RESEARCH ARTICLE
Supercapacitor
Diffusionless-Like Transformation Unlocks
Pseudocapacitance with Bulk Utilization: Reinventing Fe2O3
in Alkaline Electrolyte
Taowen Dong, Wencai Yi, Ting Deng, Tingting Qin, Xianyu Chu, He Yang, Lirong Zheng,
Seung Jo Yoo, Jin-Gyu Kim, Zizhun Wang, Yan Wang, Wei Zhang* , and Weitao Zheng*
Energy density can be substantially raised and even maximized if the bulk of
an electrode material is fully utilized. Transition metal oxides based on
conversion reaction mechanism are the imperative choice due to either
constructing nanostructure or intercalation pseudocapacitance with their
intrinsic limitations. However, the fully bulk utilization of transition metal
oxides is hindered by the poor understanding of atomic-level conversion
reaction mechanism, particularly it is largely missing at clarifying how the
phase transformation (conversion reaction) determines the electrochemical
performance such as power density and cyclic stability. Herein, α-Fe2O3 is a
case provided to claim how the diffusional and diffusionless transformation
determine the electrochemical behaviors, as of its conversion reaction
mechanism with fully bulk utilization in alkaline electrolyte. Specifically, the
discharge product α-FeOOH diffusional from Fe(OH)2 is structurally
identified as the atomic-level arch criminal for its cyclic stability
deterioration, whereas the counterpart δ-FeOOH is theoretically diffusionless-
like, unlocking the full potential of the pseudocapacitance with fully bulk
utilization. Thus, such pseudocapacitance, in proof-of-concept and termed as
conversion pseudocapacitance, is achieved via diffusionless-like
transformation. This work not only provides an atomic-level perspective to
reassess the potential electrochemical performance of the transition metal
oxides electrode materials based on conversion reaction mechanism but also
debuts a new paradigm for pseudocapacitance.
T. Dong, Dr. T. Deng, Dr. T. Qin, X. Chu, H. Yang, Z. Wang, Dr. Y. Wang,
Prof. W. Zhang, Prof. W. Zheng
State Key Laboratory of Automotive Simulation and Control, and School
of Materials Science & Engineering, Key Laboratory of Automobile
Materials MOE, and Electron Microscopy Center, and International Center
of Future Science, Jilin University, Changchun 130012, China
E-mail: wtzheng@jlu.edu.cn
Dr. W. Yi
Laboratory of High Pressure Physics and Material Science (HPPMS), School
of Physics and Physical Engineering, Qufu Normal University, Qufu
Shandong 273165, China
Prof. L. Zheng
Beijing Synchrotron Radiation Facility, Institute of High Energy Physics,
Chinese Academy of Sciences, Beijing 100049, China
Energy Environ. Mater. 2021, 0, 1–10 1 © 2021 Zhengzhou University.
1. Introduction
As a promising pseudocapacitive material,
transition metal oxides (TMOs) have attracted
considerable attention due to their potential to
simultaneously harvest high energy and power
density.[1–4] Most of TMOs store charges via
surface redox reaction (redox pseudocapaci-
tance) or ion bulk (de)intercalation (intercala-
tion pseudocapacitance).[3,5] However, redox
pseudocapacitance suffers from high costs and
low-specific capacitance (Cs) for the typical
RuO2
xH2O[6] and MnO2,[7] respectively.
Intercalation pseudocapacitance occurs only
with layered or tunnel structures for ion stor-
age and diffusion.[2,8] Therefore, toward
higher energy density (E = 1/2 CsV2, where
Cs is specific capacitance and V is potential
window),[9] how to maximize Cs with high
response rate and excellent stability is a popu-
lar challenge for the community of pseudoca-
pacitive energy storage. Undoubtedly, the fully
bulk utilization at atomic level of electrode is
an essential and ultimate direction in maxi-
mization Cs for pseudocapacitance.
To meet the optimum pseudocapacitance
with fully bulk utilization, as sketched in Fig-
ure 1, there are two choices besides the interca-
lation. One is constructing nanostructure,[10,11]
such as observed nanosize effect in LiCoO2,[12] approaching to the
wholly pseudocapacitive response with bulk reaction via shortening dif-
fusion distance of electrolyte ions along with hugely reducing size of
Dr. S. J. Yoo, Dr. J.-G. Kim
Electron Microscopy Research Center, Korea Basic Science Institute, Daejeon
34133, South Korea
Prof. W. Zhang
Wuhan National Laboratory for Optoelectronics, Huazhong University of
