2 PbO 2. Pb 3 O 4 Sn. Ti/SnO 2 -Sb 2 O 4 -CF/PbO x SnO 2 -Sb PbO 2. Sn-Sb 1:1. 1 h. Sn:Sb=10:1. PbO 2 - CeO 2 PbO 2. [8] SnO 2 +Sb 2 O 4 _

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1 41 Vol.41, No. 01 RARE METAL MATERIALS AND ENGINEERING March 01 Pb O 4 PbO ( ) SnO -Sb Pb O 4 Pb O h 970 h XRF XRD SEM Pb O 4 PbO PbO TG A X(01) [1,] 1 PbO PbO Sn-Sb SnO [] TiO SnO [4] [5] Ti PbO MnO PbO PbO PbO PbO Song [6] PbO Ce(NO ) PbO - CeO PbO PbO [1] [7] PbO Sn-Sb PbO [8] SnO +Sb O 4 Ti/SnO -Sb O 4 -CF/PbO x Ti/SnO -Sb/PbO SnO -Sb PbO Pb O 4 Pb O 4 Pb Sn Pb Sn PbO Pb O 4 Sn PbO Pb O 4 Sn Sn PbO cm cm TA μm 1:1 10%NaOH 1 h 10% h Sn:Sb=10:1 ph=1 SnO -Sb min min h _ ( ) (NCET ) ( ) stormxuhao@stu.xjtu.edu.cn

2 Pb O 4 PbO 46 Pb(NO ) Pb O 4 Ti/SnO -Sb min min h 0.5 mol L -1 Pb(NO ) mol L -1 Cu(NO ) mol L -1 NaF mol L -1 HNO (15 ma cm - ) (65 ) Ti/SnO -Sb Ti/SnO -Sb-Pb O 4 PbO Ti/SnO -Sb-PbO Ti/SnO -Sb-Pb O 4 / PbO (SEM JEOL JSM-690A) X (XRD Rigaku D/MAX-400X Cu-Kα ) X (XRF S4 PIONEER Bruker) LK00A Pt Ag/AgCl 45.0 mol L -1 H SO 4 1 A cm V XRD 1 Ti/SnO -Sb Ti/SnO -Sb-Pb O 4 Ti/SnO -Sb Sn Ti O Sb Sb XRF Ti/SnO -Sb-Pb O 4 Pb Sn Ti O Pb Ti/SnO -Sb Ti/SnO -Sb- Pb O 4 Ti Sn SnO -Sb XRF Table 1 XRF analysis result of the two electrodes (ω/%) Electrode Ti Sn O Pb Ti/SnO -Sb Ti/SnO -Sb-Pb O Ti/SnO -Sb Ti/SnO -Sb-Pb O 4 XRD Ti/SnO -Sb 8 40 Ti SnO SbO x SnO SnO 6.61 (110).89 (101) (11) ICSD917 Sb SnO Sb 5+ Sn nm nm 1% Hume-Rothery 15% [9] 1 Ti/SnO -Sb-Pb O Ti/SnO -Sb Ti Pb O 4 Pb O ICSD5 ICSD9094 ICSD65 Pb O 4 SnO Pb-Sn Pb O 4 SnO Ti/SnO -Sb Ti/SnO -Sb-Pb O 4 a SnO -Sb b Intensity/cps Ti SnO PbO4 Ti/SnO-Sb-PbO Ti/SnO-Sb XRD Fig.1 XRD patterns of the two electrodes θ/( )

3 a Voltage/V Ti/SnO-Sb/PbO Ti/SnO-Sb-PbO4/PbO b Time/h Fig. Accelerated test life of the two electrodes Fig. SEM images of the two electrodes: (a) Ti/SnO -Sb and (b) Ti/SnO -Sb-Pb O 4 Pb O 4 Pb O 4 SnO -Sb SnO -Sb Pb O 4 SnO -Sb a PbO PbO PbO Pb O 4 Ti/SnO -Sb Ti/SnO -Sb-Pb O 4 PbO SEM XRD PbO PbO PbO - PbO - 10 V 10 V Ti/SnO -Sb/PbO (Accelerated life, AL) h Ti/SnO -Sb-Pb O 4 /PbO h 9.7 Ti/SnO - Sb-Pb O 4 /PbO 50 h Ti/SnO -Sb/PbO 50 h V/h Ti/SnO -Sb-/PbO 0.08 V/h Ti/SnO -Sb-Pb O 4 /PbO Ti/SnO -Sb/PbO Ti/SnO -Sb-Pb O 4 /PbO PbO PbO ( PbO )

4 Pb O 4 PbO 465 PbO Table Contrast of accelerated test life and calculated life for different PbO electrodes Electrode type AL/h Criterion Test conditions n CL/a Ref. Ti/PbO 6 U>10 V Ti/SnO -Sb/PbO 0 U>10 V Ti/α-PbO /β-pbo 10 Mass lose=6.7% Ti/SnO -Sb O 4-CF/PbO x 10 U>10 V Ti/SnO -Sb/PbO U>10 V Ti/SnO -Sb-Pb O 4/PbO 970 U>10 V 60, 1.0 mol/l H SO 4, 4.0 A/cm [] 60, 1.0 mol/l H SO 4, 4.0 A/cm [] 90, 9.0 mol/l H SO 4, 100 ma/cm [7] 60, 1. 0 mol/ L H SO 4, 4 A/ cm [8] 45,.0 mol/l H SO 4, 1.0 A/cm This paper 45,.0 mol/l H SO 4, 1.0 A/cm This paper [10] L~1/i n 1 L i n i n 1 CL=[AL/8640*(i AL /i CL )] n CL calculated life a AL accelerated life h i AL A/m i CL 1000 A/m n 1.4~.0 n n Ti/SnO -Sb-Pb O 4 /PbO SnO -Sb PbO Pb O 4 PbO 1 Pb O 4 SnO -Sb SnO Pb Sn Pb O 4 PbO PbO Pb O 4 Sn Ti/SnO -Sb- Pb O 4 /PbO Ti/SnO -Sb/PbO SnO -Sb PbO Pb O 4 4 Pb-Sn-Sb 4 Pb O 4 5 PbO titanium; SnO -Sb layer; Pb-Sn-Sb solid solution layer; 4 Pb O 4 reticular layer; 5 electrodeposition PbO layer 4 Fig.4 Cross section structure scheme of the long-life PbO electrode 5 SnO -Sb PbO PbO PbO [11,1] Pb O 4 TiO Pb(NO ) Pb O 4 1) SnO -Sb Pb O 4 SnO -Sb PbO ) Pb O 4 PbO PbO PbO

5 ) Pb O 4 4) h References [1] Tong Shaoping, Ma Chunan, Feng Hui. Electrochimica Acta[J], 008, 5: 00 [] Feng Yujie( ), Shen Hong( ), Cui Yuhong( ) et al. Journal of Molecular Catalysis( )[J], 00, 16(): 181 [] Wang Yaqiong( ), Tong Hongyang( ), Xu Wenlin( ). Chinese Journal of Applied Chemistry( )[J], 004, 1(5): 47 [4] Liang Zhenhai( ), Zhang Fuyuan( ), Sun Yanping( ). Rare Metal Materials and Engineering( )[J], 006, 5(10): 1605 [5] Xu Liang( ), Zhao Fang( ), Nong Jiaying( ) et al. Chinese Journal of Environmental Engineering( )[J], 008, (7): 959 [6] Song Yuehai, Wei Gang, Xiong Rongchun. Electrochimica Acta[J], 007, 5: 70 [7] Zhou Minghua, Dai Qizhou, Lei Lecheng et al. Environmental Science and Technology[J], 005, 9: 6 [8] Xue Caixia( ), Liang Zhenhai( ). Journal of Taiyuan University of Technology()[J], 007, 8(5): 41 [9] Chen Xueming, Chen Guohua. Electrochimica Acta[J], 005, 50: 4155 [10] Zhang Zhaoxian( ). Titanium Electrod Industry ( nd ) ()[M]. Beijing: Metallurgical Industry Press, 005: 01 [11] Li Peiqiang, Zhao Guohua, Cui Xiao et al. Journal of Physic and Chemistry C[J], 009, 11: 75 [1] Zhao Guohua, Cui Xiao, Liu Meichuan et al. Environmental Science and Technology[J], 009, 4: 1480 Effect of Pb O 4 Layer Introduction on the Accelerated Life of the Ti-PbO Electrodes Xu Hao, Yan Wei, Chang Le (Xi an Jiaotong University, Xi an , China) Abstract: By means of thermal decomposition, Pb O 4 layer was introduced into the Ti/SnO -Sb electrode to increase the electrode service life through increasing the cohesive force between PbO and Ti. The results show that the introduction of the Pb O 4 layer greatly enhances the accelerated test life of the PbO electrode from h to 970 h. The enhancement causes of the accelerated life for the PbO electrode due to the introduction of the Pb O 4 layer were analyzed based on the results of XRF, XRD and SEM. Key words: PbO electrode; thermal decomposition; inner layer; electrode life Corresponding author: Xu Hao, Candidate for Ph. D., Department of Environmental Science and Technology, Xi an Jiaotong University, Xi an , P. R. China, Tel: , stormxuhao@stu.xjtu.edu.cn