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Characterising Polymer Self-Assemblies using Field-Flow Fractionation | Aluminium Sulphate

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The promising new material has been patented by the University of South Wales and licensed to Kubagen, a company co-owned by Antonelli, with a view to refining and scaling up for commercial applications.

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Cycling performances of the two symmetric Li|LiFSI@LPS|Li and Li|LPS|Li cells were compared at a current density of 0.3 mA cm−2 at room temperature. As shown in Fig. 2C, the Li|LPS|Li cell can only stably charge/discharge for 60 hours, and then a gradual decrease in the voltage was observed because of the progressive dendrite penetration into the LPS SSE. After about 90 hours of cycling, a sudden voltage drop due to the completely short circuit was detected, as confirmed by the electrochemical impedance spectroscopy (EIS) results (fig. S2). The fluctuating and irregular voltage variations after the short circuit suggest the serious parasitic reactions between the SSE and the penetrated Li dendrites, generating a nonzero resistance of the dendrites (12). The Li|LiFSI@LPS|Li cell with an LiF-rich SEI layer between the Li metal and the SSE showed much stable Li plating/stripping profiles for over 300 hours without any short circuit (Fig. 2D and fig. S3).

On the basis of Eq. 1 in energy analysis, for a given current, the critical length increases with the Li/SEI interfacial energy (γ) per unit interface area and the bulk modulus of passivation layer components (note S1). Figure 5C demonstrates the plot of the relationship between the interfacial energy (γ) of different SEI components and the number of Li metal formula units. Using the same method as in a previous work (34), the interfacial energy (γ) can be obtained from the intercept of the fitted line in Fig. 5C. As shown in Fig. 5D, LPS has a negative interfacial energy (−88.92 meV/Å2), indicating an intrinsically unstable interface between the LPS and the Li metal. Therefore, the LPS will spontaneously react with the Li metal, which is in agreement with previous experimental and theoretical results (32). The reaction between Li and LPS forms cracks (Fig. 5A) because the reaction between the LPS and the Li metal leads to the reconstruction of the LPS with the formation of Li-S and Li-P compounds based on the DFT-optimized atomic interlayer structure calculation (Fig. 5E). In contrast to LPS, other components in normal SEI (LiF, Li2O, Li2S, Li2CO3, and LiCl) have positive interfacial energy with Li. Among them, LiF exhibits the highest interfacial energy of 73.28 meV/Å2, suggesting worst wettability to the Li metal but highest Li dendrite suppression ability. The interfacial energy of the solid-solid interface is mainly determined by two factors: (i) lattice mismatch. Generally, the noncoherent interface exhibits higher interfacial energy than the coherent interface. (ii) Formation energies for the interphases. Larger formation energy will lead to higher interfacial energy. LiF has an extremely larger interfacial energy than other SEI components. The detailed computational model and method for the interfacial energy are shown in note S2. The bulk modulus (E) and the calculated Li dendrite suppression ability (γE) are also summarized in the table in Fig. 5D. In addition to high interfacial energy, LiF also has a high bulk modulus (70 GPa) and leads to the highest value of γE (5129 eV/Å2 Mpa). In all SEI components, LiF has the highest ability to suppress Li dendrites. In sharp contrast, LPS has a negative γE value and interfacial energy, which intrinsically promotes the dendrite propagation.

By Xiulin Fan, Xiao Ji, Fudong Han, Jie Yue, Ji Chen, Long Chen, Tao Deng, Jianjun Jiang, Chunsheng Wang

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