CN103540960B - A kind of preparation method of the Ni-based hydrogen bearing alloy of rare earth magnesium - Google Patents
A kind of preparation method of the Ni-based hydrogen bearing alloy of rare earth magnesium Download PDFInfo
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Abstract
The preparation method of the Ni-based hydrogen bearing alloy of a kind of rare earth magnesium, uses circular or square graphite electrolysis bath, and bottom of electrolytic tank is placed and accepted crucible, and preset a certain amount of addition element metal derby is in accepting crucible；With REF3‑LiF‑MgF2‑BaF2It is electrolytic medium Deng fluoride molten salt, with RE2O3Be raw material with MgO mixture, the common electrochemistry of negative electrode RE Yu Mg separate out, obtain RE Mg alloy and sink to accept crucible, be preset at crucible in metal derby alloying obtain rare earth magnesium nickel hydrogen storage alloys.This method efficiently solves volatilization and the problem of oxidation of rare earth magnesium nickel hydrogen storage alloys magnesium in fusion process, and production process safety, flow process is short, low cost.This method gained rare earth magnesium nickel hydrogen storage alloys can direct mechanical crush or the broken rare earth magnesium nickel hydrogen bearing alloy powder body that to obtain of hydrogen, or as cast or fast quenching after the foundry alloy certain raw material of interpolation, then Mechanical Crushing or hydrogen break and to obtain rare earth magnesium nickel hydrogen bearing alloy powder body.
Description
Technical field
The present invention relates to the preparation method of the Ni-based hydrogen bearing alloy of a kind of rare earth magnesium.
Background technology
RE-Mg-Ni base hydrogen storage alloy is the high-performance rare-earth hydrogen storage material of new generation that development in recent years is got up, and by composition transfer, its hydrogen storage gravimetric hydrogen storage density is between 1.4-6%, and combination property is superior.The technology of preparing of RE-Mg-Ni system alloy is various, in general, mainly has High temperature diffusion sintering technology, such as CN1271025A, CN1296083A, CN1598018A, CN1900337A；Process for vacuum induction smelting, such as CN1397658A, CN102191416A, CN102277508A, CN102286684A；Mechanical ball milling technique, such as CN1316537A, CN1644737A；Vacuum rapidly quenched technique, such as CN101624660, CN101626076A；Laser sintered, such as CN101029358A etc.；Patent has essentially related to noble gas or H2Protection in alloying process, even positive pressure protection.
Owing to magnesium, rare earth, the fusing point of nickel, boiling point differ greatly, the high activity of magnesium and volatility make the control to its content extremely difficult, in melting and heat treatment process, easily produce the volatilization of Mg, on the one hand cause Mg content off-design value in alloy, on the other hand produce dangerous.It addition, be easily generated component segregation and uneven microstructure in alloy graining process, the annealing process cycle is long, is easily caused alloy oxidized, affects the performance of alloy, causes alloy product quality to be difficult to control, even there is safety problem.The most how to overcome volatile, the oxidation of Mg, the outstanding problem of segregation, maintain the stable components, uniformly and safety in production is one of difficult point preparing RE-Mg-Ni base hydrogenous alloy of Mg.
Summary of the invention
It is an object of the invention to provide and a kind of overcome volatile, the oxidation of magnesium, the outstanding problem of segregation, maintain the stable components, uniformly and the preparation method of the Ni-based hydrogen bearing alloy of rare earth magnesium of safety in production of magnesium.
The preparation method of the Ni-based hydrogen bearing alloy of rare earth magnesium of the present invention, uses circular or square graphite electrolysis bath, and bottom of electrolytic tank is placed and accepted crucible, and preset a certain amount of addition element metal derby is in accepting crucible；With REF3-LiF-MgF2-BaF2It is electrolytic medium Deng fluoride molten salt, with RE2O3Be raw material with MgO mixture, the common electrochemistry of negative electrode RE Yu Mg separate out, obtain RE-Mg alloy and sink to accept crucible, be preset at crucible in metal derby alloying obtain rare earth magnesium nickel hydrogen storage alloys, hydrogen bearing alloy is RE by chemical formula compositionxMg1-xNiyAz, RE is La, the combination of one of Ce, Pr, Nd, Y or possible, 2≤y≤3, and preset addition element is Ni and A, and A is the combination of one of Ti, Co, Zr, Cu, Cr or possible, 0≤z≤0.5.
The preparation method of the Ni-based hydrogen bearing alloy of rare earth magnesium of the present invention, with RE2O3It is electrolysis raw material, RE with MgO mixture2O3Purity >=98%, MgO purity >=96%, wherein RE2O3Weight/mass percentage composition is 60-95%, and its ratio is by hydrogen bearing alloy chemical formula RExMg1-xNiyAzDetermine；REF with commercially available purity >=98%3, LiF, MgF2, BaF2For electrolysis fused-salt medium, REF in electrolyte3Weight/mass percentage composition change between 75-92%, MgF2Weight/mass percentage composition 0-10% change, BaF2Weight/mass percentage composition is surplus at 0-6%, LiF；It is preset at addition element purity >=96% of crucible.
The RE-Mg alloy of electrolysis gained and preset addition element metal derby are in the amount of undertaking crucible, by RExMg1-xNiyAzAnd determine according to the current value being electrolysed, current efficiency, electrolysis time meter；
Using circular or square graphite electrolysis bath (when Faradaic current is more than 3500A), bottom of electrolytic tank is placed and is accepted crucible, and preset a certain amount of addition element metal derby is in accepting crucible；With REF3-LiF-MgF2-BaF2Fluoride molten salt is electrolytic medium, RE2O3With the mixing raw material of MgO after electrolytic medium dissolves, electrolytic process occurs the electrochemistry of RE Yu Mg to separate out at cathode site, sinks to accept crucible and preset addition element alloying obtains rare earth magnesium nickel hydrogen storage alloys.
Electrolysis operating temperature is: 800-1100 DEG C, and single cavity electrolysis operating current is between 2000-30000A.
Use negative-pressure siphon or people's clamping apparatus to come out of the stove, peel off electrolytic medium, it is thus achieved that rare earth magnesium nickel hydrogen storage alloys.Faradaic current 2000A 30000A；If using siphon tapped, then using the titanium matter siphon of Φ=15-50mm, the vacuum cavitations of siphon bag is 0.3-0.5 atmospheric pressure.
It is an advantage of the current invention that; common electrolytic deposition-the alloying of fluoride molten salt electrolysis system prepares the Ni-based hydrogen bearing alloy of rare earth magnesium; rare earth separates out alloying with magnesium at electrode and sinks to accept crucible; and continue and the addition element alloying being preset in crucible; by alloying, magnesium is fettered well; being protected from volatilization and having aoxidized because of ingress of air due to fused-salt medium, it is not necessary to noble gas and H2Protection, obtain the Ni-based hydrogen bearing alloy of rare earth magnesium of stable components safely；Its composition controllable stable acquisition, electrolysis work is continuous, and technical process safety, flow process is short, low cost, has wide popularization and market prospect.
Detailed description of the invention
Embodiment 1:
Use circular graphitic electrolysis bath, with LaF3(wt%:80%)-LiF(wt%:10%)-MgF2(wt%:6%)-BaF2(wt%:4%) fluoride molten salt is electrolytic medium；In crucible, it is previously added 2.16kg nickel and 0.06kg titanium, is uniformly added into the La that 1.25kg mol ratio is 1:22O3With MgO mixing raw material, Faradaic current 2000A, electrolysis temperature 900 DEG C, after 40 minutes, people's clamping apparatus is come out of the stove and poured into a mould acquisition is La by chemical formula composition0.5Mg0.5Ni3Ti0.1Rare earth magnesium nickel hydrogen storage alloys 3.2kg.
Embodiment 2:
Use circular graphitic electrolysis bath, with LaF3(wt%:38%)-CeF3(wt%:38%)-LiF(wt%:20%)-MgF2(wt%:2%)-BaF2(wt%:2% :) fluoride molten salt is electrolytic medium；In crucible, it is previously added 3.35kg nickel and 0.13kg zirconium and 0.09kg copper, is uniformly added into the La that 2.6kg mol ratio is 1:2:32O3, CeO2With MgO mixing raw material, Faradaic current 2500A, electrolysis temperature 950 DEG C, after 60 minutes, people's clamping apparatus is come out of the stove and poured into a mould acquisition composition is La0.2Ce0.2Mg0.6Ni2Zr0.05Cu0.05Rare earth magnesium nickel hydrogen storage alloys 5.5kg.
Embodiment 3:
Use square graphite electrolysis bath, with LaF3(wt%:44%)-YF3(wt%:44%)-LiF(wt%:10%)-MgF2(wt%:2%) fluoride molten salt is electrolytic medium；In crucible, it is previously added 27.7kg nickel and 0.2kg chromium, is uniformly added into the La that 24.5kg mol ratio is 3:1:12O3, Y2O3, MgO mixing raw material, Faradaic current 10000A, electrolysis temperature 1080 DEG C, after 120 minutes, it is La that siphon tapped cast obtains composition0.6Y0.2Mg0.2Ni2.5Cr0.02Rare earth magnesium nickel hydrogen storage alloys 48kg, the titanium matter siphon of siphon tapped use Φ=20mm, the vacuum cavitations of siphon bag is 0.35 atmospheric pressure.
Claims (1)
1. the preparation method of the Ni-based hydrogen bearing alloy of rare earth magnesium, it is characterised in that: using circular or square graphite electrolysis bath, bottom of electrolytic tank is placed and is accepted crucible, and preset addition element metal derby is in accepting crucible；With REF3-LiF-MgF2-BaF2Fluoride molten salt is electrolytic medium, with RE2O3It is raw material with MgO mixture, separate out in the common electrochemistry of negative electrode RE Yu Mg, obtain RE-Mg alloy to sink to accept in crucible, and obtain rare earth magnesium nickel hydrogen storage alloys with the addition element alloying being preset at crucible, until crucible close to when filling with, use siphon or go out circular crucible with clamp forceps and cast, obtaining rare earth magnesium nickel hydrogen storage alloys；
Hydrogen bearing alloy is RE by chemical formula compositionxMg1-xNiyAz, RE is La, one or more of Ce, Pr, Nd, Y, 2≤y≤3, and preset addition element is Ni and A, and A is one or more of Ti, Co, Zr, Cu, Cr, 0≤z≤0.5, and x is 0.5；
With RE2O3It is electrolysis raw material, RE with MgO mixture2O3Purity >=98%, MgO purity >=96%, wherein RE2O3Weight/mass percentage composition is 60-95%；REF with commercially available purity >=98%3, LiF, MgF2, BaF2For electrolysis fused-salt medium, REF in electrolyte3Weight/mass percentage composition change between 75-92%, MgF2Weight/mass percentage composition 2-10% change, BaF2Weight/mass percentage composition is surplus at 2-6%, LiF；It is preset at addition element purity >=96% of crucible；
Electrolysis raw material RE2O3Chemical formula RE is pressed by hydrogen bearing alloy with the ratio of MgO mixturexMg1-xNiyAzDetermining, being preset at addition element nickel and A metal in crucible, its amount is pressed chemical formula RE by hydrogen bearing alloyxMg1-xNiyAzAnd the amount of RE-Mg alloy determines in calculating in the crucible got according to the current value being electrolysed, current efficiency, electrolysis time.
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| CN104131315B (en) * | 2014-08-20 | 2017-11-07 | 赣南师范大学 | A kind of Ni-based hydrogen bearing alloy electrolysis eutectoid alloy method of rare earth magnesium |
| CN106011506B (en) * | 2016-07-01 | 2017-10-20 | 河南理工大学 | A kind of Ni-based hydrogen bearing alloy of boron containing rare earth magnesium prepares manufacturing process |
| CN106757169A (en) * | 2016-12-10 | 2017-05-31 | 包头稀土研究院 | A kind of hydrogen bearing alloy rare earth intermediate alloy and preparation method thereof |
| CN106544535B (en) * | 2016-12-10 | 2021-04-23 | 包头稀土研究院 | Preparation method of hydrogen storage alloy containing yttrium and nickel elements |
| CN107686903B (en) * | 2017-09-03 | 2019-11-29 | 浙江中杭水泵股份有限公司 | A kind of Mg base hydrogen bearing alloy of ball-milling method preparation |
| CN108149073B (en) * | 2017-11-17 | 2020-06-23 | 安泰科技股份有限公司 | La-Mg-Ni series hydrogen storage alloy for low-temperature nickel-metal hydride battery and preparation method thereof |
| US10443132B1 (en) | 2019-02-18 | 2019-10-15 | Kuwait Institute For Scientific Research | Method for doping magnesium with nickel by cold spray technique |
| CN112080766B (en) * | 2020-09-22 | 2022-01-11 | 赣州有色冶金研究所有限公司 | Y-Al-Ni intermediate alloy and preparation method and application thereof |
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| EP0257710B1 (en) * | 1986-08-21 | 1993-01-07 | MOLTECH Invent S.A. | Molten salt electrowinning electrode, method and cell |
| US4956068A (en) * | 1987-09-02 | 1990-09-11 | Moltech Invent S.A. | Non-consumable anode for molten salt electrolysis |
| DE69625346T2 (en) * | 1995-10-25 | 2003-08-21 | Santoku Corp | METHOD FOR PRODUCING RARE EARTH METALS |
| JP4277080B2 (en) * | 2004-01-05 | 2009-06-10 | 東邦チタニウム株式会社 | Titanium metal production equipment |
| CN101212047B (en) * | 2006-12-31 | 2010-06-23 | 比亚迪股份有限公司 | Hydrogen storage alloy and its preparation method |
| CN101117723B (en) * | 2007-07-30 | 2011-01-05 | 赣南师范学院 | Method for preparing Gd-Mg intermediate alloy by fluorination system coelectrodeposition |
| CN101260547B (en) * | 2008-02-29 | 2010-06-30 | 上海大学 | Method for preparing AB5 type hydrogen-storage alloy directly from metal oxide mixture |
| CN101629308B (en) * | 2009-04-29 | 2010-12-08 | 江苏江南铁合金有限公司 | Preparation method of Tb-Fe, Dy-Fe and Tb-Dy-Fe alloys employing electro-deoxidization |
| CN101629307A (en) * | 2009-04-29 | 2010-01-20 | 江苏江南铁合金有限公司 | Preparation method of rare earth metal Tb and Dy employing electro-deoxidization |
| CN101597711B (en) * | 2009-06-19 | 2011-05-04 | 燕山大学 | Rare earth-magnesium-transition metal base hydrogen storage metal preparation method |
| CN101914699B (en) * | 2010-07-26 | 2012-07-04 | 中国科学院长春应用化学研究所 | Fused salt electrosynthesis method of hydrogen storage alloy containing magnesium, lithium, sodium and potassium |
| CN202626314U (en) * | 2012-06-07 | 2012-12-26 | 赣南师范学院 | Novel graphite anode for rare earth electrolysis |
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