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Schematic of electrochemical measurements.
| Cite this article as: |
Linhui Chang, Sheng Chen, Xionghui Xie, Buming Chen, Haihong Qiao, Hui Huang, Zhongcheng Guo, and Ruidong Xu, Effects of Zr content on electrochemical performance of Ti/Sn–Ru–Co–ZrOx electrodes, Int. J. Miner. Metall. Mater., 29(2022), No. 12, pp.2181-2188. https://dx.doi.org/10.1007/s12613-021-2326-y
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In the recent industrial electrodeposition of Mn, the sulfate and chloride systems were commonly used. Oxygen evolution reaction (OER), and chlorine evolution reaction (CER) mainly occur at the anode in the sulfuric acid system and the chlorination system, respectively.
Pb-based alloy anodes [1] have long been used for electrolytic extraction of Mn in a sulfate system. The corrosion resistance of the Pb−1wt%Ag anodes with railing structure [2] was 4.3 times that of ordinary boards in an acid solution. The excellent corrosion resistance benefits from the formation of a PbO2 protective film with good conductivity on the Pb surface in the acidic solution. Pb−Sn−1wt%Ag−Sb anodes [3] were beneficial to the precipitation of metallic Mn because of the low output of MnO2. Compared with the Pb−Sn−1wt%Ag−Sb anodes, the new Pb−Ag−Ca alloy [4] greatly reduced the amount of Ag consumption and early corrosion, the current efficiency was increased by 3.3% also. Although the new Pb-based alloys were more environmentally friendly, especially in energy consumption, the powdery MnO2 with high electrochemical activity is generated in the solution during electrolysis when using Pb-based alloys. MnO2 products would be contaminated by dissolved Pb impurities, which was not conducive for a long-term application.
There were many shortcomings during producing Mn by electrolysis in the sulfate system (MnSO4−(NH4)2SO4−H2O), such as low current efficiency, high energy consumption, and serious pollution [5]. However, in the chloride (MnCl2−NH4Cl−H2O) electrolysis system, although there are Cl2 releasing and the corrosion of the anode by the overflow Cl2, the high electrolyte conductivity and high manganese deposition efficiency still kept. The above advantages and the low energy consumption had attracted the attention of many researchers [6]. Compared with the sulfate system, high purity Mn was obtained by the diaphragm electrolysis in the chloride system with low cell voltage and high current efficiency [7−8]. The strong adsorption of MnCl+ on the cathode inhibited H2 evolution in the chloride solution and was conducive to the rapid nucleation of metals and the deposition of fine crystals, mainly generating a large-scale γ-Mn crystal system [9]. The Ti/PbO2 electrodes [10] were successfully used instead of graphite anodes to prepare high-quality electrolytic Mn from the MnCl2 system. This allows high Mn2+ concentration and high current density to be used, and the amount of Cl2 escape is greatly reduced. The anodes usually working in a strong acidic and high current density environment [11] by using IrO2, RuO2 [12] to maintain high activity. The stability of the electrodes was improved by other inert elements, such as TiO2, Ta2O5 [13]. It was found that Ti/IrO2 (70mol%)−Ta2O5 (30mol%) coated anode has high electrocatalytic activity and stability in an acidic environment. Meanwhile, to improve the stability of the Ti-based coating, other metal oxides were doped in the intermediate layer, such as Co/Sb doped Ti/SnO2 electrode [14]. This oxide intermediate layer prevented the oxygen precipitated in the reaction from diffusing into the Ti substrate and the generation of non-conductive TiO2 or other Ti oxides, so the service life of the electrode was increased [15−18]. Thus, the replacement of traditional Pb−Ag anodes by Ti-based rare metal oxide coating anodes is very valuable.
Based on the preparation of the prescriptive Ti/Sn–Ru–Co oxide electrodes, a new type of Ti/Sn−Ru−Co−Zr oxide electrode was prepared by multiple thermal decomposition oxidation with different content of Zr. The new Ti/Sn−Ru−Co−Zr anodes were investigated, and their stability of surface morphology and phase performance were compared with no Zr added electrodes. In addition, the performance of the electrode was studied by the electrochemical station.
