Materials & Design 209 (2021) 109949

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Synthesis and electrochemical properties of nanoporous CrN thin film

electrodes for supercapacitor applications
Zecui Gao a,b, Zhixin Wan c, Zhengtao Wu a, Xueli Huang a, Haiqing Li a, Teng Fei Zhang a,⇑,
Paul Heinz Mayrhofer b, Qimin Wang a,⇑
a
School of Electromechanical Engineering, Guangdong University of Technology, Guangzhou 510006, China
b
Institute of Materials Science and Technology, Technische Universität Wien, Getreidemarkt 9, 1060 Vienna, Austria
c
School of Materials Science & Engineering, Sun Yat-sen University, Guangzhou 510006, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Sufficient Ni content leads to an

interconnected Ni-network in the
CrN–Ni coating.

Nanoporous CrN can be obtained by
HCl etching of CrN–Ni.

Nanoporous CrN has an ~ 80% higher
specific capacitance than CrN.

Guideline to prepare porous
transition metal nitrides with a high
specific surface area.

a r t i c l e i n f o a b s t r a c t

Article history: Transition metal nitrides (TMN) have received widespread consideration as supercapacitor materials for a
Received 27 March 2021 variety of energy storage applications. An important requirement to such electrode materials is a very
Revised 26 June 2021 high specific surface area, which is typically obtained through a percolating pore-network. Here, we
Accepted 28 June 2021
use arc ion plating to prepare CrN-Ni composite coatings with 0, 30.4, 54.2, and 77.6 at.% Ni. Detailed
Available online 29 June 2021
X-ray diffraction and X-ray photoelectron spectroscopy showed that the coatings consist of CrN phases
next to metallic Ni. Post-deposition treatments with HCl solutions lead to selective leaching, causing a
Keywords:
porous nanostructure for the Ni-containing CrN coatings. From there, the coating with 54.2 at.% Ni in
PVD thin film
Nanoporous supercapacitor
its as-deposited state provided the highest (electrode-geometric-area)-specific capacitance after the
Specific capacitance HCl treatment, giving 58.5 mFcm2 at 1.0 mAcm2 in a 0.5 M H2SO4 aqueous electrolyte. This value
porous CrN is about 80 times higher than for the as-deposited coatings or the Ni-free CrN. Consequently, our strategy
to combine TMNs with metallic Ni and its subsequent treatment with HCl is highly effective in enlarging
the specific surface area and adsorption sites. It allows to significantly enhance the energy storage per-
formance of TMN thin film supercapacitors.
Ó 2021 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://
[Link]/licenses/by-nc-nd/4.0/).

1. Introduction

Owing to the high charge–discharge efficiency, long service life

⇑ Corresponding authors. and environmental compatibility, supercapacitors (SCs) have
E-mail addresses: tfzhang@[Link] (T.F. Zhang), qmwang@[Link] (Q. received widespread consideration to be used alone – or in combi-
Wang).

[Link]
0264-1275/Ó 2021 Published by Elsevier Ltd.
This is an open access article under the CC BY-NC-ND license ([Link]
Z. Gao, Z. Wan, Z. Wu et al. Materials & Design 209 (2021) 109949

