JOURNAL OF ALLOYS AND COMPOUNDS
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2020
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IF 4.65
Congcai Huang,Guanming Yang,Wenhao Yu,Chao Xue,Yanfang Zhai,Weiping Tang,Ning Hu,Zhaoyin Wen,Li Lu,Shufeng Song
As a possible solid electrolyte material for solid-state sodium-based batteries, gallium-substituted Na 3 Zr 2 Si 2 PO 12 in the structure of Nasicon (sodium super ion conductor) has received hardly any attention so far, though Ga 3+ has similar ionic radius close to that of Zr 4+ . Herein, a series of gallium-substituted Na 3 Zr 2 Si 2 PO 12 with formula of Na 3+x Zr 2-x Ga x Si 2 PO 12 (0 ≤ x ≤ 0.4) have been prepared through solid-state synthesis. The electrical, microstructural, and crystallographic performances of the developed solid electrolytes are systematically studied. In particular, the gallium-substituted Na 3.1 Zr 1.9 Ga 0.1 Si 2 PO 12 shows superior ionic conductivity of 1.06 × 10 −3 S cm −1 at 25 °C, which is almost one order of magnitude higher than that of the pristine Na 3 Zr 2 Si 2 PO 12 , as well as low electronic conductivity of 6.17 × 10 −8 S cm −1 and wide electrochemical stability window of 5 V vs. Na/Na + . This work demonstrates a new substituted strategy for exploring Na + -ion solid electrolytes.
研究领域:
材料科学
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能源存储与转换
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DOI
高影响因子
CHEMISTRY OF MATERIALS
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2020
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IF 9.567
Zhonghui Gao,Jiayi Yang,Haiyang Yuan,Haoyu Fu,Yutao Li,Yuyu Li,Thimo Ferber,Conrad Guhl,Huabin Sun,Wolfram Jaegermann,René Hausbrand,Yunhui Huang
Most Li+/Na+-conducting solid electrolytes are unstable in moisture, and the formed hydroxides and carbonates on their surfaces result in the increase of the interfacial resistance between solid electrolytes and alkali metal anodes. In this study, heat treatment was used to remove the byproduct coating on the surface of Na3Zr2Si2PO12 (NZSP) that also leads to the generation of Na-ion deficient surface simultaneously. This surface chemistry approach was used to reduce the interfacial resistance and suppress Na-dendrite growth during Na plating. A combination of the metallic Na wetting test, density functional theory, and electrochemical measurement was employed to investigate the origins of ultralow interfacial resistance and mechanism between the Na-ion deficient surface and the metallic Na anode. The analysis demonstrates that the Na-ion-deficient surface effectively improves the contact between NZSP and the metallic Na anode. Moreover, an ultrathin passivating layer involving Na2O was formed between NZSP with metallic Na that protected the NZSP electrolyte from the reduction by metallic Na. This study not only motivates the need for further understanding of the surface chemistry of NZSP but also provides guidelines for the future design of the Na-ion solid–electrolyte interface.
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
CHEMICAL ENGINEERING JOURNAL
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2022
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IF 16.744
Pengfeng Jiang,Guangyuan Du,Yuansheng Shi,Fengquan She,Pengqian Guo,Guoyu Qian,Xueyi Lu,Fangyan Xie,Xia Lu
The smart manufacturing of solid-state electrolytes (SSEs) plays an important role in the assembling, improvement and cost-reduction of high energy density solid-state batteries (SSBs). In this work, an ultrafast high-temperature sintering (UHS) method is employed to prepare the NASICON Na 3 Zr 2 Si 2 PO 12 ceramic SSEs in seconds. The prepared Na 3 Zr 2 Si 2 PO 12 (US-NZSPO) exhibits a high ionic conductivity of 2.62 × 10 −4 S cm −1 and low activation energy of 0.28 eV. The Na | US-NZSPO | Na symmetric cell delivers a cycling time over 270 h with a steady voltage overpotential at a current density of 0.5 mA cm −2 . Moreover, a Coulombic efficiency of 99.9 % and a capacity retention of 89 % are achieved at 0.2 C in Na 3 V 2 (PO 4 ) 3 (NVP) | US-NZSPO | Na solid cells after 800 cycles with the areal NVP loading of 4.5 mg cm −2 . These favorable electrochemical performances originate from the robust US-NZSPO pellet and well-constructed SSE-electrode interface, in which the electrochemically active interface demonstrates a strong self-stabilizing function to maintain the tight interfacial connections and the continuous Na + ion transport.
