Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Thermal Aspects and Electrolyte Mass Transport in Lithium-ion Batteries
KTH, School of Chemical Science and Engineering (CHE), Chemical Engineering and Technology, Applied Electrochemistry.ORCID iD: 0000-0003-2112-6115
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Temperature is one of the most important parameters for the performance, safety, and aging of lithium-ion batteries and has been linked to all main barriers for widespread commercial success of electric vehicles.

The aim of this thesis is to highlight the importance of temperature effects, as well as to provide engineering tools to study these.

The mass transport phenomena of the electrolyte with LiPF6  in EC:DEC was fully characterized in between 10 and 40 °C and 0.5 and 1.5 M, and all mass transport properties were found to vary strongly with temperature.

A superconcentrated electrolyte with LiTFSI in ACN was also fully characterized at 25 °C, and was found to have very different properties and interactions compared to LiPF6  in EC:DEC.

The benefit of using the benchmarking method termed electrolyte masstransport resistivity (EMTR) compared to using only ionic conductivity was illustrated for several systems, including organic liquids, ionic liquids, solid polymers, gelled polymers, and electrolytes containing flame-retardant additives.

TPP, a flame-retardant electrolyte additive, was evaluated using a HEV load cycle and was found to be unsuitable for high-power applications such as HEVs.

A large-format commercial battery cell with a thermal management system was characterized using both experiments and a coupled electrochemical and thermal model during a PHEV load cycle. Different thermal management strategies were evaluated using the model, but were found to have only minor effects since the limitations lie in the heat transfer of the jellyroll.

Abstract [sv]

Temperatur är en av de viktigaste parametrarna gällande ett litiumjonbatteris prestanda, säkerhet och åldring och har länkats till de främsta barriärerna för en storskalig kommersiell framgång för elbilar.

Syftet med den här avhandlingen är att belysa vikten av temperatureffekter, samt att bidra med ingenjörsverktyg att studera dessa.

Masstransporten för elektrolyten LiPF6  i EC:DEC karakteriserades fullständigt i temperaturintervallet 10 till 40 °C för LiPF6-koncentrationer på 0.5 till 1.5 M. Alla masstransport-egenskaper fanns variera kraftigt med temperaturen.

Den superkoncentrerade elektrolyten med LiTFSI i ACN karakteriserades även den fullständigt vid 25 °C. Dess egenskaper och interaktioner fanns vara väldigt annorlunda jämfört med LiPF6  i EC:DEC.

Fördelen med att använda utvärderingsmetoden elektrolytmasstransportresistivitet (EMTR) jämfört med att endast mäta konduktivitet illustrerades för flertalet system, däribland organiska vätskor, jonvätskor, fasta polymerer, gellade polymerer, och elektrolyter

med flamskyddsadditiv.

Flamskyddsadditivet TPP utvärderades med en hybridbils-lastcykel och fanns vara olämplig för högeffektsapplikationer, som hybridbilar.

Ett kommersiellt storformatsbatteri med ett temperatur-kontrollsystem karakteriserades med b.de experiment och en kopplad termisk och elektrokemisk modell under en lastcykel utvecklad för plug-inhybridbilar. Olika strategier för kontroll av temperaturen utvärderades, men fanns bara ha liten inverkan på batteriets temperatur då begränsningarna för värmetransport ligger i elektrodrullen, och inte i batteriets metalliska ytterhölje.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2015. , 60 p.
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2015:22
Keyword [en]
Energy storage, Lithium-ion batteries, Electrolytes, Temperature, Modeling, Hybrid electric vehicle, Plug-in hybrid electric vehicle
National Category
Chemical Engineering
Research subject
Chemical Engineering
Identifiers
URN: urn:nbn:se:kth:diva-166857ISBN: 978-91-7595-584-1 (print)OAI: oai:DiVA.org:kth-166857DiVA: diva2:812776
Public defence
2015-06-11, D2, Lindstedtsvägen 5, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Projects
Swedish Hybrid Vehicle Center
Note

QC 20150522

Available from: 2015-05-22 Created: 2015-05-20 Last updated: 2016-02-02Bibliographically approved
List of papers
1. Impact of the flame retardant additive triphenyl phosphate (TPP) on the performance of graphite/LiFePO4 cells in high power applications
Open this publication in new window or tab >>Impact of the flame retardant additive triphenyl phosphate (TPP) on the performance of graphite/LiFePO4 cells in high power applications
Show others...
2014 (English)In: Journal of Power Sources, ISSN 0378-7753, E-ISSN 1873-2755, Vol. 256, 430-439 p.Article in journal (Refereed) Published
Abstract [en]

