Journal of Physical Chemistry C
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2025
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IF 3.2
Chunying Chen,Jinjun Ren,Qing Jiao,Jingping Tang,Lili Hu
Joint doping with trivalent and monovalent ions is a widely adopted strategy to enhance the ionic conductivities of NASICON-type solid-state electrolytes (SSEs) with the general formula Na1+xZr2SixP3–xO12, but the underlying microscopic mechanism remains unclear. In this study, we synthesized a series of Na3+xLaxZr2–xSi2PO12 (NLZSPx, 0 ≤ x ≤ 0.4) ceramics and characterized their electrical properties and structures by using electrochemical impedance spectroscopy (EIS), X-ray diffraction (XRD), scanning electron microscopy (SEM), and advanced solid-state nuclear magnetic resonance (SSNMR). Among all of the samples, the composition with x = 0.2 exhibited the highest ionic conductivity, achieving 1.05 × 10–3 S/cm at 25 °C, which is 3.65 times higher than that of the undoped sample. XRD and SSNMR results prove that La3+ ions did not integrate into the main phase lattice to replace Zr4+ ions. Instead, they formed a heterogeneous phase predominantly composed of Na3La(PO4)2 at the grain boundaries. The content of Na3La(PO4)2 and the composition of the NASICON main phase were accurately determined by SSNMR. This impurity resulted in changes in the Si/P and Na/Zr ratios within the main phase. Some comparison experiments are carried out and prove that these changes were not the principal drivers of the increased conductivity. SEM results further indicated that doping with an appropriate amount of La3+ ions significantly increased the sample densification, thus promoting Na+ ions transport between grain boundaries─this being the key factor driving the observed improvement in ionic conductivity.
研究领域:
材料科学
·
固体物理
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产品关联
DOI
高影响因子
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.
研究领域:
材料科学
·
电化学
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DOI
高影响因子
JOURNAL OF THE EUROPEAN CERAMIC SOCIETY
·
2018
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IF 3.794
Zhijian Sun,Lei Liu,Yuxiao Lu,Guangyue Shi,Jiajun Li,Lei Ma,Jie Zhao,Hongli An
NASION-type Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) is prepared by a novel sol-gel method using low cost inorganic germanium (GeO 2 ) as the precursor. The composition and phase transformation during the heating of the LAGP precursors are analyzed using thermogravimetric-differential scanning calorimetry (TG-DSC) and X-ray diffraction (XRD). The structures and morphologies of the LAGP are characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that the LAGP annealed at 900 ℃ is partially crystallized and consists of a large number of nanoscale grains surrounded by amorphous regions. The LAGP particles present an irregular morphology with a large size distribution over a range of 0.2–1 μm. In addition, ionic conductivities of the prepared LAGP first increase and then decrease with an increase in the sintering temperature and time. A high ionic conductivity (4.18 × 10 −4 Scm -1 ) with an activation energy of 0.30 eV are obtained for the LAGP sample sintered at 900 °C for 8 h.
研究领域:
材料科学
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电化学
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DOI
高影响因子
Nanomaterials
·
2022
·Vol. 12
·期 12
·2082
·
IF 5.719
Aihong Xu,Ruoming Wang,Mengqin Yao,Jianxin Cao,Mengjun Li,Chunliang Yang,Fei Liu,Jun Ma
An Li1.3Al0.3SnxTi1.7−x(PO4)3(LATP-xSn) ceramic solid electrolyte was prepared by Sn doping via a solid phase method. The results showed that adding an Sn dopant with a larger ionic radius in a concentration of x = 0.35 enabled one to equivalently substitute Ti sites in the LATP crystal structure to the maximum extent. The uniform Sn doping could produce a stable LATP structure with small grain size and improved relative density. The lattice distortion induced by Sn doping also modified the transport channels of Li ions, which promoted the increase of ionic conductivity from 5.05 × 10−5to 4.71 × 10−4S/cm at room temperature. The SPE/LATP-0.35Sn/SPE composite solid