CN109136598A - A kind of magnalium indium rare earth anode material and preparation method thereof, magnesium air battery - Google Patents
A kind of magnalium indium rare earth anode material and preparation method thereof, magnesium air battery Download PDFInfo
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- CN109136598A CN109136598A CN201811143182.2A CN201811143182A CN109136598A CN 109136598 A CN109136598 A CN 109136598A CN 201811143182 A CN201811143182 A CN 201811143182A CN 109136598 A CN109136598 A CN 109136598A
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
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- C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
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Abstract
The present invention relates to a kind of magnalium indium rare earth anode materials and preparation method thereof, magnesium air battery, belong to magnesium air battery technology field.Magnalium indium rare earth anode material of the invention, consists of the following mass percentage components: aluminium 0.5~10%, indium 0.02~5%, rare earth element 0.1~5%, and surplus is magnesium and inevitable impurity.Magnalium indium rare earth anode material of the invention carries out microalloying by mixing suitable aluminium, indium and rare earth element, on the one hand discharging product is accelerated to peel off from electrode surface, maintains the stronger electric discharge activity of electrode；On the other hand the liberation of hydrogen side reaction for inhibiting electrode, improves the coulombic efficiency of electrode, this all substantially increases the chemical property of magnalium indium rare earth anode material.
Description
Technical field
The present invention relates to a kind of magnalium indium rare earth anode materials and preparation method thereof, magnesium air battery, belong to magnesium air electricity
Pool technology field.
Background technique
Due to metal-air battery have many advantages, such as efficiently, cleaning, by become 21 century ideal power power supply it
One.China has increased the Innovation Input to metal-air battery, especially magnesium-air cell and zinc-air battery etc..
Magnesium-air cell is anode with air electrode, and magnesium metal or magnesium alloy are as cathode, and neutral aqueous solution is as electrolyte, air
In O2Reach gas-solid-liquid three phase boundary by gas-diffusion electrode and metal Mg react and releases electric energy, product without
Poison and recoverable, are ideal battery systems.The battery system is abundant with material source, and energy density is big, reliability
Height, the safe and pollution-free, advantages such as price is low, has very wide application prospect.
From 1970s, numerous studies have been made to magnesium-air cell both at home and abroad, all in all, research master
Concentrate on magnesium anode material, electrolyte corrosion inhibitor and battery system etc..Since pure magnesium is a kind of gold that comparison is active
Belong to material, in actual use, after magnesium electrode and electrolyte contacts, electrode surface would generally be by magnesium hydroxide and oxidation
The film of magnesium covers, its open circuit potential is caused to become just.The surface of magnesium electrode would generally deposit one layer of discharging product during discharge
Magnesium hydroxide, which hinders effective contact of electrolyte and magnesium electrode surface, to reduce the active reaction face of electrode
Product, causes current potential gradually to be shuffled with the extension of discharge time, and discharge reduced activity.Therefore magnesium electrode is in actual use
Theoretically more negative potential and stronger electric discharge activity is not achieved.Serious liberation of hydrogen would generally occur during discharge for magnesium electrode
Side reaction or self discharge, especially when some electrode potentials exist than the micro impurity element (such as Fe, Si) that magnesium matrix is corrected
When in magnesium electrode, these impurity elements can form as local cathode and magnesium matrix and corrode micro- galvanic couple and accelerate in discharge process
Hydrogen is precipitated from electrode surface, and anode efficiency is caused to reduce.Therefore, the electronics of magnesium electrode 100% cannot be used to form electric current pair
Outer acting is seized by the proton hydrate in electrolyte there are also quite a few electronics and generates hydrogen, causes electrode anode efficiency
Loss prevents battery from giving full play to the advantage of high-energy power supply, especially under high current density operating condition, stable work
It is lower to make current potential, anode polarization is serious, limits the industrial industrialization and practical application of magnesium air battery.
Summary of the invention
The object of the present invention is to provide a kind of magnalium indium rare earth anode materials of operating potential that can be improved magnesium air battery
Material.
The present invention also provides a kind of preparation method of the magnalium indium rare earth anode material of simple process and a kind of senior engineers
Make the magnesium air battery of current potential.
In order to achieve the goal above, technical solution used by magnalium indium rare earth anode material of the invention is:
A kind of magnalium indium rare earth anode material, consists of the following mass percentage components: aluminium 0.5~10%, indium 0.02
~5%, rare earth element 0.1~5%, surplus is magnesium and inevitable impurity.
Magnalium indium rare earth anode material of the invention carries out microalloying by mixing suitable aluminium, indium and rare earth element,
On the one hand accelerate discharging product to peel off from electrode surface, maintain the stronger electric discharge activity of electrode；On the other hand inhibit the analysis of electrode
Hydrogen side reaction, improves the coulombic efficiency of electrode, and the effect of these two aspects substantially increases the chemistry of magnalium indium rare earth anode material
Performance, and expanded its application in the battery.
In magnalium indium rare earth anode material of the invention, aluminium element mainly exists in two forms: 1) with alloying element
Form be solid-solubilized in Mg matrix；2) with the second phase Mg17A112Form be present in crystal boundary or transgranular.Mg17A112To magnesium alloy
Corrosion serves both functions, and works as Mg17A112Phase amount is more and when crystal boundary is continuously distributed, can inhibit magnesium alloy as barrier
Corrosion；Work as Mg17A112Phase amount is less and discontinuously arranged when crystal boundary, then mutually accelerates the corruption of Mg matrix mainly as cathode
Erosion.
In magnalium indium rare earth anode material of the invention, In element and Mg have stronger synergistic effect, and In is with alloying element
Form be solid-solubilized in Mg matrix, the C1- ion in electrolyte can be promoted in the absorption of electrode surface.It is adsorbed on electrode surface
C1- ion can will be attached to the discharging product Mg (OH) of electrode surface indissoluble2It is changed into readily soluble MgCl2, destroy electrode surface
Passivating film is to increase the active reaction area of electrode and maintain its stronger electric discharge activity.In addition, being dissolved in constant-current discharge
In in the electrodes will be dissolved as In3+Ion, the equilibrium potential of the process than magnesium dissolution just, therefore the In dissolved3+Ion
It is easy to seize the electronics of magnesium and reduction reaction occurs and is deposited on electrode surface, to accelerate the active dissolution of magnesium electrode and enhancing
Its activity of discharging.Therefore, the magnesium air electricity of magnalium indium rare earth anode material of the invention especially suitable for electrolyte chloride ion-containing
Pond.
In magnalium indium rare earth anode material of the invention, rare earth element solubility in magnesium is minimum, but due to aluminium element
In the presence of, can with aluminium element formed the second phase, such as LaAl4、CeAl4Deng rich aluminium rare-earth phase.Rare earth element is easy to fill up in growth
Magnesium alloy crystal grain cenotype surface defect position, generate hinder magnesium crystal continue the film grown up, can Refining Mg Alloy crystal grain.But by
In enrichment of the rare earth element in freezing interface forward position, diffusion of other alloying elements to solid solution phase can be prevented, solute is reduced
Solubility of the element in solid solution increases eutectic and intermetallic compound quantity in alloy, or even generates cenotype.
In addition to Sc, the atomic radius of rare earth element is bigger than magnesium atom radius 0.172nm between 0.174~0.204nm；
In addition the normal potential of rare earth element is very low, as Ce and La normal potential be respectively -2.48V (SHE) and -2.52V (SHE),
Also there is larger difference with the electronegativity of magnesium, so solubility very little of the rare earth in matrix magnesium, rare earth and aluminium element and other conjunctions
Reciprocation generates the intermetallic compound of polynary complexity to gold element to each other, and structure and magnesium have larger difference, thus in base
It can cause biggish distortion energy in body.Since atomic arrangement than more loose, assemble caused by crystal boundary by rare earth compound in grain boundary layer
Distortion can be smaller than matrix more, so rare earth compound is mostly distributed along crystal boundary.Since rare earth is surface active element, tying
During crystalline substance, it, which is adsorbed on boundary surfaces, reduces surface tension, to reduce nucleating work, makes crystallization nuclei is poly- to increase, alloy group
Knit refinement.On the other hand, since the atomic radius of rare earth metal is big, it is easy to which the surface for filling up the magnesium alloy crystal grain in growth lacks
It falls into, hinders crystal grain continued growth, also make crystal grain refinement.Simultaneously because rare earth is in magnesium solubility very little, reciprocation each other
The intermetallic compound for generating polynary complexity, can also make more uniformly spreading for other alloying elements.When content of rare earth is lower,
Although magnesium alloy anode crystallite dimension can be obviously reduced, it has been roughened arborescent structure simultaneously, has made to be segregated phase amount increase, this
Rare earth element is primarily due in the enrichment in freezing interface forward position, prevents diffusion of other alloying elements to solid solution phase, is dropped
The distribution coefficient of low solute element is the solubility in solid solution, makes the eutectic and intermetallic compound quantity in alloy
Increase, or even generates cenotype.And content of rare earth addition is too high, then can also be roughened the arborescent structure of aluminium alloy instead, and promote crystalline substance
The formation of boundary's bulk compound can slow down magnesium alloy so only a certain amount of content of rare earth just has best thinning effect
Self-corrosion, to improve anode utilization rate.
Magnalium indium rare earth anode material of the present invention is summed up and is had the advantage that compared with existing magnesium anode material
1) electrochemical activation of magnalium indium rare earth anode material of the invention is fine, the open circuit potential in neutral electrolyte
The electromotive force of≤- 1.88V (vs.SCE), single battery are greater than 1.50V；
2) magnalium indium rare earth anode material of the invention, added in magnesium micro Al, In and rare earth element (such as La and/
Or Ce), it is therefore an objective to it realizes the rapid deterioration of product in discharge process and inhibits the liberation of hydrogen side reaction of electrode surface, especially in magnesium
Rare earth element is added in alloy, rare earth element, which is added in magnesium, has deoxidation, dehydrogenation, desulfuration to accelerate burn-off rate, reduce metal burning
Damage and fractions distribution and all effects of fine degenerate for changing the objectionable impurities such as iron, can slow down the self-corrosion of magnesium alloy, to mention
High anode utilization rate；
3) magnalium indium rare earth anode material superior performance of the invention, single battery discharge current density be 5~
100mA/cm2The electromotive force of test 5h is 1.50V~1.79V in range, and possesses good corrosion resistance and higher electrification
Activity is learned, the requirement of neutral magnesium-air cell high current density discharge is met.
Preferably, the rare earth element is at least one of lanthanum, cerium.The reason of preferred lanthanum of rare earth element, cerium be lanthanum,
Cerium mischmetal element yield is big, cheap, can reduce the cost.
The presence of impurity can accelerate the self-corrosion of anode material, and reduce the utilization rate of anode material.In order to reduce this hair
The self-corrosion of bright magnalium indium rare earth anode material, inevitable impurity account for the mass percent of magnalium indium rare earth anode material
No more than 0.1%.
Technical solution used by the preparation method of magnalium indium rare earth anode material of the invention are as follows:
A kind of preparation method of the magnalium indium rare earth anode material, comprising the following steps: protected in protective gas
Under, by the melting mixing liquid being mainly made of magnesium, aluminium, indium and rare earth element solidify to get.
The preparation method of magnalium indium rare earth anode material of the invention, simple process and low cost are easy to promote and utilize.
Preferably, the melting mixing liquid is that it is dilute that aluminium, indium and aluminium-is added after taking magnesium to melt under protective gas protection
Native alloy and/or magnesium-rare earth, melting mix, and then heat preservation obtains.In the process for preparing magnalium indium rare earth anode material
In, rare earth element is added in melt liquid in the form of aluminium-rare-earth alloy and/or magnesium-rare earth, rare earth can be reduced
The scaling loss of element reduces production cost.Protective gas protection can use protective gas SF6Rotary blowing.
Technical solution used by magnesium air battery of the invention are as follows:
A kind of magnesium air battery, including anode, electrolyte and cathode, the anode are above-mentioned magnalium indium rare earth anode material
Material.
Magnalium indium rare earth air cell of the invention, using magnalium indium rare earth anode material of the invention, monocell is being put
Electric current density is 5~100mA/cm2The electromotive force of test 5h is 1.50V~1.79V in range, can satisfy neutral magnesium-sky
The requirement of pneumoelectric pond high current density discharge.
Preferably, contain chloride ion in the electrolyte.Indium in magnalium indium rare earth anode material of the invention can promote
Into chloride ion in the absorption of anode surface, play the role of destroying passivating film, to maintain the stronger activity of electrode.In order to obtain
Electrolyte containing chloride ion, the electrolyte used when preparing electrolyte include chloride, such as sodium chloride.
Specific embodiment
In order to solve the problem of that the low serious polarization of operating potential of magnesium air battery in the prior art, the present invention provide
A kind of magnalium indium rare earth anode material, consists of the following mass percentage components: aluminium 0.5~10%, indium 0.02~5%,
Rare earth element 0.1~5%, surplus are magnesium and inevitable impurity.
Magnalium indium rare earth anode material of the invention carries out microalloying by mixing suitable aluminium, indium and rare earth element,
On the one hand accelerate discharging product to peel off from electrode surface, maintain the stronger electric discharge activity of electrode；On the other hand inhibit the analysis of electrode
Hydrogen side reaction, improves the coulombic efficiency of electrode, and the effect of these two aspects substantially increases the chemistry of magnalium indium rare earth anode material
Performance and its application in the battery.
In some embodiments of magnalium indium rare earth anode material of the invention, the rare earth element be lanthanum, in cerium extremely
Few one kind.It is cheap since lanthanum, cerium mischmetal element yield are big, cost can reduce using lanthanum and/or cerium.
The presence of impurity can accelerate the self-corrosion of anode material, and reduce the utilization rate of anode material.In order to reduce this hair
The self-corrosion of bright magnalium indium rare earth anode material, inevitable impurity account for the mass percent of magnalium indium rare earth anode material
No more than 0.1%.
The present invention also provides a kind of preparation methods of magnalium indium rare earth anode material, comprising the following steps:
Protective gas protection under, by the melting mixing liquid being mainly made of magnesium, aluminium, indium and rare earth element solidify to get.
The preparation method of magnalium indium rare earth anode material of the invention, simple process and low cost are easy to promote and utilize.
In some embodiments of magnalium indium rare earth anode material of the invention, the melting mixing liquid is in protective gas
Under protection, aluminium, indium and aluminium-rare-earth alloy and/or magnesium-rare earth are added after taking magnesium to melt, melting is mixed, then kept the temperature
It arrives.
The protective gas is not particularly limited, the protective atmosphere used when can be prior art preparation magnesium alloy.Institute
Stating protective gas is at least one of argon gas, sulfur hexafluoride.
In some embodiments of magnalium indium rare earth anode material of the invention, the aluminium-rare-earth alloy is aluminium-lanthanum conjunction
At least one of gold, aluminium-cerium alloy.The mass fraction of rare earth element is 10% in aluminium-rare-earth alloy.
In some embodiments of magnalium indium rare earth anode material of the invention, the magnesium-rare earth is that magnesium-lanthanum closes
At least one of gold, magnesium-cerium alloy.The mass fraction of rare earth element is 10% in magnesium-rare earth.
The temperature of the fusing is 680 DEG C~720 DEG C.
The temperature of the heat preservation is 730 DEG C~780 DEG C, and the time is 5min~10min.
The present invention also provides a kind of magnesium air battery, including anode, cathode and electrolyte, the anode is above-mentioned magnesium
Aluminium indium rare earth anode material.
Magnalium indium rare earth air cell of the invention, using magnalium indium rare earth anode material of the invention, monocell is being put
Electric current density is 5~100mA/cm2The electromotive force of test 5h is 1.50V~1.79V in range, can satisfy neutral magnesium-sky
The requirement of pneumoelectric pond high current density discharge.
In some embodiments of magnesium air battery of the invention, contain chloride ion in the electrolyte.Magnesium of the invention
Indium in aluminium indium rare earth anode material can promote chloride ion in the absorption of anode surface, play the role of destroying passivating film, from
And maintain the stronger activity of electrode.In order to obtain containing the electrolyte of chloride ion, the electrolyte used when preparing electrolyte includes
Chloride, such as sodium chloride.
In some embodiments of magnesium air battery of the invention, in the electrolyte concentration of chloride ion be 0.2~
2mol/L。
In some embodiments of magnesium air battery of the invention, the cathode has the conventional knot of magnesium air cell cathode
Structure such as includes Catalytic Layer, collector and waterproof ventilative layer.
Below in conjunction with specific embodiment, further description of the technical solution of the present invention.
The embodiment 1 of magnalium indium rare earth anode material
The magnalium indium rare earth anode material of the present embodiment, consists of the following mass percentage components: Al 6.0%, In
1.0%, La 1.0%, surplus are Mg and inevitable impurity.
The embodiment 2 of magnalium indium rare earth anode material
The magnalium indium rare earth anode material of the present embodiment, consists of the following mass percentage components: Al 5.0%, In
4.0%, La 2.0%, surplus are Mg and inevitable impurity.
The embodiment 3 of magnalium indium rare earth anode material
The magnalium indium rare earth anode material of the present embodiment, consists of the following mass percentage components: Al 8.0%, In
0.8%, La 1.5%, surplus are Mg and inevitable impurity.
The embodiment 4 of magnalium indium rare earth anode material
The magnalium indium rare earth anode material of the present embodiment, consists of the following mass percentage components: Al 7.0%, In
2.0%, La 3.0%, surplus are Mg and inevitable impurity.
The embodiment 5 of magnalium indium rare earth anode material
The magnalium indium rare earth anode material of the present embodiment, consists of the following mass percentage components: Al 0.5%, In
5%, Ce 0.1%, surplus are Mg and inevitable impurity.
The embodiment 6 of magnalium indium rare earth anode material
The magnalium indium rare earth anode material of the present embodiment, consists of the following mass percentage components: Al 3.0%, In
0.02%, Ce 5.0%, surplus are Mg and inevitable impurity.
The embodiment 7 of magnalium indium rare earth anode material
The magnalium indium rare earth anode material of the present embodiment, consists of the following mass percentage components: Al 10.0%, In
3.0%, Ce 3.5%, surplus are Mg and inevitable impurity.
The embodiment 8 of magnalium indium rare earth anode material
The magnalium indium rare earth anode material of the present embodiment, consists of the following mass percentage components: Al 2.0%, In
3.0%, Ce 4.0%, surplus are Mg and inevitable impurity.
The embodiment 9 of magnalium indium rare earth anode material
The magnalium indium rare earth anode material of the present embodiment, consists of the following mass percentage components: Al 2.0%, In
3.0%, Ce 2.0%, La 2.0%, surplus are Mg and inevitable impurity.
Magnalium indium rare earth anode material in the Examples 1 to 9 of magnalium indium rare earth anode material, which uses, to be included the following steps
Preparation method prepared:
The embodiment 1 of the preparation method of magnalium indium rare earth anode material
According to the composition of magnalium indium rare earth anode material take magnesium ingot, aluminium ingot, magnesium-rare earth intermediate alloy (Mg-10%Re) with
And the indium grain using aluminium foil package；Magnesium ingot is put into ZGJL0.01-40-4 induction melting furnace graphite crucible, argon gas and six are filled with
Sulfur fluoride；Under argon gas and sulfur hexafluoride protection, is kept the temperature, made magnesium ingot in ZGJL0.01-40-4 controlled at 700 DEG C
It is all melted in induction melting furnace graphite crucible, aluminium ingot, magnesium-rare earth intermediate alloy (Mg-10% is then added in graphite crucible
Re), the aluminium foil of indium grain and package indium grain, keeping 680 DEG C of temperature to rotate graphite crucible in heating mixes molten metal
Uniformly, continue to be heated to 780 DEG C of heat preservation 5min, pour into blocky slab ingot.
The embodiment 2 of the preparation method of magnalium indium rare earth anode material
According to the composition of magnalium indium rare earth anode material take magnesium ingot, aluminium ingot, magnesium-rare earth intermediate alloy (Mg-10%Re) with
And the indium grain using aluminium foil package；Magnesium ingot is put into ZGJL0.01-40-4 induction melting furnace graphite crucible, argon gas and six are filled with
Sulfur fluoride；Under argon gas and sulfur hexafluoride protection, is kept the temperature, made magnesium ingot in ZGJL0.01-40-4 controlled at 700 DEG C
It is all melted in induction melting furnace graphite crucible, aluminium ingot, magnesium-rare earth intermediate alloy (Mg-10% is then added in graphite crucible
Re), the aluminium foil of indium grain and package indium grain, keeping 720 DEG C of temperature to rotate graphite crucible in heating mixes molten metal
Uniformly, continue to be heated to 730 DEG C of heat preservation 10min, pour into blocky slab ingot.
The embodiment 3 of the preparation method of magnalium indium rare earth anode material
According to the composition of magnalium indium rare earth anode material take magnesium ingot, aluminium ingot, magnesium-rare earth intermediate alloy (Mg-10%Re) with
And the indium grain using aluminium foil package；Magnesium ingot is put into ZGJL0.01-40-4 induction melting furnace graphite crucible, argon gas and six are filled with
Sulfur fluoride；Under argon gas and sulfur hexafluoride protection, is kept the temperature, made magnesium ingot in ZGJL0.01-40-4 controlled at 700 DEG C
It is all melted in induction melting furnace graphite crucible, aluminium ingot, magnesium-rare earth intermediate alloy (Mg-10% is then added in graphite crucible
Re), the aluminium foil of indium grain and package indium grain, keeping 700 DEG C of temperature to rotate graphite crucible in heating mixes molten metal
Uniformly, continue to be heated to 760 DEG C of heat preservation 6min, pour into blocky slab ingot.
Magnalium indium rare earth anode material in the Examples 1 to 4 of magnalium indium rare earth anode material is dilute using above-mentioned magnalium indium
When prepared by the preparation method in the Examples 1 to 3 of the preparation method of native anode material, closed among used magnesium-rare earth
Gold is Mg-10%La；Magnalium indium rare earth anode material in the embodiment 5~8 of magnalium indium rare earth anode material uses above-mentioned magnesium
When prepared by the preparation method in the Examples 1 to 3 of the preparation method of aluminium indium rare earth anode material, used magnesium-rare earth
Intermediate alloy is Mg-10%Ce；Magnalium indium rare earth anode material in the embodiment 9 of magnalium indium rare earth anode material is using above-mentioned
When prepared by the preparation method in the Examples 1 to 3 of the preparation method of magnalium indium rare earth anode material, used magnesium-is dilute
Native intermediate alloy is Mg-5%Ce-5%La.
The embodiment of magnesium air battery
The magnesium air battery of the present embodiment, including anode, cathode and electrolyte；Cathode by Catalytic Layer, waterproof ventilative layer and
Nickel screen conducting matrix grain stacks gradually composition, and electrolyte is sodium chloride solution, and anode is the embodiment 1 of magnalium indium rare earth anode material
Aluminum magnesium rare earth anode material in~9 (is all made of preparation method in the embodiment 1 of the preparation method of magnalium indium rare earth anode material
It is made), the catalyst of Catalytic Layer is nanometer MnO2；When using different magnalium indium rare earth anode materials, the electrolysis of magnesium air battery
The concentration of sodium chloride is shown in Table 1 in liquid.
The concentration of sodium chloride in electrolyte when the different magnalium indium rare earth anode material of table 1 is as anode
Comparative example 1
The magnesium air battery of this comparative example, except anode is 3N magnesium anode (the pure Mg that 3N magnesium is 99.9%), electrolyte is dense
Degree is outside the sodium chloride solution of 0.6mol/L, remaining is completely the same as the embodiment of magnesium air battery.
Comparative example 2
The magnesium air battery of this comparative example, in addition to used anode material consists of the following mass percentage components:
Aluminium 7.5%, cerium 1.5%, surplus are magnesium and inevitable impurity；Remaining is completely the same as the comparative example 1 of magnesium air battery.
The anode that this comparative example uses is prepared according to method comprising the following steps:
Magnesium ingot, aluminium ingot and magnesium-rare earth intermediate alloy (Mg-10%Ce) are taken according to the composition of anode material；Magnesium ingot is put into
In ZGJL0.01-40-4 induction melting furnace graphite crucible, it is filled with argon gas and sulfur hexafluoride；Under argon gas and sulfur hexafluoride protection,
It is kept the temperature controlled at 700 DEG C, makes in ZGJL0.01-40-4 induction melting furnace graphite crucible all to melt magnesium ingot,
Then aluminium ingot, magnesium-rare earth intermediate alloy (Mg-10%Ce) are added in graphite crucible, 700 DEG C of temperature is kept to revolve in heating
Turning graphite crucible is uniformly mixed molten metal, continues to be heated to 760 DEG C of heat preservation 6min, pours into blocky slab ingot.
Experimental example
Take the magnesium in the embodiment of above-mentioned magnesium air battery using the magnesium air battery of different anodes and comparative example 1~2
Air cell tests discharge performance (open circuit potential, operating potential, anode of the magnesium air battery under different discharge current densities
Efficiency), discharge time 5h；And the anode that each magnesium air battery uses is tested using weight-loss method and is electrolysed in corresponding magnesium air battery
Self-corrosion rate under static state in liquid, testing time 10h；Test result is shown in Table 2.
The discharge performance and self-corrosion rate of each magnesium air battery of table 2
As shown in Table 2, the magnalium indium rare earth anode material compared to comparative example, in the embodiment of magnalium indium rare earth anode material
The self-corrosion rate of material in the electrolytic solution is reduced, and open circuit potential is significantly negative to move, and operating potential and anode efficiency are significantly raised.
Claims (7)
1. a kind of magnalium indium rare earth anode material, it is characterised in that: consist of the following mass percentage components: aluminium 0.5~
10%, indium 0.02~5%, rare earth element 0.1~5%, surplus is magnesium and inevitable impurity.
2. magnalium indium rare earth anode material according to claim 1, it is characterised in that: the rare earth element is lanthanum, in cerium
At least one.
3. magnalium indium rare earth anode material according to claim 1, it is characterised in that: inevitable impurity accounts for magnalium indium
The mass percent of rare earth anode material is no more than 0.1%.
4. a kind of preparation method of magnalium indium rare earth anode material as described in claim 1, it is characterised in that: including following step
It is rapid: protective gas protection under, by the melting mixing liquid being mainly made of magnesium, aluminium, indium and rare earth element solidify to get.
5. the preparation method of magnalium indium rare earth anode material according to claim 4, it is characterised in that: the melting mixing
Liquid is that aluminium, indium and aluminium-rare-earth alloy and/or magnesium-rare earth, melting are added after taking magnesium to melt under protective gas protection
It mixes, then heat preservation obtains.
6. a kind of magnesium air battery, including anode, electrolyte and cathode, it is characterised in that: the anode is such as claim 1 institute
The magnalium indium rare earth anode material stated.
7. magnesium air battery according to claim 6, it is characterised in that: contain chloride ion in the electrolyte.
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