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Page 2 of 14 Chen et al. Energy Mater. 2025, 5, 500064 https://dx.doi.org/10.20517/energymater.2024.163

electrolytes of Li La Zr O /polyethylene oxide/lithium bis(trifluoromethane-sulfonyl) imide film and nickel-rich
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high voltage cathode (LiNi Mn Co O ) has been obviously suppressed through the significantly improved anti-
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oxidation capability of the electrolyte. Simultaneously, the alucone coating layer can function as the protective
barrier for the lithium metal anode, remarkably suppressing the growth of lithium dendrites. As a result, the
obtained all-solid-state batteries with dual electrode/electrolyte interfaces show both high capacity retention and
long cycle life, whereas the contrasting battery without protection coating layers shows both the fast capacity
decay and micro-shorting behavior. This work presents an effective strategy for constructing more stable
electrode/electrolyte interfaces for polymers-based all-solid-state batteries, and also provides a design rationale
for materials and structure development in the field of energy storage and conversion.
Keywords: All-solid-state battery, lithium metal anode, atomic layer deposition, interface optimization, composite
solid-state electrolyte, alucone

INTRODUCTION
High energy density batteries are essential for mobile applications, such as battery electric vehicles (BEVs)
and plug-in hybrid vehicles (PHEVs), to realize smooth and efficient storage conversion for practical
applications . Among different types of batteries, all-solid-state batteries (ASSBs) are deemed as one of the
[1-5]
[6-8]
most promising technologies to achieve both high energy density and safety . For example, the Garnet-
type solid-state electrolytes (SSEs)-based ASSBs are considered one of the most promising batteries due to
relatively high ionic conductivity, wide electrochemical window, and excellent compatibility of SSEs with
lithium (Li) metal anodes [9-11] . However, a significant challenge arises from the substantial interfacial
resistance between the garnet SSEs and electrode materials due to the inherent rigidity of their ceramic
structure . The elevated interfacial resistance was also observed on the Li side because of the inadequate
[12]
surface wetting characteristics and the formation of lithium carbonate impurities on their surfaces [13-15] .
Regarding this interfacial contact issue, incorporation of garnet SSEs into polymer electrolytes such as
polyethylene oxide (PEO) to form composite SSEs (CSSEs) is recognized as an effective strategy, in which
an intimate contact can be formed at the electrode/electrolyte interfaces to largely lower the interfacial
resistance [16,17] .

Although CSSEs have shown good interface physical contact, their mechanical stability and electrochemical
stability still need to be further improved with respect to the long-term cycling of batteries, even using the
inorganic/polymer CSSE such as Li La Zr O (LLZO)/PEO ones . To be specific, dendrite growth still can
[18]
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penetrate the CSSE from the anode side due to the low bulk and shear modulus of the polymer matrix such
as PEO; thus, a uniform Li plating to reduce dendrite growth is required for increasing long-term cycling of
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the battery [19-21] . On the other hand, most polymer matrices tend to decompose at a relatively lower voltage;
+
for example, the decomposition voltage of PEO is only 3.9 V (vs. Li /Li). Therefore, polymer-based CSSEs
are generally limited to pared with lower voltage cathodes such as lithium iron phosphate (LFP).
Furthermore, PEO also appears unsuitable when paired with the nickel-rich LiNi Mn Co O (NCM811)
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cathode due to possible parasitic reactions, which can lead to significant performance degradation of the
battery [22-24] .
To deal with the degradation issues of ASSBs, thin-film deposition techniques have been recognized as
efficient methods for improving the electrode/electrolyte interface. For example, the coatings of Al O ,
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TiO , ZrO , ZnO and LiAlO through chemical vapor deposition (CVD), physical vapor deposition (PVD),
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and atomic layer deposition (ALD) have shown great effectiveness [25,26] . Among these methods, ALD has
stood out with its self-limiting feature, enabling precise modulation of sub-nanometer coatings, showing
great potential for applications [27,28] . In detail, ALD coatings can effectively mitigate the dissolution of