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Solid-State Divalent Ion Conduction in ZnPS_3

Martinolich, Andrew J. and Lee, Cheng-Wei and Lu, I-Te and Bevilacqua, Sarah C. and Preefer, Molleigh B. and Bernardi, Marco and Schleife, André and See, Kimberly A. (2019) Solid-State Divalent Ion Conduction in ZnPS_3. Chemistry of Materials, 31 (10). pp. 3652-3661. ISSN 0897-4756. doi:10.1021/acs.chemmater.9b00207.

[img] PDF (SEM image of ZnPS3, 31P NMR, interlayer, and intralayer migration pathways determined with NEB calculations, schematic migration pathway between edge-sharing octahedra, temperature dependent Raman and PXRD of ZnPS3, Raman and PXRD of Zn electrodes...) - Supplemental Material
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Next-generation batteries based on divalent working ions have the potential to both reduce the cost of energy storage devices and increase performance. Examples of promising divalent systems include those based on Mg^(2+), Ca^(2+), and Zn^(2+) working ions. Development of such technologies is slow, however, in part due to the difficulty associated with divalent cation conduction in the solid state. Divalent ion conduction is especially challenging in insulating materials that would be useful as solid-state electrolytes or protecting layers on the surfaces of metal anodes. Furthermore, there are no reports of divalent cation conduction in insulating, inorganic materials at reasonable temperatures, prohibiting the development of structure–property relationships. Here, we report Zn^(2+) conduction in insulating ZnPS_3, demonstrating divalent ionic conductivity in an ordered, inorganic lattice near room temperature. Importantly, the activation energy associated with the bulk conductivity is low, 351 ± 99 meV, comparable to some Li+conductors such as LTTO, although not as low as the superionic Li+ conductors. First-principles calculations suggest that the barrier corresponds to vacancy-mediated diffusion. Assessment of the structural distortions observed along the ion diffusion pathways suggests that an increase in the P–P–S bond angle in the [P_2S_6]^(4–) moiety accommodates the Zn^(2+) as it passes through the high-energy intermediate coordination environments. ZnPS_3 now represents a baseline material family to begin developing the structure–property relationships that control divalent ion diffusion and conduction in insulating solid-state hosts.

Item Type:Article
Related URLs:
URLURL TypeDescription Information
Martinolich, Andrew J.0000-0002-7866-9594
Bevilacqua, Sarah C.0000-0002-6834-7145
Preefer, Molleigh B.0000-0002-3699-8613
Bernardi, Marco0000-0001-7289-9666
Schleife, André0000-0003-0496-8214
See, Kimberly A.0000-0002-0133-9693
Alternate Title:Solid-State Divalent Ion Conduction in ZnPS3
Additional Information:© 2019 American Chemical Society. Received: January 16, 2019; Revised: February 28, 2019; Publication Date (Web): March 15, 2019. Financial support from Caltech and the Dow Next Generation Educator Fund is gratefully acknowledged. A.J.M. acknowledges postdoctoral fellowship from the Resnick Sustainability Institute at Caltech. M.B.P. acknowledges support from the Mellichamp Sustainability Fellowship at UCSB. Use of the Advanced Photon Source at Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. I.-T.L. was supported by the Air Force Office of Scientific Research through the Young Investigator Program Grant FA9550-18-1-0280. A.S. acknowledges support from the National Science Foundation under Grant No. DMR-1555153. This work made use of the Illinois Campus Cluster, a computing resource operated by the Illinois Campus Cluster Program (ICCP) in conjunction with the National Center for Supercomputing Applications (NCSA) supported by funds from the University of Illinois at Urbana-Champaign. This research is part of the Blue Waters sustained-petascale computing project, which is supported by the National Science Foundation (awards OCI-0725070 and ACI-1238993) and the state of Illinois. Blue Waters is a joint effort of the University of Illinois at Urbana-Champaign and its National Center for Supercomputing Applications. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE- AC02-05CH11231. The authors thank Dr. Chi Ma for assistance in the collection of SEM images and Dr. Sonjong Hwang for assistance in the collection of NMR spectra. The authors declare no competing financial interest.
Group:Resnick Sustainability Institute
Funding AgencyGrant Number
Dow Next Generation Educator FundUNSPECIFIED
Resnick Sustainability InstituteUNSPECIFIED
University of California, Santa BarbaraUNSPECIFIED
Department of Energy (DOE)DE-AC02-06CH11357
Air Force Office of Scientific Research (AFOSR)FA9550-18-1-0280
University of Illinois Urbana-ChampaignUNSPECIFIED
State of IllinoisUNSPECIFIED
Department of Energy (DOE)DE-AC02-05CH11231
Issue or Number:10
Record Number:CaltechAUTHORS:20190315-083524097
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Official Citation:Solid-State Divalent Ion Conduction in ZnPS3. Andrew J. Martinolich, Cheng-Wei Lee, I-Te Lu, Sarah C. Bevilacqua, Molleigh B. Preefer, Marco Bernardi, André Schleife, and Kimberly A. See. Chemistry of Materials 2019 31 (10), 3652-3661. DOI: 10.1021/acs.chemmater.9b00207
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:93857
Deposited By: Tony Diaz
Deposited On:15 Mar 2019 15:45
Last Modified:16 Nov 2021 17:01

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