CN101469433A - Active cathode for hydrochloric acid electrolysis and preparation thereof - Google Patents
Active cathode for hydrochloric acid electrolysis and preparation thereof Download PDFInfo
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- CN101469433A CN101469433A CNA2007103047086A CN200710304708A CN101469433A CN 101469433 A CN101469433 A CN 101469433A CN A2007103047086 A CNA2007103047086 A CN A2007103047086A CN 200710304708 A CN200710304708 A CN 200710304708A CN 101469433 A CN101469433 A CN 101469433A
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Abstract
The invention discloses an active cathode for hydrochloric acid electrolysis. A metallic matrix is coated with an active coating, preferably a metallic matrix of titanium, nickel or titanium palladium alloy; the active coating comprises one or more of VIII family metal salt in periodic table of elements, preferably cobalt, nickel, zinc, ruthenium, cadmium, iridium or platinum salt, one or more of IV family metal salt in the periodic table of elements, preferably titanium salt, and inorganic acid, preferably hydrochloric acid or sulfuric acid, wherein the metal content of the VIII family metal salt is 50 to 100 grams/liter; the metal content of the IV family metal salt is 0 to 90 grams/liter; and the concentration of the inorganic acid is 50 to 100 grams/liter. The active cathode is prepared by coating the active coating on the metallic matrix through thermal dissociation. The active cathode for hydrochloric acid electrolysis has stable performance, good electricity-saving effect, longer service life, simple manufacturing process and evenly distributed coating.
Description
Technical field
The present invention relates to a kind of activated cathode, particularly relate to a kind of activated cathode that is used for electrolysis of hydrochloric acid, but also relate to the preparation method of this activated cathode.
Background technology
Having put down in writing many negative electrodes that are used for electrolysis of hydrochloric acid in the prior art document, as a carbon-based cathode, is to be coated with the material of tool catalytic activity and the negative electrode that makes on carbon back; The B negative electrode is made of corrosion-resistant substrate, and has used a kind of coating of electrochemical activity thereon; The powder that c will have electrochemical activity at conductive base by thermospray is coated onto on the carrier or the like.The experiment of carrying out at conventional cathode shows that after having passed through one period short duration of service, the active layer of carrier will peel off.Reason is that the bonding force between carrier and the active layer is poor on the one hand, between active layer and carrier corrosion has taken place on the other hand, and this corrosion makes the bonding state between active layer and the carrier worsen more, thus the destruction that causes cathode.
It is before applying catalytic active layer a special middle layer to be set on negative electrode to also have a kind of negative electrode in addition, this middle layer is made up of titanium carbide and titanium boride and is coated on the carrier by flame plating or plasma spraying, this electrode has good stability, but manufacturing process is comparatively complicated.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of activated cathode that is used for electrolysis of hydrochloric acid, this activated cathode stable performance, and long service life, the bonding force of base material and activated coating is good, and coating is evenly distributed, and the manufacturing process of this activated cathode is simple.
For solving the problems of the technologies described above, the invention provides a kind of activated cathode that is used for electrolysis of hydrochloric acid, wherein, on metallic matrix, be coated with activated coating, be preferably titanium, nickel or titanium palldium alloy metallic matrix, this activated coating comprises: in the periodic table of elements in the VIII family metal-salt one or several, be preferably cobalt, nickel, zinc, ruthenium, cadmium, iridium or platinum salt, and wherein metal content is 50～100 grams per liters; In the periodic table of elements in the IV family metal-salt one or several is preferably titanium salt, and wherein metal content is 0～90 grams per liter; Mineral acid is preferably hydrochloric acid or sulfuric acid, and concentration is 50～100 grams per liters.
The above-mentioned activated cathode that is used for electrolysis of hydrochloric acid, wherein, the thickness of described activated coating is 10 μ m～30 μ m.
The present invention also provides a kind of preparation method of above-mentioned activated cathode, comprises the steps:
A) pre-treatment is with the metal base surface oil removing;
B) preparation activated coating;
C) thermal dissociation is coated on activated coating on the metallic matrix, burns in containing the atmosphere of oxygen and applies and burn till.
The preparation method of above-mentioned activated cathode, wherein, described step a) also comprises anneal, and annealing temperature is 400～750 ℃, and the treatment time is 1～2 hour.
The preparation method of above-mentioned activated cathode, wherein, described step a) also comprises the chemical erosion processing after anneal, and used acid is the sulfuric acid of 10 grams per liters～60 grams per liter weight, and temperature is 50 ℃ of extremely boilings, and be 1～4 hour duration of contact.
The preparation method of above-mentioned activated cathode, wherein, the thermal dissociation condition of described step c) is:
Dry: 20～200 ℃ of 5～30 minutes times of temperature;
Burn and apply: 300～600 ℃ of 10～50 minutes times of temperature;
Burn till: 400～700 ℃ of 10～120 minutes times of temperature.
The activated cathode that is used for electrolysis of hydrochloric acid of the present invention, stable performance have good electricity-saving effect and long work-ing life, and manufacturing process is simple, and coating is evenly distributed.
Embodiment
Describe the present invention in detail below in conjunction with embodiment.
Embodiment 1
With removers the greasy dirt on titanium net (base material) surface is removed, can be observed directly its roughness at microscopically.Carry out anneal then, treatment temp is 400 ℃, and the treatment time is 2 hours.After annealing, in 70 ℃, the sulphuric acid soln of 30 grams per liter weight, placed 3 hours, take out this wire netting, use flushing with clean water, remove residual acid solution.
Said sample is activated by metal oxide then, and this metal oxide obtains the thermolysis in stove of the activated coating of following composition.
The preparation activated coating:
Ruthenium trichloride 70 grams per liters;
Titanium tetrachloride 68 grams per liters;
Hydrochloric acid 70 grams per liters.
40 ℃ of dryings after 30 minutes, sample is placed in the stove with 400 ℃ of heating 15 minutes, be cooled to room temperature then.
Above-mentioned steps repeats repeatedly, with obtain oxide content 15～30 grams/square metre surface coating, coat-thickness is 10 μ m, can be determined by XRF.
The test piece that above-mentioned burning has been applied was burnt till under 400 ℃ 50 minutes.
Embodiment two
With removers the greasy dirt on titanium net (base material) surface is removed, can be observed directly its roughness at microscopically.Carry out anneal then, treatment temp is 600 ℃, and the treatment time is 1.5 hours.After annealing, in 50 ℃, the sulphuric acid soln of 60 grams per liter weight, placed 1 hour, take out this wire netting, use flushing with clean water, remove residual acid solution.
Said sample is activated by metal oxide then, and this metal oxide obtains the thermolysis in stove of the activated coating of following composition.
The preparation activated coating:
Ruthenium trichloride 50 grams per liters;
Titanium tetrachloride 90 grams per liters;
Hydrochloric acid 50 grams per liters.
100 ℃ of dryings after 15 minutes, sample is placed in the stove with 600 ℃ of heating 40 minutes, be cooled to room temperature then.
Above-mentioned steps repeats repeatedly, with obtain oxide content 15～30 grams/square metre surface coating, coat-thickness is 20 μ m, can be determined by XRF.
The test piece that above-mentioned burning has been applied was burnt till under 600 ℃ 10 minutes.
Embodiment three
With removers the greasy dirt on titanium palldium alloy net (base material) surface is removed, can be observed directly its roughness at microscopically.Carry out anneal then, treatment temp is 700 ℃, and the treatment time is 1 hour.After annealing, in the vitriolic boiling solution of 40 grams per liter weight, placed 2 hours, take out this wire netting, use flushing with clean water, remove residual acid solution.
Said sample is activated by metal oxide then, and this metal oxide obtains the thermolysis in stove of the activated coating of following composition.
The preparation activated coating:
Iridic chloride 75 grams per liters;
Titanium tetrachloride 30 grams per liters;
Sulfuric acid 80 grams per liters.
20 ℃ of dryings after 30 minutes, sample is placed in the stove with 300 ℃ of heating 50 minutes, be cooled to room temperature then.
Above-mentioned steps repeats repeatedly, with obtain oxide content 15～30 grams/square metre surface coating, coat-thickness is 25 μ m, can be determined by XRF.
The test piece that above-mentioned burning has been applied was burnt till under 400 ℃ 120 minutes.
Embodiment four
With removers the greasy dirt on titanium palldium alloy net (base material) surface is removed, can be observed directly its roughness at microscopically.Carry out anneal then, treatment temp is 500 ℃, and the treatment time is 1.5 hours.After annealing, in the vitriolic boiling solution of 10 grams per liter weight, placed 4 hours, take out this wire netting, use flushing with clean water, remove residual acid solution.
Said sample is activated by metal oxide then, and this metal oxide obtains the thermolysis in stove of the activated coating of following composition.
The preparation activated coating:
Ruthenium trichloride 90 grams per liters;
Hydrochloric acid 70 grams per liters.
200 ℃ of dryings after 5 minutes, sample is placed in the stove with 500 ℃ of heating 20 minutes, be cooled to room temperature then.
Above-mentioned steps repeats repeatedly, with obtain oxide content 15～30 grams/square metre surface coating, coat-thickness is 30 μ m, can be determined by XRF.
The test piece that above-mentioned burning has been applied was burnt till under 500 ℃ 80 minutes.
Embodiment five
With removers the greasy dirt on titanium net (base material) surface is removed, can be observed directly its roughness at microscopically.Carry out anneal then, treatment temp is 750 ℃, and the treatment time is 1 hour.After annealing,, placed 2 hours in the sulphuric acid soln of 30 grams per liter weight, take out this wire netting, use flushing with clean water, remove residual acid solution at 80 ℃.
Said sample is activated by metal oxide then, and this metal oxide obtains the thermolysis in stove of the activated coating of following composition.
The preparation activated coating:
Ruthenium trichloride 20 grams per liters;
Iridic chloride 50 grams per liters;
Hydrochloric acid 70 grams per liters.
40 ℃ of dryings after 20 minutes, sample is placed in the stove with 600 ℃ of heating 20 minutes, be cooled to room temperature then.
Above-mentioned steps repeats repeatedly, with obtain oxide content 15～30 grams/square metre surface coating, coat-thickness is 25 μ m, can be determined by XRF.
The test piece that above-mentioned burning has been applied was burnt till under 700 ℃ 20 minutes.
Metal active negative electrode provided by the invention, through usefulness JSM-840 type scanning electronic microscope, VANTAGE, the D14105 energy dispersive spectrometry is measured the structure of its coating, show the multi-hole type lamellar structure that this coating is made up of the crystal grain that varies in size, surface-area is big.
Performance to the activated cathode of the foregoing description detects in the laboratory, and its detected result is as follows:
1, hydrogen-evolution overpotential: (judging the important indicator of cathode performance quality), test result sees Table one.
Testing conditions:
Concentration of hydrochloric acid 1%
60 ℃ of temperature
Current density 2,3,3.6,4,5KA/m
2
2, several different negative electrodes are 3KA/m at 60 ℃, 1% hydrochloric acid, current density
2Under loss of weight experiment, test result sees Table two.
Can see that from table two test piece R, 77,88, B1-2, these several activated cathodes of M1-4 are 3.0KA/m in current density
2The time current potential lower, it is less to soak the loss of weight amount, and has higher work-ing life.
Therefore as seen, test piece number work-ing life of having good electricity-saving effect and grow for the activated cathode of R, 77,88, B1-2, M1-4.
From above embodiment detected result as can be seen: activated cathode of the present invention is under each current density, and current potential all can reach requirement.Wherein embodiment three, four, five is low than the current potential of embodiment one, two, and work-ing life is longer.
Table two
Claims (10)
1, a kind of activated cathode that is used for electrolysis of hydrochloric acid is characterized in that, is coated with activated coating on metallic matrix, and this activated coating comprises:
In the periodic table of elements in the VIII family metal-salt one or several, wherein metal content is 50～100 grams per liters;
In the periodic table of elements in the IV family metal-salt one or several, wherein metal content is 0～90 grams per liter;
Mineral acid, concentration are 50～100 grams per liters.
2, activated cathode as claimed in claim 1 is characterized in that, described metallic matrix is titanium, nickel or titanium palldium alloy.
3, activated cathode as claimed in claim 1 or 2 is characterized in that, the thickness of described activated coating is 10 μ m～30 μ m.
4, activated cathode as claimed in claim 1 or 2 is characterized in that, described VIII family metal-salt is cobalt, nickel, zinc, ruthenium, cadmium, iridium or platinum salt.
5, activated cathode as claimed in claim 1 is characterized in that, described IV family metal-salt is a titanium salt.
6, activated cathode as claimed in claim 1 or 2 is characterized in that, described mineral acid is hydrochloric acid or sulfuric acid.
7, the preparation method of the described activated cathode of a kind of claim 1 is characterized in that, comprises the steps:
A) pre-treatment is with the metal base surface oil removing;
B) preparation activated coating;
C) thermal dissociation is coated on activated coating on the metallic matrix, burns in containing the atmosphere of oxygen and applies and burn till.
8, method as claimed in claim 7 is characterized in that, described step a) also comprises anneal, and annealing temperature is 400～750 ℃, and the treatment time is 1～2 hour.
9, method as claimed in claim 8 is characterized in that, described step a) also comprises the chemical erosion processing after anneal, and used acid is the sulfuric acid of 10 grams per liters～60 grams per liter weight, and temperature is 50 ℃ of extremely boilings, and be 1～4 hour duration of contact.
10, method as claimed in claim 7 is characterized in that, the thermal dissociation condition of described step c) is:
Dry: 20～200 ℃ of 5～30 minutes times of temperature;
Burn and apply: 300～600 ℃ of 10～50 minutes times of temperature;
Burn till: 400～700 ℃ of 10～120 minutes times of temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007103047086A CN101469433A (en) | 2007-12-27 | 2007-12-27 | Active cathode for hydrochloric acid electrolysis and preparation thereof |
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| CNA2007103047086A CN101469433A (en) | 2007-12-27 | 2007-12-27 | Active cathode for hydrochloric acid electrolysis and preparation thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103014751A (en) * | 2012-12-28 | 2013-04-03 | 北京化工大学 | Active cathode and preparation method thereof |
| CN107687002A (en) * | 2017-08-17 | 2018-02-13 | 沈阳中科惠友科技发展有限责任公司 | A kind of activated cathode of doped graphene and preparation method thereof |
| CN112695339A (en) * | 2020-12-15 | 2021-04-23 | 世能氢电科技有限公司 | Hydrogen evolution catalytic electrode, preparation method and application thereof |
-
2007
- 2007-12-27 CN CNA2007103047086A patent/CN101469433A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103014751A (en) * | 2012-12-28 | 2013-04-03 | 北京化工大学 | Active cathode and preparation method thereof |
| CN103014751B (en) * | 2012-12-28 | 2015-07-08 | 北京化工大学 | Active cathode and preparation method thereof |
| CN107687002A (en) * | 2017-08-17 | 2018-02-13 | 沈阳中科惠友科技发展有限责任公司 | A kind of activated cathode of doped graphene and preparation method thereof |
| CN107687002B (en) * | 2017-08-17 | 2019-07-05 | 沈阳中科惠友科技发展有限责任公司 | A kind of activated cathode of doped graphene and preparation method thereof |
| CN112695339A (en) * | 2020-12-15 | 2021-04-23 | 世能氢电科技有限公司 | Hydrogen evolution catalytic electrode, preparation method and application thereof |
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Open date: 20090701 |