CHEMICAL ENGINEERING JOURNAL
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2026
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IF 12.5
Yiran Zheng,Yongbiao Mu,Dichang Guan,Yunze Zhang,Wei Shan,Mai Zhang,Xianhua Hou,Jian Wang
Mn Cr charge compensation is reconfigured through systematic redox peak shifts. • Cooperative Mn Cr redox suppresses transition-metal charge fluctuation. • XAS and DFT reveal the origin of cooperative redox evolution. • Regulated redox chemistry enhances structural stability and reversibility. • Mechanistic insights guide the design of stable NASICON cathodes. NASICON-type phosphates are promising cathode materials for sodium-ion batteries, owing to their open three-dimensional framework and fast Na + transport kinetics. Among them, Mn-based NASICON compounds are particularly attractive due to their high theoretical capacity, yet their practical performance is often limited by localized redox reactions and structural instability associated with Mn-centered charge compensation. Here, we report that partial substitution of Cr with electrochemically inactive Al in Na 4 MnCr(PO 4 ) 3 induces systematic redox peak shifts, enabling a redistribution of charge compensation between Mn and Cr centers. This redox reconfiguration is verified by Cyclic Voltammetry analysis and X-ray absorption spectroscopy, revealing a coordinated valence evolution of transition metals and modulated electronic structures. In addition, Density Functional Theory calculations indicate minimized fluctuations in the charge states of Mn and Cr during desodiation, suggesting a more balanced and cooperative charge compensation process. Consequently, the Al-doped cathode exhibits enhanced redox reversibility and suppressed structural distortion, delivering improved cycling stability with 90.1% capacity retention after 200 cycles at 1C. These findings highlight that tuning redox provides an effective route to regulate charge compensation and stabilize high-performance Mn-based NASICON cathodes. Download: Download high-res image (126KB) Download: Download full-size image
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CERAMICS INTERNATIONAL
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2022
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IF 5.532
Shao-Peng Shen,Geng Tang,Hong-Ji Li,Liang Zhang,Jin-Chi Zheng,Yuan Luo,Jun-Pei Yue,Yongzheng Shi,Zhe Chen
NASICON-type Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP) has attracted much attention as a fast lithium-ion conductor for all-solid-state lithium-based batteries. However, the large grain-boundary resistance and high sintering temperature above 950 °C for pure LATP electrolytes hinder their practical application in lithium-based batteries. Here, a low-temperature preparation approach for the superionic conductor LATP electrolyte with sintering aids is proposed. By introducing sintering aids Li 3 PO 4 , LiBO 2 ·0.3H 2 O, and binary 0.32Li 3 PO 4 -0.68LiBO 2 ·0.3H 2 O, LATP-based pellets can be fabricated at optimized sintering temperatures below 900 °C. The resultant LATP-based pellets maintain a high relative density and homogeneous microstructure, which arises from the sintering aid to facilitate the grain rearrangement and fill the interstices between grains. The LATP pellets using sintering aid Li 3 PO 4 achieve a high ionic conductivity of 5.2 × 10 −4 S cm −1 at a low temperature of 800 °C, 7.3 times that (7.1 × 10 −5 S cm −1 ) of pure LATP pellets sintered at 950 °C, which demonstrates the effectiveness of low-temperature preparation approach to reducing the preparation cost and optimizing the ionic conductivity of LATP-based electrolytes.
研究领域:
材料科学
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能源技术
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Inorganic Chemistry Frontiers
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2018
·Vol. 5
·期 3
·619-625
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IF 5.106
Ying Liu,Maxim S. Molokeev,Quanlin Liu,Zhiguo Xia
Crystal structure evolution and temperature-dependent phase transition of solid solutions are much desired for the understanding of the optimization of functional properties. Herein, the NASICON-type NaZr2(PO4)3–SrZr4(PO4)6 solid solutions with the formula Na(2−2x)Srx[ ]xZr4(PO4)6 (0 ≤ x ≤ 1), where [ ] represents the vacancy, were prepared by the sol–gel method, and their crystal structures, phase transitions and thermal expansion properties were investigated in detail. In the range of x = 0.3–0.35, there is a reversible structural phase transition Rc ↔ R and the different structural models of the R phase and Rc phase were built to better understand the phase transition mechanism. We determined the phase transition boundary between the Rc and R structures and predicted the phase transition temperature of Na(2−2x)Srx[ ]xZr4(PO4)6 with any x for further investigation of controlled physical properties. The results indicated that Na0.5Sr0.75[ ]0.75Zr4(PO4)6 showed a near zero thermal expansion in the temperature range of 450–600 K, which can find potential applications.
