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Diagnosis of the Lifetime Performance Degradation of Lithium-Ion Batteries: Focus on Power-Assist Hybrid Electric Vehicle and Low-Earth-Orbit Satellite Applications
KTH, School of Chemical Science and Engineering (CHE), Chemical Engineering and Technology, Applied Electrochemistry.
2008 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

Lithium-ion batteries are a possible choice for the energy storage system onboard hybrid electric vehicles and low-earth-orbit satellites, but lifetime performance remains an issue. The challenge is to diagnose the effects of ageing and then investigate the dependence of the magnitude of the deterioration on different accelerating factors (e.g. state-of-charge (SOC), depth-of-discharge (DOD) and temperature).

Lifetime studies were undertaken incorporating different accelerating factors for two different applications: (1) coin cells with a LixNi0.8Co0.15Al0.05O2-based positive electrode were studied with a EUCAR power-assist HEV cycle, and (2) laminated commercial cells with a LixMn2O4-based positive electrode were studied with a low-earth-orbit (LEO) satellite cycle. Cells were disassembled and the electrochemical performance of harvested electrodes measured with two- and three-electrode cells. The LixNi0.8Co0.15Al0.05O2-based electrode impedance results were interpreted with a physically-based three-electrode model incorporating justifiable effects of ageing.

The performance degradation of the cells with nickelate chemistry was independent of the cycling condition or target SOC, but strongly dependent on the temperature. The positive electrode was identified as the main source of impedance increase, with surface films having a composition that was independent of the target SOC, but with more of the same species present at higher temperatures. Furthermore, impedance results were shown to be highly dependent on both the electrode SOC during the measurement and the pressure applied to the electrode surface. An ageing hypothesis incorporating a resistive layer on the current collector and a local contact resistance (dependent on SOC) between the carbon and active material, both possibly leading to particle isolation, was found to be adequate in fitting the harvested aged electrode impedance data.

The performance degradation of the cells with manganese chemistry was accelerated by both higher temperatures and larger DODs. The impedance increase was small, manifested in a SOC-dependent increase of the high-frequency semicircle and a noticeable increase of the high-frequency real axis intercept. The positive electrode had a larger decrease in capacity and increase in the magnitude of the high-frequency semi-circle (particularly at high intercalated lithium-ion concentrations) in comparison with the negative electrode. This SOC-dependent change was associated with cells cycled for either extended periods of time or at higher temperatures with a large DOD. An observed change of the cycling behaviour in the second potential plateau for the LixMn2O4-based electrode provided a possible kinetic-based explanation for the change of the high-frequency semi-circle.

Abstract [sv]

Litiumjonbatteriet är en möjlig kandidat för energilagring i hybridfordon och i satelliter i låg omloppsbana, men än så länge är livslängden på batterierna ett problem. Utmaningen ligger i att kunna förstå hur batteriet åldras genom att utforska hur åldringsprocessen accelereras av faktorer som laddningstillstånd, urladdningsdjup och temperatur.

Livslängdsstudier för två olika typer av batterier tänkta för olika applikationer utfördes: (1) knappceller med positiva LixNi0,8Co0,15Al0,05O2-baserade elektroder studerades med en effektstödd (power-assist) hybridcykel från EUCAR, och (2) laminerade kommersiella celler med positiva LixMn2O4-baserade elektroder studerades med en satellitcykel, avsedd för en satellit med låg omloppsbana. Cellerna öppnades och de uttagna elektrodernas elektrokemiska egenskaper utvärderades i två- och tre-elektroduppställningar. Resultaten från elektrokemiska impedansmätningar för den positiva LixNi0,8Co0,15Al0,05O2-baserade elektroden tolkades med hjälp av en fysikalisk tre-elektrod modell som tog hänsyn till de i litteraturen främst föreslagna effekterna av åldring.

Prestandadegraderingen av celler med nickelkemi var oberoende av cykel och laddningstillståndet där åldringen skedde, men starkt beroende av temperaturen. Den positiva elektroden visade sig vara den största orsaken till impedansökningen i batteriet. Ytfilmerna på den positiva elektroden hade en sammansättning som var oberoende av laddningstillståndet men beroende av temperaturen. Impedansresultaten från de uttagna elektroderna var starkt beroende av både laddningstillstånd och yttre tryck på elektrodytan. Det visade sig att det var tillräckligt att ta hänsyn till ett resistivt skikt på strömtilledaren och en lokal kontaktresistans mellan kolet och det aktiva materialet (som är beroende av laddningstillståndet) för att anpassa modellen till impedansdata mätt på de uttagna elektroderna.