nation with other energy storage options – to offer improved bination of CrN with Ni a faster formation of the porous structure
power efficiency and enhanced cycle life. Therefore, SCs are avail- can be obtained (3 h in 3 M HCl) allowing for a specific capacitance
able for many energy storage applications, such as regenerative of even 58.5 mFcm2. All these Ca values refer to a current density
braking, short-term energy storage, miniaturized energy storage of 1.0 mAcm2 or a scanning rate of 100 mVs1, further data of
devices, and emergency power supplies [1–4]. Typically, there some literature values are given in the Table S1.
are two storage mechanisms for SCs: 1) electrochemical double- Previously reported works have been mainly focusing on the
layer capacitors (EDLC, electrochemical adsorption/desorption only optimization of material selection, composition, and deposition
occur on the surface of the electrodes, like carbons) and 2) pseudo- parameters of the thin films, while in this study, a novel
capacitor (electrosorption, reduction–oxidation reactions, and microstructure design strategy was applied to synthesize nanopor-
intercalation processes, like oxides). Thus, an ideal SC should have ous thin film electrodes through PVD and subsequent selective
a high specific surface area for charge adsorption and/or chemical chemical etching processes. This combined procedure for CrN-Ni
reaction [5,6]. As the most important constituent of SCs, various thin films showed a remarkably enhanced capacitive performance
electrode materials have been extensively developed in recent as compared with other reported thin film systems. Generally, the
years, both in their compositional and morphological design. The combination of nitride coatings with Cu [48–52], Ni [53–55], Ta
most common one is shaping high conductive carbon-based mate- [56], or Ag [57,58], is warmly welcome for reducing the friction
rials to specific morphologies (such as, nanotube, nanofiber, nano- coefficient, enhancing the toughness, increasing plastic deforma-
wire, nanoflower, and nanorods [7,8]), which are then covered with tion and corrosion resistance. The ductile metallic phase is perco-
transition metal oxides (TMO, such as Co3O4, MnO2, Nb2O5, TiO2, lating throughout the typically brittle, but corrosion resistant
TiO3, HfO2,and RuO2) [9–19] to obtain their combinations as TMN matrix [59]. Here, we used arc ion plating to prepare a CrN
TMO@C or TMO/C. The other option is to dope the shaped carbon matrix – CrN combines high strength [60] with excellent corrosion
with N/O/S/P [20–26]. This is a mutually beneficial cooperation [61] and oxidation resistance [62], and specific capacitance [34] –
of EDLC and pseudocapacitor, getting a massively increased speci- in which metallic Ni is uniformly distributed. After the deposition,
fic surface area for chemical reactions and charge absorptions, and the Ni is thoroughly etched away using an HCl solution, to prepare
greatly increasing energy density [27]. The comparison of their a sponge-like CrN coating. A schematic illustration of the fabrica-
specific capacitance is depicted in the supplementary data, in tion process of the porous CrN thin films is shown in Fig. 1. We pro-
Table S1. However, their fabrication is quite complicated and vide a detailed study on how the Ni content and the chemical
sometimes not eco-friendly, involving hydrofluoric acid etching etching parameters influence the microstructure, morphology,
and annealing. and electrochemical properties of these CrN-Ni thin films. The
Except for carbons and oxides, there are also lots of other SC maximum (electrode-geometric-area)-specific capacitance value
electrodes, such as carbides (e.g., TiC [28]), sulfides (e.g., TiS for the porous (after etching) CrN–Ni thin films exceeds those of
[29]), nitrides (e.g., TiN [30]), and borocarbonitrides [31]. Among the as-deposited CrN–Ni and CrN by a factor of ~ 80. The strategy
them, the physical vapor deposited (PVD) transition metal nitride outlined here, can be universally applied for modifying the surface
(TMN) thin films are very promising [32]. The reported TMN elec- and cross-sectional morphology of TMN films and enlarge their
trodes, such as CrN [33–35], TiN [30,36,37], VN [38,39], Mo2N [40– specific surface area and adsorption sites. This procedure shows
42], and TiNbN [43] have exhibited good performance in service great potential for optimizing the energy storage performance of
life, as a result of their high conductivity, high structural and chem- TMN thin film supercapacitors.
ical stability, and have found also their position for supercapacitor
applications. PVD techniques, especially magnetron sputtering and
arc ion plating, are widely used in high-quality TMN coating fabri-
cation [44,45]. PVD-produced transition metal nitride (TMN) film
electrodes have many advantages over traditional powder-type
electrode materials, including binder-free fabrication, good adhe-
sion, uniformity, and easily controlled composition and thickness.
This makes them promising candidates for flexible thin-film super-
capacitors and on-chip micro-supercapacitors. The specific capaci-
tance of TMN electrode materials is based on the high-speed
electrostatic adsorption. Storing the charge on the electrodes and
the interface of active materials at the electrolyte, requires a very
large relative ion-accessible surface area. Therefore, the main work
of the present study focuses on how to obtain a sufficiently porous
structure and rough surface of PVD TMN thin films. Recently we
showed that the (electrode-geometric-area)-specific capacitance
Ca of magnetron sputtered ~ 1-mm-thin HfN can be improved from
0.7 to 5.6 mFcm2 by a post-deposition etching with Ar plus Kr ion
beams, enlarging its specific surface area [46]. This is in the range
of magnetron sputtered TiN, exhibiting a Ca value of ~ 3 mFcm2
for the ~ 1-mm-thin film, increasing to 8.8 mFcm2 for the 2.2-
mm-thin film [36]. CrN (1.1 mm thin) provides already in its as-
deposited state – by conventional magnetron sputtering – a much
higher Ca value of 12.8 mFcm2 [34], which further can be
improved to 17.7 mFcm2 [33] or even 35.4 mFcm2 [35] using
glancing angle deposition. When preparing a porous CrN out of a
magnetron co-sputtered CrN-Cu coating – by a subsequent selec-
tive chemical etching for 3–4 days with an 0.5 M HNO3 – the speci-
fic capacitance can also be improved to 31.3 mFcm2 [47]. Here, Fig. 1. Schematic illustration of the fabrication process for porous CrN thin films:
we use a corresponding technique, but show that through the com- (a) as-deposited CrN, (b) as-deposited CrN–Ni, and (c) porous CrN films.

