Applied Surface Science 605 (2022) 154726

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Full Length Article

Correlating between the height of three-dimensional core-shell electrodes

and ion transport for their electrochemical performance
Jiawei Wang 1, Zheng Wang 1, Fumin Wang , Xubin Zhang *, Jian Song , Rosine Ahishakiye ,
Mingzhao Li , Xinyuan He
School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: The height of electrodes for in-situ grown 3D core-shell electrodes on a collector, which can directly affect the
Supercapacitor transport of electrolyte ions, is an important issue that needs to be concerned. Herein, nanocone Co2(OH)2CO3
Ion transport (CCH) with different heights were synthesized as representative demos to explore the possible factors, including
Core-shell electrode
the height h, ion diffusion coefficient D, and Warburg coefficient σ for addressing the ion transport issue. A
compromise balance between the height and ion diffusion coefficient was obtained after a series of dynamic
analyses. The results showed that the optimal height of CCH can improve ion transport and shorten the charge
transfer distance while avoiding stacking and curling. The best electrochemical performance renders the mini­
mum Warburg and maximum ion diffusion coefficients. Furthermore, in-situ EIS and Raman showed that the
active sites of CCH were the exposed Co in octahedral units, which can form linkage of octahedrally-electrolyte
upon suitable cycling height can reveal more cations, thereby producing more extraordinary electrochemical
performance. This work emphasizes the importance of ion diffusion behavior for electrochemical performance
within electrodes. It gives a guide for constructing core-shell electrodes with a high electrochemical performance
by engineering the microscopic height of materials.

1. Introduction Up to now, several methods have been used to improve the intrinsic
capacitance from the system and materials level.
Supercapacitors have emerged as one kind of promising energy The design of novel advanced electrode materials with special
storage systems due to their long cycle life, rapid and reversible charge/ structural characteristics is considered one of the effective ways to
discharge process, ideal power density et al. [1–4]. Different from improve the electrochemical performance of supercapacitors, and
traditional electrical double-layer capacitors (EDLCs), pseudo capacitor several 3D binder-free core-shell electrodes have been designed and
employs the fast and reversible Faradaic redox reaction over the surface demonstrated excellent electrochemical performance. For example, self-
of electrodes which can deliver much high specific capacitance [5,6]. supported 3D hollow core-shell cactus-like Ni-Co(CO3)0.5(OH)‧
Along this line, some new materials such as transition metal hydroxides/ 0.11H2O@MnNiCo–OH electrodes deprived of ZIF-67 were synthesized
oxides/sulfides/phosphides/nitrides (Ni(OH)2, Co3O4, Co9S8, CoP, etc.) in our group, and benefit from the unique architecture; the electrode
[7–11], conductive polymers (poly(3,4-ethylene dioxythiophene), pol­ exhibits an impressive specific capacity of 8.2 C cm− 2 at 1.5 mA cm− 2
yaniline, etc.) [12,13] and MXenes [14,15] have been used as electrodes [16]. Apart from this, lots of 3D core-shell electrodes have been pre­
and reached great electrochemical performance. However, these elec­ pared and proved to have superiorities for fast ion transport and electron
trodes still suffer from poor stability and low-rate capability due to the transfer, such as NiCo-P@CoNiMo-P [17], Co3O4@C@Ni3S2 [18],
materials being dependent much on the surface redox reactions and the Co3V2O8@CuV2O6 [19], and et al. However, the sophisticated archi­
unfavorable reaction dynamic behavior during the charge/discharge tectures make the loading height and mass increase a lot thereby the
process, which inhibits the practical application of pseudo capacitors. ratio of “dead zone of electrochemically active sites” improving greatly,

* Corresponding author.
E-mail addresses: [email protected] (J. Wang), [email protected] (Z. Wang), [email protected] (F. Wang), [email protected] (X. Zhang),
[email protected] (J. Song), [email protected] (R. Ahishakiye), [email protected] (M. Li), [email protected] (X. He).
1
Jiawei Wang and Zheng Wang contributed equally to this paper.

