CN206127438U - Liberation of hydrogen electrode - Google Patents
Liberation of hydrogen electrode Download PDFInfo
- Publication number
- CN206127438U CN206127438U CN201621195654.5U CN201621195654U CN206127438U CN 206127438 U CN206127438 U CN 206127438U CN 201621195654 U CN201621195654 U CN 201621195654U CN 206127438 U CN206127438 U CN 206127438U
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- Prior art keywords
- hydrogen
- metal sulfide
- transition metal
- transient metal
- transient
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The utility model discloses a liberation of hydrogen electrode, include: the electrode body, be fixed in the transition metal sulphide on electrode body surface, transition metal sulphide includes that two kind at least transition metal atoms and at least some transition metal atom are in not saturated condition, wherein, transition metal sulphide is as the liberation of hydrogen catalyst. The utility model discloses a liberation of hydrogen electrode compares with prior art, has solved current liberation of hydrogen electrode's the technical problem that catalytic activity is low.
Description
Technical field
This utility model is related to liberation of hydrogen catalyst field, more particularly to a kind of hydrogen-precipitating electrode.
Background technology
As combustion of hydrogen process can discharge huge energy and combustion product is water, therefore, hydrogen is considered as one
Plant sustainable clean energy resource.From for eco-friendly angle, (light) electrochemical catalysis hydrogen production by water decomposition is the reason for preparing hydrogen
Think one of approach.But, in water decomposition reaction, generally requiring efficient liberation of hydrogen catalyst makes the reaction can be in relatively low overpotential
It is lower to produce larger electric current.The liberation of hydrogen catalyst for using at present is mainly platinum group precious metal material, and they are in evolving hydrogen reaction process
In have very low overpotential and excellent kinetics behavior.But high cost limits their large-scale application.Cause
This, in order to meet the requirement of sustainable energy technology, develops the liberation of hydrogen catalyst of high efficiency low cost your gold of those costlinesses substituted
Metal catalyst seems particularly significant.
In recent years, existing some base metals are used as liberation of hydrogen catalyst, such as：Transition metal alloy, metal sulfur
Compound etc..Molybdenum sulphide in transient metal sulfide, due to receiving much concern the advantages of its low cost and high activity.
Molybdenum sulphide there is also some shortcomings, and molybdenum sulphide is in saturation, each molybdenum atom due to molybdenum atom
Surrounding is distributed with six sulphur atoms, and more sulphur atom distributed architecture causes active site to be wrapped, significantly limit
Its catalytic activity for hydrogen evolution.
Utility model content
This utility model provides a kind of hydrogen-precipitating electrode, compared with prior art, solves urging for existing hydrogen-precipitating electrode
Change the low technical problem of activity.
To reach above-mentioned purpose, this utility model provides technical scheme below：
A kind of hydrogen-precipitating electrode, including：
Electrode body；
The transient metal sulfide on the electrode body surface is fixed on, the transient metal sulfide includes at least two
Transition metal atoms and at least part of transition metal atoms are in undersaturated condition；
Wherein, the transient metal sulfide is used as liberation of hydrogen catalyst.
Optionally, in the transient metal sulfide, transition metal atoms are two or three or four kinds.
Optionally, in the transient metal sulfide, part transition metal atoms are in saturation.
Optionally, the transition metal atoms in undersaturated condition and the mass ratio of the transient metal sulfide are 1/4
～1/2.
Optionally, the transition metal atoms in undersaturated condition and the mass ratio of the transient metal sulfide are 1/10
～1.
Optionally, the transition metal atoms in the transient metal sulfide are the transition metal atoms of positive bivalence.
Optionally, the transient metal sulfide is cobalt molybdenum sulphide or nickel molybdenum sulphide or manganese molybdenum sulphide.
Optionally, the transient metal sulfide is the nanometer sheet of the transient metal sulfide of array distribution.
Optionally, the electrode body is carbon cloth, and the transient metal sulfide array growth is in the electrode sheet
Body surface face.
Optionally, the tensile strength of the carbon cloth is more than or equal to 3000 MPas, and stretch moduluses are more than or equal to 240000
MPa.
The hydrogen-precipitating electrode that this utility model is provided, including electrode body and the Transition Metal Sulfur for being fixed on electrode body surface
Compound, transient metal sulfide includes at least two transition metal atoms and at least part of transition metal atoms are in unsaturated shape
State.In transient metal sulfide, at least part of transition metal atoms are in undersaturated condition, the transition gold in undersaturated condition
Around category atom, sulphur atom distribution is less than six, and less sulphur atom distributed architecture can promote that active site is more to be in
Its exposed edge rather than it is wrapped, is thus greatly improved the catalysis activity of hydrogen-precipitating electrode, reduces evolving hydrogen reaction
Reaction potential, so as to be conducive to lifted hydrogen-precipitating electrode catalysis activity.