Science and Technology, Wuhan 430074, China
IKERBASQUE, Basque Foundation for Science, Bilbao 48013, Spain
E-mail: weizhang@jlu.edu.cn
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/eem2.12262.
DOI: 10.1002/eem2.12262
electrode materials. However, the nanosize issue suffers from some
undesirable electrode reaction, aggregation, and complicated prepara-
tion.[10] The other is that electrode storing charge aims at conversion
reaction, that is, undergoing reversible redox reaction via phase trans-
formation. Unfortunately, most of such materials yield low power den-
sity and rapid stability deterioration such as Fe2O3 and Bi2O3 in alkaline
electrolyte;[13,14] there are also exceptions such as Co(OH)2 and Ni
(OH)2 demonstrating high energy and power density and excellent sta-
bility.[15] Nowadays, although in the popular premise of widespread
realization of constructing nanostructure, materials with conversion
reaction mechanism show very different electrochemical signatures.
This phenomenon inspires us to pinpoint the atomic-level occurrence
and seek the true fingerprint underlying this conversion reaction mech-
anism (phase transformation). As a result, it will lead to achieve pseu-
docapacitance with fully bulk utilization at atomic level for materials
without layered or tunnel structures.
From a physics point of view, a conversion reaction mechanism
(phase transformation) can be described as diffusional and diffusionless
styles.[23,24] For such a motif of energy storage, the former requires a
long-range diffusion of atoms or ions; low power density and poor
cyclic stability result usually from time-dependent transformation and
non-memory massive rearrangement of atoms, whereas diffusionless or
diffusionless-like transformation does not require long-range diffusion
and only small atomic shifts or adjustments;[25] such non-diffusion
controlled rapid and memory process is expected to afford high power
density and excellent cyclic stability. Thus, it has a very positive impli-
cation that pseudocapacitance with fully bulk utilization based on con-
version reaction mechanism may be factually contributed via
diffusionless (-like) transformation.
Based on the aforementioned exploration, we prepared α-Fe2O3
(considerably abundant and environmentally friendly in the earth) by
using green and simple hydrothermal method. On basis of the observa-
tion of fully bulk utilization and prevailing electrochemical and ex situ
structural characterization techniques, the conversion reaction mecha-
nism (phase transformation) underlying fully bulk utilization is liber-
ated. As a consequence, the Cs of our prepared nanowire (NW)-Fe2O3,
in 1 M KOH, reaches 989 F g−1 close to its theoretical one. Such conver-
sion reaction mechanism is identified as Fe2O3 → Fe(OH)2 (charge) →
α-FeOOH (discharge). Particularly, the discharge conversion reaction
between Fe(OH)2 and α-FeOOH in a diffusional style is structurally
identified at atomic level as arch criminal for its cyclic stability deteriora-
tion, whereas the conversion reaction between Fe(OH)2 and δ-FeOOH
is theoretically demonstrated as one fundamental strategy to reverse its
poor cyclic stability by using density functional theory (DFT) calcula-
tions. The diffusionless-like transformation between the two prevents
massive random rearrangement of atoms while maintaining a high
chemical valence reversibility. That is, we give a proof-of-concept that a
pseudocapacitance with fully bulk utilization is based on conversion
reaction mechanism, reasonably termed as conversion pseudocapacitance
and thereof debuts as a new paradigm of pseudocapacitance.
2. Results and Discussion
2.1. Structural and Electrochemical Characterizations of NW-
Fe2O3
As shown in schematic illustration (Figure S1a), NW-Fe2O3 was pre-
pared via a hydrothermal reaction and following calcining in N2.[26]
The morphology was characterized by scanning electron microscopy
(SEM). The SEM images (Figure 2a, Figure S1b) indicate that NW-
Fe2O3 is uniformly spread on the carbon fiber paper (CFP). The length
and diameter of nanowires are ~700 and 20 nm, respectively. The
results of energy-dispersive X-ray spectroscopy (EDS) elemental map-
ping (Figure 2a) exhibit a uniform distribution of Fe and O elements.
To verify the phase structure of NW-Fe2O3, we conducted X-ray

