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Analysis of the Polarization in a Li-Ion Battery Cell by Numerical Simulations
KTH, School of Chemical Science and Engineering (CHE), Chemical Engineering and Technology, Applied Electrochemistry.ORCID iD: 0000-0001-9698-4136
KTH, School of Chemical Science and Engineering (CHE), Chemical Engineering and Technology, Applied Electrochemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemical Engineering and Technology, Applied Electrochemistry.ORCID iD: 0000-0002-0861-7342
KTH, School of Chemical Science and Engineering (CHE), Chemical Engineering and Technology, Applied Electrochemistry.ORCID iD: 0000-0002-9392-9059
Show others and affiliations
2010 (English)In: Journal of the Electrochemical Society, ISSN 0013-4651, E-ISSN 1945-7111, Vol. 157, no 11, A1236-A1246 p.Article in journal (Refereed) Published
Abstract [en]

An experimentally validated model was developed to analyze the polarization of a LiNi0.8Co0.15Al0.05O2 vertical bar 1.2 M LiPF6 in ethylene carbonate (EC):ethyl methyl carbonate (EMC) (3:7)vertical bar MAG-10 battery cell during a hybrid pulse power characterization (HPPC) cycle. The analysis was made with a method where the polarization was split up into parts associated with activation of the electrochemical reactions, mass transport of species in the electrolyte and in the solid phase, and inadequate contact between the materials in the electrodes. Each contribution to the polarization was quantified as a snapshot in time and as an average over the HPPC cycle. The polarization during a cycle according to EUCAR was analyzed in detail for state of charge (SOC) 40 and 80. It arose mainly due to the mass transport in the electrolyte, e. g., at SOC 40 it contributed to 43% of the total polarization. In an ISO (International Organization for Standardization)-energy cycle where the current loads are higher and applied for longer times than the EUCAR cycle, the mass transport by diffusion in the electrolyte and in the solid phase of the negative electrode became more significant. The presented method offers the possibility to find a battery cell's optimal operational condition and design.

Place, publisher, year, edition, pages
2010. Vol. 157, no 11, A1236-A1246 p.
National Category
Chemical Engineering
Identifiers
URN: urn:nbn:se:kth:diva-27674DOI: 10.1149/1.3486161ISI: 000283857900021Scopus ID: 2-s2.0-77957695680OAI: oai:DiVA.org:kth-27674DiVA: diva2:380563
Funder
Swedish Research CouncilStandUp
Note

QC 20150629

Available from: 2010-12-21 Created: 2010-12-20 Last updated: 2017-12-11Bibliographically approved
In thesis
1. An Experimental and Theoretical Study of the Mass Transport in Lithium-Ion Battery Electrolytes
Open this publication in new window or tab >>An Experimental and Theoretical Study of the Mass Transport in Lithium-Ion Battery Electrolytes
2011 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Lithium‐ion batteries are particularly suitable as energy storage solutions in high power applications, such as hybrid electric vehicles. It is generally considered that one of the processes that limit the power density for lithium‐ion batteries is the mass transport in the electrolyte. Yet, it is still difficult to find a set of properties that fully describe the mass transport for the most common electrolytes. In this work, characterization studies of the mass transport were undertaken for two technically important lithium‐ion battery electrolytes: (1) a liquid electrolyte which consist of LiPF6 dissolved in ethyl methyl carbonate (EMC) and ethylene carbonate (EC) and, (2) a gel electrolyte which consists of LiPF6 dissolved in ethylene carbonate, propylene carbonate (PC) and poly(vinylidenefluoride‐hexafluoropropylene) (P(VdFHFP)).The mass transport in the electrolytes was characterized by combining several experiments. The Maxwell‐Stefan equation was used as basis for the characterization. Models of the transport were formulated from the equation and the apparent transport properties were identified. The characterization methods were first analyzed mathematically in order to establish at which conditions the characterization experiments should be performed. The values of the apparent transport properties were then obtained by optimizing the models to the experimental responses. In order to give the characterization results a comprehensible interpretation and to allow benchmarking of electrolytes, the concept of a normalized potential gradient was introduced.The characterization results of the liquid electrolyte were used in a full cell model of a LiNi0.8Co0.15Al0.05O2 | LiPF6 EC:EMC (3:7) | MAG‐10 cell. The model was developed to analyze the mass transport during a hybrid pulse power characterization (HPPC) test. The analysis was made with a method where the polarization was split up into parts each associated with a process within the cell. The optimum composition in terms of mass transport was found to lie between 0.5 and 1.2 mol/dm3 LiPF6 for the liquid electrolyte and between 5 and 7 wt. % LiPF6 for the gel electrolyte. Less amount of polymer in the gel electrolyte gave a faster mass transport. It was also found that the mass transport in the liquid electrolyte contributed to a major part of the polarization during HPPC tests.