研究领域:
材料科学
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能源技术
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DOI
高影响因子
Advanced Energy Materials
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2019
·Vol. 9
·期 28
·1901205
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IF 24.884
Yao Lu,Jose A. Alonso,Qiang Yi,Liang Lu,Zhong Lin Wang,Chunwen Sun
Solid-state sodium batteries (SSSBs) are promising electrochemical energy storage devices due to their high energy density, high safety, and abundant resource of sodium. However, low conductivity of solid electrolyte as well as high interfacial resistance between electrolyte and electrodes are two main challenges for practical application. To address these issues, pure phase Na 3 Zr 2 Si 2 PO 12 (NZSP) materials with Ca 2+ substitution for Zr 4+ are synthesized by a sol-gel method. It shows a high ionic conductivity of more than 10 −3 S cm −1 at 25 °C. Moreover, a robust SSSB is developed by integrating sodium metal anodes into NZSP-type monolithic architecture, forming a 3D electronic and ionic conducting network. The interfacial resistance is remarkably reduced and the monolithic symmetric cell displays stable sodium platting/striping cycles with low polarization for over 600 h. Furthermore, by combining sodium metal anode with Na 3 V 2 (PO 4 ) 3 cathode, an SSSB is demonstrated with high rate capability and excellent cyclability. After 450 cycles, the capacity of the cell is still kept at 94.9 mAh g −1 at 1 C. This unique design of monolithic electrolyte architecture provides a promising strategy toward realizing high-performance SSSBs.
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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DOI
高影响因子
Nature Communications
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2025
·Vol. 16
·期 1
·1-18
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IF 15.7
Li Taiguang,Chen Butian,Wang Tenghui,Liu Chong,Yin Wen,Mao Qianjiang,Zhou Dongxu,Hao Yongmei,Liu Xiangfeng
Solid-state sodium metal batteries have attracted great interest because of their improved safety and abundant Na resources. However, the interfacial resistances and instabilities induced by parasitic reactions, together with Na dendrite issues, result in reduced rate capability and poor cycling stability. Here, we address these challenges by intrinsically inhibiting parasitic interfacial redox reactions through enhanced P-O covalency in Na 3 Zr 2 Si 2 PO 12 (NZSP) with Na 2 SiF 6 incorporation, wherein the high electronegativity of F strengthens P-O covalency. Additionally, SnF 2 coating provides a sodiophilic surface and stabilizes the NZSP interface, which is essential for effective electrochemical cycling. This integrated approach significantly reduces interfacial impedance to 2.0 Ω cm 2 , enabling stable Na plating/stripping for 3600 hours at 0.5 mA cm -2 /0.25 mAh cm -2 . The full cell with Na 3 V 2 (PO 4 ) 3 positive electrode demonstrates stable cycling with high-rate capability (87.5% capacity retention after 2500 cycles at 1 C and 96.1% capacity retention after 1200 cycles at 5 C). This study sheds light on the development of high-performance quasi-solid-state sodium batteries.
