CN104593806A - Method for preparing gas diffusion electrode for strongly acidic electrolyte - Google Patents

Method for preparing gas diffusion electrode for strongly acidic electrolyte Download PDF

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Publication number
CN104593806A
CN104593806A CN201510004122.2A CN201510004122A CN104593806A CN 104593806 A CN104593806 A CN 104593806A CN 201510004122 A CN201510004122 A CN 201510004122A CN 104593806 A CN104593806 A CN 104593806A
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China
Prior art keywords
gas diffusion
preparation
diffusion electrode
group
electrolyte
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CN201510004122.2A
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Chinese (zh)
Inventor
孟惠民
张慧
唐静
俞宏英
***
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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Priority to CN201510004122.2A priority Critical patent/CN104593806A/en
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/21—Manganese oxides
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic

Abstract

The invention belongs to the field of electrolysis materials and relates to a method for preparing an energy-saving gas diffusion electrode for strongly acidic MnSO4-H2SO4 electrolyte. The gas diffusion electrode consists of a conductive carrier, a catalysis layer and a gas diffusion layer. The preparation method comprises the following steps: pressing a flocculation-shaped mixture of the catalysis layer and the gas diffusion layer into sheets with a certain thickness, respectively putting two kinds of sheets on two sides of the conductive carrier, and pressing to form the gas diffusion electrode under certain pressure and time. When the electrolytic manganese dioxide (EMD) is prepared by electrolyzing the strongly acidic MnSO4-H2SO4 electrolyte, a hydrogen evolution cathode is replaced by the gas diffusion electrode, so that the bath voltage can be greatly reduced, and the energy is saved.

