CN109790634A - Electrode for electrolysis and preparation method thereof - Google Patents
Electrode for electrolysis and preparation method thereof Download PDFInfo
- Publication number
- CN109790634A CN109790634A CN201880003679.6A CN201880003679A CN109790634A CN 109790634 A CN109790634 A CN 109790634A CN 201880003679 A CN201880003679 A CN 201880003679A CN 109790634 A CN109790634 A CN 109790634A
- Authority
- CN
- China
- Prior art keywords
- electrode
- preparation
- electrolysis
- amine
- catalyst layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
- C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
-
- 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
Abstract
The present invention provides a kind of electrode for electrolysis and preparation method thereof.Compared with conventional electrodes, the electrode for electrolysis has the acicular texture of increased rare earth metal, therefore reduces the disengaging of catalysis material, so that electrode is excellent in terms of durability, such as shows stable performance in reverse current.Further, since the electrode for electrolysis has low overvoltage value, therefore the overvoltage requirement of electrolytic cell can be significantly reduced.Furthermore it is possible to which preparation has the electrode for electrolysis of said effect in the case where not introducing additional precursor or changing manufacturing equipment.
Description
Technical field
Cross reference to related applications
This application claims the South Korea patent application No.10- submitted on 08 11st, 2017 in Korean Intellectual Property Office
On 07 27th, the 2017-0102524 and 2018 South Korea patent application No.10-2018- submitted in Korean Intellectual Property Office
The disclosure of 0087750 equity, this two applications is fully incorporated in this specification by reference.
The present invention relates to a kind of electrode for electrolysis and preparation method thereof.More particularly it relates to a kind of electrolysis electricity consumption
Pole and preparation method thereof, the electrode for electrolysis can be such that the overvoltage value of electrode for electrolysis stablizes by increasing acicular texture
And improve durability.
Background technique
Chloralkali process is the electrolysis production chlorine (Cl by salt water2) and sodium hydroxide (NaOH) technique, in industry
On be useful because it can produce two kinds of substances for being widely used as basic substance in petrochemical industry in batches.
Chloralkali process in chlor-alkali film or with the electrode for electrolysis containing electrolytic catalyst diaphragm cell in into
Row.In chloralkali process, other than the voltage theoretically required, it is necessary to apply overvoltage to overcome the various intrinsic electricity of battery
Resistance.It is expected that developing a kind of method for making overvoltage require to minimize, transported because the reduction of this overvoltage will be saved significantly on battery
The relevant cost of energy of row.
The method required as the overvoltage for reducing electrolytic cell, it has been proposed that the side of several overvoltage for reducing electrode
Method.In the case where cathode, commonly used material such as mild steel, nickel or stainless steel have the overvoltage of 300mV to 400mV.
Then, it has been proposed that a method of make its surface active to reduce overvoltage.
However, in order to reduce the purpose of decomposition voltage, it is necessary to further decrease overvoltage.In addition, working as the operation of electrolytic cell
When stopping suddenly due to accident or power failure, because cathode and anode are electrically connected by rectifier, produced by electrolysis
Reversed decompose of object and the reverse current generated can flow.In this case, there are problems that cathode activity deterioration and by
It is eluted in the part of the metal component of cathode and causes the reduction of overvoltage efficiency.Therefore, it is also desirable to a kind of for making reverse current
Influence minimize method.
To solve the above-mentioned problems, various electrodes have been disclosed.
In JP-A-11-140680, the electrode material layer being mainly made of ruthenium-oxide is formed on the metallic substrate, and
Porous and low activity protective layer is further formed on the surface thereof, to improve the durability of electrode.
In JP-A-11-229170, a kind of electro-deposition nickel layer is provided, is dispersed with ruthenium-oxide in the electro-deposition nickel layer, and
And the conductive oxide being made of titanium oxide is coated on the surface of the layer, so as to improve the patience to mercury poisoning.
However, the shortcomings that these methods is that they need additional raw material, or it is difficult to impose a condition and complicated system
Process results are made, and there is a problem of the durability deficiency of electrode.
[existing technical literature]
Patent document 1:JP-A-11-140680
Patent document 2:JP-A-11-229170
Summary of the invention
Technical problem
To solve the above-mentioned problems, the electrolysis that the present invention provides a kind of with low overvoltage and excellent durability is used
Electrode.In addition, the present invention provides a kind of preparation method of electrode for electrolysis, the preparation method can not introduce it is additional before
Preparation shows the electrode of said effect in the case where body or change manufacturing equipment.
Technical solution
The present invention provides a kind of electrode for electrolysis, comprising: metallic substrates, and the catalysis formed in the metallic substrates
Oxidant layer,
Wherein, the catalyst layer includes nitrogen, platinum group metal and rare earth metal, and
Based on the platinum group metal, the nitrogen content of the catalyst layer is 20 moles of % to 60 moles of %.
Herein, the catalyst layer may include the acicular texture of the rare earth metal, and the acicular texture can be with
At least two needle-like structures comprising thickness and 0.5 μm to 10 μm of length with 50nm to 300nm.
