CN101429636B - Thermal treatment method for rare earth nickel based AB5 type hydrogen storage alloy - Google Patents
Thermal treatment method for rare earth nickel based AB5 type hydrogen storage alloy Download PDFInfo
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Abstract
The invention relates to a thermal processing method for rare earth nickel base AB5 type hydrogen storage alloy for the negative electrode of a nickel hydrogen cell. A staged thermal processing method using low-temperature treatment before high-temperature treatment is adopted for the rare earth nickel base AB5 type hydrogen storage alloy in the inert or reducing atmosphere after smelting and casing the rare earth nickel base AB5 type hydrogen storage alloy into ingots. In particular, the staged thermal processing is carried out by firstly keeping the rare earth nickel base AB5 type hydrogen storage alloy within the temperature range of 400 to 800 DEG C for 2 to 5 hours; and then increasing the temperature to 950 to 1100 DEG C and keeping the temperature for 0.3 to 5 hours. The staged thermal processing of the rare earth nickel base AB5 type hydrogen storage alloy can remove and improve the component segregation, the lattice stress and the lattice distortion of the hydrogen storage alloy without the merging and growing of the crystal grains of the alloy, thereby improving the anti-atomization capability of the alloy, improving the gradient of the P-C-T curve of the hydrogen storage alloy, reducing the platform pressure, improving the hydrogen absorption and desorption amount, the electrochemical content and the cycle life of the alloy, and consequently truly improving the electrochemical performance and the cycle life of the cell.
Description
[technical field]
The present invention relates to a kind of nickel-hydrogen battery negative pole rare-earth Ni-base AB
5The heat treating method of type hydrogen-storage alloy.
[background technology]
Rare-earth Ni-base AB
5The type hydrogen-storage alloy has activation performance and higher electrochemistry capacitance preferably, is used widely as the Ni-MH cell negative electrode material.Conventional founding AB
5Type hydrogen storage alloy easily produces grain segregation and lattice imperfection, and the homogeneity of composition and microtexture is relatively poor and crystal lattice stress is bigger.Though the increase speed of cooling can reduce segregation, improve homogeneity of ingredients, lattice imperfection is increased, crystal lattice stress increases.Some element of alloy such as nickel, cobalt, manganese, aluminium etc. can be deposited on the crystal boundary surface simultaneously, and alloy is corroded easily, thereby reduce the chemical property of alloy.And thermal treatment can reduce alloy lattice defective and crystal lattice stress, promotes the homogenizing of alloying constituent, strengthens the anti-efflorescence ability of alloy, obviously improves the maximum discharge capacity and the cycle life of alloy.
Rare-earth Ni-base AB
5The type hydrogen-storage alloy is generally by after the alloying constituent batching, frequently carry out melting in the induction furnace at first in a vacuum, and be cast into ingot casting, then ingot casting is packed in the vacuum heat treatment furnace, the thermal treatment of annealing, then with heat treated ingot casting through coarse reduction, fine powder is broken and the screening after, finally obtain hydrogen-storage alloy powder.Rare-earth Ni-base AB
5Type hydrogen-storage alloy ingot casting after heat treatment, can eliminate and improve the component segregation of hydrogen-storage alloy, thereby the homogeneity of ingredients of hydrogen-storage alloy is improved, simultaneously can eliminate and improve crystal lattice stress and lattice distortion that hydrogen-storage alloy is caused because of casting, thereby improve the obliquity of hydrogen-storage alloy P-C-T curve and reduce plateau pressure, raising sucking/placing hydrogen amount, electrochemistry capacitance and cycle life etc.
Rare-earth Ni-base AB
5Thermal treatment process in the type hydrogen storage alloy production process generally is that alloy cast ingot is incubated 10～12 hours for about 900 ℃～1000 ℃ in temperature.Though the component segregation of hydrogen-storage alloy also can be eliminated and improve to this thermal treatment process, particularly reduce the segregation of manganese element in the alloy, thereby make the homogenization of composition of hydrogen-storage alloy, simultaneously can eliminate and improve crystal lattice stress and lattice distortion that hydrogen-storage alloy is caused because of casting, thereby improve the obliquity of hydrogen-storage alloy P-C-T curve and reduce plateau pressure, improve sucking/placing hydrogen amount, electrochemistry capacitance and cycle life etc., but because temperature height, time is long, thereby causing alloy grain to merge grows up, thickization of alloy metallographic structure, thereby influence the powder performance of hydrogen-storage alloy, finally influence the cyclical stability of hydrogen-storage alloy.In addition, thermal treatment process is because the temperature that is adopted is higher, and soaking time is longer, thereby the electric power energy that consumes is more, and the production time is longer, and the established technology cost is bigger.
Rare-earth Ni-base AB
5The type hydrogen-storage alloy also can be at a lower temperature, and for example the insulation certain hour is heat-treated in 400 ℃～800 ℃ temperature ranges.This heat treating method is because thermal treatment temp is lower, so need very long soaking time.
Rare-earth Ni-base AB
5After adopting 1000 ℃ of first high temperature to be incubated for some time, the type hydrogen-storage alloy is incubated the heat treating methods of for some time again in 850 ℃ of insulations of lower temperature.When hydrogen-storage alloy is incubated,, then be difficult to eliminate and improve the component segregation of hydrogen-storage alloy under comparatively high temps, reduce the segregation of manganese element in the alloy if soaking time is shorter; Soaking time is longer, can cause alloy grain to merge and grow up, and increases grain-size, promptly causes thickization of alloy metallographic structure, thereby influences the powder performance of hydrogen-storage alloy.
[summary of the invention]
The contriver is through discovering, the temperature that thermal treatment process adopted under the high temperature is higher, and soaking time is longer, hydrogen-storage alloy homogenization of composition, crystal lattice stress and lattice distortion after heat treatment eliminated and when improving, can cause alloy grain to merge grows up, promptly cause thickization of alloy metallographic structure, thereby influence the powder performance of hydrogen-storage alloy, finally influence the cyclical stability of hydrogen-storage alloy.In addition, thermal treatment process is because the temperature that is adopted is higher, and soaking time is longer, thereby the electric power energy that consumes is more, and the production time is longer, and the established technology cost is bigger;
Thermal treatment process under the low temperature needs very long soaking time, so not only can prolong the production time of hydrogen-storage alloy, can not reduce production energy consumption simultaneously, promptly is unfavorable for the production of hydrogen-storage alloy.If soaking time is shorter, though can eliminate and improve crystal lattice stress and lattice distortion that hydrogen-storage alloy is caused because of casting, but be difficult to eliminate and improve the component segregation of hydrogen-storage alloy, reduce the segregation of manganese element in the alloy, thereby be difficult to improve the obliquity of hydrogen-storage alloy P-C-T curve and reduce plateau pressure, raising sucking/placing hydrogen amount, electrochemistry capacitance and cycle life etc.;
At high temperature carry out insulation low temperature under after the insulation again, established hydrogen storage property and chemical property exert an influence then to be difficult at high temperature to be incubated afterwards to hydrogen-storage alloy.This be because, if soaking time is short under the high temperature, the hydrogen-storage alloy component segregation of then not eliminating as yet and improving, insulation also is difficult to eliminate and improve at low temperatures, unless insulation for a long time at low temperatures.If soaking time is longer under the high temperature, can cause alloy grain to merge and grow up, grain-size increases, promptly cause thickization of alloy metallographic structure, thereby influence the powder performance of hydrogen-storage alloy, when continuing the insulation under the low temperature, if soaking time is longer, then can make further thickization of alloy metallographic structure; Soaking time is shorter, also can not improve thickization of alloy metallographic structure.
At rare-earth Ni-base AB
5The shortcoming of the heat treating method of type hydrogen-storage alloy, the contriver is through inquiring into repeatedly and studying, and carried out a large amount of experiments, having overcome the alloy grain merging that exists in the prior art grows up, lattice dimensions increases, and energy consumption is big, the defective that heat treatment time is long, improved the cyclical stability and the capacity of hydrogen-storage alloy, thereby a kind of nickel-hydrogen battery negative pole rare-earth Ni-base AB is provided
5The heat treating method of type hydrogen-storage alloy, rare-earth Ni-base AB
5The type hydrogen-storage alloy adopts pyritous segmentation thermal treatment behind the first low temperature in inertia or reducing atmosphere after melting and being cast into ingot casting.
The present invention can be preferably, rare-earth Ni-base AB
5The type hydrogen-storage alloy in inertia or reducing atmosphere, is incubated 2～5 hours earlier in 400～800 ℃ of temperature ranges after melting and being cast into ingot casting, be warmed up to 950～1100 ℃ of insulations then and carried out segmentation thermal treatment in 0.5～3 hour.More preferably its low-temperature zone is 550 ℃～650 ℃, and soaking time is 3.5～4.5 hours, and high temperature section is 950 ℃～1050 ℃, and soaking time is 1.5～2.5 hours.Preferably be warmed up to 1000 ℃ of insulations 2 hours after 4 hours at 600 ℃ of heat tracings.
Rare-earth Ni-base AB
5The inert atmosphere of type hydrogen-storage alloy is argon gas, helium, nitrogen and mixed gas thereof, and reducing atmosphere is to sneak into a certain amount of hydrogen to constitute in argon gas, helium, nitrogen or its mixed inert atmosphere.
Rare-earth Ni-base AB
5The type hydrogen-storage alloy can be common rare-earth Ni-base AB
5The type hydrogen-storage alloy, being preferably with cerium-rich mischmetal, electrolytic nickel, cobalt, manganese, aluminium is starting material, according to MmNi
3.55Co
0.75Mn
0.4Al
0.3The alloy composition is prepared burden.Wherein cerium-rich mischmetal weight consists of 27.28wt%La, 50.41wt%Ce, 5.03wt%Pr, 17.04wt%Nd, and other raw material metal purity are all greater than 99.9wt%.Rare-earth Ni-base AB
5The medium frequency induction melting furnace melting of type hydrogen-storage alloy under 1300 ℃～1500 ℃ cast after 2～4 hours and to be obtained.
Rare-earth Ni-base AB
5The type hydrogen-storage alloy is after above-mentioned segmentation thermal treatment, can eliminate and improve the component segregation of hydrogen-storage alloy, thereby the homogeneity of ingredients of hydrogen-storage alloy is improved, simultaneously can eliminate and improve crystal lattice stress and lattice distortion that hydrogen-storage alloy is caused because of casting, and alloy grain can not merge and grows up, thereby improved the anti-efflorescence ability of alloy, improved the obliquity of hydrogen-storage alloy P-C-T curve, reduced plateau pressure, improve alloy hydrogen absorption and desorption amount, electrochemistry capacitance and cycle life etc., thereby really improved the electrochemistry cycle life performance of battery.
[embodiment]
Rare-earth Ni-base AB
5Type hydrogen-storage alloy ingot casting at first is incubated 2～5 hours in 400～800 ℃ of temperature ranges in inertia or reducing atmosphere.Alloy cast ingot is incubated the regular hour at first at a lower temperature, can eliminate and improve crystal lattice stress and lattice distortion that hydrogen-storage alloy is caused because of casting, the internal stress of eliminating lattice imperfection such as dislocation in the alloy and eliminating alloy, reduce simultaneously the segregation of alloying element to a certain extent, make non-equilibrium second minimizing mutually in the alloy.Owing to be to be incubated for some time at a lower temperature to heat-treat, so can not cause alloy grain to merge growing up, the grain-size increase.During thermal treatment, its temperature is better 400～800 ℃ of temperature ranges under the lesser temps.Temperature is as being lower than 400 ℃, and then temperature is too low, is difficult to eliminate fully and improves hydrogen-storage alloy because of crystal lattice stress and lattice distortion that casting is caused, says nothing of the segregation that reduces alloying element etc.; Temperature is as being higher than 800 ℃, and then temperature is too high, is difficult to steadily control the thermal treatment process, can cause alloy part crystal grain to merge in the insulation later stage and grow up.Rare-earth Ni-base AB
5Type hydrogen-storage alloy ingot casting in 400～800 ℃ of temperature ranges during thermal treatment, soaking time be 2～5 hours better., then be difficult to eliminate fully and improve hydrogen-storage alloy less than 2 hours as soaking time, say nothing of the segregation that reduces alloying element etc. because of crystal lattice stress and lattice distortion that casting is caused; ,, during the soak of insulation later stage and back, can cause alloy part crystal grain to merge and grow up greater than 5 hours as soaking time though then can eliminate and improve crystal lattice stress and the lattice distortion that hydrogen-storage alloy is caused because of casting fully.
Rare-earth Ni-base AB
5Type hydrogen-storage alloy ingot casting, in inertia or reducing atmosphere, in 400～800 ℃ of temperature ranges, be incubated 2～5 hours after, be warmed up to 950～1100 ℃ of insulations and heat-treated in 0.5～3 hour.Because alloy cast ingot has been incubated the regular hour at a lower temperature, therefore eliminated and improved crystal lattice stress and lattice distortion that hydrogen-storage alloy is caused because of casting, the internal stress of having eliminated lattice imperfections such as dislocation in the alloy and having eliminated alloy, reduced simultaneously the segregation of alloying element to a certain extent, made non-equilibrium second minimizing mutually in the alloy.Alloy cast ingot continues to be warmed up to 950～1100 ℃ of insulations when heat-treating in 0.5～3 hour, because thermal treatment temp is higher, therefore can further reduce and eliminate fully the segregation of alloying element,, not grow up so can not cause alloy grain to merge simultaneously because heat treatment time is shorter.Alloy cast ingot is warmed up to 950～1100 ℃ better when continuing thermal treatment.Temperature then relatively near the holding temperature first time, is difficult to further reduce and eliminate the segregation of alloying element as being lower than 950 ℃; Temperature is as being higher than 1100 ℃, and then temperature is too high, when further reducing and eliminating the alloying element segregation, can cause alloy grain to merge and grow up.When alloy cast ingot continues to be warmed up to 950～1100 ℃ of thermal treatments soaking time be 0.5～3 hour better.Soaking time then is difficult to eliminate fully the segregation of alloying element as less than 0.5 hour; Soaking time then when eliminating the alloying element segregation, can cause alloy grain to merge and grow up as greater than 3 hours.
Embodiment 1
1. hydrogen-storage alloy is made:
With cerium-rich mischmetal, electrolytic nickel, cobalt, manganese, aluminium is starting material, according to MmNi
3.55Co
0.75Mn
0.4Al
0.3The alloy composition is prepared burden, and wherein cerium-rich mischmetal weight consists of 27.28wt%La, 50.41wt%Ce, 5.03wt%Pr, 17.04wt%Nd, and other raw material metal purity are all greater than 99.9wt%.
The alloy raw material of being joined is placed in the medium frequency induction melting furnace (electric furnace company limited in Jinzhou produces, and capacity is 500kg), and 1300 ℃～1500 ℃ following meltings 2～4 hours, casting obtained alloy pig.Ultimate analysis shows, gained hydrogen-storage alloy piece consist of MmNi
3.55Co
0.75Mn
0.4Al
0.3
With above-mentioned MmNi
5Be rare-earth Ni-base AB
5Type hydrogen-storage alloy ingot is put into the vacuum high-temperature resistance furnace (production of Jinzhou electric furnace company limited) that is filled with the 0.5atm argon gas, heat-treats according to the heat treating regime of table one respectively.After the above-mentioned alloy thermal treatment, carry out just pulverizing and in being filled with the vacuum sphere grinding machine of argon gas, grinding, cross 200 mesh sieves, obtain hydrogen-storage alloy powder.Use the size-grade distribution of BT-9300S laser particle size distribution instrument (hundred special Instr Ltd. produce) test hydrogen-storage alloy powder, the average particle diameter D50 of hydrogen-storage alloy powder is 50 microns.
2.Ni-MH open cell is made:
Get hydrogen-storage alloy powder that 0.5g makes and metal nickel powder and mix by 1: 3 mass ratio, the disk that is pressed into diameter 12.5mm with 20Mpa pressure on tabletting machine is as the open cell negative pole, parcel diaphragm paper, the anodal Ni (OH) that adopts
2, positive and negative electrode is fixed with the PVC plate, immerses in the 7mol/LKOH electrolytic solution, constitutes the open cell system of negative pole control capacity.
Electrochemical properties of hydrogen storage alloys is measured: electrochemical properties of hydrogen storage alloys is measured by the DC-5 cell tester, and for guaranteeing the identity of test condition, the test job of sample battery performance is to carry out simultaneously under same condition.
3. the hydrogen-storage alloy electrochemistry capacitance is measured:
With Experimental cell with 50mA (1/3C) constant current charge 4.5 hours, stopping behind the 30min with 30mA (0.2C) constant current discharge to voltage between the positive and negative electrode is 1.000V, begin the charge and discharge cycles of next cycle behind the placement 30min again, so repeat to activate fully until the sample battery, the maximum value that loading capacity reaches during activation is the alloy electrochemistry capacitance.
4. battery cycle life is measured:
Above-mentioned various battery is through after discharging and recharging activation for the first time, with 150mA (1C) constant current charge 1.2 hours, stopping behind the 5min with 150mA (1C) constant current discharge to voltage between the positive and negative electrode is 1.000V, begin the charge and discharge cycles of next cycle behind the placement 5min again, write down each cyclic discharge capacity, with the 200th cyclic discharge capacity ratio with high discharge capacity, as the cyclic discharge capacity conservation rate, i.e. the cycle life of hydrogen-storage alloy.
Embodiment 2-11 and comparative example 1-10
Except thermal treatment temp and time and embodiment 1 were different, other condition was all identical with embodiment 1.Specifically as shown in Table 1,
Alloy electrochemical performance under table one, the Different Heat Treatment Conditions
| Sequence number | Heat-treat condition | Loading capacity (mAh/g) | 200 circulation volume conservation rates (%) |
| Comparative example 1 | 300℃*4h，1000℃*2h | 289 | 86 |
| Embodiment 1 | 400℃*4h，1000℃*2h | 315 | 94 |
| Embodiment 2 | 500℃*4h，1000℃*2h | 314 | 95 |
| Embodiment 3 | 600℃*4h，1000℃*2h | 324 | 96 |
| Embodiment 4 | 800℃*4h，1000℃*2h | 318 | 94 |
| Comparative example 2 | 900℃*4h，1000℃*2h | 311 | 88 |
| Comparative example 3 | 600℃*1h，1000℃*2h | 294 | 87 |
| Embodiment 5 | 600℃*2h，1000℃*2h | 317 | 93 |
| Embodiment 6 | 600℃*5h，1000℃*2h | 320 | 96 |
| Comparative example 4 | 600℃*7h，1000℃*2h | 314 | 86 |
| Comparative example 5 | 600℃*4h，900℃*2h | 286 | 93 |
| Embodiment 7 | 600℃*4h，950℃*2h | 319 | 96 |
| Embodiment 8 | 600℃*4h，1100℃*2h | 318 | 94 |
| Comparative example 6 | 600℃*4h，1150℃*2h | 301 | 84 |
| Comparative example 7 | 600℃*4h | 287 | 95 |
| Embodiment 9 | 600℃*4h，1000℃*0.5h | 311 | 92 |
| Embodiment 10 | 600℃*4h，1000℃*1h | 318 | 93 |
| Embodiment 11 | 600℃*4h，1000℃*3h | 320 | 94 |
| Comparative example 8 | 600℃*4h，1000℃*6h | 299 | 83 |
| Comparative example 9 | As cast condition | 282 | 82 |
| Comparative example 10 | 1000℃*10h | 296 | 82 |
By table one data as can be known, the comparative example 9 of not heat-treating compares through heat treated alloy phase with other, and its electrochemistry capacitance and cycle life are all relatively poor, therefore must be to rare-earth Ni-base AB
5The type hydrogen-storage alloy is heat-treated.Comparative example 1～2 and embodiment 1～4 are compared, and when the temperature that can find low temperature insulation was 300 ℃ and 900 ℃, though the loading capacity of hydrogen-storage alloy is improved to some extent, its cycle performance improvement was not very big.Therefore take all factors into consideration the loading capacity and the cycle performance of hydrogen-storage alloy, when the soak condition is 1000 ℃ of * 2h, the temperature of leading portion low temperature insulation be 400～800 ℃ better.Preferably 600 ℃.
Comparative example 3～4 and embodiment 5～6 and 3 are compared, can find the comparative example 3 that soaking time is short, though the loading capacity of its alloy is higher than the as cast condition hydrogen-storage alloy, reach 294mAh/g, capability retention only is 87%; And soaking time is the comparative example 4 of 7h, though loading capacity is higher, reach 314mAh/g, and capability retention only is 86%; The embodiment 5～6 and 3 that soaking time is comparatively moderate, its loading capacity and cycle life are all better, so the time of low temperature insulation is that 2～5h is better.Preferably 4 hours.
Comparative example 5～6 and embodiment 7～8 and 3 are compared, can find that the soak temperature is 900 ℃ a comparative example 5,200 round-robin capability retentions of its alloy are up to 93%, and loading capacity is lower, only is 286mAh/g; And temperature is 1150 ℃ a comparative example 6, though its loading capacity is higher, cycle performance only is 84%; Holding temperature is 950～1100 ℃ embodiment 7～8 and 3, and its loading capacity and cycle life are all better, thus the temperature of soak be 950～1100 ℃ better.Preferably 1000 ℃.
With comparative example 7～8 and 10 and embodiment 9～11 and 3 compare, can find not have the comparative example 7 of soak, though the cycle performance of alloy is better, capability retention is 95%, loading capacity only is 287mAh/g; The comparative example 8 of 1000 ℃ of insulation 6h and the comparative example 10 that only under comparatively high temps, is incubated, the cycle performance of alloy is all relatively poor, and capability retention only is respectively 83% and 82%; And high-temperature holding time is the embodiment 9～11 and 3 of 0.5～3h, and its loading capacity and cycle life are all better, so the time of soak is that 0.5～3h is better.Preferably 2 hours.
Comprehensive above analysis, rare-earth Ni-base AB
5The type hydrogen-storage alloy is incubated 2～5 hours earlier in 400～800 ℃ of temperature ranges, be warmed up to 950～1100 ℃ of insulations then and carried out after the segmentation thermal treatment in 0.5～3 hour, particularly is warmed up to 1000 ℃ of insulations 2 hours after 4 hours at 600 ℃ of heat tracings.All be further enhanced at its electrochemistry capacitance and cycle life performance thereof.
Claims (7)
1. nickel-hydrogen battery negative pole rare-earth Ni-base AB
5The heat treating method of type hydrogen-storage alloy, rare-earth Ni-base AB
5The type hydrogen-storage alloy is after melting and being cast into ingot casting, at argon gas, helium, nitrogen and mixed gas thereof or sneak into therein in the environment of a certain amount of hydrogen and carry out segmentation thermal treatment, it is characterized in that: adopt pyritous heat treating method behind the first low temperature, the temperature of described low-temperature heat treatment is: 400～800 ℃, the temperature of described high-temperature heat treatment is: 950～1100 ℃.
2. heat treating method as claimed in claim 1, its low-temperature zone soaking time is 2～5 hours, the high temperature section soaking time is: 0.5～3 hour.
3. heat treating method as claimed in claim 2, its low-temperature zone are 550 ℃～650 ℃, and soaking time is 3.5～4.5 hours, and high temperature section is 950 ℃～1050 ℃, and soaking time is 1.5～2.5 hours.
4. heat treating method as claimed in claim 1, its rare-earth Ni-base AB
5The type hydrogen-storage alloy is to be starting material with cerium-rich mischmetal, electrolytic nickel, cobalt, manganese, aluminium, according to MmNi
3.55Co
0.75Mn
0.4Al
0.3The alloy composition is prepared burden.
5. heat treating method as claimed in claim 4, wherein cerium-rich mischmetal weight consists of 27.28wt%La, 50.41wt%Ce, 5.03wt%Pr, 17.04wt%Nd, and other raw material metal purity are all greater than 99.9wt%.
6. heat treating method as claimed in claim 5, its rare-earth Ni-base AB
5The type hydrogen-storage alloy is cast after the medium frequency induction melting furnace melting and to be obtained.
7. heat treating method as claimed in claim 6, its rare-earth Ni-base AB
5The medium frequency induction melting furnace melting of type hydrogen-storage alloy under 1300 ℃～1500 ℃ cast after 2～4 hours and to be obtained.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1089307A (en) * | 1992-12-29 | 1994-07-13 | 北京有色金属研究总院 | Complex-phase hydrogen-containing alloy and method for making thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1089307A (en) * | 1992-12-29 | 1994-07-13 | 北京有色金属研究总院 | Complex-phase hydrogen-containing alloy and method for making thereof |
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| JP特开平5-217578A 1993.08.27 |
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