CN113897522A - 一种铝合金阳极材料及制备方法 - Google Patents
一种铝合金阳极材料及制备方法 Download PDFInfo
- Publication number
- CN113897522A CN113897522A CN202111282801.8A CN202111282801A CN113897522A CN 113897522 A CN113897522 A CN 113897522A CN 202111282801 A CN202111282801 A CN 202111282801A CN 113897522 A CN113897522 A CN 113897522A
- Authority
- CN
- China
- Prior art keywords
- rolling
- time
- temperature
- aluminum alloy
- anode material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 60
- 239000010405 anode material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000000956 alloy Substances 0.000 claims description 35
- 229910045601 alloy Inorganic materials 0.000 claims description 33
- 238000005096 rolling process Methods 0.000 claims description 31
- 229910052782 aluminium Inorganic materials 0.000 claims description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 26
- 238000000137 annealing Methods 0.000 claims description 21
- 238000003723 Smelting Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 238000005098 hot rolling Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 238000005097 cold rolling Methods 0.000 claims description 7
- 229910052733 gallium Inorganic materials 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 6
- 238000003801 milling Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- 229910052745 lead Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000000265 homogenisation Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 230000010287 polarization Effects 0.000 abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- -1 aluminum-silver oxide Chemical compound 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B37/00—Control devices or methods specially adapted for metal-rolling mills or the work produced thereby
- B21B37/74—Temperature control, e.g. by cooling or heating the rolls or the product
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
-
- 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
- C22C1/026—Alloys based on aluminium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/006—Alloys based on aluminium containing Hg