This process was three steps in the pre-treated titanium substrate [19]. First, the Ti sheets (1 cm × 3 cm × 0.1 cm) were dipped into 10wt% NaOH solution at 70°C for 30 min and then rinsed with deionized water to remove grease. Secondly, the Ti sheets were etched in mixed acid solution (HF : HNO3 : H2O = 1:4:5 in volume ratio) for 3 min to remove the oxide layer, and repeated the rinsing work in the previous step. Next, etching the Ti sheets in 20wt% HCl solution at 90°C for 2 h to shape into a rough surface. Particularly, the pretreated Ti substrates were stored in ethanol solution at 25°C before use.
A mixture of SnCl4·5H2O, RuCl3·3H2O, CoCl2·6H2O, and Zr (NO3)2 was dissolved in 20wt% HCl and n-butanol at molar ratio 6:1:0.8: x (Sn = 0.006 mol; x = 0, 0.1, 0.3, 0.5, 0.7) was used as the precursor. The mixtures were completely and uniformly dissolved under an ultrasonic wave. Then, the precursor solution is painted to the pre-treated Ti substrates by using a brush. The Ti sheets were heated at a stable temperature of 500°C for 10 min after drying at 100°C. The sheets were brushed again after air-cooled to room temperature. The whole procedure was repeated 13 times and the last was heated for 1 h. After the above processes, 12–14 g/m2 oxide was loaded on the surface of the Ti sheets.
The surface morphology of the coatings and crystal structure were examined by scanning electron microscopy (SEM, SU8010, HITACHI, Japan). The phase composition of the coating was surveyed by XRD (X-ray diffraction) (RIGAKU D / MAX 2550, Japan) with Cu Kα radiation. The electrochemical tests were performed on an electrochemical workstation (RST-5200, China) with three-electrode systems. In an electrolyte solution of 1.5mol% HCl and 1mol% NH4Cl, the temperature was kept at 40°C. The working area is a single-sided insulated 1.0 cm2 electrode. The reference electrode was the saturated calomel electrode (SCE), and a Pt sheet of 6.0 cm2 was used as the auxiliary electrode. The corresponding potential range for linear sweep voltammetry (LSV) testing was 0.4–1.4 V with a scanning rate of 10 mV/s. The cyclic voltammetry (CV) testing was 0.5–0.9 V with a scanning rate of 1 mV/s, and EIS (electrochemical impedance spectroscopy) examination was conducted with an AC (alternating current) amplitude at 5 mV in the frequency range of 105 to 10−2 Hz. The additional anode potential was 1.2 V. The impedance data were converted into Nyquist data and fitted with expedient analog circuits. As shown in Fig. 1, the model was connected to the electrochemical workstation.
To shorten the experimental period, the accelerated life test of this anode coatings was evaluated using a solution containing 10wt%H2SO4, at 40°C with 1070-Al as the cathode. The distance between the electrodes was 2 cm, and the current density was 2 A/cm2. The empirical relationship between accelerated life t1 and actual service life t2 was as follows [19].
|
t2=(J2J1)nt1 |
(1) |
where n is a constant, usually taken as 2, J1 means the actual current density, and J2 denotes the accelerated current density.
The effect of coating phase with different Zr content measured by XRD is displayed in Fig. 2. The coating is mainly composed of oxides, including the crystalline phases of SnO2, RuO2, and ZrO2. The diffraction peaks of ZrO2 and RuO2 were overlapped together, indicating that solid solution probably formed between them. Through card analysis (JCPDS: RuO2-No.40-1290; SnO2-No.41-1445; ZrO2-No.37-1484; Ti-No.44-1294), it was observed that the crystal spacing d of diffraction peaks was close to that of RuO2, which is attributed to the main ruthenium-based solid solution. Furthermore, with the increase of Zr content according to XRD, the oxidation peak of the electrode coating first weakened and then enhanced. When the molar ratio of Sn : Ru : Co : Zr is 6:1:0.8:0.3, each diffraction peak was the weakest. In addition, with the increase of Zr content, the RuO2 of the (211) crystal plane increases significantly than that of SnO2. The solid solution of RuO2 and ZrO2 was turned into the crystal by strengthening and help form more stable structure. Otherwise, the intensity of Ti diffraction peak on the (101) crystal plane decreased with the increase of Zr content. However, when Sn : Ru : Co : Zr is 6:1:0.8:0.3, only trace amounts of titanium were found in the coating, indicating that the grains were refined and the Ti matrix was protected from corrosion by the addition of Zr.
