Characteristics Analysis of Lithium Metal Batteries with Ultra-High Energy Density under Pressure Conditions
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摘要:
外部压力对锂金属电池的性能起着至关重要的作用. 为研究锂金属电池在不同压力条件下宏观电池性能表现和微观锂沉积特性，首先通过加压试验及电子显微镜扫描验证施加外部压力有助于改善锂金属负极表面形貌，为揭示其作用机理，并将非线性相场模型与力模型耦合，分析微观不用压力条件对锂的沉积形貌及内部应力分布的影响. 研究结果表明：在没有外部压力作用时，锂金属电池对外膨胀加速了锂枝晶的持续生长，导致容量快速衰退；模拟数据显示，随着外部压力的逐渐增大，锂枝晶的主轴长度由2.04 μm降低到1.1 μm，宽高比由0.32提升至0.79，这种光滑粗壮的形貌演变显著降低锂枝晶的比表面积，但同时也增加了力学不稳定性. 本文所提供的在不同外部压力下锂枝晶的相图，为锂金属电池压力管理设计提供理论支持.
Abstract:External pressure plays a crucial role in the performance of lithium metal batteries. In order to study the macroscopic performance and the microscopic lithium deposition characteristics of lithium metal batteries under different pressure conditions, the pressure test and scanning electron microscope (SEM) verification were conducted to verify that applying external pressure can improve the surface morphology of negative electrodes of lithium metal batteries. The nonlinear phase field model and the force model were coupled to reveal relevant mechanisms. The influence of non-pressure conditions on the deposition morphology and internal stress distribution of lithium was analyzed from the microscopic perspective. The results show that in the absence of external pressure, the external expansion of lithium metal batteries accelerates the continuous growth of lithium dendrites, which results in rapid capacity fading. According to the simulation data, as external pressure rises, the principal axis length of lithium dendrites decreases from 2.04 μm to 1.1 μm, and the aspect ratio increases from 0.32 to 0.79. The smooth and robust morphology evolution can significantly reduce the specific surface area of lithium dendrites, but at the same time, it increases the mechanical instability. The phases of lithium dendrites under different external pressures are displayed, which provides theoretical support for the pressure management and design of lithium metal batteries.
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图 1 压力条件下锂金属电池性能测试流程
Figure 1. Performance test procedure for lithium metal batteries under pressure
图 5 锂金属电池不同压力下电化学特性
Figure 5. Electrochemical properties of lithium metal batteries under different pressures
图 7 电池充放电过程中表面压力变化
Figure 7. Surface pressure changes during battery charging and discharging
图 8 锂金属电池表面压强随循环寿命的变化
Figure 8. Variation of surface pressure of lithium metal batteries with cycle life
图 9 不同压力下电池表面压强增量
Figure 9. Pressure increment on battery surface under different pressures
图 11 不同初始压力下锂金属电池负极界面形貌对比
Figure 11. Comparison of negative electrode surface morphology of lithium metal batteries under different initial pressures
图 12 不同初始压力下锂负极沉积形貌对比
Figure 12. Comparison of negative electrode deposition morphology of lithium metal batteries under different initial pressures
图 15 无外压力下锂沉积相场模拟结果
Figure 15. Simulation results of lithium deposition phase field without external pressure
图 16 外压力对锂沉积形貌影响示意
Figure 16. Influence of external pressure on lithium deposition morphology
图 17 不同外部压力条件下锂枝晶形貌演变结果
Figure 17. Evolution results of lithium dendrite morphology under different external pressures
图 18 锂离子沉积量的归一化值及枝晶长度数值
Figure 18. Normalized amount and dendrite length of lithium-ion deposition
图 20 不同外部压力作用下最大Von Mises应力变化
Figure 20. Variation of maximum Von Mises stress with external pressure
表 1 耦合模型参数值
Table 1. Coupling model parameter values
参数 符号 数值 参考文献 界面迁移速率/(m3•（J•s）−1) $ {L_\sigma } $ 10−6 [17-18] 反应速率常数/s−1 $ {L_\eta } $ 0.5 [17-18] 能量梯度系数/(J•m−1) $ {k_0} $ 1.5 × 10−6 [17-18] 势垒高度/(J•m−3) $ w $ 3.5 × 105 [17-18] 各向异性强度 $ \delta $ 0.03 [17-18] 各向异性模数 $ \omega $ 4 [17-18] 对称因子 $ \alpha $ 0.5 [17-18] 初始电解质浓度/(mol•m3) $ {c_0} $ 1.00 × 103 [17-18] 金属锂中初始锂原
子浓度/(mol•m3)$ {c_{\mathrm{s}}} $ 7.69 × 104 [17-18] 电极扩散系数/(m2•s−1) $ {D_{\mathrm{e}}} $ 2 × 10−15 [24] 电解质扩散系数/(m2•s−1) $ {D_{\mathrm{s}}} $ 2 × 10−15 [24] 电极电导率/(S•m−1) $ {\sigma _{\mathrm{e}}} $ 107 [24] 电解质电导率/(S•m−1) $ {\sigma _{\mathrm{s}}} $ 0.1 [24] 电极杨氏模量/GPa $ {E_{\mathrm{e}}} $ 7.8 [24-25] 电解质杨氏模量/GPa $ {E_{\mathrm{s}}} $ 1.0 [24-25] 电极泊松比 $ {v_{\mathrm{e}}} $ 0.42 [24-25] 电解质泊松比 $ {v_{\mathrm{s}}} $ 0.30 [24-25] Vegard 应变系数 $ {\lambda _{\mathrm{i}}} $ −8.66 × 10−4,
−7.73 × 10−4,
−5.29 × 10−4[24-25] 
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