https://doi.org/10.1016/j.apsusc.2022.154726
Received 13 July 2022; Received in revised form 16 August 2022; Accepted 28 August 2022
Available online 5 September 2022
0169-4332/© 2022 Elsevier B.V. All rights reserved.
J. Wang et al. Applied Surface Science 605 (2022) 154726

thus the electrodes suffering the issue of high costs while limited 2. Experimental
application potential. Therefore, it is necessary to investigate the rela­
tionship between the loading height and electrochemical performance. 2.1. Fabrication of a series of CCH
Unfortunately, the research about the transport and diffusion of elec­
trolyte ions in 3D core-shell electrodes still lags far behind the modifi­ Different thickness CCH grown on the Ni foam were fabricated by
cation of materials. hydrothermal method. Firstly, Ni foam was cut into 3 × 4 cm2 and
Typically, a whole electrochemical process including three steps, washed in 3.0 M HCl by ultrasonication for 30 min and rinsed with
first, electrolyte ions diffuse to the top of electrodes, and then the top ethanol and water for several times. Then, 1.0185 g Co(NO3)2⋅6H2O,
electrodes react with the ions, and electrons can be simulated and 1.05 g urea and 0.518 g NH4F were dissolved with 70 mL water and then
transferred from the top to the bottom. Finally, the electrons have been the solution was transferred to a 100 mL autoclave with a Ni foam
collected by the collector, all of them make a great difference for the immersed into the solution for 12 h, and the thickness of active materials
electrochemical performance of supercapacitor. Inspired by this, almost on the Ni foam was adjusted only by changing the hydrothermal tem­
all the effort focused on the modification of 3D materials to build core- perature for 100, 110, 120 and 130 ◦ C. Finally, after the system cooled
shell architecture, thereby improving the charge density on the top. down to room temperature, the Ni foam was washed by water and
Co2(OH)2CO3has been considered one of the popular supporters for ethanol for several times and dried in a vacuum oven at 60 ◦ C for 12 h.
preparing the core-shell electrodes due to the unique and controllable Then the Ni foam with different thickness of CCH were prepared and
shape [20–22]. Due to the co-existence of hydraion (H) and hydroxyl denoted as CCH-100, CCH-110, CCH-120 and CCH-130.
(OH–), this carbonate-based material is inferred to promote electro­
chemical performance. However, the practical capacitance of
2.2. Characterization
Co2(OH)2CO3 is much lower than its theoretical capacities due to the
electrochemical reactions can only occur on or near the top surface of
Scanning electron microscope (SEM, S-4800, Hitachi, Japan) was
electrodes [23], while most of the bulk active sites cannot participate in
used to detected the nanostructures and morphology of as-prepared
time thereby forming “dead zone of electrochemically active sites”.
samples. Transmission electron microscope (TEM), high-resolution
Therefore, to make use of the bulk active sites as possible thereby
TEM (HRTEM) and elemental mapping were performed on JEM-2100F
improving the intrinsic electrochemical performance of electrodes, it is
(JEOL, Japan) equipped with an energy-dispersive X-ray spectrometer.
vital to regulate the aspect ratio of electrodes by investigating the
X-ray diffraction (XRD, Bruker D8 Discovery X-ray diffraction) was used
relation between the height of electrode and ion diffusion coefficient.
2
to characterize the component of as-prepared samples with Cu Kα ra­
Ion transport time can be obtained by τ = LD , where L is the transport diation over 10–80◦ at a scan rate of 10◦ min− 1. IR spectra of samples
distance, which is related to the height of nanocones in 3D materials, were recorded on Nicolet-380 Fourier transform infrared spectrometer.
and D refers to the ion diffusion coefficient [23–25], so increasing the L X-ray photoelectron spectroscopy (XPS, ESCALAB 250XI, ThermoFisher,
by loading shell on the top of the core may lead a bad electrochemical. America) was used to carry on the X-ray photoelectron spectroscopy
Aiming to reduce the height of electrode (h) while increasing the D can using Al Kα radiation with C 1s peak (284.6 eV) as the internal standard.
achieve a fast charge transfer. Nevertheless, when the height is too short Nitrogen adsorption–desorption isotherm was obtained from SSA-7000
(hmin), the 3D materials are easier to be agglomerated during the growth instrument to analyze the specific surface area and pore size distribu­
of crystal, which will be detrimental to the subsequent modification. tion of as-prepared samples by BET method and Barrett-Joyner-Halenda
Also, the ultrashort structure can destroy during the electrochemical (BJH) model. Thermogravimetric analysis were used to analyze the
activation process. Apparently, improving the height of 3D materials can thermal stability in a PerkinElmer instrument from 30 to 800 ◦ C. The
decrease the D, while when the materials are too high (hmax), the ma­ wettability of these samples were investigated by a contact angle mea­
terials will be curled inevitably. Therefore, searching for a balance be­ surement (JC200D4M, POWEREACH, China). The in-situ Raman spectra
tween h and D to produce a suitable height with the corresponding were captured one by one with the CV tests at 1 mV s− 1 under an
maximum D value is very important to improve the electrochemical excitation source of 532 nm in a Renishaw RM-1000 instrument
performance. (England).
Inspired by these, in-situ grown Co2(OH)2CO3 nanocone (CCH) with
different heights were synthesized and used to reveal the relationship
2.3. Electrochemical measurements
between h and D during the whole electrochemical reaction. The
Co2(OH)2CO3 with various heights were prepared via a traditional hy­
The electrochemical performance of the CCH was investigated by a
drothermal method. After a series of dynamic behavior analyses, as
standard three-electrode configuration in 1 M KOH electrolyte with Pt
expected, a balance between h and D existed. The CCH at a temperature
foil as counter electrode and Hg/HgO as reference electrode. And the
of 120 ◦ C showed the best electrochemical performance, including the
active materials on Ni foam with a size of 1*1 cm2 was directly used as
best capacitance of 485 F g− 1 at 1 A g− 1 and higher capacitance reten­
working electrode. The mass specific capacitance (Csp) are calculated
tion of 90.07 % even after 5000 cycles, and the suitable height rendered
using following equations, respectively.
to the smallest Warburg coefficient σ value and the highest ion transfer
coefficient D value. Furthermore, in-situ EIS and Raman spectroscopy IΔt
Csp = (1)
proved that the Co in octahedral units gave the high electrochemical mΔV
properties, and the suitable height can expose more Co in octahedral
units, thereby forming more linkage of octahedrally-electrolyte upon where m, I, Δt and ΔV are the active materials mass in electrode (g),
cycling than the others. Considering that in-situ grown core-shell ma­ current (A), discharge time (s), and the voltage window (V),
terials have been used in many fields, our findings give a fundamental respectively.
understanding of how to regulate ion transport by engineering the
height of electrodes. 3. Results and discussion

