Additives synergy for stable interface formation on rechargeable lithium metal anodes

Abstract(#br)The attention towards lithium (Li) metal anodes has been rekindled in recent years as it would boost the energy-density of Li batteries. However, notorious safety issues and cycling instability severely hinder their commercialization, especially when cycled in traditional carbonic ester electrolytes that exhibit a wide voltage window and are compatible with most of the cathode materials. Herein, lithium difluorophosphate (LiDFP) and vinylene carbonate (VC) are combined, and demonstrated to be synergistic in constructing in situ a mechanically stable and highly Li-ion conducting surface film on the Li metal anode. This results in uniform and compact Li deposition largely suppressing the formation of Li dendrites, dead lithium and irreversible Li-species as revealed by operando neutron depth profiling (NDP). This enables long-term cycling stability and enhancement of the Coulombic efficiency for rechargeable Li metal anodes. By combining solid state nuclear magnetic resonance (SSNMR) and spectroscopic studies, it is demonstrated that VC slows down the LiDFP reduction, yet promoting the breaking of the P–F bonds, which leads to a protective film. This film is rich in LiF–Li 3 PO 4 inorganic compounds, distributed homogeneously, that is embedded in a matrix of P–O–C species and macromolecular organic compounds like lithium ethylene dicarbonate. This composition is responsible for the improved ionic conductivity and mechanical stability of the protective film during extended cycles. The detailed insight in the additives interaction provides new opportunities for the design of rational surface films necessary for realizing high-performance lithium metal batteries

Data_Sheet_1_Operando Neutron Depth Profiling to Determine the Spatial Distribution of Li in Li-ion Batteries.pdf

<p>Neutron Depth Profiling (NDP) allows determination of the spatial distribution of specific isotopes, via neutron capture reactions. In a capture reaction charged particles with fixed kinetic energy are formed, where their energy loss through the material of interest can be used to provide the depth of the original isotope. As lithium-6 has a relatively large probability for such a capture reaction, it can be used by battery scientists to study the lithium concentration in the electrodes even during battery operation. The selective measurement of the ⁶Li isotope makes it a direct and sensitive technique, whereas the penetrative character of the neutrons allows practical battery pouch cells to be studied. Using NDP lithium diffusion and reaction rates can be studied operando as a function of depth, opening a large range of opportunities including the study of alloying reactions, metal plating, and (de) intercalation in insertion hosts. In the study of high rate cycling of intercalation materials the relatively low Li density challenges counting statistics while the limited change in electrode density due to the Li-ion insertion and extraction allows straightforward determination of the Li density as a function of electrode depth. If an electrode can be (dis)charged reversibly, data can be acquired and accumulated over multiple cycles to increase the time resolution. For Li metal plating and alloying reactions, the large lithium density allows good time resolution, however the large change of the electrode composition and density makes extracting the Li-density as a function of depth more challenging. Here an effective method is presented, using calibration measurements of the individual components, based on which the ratio of the components as a function of depth can be determined as well as the total Li-density. The same principles can be applied to insertion host materials, where the differences in density due to electrolyte infiltration yield the electrode porosity as a function of depth. This is of particular importance for battery electrodes where porosity has a direct influence on the energy density and charge transport.</p

Image_1_Operando Neutron Depth Profiling to Determine the Spatial Distribution of Li in Li-ion Batteries.jpg

<p>Neutron Depth Profiling (NDP) allows determination of the spatial distribution of specific isotopes, via neutron capture reactions. In a capture reaction charged particles with fixed kinetic energy are formed, where their energy loss through the material of interest can be used to provide the depth of the original isotope. As lithium-6 has a relatively large probability for such a capture reaction, it can be used by battery scientists to study the lithium concentration in the electrodes even during battery operation. The selective measurement of the ⁶Li isotope makes it a direct and sensitive technique, whereas the penetrative character of the neutrons allows practical battery pouch cells to be studied. Using NDP lithium diffusion and reaction rates can be studied operando as a function of depth, opening a large range of opportunities including the study of alloying reactions, metal plating, and (de) intercalation in insertion hosts. In the study of high rate cycling of intercalation materials the relatively low Li density challenges counting statistics while the limited change in electrode density due to the Li-ion insertion and extraction allows straightforward determination of the Li density as a function of electrode depth. If an electrode can be (dis)charged reversibly, data can be acquired and accumulated over multiple cycles to increase the time resolution. For Li metal plating and alloying reactions, the large lithium density allows good time resolution, however the large change of the electrode composition and density makes extracting the Li-density as a function of depth more challenging. Here an effective method is presented, using calibration measurements of the individual components, based on which the ratio of the components as a function of depth can be determined as well as the total Li-density. The same principles can be applied to insertion host materials, where the differences in density due to electrolyte infiltration yield the electrode porosity as a function of depth. This is of particular importance for battery electrodes where porosity has a direct influence on the energy density and charge transport.</p