CN105695826B - A kind of magnesium-alloy anode material and preparation method thereof - Google Patents
A kind of magnesium-alloy anode material and preparation method thereof Download PDFInfo
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- CN105695826B CN105695826B CN201610136115.2A CN201610136115A CN105695826B CN 105695826 B CN105695826 B CN 105695826B CN 201610136115 A CN201610136115 A CN 201610136115A CN 105695826 B CN105695826 B CN 105695826B
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
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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
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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
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Abstract
The present invention relates to the electrochmical power source anode material of metal material Field of Heat-treatment, specifically a kind of magnesium-alloy anode material and preparation method thereof.Each alloying element mass percent of magnesium-alloy anode material is Al:4 7%, Zn:2 4%, Mn:0.1 0.6%, In:0.5 2%, surplus Mg.Preparation method, using resistance furnace in proportion by pure Mg, Al, Zn, In and Mg 30%Mn alloys are heated to 680 760 DEG C, stirring, are cast in Carbon Steel Die, are placed in after air cooling in 350 420 DEG C of resistance furnaces after being incubated 24 hours, water cooling after standing.Material of the present invention has the characteristics of discharge performance is excellent, and discharging product is easily desorbed, and preparation method is simple and easy, low processing cost.
Description
Technical field
The present invention relates to the electrochmical power source anode material of metal material Field of Heat-treatment, specifically a kind of magnesium alloy
Anode material and preparation method thereof.
Background technology
Magnesium metal has relatively negative electrode potential -2.37V (vs SHE), is defeated by-the 2.31V and Zn of aluminium -1.25V, because
This, when using magnesium and magnesium alloy as the anode material of power supply in use, the electric discharge that relatively negative electrode potential can be anode carries
For larger driving force, so as to provide larger discharge current.Magnesium metal possesses larger capacitance, and theoretical capacity is
2205A.h/kg, it will be further appreciated that, the density of magnesium metal is small, therefore it possesses larger mass energy density, is suitable as
Discharge and use for anode material.
Seawater battery is one of major domain that magnesium alloy uses as power anode.Seawater battery is twentieth century 40
Age, to meet that the requirement that military equipment discharges the big energy density of battery, long service life and low temperature continuous begins one's study
's.More application is providing long-time stable for underwater facility, such as sonobuoy, lifesaving appliance, meteorological detection instrument at present
Electric current, discharged with low current density based on.Although above-mentioned field can directly use lithium battery, alkaline battery, these electricity
It is big volume, weight to be present in pond, it is necessary to the shortcomings of especially preserving, from the point of view of economical and practical, and the lithium electricity of high power density
Pond or alkaline battery, because it requires higher, the use of unsuitable oceanographic equipment to discharge environment.Seawater battery biggest advantage
It is that it need not carry electrolyte, only needs natural sea-water to activate use as electrolyte, therefore substantially increases its quality energy
Metric density.
The basic functional principle of seawater battery is to corrode realization electric discharge in the seawater by metal, there is provided anode current is cloudy
Corresponding reduction reaction then occurs for pole.The reliable dissolved oxygen of seawater of reduction reaction of negative electrode directly utilizes air in inertia
Cathodic reduction is carried out on electrode, also reliable negative electrode itself participates in reaction consumption (such as CuCl, AgCl do negative electrode).But magnesium
Alloy as anode material, there is also it is certain the defects of, as voltage is stagnant caused by the oxide and hydroxide of magnesium surface
Afterwards, the negative difference effect in process of anodic polarization, the α-Mg particles desorption in discharge process etc..Therefore, high discharge potential is developed,
High discharge stability, high current efficiency, the magnesium-alloy anode material of low processing cost, have great importance.
The content of the invention
Present invention driving current potential existing for current seawater battery magnesium-alloy anode material is low, and discharge stability is poor,
Current efficiency is low, complex manufacturing, the problem of high processing costs, discloses a kind of magnesium-alloy anode material and preparation method thereof.
To achieve the above object, the present invention use technical scheme for：
A kind of magnesium-alloy anode material, each alloying element mass percent of magnesium-alloy anode material is Al:4-7%,
Zn:2-4%, Mn:0.1-0.6%, In:0.5-2%, surplus Mg.
Each alloying element mass percent of magnesium-alloy anode material is preferably Al:5.5-6.5%, Zn:2.6-
3.2%, Mn:0.25-0.4%, In:1-1.5%, surplus Mg.
A kind of preparation method of magnesium-alloy anode material, pure magnesium ingot is mixed with other alloying elements, is heated to 680-760
DEG C after alloy compositions are completely melt, 10-20min is stirred, 30-60min is stood after stirring；Upper strata melt cast is taken in preheating
In Carbon Steel Die, natural cooling, is placed in insulation 18-24 hours in 350-420 DEG C of resistance furnace, makes its crystal boundary in atmosphere after cooling
The second phase diffusion of upper precipitation is uniform, then takes out magnesium alloy, is placed in tank and quenches, to obtain described in supersaturated solid solution
Magnesium-alloy anode material；Wherein, the Mn in alloy, added in the form of Mg-30%Mn intermediate alloys.
Specifically, pure magnesium ingot is mixed with other alloying elements and adds carbon steel crucible, carbon steel crucible is added using resistance furnace
Heat to 680-760 DEG C after alloy compositions are completely melt, stir 10-20min after stand 30-60min, take upper strata melt cast in
It is preheated in 200 DEG C of Carbon Steel Die, in atmosphere natural cooling, is placed in after cooling in 350-420 DEG C of resistance furnace and is incubated 18-24
Hour, the second phase for making to separate out on its crystal boundary spreads uniformly, then takes out magnesium alloy, is placed in tank and quenches, to be satiated
With the magnesium-alloy anode material of solid solution.
A kind of application of magnesium-alloy anode material, the magnesium-alloy anode material answering in sea-water activated seawater battery
With.
Advantage for present invention：
Magnesium-alloy anode material of the present invention has the characteristics of discharge performance is excellent, and discharging product is easily desorbed, preparation method letter
Single easy, low processing cost.
Specifically, magnesium-alloy anode material prepared by the present invention, anodic solution activity is strong, electrode surface dissolution kinetics mistake
Journey shows that product is easily desorbed, constant current discharge stable performance, and discharge potential is left in -1.7V (vs SCE) under different current densities
The right side, anode material current efficiency is close to 80%.And for magnesium alloy of the present invention without expensive extruding, rolling process, solid solution state can
It is directly used in seawater battery anode material.
Brief description of the drawings
Fig. 1 is the electrode surface dynamic process schematic diagram (a) and equivalent circuit diagram (b) of present example 1,2,3.
Fig. 2 be the magnesium-alloy anode material difference current density of example 1 provided in an embodiment of the present invention under discharge potential-when
Half interval contour.
Embodiment
The content of the invention of the present invention is elaborated with reference to following examples.
Embodiment 1
Pure magnesium ingot 1454g is placed in carbon steel crucible and is heated to 720 DEG C and it is fully melted, according to Al:98.21g,Zn:
49.1g,In:16.37g Mg-30%Mn:19.1g amount adds other alloying elements, and 30min is stood after stirring 10min.Take
Layer molten alloy, is cast in 200 DEG C of Carbon Steel Die, naturally cools to room temperature.Ingot casting is removed from the molds, is placed in 385
DEG C resistance furnace in be incubated 24 hours, spread the second phase for being separated out on its crystal boundary uniform, then take out magnesium alloy, be placed in tank
Middle quenching, to obtain magnesium-alloy anode material of the institutional framework as supersaturated solid solution.Through Inductively coupled plasma mass spectrometry
(ICP-MS) measure alloying component is：5.979%Al, 2.917%Zn, 0.981%In, 0.361%Mn., then obtained above-mentioned
Ingot casting is processed into electrode and (1 × 1 × 1cm sample, seals after the welding lead of one end, reserve 1cm2Working face), carry out electricity
Chemical property is tested.
Electrochemical impedance (EIS) test condition is：Corrosive medium is 3.5wt.%NaCl solution, treats OCP (OCP)
After stable, start EIS tests.Exchange disturbance amplitude is ± 5mV, is from high frequency to low frequency domain scanning, frequency range
100kHz-10mHz。
Constant current discharge test condition is：Choose different current densities and discharge time, respectively 10mA/cm2, 20h；
100mA/cm2, 2h；200mA/cm2, 1h, to ensure identical discharge capacity.In discharge process, potential change situation is monitored.Electric discharge
Front and rear to weigh respectively, calculating current efficiency is (referring to Tables 1 and 2；And Fig. 1 and Fig. 2).
It is visible by above-mentioned Tables 1 and 2, and Fig. 1 and Fig. 2：Alloy surface dissolution kinetics process mainly by surface electric double layer,
Corrosion product is desorbed and Mg+With H2O forms in the chemical reaction of alloy surface.Different current density electric discharges find (10mA/cm2,
20h；100mA/cm2, 2h；200mA/cm2, 1h), alloy current potential is relatively negative (- 1.7V or so), illustrates that electric discharge driving force is stronger；Electric discharge
Potential fluctuation is small, illustrates that alloy remains to provide stable electric current output under different discharging conditions；Discharge current efficiency high, illustrate to close
Output of the consumption of gold effective for electric current.Summary conclusion, it is a kind of excellent magnesium-alloy anode material to illustrate the alloy.
Embodiment 2
Pure magnesium ingot 1396g is placed in carbon steel crucible and is heated to 680 DEG C and it is fully melted, according to Al:60.26g,Zn:
30.13g,In:7.53g Mg-30%Mn:12.55g amount adds other alloying elements, and 40min is stood after stirring 15min.Take
Upper molten alloy, it is cast in 200 DEG C of Carbon Steel Die, naturally cools to room temperature.Ingot casting is removed from the molds, is placed in
18 hours are incubated in 400 DEG C of resistance furnace, the second phase for making to separate out on its crystal boundary spreads uniformly, then takes out magnesium alloy, is placed in
Quenched in tank, to obtain magnesium-alloy anode material of the institutional framework as supersaturated solid solution.Through inductive coupling plasma mass spectrometry
Instrument (ICP-MS) determines alloying component：4.031%Al, 2.045%Zn, 0.504%In, 0.245%Mn.
Above-mentioned acquisition ingot casting then is processed into electrode (1 × 1 × 1cm sample, to seal after the welding lead of one end, reserve
1cm2Working face), carry out electrochemical property test (referring to Tables 1 and 2；And Fig. 1)
Embodiment 3
Pure magnesium ingot 1412g is placed in carbon steel crucible and is heated to 680 DEG C and it is fully melted, according to Al:80.84g,Zn:
64.67g,In:32.34g Mg-30%Mn:26.95g amount adds other alloying elements, and 60min is stood after stirring 20min.Take
Upper molten alloy, it is cast in 200 DEG C of Carbon Steel Die, naturally cools to room temperature.Ingot casting is removed from the molds, is placed in
20 hours are incubated in 370 DEG C of resistance furnace, the second phase for making to separate out on its crystal boundary spreads uniformly, then takes out magnesium alloy, is placed in
Quenched in tank, to obtain magnesium-alloy anode material of the institutional framework as supersaturated solid solution.Through inductive coupling plasma mass spectrometry
Instrument (ICP-MS) determines alloying component：4.996%Al, 4.011%Zn, 1.974%In, 0.512%Mn.
Above-mentioned acquisition ingot casting then is processed into electrode (1 × 1 × 1cm sample, to seal after the welding lead of one end, reserve
1cm2Working face), carry out electrochemical property test (referring to Tables 1 and 2；And Fig. 1).
The alloy discharge current efficiency of table 1
The 2-in-1 gold electric discharge average potential of table
Claims (3)
- A kind of 1. magnesium-alloy anode material, it is characterised in that：Each alloying element mass percent of magnesium-alloy anode material is Al:5.5-6.5%, Zn:2.6-3.2%, Mn:0.25-0.4%, In:1-1.5%, surplus Mg；The preparation method of described magnesium-alloy anode material：Pure magnesium ingot is mixed with other alloying elements, is heated to 680-760 DEG C After alloy compositions are completely melt, 10-20min is stirred, 30-60min is stood after stirring；Upper strata melt cast is taken in the carbon of preheating In steel mold, natural cooling, is placed in insulation 18-24 hours in 350-420 DEG C of resistance furnace, makes on its crystal boundary in atmosphere after cooling The the second phase diffusion separated out is uniform, then takes out magnesium alloy, is placed in tank and quenches, to obtain the magnesium of supersaturated solid solution Alloy anode material；Wherein, the Mn in alloy, added in the form of Mg-30%Mn intermediate alloys.
- 2. the preparation method of the magnesium-alloy anode material as described in claim 1, it is characterised in that：, will be pure according to aforementioned proportion Magnesium ingot mixes with other alloying elements adds carbon steel crucible, is heated to 680-760 DEG C to carbon steel crucible using resistance furnace and treats alloy After component is completely melt, 30-60min is stood after stirring 10-20min, takes upper strata melt cast in the carbon steel mould for being preheated to 200 DEG C In tool, natural cooling, is placed in insulation 18-24 hours in 350-420 DEG C of resistance furnace, makes to separate out on its crystal boundary in atmosphere after cooling The diffusion of the second phase it is uniform, then take out magnesium alloy, be placed in tank and quench, to obtain the magnesium alloy of supersaturated solid solution Anode material.
- A kind of 3. application of the magnesium-alloy anode material described in claim 1, it is characterised in that：The magnesium-alloy anode material exists Application in sea-water activated seawater battery.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106245040A (en) * | 2016-08-30 | 2016-12-21 | 泉州市真匠体育用品有限公司 | High purity alumina-magnesia composite anode materials |
| CN106319532A (en) * | 2016-08-30 | 2017-01-11 | 泉州市真匠体育用品有限公司 | Composite sacrificial anode |
| CN108193111B (en) * | 2018-01-31 | 2019-10-18 | 中南大学 | A kind of magnesium-rare earth anode material and preparation method thereof |
| CN109136598A (en) * | 2018-09-28 | 2019-01-04 | 河南科技大学 | A kind of magnalium indium rare earth anode material and preparation method thereof, magnesium air battery |
| CN110380045B (en) * | 2019-07-24 | 2021-02-05 | 易航时代(北京)科技有限公司 | Magnesium alloy anode material, preparation method and application thereof, and magnesium air battery |
| 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 |
| CN112647001A (en) * | 2020-12-20 | 2021-04-13 | 东北电力大学 | AZ31M alloy and preparation method and application thereof |
| CN115011852A (en) * | 2022-04-20 | 2022-09-06 | 青岛科技大学 | Magnesium alloy anode material for seawater battery and preparation method thereof |
| CN114934220A (en) * | 2022-05-10 | 2022-08-23 | 青岛科技大学 | Seawater corrosion resistant rare earth magnesium alloy material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CA636116A (en) * | 1958-02-13 | 1962-02-06 | The Dow Chemical Company | Anode for magnesium primary cells |
| US3278338A (en) * | 1963-07-23 | 1966-10-11 | Gen Electric | Water-activated battery |
| SU1735420A1 (en) * | 1990-03-22 | 1992-05-23 | Институт Металлургии Им.А.А.Байкова | Alloy on the basis of magnesium |
| JPH09310130A (en) * | 1996-05-21 | 1997-12-02 | Sumikou Boshoku Kk | Production of magnesium alloy for galvanic anode |
| DE102007061561A1 (en) * | 2007-12-18 | 2009-06-25 | Magontec Gmbh | Galvanic sacrificial anode useful in a storage device for aqueous media such as drinking water, comprises a magnesium based alloy consisting of aluminum, zinc, manganese, strontium and other impurities |
| CN101527359A (en) * | 2009-04-17 | 2009-09-09 | 中南大学 | Magnesium alloy anode material for water activated batteries and manufacture method thereof |
| CN101956197A (en) * | 2009-07-13 | 2011-01-26 | 淄博宏泰防腐有限公司 | High-efficiency multi-element magnesium alloy sacrificial anode and preparation method thereof |
| CN101768745A (en) * | 2010-03-05 | 2010-07-07 | 陕西电力科学研究院 | Magnesium sacrificial anode with high current efficiency and preparation method thereof |
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