CN104073687B - A kind of superlattice Sm – Mg – Ni polyphase alloy and its preparation method and application and nickel metal hydride battery - Google Patents
A kind of superlattice Sm – Mg – Ni polyphase alloy and its preparation method and application and nickel metal hydride battery Download PDFInfo
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- CN104073687B CN104073687B CN201410302046.9A CN201410302046A CN104073687B CN 104073687 B CN104073687 B CN 104073687B CN 201410302046 A CN201410302046 A CN 201410302046A CN 104073687 B CN104073687 B CN 104073687B
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Abstract
The invention discloses a kind of superlattice Sm – Mg – Ni polyphase alloy and its preparation method and application and nickel metal hydride battery, belong to hydrogen storage material technical field.The Sm – Mg – Ni alloy provided is by A
2b
7type Sm
3mgNi
14and A
5b
19type Sm
4mgNi
19superlattice Phase forms, and preparation method is as follows: with Sm, Mg and Ni for raw material, adopts high-frequency induction smelting process to prepare as cast condition Sm – Mg – Ni polyphase alloy; By cast alloy grind into powder to make as cast condition mix mutually and compressing tablet; Then the style of compressing tablet process is heated to certain temperature and carries out the obtained desired superlattice Sm – Mg – Ni polyphase alloy of sintering.Superlattice Sm – Mg – Ni polyphase alloy provided by the invention at room temperature have hydrogen storage capability large, inhale the features such as the fast and reversible hydrogen storage characteristic of hydrogen discharging rate is good, effectively breach traditional LaNi
5higher and hydrogen-storage amount these two drawbacks low of base hydrogenous alloy cost.
Description
Technical field
The invention belongs to hydrogen storage material technical field, specifically, relate to a kind of novel hydrogen storage alloy and preparation method thereof, more particularly, relate to a kind of superlattice Sm – Mg – Ni polyphase alloy and its preparation method and application and nickel metal hydride battery, this alloy material is mainly used in the negative material of nickel metal hydride battery.
Background technology
As the negative material of nickel metal hydride battery, the La – Mg – Ni alloy with superstructure (comprises AB
3, A
2b
7, and A
5b
19etc. type) hydrogen storage capability be higher than practical AB
5type alloy, therefore in the past during the decade, such alloy is studied widely [Y.Liu, Y.Gao, Li.Huang, M.GaoandH.Pan, J.AlloysCompd., 509 (2011), 675].Although this kind of alloy hydrogen storage capability is higher, but in actual applications, still it is not enough to there are following several respects in them: (1) such alloy activation difficulty (generally need the suction of 3 ~ 8 times to put hydrogen cyclic activation, and activation temperature being often more than 100 DEG C); (2) with traditional LaNi
5alloy phase ratio, it is poor that hydrogen cyclical stability is put in suction, and namely service life cycle has much room for improvement; (3) material preparation process relative complex, and the cycle is relatively long, and production efficiency is low.
Develop a kind of effective way that new superlattice R – Mg – Ni (R is rare earth element) alloy system is considered to improve superlattice La – Mg – Ni alloy system existing the problems referred to above in utilization.Nearest people just have developed superlattice Pr – Mg – Ni system, and this diagram of system reveals and LaNi
5hydrogen circulation behavior is put in suitable suction.Put hydrogen cycle performance make moderate progress although inhale, but still there is problem [K.Iwase, the N.Terashita such as preparation efficiency is low and not easily-activated in this system, K.Mori, S.TsunokakeandT.Ishigaki, Int.J.HydrogenEnergy, 37 (2012), 18095].It should be noted that we are surprised to find that: Sm has the reactive behavior lower than La, thus make itself and La under equal ambient, show the ability of the attraction Sauerstoffatom more weak than La and put anti-powdering characteristic better than La in hydrogen process inhaling.Based on this, have reason to infer once Sm and Mg/Ni forms superlattice Sm – Mg – Ni alloy, it should have better to inhale than La – Mg – Ni alloy puts hydrogen and activates behavior and hydrogen cyclical stability is put in suction.
On the other hand, A is had benefited from
2b
7and A
5b
19type has mutually and compares AB
3the hydrogen storage capability that type is higher and better structural stability, therefore utilize A
2b
7and/or A
5b
19type causes the attention [K.Iwase, N.Terashita, K.Mori, H.YokotaandT.Suzuki, Inorg.Chem., 52 (2013), 14270] of investigators as the hydrogen storage property that alloy principal phase improves material.But in fact, make alloy obtain A
2b
7and/or A
5b
19type principal phase is but a very stern challenge.For La – Mg – Ni system alloy, because this is that alloy inevitably produces when solidifying and is separated, therefore certainly exist the feature of multiphase coexistence by La – Mg – Ni system alloy prepared by traditional smelting process, namely containing structural unstable AB
2type and the low AB of hydrogen-storage amount
5type, and the synergy of the two causes the comprehensive hydrogen storage property of alloy to decline.Obviously, how obtaining principal phase is A
2b
7and/or A
5b
19the alloy of type becomes the key of research.As everyone knows, the preparation path changing alloy is a kind of effective means realizing the regulation and control of alloy phase composition.Based on this, early stage our patent (patent No.: 200810122675, patent name is: a kind of preparation method of light hydrogen occluding alloy) disclose preparation method for La – Mg – Ni superlattice alloy, melting is adopted then to grind, then the method ball milling 24 ~ 48h of powdered alloy by mechanical force and chemical in ball grinder of grinding is obtained amorphous powder, amorphous powder compressing tablet becomes base and under proper temperature, utilizes sintering oven annealing 10h to obtain target material the most at last.Obviously, for this kind of material, the method there is time consumption and energy consumption and long time ball milling bring the shortcomings such as tank skin impurity into; Follow-up crystallization increases the consumption of preparation time and the energy further, and in crystallization process, hydrogen storage material is easy to oxidation so that the control of crystallization process difficulty, causes preparation cost significantly to increase.
Summary of the invention
The problem that 1, will solve
In order to break through traditional LaNi
5lower and the more high deficiency of cost of base alloy hydrogen storage capability; Also the prior art Problems existing such as to have much room for improvement to overcome La – Mg – Ni superlattice system's alloy preparation method length consuming time, cost high and comprehensive hydrogen storage property, the invention provides a kind of superlattice Sm – Mg – Ni Alloy And Preparation Method and application and nickel metal hydride battery, this novel superlattice alloy system has the advantages such as the simple and comprehensive hydrogen storage property of preparation method is excellent.
2, technical scheme
For overcoming the above problems, the technical solution used in the present invention is as follows:
The heterogeneous hydrogen storage alloy of a kind of superlattice Sm – Mg – Ni, is characterized in that, this alloy by two kinds of phase composites, be respectively: Sm
3mgNi
14phase and Sm
4mgNi
19phase.
Preferably, calculate according to mass percent (wt.%), described Sm
3mgNi
14the content of phase is 46 ~ 54%, and surplus is Sm
4mgNi
19phase.
A preparation method for the heterogeneous hydrogen storage alloy of Sm – Mg – Ni, the steps include:
(1) molten alloy: take Sm, Mg and Ni tablet raw material by foregoing component proportion, then adopts induction melting furnace directly the raw material of proportioning to be smelted into Sm – Mg – Ni ternary alloy;
(2) cast alloy obtained by step (1) is ground to form 200 ~ 300 order powdered alloys, compressing tablet obtains green compact;
(3) annealed 2 ~ 4 hours by green compact obtained for step (2), annealing temperature is controlled in 750 ~ 850 DEG C of intervals, can obtain only containing Sm after annealing
3mgNi
14and Sm
4mgNi
19the superlattice hydrogen storage alloy of phase.
Preferably, the purity of step (1) Raw is all not less than 99.0wt%, wherein Sm and Mg element is added respectively to the scaling loss compensation of 3 ~ 5wt% and 10 ~ 16wt%;
Preferably, the grinding in step (2) is placed in super purification glove box to grind, and compressing tablet is that obtained powdered alloy is directly put into stainless steel grinding tool, pressurize 1min under 20MPa pressure.
Preferably, in step (3), annealing inserts in common annealing stove after obtained green compact are sealed in the stainless steel vessel being full of rare gas element to anneal.
The application of the above-mentioned superlattice Sm – Mg heterogeneous hydrogen storage alloy of – Ni in nickel metal hydride battery.
A kind of nickel metal hydride battery, its negative material adopts the heterogeneous hydrogen storage alloy of foregoing superlattice Sm – Mg – Ni.
Principle of the present invention is as follows:
(1) the present invention utilizes the Sm lower than La reactive behavior to go to build superlattice Sm – Mg – Ni system alloy, and on the one hand, the activity of Sm is low, and resistance of oxidation is strong, and activation condition is relatively simple; On the other hand, Sm to be put in hydrogen process in suction can effective Suppress atomizing, and service life cycle is strengthened.In view of above-mentioned 2 points, constructed novel alloy just can be able to obtain than the better activation performance of La – Mg – Ni system alloy and service life cycle on the basis ensureing hydrogen storage capability.
(2) the whole A in order to make alloy obtain hydrogen storage property excellence
2b
7and/or A
5b
19type phase, also in order to utilize the A coexisted
2b
7and A
5b
19heavy alloyed apparent suction hydrogen desorption kinetics and activation performance are carried in the heterocatalysis that type is alternate.The present invention explores a kind of preparation method preparing novel Sm – Mg – Ni system alloy.Principle is, first according to composition proportion proportioning subject alloy, then each alloy slice is placed in smelting furnace melting, obtains and comprises AB
2, AB
3, A
2b
7, A
5b
19and AB
5at interior polyphase alloy; AB is comprised by what make alloy obtain after melting after grinding 200 ~ 300 object powdered alloy compressing tablet
2, AB
3, A
2b
7, A
5b
19and AB
5can fully contact and be uniformly distributed mutually; Next in common annealing stove, sinter specified time after the sample obtained by compressing tablet is sealed in the stainless steel vessel being full of inert atmosphere, utilize solid state reaction principle can obtain only containing A
2b
7and A
5b
19type phase Sm – Mg – Ni alloy.Meanwhile, the stainless steel vessel of the salable sample that this preparation method adopts, requires greatly to reduce to annealing furnace, general annealing furnace, has saved cost to a great extent and evaded the oxidized risk of sample.
3, beneficial effect
Compared with prior art, tool of the present invention has the following advantages:
(1) the present invention confirms first by A
2b
7and A
5b
19the existence of the Sm – Mg – Ni system alloy that type builds mutually, the intension of superlattice R – Mg – Ni alloy system has been enriched in this discovery, and provides nickel-hydrogen battery negative pole material of new generation;
(2) the present invention and traditional LaNi
5alloy phase ratio, the Sm – Mg – Ni alloy in the present invention had both had suction suitable with it and had put hydrogen cycle performance, had again than higher hydrogen storage capability and lower cost;
(3) the present invention and superlattice La – Mg – Ni system alloy phase ratio, the Sm – Mg – Ni alloy in the present invention had both had the hydrogen storage capability similar to La – Mg – Ni, had again the comparatively La – Mg – Ni better activation performance of system's alloy and cyclicity work-ing life;
(4) provided by the invention contains A
2b
7and A
5b
19preparation method's simple possible of the Sm – Mg – Ni alloy of type phase, Financial cost is low, and production efficiency is high, safe and reliable.
Accompanying drawing explanation
(a) in Fig. 1 is for metal Sm, Mg and Ni are according to 54wt%Sm
3mgNi
14+ 46wt%Sm
4mgNi
19the x-ray diffracting spectrum of sample after target component proportioning induction melting;
(b) in Fig. 1 is for metal Sm, Mg and Ni are according to 54wt%Sm
3mgNi
14+ 46wt%Sm
4mgNi
19the x-ray diffracting spectrum sintering gained sample (being defined as target sample A) is carried out again after target component proportioning induction melting;
(c) in Fig. 1 is for metal Sm, Mg and Ni are according to 46wt%Sm
3mgNi
14+ 54wt%Sm
4mgNi
19the x-ray diffracting spectrum of sample after target component proportioning induction melting;
(d) in Fig. 1 is for metal Sm, Mg and Ni are according to 46wt%Sm
3mgNi
14+ 54wt%Sm
4mgNi
19the x-ray diffracting spectrum sintering gained sample (being defined as target sample B) is carried out again after target component proportioning induction melting;
(a) in Fig. 2 is for Rietveld method is to the x-ray diffracting spectrum matching of target sample A;
(b) in Fig. 2 is for Rietveld method is to the x-ray diffracting spectrum matching of target sample B;
(c) in Fig. 2 for Rietveld method to metal Sm, Mg and Ni according to 50wt%Sm
3mgNi
14+ 50wt%Sm
4mgNi
19the x-ray diffracting spectrum matching of gained sample (being defined as target sample C) is sintered after the melting of target component proportioning;
Fig. 3 is the superlattice Sm of the novelty of Late Cambrian
3mgNi
14and Sm
4mgNi
19phase structure model: wherein:
3 (a) in figure is six square Sm
3mgNi
14(2H-A
2b
7) phase; 3 (b) in figure is six square Sm
4mgNi
19(2H-A
5b
19) phase; (c) in Fig. 3 is water chestnut square Sm
3mgNi
14(3R-A
2b
7) phase; (d) in Fig. 3 is water chestnut square Sm
4mgNi
19(3R-A
5b
19) phase;
The activation curve that (a) in Fig. 4 is target sample A;
The activation curve that (b) in Fig. 4 is target sample B;
Hydrogen cyclic curve is put in the suction that (a) in Fig. 5 is target sample A;
Hydrogen cyclic curve is put in the suction that (b) in Fig. 5 is target sample B;
The activation curve that (a) in Fig. 6 is target sample C;
Hydrogen cyclic curve is put in the suction that (b) in Fig. 6 is target sample C.
Embodiment
In order to understand technology contents of the present invention further, below in conjunction with the drawings and specific embodiments, the invention will be further described, but the present invention is not limited to following embodiment.
Embodiment 1
Molten alloy gross weight is 30 grams, by 54wt%Sm
3mgNi
14+ 46wt%Sm
4mgNi
19target component proportioning takes Sm sheet (purity 99%, the scaling loss for Sm many interpolations 3wt%), Mg sheet (purity is 99.5%, the scaling loss for Mg many interpolations 10wt%) and Ni sheet (purity 99%) respectively.Sm, Mg and Ni sheet taken being put into copper crucible induction melting under 18KW power and obtain Sm – Mg – Ni ternary alloy, as shown in (a) in Fig. 1, clearly there is AB in alloy in alloy phase composition
2, AB
3, A
2b
7, A
5b
19and AB
5the various phase such as type.In the glove box being filled with protection of inert gas, grind to form 300 order powdered alloys with after sharpening machine removing molten alloy surface scale, and in glove box, adopted by powdered alloy sample grinding tool to be pressed into Φ 13 × 3mm green compact, compressing tablet is compressing tablet under an argon atmosphere.Then green compact sample be placed in the stainless steel vessel sealing that is filled with rare gas element and anneal 2h in conventional vacuum annealing furnace, annealing temperature 750 DEG C, as shown in (b) in Fig. 1, only there is A2B7 and A5B19 type phase obviously in the sample phase composite after annealing.Further, carry out Full _ pattern fitting by Rietveld method as shown in (a) in Fig. 2 to the x-ray after sintering, fitting result shows the Sm of alloy by 54wt%
3mgNi
14with the Sm of 46wt%
4mgNi
19superlattice Phase is formed, and this and early stage predict the outcome mates completely.Fig. 3 gives the structural models of these Superlattice Phases simultaneously, and this is similar with corresponding superlattice La – Mg – Ni phase, this guarantees it and has higher hydrogen storage capability.Can directly use as hydrogen storage material after the alloy after sintering grinds to form powdered alloy.Superlattice Sm – Mg – Ni polyphase alloy prepared by the method has high suction and puts hydrogen activity, and material at room temperature only need once store up hydrogen reactivation process, as shown in (a) in Fig. 4, alloy activation once after, inhale hydrogen in 10 minutes substantially saturated.In addition, the Sm – Mg – Ni polyphase alloy that prepared by the method also ensure that the A that structural stability is good on the characteristic basis utilizing Sm
2b
7and A
5b
19the generation of type phase, therefore as shown in (a) in Fig. 5, even if the alloy after activation is put after hydrogen circulation through 250 suctions under 40 DEG C of conditions, capability retention still can reach about 95%, and this value is much higher than A
5b
19the La – Mg – Ni polyphase alloy of type (to put capability retention after hydrogen circulation be 89% through to inhale for 30 times), the i.e. cycle performance of alloy provided by the present invention and LaNi
5quite, show good Utilization prospects, after being prepared into nickel metal hydride battery, concrete preparation method is identical with common nickel metal hydride battery with technique.Difference is only material prepared by material selection the present embodiment of negative pole, and under nickel metal hydride battery life-span guaranteed prerequisite, hydrogen storage capability obtains to be increased.
Embodiment 2
Molten alloy gross weight is 30 grams, by 46wt%Sm
3mgNi
14+ 54wt%Sm
4mgNi
19target component proportioning takes Sm sheet (purity 99%, the scaling loss for Sm many interpolations 3wt%), Mg sheet (purity is 99.5%, the scaling loss for Mg many interpolations 10wt%) and Ni sheet (purity 99%) respectively.Sm, Mg and Ni sheet taken being put into copper crucible induction melting under 18KW power and obtain Sm – Mg – Ni ternary alloy, as shown in (c) in Fig. 1, clearly there is AB in alloy in alloy phase composition
2, AB
3, A
2b
7, A
5b
19and AB
5the various phase such as type.In the glove box being filled with protection of inert gas, grind to form 260 order powdered alloys with after sharpening machine removing molten alloy surface scale, and in glove box, adopted by powdered alloy sample grinding tool to be pressed into Φ 13 × 3mm green compact.Then green compact sample be placed in the stainless steel vessel sealing that is filled with rare gas element and anneal 4h in conventional vacuum annealing furnace, annealing temperature 850 DEG C, as shown in (d) in Fig. 1, only there is A in the sample phase composite after annealing obviously
2b
7and A
5b
19type phase.Further, carry out Full _ pattern fitting by Rietveld method as shown in (b) in Fig. 2 to the x-ray after sintering, fitting result shows the Sm of alloy by 46wt%
3mgNi
14with the Sm of 54wt%
4mgNi
19superlattice Phase is formed, and this and early stage predict the outcome mates completely.Fig. 3 gives the structural models of these Superlattice Phases simultaneously, and this is similar with corresponding superlattice La – Mg – Ni phase, this guarantees high hydrogen storage capability.Can directly use as hydrogen storage material after the alloy after sintering grinds to form powdered alloy.Superlattice Sm – Mg – Ni polyphase alloy prepared by the method has high suction and puts hydrogen activity, and material at room temperature only need once store up hydrogen reactivation process, as shown in (b) in Fig. 4, alloy activation once after, inhale hydrogen in 10 minutes substantially saturated.In addition, the Sm – Mg – Ni polyphase alloy that prepared by the method ensure that the A that structural stability is good
2b
7and A
5b
19the generation of type phase, therefore as shown in (b) in Fig. 5, even if the alloy after activation is put after hydrogen circulation through 250 suctions under 40 DEG C of conditions, capability retention still can reach about 95%, and this value is greater than A greatly
5b
19the La – Mg – Ni polyphase alloy (putting capability retention after hydrogen circulation through 30 suctions is 89%) of type, the cycle performance of alloy provided by the present invention and LaNi
5quite, good Utilization prospects is shown.
Embodiment 3
With embodiment 1, difference is according to 50wt%Sm3MgNi
14+ 50wt%Sm
4mgNi
19target component proportioning takes Sm sheet (purity 99.6% respectively, for Sm many interpolation 5wt% scaling loss), (purity is 99% to Mg sheet, for the scaling loss of Mg many interpolations 16wt%, concrete scaling loss is relevant with preparation parameter with crucible, the induction furnace adopted, this scaling loss is that those skilled in the art feel that the equipment adopted can calculate, and this place is not repeating) and Ni sheet; Cast alloy grinds to form 200 order powdered alloys; Green compact are annealed 3 hours, annealing temperature 810 DEG C, as shown in Fig. 2 (c), obtain only containing 50wt%Sm after annealing
3mgNi
14and 50wt%Sm
4mgNi
19the superlattice hydrogen storage alloy (it should be noted that: in present specification, because inevitable impurity is little on experimental result impact, so not as considering object) of phase; Fig. 6 (a) and Fig. 6 (b) point apparent go out this alloy activation curve and suction put hydrogen cycle performance, its behavior is similar with 2 to embodiment 1, is no longer described in detail herein; Material prepared by employing the present embodiment, as the negative material of nickel metal hydride battery, obviously can improve the use properties of nickel metal hydride battery, comprise the hydrogen storage capability of negative material, activation performance and suction and put hydrogen cycle performance, respond well.
Claims (6)
1. a preparation method for the heterogeneous hydrogen storage alloy of Sm – Mg – Ni, the steps include:
(1) molten alloy: take Sm, Mg and Ni tablet raw material according to the component proportion of the phase of alloy, wherein this alloy is by two kinds of phase composites, is respectively: Sm
3mgNi
14phase and Sm
4mgNi
19phase, Sm
3mgNi
14the content of phase is 46 ~ 54%, and surplus is Sm
4mgNi
19phase, then adopts induction melting furnace directly the raw material of proportioning to be smelted into Sm – Mg – Ni ternary alloy;
(2) cast alloy obtained by step (1) is ground to form 200 ~ 300 order powdered alloys, compressing tablet obtains green compact;
(3) annealed 2 ~ 4 hours by green compact obtained for step (2), annealing temperature is controlled in 750 ~ 850 DEG C of intervals, can obtain only containing Sm after annealing
3mgNi
14and Sm
4mgNi
19the superlattice hydrogen storage alloy of phase.
2. the preparation method of the heterogeneous hydrogen storage alloy of a kind of Sm – Mg – Ni according to claim 1, it is characterized in that, the purity of described step (1) Raw is all not less than 99.0wt%, wherein Sm and Mg element is added respectively to the scaling loss compensation of 3 ~ 5wt% and 10 ~ 16wt%.
3. the preparation method of the heterogeneous hydrogen storage alloy of a kind of Sm – Mg – Ni according to claim 1, it is characterized in that, grinding in described step (2) is placed in super purification glove box to grind, compressing tablet is that obtained powdered alloy is directly put into stainless steel grinding tool, pressurize 1min under 20MPa pressure.
4. the preparation method of the heterogeneous hydrogen storage alloy of a kind of Sm – Mg – Ni according to claim 1, it is characterized in that, in described step (3), annealing inserts in common annealing stove after obtained green compact are sealed in the stainless steel vessel being full of rare gas element to anneal.
5. the application of the superlattice Sm – Mg heterogeneous hydrogen storage alloy of – Ni in nickel metal hydride battery that in claim 1 or 2 prepared by the preparation method of the heterogeneous hydrogen storage alloy of a kind of Sm – Mg – Ni.
6. a nickel metal hydride battery, is characterized in that, the heterogeneous hydrogen storage alloy of superlattice Sm – Mg – Ni that its negative material adopts the preparation method of the heterogeneous hydrogen storage alloy of a kind of Sm – Mg – Ni in claim 1 or 2 to prepare.
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| CN114941058B (en) * | 2022-07-07 | 2023-05-23 | 上海大学 | High-purity Pr5Co19 type La-Y-Ni superlattice alloy and preparation method thereof |
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|---|---|---|---|---|
| CN101323918A (en) * | 2008-06-19 | 2008-12-17 | 安徽工业大学 | Preparation of light hydrogen occluding alloy |
| CN101501896A (en) * | 2006-08-09 | 2009-08-05 | 株式会社杰士汤浅 | Hydrogen storage alloy, hydrogen storage alloy electrode, secondary battery, and method for producing hydrogen storage alloy |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101501896A (en) * | 2006-08-09 | 2009-08-05 | 株式会社杰士汤浅 | Hydrogen storage alloy, hydrogen storage alloy electrode, secondary battery, and method for producing hydrogen storage alloy |
| CN101323918A (en) * | 2008-06-19 | 2008-12-17 | 安徽工业大学 | Preparation of light hydrogen occluding alloy |
Non-Patent Citations (2)
| Title |
|---|
| Microstructure and Electrochemical Characteristics of Step-Wise Annealed La0.75Mg0.25Ni3.5 Alloy with A2B7- and A5B19- type Super-Stacking Structure;Jingjing Liu et al.;《Journal of The Electrochemical Society》;20130514;第160卷(第8期);表3合金Sm1，第1139页左栏第1段，第1145页左栏第1段 * |
| 铸态及快淬态(Mg24Ni10)1-xSmx(x=0-0.2)合金气态吸放氢动力学性能研究;郭利召;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20130515(第5期);第8页第2段 * |
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