This study presents an extensive characterization of a standard Li-ion battery (LiB) electrolyte containing different concentrations of the flame retardant triphenyl phosphate (TPP) in the context of high power applications. Electrolyte characterization shows only a minor decrease in the electrolyte flammability for low TPP concentrations. The addition of TPP to the electrolyte leads to increased viscosity and decreased conductivity. The solvation of the lithium ion charge carriers seem to be directly affected by the TPP addition as evidenced by Raman spectroscopy and increased mass-transport resistivity. Graphite/LiFePO4 full cell tests show the energy efficiency to decrease with the addition of TPP. Specifically, diffusion resistivity is observed to be the main source of increased losses. Furthermore, TPP influences the interface chemistry on both the positive and the negative electrode. Higher concentrations of TPP lead to thicker interface layers on LiFePO4. Even though TPP is not electrochemically reduced on graphite, it does participate in SEI formation. TPP cannot be considered a suitable flame retardant for high power applications as there is only a minor impact of TPP on the flammability of the electrolyte for low concentrations of TPP, and a significant increase in polarization is observed for higher concentrations of TPP.

Keyword
Triphenyl phosphate (TPP), Flame retardant additive, Graphite/LiFePO4 cell, Electrolyte characterization, Hybrid Pulse Power Characterization (HPPC), Electrode/electrolyte interface
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-144920 (URN)10.1016/j.jpowsour.2014.01.022 (DOI)000333724100057 ()2-s2.0-84894204241 (Scopus ID)
Funder
StandUp
Note

QC 20140508

Available from: 2014-05-08 Created: 2014-05-05 Last updated: 2017-12-05Bibliographically approved
2. Electrochemical Characterization and Temperature Dependency of Mass-Transport Properties of LiPF6 in EC:DEC
Open this publication in new window or tab >>Electrochemical Characterization and Temperature Dependency of Mass-Transport Properties of LiPF6 in EC:DEC
2015 (English)In: Journal of the Electrochemical Society, ISSN 0013-4651, E-ISSN 1945-7111, Vol. 162, no 3, A413-A420 p.Article in journal (Refereed) Published
Abstract [en]

Mass transport in the electrolyte is one of the limiting processes when it comes to the power density and energy efficiency of lithium-ion batteries. Electrolyte characterizations are therefore of utmost importance. This study reports the ionic conductivity, diffusion coefficient, lithium-ion transport number, and thermodynamic enhancement factor, as well as density and viscosity, for the electrolyte LiPF6 in EC:DEC (1 1, by weight) at 10 degrees C, 25 degrees C, and 40 degrees C and for concentrations between 0.5 M and 1.5 M. By combining mathematical modeling and three experiments: conductivity measurements, concentration cells, and galvanostatic polarizations, the mass transport phenomena were fully characterized. All parameters were found to vary strongly with both concentration and temperature proving that temperature dependent parameters are essential when studying thermal behavior of lithium-ion batteries. Moreover, conductivity increased with temperature and showed a local maximum at around 1 M within the concentration range at all temperatures. The other parameters either showed a continuous decrease (diffusion coefficient and lithiumion transport number) or increase (thermodynamic enhancement factor) with concentration at all temperatures. Limited liquid range leading to solvent crystallization at 10 degrees C leads to very poor performance, possibly due to the strong coordination between the lithium ion and the crystallizing species, EC. Overall, the studied electrolyte is found to perform poorly compared to previously studied systems.

Keyword
Diffusion, Electric batteries, Electrolytes, Energy efficiency, Ions, Lithium, Lithium alloys, Lithium compounds, Lithium-ion batteries, Temperature, Transport properties Concentration ranges, Conductivity measurements, Electrochemical characterizations, Galvanostatic polarization, Lithium-ion transport, Solvent crystallizations, Temperature dependencies, Temperature dependent
National Category
Materials Engineering
Identifiers
urn:nbn:se:kth:diva-162975 (URN)10.1149/2.0641503jes (DOI)000349823700024 ()2-s2.0-84923323697 (Scopus ID)
Note

QC 20150331

Available from: 2015-03-31 Created: 2015-03-26 Last updated: 2017-12-04Bibliographically approved
3. Characterization of the Mass-Transport Phenomena in a Superconcentrated LiTFSI: Acetonitrile Electrolyte
Open this publication in new window or tab >>Characterization of the Mass-Transport Phenomena in a Superconcentrated LiTFSI: Acetonitrile Electrolyte
2015 (English)In: Journal of the Electrochemical Society, ISSN 0013-4651, E-ISSN 1945-7111, Vol. 162, no 7, A1334-A1340 p.Article in journal (Refereed) Published
Abstract [en]

