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NASICON
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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SOLID STATE IONICS · 2020 · IF 3.107

Facile synthesis and performance of NASICON Li1+xAlxGe2-x(PO4)3 electrolytes for all solid state lithium-ion battery

Erqing Zhao,Yudi Guo,Yuan Xin,Guangri Xu

Nasicon-type Li 1+x Al x Ge 2-x (PO 4 ) 3 (x = 0–0.5) electrolytes have been prepared via a facile and economic method. All synthetic electrolyte samples show Nasicon structure and good crystallinity . The Al doping content has a great influence on the electrical conductivity of electrolyte. The electrolyte with the composition of Li 1.4 Al 0.4 Ge 1.6 (PO 4 ) 3 exhibits a highest electrical conductivity of 2.72 × 10 −4  S/cm at room temperature , which is mainly attributable to fewer impurity and dense electrolyte structure. The LiFePO 4 /Li cell assembled with this electrolyte delivers an initial specific discharge capacity of 127.86 mAh g −1 at a charge/discharge current density of 0.5C at 60 °C, which shows an excellent cycling performance with high discharge capacity of 131.2 mAhg −1 after 150 cycles. These results suggest that the Li 1.4 Al 0.4 Ge 1.6 (PO 4 ) 3 electrolyte is a potential electrolyte for all solid state lithium-ion battery.

研究领域: 材料科学 · 电化学
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2021 · IF 8.128

NASICON type KTi2(PO4)3 decorated by NTCDA-derived carbon layer for enhanced lithium/sodium storage

Minhui Zheng,Zhoulu Wang,Qiang Ru,Haikuo Fu,Jun Zhang,Zikang Pan,Jiaqi Wang,Qizhen Xie,Xing Zhao

NASICON type KTi 2 (PO 4 ) 3 decorated by NTCDA-derived carbon layer (KTP/NC) was prepared as anode material to obtain sustainable lithium/sodium ion storage (LIBs/SIBs). Due to its prominent capacitance, good electronic conductivity and ability to constrain volume, the KTP/NC composite realizes highly electrochemical kinetics both in LIBs and SIBs . For LIBs, the KTP/NC composite delivers a superior reversible capacity of 598.1 mAh g −1 after 200 cycles at 0.5C, impressive cyclability with 225.5 mAh g −1 after 3000 cycles at an ultrahigh current density of 26.1 C and conspicuous rate performance of 160.6 mAh g −1 even at 52.2 C. In addition, the composite has a wide operation-temperature window with favorable capacities of 147.1–372.9 mAh g −1 from −10 °C to 50 °C. As for SIBs, the KTP/NC composite maintains a stable discharge capacity of 112.5 mAh g −1 after 700 cycles at a current density of 2.6 C and conspicuous rate performance of 86.7 mAh g −1 at 5.2 C. The KTP/NC anode exhibits discharge capacities of 29.9–112.6 mAh g −1 from −10 °C to 40 °C. The results demonstrate that the KTP/NC composite would be a promising electrode material for LIBs and SIBs.

研究领域: 材料科学 · 能源存储
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Materials Today Nano · 2021 · IF 8.109

Stable cycling of LiCoO2 at 4.55 V enabled by combined Mg doping and surface coating of NASICON-type electrolyte

P. Zhang,C. Xie,G. Han,Q. Zhu,L. Chen,M. Jin,Q. Liu,Y. Zhou,Q. Sun,J. Xie

Chemical/electrochemical instability of LiCoO 2 (LCO) at high voltage limits its deliverable capacity and thereby energy density of the battery , although it has a high theoretical capacity of 274 mAh/g. In this study, stable cycling of LiCoO 2 at a voltage as high as 4.55 V can be achieved by simultaneous lattice doping with Mg (LMCO) and surface coating with a NASICON-type Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 (LATP) solid-state electrolyte. Uniform coating can be realized by a facile Pechini route combined with solid-phase calcination . The LCO with 4 wt% LATP coating and 2 at% Mg doping (4 wt% LATP/LMCO-0.02) can deliver a high capacity of 204 mAh/g in the voltage range of 3.0–4.55 V (vs. Li/Li + ) at 0.4C. After 300 cycles at 0.4C, the 4 wt% LATP/LMCO-0.02 material can maintain 86.2% of its initial capacity, significantly superior to those of undoped and/or uncoated materials. The results show that both doping and coating are critical in inhibiting structural change of LCO and electrolyte decomposition at a deeply charged state of LiCoO 2 material.

研究领域: 材料科学 · 电化学
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Journal of Materials Chemistry A · 2021 ·Vol. 9 ·期 12 ·7817-7825 · IF 12.732

Competition between activation energy and migration entropy in lithium ion conduction in superionic NASICON-type Li1−3xGaxZr2(PO4)3

Shanshan Duan,Can Huang,Min Liu,Zhiwen Cao,Xiaocong Tian,Shuen Hou,Jiangyu Li,Boyuan Huang,Hongyun Jin

NASICON-type solid state electrolytes have attracted great interest in all-solid-state batteries, and many attempts have been applied to enhance the ionic conductivity. It is generally believed that low activation energy governs the high ionic conductivity while the prefactor, particularly migration entropy, is often overlooked. Here, employing a combination of electrochemical strain microscopy, speed of sound measurements, and electrochemical impedance spectra, we investigate the structure–property relationships governing ionic conduction behavior in the Li1−3xGaxZr2(PO4)3 system. A sharp increase in the prefactor upon Ga substitution is attributed to the increased migration entropy while the increase in activation energy can be rationalized in terms of the inductive effect. These two competitive factors determine the final ionic conductivity.

研究领域: 材料科学 · 电化学
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FUEL · 2023 · IF 7.4

Promotional effect of Cs modification to NASICON material on aldol condensation of acetic acid and formaldehyde to acrylic acid

Kaiwen Zheng,Qiliang Gao,Chao Li,Guojie Zhang,Qingde Zhang,Junfeng Zhang,Yizhuo Han,Yisheng Tan

The production of high value-added oxygenated chemicals from methanol and its derivatives is one of the important ways of coal conversion and clean and efficient utilization. Herein, a series of environmentally-friendly Cs-modified NASICON materials were applied to catalyze the aldol condensation of acetic acid (HAc) and formaldehyde (FA) to acrylic acid (AA) and methyl acrylate (MA). Encouragingly, the selectivity of target products (AA + MA) was highly up to 92.2%, corresponding to the space–time-yield more than 48.0 μmol·g cat - 1 ·min - 1 over the 2Cs/NSC catalyst, achieving the synchronization of good selectivity and productivity for the target products. Characterization results demonstrated that the acid-base modulation by Cs was responsible for catalyst supremacy. The weak basic sites on catalyst surface were efficient in adsorbing and activating HAc. Plenty of acidic sites especially the medium-strong and strong acidic sites were more favorable for the AA formation.

研究领域: 催化化学 · 煤化工 · 清洁能源
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2025 · IF 9.7

High-entropy doping in NASICON cathodes: Activating the V4+/V5+ redox couple and inducing a reversible single solid-solution phase reaction for advanced sodium ion batteries

Binghao Lin,Xu Wu,Xuejie He,Jiaxin Ye,Yuqin Song,Ping Jiang,Linxuan Bai,Xiangyue Liao,Yangjie Li,Yu Huo,Qiaoji Zheng,Heng Zhang,Dunmin Lin

Na 3 V 2 (PO 4 ) 3 (NVP) with typical NASICON structure is highly regarded as one of the most appealing cathodes for sodium-ion batteries (SIBs) for their excellent structural stability; however, the poor electronic conductivity and irreversible phase transition at high voltage (∼4 V) for the material result in poor rate capabilities and significant capacity degradation during electrochemical reactions. Herein, the high-entropy doping strategy of introducing six types of metal ions into the V-sites in Na 3 V 2 (PO 4 ) 3 is used to design a high-performance cathode of Na 3 V 1.73 (Mn, Ca, Mg, Al, Zr) 0.05 Nb 0.02 (PO 4 ) 3 (HE-NVP) for SIBs. After the high-entropy doping, a reversible V 4+ /V 5+ redox pair is activated at high voltage of ∼4 V, which significantly contributes to the enhancement of energy density and operating voltage. Moreover, after high entropy doping, the single solid solution phase transition in high voltage range is induced, effectively improving the material’s structural stability and exhibiting very small volume change of 1.1 % during the Na + extraction/insertion. Based on the unique advantages mentioned above, the high-entropy HE-NVP exhibits a superior discharge capacity of 122.1 mAh g −1 at a current rate of 0.5C and maintains a remarkable capacity retention of 90.1 % after 500 cycles at a rate of 5C. This work provides a useful reference for designing advanced cathodes for SIBs by regulating high entropy doping.

