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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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CERAMICS INTERNATIONAL · 2024 · IF 5.1

Transition mechanism and thermokinetic analysis of Sr0.5Zr2(PO4)3–Ce0.5Sm0.5PO4 composite ceramics for nuclear waste forms based on in-situ synthesis

Kunqi Liu,Junxia Wang,Jin Wang,Die Liu,Youqin Huang,Zhenjin Fu,Xi Zhang

In this study, the novelly designed Sr 0.5 Zr 2 (PO 4 ) 3 –Ce 0.5 Sm 0.5 PO 4 composite ceramics were utilized as nuclear waste form to simultaneously immobilize simulated fission products Sr and actinide nuclides. The phase transition mechanism, thermokinetics and densification behavior of Sr 0.5 Zr 2 (PO 4 ) 3 –Ce 0.5 Sm 0.5 PO 4 composite ceramics based on in-situ synthesis were systemically analyzed by XRD, in-situ XPS, TG-DSC, SEM and density measurements. The results demonstrate that the formation of Ce 0.5 Sm 0.5 PO 4 solid solution phase preceded that of Sr 0.5 Zr 2 (PO 4 ) 3 phase, of which there is a valence change of Ce from Ce 4+ to Ce 3+ before 1023 K. Additionally, as for the exothermic crystallization enthalpy, change of exothermic crystallization enthalpy and activation energy, the values of Sr 0.5 Zr 2 (PO 4 ) 3 and Ce 0.5 Sm 0.5 PO 4 phases in composite ceramics are 286.17 – 515.61 mJ, 19.11 – 35.38 J/g, 702.45 kJ/mol and 145.21 – 232.44 mJ, 9.26 – 15.44 J/g, 450.04 kJ/mol, respectively. It is then indicated that the formation of Ce 0.5 Sm 0.5 PO 4 phase is definitely more favorable than that of Sr 0.5 Zr 2 (PO 4 ) 3 phase. Simultaneously, the relative densities of Sr 0.5 Zr 2 (PO 4 ) 3 –Ce 0.5 Sm 0.5 PO 4 composite ceramics are more than 95 % when the sintering temperature exceeds 1273 K.

CAS / MDL: 1306-38-3
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Advanced Composites and Hybrid Materials · 2025 ·Vol. 8 ·期 4 ·286 · IF 21.8

Optimizing the electrochemical performance of LiCoO2 at 4.5 V via synergistic modification of Mg2+ ion doping and Li1.3La0.3Ti1.7(PO4)3 coating

Mao Gaoqiang,Lu Jingfan,Cai Haiyan,Yu Wanjing,Tong Hui,Guo Xueyi,Zeng Leiying,Jiang Long

Increasing the operating voltage can significantly increase the energy density of LiCoO 2 , but it is accompanied by severe structural damage and interface degradation. Especially at a high voltage above 4.5 V, LiCoO 2 faces severe challenges, such as irreversible phase transition, lattice oxygen loss, and electrode–electrolyte interface evolution. Herein, a high-voltage LiCoO 2 cathode material with bulk doping and surface coating synergistic modification was designed and prepared. The doped Mg 2+ ions entered the lithium layers as pillars, stabilizing the layered framework. Meanwhile, Li 1.3 La 0.3 Ti 1.7 (PO 4 ) 3 was uniformly coated on the surface of LiCoO 2 , which is beneficial for suppressing Co 3+/2+ ion leaching and interface side reactions during cycling. Furthermore, Li 1.3 La 0.3 Ti 1.7 (PO 4 ) 3 is a fast ion conductor, which facilitates the rapid transport of lithium ions on the surface of the cathode material. Owing to the synergistic effect of Mg 2+ ion doping and Li 1.3 La 0.3 Ti 1.7 (PO 4 ) 3 coating, the orbitals of Co 3d and O 2p in LiCoO 2 crystal are changed, and the irreversible phase transition and oxygen loss are inhibited. The modified material exhibited an excellent electrochemical performance. A discharge capacity of 175.5 mAh·g −1 at 10 C rate, as well as a capacity retention of 90.14% after 200 cycles at 1 C rate, was achieved in the modified material. This work supplies a new method for developing high-voltage oxide cathodes through bulk and interfacial modification.

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Materials Today Nano · 2022 · IF 13.364

Nano-structured Li1.3Al0.3Ti1.7(PO4)3 coated LiCoO2 enabling compatible interface with ultrathin garnet-based solid electrolyte for stable Li metal battery

Q. Sun,X. Chen,J. Xie,C. Huang,X. Xu,J. Tu,C. Shen,Y. Jin,K. Zhang,F. Chen,T. Zhu,X. Zhao,J. Cheng

Garnet-type Li 7 La 3 Zr 2 O 12 (LLZO) ceramics has been considered as an ideal solid-state electrolyte for Li metal cells because of its high ionic conductivity and relatively stable interface with Li. However, it is electrochemically incompatible with some high-voltage cathodes, e.g. LiCoO 2 . In this work, a nanoscale Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP) fast ion conductor was coated on LiCoO 2 (only 1 wt% LATP), bringing obviously enhanced interfacial compatibility with a composite electrolyte composed of Al, Nb-codoped LLZO and polyethylene oxide (PEO). A free-standing, flexible and ultrathin (20 μm) electrolyte membrane was successfully fabricated by a facile and scalable route, even though with a high ceramics content (67 wt%). Quasi-solid-state coin and pouch-type Li cells were assembled with the LATP-coated LiCoO 2 cathode, free-standing composite electrolyte and Li anode, together with soft interface modification by in-situ polymerization. The cells show stable cycling due to combined factors of enhanced electrode/electrolyte compatibility, ultrathin nature of the electrolyte membrane and the in-situ built soft interface. The pouch cells can be cycled for 300 cycles at 0.3 C and 60 °C with 80% retention. The pouch cells can endure abuse tests of bending, cutting and nail penetration. At a practical LiCoO 2 loading of 3 mAh cm −2 , the Li|LiCoO 2 pouch cell still shows stable cycling with 90% retention after 100 cycles at 60 °C (0.2 C charge/0.5 C discharge). This work provides a practical method to fabricate high-performance solid-state Li cells.

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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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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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JOURNAL OF POWER SOURCES · 2024 · IF 8.1

Composite polymer electrolytes based on poly(ether-ester) and Li1.3Al0.3Ti1.7(PO4)3 enabling high-performance all-solid-state flexible lithium metal batteries

Yang Chen,Jianda Niu,Siheng Zhang,Zhixian Dong,Jinbao Xu,Caihong Lei

The quest for next-generation energy storage systems has led to the development of high-voltage all-solid-state lithium metal batteries (ASSLMBs), which promise unprecedented energy density and safety. However, the challenge lies in creating of a robust electrolyte that can meet high room temperature ionic conductivity, Li-ion transference number and a wide electrochemical stability window (ESW) while maintaining flexibility and compatibility with lithium metal anodes. Here, novel polyurethane-based composite polymer electrolytes (CPEs) have been successfully fabricated by the cross-linking reaction of poly(1,5-dioxepan-2-one) diols (poly(ether-ester) soft segment) and hexamethylene diisocyanate trimer (hard segment) (PDH) blending with inorganic NASICON-type ceramic fillers Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (PDH@LATP). The resulting CPE exhibits an impressive ionic conductivity of 1.65 × 10 −4  S cm −1  at room temperature and a Li-ion transference number of 0.63, which is attributed to the amorphous structure of PDH and the formation of an interconnected ionic pathway by the inorganic filler. The incorporation of LATP also improve the ESW of CPE to 5.3 V while maintaining good mechanical properties. Therefore, the assembled LiFePO 4 /PDH@LATP/Li batteries displayed low interfacial resistance, Li dendrite suppression, high specific capacity and excellent cyclic performance. The high-voltage LiNi 0.5 Co 0.2 Mn 0.3 O 2 /PDH@LATP/Li batteries also exhibits good cycling performance and durability. The design principles and materials presented herein provide a blueprint for the next wave of ASSLMBs.

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APPLIED SURFACE SCIENCE · 2024 · IF 6.3

Nitrogen-doped carbon nanoframes modified Li3V2(PO4)3 derived from phytic acid with ultra-high rate performance for rechargeable Li ion batteries

Tao Huanga,Lifeng Guan,Shuai Jin,Dehui Zhang,Wangwen Liao,Xiangyang Zhou,Xingxing Liu,Chen Wu,Wei Zeng

The low electrical conductivity of Li 3 V 2 (PO 4 ) 3 (LVP) impedes its practical application. To address this issue, this study enhances its conductivity by introducing nitrogen-doped carbon nanoframes into LVP. Using phytic acid as a carbon and phosphorus source, and polyvinylpyrrolidone (PVP) as a nitrogen source, nitrogen-doped nanoframe-modified LVP material (LVP@NC) was successfully synthesized. Importantly, the carbon nanoframes of LVP@NC are entirely derived from the precursor’s thermal decomposition, simplifying the synthesis process and reducing production costs. By optimizing the process parameters, significant improvements were achieved in key performance indicators, including the initial discharge capacity at 1C (132.85 mAh·g −1 ), long cycling life at 10C (98.98 % capacity retention after 1000 cycles), and rate capability at 50C (99.65 mAh·g −1 ). These improvements are attributed to the introduction of nitrogen-doped nanoframes, where the high-temperature decomposition of PVP leads to the formation of porous honeycomb-like structures, and nitrogen doping in the nanocarbon framework introduces defects and active sites, thereby promoting lithium-ion migration and facilitating electrolyte penetration. This simple, novel, and energy-efficient method demonstrates significant potential for the large-scale preparation of high-performance cathode materials.

CAS / MDL: 872-50-4
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