Description

The preparation method of a kind of strongly-acid gas diffusion electrode used for electrolyte
Technical field
The invention belongs to electrolysis material field, relate to a kind of strongly-acid MnSO 4-H 2sO 4a kind of energy-saving gas diffusion electrode of electrolytic manganese dioxide (EMD) is prepared in electrolytic solution.Significantly can improve cathode potential by this gas diffusion electrode, thus effectively reduce bath voltage, save energy.
Background technology
ZL201010578846.5 proposes a kind of energy-saving and environmental protection and the electrolytic manganese dioxide novel method of safety: electrolysis principle is constant, anodic reaction is also constant, it is still made to produce required EMD product, the difference of positive and negative electrode potential is mainly from electrolyzer pressure, the principle that raising cathode potential also can reduce electrolyzer pressure is set out, imagination noble potential gas diffusion electrode (being called for short GDE) replaces traditional technology low potential cathode for hydrogen evolution, and cathodic reaction becomes redox reactions: O 2+ 4H ++ 4e -→ 2H 2o (E 0=+1.229V), then with the liberation of hydrogen reduction reaction of former electrolysis tech: 2H ++ 2e -→ H 2↑ (E 0=0V) compare, theoretical potential difference is up to 1.229V, namely compared with adopting the traditional method of cathode for hydrogen evolution, use the bath voltage of oxygen cathode electrolytic manganese dioxide novel method can reduce 1.229V in theory, negative electrode can not be separated out hydrogen and also can be reduced the generation of acid mist and the danger of detonation simultaneously.
Current gas diffusion electrode is mainly used in the aspects such as fuel cell, chlorine industry, synthesize hydrogen peroxide, and the main environment of research is slightly acidic, neutrality and alkaline environment, and the fundamental research of gas diffusion electrode in strongly-acid electrolytic solution is substantially blank.The object of the invention is to propose a kind of novel method preparing energy-saving gas diffusion electrode, at strongly-acid MnSO 4-H 2sO 4reduce the bath voltage producing electrolytic manganese dioxide in electrolytic solution, thus reduce energy consumption, avoid negative electrode to separate out hydrogen.
Summary of the invention
The invention relates to strongly-acid MnSO 4-H 2sO 4a kind of energy-saving gas diffusion electrode of electrolytic manganese dioxide is prepared in electrolytic solution.The gas diffusion electrode being suitable for this technique a kind ofly has energy-conservation oxygen electrode, and its structural representation as shown in Figure 1.The electrolyzer being suitable for this technique is gas-liquid electrolyzer, and the basic structure of electrolyzer proposes in ZL201010578846.5.
The invention provides a kind of method preparing gas diffusion electrode, gas diffusion electrode is made up of conductive carrier, Catalytic Layer, gas diffusion layers, and its preparation process is as follows:
(1) preparation of Catalytic Layer
High temperature preparation group cloud mixture, group's cloud mixture is made up of catalyst Pt/C, hydrophilic electroconductive Powdered Activated Carbon, hydrophobic conductive powder acetylene black, tackiness agent tetrafluoroethylene and organic solvent dehydrated alcohol, a cloud mixture is pressed into certain thickness thin slice, make Catalytic Layer, thickness is 0.3-0.4mm;
(2) preparation of gas diffusion layers
High temperature preparation group cloud mixture, group's cloud mixture is made up of inorganic pore forming particles anhydrous sodium sulphate, hydrophilic electroconductive Powdered Activated Carbon, hydrophobic conductive powder acetylene black, tackiness agent tetrafluoroethylene and organic solvent dehydrated alcohol, a cloud mixture is pressed into certain thickness thin slice, makes gas diffusion layers;
(3) Catalytic Layer and gas diffusion layers are put into conductive carrier two sides respectively, under certain pressure and time, suppress described thin slice.
Wherein conductive carrier can be foamed metal, is preferably nickel foam, titanium foam.
Consisting of of group's cloud mixture in step (1): the Pt/C of 1 ~ 15wt%, the acetylene black of 5 ~ 25wt%, the gac of 40 ~ 80wt%, the tetrafluoroethylene of 10 ~ 30wt%, group's cloud mixture mixing temperature is 60-70 DEG C, and sheet thickness is 0.3 ~ 0.4mm.
The anhydrous sodium sulphate consisting of 5 ~ 25wt% of the group's cloud mixture in step (2), the acetylene black of 10 ~ 30wt%, the gac of 5 ~ 30wt%, the tetrafluoroethylene of 15 ~ 50wt%, mixing temperature is 60 ~ 70 DEG C.Gas diffusion layers sheet thickness is 0.4 ~ 0.5mm.
Thin slice described in step (3) is extruded together with conductive carrier Catalytic Layer, gas diffusion layers.Implemented by decompressor, pressure is preferably 5 ~ 20MPa, and the time is preferably 3 ~ 8min.
The thickness of Catalytic Layer, gas diffusion layers can be controlled by the amount of fixed model, group's cloud mixture and pressure.
Gas diffusion electrode prepared by the inventive method is applicable to acid electrolyte, is particularly useful for strongly-acid MnSO 4-H 2sO 4electrolytic solution.Electrolyzed strong acid MnSO 4-H 2sO 4electrolytic solution uses this gas diffusion electrode to substitute cathode for hydrogen evolution when preparing electrolytic manganese dioxide (EMD) significantly can reduce bath voltage, save energy.
Accompanying drawing explanation
Accompanying drawing 1 is the structural representation of gas diffusion electrode
1-Catalytic Layer thickness is 0.3-0.4mm;
2-conducting matrix grain thickness is 0.1-0.2mm;
3-gas diffusion layers thickness is 0.4-0.5mm.
Embodiment
Embodiment one
Mass ratio be 5: 60: 15: 20 Pt/C, gac, acetylene black and the appropriate dehydrated alcohol of tetrafluoroethylene be uniformly dispersed, in 65 DEG C of water-baths, be heated to bulk, be then put into repeat-rolling on roll squeezer, obtaining thickness is the thin slice of 0.3mm.
Mass ratio be 20: 20: 20: 40 anhydrous sodium sulphate, gac, acetylene black and the appropriate dehydrated alcohol of tetrafluoroethylene be uniformly dispersed, bulk is heated in 65 DEG C of water-baths, then be put into repeat-rolling on roll squeezer, obtaining thickness is the thin slice of 0.4mm.
Two kinds of thin slices are put into respectively the two sides of nickel foam, at the pressure 5min of 10MPa, gained thin slice is gas diffusion electrode.
Embodiment two
Mass ratio be 1: 64: 15: 20 Pt/C, gac, acetylene black and the appropriate dehydrated alcohol of tetrafluoroethylene be uniformly dispersed, in 65 DEG C of water-baths, be heated to bulk, be then put into repeat-rolling on roll squeezer, obtaining thickness is the thin slice of 0.3mm.
Diffusion layer is identical with embodiment one.
Two kinds of thin slices are put into respectively the two sides of nickel foam, at the pressure 5min of 10MPa, gained thin slice is gas diffusion electrode.
The gas diffusion electrode prepared according to this method is for highly acid MnSO 4-H 2sO 4electrolytic manganese dioxide is prepared in electrolytic solution.Be 100Am for current density -2, sulfuric acid concentration is 30gdm -3, manganous sulfate concentration is 120gdm -3, in T=70 DEG C of electrolysis system.
The Performance comparision of table 1. two kinds of gas diffusion electrodes
Bath voltage Cathode potential Life-span Direct current consumption
Embodiment one 1.0V -0.369V 600h 630kWh·t -1
Embodiment two 1.5V -0.847V 125h 953kWh·t -1
The gas diffusion electrode performance of embodiment one is higher than embodiment two as can be seen from the table.