Superconcentration of aprotic electrolytes has recently emerged as a way to stabilize solvents that otherwise would be impossible to use, in e.g. lithium-ion batteries (LIBs). As demanding applications, such as hybrid electric vehicles and fast charging, become increasingly important, battery manufacturers are struggling to find a suitable electrolyte able to deliver high power with low polarization. Electrolyte characterizations able to accurately predict the high-power performance of such electrolytes are also of utmost importance. This study reports a full.characterization of the mass-transport phenomena for a superconcentrated LiTFSL-acetonitrile electrolyte in concentrations ranging from 2.7 M to 4.2 M. The method obtains the ionic conductivity, cationic transport number, diffusion coefficient, and the thermodynamic enhancement factor, by combining mathematical modeling and three electrochemical experiments. Furthermore, the density and the viscosity were measured. The transport number with respect to the room is found to be very high compared to other liquid LIB electrolytes, but a low diffusion coefficient lowers overall performance. The ionic conductivity decreases quickly with concentration, dropping from 12.7 mS/cm at 2.7 M to 0.76 mS/cm at 4.2 M. Considering all the effects in terms of the mass-transport of the electrolyte, the lower end of the studied concentration range is favorable.

Keyword
Transference Number Measurements, Lithium-Ion Batteries, Polymer Electrolytes, Gel Electrolytes, Salt Electrolyte, Polarization, Diffusion, Intercalation, Stability, Graphite
National Category
Materials Engineering
Identifiers
urn:nbn:se:kth:diva-167637 (URN)10.1149/2.0961507jes (DOI)000355643700029 ()2-s2.0-84929494453 (Scopus ID)
Note

QC 20150522

Available from: 2015-05-22 Created: 2015-05-22 Last updated: 2017-12-04Bibliographically approved
4. Electrolyte Mass-Transport Benchmarking of Four Types of Lithium-Ion Battery Electrolytes: Organic liquids, Ionic Liquids, Gelled Polymers, and Solid Polymers
Open this publication in new window or tab >>Electrolyte Mass-Transport Benchmarking of Four Types of Lithium-Ion Battery Electrolytes: Organic liquids, Ionic Liquids, Gelled Polymers, and Solid Polymers
(English)Manuscript (preprint) (Other academic)
National Category
Materials Engineering
Identifiers
urn:nbn:se:kth:diva-167639 (URN)
Note

QS 2015

Available from: 2015-05-22 Created: 2015-05-22 Last updated: 2015-05-22Bibliographically approved
5. Thermal Management of Large-Format Prismatic Lithium-Ion Battery in PHEV Application
Open this publication in new window or tab >>Thermal Management of Large-Format Prismatic Lithium-Ion Battery in PHEV Application
Show others...
2016 (English)In: Journal of the Electrochemical Society, ISSN 0013-4651, E-ISSN 1945-7111, Vol. 163, no 2, A309-A317 p.Article in journal (Refereed) Published
Abstract [en]

Thermal effects are linked to all main barriers to the widespread commercialization of lithium-ion battery powered vehicles. This paper presents a coupled 2D electrochemical - 3D thermal model of a large-format prismatic lithium-ion battery, including a thermal management system with a heat sink connected to the surface opposite the terminals, undergoing the dynamic current behavior of a plug-in hybrid electric (PHEV) vehicle using a load cycle with a maximum current of 8 C, validated using potential and temperature data. The model fits the data well, with small deviations at the most demanding parts of the cycle. The maximum temperature increase and temperature difference of the jellyroll is found to be 9.7 degrees C and 3.6 degrees C, respectively. The electrolyte is found to limit the performance during the high-current pulses, as the concentration reaches extreme values, leading to a very uneven current distribution. Two other thermal management strategies, short side and long side surfaces cooling, are evaluated but are found to have only minor effects on the temperature of the jellyroll, with maximum jellyroll temperatures increases of 9.4 degrees C and 8.1 degrees C, respectively, and maximum temperature differences of 3.7 degrees C and 5.0 degrees C, respectively.

Place, publisher, year, edition, pages
Electrochemical Society, 2016
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-180974 (URN)10.1149/2.09411602jes (DOI)000367324400040 ()2-s2.0-84949599677 (Scopus ID)
Note

Updated from Manuscript to Article. QC 20160202

Available from: 2016-01-28 Created: 2016-01-26 Last updated: 2017-11-30Bibliographically approved

Open Access in DiVA

Henrik Lundgren - Doctoral Thesis(11502 kB)1475 downloads
File information
File name FULLTEXT01.pdfFile size 11502 kBChecksum SHA-512
98bb0b82a3166ec3c48a69e9750f90ce7bc521aa12c3940625e44d3faba0e1dec7d67989d09e4f0e893d06f6e752895174d9523d1bff21cfa91223ad7b3bebc9
Type fulltextMimetype application/pdf

Authority records BETA

Lundgren, Henrik

Search in DiVA

By author/editor
Lundgren, Henrik
By organisation
Applied Electrochemistry
Chemical Engineering

Search outside of DiVA

GoogleGoogle Scholar
Total: 1475 downloads
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

isbn
urn-nbn

Altmetric score

isbn
urn-nbn
Total: 2530 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf