15, 0.2). • The mechanism of excellent electrochemical performance and structural stability caused by Na-site doping of K + is revealed theoretically by DFT calculation.

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JOURNAL OF ALLOYS AND COMPOUNDS · 2020 · IF 4.65

Dual-color upconversion photoluminescence induced by disordered Yb3+-Ti4+ pairs and defects in highly stable langbeinite-type Rb2Ti0.80Yb1.20(PO4)3 single crystal

Ziqing Li,Pengfei Zhu,Jimin Ding,Yang Chen,Zhenyan Wang,Nianjing Ji,Xiulan Duan,Huaidong Jiang

Inorganic upconversion materials show significant importance in both basic research and applied area, and searching for suitable host material and understanding of fundamental photophysical process are particularly worth studying in upconversion application. Herein, a heavily Yb 3+ -substituted langbeinite-type Rb 2 Ti 0.80 Yb 1.20 (PO 4 ) 3 (RTYP) millimeter-sized single crystal, which has been successfully grown by high temperature solution method, exhibits efficient dual-color upconversion photoluminescence under 980 nm excitation. The lifetimes of two-photon blue emission and one-photon red emission are 4.1 μs and 17.1 μs, respectively. X-ray structural analyses reveal that the dual-color emissions are ascribed to disordered Yb 3+ -Ti 4+ pairs and crystal defect, and the higher intensity of red emission is attributed to Yb 3+ -defect energy transfer activated by Ti 4+ . Notably, the blue emission originates from cooperative luminescence of Yb 3+ dimer, and the red emission originates dominantly from the cooperative sensitization of the intrinsic defect caused by excited Yb 3+ dimer. Moreover, RTYP with disordered structure shows high thermal stability up to 1,150 °C. This work not only demonstrates the promising potential of langbeinite-type materials in multicolor upconversion application, but also sheds light on the photophysical process associated with disordered crystal structure.

CAS / MDL: 1314-37-0 1314-61-0
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