CN104018018B - A kind of novel aluminum-air fuel cell anode material Al-Sn-Bi-Mn working method - Google Patents

Abstract

The invention discloses a kind of novel aluminum-air fuel cell anode material Al-Sn-Bi-Mn working method, first prepare Al-Sn-Bi-Mn alloy billet by powder metallurgy route, then by extruding and rolling process Al-gas battery anode sheet material further.This process routes can effectively overcome Sn, Bi element due to than great, temperature of solidification is low and the component segregation caused and tissue odds one problem, and promotes activating element Sn solid solution in Al matrix.The aluminum anode material adopting this process routes to prepare has that current potential is high, low from erosion rate, continuous surface activation, stable electrochemical property advantage.

Description

A kind of novel aluminum-air fuel cell anode material Al-Sn-Bi-Mn working method

Technical field

The present invention relates to a kind of novel aluminum-air fuel cell anode material Al-Sn-Bi-Mn alloy working method, belong to materials processing technology field.

Background technology

The contradiction of current social development and the energy, environment grows in intensity, energy dilemma and environmental degradation become human needs common faced by a challenge.Present stage, urban inhabitant income increased rapidly along with the raising of national power, and China becomes huge Automobile Market.According to statistics, end 2013 the end of the year every ten people of China just have an automobile, total vehicle reaches 1.37 hundred million.China's resident's automobile pollution sharply rises, and motor vehicle exhaust total amount straight line rises, the haze now can't get rid of frequently in overhead, the big city such as Beijing, Shanghai.In order to solve the contradiction of social development and environmental bearing capacity, human development is cleaned zero release energy paces and was never stopped.As a kind of high-efficiency cleaning energy carrier, metallic aluminium just obtains as the feasibility of fuel should demonstrate,prove as far back as the sixties in 20th century.Compared with other metal-air battery anode material, aluminium not only proportion is little, and energy density is higher, and its specific energy is only second to metal Li, and actual mass specific energy is up to 450Wh/Kg.In addition, Al element is the abundantest metallic elements of earth's crust reserves, and cost is only about 3% of Li.Be the new forms of energy of clean, sustainable use of a kind of low cost, environmental protection, Al-gas battery can be widely used in the fields such as 3C electronics, new-energy automobile and underwater submarine.

Al-gas battery especially has very bright and clear application prospect in new-energy automobile field.3 ~ 7 February of this year, Phinergy company of metal-air battery industry leader Israel is on U.S. Atlanta " AdvancedAutomotiveBatteryConference " (meeting of advanced automobile battery), show the aluminium-aerodynamic force battery of a excellent performance, battery is altogether containing 50 blocks of aluminium sheets, the energy that every block aluminium sheet produces all can drive separately 20 miles, automobile, and whole battery durable mileage can reach 1000 miles (being roughly equal to 1600 kms).Phinergy company makes people see the dawn of new forms of energy in the last word in Al-gas battery field undoubtedly.

High surface, low from erosion rate aluminum alloy anode material preparation technology be one of gordian technique manufacturing Al-gas battery.Present stage Al anode material exists subject matter to be had: in neutral or salt ionogen, aluminum anode material surface easily forms the fine and close passive film of one deck, causes current potential to decline rapidly; In strong alkaline electrolytes, aluminum anode passivating material phenomenon is eliminated to a certain extent, but wherein Fe, Si impurity element causes aluminum anode liberation of hydrogen and accelerates from erosion rate, accelerates aluminum anode local corrosion of material; The general rafifinal (99.999%) that adopts in alkaline cell is as anode material at present, and high manufacturing cost makes Al-gas battery not have industrial application meaning.Existing research work develop some ternarys even quaternary or five yuan of aluminium alloys substitute pure Al anode material, be intended to strengthen aluminum anode material surface active, improve chemical property.Add Mn element to alleviate the harm of Fe, Si element simultaneously.These alloying elements add alone or in combination, improve the surfactivity of aluminum anode material to a certain extent, inhibit aluminum anode material from erosion rate.