研究领域:
储能技术
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材料科学
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电化学
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固态电池
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界面工程
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产品关联
DOI
PubMed
高影响因子
ACS Applied Materials & Interfaces
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2018
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IF 8.097
Qiang Yi,Wenqiang Zhang,Shaoqing Li,Xinyuan Li,Chunwen Sun
High-performance electrolytes and electrode materials play a critical role in advanced sodium-ion batteries with higher energy densities. In this work, we prepared a poly(methyl methacrylate)-filled composite electrolyte (named as GHSE) by in situ polymerization of methyl methacrylate in the porous Na3Zr2Si2PO12–polymer vinylidene fluoride–hexafluoropropylene composite membrane for the first time. The GHSE membrane exhibits a high ionic conductivity (2.78 × 10–3 S cm–1), wide electrochemical window (∼4.9 V), high Na+ ion transference number (∼0.63), good thermal stability and flexibility, as well as smaller interfacial resistance. Moreover, a composite Na/C anode was prepared, which shows good dendrite suppression ability. The full cell Na0.67Ni0.23Mg0.1Mn0.67O2 |GHSE|Na/C exhibits excellent rate capability with an initial discharge capacity of 96 mAh g–1 even at a higher current density of 192 mA g–1 and excellent cyclability for 600 cycles. These results suggest that the GHSE and Na/C anode are promising electrolyte and anode materials for Na-ion batteries, respectively.
研究领域:
材料科学
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电化学
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能源存储
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产品关联
DOI
PubMed
高影响因子
Advanced Energy Materials
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2024
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IF 24.4
Zhonghui Gao,Yang Bai,Junrun Feng,Jiayi Yang,Porun Liu,Haiyang Yuan,Xuze Guan,Feng Ryan Wang,Yunhui Huang
Na 3 Zr 2 Si 2 PO 12 (NZSP)-based NASICON solid-state electrolytes (SSEs) show not only competitive ionic conductivity but also high chemical stability in air, holding a great promise for enabling the use of sodium metal anode in solid-state sodium batteries. However, sodium (Na) metal dendrite growth inside SSE always leads to undesirable short-circuiting in battery even no obvious changes in interfacial contact loss and interfacial decomposition during cycling. How to control Na metal dendrite growth and in situ observe the effect of SSE/Na interface change on dendrite growth is quite challenging. Herein, an in situ synchrotron-based X-ray imaging method is developed to systematically investigate the dendrite origin in NZSP-based SSEs. It is find that the dendrite growth intrinsically depends on the grain boundaries (GBs) in NZSP and the NZSP/Na interfacial properties. It is confirmed that Na dendrite infiltration kinetic evolution in NZSP is strongly associated with Na ion/electron conductivity and Young's modulus of GBs. Moreover, the electro-chemo-mechanical phase-field model evaluation demonstrates that the basic reason for Na metal dendrite intrusion into the GBs of SSE is a combination of local polarization potential and the presence of stress formed at GBs.
研究领域:
材料科学
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电化学
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能源存储
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DOI
高影响因子
CERAMICS INTERNATIONAL
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2020
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IF 3.83
Wenhao Yu,Yanfang Zhai,Guanming Yang,Jianyao Yao,Shufeng Song,Shuai Li,Weiping Tang,Ning Hu,Li Lu
Under considerations of material abundance, cost, redox potential, higher performance, and safety, solid-state sodium-metal batteries hold much promise. The development of solid electrolytes with superior electrical performances for the solid-state sodium batteries is at the infant stage and still remains a challenge. Herein, we for the first time report a synthetic strategy of Na 3 Zr 2 Si 2 PO 12 ceramic microtubes via a sol gel process with natural cotton fiber template. Moreover, an inorganic-organic composite electrolyte Na 3 Zr 2 Si 2 PO 12 microtube/poly (ethylene oxide) (PEO)-poly (vinylidene fluoride- co -hexafluoropropylene) (PVdF-HFP)-sodium perchlorate (NaClO 4 )-1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EmimFSI) is developed. The phase, microstructure, and electrochemical properties of the Na 3 Zr 2 Si 2 PO 12 microtubes and their composite electrolytes are systematically investigated based on X-ray diffraction, scanning electron microscope, energy dispersive spectroscopy, electrochemical impedance spectroscopy , linear sweep voltammetry , direct-current polarization, and galvanostatic cycling. The finding implies that the characteristic Na 3 Zr 2 Si 2 PO 12 microtubes and their composite electrolytes are promising for solid-state sodium-metal 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
ELECTROCHIMICA ACTA
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2026
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IF 5.8
Xiaoyu Li,Dongrong Yang,Kun Ren,Pan Liu,Fupeng Li,Song Chen,Minjie Hou,Huangkai Zhou,Bin Yang,Feng Liang
80 wt% Na 3 Zr 2 Si 2 PO 12 in ∼35 μm separator, significantly thinner than 50–200 μm membranes. • High ceramic loading achieves ∼16 GPa modulus while maintaining flexibility. • NASICON-induced α-to-β phase transition in PVDF-HFP enhances Na⁺ transport. • High ceramic loading enhances ionic conductivity and Na + transference number. • Over 2000 h stable Na|Na cycling and 96% retention at 5C over 350 cycles. Sodium metal batteries promise cost-effective energy storage, but face critical safety and stability challenges from flammable liquid electrolytes and uncontrolled dendrite growth. Quasi-solid-state electrolytes combining NASICON (Na 3 Zr 2 Si 2 PO 12 ) ceramic fillers with PVDF-HFP polymers offer a pragmatic solution, but existing freestanding membranes encounter a fundamental “thickness-performance-manufacturability” trilemma: thick films (50–200 μm) reduce energy density, high ceramic loadings cause brittleness, and specialized fabrication hinders scalability. Here, we demonstrate a separator-integrated design that resolves this trilemma by directly coating a thin (∼10 μm) high-loading (80 wt%) NASICON–PVDF-HFP–NaClO 4 composite layer onto a commercial polypropylene separator. This architecture shifts mechanical demands onto the PP substrate, allowing the active layer to be optimized for ionic transport without the brittleness that limits freestanding films. The resulting 80N membrane combines a total thickness of ∼35 μm, an ionic conductivity of 0.725 mS cm −1 , a Na + transference number of 0.54, stable Na|Na cycling over 2000 h, a critical current density(CCD) of 1.9 mA cm –2 , and full slurry-coating compatibility, with successful validation in ∼88 mAh g –1 proof-of-concept pouch cells (96.9% capacity retention after 100 cycles at 0.5 C). The work establishes the separator-integrated architecture as a practical route to high-ceramic-loading composite electrolytes for sodium metal batteries. Separator-integrated NASICON-PVDF-HFP composite electrolytes achieve 80 wt% ceramic loading—exceeding typical freestanding membrane limits (30-50 wt%)— through optimized slurry coating on porous PP substrates. High ceramic content establishes percolative Na + transport pathways, enabling stable Na plating/ stripping for over 2000 hours in symmetric cells. Flexible pouch cells validate practical viability for high-performance sodium metal batteries. Download: Download high-res image (217KB) Download: Download full-size image
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DOI
高影响因子
SOLID STATE SCIENCES
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2026
·
IF 3.6
Yudi Guo,Erqing Zhao,Jiaming Li