研究领域:
材料科学
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无机化学
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功能材料
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结构表征
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热物理性能
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高影响因子
Metals
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2023
·Vol. 13
·期 4
·677
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IF 2.9
Yuliang Chen,Xiangbiao Yin,Hao Fu,Zheyang Lin,Guangcan Ma,Xinpeng Wang,Qingsong Wang,Fangqiang Chen
Strontium, the main component of radioactive nuclear wastewater, is characterized by a high fission yield and an extended half-life. It is easily absorbed by the human body, thus greatly threatening the environment and the human body. In this study, a mesoporous composite phase sodium superionic conductor (NVP@NMP) was synthesized by the droplet template method, and the rapid capture of Sr2+from wastewater was achieved by constructing a nano-heterogeneous interface to increase the ion diffusion rate. NVP@NMP showed efficient and rapid removal of strontium ions in adsorption kinetics, isothermal adsorption, solution pH, and interfering ions concentration tests, especially using the equilibrium time of 2 min for strontium absorption by NVP@NMP and a maximum theoretical adsorption capacity of 361.36 mg/g. The adsorption process was spontaneous, endothermic, and feasible. At higher concentrations of other competing ions (Na, K, Ca, Mg, and Cs), the adsorbent exhibited higher selectivity towards Sr2+.TEM, XPS, and XRD analyses revealed that ion exchange was the main mechanism for the NVP@NMP ultrafast adsorption of Sr2+. In this research, we investigated the feasibility of ultrafast strontium capture by sodium superionic conductor structured phosphates and explained the ultrafast strontium adsorption mechanism of NASICON materials through XPS.Keywords:NASICON;ultrafast adsorption;strontium;ion exchange;wastewater
研究领域:
环境科学
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材料科学
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高影响因子
Small
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2026
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IF 11.8
Mengdi Xu,Kaiyue Zhao,Yongqiang Qiao,Xin Chen,Qingjie Wang,Baodi Sheng,Yukun Huang,Qilong Gao
Zero thermal expansion (ZTE) materials can significantly enhance the structural stability and service life of precision components, which is of great significance to industrial technology. In this work, the high-entropy strategy is adopted to design anomalous thermal expansion material KMg 1/3 Mn 1/3 Co 1/3 Sc 1/2 In 1/2 Mo 3 O 12 with a NASICON structure. It shows volumetric negative thermal expansion (NTE) behavior below 300 K ( α V = −9.97×10 −6 K −1 ) and achieves a ZTE ( α V = 1.56×10 −6 K −1 , 300–700 K). The highly anisotropic thermal vibration of O atoms causes the rigid rotation of the polyhedron within the structural unit of the lantern, further manifested as NTE. From the perspective of crystal structure, anomalous thermal expansion behavior originates from the mutual compensation between the negative thermal expansion induced by the bending vibrations of the polyhedron within the ab plane and the positive thermal expansion arising from the thermal vibrations of K + ions along the c -axis. Temperature-dependent Raman spectroscopy further confirms the role of polyhedral coupled rotation in the anomalous thermal expansion behavior of the system. This work provides a design strategy for the development of NTE and ZTE materials.
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高影响因子
ACS Applied Energy Materials
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2022
·
IF 6.959
Zhi Gu,Xing Xin,Jing Yang,Dingcheng Guo,Shujiao Yang,Jinghua Wu,Yong Sun,Xiayin Yao
The practical application of lithium–oxygen (Li–O2) batteries is limited by the formation of lithium dendrites and the use of flammable and unstable organic liquid electrolytes, which would cause safety issues and poor cycling stability. Herein, we present a bilayer organic/inorganic hybrid solid-state electrolyte to improve the safety and enhance the electrochemical performance of Li–O2 batteries. Si-doped NASICON-type electrolyte Li1.511Al0.5Ge1.5Si0.01P2.99O12 (LAGP-Si) serves as an inorganic rigid backbone to guarantee high ionic conductivity and provide a barrier between active oxygen and lithium anode. Poly(ethylene glycol) methyl ether methacrylate (PEGMEM) is chosen as a polymer buffer layer due to its compatibility with lithium. Benefiting from the synergistic effect between LAGP-Si and PEGMEM, the obtained hybrid electrolyte exhibits high ionic conductivity and good stability against lithium anode. Consequently, the polarization of the Li symmetric cell is dramatically reduced by replacing pure LAGP-Si with a bilayer hybrid electrolyte. The solid-state Li–O2 batteries employing a PEGMEM@LAGP-Si electrolyte deliver a greater initial discharge–charge capacity of 7.3 mAh cm–2 and enhanced cyclic performance for 39 cycles with a restricted capacity of 0.4 mAh cm–2. The present work delivers a promising category of hybrid solid electrolytes for high-performance solid-state Li–O2 batteries.
