Journal of Energy Storage
·
2024
·
IF 8.9
Mengyue Liu,Kexin Wan,Xinmiao Zhang,Mingkun Wang,Dawei Yang,Jishi Wei,Kun Chang,Hongwei Tang
NASICON-type cathodes as promising candidates have attracted more and more attention, and Na 3 V 2 (PO 4 ) 3 is one of the outstanding representatives. In particular, it can tolerate complex interface reaction processes during the Zn 2+ insertion/desertion in the aqueous environment. However, existing three-dimensional channels in the intrinsic Na 3 V 2 (PO 4 ) 3 always hardly play to their advantages as narrow pathways and some other defects. This work has considered both the conductivity and capacity of this vanadium-based NASICON cathode at the same time, where a sodium-rich cathode material Na 3.2 V 1.8 Mn 0.15 Mg 0.05 (PO 4 ) 3 (NVMMP) with Mn 2+ and Mg 2+ dual-substituents has been designed considering the low cost and environmentally friendly characteristics. The synergistic effects introduced by Mn 2+ and Mg 2+ substitution led to a significant increase in the capacity and cycle life of the optimized NVMMP cathode material (with a capacity retention rate of 90.6 % after 2500 cycles at 2 A g −1 ). Furthermore, the reversible storage mechanism of Zn 2+ in NVMMP cathode materials and the theoretical study of such synergistic substitution on intrinsic electronic conductivity have been revealed by different in/ex-situ characterization techniques and theoretical calculations, where redox processes generated by Mn 3+ /Mn 4+ , enhanced ionic/electron pathway, and the pinning effect caused by injecting inert MgO 6 octahedra into the NASICON framework are key points to high capacity and long-life span.
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ELECTROCHIMICA ACTA
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2026
·
IF 5.8
Zilong Fang,Qi Fan,Anyang Yu,Wei Zhou,Junwei Luo,Changhao Zhu,Xinguantong Zhou,Xiao Yu,Qingyu Xu
Achieving uniform ion flux both at the interface and in the matrix simultaneously remains a challenge with current liquid/solid electrolytes. Herein, we demonstrate a novel strategy to address the issue by designing and synthesizing a polyvinylidene fluoride hexafluoropropylene (PVDF-HFP) based ternary hybrid electrolyte (PTHE). In this unique material architecture, each component synergistically serves a specific purpose: The PVDF-HFP-Zn(OTF) 2 serves as the stable electrolyte skeleton, providing the ion transport network. The Cu-MOF regulates the Zn 2+ solvation structure and anion distribution, achieving uniform ion flux in the electrolyte matrix. Moreover, the thin liquid electrolyte film at the interface promotes ion transport and stabilizes the electrode-electrolyte interface. The PTHE exhibits balanced high performance with respect to cycling stability (3200 h at 0.2 mA cm −2 ) and excellent capacity retention when paired with the Na 3 V 2 (PO 4 ) 3 (NVP) cathode (0.0029 % capacity decay per cycle after 2000 cycles at 0.5 A g −1 ), alongside uniform Zn metal deposition and effective dendrite suppression. Furthermore, the PTHE based NVP-Zn metal quasi-solid battery demonstrates outstanding flexibility (enduring 1000 bending cycles with less than 10% decrease in capacity retention), owing to the existence of the thin liquid electrolyte film. This work provides a novel strategy for developing highly stable flexible NVP-Zn metal quasi-solid batteries by synergistically optimizing ion flux both at the interface and in the matrix.
