Automation-Accelerated Electrolyte Design Mitigates Solubility Competition between Redox-Active Molecules and Supporting Salts

Noh, Juran; Job, Heather Marie; Doan, Hieu A.; Han, Kee Sung; Robertson, Lily A.; Zhang, Lu; Assary, Rajeev Surendran; Mueller, Karl T.; Murugesan, Vijayakumar; Liang, Yangang

doi:10.1021/acsaem.5c02546

Automation-Accelerated Electrolyte Design Mitigates Solubility Competition between Redox-Active Molecules and Supporting Salts

Journal Article · Tue Sep 02 00:00:00 EDT 2025 · ACS Applied Energy Materials

DOI:https://doi.org/10.1021/acsaem.5c02546· OSTI ID:2589767

Noh, Juran ^[1]; Job, Heather Marie ^[1]; ^[2]; ^[1]; ^[2]; ^[2]; ^[2]; ^[1]; ^[1]; ^[1]

Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)

In nonaqueous redox-flow batteries (NRFBs), redox-active organic molecules (ROMs) and supporting salts compete for solvation sites, limiting achievable energy density. We combine automated high-throughput experimentation (HTE) with camera-based saturation monitoring and quantitative NMR to measure paired (ROM, salt) solubilities across single and mixed organic solvents. Using 2,1,3-benzothiadiazole (BTZ) with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as a model system, we find that a binary m-xylene/acetonitrile mixture dissolves ≈3 M of both BTZ and LiTFSI─surpassing the previously reported 2 M ceiling for neat acetonitrile─by leveraging complementary solvation (MX is BTZ-philic and salt-phobic; ACN stabilizes LiTFSI). A random-forest model (RMSE ≈ 0.24) trained on solvent descriptors highlights log P and salt concentration as dominant predictors and predicts MX/ACN ≈0.3/0.7 (v/v) to be near-optimal. These formulations retain practical viscosity and ∼5 mS·cm^–1 conductivity at high loading. In conclusion, the workflow provides a reproducible, data-centric route to NRFB electrolyte design and motivates an open, standardized dual-solute solubility resource for accelerated electrolyte discovery.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE; USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; AC05-76RL01830

OSTI ID:: 2589767

Alternate ID(s):: OSTI ID: 3014088

Report Number(s):: PNNL-SA-196038; 191456

Journal Information:: ACS Applied Energy Materials, Journal Name: ACS Applied Energy Materials Journal Issue: 18 Vol. 8; ISSN 2574-0962

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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autonomous experimentation
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electrolyte formulation
high-throughput experimentation
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Automation-Accelerated Electrolyte Design Mitigates Solubility Competition between Redox-Active Molecules and Supporting Salts

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