Inorganic Chemistry Frontiers
·
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
✓ 已验证
DOI
高影响因子
JOURNAL OF POWER SOURCES
·
2022
·
IF 9.794
Can Huang,Zhuojie Li,Shanshan Duan,Shuhong Xie,Shuoguo Yuan,Shuen Hou,Guozhong Cao,Hongyun Jin
Sodium super-ionic conductors (NASICON)-type electrolyte Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 (LATP), with high ionic conductivity and low cost, is considered as one of the most attractive alternatives to liquid electrolytes . However, the poor interfacial compatibilities of LATP electrolyte in lithium batteries lead to the failure, which hinders its further development. Herein, a MoS 2 coating layer as an artificial solid electrolyte interphase (ASEI) is used for modifying the surface of LATP (MCLATP) via an economical and uncomplicated spin coating method, which not only effectively inhibits the decomposition of LATP, but also in-situ forms a conversion layer consisting of Li 2 S and Mo metal during cycling. The conversion layer can improve the interfacial charge transfer kinetics and decrease the charge transfer resistance . According to interfacial modification of MoS 2 , the symmetric cells show slight polarization, and the Li/MCLATP/LFP cells demonstrate excellent cycling performance over 300 cycles at 1 C. The enhanced batteries performance is ascribed to interfacial modification of MoS 2 as an ASEI layer, which reduces interfacial concentration polarization caused by the formed microcracks around the surface during decomposition of LATP. This work provides a promising strategy to construct the interface between Li metal and solid-state electrolytes for other unstable electrolytes beyond NASICON .
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
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
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环境科学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2022
·
IF 7.968
MengXue Xiong,Min Yang,QianLin Chen,TingYa Cai
Bauxite residue contains a certain amount of alkali metal ions, among which sodium ions are predominant and have a great impact on its application performance. In this paper, a series of sodium ion adsorbents with different Al contents were prepared based on the structural characteristics of NASICON-type materials to study the effect on sodium ion adsorption and regeneration adsorption performance. The results showed that the adsorbent with 40% Al had the best adsorption rate (95.6%). The adsorbents were characterized by SEM, XRD, Raman spectroscopy , TG-DSC, XPS and N 2 adsorption-desorption, and the results showed that the adsorbents had a stable three-dimensional network structure. The adsorption isotherm models, adsorption kinetics and adsorption thermodynamics were discussed. The adsorption process followed the Langmuir isotherm model and pseudo-second-order kinetic model and was a spontaneous exothermic reaction . In addition, the adsorption mechanism was also discussed; this mechanism involved the participation of carbon-oxygen bonds and electrostatic interactions during adsorption. Desorption and regeneration experiments demonstrated that the adsorbent had excellent reusability, with an adsorption rate of 88.82% after three cycles. This study effectively solves the problem of sodium ion disposal in waste liquid after bauxite residue dealkalization to a certain extent, alleviating the environmental pollution caused by subsequent waste liquid discharge. Additionally, the later application of sodium ions can "turn trash into treasure". This study not only provides a new route for the separation of sodium ions in bauxite residue but also has great significance both from an environmental perspective and from a resource recovery perspective.
研究领域:
环境科学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Materials Today Nano
·
2021
·
IF 8.109
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
✓ 已验证
DOI
高影响因子
Journal of Materials Chemistry A
·
2021
·Vol. 9
·期 12
·7817-7825
·
IF 12.732
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
✓ 已验证
DOI
高影响因子
Journal of Physical Chemistry C
·
2025
·
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
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF THE EUROPEAN CERAMIC SOCIETY
·
2018
·
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
·
电化学
✓ 已验证
产品关联
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
·
电化学
·
固体化学
✓ 已验证
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
·
能源存储与转换
✓ 已验证
DOI
高影响因子
ACS Applied Energy Materials
·
2025
·
IF 5.5
Hongjie Chen,Yixuan Su,Yucong Chen,Minghan Bao,Mingjun Wu,Junyang Chen,Weitao Chen,Qiang Ru
The inherent low electronic conductivity of NASICON-type Na4MnV(PO4)3 (NMVP) impedes its use in advanced energy storage. Herein, we address this challenge by introducing a citric acid-derived carbon coating to elevate the material’s conductivity and electrochemical performance. By precisely tailoring the configuration of the carbon layer, we fabricated Na4MnV(PO4)3 encapsulated by a carbon coating (NMVP@C) and constructed a 3D hierarchical architecture with incorporated V(III) and Mn(II) states, which prompts the reversible redox reaction, augments Na+ storage capability, and mitigates volume expansion during cycling. The optimal cathode manifests superior rate capability and a long life span with 107.5 mA h g–1 at 1 C and 82.5% capacity retention over 5000 cycles at 20 C. The hard carbon//NMVP@C full cell confirms practical applicability with good electrochemical performance. This work underscores the pivotal interplay among the carbon layer, Na+ mobility, and structural integrity in NASICON cathodes, offering a pathway to develop high-performance and cost-effective cathode materials for sodium-ion 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
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
危险品化学品经营许可证（带存储）