CN103774011B - A kind of cast electrode material and preparation method - Google Patents

A kind of cast electrode material and preparation method Download PDF

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CN103774011B
CN103774011B CN201410076160.4A CN201410076160A CN103774011B CN 103774011 B CN103774011 B CN 103774011B CN 201410076160 A CN201410076160 A CN 201410076160A CN 103774011 B CN103774011 B CN 103774011B
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alloy
raw material
electrode material
crucible
preparation
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CN103774011A (en
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王玲
赵浩峰
陈文兵
潘子云
龚国庆
曹燕子
柯维雄
赵佳玉
郑泽昌
王易秋
徐小雪
何晓蕾
陆阳平
王冰
邱奕婷
宋超
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Jiangsu Di Cheng photoelectric materials Co., Ltd.
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Nanjing University of Information Science and Technology
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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 belongs to metal material field, be specifically related to a kind of cast electrode material and preparation method.The invention provides a kind of cast electrode material, the operating potential negative value of this alloy material is higher; The present invention also provides a kind of cast electrode material preparation method, and this preparation method's technique is simple, and production cost is low, is suitable for suitability for industrialized production.Cast electrode material of the present invention, does is the weight percentage of each composition: Sc0.1-0.3%, Th0.03-0.05%, As0.04-0.08%, Fe? 0.3-0.5%, Os0.02-0.04%, Se1-2%, all the other are Mg.

Description

A kind of cast electrode material and preparation method
Technical field
The invention belongs to metal material field, relate to a kind of cast electrode material and preparation method.
Background technology
CN201310222515.1 relates to a kind of aluminum alloy anode material, relates to a kind of aluminum alloy anode material of containing metal elemental vanadium specifically; The invention still further relates to the preparation method of this aluminum alloy anode material.This aluminum alloy anode material comprises aluminium, magnesium, tin and indium, also comprises vanadium; Above-mentioned elementary composition is according to mass percentage meter, and Mg is 0.5-5%, V be 0.01-0.2%, Sn be 0.01-0.4%, In is 0.01-0.3%, and surplus is metallic aluminium.But this aluminum alloy anode material operating potential negative value is on the low side.
Summary of the invention
Object of the present invention is exactly for above-mentioned technological deficiency, provides a kind of cast electrode material, and the operating potential negative value of this alloy material is higher.
Another object of the present invention is to provide a kind of cast electrode material preparation method, and this preparation method's technique is simple, and production cost is low, is suitable for suitability for industrialized production.
Technical solution of the present invention is as follows:
A kind of cast electrode material, it is characterized in that, the weight percentage of each composition is: Sc0.1-0.3%, Th0.03-0.05%, As0.04-0.08%, Fe0.3-0.5%, Os0.02-0.04%, Se1-2%, and all the other are Mg.
A preparation method for cast electrode material, is characterized in that, comprises the following steps:
1) first prepare burden according to mentioned component, raw material Sc, Th, As, Fe, Os, Se, Mg add with pure substance form, and purity is all greater than 99.9%;
2) adopt crucible electrical resistance furnace molten alloy raw material, first by crucible heating to 450 ~ 500 DEG C, then sprinkle at sidewall of crucible and bottom even the magnesium flux accounting for alloy raw material weight 3-5%; Then alloy raw material is put into crucible, the magnesium flux accounting for alloy raw material weight 0.8-1.5% is sprinkled again on alloy raw material, then heating crucible, after crucible interalloy raw material all melts, dial the slag gone on liquid level, be sprinkled into the magnesium flux accounting for alloy raw material weight 4-6%, then crucible is warming up to 720-740 DEG C, after insulation 4-8min, fused solution alloy is poured in casting mold;
3) before cast, casting mold first puts into the container being full of liquid nitrogen, to stop after 20-30 minute taking-up, after taking-up in 4-8 minute by step 2) fused solution alloy pours into the die cavity of casting mold, obtains alloy bar; After casting complete 10-20 minute, taken out by alloy bar and put into chamber type electric resistance furnace and heat, be heated to 110-120 DEG C from casting mold, insulation 20-30 minute, namely obtains cast electrode material.
Step 2) in the weight percent content of magnesium flux be: MgCl 229-36%, CaF 214-17%, NaCl3-5%, CaCl 23-4%, MgO0.5-0.9%, AgCl0.5-1%, CsCl1.1-1.4%, all the other are KCl.
In step 3), casting mold makes by the following method: each composition is atlapulgite 3-4% by weight percentage, kaolinite 3-4%, water 6-8%, boric acid 1-2%, and all the other are prepared burden for zircon sand; After manually hitting solid yardage method casting mold is carried out, be placed in 120-130 DEG C of stove and harden taking-up in 20-30 minute, be cooled to room temperature.
The chemical composition of described atlapulgite is: Al 2o 316-19%, Fe 2o 32-3%, FeO0.1-0.2%, TiO0.1-0.2%, CaO1-3%, MgO4-6%, MnO0.1-0.2%, K 2o0.5-0.8%, Na 2o0.1-0.3%, P 2o 50.02-0.05%, all the other are SiO 2; Kaolinic chemical formula is Al 4[Si 4o 10] (OH) 8, the composition of zircon sand is ZrO 265-68%, all the other are SiO 2; Atlapulgite and kaolinite are powdery, and powder is of a size of 2-4 micron, and zircon sand is granular, is of a size of 200-250 micron.
Length and width, the thick size of step 3) interalloy bar are respectively 150-200mm, 80-100mm, 15-20mm.
beneficial effect of the present invention:
Cast electrode material of the present invention is through chill casting casing and after having low temperature Homogenization Treatments, anode material is organized more even, has comparatively negative corrosion potential and operating potential, good anodic polarization performance, after showing Homogenization Treatments, anode material chemical property can be improved.Os element interaction puies forward heavy alloyed oxidation-resistance; In pure magnesium, add alloying element Se and Th, current potential is negative to be moved; After adding alloying element As, polarization curve change is mild; Mg and Fe element can form eutectic structure; After adding alloying element Sc, material structure refinement, open circuit potential is negative to be moved.
Compared with prior art, material operating potential of the present invention is negative, low from erosion rate.In the present invention's preparation, a large amount of use your element rare, institute's raw materials cost of getting reduces; Alloy is through cooling comparatively fast in addition, ensure that the homogeneity of alloying constituent, structure and properties, therefore also just ensure that the quality of alloy.This alloy preparation technology is easy, and process is simple, and the alloy of production has good performance, is very convenient to suitability for industrialized production.Alloy material of the present invention can be applied to electrode industry.
Molten alloy is poured into the die cavity of casting mold by the present invention, adopt the mode that cooling, thermal treatment and alloying fast combine, both the phase size in alloy had effectively been reduced, ensure being uniformly distributed of chemical composition, ensure that the magnetic property of alloy, also greatly reduced the internal stress cooling fast and cause by gradient process, also ensure that the mechanical property of alloy.
Accompanying drawing explanation
Fig. 1 is material structure figure prepared by the embodiment of the present invention one.
As seen from Figure 1, the homogeneous microstructure prepared of the present invention is fine and close.
Embodiment
Raw materials used as follows in following embodiment:
The chemical composition of atlapulgite is: Al 2o 316-19%, Fe 2o 32-3%, FeO0.1-0.2%, TiO0.1-0.2%, CaO1-3%, MgO4-6%, MnO0.1-0.2%, K 2o0.5-0.8%, Na 2o0.1-0.3%, P 2o 50.02-0.05%, all the other are SiO 2; Atlapulgite is powdery, and powder is of a size of 2-4 micron.
Kaolinic chemical formula is Al 4[Si 4o 10] (OH) 8, kaolinite is powdery, and powder is of a size of 2-4 micron.
The composition of zircon sand is ZrO 265-68%, all the other are SiO 2; Zircon sand is granular, is of a size of 200-250 micron.
embodiment one:
Cast electrode material of the present invention, the weight percentage of each composition is: Sc0.1%, Th0.03%, As0.04%, Fe0.3%, Os0.02%, Se1%, and all the other are Mg.
The preparation method of cast electrode material of the present invention, comprises the following steps:
1) first prepare burden according to mentioned component, raw material Sc, Th, As, Fe, Os, Se, Mg add with pure substance form, and purity is all greater than 99.9%;
2) adopt crucible electrical resistance furnace molten alloy raw material, first by crucible heating to 450 DEG C, then sprinkle at sidewall of crucible and bottom even the magnesium flux accounting for alloy raw material weight 3%; Then alloy raw material is put into crucible, the magnesium flux accounting for alloy raw material weight 0.8% is sprinkled again on alloy raw material, then heating crucible, after crucible interalloy raw material all melts, dial the slag gone on liquid level, be sprinkled into the magnesium flux accounting for alloy raw material weight 4%, again crucible is warming up to 720 DEG C, insulation 4min, object makes alloy homogenizing, then pours in casting mold by fused solution alloy; The weight percent content of described magnesium flux is: MgCl 229%, CaF 214%, NaCl3%, CaCl 23%, MgO0.5%, AgCl0.5%, CsCl1.1%, all the other are KCl; Described casting mold makes by the following method: each composition is atlapulgite 3% by weight percentage, kaolinite 3%, water 6%, boric acid 1%, all the other are prepared burden for zircon sand, after manually hitting solid yardage method and being carried out by casting mold, be placed in 120 DEG C of stove sclerosis to take out for 20 minutes, be cooled to room temperature;
3) before cast, casting mold first puts into the container being full of liquid nitrogen, to stop after 20 minutes taking-up, after taking-up in 4 minutes by step 2) fused solution alloy pours into the die cavity of casting mold, obtain alloy bar, length and width, the thick size of alloy bar are respectively 150mm, 80mm, 15mm; Temperature during cast in die cavity is-165 ~-175 DEG C, and casting complete is after 10 minutes, is taken out by alloy bar to put into chamber type electric resistance furnace and heat from casting mold, is heated to 110 DEG C, is incubated 20 minutes, namely obtains cast electrode material.
embodiment two:
Cast electrode material of the present invention, the weight percentage of each composition is: Sc0.3%, Th0.05%, As0.08%, Fe0.5%, Os0.04%, Se2%, and all the other are Mg.
The preparation method of cast electrode material of the present invention, comprises the following steps:
1) first prepare burden according to mentioned component, raw material Sc, Th, As, Fe, Os, Se, Mg add with pure substance form, and purity is all greater than 99.9%;
2) adopt crucible electrical resistance furnace molten alloy raw material, first by crucible heating to 500 DEG C, then sprinkle at sidewall of crucible and bottom even the magnesium flux accounting for alloy raw material weight 5%; Then alloy raw material is put into crucible, the magnesium flux accounting for alloy raw material weight 1.5% is sprinkled again on alloy raw material, then heating crucible, after crucible interalloy raw material all melts, dial the slag gone on liquid level, be sprinkled into the magnesium flux accounting for alloy raw material weight 6%, again crucible is warming up to 740 DEG C, insulation 8min, object makes alloy homogenizing, then pours in casting mold by fused solution alloy; The weight percent content of described magnesium flux is: MgCl 236%, CaF 217%, NaCl5%, CaCl 24%, MgO0.9%, AgCl1%, CsCl1.4%, all the other are KCl; Described casting mold makes by the following method: each composition is atlapulgite 4% by weight percentage, kaolinite 4%, water 8%, boric acid 2%, all the other are prepared burden for zircon sand, after manually hitting solid yardage method and being carried out by casting mold, be placed in 130 DEG C of stove sclerosis to take out for 30 minutes, be cooled to room temperature;
3) before cast, casting mold first puts into the container being full of liquid nitrogen, to stop after 30 minutes taking-up, after taking-up in 8 minutes by step 2) fused solution alloy pours into the die cavity of casting mold, obtain alloy bar, length and width, the thick size of alloy bar are respectively 200mm, 100mm, 20mm; Temperature during cast in die cavity is-165 ~-175 DEG C, and casting complete is after 20 minutes, is taken out by alloy bar to put into chamber type electric resistance furnace and heat from casting mold, is heated to 120 DEG C, is incubated 30 minutes, namely obtains cast electrode material.
embodiment three:
Cast electrode material of the present invention, the weight percentage of each composition is: Sc0.2%, Th0.04%, As0.06%, Fe0.4%, Os0.03%, Se1.5%, and all the other are Mg.
The preparation method of cast electrode material of the present invention, comprises the following steps:
1) first prepare burden according to mentioned component, raw material Sc, Th, As, Fe, Os, Se, Mg add with pure substance form, and purity is all greater than 99.9%;
2) adopt crucible electrical resistance furnace molten alloy raw material, first by crucible heating to 475 DEG C, then sprinkle at sidewall of crucible and bottom even the magnesium flux accounting for alloy raw material weight 4%; Then alloy raw material is put into crucible, the magnesium flux accounting for alloy raw material weight 1.1% is sprinkled again on alloy raw material, then heating crucible, after crucible interalloy raw material all melts, dial the slag gone on liquid level, be sprinkled into the magnesium flux accounting for alloy raw material weight 5%, again crucible is warming up to 730 DEG C, insulation 6min, object makes alloy homogenizing, then pours in casting mold by fused solution alloy; The weight percent content of described magnesium flux is: MgCl 232%, CaF 216%, NaCl4%, CaCl 23.5%, MgO0.7%, AgCl0.7%, CsCl1.3%, all the other are KCl; Described casting mold makes by the following method: each composition is atlapulgite 3.5% by weight percentage, kaolinite 3.5%, water 7%, boric acid 1.5%, all the other are prepared burden for zircon sand, after manually hitting solid yardage method and being carried out by casting mold, be placed in 125 DEG C of stove sclerosis to take out for 25 minutes, be cooled to room temperature;
3) before cast, casting mold first puts into the container being full of liquid nitrogen, to stop after 25 minutes taking-up, after taking-up in 6 minutes by step 2) fused solution alloy pours into the die cavity of casting mold, obtain alloy bar, length and width, the thick size of alloy bar are respectively 175mm, 90mm, 17mm; Temperature during cast in die cavity is-165 ~-175 DEG C, and casting complete is after 15 minutes, is taken out by alloy bar to put into chamber type electric resistance furnace and heat from casting mold, is heated to 115 DEG C, is incubated 25 minutes, namely obtains cast electrode material.
embodiment four: (proportioning components is not in design of the present invention)
Cast electrode material of the present invention, the weight percentage of each composition is: Sc0.05%, Th0.01%, As0.03%, Fe0.2%, Os0.01%, Se0.5%, and all the other are Mg.
Preparation method's step of cast electrode material of the present invention is with embodiment one.
embodiment five: (proportioning components is not in design of the present invention)
Cast electrode material of the present invention, the weight percentage of each composition is: Sc0.4%, Th0.06%, As0.09%, Fe0.6%, Os0.06%, Se2.4%, and all the other are Mg.
Preparation method's step of cast electrode material of the present invention is with embodiment one.
Table one
As can be seen from table one, add the raising that Sc, Th, As, Fe, Os, Se element contributes to alloy cell performance.But exceed the scope that this case specifies, not only performance raising, reduce on the contrary.Reason is that these are too much, can aggravate the formation of bad compound between element, also reduce the useful effect of element.Sc, Th, Os element is too much, no longer works, waste starting material.

Claims (6)

1. a cast electrode material, is characterized in that: the weight percentage of each composition is: Sc0.1-0.3%, Th0.03-0.05%, As0.04-0.08%, Fe0.3-0.5%, Os0.02-0.04%, Se1-2%, and all the other are Mg.
2. the preparation method of cast electrode material described in claim 1, is characterized in that: comprise the following steps:
1) first prepare burden according to mentioned component, raw material Sc, Th, As, Fe, Os, Se, Mg add with pure substance form, and purity is all greater than 99.9%;
2) adopt crucible electrical resistance furnace molten alloy raw material, first by crucible heating to 450 ~ 500 DEG C, then sprinkle at sidewall of crucible and bottom even the magnesium flux accounting for alloy raw material weight 3-5%; Then alloy raw material is put into crucible, the magnesium flux accounting for alloy raw material weight 0.8-1.5% is sprinkled again on alloy raw material, then heating crucible, after crucible interalloy raw material all melts, dial the slag gone on liquid level, be sprinkled into the magnesium flux accounting for alloy raw material weight 4-6%, then crucible is warming up to 720-740 DEG C, after insulation 4-8min, fused solution alloy is poured in casting mold;
3) before cast, casting mold first puts into the container being full of liquid nitrogen, to stop after 20-30 minute taking-up, after taking-up in 4-8 minute by step 2) fused solution alloy pours into the die cavity of casting mold, obtains alloy bar; After casting complete 10-20 minute, taken out by alloy bar and put into chamber type electric resistance furnace and heat, be heated to 110-120 DEG C from casting mold, insulation 20-30 minute, namely obtains cast electrode material.
3. the preparation method of cast electrode material according to claim 2, is characterized in that: step 2) in the weight percent content of magnesium flux be: MgCl 229-36%, CaF 214-17%, NaCl3-5%, CaCl 23-4%, MgO0.5-0.9%, AgCl0.5-1%, CsCl1.1-1.4%, all the other are KCl.
4. the preparation method of cast electrode material according to claim 2, it is characterized in that: in step 3), casting mold makes by the following method: each composition is atlapulgite 3-4% by weight percentage, kaolinite 3-4%, water 6-8%, boric acid 1-2%, all the other are prepared burden for zircon sand; After manually hitting solid yardage method casting mold is carried out, be placed in 120-130 DEG C of stove and harden taking-up in 20-30 minute, be cooled to room temperature.
5. the preparation method of cast electrode material according to claim 4, is characterized in that: the chemical composition of described atlapulgite is: Al 2o 316-19%, Fe 2o 32-3%, FeO0.1-0.2%, TiO0.1-0.2%, CaO1-3%, MgO4-6%, MnO0.1-0.2%, K 2o0.5-0.8%, Na 2o0.1-0.3%, P 2o 50.02-0.05%, all the other are SiO 2; Kaolinic chemical formula is Al 4[Si 4o 10] (OH) 8, the composition of zircon sand is ZrO 265-68%, all the other are SiO 2; Atlapulgite and kaolinite are powdery, and powder is of a size of 2-4 micron, and zircon sand is granular, is of a size of 200-250 micron.
6. the preparation method of cast electrode material according to claim 2, is characterized in that: length and width, the thick size of step 3) interalloy bar are respectively 150-200mm, 80-100mm, 15-20mm.
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CN104152767B (en) * 2014-08-22 2016-11-02 济南大学 A kind of high-ductility Mg-Al-Mn-Se magnesium alloy
CN107824742B (en) * 2017-11-27 2019-08-02 河南博威热能科技有限公司 A kind of amorphous state moulding sand for casting and its manufacturing method
CN109881057A (en) * 2019-03-08 2019-06-14 安徽信息工程学院 A kind of high-strength and high ductility material and preparation method thereof
CN109763039A (en) * 2019-03-08 2019-05-17 安徽信息工程学院 A kind of high-strength aluminum alloy material and preparation method thereof

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US4792430A (en) * 1987-07-24 1988-12-20 Aluminum Company Of America Aluminum anode alloy
CN1354893A (en) * 1999-04-20 2002-06-19 津克空气动力公司 Lanthanum nickel compound/metal mixture as third electrode in metal-air battery

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JPS5112441A (en) * 1974-07-19 1976-01-31 Matsushita Electric Ind Co Ltd KOSHUHAKANETSUKI
AU2002239222A1 (en) * 2000-06-23 2002-07-08 Millenium Energy, Llc Novel compositions for use in batteries, capacitors, fuel cells and for hydrogen production
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US4792430A (en) * 1987-07-24 1988-12-20 Aluminum Company Of America Aluminum anode alloy
CN1354893A (en) * 1999-04-20 2002-06-19 津克空气动力公司 Lanthanum nickel compound/metal mixture as third electrode in metal-air battery

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