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Z. Gao, Z. Wan, Z. Wu et al. Materials & Design 209 (2021) 109949

2. Experimental 250Xi spectrometer using a monochromatic Al Ka source (15 kV

and 15 mA). Initially, individual element survey scans were per-
2.1. Samples preparation formed to detect the elements in all samples. Prior to these mea-
surements, the surface of the coatings was Ar-ion etched (with
CrN–Ni thin films with various Ni contents were deposited by an energy of 3 keV over an area of 3  3 mm2) for 3.5 min to
arc ion plating (MD800, DG Huasheng, Inc.) using a Cr target remove surface contaminants. The recorded spectra were cali-
(99.95% purity) and a Ni80Cr20 (20 at.% Cr) alloy target (99.95% pur- brated by the C 1 s binding energy of 284.8 eV.
ity). These two targets are placed horizontally at an angle of 100° to
each other facing the substrate holder, which rotated with a speed 2.3. Electrochemical characterizations
of 1.5 rpm during the deposition, at a mean distance of 20 cm. The
polished monocrystalline Si (1 0 0)-oriented substrates An electrochemical workstation (AMETEK, 1470E) with a con-
(10  10  0.5 mm3) were ultrasonically cleaned in ethanol and ventional three-electrode setup (working electrodes: the coatings
deionized water successively and dried by nitrogen gas before presented here; reference electrode: Ag/AgCl [KCl saturated];
being mounted to the substrate holder. The system was evacuated counter electrode: Pt plate), was used to evaluate the electrochem-
to a base pressure of at least 5  103 Pa. Prior to deposition, a 30- ical properties of as-deposited and etched CrN-Ni thin films in a
min etching process using Ar+ and Kr+ from a booster ion source 0.5 M H2SO4 aqueous electrolyte. The specific capacitance was
(Pinnacle, Advanced Energy, Inc.) was conducted with a pressure measured by cyclic voltammetry (CV) and galvanostatic charge–
of 2.0 Pa and a pulsed substrate bias potential of  600 V to remove discharge (GCD), at a controlled potential window, scan rate, and
oxides and contaminants from the surface. Afterwards, a CrN adhe- current density. The conductivity and interfaces were investigated
sion layer (~0.3 lm thin) was deposited using 1.0 Pa N2 atmo- using electrochemical impedance spectroscopy (EIS), at an open-
sphere, 100 A target current, and  100 V pulsed bias potential. circuit voltage of 0.6 V, a disturbing voltage of 5 mV, and a fre-
The subsequent CrN–Ni layer (~0.7 lm thin) was deposited with quency range of 0.01 – 100000 Hz. The cycling stability was tested
the same N2 atmosphere of 1.0 Pa, pulsed bias potential by CV measurements at a constant scan rate of 100 mVs1 for
of  100 V, and deposition temperature of 400 °C. The Ni content 2000 cycles at room temperature.
of these CrN–Ni top layers was varied by adjusting the current The (electrode-geometric-area)-specific capacitance (Ca,
applied to the Ni80Cr20 and Cr targets, as listed in Table 1, using a mFcm2) of the thin film supercapacitors was calculated from gal-
pulsed DC power supply (DSP12A1, ZONGXINDA, Chengdu, Ict.) vanostatic charge–discharge by using [34]:
and adjusting the duty cycle to 15% and the frequency to 10 kHz.
We systematically varied the concentration of Ni in the CrN–Ni
C a ¼ ðI  DtÞ=S  DU ð1Þ
top layer (from 0 to 78 at.%), the exposure time in the HCl solution where I (mA) is the discharge current, Dt (s) is the discharge time,
(from 1 to 18 h), and the intensity of the HCl solution (from 1 to DU (V) is the potential window between the lowest and the highest
4 mol·l1). During this etching process, the samples were removed potentials (U a and U b , respectively), and S (cm2) is the geometric
from the HCl solution every hour, and washed with deionized area of the working electrode.
water, dried with nitrogen, and tested for their specific Integrating the area of one CV cycle, the specific capacitance of
capacitance. the thin film supercapacitors can also be obtained, using the fol-
lowing equation [34]:
2.2. Structural and chemical characterizations Z Ua
Ca ¼ IðVÞdV=2  v  S  ðU a  U b Þ ð2Þ
Ub
The surface and cross-section morphologies of the as-deposited
thin films and their best (classified through their area-specific R Ua
where Ub
IðVÞdV is the integral current area and v (mVs1) is the
capacitance) porous products (after the HCl solution treatment)
were investigated by scanning electron microscopy (SEM, FEI Nova scan rate. This was used to calculate the retention rate of the capac-
NanoSEM 430) at an accelerating voltage of 15 kV. The chemical itance during the 2000 cycle service life investigation.
composition of the samples was determined by using an integrated
energy dispersive X-ray spectroscopy (Oxford instruments X- 3. Results and discussions
MaxN). The surface morphology of the thin films was also mea-
sured using atomic force microscopy (AFM, Bruker Dimension 3.1. Structure and morphology
FastScan), with a dimension of 20  20 mm2, in peak force tapping
mode. The root-mean-square roughness (Rq) was calculated from The chemical compositions of the as-deposited CrN–Ni thin
three consecutive measurements for each sample. X-ray diffraction films and those after a distinct HCl solution treatment (next para-
(XRD) in a Bragg–Brentano configuration, using a Bruker D8 graph) are given in Table 1. For easier reading, our thin films are
Advance diffractometer (Cu Ka X-ray source, 40 kV, and 40 mA), named as CrN, CrN-Ni30, CrN-Ni54, and CrN-Ni78 according to their
was employed to investigate the crystal structure of the thin films. Ni-content of 0, 30.4, 54.2, and 77.6 at.% in the as-deposited state,
The chemical bonding states of the thin films were studied by X- respectively. This increase in Ni-content is obtained by incremen-
ray photoelectron spectroscopy (XPS) with a Thermo Fisher Escalab tally increasing the arc ion plating current at the Ni0.8Cr0.2 target

