CN101997107B - Magnesium electrode for magnesium battery and preparation method thereof - Google Patents
Magnesium electrode for magnesium battery and preparation method thereof Download PDFInfo
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- CN101997107B CN101997107B CN2009100701157A CN200910070115A CN101997107B CN 101997107 B CN101997107 B CN 101997107B CN 2009100701157 A CN2009100701157 A CN 2009100701157A CN 200910070115 A CN200910070115 A CN 200910070115A CN 101997107 B CN101997107 B CN 101997107B
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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
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a magnesium electrode for a magnesium battery and a preparation method thereof, which belong to the technical field of magnesium batteries. The magnesium electrode preparation method comprises the following steps of: depositing an electrode material in a dual-layer structure on a base material, wherein the base layer is a copper layer, and the surface layer is a magnesium or magnesium alloy layer; adopting an electroplating method for preparing a copper transition layer, and then electrodepositing magnesium in THF (Tetrahydrofolic Acid) solution of Grignard reagents. The dual-layer magnesium electrode prepared via the electrodepositing method in the invention has the advantages of firm and compact combination of the magnesium layer and the base material, good discharge performance and the like, in addition, the electrode surface does not have passive films, and magnesium plating layers have good quality.
Description
Technical field
The invention belongs to the battery technology field, relate to magnesium cell, especially a kind of magnesium cell is with magnesium electrode and preparation method thereof.
Background technology
The magnesium metal aboundresources, cheap, environmental friendliness has that density is little, electrode potential is negative, the big (2205mAhg of theoretical specific capacity
-1) characteristic.Magnesium cell is as a kind of novel green chemical power source, also has high specific energy, safety, characteristics such as pollution-free, is considered to one of following desirable regeneration product that substitutes conventional batteries.But traditional magnesium electrode adopts the rolling process preparation, and the surface has very thick passivating film, makes the utilance of magnesium reduce, and has the voltage delay phenomenon during discharge; Though through adding means such as additive, alloying; Make that surface passivated membrane is suppressed, electrical property is greatly improved; But the operating potential and the multiplying power discharging property of magnesium electrode have been sacrificed; Therefore, scientists is being attempted a kind of surface of preparation always and is not existed or the magnesium electrode of less passivating film thin layer.Thin layer electrode can pass through methods such as plating, physical deposition usually and obtain.Wherein, The electrode potential of magnesium metal is very negative and the reactivity ratio is higher, and the electro-deposition of magnesium can not be carried out in the aqueous solution and most of organic electrolysis plastidome, and corresponding bath system must adopt aprotic solvent; And each component and magnesium in the plating bath do not react; The solvent that can be used for plated metal magnesium is organic solvent and ionic liquid mostly, and what wherein effect was best is oxolane, and magnesium salts then mainly is some organic magnesium salts; Like RMgBr and aluminium chloride organic metal magnesium complex etc., bath system all belongs to the simple salt system.Therefore existing magnesium electrode exists with matrix bond not really firmly, and passivating film can appear in the surface, is inappropriate for heavy-current discharge.
Summary of the invention
The objective of the invention is to overcome the weak point of prior art, provide a kind of double-deck magnesium cell to use magnesium electrode with heavy-current discharge performance;
Another object of the present invention provides the preparation method of above-mentioned magnesium cell with magnesium electrode.
For realizing above-mentioned purpose, the present invention adopts following technical proposals:
A kind of magnesium cell is used magnesium electrode, is on basis material, to deposit double-deck electrode material, and bottom is the copper layer, and the top layer is magnesium or magnesium alloy layer.
And said basis material is polymer, porous material, the metal material of stable existence in electrolyte.
And said polymer is plastics such as PP, PE, PVC or PTFE.
And said porous material is nickel foam or foam copper.
And, said in electrolyte the metal material of stable existence comprise stainless steel band, nickel strap and chrome faced material.
A kind of magnesium cell is with the preparation method of magnesium electrode, and step is:
(1) basis material is carried out ultrasonic cleaning in acetone soln;
(2) carry out the plating of copper layer at the basis material bottom, the plating condition is temperature 50-60 ℃, and current density is 10-20mA/cm
2
(3) surface has an enterprising step of the material of copper layer and carries out the electro-deposition of magnesium, and mode is the constant current electro-deposition, and current density is 0.8-1.2mAcm
-2
And the prescription of said copper electroplating liquid is: potassium pyrophosphate 350g/L, and ammonium nitrate 20g/L, copper sulphate 90g/L, the pH value is controlled at 8.2-8.8.
And, in the electro-deposition of said magnesium, electrode and reference electrode being adopted magnesium rod, electrolyte is the EtMgBr/THF solution of 1.0M.
Advantage of the present invention and beneficial effect are:
1, the present invention adopts the double-deck magnesium electrode of electro-plating method preparation, have the magnesium layer combine with basis material firm, fine and close, advantage such as discharge performance is good, and electrode surface does not have passivating film, magnesium quality of coating good.
2, the present invention chooses EtMgBr/THF solution as electrolyte, has compared the electro-deposition behavior of magnesium on two kinds of basis material copper and mickels, has investigated the surface topography of magnesium sedimentary deposit; With nickel as basis material; Preplating metallic copper on Ni substrate, electro-deposition magnesium in EtMgBr/THF solution is prepared magnesium electrode then; Its electrochemical polarization improves, and is easy to heavy-current discharge.
Description of drawings
Fig. 1 forms the magnesium electrode SEM photo of duplicature on nickel foam for the present invention;
Wherein: a) for before electroplating magnesium; B) for after electroplating magnesium.
Fig. 2 is the SEM collection of illustrative plates of the electro-deposition magnesium of the present invention on the different matrix material;
Wherein: a) be Ni substrate; B) be the copper matrix.
Fig. 3 is the discharge curve of magnesium electrode of the present invention;
Wherein: go up to having double-deck porous magnesium electrode; It is down dull and stereotyped magnesium electrode.
Embodiment
Below in conjunction with embodiment, the present invention is further specified, following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
A kind of magnesium cell is used magnesium electrode; Adopt electro-deposition magnesium; The thickness of magnesium layer is by electrodeposition time/electric weight decision; For the catchment effect that guarantees magnesium electrode, pattern and with the bond strength of basis material, adopted the copper transition zone betwixt, promptly the electrode material of magnesium electrode is the duplicature that is made up of copper layer and magnesium layer.
The electro-deposition of magnesium is employed in the electro-deposition of the ethereal solution realization magnesium of RMgBr, and the present invention selects for use 1MEtMgBr/THF solution to carry out electro-deposition as electrolyte, and the surface can not form passivating film.Electro-deposition is 1.0mAcm in current density the best
-2Carry out under the constant current conditions, electrodeposition time is 1 hour.
The basis material that magnesium electrode adopted can be stainless steel band, nickel strap, plastics (PP, PE, PVC, PTFE etc.), chrome faced various materials etc.; Basis material can be porous material such as nickel foam, foam copper etc.The present invention is an example with nickel/nickel foam only, but is not limited only to this.
Deposited copper adopts the method for chemical plating to realize on plastic matrix material; Adopt electro-plating method to realize at the metal matrix material deposited copper, be specially: adopt the method for cupric pyrophosphate electro-coppering, the advantage of this method is that dispersibility is good; Nontoxic; Corrosivity is little, and covering power and ductility of electrodeposited film are all fine, and copper coating and Ni substrate combine firmly.
Magnesium cell describes through following two embodiment with the preparation method of magnesium electrode:
Embodiment 1:
1, the basis material nickel foam is carried out ultrasonic cleaning in acetone soln, clean up and get final product;
2, carry out the plating of copper layer at the bottom of basis material, the plating condition is about 55 ℃ of temperature, and current density is 15mA/cm
2, electroplating time is 3min.
Wherein: the prescription of copper electroplating liquid: potassium pyrophosphate 350g/L, ammonium nitrate 20g/L, copper sulphate 90g/L, the pH value is controlled at 8.2-8.8.
3, carry out the electro-deposition of magnesium on the basis material top layer, the Constant Electric Current deposition, current density is 1.0mAcm
-2, electrodeposition time is 1h.
The electrode area 0.26cm of electrode base sheet wherein
2, electrode and reference electrode are all adopted magnesium rod (purity 99.99%), electrolyte is the EtMgBr/THF solution of 1.0M, obtains thus having double-deck magnesium electrode, its surface topography is like Fig. 1 b) shown in.
4, surface topography is observed: adopt scanning electron microscopy (SEM, Hitachi S-4000) to take the deposition morphology of magnesium on basis material, and it is qualitative definite to adopt EDS that surface composition is carried out;
5, electro-chemical test:
Constant voltage discharge is adopted in the magnesium electrode discharge, and voltage is 0.5V (vs Mg), and the constant voltage discharge curve that obtains is as shown in Figure 3.
Embodiment 2:
Basis material adopts Copper Foil, and directly carries out the electro-deposition of magnesium.
All the other are identical with embodiment 1.
Repeat above test, outcome record is in table 1, and its surperficial SEM figure is like Fig. 2 b) shown in.
In order to verify advance of the present invention, it is following to the invention provides three Comparative Examples:
Comparative Examples 1:
Basis material adopts nickel foam, directly carries out the electro-deposition of magnesium, and all the other are identical with embodiment 1, repeats above test, and outcome record is in table 1.Surface SEM figure as Fig. 1 a) shown in.
Comparative Examples 2:
Basis material adopts nickel foil directly to carry out the electro-deposition of magnesium, and all the other are identical with embodiment 1, repeats above test, and outcome record is in table 1.Surface SEM figure as Fig. 2 a) shown in.
Comparative Examples 3:
Adopt Mg (ClO
4)
2THF solution on nickel foil, carry out the plating of magnesium, all the other are identical with embodiment 1, repeat above test, outcome record is in table 1.
Table 1
| Project | Basis material | Electrolyte | The Cu transition zone | Quality of coating (SEM) | Surface metal | Polarization |
| Embodiment 1 | Nickel foam | EtMgBr | Have | Continuously, good | Magnesium | Little |
| Embodiment 2 | Copper Foil | EtMgBr | - | Continuously, good | Magnesium | Little |
| Comparative Examples 1 | Nickel foam | EtMgBr | Do not have | Discontinuous, loose | Magnesium+nickel | Greatly |
| Comparative Examples 2 | Nickel foil | EtMgBr | Do not have | Discontinuous, loose | Magnesium+nickel | Greatly |
| Comparative Examples 3 | Nickel foil | Mg(ClO 4) 2 | Have | No coating | Nickel | - |
Can know from above result: magnesium deposited film on the copper matrix is fine and close continuously, be superior to the Ni substrate deposited film; Duplicature magnesium electrode through the preparation of copper transition zone has good electrochemical, and the heavy-current discharge performance of the duplicature electrode of nickel foam substrate is superior to plane electrode.Therefore, duplicature magnesium electrode of the present invention structurally with on the preparation method has novelty, and aspects such as the utilance that improves magnesium electrode, heavy-current discharge performance are had tangible effect.
The present invention has enumerated the nickel foil of magnesium electrode and the preparation method on Copper Foil and the nickel foam substrate, and further provides and have double-deck magnesium electrode and preparation method thereof.Need to prove: basis material is not limited only to this, can be the metal matrix material of other stable existences in electrolyte such as stainless steel, and the preparation method also can be methods such as plating, chemical plating or physical deposition.
Claims (7)
1. a magnesium cell is used magnesium electrode, it is characterized in that: be on basis material, to deposit double-deck electrode material, bottom is the copper layer, and the top layer is magnesium or magnesium alloy layer.
2. a kind of magnesium cell according to claim 1 is used magnesium electrode, it is characterized in that: said basis material be polymer or porous material or in electrolyte the metal material of stable existence.
3. a kind of magnesium cell according to claim 2 is used magnesium electrode, it is characterized in that: said polymer is PP, PE, PVC or PTFE.
4. a kind of magnesium cell according to claim 2 is used magnesium electrode, it is characterized in that: said porous material is nickel foam or foam copper.
5. a kind of magnesium cell according to claim 2 is used magnesium electrode, it is characterized in that: said in electrolyte the metal material of stable existence comprise stainless steel band, nickel strap.
6. a magnesium cell as claimed in claim 1 is with the preparation method of magnesium electrode, and it is characterized in that: preparation method's step is:
(1) basis material is carried out ultrasonic cleaning in acetone soln;
(2) carry out the plating of copper layer at the basis material bottom, the plating condition is temperature 50-60 ℃, and current density is 10-20mA/cm
2
(3) an enterprising step of material that has the copper layer on the surface is carried out the electro-deposition of magnesium, and mode is the Constant Electric Current deposition, and current density is 0.8-1.2mAcm
-2In the electro-deposition of said magnesium, electrode and reference electrode are adopted magnesium rod, electrolyte is the EtMgBr/THF solution of 1.0M.
7. magnesium cell according to claim 6 is characterized in that with the preparation method of magnesium electrode: the prescription of said copper electroplating liquid is: potassium pyrophosphate 350g/L, and ammonium nitrate 20g/L, copper sulphate 90g/L, the pH value is controlled at 8.2-8.8.
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|---|---|---|---|
| CN2009100701157A CN101997107B (en) | 2009-08-11 | 2009-08-11 | Magnesium electrode for magnesium battery and preparation method thereof |
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|---|---|---|---|
| CN2009100701157A CN101997107B (en) | 2009-08-11 | 2009-08-11 | Magnesium electrode for magnesium battery and preparation method thereof |
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| CN101997107A CN101997107A (en) | 2011-03-30 |
| CN101997107B true CN101997107B (en) | 2012-12-26 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103029370B (en) * | 2012-12-20 | 2015-12-09 | 桂林电子科技大学 | The electrode material of a kind of iron-based, pure copper transition layer and surperficial simple metal molybdenum or tungsten coating and preparation method |
| JP6613573B2 (en) * | 2015-02-06 | 2019-12-04 | 株式会社村田製作所 | Electrode, method for producing the same, and electrochemical device |
| CN105021677A (en) * | 2015-07-17 | 2015-11-04 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method of magnesium electrolysis reference electrode |
| JP6743885B2 (en) * | 2016-04-26 | 2020-08-19 | 株式会社村田製作所 | Negative electrode for magnesium secondary battery, manufacturing method thereof, and magnesium secondary battery |
| US10541419B1 (en) * | 2018-08-24 | 2020-01-21 | Toyota Motor Engineering & Manufacturing North America, Inc. | Electro-polymerized protective layer for 3D magnesium battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1365524A (en) * | 1999-07-29 | 2002-08-21 | 帕多瓦大学 | Magnesium-based (primary non-rechargeabel) and secondary (rechargeable) batteries |
| CN1411083A (en) * | 2002-11-01 | 2003-04-16 | 南开大学 | Chargeable magnesium battery |
| CN1905251A (en) * | 2006-03-01 | 2007-01-31 | 南开大学 | Mg secondary cell |
| CN1913219A (en) * | 2006-05-26 | 2007-02-14 | 南开大学 | Magnesium negative material and preparation method and application |
| CN101195925A (en) * | 2006-12-08 | 2008-06-11 | 辽宁师范大学 | Magnesium and method for electroplating copper on magnesium alloy surface |
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- 2009-08-11 CN CN2009100701157A patent/CN101997107B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1365524A (en) * | 1999-07-29 | 2002-08-21 | 帕多瓦大学 | Magnesium-based (primary non-rechargeabel) and secondary (rechargeable) batteries |
| CN1411083A (en) * | 2002-11-01 | 2003-04-16 | 南开大学 | Chargeable magnesium battery |
| CN1905251A (en) * | 2006-03-01 | 2007-01-31 | 南开大学 | Mg secondary cell |
| CN1913219A (en) * | 2006-05-26 | 2007-02-14 | 南开大学 | Magnesium negative material and preparation method and application |
| CN101195925A (en) * | 2006-12-08 | 2008-06-11 | 辽宁师范大学 | Magnesium and method for electroplating copper on magnesium alloy surface |
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