View Article Online

View Journal

ChemComm
Chemical Communications

Accepted Manuscript

This article can be cited before page numbers have been issued, to do this please use: S. Das, A.
Brennhagen, C. Cavallo, V. A. K. Killi, I. T. Jensen, A. Thøgersen, J. P. Mæhlen, S. Y. Lai, O. Nilsen and A. Y.
Koposov, Chem. Commun., 2024, DOI: 10.1039/D4CC05458J.
Volume 54
Number 1
4 January 2018
This is an Accepted Manuscript, which has been through the
Pages 1-112
Royal Society of Chemistry peer review process and has been
accepted for publication.
ChemComm
Chemical Communications Accepted Manuscripts are published online shortly after acceptance,
rsc.li/chemcomm

before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.

You can find more information about Accepted Manuscripts in the

Information for Authors.

Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
ISSN 1359-7345 Terms & Conditions and the Ethical guidelines still apply. In no event
COMMUNICATION
S. J. Connon, M. O. Senge et al.
Conformational control of nonplanar free base porphyrins:
shall the Royal Society of Chemistry be held responsible for any errors
towards bifunctional catalysts of tunable basicity

or omissions in this Accepted Manuscript or any consequences arising

from the use of any information it contains.

rsc.li/chemcomm
 Page 1 of 5 Please doChemComm
not adjust margins

View Article Online

ChemComm DOI: 10.1039/D4CC05458J

COMMUNICATION

Directing SEI formation on Si-based electrodes using atomic layer

deposition
Supti Das,a Anders Brennhagen,a Carmen Cavallo,a‡ Veronica Anne-Line Kathrine Killi,a Ingvild Julie
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.

Received 00th January 20xx, Thue Jensen,b Annett Thøgersen,b Jan Petter Mæhlen,c Samson Yuxiu Lai,c Ola Nilsena and Alexey
Open Access Article. Published on 21 November 2024. Downloaded on 11/22/2024 9:51:09 AM.

Accepted 00th January 20xx

Y. Koposov *a, c

ChemComm Accepted Manuscript

DOI: 10.1039/x0xx00000x

The design of artificial solid eletroctrolyte interphase is an the massive volume changes (∼300%) during Li-ion insertion
important task to minimize capacity losses in Li-ion batteries. (lithiation) and extraction (delithiation) processes, which lead to
Herein, TiO2 created through atomic layer deposition was used as severe capacity decay during continuous cycling. This most
an artificial SEI on Si nanoparticles. Such coating led to substantial intractable problem causes pulverization of Si resulting in loss
improvement of cycling stability when evaluated with FEC-free of electrical connection within the electrodes, and a continuous
electrolyte. growth of the solid electrolyte interphase (SEI) layer due to the
constant changes of the Si surface area. As a result, these anode
Since the commercialization of Li-ion batteries (LIBs) by Sony in materials typically show inferior cycling stability and low initial
early 1990s,1 it has been one of the most predominant energy Coulombic efficiency. Moreover, the continuously growing SEI
storage solutions for a wide variety of applications such as constantly consumes the electrolyte components, which
electric vehicles, grid storage, and multiple portable electronic ultimately results in cell failure.11 In addition, aggregation of Si
devices.2-5 However, the energy density of modern LIBs is not particles through electrochemical sintering results in poor
adequate to completely satisfy the growing demand for energy kinetics of the electrodes.12 These limitations hold back the
storage. Therefore, there is a necessity for low-cost LIBs that potential application of Si-based anodes for efficient, long
can safely deliver high power and energy density with a long lasting, and safe LIBs.
cycle life. This need drives the global search for new active The design of stable SEI on Si-based electrodes represents
materials and electrolytes to replace those that are currently one of the possible routes for improving their cyclability.13-15
utilized in commercially produced LIBs. Within this search, the The common strategy for this task is to use electrolyte additives,
quest for suitable high-capacity negative electrodes for high- e.g. fluoroethylene carbonate (FEC) which promotes formation
performance LIBs has led to the investigation of various of relatively stable SEI.16, 17 However, additives such as FEC are
materials that can outperform state-of-the-art graphite with a continuously consumed during electrochemical cycling, and
capacity of 372 mAh/g.6 Considerable interest has been their enhancing effect disappears when their reservoir in the
devoted to alloying-type anode materials, as they can electrolyte is depleted.18 In addition, electrolyte additives add
accommodate multiple Li-ions per alloying atom.7 weight and cost to the battery.
Among these alloying materials, silicon (Si) has gained a Alternative strategies such as surface coating and
great traction attributed to its low working potential, light hybridization with carbon-based materials have been shown to
weight, high abundance and theoretical capacity almost ten improve cyclability. Particularly, employing a suitable surface
times higher (3579 mAh/g) than that of graphite.8-10 However, coating on nanostructured Si has been observed to improve
the grand challenge of developing Si-based anodes is to mitigate cycling performance by reducing the reactivity of Si with
electrolytes, although the challenge with huge volume changes
a. Centre for Materials Science and Nanotechnology, Department of Chemistry,
cannot be eradicated entirely.19
University of Oslo, PO Box 1033, Blindern, 0315, Oslo, Norway. Among multiple coating techniques, atomic layer deposition
b. SINTEF Industry, Materials Physics, Forskningsveien 1, 0373 Oslo, Norway
c. Department of Battery Technology, Institute for Energy Technology (IFE),
(ALD) has been demonstrated to be a very versatile method for
Instituttveien 18, 2007, Kjeller, Norway. interfacial engineering. Unlike other thin film deposition
†Supplementary Information available: experimental section, detailed methods (e.g. PVD, CVD), ALD enables excellent control over the
electrochemical evaluation, detailed SEM, TEM and XPS analyses.
See DOI: 10.1039/x0xx00000x
uniformity, conformality and thickness of thin films at the
‡ Present address: FAAM, Strada Statale Via Appia 7 bis – 81030, Teverola (CE), Italy

Please do not adjust margins

 Please doChemComm
not adjust margins Page 2 of 5

COMMUNICATION ChemComm

atomic level due to its surface-controlled nature. In addition, View Article Online
ALD could be used for modification of particles and is not limited DOI: 10.1039/D4CC05458J
to only flat film surfaces. Such coating could be used to enhance
the battery performance by providing an artificial SEI layer
preventing detrimental side reactions at the
electrolyte/electrode interface.20 Several types of ALD coating
have been explored for their use in modification of battery
materials, such as transition metal oxides (Al2O3, TiO2, ZrO2, ZnO
and SiO2), metal nitride (TiN) and aluminum oxynitride
(AlOxNy).19, 21-25 Among these, TiO2 has been proven as one of
the most promising coating materials to enhance the cycle life
and rate capability of Si-based electrodes due to its small
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.

volume change during cycling (< 4%), structural stability, low

Open Access Article. Published on 21 November 2024. Downloaded on 11/22/2024 9:51:09 AM.

polarization and good electrochemical reversibility.25-27 In this

ChemComm Accepted Manuscript

study we coated Si nanoparticles with TiO2 using ALD to
examine the influence of the coating on electrochemical
performance in LIBs.
The pristine nanoparticles of amorphous Si (a-Si) with a
diameter of ∼40 nm were obtained from commercial sources
and stored in inert atmosphere. However, an oxide layer of ∼2
nm was still found on the surface, as was evidenced by Fig. 1: EDS mapping and TEM images of pristine amorphous silicon (a-Si, top) and TiO2-
transmission electron microscopy (TEM), energy dispersive X- coated silicon (a-Si-T5, bottom).
ray spectroscopy (EDS) and electron energy loss spectroscopy
(EELS) (Fig. 1 top panel, and Fig. S1, SI). This oxide layer could
have been formed during sample preparation for TEM analysis,
where the sample was exposed to air for ∼5 min.
These Si nanoparticles were successfully coated with TiO2 by
ALD after several trials during the optimization of the process
(Table S1, SI). The initial attempts, with a deposition
temperature of 150 °C (samples denoted as a-Si-Tx, where x=1-
3), resulted in an uneven TiO2 coating with a raspberry-like
morphology (TEM images are shown in Fig. S2, SI). The uneven
deposition of TiO2 was hypothesized to result from the absence
of sufficient number of OH groups on the Si surface originating
from a lack of exposure to moisture. Adding extra cycles with
H2O pulsing in the beginning of the depositions (a-Si-T4, Fig. S2,
SI) slightly improved the uniformity of the TiO2 coating. The best
results in this study were obtained by additionally increasing the
deposition temperature to 170 °C (a-Si-T5, Fig. 1 and Fig. S3),
where the a-Si nanoparticles were conformally coated with a
layer of amorphous TiO2.
Fig. 1 and Fig. S1 presents the EDS elemental mapping for
identifying the surface composition (Ti, O, C, Si) for pristine Si
(a-Si) and optimized TiO2-coated Si (a-Si-T5). The detailed
analysis revealed that the coated particles were encapsulated
by ∼2nm SiOx layer and TiO2 was coated on top of this layer. The
thickness of the TiO2 coating was found to be ∼3 nm. XPS
analysis of Ti 2p further confirmed the presence of a TiO2
coating (Fig. S5, SI).
To understand the effect of the TiO2 deposition on the Li
diffusion kinetics, electrochemical impedance spectroscopy
(EIS) measurements of a-Si and a-Si-T5 were performed at open
circuit voltage after cell assembly and after 1 charge-discharge
cycle (Fig. 2). Two types of electrolytes were used for the
evaluation of coating effect – an electrolyte with 10 wt% FEC Fig. 2: EIS of coin cells with Li-metal counter electrode assembled with active electrodes
based on pristine amorphous silicon (a-Si) and TiO2-coated amorphous silicon (a-Si-T5).
(Fig. 2A) and FEC-free electrolyte (Fig. 2B), both with 1.2 M LiPF6
The electrolytes consisted of 1.2 M LiPF6 in EC:EMC (7:3 vol%) + 2 wt% VC with 10 wt%
in EC:EMC (7:3 vol%) and 2 wt% VC. All EIS plots are composed FEC (A) and without FEC (B). Cells were measured right after cell assembly and after 1
charge-discharge cycle between 0.05-1.00 V vs Li/Li+ at C/20.

2 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx

Please do not adjust margins

 Page 3 of 5 Please doChemComm
not adjust margins

Journal Name COMMUNICATION

of a compressed semicircle in the middle frequency region and addition of FEC additive in the electrolyte.ViewAArticle careful
Online
an inclined line in low frequency region indicating the charge examination revealed that the a-Si electrodes without FEC
DOI: 10.1039/D4CC05458J
transfer process and Li-ion diffusion process, respectively. The experience a fast degradation after only a few cycles (18 cycles)
intercept at the high frequency region is attributed to the total whereas a-Si-T5 exhibits relatively stable performance for
resistance of the electrolyte, separator and the electrical approximately 60 cycles. Noteworthy, the initial Coulombic
contacts. The EIS data showed that the pristine electrodes efficiency is significantly lower for a-Si-T5 than a-Si-T0 for both
based on TiO2-coated Si (a-Si-T5) had lower impedance than the electrolytes, which is most likely due to irreversible lithiation of
uncoated samples (a-Si) with both electrolytes. The difference the TiO2-coating during the first cycle.
was largest for the FEC-free electrolyte (Fig. 2B). In addition, To gain further insights into the difference in cycling
after one charge-discharge cycle the impedance of electrodes behavior, ex situ scanning electron microscopy (SEM) were
based on a-Si-T5 was significantly lower than the pristine performed on electrodes extracted after the 23rd delithiation
electrodes, while the a-Si samples showed the opposite trend. (Fig. 4). These SEM images showed that the electrodes with
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.

This shows that the TiO2 coating improves the kinetics in the uncoated a-Si (Fig. 4A) were denser, compared to the coated
Open Access Article. Published on 21 November 2024. Downloaded on 11/22/2024 9:51:09 AM.

FEC-free electrolyte, which should lead to better performance sample (Fig. 4B). This could be a result of electrochemical

ChemComm Accepted Manuscript

during electrochemical cycling. sintering where the Si nanoparticles in the uncoated sample are
This difference in performance was further confirmed by agglomerating as a function of electrochemical cycling, while
galvanostatic cycling in coin cells vs Li-metal reference electrode the TiO2-coated sample maintains a more porous electrode
(Fig. 3, Fig. S7-S10, SI). As expected, cells cycled with FEC- structure.31
containing electrolyte retain relatively stable performance over This difference in behavior is likely linked to the TiO2 coating
the course of 200 cycles due to the improved SEI formation and its influence on the formation of the SEI layer, which was
properties of the FEC.28-30 Predictably, the uncoated Si (a-Si) further investigated through ex situ X-ray photoelectron
anode without FEC additive in electrolyte suffers from fast spectroscopy (XPS) on pristine electrodes and electrodes
capacity decay. However, the coating with 3 nm TiO2 (a-Si-T5) extracted after the 23rd delithiation (Fig. S4-S6). Due to the
provides an improvement in capacity retention without the thickness of the SEI layer and the limited penetration depth of
the X-ray probe, the XPS signals from Si and Ti after cycling were

Fig. 3: Specific capacity and Coulombic efficiency during galvanostatic cycling of pristine
amorphous silicon (a-Si) and TiO2-coated amorphous silicon (a-Si-T5). The electrolytes Fig. 4: SEM images of electrodes extracted after the 23rd delithiation from coin cells that
consisted of 1.2 M LiPF6 in EC:EMC (7:3 vol%) + 2 wt% VC with 10 wt% FEC (A) and without had been cycled vs Li-metal counter electrode with 1.2 M LiPF6 in EC:EMC (7:3 vol%) +
FEC (B). The dashed lines highlights the region where the difference in cycling stability is 2 wt% VC as electrolyte. A) uncoated sample (a-Si) and (B) TiO2-coated sample (a-Si-T5).
largest between the coated and uncoated sample.

This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 3

Please do not adjust margins

 Please doChemComm
not adjust margins Page 4 of 5

COMMUNICATION ChemComm

too weak to allow for detailed analysis of the delithiated 6. H. Cheng, J. G. Shapter, Y. Li and G. Gao, Journal of Energy
View Article Online
samples (Fig. S4-S5). Chemistry, 2021, 57, 451-468. DOI: 10.1039/D4CC05458J
However, XPS of F 1s showed a relative difference in the F- 7. M. N. Obrovac and V. L. Chevrier, Chemical Reviews, 2014, 114,
species on the surface of the coated vs uncoated samples (Fig. 11444-11502.
8. H. Wu and Y. Cui, Nano today, 2012, 7, 414-429.
S6). In the delithiated uncoated sample (a-Si), the peak assigned
9. X. Li, M. Gu, S. Hu, R. Kennard, P. Yan, X. Chen, C. Wang, M. J.
to LiPF6 (and LixPFyO2) is higher than the peak assigned to LiF.32,
33 However, in the delithiated a-Si-T5 sample the intensity of LiF
Sailor, J.-G. Zhang and J. Liu, Nature Communications, 2014, 5,
4105.
is significantly higher than that of LiPF6. This indicates formation 10. G. G. Eshetu and E. Figgemeier, ChemSusChem, 2019, 12, 2515-
of more LiF in the SEI of the TiO2-coated sample, which is 2539.
considered the key inorganic component of the SEI layer.14 This 11. N. Yuca, O. S. Taskin and E. Arici, Energy Storage, 2020, 2, e94.
difference in the composition of the SEI layer could explain the 12. D. Zhang, J. Lu, C. Pei and S. Ni, Advanced Energy Materials, 2022,
different densities of the delithiated electrodes observed by 12, 2103689.
13. B. Chen, D. Xu, S. Chai, Z. Chang and A. Pan, Advanced Functional
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.

SEM (Fig. 4). The SEI layer together with the TiO2 coating might
Open Access Article. Published on 21 November 2024. Downloaded on 11/22/2024 9:51:09 AM.

act as a barrier between the Si nanoparticles, thus mitigating Materials, 2024, 2401794.

ChemComm Accepted Manuscript

electrochemical sintering and volume change of Si during 14. D.-Y. Han, H. Y. Jang, S. Kim, J. Y. Kwon, J. Park, S. Back, S. Park
and J. Ryu, Energy Storage Materials, 2024, 65, 103176.
lithiation and delithiation, which can explain the enhanced
15. Y.-F. Tian, S.-J. Tan, C. Yang, Y.-M. Zhao, D.-X. Xu, Z.-Y. Lu, G. Li, J.-
cycling stability.
Y. Li, X.-S. Zhang and C.-H. Zhang, Nature communications, 2023,
In conclusion, we have been able to develop a method for 14, 7247.
coating of Si nanoparticles with a thin TiO2 layer, which showed 16. V. Etacheri, O. Haik, Y. Goffer, G. A. Roberts, I. C. Stefan, R.
improved cycling stability in Li-ion half cells compared to the Fasching and D. Aurbach, Langmuir, 2012, 28, 965-976.
uncoated sample, when cycled with FEC-free electrolyte. This 17. N.-S. Choi, K. H. Yew, K. Y. Lee, M. Sung, H. Kim and S.-S. Kim,
advancement can be attributed to the enhanced formation of Journal of Power Sources, 2006, 161, 1254-1259.
stable SEI layer on the surface of the coated Si particles, thereby 18. R. Jung, M. Metzger, D. Haering, S. Solchenbach, C. Marino, N.
mitigating the effects of the volume changes during Tsiouvaras, C. Stinner and H. A. Gasteiger, Journal of The
(de)lithiation and avoiding electrochemical sintering of the Electrochemical Society, 2016, 163, A1705.
particles. As a result, the coating serves as an artificial SEI at 19. M. Schnabel, E. Arca, Y. Ha, C. Stetson, G. Teeter, S.-D. Han and
P. Stradins, ACS Applied Energy Materials, 2020, 3, 8842-8849.
least during initial cycling. While there are still improvements to
20. Z. Li, J. Su and X. Wang, Carbon, 2021, 179, 299-326.
be made, continuing to improve the ALD coating of the Si
21. H. Zhu, M. H. A. Shiraz, L. Liu, Y. Zhang and J. Liu, Applied Surface
particles may lead to even better cycling performance and thus Science, 2022, 578, 151982.
become an alternative to the use of FEC as an additive in Si- 22. Y. Bai, D. Yan, C. Yu, L. Cao, C. Wang, J. Zhang, H. Zhu, Y.-S. Hu, S.
based electrodes. Dai, J. Lu and W. Zhang, Journal of Power Sources, 2016, 308, 75-
This work has been primarily funded by the Research 82.
Council of Norway within EnergiX program under grant number 23. L. Qiao, Z. Yang, X. Li and D. He, Surface and Coatings Technology,
280985. This work was performed within MoZEES, a Norwegian 2021, 424, 127669.
Center for Environment-friendly Energy Research (FME), 24. S. Casino, P. Niehoff, M. Börner and M. Winter, Journal of Energy
cosponsored by the Research Council of Norway (project Storage, 2020, 29, 101376.
25. E. M. Lotfabad, P. Kalisvaart, A. Kohandehghan, K. Cui, M. Kupsta,
number 257653), and 40 partners from research, industry, and
B. Farbod and D. Mitlin, Journal of Materials Chemistry A, 2014,
the public sector.
2, 2504-2516.
26. E. Memarzadeh Lotfabad, P. Kalisvaart, K. Cui, A. Kohandehghan,
M. Kupsta, B. Olsen and D. Mitlin, Physical Chemistry Chemical
Data availability Physics, 2013, 15, 13646-13657.
The data supporting this article have been included as part of 27. G. Jeong, J.-H. Kim, Y.-U. Kim and Y.-J. Kim, Journal of Materials
the ESI.† Chemistry, 2012, 22, 7999-8004.
28. E. Markevich, G. Salitra and D. Aurbach, ACS Energy Letters, 2017,
2, 1337-1345.
Conflicts of interest 29. Y. Jin, N.-J. H. Kneusels, L. E. Marbella, E. Castillo-Martínez, P. C.
M. M. Magusin, R. S. Weatherup, E. Jónsson, T. Liu, S. Paul and C.
There are no conflicts to declare P. Grey, Journal of the American Chemical Society, 2018, 140,
9854-9867.
30. T. Hou, G. Yang, N. N. Rajput, J. Self, S.-W. Park, J. Nanda and K.
Notes and references A. Persson, Nano Energy, 2019, 64, 103881.
1. T. Nagaura, Progress in Batteries & Solar Cells, 1990, 9, 209. 31. J. Shin and E. Cho, Chemistry of Materials, 2018, 30, 3233-3243.
2. J. M. Tarascon and M. Armand, Nature, 2001, 414, 359-367. 32. B. Philippe, R. Dedryvère, J. Allouche, F. Lindgren, M. Gorgoi, H.
3. M. Armand and J. M. Tarascon, Nature, 2008, 451, 652-657. k. Rensmo, D. Gonbeau and K. Edström, Chemistry of Materials,
4. D. Deng, M. G. Kim, J. Y. Lee and J. Cho, Energy & Environmental 2012, 24, 1107-1115.
Science, 2009, 2, 818-837. 33. B. Philippe, R. Dedryvère, M. Gorgoi, H. k. Rensmo, D. Gonbeau
5. H. Li, Z. Wang, L. Chen and X. Huang, Advanced Materials, 2009, and K. Edström, Chemistry of Materials, 2013, 25, 394-404.
21, 4593-4607.

4 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx

Please do not adjust margins

 Open Access Article. Published on 21 November 2024. Downloaded on 11/22/2024 9:51:09 AM.
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Page 5 of 5

Information.
ChemComm

The data supporting this article have been included as part of the Supplementary View Article Online
DOI: 10.1039/D4CC05458J

ChemComm Accepted Manuscript