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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固态电池
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DOI
高影响因子
MATERIALS TECHNOLOGY
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2018
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IF 1.232
Binggong Yan,Lei Kang,Masashi Kotobuki,Fei Wang,Xiaodi Huang,Xuan Song,Kaiyong Jiang
NASICON-structured Li1.5Al0.5Ge1.5(PO4)3 (LAGP) has been a promising solid-state glass-ceramic electrolyte for all-solid-state lithium ion batteries. However, the non-ideal ionic conductivity, non-uniformity of chemical composition, distortion and micro-cracks, etc., have limited its practical application. Considering these issues, in this work, we first of all introduce partial substitution of Al3+ by Ga3+. To avoid segregation of secondary phase, microwave sintering technology to prepare LAGP was used. With the help of microwave irradiation, sintering could be finished in just 30 min, and the size of crystals was homogeneous across the cross-section. No distortion and micro-cracks could be identified. Characterisations such as DTA, XRD, SEM and EIS were used to evaluate the material and electrochemical properties of the Li1.5Al0.5-xGaxGe1.5(PO4)3 (x = 0.1 ~ 0.5) samples. A high bulk conductivity of 6.67 × 10−4 S/cm at room temperature has been achieved when x = 0.1 and the activation energy was about 0.66 eV.
研究领域:
材料科学
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电化学
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储能技术
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陶瓷学
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DOI
高影响因子
CHEMICAL PHYSICS LETTERS
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2022
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IF 2.719
Zixiang Guo,Xue Qin,Yulong Xie,Chanrong Lei,Tianyu Wei,Yuzhe Zhang
Nanoparticle LiTi 2 (PO 4 ) 3 was prepared by solvothermal and calcination methods. LiTi 2 (PO 4 ) 3 -xh(x = 5, 7, 9, 13) was successfully synthesized under different calcination times in nitrogen atmosphere, and LiTi 2 (PO 4 ) 3 –7h showed excellent rate and electrochemical performance. It delivered discharge capacities of 141.2, 119.9, 109.8, 98.2, 87.3, and 76.7 mAh·g −1 at rates of 0.5, 1, 2, 5, 10, and 20C, respectively. In particular, its initial discharge capacity can reach 123.3 mAh·g −1 at the high rate of 10C. Hence, these superior properties demonstrate that LiTi 2 (PO 4 ) 3 –7h has great application advantages as a cathode for lithium-ion batteries.
研究领域:
材料科学
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电化学
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产品关联
DOI
高影响因子
Materials Today Chemistry
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2023
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IF 7.3
L. Liu,J. Su,X. Zhou,D. Liang,Y. Liu,R. Tang,Y. Xu,Y. Jiang,Z. Wei
Presently, the low ionic conductivity of Na super ionic conductor (NASICON) electrolytes is one of the main obstacles to the development of solid-state sodium batteries . Most researchers focus on the modified NASICON by doping with foreign elements and have not paid much attention to the effect of the composition changing by adjusting the ratio of elements in Na 1+x Zr 2 Si x P 3-x O 12 (0 ≤ x ≤ 3) on the ionic conductivity . In order to clarify the relationship between the ionic conductivity and the structure/composition of Na 1+x Zr 2 Si x P 3-x O 12 , the ionic conductivity dependence on the Si/P ratio is systematically investigated in this study. The obtained results demonstrate that the ionic conductivity variation of NASICON is close to an order of magnitude i.e. the ionic conductivity of Na 1+x Zr 2 Si x P 3-x O 12 is much more sensitive to the Si/P ratio in the structure. This means that it is crucial to control the composition during the preparation process to obtain the electrolyte with high ionic conductivity. The strong composition-dependent property of Na 1+x Zr 2 Si x P 3-x O 12 can be attributed to the change of current carrier concentration, crystal structure, and sintering property resulting from the Si/P ratio. The results are insightful for further understanding the conducting characteristics of Na 1+x Zr 2 Si x P 3-x O 12 material and its derivatives.
