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Functional Polymer Electrolytes for Multidimensional All-Solid-State Lithium Batteries
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Pressing demands for high power and high energy densities in novel electrical energy storage units have caused reconsiderations regarding both the choice of battery chemistry and design. Practical concerns originating in the conventional use of flammable liquid electrolytes have renewed the interests of using solvent-free polymer electrolytes (SPEs) as solid ionic conductors for safer batteries.

In this thesis work, SPEs developed from two polymer host structures, polyethers and polycarbonates, have been investigated for all-solid-state Li- and Li-ion battery applications. In the first part, functional polyether-based polymer electrolytes, such as poly(propylene glycol) triamine based oligomer and poly(propylene oxide)-based acrylates, were investigated for 3D-microbattery applications. The amine end-groups were favorable for forming conformal electrolyte coatings onto 3D electrodes via self-assembly. In-situ polymerization methods such as UV-initiated and electro-initiated polymerization techniques also showed potential to deposit uniform and conformal polymer coatings with thicknesses down to nano-dimensions.

Moreover, poly(trimethylene carbonate) (PTMC), an alternative to the commonly investigated polyether host materials, was synthesized for SPE applications and showed promising functionality as battery electrolyte. High-molecular-weight PTMC was first applied in LiFePO4-based batteries. By incorporating an oligomeric PTMC as an interfacial mediator, enhanced surface contacts at the electrode/SPE interfaces and obvious improvements in initial capacities were realized. In addition, room-temperature functionality of PTMC-based SPEs was explored through copolymerization of ε-caprolactone (CL) with TMC. Stable cycling performance at ambient temperatures was confirmed in P(TMC/CL)-based LiFePO4 half cells (e.g., around 80 and 150 mAh g-1 at 22 °C and 40 °C under C/20 rate, respectively). Through functionalization, hydroxyl-capped PTMC demonstrated good surface adhesion to metal oxides and was applied on non-planar electrodes. Ionic transport behavior in polycarbonate-SPEs was examined by both experimental and computational approaches. A coupling of Li ion transport with the polymer chain motions was demonstrated.

The final part of this work has been focused on exploring the key characteristics of the electrode/SPE interfacial chemistry using PEO and PTMC host materials, respectively. X-ray photoelectron spectroscopy (XPS) was used to get insights on the compositions of the interphase layers in both graphite and LiFePO4 half cells.  

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2015. , 89 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1243
Keyword [en]
Polymer electrolyte, Li-battery, 3D-microbattery, Functionalization, Polyether, Polycarbonate, Copolymer
National Category
Materials Chemistry
Research subject
Chemistry with specialization in Materials Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-248084ISBN: 978-91-554-9215-1 (print)OAI: oai:DiVA.org:uu-248084DiVA: diva2:798523
Public defence
2015-05-22, Häggsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 09:15 (English)
Opponent
Supervisors
Available from: 2015-04-28 Created: 2015-03-26 Last updated: 2015-07-07
List of papers
1. Solid polymer electrolyte coating from a bifunctional monomer for three-dimensional microbattery applications
Open this publication in new window or tab >>Solid polymer electrolyte coating from a bifunctional monomer for three-dimensional microbattery applications
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2013 (English)In: Journal of Power Sources, ISSN 0378-7753, E-ISSN 1873-2755, Vol. 238, 435-441 p.Article in journal (Refereed) Published
Abstract [en]

This work comprises the synthesis and characterization of a novel solid polymer electrolyte based on oligomeric polyetheramine substituted with a methacrylic group at one of its three chain ends. This modification introduces a bifunctionality to the PEA monomer it can act both as polymerizable unit and surfactant. Thin and pinhole-free polymer electrolyte layers could be constructed with thicknesses in the order of <1 mu m using UV-initiated polymerization. The electrolyte exhibits good electrochemical and chemical stability up to 4 V vs. Li+/Li. LiFePO4 cathode coated with the electrolyte was cycled against lithium at 60 degrees C, and displayed reasonable capacity values (similar to 140 mAh g(-1)) for 10 cycles, where after Li dendrite formation contributed to battery instabilities. 

