RESEARCH ARTICLE
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Synchrotron X-Ray Absorption Spectroscopy and
Electrochemical Study of BiOSe Electrode for Lithium-/
Potassium-Ion Storage
Zhibin Wu, Gemeng Liang, Jingxing Wu, Wei Kong Pang, Fuhua Yang, Libao Chen,*
Bernt Johannessen,* and Zaiping Guo*
Elucidating the battery operating mechanism is important for designing
better conversion-type anodes as it determines the strategies used to
improve electrochemical performances. Herein, the authors pioneered the
electrochemical study of layered Bi O Se as anodes for lithium-ion batteries
(LIBs) and potassium-ion batteries (PIBs). Surprisingly, the Bi O Se/
graphite composite electrode shows even better cycle stability for PIBs. The
electrochemical reaction mechanisms of the Bi OSe/graphite electrode for
LIBs and PIBs are investigated by potential-resolved in situ and ex situ X-ray
absorption spectroscopy based at the Bi L III-edge and Se K-edge through
characterizing the local atomic structure evolution, valence state change,
and charge transfer. New insights are gained regarding the electrochemical
process of Se − anions in BiO Se, where multiple Li–Se intermediates
rather than the traditional single-phase Li Se are involved in this conversion-
type anode. The advanced understanding of anionic electrochemistry in
conversion-type anodes prompts one to find appropriate ways to suppress
side-reactions and improve the battery performances.
Dr. Z. Wu, Dr. G. Liang, Dr. J. Wu, Dr. W. K. Pang,
Dr. F. Yang, Prof. Z. Guo
Institute for Superconducting & Electronic Materials
School of Mechanical, Materials, Mechatronic
and Biomedical Engineering
University of Wollongong
Wollongong, NSW , Australia
E-mail: zguo@uow.edu.au
Dr. Z. Wu, Prof. L. Chen
State Key Laboratory for Powder Metallurgy
Central South University
Changsha , China
E-mail: lbchen@csu.edu.cn
Dr. B. Johannessen
Australian Synchrotron
 Blackburn Rd, Clayton, VIC , Australia
E-mail: berntj@ansto.gov.au
Prof. Z. Guo
School of Chemical Engineering & Advanced Materials
The University of Adelaide
Adelaide, SA , Australia
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/./aenm..
DOI: ./aenm.
Adv. Energy Mater. ,   ( of )
Printed by [Technische Universitat Ilmenau - 141.024.023.198 - /doi/epdf/10.1002/aenm.202100185] at [13/04/2021].
. Introduction
The increasing demand from portable
electronics, electric vehicles, and renew-
able energy storage/conversion has cre-
ated great opportunities for developing
high-performance and scalable energy
storage systems.[] Potassium-ion batteries
(PIBs) that are attractive for abundant
potassium resources and low standard
reduction potential (−. V vs K+/K) can
be a promising alternative energy storage
system for lithium-ion batteries (LIBs)
whose lithium resources are currently lim-
ited by the high market price.[,] Under-
standing the fundamental electrochemical
mechanisms during battery operation is
critically important for expediting battery
industrial upgrade. State-of-the-art char-
acterization techniques, including in situ/
operando X-ray diraction (XRD), X-ray
absorption spectroscopy (XAS), and trans-
mission electron microscopy (TEM), were
conducted to probe crystalline structure
changes, redox reactions, and cell degradation mechanisms of
rechargeable batteries during charging/discharging. [] Electro-
chemical reaction mechanisms of alloying-type and conversion-
type anodes have been extensively studied in the past decades,
and great progress has been made by virtue of these advanced
characterization techniques. For example, the phase change
process of Sb Se for sodium-ion batteries was investigated by
in situ synchrotron XRD, showing that the SbSe electrode
underwent a typical insertion–conversion–alloying process
upon discharge. Specifically speaking, during the initial dis-
charge process, Na+ was inserted into the SbSe interlayer to
form NaxSbSe intermediate beyond . V, then Sb+ was dis-
placed by Na+ to form metallic Sb and NaSe through a conver-
sion reaction between . and .V, and metallic Sb was further
alloyed with Na + through multistep alloying reactions to form
NaSb end-phase.[] Furthermore, the electrochemical reaction
process of SnO for lithium-ion storage was investigated by in
situ synchrotron XRD, in situ synchrotron XAS, and in situ
TEM. At the start of discharge, metallic Sn and LiO were gen-
erated through the conversion reaction between SnO and Li.
Then, Sn was lithiated into amorphous LixSn intermediates and
Li.Sn end-phase by multistep alloying reactions. [] Recently,
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Figure . a) XRD patterns of the Bi O Se powder and the Bi OSe/G composite. SEM images of b,c) the BiOSe and d,e) the Bi O Se/G composite.
