JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS
·
2025
·Vol. 36
·期 23
·1-13
·
IF 2.8
Xu Cheng,Liu Ke,Lu Yong,Xu Qi
Sodium-ion batteries (SIBs), as an emerging energy storage technology, have been recognized as one of the most promising alternatives to lithium-ion batteries (LIBs). Among various cathode materials, the NASICON-type Na 4 VMn(PO 4 ) 3 (NVMP) composite material has garnered considerable attention owing to its distinctive 3D framework structure, high redox potential, stable crystal structure, and rapid Na + diffusion rate. Nevertheless, the practical application of NVMP cathodes is constrained by several inherent limitations, including inherently low electronic conductivity, Mn 3+ Jahn–Teller distortion, and structural degradation mechanisms, which collectively contribute to compromised rate capability and limited cycling durability. To tackle this challenge, an N-doped dual nano-carbon coating was applied to the NVMP material to enhance the conductivity of the composite. Building upon this foundation, a series of Na 4 VMn 1- x Cr x (PO 4 ) 3 /NC@CNTs cathode materials (where x = 0, 0.25, 0.5, 0.75, and 1) were successfully prepared using the sol–gel method, enabling targeted regulation of Mn/Cr ratios for enhanced electrochemical performance. The N-doped dual nano-carbon coating is capable of forming carbon layer defects and active sites, as well as constructing a 3D conductive network structure, which can enhance the diffusion rate of Na + ions and shorten their transport path. The results indicate that the Na 4 VMn 0.5 Cr 0.5 (PO 4 ) 3 /NC@CNTs cathode material demonstrates the highest discharge capacity, achieving 132.1 mAh·g −1 when x = 0.5. Notably, the capacity decreases rapidly at high rates, potentially attributed to the collapse of the crystal structure and excessive polarization, resulting in a deterioration of the material’s electrochemical performance. The optimized Na 4 VCr(PO 4 ) 3 /NC@CNTs (when x = 1) demonstrates exceptional rate performance with 91.2% capacity retention at 1C, accompanied by significantly reduced charge transfer resistance (Rct = 331.9 Ω). This study establishes a design paradigm for NASICON-type cathode materials through dual-transition metal synergistic doping and demonstrates the efficacy of Cr/Mn co-substitution in balancing ionic/electronic conductivity for next-generation high-power sodium-ion batteries.
研究领域:
材料科学
·
电化学
·
储能技术
·
纳米技术
·
无机化学
✓ 已验证
DOI
高影响因子
Energy & Environmental Materials
·
2022
·Vol. 6
·期 6
·e12477
·
IF 13.443
Xiangdan Zhang,Yuanyuan Huang,Xiaoyi Hu,Ruxin Guo,Yongshang Zhang,Zhiheng Wu,Guoqin Cao,Yuran Yu,Zhuo Wang,Yonglong Shen,Guosheng Shao
While sulfide solid electrolytes such as Na 11 Sn 2 PS 12 can allow fast transport of Na + ions, their utilization in solid sodium ion batteries is rather unsuccessful since they are not electrochemically compatible to both high-voltage cathodes and sodium metal anode. In this work, we devise an effective approach toward realizing solid sodium ion batteries, using the Na 11 Sn 2 PS 12 electrolyte and slurry-coated NASICON-type Na 3 MnTi(PO 4 ) 3 @C as high-voltage cathode, highly beneficial for low processing cost and high content/loading of active cathode matter. We report that through significantly improved integrity of electrolyte-cathode interface, such solid sodium ion batteries can deliver outstanding cycling and rate performance, with a charge voltage resilience up to 4.1 V, a high cathode discharge capacity of 128.7 mAh g −1 against the Na 3 MnTi(PO 4 ) 3 @C in cathode is achieved at 0.05 C, and capacity retention ratio of 82% with a rate of 0.1 C is realized after prolonged cycling at room temperature. Besides, we demonstrate that such a solid sodium ion battery can even perform at a sub-zero Celsius temperature of −10°C, when the conventional control cell using liquid electrolyte completely fail to function. This work is to offer a dependable avenue in engineering next generation of safe solid ion batteries based on highly sustainable and much cheaper material resources.
研究领域:
材料科学
·
电化学
·
电池技术
·
能源存储
✓ 已验证
产品关联
DOI
高影响因子
Energy Storage Materials
·
2019
·
IF 0
Jian Zhang,Xudong Zhao,Yuzhu Song,Qiang Li,Yongchang Liu,Jun Chen,Xianran Xing
Na 3 V 2 (PO 4 ) 3 is one of the most promising cathodes for sodium-ion batteries (SIBs) due to its three-dimensional framework. To meet practical feasibility, the substitution of vanadium with low-cost active elements is urgent. Here the Na + superionic conductor (NASICON)-type Na 3.5 Mn 0.5 V 1.5 (PO 4 ) 3 nanoparticles homogeneously embedded in porous carbon matrix are prepared and investigated as a novel cathode for SIBs. The as-prepared Na 3.5 Mn 0.5 V 1.5 (PO 4 ) 3 /C could deliver a desirable average discharge potential of 3.43 V vs. Na + /Na with fascinating rate capability of 92.7 mA h g −1 at 60C and impressive capacity retention of 87.2% after 4000 cycles at 20C. In situ X-ray diffraction reveals that the electrochemical process undergoes highly reversible biphasic transition and single phase change with a relatively small volume change (8.21%), ensuring the high structural stability and excellent cyclic capability. The reversible evolution of Mn 2+/3+ and V 3+/4+ redox couples upon Na + extraction/insertion has been revealed by the confirmation of valence state via both ex situ X-ray absorption near-edge structure spectra and X-ray photoelectron spectroscopy. The superior performance of Na 3.5 Mn 0.5 V 1.5 (PO 4 ) 3 could be attributed to the high electronic/ionic conductivity and low sodium-ion diffusion energy barrier, which is supported by the electrochemical impedance spectroscopy and cyclic voltammetry measurements, as well as density functional theory computations.
