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Solid Polymer Lithium-Ion Conducting Electrolytes for Structural Batteries
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This work comprises the manufacture and characterization of solid polymer lithium ion conducting electrolytes for structural batteries. In the study, polymer films are produced in situ via a rapid versatile UV irradiation polymerization route, in which ethylene oxide methacrylates are polymerized into thermoset networks. In the first part of the study, the simplicity and efficiency of this manufacturing route is emphasized. Polymer electrolytes are pro-duced with an ionic conductivity ranging from 5.8×10-10 S cm-1 up to 1.5×10-6 S cm-1, and a storage modulus of up to 2 GPa at 20°C. In the sec-ond part, the effect of the lithium salt content is studied, both for tightly crosslinked systems with a glass transition temperature (Tg) above room temperature but also for sparsely crosslinked system with a Tg below. It is shown that for these systems, there is a threshold amount of 4% lithium salt by weight, above which the ion conducting ability is not affected to a larger extent when the salt content is increased further. It is also shown that the influence of the salt content on the ionic conductivity is similar within both systems. However, the Tg is more affected by the addition of lithium salt for the loosely crosslinked system, and since the Tg is the main affecting parame-ter of the conductivity, the salt content plays a larger role here. In the third part of the study, a thiol functional compound is added via thiol-ene chemistry to create thio-ether segments in the polymer network. This is done in order to expand the toolbox of possible building blocks usable in the design of structural electrolytes. It is shown that solid polymer electrolytes of more homogeneous networks with a narrower glass transition region can be produced this way, and that they have the ability to function as an electrolyte. Finally, the abilities of reinforcing the electrolytes by nano fibrilar cellulose are investigated, by means to improve the mechanical properties without decreasing the ionic conductivity at any larger extent. These composites show conductivity values close to 10-4 S cm-1 and a storage modulus around 400 MPa at 25 °C.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2014. , 70 p.
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2014:7
National Category
Polymer Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-144169ISBN: 978-91-7595-035-8 (print)OAI: oai:DiVA.org:kth-144169DiVA: diva2:711388
Public defence
2014-04-25, F3, Lindstedtsvägen 26, KTH, Stockholm, 14:00 (English)
Opponent
Supervisors
Funder
Swedish Foundation for Strategic Research , RMA08-0002Swedish Energy Agency, 37712-1
Note

QC 20140410

Available from: 2014-04-10 Created: 2014-04-10 Last updated: 2014-04-10Bibliographically approved
List of papers
1. Photoinduced free radical polymerization of thermoset lithium battery electrolytes
Open this publication in new window or tab >>Photoinduced free radical polymerization of thermoset lithium battery electrolytes
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2011 (English)In: European Polymer Journal, ISSN 0014-3057, E-ISSN 1873-1945, Vol. 47, no 12, 2372-2378 p.Article in journal (Refereed) Published
Abstract [en]

Series of solid poly(ethylene oxide)-methacrylate electrolytes have successfully been manufactured with an aim to serve in a multifunctional battery both as mechanical load carrier as well as lithium ion conductor. The electrolytes produced, in a solvent free process with no post cure swelling, hold a broad range of both mechanical as well as ion conducting properties. The monomer and Li-salt mixtures have been irradiated with UV light, initiating free radical polymerization to obtain solid smooth, homogenous specimens to be utilized as ion conducting electrolytes. The storage modulus at 20 degrees C is ranging from 1 MPa to almost 2 GPa. The conducting ability of the electrolyte ranges from 5.8 x 10(-10) up to 1.5 x 10(-6) S/cm. These large variations in both mechanical properties as well as ionic conductivity are discussed, but also the versatility within the production technique is emphasized.

Keyword
Solid polymer electrolyte (SPE), Lithium ion, Mechanical properties, Ionic conductivity, Multifunctional batteries, Structural batteries
National Category
Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-63262 (URN)10.1016/j.eurpolymj.2011.09.018 (DOI)000298204500021 ()2-s2.0-81155126133 (Scopus ID)
Funder
StandUpSwedish Foundation for Strategic Research , RMA08-0002
Note

QC 20120125

Available from: 2012-01-25 Created: 2012-01-23 Last updated: 2017-12-08Bibliographically approved
2. Effect of Lithium Salt Content on the Performance of Thermoset Lithium Battery Electrolytes
Open this publication in new window or tab >>Effect of Lithium Salt Content on the Performance of Thermoset Lithium Battery Electrolytes
2012 (English)In: American Chemical Society Symposium Series (ACS), ISSN 0097-6156, E-ISSN 1947-5918, 55-65 p.Article in journal (Refereed) Published
Abstract [en]

Series of solid poly(ethylene glycol)-methacrylate electrolytes have successfully been manufactured in a solvent free process with an aim to serve in a multifunctional battery, both as mechanical load carrier as well as lithium ion conductor. The electrolytes have been studied with respect to mechanical and electrical properties. The thermoset series differs with respect to crosslink density and glass transition temperature (Tg). The results show that the conductivity increases, with salt content exhibiting similar trends, although at overall levels that differ if measured above or below the Tg of the system. The Tg transition on the other hand is more affected by the salt content for loosely crosslinked thermosets. The coordination of a lithium salt to the PEG-segments play a more important role for the physical state of the material when there are less restrictions due to crosslinking of the PEG-chains. The overall performance of the electrolyte at different temperatures will thus be more affected.

National Category
Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-107279 (URN)10.1021/bk-2012-1096.ch004 (DOI)2-s2.0-84905577275 (Scopus ID)
Note

QC 20121210

Available from: 2012-12-10 Created: 2012-12-10 Last updated: 2017-12-07Bibliographically approved
3. New structural lithium battery electrolytes using thiol-ene chemistry
Open this publication in new window or tab >>New structural lithium battery electrolytes using thiol-ene chemistry
2013 (English)In: Solid State Ionics, ISSN 0167-2738, E-ISSN 1872-7689, Vol. 236, 22-29 p.Article in journal (Refereed) Published
Abstract [en]

A series of solid poly(ethylene oxide)-methacrylate lithium ion electrolytes containing thio-ether segments have successfully been produced and evaluated with respect to mechanical and electrical performance. The series have been varied in crosslink density and thio-ether content. The study presents thiol-ene compounds as yet another tool to design multifunctional electrolytes, and that they are compatible with and usable for polymer electrolyte systems. The electrolytes, produced in a solvent free process where the oligomers are active diluents of the lithium salt, express a broad range of both mechanical as well as ion conducting properties. Conductivity values presented ranges up to about 8 x 10(-7) S/cm, and a wide spectrum of values of the storage modulus is presented in a range from 2 MPa to 2 GPa at 20 degrees C. The influence of the crosslink density of the poly(ethylene oxide)-methacrylates with and without thio-ether segments is discussed. In order to present correlations between crosslink density and how the lithium ion transport is affected by incorporating multifunctional thiol monomers, density measurements have been undertaken to calculate the average molar mass between the crosslinks.

Keyword
Solid polymer electrolyte (SPE), Mechanical properties, Ionic conductivity, Structural batteries, Thiol-ene chemistry, Multi-functionality
National Category
Engineering and Technology
Identifiers
urn:nbn:se:kth:diva-122347 (URN)10.1016/j.ssi.2013.01.019 (DOI)000317453700005 ()2-s2.0-84874924405 (Scopus ID)
Funder
Swedish Foundation for Strategic Research , RMA08-0002
Note

QC 20130521

Available from: 2013-05-21 Created: 2013-05-20 Last updated: 2017-12-06Bibliographically approved
4. Cellulose nanofibril reinforced composite electrolyte for lithium ion battery applications
Open this publication in new window or tab >>Cellulose nanofibril reinforced composite electrolyte for lithium ion battery applications
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(English)Manuscript (preprint) (Other academic)
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-144167 (URN)
Funder
Swedish Energy Agency, 37712-1
Note

QS 2014

Available from: 2014-04-10 Created: 2014-04-10 Last updated: 2014-04-10Bibliographically approved

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