CAS / MDL: 7803-55-6
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 MATERIALS SCIENCE · 2022 ·Vol. 57 ·期 25 ·11774-11782 · IF 4.682

Enhancing Na-ion conducting capacity of NASICON ceramic electrolyte Na3.4Zr2Si2.4P0.6O12 by NaF sintering aid

Liu Limin,Liang Dongshi,Zhou Xiaoliang,Liu Yujian,Su Jiawen,Xu Yao,Peng Jinsong

NASICON-type material Na 1+ x Zr 2 Si x P 3− x O 12 (0 ≤  x  ≤ 3) is considered to be one of the most promising solid-state electrolytes that can be applied in all-solid-state sodium batteries (SSNBs). However, further increasing the ionic conductivity of Na 1+ x Zr 2 Si x P 3− x O 12 (0 ≤  x  ≤ 3) to obtain higher performance electrolyte materials is still a challenge for its practical application. Herein, the Na 3.4 Zr 2 Si 2.4 P 0.6 O 12 (NZSP) powder is prepared by the solution-assisted solid-state reaction (SA-SSR), and solid-state electrolytes with excellent electrochemical properties are obtained by doping with NaF as a sintering aid. With the increase of NaF doping, the crystal structure of NZSP is changed as well as a slight excess of Na + may increase the bottleneck size of the crystal, so that it enhances the migration ability of Na + in the crystal. Also, NaF as a sintering aid lowers the sintering temperature, increases the densities and improves the effective contact between crystals, which reduces the grain boundary impedance of NZSP. However, the excessive NaF dopant leads to the generation of microcracks decreasing the Na + conducting and mechanical properties of solid-state electrolytes. Using this simple and low-cost strategy of NaF doping, NZSP-0.3NaF achieves an excellent conductivity of 4.98 mS cm −1 with unexpectedly low activation energy of 0.227 eV. Therefore, this composition is one of the few electrolytes with high conductivity reported so far and is a competitive option for solid-state sodium batteries.

研究领域: 材料科学 · 电化学 · 固态离子学 · 能源材料 · 无机非金属材料
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International Journal of Electrochemical Science · 2023 · IF 1.5

Interface Modification of NASICON-structured Li1.5Al0.5Ge1.5(PO4)3 (LAGP) by Femtosecond Laser Structuring and Ionic Liquid

Binggong Yan,Yongchao Wang,Hongliang Ren,Xizhao Lu,Masashi Kotobuki,Bin Liu,Kaiyong Jiang

NASICON-structured solid-state electrolyte, namely Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) possesses high ionic conductivity and good compatibility with lithium metal that make it an ideal electrolyte for next-generation lithium battery. However, high interfacial impedance and possible dendrite limit its practical applications. To reduce interfacial impedance, herein, surface texturing on the LAGP is conducted using a femtosecond laser, and further wetted by ionic liquids. The femtosecond laser-modified surface can effectively increase wettability and improve the interfacial contacts. Low area specific impedance of 81.4Ω cm -2 is obtained and the full battery demonstrates good electrochemical performances.

研究领域: 材料科学 · 电化学 · 固态离子学 · 能源存储 · 表面工程
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ELECTROCHIMICA ACTA · 2024 · IF 5.5

Novel NASICON-type Mn0.5Ti2(PO4)3@F-doped carbon composite with high electrochemical performance as anode materials for potassium-ion batteries

Shaoxiong Liu,Jing Dai,Xuexue Li,Jianjun Xia,Mingyang Xie,Zhifeng Huang,Li Liu

Mn 0.5 Ti 2 (PO 4 ) 3 with a NASICON structural is used as an anode material in potassium-ion batteries due to its abundance of vacancies that can hold potassium ions . This characteristic not only contributes to its excellent stability but also results in a high specific capacity. However, the poor electrical conductivity of the polyanionic type structure limits the material's ability to fully utilize its capacity. In this paper, the conductivity and electrochemical stability of the Mn 0.5 Ti 2 (PO 4 ) 3 anode material are enhanced through composite formation with an F-doped carbon layer. The introduction of F into the carbon matrix creates a large number of vacancy defects and F active sites. The vacancies enhance the transport of potassium ions on the Mn 0.5 Ti 2 (PO 4 ) 3 material's surface, while the active sites exhibit strong electronegativity , improving the absorption of potassium ions. Therefore, the diffusion impedance of potassium ions is significantly reduced, leading to an increased diffusion rate of potassium ions. Attributing to the improved reaction kinetics, the Mn 0.5 Ti 2 (PO 4 ) 3 @F-doped carbon composite demonstrates a high specific capacity of 86 mA h g −1 at 10,000 mA g −1 when used as the anode for potassium-ion batteries. Even more, the specific capacity remains a capacity of 136 mA g −1 after 3000 cycles at 1000 mA h g −1 . This study enhances our comprehension of material design by investigating the alteration of carbon matrix to promote the electrochemical characteristics of materials.