Description of the drawings
Fig. 1 is the schematic diagram of the hydrogen-precipitating electrode of one embodiment of the present utility model.
Main element description of reference numerals：
100 electrode bodies, 200 transient metal sulfides.
Specific embodiment
Below in conjunction with the accompanying drawing in this utility model embodiment, the technical scheme in this utility model embodiment is carried out
Clearly and completely describe, it is clear that described embodiment is only this utility model a part of embodiment, rather than whole
Embodiment.Based on the embodiment in this utility model, those of ordinary skill in the art are not under the premise of creative work is made
The every other embodiment for being obtained, belongs to the scope of this utility model protection.
The hydrogen-precipitating electrode of one embodiment of the present utility model, as shown in figure 1, including：
Electrode body 100；
The transient metal sulfide 200 on electrode body surface is fixed on, transient metal sulfide 200 includes at least two mistakes
Cross metallic atom and at least part of transition metal atoms are in undersaturated condition；
Wherein, transient metal sulfide is used as liberation of hydrogen catalyst.
The hydrogen-precipitating electrode of the present embodiment, including electrode body and the transient metal sulfide for being fixed on electrode body surface,
Transient metal sulfide includes at least two transition metal atoms and at least part of transition metal atoms are in undersaturated condition.Cross
Cross at least part of transition metal atoms in metal sulfide and be in undersaturated condition, in the transition metal atoms of undersaturated condition
Less than six, less sulphur atom distributed architecture can promote active site more in its exposure for surrounding sulphur atom distribution
Edge rather than be wrapped, be thus greatly improved the catalysis activity of hydrogen-precipitating electrode, reduce the reaction of evolving hydrogen reaction
Current potential, so as to be conducive to lifting the catalysis activity of hydrogen-precipitating electrode.
Specifically, in transient metal sulfide, transition metal atoms are two or three or four kinds, i.e. transition metal atoms
May be greater than a kind of various.When transition metal in transient metal sulfide is a kind of, it is impossible to or it is hardly formed part mistake
Metallic atom is crossed in undersaturated condition, but all in saturation, catalytic activity for hydrogen evolution is not enough.
Used as a kind of preferred mode, in transient metal sulfide, transition metal atoms are two kinds.So, urge as liberation of hydrogen
The composition of the transient metal sulfide of agent is relatively easy, prepares more convenient.
Used as a kind of preferred mode, in transient metal sulfide, part transition metal atoms are in saturation.Due to
It is the relatively high transition of price in transition metal mostly transition metal atoms in transient metal sulfide in undersaturated condition
Metal, if cause transition metal atoms of the transient metal sulfide entirely in undersaturated condition, Transition Metal Sulfur
The cost of compound is just higher.So, mostly the transition metal atoms in transient metal sulfide in saturation it is transition gold
The relatively low transition metal of price in category, can reduce the cost of hydrogen-precipitating electrode.
As the quality of a kind of optional mode, the transition metal atoms in undersaturated condition and transient metal sulfide
Than being 1/4～1/2.
By mass ratio of the control in the transition metal atoms and transient metal sulfide of undersaturated condition, it is possible to achieve
Control to liberation of hydrogen catalyst activity and cost.
As the quality of a kind of optional mode, the transition metal atoms in undersaturated condition and transient metal sulfide
Than can also be 1/10～1.By quality of the control in the transition metal atoms and transient metal sulfide of undersaturated condition
Than, it is possible to achieve the control to liberation of hydrogen catalyst activity and cost.
Specifically, the transition metal atoms in transient metal sulfide are the transition metal atoms of positive bivalence.
Specifically, transient metal sulfide is cobalt molybdenum sulphide or nickel molybdenum sulphide or manganese molybdenum sulphide.These three transition
Metal sulfide, it is convenient to prepare, and catalysis activity is higher, while moderate cost.
In order to increase high-specific surface area, increase active site, as shown in figure 1, transient metal sulfide 200 is array
The nanometer sheet of the transient metal sulfide of distribution.The nanometer sheet of the transient metal sulfide of array distribution significantly increases Gao Bibiao
Area, increases active site, improves the catalysis activity of liberation of hydrogen catalyst, and in reduction water electrolysis, evolving hydrogen reaction is excessively electric
Position, the generation for being conducive to reducing hydrogen ions to react.
It is a technical barrier on electrode body that transient metal sulfide array growth is controlled in prior art, and it needs
Growing carrier aperture and aperture spacing reach the nanometer chip architecture of certain array distribution for requiring and just growing ordered arrangement.
As pore-size distribution density is larger on carbon cloth, the nanometer sheet reciprocal induction for growing is conducive to form row in order
The nanometer chip architecture of the array distribution of row.Therefore, the material adopted by electrode body of the present utility model is carbon cloth, transition
Metal sulfide array growth is in electrode body surface.So, the direct array growth of transient metal sulfide is in electrode body table
Face, transient metal sulfide are high with the interface compatible degree on electrode body surface, between transient metal sulfide and electrode body
Bonding is no longer needed, the transmission of electronics is improve, transient metal sulfide is bonded in electrode sheet in entirely eliminated prior art
The bad problem of interracial contact caused by body surface face.
There must also be excellent engineering propertiess as electrode body simultaneously, meet the demand of life-time service.Therefore, this reality
It is more than or equal to 3000 MPas with the tensile strength of the carbon cloth of new employing, stretch moduluses are more than or equal to 240000 MPas.This
The engineering propertiess of sample, it is ensured that electrode body stability in the work environment；Meanwhile, the high conduction performance of carbon cloth also subtracts
Loss of the electric current on electrode body is lacked.
The preparation method of hydrogen-precipitating electrode of the present utility model, by transition metal source dissolve in deionized water (or go from
The mixed liquor of sub- water and polar solvent) mixed solution is formed, mixed solution is placed in together with carbon cloth stainless steel cauldron
It is interior, using step high temperature hydro-thermal method, the nanometer sheet of the transient metal sulfide of array distribution is grown on carbon cloth.
The hydrogen-precipitating electrode prepared by said method has the advantages that the following aspects：
First, the nanometer sheet of the transient metal sulfide of array growth is presented three-dimensional three closed structure, with larger height ratio
Surface area, active site increase；
Secondly, the degree of unsaturation of sulphur atom increased using transient metal sulfide so that catalytic site more exposes
In peripheral edge；
In addition, transient metal sulfide is grown directly upon on electrode body, it is to avoid catalyst and electricity in traditional method
Interface problem between the body of pole, improves the efficiency of transmission of electric current；
Carbon cloth aperture finally, as electrode body and its it is distributed with beneficial to the nanometer sheet for forming ordered arrangement；Carbon
The high mechanical properties of fiber cloth, good pliability are all conducive to the life-time service of electrode body.
The specific embodiment one of the preparation method of hydrogen-precipitating electrode：
By 2.4g sodium molybdate, 0.144g cobalt nitrates and 3.12g thioacetamides (TAA) be dissolved in 30mL deionized waters and
Homogeneous solution is formed in 10ml methanol.Carbon cloth (0.8cm × 1.8cm) isopyknic acetone and alcohol mixed solution ultrasound
Cleaning 30min, after taking-up is transferred to itself and above-mentioned solution in the ptfe autoclave that volume is 100mL jointly, closed
React 12 hours afterwards at 120 DEG C, 160 DEG C of reactions, 12 hours react 24 hours, then natural cooling at 200 DEG C.By carbon
Fiber cloth take out after with substantial amounts of deionized water ultrasound 30 minutes and in 60 DEG C of baking ovens dry, preparation formed cobalt molybdenum vulcanize
Thing.Scanning electron microscope (Scanning Electronic Microscopy, abbreviation SEM) can be passed through after end of synthesis,
The characterization techniques such as transmission electron microscope (Transmission Electron Microscope, abbreviation TEM) are received to formation
Rice chip arrays pattern is characterized, while can also be characterized to the electrochemical properties of electrode material by assembled battery.
The specific embodiment two of the preparation method of hydrogen-precipitating electrode：
By 0.72g molybdenum trioxides, 3.6g sodium sulfide and 0.072g nickel nitrates are dissolved in 60mL deionized waters and 2ml hydrochloric acid
Form homogeneous solution.Carbon cloth (0.8cm × 1.8cm) is cleaned by ultrasonic 30min with isopyknic acetone and alcohol mixed solution,
Itself and above-mentioned solution are transferred in the ptfe autoclave that volume is 100mL jointly after taking-up, it is closed after it is anti-at 120 DEG C
12 hours, 150 DEG C of reactions, 12 hours are answered 24 hours to be reacted at 180 DEG C, then natural cooling.Carbon cloth is taken out
Afterwards with substantial amounts of deionized water ultrasound 30 minutes and in 60 DEG C of baking ovens dry, preparation form nickel molybdenum sulphide.End of synthesis
After can be by scanning electron microscope (Scanning Electronic Microscopy, abbreviation SEM), transmission electron microscopy
Nano-chip arrays pattern of the characterization techniques such as mirror (Transmission Electron Microscope, abbreviation TEM) to formation
Characterized, while can also be characterized to the electrochemical properties of electrode material by assembled battery.
Obviously, those skilled in the art this utility model embodiment can be carried out it is various change and modification without deviating from
Spirit and scope of the present utility model.So, if these modifications of the present utility model and modification belong to this utility model right
Within the scope of requirement and its equivalent technologies, then this utility model is also intended to comprising these changes and modification.
Claims (10)
1. a kind of hydrogen-precipitating electrode, it is characterised in that include：
Electrode body；
The transient metal sulfide on the electrode body surface is fixed on, the transient metal sulfide includes at least two transition
Metallic atom and at least part of transition metal atoms are in undersaturated condition；
Wherein, the transient metal sulfide is used as liberation of hydrogen catalyst.
2. hydrogen-precipitating electrode according to claim 1, it is characterised in that transition metal atoms in the transient metal sulfide
It is two or three or four kinds.
3. hydrogen-precipitating electrode according to claim 1, it is characterised in that part transition metal in the transient metal sulfide
Atom is in saturation.
4. hydrogen-precipitating electrode according to claim 1, it is characterised in that the transition metal atoms and institute in undersaturated condition
The mass ratio for stating transient metal sulfide is 1/4～1/2.
5. hydrogen-precipitating electrode according to claim 1, it is characterised in that the transition metal atoms and institute in undersaturated condition
The mass ratio for stating transient metal sulfide is 1/10～1.
6. hydrogen-precipitating electrode according to claim 1, it is characterised in that the transition metal in the transient metal sulfide is former
Son is the transition metal atoms of positive bivalence.
7. hydrogen-precipitating electrode according to claim 1, it is characterised in that the transient metal sulfide be cobalt molybdenum sulphide or
Nickel molybdenum sulphide or manganese molybdenum sulphide.
8. hydrogen-precipitating electrode according to claim 1, it is characterised in that the transient metal sulfide is the mistake of array distribution
Cross the nanometer sheet of metal sulfide.
9. according to the arbitrary described hydrogen-precipitating electrode of claim 1 to 8, it is characterised in that the electrode body is carbon cloth, institute
Transient metal sulfide array growth is stated in the electrode body surface.
10. hydrogen-precipitating electrode according to claim 9, it is characterised in that the tensile strength of the carbon cloth is more than or equal to
3000 MPas, stretch moduluses are more than or equal to 240000 MPas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201621195654.5U CN206127438U (en) | 2016-10-31 | 2016-10-31 | Liberation of hydrogen electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201621195654.5U CN206127438U (en) | 2016-10-31 | 2016-10-31 | Liberation of hydrogen electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN206127438U true CN206127438U (en) | 2017-04-26 |
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ID=58577362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201621195654.5U Active CN206127438U (en) | 2016-10-31 | 2016-10-31 | Liberation of hydrogen electrode |
Country Status (1)
| Country | Link |
|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107557806A (en) * | 2017-08-28 | 2018-01-09 | 天津市大陆制氢设备有限公司 | A kind of Co O high efficiency composition hydrogen-precipitating electrodes being covered on Co Mo O and preparation method thereof |
| CN109208027A (en) * | 2018-10-10 | 2019-01-15 | 三峡大学 | A kind of preparation method of molybdenum disulfide-cobalt sulfide-carbon tri compound original position electrode |
| CN109235024A (en) * | 2018-09-04 | 2019-01-18 | 北京邮电大学 | A kind of heterogeneous nano-chip arrays structure of nickel sulfide-molybdenum sulfide and preparation method thereof of carbon cloth load |
-
2016
- 2016-10-31 CN CN201621195654.5U patent/CN206127438U/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107557806A (en) * | 2017-08-28 | 2018-01-09 | 天津市大陆制氢设备有限公司 | A kind of Co O high efficiency composition hydrogen-precipitating electrodes being covered on Co Mo O and preparation method thereof |
| CN107557806B (en) * | 2017-08-28 | 2019-01-15 | 天津市大陆制氢设备有限公司 | A kind of Co-O high efficiency composition hydrogen-precipitating electrode and preparation method thereof being covered on Co-Mo-O |
| CN109235024A (en) * | 2018-09-04 | 2019-01-18 | 北京邮电大学 | A kind of heterogeneous nano-chip arrays structure of nickel sulfide-molybdenum sulfide and preparation method thereof of carbon cloth load |
| CN109208027A (en) * | 2018-10-10 | 2019-01-15 | 三峡大学 | A kind of preparation method of molybdenum disulfide-cobalt sulfide-carbon tri compound original position electrode |
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