Abstract [sv]

Litiumjonbatterier är speciellt lämpliga som ackumulatorer i högeffektsapplikationer som elhybridfordon. Det är idag allmänt accepterat att en av processerna som begränsar effekttätheten för litiumjonbatterier är masstransporten i elektrolyten. Trots detta är det fortfarande svårt att få tag på data som fullständigt beskriver masstransporten i de vanligaste elektrolyterna.

I det här arbetet har masstransportkarakteriseringar gjorts för två tekniskt viktiga elektrolyter: (1) en vätskeelektrolyt som består av LiPF6 upplöst i etylenkarbonat (EC) och etylmetylkarbonat (EMC), och (2) en gel elektrolyt som består av LiPF6 upplöst i EC, propylenkarbonat (PC) och poly(vinylidene fluoride‐hexafluoro propylene) (P(VdFHFP)).

Masstransporten i elektrolyterna karakteriserades genom att kombinera ett antal karakteriseringsexperiment. Maxwell‐Stefans ekvation användes som utgångspunkt i karakteriseringarna. Modeller av transporten formulerades från ekvationen och de effektiva transportegenskaperna identifierades. En matematisk analys gjordes först av karakteriseringstekniken, så att det kunde fastslås för vilka förhållanden experimenten skulle utföras. Värderna av transportegenskaperna erhölls genom att optimera modellerna till det experimentella beteendet. För att ge karakteriseringsresultaten en begriplig tolkning och för att kunna mäta prestandan av elektrolyter, infördes konceptet normaliserad potentialgradient.

Resultatet från karakteriseringen av vätskeelektrolyten användes i en model av en LiNi0.8Co0.15Al0.05O2 | LiPF6 EC:EMC (3:7) | MAG‐10 cell. Modellen utvecklades för att analysera masstransporten i cellen under ett hybridpulstest (HPPC). Analysen gjordes med en metod där polarisationen delades upp i delar som var och en var kopplad till en process i batteriet.

Den optimala sammansättningen med avseende på masstransporten låg i regionen 0.5–1.2 mol/dm3 LiPF6 för vätskeelektrolyten och 5‐7 vikt% LiPF6 för gelelektrolyten. Mindre mängd polymer i gelelektrolyten gav en snabbare masstransport. Det konstaterades också att masstransporten i vätskeelektrolyten bidrog med en av de största delarna till polarisationen i HPPC testen.

Place, publisher, year, edition, pages
Stockholm: KTH, 2011. 64 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2011:6
Keyword
Lithium‐ion batteries, Electrolytes, Transport properties, Conductivity, Diffusion coefficients, Transport number, Maxwell-Stefan equation, Simulations, Mathematical analysis, Polarization, Hybrid electric vehicles, Litiumjonbatterier, Aprotiska elektrolyter, Transport egenskaper, Konduktivitet, Diffusion koefficienter, Transporttal, Maxwell-Stefans ekvation, Simuleringar, Matematisk analys, Polarisation, Elhybridfordon
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:kth:diva-29121 (URN)978-91-7415-852-6 (ISBN)
Public defence
2011-02-28, K2, Teknikringen 28, Entréplan, Stockholm, 10:00 (English)
Opponent
Supervisors
Note
QC 20110128Available from: 2011-01-28 Created: 2011-01-25 Last updated: 2011-05-20Bibliographically approved
2. Mathematical Models for Investigation of Performance, Safety, and Aging in Lithium-Ion Batteries
Open this publication in new window or tab >>Mathematical Models for Investigation of Performance, Safety, and Aging in Lithium-Ion Batteries
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Rechargeable lithium-ion batteries have both the power and energy capabilities to be utilized in hybrid electric vehicles and other power demanding applications. However, there are obstacles primarily related to reliability in safety and lifetime. Additionally, there is still room for improvement in the battery performance.

In this work, physics-based mathematical models have been successfully set-up and numerically solved to investigate performance, safety, and aging in lithium-ion battery systems. This modeling approach enabled a detailed analysis of the electrochemical processes related to these issues. As the models included many parameters and spatial resolution of several variables with time or frequency, strategies for investigation needed to be developed for most of the work. The accuracy of the investigation was consolidated by the utilization of parameters characterized from experimental work.