The SEM images of the different Zr content electrodes were given in Fig. 3. The surface morphology of the electrodes changed with the content of Zr. The electrochemical activity for the electrodes was related to the roughness of the electrode’s surface certainly [20]. It can be obtained from Fig. 3 that with the increase of Zr content, the surface cracks first decreased and then increased. When the molar ratio of Sn : Ru : Co : Zr is 6:1:0.8:0.3, the surface morphology cracks were the least. The substrate was well protected from the corrosion of the solution during electrolysis due to the dense surface. As shown in Fig. 3(c), an amount of rough morphology appeared upon the electrode surface, and the rough morphology was able to protect the matrix from solution erosion [20]. The X-ray dot-mapping test was performed on the Zr-0.3 added electrode, focusing on the distribution of Zr element and the protective effect on the Ti matrix. The results showed that the distribution of Zr element on the coating particles was uniform, the coating had a good protective effect on the titanium substrate, and only a small amount of Ti element was exposed.
The anodic polarization curve testing results were shown in Fig. 4. At 500 A/m2, the chlorine evolution potential of Ti/Sn–Ru–Co–Zr oxide coated anode with different Zr content was 1.238 V (Zr-0), 1.221 V (Zr-0.1), 1.210 V (Zr-0.3), 1.259 V (Zr-0.5), and 1.311 V (Zr-0.7), respectively. By comparing the above data, it is easy to calculate the potential difference of chlorine evolution, which was 101 mV. These potentials related to the level of chlorine evolution activity indicating that the Zr-0.3 electrode had the strongest chlorine evolution activity.
The value of the polarization curve and chlorine release activity can be determined by comparing the overpotential of evolution [20]. The potential value was corrected by using Eq. (2) to describe the overpotential of chlorine evolution reaction (CER, η) of electrode material [21]:
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η=E+0.241−1.260−iRs |
(2) |
where E denotes the CER measured by the anode polarization curve in the experiment [22], and 1.260 V was the standard potential in the measurement system (1.5mol% HCl and 1mol% NH4Cl, 40°C). i is the current density measured at the relative potential. Rs is the electrolyte resistance between the reference electrode and the working electrode. The equilibrium potential of chlorine release was calculated by the Nernst equation. The potential of SCE was 0.241 V compared with the standard hydrogen electrode.
The chlorine evolution overpotential η has a semi-logarithmic relationship with the current density J, as shown in Eq. (3):
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η=a+blgJ |
(3) |
where a is a constant for the anodic process, V; b is the Tafel slope, V·dec−1.
|
a=−2.3(RT/βnF)lgJ0 |
(4) |
|
b=2.3RT/βnF |
(5) |
where R is the constant of gas; T is the temperature;
According to Fig. 5 and the data in Table 1, under the following conditions about 500 and 1000 A/m2, when the molar ratio of Sn : Zr is 6:0.3, the chlorine evolution overpotential was the lowest, about 0.143 V and 0.218 V, respectively. The small value indicated that the evolution of chlorine was easier. The value of “a” was positively correlated with the size of cell voltage. The depolarization phenomenon was related to a large amount of oxide with electrocatalytic activity in the coating, and the nanoparticles formed by adding an appropriate amount of Zr in the coating were very helpful, so the Zr-0.3 electrode had the lowest voltage. Scilicet, the above-mentioned oxide electrode coating had high catalytic activity.
| Name | η / V | a / V | b / (V·dec−1) | |
| 500 A·m−2 | 1000 A·m−2 | |||
| Zr-0.1 | 0.178 | 0.267 | 0.563 | 0.296 |
| Zr-0.3 | 0.143 | 0.218 | 0.473 | 0.254 |
| Zr-0.5 | 0.253 | 0.333 | 0.597 | 0.264 |
| Zr-0.7 | 0.306 | 0.368 | 0.575 | 0.207 |
| Zr-0 | 0.226 | 0.302 | 0.554 | 0.252 |
DownLoad:
CSV
Fig. 6 showed the EIS curves of the different samples. A half-circle could be observed of all curves present with basically the same shape. The capacitive properties of the electrode impedance radius first decrease and then increase. Moreover, the capacitive reactance arc radius prepared under the molar ratio of Sn : Zr = 6:0.3 was the smallest, which indicated that the resistance to electron transfer was the lowest and the number of electron transfer per unit time was the most. ZrO2 particles accumulated on an anode surface influence the electric double layer structure and decrease the effective area of other metal oxides on the dimentionally stable anode surface [21]. The accumulation of ZrO2 particles results in the increment of impedance value from the RuO2 system with ZrO2 particles.
In Fig. 7, (RS (QdlRct) (QfRf)) was regarded as the equivalent model used to fit the pseudo data [22]. Among them, RS means solution resistance; Qf signifies internal crack of coating and grain boundary pore structure; Rf indicates the resistance of the electrode itself; Qdl is often used to characterize the number of active points, and the higher the value of Qdl, the more active points are loaded on the surface; Rct represents the activity of chlorine released from the electrode, and the lower the value of Rct, the better the electrocatalytic activity of chlorine evolution of the electrode.
According to Fig. 6 and Table 2, with the increase of Zr content, Rct first decreases and then increases. The charge mass transfer resistance of the electrode prepared under the molar ratio of Sn : Zr = 6:0.3 was the smallest, suggested that the electrode prepared under this condition was the most prone to chlorine evolution reaction. Otherwise, with the increase of Zr content, Qdl first increases and then decreases. The Qdl under the condition of Sn : Zr = 6:0.3 was the largest, indicated that the coating surface of the electrodes prepared under this condition contains the most active sites.
| Sample | Rs / (Ω·cm2) | Qf / (μF·cm−2) | n | Rf / (Ω·cm2) | Qdl / (μF·cm−2) | Calculated roughness factor | Rct / (Ω·cm2) |
| Zr-0.1 | 1.0 × 10−5 | 2.01 | 1 | 1.270 | 8600 | 430 | 6.062 |
| Zr-0.3 | 2.6 × 10−7 | 2.70 | 1 | 0.892 | 68900 | 3445 | 3.501 |
| Zr-0.5 | 2.7 × 10−7 | 2.19 | 1 | 1.040 | 39700 | 1985 | 4.014 |
| Zr-0.7 | 1.1 × 10−6 | 1.83 | 1 | 1.371 | 4400 | 220 | 10.490 |
| Zr-0 | 9.7 × 10−7 | 2.66 | 1 | 0.759 | 32400 | 1620 | 4.678 |
DownLoad:
CSV
The cyclic voltammetry curve was integrated to obtain the q*, which reflects the electrochemical activity of the electrode, and was related to the practical working area and the number of active points. A large value of q* illustrates great electrode activity. Using this method by some previous report [23–24] to calculate the q* value to estimate the electrode activity, and the equation is:
|
(q∗)−1=(qT)−1+kv1/2 |
(6) |
herein,
The CV curves of Ti/Sn–Ru–Co–ZrOx samples in the whole potential range of 0.5–0.9 V was shown in Fig. 8. q* was measured in acidic NH4Cl solution to define the electrochemically active area of the Ti/Sn–Ru–Co–ZrOx electrodes. Thus, the value of q* was defined as the electrochemically active surface area of Ti/Sn–Ru–Co–ZrOx in chlorate electrolyte. Obviously, with the increase of Zr content, the active area of the electrode first increased and then decreased, and the area enclosed by the CV of the Ti/Sn–Ru–Co–ZrOx electrodes prepared at the molar ratio of Sn : Zr = 6:0.3 was the largest. The second was the Ti/Sn–Ru–Co–ZrOx electrode prepared under the condition of Sn : Zr = 6:0.5. Too much Zr leads to excessive inert oxides on the surface of the electrode, which reduces the electrocatalytic activity of the electrode. Therefore, the active area of the Zr-0.7 added electrode was the smallest. It was also confirmed that the electrode with low chlorine emission potential had more active sites and higher chlorine emission activity. Owing to smaller grain size was favored to the formation of the large active surface area [26]. The active surface areas of Zr-0.3 electrodes were optimal. As known that larger specific area was beneficial to improve the catalytic properties, so the Zr-0.3 electrodes owned higher electrocatalysis activity than others. When Zr was added into the precursor solution, ZrO2 nanoparticles were formed during thermal oxidation and effectively embedded in the matrix. The pores were filled by a handful of ZrO2 nanoparticles to reduce the grain size of the others dioxide matrix [27–28], as shown in Fig. 3(c). The dense membrane prevented the electrolyte from penetrating through cracks or pores. Moreover, there was no high pressure inside the coating since the generation of internal Cl2 was reduced [29]. Hence, the probability of perforation of the coating was minimal. The above reasons were combined to make the Zr-0.3 electrode has an excellent electrochemical performance.
In addition, the approximate actual life was estimated by an accelerated life test. The current used in accelerated life tests is much higher than that in actual use. According to the above electrochemical test, the best performance was obtained by the molar ratio of Sn : Zr = 6:0.3, so the accelerated life test was taken to compare with that without Zr. The accelerated life test results of the electrodes were shown in Fig. 9, and the failure judged according to the voltage reachs 10 V. Absolutely the voltage of all samples quickly reached a stable state in a short time (500 h) at the beginning of the test. Hereafter, the electrode potential remained unchanged. The voltage of the coating with Zr was slightly higher than that of the coating without Zr, which was consistent with the Rf data that was fitted in Table 2. At last, the potential rose sharply and the electrode failed. The corresponding working times were 3102 h (Zr-0.3) and 2773 h (Zr-0), respectively. The electrode service life can be extended about 11.86% by adding Zr-0.3.
Attributed to the appropriate ZrO2 weight percentage in electrodes, the ZrO2 nanoparticles acted as an inert physical barrier that initiates corrosion of the substrate [30], and prevented the electrolyte from reaching the Ti surface effectively [31]. As shown in Fig. 10, the SEM images of two electrodes after the corrosion experiment were given, and the protection mechanism of nano-ZrO2 on the coating was proposed. In Fig. 10(a), it can be seen that there was a deep color different from that in Fig. 10(b). The corrosion pits on the surface were deeper here because there was no protection from Zr. The protection provided was positively related to the amount of ZrO2 nanoparticles when the Zr content was low, and these appropriate amount of ZrO2 particles (Sn : Zr = 6:0.3 in this work) would fill the gaps between the oxide coatings and link the bulk coatings to each other to better protect the Ti substrate. Due to the large specific surface area on the surface of the electrode, under the same apparent current density, its actual current density is actually low, so its surface corrosion is relatively low. Otherwise, the Cl2 evolution reaction mainly occurs on the surface of the electrode, and the electrode with a larger specific surface area has better electrochemical activity. However, the good protective effect on the titanium matrix is the key to increasing the use time instead of the surface. From the comprehensive performance test results and accelerated life test results, a certain amount of Zr addition is beneficial. Furthermore, after the addition of Zr exceeded a certain amount (Sn : Zr = 6:0.5 in this work), the coating bonded with the substrate loosely, thereby affecting its performance. Therefore, the service life of Zr-0.3 electrodes improved greatly.
To obtain a more corrosion-resistant and economical electrolytic anode, based on the traditional Ti/Sn–Ru–CoOx coating, Zr was added to modify the electrode. A series of Ti/Sn–Ru–Co–ZrOx electrodes with different Zr contents were prepared by the thermal decomposition method.
(1) With the increase of Zr content, the densification of electrode surface increased first and then decreased. The surface of the Zr-0.3 electrode was the most compact.
(2) Under the condition of Sn : Ru : Co : Zr = 6:1:0.8:0.3 (in molar ratio), the electrode had the largest active area and the best catalytic performance, as confirmed by the electrochemical testing results.
(3) The Zr modified electrode remained stable for up to 3102 h (empirical formula estimation) in a solution with 10wt% H2SO4 at 40°C under 2 A/cm2. This anode was more stable than the no Zr added anode, the serves life expectancy was increased about 11.86%.
This work was financially supported by the National Natural Science Foundation of China (Nos. 51564029, 51504111, 52064028, and 22002054), the China Postdoctoral Science Foundation (No. 2018M633418), the Technology Innovation Talents Project of Yunnan Province (No. 2019HB111), and Analysis and Testing Foundation of Kunming University of Science and Technology (Nos. 2019M20182202013, 2020M20192202035, and 2020M20192202099).
The authors declare no potential conflict of interest.
| [1] |
J.M. Lu, D. Dreisinger, and T. Glück, Manganese electrodeposition—A literature review, Hydrometallurgy, 141(2014), p. 105. DOI: 10.1016/j.hydromet.2013.11.002
|
| [2] |
S.K. Padhy, P. Patnaik, B.C. Tripathy, M.K. Ghosh, and I.N. Bhattacharya, Electrodeposition of manganese metal from sulphate solutions in the presence of sodium octyl sulphate, Hydrometallurgy, 165(2016), p. 73. DOI: 10.1016/j.hydromet.2015.10.027
|
| [3] |
G. Tsurtsumia, D. Shengelia, N. Koiava, et al., Novel hydro-electrometallurgical technology for simultaneous production of manganese metal, electrolytic manganese dioxide, and manganese sulfate monohydrate, Hydrometallurgy, 186(2019), p. 260. DOI: 10.1016/j.hydromet.2019.04.028
|
| [4] |
E. Rocca, G. Bourguignon, and J. Steinmetz, Corrosion management of PbCaSn alloys in lead-acid batteries: Effect of composition, metallographic state and voltage conditions, J. Power Sources, 161(2006), No. 1, p. 666. DOI: 10.1016/j.jpowsour.2006.04.140
|
| [5] |
E. Rudnik, Effect of gluconate ions on electroreduction phenomena during manganese deposition on glassy carbon in acidic chloride and sulfate solutions, J. Electroanal. Chem., 741(2015), p. 20. DOI: 10.1016/j.jelechem.2015.01.019
|
| [6] |
J.E. Lewis, P.H. Scaife, and D.A.J. Swinkels, Electrolytic manganese metal from chloride electrolytes. I. Study of deposition conditions, J. Appl. Electrochem., 6(1976), No. 3, p. 199. DOI: 10.1007/BF00616142
|
| [7] |
X.Z. Cao, D.B. Dreisinger, J.M. Lu, and F. Belanger, Electrorefining of high purity manganese, Hydrometallurgy, 171(2017), p. 412. DOI: 10.1016/j.hydromet.2017.06.015
|
| [8] |
A. Sulcius, E. Griskonis, K. Kantminiene, and N. Zmuidzinaviciene, Influence of different electrolysis parameters on electrodeposition of γ- and α-Mn from pure electrolytes—A review with special reference to Russian language literature, Hydrometallurgy, 137(2013), p. 33. DOI: 10.1016/j.hydromet.2013.05.002
|
| [9] |
P. Wei, O.E. Hileman Jr, M.R. Bateni, X.H. Deng, and A. Petric, Manganese deposition without additives, Surf. Coat. Technol., 201(2007), No. 18, p. 7739. DOI: 10.1016/j.surfcoat.2007.03.007
|
| [10] |
Y.X. Zheng, Preparation of electrolytic manganese metal from MnCl2 system with graphite substract lead dioxide anode, China Manganese Ind., 16(1998), No. 3, p. 30.
|
| [11] |
W.C. Yang, W.J. Peng, X.H. Li, et al., Preparation of titanium-substrate modified Ti/SnO2/MnO2 anode plate for electrolytic manganese metal and its performance study, Min. Metall. Eng., 34(2014), No. 3, p. 90.
|
| [12] |
Y.Q. Wen, W. Shang, B.H. Xie, C.B. He, Y.Y. Wang, and D. Kong, Preparation and properties of composite coating modified titanium anode for electrolytic manganese dioxide, China Surf. Eng., 30(2017), No. 2, p. 85.
|
| [13] |
J.M. Hu, H.M. Meng, J.Q. Zhang, and C.N. Cao, Degradation mechanism of long service life Ti/IrO2–Ta2O5 oxide anodes in sulphuric acid, Corros. Sci., 44(2002), No. 8, p. 1655. DOI: 10.1016/S0010-938X(01)00165-2
|
| [14] |
E. Horváth, J. Kristóf, L. Vázquez-Gómez, Á. Rédey, and V. Vágvölgyi, Investigationof RuO2–IrO2–SnO2 thin film evolution, J. Therm. Anal. Calorim., 86(2006), No. 1, p. 141. DOI: 10.1007/s10973-006-7578-2
|
| [15] |
Z.X. Zhang and D. Huang, Coated Titanium Electrode, Metallurgical Industry Press, Beijing, 2014, p. 62.
|
| [16] |
Y.Y. Chen, T. Zhang, X. Wang, Y.Q. Shao, and D. Tang, Phase structure and microstructure of a nanoscale TiO2–RuO2–IrO2–Ta2O5 anode coating on titanium, J. Am. Ceram. Soc., 91(2008), No. 12, p. 4154. DOI: 10.1111/j.1551-2916.2008.02808.x
|
| [17] |
W. Zhang, E. Ghali, and G. Houlachi, Review of oxide coated catalytic titanium anodes performance for metal electrowinning, Hydrometallurgy, 169(2017), p. 456. DOI: 10.1016/j.hydromet.2017.02.014
|
| [18] |
H. You, Y.H. Cui, Y.J. Feng, J.F. Liu, and W.M. Cai, Preparation and performance of SnO2 electrocatalytic electrode with titanium-based Co interlayer, Mater. Sci. Technol., 12(2004), No. 3, p. 230.
|
| [19] |
L.H. Chang, B.M. Chen, H.H. Qiao, et al., Study of the effects of pretreatment processing on the properties of metal oxide coatings on Ti-based sheet, J. Electrochem. Soc., 168(2021), No. 3, art. No. 033501. DOI: 10.1149/1945-7111/abe726
|
| [20] |
D.P. Wang, G. Chen, A.D. Wang, et al., Corrosion behavior of single- and poly-crystalline dual-phase TiAl–Ti3Al alloy in NaCl solution, Int. J. Miner. Metall. Mater, 2022. DOI: 10.1007/s12613-022-2513-5
|
| [21] |
R.D. Xu, L.P. Huang, J.F. Zhou, P. Zhan, Y.Y. Guan, and Y. Kong, Effects of tungsten carbide on electrochemical properties and microstructural features of Al/Pb–PANI–WC composite inert anodes used in zinc electrowinning, Hydrometallurgy, 125-126(2012), p. 8. DOI: 10.1016/j.hydromet.2012.04.012
|
| [22] |
J.H. Huang, M.J. Hou, J.Y. Wang, et al., RuO2 nanoparticles decorate belt-like anatase TiO2 for highly efficient chlorine evolution, Electrochimica Acta, 339(2020), art. No. 135878. DOI: 10.1016/j.electacta.2020.135878
|
| [23] |
B.M. Chen, S.C. Wang, J.H. Liu, et al., Corrosion resistance mechanism of a novel porous Ti/Sn–Sb–RuOx/β-PbO2 anode for zinc electrowinning, Corros. Sci., 144(2018), p. 136. DOI: 10.1016/j.corsci.2018.08.049
|
| [24] |
S. Trasatti, Structure of the metal/electrolyte solution interface: New data for theory, Electrochimica Acta, 36(1991), No. 11-12, p. 1659. DOI: 10.1016/0013-4686(91)85023-Z
|
| [25] |
H. Vogt, Note on a method to interrelate inner and outer electrode areas, Electrochimica Acta, 39(1994), No. 13, p. 1981. DOI: 10.1016/0013-4686(94)85077-1
|
| [26] |
Y. Chen, L. Hong, H.M. Xue, et al., Preparation and characterization of TiO2-NTs/SnO2–Sb electrodes by electrodeposition, J. Electroanal. Chem., 648(2010), No. 2, p. 119. DOI: 10.1016/j.jelechem.2010.08.004
|
| [27] |
Y.W. Yao, M.M. Zhao, C.M. Zhao, and H.J. Zhang, Preparation and properties of PbO2–ZrO2 nanocomposite electrodes by pulse electrodeposition, Electrochimica Acta, 117(2014), p. 453. DOI: 10.1016/j.electacta.2013.11.150
|
| [28] |
Y.W. Yao, T. Zhou, C.M. Zhao, Q.M. Jing, and Y. Wang, Influence of ZrO2 particles on fluorine-doped lead dioxide electrodeposition process from nitrate bath, Electrochim. Acta, 99(2013), p. 225. DOI: 10.1016/j.electacta.2013.03.117
|
| [29] |
Y.H. Song, G. Wei, and R.C. Xiong, Structure and properties of PbO2–CeO2 anodes on stainless steel, Electrochim. Acta, 52(2007), No. 24, p. 7022. DOI: 10.1016/j.electacta.2007.05.024
|
| [30] |
J.H. Liu, B.M. Chen, S. Chen, S.C. Wang, Z.C. Guo, Preparation and electrochemical performance of the stainless steel/α-PbO2–ZrO2/β-PbO2–ZrO2-CNT composite anode, ECS J. Solid State Sci. Technol., 9(2020), No. 12, art. No. 121011. DOI: 10.1149/2162-8777/abd263
|
| [31] |
H. Mazhari Abbasi, K. Jafarzadeh, and S.M. Mirali, An investigation of the effect of RuO2 on the deactivation and corrosion mechanism of a Ti/IrO2+Ta2O5 coating in an OER application, J. Electroanal. Chem., 777(2016), p. 67. DOI: 10.1016/j.jelechem.2016.07.036
|
| [1] | Yan-ping Zeng, Jin-dou Jia, Wen-he Cai, Shu-qing Dong, Zhi-chun Wang. Effect of long-term service on the precipitates in P92 steel [J]. International Journal of Minerals, Metallurgy and Materials, 2018, 25(8): 913-921. DOI: 10.1007/s12613-018-1640-5 |
| [2] | Xin Lu, Takahiro Miki, Tetsuya Nagasaka. Activity coefficients of NiO and CoO in CaO-Al2O3-SiO2 slag and their application to the recycling of Ni-Co-Fe-based end-of-life superalloys via remelting [J]. International Journal of Minerals, Metallurgy and Materials, 2017, 24(1): 25-36. DOI: 10.1007/s12613-017-1375-8 |
| [3] | Metin Kök. Tool life modeling for evaluating the effects of cutting speed and reinforcements on the machining of particle reinforced metal matrix composites [J]. International Journal of Minerals, Metallurgy and Materials, 2010, 17(3): 353-362. DOI: 10.1007/s12613-010-0318-4 |
| [4] | Shaohua Luo, Zilong Tang, Junbiao Lu, Linfeng Hu, Zhongtai Zhang. Synthesis and performance of carbon-modified LiFePO4 using an in situ PVA pyrolysis procedure [J]. International Journal of Minerals, Metallurgy and Materials, 2007, 14(6): 562-567. DOI: 10.1016/S1005-8850(07)60129-7 |
| [5] | Chengming Li, Qi He, Gang Lin, Xiaojun Sun, Weizhong Tang, Fanxiu Lu. TiN/CrN multilayered hard coatings with TiCrN interlayer deposited by a filtered cathodic vacuum arc technique [J]. International Journal of Minerals, Metallurgy and Materials, 2004, 11(5): 420-424. |
| [6] | Maoqiu Wang, Han Dong, Qi Wang. Elevated-temperature properties of one long-life high-strength gun steel [J]. International Journal of Minerals, Metallurgy and Materials, 2004, 11(1): 62-66. |
| [7] | Yang Hu, Yang Yang, Weidong Hao. Research of MPLS traffic engineering over differentiated services [J]. International Journal of Minerals, Metallurgy and Materials, 2002, 9(6): 474-477. |
| [8] | Jianguo Wang, Hongying Wang, Shiping Xu, Lianqing Wang, Yonglin Kang. A new model for life prediction of GH4133 under TMF conditions [J]. International Journal of Minerals, Metallurgy and Materials, 2002, 9(4): 287-291. |
| [9] | Jiyue Sun, Guoliang Chen. A Creep Equation Based on Thermal Activation [J]. International Journal of Minerals, Metallurgy and Materials, 1998, 5(1): 44-46. |
| [10] | CHEN Guoliang, GUO Hong, SUN Jiyue, SHU Guogang, LI Yiming. Extrapolation Model of High Temperature Creep for 12Cr1MoV Steel [J]. International Journal of Minerals, Metallurgy and Materials, 1997, 4(2): 37-37. |
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Figures(10) / Tables(2)
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| Name | η / V | a / V | b / (V·dec−1) | |
| 500 A·m−2 | 1000 A·m−2 | |||
| Zr-0.1 | 0.178 | 0.267 | 0.563 | 0.296 |
| Zr-0.3 | 0.143 | 0.218 | 0.473 | 0.254 |
| Zr-0.5 | 0.253 | 0.333 | 0.597 | 0.264 |
| Zr-0.7 | 0.306 | 0.368 | 0.575 | 0.207 |
| Zr-0 | 0.226 | 0.302 | 0.554 | 0.252 |
DownLoad:
CSV
| Sample | Rs / (Ω·cm2) | Qf / (μF·cm−2) | n | Rf / (Ω·cm2) | Qdl / (μF·cm−2) | Calculated roughness factor | Rct / (Ω·cm2) |
| Zr-0.1 | 1.0 × 10−5 | 2.01 | 1 | 1.270 | 8600 | 430 | 6.062 |
| Zr-0.3 | 2.6 × 10−7 | 2.70 | 1 | 0.892 | 68900 | 3445 | 3.501 |
| Zr-0.5 | 2.7 × 10−7 | 2.19 | 1 | 1.040 | 39700 | 1985 | 4.014 |
| Zr-0.7 | 1.1 × 10−6 | 1.83 | 1 | 1.371 | 4400 | 220 | 10.490 |
| Zr-0 | 9.7 × 10−7 | 2.66 | 1 | 0.759 | 32400 | 1620 | 4.678 |
DownLoad:
CSV