electrolyte with a sandwich structure was prepared by coating, which had a high ionic conductivity of 5.9 × 10−5S/cm at room temperature, a wide electrochemical window of 4.66 V vs. Li/Li+, and a good lithium-ion migration number of 0.38. The Li||Li symmetric battery test results revealed that the composite solid electrolyte could stably perform for 500 h at 60 °C under the current density of 0.2 mA/cm2, indicating its good interface stability with metallic lithium. Moreover, the analysis of the all-solid-state LiFePO4||SPE/LATP-0.35Sn/SPE||Li battery showed that the composite solid electrolyte had good cycling stability and rate performance. Under the conditions of 60 °C and 0.2 C, stable accumulation up to 200 cycles was achieved at a capacity retention ratio of 90.5% and a coulombic efficiency of about 100% after cycling test.Keywords:NASICON-type LATP;Sn doping;sandwich structure;composite solid electrolyte;lattice distortion
研究领域:
材料科学
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电化学
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固体化学
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DOI
PubMed
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2023
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IF 9.9
Shaoxiong Liu,Xiao Li,Siwei Zhong,Wenjia Jiang,Ye Liu,Wenchong Ding,Hai Hu,Zhifeng Huang,Li Liu
NASICON-structured Ti-based polyanion compounds benefit from a stable structural framework, large ion channels, and fast ion mobility . However, the large radius of potassium and its poor electronic conductivity restrict its use in potassium-ion batteries. Herein, hierarchical mesoporous Mn 0.5 Ti 2 (PO 4 ) 3 @C microspheres have been successfully synthesized using a simple electrospraying method. These microspheres consist of Mn 0.5 Ti 2 (PO 4 ) 3 nanoparticles evenly embedded in three-dimensional mesoporous carbon microspheres. The hierarchical mesoporous micro/nanostructure facilitates the rapid insertion and extraction of K + , while the three-dimensional carbon microspheres matrix enhances electrical conductivity and prevents active materials from collapsing during cycling. So the hierarchical mesoporous Mn 0.5 Ti 2 (PO 4 ) 3 @C microspheres exhibit a high reversible discharge specific capacity (306 mA h g −1 at 20 mA g −1 ), a notable rate capability (123 mA h g −1 at 5000 mA g −1 ), and exceptional cycle performance (148 mA h g −1 at 500 mA g −1 after 1000 cycles). The results show that electrosprayed Mn 0.5 Ti 2 (PO 4 ) 3 @C microspheres are a promising anode for PIBs.
研究领域:
材料科学
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能源存储
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产品关联
DOI
PubMed
高影响因子
SURFACE & COATINGS TECHNOLOGY
·
2024
·
IF 5.3
Dongjia Li,Bo Xiao,Xinyi Dai,Chao Wang,Yawei Wei,Haijun Chen,Yi Mai,Fuzhong Wu,Jiexi Wang
Amid the fast growth of lithium-ion batteries, LiNi 0.5 Mn 1.5 O 4 (LNMO) with a 4.7 V working voltage and cost advantages has gained significant attention. The instability of LNMO structure during high-voltage cycling leads to significant side reactions with the electrolyte, hindering its commercial development. Our study introduces a co-crystallization calcination strategy to enhance the optimization of LNMO. This study utilized a straightforward wet chemistry approach to combine the precursor of NASICON-type solid electrolyte Mg 0.5 Ti 2 (PO 4 ) 3 (MTP) with the precursor of LNMO. Subsequently, a MTP coating was formed in-situ on the surface of LNMO through a single-step calcination process. Co-crystallization and calcination processes limit LNMO particle secondary growth, shorten Li + diffusion path , achieve Mg 2+ and Ti 4+ co-doping, enhance structural stability , and result in triple modification, leading to a significant improvement in electrochemical performance . Among them, LNMO with a 1 % molar ratio modified by MTP reaches 81.7 % of the initial capacity after 500 cycles at room temperature and 84.3 % after 180 cycles at 55 °C. Under identical conditions, unmodified samples have 39.3 % and 76.3 %, respectively. Our research explores a novel application of NASICON-type solid electrolytes in modifying LNMO cathode material .
研究领域:
材料科学
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能源存储与转换
✓ 已验证
DOI
高影响因子
Energy Storage Materials
·
2022
·
IF 20.831
Qiao Wang,Chuang Yu,Liping Li,Xiaoqing Liu,Xin Zhang,Guichen Gao,Yaowen Wang,Guangshe Li
Solid-state sodium batteries (SSSBs) display great potential in scale energy storage for their safety, cost and sustainability. However, it is a great challenge to achieve high ionic conductivity and temperature adaptability for most sodium-ion solid electrolytes. Here, we first demonstrate that Sc 3+ -doped Na 3 Zr 2 Si 2 PO 12 (NASICON) is a promising electrolyte for a wide temperature range utilizing in SSSBs from 0 to 80 °C. Optimal Na 3.4 Zr 1.6 Sc 0.4 Si 2 PO 12 shows a superior Na-ion conductivity, up to 1.77 × 10 −3 S cm −1 at room temperature, and excellent Na metal compatibility, as confirmed by a symmetrical cell test. Furthermore, the solid-state sodium battery with the configuration of Na 3 V 2 (PO 4 ) 3 /Na 3.4 Zr 1.6 Sc 0.4 Si 2 PO 12 /Na maintains a discharge capacity of 98.7 mAh g −1 at 1C after 300 cycles at room temperature. Even at 0 °C, the battery still displays a reversible capacity of 99.2 mAh g −1 at 0.1C after 100 cycles. Through the structure analysis and ex-situ and in-situ electrochemical characterizations, the reasons that dominate the excellent performance of the assembled all-solid-state sodium battery with NASICON electrolytes are initially revealed.
研究领域:
材料科学
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电化学
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能源存储
✓ 已验证
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
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2024
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IF 5.8
Yi Luo,Xinguang Fang,Jintao Xiao,Zhen Huang,Jian Xiong,Guodong Jiang,Songdong Yuan
Na super ionic conductor (NASICON)-type Na 3 Zr 2 Si 2 PO 12 (NZSP) electrolytes, with their excellent safety and high energy density, are a promising candidate material for all-solid-state sodium-ion batteries. However, poor sintering performance and interfacial issues have limited its practical application. Herein, we propose the addition of sintering aids to densify grain boundaries and fine-tune the grain to achieve the densest microstructure, improve interfacial contact with sodium, and realize stable Na plating/stripping cycles at room temperature. (CuO) 2 -(B 2 O 3 ) 3 (CBO) is selected to reinforce grain boundary densification, inhibit dendrite growth, and ensure interfacial stability upon sintering at the lower temperature of 1000 °C. The optimized NZSP-0.2CBO demonstrates an ion conductivity reaching 6.83×10 −4 S cm −1 at room temperature, exhibiting a lower activation energy of 0.27 eV compared to bare NZSP. The interface impedance of Na/NZSP-0.2CBO (34.48 Ω cm²) is significantly lower than that of bare NZSP (373.43 Ω cm²). The corresponding Na/NZSP-0.2CBO/Na exhibits stable deposition/stripping cycles over 850 h at 0.1 mA cm −2 and room temperature, with a low polarization voltage of 65 mV. These superior performances can be attributed to the densification effect that enhances conductivity, enabling a uniform and enhanced Na + flux across the electrode/electrolyte interface without dendrite formation. A Na/NZSP-0.2CBO/Na 3 V 2 (PO 4 ) 3 battery is assembled accordingly, exhibiting a capacity of 87.4 mAh g −1 for 100 cycles with a capacity retention rate of 84.9 % and a high average coulombic efficiency of 97.6 % at room temperature.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2017
·
IF 7.504
Lei Chen,Yanming Zhao,Shenghong Liu,Long Zhao
Although the NASICON-type of Na3V2(PO4)3 is regarded as a potential cathode candidate for advanced sodium-ion batteries (SIBs), it has an undesirable rate performance and low cyclability, which are a result of its poor electronic conductivity. Here, we utilized conductive polyaniline (PANI) grown in situ to obtain the hard carbon-coated porous Na3V2(PO4)3@C composite (NVP@C@HC) with a typically simple and effective sol–gel process. Based on the restriction of double carbon layers, the NVP size decreases distinctly, which can curtail the sodium-ion diffusion distance and enhance the electronic conductivity. As expected, the product displays good discharge capacity (111.6 mA h g–1 at 1 C), outstanding rate capacity (60.4 mA h g–1 at 50 C), and remarkable cycling stability (63.3 mA h g–1 with a retention of 83.3% at 40 C over 3000 cycles). Also, it performs a long-term cycling capacity of 58.5 mA h g–1 exceeding 15 000 cycles at 20 C (with a capacity loss of 0.24% per cycle).
