Designing Alloying Interlayers for Metal Anodes in Batteries: Does Nanostructuring Improve Reversibility?
4 affiliations
- 1Department of Chemical Engineering
- 2University of Texas at Austin
- 3Texas Materials Institute
- 4Bard Center for Electrochemistry
Abstract
Metal anodes have been extensively explored as candidates for high-energy rechargeable batteries. However, uncontrolled electrodeposition of metals such as Zn often produces porous, disconnected “dead” metal that limits reversibility. A common mitigation strategy is to introduce an alloying functional layer, which is in general assumed to perform better when nanostructured due to its increased specific surface area and the diffusion scaling relation 𝜏~ 𝐿 2 𝐷 ⁄ . Here, we directly interrogate how the characteristic feature size of an alloying interlayer governs reversibility, using Ag functional layers with building blocks at three representative length scales: 100 nm, a few μm, and 100 μm, approximately. Combining operando visualization with ex-situ structural characterization, we find that Ag layers composed of few-μm particles exhibit the highest Zn plating and stripping reversibility. Coarse, 100-μm Ag particles provide poor areal coverage, such that beneficial Ag–Zn alloying is confined to isolated regions and does not effectively regulate deposition. In contrast, nanostructured Ag reacts rapidly and nearly completely, transforming into bulk intermetallic phases with large volume change that crack and delaminate from the current collector. Few-μm Ag features, on the one hand, provide sufficient surface coverage to promote uniform nucleation; on the other, Ag particles at this few-μm length scale prevent excessive intermetallic conversion and the associated mechanical failure. These results challenge the conventional wisdom that nanostructured layers are inherently more effective and reveal a previously overlooked mesoscopic design window for alloying interlayers. By explicitly linking alloying-layer feature size to diffusion-controlled phase transformation, mesoscale mechanical stability, and electrochemical behavior, this work identifies surface topography as a key design parameter for stabilizing multivalent metal anodes of high-energy batteries.
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BibTeX
@misc{manning2026designing,
title = {{Designing Alloying Interlayers for Metal Anodes in Batteries: Does Nanostructuring Improve Reversibility?}},
author = {Sydney C. Manning and J. X. Kent Zheng},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010155/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010155/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - Designing Alloying Interlayers for Metal Anodes in Batteries: Does Nanostructuring Improve Reversibility?
AU - Sydney C. Manning
AU - J. X. Kent Zheng
PY - 2026
DA - 2026/10/09
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010155/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010155/v1
AB - Metal anodes have been extensively explored as candidates for high-energy rechargeable batteries. However, uncontrolled electrodeposition of metals such as Zn often produces porous, disconnected “dead” metal that limits reversibility. A common mitigation strategy is to introduce an alloying functional layer, which is in general assumed to perform better when nanostructured due to its increased specific surface area and the diffusion scaling relation 𝜏~ 𝐿 2 𝐷 ⁄ . Here, we directly interrogate how the characteristic feature size of an alloying interlayer governs reversibility, using Ag functional layers with building blocks at three representative length scales: 100 nm, a few μm, and 100 μm, approximately. Combining operando visualization with ex-situ structural characterization, we find that Ag layers composed of few-μm particles exhibit the highest Zn plating and stripping reversibility. Coarse, 100-μm Ag particles provide poor areal coverage, such that beneficial Ag–Zn alloying is confined to isolated regions and does not effectively regulate deposition. In contrast, nanostructured Ag reacts rapidly and nearly completely, transforming into bulk intermetallic phases with large volume change that crack and delaminate from the current collector. Few-μm Ag features, on the one hand, provide sufficient surface coverage to promote uniform nucleation; on the other, Ag particles at this few-μm length scale prevent excessive intermetallic conversion and the associated mechanical failure. These results challenge the conventional wisdom that nanostructured layers are inherently more effective and reveal a previously overlooked mesoscopic design window for alloying interlayers. By explicitly linking alloying-layer feature size to diffusion-controlled phase transformation, mesoscale mechanical stability, and electrochemical behavior, this work identifies surface topography as a key design parameter for stabilizing multivalent metal anodes of high-energy batteries.
ER -