CN101285142A - A kind of magnesium lithium-samarium alloy and its molten salt electrolytic preparation method - Google Patents
A kind of magnesium lithium-samarium alloy and its molten salt electrolytic preparation method Download PDFInfo
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- 229910000612 Sm alloy Inorganic materials 0.000 title claims abstract description 36
- AMJDYLVILDHUQE-UHFFFAOYSA-N [Sm].[Li].[Mg] Chemical compound [Sm].[Li].[Mg] AMJDYLVILDHUQE-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 150000003839 salts Chemical class 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 45
- 239000011777 magnesium Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 41
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 37
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 28
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 26
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 21
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003792 electrolyte Substances 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 8
- 239000010439 graphite Substances 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 239000011733 molybdenum Substances 0.000 claims abstract description 8
- 239000000956 alloy Substances 0.000 claims description 29
- 229910045601 alloy Inorganic materials 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 6
- 230000004927 fusion Effects 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000002844 melting Methods 0.000 abstract description 5
- 230000008018 melting Effects 0.000 abstract description 5
- 150000002736 metal compounds Chemical class 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 12
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 10
- 239000001989 lithium alloy Substances 0.000 description 9
- 150000002910 rare earth metals Chemical class 0.000 description 9
- 229910000861 Mg alloy Inorganic materials 0.000 description 8
- 229910019400 Mg—Li Inorganic materials 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 229910001629 magnesium chloride Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000004070 electrodeposition Methods 0.000 description 4
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 4
- 229910000733 Li alloy Inorganic materials 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
- 238000005275 alloying Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910003110 Mg K Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- SJEHNNYPSGXYBJ-UHFFFAOYSA-N [Ce].[Pr].[La].[Mg] Chemical compound [Ce].[Pr].[La].[Mg] SJEHNNYPSGXYBJ-UHFFFAOYSA-N 0.000 description 1
- TXOOFPKWIBQNBT-UHFFFAOYSA-N [La].[Ce].[Pr] Chemical compound [La].[Ce].[Pr] TXOOFPKWIBQNBT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- WOLXATBVPOGEQE-UHFFFAOYSA-N lithium samarium Chemical compound [Li][Sm] WOLXATBVPOGEQE-UHFFFAOYSA-N 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000028161 membrane depolarization Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000918 plasma mass spectrometry Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供的是一种镁锂－钐合金及其熔盐电解制备方法。在电解炉内，以MgCl2+LiCl+KCl+KF为电解质体系，加入无水Sm2O3粉末加热至680℃熔融，或者加入无水SmCl3粉末加热至630℃熔融，以金属钼(Mo)为阴极，石墨为阳极，电解温度630～810℃下，采取下沉阴极法，阴极电流密度为6.4～16.0A/cm2，阳极电流密度0.5A/cm2，槽电压5.1～8.4V，经40～120分钟的电解，在熔盐电解槽中于阴极附近沉积出Mg－Li－Sm合金。本发明既不用金属镁和金属锂，也不用金属钐，而是全部采用金属化合物为原料通过熔盐电解的方法直接制备镁锂钐合金。因此该方法使生产流程大大缩短，且工艺简单，采用低温电解，可以降低能耗和生产成本。The invention provides a magnesium-lithium-samarium alloy and a molten salt electrolytic preparation method thereof. In the electrolytic furnace, use MgCl 2 +LiCl+KCl+KF as the electrolyte system, add anhydrous Sm 2 O 3 powder and heat to 680°C for melting, or add anhydrous SmCl 3 powder and heat to 630°C for melting, and metal molybdenum (Mo ) is the cathode, graphite is the anode, the electrolysis temperature is 630-810°C, the sinking cathode method is adopted, the cathode current density is 6.4-16.0A/cm 2 , the anode current density is 0.5A/cm 2 , the cell voltage is 5.1-8.4V, After 40-120 minutes of electrolysis, Mg-Li-Sm alloy is deposited near the cathode in the molten salt electrolytic cell. The present invention neither uses metal magnesium, metal lithium, nor metal samarium, but uses metal compounds as raw materials to directly prepare magnesium-lithium-samarium alloy through molten salt electrolysis. Therefore, the method greatly shortens the production process, and the process is simple, and the low-temperature electrolysis can reduce energy consumption and production cost.
