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How the Negative Electrode Influences Interfacial and Electrochemical Properties of LiNi1/3Co1/3Mn1/3O2 Cathodes in Li-Ion Batteries
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för kemi - Ångström, Strukturkemi.ORCID-id: 0000-0002-2736-9145
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för kemi - Ångström, Strukturkemi.ORCID-id: 0000-0002-8019-2801
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Fysiska sektionen, Institutionen för fysik och astronomi, Molekyl- och kondenserade materiens fysik.
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för kemi - Ångström, Strukturkemi.ORCID-id: 0000-0003-4440-2952
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2017 (Engelska)Ingår i: Journal of the Electrochemical Society, ISSN 0013-4651, E-ISSN 1945-7111, Vol. 164, nr 13, s. A3054-A3059Artikel i tidskrift (Refereegranskat) Published
Abstract [en]

The cycle life of LiNi1/3Co1/3Mn1/3O2 (NMC) based cells are significantly influenced by the choice of the negative electrode. Electrochemical testing and post mortem surface analysis are here used to investigate NMC electrodes cycled vs. either Li-metal, graphite or Li4Ti5O12 (LTO) as negative electrodes. While NMC-LTO and NMC-graphite cells show small capacity fading over 200 cycles, NMC-Li-metal cell suffers from rapid capacity fading accompanied with an increased voltage hysteresis despite the almost unlimited access of lithium. X-ray absorption near edge structure (XANES) results show that no structural degradation occurs on the positive electrode even after >200 cycles, however, X-ray photoelectron spectroscopy (XPS) results shows that the composition of the surface layer formed on the NMC cathode in the NMC-Li-metal cell is largely different from that of the other NMC cathodes (cycled in the NMC-graphite or NMC-LTO cells). Furthermore, it is shown that the surface layer thickness on NMC increases with the number of cycles, caused by continuous electrolyte degradation products formed at the Li-metal negative electrode and then transferred to NMC positive electrode.

Ort, förlag, år, upplaga, sidor
2017. Vol. 164, nr 13, s. A3054-A3059
Nationell ämneskategori
Kemi
Identifikatorer
URN: urn:nbn:se:uu:diva-338161DOI: 10.1149/2.0711713jesISI: 000418409800021OAI: oai:DiVA.org:uu-338161DiVA, id: diva2:1171560
Forskningsfinansiär
Energimyndigheten, 37725-1; 40495-1StandUpTillgänglig från: 2018-01-08 Skapad: 2018-01-08 Senast uppdaterad: 2019-04-11Bibliografiskt granskad
Ingår i avhandling
1. Avoiding ageing: Surface degradation of commercial electrode materials in lithium-ion batteries
Öppna denna publikation i ny flik eller fönster >>Avoiding ageing: Surface degradation of commercial electrode materials in lithium-ion batteries
2019 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
Abstract [en]

The battery market today expands rapidly, not least for electric vehicles. But to compete against the combustion engine, the cost of batteries must be reduced. After years of usage, the batteries degrade and need to be exchanged, increasing the cost over the vehicle lifecycle. This can be mitigated by tailoring the usage conditions and the battery materials. Understanding and avoiding ageing can be key to a more sustainable transport system. This thesis contains studies on degradation processes in Li-ion batteries utilizing the LiNixMnyCozO2 (NMC) cathode material, and suggests strategies for the improvement of battery life time.

When cycling different negative electrodes – including graphite, lithium foil and lithium titanium oxide (LTO) – against NMC electrodes, only minor capacity fading was observed in the NMC-LTO and NMC-graphite cells, in contrast to the NMC-Li-metal cells. The capacity fading for Li-metal cells was determined to be caused by degradation products formed at the lithium foil which thereafter diffused to the NMC electrode, leading to a higher resistance. Commercial NMC/LiMn2O4-graphite cells were also investigated after cycling in limited state of charge (SOC)-intervals. The cycle life was far longer in the low-SOC cell than in the high-SOC cell. Photoelectron spectroscopy revealed increased manganese dissolution in the high-SOC cell, likely causing a less stable solid electrolyte interphase layer on the negative electrode. This, in turn, limits the capacity. How temperature influence ageing in NMC-LTO was analysed in cells cycled at -10 °C, 30 °C and 55 °C. It was found that the initial side reactions at the LTO electrode limited the cell capacity, but that these also stabilized the NMC electrode. At 55 °C, excessive side reactions at LTO caused capacity fading due to loss of active lithium. At -10 °C, high cell resistance limited the capacity. Switching to a PC based electrolyte allowed stable low temperature cycling, although it was found that PC degraded and formed thick electrode surface layers. Also sulfolane-based electrolytes were investigated, showing thinner surface layers than the EC containing reference electrolyte at high potentials, thus indicating a more stable electrolyte system.

Ort, förlag, år, upplaga, sidor
Uppsala: Acta Universitatis Upsaliensis, 2019. s. 72
Serie
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1802
Nyckelord
Li-ion battery, Ageing, Photoelectron spectroscopy, Nickel Manganese Cobalt Oxide
Nationell ämneskategori
Kemi
Identifikatorer
urn:nbn:se:uu:diva-381548 (URN)978-91-513-0639-1 (ISBN)
Disputation
2019-06-05, Room 4001, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 09:15 (Engelska)
Opponent
Handledare
Tillgänglig från: 2019-05-09 Skapad: 2019-04-11 Senast uppdaterad: 2019-06-17

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Björklund, ErikBrandell, DanielHahlin, MariaEdström, KristinaYounesi, Reza

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