CN102321892B - Method for preparing composite active cathode - Google Patents

Method for preparing composite active cathode Download PDF

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CN102321892B
CN102321892B CN201110266645.6A CN201110266645A CN102321892B CN 102321892 B CN102321892 B CN 102321892B CN 201110266645 A CN201110266645 A CN 201110266645A CN 102321892 B CN102321892 B CN 102321892B
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transition layer
net
coating liquid
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coating
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CN102321892A (en
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黎学明
黄舒
李武林
王雯
杨建春
杨文静
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Chongqing University
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Abstract

The invention relates to a method for preparing a composite active cathode. The method comprises the following steps of: providing a Ni net as a cathode matrix; configuring a coating solution of a transition layer, wherein the content of Pd(NO3)2 is 5-10 g/L; coating the coating solution of the transition layer onto the Ni net, and drying and thermally decomposing the coating solution to obtain the transition layer on the Ni net; configuring a coating solution of an active layer, wherein the contents of H2PtCl6.6H2O and RuCl3.3H2O are 10-15 g/L and 6-10 g/L respectively; and coating the coating solution of the active layer onto the Ni net with the transition layer, and drying and thermally decomposing the coating solution to obtain the active layer on the transition layer. According to the method disclosed by the invention, the prepared composite active cathode includes Ni, PdO and RuO2-Pt; the transition layer and the active layer on the surface of the matrix are realized by separate coating; the loading capacity of Pd in a coated layer is only 0.3-0.4 g/m<2>; the process for preparing the coated layer comprises the steps of pre-drying and thermal decomposing, thereby avoiding air holes; the bonding force between the transition layer and the Ni matrix is greatly increased; the integral stability of the electrode is good; and the reverse current impact resistance capacity and the anti-poisoning capacity are greatly increased.

Description

A kind of preparation method of composite active cathode
Technical field
The present invention relates to a kind of preparation method of composite active cathode of suitable especially chlorine industry ion-exchange membrane electrolyzer use.
Background technology
At present, global energy is nervous, and oil is exhausted.Chemical industry is big power consumer, and chlorine industry power consumption accounts for it more than 10%, accounts for 60%～70% of preparation total cost.Chlorine industry, in order to reduce its energy consumption, adopts the methods such as ion-exchange membrane electrolyzer, DSA anode to reduce electrolytic bath and presses, and obtains very good effect.But the problem that cathode hydrogen evolution overpotential is higher affects electrolytic bath and presses further reduction always.Therefore, the preparation of low overpotential of hydrogen evolution activated cathode is always by everybody broad research.
JP-B-55-22556 is coated to the solution that contains platinum metal oxides in heated metal base, and then the coated material of roasting is to form oxide compound; JP-B-59-48872, JP-B-60-13074 are electroplated the powder of the oxide compounds such as ruthenium are attached on nickeliferous substrate surface by suspension.Although cathode hydrogen evolution overpotential prepared by these methods is low, is not subject to the impact of impurity iron in electrolytic solution, because cathode surface relates to unstable oxide, make the negative electrode of preparation there is no enough weather resistance, working time is shorter.JP-B-6-33492 is by the catalyst-coated containing at least one platinum, platinum metal oxides on negative electrode, but catalyst coat and substrate tack are poor, and the life-span is short.US4465580 and 4238311 preparations have the Ni-based negative electrode of Ru oxide compound and Ni oxide coating, also do not overcome short problem in work-ing life.EP298055 adopts the mixture activated ni matrix of platinum or other precious metal and cerium; after thermolysis, obtain the Catalytic Layer of the mixture based on platinum or other precious metal and cerium; then with the porous layer of cerium, protect the negative electrode of preparation, can partly improve the bonding force of coating and matrix, increase the service life.
JP-A-57-23083 proposes electroless plating platinum or its alloy method in nickel substrate, though there is the features such as overpotential of hydrogen evolution is low, good endurance, easily poisoning by the iron contamination in electrolytic solution.
(the electrochemistry such as Fu Yinhui, 2010,16 (2): 202～205) adopt thermolytic to prepare Ni-Ru-Ir oxide compound activated cathode, by cyclic voltammetry, Ta Feier curve and timing testing current, show that this activated cathode overpotential of hydrogen evolution is low, surfaceness is large, but electrode stability is not carried out to deep evaluation.
CN1265432A proposes a kind of method that reduces cathode hydrogen evolution overpotential, on conductive substrates surface, form the interlayer that comprises nickel oxide, and form containing at least one and be selected from the lanthanum composition of lanthanide metal oxide and oxyhydroxide on interlayer, with at least one be selected from platinum metals and silver with and the platinum composition of oxide compound and oxyhydroxide, thereby obtain a kind of activated cathode.Main preparation methods be nickel coating on nickel conducting base nitrate solution, containing at least one, be selected from the nitrate solution that lanthanide series metal and at least one are selected from platinum metals and silver, then thermolysis obtains oxide compound interlayer and the Catalytic Layer of nickel.This activated cathode, its catalyst coatings is not easy to peel off or be not easy fall in flakes, can effectively utilize its distinctive high reactivity and anti-toxic.But the nickel oxide interlayer of this activated cathode can not resist open circuit oxidation and reversible circulation to impact.
In order to improve anti-power-off and the reversible circulation impact capacity of electrode, CN101029405 prepares the coating of 10um～30um at wire netting matrix surface, one or several metal-salts in of containing cobalt in period of element Table VIII family metal, nickel, zinc, ruthenium, cadmium, iridium, platinum of coated material or several metal-salt and the periodic table of elements in lanthanide series metal lanthanum, cerium, praseodymium, and mineral acid or organic acid acidic substance.Main method is that coating liquid is coated on wire netting matrix, then the method by thermolysis forms metal and oxide coating thereof on wire netting matrix, kind electrode preparation technology is simple, there is high Hydrogen Evolution Performance and certain anti-power-off and reversible circulation impact capacity, but the bonding force of kind electrode active coating and matrix is poor, in use procedure, active substance easily comes off, and work-ing life is limited, and cost is high.
(Electrochimica Acta, 2008,53 (25): 7410～7416) adopt electro-deposition method in Ni rotating disk electrode, to generate porous Ni and Ni+RuO such as Antonio A L 2settling, thereby obtain Ni+RuO 2combined electrode, has studied its Hydrogen Evolution Performance and stability by AC impedence method and cyclic voltammetry, and result shows RuO in this electrode 2be the most active catalytic core, and electrode stability is better.
Wang Wen etc. (Chinese Journal of Inorganic Chemistry, 2010,26 (9): 1633～1638) propose to prepare on Ni matrix with thermolytic take PdO as middle layer, RuO 2ni/PdO/RuO for active coating 2composite active cathode, test result shows that this activated cathode is large compared with pure nickel electrode specific surface area, and overpotential of hydrogen evolution is low, and stability strengthens, and the material of raising stability and catalytic activity is respectively PdO and RuO 2.Kind electrode preparation technology is simple, good stability, but still needs further to reduce its overpotential of hydrogen evolution.
Thereby US2008043766 and US2009194411 propose to form a coat on nickel screen matrix to be improved electrode reverse current impact capacity and reduces overpotential of hydrogen evolution.Coat has the composition of two kinds of difference in functionalitys: a kind of composition contains Pd or Pd-Ag metallic element and oxide compound thereof, for electric current, oppositely shields; A kind of composition at least contains platinum, a kind of metal of ruthenium and oxide compound thereof or at least platinum, a kind of metal of ruthenium and a small amount of rhodium and oxide compound thereof, there is good katalysis, but coat Pd content is higher, and making processes is that direct heat is decomposed, easily produce pore, be all unfavorable for transition layer and Ni matrix good combination.
Summary of the invention
The present invention aim to provide a kind of high catalytic activity, low overpotential of hydrogen evolution, good stability and/or long service life composite active cathode preparation method and thus preparation the negative electrode that is mainly used in chlorine industry ion-exchange membrane electrolyzer.
Composite active cathode preparation method according to the present invention comprises:
Be provided as the Ni net of cathode base;
Configuration transition layer coating liquid, wherein Pd (NO 3) 2content be 5～10g/L;
Transition layer coating liquid is coated on to Ni on the net and dries with thermal decomposition process to obtain transition layer on the net at Ni;
Configuration active coating coating liquid, wherein H 2ptCl 66H 2o and RuCl 33H 2the content of O is respectively 10～15g/L and 6～10g/L; And
Active coating coating liquid is coated on to have the Ni of transition layer online and dries with thermal decomposition process to obtain active coating on transition layer.
Method of the present invention cleans pre-treatment to Ni net before being also preferably included in and applying transition layer coating liquid.Clean pre-treatment generally includes step: alkali liquor oil removing, washing, acid etch, ultrasonic wave water washing and oven dry.The alkaline wash using in alkali liquor oil removing step can be the mixing solutions of sodium hydroxide, sodium-chlor and anhydrous sodium sulphate, and its massfraction is 5～10%, and treatment temp is 60～90 ℃, and the treatment time is 10～15 minutes.The etching liquid using in acid etch step can be that massfraction is 10% oxalic acid boiling solution, to the etching time of Ni net, is 3～5 hours.
In the method for the invention, can repeat that transition layer coating liquid is coated on to Ni online and dries that to take with the process of thermal decomposition process the charge capacity that obtains palladium element on the net at Ni be 0.3～0.4g/m 2transition layer.
In the method for the invention, can also repeat active coating coating liquid to be coated on that to have the Ni of transition layer online and dries that to take with the process of thermal decomposition process the load total amount that obtains ruthenium element and platinum element on transition layer be 5.5～6.5g/m 2active coating.
In the method for the invention, transition layer coating liquid can also comprise that content is 15% nitric acid of 5ml/L.
In the method for the invention, active coating coating liquid can also comprise citric acid and ethylene glycol, and wherein citric acid content is 400g/L, and surplus is ethylene glycol.
Composite active cathode of the present invention is prepared by aforesaid method, is particularly useful for chlorine industry ion-exchange membrane electrolyzer.
Composite active cathode prepared according to the methods of the invention comprises transition layer PdO and active coating RuO 2-Pt, consists of Ni/PdO/RuO 2-Pt, the transition layer of matrix surface is realized by separating to apply with active coating, and in coat, palladium element charge capacity is only 0.3～0.4g/m 2, coat making processes is " prebake+thermolysis ", avoids the generation of pore, has greatly improved transition layer and Ni basal body binding force." prebake+thermolysis " process for transition layer, active coating, by control temperature, time, can guarantee that Ni matrix surface forms the active coating of transition layer, ruthenium dioxide and the platinum grain of one deck nickel oxide and thin palladous oxide, improve the bonding force of transition layer and Ni matrix, make electrode integral good stability, anti-reversible circulation impacts and anti-poisoning capability strengthens greatly.
Embodiment
For better explanation the present invention, provide following examples and set forth, and with the activated cathode contrast without PdO transition layer.
the configuration of transition layer coating liquid
By Pd (NO 3) 2powder is dissolved in the deionized water of certain volume, dissolves form the Pd (NO that concentration is 5～10g/L completely 3) 2solution, after a small amount of nitric acid acidifying, through the full and uniform mixing of ultrasonic wave.
the configuration of active coating presoma coating liquid
By H 2ptCl 66H 2o and RuCl 33H 2o takes according to a certain percentage, is dissolved in the mixing solutions of citric acid and ethylene glycol, and ultrasonic wave is fully mixed, and within standing 12 hours, forms reddish-brown colloidal solution, wherein H 2ptCl 66H 2o and RuCl 33H 2the concentration in mixing solutions of O is respectively 10～15g/L and 6～10g/L.
the measurement of electropotential
Adopt continuous current method to measure the composite active cathode overpotential of hydrogen evolution of fresh preparation, reference electrode is saturated calomel electrode, to electrode, is Pt electrode, and condition determination is: current density 3kA/m 2, 30% NaOH solution, 90 ℃ of temperature, record its electropotential.
At electrode apparent area 4 * 4cm 2simulation electrolyzer in, with 3kA/m 2current density continuously operation, after 4000 hours, is taken out its electropotential of determination of electrode, and measuring method is with fresh electrode.
Comparative example
Nickel screen is successively through sandblast, the mixing solutions that massfraction is 8% sodium hydroxide, sodium-chlor, anhydrous sodium sulphate is made alkaline wash and in the water-bath of 90 ℃, is processed alkali cleaning oil removing in 10 minutes, second distillation washing, in 10% oxalic acid boiling solution, acid etching is 4 hours, in redistilled water, ultrasonic oscillation dries standby to clean up in 5 minutes.With wool brush, coating liquid is coated on the Ni net matrix that pre-treatment is good, thermolysis obtains active coating.
Active coating coating liquid consists of:
Figure BSA00000571053000051
Solution left standstill was coated on nickel-base material after 12 hours, dried 20 minutes at 150 ℃, was then placed in retort furnace and at 500 ℃, carried out roasting 10 minutes, repeated after cooling same process, made the charge capacity of activated cathode surface Ru, Pt element add up to 6g/m 2.
The hydrogen-evolution overpotential of fresh activated cathode is-1.153V; Move after 4000 hours, the hydrogen-evolution overpotential of activated cathode is-1.323V.Electropotential amount of movement 0.170V.
Embodiment 1
Nickel screen is successively through sandblast, the mixing solutions that massfraction is 6% sodium hydroxide, sodium-chlor, anhydrous sodium sulphate is made alkaline wash and in the water-bath of 75 ℃, is processed alkali cleaning oil removing in 10 minutes, second distillation washing, in 10% oxalic acid boiling solution, acid etching is 4 hours, in redistilled water, ultrasonic oscillation dries standby to clean up in 5 minutes.With wool brush, coating liquid is coated on the Ni net matrix that pre-treatment is good, thermolysis obtains transition layer and active coating.
Transition layer coating liquid consists of:
Palladous nitrate 8g/L
15% nitric acid 5ml/L
Active coating coating liquid consists of:
The coating liquid that applies transition layer is online to Ni, and 160 ℃ are dried 18 minutes, then puts it in High Temperature Furnaces Heating Apparatus, and 600 ℃ of roastings 10 minutes, are cooled to room temperature; Repeat above-mentioned steps, make the Pd charge capacity 0.32g/m on activated cathode surface 2.
Apply the active coating coating liquid after standing 12 hours scribbling on the Ni net matrix of Pd, 160 ℃ dry 15 minutes, put it in High Temperature Furnaces Heating Apparatus, 550 ℃ of roastings 15 minutes, are cooled to room temperature; Repeat above-mentioned steps, make the Ru on activated cathode surface, Pt charge capacity add up to 5.8g/m 2.
The hydrogen-evolution overpotential value of fresh activated cathode is-1.155V; Move after 4000 hours, the hydrogen-evolution overpotential of activated cathode is-1.223V.Electropotential amount of movement 0.068V.
Embodiment 2
Nickel screen is successively through sandblast, the mixing solutions that massfraction is 10% sodium hydroxide, sodium-chlor, anhydrous sodium sulphate is made alkaline wash and in the water-bath of 70 ℃, is processed 12 minutes, alkali cleaning oil removing, second distillation washing, in 10% oxalic acid boiling solution, acid etching is 5 hours, in redistilled water, ultrasonic oscillation dries standby to clean up in 5 minutes.With wool brush, coating liquid is coated on the Ni net matrix that pre-treatment is good, thermolysis obtains transition layer and active coating.
Transition layer coating liquid consists of:
Palladous nitrate 10g/L
15% nitric acid 5ml/L
Active coating coating liquid consists of:
Figure BSA00000571053000061
The coating liquid that applies transition layer is online to Ni, and 170 ℃ are dried 15 minutes, then puts it in High Temperature Furnaces Heating Apparatus, and 450 ℃ of roastings 20 minutes, are cooled to room temperature; Repeat above-mentioned steps, make the Pd charge capacity 0.40g/m on activated cathode surface 2.
Apply the active coating coating liquid after standing 12 hours scribbling on the Ni net matrix of Pd, 180 ℃ dry 10 minutes, put it in High Temperature Furnaces Heating Apparatus, 600 ℃ of roastings 12 minutes, are cooled to room temperature; Repeat above-mentioned steps, make the Ru on activated cathode surface, Pt charge capacity add up to 6.2g/m 2.
The hydrogen-evolution overpotential of fresh activated cathode is-1.113V; Move after 4000 hours, the hydrogen-evolution overpotential of activated cathode is-1.169V.Electropotential amount of movement 0.056V.
Embodiment 3
Nickel screen is successively through sandblast, the mixing solutions that massfraction is 7% sodium hydroxide, sodium-chlor, anhydrous sodium sulphate is made alkaline wash and in the water-bath of 80 ℃, is processed 15 minutes, alkali cleaning oil removing, second distillation washing, in 10% oxalic acid boiling solution, acid etching is 3 hours, in redistilled water, ultrasonic oscillation dries standby to clean up in 5 minutes.
With wool brush, coating liquid is coated on the Ni net matrix that pre-treatment is good, thermolysis obtains transition layer and active coating.
Transition layer coating liquid consists of:
Palladous nitrate 5g/L
15% nitric acid 5ml/L
Active coating coating liquid consists of:
Figure BSA00000571053000071
The coating liquid that applies transition layer is online to Ni, and 180 ℃ are dried 10 minutes, then puts it in High Temperature Furnaces Heating Apparatus, and 500 ℃ of roastings 18 minutes, are cooled to room temperature; Repeat above-mentioned steps, the Pd charge capacity that makes activated cathode surface is 0.38g/m 2.
Apply the active coating coating liquid after standing 12 hours scribbling on the Ni net matrix of Pd, 150 ℃ dry 20 minutes, put it in High Temperature Furnaces Heating Apparatus, 600 ℃ of roastings 12 minutes, are cooled to room temperature; Repeat above-mentioned steps, make the Ru on activated cathode surface, Pt charge capacity add up to 5.9g/m 2.
The hydrogen-evolution overpotential of fresh activated cathode is-1.148V; Move after 4000 hours, the hydrogen-evolution overpotential of activated cathode is-1.209V.Electropotential amount of movement 0.061V.

Claims (1)

1. a composite active cathode preparation method, comprising:
Be provided as the Ni net of cathode base;
Ni net is cleaned to pre-treatment, clean pre-treatment comprises step: alkali liquor oil removing, washing, acid etch, ultrasonic wave water washing and oven dry, the mixing solutions that the alkaline wash wherein using in alkali liquor oil removing step is sodium hydroxide, sodium-chlor and anhydrous sodium sulphate, its massfraction is 5～10%, treatment temp is 60～90 ℃, treatment time is 10～15 minutes, the etching liquid wherein using in acid etch step is that massfraction is 10% oxalic acid boiling solution, to the etching time of Ni net, is 3～5 hours;
Configuration transition layer coating liquid, wherein Pd (NO 3) 2content be 5～10g/L, transition layer coating liquid also comprises that content is 15% nitric acid of 5mL/L;
Repeating that transition layer coating liquid is coated on to Ni process online and that carry out 170 ℃ of oven dry of dry 15 minutes and 450 ℃ of roastings thermal decomposition process of 20 minutes, to take the charge capacity that obtains palladium element on the net at Ni be 0.3～0.4g/m 2transition layer;
Configuration active coating coating liquid, wherein H 2ptCl 66H 2o and RuCl 33H 2the content of O is respectively 10～15g/L and 6～10g/L, and active coating coating liquid also comprises citric acid and ethylene glycol, and wherein citric acid content is 400g/L, and surplus is ethylene glycol; And
Repeat active coating coating liquid to be coated on and to there is the Ni of transition layer process online and that carry out 180 ℃ of oven dry of dry 10 minutes and 600 ℃ of roastings thermal decomposition process of 12 minutes to take the load total amount that obtains ruthenium element and platinum element on transition layer be 5.5～6.5g/m 2active coating.
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CN102864464A (en) * 2012-08-31 2013-01-09 重庆大学 Preparation method of hydrogen evolution electrode with high catalytic activity and high stability
CN105582931B (en) * 2014-10-22 2020-03-06 中国科学院上海高等研究院 Cobalt-based Fischer-Tropsch synthesis catalyst loaded by mixed oxide carrier and preparation method thereof
CN109234760B (en) * 2018-10-31 2020-12-25 北京化工大学 Active cathode and preparation method and application thereof

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