Table 1
Target currents, etching time, and compositions of the CrN–Ni thin films in the as-deposited state and after the treatment in a 3.0 mol·l1 HCl bath (indicated with an asterisk).

Sample CrN CrN* CrN-Ni30 CrN-Ni30* CrN-Ni54 CrN-Ni54* CrN-Ni78 CrN-Ni78*

Cr target current (A) 90 90 80 0
Ni80Cr20 target current (A) 0 50 80 90
3.0 M HCl etching time (h) 18 11 3 4
N (at.%) 48.9 49.9 36.5 50.0 15.1 49.4 8.3 23.7
Cr (at.%) 51.1 50.1 33.1 41.8 20.7 43.5 14.1 22.3
Ni (at.%) 0 0 30.4 8.2 54.2 7.1 77.6 54.0

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Z. Gao, Z. Wan, Z. Wu et al. Materials & Design 209 (2021) 109949

from 0 to 90 A and simultaneously decreasing the current at the Cr coating – basically a Ni matrix with CrN precipitates is formed –
target from 90 to 0 A, see Table 1. Therefore, their Cr and N con- chemical etching with the 3.0 M HCl would require significantly
tents decreased continuously from around 50 to 10 at.%. longer times for a more pronounced dissolution. The removal of
Detailed studies on the effect of the HCl solution concentration Ni from the CrN-Ni30 and CrN-Ni54 coatings is promoted by their
over the potential range from 0.2 and 0.8 V showed best results in high fraction of phase-boundaries between Ni and CrN supporting
current density for the CrN-Ni54 thin film (as measured by the cyc- access of the HCl solution.
lic voltammetry (CV) at a scan rate of 100 mVs1 and galvanostatic XRD investigations of the as-deposited coatings show the face
charge–discharge (GCD) at a current density of 1.0 mAcm2), centered cubic (fcc) CrN phase, see their (1 1 1) and (2 0 0) diffrac-
when using a 3.0 mol·l1 concentration (the curves for the individ- tion peaks at 37.5 and 43.7° in Fig. 3a. The small peak at the left-
ual HCl concentrations are provided in the supplementary data hand shoulder of the (2 0 0) fcc CrN peak for the CrN-Ni54 coating
Fig. S1). The area-specific capacitance Ca of the Ni-containing sam- might indicate the presence of a small fraction of the hexagonal
ples CrN-Ni30, CrN-Ni54, and CrN-Ni78 peaked with 11 h, 3 h, and Cr2N phase. For the other coatings, this is probably hidden behind
4 h of dissolution time within the 3.0 M HCl bath, respectively, their relatively broader XRD peaks. With increasing Ni-content, the
see Fig. 2a (and supplementary data Fig. S2). The samples providing XRD peaks at 44.5 and 51.8° (indicative for the (1 1 1) and (2 0 0)
the Ca peak-values are indicated with an asterisk: CrN-Ni30* (11 h lattice plane distances of fcc-Ni) increase in intensity. No nickel
treatment time), CrN-Ni54* (3 h treatment time), and CrN-Ni78* nitride phase could be detected, in agreement to the known weak
(4 h treatment time). As expected, there is no change for the Ni- nitride forming tendency of Ni [63]. After the HCl solution treat-
free CrN thin film, but the sample CrN* refers to the maximum ment, almost no crystalline Ni phase can be detected anymore
treatment time of 18 h in the 3.0 M HCl solution. Fig. 2b shows for CrN-Ni30* and CrN-Ni54*, see Fig. 3b. Contrary, the CrN-Ni78*
the Ca peak-values for our samples with respect to the Ca values coating still shows a pronounced crystalline Ni phase content in
in their as-deposited state, obtained at a current density of agreement with the chemical investigations, see Table 1. The pro-
1.0 mAcm2. This comparison clearly shows that the highest Ca file of the XRD peaks from the CrN phase did not change due to the
value with ~ 58.5 mFcm2 is obtained with the CrN-Ni54 coating HCl solution treatment (please compare Fig. 3a and b), especially
(54.2 at.% Ni), followed by ~ 18.0 mFcm2 for the CrN-Ni78 coating when considering the changed contribution from the Ni phase. This
(77.6 at.% Ni). When compared to their as-deposited condition, the furthermore indicates the excellent chemical stability and corro-
CrN-Ni30, CrN-Ni54, and CrN-Ni78 coatings experienced an increase sion resistance of CrN.
in their Ca values by a factor of ~ 16, 80, and 11, respectively, clearly SEM top view investigations of the coatings clearly show the
highlighting the massive improvement in Ca due to the HCl treat- formation of a porous structure due to the HCl solution treatment,
ment. This is because, by the HCl treatment a porous structure is when Ni was present in the as-deposited state. The Ni-free CrN
formed, which will be presented later. The Ni content of the sam- thin film exhibits a dense and smooth surface before and after
ples massively decreased due to the HCl solution treatment, from etching, see Fig. 4a and b, respectively, again underlining the excel-
30.4 to 8.2 at.% for CrN-Ni30, from 54.2 to 7.1 at.% for CrN-Ni54, lent corrosion resistance of CrN [64]. The 30.4 at.% Ni containing
and from 77.6 to 54.0 at.% for CrN-Ni78, see Table 1. As expected, sample (CrN-Ni30) shows some small particles at the surface
the chemical composition of the Ni-free CrN sample shows no (Fig. 4c), which were removed by the etching treatment (CrN-
obvious difference before and after 18 h of HCl etching, indicating Ni30*, Fig. 4d). The sensitivity to the HCl solution treatment sug-
the excellent chemical stability of CrN. Due to the etching proce- gests these particles to be metallic Ni. Independent on the HCl
dure – as most of the Ni is etched away especially for the CrN- solution treatment-time, the surface of this sample always was
Ni30 and CrN-Ni54 coatings – also their overall Cr content increased rather smooth, indicating that the Ni content of this sample
to 41.8 and 43.5 at.%, respectively, Table 1. The HCl solution nicely (CrN-Ni30) is too low to allow its complete percolation throughout
changed its color into green, due to Ni dissolution (Fig. S3, supple- the matrix. In other words, the metallic Ni phase is not intercon-
mentary data). Due to the very high Ni content of the CrN-Ni78 nected but rather present as pockets encapsulated by the
corrosion-resistant ceramic CrN.

Fig. 2. (a) Comparison of specific capacitance of the coatings CrN, CrN-Ni30, CrN-
Ni54, and CrN-Ni78 after different immersion times in HCl solution (current density:
1.0 mAcm2). (b) Comparison of the peak-values in specific capacitance of these Fig. 3. XRD patterns of (a) as-deposited coatings and (b) coatings after the HCl
samples to their as-deposited state (current density: 1.0 mAcm2). treatment for various times to obtain their highest specific capacitance (Fig. 2).

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Z. Gao, Z. Wan, Z. Wu et al. Materials & Design 209 (2021) 109949

Fig. 4. Top-view SEM images of CrN (a and b), CrN-Ni30 (c and d), CrN-Ni54 (e and f), and CrN-Ni78 (g and h) coatings in their as-deposited state and after the HCl treatment
to obtain their highest specific capacitance (Fig. 2), respectively. The white horizontal line has the same length in all SEM images and represents the scale bar of 1 mm.

The CrN-Ni54 coating (54.2 at.% Ni) shows much larger particles enced by the HCl treatment for 18 h (Fig. 5b). In agreement with
at the surface already in its as-deposited state, Fig. 4e. After the 3 h the plan-view SEM investigations (Fig. 4), also the cross-sectional
treatment in the HCl bath, the SEM top-view investigations already morphology of the CrN-Ni30 coating is only slightly influenced by
indicate for a sponge-like morphology with a high porosity (CrN- the HCl solution treatment. Considering the noticeable change in
Ni54*, Fig. 4f). Consequently, here the Ni content was sufficiently Ni content (from 30.4 down to 8.2 at.%) this is somehow surprising
high to allow for the formation of an interconnected Ni-network and suggests the formation of rather small pores. Contrary, the
in the as-deposited state. Our data furthermore show that the CrN-Ni54 coating shows a significant change in cross-sectional
HCl solution treatment-time needs to be controlled, to allow that morphology across the entire thickness of the Ni-containing part,
most of the Ni-phase is dissolved, leading to a maximization of due to the HCl solution treatment. Already in its as-deposited state,
the porosity. However, if the treatment time is too long, the this coating is characterized by a rather rough cross-sectional mor-
remaining CrN-skeleton may be separated from the CrN adhesion phology due to the competitive growth of the Ni and CrN phases.
layer and influence the electrodes’ service life. These SEM studies nicely show that the generated pores (due to
The impressions from the top-view SEM investigations are in- the dissolution of most of the Ni-phase, please remember that here
line with detailed AFM analysis (supplementary data Fig. S4, scan- the Ni-content decreased from 54.2 to 7.1 at.%) percolate through-
ning over a surface area of 20  20 mm2) yielding root mean square out the entire outer CrN–Ni layer (Fig. 5f). The highest Ni contain-
roughness (Rq) values of 7.8 and 152.0 nm for the coatings CrN and ing coating, CrN-Ni78, reveals a smoother appearance especially of
CrN-Ni54, respectively. By the HCl solution treatment for 3 h, the Rq the surface-near region in the as-deposited state (Fig. 5g), with
value of the CrN-Ni54 coating increased further to 185.0 nm. The even some pores present underneath this area. However, after
SEM top-view investigations already indicated the increased sur- the HCl solution treatment, no percolating pore-network formed
face roughness by this HCl solution treatment (compare Fig. 4e (Fig. 5h). The studies furthermore show that all samples have
and f). nearly the same entire coating thickness of ~ 1.0 mm.
Further increasing the Ni content to 77.6 at.% leads to a coating Based on these SEM top-view (Fig. 4) and SEM fracture cross-
(CrN-Ni78) that shows already in the as-deposited state (Fig. 4g) a section (Fig. 5) studies, we can conclude that the most effective
less promising surface quality than the CrN-Ni54 coating. The sur- form of a fully percolating pore-network, due to the HCl solution
face is characterized by fewer homogenously distributed particles, treatment, is obtained for the 54.2 at.% Ni containing coating,
but some very large ones as well. After a 4 h treatment in the HCl CrN-Ni54. This coating exhibits a high porosity after the HCl treat-
bath, ring-shaped holes formed at the surface, suggesting that ment (considering that the coating thickness remained the same,
especially at the CrN–Ni interfaces the dissolution kinetic is faster. but its Ni content decreased from 54.2 to 7.1 at.%), with well-
In general, these SEM investigations indicate that for this sample distributed pore-sizes (Fig. 6), where ~ 30-nm-sized ones build
the Ni content is too high. Thus, out of the three Ni-containing the highest fraction. According to Huang et al. [65], the most ideal
CrN samples, the CrN-Ni54 coating showed the most promising for- pore size for providing aqueous electrolyte pools and fast ionic
mation of a porous material after the HCl solution treatment, based transport channels for supercapacitor electrodes is in the range
on these SEM top-view investigations. 2–50 nm. Smaller pores (<2 nm) – smaller than the size of solvated
Whether the formed pores also expand throughout the coating electrolyte ions – do not contribute to energy storage, and larger
thickness was studied by SEM fracture cross-sections, Fig. 5. The pores (>50 nm) do not provide a sufficient specific surface.
Ni-free CrN thin film shows the most compact cross-sectional mor- Although the CrN-Ni78* is also very porous (Fig. 4h), the pore size
phology in the as-deposited state (Fig. 5a), which is only a bit influ- is not nicely distributed. CrN-Ni54* offers the highest area-
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Z. Gao, Z. Wan, Z. Wu et al. Materials & Design 209 (2021) 109949

Fig. 5. Fracture cross-sectional SEM images of CrN (a and b), CrN-Ni30 (c and d), CrN-Ni54 (e and f), and CrN-Ni78 (g and h) coatings in their as-deposited state and after the
3.0 M HCl treatment to obtain their highest specific capacitance (Fig. 2), respectively. The solid and dashed white horizontal lines have the same length in all SEM images and
represent the scale bar of 1 mm. The dashed line indicates the interface between CrN adhesion layer and CrN-Ni coating, the solid line indicates the interface between Si
substrate and CrN adhesion layer.

N 1 s XPS core-level spectra of CrN-Ni54 (Fig. 7a) and CrN-Ni54*

(Fig. 7b) are very similar even with their contributions from CrN
(binding energy between 396.5 and 397.8 eV [66]) and Cr2N (bind-
ing energies between 397.5 and 398.0 eV). The major contribution
comes from CrN, in agreement with XRD studies, which indicated
only a tiny fraction of the Cr2N phase. The Cr 2p3/2 XPS core-level
spectra also suggest the presence of Cr2O3 (at 576.1 eV [67]), but
also here, the features at 574.8 eV (indicative for CrN [67]) and
576.1 eV (indicative for Cr2N) are almost identical prior-to and
after the HCl treatment, Fig. 7c and d, respectively. A small contri-
bution of Ni–O bonds next to the major metallic Ni (at about
852.8 eV) can also be concluded from the Ni 2p3/2 XPS core-level
spectra of this sample prior-to and after the HCl treatment,
Fig. 7e and f, respectively. In excellent agreement with XRD, the
XPS studies do not show any Ni–N bonds in these films.