In addition, the present invention provides a kind of preparation method of electrode for electrolysis, comprising the following steps:
Preparation is used to prepare the coating solution of electrode, which contains platinum group metal precursor, Rare earth metal precursors, has
Solvent and amine solvent；
The coating solution for being used to prepare electrode is coated on the metallic substrate to form catalyst layer；
The dry catalyst layer；And
The catalyst layer is heat-treated.
Herein, the platinum group metal precursor can be selected from ruthenium chloride hydrate (RuCl3·nH2O), four ammonia platinum of chlorination
(II) hydrate (Pt (NH3)4Cl2·H2O), radium chloride (RhCl3), rhodium nitrate hydrate (Rh (NO3)3·nH2O), iridium chloride water
Close object (IrCl3·nH2) and palladium nitrate (Pd (NO O3)2At least one of).
In addition, the Rare earth metal precursors can be selected from cerous nitrate (III) (Ce (NO3)3), cerous carbonate (III) (Ce2
(CO3)3), cerium chloride (III) (CeCl3), yttrium oxide (Y2O3) and yttrium carbonate (Y2(CO3)3At least one of).
The organic solvent can be the mixed solvent comprising the pure and mild C4 of C1 to C6 to C8 glycol ethers, and the C1 to C6
The ratio of the pure and mild C4 to C8 glycol ethers can be 10:1 to 1:2.
The amine solvent can be C6 to C30 saturation or unsaturated aliphatic amine, and may be preferred that selected from octylame,
At least one of decyl amine, dodecyl amine, oleyl amine, lauryl amine and hexadecylamine.Based on being used to prepare described in 100 volume %
The coating solution of electrode, the amine solvent can exist with the amount of 3 volume % to 40 volume %.
The platinum group metal precursor and the Rare earth metal precursors can exist with the molar ratio of 1:1 to 10:1.
The concentration of the coating solution for being used to prepare electrode can be 50g/L to 150g/L.
The drying steps can 70 DEG C to 200 DEG C at a temperature of carry out, and the heat treatment step can be 300
DEG C to carrying out at a temperature of 600 DEG C.
In addition, the present invention provides a kind of electrode for electrolysis prepared by preparation method described in this specification.
Beneficial effect
Compared with conventional electrodes, electrode for electrolysis according to the present invention has the acicular texture of increased rare earth metal, because
This reduces disengaging of the catalysis material from electrode, so that electrode is excellent in terms of durability, such as table in reverse current
Reveal stable performance.Further, since electrode for electrolysis of the invention has low overvoltage value, therefore electricity can be significantly reduced
The overvoltage requirement of Xie Chi.In addition, preparation method according to the present invention, can not introduce additional precursor or change manufacture
Preparation has the electrode for electrolysis of said effect in the case where equipment.
Detailed description of the invention
Fig. 1 shows the evaluation result of the electrode for electrolysis of embodiment 1 and the durability of commercial electrode；
Fig. 2 shows embodiment 1 after battery operation and embodiment 2 and the SEM on the surface of the electrode for electrolysis of comparative example 1
Image.
Specific embodiment
Term used in this specification is only used for description exemplary implementation scheme, and is not intended to be limited to the present invention.It removes
Non- differently to state within a context, otherwise singular references may include plural statement.It must be understood that the term in this specification
" comprising ", " equipment " or " having " are only used for the presence of specific characteristic, step, component or their combination, and are not excluded for one
The presence or pre-added possibility of a or multiple and different features, step, component or their combination.
Various modifications can be carried out and has various forms by the present invention, and specific example of the invention is described below.So
And, it is no intended to specific example is limited the invention to, and it must be understood that the present invention includes in spirit and skill of the invention
All modifications, equivalent or replacement within the scope of art.
Hereinafter, the present invention will be described in further detail.
The present invention provides a kind of electrode for electrolysis, comprising: metallic substrates, and the catalysis formed in the metallic substrates
Oxidant layer,
Wherein, the catalyst layer includes nitrogen, platinum group metal and rare earth metal, and
Based on the platinum group metal, the nitrogen content of the catalyst layer is 20 moles of % to 60 moles of %.
In electrode for electrolysis of the invention, the catalyst layer can be prepared by the inclusion of amine solvent, therefore nitrogen
Included in catalyst layer.Electrode for electrolysis performance of the invention with the acicular texture occurred by using amine solvent
Excellent durability out, therefore have the advantages that stable performance may be implemented in reverse current.Moreover, with routine
Commercial electrode is compared, and above-mentioned electrode has the effect of improving overvoltage value.
Herein, it is based on platinum group metal, the nitrogen content of catalyst layer is preferably 35 moles of % or more or 40 mole of % or more,
It and is 55 moles of % or less or 50 mole of % or less.If being based on platinum group metal, nitrogen content rubs less than 20 moles of % or 60
You are % or more, then can be difficult to ensure the durability improvement effect of electrode.
In the present invention, any conductive metallic substrates commonly used in the art can be used without limiting.
The type of metallic substrates is not particularly limited.It is, for example, possible to use perforated substrates, such as net, non-woven metal to knit
Object, metal foam, multiple piercing plate, braided metal (a braided metal), expanding metal etc..
The material of metallic substrates can be nickel, nickel alloy, stainless steel, copper, cobalt, iron, steel or their alloy.In conduction
Property and durability in terms of, nickel or nickel alloy are preferred.
Platinum group metal refers to the transition metal of the 8th race to the 10th race similar with platinum in performance, including ruthenium (Ru), platinum
(Pt), rhodium (Rh), iridium (Ir), osmium (Os) and palladium (Pd).Platinum group metal has catalytic activity, and can be by the inclusion of being electrolysed
With reducing overvoltage in electrode and improve life characteristic.An embodiment according to the present invention, platinum group metal can be
Ruthenium.
The rare earth metal refers to cerium (Ce), yttrium (Y), lanthanum (La), scandium (Sc) etc..An embodiment party according to the present invention
Case, the rare earth metal can be cerium.
Meanwhile the catalyst layer may include the acicular texture of rare earth metal.The acicular texture refers to comprising two kinds
Or more acicular texture (needle-like structures) structure.When forming the acicular texture of rare earth metal in catalyst layer, it can
To load as the platinum group metal of electrode catalytic materials, to reduce the disengaging of platinum group metal.Therefore, even if in reverse current item
Under part, electrode performance will not be deteriorated, and show excellent durability.
Specifically, the structure for forming acicular texture can have the thickness of 50nm to 300nm or 50nm to 200nm, and
0.5 μm to 10 μm or 0.5 μm to 5 μm of length.As by described in, electrode for electrolysis of the invention passes through in EXPERIMENTAL EXAMPLE
It is prepared comprising amine solvent, so that the acicular texture of rare earth metal is formed in catalyst layer, thus with conventional electrolysis electricity consumption
Pole is compared, and stable electrode characteristic and durability are shown.
In addition, the present invention provides a kind of preparation methods of electrode for electrolysis, comprising the following steps:
Preparation is used to prepare the coating solution of electrode, which contains platinum group metal precursor, Rare earth metal precursors, has
Solvent and amine solvent；
The coating solution for being used to prepare electrode is coated on the metallic substrate to form catalyst layer；
The dry catalyst layer；And
The catalyst layer is heat-treated.
Electrode for electrolysis prepared in accordance with the present invention significantly improves overvoltage in cell operation and shows to increase
It is powered on the effect of the acicular texture of the rare earth metal on the surface of pole.Therefore, electrode has the durability significantly improved, so that i.e.
Make that stable overvoltage efficiency is also ensured after reverse current phenomenon occurs.
In the present invention, the coating solution for being used to prepare electrode contains at least one platinum group metal precursor and at least one is dilute
Earth metal precursor.
In the present invention, the platinum group metal precursor can be the salt or oxide of platinum group metal.Herein, salt or oxide
It can be the form of hydrate.
For example, the platinum group metal precursor can be selected from ruthenium chloride hydrate (RuCl3·nH2O), four ammonia platinum of chlorination
(II) hydrate (Pt (NH3)4Cl2·H2O), radium chloride (RhCl3), rhodium nitrate hydrate (Rh (NO3)3·nH2O), iridium chloride water
Close object (IrCl3·nH2) and palladium nitrate (Pd (NO O3)2At least one of).
The platinum group metal precursor is calcined in the heat treatment step and is converted to catalytic activity particle, that is, for water
Reduction have catalytic activity metal or compound particles.When platinum group metal or compound include in the electrodes, can obtain
To the effect for improving electrode overvoltage.
The Rare earth metal precursors are salt or oxide containing above-mentioned rare earth metal.Specifically, Rare earth metal precursors can
To be selected from cerous nitrate (III) (Ce (NO3)3), cerous carbonate (III) (Ce2(CO3)3), cerium chloride (III) (CeCl3), yttrium oxide
(Y2O3) and yttrium carbonate (Y2(CO3)3At least one of), but the invention is not restricted to this.
The salt or oxide can be the form of hydrate.It is, for example, possible to use cerous nitrate hexahydrate, cerous carbonates
Five, eight or nonahydrate, cerium chloride one, three, six or heptahydrate, yttrium carbonate trihydrate etc..
The Rare earth metal precursors are calcined in the heat treatment step and are converted to rare-earth oxide.The rare earth
The production hydrogen activity of metal oxide is insufficient, but becomes needle form from particle form in the environment of generating hydrogen.The needle-shaped shape
Formula loads the catalyst layer of platinum group compound and has the function of reducing the disengaging of catalyst layer.
It has been confirmed that compared with the electrode being prepared by a conventional method, in electrode for electrolysis prepared in accordance with the present invention,
In cell operation, the acicular texture of rare-earth oxide is dramatically increased.Therefore, electrode for electrolysis of the invention performance
Excellent durability out, such as even if stably keeping electrode performance occurring after reverse current.
Preferably, in the present invention, the Rare earth metal precursors include at least one cerium (Ce) salt or oxide.According to this
One preferred embodiment of invention, can be used cerous nitrate hexahydrate (Ce (NO3)3·6H2O Rare earth metal precursors) are used as,
And ruthenium chloride hydrate (RuCl can be used3·nH2O) it is used as platinum group metal precursor.
The ratio of platinum group metal precursor and Rare earth metal precursors is not particularly limited, and can be according to the type of precursor
Appropriate adjustment.In order to optimize the catalytic activity of the electrode for electrolysis finally prepared, before platinum group metal precursor and rare earth metal
Body can be used with the molar ratio of 1:1 to 10:1 or 3:1 to 10:1.
In the present invention, being used to prepare solvent used in the coating solution of electrode is before capable of dissolving the platinum group metal
The organic solvent of body and Rare earth metal precursors, and preferably, it is that can volatilize dry in heat treatment step at least 95%
Solvent.
For example, the organic solvent can be organic polar solvent, such as alcohols solvent, glycol ethers solvent, esters are molten
Agent or ketones solvent, and any in these may be used singly or in combin.Preferably, organic solvent can be
Alcohols solvent, glycol ethers solvent or their combination.
The alcohols solvent is preferably C1 to C6 alcohol, specifically, can be used selected from methanol, ethyl alcohol, propyl alcohol, isopropanol,
At least one of butanol, ethylene glycol and propylene glycol, but the invention is not restricted to this.
The glycol ethers solvent is preferably C4 to C8 glycol ethers, specifically being selected from cellosolvo, 2- propoxyl group
At least one of ethyl alcohol, 2- isopropoxide ethanol, butoxy ethanol and 2- (2- methoxy ethoxy) ethyl alcohol, can be used
Any of which, but the invention is not restricted to this.
In one embodiment of the invention, the organic solvent can be the pure and mild C4 of C1 to C6 mixing to C8 glycol ethers
Bonding solvent.When using mixed solvent, compared with the electrode that the preparation of single alcohols solvent is used only, has and substantially reduce preparation
The removing of electrode and the effect of crackle.Further, since the drying time extension in large area coating, therefore can carry out more evenly
Coating, this is preferred.
In order to ensure said effect, the ratio of the pure and mild C4 of C1 to C6 to C8 glycol ethers preferably in the range of 10:1 to 1:2,
More preferably in the range of 4:1 to 1:1.In one embodiment of the invention, using isopropanol and butoxy ethanol
The 1:1 mixed solvent of 1:1 mixed solvent or ethyl alcohol and butoxy ethanol is as organic solvent, and but the invention is not restricted to this.
In the present invention, other than organic solvent, the coating solution for being used to prepare electrode also contains amine solvent conduct
Stabilizer.When amine solvent includes in coating solution, the electrode finally prepared has on the surface in cell operation
There is increased rare earth metal acicular texture, to improve the durability of electrode and further decrease the overvoltage of electrode.
The amine solvent can be C6 to C30 saturation or unsaturated aliphatic amine, and not limit especially its type
System.It is, for example, possible to use selected from least one of octylame, decyl amine, dodecyl amine, oleyl amine, lauryl amine and hexadecylamine.Or
Person, amine solvent can be octylame, oleyl amine or their combination.
In the present invention, based on the coating solution for being used to prepare electrode of 100 volume %, amine solvent with 3 volume % extremely
The amount of 40 volume % or 5 volume % to 30 volume % exists.If the amount of amine solvent can not achieve electricity less than 3 volume %
The durability improvement effect and overvoltage reducing effect of pole.If it is more than 40 volume %, it is difficult to dissolve metal precursor, and
It cannot obtain the evenly dispersed coating solution for being used to prepare electrode of wherein precursor.
In the present invention, the preparation method for the coating solution for being used to prepare electrode is not particularly limited.For example, can make
It is added and is dissolved in wherein platinum group metal precursor and Rare earth metal precursors and obtained by mixed organic solvents and amine solvent
The method of the in the mixed solvent arrived.Alternatively, the dissolution in order to promote metal precursor, it can be by the way that metal precursor be dissolved completely in
Coating solution then is prepared with mixing addition amine solvent in organic solvent.
Herein, the ultimate density for being used to prepare the coating solution of electrode can be 50g/L to 150g/L or 80g/L extremely
120g/L.When concentration is within the scope of these, the content for the metal precursor being coated in solution become to be enough to ensure that electrode performance and
Durability, and be coated with solution and can be coated in substrate with thickness appropriate, so that process efficiency be made to maximize.
Then, the coating solution for being used to prepare electrode is coated on the metallic substrate to form catalyst layer, then to it
It is dried and is heat-treated to prepare electrode for electrolysis.Herein, before forming catalyst layer, metallic substrates can be carried out all
Such as the cleaning treatment or surface roughening treatment of degreasing and sandblasting, further to improve the adhesiveness with catalyst layer.
In addition, the coating, drying and heat treatment step for being coated with solution can weigh in order to form the electrode with suitable thickness
Again several times.
The method for the coating solution that coating is used to prepare electrode is not particularly limited, can be used as known in the art
Coating method, such as spraying, brushing, scraper, dip-coating, spin coating etc..
Step is dried to remove the solvent contained in catalyst layer.Drying condition is not particularly limited, and can
According to the thickness appropriate adjustment of the type of solvent and catalyst layer.For example, drying steps can be in 70 DEG C to 200 DEG C of temperature
It is lower to carry out 5 minutes to 15 minutes.
Then, the heat treatment step for calcining metal precursor is carried out.
In the heat treatment step, the platinum group metal precursor in catalyst layer and Rare earth metal precursors thermally decompose, thus
It is converted to platinum group metal, its compound and rare-earth oxide with catalytic activity.
Heat treatment condition can change according to the type of metal precursor, but specifically, heat treatment temperature can be 300
DEG C to 600 DEG C or 400 DEG C to 550 DEG C, and it is heat-treated and can carries out 10 minutes to 2 hours.
When applying by the way that as described above coating, dry and heat treatment step to be repeated one or more times when preparing electrode
The heat treatment step carried out after covering with drying steps foreshortens to 5 minutes to 15 minutes, and the last one drying steps it
The final heat treatment step carried out afterwards can carry out the grace time of 30 minutes or more or 1 hour to 2 hours.When last heat
When processing step carries out long-time, metal precursor can thermally decompose completely, and the interface between catalyst layer can be minimized,
So as to improve electrode performance.
The thickness of catalyst layer in the electrode for electrolysis prepared by the above method is not particularly limited, but can be with
In the range of 0.5 μm to 5 μm or 1 μm to 3 μm.
The electrode for electrolysis of preparation method according to the present invention preparation can be applied to the various electrolysis for industrial electrolysis
Pond, and the cathode of chlor-alkali cell can be suitable as.
Hereinafter, will the present invention will be described in more detail with reference to preferred embodiment below, but be to provide these embodiments only
For illustration purposes.It will be apparent to one skilled in the art that can carry out within the scope and spirit of this invention each
Kind changes and modification., it will thus be apparent that the change and modification are within the scope of the invention.
[embodiment]
Embodiment 1
Pass through the RuCl that will be 6:1 containing molar ratio3·nH2O and Ce (NO3)2·6H2The metal precursor of O is dissolved in volume
In the mixed solvent than isopropanol (IPA) and butoxy ethanol for 1:1 prepares precursor solution.Then, by precursor solution and
Amine solvent (oleyl amine) is mixed with the volume ratio of 2:1, the coating solution for being used to prepare electrode that preparation concentration is 100g/L.It will apply
Cloth solution is brushed on nickel screen, 10 minutes dry at 200 DEG C, and is heat-treated 10 minutes at 500 DEG C.The process weighs in total
It is ten times multiple, it is then heat-treated 1 hour at 500 DEG C, obtains electrode for electrolysis.
Embodiment 2
In addition to use octylame replace oleyl amine as amine solvent other than, prepare in the same manner as example 1 electrolysis use
Electrode.
Comparative example 1
Pass through the RuCl that will be 6:1 containing molar ratio3·nH2O and Ce (NO3)2·6H2The metal precursor of O is dissolved in volume
The coating solution that in the mixed solvent preparation concentration than isopropanol (IPA) and butoxy ethanol for 1:1 is 100g/L.It will apply
Cloth solution is brushed on nickel screen, 10 minutes dry at 200 DEG C, and is heat-treated 10 minutes at 500 DEG C.The process weighs in total
It is ten times multiple, it is then heat-treated 1 hour at 500 DEG C, obtains electrode for electrolysis.
Comparative example 2
Pass through the RuCl that will be 6:1 containing molar ratio3·nH2O and Ce (NO3)2·6H2The metal precursor of O is dissolved in volume
In the mixed solvent than isopropanol (IPA) and butoxy ethanol for 1:1 prepares precursor solution.Then, addition is careless thereto
Acid so that the molar ratio of oxalic acid and ruthenium is 0.5 times, and is dissolved as other additive to prepare concentration as the painting of 100g/L
Cloth solution.Coating solution is brushed on nickel screen, it is 10 minutes dry at 200 DEG C, and be heat-treated 10 minutes at 500 DEG C.
The process repeats ten times in total, is then heat-treated 1 hour at 500 DEG C, obtains electrode for electrolysis.
Prepare embodiment
The electrode for electrolysis (10mm × 10mm) with above-described embodiment or comparative example is prepared by the following method as yin
The half-cell of pole.Use the electrode of embodiment or comparative example as cathode, use the NaOH aqueous solution of 32 weight % as electrolysis
Liquid uses Pt line as to electrode and using saturated calomel electrode (SCE) as reference electrode and prepare half-cell.
EXPERIMENTAL EXAMPLE 1: evaluation overvoltage improves degree
Using the half-cell of above-mentioned preparation embodiment, each electrode for electrolysis is measured by linear sweep voltammetry and is existed
4.4kA/m2Current density under voltage.Above-mentioned experiment is repeated 10 times, and the average value of the voltage measured was determined as
The average value that voltage improves.By being compared to count with the voltage of commercial electrode (Asahi Kasei commercialization cathode: ncz-2)
Calculating overvoltage improves degree.
<LSV experimental condition>
Electrode size: 10mm × 10mm, temperature: 90 DEG C, electrolyte: the NaOH aqueous solution of 32 weight %
The pretreatment (electrode for electrolysis) of sample: in -6A/cm2Current density under be electrolysed 1 hour to generate hydrogen.
