Role of Scaffold Architecture and Excess Surface Polymer Layers in a 3D-Interconnected Ceramic/Polymer Composite Electrolyte

Ritu Sahore; Beth L. Armstrong; Xiaomin Tang; Changhao Liu; Kyra Owensby; Sergiy Kalnaus; Xi Chelsea Chen

doi:10.1002/aenm.202203663

Role of Scaffold Architecture and Excess Surface Polymer Layers in a 3D-Interconnected Ceramic/Polymer Composite Electrolyte

Ritu Sahore, Beth L. Armstrong, Xiaomin Tang, Changhao Liu, Kyra Owensby, Sergiy Kalnaus, Xi Chelsea Chen

Research output: Contribution to journal › Article › peer-review

7 Scopus citations

Abstract

3D-interconnected ceramic/polymer composite electrolytes offer promise to combine the benefits of both ceramic and polymer electrolytes. However, an in-depth understanding of the role of the ceramic scaffold's architecture, and the associated polymer/ceramic interfaces on the electrochemical properties of such composite electrolytes is still incomplete. Here, these factors are systematically evaluated using an interconnected composite electrolyte with a tunable and well-defined architecture. The ionic conductivity of the ceramic scaffold is strongly dependent on its porosity and tortuosity, as demonstrated experimentally and via theoretical modeling. The connectivity of the ceramic framework avoids the high interfacial impedance at the polymer/ceramic electrolyte interface within the composite. However, this work discovers that the interfacial impedance between the bulk composite and excess surface polymer layers of the composite membrane dominates the overall impedance, resulting in a 1–2 order drop of ionic conductivity compared to the ceramic scaffold. Despite the high impedance interfaces, an improved Li⁺ transference number is found compared to the neat polymer (0.29 vs 0.05), attributed to the ceramic phase's contributions toward ion transport. This leads to flatter overpotentials in lithium symmetric cell cycling. These results are expected to guide future research directions toward scalable manufacturing of composite electrolytes with optimized architecture and interfaces.

Original language	English
Article number	2203663
Journal	Advanced Energy Materials
Volume	13
Issue number	19
DOIs	https://doi.org/10.1002/aenm.202203663
State	Published - May 19 2023

Funding

This research was sponsored by the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy for the Vehicle Technologies Office's Advanced Battery Materials Research Program (Simon Thompson, Program Manager). The SEM in this work was performed and supported at the Center for Nanophase Materials Sciences in Oak Ridge National Lab, a DOE Office of Science user facility. The authors also thank Katie Browning for help with ionic conductivity measurements. This paper was authored by UT-Battelle, LLC, under Contract No. DE-AC05-00OR22725 with the U.S. DOE. The US government retained and the publisher, by accepting the article for publication, acknowledged that the US government retained a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this paper, or allow others to do so, for US government purposes. DOE would provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan). This research was sponsored by the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy for the Vehicle Technologies Office's Advanced Battery Materials Research Program (Simon Thompson, Program Manager). The SEM in this work was performed and supported at the Center for Nanophase Materials Sciences in Oak Ridge National Lab, a DOE Office of Science user facility. The authors also thank Katie Browning for help with ionic conductivity measurements. This paper was authored by UT‐Battelle, LLC, under Contract No. DE‐AC05‐00OR22725 with the U.S. DOE. The US government retained and the publisher, by accepting the article for publication, acknowledged that the US government retained a nonexclusive, paid‐up, irrevocable, worldwide license to publish or reproduce the published form of this paper, or allow others to do so, for US government purposes. DOE would provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ).

Funders	Funder number
DOE Public Access Plan
Office of Energy Efficiency and Renewable Energy for the Vehicle Technologies Office
U.S. Department of Energy
Office of Science	DE-AC05-00OR22725

Keywords

ceramic electrolytes
composite electrolytes
interconnected ceramics
lithium
polymer electrolytes
polymer/ceramic interfaces
solid-state batteries

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1002/aenm.202203663

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title = "Role of Scaffold Architecture and Excess Surface Polymer Layers in a 3D-Interconnected Ceramic/Polymer Composite Electrolyte",

abstract = "3D-interconnected ceramic/polymer composite electrolytes offer promise to combine the benefits of both ceramic and polymer electrolytes. However, an in-depth understanding of the role of the ceramic scaffold's architecture, and the associated polymer/ceramic interfaces on the electrochemical properties of such composite electrolytes is still incomplete. Here, these factors are systematically evaluated using an interconnected composite electrolyte with a tunable and well-defined architecture. The ionic conductivity of the ceramic scaffold is strongly dependent on its porosity and tortuosity, as demonstrated experimentally and via theoretical modeling. The connectivity of the ceramic framework avoids the high interfacial impedance at the polymer/ceramic electrolyte interface within the composite. However, this work discovers that the interfacial impedance between the bulk composite and excess surface polymer layers of the composite membrane dominates the overall impedance, resulting in a 1–2 order drop of ionic conductivity compared to the ceramic scaffold. Despite the high impedance interfaces, an improved Li+ transference number is found compared to the neat polymer (0.29 vs 0.05), attributed to the ceramic phase's contributions toward ion transport. This leads to flatter overpotentials in lithium symmetric cell cycling. These results are expected to guide future research directions toward scalable manufacturing of composite electrolytes with optimized architecture and interfaces.",

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N2 - 3D-interconnected ceramic/polymer composite electrolytes offer promise to combine the benefits of both ceramic and polymer electrolytes. However, an in-depth understanding of the role of the ceramic scaffold's architecture, and the associated polymer/ceramic interfaces on the electrochemical properties of such composite electrolytes is still incomplete. Here, these factors are systematically evaluated using an interconnected composite electrolyte with a tunable and well-defined architecture. The ionic conductivity of the ceramic scaffold is strongly dependent on its porosity and tortuosity, as demonstrated experimentally and via theoretical modeling. The connectivity of the ceramic framework avoids the high interfacial impedance at the polymer/ceramic electrolyte interface within the composite. However, this work discovers that the interfacial impedance between the bulk composite and excess surface polymer layers of the composite membrane dominates the overall impedance, resulting in a 1–2 order drop of ionic conductivity compared to the ceramic scaffold. Despite the high impedance interfaces, an improved Li+ transference number is found compared to the neat polymer (0.29 vs 0.05), attributed to the ceramic phase's contributions toward ion transport. This leads to flatter overpotentials in lithium symmetric cell cycling. These results are expected to guide future research directions toward scalable manufacturing of composite electrolytes with optimized architecture and interfaces.

AB - 3D-interconnected ceramic/polymer composite electrolytes offer promise to combine the benefits of both ceramic and polymer electrolytes. However, an in-depth understanding of the role of the ceramic scaffold's architecture, and the associated polymer/ceramic interfaces on the electrochemical properties of such composite electrolytes is still incomplete. Here, these factors are systematically evaluated using an interconnected composite electrolyte with a tunable and well-defined architecture. The ionic conductivity of the ceramic scaffold is strongly dependent on its porosity and tortuosity, as demonstrated experimentally and via theoretical modeling. The connectivity of the ceramic framework avoids the high interfacial impedance at the polymer/ceramic electrolyte interface within the composite. However, this work discovers that the interfacial impedance between the bulk composite and excess surface polymer layers of the composite membrane dominates the overall impedance, resulting in a 1–2 order drop of ionic conductivity compared to the ceramic scaffold. Despite the high impedance interfaces, an improved Li+ transference number is found compared to the neat polymer (0.29 vs 0.05), attributed to the ceramic phase's contributions toward ion transport. This leads to flatter overpotentials in lithium symmetric cell cycling. These results are expected to guide future research directions toward scalable manufacturing of composite electrolytes with optimized architecture and interfaces.

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Role of Scaffold Architecture and Excess Surface Polymer Layers in a 3D-Interconnected Ceramic/Polymer Composite Electrolyte

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Keywords

UN SDGs

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