CN1190677A - Method for preparing rare earth nickel hydrogen-storage alloy - Google Patents
Method for preparing rare earth nickel hydrogen-storage alloy Download PDFInfo
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- CN1190677A CN1190677A CN97120151A CN97120151A CN1190677A CN 1190677 A CN1190677 A CN 1190677A CN 97120151 A CN97120151 A CN 97120151A CN 97120151 A CN97120151 A CN 97120151A CN 1190677 A CN1190677 A CN 1190677A
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Abstract
The preparation method of rare earth nickel-base hydrogen storage alloy includes the following main technological processes; vacuum induction smelting of mother alloy, remelting mother alloy, quick-setting and spray-making alloy lamel by using single-roll method and heat treatment of alloy lamel. Said invention adopts two-stage process of high cooling roll surface line speed and low-temp. short-time treatment, so that the charging and discharging circulating stability of the alloy, and its discharging capacity and discharge voltage platform characteristics are greatly raised.
Description
The invention belongs to a kind of preparation method of rare-earth Ni-base hydrogen bearing alloy, this method mainly comprises vacuum induction melting RE (NiM)
5 ± xMother alloy, mother alloy remelting, single-roller method rapid solidification spray alloy sheet, thin slice thermal treatment.
Steel ingot is made in the common medium-frequency induction furnace melting of the general employing of preparation rare-earth Ni-base hydrogen bearing alloy, is ground into powder then.This method cooling performance is poor, and alloy grain is thick, component segregation, and alloy charge and discharge cycles stability, electrochemistry capacitance and discharge voltage plateau characteristic are all very poor as a result.
Chinese patent CN1134046A provides a kind of employing single-roller method fast solidification technology that the mother alloy spray is become alloy sheet with European patent EP 0588310A2, the method of heat treatable alloy thin slice, but in these methods, what the cooling roller linear resonance surface velocity was all controlled during the single-roller method rapid solidification is very low, generally have only about 10m/s, thereby its alloy sheet that makes is thicker, be generally 80～350 μ m, crystal grain is just thick in the thin slice, general grain-size is more than 2 μ m, and back flow roll face grain-size can be up to 20 μ m, and the thermal treatment of this method interalloy thin slice simultaneously all is one section and carries out, thermal treatment temp is very high, and soaking time is longer.The regulation thermal treatment temp is up to 750～1000 ℃ among the CN1134046A, and soaking time reaches 1～10 hour, thereby the crystal grain of alloy sheet is too grown up.The alloy charge and discharge cycles stability that the result makes, loading capacity and discharge voltage plateau characteristic are still very poor.
The objective of the invention is for fear of the deficiency of above-mentioned prior art, a kind of cooling roller linear resonance surface velocity height is provided, low temperature is the RE of two sections heat treatable alloy thin slices (NiM) in short-term
5 ± xThe preparation method of Ni-base hydrogen bearing alloy, this method have improved alloy charge and discharge cycles stability effectively, loading capacity and discharge voltage plateau characteristic.
Purpose of the present invention reaches by following measure.Adopt medium-frequency induction furnace melting RE (NiM)
5 ± x(wherein RE is one or more rare earth elements, comprise lanthanon and yttrium, among M=Ni, Co, Mn, Ti, Al, Zn, Cu, Sn, W, Mo, Fe, Cr and non-metallic element Si, B, C, the N one or more, 0≤x≤0.75) nickel-base alloy becomes mother alloy, then the mother alloy of this qualified composition is placed the induction furnace remelting of single roller quick solidification apparatus, again with the fusing the alloy spray on the copper water cooled rolls of high speed rotating, make alloy sheet.At last, this alloy sheet is through two sections low temperature thermal treatments in short-term, and it is suitable to make structural state, the RE that hydrogen storage performance is good (NiM)
5 ± xAlloy.Because final alloy is the structure by amorphous, nanocrystalline and crystallite coexistence, and the grains constitute of grain-size below 2 μ m is more than 95%, chemical ingredients is extremely even again, surface passivated membrane is evenly anti-corrosion, so the alloy charge and discharge cycles stability that makes, loading capacity and discharge voltage plateau characteristic are all improved significantly.