the potassium storage mechanism of Sn P was also investi-
gated by in situ XRD, demonstrating that Sn and amorphous
K xP was formed via the conversion reaction between Sn P
and K, and Kx P was further alloyed to be K P at the second
stage, and then Sn and KP was further alloyed with K to form
KSn and K P at the end of discharge.[] Besides, the failure
mechanism of Sn P for lithium-ion storage was investigated
by synchrotron XAS, indicating that Sn P  is fully converted to
an amorphous SnP x phase after the initial two cycles, and the
SnP x phase was gradually unrecoverable during the long-term
cycling, which leads to the capacity fading of the Sn P anode.[]
It is worth noting that the conversion reaction mechanism
of MoS as a LIB anode seems like controversial, which was
studied by Mo K-edge and S K-edge XAS measurement. Liang
Zhang et al.[] regarded that the conversion reaction of MoS
is not reversible since the formed Li S is converted to sulfur
upon the first full charge and Li S/sulfur becomes the main
redox couple in the subsequent cycles. However, Zhiqiang Zhu
etal. [] suggested that amorphous MoS nanograins are gener-
ated at the end of the initial charge, and the completely lithiated
MoS  electrode consists of Mo, LiS, and additional unknown
Mo–S related phases. Therefore, elucidating the detailed oper-
ating mechanism is important for designing better conversion-
type anodes as it determines the appropriate strategies, whether
buering the large volume changes or enhancing electrode
reversibility or suppressing the possible shuttle eect of poly-
sulfides, to improve electrochemical performances.
Although progress has been made in detecting electrochem-
ical reaction mechanisms of conversion-type anode materials,
most studies focused on metallic cations primarily rather than
non-metallic anions. XAS that is comprised of X-ray absorp-
tion near edge structure (XANES) and extended X-ray absorp-
tion fine structure (EXAFS) is a useful tool to detect the elec-
tronic and local atomic structure information of a selected ele-
ment in a material. Given to the tunable wavelength and high
throughput of synchrotron X-rays, an XAS beamline is able to
conduct in situ/ex situ, qualitative/quantitative, and element-
selective experiments. [] Therefore, it is advantageous to use
synchrotron XAS to study their comprehensive electrochemical
reaction mechanisms involving charge transfer, oxidation state
Adv. Energy Mater. ,   ( of )
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changes, and local atomic structure evolutions (also detectable
of amorphous intermediates) of a selected absorber in a cell
where other characterization techniques such as XRD and TEM
are unable to tell a complete story.
In addition, new electrode materials are of great importance
to boost the development of rechargeable batteries. Multinary
metal oxides/chalcogenides are attractive for their diverse com-
position and tunable crystal structure, endowing them with
outstanding physical, chemical, optical, and electronic prop-
erties.[] BiOSe semiconductor is an excellent candidate for
field-eect devices due to its air-stable layered structure, ultra-
high carrier mobility, and moderate bandgap, but its relevant
electrochemical performance has not been studied yet. [,]
In this work, Bi OSe flakes were synthesized by a facile and
scalable method through heating the reagents in the evacuated
quartz glass ampoule. The BiOSe/graphite (BiOSe/G) com-
posite prepared by ball-milling Bi OSe with graphite has excel-
lent electrochemical performances for potassium-ion storage,
even better than that used for lithium-ion storage. Bi LIII -edge
and Se K-edge XAS studies were conducted to investigate the
electrochemical reaction mechanisms of BiOSe/G electrodes
for LIBs and PIBs, where the charge transfer, redox reactions,
and local atomic structure changes of the Bi OSe/G electrode
were uncovered. More importantly, new insights were gained on
the Li–Se intermediates, which were based on these Se K-edge
spectra collected from the Bi OSe/G electrode. The advanced
understanding of the multiple Li–Se intermediates in conver-
sion-type anodes sheds light on designing high-performance
conversion-type anodes through suppressing the detrimental
shuttle-eect.
. Results and Discussions
.. Synthesis and Structure Characterization
Bi OSe was prepared by heating the mixture of Bi O , Bi,
and Se in an evacuated quartz glass ampoule at  °C for
h. Figure a shows the XRD patterns of the as-synthesized
Bi OSe powder and the ball-milled Bi O Se/G composite
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Figure . Discharge–charge curves of a) Bi O , b) BiSe , and c) Bi O Se electrode for LIBs measured at mAg−. d) Comparison of the cycling per-
formances of Bi O, BiSe , BiOSe, and BiO Se/G electrode for LIBs measured at mAg− . e) Comparison of the cycling performances of BiO Se,
Bi OSe/super P, and Bi O Se/G electrode for LIBs measured at Ag−. f) Rate performance of the BiOSe/G electrode measured from . to Ag−.
(prepared by ball-milling Bi O Se and graphite). All the dirac-
tion peaks of the Bi O Se powder can be indexed into a tetrag-
onal BiOSe phase (JCPDF card –) without evidence
of any second phase, revealing high purity and good crystal-
line degree of the as-synthesized Bi OSe powder. In contrast,
the Bi O Se/G composite shows much weaker peak intensity,
due to the poor crystalline degree and reduced particle size
caused by mechanical ball-milling. The morphologies and
structures of the as-synthesized samples were probed by scan-
ning electron microscopy (SEM) and TEM. The SEM images
in Figureb,c show that Bi O Se is composed of micron-level
stacked flakes. These stacked large flakes can be exfoliated
during the ultrasonic treatment when preparing specimens for
TEM study, as is confirmed by the corresponding TEM images
in Figure S, Supporting Information, which show the char-
acter of thin sheets. The interplanar spacing of . nm can
be indexed into the () lattice plane of tetragonal Bi O Se.
As shown in Figure d,e, the BiOSe/G composite is com-
posed of uniform nanometer-scale particles, which facilitates
to improve electrochemical performances by shortening ion
transport paths and alleviating volume change during electro-
chemical cycling.
.. Electrochemical Measurement
The electrochemical performances of Bi O Se and BiOSe/G
composite were evaluated as anodes for LIBs in coin-type 
half-cells. The galvanostatic discharge/charge profiles of the
Adv. Energy Mater. , 
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first two cycles of the Bi O, Bi Se , and BiO Se electrode for
LIBs are compared in Figure a–c. BiO Se electrode resem-
bles BiO and Bi Se electrode in voltage profile, which means
that the reaction mechanism involved in the BiO Se electrode
can be similar to the BiO and Bi Se electrode for LIBs. The
BiO Se electrode has a high initial Coulombic eciency of
.% with an initial discharge capacity of mAhg −, which
is higher than that of the Bi O electrode (.%) and the BiSe
electrode (.%). Thus, the initial Coulombic eciency and
reversible specific capacity could be enhanced via a synergistic
eect originating from abundant anion vacancies induced by
mixed anions [] and/or expanded interlayer distance due to
the partial replacement of O with Se.[] To character the redox
reactions of the Bi OSe electrode during cycling, cyclic vol-
tammogram (CV) test was conducted (Figure S, Supporting
Information). During the first cathodic scan, the Bi OSe elec-
trode shows a broad reduction peak centered at around . V,
possibly owing to the insertion and conversion reactions, and
the formation of solid electrolyte interphase (SEI) layer. The fol-
lowing two reduction peaks at . and .V can be ascribed
to the alloying reaction to form LiBi and Li Bi alloys, respec-
tively. During the first anodic scan, the sharp peak at .V can
be owing to the de-alloying reaction to generate Bi metal. The
following flatten and obscure peaks can be owing to the recom-
bination process of Bi metal, LiO, and Li Se to form Bi OSe
phase. During the second cathode scan, minor reduction peaks
at ≈., ., and .V should correspond to the Li-ion inser-
tion process to form LixBi OSe, the conversion process to form
LiSe, and LiO, respectively.[,] Based on CV curves of the
 ( of ) ©  Wiley-VCH GmbH
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Figure . a) Cycling stability and b) rate performance of the BiO  Se and BiOSe/G electrode for PIBs. c) Discharge–charge curves of the Bi OSe/G
electrode at dierent current densities. d) CV curves of the Bi O Se/G electrode for PIBs measured at a scan rate of .mVs− .
Bi OSe electrode and the empirical principle for conversion-
type anodes, an insertion–conversion–alloying process during
lithiation can be proposed for the Bi OSe electrode as an anode
for LIBs, with lithiated end-phases of Li Bi, Li Se, and LiO.
The cycling performances of these electrodes were compared
by repeated galvanostatic discharge/charge test at  mA g−
in Figured. The Bi OSe electrode has the highest reversible
capacity, and it delivers better cycling stability than the Bi O
electrode but worse cycling stability than the Bi Se  electrode.
The cycling performance of Bi O Se can be further improved
by combining it with carbonaceous material. As shown in
Figure e, the Bi OSe/G electrode prepared by ball-milled
Bi OSe with graphite shows a good capacity retention of
.% over  cycles, delivering better cycling stability than
the Bi OSe/super P electrode and bare Bi OSe electrode.
Moreover, the Bi OSe/G electrode has a high initial Coulombic
eciency of .%, indicating that the incorporation of graphite
improved the cycling stability of BiO Se without sacrifice of
initial Coulombic eciency largely. The rate performance of the
Bi OSe/G electrode was evaluated at the current densities of
., ., ., , , , and Ag−, showing a reversible specific
capacity of , , , , , , and mAhg −, respec-
tively (Figuref ).
To explore alternative energy storage systems, bare Bi OSe
and the BiO Se/G composite were also evaluated as anodes for
advanced PIBs (Figure ). In comparison with the bare Bi OSe
electrode, the Bi O Se/G composite electrode shows much
better cycling stability with a high capacity retention of .%
at  mA g− and .% at  mA g− over  cycles. The
Adv. Energy Mater. ,   ( of )
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Bi OSe/G composite electrode also has better rate capability
than the BiOSe electrode, showing a high reversible capacity
of , , , , , and mAhg− at the current densi-
ties of ., ., ., ., , and Ag−, respectively, whose cor-
responding discharge–charge curves are plotted in Figurec. It
is worth mentioning that the cycling stability of the Bi OSe/G
composite electrode holds a conspicuous position among
Bi/rGO composite, [] dual-shell bismuth boxes/C, [] Bi S /
rGO composite,[] and BiSe/C composite[] as anodes for
PIBs (Table S, Supporting Information). The electrochemical
reaction process of the Bi OSe/G electrode for PIBs were
studied by CVs (Figure d). During the first cathode scan, a
large broad reduction peak can be observed, which originates
from the mixed contribution that involves the reduction of Bi+ ,
the alloying reaction between K+ and Bi metal, and the forma-
tion of SEI layers.[,,] This irreversible broad peak vanished
in the following cathode scans, whereas a new broad reduction
peak centered at around . V appeared owing to the conver-
sion reaction between BiO Se and K +, and the partial alloying
reaction to form K–Bi alloy. The other peak centered at .V
can be owing to the further alloying reaction to form K  Bi
end-phase. It is noted that possible K–Bi alloying intermedi-
ates contain KBi , KBi , and K Bi.[] The discharge–charge
profiles at dierent cycles were also investigated (Figure S,
Supporting Information). It reveals that the degraded capacity
in the BiO Se electrode should mainly come from the irrevers-
ible conversion reaction process rather than the alloying reac-
tion process, whilst the incorporation of graphite can enhance
the reversibility of the conversion reaction process significantly.
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Figure . a) Bi LIII -edge XANES spectra and b) FTs of k -weighted Bi L III-edge EXAFS spectra of Bi OSe, BiOSe/G, Bi reference, and Bi O  reference.
c) Se K-edge XANES spectra and d) FTs of k -weighted Se K-edge EXAFS spectra of BiO Se, Bi O Se/G, and Se reference. e,f) Dierent crystal structures
of BiO Se. g) A view of the structure type II down a-axis.

.. Synchrotron X-Ray Absorption Spectroscopy Study
To study the electronic and local atomic structure information
of powders, ex situ electrodes, and in situ batteries, both Bi–L III-
edge XAS and Se K-edge XAS were measured in transmission
mode at the XAS beamline of Australian Synchrotron, Australia.
Bismuth element occupies a ground state electron configura-
tion of [Xe]fd sp with valence electrons situated at the
s and p orbitals. As shown in Figure a, Bi L III-edge XANES
spectra were collected for BiO Se, Bi OSe/G composite, Bi
reference, and BiO reference, with the absorption edge fea-
ture probing the excitation of an electron from the p/ orbital
to the empty d orbitals based on the dipole selection rules
(∆l = ±).[] The absorption edge (defined as halfway up the
edge step, at xµ[E] =.) of Bi OSe and Bi OSe/G nearly over-
laps with that of Bi O, indicating that the formal valence state
of Bi element in Bi OSe is also trivalent. In comparison with
BiO , the white-line peak of Bi OSe locates at lower photon
energy value, indicating longer average BiO bond length in
BiO Se, according to the empirical rule that the photon energy
value of the white-line peak are inversely correlated with the
bond length.[] Fourier transformations (FTs) of the corre-
sponding k -weighted Bi LIII-edge EXAFS spectra as a function
of the non-phase-corrected radial distance R are displayed in

Adv. Energy Mater. ,   ( of ) ©  Wiley-VCH GmbH
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Figureb. The BiO Se and Bi O Se/G composite have longer
Bi  O bond length than Bi O , which is consistent with the
analysis result from XANES. In comparison with Bi O Se, the
Bi OSe/G composite has a shorter average BiO bond length
with smaller radial distance, R, and higher structure disorder
degree (or lower coordination number) with decreased peak
area. A quantitative analysis of the local structure of Bi OSe
is performed by fitting the k -weighted Bi L III -edge EXAFS
spectra, with the fitted structural parameters summarized in
Table S, Supporting Information. As reported, there are two
types of crystal structure with the same I/mmm space group
for tetragonal Bi OSe, whose structural discrepancy lies in the
O atom position as was shown in Figure e,f, which makes
it dicult to be distinguished by using XRD.[] As shown in
Figure Sa,b, Supporting Information, the experimental data
fits well with the simulated model both in R space and k space,
indicating the robust structural model based on structure type
II. In contrary, the other fit model based on structure type I was
rejected with a considerable large R-factor. Besides, the XAS
spectra based on Se K-edge were also collected to provide com-
prehensive local atomic structure information for the Bi OSe
and BiO Se/G powder. The Se K-edge XANES spectra of
Bi OSe, Bi O Se/G and Se powder are compared in Figurec.
It is noted that the absorption edge originates from the dipole-
allowed transition from s to p. The maximum of the first peak
derivative of the XANES spectrum (the inset) of Bi OSe almost
overlaps with that of the BiOSe/G composite, but they reveal
lower photon energy value than the Se reference at the absorp-
tion edge. [] This indicates that the valence state of Se element
in both Bi O Se and Bi O Se/G composite is bivalent (Se−).
Unlike the similar Bi LIII -edge XANES spectra for BiOSe and
Bi OSe/G, their Se K-edge XANES spectra show much dier-
ence in peak shape, which implies large local structure dier-
ences between Bi OSe and BiO Se/G around Se absorber. By
ball-milling bulk Bi O Se flakes with graphite, bulk Bi OSe
flakes can be possibly exfoliated into few-layered Bi OSe sheets
with cleavage along Se planes, which is triggered by the high
shear and fragmentation forces from ball-milling.[,] The par-
tial absence of coordinated atom around Se planes gives rise
to the decrease of peak intensity in the BiO Se/G composite,
as shown in Figure d. The k-weighted χ(k) function (k χ[k])
spectra shows more clear evidence that Bi O Se has less coordi-
nated atoms around Se element after ball-milling with graphite
(Figure S, Supporting Information). Furthermore, the local
structure information of Bi O Se is further quantified by Se
K-edge EXAFS fitting, whose experimental data also fits well
the calculated model based on type II (Figure Sc,d, Supporting
Information). The fitted structural parameters are presented in
Table S, Supporting Information, and it is consistent with the
structural parameters obtained from Bi L III-edge EXAFS fitting.
In conclusion, the crystal structure of BiO Se fits well into a
tetragonal structure with I/mmm space group, which consists
of planar oxide layers (Bi O ) sandwiched by Se square arrays
(Figuref,g). The Bi O Se/G composite is more disordered and
thinner than the bare BiO Se.[]
To understand the charge transfer and local structure
changes of the Bi OSe/G electrode during lithiation/delithi-
ation, potential-resolved in situ customized coin-cells and ex
situ BiOSe/G electrodes were measured by both Bi LIII -edge
Adv. Energy Mater. ,   ( of )
www.advenergymat.de
and Se K-edge XAS. Figure b displays potential-resolved in
situ Bi LIII -edge XANES and EXAFS patterns in the first dis-
charge region (I) of Figurea. The oxidation state of Bi in the
Bi OSe/G composite electrode before discharge is determined
to be Bi+, which is the same as the Bi OSe/G powder. At the
start of discharge, a few Li ions was inserted into the Bi OSe
interlayer, leading to the slight reduction of Bi+ with the Bi LIII -
edge shifting toward lower energy value, and the lattice expan-
sion of interlayers with the white-line intensity decreasing
gradually. The corresponding radical distribution of R-space
Printed by [Technische Universitat Ilmenau - 141.024.023.198 - /doi/epdf/10.1002/aenm.202100185] at [13/04/2021].
obtained by FTs of k-weighted Bi LIII -edge EXAFS spectra is
shown in Figure c. The first prominent peak at ≈. Å in Bi
LIII-edge EXAFS spectra corresponds to the Bi−O interaction
in the first shell, and the further peaks centered at . and
. Å are mainly ascribed to the Bi−Se and Bi–Bi interactions
in the further shells, respectively. The lattice expansion is also
revealed with the average Bi O bond and the average BiSe
bond slightly elongates upon discharge in the first discharge
region (I). The Se K-edge XANES spectra in Figured remains
almost unchanged in the first discharge region except for a tiny
shift toward lower energy side, indicating that the insertion pro-
cess that is a single solid-solution reaction to form Lix Bi OSe
intermediates does not give rise to new phase, which has little
eect on the local environment around Se absorber.
Figure e–g shows the XAS data obtained in the middle
discharge region (II). The conversion reaction occurs in the
middle discharge region (II), as the Bi L III-edge XANES spectra
show prominent shift toward lower photon energy values,
revealing the obvious decrease of the oxidation state of Bi in
Bi OSe. With the reduction of Bi+ during the conversion
reaction, the local coordination environment around the Bi
absorber is also obviously changed. The amplitude of the first
Bi–O shell decreases prominently due to the displacement of
reacting species with the consumption of Bi O bond during
conversion reaction. It is noted that the average Bi O bond
length decreases with the increase of discharge depth, and the
Bi–O peak disappears completely when the voltage approaches
.V, which shows the completion of the conversion reaction,
and the remaining discharge capacity should only be ascribed
to the alloying reaction. Furthermore, the break of Bi Se bond
peaked at ≈.Å does not show obvious decrease in peak inten-
sity, as the Bi Bi bond from the metallic Bi also contributes
to the peak at ≈.Å whose intensity would increase with the
generation of metallic Bi during the conversion reaction. The
generation of metallic Bi phase involved in the conversion reac-
tion can be revealed by the D. electrode who resembles the
Bi reference in peak shapes and positions in R-space but show
dierent peak areas, which may be owing to their dierences in
crystal disorder degree and particle size.[] The corresponding
Se K-edge spectra collected in the middle discharge region (II)
show obvious shift toward higher energy values, owing to the
break of Se Bi bond and the generation of lithium polysele-
nides (LiSe n; n≥) intermediates. It is reported that the shift of
Se K-edge toward higher photon energy value can be ascribed to
the reduced screening eect from the bonding between Se and
Li.[] More importantly, these in situ Se-XANES spectra cannot
be well fitted by linear combination fitting with the Bi OSe
spectrum and the Li Se spectrum, which further clarifies the
existence of multiple Li–Se intermediates.
©  Wiley-VCH GmbH
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Printed by [Technische Universitat Ilmenau - 141.024.023.198 - /doi/epdf/10.1002/aenm.202100185] at [13/04/2021].

Figure . a) Voltage profiles of the Bi O Se/G electrode for the first discharge process as LIB anodes. In situ b) Bi LIII -edge XANES, c) FTs of k -weighted
Bi LIII-edge EXAFS, and d) Se K-edge XANES spectra collected in the discharge region of (I). In situ e) Bi LIII -edge XANES, f) FTs of k-weighted Bi
LIII -edge EXAFS, and g) Se K-edge XANES spectra collected in the discharge region of (II). In situ h) Bi L III-edge XANES, i) FTs of k -weighted Bi LIII-
edge EXAFS, and j) Se K-edge XANES spectra collected in the discharge region of (III). Notation: D. represents the electrode discharged to .V.

Figure h–j shows the XAS spectra collected in the last
discharge region (III). The last discharge region (III) can be
assigned to the alloying reaction process, as the absorption
edge of Bi K-edge XANES spectra shift toward lower energy
slightly and the white-line intensity decreased gradually upon
further lithiation.[] The descending absorption Bi-edge indi-
cates the incorporation of lithium to the Bi lattice forming Li−Bi
alloying phases, which provides an electron shielding eect
on the Bi atoms, thus lowering the energy level required to
excite the Bi electrons from p to d states. [] The decreasing
white-line intensity indicates the decreased holes in d band
of Bi due to the charge transfer from Li to Bi. Moreover, the
fluctuated peak intensity in Figure i between  and . Å
represents the mixed contribution of Bi–Li and Bi Bi bond
from the Bi–Li intermediate phase. The corresponding Se
K-edge spectra show minor changes during this period, indi-
cating that the local structure around Se absorber does not
change significantly in this discharge region. The spectral dif-
ferences were caused by the partial dissolution of Li–Se inter-
mediates in the electrolyte before forming main end-phase
Li Se in the D. electrode.[]
Ex situ Bi O  Se/G electrodes, prepared by disassembling
the normal coin-cells at specific cut-o voltage during the first
one and a half cycle, were investigated by Bi L III-edge and Se
K-edge XAS in Figure . During the initial discharge process,
the Bi LIII -edge XANES spectra shift toward lower energy in
sequence with the increase of discharge depth, as shown in
Figure b. Bi+ was almost fully reduced to metallic Bi phase
in the discharge region (I and II) with a prominent shift of
the Bi-edge, then metallic Bi was further alloyed with Li in the
discharge region III with a minor shift of the Bi-edge. This is
further supported by the corresponding Fourier-transformed
Bi LIII-edge EXAFS spectra in Figure c, with dumping Bi–O
peak and overlapping/fluctuating Bi–Bi and Bi–Li peak. Inter-
estingly, the Se K-edge spectra in Figured shift toward lower
energy value when discharged to . V, possibly owing to the
formation of specific polyselenides at the start of conversion
reaction with the consumption of the insertion product of
LixBiO Se. After that, the Se K-edge spectra shift toward higher
energy value sequentially with the increase of discharge depth,
owing to the continuous combination of Li to Se giving rise to
the formation of multiple lithium polyselenides (LiSen; n ≥)
intermediates.[]
During the initial charge process, the Bi LIII-edge spectra shift
toward higher energy value continually (Figure e). The charge
process can be an inverse process of the discharge process,

Adv. Energy Mater. ,   ( of ) ©  Wiley-VCH GmbH
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Printed by [Technische Universitat Ilmenau - 141.024.023.198 - /doi/epdf/10.1002/aenm.202100185] at [13/04/2021].

Figure . a) Voltage profiles of the Bi O Se/G electrode for the first one and half cycles as LIB anodes. Ex situ b) Bi L III-edge XANES, c) FTs of k  -weighted
Bi L III-edge EXAFS, and d) Se K-edge XANES spectra collected in the first discharge process involving I, II, and III region. Ex situ e) Bi LIII -edge XANES,
f) FTs of k -weighted Bi L III-edge EXAFS, and g) Se K-edge XANES spectra collected in the first charge process involving IV and V region. Ex situ h) Bi
L III-edge XANES, i) FTs of k -weighted Bi LIII-edge EXAFS, and j) Se K-edge XANES spectra collected in the second discharge process involving VI, VII,
and VIII region. Notation: D. represents the electrode discharged to .V. DC. represents the electrode fully discharged then charged to .V.
DCD. represents the electrode discharged fully, charged fully, and then discharged to . V.

experiencing the typical de-alloying-recombination process. How- the pristine electrode and the fully charged electrode, meaning
ever, the fully charged product did not come back to the initial that the local structure of the pristine electrode has changed after
state with large dierences in Bi L III-edge XANES spectra between a complete cycle. This is further supported by the corresponding

Adv. Energy Mater. ,   ( of ) ©  Wiley-VCH GmbH
www.advancedsciencenews.com www.advenergymat.de

Printed by [Technische Universitat Ilmenau - 141.024.023.198 - /doi/epdf/10.1002/aenm.202100185] at [13/04/2021].

Figure . Potential-resolved in situ a) Bi LIII-edge XANES spectra and c) Se K-edge XANES spectra of the Bi  OSe/G electrode for PIBs collected during
the initial discharge process.

Fourier-transformed Bi L III-edge EXAFS spectra in Figuref. The but the side-reactions involving the multiple polyselenides
local structure of the pristine electrode has not recovered when (i.e., LiSe  and LiSe n [n≥]) cannot be neglected.[,]
fully charged although obvious Bi–O peak can be observed in the During discharge,
fully charged electrode (DC.). This irreversibility can be ascribed
to the altered disorder degree, variable particle sizes, and the so- Bi2 O2 Se + xLi+ + xe− → Li xBi2 O2 Se (Insertion ) ()
called shuttle eect (also observed in Li–S battery) resulting from
the dissolution of lithium polyselenides intermediates in the
electrolyte.[,] Regarding the Se K-edge spectra of the electrode ix Bi2 O2 Se + (6 − x )Li + + (6 − x )e −
collected upon charging, the Se K-edge XANES spectra remains ()
→ 2Bi + 2Li2 O + Li2 Se ( Conversion )
almost unchanged even though the electrode was charged to .V,
indicating that there is almost no local structure change and charge
transfer around Se absorber during this period (Figureg).There- i+ Li + + e − → LiBi ( Alloying) ()
fore, in the charge region IV, the LiSe was not involved in the elec-
trochemical reaction. In the charge region V, the Se K-edge spectra
start to shift toward lower energy value when charged to .V due LiBi + 2Li + + 2e − → Li 3Bi (Alloying ) ()
to the partial extraction of Li from LiSe, and show significant shift
when charged to  V due to the recombination process and the
possible extraction process. During charge,
During the nd discharge process, the Bi LIII -edge spectra
shift toward lower energy value due to the reduction of Bi+ Li3 Bi → Bi +3Li + +3e − (Dealloying ) ()
ion and the further alloying of metallic Bi with Li (Figureh).
Meanwhile, the Bi–O peak disappeared and the overlapped
Bi–Bi and Bi–Li peak fluctuated with the increase of discharge Bi + 2Li2 O + Li2 Se → Bi2 O2 Se + 6Li+ + 6e− ( Recombination)
depth (Figurei). Moreover, the Se K-edge spectra shift toward
higher energy side, indicating the formation of a series of ()
lithium polyselenides intermediates upon nd discharging Apart from the reaction mechanism of LIBs, the reaction
(Figurej). mechanism of PIBs based on the BiO Se electrode was also
As shown in Figure S, Supporting Information, the Bi investigated by potential-resolved in situ Bi LIII-edge XANES
L III-edge XANES spectrum of the fully discharged product spectra and Se K-edge XANES spectra during the initial dis-
in the nd discharge process almost overlapped with the charge process (Figure ). Similar to the LIBs, the Bi LIII -edge
spectrum of the fully discharged product in the st discharge XANES spectra show obvious edge shift toward higher energy
process, indicating that the same Li Bi product was formed at side and decreased white-line intensity upon discharge, due to
the end of the st discharge and nd discharge. However, the the reduction of Bi+ and the potassiation of the generated Bi
Se K-edge XANES spectrum of the nd fully discharged elec- phase. The corresponding Se K-edge spectra show edge shift
trode show considerable dierence with the spectrum of the st toward higher energy side upon discharge, due to the break
fully discharged electrode, which can be owing to the possible of Bi–Se and the formation of K–Se intermediate phases. It is
dissolution of Li Se in the electrolyte. noted that the full potassiation phases regarding Se anion in
Therefore, the main charging–discharging process of the BiOSe may involve K Se, K Se, and K Se, which can be sim-
Bi OSe electrode for LIBs can be as proposed as follows,[,] ilar to MoSe as anodes for PIBs.[]

Adv. Energy Mater. ,   ( of ) ©  Wiley-VCH GmbH
www.advancedsciencenews.com
. Conclusion
In summary, the electrochemical mechanisms of the BiOSe/G
electrode for LIBs and PIBs were studied by using ex situ and
potential-resolved in situ XAS, with the valence state change,
charge transfer, and local atomic environment change of elec-
trodes probed in detail by Bi L III-edge and Se K-edge XAS. A typ-
ical insertion–conversion–alloying process was demonstrated in
the Bi OSe/G electrode during lithiation, and the dissolution
of Li–Se intermediate phases in the electrolyte were revealed
in this conversion-type electrode. We believe that these results
will not only help deepen the understanding of the complicated
reaction mechanism of ternary metal chalcogenides but provide
a new insight into designing high-performance conversion-type
anodes by suppressing the possible shuttle-eect originating
from polyselenides or polysulfides based on optimized electro-
lytes and electrode structures.
. Experimental Section
Materials Preparation: Bi OSe was grown by comelting Bi O powder
(.%), Bi beads (.%), and Se powder (.%) in an evacuated
quartz ampoule with a molar ratio of ::. The sealed ampoule was
then heated at °C for h with a heating rate of °Cmin− in a tube
furnace. After it was naturally cooled down, the sealed ampoule was cut
o by a glass cutter and brown BiO Se powders were collected.
To prepare Bi O Se/G composite, the as-synthesized Bi O Se powder
( g) was ball-milled with synthetic graphite (. g) in a planetary ball
mill at rmin− for h.
To prepare Bi O Se/super P composite, the as-synthesized Bi  OSe
powder (g) was ball-milled with super P (.g) in a planetary ball mill
at rmin − for h.
Structural Characterizations: The crystallographic information was
probed by a GBC MMA diractometer with a Cu Kα source (λ=. Å)
at a scan rate of ° min− at room temperature, with working voltage
and current set as  kV and  mA, respectively. The structures and
morphologies of these samples were probed by field emission scanning
electron microscopy (JEOL-) and TEM (JEOL-).
Electrochemical Characterizations: The working electrode was made by
the active material, super P, and carboxymethyl cellulose in a mass ratio
of ::. After dispersing the mixed powders (::) in deionized
water by using planetary ball mill, the resultant slurries were coated
on copper foils and then vacuum-dried in a vacuum oven at  °C
overnight. After that, the dried electrode was cut into small discs and
pressed for min under MPa.
CR coin-cells of LIBs were assembled in an argon-filled glove
box (O  and H O level <. ppm), where the as-synthesized electrode
was used as working electrode, metallic Li foil was used as both counter
and reference electrode, Celgard (product ) film was served as
separator, and a mixture of .  LiPF  in dimethyl carbonate (DMC)
and fluoroethylene carbonate (wt%) was employed as electrolyte. The
galvanostatic discharge/charge test was performed by using a Land
CTA battery testing system within the voltage window of .–.V
at room temperature. CV test was performed over the voltage range
from .–. V at a scan rate of . mV s − using a Biologic VPM
electrochemical workstation.
CR coin-cells of PIBs were assembled in an argon-filled glove
box (O  and H O level <. ppm), where the as-synthesized electrode
was used as working electrode, metallic K foils was employed as both
counter and reference electrode, glass microfiber (Whatman) was
served as separators, and a mixture of .  solution of potassium
bis(fluorosulfonyl)imide (KFSI) salt in DMC solvent was applied as
electrolytes. The galvanostatic discharge/charge test was performed by
using a Land CTA battery testing system under the voltage window
Adv. Energy Mater. ,   ( of )
www.advenergymat.de
between . and . V at room temperature. CV test was performed
over the voltage range from . to . V at a scan rate of . mV s−
using a Biologic VPM electrochemical workstation.
Synchrotron X-Ray Absorption Spectroscopy: Synchrotron XAS
experiments were conducted at the wiggler XAS Beamline (ID) in
Hutch B in Mode  at the Australian Synchrotron (Melbourne, Australia)
using a Si () double-crystal monochromator. These powder samples,
ex situ electrodes and in situ customized coin-cells were all probed
by both Bi L III-edge (  eV) and Se K-edge (  eV) XAS in
transmission mode under room temperature, where Bi O foil and Se foil
were measured synchronously as references for each scan, respectively.
Printed by [Technische Universitat Ilmenau - 141.024.023.198 - /doi/epdf/10.1002/aenm.202100185] at [13/04/2021].
Potential-resolved in situ experiment was conducted by recording Bi
L III-edge and Se K-edge spectra alternatively in one customized coin-
cell at a selected voltage. These customized coin-cells used here were
the same as with the authors′ previous work,[] but the electrode had
a high mass loading of ≈mgcm− and used carbon paper as current
collector. Typically, the positive cap, negative cap, and spacer were dug
with a hole (D=mm) at first to facilitate the beam to go through, then
the holes on the caps were sealed by Kapton tape with the help of super
glue to ensure a closed environment. To prepare the pellets of Bi O Se,
Bi O Se/G, and Bi, the powder was diluted with cellulose in appropriate
amount and well-ground in agate mortar to ensure even particle size
and good homogeneity, thus avoiding distortions to the XAS spectra. At
last, the mixed powder was pressed into a disc (D=mm) by a manual
pellet press. The amount of powder used was determined by satisfying
an optimum absorption edge jump for transmission mode. The ex
situ samples were prepared by disassembling the normal coin-cells at
dierent charge states in Ar-filled glove box and then sealed with Kapton
tapes for further use.
Data normalization, background removal, calibration and alignment,
merging, and parameter constraint were conducted by using the Athena
program in the Demeter package running IFEFFIT computation code
following standard procedures.[] The EXAFS spectrum based on Bi L III-
edge was first converted to k-space, which was then multiplied by k to
weight the oscillations of k-space (kχ[k]), whilst the EXAFS spectrum
based on Se K-edge was first converted to k-space (χ[k]), which was
then multiplied by k to amplify the oscillations in upper end of k-space
(k χ[k]). FTs of the k - or k -weighted χ(k) signal were performed to
provide radical distribution information around the absorbed atom
with uncorrected phase shift. The EXAFS data were simulated with the
Artemis program using the FEFF algorithm. The Bi LIII-edge spectra
of the powder samples were fitted with k, k, and k  weighting over a
k-range from . to . Å− and an R-range from . to . Å, whilst
the Se K-edge spectra of the powder samples were fitted in k, k , and
k weighting over a k-range from . to .Å− and a R-range from .
to .Å. Major EXAFS parameters, including the coordination distance
(R + ∆R), coordination number (N), amplitude reduction factor (S ),
Debye–Waller factor (σ), energy shift (∆E ), and the R-factor, could be
obtained by fitting by using the Artemis program. S  were fixed to .
and . for Bi LIII -edge and Se K-edge spectra, respectively, based on
the S value obtained from fitting the Bi O foil reference and Se foil
reference. The error range of the coordination number (N) was below
%, and the uncertainty of coordination distance was below .Å, and
all R-factors were controlled to be below .%.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
Financial support from the Australian Research Council (ARC)
(DP, FT, and DP) and National Natural
Science Foundation of China (U) is gratefully acknowledged. The
©  Wiley-VCH GmbH
www.advancedsciencenews.com
authors also would like to thank AINSE Limited for providing financial
assistance (Award-PGRA). Part of this research was undertaken on the
X-ray Absorption Spectroscopy beamline and the Powder Diraction
beamline at the Australian Synchrotron, and the Neutron beamline at
the Australian Centre for Neutron Scattering, all part of ANSTO. The
authors thank the Electron Microscopy Centre (EMC) at the University of
Wollongong for the electron microscopy characterizations.
Conflict of Interest
The authors declare no conflict of interest.
Data Availability Statement
Research data are not shared.
Keywords
batteries, Bi O Se, in situ investigations, X-ray absorption spectroscopy
Received: January , 
Revised: February , 
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