New-type Hf-based NASICON electrolyte for solid-state Na-ion batteries with superior long-cycling stability and rate capability

Tian, Haoqing; Liu, Shan; Deng, Lijun; Wang, Ling; Dai, Lei

doi:10.1016/j.ensm.2021.04.026

Cited by 49 publications

(44 citation statements)

References 43 publications

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“…[ 9 ] Inorganic electrolytes had attracted more attentions because of their high ionic conductivity, good thermal stability, and high safety. [ 10,11 ] β″‐Al 2 O 3 was the mostly studied sodium‐ion conductor. And it had been successfully used in commercial sodium‐sulfur batteries.…”

Section: Introductionmentioning

confidence: 99%

“…Additionally, it should be noted that the impurity phase (HfO 2 , 5.06%) was also observed, and it seems that there has certain correlation between the impurity phase and doping amount (Table S1, Supporting Information). [11,26] As the presence of a large number of HfO 2 on the grain surface will deteriorate the ion transport and reduce the ionic conductivity, the amount of F − doping should be accurately controlled.…”

Section: Introductionmentioning

confidence: 99%

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Designing a Novel Electrolyte Na_3.2Hf₂Si_2.2P_0.8O_11.85F_0.3 for All‐Solid‐State Na‐O₂ Batteries

et al. 2022

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their high ionic conductivity, good thermal stability, and high safety. [10,11] β″-Al 2 O 3 was the mostly studied sodium-ion conductor. And it had been successfully used in commercial sodium-sulfur batteries. [12] However, β″-Al 2 O 3 was sensitive to water, and the ionic conductivity decreased significantly after contacting with water, which severely limited its application in sodium-air batteries. Sulfide electrolytes had great advantages in ionic conductivity, but they are very easy to react with air and water. [13,14] NASICON electrolytes Na 1+x Zr 2 Si x P 3−x O 12 (0 ≤ x ≤ 3) had a high ionic conductivity, wide electrochemical window, and insensitive to water vapor, which helped them get a good application potential in sodium-air batteries. [15][16][17][18] In fact, NASICON electrolytes had been used in hybrid system sodium-air batteries. [19][20][21][22][23] However, the research of all-solid-state sodium-air batteries based on NASICON electrolyte was still insufficient and the catalytic mechanism in solid cathode was still unclear.Herein, we prepared an all-solid-state Na-O 2 battery based on elaborately designed NASICON electrolyte Na 3.2 Hf 2 Si 2.2 P 0.8 O 11.85 F 0.3 . Firstly, the conductivity of the electrolyte was regulated by F − -doping, and all the samples Na 3.2 Hf 2 Si 2.2 P 0.8 O 12−x F 2x (x = 0-0.25) were noted as NHSP-F 2x . The results proved that NHSP-F 0.3 electrolyte exhibited the highest ionic conductivity (2.39 × 10 −3 S cm −1 ) and the highest relative density than others. In addition, it is noteworthy that humidity has a significant influence on the performance of battery. The existence of water in atmosphere may change the path of cathodic reaction, which facilitated the generation of soluble discharge product (NaOH) and promoted reversible cycling performance. However, owing to NASICON electrolyte itself being hydrophilic, the water released during charging is unfavorable, and may reduce the sodium or discharge product percolate electrolyte. Therefore, how to ensure the compactness of electrolyte and the hydrophobicity of electrolyte/cathode interface is of great value for the development of all-solid-state sodium-air battery. This study provides important support for the research of all-solid-state sodium-air battery, and also has significant reference value for other solid-state metal-air batteries. Results and DiscussionAs shown in Figure 1a, the prepared electrolyte pellet is white and the diameter is about 1 cm. The NHSP-F 2x (x ≤ 0.25) electrolytes Sodium-air battery has great development potential due to its high energy density and high safety. However, most previous works are based on liquid electrolyte or polymer electrolyte, which will inevitably result in safety hazards such as electrolyte leakage and sodium dendrite growth. Herein, an all-solid-state Na-O 2 battery based on a well-designed NASICON-type electrolyte Na 3.2 Hf 2 Si 2.2 P 0.8 O 11.85 F 0.3 , which has high ionic conductivity (2.39 × 10 −3 S cm −1 ) and excellent chemical stability, is developed. Collabor...

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Designing a Novel Electrolyte Na_3.2Hf₂Si_2.2P_0.8O_11.85F_0.3 for All‐Solid‐State Na‐O₂ Batteries

et al. 2022

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“…f) Comparison of electrochemical performance for recently published NZSP‐based solid‐state sodium metal batteries. [ 17,31–34 ]…”

Section: Resultsmentioning

confidence: 99%

“…This work provides an effective strategy to improve the dendrite suppression capability of solid-state inorganic electrolyte and paves the way for the application of all-solid-state metal batteries in scale-up energy storage. [17,[31][32][33][34]…”

Section: Discussionmentioning

confidence: 99%

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Solid‐State Na Metal Batteries with Superior Cycling Stability Enabled by Ferroelectric Enhanced Na/Na₃Zr₂Si₂PO₁₂ Interface

Sun

Zhao

et al. 2022

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Solid‐state metal batteries are attracting unprecedented concern because of their high energy density and safety. However, their service life, especially at high specific density, is hindered by the undesirable reversibility of metal anodes, owing to the inhomogeneous ion distribution and awkward charge transfer dynamics at the electrode/electrolyte interface. In this work, it is well demonstrated that ferroelectric phase BaTiO3 reinforced Na3Zr2Si2PO12 ceramic electrolyte can deconcentrate the distribution of charge transfer and self‐accelerate Na+ migration at the Na/Na3Zr2Si2PO12 interface upon cycling, realizing a compact Na deposition morphology together with a high critical current density (1.05 mA cm‐2 at ambient conditions). Assembled symmetric cells based on the proposed composite electrolyte render stable cycling up to 1000 h at 0.3 mA cm‐2. Specifically, the all solid‐state sodium metal batteries paired with Na3V1.5Cr0.5(PO4)3 cathode material can deliver a capacity of 95 mAh g‐1 at 100 mA g‐1 and maintain 84.4% of the initial capacity after 400 cycles. This excellent electrochemical performance clearly confirm the feasibility of the introduction of ferroelectric BaTiO3 to suppress the dendrite nucleation and Na propagation within ceramic electrolyte. This research offers new insight into the rational design of inorganic electrolyte, revealing dendrite‐free and long‐term all‐solid‐state sodium batteries.

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Electrolyte, Separator, Binder and Other Devices of Sodium Ion Batteries

Yi,

Jing,

Deng

et al. 2023

Sodium‐Ion Batteries

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New-type Hf-based NASICON electrolyte for solid-state Na-ion batteries with superior long-cycling stability and rate capability

Cited by 49 publications

References 43 publications

Designing a Novel Electrolyte Na_3.2Hf₂Si_2.2P_0.8O_11.85F_0.3 for All‐Solid‐State Na‐O₂ Batteries

Designing a Novel Electrolyte Na_3.2Hf₂Si_2.2P_0.8O_11.85F_0.3 for All‐Solid‐State Na‐O₂ Batteries

Solid‐State Na Metal Batteries with Superior Cycling Stability Enabled by Ferroelectric Enhanced Na/Na₃Zr₂Si₂PO₁₂ Interface

Electrolyte, Separator, Binder and Other Devices of Sodium Ion Batteries

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New-type Hf-based NASICON electrolyte for solid-state Na-ion batteries with superior long-cycling stability and rate capability

Cited by 49 publications

References 43 publications

Designing a Novel Electrolyte Na3.2Hf2Si2.2P0.8O11.85F0.3 for All‐Solid‐State Na‐O2 Batteries

Designing a Novel Electrolyte Na3.2Hf2Si2.2P0.8O11.85F0.3 for All‐Solid‐State Na‐O2 Batteries

Solid‐State Na Metal Batteries with Superior Cycling Stability Enabled by Ferroelectric Enhanced Na/Na3Zr2Si2PO12 Interface

Electrolyte, Separator, Binder and Other Devices of Sodium Ion Batteries

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Designing a Novel Electrolyte Na_3.2Hf₂Si_2.2P_0.8O_11.85F_0.3 for All‐Solid‐State Na‐O₂ Batteries

Designing a Novel Electrolyte Na_3.2Hf₂Si_2.2P_0.8O_11.85F_0.3 for All‐Solid‐State Na‐O₂ Batteries

Solid‐State Na Metal Batteries with Superior Cycling Stability Enabled by Ferroelectric Enhanced Na/Na₃Zr₂Si₂PO₁₂ Interface