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Lindgren, Fredrik
Publications (10 of 14) Show all publications
Lindgren, F., Rehnlund, D., Pan, R., Pettersson, J., Younesi, R., Xu, C., . . . Nyholm, L. (2019). On the Capacity Losses Seen for Optimized Nano-Si Composite Electrodes in Li-Metal Half-Cells. Advanced Energy Materials, 9(33), Article ID 1901608.
Open this publication in new window or tab >>On the Capacity Losses Seen for Optimized Nano-Si Composite Electrodes in Li-Metal Half-Cells
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2019 (English)In: Advanced Energy Materials, ISSN 1614-6832, Vol. 9, no 33, article id 1901608Article in journal (Refereed) Published
Abstract [en]

While the use of silicon‐based electrodes can increase the capacity of Li‐ion batteries considerably, their application is associated with significant capacity losses. In this work, the influences of solid electrolyte interphase (SEI) formation, volume expansion, and lithium trapping are evaluated for two different electrochemical cycling schemes using lithium‐metal half‐cells containing silicon nanoparticle–based composite electrodes. Lithium trapping, caused by incomplete delithiation, is demonstrated to be the main reason for the capacity loss while SEI formation and dissolution affect the accumulated capacity loss due to a decreased coulombic efficiency. The capacity losses can be explained by the increasing lithium concentration in the electrode causing a decreasing lithiation potential and the lithiation cut‐off limit being reached faster. A lithium‐to‐silicon atomic ratio of 3.28 is found for a silicon electrode after 650 cycles using 1200 mAhg−1 capacity limited cycling. The results further show that the lithiation step is the capacity‐limiting step and that the capacity losses can be minimized by increasing the efficiency of the delithiation step via the inclusion of constant voltage delithiation steps. Lithium trapping due to incomplete delithiation consequently constitutes a very important capacity loss phenomenon for silicon composite electrodes.

Keywords
asymmetric cycling, hard X-ray photoelectron spectroscopy, lithium trapping, silicon, solid electrolyte interphase layer
National Category
Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-398839 (URN)10.1002/aenm.201901608 (DOI)000477265600001 ()
Funder
Swedish Research Council, VR-2015-04421Swedish Research Council, VR-2017-06320StandUp
Note

De 2 första författarna delar förstaförfattarskapet.

Available from: 2019-12-11 Created: 2019-12-11 Last updated: 2019-12-11Bibliographically approved
Rehnlund, D., Lindgren, F., Pettersson, J., Edström, K. & Nyholm, L. (2018). Lithium Trapping in Alloy forming Electrodes and Current Collectors for Lithium based Batteries. In: : . Paper presented at The 233rd ECS Meeting, Seattle, USA, May 13-17 2018.
Open this publication in new window or tab >>Lithium Trapping in Alloy forming Electrodes and Current Collectors for Lithium based Batteries
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2018 (English)Conference paper, Oral presentation with published abstract (Other academic)
Abstract [en]

The next generation of lithium based batteries can be expected to be based on lithium alloy forming anode materials which can store up to ten times more charge than the currently used graphite anodes. This increase in the charge storage capability has motivated significant research towards the commercialization of anode materials such as Si, Sn and Al. These alloy forming anode materials are, however, known to exhibit significant capacity losses during cycling. This is typically ascribed to the volume expansion associated with the formation of the lithium alloys (the volume expansion is e.g. about 280 % for Li3.75Si) resulting in electrode pulverization as well as continuous solid electrolyte interphase (SEI) layer formation [1-3]. While significant progress has been made to decrease the volume expansion problems by the use of e.g. nanoparticles, nanorods and thin films, and/or capacity limitations [1-3], capacity losses are still generally seen [4,5]. This and previously published data suggest that the phenomenon may be due to another effect and that this in fact could stem from lithium trapping in the electrodes [6-8].

In the present work it is demonstrated (based on e.g. elemental analyses of cycled Sn, Al and Si electrodes) that lithium trapping can account for the capacity losses seen when alloy forming anode materials are cycled versus lithium electrodes, see Figure 1. It is shown that small amounts of elemental lithium are trapped within the electrode material during the cycling as a result of a two-way diffusion process [8] causing the lithium to move into the bulk material even during the delithiation step. This phenomenon, which can be explained by the lithium concentration profiles in the electrodes, makes a complete delithiation process very time consuming. As a result of the lithium trapping effect, the lithium concentration in the electrode increases continuously during the cycling. The experimental results also show that a similar effect can be seen also for commonly used current collector metals such as Cu, Ni and Ti. The latter means that these metals are unsuitable as current collector materials for lithium alloy forming materials in the absence of a thin layer of boron doped diamond serving as a lithium diffusion barrier layer [8].

References

1    M. N. Obrovac and V. L. Chevrier, Chem. Rev., 2014, 114, 11444.

2    X. Su, Q. Wu, J. Li, X. Xiao, A. Lott, W. Lu, B. W. Sheldon and J. Wu, Adv. Energy Mater., 2014, 4, 1300882.

3    J. R. Szczech and S. Jin, Energy Environ. Sci., 2011, 4, 56.

4    G. Zheng, S. W. Lee, Z. Liang, H-W. Lee, K. Yan, H. Yao, H. Wang, W. Li, S. Chu and Y. Cui, Nat. Nanotechnol., 2014, 9, 618.

5    K. Yan, H-W. Lee, T. Gao, G. Zheng, H. Yao, H. Wang, Z. Lu, Y. Zhou, Z. Liang, Z. Liu, S. Chu and Y. Cui, Nano Letters, 2014, 14, 6016.

6    G. Oltean, C-W. Tai, K. Edström and L. Nyholm, J. Power Sources, 2014, 269, 266.

7    A. L. Michan, G. Divitini, A. J. Pell, M. Leskes, C. Ducati and C. P. Grey, J. Am. Chem. Soc., 2016, 138, 7918.

8    D. Rehnlund, F. Lindgren, S. Böhme, T. Nordh, Y. Zou, J. Pettersson, U. Bexell, M. Boman, K. Edström and L. Nyholm, Energy Environ. Sci., 10 (2017) 1350.

 

Keywords
Lithium, trapping, diffusion, alloy formation, silicon, tin, aluminium
National Category
Inorganic Chemistry
Research subject
Chemistry with specialization in Inorganic Chemistry; Chemistry with specialization in Materials Chemistry; Chemistry with specialization in Organic Chemistry; Chemistry with specialization in Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-355546 (URN)
Conference
The 233rd ECS Meeting, Seattle, USA, May 13-17 2018
Funder
Swedish Research Council, 2015-04421
Available from: 2018-07-01 Created: 2018-07-01 Last updated: 2018-10-31Bibliographically approved
Lindgren, F., Rehnlund, D., Källquist, I., Nyholm, L., Edström, K., Hahlin, M. & Maibach, J. (2017). Breaking Down a Complex System: Interpreting PES Peak Positions for Cycled Li-ion Battery Electrodes. The Journal of Physical Chemistry C, 121, 27303-27312
Open this publication in new window or tab >>Breaking Down a Complex System: Interpreting PES Peak Positions for Cycled Li-ion Battery Electrodes
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2017 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 121, p. 27303-27312Article in journal (Refereed) Published
Abstract [en]

Photoelectron spectroscopy (PES) is an important technique for tracing and understanding the side reactions responsible for decreasing performance of Li-ion batteries. Interpretation of different spectral components is dependent on correct binding energy referencing and for battery electrodes this is highly complex. In this work, we investigate the effect on binding energy reference points in PES in correlation to solid electrolyte interphase (SEI) formation, changing electrode potentials and state of charge variations in Li-ion battery electrodes. The results show that components in the SEI have a significantly different binding energy reference point relative to the bulk electrode material (i.e. up to 2 eV). It is also shown that electrode components with electronically insulating/semi-conducting nature are shifted as a function of electrode potential relative to highly conducting materials. Further, spectral changes due to lithiation are highly depending on the nature of the active material and its lithiation mechanism. Finally, a strategy for planning and evaluating PES experiments on battery electrodes is proposed where some materials require careful choice of one or more internal reference points while others may be treated essentially without internal calibration.

National Category
Physical Sciences Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-336952 (URN)10.1021/acs.jpcc.7b08923 (DOI)000418393900008 ()
Funder
Swedish Energy Agency, 40495-1EU, FP7, Seventh Framework Programme, Eurolion & HiCSwedish Research Council, 2016-03545VINNOVA, High Voltage ValleyStandUp
Available from: 2017-12-19 Created: 2017-12-19 Last updated: 2018-02-16Bibliographically approved
Rehnlund, D., Lindgren, F., Bohme, S., Nordh, T., Zou, Y., Pettersson, J., . . . Nyholm, L. (2017). Lithium trapping in alloy forming electrodes and current collectors for lithium based batteries. Energy & Environmental Science, 10(6), 1350-1357
Open this publication in new window or tab >>Lithium trapping in alloy forming electrodes and current collectors for lithium based batteries
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2017 (English)In: Energy & Environmental Science, ISSN 1754-5692, E-ISSN 1754-5706, Vol. 10, no 6, p. 1350-1357Article in journal (Refereed) Published
Abstract [en]

Significant capacity losses are generally seen for batteries containing high-capacity lithium alloy forming anode materials such as silicon, tin and aluminium. These losses are generally ascribed to a combination of volume expansion effects and irreversible electrolyte reduction reactions. Here, it is shown, based on e.g. elemental analyses of cycled electrodes, that the capacity losses for tin nanorod and silicon composite electrodes in fact involve diffusion controlled trapping of lithium in the electrodes. While an analogous effect is also demonstrated for copper, nickel and titanium current collectors, boron-doped diamond is shown to function as an effective lithium diffusion barrier. The present findings indicate that the durability of lithium based batteries can be improved significantly via proper electrode design or regeneration of the used electrodes.

Place, publisher, year, edition, pages
ROYAL SOC CHEMISTRY, 2017
Keywords
LI-ION BATTERIES; ENERGY-STORAGE DEVICES; NEGATIVE ELECTRODES; ELECTROCHEMICAL LITHIATION; PHOTOELECTRON-SPECTROSCOPY; SILICON ELECTRODES; METAL ANODES; ELECTROLYTES; INSERTION; SURFACE
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-328278 (URN)10.1039/c7ee00244k (DOI)000403320300006 ()
Funder
Swedish Research Council, VR 2012-4681
Available from: 2017-12-20 Created: 2017-12-20 Last updated: 2017-12-28Bibliographically approved
Lindgren, F., Xu, C., Maibach, J., Andersson, A. M., Marcinek, M., Niedzicki, L., . . . Edström, K. (2016). A hard X-ray photoelectron spectroscopy study on the solid electrolyte interphase of a lithium 4,5-dicyano-2-(trifluoromethyl)imidazolide based electrolyte for Si-electrodes. Journal of Power Sources, 301, 105-112
Open this publication in new window or tab >>A hard X-ray photoelectron spectroscopy study on the solid electrolyte interphase of a lithium 4,5-dicyano-2-(trifluoromethyl)imidazolide based electrolyte for Si-electrodes
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2016 (English)In: Journal of Power Sources, ISSN 0378-7753, E-ISSN 1873-2755, Vol. 301, p. 105-112Article in journal (Refereed) Published
Abstract [en]

This report focuses on the relatively new salt, lithium 4,5-dicyano-2-(trifluoromethyl)imidazolide (LiTDI), and its functionality together with a silicon based composite electrode in a half-cell lithium ion battery context. LiTDI is a promising alternative to the commonly used LiPF6 salt because it does not form HF which can decompose the oxide layer on Si. The formation of a solid electrolyte interphase (SEI) as well as the development of the active Si-particles are investigated during the first electrochemical lithiation and de-lithiation. Characterizations are carried out at different state of charge with scanning electron microscopy (SEM) as well as hard x-ray photoelectron spectroscopy (HAXPES) at two different photon energies. This enables a depth resolved picture of the reaction processes and gives an idea of the chemical buildup of the SEI. The SEI is formed by solvent and LiTDI decomposition products and its composition is similar to SEI formed by other carbonate based electrolytes. The LiTDI salt or its decomposition products are not in itself reactive towards the active Si-material and no unwanted side reactions occurs with the active Si-particles. Despite some decomposition of the LiTDI salt, it is a promising alternative for electrolytes aimed towards Si-based electrodes.

Keywords
Lithium 4, 5-dicyano-2-(trifluoromethyl), imidazolide, Silicon negative electrode, Solid electrolyte interphase, Hard x-ray photoelectron spectroscopy
National Category
Materials Chemistry Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-261159 (URN)10.1016/j.jpowsour.2015.09.112 (DOI)000365060500014 ()
Funder
Vinnova, P37446-1EU, FP7, Seventh Framework Programme, 312284
Available from: 2015-08-31 Created: 2015-08-31 Last updated: 2019-12-11Bibliographically approved
Maibach, J., Lindgren, F., Eriksson, H., Edström, K. & Hahlin, M. (2016). Electric potential gradient at the buried interface between Lithium-ion battery electrodes and the SEI observed using photoelectron spectroscopy. Journal of Physical Chemistry Letters, 7(10), 1775-1780
Open this publication in new window or tab >>Electric potential gradient at the buried interface between Lithium-ion battery electrodes and the SEI observed using photoelectron spectroscopy
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2016 (English)In: Journal of Physical Chemistry Letters, ISSN 1948-7185, E-ISSN 1948-7185, Vol. 7, no 10, p. 1775-1780Article in journal (Refereed) Published
Abstract [en]

The buried interface between the bulk electrode material and the solid electrolyte interphase (SEI) in cycled Li-ion battery anodes is suggested to incorporate an electric potential gradient. This suggestion is based on photoelectron spectroscopy (PES) results from different anode materials that all show relative binding energy shifts between the components of the SEI and the active anode. Implications of this electric potential gradient on binding energy reference points in PES as well as on charge-transfer kinetics in Li-ion batteries are discussed. Specifically, we show that the separation of surface layer and bulk material spectral contributions (depth profiling) is crucial for consistent data interpretation. We conclude that previous interpretations of lithiation as cause for changes in PES spectra may need to be revised.

National Category
Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-281687 (URN)10.1021/acs.jpclett.6b00391 (DOI)000376421200004 ()27104985 (PubMedID)
Funder
EU, FP7, Seventh Framework Programme, 608575StandUpSwedish Research Council, VR-2012-4681
Available from: 2016-03-29 Created: 2016-03-29 Last updated: 2017-12-30
Valvo, M., Philippe, B., Lindgren, F., Check-Wai, T. & Edström, K. (2016). Insight into the processes controlling the electrochemical reactions of nanostructured iron oxide electrodes in Li- and Na-half cells. Electrochimica Acta, 194, 74-83
Open this publication in new window or tab >>Insight into the processes controlling the electrochemical reactions of nanostructured iron oxide electrodes in Li- and Na-half cells
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2016 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 194, p. 74-83Article in journal (Refereed) Published
Abstract [en]

The kinetics and the processes governing the electrochemical reactions of various types of iron oxide nanostructures (i.e., nanopowders, nanowires and thin-films) have been studied via cyclic voltammetry in parallel with Li- and Na-half cells containing analogous electrolytes (Li+/Na+, ClO4 in EC:DEC). The particular features arising from each electrode architecture are discussed and compared to shed light on the associated behaviour of the reacting nanostructured active materials. The influence of their characteristic structure, texture and electrical wiring on the overall conversion reaction upon their respective lithiation and sodiation has been analyzed carefully. The limiting factors existing for this reaction upon uptake of Li+ and Na+ ions are highlighted and the related issues in both systems are addressed. The results of this investigation clearly prove that the conversion of iron oxide into metallic Fe and Na2O is severely impeded compared to its analogous process upon lithiation, independently of the type of nanostructure involved in such reaction. The diffusion mechanisms of the different ions (i.e., Li+vs. Na+) through the phases formed upon conversion, as well as the influence of various interfaces on the resulting reaction, appear to pose further constraints on an efficient use of these compounds.

Place, publisher, year, edition, pages
Elsevier, 2016
Keywords
Iron oxide; Na-ion batteries; Li-ion batteries; Electrode architectures; Limiting processes
National Category
Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-283229 (URN)10.1016/j.electacta.2016.02.071 (DOI)000372523300009 ()
Funder
Swedish Research Council Formas, 245-2014-668Swedish Research Council, 2012-3392Knut and Alice Wallenberg Foundation
Available from: 2016-04-12 Created: 2016-04-12 Last updated: 2017-11-30Bibliographically approved
Lindgren, F., Xu, C., Niedzicki, L., Marcinek, M., Gustafsson, T., Björefors, F., . . . Younesi, R. (2016). SEI Formation and Interfacial Stability of a Si Electrode in a LiTDI-Salt Based Electrolyte with FEC and VC Additives for Li-Ion Batteries. ACS Applied Materials and Interfaces, 8(24), 15758-15766
Open this publication in new window or tab >>SEI Formation and Interfacial Stability of a Si Electrode in a LiTDI-Salt Based Electrolyte with FEC and VC Additives for Li-Ion Batteries
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2016 (English)In: ACS Applied Materials and Interfaces, ISSN 1944-8244, E-ISSN 1944-8252, Vol. 8, no 24, p. 15758-15766Article in journal (Refereed) Published
Abstract [en]

An electrolyte based on the new salt, lithium 4,5-dicyano-2-(trifluoromethyl)imidazolide (LiTDI), is evaluated in combination with nano-Si composite electrodes for potential use in Li-ion batteries. The additives fluoroethylene carbonate (FEC) and vinylene carbonate (VC) are also added to the electrolyte to enable an efficient SEI formation. By employing hard X-ray photoelectron spectroscopy (HAXPES), the SEI formation and the development of the active material is probed during the first 100 cycles. With this electrolyte formulation, the Si electrode can cycle at 1200 mAh g(-1) for more than 100 cycles at a coulombic efficiency of 99%. With extended cycling, a decrease in Si particle size is observed as well as an increase in silicon oxide amount. As opposed to LiPF6 based electrolytes, this electrolyte or its decomposition products has no side reactions with the active Si material. The present results further acknowledge the positive effects of SEI forming additives. It is suggested that polycarbonates and a high LiF content are favorable components in the SEI over other kinds of carbonates formed by ethylene carbonate (EC) and dimethyl carbonate (DMC) decomposition. This work thus confirms that LiTDI in combination with the investigated additives is a promising salt for Si electrodes in future Li-ion batteries.

Keywords
lithium 4, 5-dicyano-2-(trifluoromethyl)imidazolide, fluoroethylene carbonate, vinylene carbonate, silicon negative electrode, solid electrolyte interphase, hard X-ray photoelectron spectroscopy
National Category
Physical Chemistry
Identifiers
urn:nbn:se:uu:diva-299892 (URN)10.1021/acsami.6b02650 (DOI)000378584800099 ()27220376 (PubMedID)
Funder
VINNOVAEU, European Research Council, 312284StandUp
Note

Kan vara artikeln från manuskriptet http://uu.diva-portal.org/smash/record.jsf?pid=diva2:915177

Available from: 2016-07-29 Created: 2016-07-29 Last updated: 2019-12-11
Lindgren, F. (2016). Si negative electrodes for Li-ion batteries: Aging mechanism studies by electrochemistry and photoelectron spectroscopy. (Doctoral dissertation). Uppsala: Acta Universitatis Upsaliensis
Open this publication in new window or tab >>Si negative electrodes for Li-ion batteries: Aging mechanism studies by electrochemistry and photoelectron spectroscopy
2016 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis is focusing on the challenges when using Si as a possible new negative electrode material in Li-ion batteries. The overall aim is to contribute to a general understanding of the processes in the Si electrode, to identify aging mechanisms, and to evaluate how they influence the cycling performance. Another objective is to investigate how photoelectron spectroscopy (PES) can be used to analyze these mechanisms.

LiPF6 based electrolytes are aggressive towards the oxide layer present at the surface of the Si particles. With the use of fluoroethylene carbonate (FEC) as an electrolyte additive the cycling performance is improved, but the oxide layer is still affected. A recently developed salt, lithium 4,5-dicyano-2-(trifluoromethyl)imidazolide (LiTDI), is shown not to have any detrimental effects on the oxide. The SEI with FEC and vinylene carbonate (VC) as contains a high concentration of LiF and polymeric carbonate species and this composition seems to be beneficial for the cycling performance, but the results indicate that additional aging mechanisms occur. Therefore, electrochemical analysis is performed and confirms a continuous SEI formation. However, it also reveals a self-discharge mechanism and that a considerable amount of Li is remaining in the Si material after standard cycling.

PES is used in this work to analyze the SEI-layers as well as the surface and the bulk of the Si material. With this technique it is hence possible to distinguish changes in the Si material as a function of lithiation. To improve the data interpretation of PES spectra, a range of battery electrode model systems are investigated. These results show shifts of the SEI peaks relative to the electrode specific peaks as a result of the SEI thickness and the presence of a dipole layer. Also other electronically insulating composite electrode components show relative peak shifts as a function of the electrochemical potential.

To summarize, these studies investigate a number of well recognized aging mechanisms in detail and also establish additional processes contributing to aging in Si electrodes. Furthermore, this work highlights phenomena that influence data interpretation of PES measurements from battery materials.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2016. p. 67
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1362
National Category
Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-281694 (URN)978-91-554-9533-6 (ISBN)
Public defence
2016-06-02, Polhemsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 13:15 (English)
Opponent
Supervisors
Available from: 2016-05-09 Created: 2016-03-29 Last updated: 2016-05-12
Edström, K., Xu, C., Lindgren, F., Ma, Y. & Gustafsson, T. (2016). Silicon anodes and electrolyte interactions. In: : . Paper presented at ICACC (40th International Conference and Expo on Advanced Ceramics and Composites) Daytona Beach US Jan. 2016..
Open this publication in new window or tab >>Silicon anodes and electrolyte interactions
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2016 (English)Conference paper, Oral presentation with published abstract (Refereed)
National Category
Natural Sciences
Research subject
Chemistry with specialization in Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-287381 (URN)
Conference
ICACC (40th International Conference and Expo on Advanced Ceramics and Composites) Daytona Beach US Jan. 2016.
Funder
Swedish Energy AgencyStandUpSwedish Research Council
Available from: 2016-04-24 Created: 2016-04-24 Last updated: 2019-12-11
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