Anomalous Self-Assembly and Ion Transport in Nanostructured Organic–Inorganic Solid Electrolytes

doi:https://doi.org/10.1021/acsmacrolett.8b00583

Title: Anomalous Self-Assembly and Ion Transport in Nanostructured Organic–Inorganic Solid Electrolytes

Abstract

Nanostructured solid electrolytes containing ion-conducting domains and rigid nonconducting domains are obtained by block copolymer self-assembly. Here, we report on the synthesis and characteristics of mixtures of a hybrid diblock copolymer with an organic and inorganic block: poly(ethylene oxide)-b-poly(acryloisobutyl polyhedral oligomeric silsesquioxane) (PEO-POSS) and a lithium salt. In the neat state, PEO-POSS exhibits a classical order-to-disorder transition upon heating. Dilute electrolytes exhibit a dramatic reversal; a disorder-to-order transition upon heating is obtained, indicating that the addition of salt fundamentally changes interactions between the organic and inorganic chains. At higher salt concentrations, the electrolytes primarily form a lamellar phase. Coexisting lamellae and cylinders are found at intermediate salt concentrations and high temperatures. The conductivity and shear modulus of PEO-POSS are significantly higher than that of an all-organic block copolymer electrolyte with similar molecular weight and morphology, demonstrating that organic-inorganic block copolymers provide a promising route for developing the next generation of solid electrolytes for lithium batteries.

Authors:

^[1];

^[2]; Chakraborty, Rohan ^[3];

^[3];

^[4];

^[5]

Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Energy Storage Research (JCESR) and Materials Sciences Division
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Energy Storage Research (JCESR), Materials Sciences Division and Energy Storage and Distributed Resources Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering

Publication Date:: 2018-08-14

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Science Foundation (NSF)

OSTI Identifier:: 1464098

Alternate Identifier(s):: OSTI ID: 1601191

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515

Resource Type:: Journal Article: Accepted Manuscript

Journal Name:: ACS Macro Letters

Additional Journal Information:: Journal Volume: 7; Journal Issue: 9; Journal ID: ISSN 2161-1653

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 77 NANOSCIENCE AND NANOTECHNOLOGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 25 ENERGY STORAGE; diblock copolymer; polyhedral oligomeric silsesquioxane; phase diagram; poly(ethylene oxide); solid polymer electrolyte

Citation Formats


                    Sethi, Gurmukh K., Jiang, Xi, Chakraborty, Rohan, Loo, Whitney S., Villaluenga, Irune, and Balsara, Nitash P. Anomalous Self-Assembly and Ion Transport in Nanostructured Organic–Inorganic Solid Electrolytes.  United States: N. p., 2018. 
        Web.  doi:10.1021/acsmacrolett.8b00583.

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                    Sethi, Gurmukh K., Jiang, Xi, Chakraborty, Rohan, Loo, Whitney S., Villaluenga, Irune, & Balsara, Nitash P. Anomalous Self-Assembly and Ion Transport in Nanostructured Organic–Inorganic Solid Electrolytes.  United States.  https://doi.org/10.1021/acsmacrolett.8b00583

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                    Sethi, Gurmukh K., Jiang, Xi, Chakraborty, Rohan, Loo, Whitney S., Villaluenga, Irune, and Balsara, Nitash P. Tue .  
        "Anomalous Self-Assembly and Ion Transport in Nanostructured Organic–Inorganic Solid Electrolytes".  United States.  https://doi.org/10.1021/acsmacrolett.8b00583.  https://www.osti.gov/servlets/purl/1464098.

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@article{osti_1464098,

  title        = {Anomalous Self-Assembly and Ion Transport in Nanostructured Organic–Inorganic Solid Electrolytes},

  author       = {Sethi, Gurmukh K. and Jiang, Xi and Chakraborty, Rohan and Loo, Whitney S. and Villaluenga, Irune and Balsara, Nitash P.},

  abstractNote = {Nanostructured solid electrolytes containing ion-conducting domains and rigid nonconducting domains are obtained by block copolymer self-assembly. Here, we report on the synthesis and characteristics of mixtures of a hybrid diblock copolymer with an organic and inorganic block: poly(ethylene oxide)-b-poly(acryloisobutyl polyhedral oligomeric silsesquioxane) (PEO-POSS) and a lithium salt. In the neat state, PEO-POSS exhibits a classical order-to-disorder transition upon heating. Dilute electrolytes exhibit a dramatic reversal; a disorder-to-order transition upon heating is obtained, indicating that the addition of salt fundamentally changes interactions between the organic and inorganic chains. At higher salt concentrations, the electrolytes primarily form a lamellar phase. Coexisting lamellae and cylinders are found at intermediate salt concentrations and high temperatures. The conductivity and shear modulus of PEO-POSS are significantly higher than that of an all-organic block copolymer electrolyte with similar molecular weight and morphology, demonstrating that organic-inorganic block copolymers provide a promising route for developing the next generation of solid electrolytes for lithium batteries.},

  doi          = {10.1021/acsmacrolett.8b00583},

  url          = {https://www.osti.gov/biblio/1464098},
  journal      = {ACS Macro Letters},

  issn         = {2161-1653},

  number       = 9,

  volume       = 7,

  place        = {United States},

  year         = {2018},

  month        = {8}

}

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https://doi.org/10.1021/acsmacrolett.8b00583

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Works referencing / citing this record:

Optimizing the monomer structure of polyhedral oligomeric silsesquioxane for ion transport in hybrid organic–inorganic block copolymers
journal, January 2020

Gao, Kevin W.; Jiang, Xi; Hoffman, Zach J.
Journal of Polymer Science, Vol. 58, Issue 2
https://doi.org/10.1002/pol.20190073

Superlattice by charged block copolymer self-assembly
journal, May 2019

Shim, Jimin; Bates, Frank S.; Lodge, Timothy P.
Nature Communications, Vol. 10, Issue 1
https://doi.org/10.1038/s41467-019-10141-z

Ion diffusion across a disorder-to-order phase transition in a poly(ethylene oxide)- b -poly(silsesquioxane) block copolymer electrolyte
journal, January 2019

Timachova, Ksenia; Sethi, Gurmukh K.; Bhattacharya, Rajashree
Molecular Systems Design & Engineering, Vol. 4, Issue 2
https://doi.org/10.1039/c8me00077h

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Similar Records

Title: Anomalous Self-Assembly and Ion Transport in Nanostructured Organic–Inorganic Solid Electrolytes

Abstract

Citation Formats

Optimizing the monomer structure of polyhedral oligomeric silsesquioxane for ion transport in hybrid organic–inorganic block copolymers journal, January 2020

Superlattice by charged block copolymer self-assembly journal, May 2019

Ion diffusion across a disorder-to-order phase transition in a poly(ethylene oxide)- b -poly(silsesquioxane) block copolymer electrolyte journal, January 2019

Optimizing the monomer structure of polyhedral oligomeric silsesquioxane for ion transport in hybrid organic–inorganic block copolymers
journal, January 2020

Superlattice by charged block copolymer self-assembly
journal, May 2019

Ion diffusion across a disorder-to-order phase transition in a poly(ethylene oxide)- b -poly(silsesquioxane) block copolymer electrolyte
journal, January 2019