Figure 1. Three strategies toward optimum pseudocapacitance with fully bulk utilization. a) Intercalation pseudocapacitance achieves bulk utilization via ion
(de) intercalation within materials, such as observed in TiO2(B),[16] T-Nb2O5,[17] Ti3C2Tx MXene,[18,19] LaMnO3[20] and MoO3-x,[21] but limited to layered or
tunnel structures. b) Constructing nanostructure achieves bulk utilization via enlarging electrode/electrolyte contact area and shortening ion diffusion
distance, such as cases in LiCoO2[12] and Fe2O3,[22] but limited to its side reaction and challenging preparation. c) Conversion reaction based on diffusionless
(-like) transformation achieves fully bulk utilization via military transformation with structural memory, free of long-distance diffusion and massive atomic
rearrangement.

Energy Environ. Mater. 2021, 0, 1–10 2 © 2021 Zhengzhou University.

diffraction (XRD) and Raman analysis. From the XRD pattern (Fig-
ure 2b), α-Fe2O3 is indexed (PDF #33-0664, space group: R3ch
(167)) except for the CFP marked in yellow circles. As shown by the
strongest (110) peak of NW-Fe2O3, <110> is the preferentially grow-
ing direction. Raman spectrum (Figure 2b inset right) contains the
peaks at 217, 480, and 1369 cm−1 indexed to A1g vibration mode, and
the rest peaks are assigned to E1g vibration mode, which is completely
coincident with the reported α-Fe2O3.[27] The hexagonal close-packed
unit cell of α-Fe2O3 is inserted in upper left of Figure 2b. It is a corun-
dum type rather than layered or tunnel structure. The prepared NW-
Fe2O3 was furtherly characterized by using high-resolution transmis-
sion electron microscopy (HRTEM). In Figure 2c, one can see the lat-
tice fringe is measured as 0.252 nm indexed to α-Fe2O3 (110) plane,
which is in good agreement with the aforementioned XRD results. The
corresponding fast Fourier transform (FFT) pattern along the [001]
zone axis shows the exposed {110} planes. The inverse fast Fourier
transform (IFFT) pattern is inserted in Figure 2c, and one can see the
abundance of dislocations. X-ray photoelectron spectroscopy (XPS) was
used to investigate the surface chemical bonding and valence state of
NW-Fe2O3. Fe 2p spectrum (Figure S1e) contains two main peaks
located at 711.2 and 725.0 eV assigned to Fe 2p3/2 and Fe 2p1/2,
respectively. Specially, the satellite peak at 719.2 eV is a typical charac-
ter of trivalent iron.[28] O1s spectrum (Figure S1f) is deconvoluted into
two peaks at 530.3 and 531.5 eV corresponding to O2− and Fe–O–
H,[27] respectively.
For the electrochemical behaviors of NW-Fe2O3, the cyclic voltam-
metry (CV), galvanostatic charge/discharge (GCD), rate, and cycle sta-
bility were obtained via a three-electrode system within 1 M KOH. CV
(a) (b)
(d) (e)
Figure 2. Structural and electrochemical characterizations of NW-Fe2O3. a) SEM images and EDS elemental mapping, b) XRD pattern with insert of crystal
structure (left, red, and blue ball represent O and Fe, respectively) and Raman spectrum (right), c) HRTEM image with inserted corresponding FFT and IFFT
patterns, d) CV curves at different scan rates, e) GCD curves at different current densities, f) The competition relationship between Cs and cyclic stability.
Energy Environ. Mater. 2021, 0, 1–10
curves (Figure 2d) at different scan rates display redox peaks at ca.
−0.7 and −1.0 V within a potential window of 1.2 V. The wide sepa-
ration exists between anodic peak current (ipa) and cathodic peak cur-
rent (ipc) (0.3 V at 5 mV s−1), and the ratio of ipa to ipc > 1. Such
features imply that the electrode reaction is a quasi-reversible process
and a conversion reaction occurs during this process.[29–31] Such con-
version reaction mechanism is the motif of next section. ipa and ipc,
respectively, move toward negative and positive position along with
increasing scan rate, which results from electrode polarization at high
scan rates.[32,33] Such polarization emergence implies that the electro-
chemical process is diffusion controlled. As demonstrated in Figure 2e,
GCD curves at different current densities show a pair of plateaus at
−0.9 and −0.7 V in charge and discharge processes, which is in accor-
dance with the CV results. GCD curves also exhibit a poor coulombic
efficiency (77% at current density of 2 A g−1), that is, the electrode
reaction is not a totally reversible one. The reason for this irreversibility
will be also investigated in next section. The Cs at current density of
2 A g−1 reaches 989 F g−1, almost closing to the theoretical one
(1008 F g−1, Cs = (n × F)/(M × V), where n is the number of elec-
tron transferred and is equal to 1, F is Faradays constant, M is molecular
weight and V is the potential window of −1.2 to 0 V). Such high Cs
indicates a fully bulk utilization of electrode material. We should not
rule out the positive influence of nanowire morphology with high
aspect ratio and existence of dislocation demonstrated in last paragraph
on this high Cs, but the conversion reaction mechanism really func-
tions. Unfortunately, as shown in Figure S2b, the cyclic stability rapidly
degrades, that is, the Cs reduces to 173 F g−1 merely after five cycles.
Meanwhile, in Figure 1f and Figure S3, the Cs and cyclic stability show
(c)
(f)
3 © 2021 Zhengzhou University.
a competition relationship with narrowing of potential window. Thus,
the high Cs and unacceptable cyclic stability inspire us to investigate the
conversion reaction mechanism underlying the fully bulk utilization.
2.2. Fully Bulk Utilization Toward High Specific Capacitance:
Conversion Reaction Mechanism and Cyclic Stability
Deterioration
Several ex situ structural and chemical state characterization techniques
such as SEM, synchrotron X-ray diffraction, TEM and electron energy
loss spectroscopy (EELS), X-ray absorption spectroscopy (XAS), and XPS
were used to shed light on the conversion reaction mechanism and
pinpoint the cause of cyclic stability deterioration (as marked in the
Figure 3a, nine points (o-g) are selected). This conversion reaction
mechanism is expressed as Fe2O3 → Fe(OH)2 (charge) → α-FeOOH
(discharge), and the discharge conversion reaction Fe(OH)2 → α-
FeOOH, in particular the discharge product FeOOH adapted as α phase,
is identified as the atomic-level arch criminal for its cyclic stability dete-
rioration.
SEM is a powerful tool for the clarification of morphology evo-
lution during charge and discharge processes. As illustrated in Fig-
ure 3a inset and Figures S4 and S5, the original nanowires totally
evolve to hexagonal nanoflakes with smooth surface during the
first charge process. The gradual emergence of nanoflakes also indi-
cates that this charge process is a diffusional transformation