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JOURNAL OF ALLOYS AND COMPOUNDS
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2026
·
IF 6.7
Xiaokun Li,Jiejun Ren,Lina Chen,Xianbao Duan,Zhanhui Zhang
Mn 2+ -doped dual-emission luminescent materials have recently attracted significant interest. However, the distribution of Mn 2+ ions is highly dependent on the host crystal structure, the lattice sites, and the doping concentration. How to analyze and clarify the dual-emission mechanism of Mn 2+ has become a major challenge; thus, this work synthesized NaZr 2 (PO 4 ) 3 : Mn 2+ phosphate phosphors and systematically investigated their doping behavior and luminescence mechanisms. The synthesized NaZr 2 (PO 4 ) 3 : Mn 2+ phosphate phosphors exhibited dual broadband emission centered at 480 nm and 565 nm, respectively. Density functional theory (DFT) calculations confirmed the existence of different Mn doping configurations and their corresponding formation energies. The results revealed that at low concentrations, the Mn ions (Mn1) preferentially substitute Na sites; while at high concentrations, the later Mn ions (Mn2) substitutes Zr sites and interact with pre-existing Mn1 to form Mn-Mn dimer. Notably, the emission spectra of the phosphors were sensitive to both Mn 2+ doping concentration and excitation wavelength. The Commission Internationale de l′Éclairage (CIE) chromaticity coordinates could be tuned within the range of (0.2463, 0.3478) to (0.4128, 0.4733), enabling adjustable luminescence from cyan to yellow. Furthermore, leveraging the dual-wavelength emission and high contrast characteristics of this phosphor, we fabricated an anti-counterfeiting dot matrix displaying the information "WIT" via ASCII code and achieved clear fingerprint visualization. This work clarifies the doping site preference of Mn 2+ and the underlying mechanism of dual luminescence, paving the way for the applications of transition metal phosphors in fields such as information encryption and fingerprint visualization.
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APPLIED SURFACE SCIENCE
·
2026
·
IF 6.6
Xinbo Li,Qinghao Cao,Junyang Chen,Chuanpu Zhang,Qiang Ru
Dual-layer artificial interface of carbon/AlF 3 enhances conductivity and Na + transport, suppressing structural degradation. • NTVP@C/AF-1%: 184.58mAh g −1 at 0.1C, 93.66% capacity retention after 2500 cycles at 20C. • NTVP@C/AF-1% full cell: 81.88% capacity retention of after 300 cycles at 1C. The vanadium-based NASICON-type cathodes face challenges of excessive cost and capacity decay induced by structural degradation during cycling. Surface modification has been confirmed as a favorable strategy to purchase a reasonable balance between sodium storage performance and long lifespan for cathodes. A carbon/AlF 3 dual-layer artificial interface was ingeniously engineered to encapsulate the Na 2 TiV(PO 4 ) 3 cathode (NTVP). Through modulating AlF 3 coating content, the NTVP@C/AF-x% series (x = 0.5, 1, 2, 3, 5) were harvested to accelerate Na-ion diffusion and alleviate structural collapse, thereby strengthening the rate capability under high-rate conditions. Furthermore, the dual-layer artificial interface effectively reduces the polarization voltage and boosts the Na-ion diffusion coefficient. The strategy-modified NTVP@C/AF-1% cathode delivers a high specific capacity of 184.58 mAh g −1 at 0.1C, and maintains a capacity retention of 93.66% after 2500 cycles at 20C. Furthermore, the NTVP@C/AF-1% also serves as an anode, demonstrating favorable cycling durability with 91.67% capacity retention after 400 cycles at 1C. The NTVP@C/AF-1% cathode demonstrated excellent compatibility with the hard carbon anode. The assembled NTVP@C/AF-1% full cell exhibits enhanced electrochemical performance with a capacity retention of 81.88% after 300 cycles. This work demonstrates the modified interfacial structures can unlock more possibilities for the further development of NASICON-type cathodes. Download: Download high-res image (101KB) Download: Download full-size image
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ADVANCED POWDER TECHNOLOGY
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2024
·
IF 4.2
Jiuxiang Zhang,Xiaoping Zhang,Shengxing Lu,Yian Wang,Yulei Sui,Keyi Sun,Mengting Deng,Wenbin Fei,Ling Wu
Na 4 MnCr(PO 4 ) 3 is a promising cathode material with high redox potential and high energy density, but the intrinsic poor electronic conductivity and substandard structural stability restrict its practical application. Herein, porous Na 4 MnCr(PO 4 ) 3 /C with conductive networks and improved electrochemical properties is synthesized by a facile modified solid-state process using citric acid as a multifunctional additive. The results reveal that citric acid can be used as a grinding aid to make the raw materials mix more evenly and speed up the efficiency of ball milling. Besides, 3D conductive network and porous structure originated from polycondensation and carbonization of citric acid can promote the electrochemical properties of Na 4 MnCr(PO 4 ) 3 /C by enhancing the electronic/ionic conductivity and (de)intercalation reaction kinetics. As expected, the optimal Na 4 MnCr(PO 4 ) 3 /C delivers a high reversible capacity of 130.5 mAh g −1 at 0.1C rate, and exhibits a capacity retention of 82.62% at 10C rate after 500 cycles. In addition, the reversible biphasic reaction of the cathode is confirmed by the constant galvanostatic intermittent titration technique and ex-situ XRD, which shows great potential of the synthesized Na 4 MnCr(PO 4 ) 3 /C for practical applications.
研究领域:
材料科学
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电化学
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能源存储
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无机固体化学
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纳米材料
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Journal of Energy Storage
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2024
·
IF 8.9
Tao Zhou,Yanjun Chen
The advancement of Na 3 V 2 (PO 4 ) 3 has been impeded by its subpar kinetic characteristics, resulting in suboptimal electrochemical performance . In this case, a dual modification strategy involving Ta and F co-doping is employed, along with the incorporation of carbon nanotubes (CNTs), is introduced. Notably, the substitution of high-valence Ta 5+ for V 3+ ions induces an n-type doping effect, thereby increasing the density of free electrons and enhancing electrochemical performance. Moreover, Ta 5+ possesses a comparatively larger ionic radius than V 3+ , which enhances the ease of Na + transport, leading to an increased rate of ionic diffusion. Furthermore, Ta 5+ ions play a crucial role in reinforcing the crystal structure, thereby strengthening the stability of the NVP system. Importantly, during the high-temperature calcination process, the reduction of carbon results in the conversion of Ta 5+ to Ta 3+ , forming a novel conductive TaN phase through its reaction with N 2 . This TaN phase, known for its high conductivity, intercalates into the NVP bulk as interlayers, forming beneficial grain boundaries. Thanks to this unique TaN//NVP heterojunction , the migration of Na + ions is notably accelerated along the grain boundaries rather than within the NVP bulk. The introduction of F contributes to reducing the grain size of active particles, consequently shortening the pathways for Na + migration and improving kinetic properties. Moreover, the presence of carbon layers and the encapsulation of CNTs collaboratively construct a highly conductive cross-linking network, elevating both electronic conductivity and mitigating NVP particle aggregation during high-temperature sintering. Consequently, the modified NVTPF0.07/@CNTs sample exhibits outstanding performance in both half and full cells, underscoring its substantial potential for application in the field of sodium-ion batteries.
研究领域:
材料科学
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电化学
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能源存储
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无机固体化学
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纳米复合材料
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APPLIED SURFACE SCIENCE
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2026
·
IF 6.6
Xianyue Zhang,Yongguang Zhang,Nianxue Dong,Jiawei Fan,Haipeng Li,Baoe Li
The slow Na + diffusion and low intrinsic electrical conductivity of Na 3 V 2 (PO 4 ) 3 (NVP) limit its practical application in sodium-ion batteries (SIBs). A synergistic enhancement approach of Si 4+ substitution and N-doped carbon coating has been introduced in this paper to produce a porous coral-like Na 3.1 V 2 (PO 4 ) 2.9 (SiO 4 ) 0.1 @NC-2 (NVPS@NC-2) composite. Si 4+ incorporation into the NVP lattice expands the Na + migration channels and decreases the bandgap so that intrinsic electronic conductivity of NVP was enhanced as confirmed by density functional theory calculations. Additionally, the N-doped carbon coating forms numerous extrinsic defects and creates a novel porous coral-like morphology that boosts the specific surface area. The initial specific capacity of NVPS@NC-2 cathode achieves 115.7 mAh g −1 at a current density of 0.1C. And even at 60/120C, NVPS@NC-2 cathode still exhibits 98.9/66.2 mAh g −1 , maintaining 92.9% and 90.6% capacities after 5000/10000 cycles, respectively, showing its viability for advanced SIBs applications.
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Batteries & Supercaps
·
2021
·Vol. 5
·期 4
·e202100367
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IF 7.093
Yuyao Zhang,Xiaoying Zhu,Dan Kai,Baoliang Chen
Graphical Towards high energy density SIB : Biomass hyaluronic acid (HA) is developed as a novel binder for high-loading Na 3 V 2 (PO 4 ) 3 cathodes in sodium-ion batteries, which delivers a high reversible capacity, a superior rate capability, and a targeted energy density. Fast ion transport, network volume buffer and stable solid permeable interface are demonstrated along with structure-performance mechanisms. Sodium-ion batteries (SIBs) are considered a promising candidate in green energy storage due to their considerable abundance. The low mass loading (less than 2.0 mg cm −2 ) of SIBs-based cathodes cannot meet the energy density on the practical device level, which is mainly restricted by sluggish Na + transport. To the end, a facile and compatible strategy was demonstrated by utilizing hyaluronic acid (HA) binder to achieve fast ion transport and targeted energy density for Na 3 V 2 (PO 4 ) 3 (NVP) cathodes. As a novel functional aqueous binder, HA allowed cathodic materials to organize the unique conductive network. The network-like electrode structure could buffer volume changes during sodiation/desodiation process and provide bi-continuous charge transport channels for both Na + and electrons at the interface. HA promoted the formation of the stable solid permeable interface films, protecting the electrochemical stability of the cathode and ensuring its good cycle performance. These functions of HA binder enabled that NVP delivered a reversible discharge capacity of 107.3 mAh g −1 at 0.5 C (1 C=117 mA g −1 ), which showed no sacrifice of electrochemical performances with mass loading increasing from 1.1 to 4.4 mg cm −2 . Even at a high rate of 20 C, NVP-HA (loading 4.0 mg cm −2 ) could reserve a good capacity of 76.8 mAh g −1 with the retention of 99.3 % after 2000 cycles. This study provides a novel strategy to achieve high energy density for SIBs in large-scale energy storage.
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ACS Sustainable Chemistry & Engineering
·
2020
·
IF 7.632
Dan Zhao,Shi-Rui Zhang,Yan-Ping Fan,Bao-Zhong Liu,Ya-Nan Li,Lin-Ying Shi,Shao-Jie Dai
Developing broad-band-emitting phosphors is very important to light-emitting diode (LED) lighting and displays. We introduced Eu2+ to solid solutions K2YZr1–yHfy(PO4)3 with a langbeinite-type structure to prepare a series of new phosphors. In this structure, two K+ sites could be occupied by Eu2+ cations to provide two different kinds of coordination environments, leading to broad emitting bands in the range of 390–700 nm. The coordination circumstance of Eu2+ was analyzed by Gaussian fitting and time-resolved emission spectra. Furthermore, the emitting intensity and thermal stability can be improved by modulating the crystalline field via substituting Zr4+ by Hf4+. When the Zr4+ was fully substituted by Hf4+, the external quantum efficiency increased by 53.75%, giving a bright cyan emission. Finally, an archetype white-LED lamp was made using cyan phosphor K2YHf(PO4)3:0.04Eu, red phosphor CaAlSiN3:Eu2+, and a 365 nm LED chip, which realized an applicable color rendering index (Ra = 81) and a correlated color temperature (CCT = 3792 K).