CAS / MDL: 24937-79-9
研究领域: 材料科学 · 电化学
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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

A novel and environmentally friendly NASICON-type material: Efficient catalyst for condensation of formaldehyde and acetic acid to acrylic acid and methyl acrylate

Kaiwen Zheng,Qiliang Gao,Chao Li,Guojie Zhang,Yingquan Wu,Qingde Zhang,Xiaoxing Wang,Junfeng Zhang,Yizhuo Han,Yisheng Tan

The development of environmentally friendly and efficient catalysts for the production of essential chemicals has always been a desirable goal for technology in the chemical industry. In this paper, we fabricated a kind of sodium (Na) super ionic conductor (NASICON)-type materials (H 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x ) with different Ti/P ratios through tuning titanium content in synthetic mother liquor, and applied them to the aldol condensation reaction of acetic acid (HAc) and formaldehyde (FA) to acrylic acid (AA) and methyl acrylate (MA), which has never been not reported in previous researches. More importantly, these novel catalysts have showed their tremendous potential at the efficiency of AA + MA production, and over an optimized catalyst of NSC-Ti/P-0.53, the AA + MA selectivity being 71% (HAc input-based) was achieved at 360 ℃ when the reactant with FA/HAc molar ratio of 5:1 was fed; whereas, a highest space–time-yield (STY) of target products (∼37.2 μmol·g −1 ·min −1 ) was obtained with the FA/HAc molar ratio of 1:2.5, which is comparable to the best result reported previously. The detailed analysis of characterizations demonstrated that the change in the Ti/P ratio in the series NASICON catalysts led to the variation in the phase composition, the textural properties, surface titanium oxidation state, etc. thereby tuning the surface acid-base property, which is quite important for the present condensation reaction. More amounts of acidic sites and basic sites as well as their moderate distribution were proved to exert the promotional effects on the formation of AA and MA.

研究领域: 催化化学 · 环境科学 · 材料科学
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Materials Today Energy · 2021 · IF 7.311

High ionic conductivity and dendrite-resistant NASICON solid electrolyte for all-solid-state sodium batteries

L. Shen,J. Yang,G. Liu,M. Avdeev,X. Yao

The low ionic conductivity and poor dendrites suppression capability of Na 3 Zr 2 Si 2 PO 12 solid electrolyte limit the practical application of all-solid-state sodium batteries . Herein, the optimized Na 3.4 Mg 0.1 Zr 1.9 Si 2.2 P 0.8 O 12 electrolyte is obtained by simultaneously substituting the Zr 4+ with Mg 2+ and P 5+ with Si 4+ through solid-state reaction. The Na 3.4 Mg 0.1 Zr 1.9 Si 2.2 P 0.8 O 12 electrolyte has superior room temperature ionic conductivity of 3.6 × 10 −3  S cm −1 , which is 17 times higher than that of pristine Na 3 Zr 2 Si 2 PO 12 . No short circuit of the Na/Na 3.4 Mg 0.1 Zr 1.9 Si 2.2 P 0.8 O 12 /Na symmetric battery is observed up to 2.0 mA cm −2 , and the symmetric battery displays stable sodium plating/stripping cycles for over 2000 h at 0.1 mA cm −2 and 300 h at 1.0 mA cm −2 . The resultant Na 3.4 Mg 0.1 Zr 1.9 Si 2.2 P 0.8 O 12 electrolyte is further employed in two all-solid-state sodium batteries. The Na 3 V 2 (PO 4 ) 3 /Na 3.4 Mg 0.1 Zr 1.9 Si 2.2 P 0.8 O 12 /Na all-solid-state sodium battery maintains a discharge capacity of 93.3 mAh g −1 at 0.1C after 50 cycles, and the FeS 2 /Na 3.4 Mg 0.1 Zr 1.9 Si 2.2 P 0.8 O 12 /Na all-solid-state sodium battery delivers a discharge capacity of 173.1 mAh g −1 at 0.1C after 20 cycles, which are significantly enhanced compared with those based on pristine Na 3 Zr 2 Si 2 PO 12 . This strategy provides an efficient method to prepare optimized NASICON solid electrolytes with high ionic conductivity and excellent dendrites suppression capability and promotes the practical application of all-solid-state sodium batteries.

研究领域: 材料科学 · 电化学 · 固态离子学 · 能源存储 · 电池技术
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