CN104073687A - Superlattice Sm-Mg-Ni multiphase alloy, preparation method and application of superlattice Sm-Mg-Ni multiphase alloy as well as nickel-metal hydride battery - Google Patents
Superlattice Sm-Mg-Ni multiphase alloy, preparation method and application of superlattice Sm-Mg-Ni multiphase alloy as well as nickel-metal hydride battery Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 93
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910052987 metal hydride Inorganic materials 0.000 title claims abstract description 16
- 229910019083 Mg-Ni Inorganic materials 0.000 title abstract 8
- 229910019403 Mg—Ni Inorganic materials 0.000 title abstract 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 70
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 70
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000003860 storage Methods 0.000 claims abstract description 37
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 29
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 26
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 13
- 238000002844 melting Methods 0.000 claims abstract description 13
- 230000008018 melting Effects 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 230000006698 induction Effects 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 66
- 238000000137 annealing Methods 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 15
- -1 nickel metal hydride Chemical class 0.000 claims description 14
- 239000010935 stainless steel Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- 229910002058 ternary alloy Inorganic materials 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 15
- 238000005245 sintering Methods 0.000 abstract description 10
- 239000011232 storage material Substances 0.000 abstract description 5
- 239000000843 powder Substances 0.000 abstract description 3
- 229910002335 LaNi5 Inorganic materials 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 230000002441 reversible effect Effects 0.000 abstract 1
- 230000004913 activation Effects 0.000 description 16
- 229910000990 Ni alloy Inorganic materials 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 238000003991 Rietveld refinement Methods 0.000 description 5
- 229910000905 alloy phase Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 235000003283 Pachira macrocarpa Nutrition 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 241001083492 Trapa Species 0.000 description 2
- 235000014364 Trapa natans Nutrition 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000007420 reactivation Effects 0.000 description 2
- 235000009165 saligot Nutrition 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a superlattice Sm-Mg-Ni multiphase alloy, a preparation method and an application of the superlattice Sm-Mg-Ni multiphase alloy as well as a nickel-metal hydride battery and belongs to the technical field of hydrogen storage material. The Sm-Mg-Ni alloy provided by the invention comprises A2B7 type Sm3MgNi14 and an A5B19 type Sm4MgNi19 superlattice phase. The preparation method comprises the following steps of preparing a cast Sm-Mg-Ni multiphase alloy from Sm, Mg and Ni as raw materials by virtue of a high-frequency induction melting method; grinding the cast alloy into powder, uniformly mixing the cast phase and sheeting; and then heating the sheeted sample to a certain temperature and sintering to obtain the superlattice Sm-Mg-Ni multiphase alloy. Superlattice Sm-Mg-Ni multiphase alloy provided by the invention has the characteristics of large hydrogen storage capacity, fast hydrogen absorption and release rate, good reversible hydrogen storage property and the like at room temperature and two drawbacks of relatively high cost and low hydrogen storage capacity of the traditional LaNi5-based hydrogen storage alloy are effectively broken.
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 will be higher than practical AB
5type alloy, therefore in the past during the decade, such alloy is studied [Y.Liu, Y.Gao, Li.Huang, M.Gao and H.Pan, J.Alloys Compd., 509 (2011), 675] widely.Although this class alloy hydrogen storage capability is higher, but in actual applications, still there is following several respects deficiency 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 service life cycle has much room for improvement; (3) material preparation process relative complex, and 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.People have just developed superlattice Pr – Mg – Ni system recently, and this diagram of system reveals and LaNi
5hydrogen circulation behavior is put in suitable suction.Put hydrogen cycle performance and 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.Tsunokake and T.Ishigaki, Int.J.Hydrogen Energy, 37 (2012), 18095].It should be noted that we are surprised to find that: Sm has the reactive behavior lower than La, thereby make itself and La show the ability of the attraction Sauerstoffatom more weak than La and put anti-efflorescence characteristic better than La in hydrogen process in suction under equal environment.Based on this, once have reason to infer that Sm and Mg/Ni form superlattice Sm – Mg – Ni alloy, it should have than La – Mg – Ni alloy better inhales and puts that hydrogen activates behavior and hydrogen cyclical stability is put in suction.
On the other hand, have benefited from A
2b
7and A
5b
19type has the AB of ratio mutually
3the hydrogen storage capability that type is higher and better structural stability, therefore utilize A
2b
7and/or A
5b
19the hydrogen storage property that type improves material as alloy principal phase has caused investigators' attention [K.Iwase, N.Terashita, K.Mori, H.Yokota and T.Suzuki, Inorg.Chem., 52 (2013), 14270].But in fact, make alloy obtain A
2b
7and/or A
5b
19type principal phase is but a very stern challenge.Be associated gold as example taking La – Mg – Ni, inevitably produce and be separated in the time solidifying because this is associated gold, certainly exist the feature of multiphase coexistence therefore the La – Mg – Ni preparing by traditional smelting process is associated gold, contain structural unstable AB
2the AB that type and hydrogen-storage amount are low
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 of change alloy is a kind of effective means that realizes 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) preparation method for La – Mg – Ni superlattice alloy disclosed, adopt melting then to grind, then powdered alloy grinding being formed method ball milling 24～48h by mechanical force and chemical in ball grinder obtains amorphous powder, and amorphous powder compressing tablet becomes base and under proper temperature, utilizes sintering oven annealing 10h can obtain target material the most at last.Obviously, for this class material, when the method has time consumption and energy consumption and length, ball milling is brought the shortcomings such as tank skin impurity into; Follow-up crystallization further increases the consumption of preparation time and the energy, and in crystallization process, hydrogen storage material is easy to oxidation so that the difficult control of crystallization process, 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 be the problem that the prior aries such as the high and comprehensive hydrogen storage property of alloy preparation method length consuming time, cost has much room for improvement exist in order to overcome La – Mg – Ni superlattice, 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 excellence of preparation method.
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 described Sm according to mass percent (wt.%)
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 adopt induction melting furnace directly the raw material of proportioning to be smelted into Sm – Mg – Ni ternary alloy;
(2) the prepared cast alloy of step (1) is ground to form to 200～300 order powdered alloys, compressing tablet obtains green compact;
(3) green compact annealing step (2) being made 2～4 hours, annealing temperature is controlled in 750～850 DEG C of intervals, can obtain and only contain 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 the scaling loss compensation of 3～5wt% and 10～16wt%;
Preferably, the grinding in step (2) is to be placed in super purification glove box to grind, and compressing tablet is that the powdered alloy making is directly put into stainless steel grinding tool, pressurize 1min under 20MPa pressure.
Preferably, annealing is that the green compact that make are sealed in after the stainless steel vessel that is full of rare gas element and insert in common annealing stove and anneal in step (3).
The application of the heterogeneous hydrogen storage alloy of above-mentioned superlattice Sm – Mg – 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 utilization of the present invention Sm lower than La reactive behavior removes to build superlattice Sm – Mg – Ni and is associated gold, 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 is put in hydrogen process effectively Suppress atomizing in suction, and service life cycle is strengthened.In view of above-mentioned 2 points, constructed novel alloy just can obtain than La – Mg – Ni and be associated better activation performance and service life cycle of gold on the basis that ensures hydrogen storage capability.
(2) in order to make alloy obtain whole A of hydrogen storage property excellence
2b
7and/or A
5b
19type phase, also in order to utilize the A coexisting
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 has explored and has a kind ofly prepared novel Sm – Mg – Ni and be associated golden preparation method.Principle is, first, according to composition proportion proportioning target alloy, then each alloy slice is placed in to smelting furnace melting, obtains and comprises AB
2, AB
3, A
2b
7, A
5b
19and AB
5at interior polyphase alloy; Make by grinding the AB that comprises that alloy obtains after melting after 200～300 object powdered alloy compressing tablets
2, AB
3, A
2b
7, A
5b
19and AB
5can fully contact and be uniformly distributed mutually; Next sample compressing tablet being made is sealed in after the stainless steel vessel that is full of inert atmosphere sintering specified time in common annealing stove, utilizes solid state reaction principle to obtain and only contains 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, and general annealing furnace has been saved to a great extent cost 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 has confirmed first by A
2b
7and A
5b
19the Sm – Mg – Ni that type builds is mutually associated golden existence, and the intension of superlattice R – Mg – Ni alloy system has been enriched in this discovery, and nickel-hydrogen battery negative pole material of new generation is provided;
(2) the present invention and traditional LaNi
5alloy phase ratio, the Sm – Mg – Ni alloy in the present invention had both had suitable with it suction and had put hydrogen cycle performance, had again than higher hydrogen storage capability and lower cost;
(3) the present invention is associated metallographic ratio with superlattice La – Mg – Ni, and the Sm – Mg – Ni alloy in the present invention had both had the hydrogen storage capability similar to La – Mg – Ni, has again compared with La – Mg – Ni and is associated gold better activation performance 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.
Brief description of the drawings
(a) in Fig. 1 is that metal Sm, Mg and Ni are according to 54wt%Sm
3mgNi
14+ 46wt%Sm
4mgNi
19the x ray diffraction collection of illustrative plates of sample after target component proportioning induction melting;
(b) in Fig. 1 is that metal Sm, Mg and Ni are according to 54wt%Sm
3mgNi
14+ 46wt%Sm
4mgNi
19after target component proportioning induction melting, carry out again the x ray diffraction collection of illustrative plates of sintering gained sample (being defined as target sample A);
(c) in Fig. 1 is that metal Sm, Mg and Ni are according to 46wt%Sm
3mgNi
14+ 54wt%Sm
4mgNi
19the x ray diffraction collection of illustrative plates of sample after target component proportioning induction melting;
(d) in Fig. 1 is that metal Sm, Mg and Ni are according to 46wt%Sm
3mgNi
14+ 54wt%Sm
4mgNi
19after target component proportioning induction melting, carry out again the x ray diffraction collection of illustrative plates of sintering gained sample (being defined as target sample B);
(a) in Fig. 2 is the x ray diffraction collection of illustrative plates matching of Rietveld method to target sample A;
(b) in Fig. 2 is the x ray diffraction collection of illustrative plates matching of Rietveld method to target sample B;
(c) in Fig. 2 is Rietveld method to metal Sm, Mg and Ni according to 50wt%Sm
3mgNi
14+ 50wt%Sm
4mgNi
19the x ray diffraction collection of illustrative plates matching of sintering gained sample (being defined as target sample C) after the melting of target component proportioning;
Fig. 3 is the novel superlattice Sm finding first
3mgNi
14and Sm
4mgNi
19phase structure model: wherein:
In figure 3 (a) is six square Sm
3mgNi
14(2H-A
2b
7) phase; In figure 3 (b) 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;
(a) in Fig. 4 is the activation curve of target sample A;
(b) in Fig. 4 is the activation curve of 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;
(a) in Fig. 6 is the activation curve of target sample C;
Hydrogen cyclic curve is put in the suction that (b) in Fig. 6 is target sample C.
Embodiment
In order further to understand technology contents of the present invention, 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 respectively Sm sheet (purity 99%, the scaling loss of adding 3wt% for Sm), Mg sheet (purity is 99.5%, the scaling loss of adding 10wt% for Mg more) and Ni sheet (purity 99%) more.The Sm taking, Mg and Ni sheet 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 phases such as type.After removing molten alloy surface scale with sharpening machine, grind to form 300 order powdered alloys in the glove box that is filled with protection of inert gas, and in glove box, adopt grinding tool to be pressed into Φ 13 × 3mm green compact in powdered alloy sample, compressing tablet is at argon gas atmosphere lower sheeting.Then green compact sample is placed in and is filled with the stainless steel vessel sealing of rare gas element and in the conventional vacuum annealing furnace 2h that anneals, 750 DEG C of annealing temperatures, as shown in (b) in Fig. 1, only there is obviously A in the sample phase composite after annealing
2b
7and A
5b
19type phase.Further, the x ray by Rietveld method after to sintering is composed matching entirely as shown in (a) in Fig. 2, and fitting result shows the Sm of alloy by 54wt%
3mgNi
14sm with 46wt%
4mgNi
19superlattice Phase forms, and this predicted the outcome and mate completely with early stage.Fig. 3 has provided the structural models of these Superlattice Phases simultaneously, and this is mutually similar with corresponding superlattice La – Mg – Ni, and this has just ensured that it has higher hydrogen storage capability.After grinding to form powdered alloy, the alloy after sintering can directly use as hydrogen storage material.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, after alloy activation once, inhales hydrogen in 10 minutes substantially saturated.In addition the Sm – Mg – Ni polyphase alloy that, prepared by the method has also ensured the A of structure good stability on the characteristic basis that utilizes 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 inhaled and put after hydrogen circulation through 250 times under 40 DEG C of conditions, capability retention still can reach approximately 95%, and this value is much higher than A
5b
19the La – Mg – Ni polyphase alloy (capability retention is 89% after hydrogen circulation is put in 30 suctions) of type, i.e. the cycle performance of alloy provided by the present invention and LaNi
5quite, show the prospect of well utilizing, be prepared into after 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 guaranteed prerequisite of nickel metal hydride battery life-span, 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 respectively Sm sheet (purity 99%, the scaling loss of adding 3wt% for Sm), Mg sheet (purity is 99.5%, the scaling loss of adding 10wt% for Mg more) and Ni sheet (purity 99%) more.The Sm taking, Mg and Ni sheet 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 phases such as type.After removing molten alloy surface scale with sharpening machine, in the glove box that is filled with protection of inert gas, grind to form 260 order powdered alloys, and in glove box, adopt grinding tool to be pressed into Φ 13 × 3mm green compact in powdered alloy sample.Then green compact sample is placed in and is filled with the stainless steel vessel sealing of rare gas element and in the conventional vacuum annealing furnace 4h that anneals, 850 DEG C of annealing temperatures, as shown in (d) in Fig. 1, only there is obviously A in the sample phase composite after annealing
2b
7and A
5b
19type phase.Further, the x ray by Rietveld method after to sintering is composed matching entirely as shown in (b) in Fig. 2, and fitting result shows the Sm of alloy by 46wt%
3mgNi
14sm with 54wt%
4mgNi
19superlattice Phase forms, and this predicted the outcome and mate completely with early stage.Fig. 3 has provided the structural models of these Superlattice Phases simultaneously, and this is mutually similar with corresponding superlattice La – Mg – Ni, and this has just ensured high hydrogen storage capability.After grinding to form powdered alloy, the alloy after sintering can directly use as hydrogen storage material.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, after alloy activation once, inhales hydrogen in 10 minutes substantially saturated.In addition the Sm – Mg – Ni polyphase alloy that, prepared by the method has ensured the A of structure good stability
2b
7and A
5b
19the generation of type phase, therefore, as shown in (b) in Fig. 5, even if the alloy after activation is inhaled and put after hydrogen circulation through 250 times under 40 DEG C of conditions, capability retention still can reach approximately 95%, and this value is greater than A greatly
5b
19the La – Mg – Ni polyphase alloy (capability retention is 89% after hydrogen circulation is put in 30 suctions) of type, the cycle performance of alloy provided by the present invention and LaNi
5quite, show the prospect of well utilizing.
Embodiment 3
With embodiment 1, difference is according to 50wt%Sm
3mgNi
14+ 50wt%Sm
4mgNi
19target component proportioning takes respectively Sm sheet (purity 99.6%, add the scaling loss of 5wt% for Sm more), (purity is 99% to Mg sheet, add the scaling loss of 16wt% for Mg more, concrete scaling loss is relevant with the crucible, induction furnace and the preparation parameter that adopt, this scaling loss is that those skilled in the art feel that the equipment adopting can calculate, and this place is not repeating) and Ni sheet; Cast alloy grinds to form 200 order powdered alloys; Green compact annealing 3 hours, 810 DEG C of annealing temperatures, as shown in Fig. 2 (c), have obtained after annealing and have only contained 50wt%Sm
3mgNi
14and 50wt%Sm
4mgNi
19the superlattice hydrogen storage alloy (it should be noted that: in present specification, because inevitably 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, can obviously improve the use properties of nickel metal hydride battery, comprises that hydrogen cycle performance is put in hydrogen storage capability, activation performance and the suction of negative material, respond well.
Claims (8)
1. the heterogeneous hydrogen storage alloy 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.
2. the heterogeneous hydrogen storage alloy of a kind of Sm – Mg – Ni according to claim 1, is characterized in that, calculates described Sm according to mass percent
3mgNi
14the content of phase is 46～54%, and surplus is Sm
4mgNi
19phase.
3. 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 component proportion claimed in claim 2, then adopt induction melting furnace directly the raw material of proportioning to be smelted into Sm – Mg – Ni ternary alloy;
(2) the prepared cast alloy of step (1) is ground to form to 200～300 order powdered alloys, compressing tablet makes green compact;
(3) green compact annealing step (2) being made 2～4 hours, annealing temperature is controlled in 750～850 DEG C of intervals, can obtain and only contain Sm after annealing
3mgNi
14and Sm
4mgNi
19the superlattice hydrogen storage alloy of phase.
4. the preparation method of the heterogeneous hydrogen storage alloy of a kind of Sm – Mg – Ni according to claim 3, 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 the scaling loss compensation of 3～5wt% and 10～16wt%.
5. the preparation method of the heterogeneous hydrogen storage alloy of a kind of Sm – Mg – Ni according to claim 3, it is characterized in that, grinding in described step (2) is to be placed in super purification glove box to grind, compressing tablet is that the powdered alloy making is directly put into stainless steel grinding tool, pressurize 1min under 20MPa pressure.
6. the preparation method of the heterogeneous hydrogen storage alloy of a kind of Sm – Mg – Ni according to claim 3, it is characterized in that, in described step (3), annealing is that the green compact that make are sealed in after the stainless steel vessel that is full of rare gas element and insert in common annealing stove and anneal.
7. the application of the heterogeneous hydrogen storage alloy of superlattice Sm – Mg – Ni in claim 1 or 2 in nickel metal hydride battery.
8. a nickel metal hydride battery, is characterized in that, its negative material adopts the heterogeneous hydrogen storage alloy of superlattice Sm – Mg – Ni in claim 1 or 2.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108493436A (en) * | 2018-03-09 | 2018-09-04 | 燕山大学 | Ni-based quaternary hydrogen-storing alloy electrode material of a kind of super stacking provisions lanthanum-M-magnesium-of 2H types A5B19 and preparation method thereof |
| CN114941058A (en) * | 2022-07-07 | 2022-08-26 | 上海大学 | High-purity Pr5Co19 type La-Y-Ni superlattice alloy and preparation method thereof |
| CN116219228A (en) * | 2023-03-03 | 2023-06-06 | 包头中科轩达新能源科技有限公司 | A kind of (Gd, mg) 2 Ni 7 Preparation method of superlattice hydrogen storage alloy |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2014
- 2014-06-27 CN CN201410302046.9A patent/CN104073687B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|
| JINGJING LIU ET AL.: "Microstructure and Electrochemical Characteristics of Step-Wise Annealed La0.75Mg0.25Ni3.5 Alloy with A2B7- and A5B19- type Super-Stacking Structure", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》, vol. 160, no. 8, 14 May 2013 (2013-05-14) * |
| 郭利召: "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", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 5, 15 May 2013 (2013-05-15) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108493436A (en) * | 2018-03-09 | 2018-09-04 | 燕山大学 | Ni-based quaternary hydrogen-storing alloy electrode material of a kind of super stacking provisions lanthanum-M-magnesium-of 2H types A5B19 and preparation method thereof |
| CN114941058A (en) * | 2022-07-07 | 2022-08-26 | 上海大学 | High-purity Pr5Co19 type La-Y-Ni superlattice alloy and preparation method thereof |
| 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 |
| CN116219228A (en) * | 2023-03-03 | 2023-06-06 | 包头中科轩达新能源科技有限公司 | A kind of (Gd, mg) 2 Ni 7 Preparation method of superlattice hydrogen storage alloy |
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