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JOURNAL OF MATERIALS SCIENCE
·
2020
·Vol. 55
·期 14
·6017-6029
·
IF 3.553
Liang Shujie,Han Cuilian,Meng Qinghan,Tian Guiying
In this study, a nitrogen and sulfur co-doped sodium titanium phosphate/hole graphene (N,S-NTP/rHGO) was synthesized by one-step hydrothermal method using thiourea as N/S source. The microstructure characterization confirms that N and S heteroatoms have been integrated into the graphene skeleton. The electrochemistry and electrosorption properties of the N,S-NTP/rHGO electrodes were investigated for hybrid capacitor deionization (HCDI). The results indicate that the specific capacitance of N,S-NTP/rHGO electrodes can reach 530.46 F g −1 at a scan rate of 0.2 mV s −1 , which is 33.8% higher than that of the sample without doping. Moreover, the HCDI cell based on the N,S-NTP/rHGO-2 shows a high desalination capacity of 36.87 mg g −1 and a rapid ion removal rate of 0.66 mg g −1 s −1 , which is more than twice as high as the sample without doping (0.3 mg g −1 s −1 ) at an initial NaCl concentration of 800 mg L −1 and applied voltage of 1.4 V. Further, the N,S-NTP/rHGO electrode exhibits excellent regeneration ability. Therefore, this study suggests that as-prepared N,S-NTP/rHGO composite exhibits a great potential application for high-performance HCDI systems.
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Inorganic Chemistry Frontiers
·
2020
·Vol. 7
·期 5
·1289-1297
·
IF 5.958
Zhaoyang Wang,Jinmei Liu,Zijuan Du,Haizheng Tao,Yuanzheng Yue
Na3V2(PO4)3 (NVP) features a three-dimensional open structure, which allows fast migration of Na+ ions, and thus, NVP is a superior cathode material for sodium ion batteries. However, the application of the NVP cathode is limited by its low electronic conductivity. To overcome this limitation, we developed an NVP nanocomposite cathode by doping carbon with bromine (Br) and nitrogen (N) during the sol–gel assisted hydrothermal reaction. The Br- and N-doping leads to the formation of amorphous carbon (a-C) on the surface of NVP particles. The nanocomposite possesses multilevel structures containing both pores with different sizes and aggregated grains (200–300 nm). Since the doped N provides electrons to the carbon matrix, the electronic conductivity of the nanocomposite is enhanced. Br-Doping leads to the drop of activation energy for V4+/V5+ redox reaction. The nanocomposite cathode exhibits a high reversible capacity of 41 mA h g−1 at 10C. Both the superior rate and cycling performances could be attributed to the synergistic effect of the multilevel structure and amorphous carbon.
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JOURNAL OF ELECTROANALYTICAL CHEMISTRY
·
2019
·
IF 3.218
Dongxue Luo,Ping Lei,Yunxuan Huang,Guorong Tian,Xingde Xiang
Rechargeable aqueous sodium-ion batteries (SIBs) are urgently pursued as a low-cost candidate for grid-scale storage of intermittent renewable energies. NASICON-type NaTi 2 (PO 4 ) 3 holds great promises as anode material for aqueous SIBs owing to the high theoretical capacity and low redox potential , but being severely challenged by poor cycling performance and low reaction kinetics. Herein, graphene-integrated NaTi 2 (PO 4 ) 3 /C composite is prepared with a facile sol-gel approach as anode material for aqueous SIBs. Electrochemical properties of the material in high-concentration aqueous electrolyte (6 M NaClO 4 ) are systematically investigated by using cycling voltammetry , galvanostatic technique and electrochemical impedance spectroscopy . It is found that it shows an improved charge/discharge performance with a high practical capacity of 104.6 mAh g −1 at 100 mA g −1 , excellent high-rate capability with a reversible capacity of 88.0 mAh g −1 at 2000 mA g −1 , and good cycling stability with 92% capacity retention after 100 cycles. The improved electrochemical performance is attributed to the synergetic contribution of carbon-blending nanostructure and high-concentration electrolyte, which largely enhances structural stability and reaction kinetics of the material. In addition, the redox mechanism is discussed based on experimental results from cyclic voltammetry and X-ray diffraction technique.
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