Purpose of the present invention specifically reaches by following measure.RE (NiM)
5 ± xThe starting material of composition proportion place the vacuum induction furnace melting, make steel ingot, become mother alloy after crushed, the then induction furnace remelting that the mother alloy of this qualified composition is put into single roller quick solidification apparatus, fusing back alloy liquation splash apace is on the water cooled rolls made of copper on the surface, this water cooled rolls linear resonance surface velocity is controlled at 31～45m/s, and alloy liquation quick cooled and solidified on the cooling roller of this high speed rotating becomes alloy sheet.Because the water-cooled copper roller has the high linear speed of 31～45m/s, the alloy sheet thickness that makes has only about 10～70 μ m, and alloy organizing is an amorphous, the coexisting state of nanocrystalline and crystallite.Crystal grain refinement like this, crystal boundary increases, and crystal boundary increases as the passage of hydrogen atom diffusion, can improve the initial activation speed of alloy, improves the high current charge-discharge ability.Simultaneously, fine crystal grain reduces the internal stress that alloy produces in charging and discharging the hydrogen process, add rapid solidification and make alloy surface form uniform passive film, improves the anti-corrosion capability of alloy, make alloy Pulverization ratio in charging and discharging the hydrogen process descend effectively, improved alloy charge and discharge cycles stability.The alloy sheet composition of this quick setting method spray is very even, and alloy has good discharge voltage plateau characteristic.Then the alloy sheet of rapid solidification spray is heat-treated in two stages, 550～680 ℃ of fs thermal treatment temps are incubated 10～30 minutes, 150～550 ℃ of subordinate phase thermal treatment temps, be incubated 15～60 minutes, the atmosphere in the heat treatment furnace is vacuum or rare gas element.The two sections thermal treatments in short-term of this low temperature make part amorphous structure crystallization in the alloy sheet of spray, increase the loading capacity of alloy.This thermal treatment is simultaneously preventing that same fashion that grain growth and second is separated out mutually from can reduce the lattice imperfection in the alloy, improves the degree of order of atom, thereby improve the initial activation performance of alloy.Make alloy be rendered as the structural state of amorphous, the nanocrystalline and an amount of proportioning of crystallite at last, alloy just has high charge and discharge cycles stability, loading capacity and good discharge voltage plateau characteristic.
RE of the present invention (NiM)
5 ± xThe preparation method of Ni-base hydrogen bearing alloy, the best surface linear velocity of cooling roller is 38m/s during its single-roller method rapid solidification, the optimum temps that alloy sheet thermal treatment is first section is 610 ℃, is incubated 20 minutes; 330 ℃ of second section optimum tempss are incubated 35 minutes, and this processing parameter can obtain best chemical property.
Be described in further detail the present invention below in conjunction with embodiment.Embodiment 1
Selecting composition for use is MmNi
3.8Co
0.5Mn
0.6Ti
0.1Proportioning, vacuum induction melting is cast into ingot, is crushed into mother alloy, mother alloy is placed the induction furnace remelting of single-roller method quick solidification apparatus.Under different cooling roller linear resonance surface velocities, make the hydrogen-storage alloy thin slice.The speed of selecting for use has 20m/s, 31m/s, 35m/s, 38m/s, 42m/s, 45m/s, 55m/s.Alloy is made into test result behind the electrode slice shown in table 1,2.
Table 1
Annotate: this shows employed nomenclature following (down together):
| Sample | The 60mA/g loading capacity | The 300mA/g loading capacity | ||
| ????C 60，max??(mAh/g) | ????S 60,?550????(％) | ????C 300，max??(mAh/g) | S 300，550????(％) | |
| The present invention (31m/s) | ????314 | ????9.6 | ????290 | ????9.4 |
| The present invention (35m/s) | ????315 | ????9.4 | ????294 | ????8.2 |
| The present invention (38m/s) | ????317 | ????8.3 | ????298 | ????7.4 |
| The present invention (42m/s) | ????316 | ????8.2 | ????295 | ????7.1 |
| The present invention (45m/s) | ????311 | ????8.1 | ????293 | ????6.9 |
| Comparative Examples (20m/s) | ????310 | ????40.3 | ????291 | ????39.6 |
| Comparative Examples (55m/s) | ????250 | ????7.4 | ????210 | ????6.2 |
C
60, max: discharge system is the maximum discharge capacity of 60mA/g, and unit is mAh/g;
C
60,550: the 550th time the circulation time discharge system is the loading capacity of 60mA/g, and unit is mAh/g;
C
300, max: discharge system is the maximum discharge capacity of 300mA/g, and unit is mAh/g;
C
300,550: the 550th time the circulation time discharge system is the loading capacity of 300mA/g, and unit is mAh/g;
S
60,550: the 550th circulation time discharge system is the loading capacity rate of fall-off of 60mA/g, and unit is
Per-cent, i.e. S
60,550(C
60, max-C
60,550)/C
60, max* 100%;
S
300,550: the 550th circulation time discharge system is the loading capacity rate of fall-off of 300mA/g, and unit is
Per-cent, i.e. S
300,550=(C
300, max-C
300,550) C
300, max* 100%;
As can be seen from Table 1, using this prepared composition is MmNi
3.8Co
0.5Mn
0.6Ti
0.1The hydrogen-storage alloy of (Mm is rich Ce mishmetal) can obtain higher loading capacity and cyclical stability.When roller speed is optimum value (38m/s), alloy height (300mA/g), low (60mA/g) multiplying power discharging capacity all reach maximum value, up to 298mAh/g and 317mAh/g, the loading capacity rate of fall-off of alloy after 550 circulations is lower simultaneously, has only 7.4% and 8.3% respectively respectively.