Claims (6)

1. a preparation method for strongly-acid gas diffusion electrode used for electrolyte, gas diffusion electrode is made up of conductive carrier, Catalytic Layer, gas diffusion layers, it is characterized in that preparation process is as follows:
(1) preparation of Catalytic Layer
High temperature preparation group cloud mixture, group's cloud mixture is made up of catalyst Pt/C, hydrophilic electroconductive Powdered Activated Carbon, hydrophobic conductive powder acetylene black, tackiness agent tetrafluoroethylene and organic solvent dehydrated alcohol, a cloud mixture is pressed into certain thickness thin slice, make Catalytic Layer, thickness is 0.3-0.4mm;
(2) preparation of gas diffusion layers
High temperature preparation group cloud mixture, group's cloud mixture is made up of inorganic pore forming particles anhydrous sodium sulphate, hydrophilic electroconductive Powdered Activated Carbon, hydrophobic conductive powder acetylene black, tackiness agent tetrafluoroethylene and organic solvent dehydrated alcohol, a cloud mixture is pressed into certain thickness thin slice, makes gas diffusion layers;
(3) Catalytic Layer and gas diffusion layers are put into conductive carrier two sides respectively, under certain pressure and time, suppress described thin slice.
2. the preparation method of a kind of strongly-acid gas diffusion electrode used for electrolyte as claimed in claim 1, is characterized in that wherein conductive carrier is foamed metal.
3. the preparation method of a kind of strongly-acid gas diffusion electrode used for electrolyte as claimed in claim 2, is characterized in that foamed metal is nickel foam, titanium foam.
4. the preparation method of a kind of strongly-acid gas diffusion electrode used for electrolyte as claimed in claim 1, it is characterized in that consisting of of the group's cloud mixture in step (1): the Pt/C of 1 ~ 15wt%, the acetylene black of 5 ~ 25wt%, the gac of 40 ~ 80wt%, the tetrafluoroethylene of 10 ~ 30wt%, group's cloud mixture mixing temperature is 60-70 DEG C, and sheet thickness is 0.3 ~ 0.4mm.
5. the preparation method of a kind of strongly-acid gas diffusion electrode used for electrolyte as claimed in claim 1, it is characterized in that the acetylene black of the anhydrous sodium sulphate consisting of 5 ~ 25wt% of the group's cloud mixture in step (2), 10 ~ 30wt%, the gac of 5 ~ 30wt%, the tetrafluoroethylene of 15 ~ 50wt%, group's cloud mixture mixing temperature is 60-70 DEG C; Gas diffusion layers sheet thickness is 0.4 ~ 0.5mm.
6. the preparation method of a kind of strongly-acid gas diffusion electrode used for electrolyte as claimed in claim 1, it is characterized in that thin slice described in step (3) is extruded together with conductive carrier Catalytic Layer, gas diffusion layers, implemented by decompressor, pressure is 5 ~ 20MPa, and the time is 3 ~ 8min.
CN201510004122.2A 2015-01-04 2015-01-04 Method for preparing gas diffusion electrode for strongly acidic electrolyte Pending CN104593806A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105601003A (en) * 2016-03-04 2016-05-25 山东大学 Ferroferric oxide @ activated carbon doped gas diffusion electrode and preparation method and application thereof
CN106637281A (en) * 2017-01-17 2017-05-10 北京科技大学 Method for producing electrolytic manganese dioxide
CN113718280A (en) * 2021-08-31 2021-11-30 苏州清缘环保科技有限公司 Gas diffusion electrode and method for producing same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101212054A (en) * 2006-12-31 2008-07-02 比亚迪股份有限公司 Fuel cell membrane electrode and its preparation method
CN101388463A (en) * 2008-10-23 2009-03-18 上海交通大学 Membrane electrode for proton exchange membrane water electrolysis battery and preparation thereof
CN102031532A (en) * 2010-12-03 2011-04-27 北京科技大学 Energy-saving electrolytic manganese dioxide preparation method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101212054A (en) * 2006-12-31 2008-07-02 比亚迪股份有限公司 Fuel cell membrane electrode and its preparation method
CN101388463A (en) * 2008-10-23 2009-03-18 上海交通大学 Membrane electrode for proton exchange membrane water electrolysis battery and preparation thereof
CN102031532A (en) * 2010-12-03 2011-04-27 北京科技大学 Energy-saving electrolytic manganese dioxide preparation method

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105601003A (en) * 2016-03-04 2016-05-25 山东大学 Ferroferric oxide @ activated carbon doped gas diffusion electrode and preparation method and application thereof
CN105601003B (en) * 2016-03-04 2018-08-03 山东大学 A kind of gas-diffusion electrode and the preparation method and application thereof of doped ferroferric oxide@activated carbons
CN106637281A (en) * 2017-01-17 2017-05-10 北京科技大学 Method for producing electrolytic manganese dioxide
CN113718280A (en) * 2021-08-31 2021-11-30 苏州清缘环保科技有限公司 Gas diffusion electrode and method for producing same
CN113718280B (en) * 2021-08-31 2024-04-26 苏州清氧环境科技有限公司 Gas diffusion electrode and method for producing same

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Application publication date: 20150506