Figure 3. Conversion reaction mechanism of NW-Fe2O3. a) The first charge/discharge process with selected states, insets are SEM and HRTEM images for
charge state d and discharge state g, and the roadmap of crystal structure evolution and the illustration of morphological evolution, b) Synchrotron X-ray
diffraction patterns at state d, e and g, c) XANES spectra at state b, d, and g, d, e) XPS Fe 2p and O 1s data at selected states, respectively, f, g) EELS of Fe
L3,2 and O K edges, respectively.

Energy Environ. Mater. 2021, 0, 1–10 4 © 2021 Zhengzhou University.

involved with nucleation and growth, while the nanoflakes either
reserve with rough surface or partially transfer to non-oriented
nanorods (Figure 3a discharge state) during the following dis-
charge process. The new nanorods are ~350 and 50 nm in length
and width, respectively. Although smaller than the original nano-
wires, they are similar to hexagonal nanoflakes (Figure 3a charge
state), indicating those nanorods are rooted from the charge
product nanoflakes. In addition, the coexistence of nanorods and
nanoflakes in discharge step implies that not all the charge product
hexagonal nanoflakes are discharged. The change in morphologies
confirms that a bulk reaction occurred in the electrode. Meanwhile,
visually, such morphology irreversibility means the poor cyclic sta-
bility of NW-Fe2O3. Herein, the underlying crystal structural evo-
lution should be dissected at atomic level.

(a) (a1) (a2)

(b) (b1) (b2)

(c) (c1) (c2)

(d) (d1) (d2)

Figure 4. Ex situ HRTEM images for the first charge process from state a to d. a–a2) The electrode material Fe2O3 remains, b–b2) Fe(OH)2 and Fe3O4 were
observed besides Fe2O3, c–c2) Fe(OH)2 was observed in nanowires besides in hexagonal nanoflakes, d–d2) FeO was observed besides Fe(OH)2.

Energy Environ. Mater. 2021, 0, 1–10 5 © 2021 Zhengzhou University.

 (e) (e1)
(f) (f1)
(g) (g1)
Figure 5. Ex situ HRTEM images for the first discharge process from state e to g. e–e2) Fe2O3 was detected besides FeO and Fe(OH)2, f–f2) α-FeOOH was
firstly observed besides Fe(OH)2 and Fe2O3, g–g2) Coexistence of Fe(OH)2 and α-FeOOH was observed.
HRTEM and synchrotron X-ray diffraction were used to furtherly
identify the structural evolution. It was found,
1 As shown in Figure 3a, inset charge state d, the charge product
hexagonal nanoflakes is identified as Fe(OH)2 by using
HRTEM.[34,35] The single crystal of Fe(OH)2 was observed and
the interplanar spacing of (100), (010), and (−110) is
0.255 nm. The interplanar spacing of these planes is smaller
than 0.282 nm from the standard PDF #13-0089. However, the
diffraction angle of this interplanar spacing of 0.255 nm is cal-
culated to 35.1°, consistent with the result of synchrotron X-ray
diffraction (Figure 3b). Such deviation may originate from the
loss of water molecules induced by ex situ measurement envi-
ronment, which results in the shrinking of lattice spacing.[36]
Also, we cannot exclude some unknown factors. In charge state
d, FeO (PDF #49-1447) was also detected, as shown in Fig-
ure 4d1, and the interplanar spacing of (100), (010), and
Energy Environ. Mater. 2021, 0, 1–10
(e2)
(f2)
(g2)
(−110) is measured as 0.227 nm, confirmed by the results of
synchrotron X-ray diffraction (Figure 3b), while the majority is
Fe(OH)2 based on the intensity of synchrotron X-ray diffraction
and the statistics from HRTEM images. Besides, it should be
emphasized that Fe0 was not detected in state d. The more
detailed structural evolution analyzed via HRTEM is demon-
strated in Figure 4.
2 As shown in Figure 3a inset discharge state g, the coexistence of
α-FeOOH (PDF #29-0713) and Fe(OH)2 was detected, which
agrees with the results of synchrotron X-ray diffraction in Fig-
ure 3b. The more detailed structural evolution during discharge
process is described in Figure 5. Fe2O3 was also detected in dis-
charge process (Figure 5f2). The crystal growth direction of this
Fe2O3 is <012>, confirming that the Fe2O3 as side-reaction pro-
duct is obtained. While the conversion to α-FeOOH dominated
the discharge process according to the synchrotron X-ray diffrac-
tion (Figure 3b), indicating the process is diffusional transfor-
mation controlled without structural memory.
6 © 2021 Zhengzhou University.
 (a) (b)
(d) (e)
Figure 6. Cyclic stability deterioration mechanism of NW-Fe2O3. a) SEM images for state 5d and 5g, respectively, both states include the nanoflakes and
nanorods, b, c) HRTEM images and corresponding FFT for state 5d and 5g, respectively, d) XANES spectra at state 5d, 5g, 10d, and 10g, e) XPS Fe 2p data at
selected states, f) Fe(OH)2 conversion to α-FeOOH in diffusional style leads to bulk utilization fading and irreversibility of chemical valence if iron.
3 The roadmap of crystal structural evolution is collected in Fig-
ure 3a inset. Combined with the analysis of electrochemical
behavior of NW-Fe2O3, this structure analysis indicates the con-
version reaction process (charge and discharge) is a diffusional
transformation controlled. The discharge product is FeOOH
instead of α-Fe2O3, further confirming the process is non-
structural memory. The cyclic stability of this conversion reac-
tion mechanism must be unsatisfactory (Figure S2b).
X-ray absorption near-edge structure spectra (XANES) and XPS
experiments were conducted to further investigate the chemical valence
state during the conversion reaction process. As plotted in Figure 3c,
XANES spectra indicate that the valence state of iron reduces from Fe3+
to Fe2+ during charge process, while Fe2+ is not fully oxidized to the
expected Fe3+,[37] demonstrating that the charge product Fe(OH)2 is
difficult to be oxidized to α-FeOOH. The irreversibility of chemical
valence state corresponds to the low coulombic efficiency, which is in
accordance with the foregoing structural and electrochemical analysis.
As shown in Figure 3d, XPS Fe 2p data also support this conclusion of
valence state change. From state o to d, the peaks of Fe 2p move to
lower bonding energy suggesting that the state valence reduces from
Fe3+ to Fe2+.[38] Whereas in discharge process, Fe 2p data demonstrate
the area of Fe3+ increased, but the Fe2+ still was detected, which is in
accordance with XANES results. As plotted in Figure 3e, the peaks for
Fe–O–H in XPS O 1s are boosted during charge process (state b–d) and
maintain during discharge process, corresponding to the formation of
the Fe(OH)2 and α-FeOOH,[39,40] respectively. EELS is considered as an
effective method with high spatial resolution to investigate the chemical
valence state. As shown in Figure 3f, compared with the state o, the Fe
L3 peaks at state c, charge state d and discharge state g shift to lower
Energy Environ. Mater. 2021, 0, 1–10
(c)
(f)
energy, while Fe L2 peaks move to higher energy. The energy separa-
tion (ΔE) and Fe L3/L2 intensity ratio are two main parameters to ana-
lyze the EELS data.[41–43] Between state o and discharge state g, the ΔE
increases in charge states and then decreases in discharge. Although the
Fe L3/L2 ratio at state d is a little higher than that of state c, as a whole,
it decreases at first and then increases. Both imply that the valence state
of Fe decreases in charge process and then increases in discharge pro-
cess rather than totally reversible. For the reference, Figure 3g shows
the EELS of oxygen in these states. These chemical valence state analyses
also further confirm it is the diffusional transformation results in the
reversibility of chemical valence state during the energy storage pro-
cess.
Thus, we not only liberate the dominant conversion reaction mecha-
nism from fully bulk utilization but also identify this process is a diffu-
sional transformation and unfavorable for its electrochemical behaviors.
Although the NW-Fe2O3 prepared in nanosize, the conversion reaction
in diffusional style enables an unacceptable cyclic stability due to the
massive rearrangement of atoms and structural evolution without mem-
ory. For the detailed description and discussion on this conversion reac-
tion mechanism, one can see in the Data S1.
Further, we pinpoint the atomic-level arch criminal of cyclic stability
deterioration for ultimate harvesting pseudocapacitance with fully bulk
utilization. As shown in Figure S2b inset, the GCD curve exhibits that
the charge and discharge plateau disappear along with the increase in
cycles. Therefore, we investigated the typical fifth charge/discharge
process, as illustrated in Figure S8, and made a comparison with the
first one. As demonstrated in Figure 6a and Figures S9–S12, SEM
images exhibit that the morphology is a hybrid of randomly distributed
nanorods and non-hexagonal nanosheets at all states. In Figure 6b,c
and Figures S13–15, HRTEM images show that all states include both
7 © 2021 Zhengzhou University.
 To be sure, the conversion reaction mechanism of
Fe2O3 + 2e− + 3H2O → 2Fe(OH)2 + 2OH−-
→ 2α-FeOOH + 2e− + 2H2O has two sides on
one coin. It enables driving fully bulk utilization
for high energy density. However, the discharge
conversion reaction, particularly its product α-
FeOOH, often leads to a rapid cyclic stability dete-
rioration, ascribed to the diffusional transforma-
tion. Obviously, it is of great interests for the
Renaissance of this discharge process, definitely
approaching to our aim.