In-doped NZSP solid electrolytes were prepared via a modified solid-state reaction method. • The doping of In induces a monoclinic-to -rhombohedral phase transition. • In doping promotes the growth of grains, resulting in grain boundary reduction. • The Na 3.3 Zr 1.7 In 0.3 Si 2 PO 12 electrolyte shows the highest ionic conductivity of 1.24 mS/cm. NASICON-type Na 3 Zr 2 Si 2 PO 12 (NZSP) solid electrolytes are promising candidates for solid-state sodium-ion batteries (SSSIBs) owing to their high ionic conductivity, and excellent air stability. In this study, Na 3+x Zr 2-x In x Si 2 PO 12 (x = 0, 0.1, 0.2, 0.3, and 0.4) solid electrolytes were synthesized using a modified solid-state reaction method, and the effect of the In dopant content on the structure and properties of the NZSP electrolytes was investigated by XRD, SEM, and EIS. The introduction of In induces a monoclinic-to -rhombohedral phase transition. The rhombohedral phase has a large unit cell volume, which provides bigger channels for the conduction of Na ions. Moreover, In doping also promotes the growth of grains within the electrolyte, resulting in grain boundary reduction. The Na 3.3 Zr 1.7 In 0.3 Si 2 PO 12 electrolyte exhibits the highest ionic conductivity of 1.24 mS/cm at 30 °C, the lowest activation energy of 0.345 eV, and a negligible electronic conductivity of 1.81 × 10 −8 S/cm. A Na/Na 3.3 Zr 1.7 In 0.3 Si 2 PO 12 /Na symmetric cell shows an excellent cycling stability. These results demonstrate the good promise of Na 3.3 Zr 1.7 In 0.3 Si 2 PO 12 material as an alternative solid electrolyte for SSSIBs. Download: Download high-res image (446KB) Download: Download full-size image
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产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
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2025
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IF 8.2
Yuyao Zhang,Tianyi Gao,Jiameng Yu,Yining Zhang,Yue Zhang,Shaojie Chen,Ning Xue,Xinshui Zhang,Qiong Yuan,Luyao Wang,Wei Liu
As a promising solid electrolyte, the NASICON-type Na3Zr2Si2PO12 holds excellent application in solid-state sodium-ion batteries, which are an alternative to lithium batteries. However, its insufficient conductivity is one of the key factors impeding its applications. Herein, we report Mn2+-doped Na3Zr2Si2PO12, demonstrating enhanced ionic conductivity and electrochemical properties. We systematically investigate the effect of doping content on the ionic conductivity. The results show that Na3.4Zr1.8Mn0.2Si2PO12 has an extremely high room-temperature ionic conductivity of 3.3 mS cm–1, which is 4 times that of undoped Na3Zr2Si2PO12. According to the Meyer–Nedle rule, it can be known that as the activation energy decreases, the ionic conductivity shows a gradually increasing trend. Additionally, the Na symmetric batteries using Mn2+-doped Na3Zr2Si2PO12 exhibit improved cycling performance. The quasi-solid-state sodium–metal battery using Na3V2(PO4)3 achieves a high discharge specific capacity of 91.3 mAh g–1 at 0.1C, with a high capacity retention of 92.2% after 260 cycles, far surpassing the counterpart based on undoped Na3Zr2Si2PO12. This work provides an effective strategy for enhancing the performance of Na3Zr2Si2PO12 for its application in sodium–metal 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
PubMed
高影响因子
Advanced Energy Materials
·
2022
·Vol. 12
·期 9
·2103607
·
IF 29.698
Zhonghui Gao,Jiayi Yang,Guanchen Li,Thimo Ferber,Junrun Feng,Yuyu Li,Haoyu Fu,Wolfram Jaegermann,Charles W. Monroe,Yunhui Huang
Solid-state sodium–metal batteries will not achieve reasonable power density without electrolytes that solve the dendrite (filamentation) problem. Metal-filament formation during plating at ceramic/metal interfaces can cause electrical failure by internal short-circuit or mechanical failure by electrolyte fracture. Herein, an Na 3 Zr 2 Si 2 PO 12 (NZSP) sodium-ion-conducting NASICON electrolyte in which TiO 2 is incorporated as an additive is presented, leading to a two-phase composite NZSP(TiO 2 ) with improved density, Young's modulus, hardness, grain structure, and bulk permittivity. These features of NZSP(TiO 2 ) suppress dendrite growth along grain boundaries, microcracks, and micropores. As well as demonstrating ultralow ceramic/Na kinetic resistance with electrochemical measurements, X-ray photoelectron spectroscopy is performed to probe interfacial reaction mechanisms. The TiO 2 phase forms within grain boundaries and along NZSP surfaces. This modifies the two-phase material's microstructure and improves its electrochemical performance, while also increasing the critical current density for dendrite formation. Design guidelines are discussed to mitigate microscopic defects and dendrites in two-phase ceramic electrolytes.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）