研究领域:
材料科学
·
能源存储
·
电化学
·
电池技术
✓ 已验证
DOI
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.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
DOI
高影响因子
JOURNAL OF POWER SOURCES
·
2018
·
IF 6.945
Peng Zhang,Xiaotong Yang,Tong Wang,Nobuyuki Imanishi,Osamu Yamamoto,Miao Wang
We demonstrate a novel rechargeable energy storage system having a metallic lithium negative electrode and a liquid–solid hybrid positive electrode of Fe 3+ /Fe 2+ /Fe in N,N-Dimethylformamide, which are separated by an impermeable NASICON–type Li 1.4 Al 0.4 Ge 0.2 Ti 1.4 (PO 4 ) 3 –epoxy resin composite film with a lithium ion conductivity of ca. 5.0 × 10 −4 S cm −1 . The discharge curve for the battery shows two plateaus. The first plateau corresponds to Li + FeCl 3 = LiCl + FeCl 2 , while the second one is associated with 2 Li + FeCl 2 = 2 LiCl + Fe. In the process of reduction of Fe 3+ to Fe 2+ , it delivers a stable discharge capacity of ca. 110 mAh g FeCl3 −1 with a Coulombic efficiency higher than 95% and is capable of enduring over 60 circles at a high current density of 1.0 mA cm −2 without any catalyst. Furthermore, a stable discharge capacity up to ca. 455 mAh g FeCl3 −1 is achieved for conversion of FeCl 3 /FeCl 2 /Fe with a three–electron reaction. This work demonstrates a proof of feasibility of hybrid liquid–solid hybrid positive electrode, since these reactions are reversible confirmed by x–ray diffraction patterns and EDX mapping test.
研究领域:
材料科学
·
电化学
·
能源存储系统
·
电池技术
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF POWER SOURCES
·
2021
·
IF 9.127
Yujian Liu,Limin Liu,Jinsong Peng,Xiaoliang Zhou,Dongshi Liang,Lei Zhao,Jiawen Su,Bo Zhang,Si Li,Naiqing Zhang,Qianli Ma,Frank Tietz
Although research on all-solid-state sodium batteries (ASSSBs) have been conducted for many years, the solid-state electrolyte (SSE) material is still far from practical application at room temperature . One major reason is that no suitable electrolyte material with high ionic conductivity has been found yet. In this study, Nb 5+ is introduced into NASICON-type solid electrolyte, where Nb 5+ substituted Na 3.4 Zr 2 Si 2.4 P 0.6 O 12 (NZSP) is prepared by a solution-assisted solid-state reaction method. The best ionic conductivity is as high as 5.51 mS cm −1 which is a significant improvement. High-frequency electrochemical impedance spectroscopy shows that the increase in total conductivity is mainly due to the decrease of grain boundary impedance as well as bulk impedance. The decrease in grain boundary impedance is probably owing to the increase in density of the electrolyte material after incorporation of the Nb content, which has a beneficial impact of the sintering of NZSP. The decrease in bulk impedance rather results from the ratio of sodium ion concentration and sodium vacancy concentration of 3.3:0.7 in the crystal structure, thus facilitating the sodium ion transport. Symmetric cells with sodium metal as electrodes (Na|Nb 5+ substituted NZSP|Na) are subsequently assembled and cycled stably for 60 cycles at a current density of 0.05 mA/cm 2 .
研究领域:
材料科学
·
电化学
·
能量存储
·
固态电解质
✓ 已验证
DOI
高影响因子
Energy Storage Materials
·
2023
·
IF 20.4
Xiaoyu Zhang,Jinhuan Wang,Dongqi Hu,Wei Du,Chuanxin Hou,Huiyu Jiang,Yuting Wei,Xiao Liu,Fuyi Jiang,Jianchao Sun,Hua Yuan,Xiaoyu Huang
The large scale application of solid state lithium metal batteries based on NASICON-type Li 1+x Al x Ti 2-x (PO 4 ) 3 (LATP) electrolyte has been hindered by insufficient ion conductivity and interface instability due to the spontaneous Ti 4+ reduction reaction between Li metal and LATP. To address these issues, Li 1.7 Al 0.3-x Bi x Ti 1.7 (PO 4 ) 3 (0 ≤ x ≤ 0.03) (LABTP) electrolytes were prepared, and the influence of Bi substitution on the microstructure and conductivity of LATP were investigated. Suitable amount of Bi substitution accelerates densification and improves the ionic conductivity . Furthermore, unlike commonly used polyethylene oxide (PEO) and polyvinylidene difluoride (PVDF), polyvinylbutyral (PVB)-based quasi-solid electrolytes with LABTP is first-time proposed to improve the compatibility and stability of the LATP/Li interface. The synergistic effect of Bi doping and PVB reduces the reduction reaction of Ti 4+ . Small voltage hysteresis is observed in the corresponding Li||Li symmetric cells. The solid-state Li|LABTP@PVB|LiFePO 4 full cell can deliver a high capacity of 146.2 mAh g −1 and a stable cycling performance without reduction after 200 cycles.
研究领域:
材料科学
·
电化学
·
电池技术
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）