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
ChemSusChem
·
2023
·Vol. 16
·期 8
·e202202257
·
IF 8.4
Wensheng Yang,Xinhai Wang,Shengshang Lu,Yue Gao,Tinghong Gao,Tong Guo,Quan Xie,Yunjun Ruan
Graphical Going uphill : The dissolution mechanism of sodium vanadium phosphate (NVP) in an aqueous electrolyte is investigated in detail. Using metal (Fe or W) doping can enhance the strength of the metal-oxygen bond to suppress partial vanadium dissolution in NVP. Furthermore, the synergy of bimetallic doping completely inhibits V dissolution to improve the cycling stability of NVP. Aqueous sodium-ion batteries (ASIB) offer many potential applications in large-scale power grids since they are inexpensive, safe, and environmentally friendly. Sodium superionic conductors (NASICON), especially carbon-coated Na 3 V 2 (PO 4 ) 3 (NVP), have attracted much attention due to the full use of their high ion migration speed. However, the poor cycle lifespan and capacity retention of NVP hinder its application in ASIB. Herein, a novel bimetal-doped Na 3 V 1.3 Fe 0.5 W 0.2 (PO 4 ) 3 (NV 1.3 Fe 0.5 W 0.2 P) cathode is designed and synthesized to achieve outstanding cycling stability (95 % of initial capacity at 50th cycle). The electrochemical behavior and charge storage mechanism of NV 1.3 Fe 0.5 W 0.2 P are systematically investigated by various in situ and ex situ characterizations. The Fe and W codoping could stabilize the NASICON framework to suppress the proton attack on the Na site in the aqueous electrolyte, thus resulting in excellent cycling stability. DFT calculations show that bimetallic doping increases the structural stability of NVP. Moreover, an ASIB fabricated using a NV 1.3 Fe 0.5 W 0.2 P cathode and a NaTi 2 (PO 4 ) 3 anode delivers 64 mAh g −1 at room temperature, 95 % capacity retention after 50 cycles (1 A g −1 ).
研究领域:
材料科学
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电化学
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产品关联
DOI
PubMed
高影响因子
ELECTROCHIMICA ACTA
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2023
·
IF 6.6
Jiepeng Chen,Yun Huang,Jiapin liu,Chengwei Li,He Zheng,Xi Xu,Lei Fu,Xing Li,Mingshan Wang,Yuanhua Lin,Haijun Cao
The sodium super ion conductor (NASICON) structure materials have attracted extensive attention because of its open three-dimensional crystal network framework and fast sodium ion migration rate. However, the poor electronic conductivity due to the presence of phosphate groups and the consequent high cost have been a barrier to commercialization. In this work, Na 4 MnV(PO 4 ) 3 (NMVP) with three-dimensional porous structure is synthesized in situ using Aspergillus niger as a biological template (noted as NMVP/ANDC). The cell wall of Aspergillus niger is rich in hydroxyl groups , which can adsorb metal ions well, so that NMVP particles can be synthesized on Aspergillus niger without stacking and agglomeration. NMVP grows along Aspergillus niger mycelium has a spongy-like three-dimensional porous network structure, which helps the contact between active materials and electrolyte, reduces the migration distance of sodium ions, and improves the conductivity of active materials. Therefore, NMVP/ANDC has good rate performance and cycle stability. It can provide 109 mAh g −1 at 0.5 C and 79.6% capacity retention after 3000 cycles at 5 C. The biological template method is proposed in this paper opens up a simple way for the preparation of other three-dimensional porous network structural materials.
研究领域:
材料科学
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电化学
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生物学
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高影响因子
JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY
·
2022
·Vol. 103
·期 1
·205-213
·
IF 2.606
Zhao Qian,Yang Wensheng,Zhang Qin,Qiu Liren,Zhou Min,Lu Shengshang,Tao Benfu,Wang Xinhai,Xie Quan,Ruan Yunjun
Sodium super ion conductor (NASICON) structure materials, known for fast diffusion channels for Na + , are promising solid electrolyte materials for sodium-ion batteries (SIBs). However, the high carbon content in the NASICON electrolyte materials originated from the carbothermal reduction (CR) reaction will cause short-circuit and self-discharge of the batteries. Herein, we developed a facile and straightforward two-stage calcining strategy to prepare Na 3 V 2 (PO 4 ) 3 (NVP) with high purity and crystallinity. By precisely controlling the dosage of reducing agent and heat temperature, the purity of NVP can reach 99.97%. Moreover, the NVP film was prepared by the as-synthesized pure NVP powder via fast hot-pressing sinter, whose Vickers hardness is (5.0 ± 0.4) × 10 2 HV and relative density is 99.05%. This study provides a safe and facile strategy to prepare high-purity NVP powder and high-quality NVP films, which is of great significance in exploring NVP as a solid electrolyte for SIBs.
Graphical abstract
研究领域:
材料科学
·
电化学
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高影响因子
危险品化学品经营许可证（带存储）