Application roll speed is lower than the prepared alloy of the present invention, and its loading capacity is on the low side, and particularly cyclical stability is starkly lower than the alloy of the present invention's preparation.The loading capacity of the alloy for preparing during for 20m/s as roller speed is (300mA/g and 60mA/g loading capacity are respectively 290mAh/g, 314mAh/g) on the low side slightly, but the cyclical stability extreme difference, 550 circulation backs high (300mA/g), low (60mA/g) multiplying power discharging capacity attenuation rate are up to 39.6% and 40.1%.
Application roll speed is higher than the prepared alloy of the present invention, although its cyclical stability is higher, loading capacity is starkly lower than the alloy, particularly large current discharging capability of the present invention's preparation.Height (300mA/g), low range (60mA/g) loading capacity as the alloy for preparing during for 55m/s when roller speed have only 210mAh/g, 250mAh/g respectively, and high (300mA/g), low (60mA/g) multiplying power discharging capacity differ greatly (40mAh/g), and it is very low to embody high-rate discharge capacity.
In a word, roller speed is high more, and the cyclical stability of alloy is high more, but can cause the particularly decline of high-multiplying power discharge capacity of alloy loading capacity again when roller speed is too high.Do not reach the effect of extensive raising alloy cyclical stability when roller speed is too low again.Take all factors into consideration the cycle life and the loading capacity of alloy, guaranteeing that alloy has under the prerequisite of sufficiently high loading capacity, still have suitable cyclical stability, this processing parameter of fixed roll speed of the present invention is 31～45m/s.Because when roller speed is 38m/s, alloy has maximum loading capacity (the 60mA/g loading capacity is 317mAh/g), cyclical stability has also reached higher level (550 circulation backs high (300mA/g), low range (60mA/g) loading capacity rate of fall-off have only 7.4% and 8.3%), is that roller speed is 38m/s so decide optimal processing parameter.Table 2
Annotate: this shows employed nomenclature following (down together):
| Sample | The 60mA/g discharge | The 300mA/g discharge | |||
| ??λ 60，0.85????(％) | λ 60，0.80????(％) | ?λ 60，0.70????(％) | ??λ 300，0.80????(％) | ??λ 300，0.70????(％) | |
| The present invention (31m/s) | ????91.0 | ????96.9 | ????98.8 | ????78.0 | ????91.4 |
| The present invention (35m/s) | ????92.2 | ????98.1 | ????99.0 | ????79.3 | ????96.2 |
| The present invention (38m/s) | ????93.8 | ????98.9 | ????99.6 | ????84.0 | ????98.2 |
| The present invention (42m/s) | ????92.4 | ????98.2 | ????99.1 | ????79.7 | ????96.8 |
| The present invention (45m/s) | ????92.0 | ????98.1 | ????98.9 | ????79.8 | ????96.6 |
| Comparative Examples (20m/s) | ????87.6 | ????95.4 | ????97.6 | ????75.3 | ????88.9 |
| Comparative Examples (55m/s) | ????81.3 | ????90.2 | ????97.4 | ????68.2 | ????81.1 |
λ
60,0.85: the per-cent that discharge system is 60mA/g, the loading capacity when being discharged to 0.85V (vs.Hg/HgO) accounts for the loading capacity when being discharged to 0.5 00V (vs.Hg/HgO).
λ
60,0.85: the per-cent that discharge system is 60mA/g, the loading capacity when being discharged to 0.80V (vs.Hg/HgO) accounts for the loading capacity when being discharged to 0.500V (vs.Hg/HgO).
λ
60,0.70: the per-cent that discharge system is 60mA/g, the loading capacity when being discharged to 0.70V (vs.Hg/HgO) accounts for the loading capacity when being discharged to 0.500V (vs.Hg/HgO).
λ
300,0.80: the per-cent that discharge system is 300mA/g, the loading capacity when being discharged to 0.80V (vs.Hg/HgO) accounts for the loading capacity when being discharged to 0.500V (vs.Hg/HgO).
λ
300,0.70: the per-cent that discharge system is 300mA/g, the loading capacity when being discharged to 0.70V (vs.Hg/HgO) accounts for the loading capacity when being discharged to 0.500V (vs.Hg/HgO).
As can be seen from Table 2, using this prepared composition is MmNi
3.8Co
0.5Mn
0.6Ti
0.1Hydrogen-storage alloy can obtain discharging voltage characteristic preferably, the discharging voltage characteristic during heavy-current discharge particularly.Application roll speed is below or above the prepared alloy of the present invention, and its discharging voltage characteristic all is lower than the alloy of the present invention's preparation.As when roller speed is 38m/s, λ
60,0.85And λ
300,0.80Reach optimum value, be respectively 93.8% and 84.0%.When roller speed is between 31～45m/s, λ
60,0.85Between 91.0～93.8%, λ
60,0.80Between 96.9～98.9%, λ
60,0.70Between 98.8～99.6%, λ
300,0.80Between 78.0～84.0%, λ
300,0.70Between 91.4～98.2, all occupy higher level, can demonstrate fully the improvement effect of technology of the present invention to alloy sparking voltage performance.As a comparison case, when roller speed is lower than the scope of the invention (as 20m/s) or is higher than the scope of the invention (as 55m/s), characterize the λ of alloy large current discharging capability
300,0.80Have only 75.3% and 68.2% respectively, have only the corresponding λ of the alloy of optimal processing parameter (38m/s) preparation
300,0.8089.6%, 81.2% of value.Embodiment 2
Selecting composition for use is MmNi
3.8Co
0.5Mn
0.6Ti
0.1Proportioning (Mm is rich Ce mishmetal), vacuum induction melting, casting ingot-forming is ground into mother alloy, with the induction furnace remelting that mother alloy places the single-roller method quick solidification apparatus, is to make the hydrogen-storage alloy thin slice under the 38m/s at the cooling roller linear resonance surface velocity.Alloy is carried out the thermal treatment (as shown in table 3) of different systems.Carry out electro-chemical test after will being made into electrode slice respectively through the alloy that the different heat treatment system is handled, test result is shown in table 4～11.
Table 3
Table 3 (continuing)
Table 4
Table 5
| Sample number into spectrum | Heat treating regime | Remarks |
| 1# (the present invention) | 550 ℃ * 20 minutes+330 ℃ * 35 minutes | Fs thermal treatment temp difference is surplus identical |
| 2# (the present invention) | 580 ℃ * 20 minutes+330 ℃ * 35 minutes | |
| 3# (the present invention) | 610 ℃ * 20 minutes+330 ℃ * 35 minutes | |
| 4# (the present invention) | 640 ℃ * 20 minutes+330 ℃ * 35 minutes | |
| 5# (the present invention) | 680 ℃ * 20 minutes+330 ℃ * 35 minutes | |
| 6# (Comparative Examples) | 400 ℃ * 20 minutes+330 ℃ * 35 minutes | |
| 7# (Comparative Examples) | 800 ℃ * 20 minutes+330 ℃ * 35 minutes | |
| 8# (the present invention) | 610 ℃ * 15 minutes+330 ℃ * 35 minutes | Fs heat treatment time difference is surplus identical |
| 9# (the present invention) | 610 ℃ * 18 minutes+330 ℃ * 35 minutes |
| 10# (the present invention) | 610 ℃ * 20 minutes+330 ℃ * 35 minutes | The heat treatment time difference is surplus identical |
| 11# (the present invention) | 610 ℃ * 25 minutes+330 ℃ * 35 minutes | |
| 12# (the present invention) | 610 ℃ * 30 minutes+330 ℃ * 35 minutes | |
| 13# (Comparative Examples) | 610 ℃ * 5 minutes+330 ℃ * 35 minutes | |
| 14# (Comparative Examples) | 610 ℃ * 60 minutes+330 ℃ * 35 minutes | |
| 15# (the present invention) | 610 ℃ * 20 minutes+150 ℃ * 35 minutes | Subordinate phase thermal treatment temp difference is surplus identical |
| 16# (the present invention) | 610 ℃ * 20 minutes+250 ℃ * 35 minutes | |
| 17# (the present invention) | 610 ℃ * 20 minutes+330 ℃ * 35 minutes | |
| 18# (the present invention) | 610 ℃ * 20 minutes+450 ℃ * 35 minutes | |
| 19# (the present invention) | 610 ℃ * 20 minutes+550 ℃ * 35 minutes | |
| 20# (Comparative Examples) | 610 ℃ * 20 minutes+100 ℃ * 35 minutes | |
| 21# (Comparative Examples) | 610 ℃ * 20 minutes+800 ℃ * 35 minutes | |
| 22# (the present invention) | 610 ℃ * 20 minutes+330 ℃ * 15 minutes | Subordinate phase heat treatment time difference is surplus identical |
| 23# (the present invention) | 610 ℃ * 20 minutes+330 ℃ * 25 minutes | |
| 24# (the present invention) | 610 ℃ * 20 minutes+330 ℃ * 35 minutes | |
| 25# (the present invention) | 610 ℃ * 20 minutes+330 ℃ * 45 minutes | |
| 26# (the present invention) | 610 ℃ * 20 minutes+330 ℃ * 60 minutes | |
| 27# (Comparative Examples) | 610 ℃ * 20 minutes+330 ℃ * 5 minutes | |
| 28# (Comparative Examples) | 610 ℃ * 20 minutes+330 ℃ * 120 minutes |
| Sample | The 60mA/g loading capacity | The 300mA/g loading capacity | ||
| ????C 60，max??(mAh/g) | ??S 60，550????(％) | ????C 300，max???(mAh/g) | ?S 300，550????(％) | |
| 1# (the present invention) | ????319 | ????7.5 | ????310 | ????7.4 |
| 2# (the present invention) | ????322 | ????6.2 | ????314 | ????6.0 |
| 3# (the present invention) | ????324 | ????5.2 | ????316 | ????5.0 |
| 4# (the present invention) | ????324 | ????6.3 | ????317 | ????6.2 |
| 5# (the present invention) | ????324 | ????7.4 | ????318 | ????7.2 |
| 6# (Comparative Examples) | ????318 | ????8.2 | ????299 | ????8.0 |
| 7# (Comparative Examples) | ????325 | ????50.8 | ????319 | ????50.0 |
| Sample | The 60mA/g discharge | The 300mA/g discharge | |||
| ????λ 60，0.85????(％) | ????λ 60，0.80????(％) | λ 60，0.70????(％) | λ 300，0.8????0(％) | ??λ 300，0.70????(％) | |
| 1# (the present invention) | ????95.2 | ????99.4 | ????99.8 | ????90.0 | ????89.9 |
| 2# (the present invention) | ????95.3 | ????99.5 | ????99.9 | ????90.1 | ????99.0 |
| 3# (the present invention) | ????95.4 | ????99.5 | ????100 | ????90.2 | ????99.1 |
| 4# (the present invention) | ????95.6 | ????99.6 | ????100 | ????90.2 | ????99.2 |
| 5# (the present invention) | ????95.8 | ????99.8 | ????100 | ????90.3 | ????99.2 |
| 6# (Comparative Examples) | ????93.8 | ????99.0 | ????99.7 | ????84.1 | ????98.3 |
| 7# (Comparative Examples) | ????95.8 | ????99.9 | ????100 | ????90.4 | ????99.3 |
Table 4,5 is the not comparison of alloy property simultaneously of first section thermal treatment temp.Be 550 ℃～680 ℃ in processing range of the present invention between, the performance of alloy is all better than the attitude alloy of quenching.
From of the influence of first section thermal treatment temp to alloy loading capacity and cyclical stability, (550 ℃～680 ℃) within the scope of the present invention, the loading capacity of alloy raises with the rising of thermal treatment temp, but the cyclical stability of alloy presents the trend of falling after rising.Loading capacity rate of fall-off after 550 circulations of alloy reaches minimum in the time of 610 ℃, promptly cyclical stability is best, and height (300mA/g), low (60mA/g) multiplying power discharging capacity attenuation rate after corresponding 550 circulations have only 5.0% and 5.2%.When temperature low excessively (as 400 ℃), do not reach the purpose that first section thermal treatment improves capacity; But when temperature too high (as 800 ℃), the cyclical stability of alloy then is seriously damaged.
From of the influence of first section thermal treatment temp to the discharging voltage characteristic of alloy, the discharging voltage characteristic of alloy becomes better with the rising of first section thermal treatment temp, but after temperature surpasses 610 ℃, the rising amplitude diminishes, and has reached optimum value during to 680 ℃, promptly reaches capacity, higher temperature there is no need, and, as shown in Table 4, the cyclical stability extreme difference of alloy when temperature too high (as 800 ℃).
Take all factors into consideration the influence of first section thermal treatment temp to alloy loading capacity, cyclical stability, discharging voltage characteristic, technology of the present invention is between 550 ℃～680 ℃ with first section thermal treatment temp limited range, and the corresponding optimum value is 610 ℃.
Table 6
Table 7
| Sample | The 60mA/g loading capacity | The 300mA/g loading capacity | ||
| ????C 60，max??(mAh/g) | ????S 60，550????(％) | ????C 300，max????(mAh/g) | ?S 300，550????(％) | |
| 8# (the present invention) | ????319 | ????7.2 | ????305 | ????7.1 |
| 9# (the present invention) | ????321 | ????6.1 | ????310 | ????5.9 |
| 10# (the present invention) | ????324 | ????5.2 | ????316 | ????5.0 |
| 11# (the present invention) | ????324 | ????5.4 | ????317 | ????5.2 |
| 12# (the present invention) | ????325 | ????6.0 | ????318 | ????5.8 |
| 13# (Comparative Examples) | ????318 | ????8.2 | ????299 | ????8.0 |
| 14# (Comparative Examples) | ????325 | ????12.5 | ????318 | ????12.4 |
| Sample | The 60mA/g discharge | The 300mA/g discharge | |||
| λ 60，0.85????(％) | ?λ 60，0.80????(％) | λ 60，0.70????(％) | λ 300，0.80????(％) | λ 300，0.70????(％) | |
| 8# (the present invention) | ????94.6 | ????99.2 | ????99.9 | ????87.6 | ????98.5 |
| 9# (the present invention) | ????95.0 | ????99.4 | ????100 | ????89.0 | ????98.8 |
| 10# (the present invention) | ????95.4 | ????99.5 | ????100 | ????90.2 | ????99.1 |
| 11# (the present invention) | ????95.4 | ????99.6 | ????100 | ????90.3 | ????99.2 |
| 12# (the present invention) | ????95.5 | ????99.6 | ????100 | ????90.4 | ????99.2 |
| 13# (Comparative Examples) | ????93.9 | ????99.0 | ????99.7 | ????84.5 | ????98.3 |
| 14# (Comparative Examples) | ????95.6 | ????99.8 | ????100 | ????90.5 | ????99.4 |
Table 6,7 is the influence of first section heat treatment time to alloy.First section heat treated temperature and second section heat treated temperature and time are optimal processing parameter.
First section heat treatment time can be as seen from Table 6 to the rule that influences of alloy capacity: the time is long more, the height of alloy (300mA/g), low (60mA/g) multiplying power discharging capacity are high more, but after heat treatment time surpasses 20 minutes, it is slow that the growth of capacity prolongation in time becomes, when being 30 minutes, heat treatment time just reached maximum value, promptly near saturated, no longer the growth with heat treatment time increases.
The cyclical stability of alloy is Shi Zuigao about 20 minutes at heat treatment time, and promptly the capacity attenuation rate is minimum, and height (300mA/g), low (60mA/g) multiplying power discharging capacity attenuation rate after corresponding 550 circulations have only 5.0% and 5.2%.With the prolongation of heat treatment time, descending then appears in the cyclical stability of alloy.When heat treatment time long (as 60 minutes), the cyclical stability of alloy has dropped to lower level, and the height (300mA/g) after corresponding 550 circulations, low (60mA/g) multiplying power discharging capacity attenuation rate are up to 12.4% and 12.5%.
As shown in Table 7, first section heat treatment time is long more, the sparking voltage performance of alloy is good more, but equally as its influence to loading capacity, after heat treatment time surpassed 20 minutes, it is slow that this improvement effect prolongation in time becomes, and just reached highest level when heat treatment time is 30 minutes, promptly near saturated, no longer with the growth of heat treatment time become better.
Also can find out by table 6,7, when first section heat treatment time is too short, as 5 minutes, then do not reach the purpose that first section thermal treatment is used for improving the alloy loading capacity, do not reach first section due effect of thermal treatment, capacity and voltage performance are still on the low side, than quench attitude alloy height not what.But when first section heat treatment time was long, as 60 minutes, though the capacity of alloy and voltage performance have reached highest level, its cyclical stability dropped to lower level, had lost the effect that technology of the present invention improves the alloy cyclical stability.
Take all factors into consideration the influence of first section heat treatment time to alloy loading capacity, cyclical stability, discharging voltage characteristic, technology of the present invention is 15～30 minutes with first section heat treatment time limited range, and the corresponding optimum value is 20 minutes.