3.2. Electrochemical properties

To demonstrate the merits of the porous structure, we com-

pared the electrochemical performance of our samples (CrN, CrN-
Fig. 6. Pore size distribution (as obtained by digital image processing of Fig. 4f) of
Ni30, CrN-Ni54, and CrN-Ni78) in their as-deposited state with that
the CrN-Ni54 after the 3.0 M HCl treatment (CrN-Ni54*) to obtain its highest specific after the HCl treatment providing their Ca peak-values (CrN*,
capacitance (Fig. 2). CrN-Ni30*, CrN-Ni54*, and CrN-Ni78*) using a three-electrode sys-
tem. The CV curves at a scan rate of 100 mVs1 show that the
as-deposited samples (Fig. 8a) and the HCl treated samples
specific capacitance Ca among all coatings and HCl-treated coatings (Fig. 8b) demonstrate appropriate symmetry, which allows for a
studied, which is also depicted in Fig. 2. good electric double-layer energy storage mechanism. The much
This most promising sample, CrN-Ni54, was studied in detail by more extensive range in current density for the HCl treated sam-
XPS to characterize any changes in their chemical bonding states ples, the y-axis of Fig. 8b, than that of the as-deposited ones,
from the as-deposited state to the HCl-treated state. Before these Fig. 8a, is due to their massively higher Ca values. Similarly, the
measurements, their surface was Ar-ion etched to a depth GCD curves, measured with a current density of 1.0 mAcm-2, are
of ~ 50 nm to avoid interference by unwanted surface contamina- nearly symmetric. The times for obtaining the discharge-peak also
tions. The XPS spectra of the CrN-Ni54 coating prior-to and after the massively increase due to the HCl solution treatment. Please com-
HCl treatment are almost identical; therefore, we only briefly con- pare Fig. 8c and d, which again demonstrates the significant
centrate on the N 1 s, Cr 2p, and Ni 2p3/2 XPS core-level spectra. The improvement in specific capacitance.
6
Z. Gao, Z. Wan, Z. Wu et al. Materials & Design 209 (2021) 109949

Fig. 7. XPS core-level spectra of (a and b) N 1 s, (c and d) Cr 2p, and (e and f) Ni 2p3/2 energy regions for the CrN-Ni54 coating in its as-deposited state (CrN-Ni54) and after the
3.0 M HCl treatment (CrN-Ni54*) to obtain its highest specific capacitance (Fig. 2), respectively.

Fig. 8. (a) CV curves (scan rate: 100 mVs1) and (b) GCD curves (current density: 1.0 mAcm2) of CrN, CrN-Ni30, CrN-Ni54, and CrN-Ni78 in their as-deposited state. (c) CV
curves (scan rate: 100 mVs1) and (d) GCD curves (current density: 1.0 mAcm2) of these coatings after 3.0 M HCl treatment to obtain their highest specific capacitance
(CrN*, CrN-Ni30*, CrN-Ni54*, and CrN-Ni78*).

Electrochemical impedance spectroscopy (EIS) was conducted high-frequency region, and the equivalent circuit diagram for these
to study the charge transfer and ion diffusion properties of the EIS measurements is given in Fig. 9c. Just for a brief recall: in such
electrode materials. Fig. 9a and b show the Nyquist plots obtained Nyquist plots, Z’ and Z’’ represent the real and imaginary part of
by these EIS measurements of our samples in their as-deposited impedance, respectively. At the left side of these diagrams (close
state and after the HCl solution treatment leading to their Ca to 0 of Z’ and Z’’, the high-frequency side) a semicircle followed
peak-values, respectively. The insets show a detailed view of the by a straight line indicates capacitive behavior. Their small impe-

7
Z. Gao, Z. Wan, Z. Wu et al. Materials & Design 209 (2021) 109949

To further investigate the CrN-Ni54 thin film electrode’s suit-

ability after the 3 h treatment in a 3.0 M HCl solution (CrN-Ni54*)
for potential applications, its capacitive behavior is studied by CV
curves at different scan rates from 10 to 1000 mV·s1, see
Fig. 10a. Notably, these CV curves show a gradual increase in cur-
rent density, with quasi-rectangular shapes even up to
1000 mVs1, indicating excellent capacitive behavior and high-
rate capability. Fig. 10b depicts the CrN-Ni54* electrode’s GCD
curves at current densities from 0.5 to 10 mAcm2. The nearly
symmetric potential–time curves for all current densities imply a
high charge–discharge Coulombic efficiency (97%) and low polar-
ization of this electrode material (supplementary data Fig. S5).
With an increase of the current density from 0.5 to 10.0 mAcm2,
the area-specific capacitance Ca decreases from 62.5 to 42.2
mFcm2. This relatively small reduction in Ca by 67.5% during this
increase in current density, suggests good reversibility of the elec-
trochemical reaction at the surface of the CrN-Ni54* thin film. Cor-
responding Coulombic efficiency investigations of CrN-Ni30* and
CrN-Ni78* are provided in the supplementary data, Fig. S5. They
Fig. 9. Nyquist plots of CrN, CrN-Ni30, CrN-Ni54, and CrN-Ni78 coatings in their as-
also depict roughly 100% charge–discharge Coulombic efficiency.
deposited state (a) and after the 3.0 M HCl treatment to obtain their peak in their
specific capacitance (b). (c) Equivalent circuit diagram. The related studies of GCD and CV with different current densities
and scan rates for CrN-Ni30* and CrN-Ni78* are provided in the sup-
dance in the high-frequency region indicates meager charge trans- plementary data, Fig. S6. Compared with another porous CrN thin
fer resistance (Rct), a testament to their intrinsically outstanding film, which was obtained by etching away the ~ 19 at% Cu from
electrical conductivity and electrochemical activity [68]. The high- the CrN–Cu [47], the Ca value of the CrN-Ni54* thin film (with
est frequency point (the first intersection with the x-axis) refers to 58.5 mFcm2 at 1.0 mAcm2) is higher than the reported one of
the electrolyte resistance (Rs) because, at such high frequencies 33.1 mFcm2 (at 1.0 mAcm2) for a porous CrN.
there is no resistance in capacitance. Therefore, they have similar The cycling stability of the CrN-Ni54* electrode was proven by
Rs values, which are 1.2–1.5 X due to the resistance of the 0.5 M 2000 successive CV measurement cycles using a scan rate of
H2SO4 electrolyte [69]. The higher the imaginary part of impedance 100 mVs1. The CV curves of the 1st and 1000th cycle have a sim-
(hence the steeper the Nyquist curve), the easier the electrolyte ilar shape but cover a slightly different area, being unchanged for
can access the surface, and the materials exhibit ideal capacitive the subsequent 1000 cycles, Fig. 10c. The capacitance retention,
behavior [70], which is the case for all of our samples (as- Fig. 10d, clearly shows that the CrN-Ni54* electrode undergoes a
deposited, Fig. 9a, or HCl treated, Fig. 9b) except for the highest more rapid decay down to 91.7% for the first 300 cycles, and after
Ni-containing coating in its as-deposited state (CrN-Ni78). The around 600 cycles, a steady-state behavior is obtained. Essentially,
HCl-treated samples show a smaller impedance range than the there is no change between the 600th and 2000th cycles, during
as-deposited ones, suggesting excellent capacitance behavior.

Fig. 10. (a) CV curves at different scan rates (in mVs1), (b) GCD curves at different current densities (at mAcm2), (c) CV curves of the 1st, 300th, 1000th and 2000th cycle
and (d) cycling performance at a scan rate of 100 mVs1, for the CrN-Ni54 coating after the 3 h treatment time in a 3.0 M HCl bath (after which this coating reached its peak
area specific capacitance, Fig. 2, due to the formation of a fine porous morphology, Figs. 4 and 5).

8
Z. Gao, Z. Wan, Z. Wu et al. Materials & Design 209 (2021) 109949

which still 88.5 ± 0.5% of the initial capacitance remains. The initial Acknowledgements
decrease in capacitance comes from the irreversible consumption
of the electrode (basically remaining Ni) in the electrolyte. This This work was supported by the projects of the National Natural
leaves room to further optimize the pre-treatment procedure. Science Foundation of China (Grant No. 51875109), and Natural
However, the cycling performance is better than that of nitride- Science Foundation of Guangdong Province of China (Grant No.
based electrodes prepared from nitridation of metal oxides, such 2020A1515010968), and the National Key Research and Develop-
as VN@CF (which exhibit 82% capacitance retention after 1000 ment Project of China (Grant No. 2017YFE0125400). ZG thanks
cycles) [71]. Still, it seems to be slightly less stable than that of the support of the State Scholarship Fund of China (No.
other nitride-based electrodes prepared by PVD, such as CrN 201908440933) during her PhD at TU Wien.
(92.1% retention after 20,000 cycles) [34], TiVN (99% retention after
10,000 cycles) [72], and CrCuN (94% capacitance retention over Appendix A. Supplementary material
20,000 cycles) [47]. However, our data suggest that after the
‘‘running-in” period (for the first 600 cycles), a steady state behav- Supplementary data to this article can be found online at
ior is obtained during which the area-specific capacitance of the [Link]
CrN-Ni54* film electrode is unchanged at 88.5 ± 0.5% (Ca ffi 50.0
mFcm2) of its initial value (58.5 mFcm2). References

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