The performance expressed in terms of polarization was determined for a power-optimized battery cell undergoing various operating conditions. A methodology that separated and quantified the contribution of each process to the polarization was set up, allowing the study of the contributions as a snapshot in time and as an average over a cycle. Mass transport in electrolyte was shown to be a crucial feature to improve especially if the battery is expected to undergo high current-loads for long periods of time.

Safety-concerns when a battery cell is short-circuited were investigated for three types of short-circuit scenarios. All scenarios raised the temperature to the point where exothermic side reactions were initiated. The similarities between the scenarios in temperature increase were a result of the limiting current being reached. The differences, however small, were related to the placement of the short-circuit. Especially when the current collectors were not directly connected by the short circuit, an increased electronic resistance was observed which lowered both the generated current and heat.

The aging of a battery cell was investigated by model analysis of electrodes harvested from fresh and aged cells. A methodology was used where a frequency-dependent model was fitted to three-electrode impedance experiments by tuning parameters associated to electrode degradation. For cycled cells, electrolyte decomposition products inhibiting the mass transport in the electrolyte and particle cracking in the positive electrode increased the impedance. A similar model was also set up for investigation of the lithium intercalation processes in PAN-based carbon fibers, showing it to have both good mass transport and kinetic capabilities.

Abstract [sv]

Laddningsbara litiumjonbatterier har både ur energi- och effektsynpunkt möjligheten att kunna användas i elhybridfordon och inom andra effektkrävande tillämpningsområden. Batteriets säkerhet och livslängd är dock inte helt tillförlitliga. Dessutom finns det fortfarande utrymme för förbättringar av litiumjonbatteriets prestanda.

I det här arbetet har matematiska modeller baserade på fysikaliska egenskaper framgångsrikt ställts upp och lösts numeriskt för att studera prestandan, säkerheten samt åldrandet hos litiumjonbatterisystem. Denna typ av modellering gjorde det möjligt att detaljerat analysera hur de elektrokemiska processerna bidrar. Eftersom modellerna omfattade ett stort antal parametrar och har variabler som förändras i åtminstone en dimension med tid eller frekvens, krävdes det att tydliga strategier för arbetet ställdes upp. Modelleringsstudiens noggrannhet stärktes av att flertalet av de använda parametrarna hade bestämts experimentellt.

Polarisationen som ett mått på prestanda bestämdes för ett effektoptimerat batteri under olika laster. En metodik som separerar och beräknar hur mycket varje process bidrar till polarisationen skapades och användes för att studera bidragen över tid eller över en hel lastcykel. Resultaten visade att masstransporten i elektrolyten påverkar till stor del och bör förbättras om batteriet förväntas belastas med hög ström under lång tid.

Säkerheten i samband med kortslutning av en battericell undersöktes för tre olika fall av kortslutningar. Alla fall uppvisade en temperaturökning som skulle kunna bidra till att exoterma reaktioner startas och termisk rusning uppstår. Temperaturökningen var liknande i samtliga kortslutningsfall och berodde på att gränsströmmen nåddes inom cellen. Skillnaderna mellan kortslutningsfallen var inte så betydande men kunde härledas till kortslutningens placering. Framförallt fallet då strömtilledarna inte kontakterades av kortslutningen observerades en ökad elektronisk resistans som sänkte både strömmen och värmeproduktionen.

Åldringen i en battericell undersöktes genom modellanalys av elektroder som tagits från nya eller åldrade celler. Som metod användes en frekvensberoende modell som anpassades till tre-elektrod-impedansmätningar genom förändring av parametrar som beskriver elektrodnedbrytning. Då cellerna cyklats, visade förändringen av dessa parametrar att impedansen ökar på grund av nedbrytningsprodukter från elektrolyten som hindrar masstransporten och att det aktiva materialet i positiva elektroden spricker. En liknande modell användes också till att undersöka PAN-baserade kolfibrers förmåga att interkalera litium och resultaten visade på att den har mycket goda elektrokemiska egenskaper.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2013. 66 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2013:25
Keyword
lithium-ion battery, modeling, electrochemical processes, impedance, polarization, performance, safety, aging, power optimized battery, litiumjonbatteri, modellering, elektrokemiska processer, impedans, polarisation, prestanda, säkerhet, åldring, effektoptimerat batteri
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-122308 (URN)978-91-7501-745-7 (ISBN)
Public defence
2013-06-10, H1, Teknikringen 33, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
The Swedish Energy Agency
Note

QC 20130520

Available from: 2013-05-20 Created: 2013-05-17 Last updated: 2013-05-20Bibliographically approved

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