-
- 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
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
- C22F1/047—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with magnesium 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
- 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
- H01M4/463—Aluminium based
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
- B21B2003/001—Aluminium or its alloys
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Metal Rolling (AREA)
Abstract
一种铝合金阳极材料及制备方法,所述铝合金阳极材料包括以下质量百分数的组分:Mg 0.5~1.0%,Hg 0.01~0.20%,Ga 0.01~0.20%,Sn 0.02~0.20%,Pb 0.01~0.10%,Sb 0.02~0.20%,Ce 0.02~0.40%,余为Al。本发明方法还公开了所述铝合金阳极材料的制备方法。本发明铝合金阳极材料高活性、抗极化、电压平台高、析氢量低;本发明方法所得铝合金阳极材料抗腐蚀性强,工艺简单,成本低,适宜于工业化生产。
Description
技术领域
本发明涉及一种阳极材料及制备方法,具体涉及一种铝合金阳极材料及制备方法。
背景技术
Al/AgO电池是一种新型化学动力储备电池,具有体积小、比功率大、比能量高、激活快、无噪音、工作时不污染环境等优点。铝作为电池的阳极材料有电化当量高(2980A·h·kg-1),是除锂之外质量比能量最高的金属;电极电位较负(强碱性溶液中的标准电极电位为-2.35V);铝资源丰富,价格低廉;可广泛应用于碱性电池、中性电池和有机电池等优势。但由于纯铝是一种较活泼的两性金属材料,在碱性电解液中自腐蚀速度较快,并产生大量的氢气,并且自身极化严重,电流效率不高,削弱了其成为需要高的电压和低的腐蚀析氢速度的电池材料的优势。
目前,应用的较多的用于改善铝阳极材料性能的途径主要是:向铝中加入微量合金元素,制成铝合金,以提高铝合金电极电化学活性,减少自腐蚀速率,提高电流效率。
CN 106676343A公开了一种海水电池用铝合金阳极材料及其制备方法,铝合金中各组分质量百分比为:Mg0.4~1.2%、Ga0.01~0.2%、Sn0.01~0.3%、Bi0.01~0.1%、In0.01~0.1%、Pb0.01~0.1%和Ce0.01~0.5%。制备方法为:纯铝块先进行保温,然后在750℃~900℃条件下进行熔炼,再加入纯铝箔包覆的占铝质量百分比为0.4~1.2%Mg、0.01~0.2%Ga、0.01~0.3%Sn、0.01~0.1%Bi、0.01~0.1%In、0.01~0.1%Pb和0.01~0.5%Ce合金元素,保温,浇注于钢模中,均匀化后铣面,然后350~450℃轧制成板材,保温退火后,冷轧制,成品退火,得铝合金阳极材料。但是,所述铝合金材料在开路电压(最高1.920V)、工作时间(最高1285s)、析氢量(静态最低0.67mL/(min·cm2))上的性能欠佳。
CN 106917010A公开了一种铝合金阳极材料及其铸造方法与应用,所述铝合金阳极材料由以下组分铸造而成:Pb:0.01~0.1wt%;Sn:0.01~0.1wt%;Ga:0.01~0.2wt%;Ti:0.01~0.07wt%;余量为Al。所述铸造方法为:一、精炼合金:(1)分次将纯度为99.99%的纯铝块置入井式炉中, 将铝块加热到700~750℃进行熔化;(2)待所有的铝块完全融化后,将按一定配比称量好的微量金属元素加入到高温井式炉中;(3)待所有组分全部熔化后,使用石墨棒进行搅拌;(4)加入六氯乙烷,除去熔融铝中的废渣;二、浇铸成型:(1)在模具内表面涂上一层脱模剂,加热到150~250℃并保温;(2)将熔融的铝合金倒入模具中,将熔融的铝合金浇铸成铝锭。但是,所述铝合金阳极材料仅公开其开路电位可达-1.82V(vs.Hg/HgO),对于析氢量等关键材料性能参数并未公开。
CN 109778029 A公开了一种含稀土铝合金阳极材料及其制备方法和应用,所述含稀土铝合金阳极材料的组分及质量百分比含量为镁0.5~2%、锡0.02~0.12%、稀土元素0.01~1.0%,余量为铝;所述的稀土元素为锆或钇。所述制备方法是经750~780℃的熔炼浇注后,依次经均匀化处理、热轧固溶和时效处理后得到。但是,所述铝合金材料在开路电压(最高1.97V)、自腐蚀率(最低6.54mg/(cm2·h))上的性能欠佳,且未公开工作时间等关键材料性能参数。
发明内容
本发明所要解决的技术问题是,克服现有技术存在的上述缺陷,提供一种高活性、抗极化、电压平台高、析氢量低的铝合金阳极材料。
本发明进一步要解决的技术问题是,克服现有技术存在的上述缺陷,提供一种所得铝合金阳极材料抗腐蚀性强,工艺简单,成本低,适宜于工业化生产的铝合金阳极材料的制备方法。
本发明解决其技术问题所采用的技术方案如下:一种铝合金阳极材料,包括以下质量百分数的组分:Mg 0.5~1.0%,Hg 0.01~0.20%,Ga 0.01~0.20%,Sn 0.02~0.20%,Pb0.01~0.10%,Sb 0.02~0.20%,Ce 0.02~0.40%,余为Al。所述元素的选择和用量主要考虑了它们在铝中的溶解度、熔点以及溶质元素在凝固的晶界的液相析出等因素。当总的溶质元素含量较低时,对高温塑性影响较大,当总的溶质元素含量较高时,会产生强烈的阳极极化效应,影响材料的综合性能。
本发明进一步解决其技术问题所采用的技术方案如下:一种铝合金阳极材料的制备方法,包括以下步骤:
(1)制备Mg-Hg-Ga中间合金;
(2)先将纯铝块加热保温,升温熔炼,再依次将Sn、Pb、Sb、Ce和步骤(1)所得Mg-Hg-Ga中间合金加入铝液中,在通入保护性气体的过程中,进行保温熔炼,随炉降温进行变质处理,过滤,浇注后,得合金锭;
(3)将步骤(2)所得合金锭均匀化处理,铣面,热轧制,深冷轧制,成品退火,得铝合金阳极材料。
优选地,步骤(1)、(2)中,各金属的用量按照目标产物中各组分比例进行配制。
优选地,步骤(1)中,所述制备Mg-Hg-Ga中间合金的方法为:将Mg、Hg和Ga置于密封罐中,加热密封熔炼,在平地上倾倒≥3次,水冷,得Mg-Hg-Ga中间合金。
优选地,所述Mg、Hg、Ga的质量比为0.5~1.0:0.01~0.2:0.01~0.2。
优选地,所述加热密封熔炼的温度为720~740℃,时间为1~2h。
优选地,步骤(2)中,所述纯铝块的纯度≥99.996%。
优选地,步骤(2)中,所述加热保温的温度为350~450℃。
优选地,步骤(2)中,所述升温熔炼的温度为800~850℃,时间为50~70min。
优选地,步骤(2)中,所述保护性气体为氩气和/或氦气等。
优选地,步骤(2)中,所述保温熔炼的温度为800~850℃,时间为8~15min。
优选地,步骤(2)中,所述变质处理的温度为600~720℃,时间为1~2h。
优选地,步骤(2)中,所述浇注的温度为600~720℃。
优选地,步骤(3)中,所述均匀化处理的温度为460~600℃,时间为18~30h。
优选地,步骤(3)中,所述热轧制是指进行4~8道次的往复加热轧制,每一道次进行一次中间退火。
优选地,步骤(3)中,所述热轧制的温度为360~440℃,每次压下量为30~50%。
优选地,步骤(3)中,所述中间退火的温度为280~330℃,时间为100~120min。
优选地,步骤(3)中,所述热轧制后板材的厚度为1~2mm。
优选地,步骤(3)中,所述深冷轧制是指进行4~8道次的往复冷轧制,每一道次轧制前置于液氮中浸泡20~25min。
优选地,步骤(3)中,所述深冷轧制的总压下量为70~85%。
优选地,步骤(3)中,所述深冷轧制后板材的厚度为0.3~0.6mm。
优选地,步骤(3)中,所述成品退火的温度为200~230℃,时间为1~3h。
本发明所使用的其它金属原料的纯度均≥99.96%;本发明所使用的保护性气体均为纯度≥99.99%的高纯气体。
本发明的有益效果如下:
(1)本发明铝合金阳极材料高活性、抗极化、电压平台高、析氢量低;
(2)本发明方法所得铝合金阳极材料抗腐蚀性强,工艺简单,成本低,适宜于工业化生产。
附图说明
图1是本发明铝合金阳极材料实施例1~3和商用铝合金阳极1、2组装的Al-AgO电池的放电曲线。
具体实施方式
下面结合实施例和附图对本发明作进一步说明。
本发明实施例所使用的纯铝块的纯度≥99.996%,本发明实施例所使用的其它金属原料的纯度均≥99.98%;本发明所使用的保护性气体均为纯度≥99.99%的高纯气体;本发明实施例所使用的原料或化学试剂,如无特殊说明,均通过常规商业途径获得。
一种铝合金阳极材料实施例1~3
一种铝合金阳极材料实施例1~3的组分及重量份如表1所示。
表1 一种铝合金阳极材料实施例1~3的组分及重量份表
一种铝合金阳极材料的制备方法实施例1
(1)按照表1实施例1所述各原料及重量份,制备Mg-Hg-Ga中间合金;
所述制备Mg-Hg-Ga中间合金的方法为:将Mg、Hg和Ga置于密封罐中,在720℃下,加热密封熔炼2h,在平地上倾倒4次,水冷,得Mg-Hg-Ga中间合金;
(2)按照表1实施例1所述各原料及重量份,先将纯铝块在350℃下,加热保温,在800℃下,升温熔炼60min,再依次将Sn、Pb、Sb、Ce和步骤(1)所得Mg-Hg-Ga中间合金加入铝液中,在通入高纯氩气的过程中,在800℃下,进行保温熔炼15min,随炉降温至720℃进行变质处理2h,过滤,在720℃下,浇注于300mm×200mm×30mm的钢模后,得合金锭;
(3)将步骤(2)所得合金锭在500℃下,均匀化处理30h,铣面,在360℃下,进行8道次的往复加热轧制,每次压下量为30%,每一道次在280℃下,进行一次中间退火120min,至板材的厚度为1mm,进行8道次的往复冷轧制,每一道次轧制前置于液氮中浸泡20min,深冷轧制的总压下量为70%,至板材的厚度为0.4mm,在200℃下,成品退火3h,得铝合金阳极材料1。
如图1所示,本发明实施例所得铝合金阳极材料1相对于商用1、2铝合金阳极材料具有更负的恒流极化曲线和更高的工作电压。
一种铝合金阳极材料的制备方法实施例2
(1)按照表1实施例2所述各原料及重量份,制备Mg-Hg-Ga中间合金;
所述制备Mg-Hg-Ga中间合金的方法为:将Mg、Hg和Ga置于密封罐中,在730℃下,加热密封熔炼1.5h,在平地上倾倒3次,水冷,得Mg-Hg-Ga中间合金;
(2)按照表1实施例2所述各原料及重量份,先将纯铝块在400℃下,加热保温,在820℃下,升温熔炼70min,再依次将Sn、Pb、Sb、Ce和Mg-Hg-Ga中间合金加入铝液中,在通入高纯氩气的过程中,在820℃下,进行保温熔炼10min,随炉降温至650℃进行变质处理1.5h,过滤,在650℃下,浇注于300mm×200mm×30mm的钢模后,得合金锭;
(3)将步骤(2)所得合金锭在550℃下,均匀化处理24h,铣面,在400℃下,进行6道次的往复加热轧制,每次压下量为40%,每一道次在300℃下,进行一次中间退火110min,至板材的厚度为1.5mm,进行6道次的往复冷轧制,每一道次轧制前置于液氮中浸泡22min,深冷轧制的总压下量为75%,至板材的厚度为0.45mm,在220℃下,成品退火2h,得铝合金阳极材料2。
如图1所示,本发明实施例所得铝合金阳极材料2相对于商用1、2铝合金阳极材料具有更负的恒流极化曲线和更高的工作电压。
一种铝合金阳极材料的制备方法实施例3
(1)按照表1实施例3所述各原料及重量份,制备Mg-Hg-Ga中间合金;
所述制备Mg-Hg-Ga中间合金的方法为:将Mg、Hg和Ga置于密封罐中,在740℃下,加热密封熔炼1.0h,在平地上倾倒3次,水冷,得Mg-Hg-Ga中间合金;
(2)按照表1实施例3所述各原料及重量份,先将纯铝块在450℃下,加热保温,在850℃下,升温熔炼70min,再依次将Sn、Pb、Sb、Ce和步骤(1)所得Mg-Hg-Ga中间合金加入铝液中,在通入高纯氦气的过程中,在850℃下,进行保温熔炼8min,随炉降温至700℃进行变质处理1h,过滤,在700℃下,浇注于300mm×200mm×30mm的钢模后,得合金锭;
(3)将步骤(2)所得合金锭在600℃下,均匀化处理20h,铣面,在440℃下,进行4道次的往复加热轧制,每次压下量为50%,每一道次在320℃下,进行一次中间退火100min,至板材的厚度为2mm,进行4道次的往复冷轧制,每一道次轧制前置于液氮中浸泡25min,深冷轧制的总压下量为80%,至板材的厚度为0.5mm,在230℃下,成品退火1h,得铝合金阳极材料3。
如图1所示,本发明实施例所得铝合金阳极材料3相对于商用1、2铝合金阳极材料具有更负的恒流极化曲线和更高的工作电压。
为了评价实施例1~3所得铝合金阳极材料1~3的电化学性能,按照以下方法进行检测,结果如表2、3所示:
电池组装环境:在大气环境下组装成铝氧化银单体电池。
电流密度:600mA/cm2;
电液温度:80℃;
电液组成:4.5mol/L NaOH+20g/LNa2SnO3;
流量:151mL/min。
表2 实施例1~3和商用1、2铝合金阳极材料的恒流极化电位和静态析氢速率表
由表2可知,本发明铝合金阳极材料1~3相对于商用1、2铝合金阳极材料具有更高的恒流极化电位以及较低的静态析氢量。
表3 实施例1~3和商用1、2铝合金阳极材料的电性能数据表
由表3可知,本发明铝合金阳极材料1~3相对于商用1、2铝合金阳极材料具有更高的电压、15min工作时间平均电压和额定1.475V工作时间平均电压,以及更短的达到额定电压时间。
Claims (6)
1.一种铝合金阳极材料,其特征在于,包括以下质量百分数的组分:Mg 0.5~1.0%,Hg0.01~0.20%,Ga 0.01~0.20%,Sn 0.02~0.20%,Pb 0.01~0.10%,Sb 0.02~0.20%,Ce0.02~0.40%,余为Al。
2.一种如权利要求1所述铝合金阳极材料的制备方法,其特征在于,包括以下步骤:
(1)制备Mg-Hg-Ga中间合金;
(2)先将纯铝块加热保温,升温熔炼,再依次将Sn、Pb、Sb、Ce和步骤(1)所得Mg-Hg-Ga中间合金加入铝液中,在通入保护性气体的过程中,进行保温熔炼,随炉降温进行变质处理,过滤,浇注后,得合金锭;
(3)将步骤(2)所得合金锭均匀化处理,铣面,热轧制,深冷轧制,成品退火,得铝合金阳极材料。
3.根据权利要求2所述铝合金阳极材料的制备方法,其特征在于:步骤(1)中,所述制备Mg-Hg-Ga中间合金的方法为:将Mg、Hg和Ga置于密封罐中,加热密封熔炼,在平地上倾倒≥3次,水冷,得Mg-Hg-Ga中间合金;所述Mg、Hg、Ga的质量比为0.5~1.0:0.01~0.2:0.01~0.2;所述加热密封熔炼的温度为720~740℃,时间为1~2h。
4.根据权利要求2或3所述铝合金阳极材料的制备方法,其特征在于:步骤(2)中,所述纯铝块的纯度≥99.996%;所述加热保温的温度为350~450℃;所述升温熔炼的温度为800~850℃,时间为50~70min;所述保护性气体为氩气和/或氦气;所述保温熔炼的温度为800~850℃,时间为8~15min;所述变质处理的温度为600~720℃,时间为1~2h;所述浇注的温度为600~720℃。
5.根据权利要求2或3所述铝合金阳极材料的制备方法,其特征在于:步骤(3)中,所述均匀化处理的温度为460~600℃,时间为18~30h;所述热轧制是指进行4~8道次的往复加热轧制,每一道次进行一次中间退火;所述热轧制的温度为360~440℃,每次压下量为30~50%;所述中间退火的温度为280~330℃,时间为100~120min;所述热轧制后板材的厚度为1~2mm;所述深冷轧制是指进行4~8道次的往复冷轧制,每一道次轧制前置于液氮中浸泡20~25min;所述深冷轧制的总压下量为70~85%;所述深冷轧制后板材的厚度为0.3~0.6mm;所述成品退火的温度为200~230℃,时间为1~3h。
6.根据权利要求4所述铝合金阳极材料的制备方法,其特征在于:步骤(3)中,所述均匀化处理的温度为460~600℃,时间为18~30h;所述热轧制是指进行4~8道次的往复加热轧制,每一道次进行一次中间退火;所述热轧制的温度为360~440℃,每次压下量为30~50%;所述中间退火的温度为280~330℃,时间为100~120min;所述热轧制后板材的厚度为1~2mm;所述深冷轧制是指进行4~8道次的往复冷轧制,每一道次轧制前置于液氮中浸泡20~25min;所述深冷轧制的总压下量为70~85%;所述深冷轧制后板材的厚度为0.3~0.6mm;所述成品退火的温度为200~230℃,时间为1~3h。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111282801.8A CN113897522B (zh) | 2021-11-01 | 2021-11-01 | 一种铝合金阳极材料及制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111282801.8A CN113897522B (zh) | 2021-11-01 | 2021-11-01 | 一种铝合金阳极材料及制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113897522A true CN113897522A (zh) | 2022-01-07 |
CN113897522B CN113897522B (zh) | 2022-09-02 |
Family
ID=79027766
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111282801.8A Active CN113897522B (zh) | 2021-11-01 | 2021-11-01 | 一种铝合金阳极材料及制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113897522B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113459609A (zh) * | 2021-06-30 | 2021-10-01 | 中南大学 | 一种太阳能电池阵互连材料及其制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105349925A (zh) * | 2015-12-02 | 2016-02-24 | 北京工业大学 | 一种Al-Mg系合金的液氮温区冷加工工艺 |
CN109461942A (zh) * | 2018-11-22 | 2019-03-12 | 河南科技大学 | 一种空气电池用铝合金阳极材料及其制备方法、空气电池 |
CN112708809A (zh) * | 2020-11-27 | 2021-04-27 | 中国电子科技集团公司第十八研究所 | 一种耐偏铝酸盐稀土铝合金阳极材料及其制造方法 |
-
2021
- 2021-11-01 CN CN202111282801.8A patent/CN113897522B/zh active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105349925A (zh) * | 2015-12-02 | 2016-02-24 | 北京工业大学 | 一种Al-Mg系合金的液氮温区冷加工工艺 |
CN109461942A (zh) * | 2018-11-22 | 2019-03-12 | 河南科技大学 | 一种空气电池用铝合金阳极材料及其制备方法、空气电池 |
CN112708809A (zh) * | 2020-11-27 | 2021-04-27 | 中国电子科技集团公司第十八研究所 | 一种耐偏铝酸盐稀土铝合金阳极材料及其制造方法 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113459609A (zh) * | 2021-06-30 | 2021-10-01 | 中南大学 | 一种太阳能电池阵互连材料及其制备方法 |
CN113459609B (zh) * | 2021-06-30 | 2023-04-28 | 中南大学 | 一种太阳能电池阵互连材料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN113897522B (zh) | 2022-09-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109321766B (zh) | 一种铝空气电池阳极材料及其制备方法 | |
CN113921802B (zh) | 一种电池用铝合金负极材料、碱性电解液缓蚀剂、制备方法及应用 | |
CN111057914B (zh) | 一种阳极合金材料、其制备方法、铝空气电池用阳极以及铝空气电池 | |
CN106676343A (zh) | 一种海水电池用铝合金阳极材料及其制备方法 | |
CN103146943A (zh) | 一种紫杂铜精炼剂及其制备方法 | |
CN112952079A (zh) | 一种铝-空气电池用铝合金阳极材料及制备方法 | |
CN109295350B (zh) | 一种海水铝-空气电池用阳极材料及其制备方法 | |
CN111793760B (zh) | 镁空气电池用阳极合金材料及其制备方法以及电池 | |
CN113897522B (zh) | 一种铝合金阳极材料及制备方法 | |
CN109694964A (zh) | 一种铝空气电池阳极材料的制备方法 | |
CN112048652A (zh) | 一种镁空气电池阳极材料及其制备方法 | |
CN106756665A (zh) | 铝合金、制备方法以及用途 | |
LU102451B1 (en) | Aluminum (al) anode plate material for al-air battery and preparation method thereof, al anode plate for al-air battery and preparation method and use thereof | |
CN104313386A (zh) | 一种锂离子电池负极集流体用铜合金 | |
CN111560542A (zh) | 一种碱性铝-空气电池用含钙铝合金阳极材料及制备方法 | |
CN101877278B (zh) | 中压电解电容器阳极用铝箔及生产方法 | |
CN110042278A (zh) | 一种铝空气电池阳极材料及其制备方法 | |
CN111180720B (zh) | 一种铝空气电池阳极及其制备方法 | |
CN111560544B (zh) | 一种空气电池用阳极铝合金的制备方法和空气电池 | |
CN110931812B (zh) | 铝空气电池用合金阳极材料及其制备方法以及铝空气电池 | |
CN114737036A (zh) | 一种氢燃料电池双极板用高塑性钛合金超薄板材的制备方法 | |
CN110129623B (zh) | 一种稀土铝合金箔及其制备方法和应用 | |
CN114351011B (zh) | 用于低温下的高功率铝空气电池阳极材料及其制备方法 | |
CN112030014A (zh) | 动力电池用铝合金材料及其制备方法与应用 | |
CN114645151A (zh) | 一种高强高导铜合金及其生产方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |