PHYSICAL CHEMISTRY CHEMICAL PHYSICS
·
2025
·Vol. 27
·期 45
·24273-24283
·
IF 2.9
Jin Zou,Daoyun Zhu,Zhongfei Mu,Song Xu,Nurahmat Wali,Fugen Wu,Huafeng Dong,Xin Zhang,Xiao Wu,Yifei Luo,Yuchun Zhan
Near-infrared (NIR) spectroscopic technology has shown extensive application prospects. However, developing NIR phosphors with tunability and high thermal stability is a huge challenge. In this work, a highly promising phosphate compound, K3Ga2(PO4)3, has been successfully synthesized. When doped with Cr3+ ions, it is particularly noteworthy that Cr3+ exhibits highly efficient and thermally stable broadband NIR luminescence in the tetrahedral coordination environment. This unique property makes K3Ga2(PO4)3:Cr3+ a compelling candidate for advanced photonic applications. Therefore, studying the luminescent properties of Cr3+ rare earth ions doped into tetrahedral sites is of great significance. In the tetrahedral coordination environment of K3Ga2(PO4)3:Cr3+ ions exhibit broadband near-infrared emission spanning from 700 to 1100 nm (λem = 822 nm, FWHM = 124 nm) under 452 nm blue light excitation. Remarkably, the quantum efficiency reaches as high as 70.9%, demonstrating its exceptional potential for advanced photonic applications. In addition, the phosphors demonstrated exceptional thermal stability with near-zero thermal quenching. The NIR luminescence intensity at 373 K and 423 K retained 109.0% and 90.4% of its initial room-temperature value, respectively. This remarkable performance can be attributed to the material's ultra-wide band gap, and minimal electron–phonon coupling. The NIR pc-LED devices, fabricated by integrating the optimized K3Ga1.93(PO4)3:0.07Cr3+ phosphors with a blue LED chip (λex = 455 nm), achieved a near-infrared output power of 274 mW with a conversion efficiency of 5.42% under a driving current of 100 mA. Experimental results demonstrate that the fabricated NIR pc-LED exhibits significant potential for applications in night vision and vein imaging technologies. This study provides a strategic framework for designing high-performance NIR pc-LED devices, utilizing K3Ga2(PO4)3:Cr3+ as an efficient phosphor-converted light source, and offers valuable insights for practical implementation in advanced optical systems.
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Chemical Science
·
2023
·Vol. 14
·期 44
·12570-12581
·
IF 8.4
Mingli Xu,Fengxue Zhang,Yanhui Zhang,Chen Wu,Xue Zhou,Xinping Ai,Jiangfeng Qian
Exploring a sodium-enriched cathode (i.e. Na4V2(PO4)3, which differs from its traditional stoichiometric counterpart Na3V2(PO4)3 that can provide extra endogenous sodium reserves to mitigate the irreversible capacity loss of the anode material (i.e. hard carbon), is an intriguing presodiation method for the development of high energy sodium-ion batteries. To meet this challenge, herein, we first propose a redox-potential-matched chemical sodiation approach, utilizing phenazine-sodium (PNZ-Na) as the optimal reagent to sodiate the Na3V2(PO4)3 precursor into Na-enriched Na4V2(PO4)3. The spontaneous sodiation reaction enables a fast reduction of one-half V ions from V3+ to V2+, followed by the insertion of one Na+ ion into the NASICON framework, which only takes 90 s to obtain the phase-pure Na4V2(PO4)3 product. When paired with a hard carbon anode, the resulting Na4VP‖HC full cell exhibits a high energy density of 251 W h kg−1, which is 58% higher than that of 159 W h kg−1 for the Na3VP‖HC control cell. Our chemical sodiation methodology provides an innovative approach for designing sodium-rich cathode materials and could serve as an impetus to the development of advanced sodium-ion batteries.
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ELECTROCHIMICA ACTA
·
2015
·
IF 4.504
Jinli Mao,Lianyi Shao,Peng Li,Xiaoting Lin,Miao Shui,Nengbing Long,Jie Shu
Three Li 3-x Na x V 2 (PO 4 ) 3 (x=0.5, 1.5 and 2.0) samples are synthesized by a traditional solid-state reaction method in this work. Their phase composition, surface morphology and electrochemical property are described and compared by using various physical/chemical methods. Phase analysis results reveal that Li 2.5 Na 0.5 V 2 (PO 4 ) 3 consists of monoclinic Li 3 V 2 (PO 4 ) 3 , rhombohedral Li 3 V 2 (PO 4 ) 3 and rhombohedral Na 3 V 2 (PO 4 ) 3. While, both Li 1.5 Na 1.5 V 2 (PO 4 ) 3 and LiNa 2 V 2 (PO 4 ) 3 are the two-phase mixture consisted of rhombohedral Li 3 V 2 (PO 4 ) 3 and rhombohedral Na 3 V 2 (PO 4 ) 3 . Electrochemical testing results reveal that LiNa 2 V 2 (PO 4 ) 3 and Li 1.5 Na 1.5 V 2 (PO 4 ) 3 can deliver the initial discharge capacities of 101.4 mAh g −1 and 108.6 mAh g −1 with a long potential plateau at 3.69 V, respectively. In contrast, Li 2.5 Na 0.5 V 2 (PO 4 ) 3 presents an initial discharge capacity of 111.7 mAh g −1 with four potential plateaus. High lithium ion diffusion coefficient in Li 2.5 Na 0.5 V 2 (PO 4 ) 3 indicates that the existence of monoclinic Li 3 V 2 (PO 4 ) 3 phase can improve the ionic conductivity and then be responsible for good electrochemical performance. Besides, in-situ X-ray diffraction observation of LiNa 2 V 2 (PO 4 ) 3 demonstrates that the phase transition is not fully reversible but quasi-reversible during the lithiation-delithiation process. The partial irreversibility of structural evolution for LiNa 2 V 2 (PO 4 ) 3 induces the capacity loss upon repeated cycles.
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Nanomaterials
·
2024
·Vol. 14
·期 21
·1721
·
IF 4.4
Qi You,Xuan Zhou,Chengxiang Yang,Mu Liu,Wei Liu,Jinkai Li,Xuchuan Jiang
A series of red-emitting phosphors, Na3.6Y1.8−x(PO4)3:xEu3+, have been synthesized by a high-temperature solid-phase method. The impact of the partial Li+/K+ion substitution on the crystal structure and photoluminescence (PL) performance of Na3.6Y1.05(PO4)3:0.75Eu3+phosphor have been investigated. Various techniques have been used for characterization of the as-obtained materials. X-ray diffraction (XRD) analysis was utilized to confirm the composites of these samples, and the morphology and element distribution were examined by scanning electron microscope (SEM) and transmission electron microscope (TEM). This study found that the developed Na3.6Y1.8−x(PO4)3:xEu3+phosphors exhibited a prominent emission peak at ~620 nm when excited at 393 nm, which corresponded to5D0→7F2transitions of Eu3+ions. Furthermore, the robust emission peak at ~705 nm (5D0→7F4) of these phosphors enables a better match with plant pigment absorption. Beyond that, the partial substitution of Li+/K+ions probably changed the crystal structure, and reduces the symmetry around Eu3+, leading to significantly enhanced luminous intensities by 23.24% and 18.29%, with the highest quantum yields (QYs) reaching 99.85% and 96.29%, respectively. Additionally, the prepared phosphors show non-thermal quenching and superior thermal stability at elevated temperatures from 298 to 473 K. These findings and results suggest that Li⁺/K⁺-substituted Na3.6Y1.05(PO₄)₃:0.75Eu3⁺ phosphors can serve as promising red-emitting phosphors for plant lighting applications.
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JOURNAL OF POWER SOURCES
·
2024
·
IF 8.1
Yuchen Wu,Ming Chao,Chengyi Lu,Hanyu Xu,Kai Zeng,Decheng Li,Ruizhi Yang
Surface functionalization is one effective strategy for optimizing the stability of Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP) with Li metal anodes and the compatibility between the components of an electrolyte for lithium battery. Herein, a bifunctional modification layer induced by the silane coupling agent (SCA) and ionic liquid (IL) are successfully introduced onto the surface of LATP particles (defined as [email protected] ) through chemical grafting and ion exchange strategies. Benefitting from the synergistic effect between the protection of modification layer and the effectively reduced interaction of PEO chain segments with Li + , the compatibility of LATP with the Li metal anode is improved, and the dispersion of LATP in PEO matrix is enhanced, a faster Li + transfer is thereby enabled. As a result, thus-prepared [email protected] composite polymer electrolyte (CPE) shows an excellent electrochemical property with high ionic conductivity (1.455 × 10 −3 S cm −1 at 60 °C), enhanced Li-ion transference number (0.40), wide electrochemical stability window (4.76 V vs. Li + /Li) and favorable Li metal compatibility (over 1200 h). Furthermore, separately assembled Li/ [email protected] CPE/LFP coin full cells and pouch cells verify the operational feasibility under extreme conditions. This work paves a new way to protect LATP and promote its practical application in all-solid-state lithium batteries.
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JOURNAL OF POWER SOURCES
·
2024
·
IF 8.1
Shuting Zhao,Wentao Qi,Chao Yang,Rui Ling
Na 3 V 2 (PO 4 ) 3 has received a lot of attention as a prospective cathode for sodium-ion batteries (SIBs) owing to its strong 3D wide-open architecture for Na + transport. However, the practical application is still hampered by its poor electronic conductivity and weak Na + diffusion kinetics . In this paper, a novel Mg 2+ -doped Na 3 V 2 (PO 4 ) 3 flower-like cathode (Na 3+x V 2-x Mg x (PO 4 ) 3 /C, x = 0, 0.02, 0.04, 0.06) with abundant mesoporous has been synthesized by a convenient template-assisted sol-gel method. Mg 2+ doping successfully triggers V 4+ /V 5+ reversible redox with improved voltage plateau and reversible capacity. The hierarchical mesoporous structure combined with carbon layers is beneficial to the fast transport of Na + and e − , which guarantee improved kinetic properties and enhanced conductivity. Attributed to these competitive advantages, significantly improved electrochemical properties of Na 3.04 V 1.96 Mg 0.04 (PO 4 ) 3 /C (NVMP-4) are acquired, including extremely high specific capacity (123.8 mAh g −1 at 1C), excellent rate performance (73.8 mAh·g −1 at 100C) and exceptionally stable energy output with 89.1 % capacity retention after 3000 cycles at 20C. Additionally, when assembled with a hard carbon anode (HC), NVMP-4||HC provides an exceptional energy density of 216.9 Wh kg −1 at 0.2C. By enhancing nanostructure and rational surface engineering, this project offers fresh perspectives for creating superior electrodes, increasing the energy density of SIBs.
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Small
·
2020
·Vol. 16
·期 25
·2001524
·
IF 11.459
Wei Zhang,Huangxu Li,Zhian Zhang,Ming Xu,Yanqing Lai,Shu-Lei Chou
Developing high-voltage cathode materials is critical for sodium-ion batteries to boost energy density. NASICON (Na super-ionic conductor)-structured Na x MnM(PO 4 ) 3 materials (M represents transition metal) have drawn increasing attention due to their features of robust crystal framework, low cost, as well as high voltage based on Mn 4+ /Mn 3+ and Mn 3+ /Mn 2+ redox couples. However, full activation of Mn 4+ /Mn 3+ redox couple within NASICON framework is still a great challenge. Herein, a novel NASICON-type Na 4 MnCr(PO 4 ) 3 material with highly reversible Mn 4+ /Mn 3+ redox reaction is discovered. It proceeds a two-step reaction with voltage platforms centered at 4.15 and 3.52 V versus Na + /Na, delivering a capacity of 108.4 mA h g −1 . The Na 4 MnCr(PO 4 ) 3 cathode also exhibits long durability over 500 cycles and impressive rate capability up to 10 C. The galvanostatic intermittent titration technique (GITT) test shows fast Na diffusivity which is further verified by density functional theory calculations. The high electrochemical activity derives from the 3D robust framework structure, fast kinetics, and pseudocapacitive contribution. The sodium storage mechanism of the Na 4 MnCr(PO 4 ) 3 cathode is deeply studied by ex situ X-ray diffraction (XRD) and ex situ X-ray photoelectron spectroscopy (XPS), revealing that both solid-solution and two-phase reactions are involved in the Na + ions extraction/insertion process.
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Inorganic Chemistry Frontiers
·
2024
·
IF 6.1
Yongquan Zhang,Hongchang Gao,Jingshun Wang,Qingguo Chi,Tiandong Zhang,Changhai Zhang,Yu Feng,Yue Zhang,Dianxue Cao,Kai Zhu
All-solid-state lithium metal batteries (ASSLMBs) are considered the most competitive next-generation energy storage batteries due to their high energy density and high safety. Polyethylene oxide (PEO) is an ideal solid-state electrolyte due to its high chain flexibility, high dielectric constant, and strong dissociation ability towards lithium salts. However, the application of PEO is severely hindered by drawbacks such as low ion conductivity at room temperature and low electrochemical window. In this work, we constructed a Li1.25Al0.25Zr1.75(PO4)3 (LAZP)/PEO composite solid-state electrolyte (CSSE) with improved ion conductivity, enlarged electrochemical window, and stable charge–discharge cycle performance. The CSSE leads to an obvious LiF layer and Li2CO3 formation at the interface of lithium metal. Meanwhile, the addition of LAZP reduces the side reaction between PEO and the lithium metal significantly and suppresses the deterioration of ion conductivity. In addition, we modified LiFePO4 (M-LFP), the cathode sheet of the ASSLMBs, by adding an appropriate proportion of multi-walled carbon nanotubes (MWCNTs), PEO and lithium bis(trifluoromethane sulfonimide) (LiTFSI) to improve the ionic and electronic conductivity inside the cathode of the ASSLMBs. The Li/CSSE/M-LFP full cell exhibits a specific discharge capacity of 152 mA h g−1 at 60 °C and 2 C rate and a capacity retention rate of 93.5% after 200 cycles at 1 C. This work demonstrates an effective strategy for increasing the specific capacity, rate ability and long-cycle performance of ASSLMBs.
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COMPOSITES PART B-ENGINEERING
·
2024
·
IF 12.7
Rui Du,Changcheng Liu,Que Huang,Baofeng Zhang,Hongyuan Ding,Jianghui Xie,Shengnan He,Yaxiong Yang,Chao Zheng,Yanjun Chen
Currently, the both low electronic and ionic conductivity have seriously hindered the further application of Na 3 V 2 (PO 4 ) 3 (NVP). Nevertheless, traditional carbon materials modification only improves the electronic conductive property, rather than modifying the ionic conductivity. Herein, N-rich carbon resources of glycine (GLY) is introduced to synthesize NVP, which can act as reducing agent and morphology inducer to optimize NVP sample. Notably, GLY supplies favorable N-doped carbon skeleton, and this defective carbon structure benefits for the accelerated electronic conductivity. Besides, porous construction is established after introducing GLY. This unique morphology significantly improves the infiltration effects of electrolyte, thus providing more electrochemical active sites for Na + de-intercalation to improve the ionic conductivity. Meanwhile, porous framework supplies enough space for the shrinkage of crystal cells, so the stress-strain effect is highly restrained, which is demonstrated by Ex-situ XRD. The stabilized crystal and morphological structure of NVP@GLY-2 has been verified by after-cycled XRD/SEM/XPS. Highly improved kinetic characteristics are also investigated by In-situ EIS. Moreover, Accelerating Rate Calorimeter (ARC) measurements indicate that NVP@GLY-2-based half and full cells also have excellent thermal safety properties. Comprehensively, NVP@GLY-2 reveals a high capacity of 119 mAh g −1 at 0.1 C. It reveals 84.5 and 71.2 mAh g −1 at 10 and 50 C, with capacity retention rates of 88.9 % and 85.8 % after 1000 cycles.
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PHYSICAL CHEMISTRY CHEMICAL PHYSICS
·
2018
·Vol. 20
·期 22
·15192-15202
·
IF 3.906
Jinggao Wu,Maowen Xu,Chun Tang,Guannan Li,Hong He,Chang Ming Li
F-Doping effects on polyaniline-derived carbon coated Li3V2(PO4)3 (Li3V2(PO4)3−xFx@C) as a cathode for high performance Li rechargeable batteries are systematically investigated with a combined experimental and DFT theoretical calculation approach. The results clearly indicate that the doping amount has a significant impact on the rate capability and long cycle life. The optimal material (Li3V2(PO4)2.88F0.12@C) delivers 123.16 mA h g−1@2C, which is close to the theoretical value (133 mA h g−1), while showing a greatly improved cycle stability. Rietveld refinements show that the F− doping does not obey Vegard's Law, which may be attributed to the generated lower valence of V ions. AC impedance spectroscopy shows that the F-doping can achieve faster interfacial charge transfer for higher reaction reversibility. DFT calculations confirm that the lower V2+ (t2g↑)3 does exist in Li3V2(PO4)2.88F0.12, and the mean nearest neighbor Li–O bond length also increases for faster electrochemical kinetics, and further reveal that there is a tendency for a transition from the insulator to the n-type semiconductor due to the F dopant. The combined experimental and calculated results suggest that F-doping indeed greatly facilitates the charge transfer rate of the Li+ insertion/de-insertion process for better reversibility and enhances the Li+ diffusion rate to access the reaction sites, thus resulting in high rate capacity and cycling stability. This work not only offers a facile and effective approach to synthesize high performance Li-ion battery material for very promising practical applications, but also discloses scientific insights on element coating and doping to guide the electrode material design for fast electrode kinetics in energy storage devices.
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JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2023
·
IF 9.9
Yali Liu,Youlong Xu,Yuan Zhang,Cheng Yu,Xuekai Sun
Composite solid electrolytes (CSEs) exhibit great potential due to their advantages of both sufficient strength and high ionic conductivity . However, their interfacial impendence and thickness hinder potential applications. Herein, a thin CSE with good interface performance is designed through the combination of immersion precipitation and in situ polymerization. By employing a nonsolvent in immersion precipitation, a porous poly(vinylidene fluoride-cohexafluoropropylene) (PVDF-HFP) membrane could be rapidly created. The pores in the membrane could accommodate sufficient well-dispersed inorganic Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP) particles. Subsequent in situ polymerized 1,3‑dioxolane (PDOL) further protects LATP from reacting with lithium metal and supplies superior interfacial performance. The CSE has a thickness of ∼ 60 μm, ionic conductivity of 1.57 × 10 −4 S cm −1 , and oxidation stability of 5.3 V. The Li/1.25LATP-CSE/Li symmetric cell has a long cycling performance of 780 h at 0.3 mA cm −2 for 0.3 mAh cm −2 . The Li/1.25LATP-CSE/LiFePO 4 cell exhibits a discharge capacity of 144.6 mAh/g at 1C and a capacity retention of 97.72 % after 300 cycles. Continuous depletion of lithium salts due to the reconstruction of the solid electrolyte interface (SEI) may be responsible for battery failure. The combination of the fabrication method and failure mechanism gives new insight into designing CSEs.
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RSC Advances
·
2023
·Vol. 13
·期 35
·24385-24392
·
IF 3.9
Shiyu Cao,Yanhong Xiang,Qiuling Zou,Youliang Jiang,Hanzhang Zeng,Jian Li,Jianhua Wu,Xiangsi Wu,Xianwen Wu,Lizhi Xiong
To alleviate the depletion of lithium resources and improve battery capacity and rate capacity, the development of aqueous zinc-ion batteries (AZIBs) is crucial. The open channels monoclinic structure Li3V2(PO4)3 is conducive to the transfer and diffusion of guest ions, making it a promising cathode material for AZIBs. Therefore, in this study, nanoneedles and particles Li3V2(PO4)3 cathode materials for AZIBs were prepared by a hydrothermal assisted sol–gel method, and the effect of synthesized pH values was studied. XRD results show that all samples had the monoclinic structure, and the Li3V2(PO4)3 sample prepared at pH = 7 exhibits (LVP-pH7) the highest peak tips and narrowest peak widths. SEM images demonstrate that all samples have the morphology character of randomly oriented needles and irregular particles, with the LVP-pH7 sample having more needle-like particles that contribute to ion diffusion. EDS results show uniform distribution of P, V, and O elements in the LVP-pH7 sample, and no obvious aggregation phenomenon is observed. Electrochemical tests have shown that the LVP-pH7 sample exhibits excellent cycling performance (97.37% after 50 cycles at 200 mA g−1) and rate ability compared to other samples. The CV test results showed that compared with other samples, the LVP-pH7 sample had the most excellent ionic diffusion coefficient (2.44 × 10−12 cm2 s−1). Additionally, the Rct of LVP-pH7 is the lowest (319.83 Ω) according to the findings of EIS and Nyquist plot fitting, showing a decreased charge transfer resistance and raising the kinetics of the reaction.
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