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2023
·
IF 15.1
Hanwen Zhang,Liuxue Shen,Xiaodong Geng,Jianxin Zhang,Yue Jiang,Hongting Ma,Quanli Liu,Kai Yang,Junlin Ma,Nan Zhu
Sodium superionic conductor (NASICON) structured polyanionic materials have recently attracted great attention for robust crystal structures. However, inherent properties of NASICON presents poor electrical conductivity and low energy density. Herein, non-stoichiometric synthesized strategy is used for acquiring N 3.5 MTP, effectively suppressing voltage hysteresis. Besides, as-fabricated N 3.5 MTP grains in-situ grow on MXene-rGO aerogels by sol–gel synthesis approach obtaining N 3.5 MTP@MXene-rGO. MXene-rGO aerogel as an excellent conductive matrix can effectively avoid agglomeration of Na 3.5 MnTi(PO 4 ) 3 particles and alleviate volume change of the lattice during sodium ion intercalation/deintercalation. Moreover, cross-linked network of N 3.5 MTP@MXene-rGO provides fast electron transfer and ion transport rates. The above synergistic effect and contribution of pseudocapacitance make it an excellent discharge capacity of 189 mA h g −1 at 50 mA g −1 for N 3.5 MTP@MXene-rGO, long cycles of 5000 cycles, as well as 98 mA g −1 at −30 °C (50 mA g −1 ). Prospectively, this study provides an effective strategy for improving electrochemical performance of NASICON-type cathode for sodium batteries.
研究领域:
材料科学
·
能源存储
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS
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2023
·
IF 4
Wenxuan Wang,Shan Hu,Zihan Liu,Zelang Jian,Wen Chen
The NASICON-type (Na 1+x Zr 2 Si x P 3-x O 12 , 0≤x ≤ 3) sodium-ion solid state electrolyte (SSE) has emerged as an alternative for liquid electrolyte due to its good chemical/electrochemical stability, high thermal stability and high safety. However, the insufficient ionic conductivity and poor understanding of Na + transport mechanism hinder the further development of sodium-ion SSE. Herein, we report Sm modified Na 3+x Zr 2-x Sm x Si 2 PO 12 (0≤x ≤ 0.4) electrolytes with a highest ionic conductivity of 2.25 × 10 −3 S cm −1 at 25 °C when x = 0.2. The introduction of Sm element adjusts the Si/P ratio in NASICON phase and densifies the electrolyte pellets by formation of Na 3 Sm(PO 4 ) 2 . To get a deep insight into the enhanced mechanism of Na + transport in grains, low-temperature electrochemical impedance spectra (LT-EIS) and Jonscher's power law relationship are employed to analyze the electrical behavior of grains. The results demonstrate that the regulation of Si/P ratio can evoke lower migration energy, more charge carrier concentration and higher hopping frequency , which synergistically improve the ionic conductivity in grains.
研究领域:
材料科学
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电化学
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储能
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固体离子学
✓ 已验证
DOI
高影响因子
PROGRESS IN SOLID STATE CHEMISTRY
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2026
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IF 9.7
Yuhan Yi,Qiao Wang,Chuang Yu,Liping Li,Xin Zhang,Guangshe Li
Both the electrochemical and mechanical properties of solid-state electrolytes are crucial for achieving stable battery performance, while the widely studied NASICON-type electrolytes such as Na 3 Zr 2 Si 2 PO 12 (NZSP) still suffer from poor conductivity and a tendency to Na metal penetration. To address these problems simultaneously, we propose an integrated chemistry-structure-mechanics design principle, in which aliovalent Sc/Mg co-doping (chemistry) regulates lattice framework and grain-boundary evolution (structure), thereby enhancing mechanical robustness (mechanics) without compromising ionic transport. The optimized sample (Na 3.4 Zr 1.7 Sc 0.2 Mg 0.1 Si 2 PO 12 ) achieves a high room-temperature conductivity of 1.26 × 10 −3 S cm −1 and a 25% increase in hardness compared with the Mg-free analogue. The solid-state cell assembled with this electrolyte (Na/Na 3.4 Zr 1.7 Sc 0.2 Mg 0.1 Si 2 PO 12 /Na 3 V 2 (PO 4 ) 3 ) shows excellent cycling stability in a wide temperature range of 0-80 °C, and retains 90% of its initial capacity after 440 cycles at 30 °C and 1C. These results demonstrate that aliovalent co-doping to concurrently optimize lattice chemistry and ceramic microstructure is an effective route to high-performance NASICON electrolytes.
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）