Initial potential (V): -500.0e-3
Final potential (V): -1.500.0e0
Sweep speed (V/s): 10.0e-3
Sampling period (V): 1.0e-3
[table 1]
As shown in table 1, compared with commercial electrode, have by adding the embodiment 1 that oleyl amine is prepared as amine solvent-
The average overvoltage of 51mV improves degree, this shows that embodiment 1 is better than being not added with the comparative example 1 of amine solvent preparation, and
The comparative example 2 of amine solvent preparation is replaced by addition oxalic acid.In addition, the implementation prepared by adding octylame as amine solvent
The overvoltage that the electrode of example 2 shows -55mV improves degree.
From result above it has been confirmed that when in the coating solution for being used to prepare electrode including amine solvent, Ke Yi
There is the electrode of better overvoltage improvement with preparation under conventional use of identical process conditions.
EXPERIMENTAL EXAMPLE 2: the evaluation of durability
Reverse current test is carried out to the half-cell of above-mentioned preparation embodiment under the conditions of following tests, to evaluate embodiment
The durability of 1 electrode and commercial electrode (identical as EXPERIMENTAL EXAMPLE 1).As a result show in table 2 and Fig. 1.
<reverse current experimental condition>
Electrode size: 10mm × 10mm, temperature: 90 DEG C, electrolyte: the NaOH aqueous solution of 32 weight %
The pretreatment of sample: respectively in -0.1A/cm2Current density under be electrolysed 20 minutes, in -0.2A/cm2With -0.3A/
cm2Lower electrolysis 3 minutes, and in -0.4A/cm2Lower electrolysis 30 minutes, to generate hydrogen.
Reverse current condition :+0.05kA/m2
[table 2]
| Electrode | Relative time needed for reaching -0.1V (based on commercial electrode) |
| Commercial electrode | 1 |
| Embodiment 1 | 2.29 |
In reverse current test, the electrolysis of active layer occurs at this time for the time needed for inspection reaches -0.1V, and really
The electrode (2.31 hours) for recognizing embodiment 1 is 2.29 times longer than (1.01 hours) required times of commercial electrode.
From result above it has been confirmed that even if under reverse current, electrode prepared in accordance with the present invention and commercial electrode phase
In terms of also having the advantages that durability.
EXPERIMENTAL EXAMPLE 3: the comparison of electrode surface structures
The battery dismantling of the test of EXPERIMENTAL EXAMPLE 1 will be completed, and through SEM respectively under 1000 times and 10,000 times
Confirm the surface state (Fig. 2) of the electrode of embodiment 1 and embodiment 2 and comparative example 1.It is surveyed by the dimensional measuring instrument of SEM
Measure the thickness and length of acicular texture.
With reference to Fig. 2, it has been confirmed that amine solvent is added to and is used to make compared with the comparative example 1 for not adding amine solvent
Embodiment 1 and embodiment 2 in the precursor solution of standby electrode have at the electrode surface after battery operation to be clearly observed
Cerium acicular texture.
Specifically, in the case of example 1, each acicular texture is formed to have the thickness and 0.5 of 50nm to 200nm
μm to 5 μm of length, and in comparative example 1, thickness is only 20nm to 50nm and length is 0.2 μm to 0.5 μm.Namely
It says, it has been confirmed that the acicular texture of cerium increases 2 times to 4 times in the electrode of addition amine.
In addition, removing or crackle are not observed in embodiment 1 and embodiment 2, and on the electrode surface of comparative example 1
Peeling-off and crackle.
From result above it has been confirmed that preparation method of the invention can increase the acicular texture of rare earth metal, thus aobvious
Write the durability for improving electrode.
EXPERIMENTAL EXAMPLE 4: the comparison of electrode surface component
The electrode prepared in embodiment 1 and embodiment 2 and comparative example 1 is measured by EDX (Energy Dispersive Spectrometer)
Component.It is measured three times in the difference of each electrode, mole % of Ru and N is shown in following table 3 in electrode.
[table 3]
As measurement as a result, using the feelings of the embodiment 1 of amine solvent and embodiment 2 in the preparation of electrode for electrolysis
Under condition, the molar ratio of nitrogen and ruthenium is up to 35% to 50%, and in the comparative example 1 without using amine, the molar ratio of nitrogen and ruthenium is
13% to 19%.
From result above it has been confirmed that even if after the heat treatment, electrode prepared according to the methods of the invention also shows
Out than not containing the higher nitrogen content as amine component of electrode of amine solvent in preparation process.
Claims (16)
1. a kind of electrode for electrolysis, comprising: metallic substrates, and the catalyst layer formed in the metallic substrates,
Wherein, the catalyst layer includes nitrogen, platinum group metal and rare earth metal, and
Based on the platinum group metal, the nitrogen content of the catalyst layer is 20 moles of % to 60 moles of %.
2. electrode for electrolysis according to claim 1,
Wherein, the catalyst layer includes the acicular texture of the rare earth metal.
3. electrode for electrolysis according to claim 2,
Wherein, the acicular texture includes the thickness with 50nm to 300nm and at least two needles of 0.5 μm to 10 μm of length
Shape structure.
4. a kind of preparation method of electrode for electrolysis, comprising the following steps:
Preparation is used to prepare the coating solution of electrode, which contains platinum group metal precursor, Rare earth metal precursors, You Jirong
Agent and amine solvent；
The coating solution for being used to prepare electrode is coated on the metallic substrate to form catalyst layer；
The dry catalyst layer；And
The catalyst layer is heat-treated.
5. the preparation method of electrode for electrolysis according to claim 4,
Wherein, the platinum group metal precursor is selected from ruthenium chloride hydrate (RuCl3·nH2O), chlorination four ammonia platinum (II) hydrate
(Pt(NH3)4Cl2·H2O), radium chloride (RhCl3), rhodium nitrate hydrate (Rh (NO3)3·nH2O), iridium chloride hydrate
(IrCl3·nH2) and palladium nitrate (Pd (NO O3)2At least one of).
6. the preparation method of electrode for electrolysis according to claim 4,
Wherein, the Rare earth metal precursors are selected from cerous nitrate (III) (Ce (NO3)3), cerous carbonate (III) (Ce2(CO3)3), chlorine
Change cerium (III) (CeCl3), yttrium oxide (Y2O3) and yttrium carbonate (Y2(CO3)3At least one of).
7. the preparation method of electrode for electrolysis according to claim 4,
Wherein, the organic solvent is mixed solvent of the pure and mild C4 of C1 to C6 to C8 glycol ethers.
8. the preparation method of electrode for electrolysis according to claim 7,
Wherein, the mixed proportion of the pure and mild C4 of the C1 to C6 to C8 glycol ethers is 10:1 to 1:2.
9. the preparation method of electrode for electrolysis according to claim 4,
Wherein, the amine solvent is C6 to C30 saturation or unsaturated aliphatic amine.
10. the preparation method of electrode for electrolysis according to claim 4,
Wherein, the amine solvent be in octylame, decyl amine, dodecyl amine, oleyl amine, lauryl amine and hexadecylamine at least
It is a kind of.
11. the preparation method of electrode for electrolysis according to claim 4,
Wherein, the platinum group metal precursor and the Rare earth metal precursors exist with the molar ratio of 1:1 to 10:1.
12. the preparation method of electrode for electrolysis according to claim 4,
Wherein, based on the coating solution for being used to prepare electrode described in 100 volume %, the amine solvent is with 3 volume % to 40
The amount of volume % exists.
13. the preparation method of electrode for electrolysis according to claim 4,
Wherein, the concentration of the coating solution for being used to prepare electrode is 50g/L to 150g/L.
14. the preparation method of electrode for electrolysis according to claim 4,
Wherein, the drying steps 70 DEG C to 200 DEG C at a temperature of carry out.
15. the preparation method of electrode for electrolysis according to claim 4,
Wherein, the heat treatment step 300 DEG C to 600 DEG C at a temperature of carry out.
16. a kind of electrode for electrolysis prepared by preparation method described in any one of claim 4 to 15.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2017-0102524 | 2017-08-11 | ||
| KR20170102524 | 2017-08-11 | ||
| KR10-2018-0087750 | 2018-07-27 | ||
| KR1020180087750A KR101950465B1 (en) | 2017-08-11 | 2018-07-27 | Electrode for electrolysis and preparation method thereof |
| PCT/KR2018/008645 WO2019031753A1 (en) | 2017-08-11 | 2018-07-30 | Electrolytic electrode and manufacturing method therefor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109790634A true CN109790634A (en) | 2019-05-21 |
| CN109790634B CN109790634B (en) | 2021-02-23 |
Family
ID=65271720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201880003679.6A Active CN109790634B (en) | 2017-08-11 | 2018-07-30 | Electrode for electrolysis and preparation method thereof |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP3492631B1 (en) |
| CN (1) | CN109790634B (en) |
| WO (1) | WO2019031753A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114008249A (en) * | 2020-01-09 | 2022-02-01 | 株式会社Lg化学 | Electrode for electrolysis |
| CN114008248A (en) * | 2019-12-19 | 2022-02-01 | 株式会社Lg化学 | Electrode for electrolysis |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102503553B1 (en) * | 2019-02-22 | 2023-02-27 | 주식회사 엘지화학 | Electrode for Electrolysis |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08269763A (en) * | 1995-03-28 | 1996-10-15 | Toyo Seikan Kaisha Ltd | Electrode and its production |
| CN101525755A (en) * | 2008-03-07 | 2009-09-09 | 培尔梅烈克电极股份有限公司 | Cathode for hydrogen generation |
| CN101861412A (en) * | 2007-11-16 | 2010-10-13 | 阿克佐诺贝尔股份有限公司 | Electrode |
| CN102762776A (en) * | 2010-02-10 | 2012-10-31 | 培尔梅烈克电极股份有限公司 | Activated cathode for hydrogen evolution |
| CN104937142A (en) * | 2013-09-06 | 2015-09-23 | 培尔梅烈克电极股份有限公司 | Production method for electrode for electrolysis |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003277966A (en) * | 2002-03-22 | 2003-10-02 | Asahi Kasei Corp | Hydrogen generating cathode of low overvoltage and excellent durability |
| ZA200601219B (en) * | 2003-10-08 | 2007-05-30 | Akzo Nobel Nv | Electrode |
| JP2013166994A (en) * | 2012-02-15 | 2013-08-29 | Asahi Kasei Chemicals Corp | Electrolysis electrode, electrolysis tank, and method for manufacturing electrolysis electrode |
| JP6515509B2 (en) * | 2013-12-26 | 2019-05-22 | 東ソー株式会社 | ELECTRODE FOR HYDROGEN GENERATION, METHOD FOR PRODUCING THE SAME, AND ELECTROLYTIC METHOD USING THE SAME |
-
2018
- 2018-07-30 EP EP18843984.8A patent/EP3492631B1/en active Active
- 2018-07-30 CN CN201880003679.6A patent/CN109790634B/en active Active
- 2018-07-30 WO PCT/KR2018/008645 patent/WO2019031753A1/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08269763A (en) * | 1995-03-28 | 1996-10-15 | Toyo Seikan Kaisha Ltd | Electrode and its production |
| CN101861412A (en) * | 2007-11-16 | 2010-10-13 | 阿克佐诺贝尔股份有限公司 | Electrode |
| CN101525755A (en) * | 2008-03-07 | 2009-09-09 | 培尔梅烈克电极股份有限公司 | Cathode for hydrogen generation |
| CN102762776A (en) * | 2010-02-10 | 2012-10-31 | 培尔梅烈克电极股份有限公司 | Activated cathode for hydrogen evolution |
| CN104937142A (en) * | 2013-09-06 | 2015-09-23 | 培尔梅烈克电极股份有限公司 | Production method for electrode for electrolysis |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114008248A (en) * | 2019-12-19 | 2022-02-01 | 株式会社Lg化学 | Electrode for electrolysis |
| CN114008249A (en) * | 2020-01-09 | 2022-02-01 | 株式会社Lg化学 | Electrode for electrolysis |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3492631A1 (en) | 2019-06-05 |
| EP3492631B1 (en) | 2021-03-03 |
| CN109790634B (en) | 2021-02-23 |
| EP3492631A4 (en) | 2019-11-20 |
| WO2019031753A1 (en) | 2019-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cossar et al. | Comparison of electrochemical active surface area methods for various nickel nanostructures | |
| JP6790241B2 (en) | Electrode for electrolysis and its manufacturing method | |
| Kuleshov et al. | Development and characterization of new nickel coatings for application in alkaline water electrolysis | |
| Jović et al. | Kinetics of the oxygen evolution reaction on NiSn electrodes in alkaline solutions | |
| CN105297107B (en) | A kind of method of cyclic voltammetric electrodeposited nanocrystalline platinum nickel/titanium dioxide nanotube electrode | |
| CN105780050B (en) | A kind of preparation method for decomposing the doping phosphoric acid group Ni-Fe hydroxide nano film catalysts of water | |
| CN109790634A (en) | Electrode for electrolysis and preparation method thereof | |
| WO2015098058A1 (en) | Electrode for hydrogen generation, process for producing same, and method of electrolysis therewith | |
| DE102013202143A1 (en) | Catalyst coating and process for its preparation | |
| Yang et al. | Effects of current density on preparation and performance of Al/conductive coating/a-PbO2-CeO2-TiO2/ß-PbO2-MnO2-WC-ZrO2 composite electrode materials | |
| JP2013166994A (en) | Electrolysis electrode, electrolysis tank, and method for manufacturing electrolysis electrode | |
| Shatla et al. | Poly 1, 5 diaminonaphthalene supported Pt, Pd, Pt/Pd and Pd/Pt nanoparticles for direct formic acid oxidation | |
| JP2010059446A (en) | Electrode for electrolysis | |
| Cherevko | Stabilization of non-noble metal electrocatalysts for acidic oxygen evolution reaction | |
| Arabaci et al. | Ceria supported nickel (0) nanoparticles: a highly active and low cost electrocatalyst for hydrogen evolution reaction | |
| CN107687002B (en) | A kind of activated cathode of doped graphene and preparation method thereof | |
| Wang et al. | Amorphous nickel oxide as efficient electrocatalyst for urea oxidation reaction | |
| JP2015143388A (en) | Electrode for hydrogen generation, method for producing the same, and method of electrolysis therewith | |
| KR101555532B1 (en) | Fabrication Method of Cobalt-promoted Metal sulfide Electrode for Alkaline Water Electrolysis System | |
| Jin et al. | High catalytic activity of Pt-modified Ag electrodes for oxidation of glycerol and allyl alcohol | |
| CN108998807A (en) | A kind of improved Ru-Ce coated electrode | |
| JP2006265649A (en) | Method for producing electrode for generating hydrogen | |
| KR890003514B1 (en) | Cathode for electrolysis and a process for making the said cathode | |
| CN108048895B (en) | nickel-based active electrode material embedded with ruthenium-zirconium composite oxide and preparation method thereof | |
| WO2020110527A1 (en) | Hydrogen generation electrode, method of producing same, and hydrogen production method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |