Electrochemistry Communications 160 (2024) 107680

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Electrochemistry Communications
journal homepage: www.elsevier.com/locate/elecom

Effect of reverse pulse current density on microstructure and properties of

supercritical Ni-GQDs nanocomposite coatings
Cong Fang a, Weining Lei a, b, *, Tianle Xu a, Haoyu Zhong a, Bin He a, b, Linglei Kong a, b,
Yiliang He a
a
School of Mechanical Engineering, Jiangsu University of Technology, Changzhou 213001, China
b
Jiangsu Key Laboratory of Advanced Material Design and Additive Manufacturing, Jiangsu University of Technology, Changzhou 213001, China

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

Keywords: In this study, Ni-GQDs nanocomposite coatings were prepared by double-pulse electrodeposition under super­
Supercritical CO2 critical CO2 with graphene quantum dots (GQDs) as the second phase additive. The effects of supercritical CO2
Graphene quantum dots (GQDs) conditions and reverse pulse current density on microstructure, crystal orientation, grain size, GQDs quality,
Reverse pulse current density
mechanical properties, and corrosion resistance of Ni-GQDs nanocomposite coatings were investigated. The
Micro-morphology
results show that when the reverse pulse current density is 0.8 A /dm2, the surface of Ni-GQDs-II nanocomposite
Mechanical properties
Corrosion resistance coating is compact and flat, GQDs is uniformly dispersed in the coating, and GQDs is closely bound to Ni grains.
Compared with the coating prepared at normal temperature and pressure. The grain size of the Ni-GQDs-II
nanocomposite coating is 4.58 nm, and the grain size is reduced by 75.3 %. The quality of GQDs in the coating
was improved. The coating hardness is 867.22 HV, which is significantly increased by 53.7 %. The roughness is
0.236 μm, which is significantly reduced by 37.2 %. The friction coefficient and volume wear were 0.262 and
3.395 × 107 μm3, respectively, which were significantly reduced by 27.4 % and 57.9 %. After electrochemical
corrosion, the self-corrosion voltage of the coating was − 139 mV, and the self-corrosion current density was 3.19
× 10− 7 A/cm2. The self-corrosion voltage was significantly increased by 61.2 %, and the self-corrosion current
density was significantly decreased by 71.2 %. The Rct value and Ndl value of the coating are 31594.53 Ω⋅cm2 and
0.862, respectively. Significantly increased by 226.2 % and 67.1 %, respectively. The coating has excellent
mechanical properties and corrosion resistance.

1. Introduction stress (55 MPa), and the best electrochemical passivation protection,
which effectively improves the comprehensive properties of nickel films
Metal and dispersed particles from suspension electrolytes form a and has a good industrial application prospect.
composite electrochemical coating during electrodeposition. Nickel is Supercritical fluid technology [7–10] applies fluids higher than
one of the most common single metal coatings. As a decorative or critical pressure and temperature. Supercritical fluid has no obvious
functional coating, it can improve surface gloss and strengthen surface gas–liquid interface and is in a state of gas–liquid separation. It has
wear and corrosion resistance. Nickel-based nanocomposite coatings are unique physical characteristics, low viscosity, high density, good mass
characterized by higher hardness, better stability in various corrosion transfer, heat transfer, flow, and dissolution performance. It is widely
environments, and better adhesion to the substrate on the basis of the used in energy saving, extraction of natural products, polymerization
original nickel coatings, so they are widely used in composite electro­ reactions, and catalytic processes. Supercritical CO2 condition means
chemical coatings [1–5]. Haixiang Chen et al. [6] introduced soluble that the CO2 pressure is higher than 7.39 MPa and higher than 31.26℃,
rare earth compounds CeCl3 or LaCl3 in order to optimize the micro­ the critical condition of CO2 is easy to reach, and the chemical properties
structure and properties of nickel electroplating and electrodeposited on of CO2 are not active, non-toxic and harmless, low price and easy to
copper substrate by direct current (DC) and pulse current (PC) methods, obtain. Supercritical CO2 technology [11–14] is widely used in func­
respectively. The results show that the PC-electrodeposited nickel tional component extraction, semiconductor cleaning, dry cleaning
/LaCl3 films exhibit the highest hardness (320 HV), the lowest tensile technology, and chemical reactions. Under the condition of supercritical

* Corresponding author at: School of Mechanical Engineering, Jiangsu University of Technology, Changzhou 213001, China.
E-mail address: [email protected] (W. Lei).

https://doi.org/10.1016/j.elecom.2024.107680
Received 30 November 2023; Received in revised form 1 February 2024; Accepted 6 February 2024
Available online 9 February 2024
1388-2481/© 2024 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
C. Fang et al. Electrochemistry Communications 160 (2024) 107680

CO2, the addition of surfactants makes the water-based electrolyte form double-pulse electrodeposition process under supercritical CO2 condi­
a supercritical emulsion with excellent conduction properties. After tions using graphene quantum dots (GQDs) with unique properties as
electrodeposition, the surface of the coating is brighter and smoother, the second phase additive. In the experimental study, the optimal
and the grains are finer. Supercritical CO2 significantly improves the experimental parameter was preliminarily determined: the additional
coating’s surface quality and mechanical properties [15–17]. amount of GQDs was 1.5 g/L. The forward pulse current density is 5 A/
Graphene quantum dots (GQDs) [18–20] are a new carbon fluores­ dm2. The forward pulse duty cycle is 0.25. The reverse pulse duty cycle
cent material. The graphene layer size is less than 100 nm, and the is 0.25. The frequency is 1000 Hz. The pressure is 10.5 MPa. The tem­
number of layers is less than ten layers. It has the advantages of low cost, perature is 50℃; The plating time is 60 min. In order to study the effects
simple preparation, low toxicity, and good light stability. GQDs also of reverse pulse current density and supercritical CO2 conditions on the
have the characteristics of high electrical conductivity, excellent me­ microstructure and properties of Ni-GODs nanocomposite coatings, four
chanical strength, and thermal stability and are applied in biomedicine, kinds of Ni-GODs nanocomposite coatings were prepared by different
optoelectronics, electronic devices, and other fields [21–24]. When the processes. Subsequently, the surface morphology, crystal orientation,
GQDs are used as the second phase additive to prepare the nickel base grain size, mechanical properties, and corrosion resistance of the coating
composite coating under supercritical CO2, the addition of GQDs can were compared and analyzed, and the most suitable reverse pulse cur­
improve the surface quality of the coating and the mechanical properties rent density was explored, which provided a basis for the optimization of
and corrosion resistance [25]. double-pulse electrodeposition process under supercritical CO2 condi­
Compared with direct current electrodeposition, by adjusting the tions and the study of new nickel-based nanocomposites.
pulse duty cycle, frequency, and other parameters, a higher peak current
can be used to refine the grain size, and it is easier to obtain nano­ 2. Experiment
composite coatings and improve the surface quality and mechanical
properties of the coatings. Pulse electrodeposition technology has the 2.1. Preparation of Ni-GQDs nanocomposite coating
advantages of high efficiency, economy, and environmental protection,
and the coating has excellent physical and chemical properties, which The supercritical CO2-assisted electrodeposition device is shown in
are widely used in optoelectronics, electronics, the chemical industry, Fig. 1. The device was independently designed by our research group. By
and medical fields [26–28]. Compared with single-pulse electrodeposi­ controlling the temperature of supercritical fluid, the pressure of the
tion, double-pulse electrodeposition [29,30] introduces a set of reverse reactor, and the temperature of the electroplating solution through a
pulse currents, which can remove the defects such as bumps, burrs, and cooler, pressure pump, and temperature control system, the electrode­
nodules on the surface of the coating during electrodeposition. Double position under the condition of supercritical CO2 is realized. The power
pulse electrodeposition makes the thickness of the coating more uni­ supply adopts an intelligent multi-group commutation pulse plating
form, the surface more compact and flat, and also plays a role in power supply (Handan Dashun Plating Equipment Co., Ltd.).
improving the mechanical properties of the coating. Dongai Wang et al. Experimental method
[31] studied the effects of double pulse positive and negative duty cycle
and reverse working time on the properties of Ni/nanodiamond com­ (1) The cathode and anode of the electrodeposited fixture are treated
posite coatings. The experimental results show that when the nano­ to meet the requirements of the experiment.
diamond particle content in the plating solution is 5 g/L, the reverse (2) Configure graphene quantum dots (GQDs), the second phase
pulse working time, forward pulse duty cycle, and reverse pulse duty additive required for electrodeposition.
cycle of the double pulse electroplating parameters are 20 ms, 0.3, and (3) The plating solution used for electrodeposition is configured.
0.2, respectively. The composite coatings prepared by double pulse have (4) Electrodeposition is carried out after constructing supercritical
good comprehensive properties. CO2 conditions in the reactor.
In this paper, Ni-GODs nanocomposite coatings were prepared by