Prestandadegraderingen av celler med mangankemi påskyndades av både högre temperaturer och högre urladdningsdjup. Impedansen ökade något, då både högfrekvenshalvcirkeln och högfrekvensintercepten ändrades. Positiva elektroden hade en större degradering i kapaciteten och en större ökning i magnituden av högfrekvenshalvcirkeln (speciellt vid högre litiumjon koncentrationer i elektroden) jämfört med den negativa elektroden. Denna laddningstillståndsberoende impedans-ökning var kopplad till celler som hade cyklats under en längre tid eller vid en högre temperatur och med ett högt urladdningsdjup. Ökningen i magnituden av högfrekvenshalvcirkeln skulle kunna vara relaterad till kinetiska begränsningar eftersom cyklingsbeteendet vid andra spänningsplatån ändrades samtidigt för de LixMn2O4-baserade elektroderna.

Place, publisher, year, edition, pages
Stockholm: KTH , 2008. , x, 132 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2008:13
Keyword [en]
lithium-ion battery, LixNi0.8Co0.15Al0.05O2, LixMn2O4, LiyC6, ageing, three-electrode measurements, impedance modelling, surface film characterisation, hybrid electric vehicle, low-earth-orbit satellite
Keyword [sv]
litiumjonbatteri, åldring, treelektroduppställning, impedansmodell, ytfilmskarakterisering, hybridfordon, satelliter
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-4722ISBN: 978-91-7178-875-7 (print)OAI: oai:DiVA.org:kth-4722DiVA: diva2:13625
Public defence
2008-05-23, D2, Lindstedtsvägen 5, Entreplan, KTH, 10:00
Opponent
Supervisors
Note
QC 20100621Available from: 2008-05-06 Created: 2008-05-06 Last updated: 2010-07-13Bibliographically approved
List of papers
1. Impedance as a Tool for Investigating Aging in Lithium-Ion Porous Electrodes: I. Physically Based Electrochemical Model
Open this publication in new window or tab >>Impedance as a Tool for Investigating Aging in Lithium-Ion Porous Electrodes: I. Physically Based Electrochemical Model
2008 (English)In: Journal of the Electrochemical Society, ISSN 0013-4651, E-ISSN 1945-7111, Vol. 155, no 4, A304-A319 p.Article in journal (Refereed) Published
Abstract [en]

Electrochemical impedance spectroscopy is potentially a powerful diagnostic tool for the investigation of the effects of aging in porous electrodes. A physically based three-electrode model was developed for a LixNi0.8Co0.15Al0.05O2 composite porous electrode with three porous separators and a reference electrode between a current collector and a plane electrode. Two effects of aging were modeled for this particular electrode chemistry, namely, a resistive corrosion layer on the current collector and a contact resistance between the electronic conductor and the active material of the porous electrode. The derivation of an analytical solution for the impedances between each pair of electrodes in this model yielded a computationally fast, versatile, and modular formulation. The solution was used to study the impact of selected components of the physical model on the impedance spectrum of the porous electrode for a physically relevant base case. Approximating the active material particles as spherical or flake-shaped particles, lognormally or Dirac distributed in size, revealed that the distribution has a negligible impact while the shape makes a noticeable difference. The main aging-related parameters were shown to have quite distinct effects on the impedance spectrum, which is essential for the regression of experimental data and the study of aging hypotheses.

Place, publisher, year, edition, pages
PENNINGTON: ELECTROCHEMICAL SOC INC, 2008
Keyword
HIGH-POWER; ELECTROCHEMICAL IMPEDANCE; INTERCALATION PARTICLES; BATTERY ELECTROLYTES; CURRENT COLLECTORS; CAPACITY FADE; PASSIVE FILM; CELLS; ALUMINUM; CATHODES
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:kth:diva-8326 (URN)10.1149/1.2840015 (DOI)000253761700006 ()2-s2.0-40549116713 (Scopus ID)
Note
QC 20100618Available from: 2008-05-06 Created: 2008-05-06 Last updated: 2017-12-14Bibliographically approved
2. Impedance as a Tool for Investigating Aging in Lithium-Ion Porous Electrodes: II. Positive Electrode Examination
Open this publication in new window or tab >>Impedance as a Tool for Investigating Aging in Lithium-Ion Porous Electrodes: II. Positive Electrode Examination
2008 (English)In: Journal of the Electrochemical Society, ISSN 0013-4651, E-ISSN 1945-7111, Vol. 155, no 4, A320-A338 p.Article in journal (Refereed) Published
Abstract [en]

High-power positive LixNi0.8Co0.15Al0.05O2 composite porous electrodes are known to be the main source of impedance increase in batteries based on GEN2 chemistry. The impedance of positive electrodes, both fresh and harvested from coin cells aged in an accelerated EUCAR hybrid electric vehicle lifetime matrix, was measured in a three-electrode setup and the results fitted with a physically based impedance model. A methodology for fitting the impedance data, including an optimization strategy incorporating a global genetic routine, was used to fit either fresh or aged positive electrodes simultaneously at different states of charge down to 0.5 mHz. The fresh electrodes had an exchange current density of approximately 1.0 A m(-2), a solid-phase diffusion coefficient of approximately 1.4 x 10(-1)5 m(2) s(-1), and a log-normal active particle size distribution with a mean radius of 0.25 mu m. Aged electrode impedance results were shown to be highly dependent on both the electrode state of charge and the pressure applied to the electrode surface. An aging scenario incorporating loss of active particles, coupled with an increase both in the local contact resistance between the active material and the conductive carbon and the resistance of a layer on the current collector, was shown to be adequate in describing the measured aged electrode impedance behavior.

Keyword
X-RAY-DIFFRACTION; HIGH-POWER; CURRENT COLLECTORS; BATTERY ELECTROLYTES; CATHODE COMPOSITION; STRESS GENERATION; SOLID-SOLUTIONS; INSERTION CELL; CAPACITY FADE; PASSIVE FILM
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:kth:diva-8327 (URN)10.1149/1.2832654 (DOI)000253761700007 ()2-s2.0-40549091380 (Scopus ID)
Note
QC 20100618Available from: 2008-05-06 Created: 2008-05-06 Last updated: 2017-12-14Bibliographically approved
3. Temperature and SOC Dependence of the Lifetime Cycling and Calendar Performance of LixNi0.8Co0.15Al0.05O2/Graphite High-Power Batteries for Power-Assist HEV Applications
Open this publication in new window or tab >>Temperature and SOC Dependence of the Lifetime Cycling and Calendar Performance of LixNi0.8Co0.15Al0.05O2/Graphite High-Power Batteries for Power-Assist HEV Applications
(English)Manuscript (Other academic)
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:kth:diva-8328 (URN)
Note
QC 20100618Available from: 2008-05-06 Created: 2008-05-06 Last updated: 2010-07-13Bibliographically approved
4. Impact of SOC and Temperature on Surface Film Characteristics of LixNi0.8Co0.15Al0.05O2-based Positive Electrodes Harvested from an Accelerated HEV Ageing Matrix
Open this publication in new window or tab >>Impact of SOC and Temperature on Surface Film Characteristics of LixNi0.8Co0.15Al0.05O2-based Positive Electrodes Harvested from an Accelerated HEV Ageing Matrix
(English)Manuscript (Other academic)
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:kth:diva-8329 (URN)
Note
QC 20100618Available from: 2008-05-06 Created: 2008-05-06 Last updated: 2010-07-13Bibliographically approved
5. Cycle Life Evaluation of 3 Ah LixMn2O4-based Lithium-Ion Secondary Cells for Low-Earth-Orbit Satellites: I. Full Cell Results
Open this publication in new window or tab >>Cycle Life Evaluation of 3 Ah LixMn2O4-based Lithium-Ion Secondary Cells for Low-Earth-Orbit Satellites: I. Full Cell Results
Show others...
2008 (English)In: Journal of Power Sources, ISSN 0378-7753, E-ISSN 1873-2755, Vol. 185, no 2, 1444-1453 p.Article in journal (Refereed) Published
Abstract [en]

Lithium-ion batteries are a candidate for the energy storage system onboard low-earth-orbit satellites. Cycle life performance under both orbital and terrestrial conditions must be investigated in order to evaluate any inadvertent effects due to the former and the validity of the latter, with a successful comparison allowing for the extension of terrestrial experimental matrices in order to identify the effects of ageing. The orbital Performance of LixMn2O4-based pouch cells onboard the microsatellite REIMEI was monitored and compared with terrestrial experiments, with the cells found to be unaffected by orbital conditions. A lifetime matrix of different cycling depths-of-discharge (DODs: 0,20,40%) and temperatures (25, 45 degrees C) was undertaken with periodic reference performance tests. A decrease in both the cell end of-discharge cycling voltage and capacity was accelerated by both higher temperatures and larger DODs. Impedance spectra measured for all ageing conditions indicated that the increase was small, manifested in a state-of-charge dependent increase of the high-frequency semi-circle and a noticeable increase in the high-frequency real axis intercept. An evaluation of the change of both the resistance and capacity of 3 Ah cells led to the development of a potential prognostic state-of-health indicator. The use of elevated temperatures to accelerate cell ageing was validated.

Keyword
Lithium-ion; LEO satellite; Ageing
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:kth:diva-8330 (URN)10.1016/j.jpowsour.2008.07.070 (DOI)000261748900125 ()2-s2.0-56249138923 (Scopus ID)
Note
QC 20100618. Uppdaterad från submitted till published (20100708).Available from: 2008-05-06 Created: 2008-05-06 Last updated: 2017-12-14Bibliographically approved
6. Cycle Life Evaluation of 3 Ah LixMn2O4-based Lithium-Ion Secondary Cells for Low-Earth-Orbit Satellites: II. Harvested Electrode Examination
Open this publication in new window or tab >>Cycle Life Evaluation of 3 Ah LixMn2O4-based Lithium-Ion Secondary Cells for Low-Earth-Orbit Satellites: II. Harvested Electrode Examination
Show others...
2008 (English)In: Journal of Power Sources, ISSN 0378-7753, E-ISSN 1873-2755, Vol. 185, no 2, 1454-1464 p.Article in journal (Refereed) Published
Abstract [en]

Lithium-ion batteries area candidate for the energy storage system onboard low-earth-orbit satellites. Terrestrial experiments are able to capture the performance degradation of cells in orbit, therefore providing the opportunity for lifetime investigations. The lifetime performance of 3 Ah commercial LixMn2O4-based pouch cells was evaluated in a matrix of different cycling depths-of-discharge (DODs: 0, 20,40%) and temperatures (25, 45 degrees C). Aged cells were disassembled and the electrochemical performance of harvested electrodes investigated with two- and three-electrode pouch cells. The positive electrode had a larger decrease in capacity than the negative electrode. Both the positive and negative electrode contributed to the increase of cell impedance measured at high states-of-charge (SOCs). The data at low SOCs indicated that the increase of cell impedance was associated with the positive electrode, which showed a significant increase in the magnitude of the high-frequency semi-circle. This SOC-dependence was observed for cells cycled for either extended periods of time or at higher temperatures with a 40% DOD swing. Low-current cycling of positive electrodes revealed a change in the second potential plateau, possibly reflecting a structural change of the LixMn2O4. This could impact on the electrode kinetics and provide a possible explanation for the SOC-dependent change of the impedance.

Place, publisher, year, edition, pages
Amsterdam: ELSEVIER, 2008
Keyword
Lithium-ion; LEO satellite; Ageing; Porous electrode; Impedance; Three-electrode measurement
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:kth:diva-8331 (URN)10.1016/j.jpowsour.2008.07.071 (DOI)000261748900126 ()2-s2.0-56249131732 (Scopus ID)
Note
QC 20100618. Uppdaterad från submitted till published (20100709).Available from: 2008-05-06 Created: 2008-05-06 Last updated: 2017-12-14Bibliographically approved
7. Calibration of the Lithium-Ion Secondary Battery for 'REIMEI'
Open this publication in new window or tab >>Calibration of the Lithium-Ion Secondary Battery for 'REIMEI'
Show others...
(English)In: Journal of the Japanese Electrochemical SocietyArticle in journal (Other academic) Submitted
Keyword
Lithium-ion cell; Secondary Battery; Space application; Life estimation
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:kth:diva-8332 (URN)
Note
QC 20100618Available from: 2008-05-06 Created: 2008-05-06 Last updated: 2010-07-13Bibliographically approved

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