ACS Applied Materials & Interfaces
·
2021
·
IF 9.229
Zhen Sun,Yanqing Lai,Na lv,Yaqi Hu,Bingqin Li,Liangxing Jiang,Jiong Wang,Shuo Yin,Kui Li,Fangyang Liu
Argyrodite sulfide solid electrolytes, such as Li6PS5Cl (LPSC), have received much attention due to their high ionic conductivity (>1 mS cm–1) and success in all-solid-state batteries (long cycle performance, high energy density, etc.). Numerous efforts are spent on modifying the properties of the electrolyte itself. Here, we combine first-principles calculations with experiments to investigate O-doped argyrodite sulfide solid electrolytes (Li6PS5–xClOx,x = 0–1). It is found that Li6PS4.75ClO0.25 (LPSCO0.25) with x = 0.25 and cubic phase (F4̅3 m) shows the highest ion conductivity of 4.7 mS cm–1 (cold-pressed), higher than that of undoped Li6PS5Cl (4.2 mS cm–1). The bare LiCoO2/LPSCO0.25/Li–In all-solid-state battery exhibits an initial capacity of 131 mA h g–1 at 0.1 C and satisfactory cycling stability with 86% capacity retention after 250 cycles to the 4th cycle at 0.3 C under 25 °C. In addition, the NCM811/LPSCO0.25/Li–In cell is assembled using bare LiNi0.83Co0.06Mn0.11O2 cathode and shows an initial discharge capacity of 181 mA h g–1 at 0.1 C and 160 mA h g–1 at 0.3 C. The doping of oxygen-forming Li6PS5–xClOx also improves the stability to Li metal, proven by cyclic voltammetry and powder X-ray diffraction tests. The calculation results for the band structure reveals that LPSC has the lowest unoccupied molecular orbital than LPSCO0.25, further confirming the above conclusion.
研究领域:
材料科学
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电化学
·
能量存储
✓ 已验证
DOI
高影响因子
Journal of Energy Storage
·
2024
·
IF 8.9
Yi Duan,Xiaopeng Qi,Xiangtao Bai,Tianwei Yu,Yanlong Wu,Zenghua Chang,Jiantao Wang
Argyrodite Li 6-x PS 5-x Cl 1+x with high ionic conductivity and excellent mechanical performance is an attractive solid electrolyte candidate for all-solid-state lithium batteries (ASSLBs). Adjusting Cl content is an effective strategy to enhance the ionic conductivity, however its effect on the thermal stability remain uncovered. Herein, our study shows that the increase of Cl content in Li 6-x PS 5-x Cl 1+x significantly enhances the ionic conductivity and electrochemical properties but significantly reduces its thermal stability. We reveal that the thermal stability of Li 6-x PS 5-x Cl 1+x is heavily dependent on its Cl content and can be significantly enhanced by elemental doping. LiNi 0.6 Co 0.2 Mn 0.2 O 2 based ASSLBs using Cl-rich argyrodite with pure phase shows better cycle performance. Achievements from this study could serve as a guidance for optimizing and applicating argyrodite solid electrolytes towards high-performance and safe ASSLBs.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
DOI
高影响因子
EcoMat
·
2023
·Vol. 5
·期 4
·e12327
·
IF 14.6
Zhan Wu,Wenkui Zhang,Yang Xia,Hui Huang,Yongping Gan,Xinping He,Xinhui Xia,Jun Zhang
Sulfide solid state electrolyte (SSE) possesses high ionic conductivity and great processability but suffers from narrow electrochemical window. Conversion sulfide cathode FeS 2 has higher specific capacity and moderate redox potential, making it appropriate toward sulfide SSE. However, the complex reaction pathway and capacity fading mechanism in FeS 2 are rarely studied, especially in all-solid-state lithium battery (ASSLB). Herein, argyrodite sulfide SSE is paired with FeS 2 to investigate the electrochemical reaction pathways and the capacity fade mechanism. Instead of single conversion reaction, an anionic redox driven reaction of FeS 2 is revealed. The oxidization of Li 2 S vanishes and large quantity of inactive Li 2 S accumulates to cause the interfacial deterioration, along with the stress concentration during cycling, which leads to the rapid capacity fade of FeS 2 . Finally, a simple strategy of slurry-coated composite electrode with highly conductive network is proposed to direct the uniform deposition of Li 2 S and alleviate the stress concentration.
研究领域:
材料科学
·
电化学
·
电池技术
✓ 已验证
DOI
高影响因子
ChemSusChem
·
2024
·
IF 7.5
Ziling Jiang,Yujie Xiao,Lin Li,Siwu Li,Qiyue Luo,Chuang Yu
Graphical Bi−F dual-doped Li 5.5 PS 4.5 Cl 1.5 electrolyte is synthesized and exhibits significant compatibility for bare lithium metal, directs uniform Li + deposition/stripping by forming a Li−Bi alloy, and forms a robust LiF phase to inhibit the growth of lithium dendrites. In addition, the formation of BiS 4 ⁵ − unit and LiBiS 2 phase gives it a high air/moisture resistance. Chlorine-rich lithium argyrodite is considered as a promising superionic conductor electrolyte, but its practical application is limited due to poor air stability and instability toward lithium metal. In this work, BiF 3 is proposed as a multi-functional dopant for electrolyte modification, and the effects on the ionic conductivity, air stability, critical current density, and electrolyte/Li metal interfacial stability are studied. The results show that the doped electrolyte Li 5.54 P 0.98 Bi 0.02 S 4.5 Cl 1.44 F 0.06 (LPBiSClF 0.06 ) still maintains a relatively high ionic conductivity of 5.37 mS cm −1 . Additionally, the formation of BiS 4 5− unit and LiBiS 2 phase provides high air/moisture resistibility. Meanwhile, the critical current density of the Li/LPBiSClF 0.06 /Li cell is increased two-fold (2.1 mA cm −2 ). The in-situ formation of LiF and Li−Bi alloy at the lithium metal/electrolyte interface plays a key role in achieving high performance. As a result, the assembled LCO@LNO/LPBiSClF 0.06 /Li battery retains 78.4 % of its capacity after 100 cycles at 0.2C.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ELECTROCHIMICA ACTA
·
2024
·
IF 5.5
Shulin Li,Qiaoquan Lin,Han Yan,Qiaodong Li,Yu Yang,Xinlin Yan,Zhenyu Wang,Chuang Yu,Long Zhang
Cl-rich Li-argyrodites are one type of sulfide solid electrolytes (SSEs) with a high ionic conductivity and suitable mechanical properties for practical application. However, their tolerance against moisture in air and compatibility with metallic Li need further improvements. Here, we demonstrate that Nb-O dual-doping can be a good strategy for advanced Cl-rich Li-argyrodite SSEs, prepared by high energy ball milling and annealing method. Our results show that the Nb-O co-doping enhances the interface compatibility towards metallic Li and improves the moisture resistance, while maintains a fast ion transport. The Nb-O incorporation improves the Young's modulus and mitigates the side reaction of Li-argyrodite with Li. The doping-optimized sample demonstrates a high critical current density of 2.28 mA cm −2 and a long-term Li plating/stripping stability under a relatively high current density (1 mA cm −2 ) for nearly 3000 cycles. Notably, the corresponding all-solid-state lithium batteries (ASSLBs), using a Li metal electrode, can maintain a superior cycling stability for over 1000 cycles at 1 C.
研究领域:
材料科学
·
电化学
·
电池技术
✓ 已验证
DOI
高影响因子
Nature Communications
·
2024
·Vol. 15
·期 1
·1-14
·
IF 14.7
Su Han,Zhong Yu,Wang Changhong,Liu Yu,Hu Yang,Li Jingru,Wang Minkang,Jiao Longan,Zhou Ningning,Xiao Bing,Wang Xiuli,Sun Xueliang,Tu Jiangping
Sulfide electrolytes represent a crucial category of superionic conductors for all-solid-state lithium metal batteries. Among sulfide electrolytes, glassy sulfide is highly promising due to its long-range disorder and grain-boundary-free nature. However, the lack of comprehension regarding glass formation chemistry has hindered their progress. Herein, we propose interstitial volume as the decisive factor influencing halogen dopant solubility within a glass matrix. We engineer a Li 3 PS 4 -Li 4 SiS 4 complex structure within the sulfide glassy network to facilitate the release of interstitial volume. Consequently, we increase the dissolution capacity of LiI to 40 mol% in 75Li 2 S-25P 2 S 5 glass. The synthesized glass exhibits one of the highest ionic conductivities among reported glass sulfides. Furthermore, we develop a glassy/crystalline composite electrolyte to mitigate the shortcomings of argyrodite-type sulfides by utilizing our synthesized glass as the filler. The composite electrolytes effectively mitigate Li intrusion. This work unveils a protocol for the dissolution of halogen dopants in glass electrolytes.
研究领域:
材料科学
·
电化学
·
电池技术
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）