Table 8
Table 9
Table 8,9 is first section thermal treatment temp and time, when second section heat treatment time is the optimal processing parameter of technology of the present invention, second section thermal treatment temp be the rule of alloy property simultaneously not.
| Sample | The 60mA/g loading capacity | The 300mA/g loading capacity | ||
| ????C 60，max??(mAh/g) | ??S 60，550????(％) | ????C 300，max??(mAh/g) | S 300，550????(％) | |
| 15# (the present invention) | ????321 | ????5.3 | ????313 | ????5.1 |
| 16# (the present invention) | ????323 | ????5.2 | ????315 | ????5.0 |
| 17# (the present invention) | ????324 | ????5.2 | ????316 | ????5.0 |
| 18# (the present invention) | ????324 | ????5.2 | ????316 | ????5.0 |
| 19# (the present invention) | ????325 | ????5.4 | ????317 | ????5.2 |
| 20# (Comparative Examples) | ????320 | ????5.4 | ????312 | ????5.2 |
| 21# (Comparative Examples) | ????325 | ????16.7 | ????317 | ????15.9 |
| Sample | The 60mA/g discharge | The 300mA/g discharge | |||
| ????λ 60，0.85????(％) | ??λ 60，0.80????(％) | ??λ 60，0.70????(％) | λ 300，0.80????(％) | ??λ 300，0.70????(％) | |
| 15# (the present invention) | ????94.7 | ????99.2 | ????99.9 | ????89.0 | ????98.9 |
| 16# (the present invention) | ????95.2 | ????99.3 | ????100 | ????89.9 | ????99.0 |
| 17# (the present invention) | ????95.4 | ????99.5 | ????100 | ????90.2 | ????99.1 |
| 18# (the present invention) | ????95.4 | ????99.5 | ????100 | ????90.2 | ????99.1 |
| 19# (the present invention) | ????95.4 | ????99.5 | ????100 | ????90.3 | ????99.2 |
| 20# (Comparative Examples) | ????94.0 | ????99.0 | ????99.7 | ????86.1 | ????98.6 |
| 21# (Comparative Examples) | ????95.4 | ????99.5 | ????100 | ????90.3 | ????99.2 |
As can be seen from Table 8, second section thermal treatment temp is just influential slightly to the alloy loading capacity, but can be directed at the decline of alloy cyclical stability during temperature too high (as 800 ℃), the height (300mA/g) after corresponding 550 circulations, low (60mA/g) multiplying power discharging capacity attenuation rate are up to 15.9% and 16.7%.Second section heat treated temperature can not too high (limitting 550 ℃), otherwise reduce the cyclical stability of alloy; But can not too low (as 100 ℃), otherwise capacity and cyclical stability reach due high level.When thermal treatment temp is 330 ℃, reach nearly saturation value, and the capacity attenuation rate is minimum.
Although (150～550 ℃) second section heat treated temperature is not too big to the capacity and the cyclical stability influence of alloy in processing range of the present invention, it has good effect to the sparking voltage performance of alloy, and is as shown in table 9.The discharging voltage characteristic of alloy raises with the rising of second section thermal treatment temp, during to 330 ℃ near maximum, value of reaching capacity (maximum value) during to 550 ℃, best performance.The thermal treatment temp that surpasses 550 ℃ there is no need the voltage characteristic that improves alloy, and can bring the reduction of alloy cyclical stability.Cross low temperature and then can not reach the purpose (as 100 ℃ of Comparative Examples) that second section thermal treatment further improves the alloy discharging voltage characteristic.
Take all factors into consideration above second section thermal treatment temp to alloy Effect on Performance rule, technology of the present invention is between 150 ℃～550 ℃ with second section thermal treatment temp limited range, and the corresponding optimum value is 330 ℃.
Table 10
Table 11
| Sample | The 60mA/g loading capacity | The 300mA/g loading capacity | ||
| ????C 60，max??(mAh/g) | ??S 60，550????(％) | ??C 300，max??(mAh/g) | S 300，550????(％) | |
| 22# (the present invention) | ????323 | ????5.3 | ????314 | ????5.1 |
| 23# (the present invention) | ????324 | ????5.2 | ????315 | ????5.0 |
| 24# (the present invention) | ????324 | ????5.2 | ????316 | ????5.0 |
| 25# (the present invention) | ????324 | ????5.2 | ????316 | ????5.0 |
| 26# (the present invention) | ????324 | ????5.2 | ????316 | ????5.0 |
| 27# (Comparative Examples) | ????322 | ????5.5 | ????313 | ????5.3 |
| 28# (Comparative Examples) | ????324 | ????5.3 | ????316 | ????5.2 |
| Sample | The 60mA/g discharge | The 300mA/g discharge | |||
| ??λ 60，0.85????(％) | ????λ 60，0.80????(％) | ????λ 60，0.70????(％) | λ 300，0.80????(％) | ??λ 300，0.70????(％) | |
| 22# (the present invention) | ????95.3 | ????99.4 | ????100 | ????89.9 | ????98.0 |
| 23# (the present invention) | ????95.4 | ????99.5 | ????100 | ????90.0 | ????98.9 |
| 24# (the present invention) | ????95.4 | ????99.5 | ????100 | ????90.2 | ????99.1 |
| 25# (the present invention) | ????95.4 | ????99.5 | ????100 | ????90.2 | ????99.1 |
| 26# (the present invention) | ????95.4 | ????99.6 | ????100 | ????90.2 | ????99.1 |
| 27# (Comparative Examples) | ????95.0 | ????99.2 | ????99.8 | ????89.3 | ????89.8 |
| 28# (Comparative Examples) | ????95.5 | ????99.6 | ????100 | ????90.3 | ????99.2 |
Table 10,11 is the relation between second section heat treatment time and alloy property.First section heat treated temperature and time and second section heat treated temperature are optimal processing parameter.
As shown in Table 10, second section heat treatment time is less to the loading capacity and the cyclical stability influence of alloy, but bigger to the discharging voltage characteristic influence of alloy.
Also can find out by table 10,11, when second section heat treatment time is too short, as 5 minutes, then second section thermal treatment effect of improving the alloy discharging voltage characteristic is not obvious, do not reach second section heat treated purpose, but when the time reaches 35 minutes, just reach intimate vertex, after 60 minutes, just no longer raise.Long heat treatment time (as 120 minutes) there is no need the voltage performance that improves alloy and can reduce production efficiency, increase cost.
Take all factors into consideration second section heat treatment time to the particularly influence of discharging voltage characteristic of alloy loading capacity, cyclical stability, technology of the present invention is 15～60 minutes with second section heat treatment time limited range, and the corresponding optimum value is 35 minutes.
Compared with prior art, the preparation method of Ni-base hydrogen bearing alloy of the present invention has the following advantages:
1. because the inventive method adopts suitable high chill roll linear resonance surface velocity, guarantee that not only alloy has sufficiently high discharge capacity, but also obtained quite high cyclical stability.
2. because the present invention adopts two sections heat treating regimes of low temperature, isothermal treatment for short time when alloy sheet heat treatment, further improved discharge capacity and the cyclical stability of the attitude alloy of quenching, especially very large to proposing the effect of heavy alloyed discharge voltage plateau characteristic.
Claims (2)
1. the preparation method of rare-earth Ni-base hydrogen bearing alloy is comprising vacuum induction melting RE (NiM)
5 ± xMother alloy, the mother alloy remelting, single-roller method rapid solidification spray alloy sheet, alloy sheet thermal treatment, copper cooling roller linear resonance surface velocity is controlled at 31～45m/s when it is characterized in that single-roller method rapid solidification spray alloy sheet, and alloy sheet thermal treatment is carried out in two stages, the fs thermal treatment temp is 550 ℃～680 ℃, be incubated 15～30 minutes, the subordinate phase thermal treatment temp is 150 ℃～550 ℃, is incubated 15～60 minutes.
2. the preparation method of rare-earth Ni-base hydrogen bearing alloy according to claim 1, the linear velocity optimum value that it is characterized in that the cooling roller surface is 38m/s, optimum treatment temperature and soaking time that two sections thermal treatment is first section are respectively 610 ℃, 20 minutes, second section optimum treatment temperature and soaking time are respectively 330 ℃, 35 minutes.
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| CN103633301A (en) * | 2013-10-22 | 2014-03-12 | 钢铁研究总院 | RE-Mg-Ni-Zr-B electrode alloy used for Ni-MH secondary battery and preparation method thereof |
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| US5629000A (en) * | 1994-11-25 | 1997-05-13 | Sanyo Electric Co., Ltd. | Hydrogen-absorbing alloy electrode for metal hydride alkaline batteries and process for producing the same |
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| CN103633301A (en) * | 2013-10-22 | 2014-03-12 | 钢铁研究总院 | RE-Mg-Ni-Zr-B electrode alloy used for Ni-MH secondary battery and preparation method thereof |
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