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Methods for Testing and Analyzing Lithium-Ion Battery Cells intended for Heavy-Duty Hybrid Electric Vehicles
KTH, School of Chemical Science and Engineering (CHE), Chemical Engineering and Technology, Applied Electrochemistry.ORCID iD: 0000-0001-9559-0004
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Lithium-ion batteries designed for use in heavy-duty hybrid vehicles are continuously improved in terms of performance and longevity, but they still have limitations that need to be considered when developing new hybrid vehicles.               

The aim of this thesis has been to study and evaluate potential test and analysis methods suitable for being used in the design process when maximizing lifetime and utilization of batteries in heavy-duty hybrid vehicles.

A concept for battery cell cycling on vehicles has been evaluated. The work included development of test equipment, verification of hardware and software as well as an extended period of validation on heavy-duty trucks. The work showed that the concept has great potential for evaluating strategies for battery usage in hybrid vehicles, but is less useful for accelerated aging of battery cells.                            

Battery cells encapsulated in flexible packaging material have been investigated with respect to the durability of the encapsulation in a demanding heavy-duty hybrid truck environment. No effect on water intrusion was detected after vibration and temperature cycling of the battery cells.                   

Aging of commercial battery cells of the type lithium manganese oxide - lithium cobalt oxide / lithium titanium oxide (LMO-LCO/LTO) was investigated with different electrochemical methods to gain a deeper understanding of the origin of performance deterioration, and to understand the consequences of aging from a vehicle manufacturer's perspective. The investigation revealed that both capacity loss and impedance rise were largely linked to the positive electrode for this type of battery chemistry.                          

Postmortem analysis of material from cycle-aged and calendar-aged battery cells of the type LMO-LCO/LTO and LiFePO4/graphite was performed to reveal details about aging mechanisms for those cell chemistries. Analysis of cycle-aged LMO-LCO/LTO cells revealed traces of manganese in the negative electrode and that the positive electrode exhibited the most severe aging. Analysis of cycle-aged LFP/graphite cells revealed traces of iron in the negative electrode and that the negative electrode exhibited the most severe aging.

Abstract [sv]

Litiumjonbatterier anpassade för användning i tunga hybridfordon förbättras kontinuerligt med avseende på prestanda och livslängd men har fortfarande begränsningar som måste beaktas vid utveckling av nya hybridfordon.                

Syftet med denna avhandling har varit att studera och utvärdera potentiella prov- och analysmetoder lämpliga för användning i arbetet med att maximera livslängd och utnyttjandegrad av batterier i tunga hybridfordon.                              

Ett koncept för battericykling på fordon har utvärderats. Arbetet innefattade utveckling av testutrustning, verifiering av hårdvara och mjukvara samt en längre periods validering på lastbilar. Arbetet har visat att konceptet har stor potential för utvärdering av strategier för användandet av batterier i hybridfordon, men är mindre användbar för åldring av batterier.                               

Batterier kapslade i flexibelt förpackningsmaterial har undersökts med avseende på kapslingens hållbarhet i en krävande hybridlastbilsmiljö. Ingen påverkan på fuktinträngning kunde påvisas efter vibration och temperaturcykling av de testade battericellerna.                    

Åldring av kommersiella battericeller av typen litiummanganoxid - litiumkoboltoxid/litiumtitanoxid (LMO-LCO/LTO) undersöktes med olika elektrokemiska metoder för att få en djupare förståelse för prestandaförändringens ursprung och för att förstå konsekvenserna av åldrandet ur en fordonstillverkares användarperspektiv. Undersökningen visade att både kapacitetsförlust och impedanshöjning till största delen var kopplat till den positiva elektroden för denna batterityp.                 

Post-mortem analys av material från cyklade och kalenderåldrade kommersiella battericeller av typen LMO-LCO/LTO och LiFePO4/grafit utfördes för att avslöja detaljer kring åldringsmekanismerna för dessa cellkemier. Vid analys av cyklade LMO-LCO/LTO celler påvisades mangan i den negativa elektroden samt uppvisade den positiva elektroden kraftigast åldring. Vid analys av cyklade LFP/grafit celler påvisades järn i den negativa elektroden samt uppvisade den negativa elektroden kraftigast åldring.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2014. , xii, 75 p.
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2014:21
Keyword [en]
Li-ion, battery, hybrid electric vehicle
National Category
Other Chemical Engineering
Research subject
Chemical Engineering
Identifiers
URN: urn:nbn:se:kth:diva-145166ISBN: 978-91-7595-127-0 (print)OAI: oai:DiVA.org:kth-145166DiVA: diva2:716986
Public defence
2014-06-03, K2, Teknikringen 28, KTH, Stockholm, 16:06 (English)
Opponent
Supervisors
Funder
Swedish Energy Agency, 35088-1
Note