Foreign study shows that Sn, Bi and Ga element is still the most effective surface active element of aluminum anode material, and microalloying principle is still the optimal selection of aluminum anode material alloys.Because Sn, Bi element fusing point is low and than great, the segregation phenomena that conventional fusion-cast technique very easily causes Sn, Bi element serious in Al matrix, cause that anode surface activation degree differs, reactivation process is discontinuous, thus cause the problems such as anode material non-uniform corrosion, too high from erosion rate, sequent surface does not activate.Therefore novel process approach how is developed, Sn element is made to be solid-solubilized in Al matrix to greatest extent, eliminate gravity segregation and process of setting segregation, to obtain that corrosion surface is smooth, reactivation process continuously consistent, from the low aluminum anode material of erosion rate, be that a problem anxious to be resolved developed by aluminum current anode material.

Summary of the invention

The present invention is directed to traditional founding and easily cause the serious proportion of Al-Sn-Bi-Mn material, process of setting segregation problems, a kind of novel aluminum-air fuel cell anode material Al-Sn-Bi-Mn alloy working method is proposed effectively to solve the problem, the weave construction be optimized, makes the chemical property of Al-Sn-Bi-Mn material significantly improve.

For achieving the above object, solution of the present invention is:

A kind of novel aluminum-air fuel cell anode material Al-Sn-Bi-Mn alloy working method, its step comprises:

The thermal sintering of step 1, blank: under nitrogen protection environment, be after the aluminium of the tin of 0.10 ~ 0.16, the bismuth of 0.15 ~ 0.20, the manganese of 0.01 ~ 0.02 and surplus fully mixes by weight percent, inject steel mould, after pressurization, heating, insulation, cooling forms blank;

The extrusion molding of step 2, blank: under nitrogen protection environment, is squeezed into sheet material and is cooled to room temperature formation slab by blank heating;

The rolling of step 3, slab: under nitrogen protection environment, divides heating of plate blank three passes to become sheet material, rolls rear water-cooled.

In described step 1, tin, bismuth, manganese and aluminium fully mix, until after mixing completely, inject with the cylindrical steel mould of piston 120mm, propelling piston makes mold cavity pressure rise to 60 ~ 80MPa, simultaneously by inner powder induction heating to 620 ~ 650 DEG C, after insulation 15 ~ 20min, water-cooled forms blank.

Be 100 × 10mm aluminium sheet by blank being squeezed into specification by 120mm behind blank induction heating to 480 ~ 560 DEG C in described step 2, extrusion temperature is 450 ~ 550 DEG C, and after extruding, water-spraying control forms slab to room temperature immediately;

In described step 3, the rolling of slab: under nitrogen protection environment, slab is heated to 380 ~ 480 DEG C in induction furnace, divide three passes to become the sheet material of thickness 1mm according to 10mm → 5mm → 1mm blank, rolling temperature is 350 ~ 450 DEG C, rolls rear water-cooled.

The present invention solves the technical problem of the present invention's proposition with powder metallurgy+hot-pressed+thermal treatment process approach.Adopt powder metallurgy route, under high-temperature and high-pressure conditions, thermal sintering is carried out after fully being mixed by Al, Sn, Bi powder of different ratios, make it in Al matrix, reach homogenizing by Sn, Bi element original position expanding effect, further extruding and roll forming process cause dislocation to spread making alloying constituent obtain further homogenization.This complete processing approach effectively can eliminate proportion, the process of setting segregation of Sn, Bi element, and can realize the maximum solid solution of Sn element in Al matrix.The Al anode product of preparation has that current potential is high, surfactant property good, from the low advantage of erosion rate.The art of this patent can advance Al-gas battery industrial-scale application process, to alleviating industrial development cause to environmental stress.

Embodiment

The invention discloses a kind of novel aluminum-air fuel cell anode material Al-Sn-Bi-Mn alloy working method, its step comprises:

The thermal sintering of step 1, blank: under nitrogen protection environment, be that the aluminium of the tin of 0.10 ~ 0.16, the bismuth of 0.15 ~ 0.20, the manganese of 0.01 ~ 0.02 and surplus fully mixes by weight percent, until after mixing completely, inject with the cylindrical steel mould of piston 120mm, propelling piston makes mold cavity pressure rise to 60 ~ 80MPa, simultaneously by inner powder induction heating to 620 ~ 650 DEG C, after insulation 15 ~ 20min, water-cooled forms blank;

The extrusion molding of step 2, blank: under nitrogen protection environment, be 100 × 10mm aluminium sheet by blank being squeezed into specification by 120mm behind blank induction heating to 480 ~ 560 DEG C, extrusion temperature is 450 ~ 550 DEG C, and after extruding, water-spraying control forms slab to room temperature immediately;

The rolling of step 3, slab: under nitrogen protection environment, is heated to 380 ~ 480 DEG C by slab in induction furnace, and divide three passes to become the sheet material of thickness 1mm according to 10mm → 5mm → 1mm blank, rolling temperature is 350 ~ 450 DEG C, rolls rear water-cooled.

Below in conjunction with embodiment, the invention will be further described.

embodiment one

Aluminium powder+18g glass putty+20g bismuth meal+2.0g the manganese powder of 12Kg is fully mixed, until after mixing completely, inject with the cylindrical steel mould of piston 120mm, propelling piston makes mold cavity pressure rise to about 60MPa, simultaneously by inner powder induction heating to 640 ± 10 DEG C, water-cooled after insulation 20min; Afterwards, it is 100 × 10mm aluminium sheet that blank is squeezed into specification by 120mm, and extrusion temperature is 530 ± 10 DEG C, after extruding immediately water-spraying control to room temperature; The sheet material (thickness 10mm → 5mm → 1mm) finally dividing three passes to become 1mm, rolling temperature is 430 ± 10 DEG C, rolls rear water-cooled.Slab carries out composition analysis along in rolling direction every 100mm sampling, gets five points altogether, analyzes and carry out on direct-reading spectrometer, composition tolerances <0.02% in test specification, and conventional continuous casting process composition tolerances >4.1%; Specification is become by extrusion billet car to be the ganoid spillikin of 6 × 50mm, test open circuit potential and current efficiency (testing standard: ASTMG97-1997 (2002)), current efficiency >55%, open circuit potential is 1.50 (-VvsSCE); Conventional continuous casting process current efficiency >40%, open circuit potential is 1.45 (-VvsSCE).Test result shows, the present invention to Al-Sn-Bi-Mn anode material components homogeneity and electro-chemical properties increase rate remarkable.

Embodiment two

Aluminium powder+18g glass putty+20g bismuth meal+2.0g the manganese powder of 12Kg is fully mixed, until after mixing completely, inject with the cylindrical steel mould of piston 120mm, propelling piston makes mold cavity pressure rise to about 80MPa, simultaneously by inner powder induction heating to 620 ± 10 DEG C, water-cooled after insulation 15min; Afterwards, it is 100 × 10mm aluminium sheet that blank is squeezed into specification by 120mm, and extrusion temperature is 440 ± 10 DEG C, after extruding immediately water-spraying control to room temperature; The sheet material (thickness 10mm → 5mm → 1mm) finally dividing three passes to become 1mm, rolling temperature is 360 ± 10 DEG C, rolls rear water-cooled; Slab carries out composition analysis along in rolling direction every 100mm sampling, gets five points altogether, analyzes and carry out on direct-reading spectrometer, composition tolerances <0.01% in test specification; Test open circuit potential and current efficiency (testing standard: ASTMG97-1997 (2002)), current efficiency >54%, open circuit potential is 1.51 (-VvsSCE); Test result shows, the present invention to Al-Sn-Bi-Mn anode material components homogeneity and electro-chemical properties increase rate remarkable.

Claims (1)

1. novel aluminum-air fuel cell anode material Al-Sn-Bi-Mn alloy working method, its step comprises:

The thermal sintering of step 1, blank: under nitrogen protection environment, be after the aluminium of the tin of 0.10 ~ 0.16, the bismuth of 0.15 ~ 0.20, the manganese of 0.01 ~ 0.02 and surplus fully mixes by weight percent, inject steel mould, propelling piston makes mold cavity pressure rise to 60 ~ 80MPa, simultaneously by inner powder induction heating to 620 ~ 650 DEG C, after insulation 15 ~ 20min, water-cooled forms blank;

The extrusion molding of step 2, blank: under nitrogen protection environment, be squeezed into sheet material by behind blank induction heating to 480 ~ 560 DEG C, extrusion temperature is 450 ~ 550 DEG C, and after extruding, water-spraying control forms slab to room temperature immediately;

The rolling of step 3, slab: under nitrogen protection environment, is heated to 380 ~ 480 DEG C by slab in induction furnace, and divide three passes to become the sheet material of thickness 1mm according to 10mm → 5mm → 1mm blank, rolling temperature is 350 ~ 450 DEG C, rolls rear water-cooled.