Fig. 1. Schematic diagram of supercritical CO2 electrodeposition device.

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Experimental steps: Table 2

Plating solution formulations.
(1) The cathode of the fixture is a nickel plate, the anode is a copper Reagent name Proportions (g•L− 1) Weight (g)
plate, the purity of the copper plate and the nickel plate are 99.9
NiSO4⋅6H2O 300.00 45.0000
%, the size is 20 mm × 20 mm, and the cathode and anode are 20 NiCl2⋅6H2O 30.00 4.5000
mm apart. Sandpaper of 400 #, 1200 #, 2000 #, 3000 #, 5000 #, H3BO3 35.00 5.2500
and 7000 # is used to polish the copper sheet to achieve rust C12H25SO4Na 0.20 0.0300
removal, oil removal, and oxidation oxidation film removal. At GQDs 1.50 0.2250

the same time, the sandpaper of 400 # and 1200 # is used to

polish the nickel sheet to smooth the surface and remove stains. Then, the Ni-GQDs nanocomposite coating was prepared by turning on
Then, the copper and nickel plates meeting the experimental re­ the double pulse power supply.
quirements were fixed on the electrodeposited cathode and The effect of reverse pulse current density on the organization and
anode, respectively, with cyanoacrylate glue. properties of Ni-GQDs nanocomposite coatings was investigated using a
(2) The solution formula required for the preparation of graphene double-pulse current electrodeposition process under supercritical CO2
quantum dots is shown in Table 1. According to the solution conditions. Three groups of nanocomposite coatings with reverse pulse
formula, use EL204 electronic balance (Mettler Toledo Instru­ current densities of 0.3 A/dm2, 0.8 A/dm2, and 1.3 A/dm2 (Ni-GQDs-I ~
ment (Shanghai) Co., LTD.) to weigh quantitative citric acid Ni-GQDs-III) were prepared for comparative analysis. Meanwhile, in
(C6H8O7⋅H2O) and urea (CH4N2O) into a beaker with a capacity order to investigate the effect of supercritical CO2 on the organization
of 200 ml, add 100 ml ultra-pure water and stir well. Pour the and properties of Ni-GQDs nanocomposite coatings. Ni-GQDs-IV nano­
mixture into the teflon reactor and place the reactor in an oven at composite coatings with a reverse pulse current density of 0.8 A/dm2
180 ◦ C for 8 h. After the set time is over, the reactor solution is were prepared at normal temperature and atmospheric pressure. The Ni-
poured into the beaker, and then the anhydrous ethanol is poured GQDs-IV nanocomposite coatings were compared and analyzed with the
into the mixed solution and into the centrifugal tube. The Ni-GQDs-II nanocomposite coatings. Four different sets of electrodepo­
centrifuge tube was put into a centrifuge for high-speed centri­ sition process parameters are listed in Table 3.
fuge treatment, the waste liquid was poured out, GQDs were
extracted, and GQDs were prepared by drying treatment. 2.2. Characterization and performance analysis methods

(3) The formula for the electroplating solution is shown in Table 2. SIGMA500 field emission scanning electron microscope (Carl Zeiss
According to the formula of the plating solution, the quantitative nickel AG, Germany) was used to observe and analyze the coating’s surface
sulfate (NiSO4⋅6H2O), nickel chloride (NiCl2⋅6H2O), boric acid (H3BO3), morphology. EDS plane scanning and spot scanning were performed on
and sodium dodecyl sulfate (C12H25SO4Na) were weighed with EL204 the coating, and the EDS scanning results were analyzed. The coating
electronic balance (Mettler Toledo Instrument (Shanghai) Co., LTD.) was thinned to about 100 nm using a Gatan691 ion thinning instrument
and placed in a 400 ml beaker. Then 100 ml of ultra-pure water was (Gatan, USA). Then, the combination of graphene quantum dots (GQDs)
added to the beaker using a measuring cylinder, 0.1 ml of surfactant and nickel grains in the coating was observed by the FEI Talos F200X
(polyethylene glycol trimethyl nonyl ether), and the magnetic rotor was transmission microscope (EFI Technology, USA). HD-XpertPRO X-ray
placed into the beaker. According to the formula of the plating solution, diffractometer (Panalytical Company of the Netherlands) was used to
the quantitative graphene quantum dots (GQDs) were weighed with an test the coating. XRD used Cu target Kα radiation, the scanning Angle
electronic balance and placed in a 100 ml capacity beaker, and 50 ml was 5 ~ 80◦ , and the XRD pattern of the coating was analyzed and
ultra-pure water was measured with a measuring cylinder and put into calculated after the test. The HORIBA HR Evolution Raman spectrom­
the beaker. Place a 400 ml beaker into the EMS-12 split-type magnetic eter (Jobin Yvon, France) determined the coating’s chemical structure
stirrer (Tianjin Ounuo Instrument Co., Ltd.), turn on the magnetic stir­ and analyzed the Raman spectra. TR200 surface roughness meter (Bei­
ring function of the EMS-12 split-type magnetic stirrer, and stir the so­ jing Times Company) was used to measure the coating’s surface
lution. Then, place a beaker with a capacity of 100 ml into the Chunlin roughness, and the results were analyzed. HXD-1000TMS digital
Ultrasonic Cleaning Machine (Shenzhen Chunlin Cleaning Equipment microhardness tester (Beijing Shangguang Instrument Co., LTD.) was
Co., Ltd.) and use the ultrasonic function to vibrate the GQDs solution. used to test the hardness of the coating. The test force was 200 gf. Five
After 10 min, the GQDs solution will be completely dispersed. Pour the different points on the surface of the coating were tested, and the
dispersed GQDs solution into a 400 ml beaker, turn on the ultrasonic average hardness was taken for analysis.
vibration function of the EMS-12 split magnetic stirrers, and stir the The friction and wear of the coating were measured by Nanovea
solution with ultrasonic magnetic force simultaneously. After about 45 tribometer (USA Nanovea Company). A high-chromium steel bearing
~ 60 min, the electroplating solution will be evenly dispersed. Make the
solution meet the experimental requirements.
Table 3
(4) Pour the uniformly dispersed electroplating solution into the
Electrodeposition process parameters.
reactor of the supercritical unit, install a fixed electrodeposition device,
and then turn on the supercritical CO2 electrodeposition device, cool the Samples Ni- Ni- Ni- Ni-GQDs-IV
GQDs-I GQDs-II GQDs-III
CO2 gas below 5℃, control the temperature of the reactor at 50℃, and
input the CO2 gas into the reactor after the temperature of the reactor is GQDs (g/L) 1.5 1.5 1.5 1.5
Forward pulse current 5 5 5 5
stable, and then start the pressure pump to increase the pressure. The
density/(A/dm2)
pressure inside the reactor was controlled at 10.5 MPa so that the Forward pulse duty cycle 0.25 0.25 0.25 0.25
environment inside the reactor reached the state of supercritical CO2. Reverse pulse current 0.3 0.8 1.3 0.8
density/(A/dm2)
Reverse pulse duty cycle 0.25 0.25 0.25 0.25
Table 1 Frequency/Hz 1 1 1 1
Solution formulations for the preparation of graphene quantum dots (GQDs). Stresses/MPa 10.5 10.5 10.5 Normal
temperature
Reagent name Proportions (g•L− 1) Weight (g)
Temperature/℃ 50 50 50 Atmospheric
C6H8O7⋅H2O 42 4.2 pressure
CH4N2O 36 3.6 Time/min 60 60 60 60

