阅读说明：本技术 一种Ti/Ru0.4Sn0.2Mn0.4O2电极及其制备方法 (Ti/Ru0.4Sn0.2Mn0.4O2 electrode and preparation method thereof ) 是由 庄建煌 林瑞宗 周静 陈清谅 朱朝阳 林荔晟 林芳 谢可及 于 2018-05-28 设计创作，主要内容包括：本发明公开了Ti/Ru_(0.4)Sn_(0.2)Mn_(0.4)O_2三元氧化物电极材料及其制备方法。本发明通过综合研究,发现290℃制备的电极材料拥有良好的电子导电性能和质子传导能力,能充分利用氧化物涂层的内活性表面和外活性表面,因此具有最高的比电容,在5mA/cm~2的电流密度下放电,比电容可达743.2F/g。当功率密度为1.28kW/kg时,其对应的能量密度为85.56Wh/kg。(the invention discloses a Ti/Ru0.4Sn0.2Mn0.4O2 ternary oxide electrode material and a preparation method thereof. Through comprehensive research, the electrode material prepared at 290 ℃ has good electronic conductivity and proton conductivity, and can fully utilize the inner active surface and the outer active surface of the oxide coating, so that the electrode material has the highest specific capacitance, and the specific capacitance can reach 743.2F/g when the electrode material discharges at the current density of 5mA/cm 2. When the power density is 1.28kW/kg, the corresponding energy density is 85.56 Wh/kg.)

1. A Ti/Ru0.4Sn0.2Mn0.4O2 electrode, which is prepared by a method comprising the following steps:

1) Preparing a clean titanium plate;

2) dissolving ruthenium chloride, tin tetrachloride and manganous chloride in absolute ethyl alcohol according to a certain proportion, and performing ultrasonic oscillation to uniformly disperse the materials to obtain a precursor coating liquid; wherein the molar ratio of metal ions of ruthenium chloride, tin tetrachloride and manganous chloride is Ru: sn: mn is 2-6:1-3: 2-6;

3) Coating one side of the precursor coating liquid on a titanium plate, curing by infrared illumination after each coating, thermally oxidizing for 5-15min in a box type resistance furnace at 260-280 ℃, discharging and cooling; repeating the steps until the loading capacity of the RuO2 is more than or equal to 1.0mg cm < -2 >;

4) Keeping the temperature of the sample at 280-300 ℃ for 0.5-1.5 hours, and then discharging the sample from the furnace and cooling the sample by air.

2. a Ti/ru0.4sn0.2mn0.4o2 electrode according to claim 1, characterized in that: step 1) is that an industrial TA 1-grade titanium plate with the thickness of 1mm is degreased, sand-blasted, etched for 90min in a mixed solution of 5% oxalic acid and 20% sulfuric acid, washed with water and dried for later use.

3. A Ti/ru0.4sn0.2mn0.4o2 electrode according to claim 1, characterized in that: the molar ratio of metal ions of ruthenium chloride, tin tetrachloride and manganous chloride is Ru: sn: mn is 4:2: 4.

4. A Ti/ru0.4sn0.2mn0.4o2 electrode according to claim 1, characterized in that: and 4) keeping the temperature of the sample at 285-295 ℃ for 0.5-1.5 hours, and then discharging the sample from the furnace and cooling the sample by air.

5. a Ti/Ru0.4Sn0.2Mn0.4O2 electrode according to any one of claims 1 to 4, characterized in that: and 4) keeping the temperature of the sample at 290 ℃ for 1 hour, and then discharging the sample from the furnace and cooling the sample by air.

6. A preparation method of a Ti/Ru0.4Sn0.2Mn0.4O2 electrode comprises the following steps:

1) preparing a clean titanium plate;

2) Dissolving ruthenium chloride, tin tetrachloride and manganous chloride in absolute ethyl alcohol according to a certain proportion, and performing ultrasonic oscillation to uniformly disperse the materials to obtain a precursor coating liquid; wherein the molar ratio of metal ions of ruthenium chloride, tin tetrachloride and manganous chloride is Ru: sn: mn is 2-6:1-3: 2-6;

3) Coating one side of the precursor coating liquid on a titanium plate, curing by infrared illumination after each coating, thermally oxidizing for 5-15min in a box type resistance furnace at 260-280 ℃, discharging and cooling; repeating the steps until the loading capacity of the RuO2 is more than or equal to 1.0mg cm < -2 >;

4) Keeping the temperature of the sample at 280-300 ℃ for 0.5-1.5 hours, and then discharging the sample from the furnace and cooling the sample by air.

7. The method for preparing a Ti/Ru0.4Sn0.2Mn0.4O2 electrode according to claim 6, wherein: step 1) is that an industrial TA 1-grade titanium plate with the thickness of 1mm is degreased, sand-blasted, etched for 90min in a mixed solution of 5% oxalic acid and 20% sulfuric acid, washed with water and dried for later use.

8. The method for preparing a Ti/Ru0.4Sn0.2Mn0.4O2 electrode according to claim 6, wherein: the molar ratio of metal ions of ruthenium chloride, tin tetrachloride and manganous chloride is Ru: sn: mn is 4:2: 4.

9. The method for preparing a Ti/Ru0.4Sn0.2Mn0.4O2 electrode according to claim 6, wherein: and 4) keeping the temperature of the sample at 285-295 ℃ for 0.5-1.5 hours, and then discharging the sample from the furnace and cooling the sample by air.

10. The method of any of claims 6 to 9 for making Ti/ru0.4sn0.2mn0.4o2 electrodes, wherein: and 4) keeping the temperature of the sample at 290 ℃ for 1 hour, and then discharging the sample from the furnace and cooling the sample by air.

Technical Field

The invention relates to a Ti/Ru0.4Sn0.2Mn0.4O2 electrode and a preparation method thereof.

background

The study of metal oxides began with Conway's discovery of its unique faraday capacitance storage. The pseudofaradaic capacitance of active oxides has a higher energy density than carbon materials and a better electrochemical stability than conductive polymers and is of great interest [1 ]. Although ruthenium oxide has a high theoretical specific capacitance (1360F/g, RuO2 & 0.5H2O) [2], in practice, the addition of graphene [5] by RuO2 arrays [3-4] is still far from theoretical values, e.g., the specific capacitance is only 570F/g when the Ru loading is 38.3 wt% Ru, and the energy density at low operating rates (100mA/g) is 20.1Wh/kg [5 ].

[1]Le Luu T,Kim J,Yoon J.Physicochemical properties of RuOand IrOelectrodes affecting chlorine evolutions[J].Journal of Industrial and Engineering Chemistry,2015,21(25):400-404.

[2]Doubova LM,De Battisti A,Daolio S,et al.Effect of surface structure on behavior of RuOelectrodes in sulfuric acid aqueous solution[J] .Russian Journal of Electrochemistry,2004,40(11):1115-1122.

[3]Hsu H P,HuangY S,Yeh C N,et al.Growth and Characterization of Well-Aligned RuO/R-TiOHeteronanostructures on Sapphire(100)Substrates by Reactive Magnetron Sputtering[J].Solid State Phenomena,2011,170(4):78-82

[4]Korotcov A V,Huang Y S,Tiong K K,et al.Raman scattering characterization of well-aligned RuOand IrOnanocrystals[J].Journal of Raman Spectroscopy,2010,38(6):737-749

[5]Lingjuan Deng,Jianfang Wang,Gang Zhu,et al.RuO/graphene hybrid material for high performance electrochemical capacitor[J].Journal of Power Sources,2014,248(7):407-415

disclosure of Invention

The invention provides a Ti/Ru0.4Sn0.2Mn0.4O2 electrode and a preparation method thereof, which overcome the defects in the prior art.

The technical scheme adopted by the invention for solving the technical problem is as follows:

A Ti/Ru0.4Sn0.2Mn0.4O2 electrode is prepared by the following steps:

1) Preparing a clean titanium plate;

2) Dissolving ruthenium chloride (RuCl3 & 3H2O), tin tetrachloride (SnCl4 & 5H2O) and manganous chloride (MnCl2 & 4H2O) in absolute ethyl alcohol according to a proportion, and performing ultrasonic oscillation to uniformly disperse the materials to obtain a precursor coating liquid; wherein the molar ratio of metal ions of ruthenium chloride, tin tetrachloride and manganous chloride is Ru: sn: mn is 2-6:1-3: 2-6;

3) Coating one side of the precursor coating liquid on a titanium plate, curing by infrared illumination after each coating, thermally oxidizing for 5-15min in a box type resistance furnace at 260-280 ℃, discharging and cooling; repeating the steps until the loading capacity of the RuO2 is more than or equal to 1.0mg cm < -2 >;

4) Keeping the temperature of the sample at 280-300 ℃ for 0.5-1.5 hours, and then discharging the sample from the furnace and cooling the sample by air.

in one embodiment, the step 1) is that an industrial TA 1-grade titanium plate with the thickness of 1mm is degreased, sand-blasted, etched for 90min in a mixed solution of 5% oxalic acid and 20% sulfuric acid, washed with water and dried for later use.

In one embodiment, the molar ratio of the metal ions of ruthenium chloride (RuCl 3.3h2O), tin tetrachloride (SnCl 4.5h2O) and manganous chloride (MnCl 2.4h2O) is Ru: sn: mn is 4:2: 4.

In one embodiment, step 4) cuts the sample to a size of 1cm by 1 cm.

Preferably, in the step 4), the sample is taken out of the furnace and cooled by air after being kept at 285-295 ℃ for 0.5-1.5 hours

Further preferably, step 4) is carried out by taking the sample out of the furnace and cooling the sample by air after keeping the sample at 290 ℃ for 1 hour.

The invention also provides a preparation method of the Ti/Ru0.4Sn0.2Mn0.4O2 electrode, which comprises the following steps: 1) preparing a clean titanium plate;

2) dissolving ruthenium chloride (RuCl3 & 3H2O), tin tetrachloride (SnCl4 & 5H2O) and manganous chloride (MnCl2 & 4H2O) in absolute ethyl alcohol according to a proportion, and performing ultrasonic oscillation to uniformly disperse the materials to obtain a precursor coating liquid; wherein the molar ratio of metal ions of ruthenium chloride, tin tetrachloride and manganous chloride is Ru: sn: mn is 2-6:1-3: 2-6;

3) Coating one side of the precursor coating liquid on a titanium plate, curing by infrared illumination after each coating, thermally oxidizing for 5-15min in a box type resistance furnace at 260-280 ℃, discharging and cooling; repeating the steps until the loading capacity of the RuO2 is more than or equal to 1.0mg cm < -2 >;

4) keeping the temperature of the sample at 280-300 ℃ for 0.5-1.5 hours, and then discharging the sample from the furnace and cooling the sample by air.

compared with the background technology, the technical scheme of the invention has the following advantages:

The electrode material prepared at 280-300 ℃ has good electronic conductivity and proton conductivity, and can fully utilize the inner active surface and the outer active surface of the oxide coating, so that the electrode material has the highest specific capacitance, and particularly, the electrode material prepared at 290 ℃ discharges under the current density of 5mA/cm2, and the specific capacitance can reach 743.2F/g. When the power density is 1.28kW/kg, the corresponding energy density is 85.56 Wh/kg.

Drawings

The invention is further illustrated by the following figures and examples.

FIG. 1 is a Ti/Ru0.4Sn0.2Mn0.4O2 electrode XRD spectral line prepared at different temperatures.

FIG. 2a is a cyclic voltammetry curve of Ti/Ru0.4Sn0.2Mn0.4O2 ternary oxide coating prepared at different temperatures, the scanning speed is 10mV/s, and FIG. 2b is a voltammetry integral electric quantity of Ti/Ru0.4Sn0.2Mn0.4O2 ternary oxide coating prepared at different heat treatment temperatures.

FIG. 3 shows cyclic voltammograms of Ti/Ru0.4Sn0.2Mn0.4O2 electrodes at different sweep rates (1) at 15mV/s, (2) at 50mV/s, (3) at 100mV/s, and (4) at 200 mV/s.

FIG. 4 is a plot of voltammetric capacity q versus scan rate for Ti/Ru0.4Sn0.2Mn0.4O2 electrodes prepared at different temperatures.

FIG. 5 "energy density-power density" curves for Ti/Ru0.4Sn0.2Mn0.4O2 electrodes prepared at different temperatures.

Fig. 6 extrapolation of the integrated charge q at different preparation temperatures, (a) v → ∞ and (b) v → 0;

FIG. 7 is a Nyquist plot (the inset is an equivalent circuit plot and an enlarged plot of the impedance in the high frequency region) of a Ti/Ru0.4Sn0.2Mn0.4O2 electrode prepared at different temperatures with a test potential of 0.75V and a frequency interval of 0.005Hz to 10 KHz. (ii) a

FIG. 8 shows (a) constant current charging and discharging curve (b) specific capacitance of Ti/Ru0.4Sn0.2Mn0.4O2 electrode material prepared at different preparation temperatures.

Detailed Description