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CERAMICS INTERNATIONAL · 2017 ·Vol. 43 ·期 12 ·9327-9333 · IF 2.986

High-performance LiTi2(PO4)3@carbon anode using double carbon sources for aqueous lithium ion battery

Nan Zhou,Shengxiong Huang,Tao Hong,Wei Luo,Yun Tian,Xiangyang Lu,Zhi Zhou

In this paper, LiTi 2 (PO 4 ) 3 @carbon composite as anode for aqueous lithium ion battery has been successfully synthesized by in-situ carbon coating method using oxalic acid and glucose as double carbon sources. XRD results confirm the rhombohedral NASICON-type LiTi 2 (PO 4 ) 3 structure of the as-prepared composite. The LiTi 2 (PO 4 ) 3 @carbon composite using double carbon sources (LTP-OG-10) disperses well, and the coated carbon layer has the appropriate thickness of 3–7   nm, which result in proper balance of the good electrical conductivity and the fast kinetics of diffusion of lithium ions . LTP-OG-10 exhibits better electrochemical performance compared with those using oxalic acid (LTP-O) or glucose (LTP-G) single carbon source. LTP-OG-10 anode delivers the discharge capacity of 112.5 mA   h g −1 , 96.8 mA   h g −1 , and 54.2 mA   h g −1 at 0.2   C, 5   C and 20   C, respectively, much larger than that of LTP-O and LTP-G. Moreover, LTP-OG-10 demonstrated excellent cycling performance, with the capacity retention of 71.1% after 400 cycles at 0.2   C, 22.9% higher than that of LTP-G. The good electrochemical properties of LTP-OG-10 is mainly ascribed to the increase of defects, high-quality and appropriate thickness of carbon layer. Our study reveals that preparing LiTi 2 (PO 4 ) 3 @carbon composite using double carbon sources is an efficient approach to enhance its electrochemical properties.

研究领域: 材料科学 · 电化学 · 能源存储 · 无机非金属材料 · 功能材料
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ACS Applied Materials & Interfaces · 2024 · IF 8.3

Efficient and Tunable Near-Infrared Luminescence in Cubic Phosphate K2AlTi(PO4)3:Cr3+ for Spectroscopy Applications

Long Chen,Jiyou Zhong

Broadband near-infrared (NIR) phosphors are crucial components of NIR phosphor-converted light-emitting diode (pc-LED) sources for various smart spectroscopy applications. However, developing an efficient, tunable, and inexpensive broadband NIR phosphor with sufficient spectral coverage remains a great challenge. In this work, a cubic phosphate K2AlTi(PO4)3 with highly structural rigidity was chosen as host material for Cr3+ substitution to create an efficient NIR emission. Synthesizing this compound, the obtained material exhibits a broadband NIR emission covering 700–1200 nm with a peak wavelength ranging from 820 to 860 nm depending on the Cr3+ substituting concentration. The Cr3+ concentration optimized sample possesses a photoluminescence quantum yield (PLQY) of 76.4% with an emission peak centered at 857 nm and a full width at half-maximum (fwhm) of 184 nm under 464 nm exaction, demonstrating an efficient and relatively long-wavelength NIR emission with wide spectral coverage. This broadband NIR emission is mainly derived from a single kind of emission center deduced from spectral analysis, luminescence dynamics, and first-principle calculations. Using this material, the fabricated NIR pc-LED device presents an excellent NIR output power and NIR photoelectric conversion efficiency, making this material attractive in practical applications of night-vision and bioimaging. Therefore, this work not only provides a broadband NIR material with superiorities of low cost, high efficiency, wide-range tunability, wide spectral coverage, and relatively long-wavelength NIR emission for spectroscopy applications but also highlights some clues to discover this kind of materials.

研究领域: 材料科学 · 光学材料 · 固态照明 · 光谱学 · 光子学
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IONICS · 2022 ·Vol. 28 ·期 6 ·2693-2700 · IF 2.961

Asymmetric polymer solid electrolyte constructed by dopamine-modified Li1.4Al0.4Ti1.6(PO4)3 for dendrite-free lithium battery

Ma Dongjuan,Chen Long,Li Yuan,Liu Yan,Zhang Hao,Wang Biyan

Solid polymer electrolyte (SPE) is an ideal substitute for routine liquid electrolyte for next-generation safety lithium (Li) batteries. Nevertheless, SPE cannot effectively impede Li dendrite growth due to the poor mechanical strength, which prevents its practical applications. Herein, an asymmetric sandwich solid electrolyte constructed by dopamine-modified Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 (PDA@LATP) on one side was prepared by solution casting method. The asymmetric electrolyte exhibits admirable ionic conductivity (1.2 × 10 –4 S cm −1 at 25 °C), high ionic transference number (0.47), wide voltage window (4.6 V vs . Li/Li + ) and good thermal stabilities. The PDA@LATP can not only impede Li dendrite growth, but also avoid the LATP reaction with Li anode. The assembled solid-state LiFePO 4 |Li battery assembled with asymmetric solid electrolyte delivers a satisfactory capacity retention up to 88.2% after 300 cycles at 0.5 C and under 25 °C (88.1% after 100 cycles at 0.5 C and under 70 °C). The asymmetric design of solid electrolyte provides a promising options for realizing safe energy storage systems. Graphical abstract We propose an asymmetric sandwich solid electrolyte, which can enable LiFePO 4 |Li battery stably and safely cycled at 25 °C and 70 °C, respectively, with excellent ionic conductivity, electrochemical and thermal stability. This asymmetric electrolyte ensures the inhibition of Li dendrites and stable electrolyte/anode interface.

研究领域: 材料科学 · 储能 · 电化学 · 电池技术
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International Journal of Electrochemical Science · 2023 ·Vol. 14 ·期 3 ·2815-2821 · IF 1.5

Synthesis of Na3V2(PO4)3/C Composites as High-Performance Cathode Materials for Sodium Ion Batteries

Xiang Ding,Xiaobing Huang,Shibiao Zhou,Anguo Xiao,Yuandao Chen,Chenggang Zuo,Junling Jin

Na 3 V 2 (PO 4 ) 3 (NVP) is a potential cathode material for sodium ion batteries (SIBs) due to its stable three-dimensional NASICON structure and high theoretical energy density. In this paper, the carbon-coated Na 3 V 2 (PO 4 ) 3 (NVP/C) cathode materials using pitch as carbon source were synthesized by a simple solid-state reaction method combined with microwave calcinations. The electrode performance of as-prepared NVP/C materials were investigated and the results demonstrated that the NVP/C composite with 13.1 wt.% carbon shows the best electrochemical properties. It possesses a high initial discharge capacity of 108.2 mAh g -1 , 90.5 mAh g -1 at 0.2 C and 10 C. After 1000 cycles at the rate of 10 C, the discharge capacity remained almost unchanged, with no capacity fading.

研究领域: 材料科学 · 电化学 · 储能技术 · 电池技术
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JOURNAL OF ALLOYS AND COMPOUNDS · 2024 · IF 5.8

Ultrahigh electrochemical properties of Na3V2(PO4)3 under synergistic effects of Er3+ substitution and CNTs coating

Rui Du,Chenghao Qian,Changcheng Liu,Que Huang,Yanjun Chen

Currently, the low ionic and electronic conductivities of Na 3 V 2 (PO 4 ) 3 (NVP) have been hindered its further application. In this paper, a simultaneous optimized method of Er 3+ substitution and carbon nanotubes (CNTs) enwrapping is proposed for the first time. Due to the large ionic radius of Er 3+ (89 pm vs 64 pm of V 3+ ), Er 3+ occupying the position of V 3+ makes the crystal structure more stable and alleviates the deformation of the crystal cell. Meanwhile, the interplanar spacing of NVP is broadened after introducing Er 3+ , so the de-intercalation rate of Na + can be accelerated and the kinetic properties are improved. In addition, the enwrapped CNTs connecting with amorphous carbon layers construct a conductive substrate for the fast electronic transportation, which significantly modifies the electronic conductivity. Moreover, the CNTs benefits to inhibit the agglomeration of NVP active materials and make the distribution more uniform and grain size more smaller. The decreasing size indicates a shorter pathway for Na + migration, which improves its apparent ionic diffusivity . Through the above analysis, the dual modification strategy can efficiently improve the kinetic properties of NVP system. Notably, Na 3 V 1.93 Er 0.07 (PO 4 ) 3 / C@CNTs (NVEP-0.07) submits a high capacity of 84.2 mAh g −1 at 50 C and maintains 70.6 mAh g −1 after 8000 cycles, corresponding to a high retention ratio of 83.9 %. The assembled NVEP-0.07 // CHC full cell reveals 146.2 mAh g −1 at 0.1 C, which successfully lightens the LED bulbs, indicating the excellent application potential of NVEP-0.07. Impressively, the recycled XRD/SEM/XPS results demonstrate the significantly improved crystal stability and chemical state of NVEP-0.07.

研究领域: 材料科学 · 电化学 · 储能技术 · 钠离子电池
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ADVANCED FUNCTIONAL MATERIALS · 2018 ·Vol. 28 ·期 36 ·1802684 · IF 13.325

Fast Potassium Storage in Hierarchical Ca0.5Ti2(PO4)3@C Microspheres Enabling High-Performance Potassium-Ion Capacitors

Zhongyu Zhang,Malin Li,Yu Gao,Zhixuan Wei,Meina Zhang,Chunzhong Wang,Yi Zeng,Bo Zou,Gang Chen,Fei Du

Hybrid potassium-ion capacitors (KICs) show great promise for large-scale storage on the power grid because of cost advantages, the weaker Lewis acidity of K + and low redox potential of K + /K. However, a huge challenge remains for designing high-performance K + storage materials since K + ions are heavier and larger than Li + and Na + . Herein, the synthesis of hierarchical Ca 0.5 Ti 2 (PO 4 ) 3 @C microspheres by use of the electrospraying method is reported. Benefiting from the rich vacancies in the crystal structure and rational nanostructural design, the hybrid Ca 0.5 Ti 2 (PO 4 ) 3 @C electrode delivers a high reversible capacity (239 mA h g −1 ) and superior rate performance (63 mA h g −1 at 5 A g −1 ). Moreover, the KIC employing a Ca 0.5 Ti 2 (PO 4 ) 3 @C anode and activated carbon cathode, affords a high energy/power density (80 W h kg −1 and 5144 W kg −1 ) in a potential window of 1.0–4.0 V, as well as a long lifespan of over 4000 cycles. In addition, in situ X-ray diffraction is used to unravel the structural transition in Ca 0.5 Ti 2 (PO 4 ) 3 , suggesting a two-phase transition above 0.5 V during the initial discharge and solid solution processes during the subsequent K + insertion/extraction. The present study demonstrates a low-cost potassium-based energy storage device with high energy/power densities and a long lifespan.

研究领域: 储能技术 · 材料科学 · 电化学 · 可持续能源技术
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Carbon Neutralization · 2022 ·Vol. 1 ·期 1 ·49-58 · IF 0

A NASICON-typed Na4Mn0.5Fe0.5Al(PO4)3 cathode for low-cost and high-energy sodium-ion batteries

Xiao-Hao Liu,Wei-Hong Lai,Jian Peng,Yun Gao,Hang Zhang,Zhuo Yang,Xiang-Xi He,Zhe Hu,Li Li,Yun Qiao,Ming-Hong Wu,Hua-Kun Liu

Developing low-cost and high-voltage manganese (Mn)-based Na superionic conductor (NASICON) cathode materials have attracted extensive interest. The low capacity and cycling instability of Na 4 MnAl(PO 4 ) 3 (NMAP), however, limits its performance in sodium-ion batteries (SIBs). Herein, a binary Na 4 Mn 0.5 Fe 0.5 Al(PO 4 ) 3 (MNFAP) is fabricated to ease the structural instability and, in turn, deliver an improved reversible capacity of 102 mAh g −1 at 0.1 C and a high energy density of 287.7 Wh kg −1 . The synergistic interaction of Fe and Mn in Na 4 Mn 0.5 Fe 0.5 Al(PO 4 ) 3 /C composite leads to a one-phase solid-solution reaction mechanism with high structural reversibility. Theoretical calculations have also been performed to explain the upshifted voltage platform of both Fe 2+ /Fe 3+ and Mn 3+ /Mn 4+ redox potentials. The rational design of NASICON-type cathodes by regulating their composition with dual metal ions provides new perspectives for developing high-performance SIBs.

研究领域: 材料科学 · 电化学 · 能源存储
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ACS Applied Energy Materials · 2026 · IF 5.5

High-Performance Na1.9K0.1VTi(PO4)3-GNP with Multielectron Redox for Printed Aqueous Symmetric Sodium-Ion Batteries

Jiaoyang Shen,Hehe Ren,Jian Zou,Xin Guo,Yuanjie Wei,Quancai Li,Jing Liang,Wei Wu

Aqueous symmetric sodium-ion batteries (ASSIBs) are gaining attention as attractive energy storage devices for flexible and wearable electronics due to their excellent structural stability, inherent safety, environmental friendliness, and the abundant sodium resources. NASICON-structured Na2VTi(PO4)3 (NVTP) features a three-dimensional framework structure; Ti4+/Ti3+ and V4+/V3+ redox couples can be used to fabricate symmetrical sodium-ion batteries as both the anode and the cathode. However, poor cycle stability and irreversible dissolution in aqueous solutions limit the application of NVTP in flexible ASSIBs. Herein, the Na1.9K0.1VTi(PO4)3-10% GNP (NKVTP-GNP) composite was synthesized by partially substituting Na+ in Na2VTi(PO4)3 with K+ and coating graphene nanoplatelets (GNP). The K+ doping and GNP coating successfully promoted the conversion of V4+ to V5+ and enhanced the cycling stability of the materials. The capacity retention rate of the NKVTP-GNP cathode is 99% after 1000 cycles, while the anode maintains 81% of its capacity after 500 cycles. Additionally, a flexible symmetric battery NKVTP-GNP//NKVTP-GNP was fabricated via a screen-printing technique, which delivered a wide voltage window of 1.8 V, an energy density of 63 Wh kg−1, and excellent cycling stability, retaining 90% of its capacity after 2000 cycles at 10 C. More importantly, the battery shows high flexibility, adjustable shapes, and high-throughput manufacturing. This work provides insights into the development of high-performance flexible ASSIBs.

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CHEMICAL ENGINEERING JOURNAL · 2025 · IF 13.2

Spatially engineered Y2O3/rGO dual-modification empowers ultra-stable and high-rate Na3V2(PO4)3 cathodes

Houlin Cheng,Jingxuan Li,Pengcheng Wang,Youzu Xu,Zhiyang Zhang,Qian Feng,Hurong Yao,Zhigao Huang,Jiaxin Li

This work utilized Y 2 O 3 and rGO as additives, and systematically regulated their spatial distribution and composite ratio with Na 3 V 2 (PO 4 ) 3 (NVP) to overcome the bottlenecks faced by NVP, such as intrinsically low electronic conductivity, severe interfacial side reactions, and structural instability during cycling. The modified NVP cathode can significantly enhance its electrochemical performance, and improve its sodium storage and thermal safety performance in the pouch-type full cell. The as-prepared NVP@Y 2 O 3 @rGO material achieves an 84 % capacity retention rate after 1000 cycles at 1C&27 °C, while still delivering a specific capacity of 49.6 mAh g −1 at an ultra-high rate of 30C. Under elevated temperature of 45 °C, it maintains 91.5 % capacity retention after 400 cycles at 1C. In contrast, the pristine NVP retains only 38.2 %. Moreover, it exhibits a reversible capacity of 63.6 mAh g −1 even at an ultra-high rate of 40C. More importantly, pouch-type full cell testing further confirms its superior cycling stability (60.8 % capacity retention after 100 cycles, representing a 30.5 % improvement over the unmodified sample). Mechanistic studies reveal that the combined effects of Y 2 O 3 and rGO effectively facilitate electron/ion transport, suppress electrode-electrolyte interfacial side reactions, mitigate volume change stress, and enhance structural integrity. This work offers new insights for designing high-stability cathode materials for sodium-ion batteries.

研究领域: 材料科学 · 电化学 · 能源存储 · 无机非金属材料 · 固态化学 · 纳米复合材料
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ACS Applied Materials & Interfaces · 2024 · IF 8.3

Enhancing Kinetics in Sodium Super Ion Conductor Na3MnTi(PO4)3 through Microbe-Assisted and Structural Optimization

Caixia Li,Shuping Pu,Jiapin Liu,Yun Huang,Jiepeng Chen,Xinyan Xiang,Lei Fu,Chao Zou,Xing Li,Mingshan Wang,Yuanhua Lin,Haijun Cao

Sodium (Na) super ion conductor (NASICON) structure Na3MnTi(PO4)3 (NMTP) is considered a promising cathode for sodium-ion batteries due to its reversible three-electron reaction. However, the inferior electronic conductivity and sluggish reaction kinetics limit its practical applications. Herein, we successfully constructed a three-dimensional cross-linked porous architecture NMTP material (AsN@NMTP/C) by a natural microbe of Aspergillus niger (AsN), and the structure of different NMTP cathodes was optimized by adjusting different transition metal Mn/Ti ratios. Both approaches effectively altered the three-dimensional NMTP structure, not only improving electronic conductivity and controlling Na+ diffusion pathways but also enhancing the electrochemical kinetics of the material. The resultant AsN@NMTP/C-650, sintered at 650 °C, exhibits better electrochemical performance with higher reversible three-electron reactions corresponding to the voltage platforms of Ti4+/3+, Mn3+/2+, and Mn4+/3+ around 2.1, 3.6, and 4.1 V (vs Na+/Na), respectively. The capacity retention rate is up to 89.3% after 1000 cycles at a 2C rate. Moreover, a series of results confirms that the Na3.4Mn1.2Ti0.8(PO4)3 cathode has the most excellent electrochemical performance when the Mn/Ti ratio is 1.2/0.8, with a high capacity of 96.59 mAh g–1 and 97.1% capacity retention after 500 cycles.

研究领域: 材料科学 · 电化学 · 微生物学
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CARBON · 2025 · IF 11.6

Achieving long-term cycling stability in Na3V2(PO4)3 cathode material through polymorphic carbon network coating

Jin Chen,Pei Liu,Kai Xu,Zhilei Hao,Guohui Tang,Changtian Zhu,Zixuan Ding,Shuai Yin,Zhiqiang Li,Zhen Ding,Yi Wang,Zhanpeng Liu,Siwen Yu,Xing Xin,Fenghua Liu

Na 3 V 2 (PO 4 ) 3 (NVP) material has evolved as a significant candidate for electrode materials in the development of sodium-ion batteries. However, the low conductivity of NVP material leads to low cycling performance, limiting their application in high-efficiency battery materials. To address this issue, this work proposes a novel strategy for materials design through constructing 3D network carbon-coatings on the surface of NVP materials. The carbon-coatings are achieved via a combination of sol-gel technique and heat treatment using pyrolytic carbon (C), carbon nanotubes (CNTs) and graphene (GN). In comparison to NVP@C, the electrochemical properties of NVP@C/GN, NVP@C/CNTs, and NVP@C/GN/CNTs have shown improvements. Among these, NVP@C/GN/CNTs exhibit the most outstanding electrochemical performance in the half-cell test. Specifically, this material demonstrates exceptional cycling stability, with a capacity of 92 mAh g −1 that can be maintained even after 800 cycles at a high-rate performance of 10C, with an attenuation of 10.6 %. The enhanced electrochemical performance is attributed to the specific ternary carbon-coating conductive structure, which significantly shortens the diffusion paths of Na + ions and electrons within NVP, resulting in improved Na + ion and electron transport kinetics. This study provides a new design paradigm for improving the conductivity of cathode material for sodium-ion batteries.

研究领域: 材料科学 · 电化学
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Crystals · 2024 ·Vol. 15 ·期 1 ·31 · IF 2.4

Preparation and Electrochemical Characterization of Y-Doped Li1.3Al0.3Ti1.7(PO4)3 Solid Electrolytes for Lithium-Metal Batteries

Zhongran Yao,Fen Qi,Qiang Sun,Lin Ye,Xiaowei Yang,Guojie Chao,Pei Tang,Kongjun Zhu

Lithium-conducting NASICON materials have emerged as a promising alternative to organic liquid electrolytes for high-energy-density Li-metal batteries, owing to their superior ionic conductivity and excellent air stability. However, their practical application is hindered by poor sintering characteristics and high grain boundary resistance. In this investigation, Li1.3Al0.3−xYxTi1.7(PO4)3(LAYTP-x,x= 0.00, 0.01, 0.03, 0.05, and 0.07) were successfully synthesized via conventional solid-state reaction to explore the impact of Y3+on both ionic conductivity and chemical stability. The structural, morphological, and transport properties of the samples were comprehensively characterized in order to identify the optimal doping concentration. All samples exhibited a NASICON structure with a uniform distribution of Y elements within the electrolyte. Due to its highest relative density (95.8%), the LAYTP-0.03 electrolyte demonstrated the highest total conductivity of 2.03 × 10−4S cm−1with a relatively low activation energy of 0.33 eV, making it suitable for solid-state batteries. When paired with the NCM811 cathode, the Li/LAYTP-0.03/NCM811 cell exhibited outstanding electrochemical performance: a high capacity of 155 mAh/g was achieved at 0.2C after 50 cycles with a Coulombic efficiency of approximately 100%, indicating highly reversible lithium plating/stripping facilitated by the LAYTP-0.03 electrolyte. These results suggest that the LAYTP-0.03 ceramic electrolyte could be a promising alternative for developing safe solid-state Li-metal batteries.

研究领域: 材料科学 · 电化学
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