![]() The optimized 1.6Li 2O-TaCl 5 amorphous SE possesses a high ionic conductivity of 6.6 × 10 −3 S cm −1 at 25 ☌, surpassing most of the other amorphous SEs. One-step ball-milling method can easily yield the desired products in amorphous state. The newly developed SEs display several desirable features compared to the existing SEs. Herein, we report a family of lithium-based oxychloride amorphous SEs (xLi 2O-MCl y, M = Ta or Hf, 0.8 ≤ x ≤ 2, y = 5 or 4). Nevertheless, if amorphous SEs were to be competitive with the crystalline SEs, both high conductivity and good compatibility with favorable layered oxide cathodes are required. 26, 27, 28, 29, and lithium phosphorus oxynitride 30) exhibit improved (electro)chemical stability compared to the sulfide compounds, but their poor ionic conductivities of 10 −9–10 −6 S cm −1 at room temperature (RT, 25 ☌) are far away from the benchmark (10 −3 S/cm) for bulk-type ASSBs 31. Oxide-based amorphous SEs (such as Li 2O-MO x, M = Si, B, P, Ge, etc. ![]() Li +/Li) 23, 24 and poor electrode compatibility 25 significantly limit their application in ASSBs. The sulfide-based amorphous SEs, such as Li 2S-P 2S 5 21 and Li 2S-SiS 2 22, show decent ionic conductivities around 10 −4 S cm −1, but their narrow electrochemical stability window (1.5–2.5 V vs. Early researches for amorphous SEs have been reported since the 1960s 19. Different types of reported amorphous SEs have their own advantages and disadvantages. There are very limited established universal theories for structure modeling and ionic diffusivity prediction for amorphous materials 20. Another challenge is lacking long-range periodicity that makes it difficult to understand the ion conduction mechanism in amorphous materials. One major challenge is that the ionic conductivities of amorphous SEs are generally lower than those of the typical crystalline SEs. Despite the diligent efforts, the research for amorphous SEs has been proceeding slowly. While the ion conduction mechanisms of crystalline SEs have been widely studied to provide guidance for the search of new superionic conductors, some amorphous SEs also show good potentials but are less studied 18.Īmorphous SEs present the primary advantages of softness, easy fabrication, low grain boundaries, wider compositional variations, and isotropic ionic conduction 19, which are expected to compensate the drawbacks of some crystalline SEs with high grain boundary resistance, poor processibility, and high cost. Other types of crystalline SEs including oxide-based SEs (e.g., perovskite-type 9, sodium superionic conductor (NASICON)-type 10, and garnet-type 11, 12) and halide-based SEs (e.g., Li-M-Cl system, M = Y, In, Sc 13, 14, 15, 16, 17) also demonstrate good conductivities of 10 −4–10 −3 S cm −1. For example, representative sulfide-based SEs, such as Li Argyodites 5, 6 and Li 10GeP 2S 12 (LGPS)-type 7, 8, exhibit attractive ionic conductivities in the order of 10 −2 S cm −1. Crystalline SEs with long-range ordered structures have shown continuous and fast Li-ion conduction. One of the essential requirements for a favorable SE is high ionic conductivity. A key component for ASSBs is solid electrolyte (SE) which can potentially enable the use of high-voltage cathodes and Li metal anode to boost the energy density 3, 4. Long cycle life (more than 2400 times of charging and discharging) can be achieved for all-solid-state batteries using the xLi 2O-TaCl 5 amorphous solid electrolyte at 400 mA g −1, demonstrating vast application prospects of the oxychloride amorphous solid electrolytes.Īlong with the fast growing market of rechargeable electric vehicles (REVs), the development of all-solid-state batteries (ASSBs) is of high expectation due to their promises of safety, reliability, and high energy density 1, 2. ![]() More importantly, all-solid-state batteries using the amorphous solid electrolytes show excellent electrochemical performance at both 25 ☌ and −10 ☌. It is found that the oxygen-jointed anion networks with abundant terminal chlorines in xLi 2O-MCl y amorphous solid electrolytes play an important role for the fast Li-ion conduction. The mixed-anion structural models of xLi 2O-MCl y amorphous SEs are well established and correlated to the ionic conductivities. xLi 2O-MCl y amorphous solid electrolytes can achieve desirable ionic conductivities up to 6.6 × 10 −3 S cm −1 at 25 ☌, which is one of the highest values among all the reported amorphous solid electrolytes and comparable to those of the popular crystalline ones. Herein, we report a new family of amorphous solid electrolytes, xLi 2O-MCl y (M = Ta or Hf, 0.8 ≤ x ≤ 2, y = 5 or 4). Solid electrolyte is vital to ensure all-solid-state batteries with improved safety, long cyclability, and feasibility at different temperatures.
0 Comments
Leave a Reply. |