CN108977843A - A kind of ni-based amorphous alloy catalysis electrode and preparation method thereof - Google Patents
A kind of ni-based amorphous alloy catalysis electrode and preparation method thereof Download PDFInfo
- Publication number
- CN108977843A CN108977843A CN201710400630.1A CN201710400630A CN108977843A CN 108977843 A CN108977843 A CN 108977843A CN 201710400630 A CN201710400630 A CN 201710400630A CN 108977843 A CN108977843 A CN 108977843A
- Authority
- CN
- China
- Prior art keywords
- amorphous alloy
- based amorphous
- particle
- electrode
- metal mesh
- 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.)
- Pending
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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/002—Making metallic powder or suspensions thereof amorphous or microcrystalline
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
Abstract
A kind of ni-based amorphous alloy catalysis electrode; electrode outer layer is metal mesh; internal layer is the sheet-like particle or powder of ni-based amorphous alloy; the specific alloying component of ni-based amorphous alloy is Ni 30-95 wt%; alloying element be can together with nickel one of element, such as P, Co, Fe, Cr, Mo, W, Re of electro-deposition or multiple element combination.The preparation method of electrode, comprising the following steps: the 1) preparation of ni-based amorphous alloy coating；2) ni-based amorphous alloy coating is made to fall off using method mechanically or physically；3) particle is broken；4) metal mesh is used, cuts, be bent, soldering is prepared into clad metal mesh；5) the suitable ni-based amorphous alloy particle of thickness is injected, ni-based amorphous alloy catalysis electrode is made.
Description
Technical field
The present invention relates to the catalysis electrodes of electrochemical field, and being related specifically to one kind with ni-based amorphous alloy powder is to urge
Electrode of agent and preparation method thereof.
Background technique
Amorphous alloy is due to having the characteristics that；1. various compositions can be made in amorphous alloy in a wide range
Sample, so as to their electronic property of modulation in compared with broad range；2. catalytic active center can be in single form
It is evenly distributed in the environment of chemical homogeneous；3. amorphous alloy surface has the higher unsaturated center of concentration, and unsaturated
The ligancy at center has certain range, thus its catalytic activity and selectivity is made to be generally preferred over corresponding crystalline-state catalyst；
4. the imporosity on its surface is the problem of its surface that extends influence for getting rid of reaction species existing for multinomial catalyst is reacted.
Amorphous alloy catalyst can be used for plus the reactions such as hydrogen, oxidation, cracking, isomerization.Currently, amorphous alloy is urged
There are many preparation methods of agent, in general can be classified as two major classes: liquid is quenched method and atom (ion) sedimentation.
Currently, amorphous alloy catalysis electrode is based on the two-dimentional catalysis electrode of deposition film or coating, but its reactor areas is smaller, leads
Cause yield smaller.
Summary of the invention
In view of the above problems, the present invention proposes a kind of ni-based amorphous alloy catalysis electrode and preparation method thereof.On reaching
Purpose is stated, technical solution of the invention provides a kind of ni-based amorphous alloy catalysis electrode, and electrode is two layers of composition, and outer layer is
Metal mesh, internal layer are the sheet-like particle or powder of ni-based amorphous alloy, and the specific alloying component of ni-based amorphous alloy is Ni 30-
95 wt %, alloying element be can together with nickel one of element, such as P, Co, Fe, Cr, Mo, W, Re of electro-deposition or more
The combination of kind element.
Technical solution of the invention provides a kind of preparation method of ni-based amorphous alloy catalysis electrode, including following step
It is rapid:
1) preparation of ni-based amorphous alloy coating
(a) metal substrate is plated the degreasing and oxidation film removal on surface；
(b) electroplate liquid forms；Main salt is soluble nickel salt 0.5-4.5mol/L, sour 0.2-1mol/L, complexing agent 0.5-8g/L, is closed
Gold element additive 0.3-4.5mol/L, water surplus；
In the upper alloying element additive, iron with ferrous sulfate or frerrous chloride (matching reducing agent 0.5-2g/L), chromium with chromic anhydride,
Molybdenum with sodium molybdate, tungsten with sodium tungstate, cobalt with cobaltous sulfate, phosphorus with phosphorous acid or soluble hypophosphites, Re with the shape of Re soluble salt
Formula addition；
Above-mentioned acid is polynary middle strong acid such as phosphoric acid, boric acid etc.；
Above-mentioned complexing agent includes neopelex, tartaric acid, lauryl sodium sulfate, citrate etc.；
(c) preparation of amorphous alloy coating: titration strong acid make bath pH values less than 1, metallic substrate surfaces using plating or
Brush Plating prepares ni-based amorphous alloy coating,；
2) using method mechanically or physically, such as the methods of stretching, rolling reductions make ni-based amorphous alloy coating fall off；
3) particle is broken
(a) Amorphous Alloy Grain is broken, by the amorphous particle of peeling under the conditions of vacuum or inert gas shielding, using ball milling
Machine, planetary ball mill etc. are crushed, and ball milling method is ball milling 2-5min, stop the mode at the interval 2-5min, total Ball-milling Time
(including ball milling and downtime) is 0.5-5h, ratio of grinding media to material 1-5:1；
(b) it is sieved into the ni-based amorphous alloy particle of different thicknesses；
4) molding of electrode outer layer
Using metal mesh, cuts, is bent, soldering is prepared into clad metal mesh；
5) encapsulation of the injection of Amorphous Alloy Grain and electrode
The suitable ni-based amorphous alloy particle of thickness is injected into cladding metal mesh, then closes cladding gold using modes such as solderings
Belong to net, ni-based amorphous alloy catalysis electrode is made.
Compared with prior art, advantages of the present invention:
1. compared with noble metal catalyst, due to using nickel-base alloy ingredient, raw material can be guaranteed and cheap；
2. due to that, as catalyst, the catalytic performance of electrode can be greatly improved using amorphous alloy material；
3. particle basic configuration is lamellar, Ke Yitong due to preparing Fe-based amorphous alloy particle using plating+removing+broken
The control for crossing ball-milling technology is easier to that more coarse Amorphous Alloy Grain can be obtained, so that apparent density is smaller, electrode envelope
Gap after dress between particle is larger, causes solution that can be relatively easy to flow through from electrode interior, this can make full use of in electrode
The catalytic effect of portion's particle, this greatly improves the surface area of catalyst reaction, improves catalytic efficiency；
4. it is excessively high to avoid temperature rise of the powder in mechanical milling process due to the ball milling method for stopping interval using ball milling-, and occur
The crystallization change of powder ensure that the activity of catalyst；
5. due to the clad using metal mesh as catalysis electrode, therefore, it is possible to by bending or be folded into annulus or groove profile
, can be in the case where electrode size be limited etc. the special structure form of some electrodes, the catalysis effect of the raising electrode of maximum possible
Rate.
Specific embodiment
The invention will be further described with reference to embodiments.
1. the preparation of plate-shaped nickel-phosphor amorphous alloy catalysis electrode
1) preparation of nickel-phosphor amorphous alloy coating
(a) metal substrate is plated the degreasing and oxidation film removal on surface；
(b) electroplate liquid forms；Nickel sulfate 1.8 mol/L, boric acid 0.4mol/L, tartaric acid 1.5g/L, 0.6 mol/ of sodium hypophosphite
L, water surplus；
(c) preparation of amorphous alloy coating: ni-based amorphous alloy coating is prepared using plating mode, anode uses industrial pure ni
Plate, electrolyte temperature are 60 DEG C, and titrated sulfuric acid makes pH value less than 1, and the average current density of electrode plate is 0.2 A/ when plating
cm2；
2) removing of amorphous alloy coating
Separate amorphous alloy coating with substrate using the method for biaxial tension the composite plate of plating, the elongation percentage in each direction
It is 5%；
3) particle is broken
(a) Amorphous Alloy Grain is broken, and the amorphous alloy coating of peeling is carried out comminuted ball milling under the conditions of nitrogen protection,
Ball milling method is ball milling 3min, stops the mode at the interval 3min, total Ball-milling Time (including ball milling and downtime) is 1h, ratio of grinding media to material
For 2:1；
(b) it is sieved into the Amorphous Alloy Grain of different thicknesses；
4) molding of electrode outer layer
Using the metallic sieve of 100 mesh, cuts, is bent, soldering is prepared into plate-shaped cladding metal mesh closed at one end；
5) encapsulation of the injection of Amorphous Alloy Grain and electrode
It will be greater than 100 mesh Amorphous Alloy Grains to import in plate-shaped cladding metal mesh, injection hole then closed using soldering form,
The shape that laminates ni-based amorphous alloy catalysis electrode.
2. the preparation of circular ring shape Ni-Fe-phosphorus non-crystalline alloy catalysis electrode
1) preparation of Ni-Fe-P alloy amorphous deposit
(a) metal substrate is plated the degreasing and oxidation film removal on surface；
(b) electroplate liquid forms；Nickel sulfate 3.5 mol/L, ferrous sulfate 0.45mol/L, boric acid 0.6mol/L, tartaric acid 2g/L,
Neopelex 0.5g/L, hypophosphites sodium 0.5 mol/L, potassium iodide 1g/L, water surplus；
(c) preparation of amorphous alloy coating: amorphous alloy coating is prepared using Brush Plating mode, plating pen uses the board-like knot of graphite
Structure, electrolyte temperature are 75 DEG C, and titration hydrochloric acid makes pH value less than 1, and the relative moving speed of electrode is 20 0mm/s, electricity when plating
The average current density of pole is 10 A/cm2；
2) removing of amorphous alloy coating
Separate amorphous alloy coating with substrate using the method for biaxial tension the composite plate of plating, the elongation percentage in each direction
It is 5%；
3) particle is broken
(a) Amorphous Alloy Grain is broken, by the amorphous alloy coating of peeling comminuted ball milling under vacuum conditions, ball milling method
For ball milling 3min, stop the mode at the interval 3min, total Ball-milling Time (including ball milling and downtime) is 0.5h, ratio of grinding media to material 3:1；
(b) it is sieved into the Amorphous Alloy Grain of different thicknesses；
4) molding of electrode outer layer
Using 50 mesh metallic sieves, cuts, is bent, soldering is prepared into circular ring shape cladding metal mesh closed at one end；
5) encapsulation of the injection of Amorphous Alloy Grain and electrode
It will be greater than 50 mesh Ni-Fes-phosphorus amorphous Amorphous Alloy Grain to import in circular ring shape cladding metal mesh, then use soldering form
Annulus Ni-Fe-phosphorus non-crystalline alloy catalysis electrode is made.
Claims (2)
1. a kind of ni-based amorphous alloy catalysis electrode, it is characterised in that: electrode is two layers of composition, and outer layer is metal mesh, and internal layer is
The sheet-like particle or powder of ni-based amorphous alloy, the specific alloying component of ni-based amorphous alloy are Ni 30-95 wt %, alloy member
Element for can together with nickel one of element, such as P, Co, Fe, Cr, Mo, W, Re of electro-deposition or multiple element combination.
2. a kind of preparation method of ni-based amorphous alloy catalysis electrode, it is characterised in that: the following steps are included:
1) preparation of ni-based amorphous alloy coating
(a) metal substrate is plated the degreasing and oxidation film removal on surface；
(b) electroplate liquid forms；Main salt is soluble nickel salt 0.5-4.5mol/L, sour 0.2-1mol/L, complexing agent 0.5-8g/L, is closed
Gold element additive 0.3-4.5mol/L, water surplus；
In the upper alloying element additive, iron with ferrous sulfate or frerrous chloride (matching reducing agent 0.5-2g/L), chromium with chromic anhydride,
Molybdenum with sodium molybdate, tungsten with sodium tungstate, cobalt with cobaltous sulfate, phosphorus with phosphorous acid or soluble hypophosphites, Re with the shape of Re soluble salt
Formula addition；
Above-mentioned acid is polynary middle strong acid such as phosphoric acid, boric acid etc.；
Above-mentioned complexing agent includes neopelex, tartaric acid, lauryl sodium sulfate, citrate etc.；
(c) preparation of amorphous alloy coating: titration strong acid make bath pH values less than 1, metallic substrate surfaces using plating or
Brush Plating prepares ni-based amorphous alloy coating；
2) ni-based amorphous alloy coating is made to fall off using method mechanically or physically；
3) particle is broken
(a) amorphous particle of peeling being crushed using ball mill, planetary ball mill, ball milling method is ball milling 2-5min,
Stop the mode at the interval 2-5min, total Ball-milling Time (including ball milling and downtime) is 0.5-5h, ratio of grinding media to material 1-5:1；
(b) it is sieved into the ni-based amorphous alloy particle of different thicknesses；
4) metal mesh is used, cuts, be bent, soldering is prepared into clad metal mesh；
5) the suitable ni-based amorphous alloy particle of thickness is injected into cladding metal mesh, then closes cladding using modes such as solderings
Ni-based amorphous alloy catalysis electrode is made in metal mesh.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710400630.1A CN108977843A (en) | 2017-05-31 | 2017-05-31 | A kind of ni-based amorphous alloy catalysis electrode and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710400630.1A CN108977843A (en) | 2017-05-31 | 2017-05-31 | A kind of ni-based amorphous alloy catalysis electrode and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108977843A true CN108977843A (en) | 2018-12-11 |
Family
ID=64502175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710400630.1A Pending CN108977843A (en) | 2017-05-31 | 2017-05-31 | A kind of ni-based amorphous alloy catalysis electrode and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108977843A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109750317A (en) * | 2018-12-26 | 2019-05-14 | 浙江工业大学 | A kind of preparation method of the compound hydrogen-precipitating electrode of porous Ni-base copper rhenium |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007090157A (en) * | 2005-09-27 | 2007-04-12 | Furukawa Electric Co Ltd:The | Cathode catalyst for fuel cell and fuel cell using the same |
| CN102703840A (en) * | 2012-05-25 | 2012-10-03 | 燕山大学 | Block ternary nickel-tungsten-phosphorus amorphous alloy and preparation method thereof |
| CN106381510A (en) * | 2016-12-06 | 2017-02-08 | 刘志红 | Preparing technology of Ni-Fe-P alloy-based compound coating |
-
2017
- 2017-05-31 CN CN201710400630.1A patent/CN108977843A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007090157A (en) * | 2005-09-27 | 2007-04-12 | Furukawa Electric Co Ltd:The | Cathode catalyst for fuel cell and fuel cell using the same |
| CN102703840A (en) * | 2012-05-25 | 2012-10-03 | 燕山大学 | Block ternary nickel-tungsten-phosphorus amorphous alloy and preparation method thereof |
| CN106381510A (en) * | 2016-12-06 | 2017-02-08 | 刘志红 | Preparing technology of Ni-Fe-P alloy-based compound coating |
Non-Patent Citations (2)
| Title |
|---|
| 朱艳兵: "镍基合金析氢电极的研究进展", 《舰船防化》 * |
| 郑一雄: "镍基非晶态合金纳米颗粒材料的制备、结构与电催化性能研究", 《中国博士学位论文库 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109750317A (en) * | 2018-12-26 | 2019-05-14 | 浙江工业大学 | A kind of preparation method of the compound hydrogen-precipitating electrode of porous Ni-base copper rhenium |
| CN109750317B (en) * | 2018-12-26 | 2020-06-30 | 浙江工业大学 | Preparation method of porous nickel-based copper-rhenium composite hydrogen evolution electrode |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106756641B (en) | A kind of Fe based amorphous alloy powder and its preparation process | |
| Bi et al. | Effect of Co addition into Ni film on shear strength of solder/Ni/Cu system: experimental and theoretical investigations | |
| CN106893953B (en) | A kind of cobalt base amorphous alloy powder and production method | |
| CN106893954B (en) | A kind of Co based amorphous alloy powders and its preparation process | |
| CN107267892B (en) | A kind of ni-based amorphous alloy catalysis electrode and production method | |
| Ma et al. | Electrodeposition and characterization of Co-W alloy from regenerated tungsten salt | |
| KR950704542A (en) | Nanocrystalline Metals (NANOCRYSTALLINE METALS) | |
| CN105063685B (en) | A kind of nickel plating copper material of nickel and cobalt containing alloy layer and its preparation method and application | |
| Ćirović et al. | Synthesis, structure and properties of nickel-iron-tungsten alloy electrodeposits-part I: Effect of synthesis parameters on chemical composition, microstructure and morphology | |
| Larson et al. | Recent trends in metal alloy electrolytic and electroless plating research: a review | |
| CN107268018B (en) | A kind of Fe-based amorphous alloy catalysis electrode and production method | |
| CN101899690A (en) | Multi-porous alloy material and method for preparing same | |
| CN108193146B (en) | Nickel-based amorphous alloy powder and production method thereof | |
| CN108977843A (en) | A kind of ni-based amorphous alloy catalysis electrode and preparation method thereof | |
| Bakonyi et al. | Development of pulse-plating technology for the preparation of coatings with varying composition along their thickness: A historical overview | |
| CN108220825A (en) | A kind of Ni based amorphous alloy powders and its preparation process | |
| CN107267891B (en) | A kind of cobalt base amorphous alloy catalysis electrode and production method | |
| CN108977844A (en) | A kind of cobalt base amorphous alloy catalysis electrode and preparation method thereof | |
| CN108977845A (en) | A kind of Fe-based amorphous alloy catalysis electrode and preparation method thereof | |
| CN108149158A (en) | A kind of Co-Ni-P amorphous powders preparation process | |
| CN108203792B (en) | Iron-based amorphous powder and preparation method thereof | |
| CN108231314B (en) | Iron-based amorphous alloy powder and production method thereof | |
| CN109200951A (en) | A kind of catalytic reactor and production method | |
| CN107937945A (en) | A kind of galvanoplastic prepare Ni Fe P amorphous powder techniques | |
| CN108103539A (en) | A kind of Ni-Fe-phosphorus amorphous powder 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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20181211 |
|
| WD01 | Invention patent application deemed withdrawn after publication |