QC 20140520

Available from: 2014-05-20 Created: 2014-05-13 Last updated: 2014-06-03Bibliographically approved
List of papers
1. Novel Field Test Equipment for Lithium-Ion Batteries in Hybrid Electrical Vehicle Applications
Open this publication in new window or tab >>Novel Field Test Equipment for Lithium-Ion Batteries in Hybrid Electrical Vehicle Applications
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2011 (English)In: Energies, ISSN 1996-1073, E-ISSN 1996-1073, Vol. 4, no 5, 741-757 p.Article in journal (Refereed) Published
Abstract [en]

Lifetime testing of batteries for hybrid-electrical vehicles (HEV) is usually performed in the lab, either at the cell, module or battery pack level. Complementary field tests of battery packs in vehicles are also often performed. There are, however, difficulties related to field testing of battery-packs. Some examples are cost issues and the complexity of continuously collecting battery performance data, such as capacity fade and impedance increase. In this paper, a novel field test equipment designed primarily for lithium-ion battery cell testing is presented. This equipment is intended to be used on conventional vehicles, not hybrid vehicles, as a cheaper and faster field testing method for batteries, compared to full scale HEV testing. The equipment emulates an HEV environment for the tested battery cell by using real time vehicle sensor information and the existing starter battery as load and source. In addition to the emulated battery cycling, periodical capacity and pulse testing capability are implemented as well. This paper begins with presenting some background information about hybrid electrical vehicles and describing the limitations with today's HEV battery testing. Furthermore, the functionality of the test equipment is described in detail and, finally, results from verification of the equipment are presented and discussed.

Keyword
battery testing, hybrid electrical vehicle (HEV), lithium ion battery
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:kth:diva-34677 (URN)10.3390/en4050741 (DOI)000291050600003 ()2-s2.0-79957673703 (Scopus ID)
Funder
StandUp
Note

QC 20110613

Available from: 2011-06-13 Created: 2011-06-13 Last updated: 2017-12-11Bibliographically approved
2. Li-Ion Pouch Cells for Vehicle Applications-Studies of Water Transmission and Packing Materials
Open this publication in new window or tab >>Li-Ion Pouch Cells for Vehicle Applications-Studies of Water Transmission and Packing Materials
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2013 (English)In: Energies, ISSN 1996-1073, E-ISSN 1996-1073, Vol. 6, no 1, 400-410 p.Article in journal (Refereed) Published
Abstract [en]

This study includes analysis of encapsulation materials from lithium-ion pouch cells and water vapour transmission rate (WVTR) measurements. WVTR measurements are performed on both fresh and environmentally stressed lithium-ion pouch cells. Capacity measurements are performed on both the fresh and the environmentally stressed battery cells to identify possible influences on electrochemical performance. Preparation of the battery cells prior to WVTR measurements includes opening of battery cells and extraction of electrode material, followed by resealing the encapsulations and adhesively mounting of gas couplings. A model describing the water diffusion through the thermal welds of the encapsulation are set up based on material analysis of the encapsulation material. Two WVTR equipments with different type of detectors are evaluated in this study. The results from the WVTR measurements show how important it is to perform this type of studies in dry environment and apply a rigorous precondition sequence before testing. Results from modelling confirm that the WVTR method has potential to be used for measurements of water diffusion into lithium-ion pouch cells. Consequently, WVTR measurements should be possible to use as a complement or alternative method to for example Karl Fisher titration.

Keyword
hybrid electrical vehicle (HEV), lithium ion battery, pouch cell, water vapor transmission
National Category
Energy Systems
Identifiers
urn:nbn:se:kth:diva-119059 (URN)10.3390/en6010400 (DOI)000314021900022 ()2-s2.0-84873208505 (Scopus ID)
Note

QC 20130305

Available from: 2013-03-05 Created: 2013-03-05 Last updated: 2017-12-06Bibliographically approved
3. Non-uniform aging of cycled commercial LiFePO4//graphite cylindrical cells revealed by post-mortem analysis
Open this publication in new window or tab >>Non-uniform aging of cycled commercial LiFePO4//graphite cylindrical cells revealed by post-mortem analysis
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2014 (English)In: Journal of Power Sources, ISSN 0378-7753, E-ISSN 1873-2755, Vol. 257, 126-137 p.Article in journal (Refereed) Published
Abstract [en]

Aging of power-optimized commercial 2.3 Ah cylindrical LiFePO4//graphite cells to be used in hybrid electric vehicle is investigated and compared for three different aging procedures; (i) using a simulated hybrid electric vehicle cycle within a narrow SOC-range, (ii) using a constant-current cycle over a 100% SOC-range, and (iii) stored during three years at 22 degrees C. Postmortem analysis of the cells is performed after full-cell electrochemical characterization and discharge. EIS and capacity measurements are made on different parts of the disassembled cells. Material characterization includes SEM, EDX, HAXPES/XPS and XRD. The most remarkable result is that both cycled cells displayed highly uneven aging primarily of the graphite electrodes, showing large differences between the central parts of the jellyroll compared to the outer parts. The aging variations are identified as differences in capacity and impedance of the graphite electrode, associated with different SEI characteristics. Loss of cyclable lithium is mirrored by a varying degree of lithiation in the positive electrode and electrode slippage. The spatial variation in negative electrode degradation and utilization observed is most likely connected to gradients in temperature and pressure, that can give rise to current density and potential distributions within the jellyroll during cycling.

Keyword
Battery aging, LiFePO4/graphite cells, Hybrid electric vehicle, Synchrotron material characterization, Electrode utilization
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-145047 (URN)10.1016/j.jpowsour.2014.01.105 (DOI)000333780000017 ()2-s2.0-84894504735 (Scopus ID)
Funder
Swedish Energy Agency
Note

QC 20140509

Available from: 2014-05-07 Created: 2014-05-07 Last updated: 2017-12-05Bibliographically approved
4. Analysis of ageing of commercial composite metal oxide: Li4Ti5O12 battery cells
Open this publication in new window or tab >>Analysis of ageing of commercial composite metal oxide: Li4Ti5O12 battery cells
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

Commercial battery cells with Li4Ti5O12 negative electrode and composite metal oxidepositive electrode have been analyzed with respect to ageing mechanisms. Electrochemical impedancespectroscopy (EIS), differential capacity analysis (dQ/dV), differential voltage analysis (dV/dQ) andscanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDX) were used to identifydifferent ageing mechanisms such as lithium inventory loss, loss of active electrode material andsurface film growth. The active material of the positive electrode was also examined by X-raydiffraction (XRD). Ageing mechanisms were studied for both calendar-aged and cycle-aged cells. Datafrom half cells prepared from post mortem harvested electrode material, using lithium foil as negativeelectrode and pouch material as encapsulation, were used as reference to full cell data. Electrochemicalanalysis of full and half cells combined with material analysis showed to be a powerful method toidentify ageing mechanisms in this type of commercial cells. The calendar-aged cell showedinsignificant ageing while the cycle-aged cell showed noticeable loss of positive electrode activematerial and loss of cyclable lithium, but only minor loss of negative electrode active material. Theresults imply that Li4Ti5O12 negative electrode material is a good alternative to other materials if highenergy density is not the primary goal.

National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-145415 (URN)
Note

QS 2014

Available from: 2014-05-20 Created: 2014-05-20 Last updated: 2014-05-20Bibliographically approved
5. Lithium-Ion Battery Cell Cycling and Usage Analysis in a Heavy-Duty Truck Field Study
Open this publication in new window or tab >>Lithium-Ion Battery Cell Cycling and Usage Analysis in a Heavy-Duty Truck Field Study
2015 (English)In: Energies, ISSN 1996-1073, E-ISSN 1996-1073, Vol. 8, no 5, 4513-4528 p.Article in journal (Refereed) Published
Abstract [en]

This paper presents results from a field test performed on commercial power-optimized lithium-ion battery cells cycled on three heavy-duty trucks. The goal with this study was to age battery cells in a hybrid electric vehicle (HEV) environment and find suitable methods for identifying cell ageing. The battery cells were cycled on in-house developed equipment intended for testing on conventional vehicles by emulating an HEV environment. A hybrid strategy that allows battery usage to vary within certain limits depending on driving patterns was used. This concept allows unobtrusive and low-cost testing of battery cells under realistic conditions. Each truck was equipped with one cell cycling equipment and two battery cells. One cell per vehicle was cycled during the test period while a reference cell on each vehicle experienced the same environmental conditions without being cycled. Differential voltage analysis and electrochemical impedance spectroscopy were used to identify ageing of the tested battery cells. Analysis of driving patterns and battery usage was performed from collected vehicle data and battery cell data.

Keyword
DV/dQ, Electrochemical Impedance Spectroscopy (EIS), HEV, Hybrid electric vehicle, Lithium-ion battery
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-145417 (URN)10.3390/en8054513 (DOI)000356879600061 ()2-s2.0-84930260888 (Scopus ID)
Funder
Swedish Energy Agency
Note

QC 20150825. Updated from Manuscript to Article in journal.

Available from: 2014-05-20 Created: 2014-05-20 Last updated: 2017-12-05Bibliographically approved
6. Uneven film formation across depth of porous graphite electrodes from cycling in commercial Li-ion batteries
Open this publication in new window or tab >>Uneven film formation across depth of porous graphite electrodes from cycling in commercial Li-ion batteries
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(English)Manuscript (preprint) (Other academic)
Keyword
aging, graphite, EIS modeling, Li-ion batteries, SEI
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-145054 (URN)
Note

QS 2014

Available from: 2014-05-07 Created: 2014-05-07 Last updated: 2014-05-20Bibliographically approved

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