The CCH with different height is synthesized by the conventional

hydrothermal method, and the morphology of obtained samples are
shown in Fig. 1. All the samples show 1D nanocones morphology, and
the height of CCH is increased with the development of temperature. In
the lower temperature, partial CCH gathers together, and only a few

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J. Wang et al. Applied Surface Science 605 (2022) 154726

Fig. 1. SEM images of CCH-100 (a), CCH-110 (b), CCH-120 (c) and CCH-130 (d). XRD patterns (e), FT-IR spectra (f), TG and DTG curves (g) of as-prepared sample.
High resolution C 1s (h), Co 2p (i) and O 1s (j) of as-prepared samples.

individual nanocones can be observed. Besides, as the temperature in­ crystallinity of CCH increase, and the results are well consistent with the
creases, the height of CCH increases accordingly to 6.3–6.5 μm with no SEM photos. Meanwhile, FT-IR spectra (Fig. 1(f)) at 3570 cm− 1 is
obvious agglomeration. As the temperature keeps rising, the height of attributed to the stretching vibration peak of O–H bond, and the peak at
CCH increase to 8.37 nm and the top begins to curl, which is unfavorable 3409 cm− 1 is the interaction between O–H and CO2– 3 [7]. The peaks
for ion transmission. The top view of as-prepared samples is presented in appeared in 1502, 1384, 831, and 673 cm− 1 are indexed to ν(OCO2),
Fig. S1, and the results are consistent with the side view of these. ν(CO3)/CO, δ(CO3), and ρ(OCO), respectively, which give strong evi­
Furthermore, detailed nanostructure information of CCH with different dence for the existence of CO2–3 [25]. And the characteristic peak in 984
thicknesses are shown in Fig. S2. All of the samples are 1D nanocones cm− 1 can be ascribed as the bending vibration of Co/Ni-OH [26,27]. N2
with a lattice fringes spacing of 0.26 nm in the high-resolution TEM adsorption/desorption isotherms presented in Fig. S3(a) show these
(HRTEM), which is indexed as (0 4 0) plane, and the EDS mappings prove samples are mesoporous structures with an H3 hysteresis loop, and the
the existence of Co, C, and O atoms in all the samples (Fig. S2). The obtained specific surface area are 13.4, 15.1, 20.9, and 13.7 m2 g− 1,
phases and crystal structure of as prepared samples are further investi­ respectively, indicating that with the temperature rising, the radius
gated by XRD (Fig. 1(e)). Obviously, all the samples are well indexed to decrease and the height increase, while with the temperature rises to
orthorhombic Co(CO3)0.5(OH)⋅0.11H2O (JCPDS No. 48–0083) with 120 ◦ C, the radius merely no change but the height continues to in­
a0 = 8.792 Å, b0 = 10.150 Å and c0 = 4.433 Å except the diffraction crease, making the specific surface area decrease greatly, and the results
peaks shift to low 2θ angles, indicating partial Ni atoms in Ni foam are are well consistent with SEM and TEM photos. Moreover, the pore
inserted in the phase, and the lattice parameters change a lot. Further­ volume of these samples are 0.056, 0.056, 0.068, and 0.059 m3 g− 1,
more, the diffraction intensity of (0 0 1) crystal plane is enhanced with respectively. The suitable height, large specific surface area and the pore
the development of temperature, which illustrates the grains grow and structure not only can facilitate the mass transfer from the electrolyte to

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J. Wang et al. Applied Surface Science 605 (2022) 154726