Description
(一)技术领域(1) Technical field
本发明涉及的是一种合金，具体地说是一种镁锂-钐合金。本发明还涉及一种镁锂-钐合金的制备方法。The present invention relates to an alloy, specifically a magnesium-lithium-samarium alloy. The invention also relates to a preparation method of the magnesium lithium-samarium alloy.
(二)背景技术(2) Background technology
镁合金具有比重低、比强度高、易加工和回收等优良性能，以及良好的阻尼减震和电磁屏蔽性能，在汽车、航空航天工业中得到广泛的应用。镁合金中，Mg-Li合金是目前最轻的合金，其二元合金的密度仅为1.3～1.59g/cm3，但其比强度比铝合金还高得多。Li加入Mg中，不仅使其密度下降，而且使其加工性能大大改善，因此受到研究者和工业界的关注，并在航空航天领域中得到了一定应用。Mg-Li合金除了具备一般镁合金的特性之外，还拥有自己独特的性能：合金密度很低，是唯一低于镁基体密度的镁合金体系，甚至可以低于水的密度。随着Li含量的增加，合金的结构将发生由密排六方(hcp)→密排六方+体心立方→体心立方(bcc)的转变，合金的塑性成形性能优良。Mg-Li合金具有低密度、高比强度、易于加工等很多特别有吸引力的优点。Magnesium alloys have excellent properties such as low specific gravity, high specific strength, easy processing and recycling, as well as good damping and shock absorption and electromagnetic shielding properties, and are widely used in the automotive and aerospace industries. Among the magnesium alloys, the Mg-Li alloy is currently the lightest alloy, and the density of its binary alloy is only 1.3-1.59g/cm 3 , but its specific strength is much higher than that of aluminum alloy. The addition of Li to Mg not only reduces its density, but also greatly improves its processing performance, so it has attracted the attention of researchers and industries, and has been applied in the aerospace field. In addition to the characteristics of general magnesium alloys, Mg-Li alloy also has its own unique properties: the density of the alloy is very low, and it is the only magnesium alloy system with a density lower than that of the magnesium matrix, even lower than the density of water. With the increase of Li content, the structure of the alloy will change from hexagonal close-packed (hcp) → hexagonal close-packed + body-centered cubic → body-centered cubic (bcc), and the plastic formability of the alloy is excellent. Mg-Li alloys have many particularly attractive advantages such as low density, high specific strength, and easy processing.
镁锂合金的生产方法主要有以下几种：对掺法、阴极合金化法、液态阴极法、共电沉积法。The production methods of magnesium-lithium alloy mainly include the following types: pair mixing method, cathode alloying method, liquid cathode method, and co-electrodeposition method.
(1)对掺法：在金属熔化的状态下，把金属镁和金属锂按一定比例对掺而成。该方法金属损失大，成本高，劳动环境差，金属偏析严重。(1) Counter-doping method: In the state of metal melting, metal magnesium and metal lithium are mixed in a certain proportion. This method has large metal loss, high cost, poor working environment and serious metal segregation.
(2)阴极合金化法：把金属镁作为阴极放于电解槽中，锂盐为电解质，在电解的过程中锂析出并和镁阴极合金化，从而形成镁锂合金。该方法使用的是价格高昂的金属镁，成本高。而且合金的成分难以控制，存在偏析现象。(2) Cathode alloying method: Metal magnesium is placed in the electrolytic cell as the cathode, and lithium salt is used as the electrolyte. During the electrolysis process, lithium is precipitated and alloyed with the magnesium cathode to form a magnesium-lithium alloy. What this method used is the expensive metal magnesium, and the cost is high. Moreover, the composition of the alloy is difficult to control, and there is segregation phenomenon.
(3)液态阴极法：以液态金属锂作为阴极，镁盐作为电解质，在电解的过程中镁析出并和锂阴极合金化。该法主要制取中间合金和母合金。(3) Liquid cathode method: liquid metal lithium is used as the cathode, and magnesium salt is used as the electrolyte. During the electrolysis process, magnesium is precipitated and alloyed with the lithium cathode. This method mainly prepares master alloys and master alloys.