2.3. Diffusionless Transformation Revitalizes

Conversion Reaction Mechanism for Excellent
Cyclic Stability: Conversion Pseudocapacitance

To revitalize this discharge process for the desired sta-

bility, we must maintain the bulk conversion reaction
and realize the reversibility of chemical valence of
iron. It may be an essential pathway to apply diffu-
sionless transformation into the discharge process.
Herein, the crystal structure of FeOOH in α-, β-, γ-
and δ- is carefully studied.[47–49] As illustrated in Fig-
ures S16 and S17, δ-FeOOH is focused on due to its
similar crystal structure to Fe(OH)2. We note that the
conversion from Fe(OH)2 to δ-FeOOH can be con-
Figure 7. Diffusionless-like transformation enhances the cycle stability of NW-Fe2O3. a) Potential
ducted by non-massive civilian atomic movements,
energy diagram for the reaction model of MOOH phase transformation (M=Fe, Co, and Ni).
States T and T* stand for minima and transition structures from A to B and from A* to B*, indicating the intermediation of diffusionless or
respectively, and their structures are schematically shown at the bottom of figure. Asterisks diffusionless-like transformation. In addition, the
denote the use of the lattice constants of MOOH ground state instead of those of M(OH)2. structural analysis of Co(OH)2 and Ni(OH)2 shows
Noticing that all the structures contain the same amount of H atoms. All energies are that their energy storage process can be treated as a
referenced to the total energy of the MOOH ground state, b) Illustration shows how the phase typical diffusionless transformation. Thus, to prove
transformation influence on the electrochemical behaviors. such idea, a suite of energy profile for phase transfor-
mation between the Fe(OH)2 and δ-FeOOH was
obtained by using DFT calculations, as well as taking
bivalent and trivalent iron. For chemical valence state, XANES (Fig- Co(OH)2 and Ni(OH)2 as references into consideration.
ure 6d) at state 5d and 5g does not shift as the first cycle and quite We first optimized the crystal structure of Fe(OH)2 and δ-FeOOH.
close to the reference curve of Fe3O4. It not only indicates the coexis- The optimized lattice constants of Fe(OH)2 and δ-FeOOH are a = b =
tence of Fe2+ and Fe3+, but also confirms the charge product Fe(OH)2 3.25 Å, c = 9.48 Å, and a = b = 3.06 Å, c = 8.96 Å, respectively,
is difficult to be oxidized to α-FeOOH. The intensity of XANES at the which is good agreement with the experimental values. Then, the ini-
marked area gains decrease significantly at state 10d and 10g compared tial FeOOH structure was constructed by removing one H atom from
with state 5d and 5g, indicating an increase in local structure disor- each Fe(OH)2 chemical formula, and the configuration with the lowest
der.[15] Such change is consistent with the aforementioned morphology energy was chosen in this work. As shown in Figure 7a, the transfor-
analysis. The chemical valence change is also confirmed by the results mation between initial FeOOH (marked as A) and δ-FeOOH (marked
of XPS Fe 2p. As shown in Figure 6e, the energy separation between as B) was simulated at the optimized lattice constants of Fe(OH)2, and
two main peaks is 13.6 eV, typical of Fe3+.[44,45] Whereas the peaks of the calculated energy barrier is 0.87 eV. The transformation between A
Fe 2p3/2 have shift to lower binding energy and the existence of satel- and B for the case of Co(OH)2 and Ni(OH)2 was calculated in similar
lite peaks at ~715 eV, both of which indicate the occurrence of way. The energy barrier is 0.68 and 1.01 eV, respectively, and those
Fe2+.[38,46] The valence of iron does not shift as expected and is more values are close to that of Fe(OH)2. To eliminate the effects of lattices,
close to Fe2+. This fact leads us to aim at the discharge product α- we also simulated the transformation between A and B at lattice con-
FeOOH. As shown in Figure 7b, one can see that the crystal structure stants at MOOH (M=Fe, Co, Ni); the calculated results indicate that the
has a huge difference between Fe(OH)2 and α-FeOOH, underlying that energy of all the compounds decreases and the Co(OH)2 still possess
the overcoming higher energy barriers are inevitable and a massive the minimum energy barrier of 0.09 eV; meanwhile, the energy bar-
atomic rearrangement via diffusion are required for this conversion rier of Fe(OH)2 (0.33 eV) and Ni(OH)2 (0.42 eV) is very close. All in
reaction. Thus, as illustrated in Figure 6f, this conversion reaction (dif- all, the DFT calculated results show that δ-FeOOH could be easily trans-
fusional transformation), in particular discharge product α-FeOOH, formed from Fe(OH)2 when charge and discharge in the way of typical
renders both the fully bulk utilization fading to surface and irreversibil- diffusionless transformation, which is similar with the conversion reac-
ity of chemical valence of iron. tion mechanism of Co(OH)2 and Ni(OH)2. Herein, considering the

Energy Environ. Mater. 2021, 0, 1–10 8 © 2021 Zhengzhou University.

effect of energy barrier on cyclic stability, on the whole, the Fe(OH)2
would possess good cyclic stability if the discharge product is δ-
FeOOH due to reaction energy barrier of Fe(OH)2 is a bit higher than
Co(OH)2[15] and is almost comparable to Ni(OH)2.[50]
In fact, Owusu et al.[35] have experimentally proved our design.
They demonstrate an excellent cyclic stability, retaining 91.6% of Cs
after 10000 cycles, just based on our conducted conversion between Fe
(OH)2 and δ-FeOOH. As shown in Figure S18, we also repeated this
experiment, and an excellent cyclic stability remains.
As described in Data S2, it is the cyclic stability deterioration to
mainly constrain Fe2O3 as supercapacitor electrode. To the best of our
knowledge, our proposed design, for the first time, is rooted from its
atomic-level conversion reaction mechanism. Thus, the conversion reac-
tion mechanism via diffusionless transformation is an ultimate strategy
to achieve pseudocapacitance concentrated on the fully bulk utilization.
In particular, we suggest such termed conversion pseudocapacitance
into a new paradigm of pseudocapacitance.
3. Conclusions
We clarify the atomic-level conversion reaction mechanism of α-Fe2O3,
pinpoint the cyclic stability deterioration in alkaline electrolyte, as a
proof of concept, and achieve the pseudocapacitance with fully
bulk utilization, hereafter termed as conversion pseudocapacitance.
In particular, phase transformation theory is introduced into con-
version reaction process; the diffusional transformation is demon-
strated as atomic-level arch criminal to the cyclic stability
deterioration of α-Fe2O3. Theoretically, the diffusionless transfor-
mation between Fe(OH)2 and δ-FeOOH was proposed as one strat-
egy to optimize its electrochemical performance. Based on such
conversion reaction mechanism with diffusionless transformation,
our work provides a refreshing perspective and strategy to reassess
and design electrochemical performance of the TMOs electrode
materials, respectively. Moreover, a new paradigm is thereof estab-
lished for pseudocapacitance.
4. Experimental and DFT Calculations Section
Preparation of NW-Fe2O3: All chemical reagents were purchased from Sino-
pharm Chemical Reagent Co., Ltd. The NW-Fe2O3 was prepared by using
hydrothermal method and the following calcination in N2 atmosphere. Firstly,
the carbon fiber paper (CFP) was cut into 1*4.5 cm2. The CFP was cleaned
ultrasonically by acetone, ethanol, and distilled water (DW) for 20 min succes-
sively and was dried in an oven at 60 °C for at least 6 h. Then, the CPF was
dealt with plasma cleaner in 50 kW for 15 min. Secondly, 1.62 g FeCl3
6H2O
was dissolved in 250 ml DW and 1.06 g Na2SO4 was dissolved in 50 ml DW.
The later colorless solution was poured into the former faint yellow solution
under stirring. Thirdly, the 40 ml mixed solution and one 1*4.5 cm2 cleaned
CFP was put into one 50 ml Teflon lined stainless autoclave. Then, the auto-
clave was transferred into an oven at 60 °C for 10 h. The CFP with precursor
was taken out and treated ultrasonically and dried in an oven at 60 °C for at
least 6 h. Lastly, the CFP with precursor was calcined by a tubular furnace. The
temperature, holding time, and heating rate were 400 °C, 2 h, and 1 °C min−1,
respectively. This procedure of preparation refers to the reported literature with
the modified key parameters.[25]
Preparation of sample at selected state: The sample was prepared via GCD
measurement with current density of 2 A g−1. The sample was taken out from
three-electrode system when the potential scan to selected point. The sample
was dried in an oven at 60 °C for 6 h after cleaning with DW.
Energy Environ. Mater. 2021, 0, 1–10
Structural characterization: XRD (Brucker D8 with Cu Kα radiation) and
Raman (Princeton, GRS TR777-2, with wavelength 473 nm) were used to identify
the NW-Fe2O3 phase. The morphology of NW-Fe2O3 and samples at selected
states during charge and discharge process were characterized by using SEM
(HITACHI, SU8010). TEM (JEOL, JEM-2100F) was used to investigate the
microstructure of prepared NW-Fe2O3 and the samples at selected states during
energy storage process. The synchrotron X-ray diffraction (Shanghai Synchrotron
Radiation Facility on beamlines BL14B1) with an electron energy of 2 GeV was
used to identify the phase structure at states d, e, and g. The XPS (Thermo Scien-
tific ESCALAB-250) and XAS (Beijing Synchrotron Facility (BSRF) on beamlines
1W2B) were employed to analyze the chemical valence state of prepared NW-
Fe2O3 and the samples at selected states during energy storage process. TEM
(JEM ARM 1300S) was used to collect the EELS data at state o, c, d, and g.
Electrochemical characterization: Electrochemical performance was charac-
terized by an electrochemical workstation (Vertex.ONE, IVIUM, Holland). Three-
electrode electrochemical system was used for testing of single electrodes. NW-
Fe2O3 was treated as working electrode. A saturated calomel electrode (SCE) was
reference electrode. A Pt-electrode was used as counter electrode. The electrolyte
is 1 M KOH. The Cs was calculated by formula Cs = (I × Δt)/(m × ΔV). I is the
current (A), Δt is discharge time (s), m is mass of active materials and ΔV is
potential difference during discharge process.
DFT calculations: All the density functional theory (DFT) calculations were
based on the Hubbard correction (DFT+U) and were performed by using the
Vienna ab initio simulation package (VASP).[51–53] The exchange-correlation func-
tional was described by generalized gradient approximation of Perdew–Burke–
Ernzerhof (GGA-PBE)[54,55] and an energy cutoff of 700 eV for the plane-wave
basis was set to expand the one-electron wave function, and Brillouin zone (BZ)
integrations were performed using a Monkhorst-Pack theme[56] with k-point
mesh with a resolution of 2π × 0.03 Å−1. Geometry optimizations were stopped
until the forces on each atom were less than 0.02 eV Å−1, and the energy is con-
verged until the change is smaller than 1.0 × 10−5 eV atom−1. Regarding DFT+U,
we considered PBE with a Hubbard U-like term to describe the onsite Coulomb
interactions (Ueff = U-J). According to previous reports,[15,57,58] we used a value
of Ueff = 3.3, 3.8 and 4.3 eV for Co, Ni, and Fe atoms. The qvasp was used to
post-process the VASP calculated raw data.[59]
Acknowledgements
This research is supported by the National Natural Science Foundation of China
(51932003, 51872115), 2020 International Cooperation Project of the Department
of Science and Technology of Jilin Province (20200801001GH), Program for the
Development of Science and Technology of Jilin Province (20190201309JC), the
Jilin Province/Jilin University Co-Construction Project-Funds for New Materials
(SXGJSF2017-3, Branch-2/440050316A36), Project for Self-innovation Capability
Construction of Jilin Province Development and Reform Commission (2021C026),
the Open Project Program of Wuhan National Laboratory for Optoelectronics
(2018WNLOKF022), the Program for JLU Science and Technology Innovative
Research Team (JLUSTIRT, 2017TD-09), the Fundamental Research Funds for the
Central Universities JLU, and “Double-First Class” Discipline for Materials Science
& Engineering. The Beijing Synchrotron Radiation Facility (BSRF) is greatly
acknowledged for providing us the beamtime on beamlines 1W2B and 4W9B for
the XAFS measurements. The authors thank Beamline BL14B1 (Shanghai Syn-
chrotron Radiation Facility) for synchrotron X-ray diffraction measurements.
Conflict of Interest
The authors declare no conflict of interest.
Supporting Information
Supporting Information is available from the Wiley Online Library or from
the author.
9 © 2021 Zhengzhou University.
Keywords
bulk utilization, conversion pseudocapacitance, diffusionless transformation,
Fe2O3, phase transformation
Received: June 15, 2021
Revised: August 2, 2021
Published online: August 3, 2021
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