CCH but also accelerate the transmission speed in CCH. The thermog­ [28]. Furthermore, GCD curves of all the samples at different current
ravimetric analysis of these materials are explored by TGA and DTG densities are exhibited in Fig. S6, and the specific capacitances calcu­
analyses and the results presented in Fig. 1(g) shows that CCH-x have lated from GCD curve are shown in Fig. 2(c). As expected, CCH-120
good thermal stability. And 4.6 % of the weight reduction below 240 ◦ C gives the best mass specific capacitance up to 485 F g− 1 at 1 A g− 1,
is due to the loss of conjugated water adsorbed in the pores and within which is much superior to that of CCH-100 (48 F g− 1), CCH-110 (160 F
the structure. 15.1 % of the weightlessness in the range of 240–500 ◦ C is g− 1), and CCH-130 (166 F g− 1). With the increase of current density, the
attributable to the conversion of CCH to CO3O4. When the temperature mass specific capacitance decreases gradually, while the capacitance
is higher than 500 ◦ C, the sample quality has almost no change, indi­ retention of CCH-120 is still up to 70.8 % even at 5 A g− 1, indicating a
cating that it has been completely converted to CO3O4. Besides, the DTG good rate capability compared with the others (CCH-100 (25.2 %), CCH-
curves show that the linker decomposition temperature of CCH-120 and 110 (31.3 %), and CCH-130 (54.2 %)). Notably, the good performance of
CCH-130 are later than the others, indicating the great thermal stability. CCH-120 can be attributed to the moderate height of CCH giving fast
In addition, all of the samples show a small water contact angle which is dynamic behavior during electrochemical process by shortening the
less than 90◦ , indicating the similar hydrophilicity (Fig. S4), which is electronic transmission path and reducing the ion transport resistance.
benefit for the penetration of the electrolyte in electrodes. To further understand the reaction dynamic characteristic of these
Furthermore, XPS is used to deeply understand the surface elements samples, capacitive contributions are studied. As shown in Fig. S7, all of
state of these samples. As shown in Fig. S5, all the full spectra of CCH-x the CV curves of these samples at various scan rates show a couple of
present obvious peaks of Co, C, and O elements, and the related contents redox peaks and the shape of CV curves merely no change even at 50 mV
are summarized in Table S1. The high-resolution spectra of C 1s pre­ s− 1, proving the excellent rate performance [29]. According to the
sented in Fig. 1(h) can be divided into three peaks located at around following equations (2) and (3),
284.6, 286.8 and 289.2 eV, which corresponding to C–C, C– – O, and
i = avb (2)
O–C– – O, respectively. Furthermore, Co 2p spectra of these samples can
be deconvoluted into four peaks (Fig. 1(i)), and the peaks at 781.5 and
logi = loga + blogv (3)
797.6 eV are corresponded to Co 2P3/2 and Co 2P1/2, while the other
peaks at 786.8 and 803.2 eV are the shakeup satellite peaks. The O 1s where a and b are the parameters. And the fitting line of log i versus log v
spectra reveal three types of O species (Fig. 1(j)), and the binding energy provide a slope which equal to b. When b = 1, the contribution of
of C–– O, M–OH and H–O–H are located at around 530.8, 531.5, and
electrodes is capacitive-controlled process; while when b = 0.5, the
532.2 eV, respectively, and these oxygen-containing functional group on contribution mostly owing to the diffusion-controlled process. As
the surface of CCH is the main reason for the great wettability. depicted in Fig. 2(d), the oxidation and reduction b values of CCH-100,
The electrochemical performance of these samples is tested by CCH-110, CCH-120 and CCH-130 are all between 0.5 and 1, indicating
traditional three electrodes configuration in 1 M KOH aqueous electro­ that the contribution are more come from capacitive process. Moreover,
lyte. As shown in Fig. 2(a), the surrounded CV curve area of CCH-120 is the capacitive contribution to the energy storage of the samples are
bigger than the others at 10 mV s− 1, indicating the CCH-120 delivers the further calculating by k1 and k2 at various scan rates according to the
higher specific capacitance. GCD profiles of these samples at a current following formula (4) [30,31]:
density of 1 A g− 1 are presented in Fig. 2(b), same as the CV results,
CCH-120 exhibits the longest discharge time, which demonstrates the i(V) = k1 v + k2 v1/2 (4)
CCH-120 possess the better specific capacitance compared the others.
Besides, the IR drop of CCH-120 is much lower than that of other sam­ where k is the constants. Plotting the relationship between i and v1/2 can
ples, strongly demonstrating the low charge transfer resistance, which obtain the values of k1 and k2 and then the capacitive contribution can
has been proven beneficial to the collection and transfer of electrons be calculated. Fig. S8-S11 give the capacitive contribution at different

Fig. 2. CV (a) and GCD (b) curves of as-prepared samples at different scan rats and various current densities. (c) The specific capacitances calculated from GCD curve
of as-prepared samples. (d) Relationship between peak current and scan rates of as-prepared samples. (e) Capacitive contribution ratios of CCH-120. (f) Capacitance
retention and coulomb efficiency of as-prepared samples.

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J. Wang et al. Applied Surface Science 605 (2022) 154726

scan rates and the related normalized contribution ratios of capacitive impedance, which can be obtained from the slope by plotting Z′ and ω-1/
2
capacitance are presented in Fig. 2(e) (CCH-120) and Fig. S12 (CCH- according the following formula, where Z′ is the real part of impedance
100, CCH-110 and CCH-130). Evidently, the capacitive contribution of and ω is the sampling frequency [31,32].
CCH-120 to energy storage is about 30 % at 1 mV s− 1, and as the scan
(5)
′ 1

rates increase to 50 mV s− 1, the capacitive contribution increases to 92 Z = σω− 2 + Rs + Rct

%, indicating that the Faradaic pseudocapacitive behavior makes lead­ Fig. 3(b) gives the linear fitting of the selected Warburg region for all
ing role rather than diffusion-controlled process. Moreover, the other CCH samples and the slopes of fitting line are σ . The results show that the
CCH-100, CCH-110 and CCH-130 show capacitive contribution with 27 σ value of these samples in the following order: CCH-100 (1.37) > CCH-
%, 40 %, 30 % at 1 mV s− 1 and increase to 95 %, 90 %, 94 % at 50 mV 130 (0.38) > CCH-110 (0.367) > CCH-120 (0.23), implying the CCH-
s− 1, respectively, showing that the increased electrochemical perfor­ 120 achieve the quick diffusion of electrolyte ions.
mance of CCH-120 is mainly due to the enhanced diffusion-controlled The relationship between ion diffusion coefficient (D) and the height
process. Long-term cycling stability of as-prepared samples are pre­ are further investigated by the following equation [32–34],
sented in Fig. 2(f), the CCH-100, CCH-110, CCH-120 and CCH-130
exhibit 65.15 %, 77.65 %, 90.07 % and 82.15 % capacitance retention D=
R2 T 2
(6)
after 5000 cycles, respectively, indicating that CCH-120 shows great 2A2 n4 F 4 C2 2σ
practical application. Furthermore, the coulomb efficiency of all the
where the R, F, T, C, n is gas constant, Faraday constant, absolute tem­
samples achieve approximately 99 %, and the results demonstrated
perature, electrolyte concentration and the number of transfer electrons
excellent electrochemical reversibility. The SEM images of CCH-120
in electrode reaction, respectively, which can be considered as constant
after 5000 cycles are shown in Fig. S13. The structure and height of
K for a specific system. Thus the ion diffusion coefficient can be regarded
CCH-120 merely no change while some particles appear on the top of the
to be inversely proportional to A (surface area of electrode) and σ.
electrode, which is due to the electrolyte ions gathering on the top of
Meanwhile, the surface area of electrode is related to the intrinsic
nanocone and the electrochemical reactions can only occur on or near
structure including the pore size and pore distribution, which can affect
the surface of electrodes.
the transport of electrolyte ions. Thus the formula can be simplified as
Electrochemical dynamic behavior of these samples is further
formula (7):
investigated by EIS measurement. Traditionally, the Nyquist plots
consist of three parts including the intercept at the X-axis, a semicircle in K R2 T 2
D= (K = 4 4 2 ) (7)
the high frequency region and a straight line in low frequency region, Aσ
2 2 2n F C
which represents the series resistance (Rs), charge transfer resistance
Therefore, the D value of CCH is related to the height and Warburg
(Rct) and Warburg impedance (W), respectively. For detail, a minor
coefficient, and the related values of these samples are summarized in
intercept, a small diameter of semicircle and a big slop of straight line
Table S3 (D value is relative to that of CCH-130). As shown in Fig. 3(c),
correspond to great electrochemical performance. The detailed Nyquist
there is a balance between the height of CCH and D value, and the CCH-
plots are shown in Fig. 3(a), as expected, CCH-120 possesses the lowest
120 possesses the suitable height with smallest σ and biggest D.
Rs (1.73 Ω) than those of CCH-100 (2.15 Ω), CCH-110 (1.92 Ω) and CCH-
Furthermore, complex model is used to analyze the capacitance varia­
130 (2.15 Ω) indicates the lower intrinsic resistance, electrolyte resis­
tion in the larger frequency region, and the imaginary part C’’(ω) of the
tance and interfacial contact resistance (Table S2). In addition, a smaller
capacitance can be obtained from the impedance data from the relation
diameter of semicircle can be observed in high frequency region for
(8):
CCH-120 (0.51 Ω), which presents a smaller Rct compared with CCH-100
(1.21 Ω), CCH-110 (0.85 Ω) and CCH-130 (0.74 Ω), indicating a fast Z ′ (ω)
C′′ = (8)
charge transfer dynamic [30]. Furthermore, the biggest slope of straight 2ω|Z(ω)|2
line in low frequency region is presented for CCH-120, indicating a small
diffusion restriction of electrolyte ions. where Z(ω) and Z’(ω) are the complex impedance and the real part of the
Moreover, σ (Warburg coefficient) is related to the ion diffusion complex impedance. And the relaxation time constant τ0 is an important

1
Fig. 3. (a) Nyquist plots of as-prepared samples, and the insets are the enlarged high frequency region and equivalent circuit. (b) Relationship between Zʹ and ω− 2 in
the low-frequency part. (c) The balance between h and D over the CCH-x. (d) The normalized imaginary part capacitance. (e) The relationship of the four parameters.

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J. Wang et al. Applied Surface Science 605 (2022) 154726

merit to evaluate the charge and discharge rate of electrode, which can more active sites thereby increasing the charge transfer rate.
be calculated as τ0 = f10 , where f0 is the frequency corresponding to the To further understand the electrochemical dynamic behavior of
maximum C’’(ω). As shown in Fig. 3(d), the CCH-120 is characterized by CCH-120, in-situ Raman with a three-electrode cell was performed.
a smallest τ0 value of 17.85 s, while the others are much higher than that Notably, s significant Raman peak at 1073 cm− 1 can be observed during
of CCH-120 (CCH-100, 56.18 s; CCH-110, 26.31 s; CCH-120, 21.74 s), the whole charging-discharging process, which can be attributed to the
indicating that the CCH-120 presents best ion diffusion rate. In general, formation of superoxide on the surface of samples when the electrodes
the biggest D value and smallest τ0 of CCH-120 indicate the fast diffusion were immersed in the KOH electrolyte [36]. The CCH-120 is in a
and transport of electrolyte ions, which give valid reasons for the monoclinic system and the related crystal structure is presented in Fig. 5
enhanced electrochemical performance of CCH-120 due to the suitable (a). It can be observed that all the species including the Co2+, CO2–3 and
height. These results illustrate the CCH with suitable height can facili­ OH– are occupied by the C1 site system. Obviously, two kinds of Co can
tate the ion diffusion as well as shorten the transfer distance of ions, be observed in the structure, one is coordinated to CO2– 3 and two OH
–

which make great contributions to the electrode with low resistance ions and the other is coordinated to CO2– 3 and four OH –
ions, thereby
corresponding to lower Warburg coefficient and high maximum ion forming a distorted octahedron with (4 + 2) coordination [37]. The in-
diffusion coefficient for fast transport of electrolyte ions. situ Raman results during a whole CV cycle are shown in Fig. 5(b) and
Moreover, in-situ EIS was also carried out to understand the charge (c), and two major peaks in 501 cm− 1 (V1) and 623 cm− 1 (V2) corre­
transfer dynamic behavior of CCH-x (see Fig. 4(a) to (c)). For CCH-100, spond to the characteristic vibrational modes of Co-O-Co and Co (Co in
the Rct values merely show no change during the whole charging- octahedral site). To better understand the active sites, the relative in­
discharging process, indicating the fast and reversible surface capaci­ tensity ratio of IV1/IV2 according to the in-situ Raman are presented in
tive process. While for the other electrodes, a “V” shape evolution of Fig. 5(d). For CCH-120, the value of IV1/IV2 merely no change until 0.2 V
impedance can be observed obviously, and the Rct value reaches the upon charging process, indicating no redox or structural changes, which
lowest level when charged to 0.5 V. One possible reason for the decrease is well consistent with the CV curves. Then, IV1/IV2 increases gradually
is due to initial delithiation can make the charge conductivity enhanced with the increasing potential, which is due to the oxidation of Co3+ to
greatly, and the other reason is the electronic structure of Co and oxygen Co4+ in the octahedral site, and the result can be embodied in the
change a lot during charging process [35]. And the lowest Rct value of oxidation peak of CV [38]. The same phenomenon also can be observed
CCH-120 can be attributed to the suitable height of CCH can expose during discharging process, which further indicates that the Co in

