CN105591089A - Magnesium battery - Google Patents

Magnesium battery Download PDF

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Publication number
CN105591089A
CN105591089A CN201510896415.6A CN201510896415A CN105591089A CN 105591089 A CN105591089 A CN 105591089A CN 201510896415 A CN201510896415 A CN 201510896415A CN 105591089 A CN105591089 A CN 105591089A
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CN
China
Prior art keywords
magnesium
electrode
alloy
magnesium alloy
corrosion
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Pending
Application number
CN201510896415.6A
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Chinese (zh)
Inventor
黄静
方耀增
李铮
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Individual
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Priority to CN201510896415.6A priority Critical patent/CN105591089A/en
Publication of CN105591089A publication Critical patent/CN105591089A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46—Alloys based on magnesium or aluminium
    • H01M4/466—Magnesium based
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 discloses a magnesium battery. Magnesium alloy serves as a negative electrode material of the magnesium battery. With the total weight of the magnesium alloy as a datum, the magnesium alloy contains 0.01-0.3% of Er, 0.05-0.5% of Sn, 0.01-0.03% of Y, 0.01-0.1% of Ce, 0.1-0.5% of Nd and 0.02-0.2% of Bi. The alloyed elements for damaging a magnesium oxidation film structure are added into a magnesium electrode, falling-off of corrosion products can be promoted effectively, self-corrosion speed is reduced, and the utilization rate of magnesium negative electrodes is increased greatly.

Description

A kind of magnesium cell
Technical field
The present invention relates to a kind of battery, be specifically related to a kind of magnesium cell.
Background technology
The chemism of magnesium is high, and electronegativity is 1.31, and standard electrode potential is-2.36v, makes the battery of negative material with magnesium, and theoretical specific capacity is 2.22Ah/g, in common metal, only little than lithium, aluminium, is far longer than zinc. Meanwhile, the reserves of magnesium in the earth's crust are very abundant, so magnesium and alloy thereof are cheap, and magnesium and most compound all nontoxic, environmentally friendly. Visible, magnesium and alloy thereof are made anode (negative pole) has very large application potential in field of batteries. But magnesium alloy is when the cell negative electrode material, due to the reason such as large from corrosion rate, anode utilization rate is low, and especially anode polarization is serious, its operating potential is shuffled larger, be difficult to meet industrial requirement. On the other hand, magnesium alloy is covered with one deck passivating film in electrolyte, and this layer of passivating film can passivated magnesium electrode, cause magnesium cell in use after voltage the time longer.
Summary of the invention
The technical problem to be solved in the present invention is to provide one both can reduce magnesium negative plate and controllable a kind of magnesium cell of voltage delay time.
Technical scheme provided by the invention provides a kind of magnesium cell, it by magnesium alloy as negative material, taking this magnesium alloy gross weight as benchmark, in this magnesium alloy, contain Er0.01～0.3%, Sn0.05～0.5%, Y0.01～0.03%, Ce0.01～0.1%, Nd0.1～0.5% and Bi0.02～0.2%.
Impurity F e < 0.002%, Ni < 0.001% in magnesium alloy of the present invention.
Due to the interpolation of Er, Y, Ce and Nd, refinement magnesium alloy crystal grain, improved the electrochemistry uniformity of microstructure, dwindle electro-chemical activity difference, thereby reduce microcosmic galvanic corrosion, whole electrode surface corrosion evenly, simultaneously due to the interpolation of Ga, Bi element, has increased the overpotential of anodal hydrogen evolution reaction, hydrogen depolarization reaction is slowed down, thereby there is the retardance of microcosmic galvanic corrosion course of dissolution, appearance dress ornament Speed Reduction, anode utilization rate is high.
On the other hand, Bi and Sn are low-melting alloy element, and be uniformly distributed in magnesium alloy grain boundaries, dissolve along with the reaction of magnesium electrode, destroyed the structure of passivating film, the dissolving of accelerating oxidation film, make the passivating film of comparatively complete densification become loose porous, caducous corrosion product, thereby increase electrochemical reaction active site, its anode reaction polarization is died down, reduced the voltage delay time.
In magnesium alloy, also contain 1～10% aluminium; with 0.5～5% zinc; this is because the corrosion reaction that aluminium can further alleviate magnesium; can avoid the self discharge of magnesium; and aluminium can form passivating film on magnesium electrode surface, shields, and it also has good ductility simultaneously; can make structure refinement with the melting of magnesium phase, thereby also reduce corrosion. Aluminium can make again alloy form dense oxidation film and increased lag time, thereby add zinc can impel the further refinement of alloy, and reducing corrosion, the crystal grain that simultaneously adds zinc to reduce again aluminium is assembled, make magnesium electrode corrosion more even, thereby weaken the voltage delay phenomenon of aluminium.
In this alloy, also contain 0.2～0.6% manganese. In magnesium metal, generally all contain impurity iron, adding of manganese can generate MnAl with aluminium6, iron is dissolved in wherein and is removed. Those skilled in the art can be correct by conventional means the addition of definite manganese.
The electrolyte that a kind of magnesium cell of the present invention adopts is the halogen that contains magnesium, or the solution of the oxysalt of magnesium, and the halogen of magnesium is MgBr2Or MgCl2, the oxysalt of magnesium is Mg (ClO4)2。
In chromateIon moves to metal surface, and makes the magnesium chromate of Surface Creation indissoluble and the composite membrane of trivalent chromate of magnesium alloy, thereby hinders the transmission inhibition anode reaction of reaction particle, suppresses the anodic solution of metal, can be specifically Li2CrO4、Na2CrO4、(NH4)2CrO4。
Compared with prior art, the present invention has following beneficial effect:
1) the present invention adds the alloy element that destroys magnesia membrane structure in magnesium electrode, can effectively promote coming off of corrosion product, thereby increase electrochemical reaction active site, anode reaction polarization is died down, magnesium negative pole suppresses in active dissolution, maintains battery steady operation.
2) in magnesium electrode of the present invention, added the element of refinement alloy grain, improve the electrochemistry uniformity of magnesium electrode microstructure, dwindle electro-chemical activity difference, thereby reduce the corrosion of microcosmic galvanic cell, make the corrosion of whole electrode surface evenly, and the adding of high hydrogen overpotential element, the overpotential of anodal hydrogen evolution reaction increased, thereby reduce from corrosion rate, greatly improved magnesium negative pole utilization rate.
Detailed description of the invention
The present invention is further elaborated for following specific embodiment, but not as a limitation of the invention.
Embodiment 1
Magnesium electrode: taking this magnesium alloy gross weight as benchmark, contain Er0.01%, Sn0.05%, Y0.01%, Ce0.01%, Nd0.1% and Bi0.02% in this magnesium alloy, surplus is Mg.
Electrolyte is the Mg (ClO of 1mol/L4)2Solution, adds 0.1% Li2CrO4。
Embodiment 2
Magnesium electrode: taking this magnesium alloy gross weight as benchmark, contain Er0.3%, Sn0.5%, Y0.03%, Ce0.1%, Nd0.5% and Bi0.2% in this magnesium alloy, surplus is Mg.
Electrolyte is the MgBr of 1mol/L2Solution, adds 0.1% Na2CrO4。
Embodiment 3
Magnesium electrode: taking this magnesium alloy gross weight as benchmark, contain Er0.01%, Sn0.05%, Y0.01%, Ce0.01%, Nd0.1% and Bi0.02%, Al1%, Zn0.5% in this magnesium alloy, surplus is Mg.
Electrolyte is the Mg (ClO of 1mol/L4)2Solution, adds 0.1% Li2CrO4。
Embodiment 4
Magnesium electrode: taking this magnesium alloy gross weight as benchmark, contain Er0.3%, Sn0.5%, Y0.03%, Ce0.1%, Nd0.5% and Bi0.2%, Al10%, Zn5% in this magnesium alloy, surplus is Mg.
Electrolyte is the MgCl of 1mol/L2Solution, adds 0.1% (NH4)2CrO4。
Embodiment 5
Magnesium electrode: taking this magnesium alloy gross weight as benchmark, contain Er0.1%, Sn0.2%, Y0.02%, Ce0.06%, Nd0.3%, Bi0.15%, Al6%, Zn2.5%, Mn0.2% in this magnesium alloy, surplus is Mg.
Electrolyte is the Mg (ClO of 1mol/L4)2Solution, adds 0.1% Li2CrO4。
Embodiment 6
Magnesium electrode: taking this magnesium alloy gross weight as benchmark, contain Er0.2%, Sn0.35%, Y0.015%, Ce0.08%, Nd0.4%, Bi0.08%, Al3%, Zn4%, Mn0.6% in this magnesium alloy, surplus is Mg.
Electrolyte is the Mg (ClO of 1mol/L4)2Solution, adds 0.1% Li2CrO4。
Reference examples 1
Taking pure magnesium as magnesium negative pole, magnesium weight content is 99.97%.
Electrolyte is the Mg (ClO of 1mol/L4)2Solution, adds 0.1% Li2CrO4。
Reference examples 2
Taking magnesium alloy AZ31 as magnesium negative pole, Al weight content is 3.2903%, Zn weight content is 0.8232%, and surplus is Mg.
Electrolyte is the Mg (ClO of 1mol/L4)2Solution, adds 0.1% Li2CrO4。
Experimental example
Taking the magnesium alloy of embodiment 1,3,5,6 and reference examples 1～2 as raw material, being cut to sectional area is 1cm2Disk, in acetone, the impurity such as the machine oil of clean surface, then uses the abrasive paper for metallograph water mill of 400#, 600#, 800#, 1000# to smooth surface successively, and after alcohol rinses, cold wind dries up, be used as a kind of negative material of magnesium cell, Measurement accuracy magnesium alloy area also weighs its quality.
In this experiment, adopt saturated potassium chloride calomel electrode SCE to make reference electrode in electrolyte solution, standard electrode potential is 0.2412V (vsSHE). Except special indicating, the electrode potential in result part is all corresponding reference electrode and obtaining.
1, magnesium electrode is tested from corrosion rate
Accurately measure surface area (S) and the initial weight (m of magnesium electrode to be measured0), put in the beaker that contains 50ml solution, for preventing Contact Effect test data at the bottom of style and beaker, at the bottom of beaker, put some plastic cords, so that sample is held up. After soaking certain hour, sample is taken out, clean, then put into the Mg (ClO of the 1mol/L of 65 DEG C4)2Solution (adds 0.1% Li2CrO4) in soak 15min, after taking out, distilled water cleans, the hot blast drying (m that weighs1). Self-discharge rate is calculated as follows:
j＝[(m0-m1)×2×96500]/(24×t×S)
Wherein: j is self-discharge rate (mA/cm2), m is quality (mg), and t is time (sec), and S is area (cm2)。
From Corrosion results in table 1.
The different magnesium electrodes of table 1 from corrosion condition
As shown in Table 1, the magnesium negative pole of embodiment from corrosion rate well below reference examples, illustrate that the magnesium electrode decay resistance of embodiment is better.
2, magnesium electrode constant-current discharge test
Adopt single current step mode to study its constant-current discharge, accurately measure initial weight and the surface area of test electrode, with 50mA/cm2Constant-current discharge, electric discharge finishes rear with distilled water cleaning, puts into the Mg (ClO of the 1mol/L of 65 DEG C4)2Solution (adds 0.1% Li2CrO4) in soak 15min, after taking out, distilled water cleans, the hot blast drying (m that weighs1), current efficiency η is calculated as follows:
η＝(j×S×t)/[(m0-m1)/24×2×96500]×100％
Different magnesium negative poles are placed in to the Li that adds 0.1%2CrO4The Mg (ClO of 1.01mol/L4)2Sweep speed with 10mV/s in solution scans the polarization curve obtaining between-2.0～-0.8V (vsSHE).
The impact of the different magnesium electrodes of table 2 on battery constant-current discharge performance
The activation potential of the magnesium electrode of embodiment, apparently higher than reference examples, illustrates the magnesium electrode passivation of embodiment, and electro-chemical activity reduces, and decay resistance improves. The current efficiency of embodiment is apparently higher than reference examples, and the voltage delay time of embodiment be far smaller than reference examples, illustrate that the passivating film that the magnesium electrode of embodiment forms easily comes off or dissolves.

Claims (6)

1. a magnesium cell, it, be is characterized in that as negative material by magnesium alloy: close with this magnesiumGold gross weight is benchmark, contains Er0.01～0.3%, Sn0.05～0.5%, Y in this magnesium alloy0.01～0.03%, Ce0.01～0.1%, Nd0.1～0.5% and Bi0.02～0.2%.
2. a kind of magnesium cell according to claim 1, is characterized in that: in this magnesium alloy, go backContain 1～10% aluminium and 0.5～5% zinc.
3. a kind of magnesium cell according to claim 1, is characterized in that: in this magnesium alloy, go backContain 0.2～0.6% manganese.
4. a kind of magnesium cell according to claim 1, is characterized in that: this one magnesium cellElectrolyte be the solution of the oxysalt of the halogen that contains magnesium or magnesium.
5. a kind of magnesium cell according to claim 4, is characterized in that: described electrolyte is moltenIn liquid, also adding chromate is corrosion inhibiter.
6. a kind of magnesium cell according to claim 5, is characterized in that: described chromate isLithium chromate, sodium chromate or ammonium chromate.
CN201510896415.6A 2015-12-08 2015-12-08 Magnesium battery Pending CN105591089A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108193111A (en) * 2018-01-31 2018-06-22 中南大学 A kind of magnesium-rare earth anode material and preparation method thereof
CN108441729A (en) * 2018-03-28 2018-08-24 武汉中原长江科技发展有限公司 A kind of magnesium-alloy anode material and preparation method thereof
CN110923532A (en) * 2019-12-13 2020-03-27 陕西易莱德新材料科技有限公司 Alloy magnesium anode material and preparation method thereof
CN112993274A (en) * 2019-12-12 2021-06-18 中国科学院大连化学物理研究所 Magnesium alloy anode material and preparation and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1260408A (en) * 2000-01-26 2000-07-19 冶金工业部钢铁研究总院 Aluminium alloy sacrificial anode material to be used in fresh water
CN1466237A (en) * 2002-08-06 2004-01-07 李华伦 Magnesium dry cell
CN101388457A (en) * 2008-11-07 2009-03-18 中南大学 Aluminum alloy anode material for battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1260408A (en) * 2000-01-26 2000-07-19 冶金工业部钢铁研究总院 Aluminium alloy sacrificial anode material to be used in fresh water
CN1466237A (en) * 2002-08-06 2004-01-07 李华伦 Magnesium dry cell
CN101388457A (en) * 2008-11-07 2009-03-18 中南大学 Aluminum alloy anode material for battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李凌杰 等: "合金元素对镁合金耐腐蚀性能影响的研究进展", 《材料导报Ａ：综述篇》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108193111A (en) * 2018-01-31 2018-06-22 中南大学 A kind of magnesium-rare earth anode material and preparation method thereof
CN108193111B (en) * 2018-01-31 2019-10-18 中南大学 A kind of magnesium-rare earth anode material and preparation method thereof
CN108441729A (en) * 2018-03-28 2018-08-24 武汉中原长江科技发展有限公司 A kind of magnesium-alloy anode material and preparation method thereof
CN112993274A (en) * 2019-12-12 2021-06-18 中国科学院大连化学物理研究所 Magnesium alloy anode material and preparation and application thereof
CN110923532A (en) * 2019-12-13 2020-03-27 陕西易莱德新材料科技有限公司 Alloy magnesium anode material and preparation method thereof

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Application publication date: 20160518