(4)共电沉积法：镁锂的析出电位相差0.9V左右，差距太大，会造成析出Mg而不析出Li。要设法降低Mg2+离子的析出电位、升高Li+离子的析出电位，可以采用以下方法实现Mg2+、Li+离子共电沉积：①以KCl为导电电解质，在大量KCl存在的熔体中MgCl2的活度会大幅度降低，以达到降低Mg2+离子的析出电位的目的；②通过提高熔盐电解时的电流密度，达到Mg2+离子的极限电流密度后，导致Mg2+离子的析出电位迅速向负移动，达到Li+离子还原的电位，就可以达到Mg-Li共沉积。③电解之初，生成的是Mg，故Li+在Mg上沉积，随之在Mg-Li上沉积。而Li+在Mg(Mg-Li合金)上析出时有很大的去极化效应，使Li+析出电位向正移，有利于生成Mg-Li合金。(4) Co-electrodeposition method: The precipitation potential of magnesium and lithium differs by about 0.9V. If the difference is too large, Mg will be precipitated but Li will not. To try to reduce the precipitation potential of Mg 2+ ions and increase the precipitation potential of Li + ions, the following methods can be used to realize the co-electrodeposition of Mg 2+ and Li + ions: ① Using KCl as the conductive electrolyte, in a melt with a large amount of KCl The activity of MgCl 2 in the medium will be greatly reduced to achieve the purpose of reducing the precipitation potential of Mg 2+ ions ; The precipitation potential of ions moves negatively rapidly, reaching the potential of Li + ion reduction, and Mg-Li co-deposition can be achieved. ③ At the beginning of electrolysis, Mg is generated, so Li + is deposited on Mg, and then deposited on Mg-Li. However, when Li + precipitates on Mg (Mg-Li alloy), it has a great depolarization effect, which makes the Li + precipitation potential shift positively, which is beneficial to the formation of Mg-Li alloy.
液态阴极法在稀有金属冶炼中应用较广，该法广泛应用于制取镁基中间合金。例如专利申请号200510017229.7的“低温下沉液态阴极电解制备镁稀土中间合金的方法”，该法采用稀土含量为5～8wt％的镁-镧镨铈中间合金作为初始下沉液态阴极，在700-900℃下电解制取较高稀土含量的镁-(8～30)wt％镧镨铈中间合金。同时复合阴极法也有所应用，例如申请号200510119117.2的“复合阴极熔盐电解稀土-镁中间合金的制备方法”：在同一电解槽中，上浮液态镁阴极、下沉液态高浓度稀土镁阴极和非自耗铅直表面中等浓度稀土镁液态阴极共存，电化学沉积同时发生在三维空间的阴极表面，电解制备稀土-镁中间合金。The liquid cathode method is widely used in rare metal smelting, and this method is widely used in the preparation of magnesium-based master alloys. For example, Patent Application No. 200510017229.7 "Method for preparing magnesium-rare-earth master alloy by electrolysis of low-temperature sinking liquid cathode", this method adopts magnesium-lanthanum-praseodymium-cerium master alloy with a rare earth content of 5-8 wt% as the initial sinking liquid cathode, at 700- The magnesium-(8-30)wt% lanthanum-praseodymium-cerium master alloy with relatively high rare earth content is electrolyzed at 900°C. At the same time, the composite cathode method is also applied, such as the "preparation method of composite cathode molten salt electrolysis rare earth-magnesium master alloy" of application number 200510119117.2: in the same electrolytic cell, the floating liquid magnesium cathode, the sinking liquid high-concentration rare earth magnesium cathode and the non- The medium-concentration rare earth magnesium liquid cathode coexists on the consumable vertical surface, and the electrochemical deposition occurs simultaneously on the cathode surface in three-dimensional space, and the rare earth-magnesium master alloy is prepared by electrolysis.
(三)发明内容(3) Contents of the invention
本发明的目的在于提供一种流动性和加工性能得以改善，塑性、耐磨性和耐腐蚀性好的镁锂-钐合金。本发明的目的还在于提供一种不用金属镁、金属锂，也不用稀土金属，工艺简单，可以改善合金的流动性和加工性能，提高合金的强度，塑性，耐磨性和耐腐蚀性的镁锂-钐合金的熔盐电解制备方法。The purpose of the present invention is to provide a magnesium-lithium-samarium alloy with improved fluidity and processability, good plasticity, wear resistance and corrosion resistance. The object of the present invention is also to provide a kind of magnesium that does not use metal magnesium, metal lithium, or rare earth metal, and has simple process, can improve the fluidity and processability of the alloy, and improve the strength, plasticity, wear resistance and corrosion resistance of the alloy. A method for preparing lithium-samarium alloy by molten salt electrolysis.
本发明的镁锂-钐合金是由重量比为：锂7.2～56.4％、钐0.3～2.1％和余量的镁组成的。The magnesium-lithium-samarium alloy of the invention is composed of 7.2-56.4% of lithium, 0.3-2.1% of samarium and the rest of magnesium in weight ratio.
本发明的镁锂-钐合金是采用这样的方法来制备的：在电解炉内，以MgCl2+LiCl+KCl+KF为电解质体系，各电解质的质量配比为6～13.3％、39.8～44.5％、39.8～44.5％、4.8～7.1％，再按MgCl2重量的1～4％加入无水Sm2O3加热至680℃熔融，或者按MgCl2重量的1～4％加入无水SmCl3粉末加热至630℃熔融，以金属钼为阴极，石墨为阳极，电解温度630～810℃下，阴极电流密度为6.4～16.0A/cm2，阳极电流密度0.5A/cm2，槽电压5.1～8.4V，经40～120分钟的电解，在熔盐电解槽于阴极附近沉积出Mg-Li-Sm合金。The magnesium-lithium-samarium alloy of the present invention is prepared by the following method: in the electrolytic furnace, MgCl 2 +LiCl+KCl+KF is used as the electrolyte system, and the mass ratio of each electrolyte is 6-13.3%, 39.8-44.5% %, 39.8~44.5%, 4.8~7.1%, and then add anhydrous Sm2O3 according to 1~ 4 % of the weight of MgCl2 and heat to 680°C for melting, or add anhydrous SmCl3 according to 1~4% of the weight of MgCl2 The powder is heated to 630°C and melted, the metal molybdenum is used as the cathode, and the graphite is used as the anode. At an electrolysis temperature of 630-810°C, the cathode current density is 6.4-16.0A/cm 2 , the anode current density is 0.5A/cm 2 , and the cell voltage is 5.1- 8.4V, after 40-120 minutes of electrolysis, the Mg-Li-Sm alloy is deposited near the cathode in the molten salt electrolytic cell.
本发明中的LiCl、KCl分别在300℃、600℃干燥24小时，KF是由KF·2H2O在真空干燥箱经脱水制备，脱水温度为130～180℃。LiCl and KCl in the present invention are dried at 300°C and 600°C for 24 hours respectively, and KF is prepared by dehydrating KF·2H 2 O in a vacuum oven at a dehydration temperature of 130-180°C.
本发明采用的的是镁锂电解共沉积法制取镁锂合金。与背景技术相比相比，不用金属镁也不用金属锂，而是全部采用金属化合物为原料通过熔盐电解的方法经电解一步直接制备镁锂-钐合金。不用金属降低了生产的成本。而且可以通过控制电解质配比、电解时间、温度、电流密度等条件来得到不同组成的Mg-Li-Sm合金，合金组分可以为锂7.2～56.4％、钐0.3～2.1％和余量的镁。整套工艺简单，对设备的要求低，实验条件容易实现。能耗低，污染小。What the present invention adopts is magnesium-lithium electrolytic co-deposition method to prepare magnesium-lithium alloy. Compared with the background technology, neither metal magnesium nor metal lithium is used, but all metal compounds are used as raw materials to directly prepare magnesium-lithium-samarium alloy by electrolysis in one step through molten salt electrolysis. The absence of metal reduces the cost of production. Moreover, Mg-Li-Sm alloys with different compositions can be obtained by controlling the electrolyte ratio, electrolysis time, temperature, current density and other conditions. The alloy components can be lithium 7.2-56.4%, samarium 0.3-2.1% and the balance of magnesium . The whole process is simple, the requirements for equipment are low, and the experimental conditions are easy to realize. Low energy consumption and little pollution.
Mg-Li合金作为结构材料需有好的综合性能，欲提高合金材料强度而又不过分牺牲其优良性能，可以采用添加稀土元素的方法。据报道，稀土加入到镁合金中可以有效的改变镁合金的机械加工性能和物理性能，净化杂质，可以同镁合金中呈溶质状态的金属形成金属间化合物。改善了合金的流动性和加工性能，提高了镁合金的强度，塑性，耐磨性，耐腐蚀性。As a structural material, Mg-Li alloy needs to have good comprehensive performance. To improve the strength of the alloy material without sacrificing its excellent performance, the method of adding rare earth elements can be used. According to reports, the addition of rare earths to magnesium alloys can effectively change the machinability and physical properties of magnesium alloys, purify impurities, and form intermetallic compounds with metals in a solute state in magnesium alloys. It improves the fluidity and processing performance of the alloy, and improves the strength, plasticity, wear resistance and corrosion resistance of the magnesium alloy.
本发明采用添加稀土元素Sm的方法，开发Mg-Li-Sm合金。The invention adopts the method of adding rare earth element Sm to develop Mg-Li-Sm alloy.
本发明提供一种工艺简单，生产成本低的镁锂-钐合金制备方法。本发明的特点在于：(1)即不用金属镁和锂，也不用稀土金属，而是全部采用金属化合物为原料，采用熔盐电解直接制备镁锂-钐合金，因此使生产流程大大缩短，工艺简单；(2)本发明的电解温度低(630～810℃)，远远低于金属Sm(1072℃)的熔点，因此，可以延长设备的使用寿命，节省能源，降低生产成本。The invention provides a preparation method of magnesium-lithium-samarium alloy with simple process and low production cost. The present invention is characterized in that: (1) no metal magnesium and lithium, nor rare earth metals are used, but all metal compounds are used as raw materials, and magnesium-lithium-samarium alloys are directly prepared by molten salt electrolysis, so that the production process is greatly shortened and the process Simple; (2) The electrolysis temperature of the present invention is low (630-810° C.), which is far lower than the melting point of metal Sm (1072° C.). Therefore, the service life of the equipment can be extended, energy can be saved, and production costs can be reduced.
(四)附图说明(4) Description of drawings
附图是实例5中制备的合金样品的扫瞄电子显微镜(SEM)照片及面扫描(EPMA)照片。Accompanying drawing is the scanning electron microscope (SEM) picture and the surface scanning (EPMA) picture of the alloy sample prepared in Example 5.
其中：图1是SEM照片；图2是002点的EDS图谱；图3是合金中镁分布的面扫描(Mg K)；图4是合金中钐分布的面扫描(Sm L)。Among them: Figure 1 is a SEM photo; Figure 2 is the EDS spectrum of
(五)具体实施方式(5) Specific implementation methods
下面举例对本发明做更详细地描述。The following examples describe the present invention in more detail.
实施例1：以MgCl2+LiCl+KCl+KF为电解质体系，各成分的质量百分比分别为6.0％、44.5％、44.5％、5.0％，再按MgCl2重量的3.3％加入固体SmCl3粉末，以惰性金属钼(Mo)为阴极，石墨为阳极，电解温度630℃下，采取下沉阴极法，极距为4cm，阴极电流密度为9.5A/cm2，阳极电流密度0.5A/cm2，槽电压5.6～5.8V，经40分钟的电解，在熔盐电解槽于阴极附近沉积出Mg-Li-Sm合金，镁、锂、钐的含量分别为：43.3％、56.4％、0.3％。Embodiment 1: with MgCl 2 +LiCl+KCl+KF as the electrolyte system, the mass percent of each component is respectively 6.0%, 44.5%, 44.5%, 5.0%, then add solid SmCl 3 powder by 3.3% of MgCl 2 weight, Using inert metal molybdenum (Mo) as the cathode and graphite as the anode, the electrolysis temperature is 630°C, the sinking cathode method is adopted, the pole distance is 4cm, the cathode current density is 9.5A/cm 2 , and the anode current density is 0.5A/cm 2 . The cell voltage is 5.6-5.8V. After 40 minutes of electrolysis, Mg-Li-Sm alloy is deposited near the cathode in the molten salt electrolytic cell. The contents of magnesium, lithium, and samarium are 43.3%, 56.4%, and 0.3%, respectively.
实施例2：以MgCl2+LiCl+KCl+KF为电解质体系，各成分的质量百分比分别为6.0％、44.5％、44.5％、5.0％，再按MgCl2重量的3.3％加入固体SmCl3粉末，以惰性金属钼(Mo)为阴极，石墨为阳极，电解温度660℃下，采取下沉阴极法，极距为4cm，阴极电流密度为6.4A/cm2，阳极电流密度0.5A/cm2，槽电压5.0～5.3V，经40分钟的电解，在熔盐电解槽于阴极附近沉积出Mg-Li-Sm合金，镁、锂、钐的含量分别为：59.6％、39.5％、0.9％Embodiment 2: with MgCl2 +LiCl+KCl+KF as the electrolyte system, the mass percent of each component is respectively 6.0%, 44.5%, 44.5%, 5.0%, then add solid SmCl3 powder by 3.3% of MgCl2 weight, Using inert metal molybdenum (Mo) as the cathode and graphite as the anode, the electrolysis temperature is 660°C, the sinking cathode method is adopted, the pole distance is 4cm, the cathode current density is 6.4A/cm 2 , and the anode current density is 0.5A/cm 2 . The cell voltage is 5.0-5.3V. After 40 minutes of electrolysis, a Mg-Li-Sm alloy is deposited near the cathode in the molten salt electrolytic cell. The contents of magnesium, lithium, and samarium are respectively: 59.6%, 39.5%, and 0.9%.
实施例3：以MgCl2+LiCl+KCl+KF为电解质体系，各成分的质量百分比分别为6.0％、44.5％、44.5％、5.0％，再按MgCl2重量的3.3％加入固体Sm2Cl3粉末，以惰性金属钼(Mo)为阴极，石墨为阳极，电解温度660℃下，采取下沉阴极法，极距为4cm，阴极电流密度为12.7A/cm2，阳极电流密度0.5A/cm2，槽电压8.0～8.4V，经40分钟的电解，在熔盐电解槽与阴极附近沉积出Mg-Li-Sm合金，镁、锂、钐的含量分别为：45.5％、54.0％、0.5％。Example 3: Using MgCl 2 +LiCl+KCl+KF as the electrolyte system, the mass percentages of each component are 6.0%, 44.5%, 44.5%, 5.0% respectively, and then add solid Sm 2 Cl 3 according to 3.3% of the weight of MgCl 2 Powder, with inert metal molybdenum (Mo) as the cathode, graphite as the anode, at an electrolysis temperature of 660°C, the sinking cathode method is adopted, the pole distance is 4cm, the cathode current density is 12.7A/cm 2 , and the anode current density is 0.5A/cm 2. The cell voltage is 8.0-8.4V. After 40 minutes of electrolysis, a Mg-Li-Sm alloy is deposited near the molten salt electrolytic cell and the cathode. The contents of magnesium, lithium, and samarium are respectively: 45.5%, 54.0%, and 0.5%. .
实施例4：以MgCl2+LiCl+KCl+KF为电解质体系，各成分的质量百分比分别为7.8％、43.7％、43.7％、4.8％，再按MgCl2重量的3.7％加入固体Sm2O3粉末，以惰性金属钼(Mo)为阴极，石墨为阳极，电解温度780℃下，采取下沉阴极法，极距为4cm，阴极电流密度为12.7A/cm2，阳极电流密度0.5A/cm2，槽电压6.0～6.9V，经90分钟电解，在熔盐电解槽与阴极附近沉积出Mg-Li-Sm合金，镁、锂、钐的含量分别为：78.9％、19.1％、2.0％。Example 4: Using MgCl 2 +LiCl+KCl+KF as the electrolyte system, the mass percentages of each component are 7.8%, 43.7%, 43.7%, 4.8%, and then add solid Sm 2 O 3 according to 3.7% of the weight of MgCl 2 Powder, with inert metal molybdenum (Mo) as the cathode, graphite as the anode, at an electrolysis temperature of 780°C, the sinking cathode method is adopted, the pole distance is 4cm, the cathode current density is 12.7A/cm 2 , and the anode current density is 0.5A/cm 2. The cell voltage is 6.0-6.9V. After 90 minutes of electrolysis, Mg-Li-Sm alloys are deposited near the molten salt electrolytic cell and the cathode. The contents of magnesium, lithium, and samarium are 78.9%, 19.1%, and 2.0%, respectively.
实施例5：以MgCl2+LiCl+KCl+KF为电解质体系，各成分的质量百分比分别为13.3％、39.8％、39.8％、7.1％，再按MgCl2重量的3.3％加入固体Sm2O3粉末，以惰性金属钼(Mo)为阴极，石墨为阳极，电解温度810℃下，采取下沉阴极法，极距为4cm，阴极电流密度为16.0A/cm2，阳极电流密度0.5A/cm2，槽电压5.1～6.0V，经120分钟电解，在熔盐电解槽与阴极附近沉积出Mg-Li-Sm合金，镁、锂、钐的含量分别为：90.7％、7.2％、2.1％。Example 5: Using MgCl 2 +LiCl+KCl+KF as the electrolyte system, the mass percentages of each component are 13.3%, 39.8%, 39.8%, and 7.1% respectively, and then adding solid Sm 2 O 3 according to 3.3% of the weight of MgCl 2 Powder, with inert metal molybdenum (Mo) as the cathode, graphite as the anode, at an electrolysis temperature of 810°C, the sinking cathode method is adopted, the pole distance is 4cm, the cathode current density is 16.0A/cm 2 , and the anode current density is 0.5A/cm 2. The cell voltage is 5.1-6.0V. After 120 minutes of electrolysis, Mg-Li-Sm alloy is deposited near the molten salt electrolytic cell and the cathode. The contents of magnesium, lithium, and samarium are 90.7%, 7.2%, and 2.1%, respectively.
在以上的实施例中可以看出：加大氯化镁的投入量其余条件不变可以明显提高合金中的镁含量(例1和例5)；加大电流密度其余条件不变，有利于金属锂的析出，可以提高合金中锂的含量(例2和例3)，延长电解时间有利于稀土钐的析出，电解温度过高会加重锂的损失。Can find out in above embodiment: increase the input amount of magnesium chloride all the other conditions are constant and can obviously improve the magnesium content (example 1 and example 5) in the alloy; Enhancing current density all the other conditions are constant, help metal lithium Precipitation can improve the content of lithium in the alloy (example 2 and example 3), prolonging the electrolysis time is conducive to the precipitation of rare earth samarium, and the excessive electrolysis temperature will increase the weight of the loss of lithium.
附图1是实例5中制备的合金样品的扫瞄电子显微镜(SEM)照片及面扫描(EPMA)照片。SEM附带能谱(EDS)对样品002点进行了元素分析，其结果显示，合金中是有稀土钐存在的，与等离子体质谱分析数据相吻合。EPMA面扫描照片中可以清楚的看到：合金中金属镁和稀土钐的分布是均匀的，无偏析现象。Accompanying drawing 1 is the scanning electron microscope (SEM) picture and the surface scanning (EPMA) picture of the alloy sample prepared in example 5. The elemental analysis of
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014194745A1 (en) * | 2013-06-04 | 2014-12-11 | 中国科学院过程工程研究所 | Method for preparing magnesium alloy by electrolysis using magnesium chloride hydrate as raw material |
| CN109837561A (en) * | 2017-11-27 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of metallic lithium powder and its electrochemical preparation method |
| CN112030193A (en) * | 2020-08-27 | 2020-12-04 | 包头稀土研究院 | Method for reducing segregation of gadolinium yttrium magnesium alloy |
| CN116397270A (en) * | 2023-04-18 | 2023-07-07 | 中国科学院青海盐湖研究所 | A kind of preparation method of magnesium-lithium-strontium alloy based on molten salt co-deposition |
| CN116397269A (en) * | 2023-04-18 | 2023-07-07 | 中国科学院青海盐湖研究所 | A kind of preparation method of magnesium-lithium-rare earth alloy based on molten salt co-deposition |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014194745A1 (en) * | 2013-06-04 | 2014-12-11 | 中国科学院过程工程研究所 | Method for preparing magnesium alloy by electrolysis using magnesium chloride hydrate as raw material |
| CN109837561A (en) * | 2017-11-27 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of metallic lithium powder and its electrochemical preparation method |
| CN112030193A (en) * | 2020-08-27 | 2020-12-04 | 包头稀土研究院 | Method for reducing segregation of gadolinium yttrium magnesium alloy |
| CN112030193B (en) * | 2020-08-27 | 2021-11-09 | 包头稀土研究院 | Method for reducing segregation of gadolinium-yttrium-magnesium alloy |
| CN116397270A (en) * | 2023-04-18 | 2023-07-07 | 中国科学院青海盐湖研究所 | A kind of preparation method of magnesium-lithium-strontium alloy based on molten salt co-deposition |
| CN116397269A (en) * | 2023-04-18 | 2023-07-07 | 中国科学院青海盐湖研究所 | A kind of preparation method of magnesium-lithium-rare earth alloy based on molten salt co-deposition |
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