Fig. 4. Nyquist plots of CCH-100 (a), CCH-110 (b), CCH-120 (c) and CCH-130 (d) during whole charge/discharge process. (e) Summarize of the Rct values at fully
charge/discharge state of as-prepared samples.

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J. Wang et al. Applied Surface Science 605 (2022) 154726

Fig. 5. (a) Crystal structure of CCH and in-situ Raman spectra of CCH-120 during one charging (b) and discharging (c) cycle at 1 mV s− 1. (d) The relationship
between the potential and the intensity ratio (IV1/ IV2) of CCH-120 electrode.

octahedral site is the electrochemically active sites and the easily special morphology have been used as the core to build 3D core-shell
charged oxidation states can lead to enhanced CV redox peaks and architecture in many fields, these findings may provide a guide for
electrochemical performance. designing the complex in-situ binder-free 3D core-shell architecture
with enhanced electrochemical performance.
4. Conclusions
CRediT authorship contribution statement
In summary, binder-free nanocones Co2(OH)2CO3 electrodes with
different height were synthesized and used as demos to explore the Jiawei Wang: Methodology, Investigation, Writing – original draft.
balance between the height and ion transport behavior. Simultaneously, Zheng Wang: Methodology. Fumin Wang: Writing – review & editing,
some important parameters such as the height h, ion diffusion coefficient Supervision, Funding acquisition. Xubin Zhang: Writing – review &
D, and Warburg coefficient σ related to the ion transport were also editing, Supervision, Funding acquisition. Jian Song: Writing – review
analyzed to further decouple the relationship among them. Results & editing. Rosine Ahishakiye: Conceptualization, Supervision. Min­
showed that the suitable loading height for electrodes can improve ion gzhao Li: Formal analysis. Xinyuan He: Formal analysis.
transport and shorten the ion transport distance while avoiding stacking
and curling. All the favorable conditions can make the electrodes pro­
Declaration of Competing Interest
cess the smallest Warburg coefficient σ value thereby achieving the
highest ion diffusion coefficient D value. After adjusting the height of
The authors declare that they have no known competing financial
CCH, the as-prepared electrode CCH-120 delivered a high mass specific
interests or personal relationships that could have appeared to influence
capacitance value up to 485 F g− 1 at 1 A g− 1 and a higher capacitance
the work reported in this paper.
retention of 90.07 % even after 5000 cycles, which is much higher than
the other CO2(OH)2CO3 without regulation reported in recent litera­
Data availability
tures. Furthermore, in-situ EIS and Raman measurements demonstrated
that the exposed Co in octahedral units were the main contributing
Data will be made available on request.
factor for the enhanced pseudocapacitive performance, and the suitable
loading height can expose more cations thus forming linkage of
octahedrally-electrolyte upon cycling. Considering that nanocones, Acknowledgements
nanorods, nanosheets and the other transition metal (hydro)oxides with
This work is supported by National Natural Science Foundation of

7
J. Wang et al. Applied Surface Science 605 (2022) 154726

China [grant numbers: 21978198]. This work is supported by Tianjin performance flexible all-solid-state asymmetric supercapacitors, J. Mater. Chem. A
3 (2015) 16150–16161, https://doi.org/10.1039/c5ta03469h.
Research Innovation Project [grant numbers: 2021YJSB164].
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