Towards Safer All-Solid-State Lithium Metal Batteries by an Artificial Protection Layers
Authors: Perner Verena , Bela Marlena Maria , Herbers Lukas , Winter Martin , Börner Markus 
Published: September 2023

Lithium ion batteries (LIB) are representing a milestone in electrochemical energy storage and are still the state-of-the-art battery system for various mobile and stationary energy storage applications. However, the practical energy density of LIBs starts to reach an asymptotic limit. Beside LIBs, an auspicious variety of battery systems comprising a better option for specific applications in terms of e.g. energy density, so establishing a diversity of specific battery systems for specific applications is a good strategy.[1
] After initially paving the way for the LIB, the lithium metal battery (LMB) experiences a revival due to an outstanding theoretical specific capacity (3 860 mAh g−1) and low electrochemical potential (−3.04 V vs. SHE). However, continuous electrolyte consumption, the formation of an inhomogeneous SEI and high surface area lithium (HSAL), whose growth is induced by the heterogeneous and fragile structure of the SEI film, are still dominant challenges that need to be overcome. The liquid electrolytes also deal with safety issues like risk of leakage and flammability. The combination of Li metal with solid polymer electrolytes (SPE) could supress HSAL formation and avoid those safety hazards. However, SPEs deal with poor ionic conductivity at room temperature (10−8 S cm−1 ≤ σ ≤ 10−5 S cm−1) and, additionally, it is necessary to control the Li morphology during electrodeposition/dissolution to realize high-energy all-solid-state batteries (ASSB) based on Li metal anodes.[2
,3
]

Several artificial protective coatings have been proposed to improve the LMA/SPE interface by facilitating the Li ion flux, promoting a homogeneous Li electrodeposition/dissolution and protecting the LMA against electrolyte degradation as well as enhancing the Li wetting interface. The SPE induces a more flexible interphase that withstands the volume change. Recently, metal oxides coated by atomic layer deposition (ALD) have gained attention due to a great thickness control, the possibility of monolayer deposition as well as a consequential homogeneity of the deposited protection layer. Furthermore, ALD is suitable for roll-to-roll coatings which is feasible for industrial application.[3,4
]

Herein, the setup of Li-metal-polymer batteries (LMP® technology) commercialized by Blue Solutions and applied in their “blue cars” (30 kWh, 100 Wh kg-1) was modified in several points. Li metal was coated with a metal oxide via atomic layer deposition (ALD) to form an intermetallic phase as protective layer and to improve the Li+ flux. The artificial protective coating at Li metal was combined with a PEO- and/or polyether-based SPE and the effect of the modifications on the electrochemical performance in different ASSB setups was investigated and characterized.
[1] Placke, T.; Kloepsch, R.; Dühnen, S.; Winter, M. Lithium ion, lithium metal, and alternative rechargeable battery technologies: the odyssey for high energy density. Journal of Solid State Electrochemistry
2017, 21, 1939-1964.
[2] Cheng, X.-B.; Zhang, R.; Zhao, C.-Z.; Zhang, Q. Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review. Chemical Reviews
2017, 117, 10403-10473.
[3] Han, Z.; Zhang, C.; Lin, Q.; Zhang, Y.; Deng, Y.; Han, J.; Wu, D.; Kang, F.; Yang, Q. H.; Lv, W. A Protective Layer for Lithium Metal Anode: Why and How. Small Methods
2021, 5, 2001035.
[4] Han, Y.; Liu, B.; Xiao, Z.; Zhang, W.; Wang, X.; Pan, G.; Xia, Y.; Xia, X.; Tu, J. Interface issues of lithium metal anode for high‐energy batteries: Challenges, strategies, and perspectives. InfoMat
2021, 3, 155-174.