Keyword
3D-microbattery solid electrolyte, Polymer electrolyte, Bifunctional monomer, Polyetheramine
National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-204760 (URN)10.1016/j.jpowsour.2013.04.058 (DOI)000320901900058 ()
Available from: 2013-08-15 Created: 2013-08-12 Last updated: 2017-12-06Bibliographically approved
2. Electrodeposition of thin poly(propylene glycol) acrylate electrolytes on 3D-nanopillar electrodes
Open this publication in new window or tab >>Electrodeposition of thin poly(propylene glycol) acrylate electrolytes on 3D-nanopillar electrodes
2014 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 137, 320-327 p.Article in journal (Refereed) Published
Keyword
3D-microbattery, Electropolymerization, Polymer electrolyte, Cu nano-pillars
National Category
Materials Chemistry
Research subject
Chemistry with specialization in Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-233516 (URN)10.1016/j.electacta.2014.06.008 (DOI)000341462500040 ()
Available from: 2014-10-06 Created: 2014-10-06 Last updated: 2017-12-05
3. Hydroxyl-functionalized poly(trimethylene carbonate) electrolytes for 3D-electrode configurations
Open this publication in new window or tab >>Hydroxyl-functionalized poly(trimethylene carbonate) electrolytes for 3D-electrode configurations
2015 (English)In: Polymer Chemistry, ISSN 1759-9954, E-ISSN 1759-9962, Vol. 6, no 26, 4766-4774 p.Article in journal (Refereed) Published
Abstract [en]

Polymer electrolytes were prepared from an aliphatic polycarbonate with 10 mol% of repeating units having a hydroxyl-functional side group, with the addition of LiTFSI salt. The hydrogen bond-interacting side groups were found to be beneficial for improving adhesion to 2D planar electrode material surfaces. These favorable surface properties proved to be valid also for 3D-structured systems since thin, conformal coatings could be cast on 3D-microstructured electrodes. In addition, the electrolytes were found to have reasonable ionic conductivity (up to 2.7 x 10(-8) S cm(-1) at 25 degrees C and 2.3 x 10(-6) S cm(-1) at 60 degrees C) that was almost independent of salt concentration. This demonstrates how a hydroxyl-functional polymer approach is suitable for the creation of 3D-structured electrode-electrolyte assemblies for microbattery applications.

National Category
Materials Chemistry
Research subject
Chemistry with specialization in Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-248051 (URN)10.1039/c5py00446b (DOI)000356700100009 ()
Funder
Swedish Research Council, 2012-4681StandUpCarl Tryggers foundation
Available from: 2015-03-26 Created: 2015-03-26 Last updated: 2017-12-04Bibliographically approved
4. Fabrication of 3D microbatteries using solid polymer electrolytes
Open this publication in new window or tab >>Fabrication of 3D microbatteries using solid polymer electrolytes
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(English)Manuscript (preprint) (Other academic)
National Category
Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-248073 (URN)
Available from: 2015-03-26 Created: 2015-03-26 Last updated: 2015-05-12
5. Polycarbonate-based solid polymer electrolytes for Li-ion batteries
Open this publication in new window or tab >>Polycarbonate-based solid polymer electrolytes for Li-ion batteries
2013 (English)In: Solid State Ionics, ISSN 0167-2738, E-ISSN 1872-7689, Vol. 262, 738-742 p.Article in journal (Refereed) Published
Abstract [en]

This paper reports the synthesis and application of high-molecular-weight poly(trimethylene carbonate) (PTMC) as a new host material for solid polymer electrolyte-based Li-ion batteries. PTMC was synthesized through bulk ring-opening polymerization of the cyclic monomer to yield a high-molecular-weight polymer to serve as a base material for the electrolytes. The thermal properties and ionic conductivity of polymer electrolytes with different salt ratios were measured by TGA/DSC and electrochemical impedance spectroscopy, respectively. The most conductive systems were found at [Li+]:[carbonate] ratios of 1:13 and 1:8, which showed electrochemical stability up to 5.0 V vs. Li/Li+ and an ionic conductivity on the order of 10− 7 Scm(-1) at 60 °C. LiFePO4 half-cells using the electrolytes demonstrated a plateau in the specific discharge capacity around 153 mAhg(-1) after long-term cycling. The functionality of the electrolytes for three-dimensional microbatteries was also confirmed.

Keyword
Polycarbonate; Trimethylene carbonate; Polymer electrolyte; Li-ion battery; 3D-microbattery
National Category
Chemical Sciences
Research subject
Chemistry
Identifiers
urn:nbn:se:uu:diva-208985 (URN)10.1016/j.ssi.2013.08.014 (DOI)000338810500161 ()
Conference
19th International Conference on Solid State Ionics (SSI), Kyoto, Japan, June 02-07, 2013
Available from: 2013-10-12 Created: 2013-10-12 Last updated: 2017-12-06Bibliographically approved
6. Realization of high performance polycarbonate-based Li polymer batteries
Open this publication in new window or tab >>Realization of high performance polycarbonate-based Li polymer batteries
2015 (English)In: Electrochemistry communications, ISSN 1388-2481, E-ISSN 1873-1902, Vol. 52, 71-74 p.Article in journal (Refereed) Published
Keyword
Polymer electrolyte, Polycarbonate, Trimethylene carbonate, Li-ion battery, Interfaces
National Category
Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-245865 (URN)10.1016/j.elecom.2015.01.020 (DOI)000352850700019 ()
Available from: 2015-03-02 Created: 2015-03-02 Last updated: 2017-12-04Bibliographically approved
7. High-performance solid polymer electrolytes for lithium batteries operational at ambient temperature
Open this publication in new window or tab >>High-performance solid polymer electrolytes for lithium batteries operational at ambient temperature
(English)Article in journal (Other academic) Submitted
National Category
Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-248053 (URN)
Available from: 2015-03-26 Created: 2015-03-26 Last updated: 2015-05-12
8. Ion transport in polycarbonate based solid polymer electrolytes: experimental and computational investigations
Open this publication in new window or tab >>Ion transport in polycarbonate based solid polymer electrolytes: experimental and computational investigations
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2016 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 18, no 14, 9504-9513 p.Article in journal (Refereed) Published
Abstract [en]

Among the alternative host materials for solid polymer electrolytes (SPEs), polycarbonates have recently shown promising functionality in all-solid-state lithium batteries from ambient to elevated temperatures. While the computational and experimental investigations of ion conduction in conventional polyethers have been extensive, the ion transport in polycarbonates has been much less studied. The present work investigates the ionic transport behavior in SPEs based on poly(trimethylene carbonate) (PTMC) and its co-polymer with epsilon-caprolactone (CL) via both experimental and computational approaches. FTIR spectra indicated a preferential local coordination between Li+ and ester carbonyl oxygen atoms in the P(TMC20CL80) co-polymer SPE. Diffusion NMR revealed that the co-polymer SPE also displays higher ion mobilities than PTMC. For both systems, locally oriented polymer domains, a few hundred nanometers in size and with limited connections between them, were inferred from the NMR spin relaxation and diffusion data. Potentiostatic polarization experiments revealed notably higher cationic transference numbers in the polycarbonate based SPEs as compared to conventional polyether based SPEs. In addition, MD simulations provided atomic-scale insight into the structure-dynamics properties, including confirmation of a preferential Li+-carbonyl oxygen atom coordination, with a preference in coordination to the ester based monomers. A coupling of the Li-ion dynamics to the polymer chain dynamics was indicated by both simulations and experiments.

National Category
Materials Chemistry Physical Chemistry Theoretical Chemistry Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-248057 (URN)10.1039/c6cp00757k (DOI)000373570200024 ()26984668 (PubMedID)
Funder
StandUpSwedish Research Council, 2012-3837, 2012-3244Carl Tryggers foundation Swedish Foundation for Strategic Research
Available from: 2015-03-26 Created: 2015-03-26 Last updated: 2017-12-04Bibliographically approved
9. Interface layer formation in solid polymer electrolyte lithium batteries: an XPS study
Open this publication in new window or tab >>Interface layer formation in solid polymer electrolyte lithium batteries: an XPS study
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2014 (English)In: JOURNAL OF MATERIALS CHEMISTRY A, ISSN 2050-7488, Vol. 2, no 20, 7256-7264 p.Article in journal (Refereed) Published
Abstract [en]

The first characterization studies of the interface layer formed between a Li-ion battery electrode and a solid polymer electrolyte (SPE) are presented here. SPEs are well known for their electrochemical stability and excellent safety, and thus considered good alternatives to conventional liquid/gel electrolytes in high-energy density battery devices. This work comprises studies of solid electrolyte interphase (SEI) formation in SPE-based graphite|Li cells using X-ray photoelectron spectroscopy (XPS). SPEs based on high molecular weight poly(ethylene oxide) (PEO) and lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) salt are studied. Large amounts of LiOH are observed, and the XPS results indicate a correlation with moisture contamination in the SPEs. The water contents are quantitatively determined to be in the range of hundreds of ppm in the pure PEO as well as in the polymer electrolytes, which are prepared by a conventional SPE preparation method using different batches of PEO and at different drying temperatures. Moreover, severe salt degradation is observed at the graphite-SPE interface after the 1st discharge, while the salt is found to be more stable at the Li-SPE interface or when using LiTFSI-based liquid electrolyte equivalents.

National Category
Biomaterials Science Energy Engineering
Identifiers
urn:nbn:se:uu:diva-227147 (URN)10.1039/c4ta00214h (DOI)000334998400019 ()
Available from: 2014-06-24 Created: 2014-06-24 Last updated: 2015-05-12Bibliographically approved
10. At the polymer electrolyte interfaces: the role of the host material for surface decomposition mechanisms in Li-polymer batteries
Open this publication in new window or tab >>At the polymer electrolyte interfaces: the role of the host material for surface decomposition mechanisms in Li-polymer batteries
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(English)Manuscript (preprint) (Other academic)
National Category
Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-248074 (URN)
Available from: 2015-03-26 Created: 2015-03-26 Last updated: 2015-05-12

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