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C. Fang et al. Electrochemistry Communications 160 (2024) 107680

ball with a diameter of 6 mm was selected as the grinding part. The test reverse pulse current densities under supercritical CO2 conditions. It can
parameters were as follows: The load is 10 N, the speed is 200 r/min, and be seen from Fig. 2 (a) that when the reverse pulse current density is 0.3
the test time is 10 min. After the experiment, the friction coefficient A/dm2, the surface topography of Ni-GQDs-I nanocomposite coating is
diagram is derived and analyzed. A Nanovea PS50 optical profiler (USA poor, and the surface of the coating is not flat and dense. There are
Nanovea Company) was used to profile the wear marks of the coating. defects such as pores, irregular nodules, and protrusions. It can be seen
The scanning area is 2 mm × 2 mm, the scanning rate is 3.33 mm/s, and from Fig. 2 (b) that when the reverse pulse current density is increased to
the step size is 5 μm. The results were analyzed after the scanning. The 0.8 A/dm2, the surface of Ni-GQDs-II nanocomposite coating is rela­
surface morphology of the coating wear marks was observed and tively flat and dense, and there are no defects such as bumps and nod­
analyzed by scanning electron microscopy. The electrochemistry ules, and the surface topography is good. It can be seen from Fig. 2 (c)
corrosion experiment of the coating was carried out in a three-electrode that when the reverse current density is increased to 1.3 A/dm2, the
system using a Metrohm PGSTAT302N electrochemical workstation surface morphology of Ni-GQDs-III nanocomposite coating is poor, with
(Metrohm, Switzerland). The experiment was carried out in 3.5 % NaCl defects such as massive spalling, surface pitting, holes, and irregular
solution with the platinum sheet as the counter electrode, the coating as protruding.
the working electrode, and Ag/AgCl− (1 M) as the reference electrode. The reasons for the above phenomenon are as follows: when the
The scanning rate of the measured potential polarization curve is 0.5 reverse pulse current density is 0.3 A/dm2, the current density is small,
mV/s, and the voltage range is − 0.2 V ~ 0.2 V. When the AC impedance which leads to a low dissolution effect of the reverse pulse current on the
spectrum is measured, the frequency range is 0.01 ~ 10000 Hz, and the cathode. The reverse pulse current cannot effectively remove the bumps
sine amplitude is 10 mV. The results are analyzed after the test. The and nodules on the Ni-GQDs nanocomposite coating. It leads to lower
coating was immersed in 3.5 % NaCl solution for 120 h, and the ion concentration at the cathode and a poorer electrodeposition effect.
corrosion morphology of the coating was observed and analyzed by SEM As a result, the surface density and flatness of Ni-GQDs-I nanocomposite
after corrosion. coating are poor, and there are irregular nodules and protrusions. With
the increase of the reverse pulse current density to 0.8 A/dm2, the
3. Results and analysis cathode dissolution effect of the reverse pulse current is increased, and
the ion concentration on the cathode surface is increased, which is
3.1. Effect of reverse pulse current density on the microstructure of Ni- conducive to the role of higher forward pulse current density in the
GQDs nanocomposite coatings subsequent cathode cycle. At higher forward pulse current densities, the
rate of crystal nucleation is greater than the rate of crystal growth,
Fig. 2 shows 1000-fold SEM images of Ni-GQDs nanocomposite resulting in smaller grain sizes in the coating. Therefore, the surface of
coatings prepared by different processes. Fig. 2 (a) ~ 2 (c) are SEM Ni-GQDs-II nanocomposite coating is relatively dense, flat, and has
images of Ni-GQDs nanocomposite coatings prepared with different fewer defects. When the reverse pulse current density continues to

Fig. 2. 1000-fold SEM images of Ni-GQDs nanocomposite coatings prepared by different processes; (a) Ni-GQDs-I; (b) Ni-GQDs-II; (c) Ni-GQDs-III; (d) Ni-GQDs-IV.

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C. Fang et al. Electrochemistry Communications 160 (2024) 107680

increase to 1.3 A/dm2, the cathode dissolution effect of the reverse pulse grains smaller. There is no supercritical CO2-assisted electrodeposition
current is too high, the surface of Ni-GQDs-III nanocomposite coating is at normal temperature and atmospheric pressure, so the surface quality
over-dissolved, the cathode ion concentration is too high, the effect of of Ni-GQDs-IV nanocomposite coating is poor, and there are many
electrodeposition is poor, the surface of the coating has massive spalling, defects.
holes and protrusions, and the surface density of the coating is low and In order to determine the distribution and percentage of elements in
the flatness is poor. the Ni-GQDs-II nanocomposite coatings, EDS planar and spot scans of
Fig. 2 (d) shows the SEM image of the surface of Ni-GQDs-IV nano­ the coatings were performed using SEM. The results were also analyzed.
composite coating prepared at normal temperature and atmospheric Fig. 3, Table 4 and Table 5 show the EDS scan results of the coatings. The
pressure with a reverse pulse current density of 0.8 A/dm2. As shown in surface morphology of the coating is shown in Fig. 3 (a). The EDS planar
Fig. 2 (d), the surface density of the coating is poor, the flatness is low,
and there are obvious defects such as bumps, holes, cracks, and so on.
Due to the low conductivity and solubility of metal salts in supercritical Table 4
CO2, crystal growth is hindered when supercritical CO2 comes into Elemental occupancy of EDS planar scans of Ni-
contact with the cathode. When the plating solution is in contact with GQDs-II nanocomposite coatings.
the cathode, new atomic nuclei are formed, and crystals grow. In addi­ Elemental wt%
tion, supercritical CO2 can effectively disperse graphene quantum dots C 18.67
(GQDs). GQDs form an active nucleation site in the coating, and the Ni 81.33
increase of the nucleation site inhibits crystal growth and makes the Overall amount 100.00

Fig. 3. EDS scans of Ni-GQDs-II nanocomposite coatings; (a) surface of the coating; (b) distribution of Ni-elements; (c) distribution of C-elements; (d) planar
scanning; (e) scanning of point 1; (f) scanning of point 2; (g) scanning of point 3.

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Table 5 microstructure of Ni-GQDs-II nanocomposite coating, and TEM results

Elemental percentage of EDS spot scans of Ni-GQDs-II nanocomposite coating. are shown in Fig. 4. It can be seen from Fig. 4 (a) that there are large
Atlas number Atlas 1 Atlas 2 Atlas 3 differences in the size of individual grains of nickel grains. Still, the
overall size of the grains is relatively uniform; all of them are in the
C 21.21 19.40 16.38
Ni 78.79 80.60 83.62 range of nanometer grain size, and the connection between the Ni grains
Overall amount 100.00 100.00 100.00 is relatively tight, and there are obvious grain boundaries. It can be seen
from Fig. 4 (b) that GQDs particles can be found in the coating under
TEM at higher multiples, indicating that GQDs are successfully depos­
scanning results are shown in Fig. 3 (b), Fig. 3 (c), Fig. 3 (d) and Table 4. ited on the coating, and GQDs are closely associated with Ni grains,
From Fig. 3 (d) and Table 4, it can be seen that the coating contains only indicating that the properties of GQDs do not change and no interface
Ni and C elements. The percentage of C element in the coating is 18.67 reaction occurs. This good interface combination is conducive to the
%. This proves the presence of graphene quantum dots (GQDs) in the transfer of loading force between the coating and the substrate and then
coating. Fig. 3 (b) and Fig. 3 (c) show that Ni grains and GQDs are improves the mechanical properties of the coating. Fig. 4 (c) shows the
uniformly distributed and closely connected in the coating. However, SADP diagram at point A. The white points in the diagram are arranged
because of the low percentage of GQDs in the coating, the distribution of regularly and distributed symmetrically relative to the center point,
Ni elements is denser and the distribution of C elements is sparse. Fig. 3 indicating that the large-sized Ni grains of the composite coating are in a
(e), Fig. 3(f), Fig. 3(g) and Table 5 show the EDS scanning results of the single crystal state and there is no subgrain boundary, which is consis­
three points in Fig. 3(a). The results show that the coating contains only tent with the results of the XRD pattern. Fig. 4 (d) shows the EDS dia­
Ni and C elements. The percentage of C elements in the three points is gram at point B in the middle of Fig. 4. It can be seen from Fig. 4 that the
21.21 %, 19.40 %, and 16.38 % respectively, with an average percentage proportion of C element and Ni element at point B is 25.23 % and 77.77
of 18.99 %. This also proves the existence of GQDs. %, respectively, which is consistent with the EDS point scanning results
To observe the presence of graphene quantum dots (GQDs) in Ni- of SEM, proving that the C element exists in the coating, and graphene
GQDs nanocomposite coating, TEM was used to observe the

Fig. 4. TEM results of Ni-GQDs-II nanocomposite coating; (a) TEM image of the coating; (b) high magnification TEM image of the coating; (c) SADP map of point A;
(d) EDS map of point B.

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quantum dots (GQDs) are successfully embedded in the composite Table 6

coating and combined between Ni grains. Grain size of Ni-GQDs nanocomposite coatings.
Samples 2θ(◦ ) hlk FWHM Grain size Average grain size
(nm) (nm)
3.2. Effects of reverse pulse current density on the preferred orientation
and grain size of Ni-GQDs nanocomposite coatings 44.82 111 1.125 7.55
Ni-GQDs-I 52.04 200 2.433 3.59 5.10
76.66 220 2.415 4.15
Fig. 5 shows the XRD patterns of Ni-GQDs nanocomposite coatings 44.77 111 1.095 7.76
prepared by different processes. It can be seen from Fig. 5 that the Ni-GQDs-II 51.88 200 2.593 3.37 4.58
diffraction peak Angle of Ni-GQDs nanocomposite coatings prepared 76.55 220 3.821 2.62
under supercritical CO2 conditions is the same. The crystal faces corre­ 44.81 111 1.095 7.96
Ni-GQDs- 51.99 200 2.594 3.64 5.11
sponding to each diffraction peak are (1 1 1), (2 0 0), and (2 2 0),
III
respectively, indicating that the crystal structure of Ni is a face-centered 76.59 220 3.821 3.74
cubic structure [32]. The diffraction intensities of (1 1 1) and (2 0 0) faces 44.95 111 0.436 19.52
of Ni-GQDs-IV nanocomposite coatings prepared under normal tem­ Ni-GQDs- 52.51 200 0.629 13.92 18.55
IV
perature and atmospheric pressure are lower than those of (1 1 1) and
76.99 220 0.452 22.22
(2 0 0) faces of Ni-GQDs nanocomposite coatings prepared under su­
percritical CO2. However, the diffraction intensity of Ni-GQDs-IV
nanocomposite coating (2 2 0) face prepared at normal temperature and Ni-GQDs-IV, and the grain size is reduced by 75.3 %. Since the reverse
pressure is higher than that of Ni-GQDs nanocomposite coating (2 2 0) pulse current density of 0.8 A/dm2 has the best dissolution effect on the
face prepared under supercritical conditions, and the diffraction in­ surface of the coating, the cathode ion concentration at this time is more
tensity of Ni-GQDs-IV nanocomposite coating (2 2 0) face shows a pref­ suitable for the larger forward pulse current in the next cathode cycle to
erential orientation. Due to the low conductivity and solubility of metal play a role, so the electrodeposited coating is the most flat and dense, the
salts in supercritical CO2, when supercritical CO2 comes into contact lowest porosity, the tightest intergranular bond, and therefore the grain
with the cathode, it impedes crystal growth, thus providing time for size is small. At normal temperature and atmospheric pressure, the
atoms to migrate to the most stable position during electrodeposition, so maximum grain size of Ni-GQDs-IV nanocomposite coating is 18.55 nm.
the preferred orientation of nickel crystals is the (1 1 1) face. However, The reason for the above phenomenon is that at normal temperature and
under normal temperature and pressure conditions, there is no super­ atmospheric pressure, there is no supercritical CO2 to prevent grain
critical CO2 to hinder the growth of crystals. Atoms cannot migrate to growth. In addition, in the absence of supercritical CO2 dispersed gra­
stable positions, so the preferred orientation of Ni crystals is (2 2 0) face. phene quantum dots (GQDs), the GQDs were not uniformly distributed
The average grain size of nickel grains with different coatings was in the coatings and did not form more nucleation sites to prevent Ni
calculated using the diffraction peak width and Debye-Scherrer [33] grain growth, resulting in larger grain sizes in the coatings.
formula, as shown below.
Kγ 3.3. Characterization of graphene quantum dots (GQDs) in Ni-GQDs
D= (1) nanocomposite coatings prepared by different processes
BCOSθ
In the formula, Scherrer constant K is 0.89, X-ray wavelength γ is Fig. 6 shows the Raman spectra of graphene quantum dots (GQDs).
0.154056 nm, B is the half-height and width of the diffraction peak, and Raman spectra of Ni-GQDs-II nanocomposite coatings prepared under
θ is the diffraction Angle. The grain size of the coating is obtained from supercritical CO2 and Ni-GQDs-IV nanocomposite coatings prepared
formula (1), and the results are shown in Table 6. under normal temperature and atmospheric pressure. Table 7 shows the
It can be seen from Table 6 that under supercritical conditions, the positions of D and G bands, the intensity values, and the ratios of D and G
grain size of Ni-GQDs nanocomposite coating first decreases and then peaks in the Raman spectra. It is known that incomplete graphite mi­
increases with the increase of reverse pulse current density, in which the crocrystals cause the D-peak, many structural defects, and unsaturated
grain size of Ni-GQDs-II is the smallest (4.58 nm), smaller than that of edge carbon atoms, and the D-peak represents the defects of the crystal
Ni-GQDs-I and Ni-GQDs-III. The grain size is much smaller than that of lattice, so the larger the value, the more defects of the C atom crystal, the

Fig. 5. XRD patterns of Ni-GQDs nanocomposite coatings prepared by Fig. 6. Raman spectra of Ni-GQDs composite coatings prepared by different
different processes. processes and graphene quantum dots (GQDs).

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C. Fang et al. Electrochemistry Communications 160 (2024) 107680

Table 7 prepared with a reverse current density of 0.8 A/dm2 has a higher
Positions of D and G bands and intensity values in Raman spectrograms. hardness of 867.2 HV. Compared with Ni-GQDs-IV nanocomposite
Samples D-Band G-Band D-Band G-Band ID/IG coating prepared at normal temperature and atmospheric pressure, the
Position Position Strength Strength hardness is significantly increased by 53.7 %. Because when the reverse
(cm− 1) (cm− 1) (ID) (IG) pulse current density is 0.8 A/dm2, the cathode dissolution effect is most
GQDs 1336.64 1551.22 4475.6 5304.8 0.8437 suitable. At this time, the ion concentration near the cathode is higher,
Ni- / / / / / which is conducive to the higher forward pulse current density in the
GQDs- subsequent cathode cycle. Higher forward pulse current density can
IV
Ni- 1327.04 1573.78 2762.1 4224.8 0.6538
make the nucleation rate larger than the crystal growth rate and the
GQDs- grain size smaller. At the same time, supercritical CO2 can effectively
II refine the grain [34], so the grain size of Ni-GQDs-II nanocomposite
coating is smaller. According to the Hall-Petch relationship [35], the
presence of small grains obstructs the movement of the dislocation and
G-peak strength can be used to characterize the integrity of the SP2
effectively improves the hardness of the coating. The surface of the
hybrid bond structure in the graphite structure. The intensity of the G-
coating is compact and flat, and the porosity is low, so the Ni-GQDs-II
peak reflects the material’s number of layers and the crystal lattice’s
nanocomposite coating has a higher hardness.
integrity. The quality of GQDs is determined by the D-band and G-band
Compared with coatings prepared by other processes. The micro­
intensity ratio ID/IG. The smaller the ratio of ID/IG, the better the quality
hardness of Ni-GQDs-IV nanocomposite coatings prepared at normal
of GQDs.
temperature and atmospheric pressure was even lower at 564.4 HV.
From Fig. 6 and Table 7, it can be seen that the ratio of the D peak
Because at normal temperature and atmospheric pressure. There was no
intensity to the G peak intensity of the Ni-GQDs-II nanocomposite
supercritical CO2-assisted electrodeposition, so the growth of the
coating is 0.6538. The ratio of D-peak strength to G-peak strength of
coating crystals failed to be limited. In addition, graphene quantum dots
GQDs is 0.8437, and the ratio of D-peak strength to G-peak strength of
(GQDs) are easy to agglomerate during electrodeposition, their distri­
GQDs is higher than that of Ni-GQDs-II nanocomposite coating. In Ni-
bution in the coating is not uniform, and they cannot form more
GQDs-II nanocomposite coating, the defects of GQDs are reduced, and
nucleation points to prevent the growth of grains. Therefore, the Ni-
the quality of GQDs is improved, possibly because the integrity of GQDs
GQDs-IV nanocomposite coating has a larger grain size. Therefore, the
is improved by the action of supercritical CO2. No D and G peaks were
combination between grains is not tight enough, and there are more
detected in Ni-GQDs-IV composite coating. It may be because GQDs are
voids between grains. Moreover, the microstructure density of the
easy to agglomerate during electrodeposition at normal temperature and
coating is poor, the surface is uneven, and the porosity is high, so the
atmospheric pressure, so the binding effect of GQDs and Ni ions is poor
hardness of the coating is low.
during electrodeposition. GQDs are unevenly distributed and make up a
relatively small proportion of the coating. Therefore, it is not easy to
3.4.2. Effect of reverse pulse current density on surface roughness of Ni-
detect the presence of GQDs in Ni-GQDs-IV nanocomposite coatings by
GQDs nanocomposite coating
Raman spectroscopy.
Fig. 8 shows the surface roughness of Ni-GQDs nanocomposite
coatings prepared by different processes. As can be seen from Fig. 8, the
3.4. Effect of reverse pulse current density on properties of Ni-GQDs roughness of Ni-GQDs-II nanocomposite coatings prepared under su­
nanocomposite coating percritical CO2 condition with reverse pulse current density of 0.8A
/dm2 is lower, which is 0.236 μm. Compared with that of the Ni-GQDs-
3.4.1. Influence of reverse pulse current density on the microhardness of Ni- IV nanocomposite coatings prepared at normal temperature and atmo­
GQDs nanocomposite coating spheric pressure, the roughness of Ni-GQDs-II nanocomposite coatings is
Fig. 7 shows the microhardness of Ni-GQDs nanocomposite coatings significantly reduced by 37 %. Since the reverse pulse current density of
prepared by different processes. As can be seen from Fig. 7, under the 0.8 A /dm2 has the best dissolution effect on bumps, burrs, nodules, and
condition of supercritical CO2, the Ni-GQDs-II nanocomposite coating other defects on the coating surface, the cathode ion concentration is

Fig. 7. Microhardness values of Ni-GQDs nanocomposite coatings prepared by Fig. 8. Surface roughness values of Ni-GQDs nanocomposite coatings prepared
different processes. by different processes.

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C. Fang et al. Electrochemistry Communications 160 (2024) 107680

higher at this time, which is conducive to playing a higher role in the Archard’s law [37] is shown in formula (2), where Q is the wear rate,
next cathode cycle. In the electrodeposition process, the formation rate K is the friction coefficient, W is the applied load (N), and H is the
of the crystal nucleus is greater than the growth rate of the crystal, and hardness. According to Archard’s law, under the same wear conditions,
the growth of the grain is hindered. When supercritical CO2 comes into the higher the hardness, the better the wear resistance. By comparing
contact with the cathode, grain growth is also hindered. At this time, the the hardness of the four coatings, it is found that the hardness of Ni-
degree of grain refinement is higher. Therefore, the grain size of the GQDs-II nanocomposite coating is higher. The hardness of Ni-GQDs-I
coating is small. The surface of the coating is flat and dense, so the nanocomposite coating is not much different from that of Ni-GQDs-III
roughness of the coating is low. nanocomposite coating, but both are lower than that of Ni-GQDs-II
Under normal temperature and atmospheric pressure conditions, nanocomposite coating. The hardness of Ni-GQDs-IV nanocomposite
there is no supercritical CO2 assist during electrodeposition, and the coating is much lower than the other coatings. Since the hardness of Ni-
grains cannot be refined effectively. Moreover, the second phase addi­ GQDs-II nanocomposite coating is higher, the wear resistance of the
tive graphene quantum dots (GQDs) are easy to agglomerate, which is coating is better.
unevenly distributed in the coating, and there are no more nucleation
KW
sites to limit the growth of Ni grains. Currently, the grains are coarse, Q= (2)
H
and there are more intergranular Spaces. The results show that the Ni-
GQDs-IV nanocomposite coating has poor microstructure density, un­ After friction and wear experiments, the cross-section and three-
even surface, and high porosity. Therefore, the surface roughness of the dimensional surface of Ni-GQDs nanocomposite coatings prepared by
coating is high. different processes are shown in Fig. 10. The maximum depth, cross-
sectional area, and volume wear of Ni-GQDs nanocomposite coatings
3.4.3. Effect of reverse pulse current density on wear resistance of Ni-GQDs prepared by different processes are shown in Table 8. According to
nanocomposite coating Fig. 10 and Table 8, compared with other coatings, the wear traces of Ni-
Fig. 9 shows the friction coefficient of Ni-GQDs nanocomposite GQDs-II nanocomposite coatings are relatively shallow. The cross-
coatings prepared by different processes. As can be seen from Fig. 9, the sectional area and volume of wear marks are relatively small. The
friction coefficient of Ni-GQDs-I, Ni-GQDs-II, Ni-GQDs-III, and Ni-GQDs- volumetric wear of Ni-GQDs-II nanocomposite coating is 3.395 × 107
IV nanocomposite coatings changes with the change of friction and wear µm3, which is 74.7 %, 65.5 %, and 42.1 % of the volumetric wear of Ni-
time. The friction curve of the coating includes the process of removing GQDs-I nanocomposite coating, Ni-GQDs-III nanocomposite coating,
the roughness of the coating surface and flattening the uneven coating. and Ni-GQDs-IV nanocomposite coating, respectively. The Ni-GQDs-II
This stage is the initial run-in stage. At this time, the contact area be­ nanocomposite coating showed less volumetric wear compared to
tween the surface of the coating and the steel ball is small, and the stress other coatings, with up to 57.9 % reduction. Due to the small volume
concentration and plastic deformation occur in some uneven positions. wear of Ni-GQDs-II nanocomposite coatings, they have excellent wear
When the surface of the coating becomes smooth, the wear enters the resistance.
stable stage and shows a stable friction coefficient, and the final friction The reason for the above phenomenon is that the cathodic dissolu­
coefficient is stable at 0.314, 0.262, 0.299, and 0.361. It is well known tion effect of the reverse pulse current is poor when the reverse pulse
that the smaller the coefficient of friction, the better the wear resistance current density is 0.3 A/dm2 under supercritical CO2 conditions,
[36]. Among the coatings prepared with different process parameters, resulting in nodular and raised defects on the surface of Ni-GQDs-I
the friction coefficient of Ni-GQDs-II nanocomposite coating is smaller nanocomposite coatings. This leads to poor surface flatness, high
at 0.262, which is significantly reduced by 27.4 %. Therefore, the wear roughness, and low hardness of the coating. As a result, the resistance of
resistance of Ni-GQDs-II nanocomposite coating is better. The friction the coating to the shear force during friction contact is low, so the
coefficients of Ni-GQDs-I nanocomposite coatings and Ni-GQDs-III friction coefficient of the coating is high, and the volume wear is large.
nanocomposite coatings are similar, but they have higher friction co­ When the reverse pulse current density is 1.3 A/dm2, the cathode
efficients, so the wear resistance is poor. The Ni-GQDs-IV nano­ dissolution effect of the reverse pulse current density is stronger. The
composite coating has a higher coefficient of friction compared to other cathode ion concentration is higher at this time, resulting in massive
coatings, so the wear resistance is worse. spalling and pitting defects on the surface of Ni-GQDs-III nanocomposite
coating, resulting in poor surface flatness, high porosity, high roughness,
and low hardness of the coating. As a result, the resistance of the coating
to the shear force during friction contact is low, so the friction coefficient
of the coating is high, and the volume wear is large. When the reverse
pulse current density is 0.8 A/dm2, the cathodic dissolution effect of the
reverse pulse current is good, and the surface of Ni-GQDs-II nano­
composite coating is flat and dense. Moreover, the roughness of the
coating is small and the hardness is high. As a result, the coating has a
strong resistance to the shear force generated by friction and wear. As a
result, the coefficient of friction of the coating is relatively low. The
volume wear of the coating is minimal. At normal temperature and at­
mospheric pressure conditions, because there is no supercritical CO2-
assisted electrodeposition, the grain size of the Ni-GQDs-IV nano­
composite coating is relatively large, and the bonding effect between the
grains is poor. This leads to defects such as protrusions, pores, and cracks
on the surface of the coating and poor surface quality. Moreover, due to
the high roughness and low hardness of the coating. As a result, the
coating has low resistance to shear forces generated by friction and
wear. As a result, the coating has a high coefficient of friction and
volumetric wear.
Fig. 11 shows the 1500-fold SEM image of the wear marks of Ni-
Fig. 9. Friction coefficient of Ni-GQDs nanocomposite coatings prepared by
GQDs nanocomposite coatings prepared by different processes. In the
different processes. friction and wear experiment, the steel ball with higher hardness will

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C. Fang et al. Electrochemistry Communications 160 (2024) 107680

Fig. 10. Cross-sectional and three-dimensional profiles of abrasion marks of Ni-GQDs nanocomposite coatings prepared by different processes; (a) Ni-GQDs-I; (b) Ni-
GQDs-II; (c) Ni-GQDs-III; (d) Ni-GQDs-IV.

produce plowing on the surface of the coating. It can be seen from only some plastic flow. The reverse pulse current density used at this
Fig. 11 (a) that the surface quality of Ni-GQDs-I nanocomposite coating time is suitable for preparing coatings with dense and flat surfaces, low
wear is poor, and there are many defects on the surface of the wear, porosity, and high hardness. High hardness has a good supporting effect
including obvious large-area adhesive wear and some faults. Due to the on the load in friction and reduces the plowing effect of the steel ball on
low reverse pulse current density during the preparation of Ni-GQDs-I the coating in friction and wear tests, so the surface morphology of the
nanocomposite coating, the coating is uneven and dense, with high coating wear marks is good.
porosity and low hardness. The lower hardness leads to poor support From Fig. 11 (c), it can be seen that the surface morphology of the Ni-
load effect of the coating in the friction and wear test, which enhances GQDs-III nanocomposite coating wear marks is poor, with some cracks
the plowing effect of the steel ball on the coating, so the surface and wear adhesion defects on the surface of the wear marks. Due to the
topography of the wear marks is poor. From Fig. 11 (b), it can be seen excessive reverse pulse current density during electrodeposition, there is
that the wear degree of Ni-GQDs-II nanocomposite coating is relatively much blocky peeling and surface pitting on the surface of the coating,
low, and there are no obvious defects on the surface of the wear marks, resulting in a higher porosity of the coating. The surface of the coating is

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C. Fang et al. Electrochemistry Communications 160 (2024) 107680

Table 8 on the coating is stronger, so the surface morphology of the coating

Maximum depth of abrasion marks, cross-sectional area of abrasion marks, and abrasion marks is poorer.
volumetric wear of Ni-GQDs nanocomposite coatings.
Samples Maximum depth of The cross-sectional Volumetric wear of 3.4.4. Effect of reverse pulse current density on corrosion resistance of Ni-
abrasion marks (µm) area of abrasion marks coatings (µm3) GQDs nanocomposite coating
(µm2) Fig. 12 shows the electrochemical corrosion results of Ni-GQDs
Ni- 18.9 4543 4.543 × 107 nanocomposite coatings prepared by different processes in a 3.5 %
GQDs-I NaCl solution. Fig. 12 (a) shows the Tafel polarization curve of Ni-GQDs
Ni- 16.0 3395 3.395 × 107
nanocomposite coating. The self-corrosion voltage and self-corrosion
GQDs-
II current density of Ni-GQDs nanocomposite coatings prepared by
Ni- 21.7 5180 5.180 × 107 different processes can be obtained from the Tafel polarization curves,
GQDs- and the data are shown in Table 9.
III From Fig. 12(a) and Table 9, it can be seen that the self-corrosion
Ni- 18.6 8061 8.061 × 107
GQDs-
voltage of the Ni-GQDs-II nanocomposite coating is higher at − 139
IV mV. The self-corrosion voltage is significantly increased by 68.7 %
compared to that of the Ni-GQDs-IV nanocomposite coating. The self-
corrosion voltage reflects the stability of the coating surface, and the
uneven, with poor surface tissue density and low hardness. The lower higher the self-corrosion voltage, the better the stability of the coating
hardness results in poor support of the coating for load in friction and surface and the stronger the corrosion resistance of the coating surface.
wear experiments, enhancing the plowing effect of the steel ball on the Therefore, the Ni-GQDs-II nanocomposite coating has superior corrosion
coating and resulting in poor surface morphology of wear marks. From resistance. Since the self-corrosion current is caused by the dissolution of
Fig. 11 (d), it can be seen that the surface quality of the Ni-GQDs-IV the material, the lower the self-corrosion current density and the higher
nanocomposite coating abrasion marks is poor, with a large number of the charge transfer resistance, the better the corrosion resistance of the
blemishes and wear attachments on the surface. Compared with other coating. From Fig. 12(a) and Table 9, it can be seen that among the four
coatings, the surface morphology of the abrasion marks is poor. This is coatings, the self-corrosion current density of the Ni-GQDs-II nano­
because there is no supercritical CO2-assisted electrodeposition at composite coating is lower at 3.19 × 10− 7 A/cm2, which is significantly
normal temperature and atmospheric pressure, resulting in the failure of reduced by 71.2 % compared with that of the Ni-GQDs-IV nano­
graphene quantum dots (GQDs) to be effectively dispersed. Therefore, composite coating. It is known that the higher the self-corrosion voltage
the distribution of GQDs in the coating is uneven and the content is low. and the lower the self-corrosion current density of a coating, the better
Because the aggregation of GQDs in the coating increases the adhesion the corrosion resistance of the coating [38]. Because Ni-GQDs-II nano­
area of the friction surface, the adhesive wear of the coating becomes composite coating has higher self-corrosion voltage and lower self-
stronger as the adhesion effect increases. The surface of the coating is corrosion current density, the corrosion resistance is more excellent.
uneven, with low tissue density as well as high porosity. Also, because of In order to further compare and analyze the corrosion resistance of
the low hardness of the coating, the supporting load in the friction and Ni-GQDs nanocomposite coatings, EIS experiments were conducted on
wear experiments is poor. At this time, the plowing effect of the steel ball Ni-GQDs nanocomposite coatings, and the experimental results were

Fig. 11. 1500-fold SEM images of wear marks of Ni-GQDs nanocomposite coatings prepared by different processes; (a) Ni-GQDs-I; (b) Ni-GQDs-II; (c) Ni-GQDs-III;
(d) Ni-GQDs-IV.

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C. Fang et al. Electrochemistry Communications 160 (2024) 107680

Fig. 12. Electrochemical corrosion results of Ni-GQDs nanocomposite coatings with different processes. (a) Tafel polarization curve, (b) Nyquist spectrum, (c)
equivalent electrochemical circuit.

Subsequently, the EIS experimental results were fitted and analyzed

Table 9
using the equivalent circuit model shown in Fig. 12 (c). The fitting pa­
Electrochemical parameters of Ni-GQDs composite coatings in 3.5% NaCl
rameters are shown in Table 9. From Table 9, it can be seen that the Rct
solution.
value of Ni-GQDs-II nanocomposite coating is relatively large, at
7
Sample Ecorr（mV） Icorr（10− A/ Rs, Rct, Ndl
31594.53 Ω⋅cm2. The dispersion index Ndl value is relatively high, at
cm2） Ω⋅cm2 Ω⋅cm2
0.862. Compared with the Ni-GQDs-IV nanocomposite coating, the Rct
Ni-GQDs-I − 202 8.09 23.23 18827.71 0.763 value and Ndl value of the Ni-GQDs-II nanocomposite coating were
Ni-GQDs- − 139 3.19 23.56 31594.53 0.862
II
significantly increased by 226.2 % and 67.1 %, respectively. The higher
Ni-GQDs- − 179 7.78 22.86 19805.98 0.791 the Rct value, the more difficult it is for the electrochemical anodic
III dissolution reaction to occur. The Ndl value represents the density of the
Ni-GQDs- − 358 11.07 20.56 9686.29 0.516 oxide film on the coating, and the higher the Ndl value, the greater the
IV
density of the oxide film. The higher the Rct and Ndl values, the better the
corrosion resistance of the coating. The Rct and Ndl values of Ni-GQDs-II
fitted. Fig. 12 (b) shows the Nyquist plots of Ni-GQDs nanocomposite nanocomposite coatings are higher, so they have excellent corrosion
coatings, where solid symbols represent the experimental results and resistance.
solid lines represent the fitting results. As shown in Fig. 12(b), among Fig. 13 shows the surface 1000-fold SEM image of Ni-GQDs nano­
the four coatings, the impedance spectral radius of Ni-GQDs-II nano­ composite coatings prepared by different processes after immersion and
composite coating is larger, and the impedance spectral radius of Ni- corrosion in 3.5 % NaCl solution for 120 h. From Fig. 13 (a), it can be
GQDs-I nanocomposite coating and Ni-GQDs-III nanocomposite seen that the Ni-GQDs-I nanocomposite coating shows large corrosion
coating are not very much different from each other, but both of them pits on the coating after being corroded by corrosive media such as Cl− ,
are lower than that of Ni-GQDs-II nanocomposite coating. The imped­ with a larger diameter and some corrosion points, indicating poor
ance spectral radius of Ni-GQDs-IV nanocomposite coating is lower than corrosion resistance of the coating. The Ni-GQDs-II nanocomposite
that of other coatings. Because the larger the impedance spectral radius, coating shown in Fig. 13 (b) has only some corrosion points on the
the larger the impedance. The larger the impedance, the better the in­ surface after corrosion, and the surface morphology after corrosion is
hibition of electron and ion transport, thus inhibiting the occurrence of good, indicating that the coating has good corrosion resistance. The Ni-
electrochemical reactions, slowing down the rate of electrochemical GQDs-III nanocomposite coating shown in Fig. 13 (c) showed more
reactions on the surface of the coating, and reducing the degree of corrosion pits on the surface after corrosion, and the diameter of the
oxidation and corrosion on the surface of the coating. It is known that corrosion pits was larger than that of the Ni-GQDs-I nanocomposite
the higher the impedance, the better the corrosion resistance [39]. Since coating, indicating that the corrosion resistance of the Ni GQDs-III
the Ni-GQDs-II nanocomposite coating has relatively high impedance, it nanocomposite coating was worse. The Ni-GQDs-IV nanocomposite
has more excellent corrosion resistance. coating shown in Fig. 13 (d) showed large corrosion pits on the surface
after corrosion. The diameter of the corrosion pits was smaller than that

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C. Fang et al. Electrochemistry Communications 160 (2024) 107680

Fig. 13. 1000-fold SEM of Ni-GQDs nanocomposite coatings prepared by different processes after immersion and corrosion in 3.5% NaCl solution for 120 h; (a) Ni-
GQDs-I; (b) Ni-GQDs-II; (c) Ni-GQDs-III; (d) Ni-GQDs-IV.

of the Ni-GQDs-III nanocomposite coating, but the depth was deeper, the relatively large grains in the coating. This leads to a low density of
indicating that the corrosion resistance of the Ni-GQDs-IV nano­ the organizational structure of the coating and a high porosity. At this
composite coating was poor. The above results show that the Ni-GQDs-II time, the corrosive medium is relatively easy to penetrate into the
nanocomposite coating has better corrosion resistance. coating, so the corrosion resistance of the Ni-GQDs-IV nanocomposite
The reasons for the above phenomenon are as follows: when the coating is poor.
reverse pulse current density is 0.3 A/dm2, the current density is small,
and the optimization effect on the coating during the electrodeposition 4. Conclusion
process is small, resulting in poor microstructure density and high
porosity of the coating. In this way, the corrosive medium is easier to (1) The Ni-GQDs-II nanocomposite coating prepared with reverse
penetrate into the coating, so the corrosion resistance of Ni-GQDs-I pulse current density of 0.8A /dm2 under supercritical CO2 con­
nanocomposite coating is poor. When the reverse pulse current density ditions has a compact and flat surface, no obvious defects on the
was increased to 0.8 A/dm2, the coating quality was optimized to a surface, and excellent surface quality. Graphene quantum dots
greater extent due to the reverse pulse current. The coating has a higher (GQDs) and Ni ions are uniformly distributed in Ni-GQDs-II
tissue density and lower porosity. Moreover, graphene quantum dots nanocomposite coating.
(GQDs) are uniformly dispersed on the surface of the coating, which can (2) Supercritical CO2 effectively dispersed the graphene quantum
effectively reduce the anodic dissolution area and serve as a physical dots and greatly restricted the grain growth. The grain size was
barrier to prevent corrosion of the coating by corrosive media. There­ smaller at the appropriate reverse pulse current density.
fore, the corrosion resistance of Ni-GQDs-II nanocomposite coating is (3) The variation of process parameters has a large impact on the
good. When the reverse pulse current density was increased to 1.3 A/ mechanical properties of the deposited layer. The mechanical
dm2, the higher reverse pulse current density produced a strong cathodic properties of the deposited layer were improved by 53.7 % under
dissolution effect on the surface of the coating, resulting in a high con­ more appropriate process parameters.
centration of ions near the cathode and a poor electrodeposition effect. (4) The corrosion resistance of the deposited layers was also affected
Defects such as lumpy spalling and pitting appear on the coating surface. by the variation of process parameters. When graphene quantum
Also because of the low tissue density and high porosity of the coating. dots (GQDs) were uniformly dispersed in the coating, the grain
So the coating is less resistant to corrosive media. So the corrosion refinement of the deposited layer was higher. The corrosion
resistance of Ni-GQDs-III nanocomposite coating is poor. When elec­ resistance of the deposited layer increased by 61.2 %.
trodeposited at normal temperature and atmospheric pressure, graphene
quantum dots (GQDs) tend to agglomerate due to the lack of assistance Funding
from supercritical CO2. This leads to uneven distribution of GQDs in the This research was funded by “National Natural Science Foundation
coating and poor shielding against corrosive media. In addition, due to of China (51975264)”.

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C. Fang et al. Electrochemistry Communications 160 (2024) 107680

CRediT authorship contribution statement [15] H.-B. Lee, H.-H. Sheu, J.-S. Jian, et al., Supercritical-CO2 electroless nickel plating
enhanced anti-corrosion properties of micro-arc oxidized AZ31 magnesium alloy,
Mater. Today Commun. 33 (2022) 104475, https://doi.org/10.1016/j.
Cong Fang: Writing – review & editing, Writing – original draft, mtcomm.2022.104475.
Visualization, Validation, Supervision, Software, Methodology, Investi­ [16] K. Higuchi, T.F.M. Chang, M. Sone, Electrode Kinetic Study of Cu Electrodeposition
gation, Formal analysis, Data curation, Conceptualization. Weining Lei: with Supercritical CO2 by High Pressure Rotating Disk Electrode Method,
J. Electrochem. Soc. 169 (2) (2022) 020558, https://doi.org/10.1149/1945-7111/
Writing – review & editing, Supervision, Resources, Methodology, ac534a.
Funding acquisition, Formal analysis, Conceptualization. Tianle Xu: [17] S. Pandiyarajan, P.-J. Hsiao, A.-H. Liao, et al., High-performance
Visualization, Software, Investigation, Formal analysis. Haoyu Zhong: polyvinylpyrrolidone capped copper coatings via ultrasonic-assisted supercritical-
CO2 electrodeposition: Electrochemical evaluation, Surf. Coat. Technol. 409 (2021)
Validation, Software, Methodology, Investigation. Bin He: Supervision, 126926, https://doi.org/10.1016/j.surfcoat.2021.126926.
Methodology, Investigation. Linglei Kong: Supervision, Methodology, [18] A. Ghaffarkhah, E. Hosseini, M. Kamkar, et al., Synthesis, applications, and
Formal analysis. Yiliang He: Software, Methodology, Investigation. prospects of graphene quantum dots: A comprehensive review, Small 18 (2) (2022)
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[19] L. Sun, Y. Chen, M. Sun, et al., Physical Mechanism of Fluorescence and Chirality of
Declaration of competing interest Functionalized Graphene Quantum Dots, J. Phys. Chem. C 126 (2022)
12845–12859, https://doi.org/10.1021/acs.jpcc.2c02896.
[20] S.-Y. Li, L. He, Recent progresses of quantum confinement in graphene quantum
The authors declare that they have no known competing financial dots, Front. Phys. 17 (2021) 33201, https://doi.org/10.1007/s11467-021-1125-2.
interests or personal relationships that could have appeared to influence [21] S.A. Ansari, Graphene quantum dots: novel properties and their applications for
the work reported in this paper. energy storage devices, Nanomaterials 12 (21) (2022) 3814, https://doi.org/
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