CN101471440A - Hydrogen storage alloy and alkaline storage battery employing hydrogen storage alloy as negative electrode active material - Google Patents
Hydrogen storage alloy and alkaline storage battery employing hydrogen storage alloy as negative electrode active material Download PDFInfo
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- CN101471440A CN101471440A CNA2008101902021A CN200810190202A CN101471440A CN 101471440 A CN101471440 A CN 101471440A CN A2008101902021 A CNA2008101902021 A CN A2008101902021A CN 200810190202 A CN200810190202 A CN 200810190202A CN 101471440 A CN101471440 A CN 101471440A
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Abstract
A hydrogen storage alloy of the present invention includes component A including a rare earth element represented by Ln and magnesium and component B including elements containing at least nickel and aluminum, wherein a primary alloy phase of a hydrogen storage alloy represents an A5B19 type structure; a general formula is represented as Ln1-xMgxNiy-a-bAlaMb (wherein M represents at least one element selected from Co, Mn, and Zn; and 0.1<=x<=0.2, 3.6<=y<=3.9, 0.1<=a<=0.2, and 0<=b<=0.1); a rare earth element Ln includes maximally two elements containing at least La; and absorption hydrogen equilibrium pressure (Pa) is 0.03-0.17 MPa when the hydrogen amount absorbed in the hydrogen storage alloy (H/M (atomic ratio)) at 40 DEG C. is 0.5.
Description
Technical field
The present invention relates to as the hydrogen-storage alloy of the negative electrode active material of alkaline cell and be the alkaline cell of negative electrode active material with this hydrogen-storage alloy, described alkaline cell is suitable for the purposes that hybrid-power electric vehicle (HEV:Hybrid Electric Vehicle) or pure electric automobile (PEV:Pure Electric Vehicle) etc. need heavy-current discharge.
Background technology
In recent years, require the power supply of the machine of power output, used especially nickel-hydrogen dattery of alkaline cell as hybrid-power electric vehicle (HEV) or pure electric automobile (PEV) etc.Generally speaking, as the hydrogen-storage alloy that the negative electrode active material of nickel-hydrogen dattery uses, using with aluminium (Al) or manganese elements such as (Mn) LaNi
5Deng AB
5Alloy after the part of the B composition (Ni) of type terres rares hydrogen-storage alloy replaces.Except this type of AB
5Beyond the type terres rares hydrogen-storage alloy, also has AB
2Type structure etc.In addition, having known also can be by combination AB
2Type structure and AB
5The type structure obtains various crystalline textures.
In the middle of these, by AB
2Type structure and AB
5The type structure is the A that the cycle overlaps each other and form with 2 layers
2B
7The hydrogen-storage alloy of type structure has carried out various discussions in for example patent documentation 1 (TOHKEMY 2002-164045 communique) etc.This A
2B
7The hydrogen-storage alloy of type structure has the crystalline texture (2H) of hexagonal crystal system, the occlusion release cycle life-span that can improve hydrogen.But, because A
2B
7The flash-over characteristic of the hydrogen-storage alloy of type structure (auxiliary power output) is insufficient, exist as head and shoulders above in the past the power output purposes of scope still do not have the problem of satisfied performance.
Here, as the crystalline texture that can become the quasi-steady structure, known except A
2B
7Also has A beyond the type structure
5B
19The type structure.In this case, A
5B
19The type structure is by AB
2Type structure and AB
5The type structure is to overlap each other in the cycle to form with 3 layers, because and A
2B
7The type structure is compared the ratio of the nickel (Ni) that can increase every elementary cell, so can increase the occlusion that promotes hydrogen molecule and to the active site that dissociates of hydrogen atom.
[patent documentation 1] TOHKEMY 2002-164045 communique
Summary of the invention
But, known at A
5B
19In the hydrogen-storage alloy of type structure, it is less that nickel (Ni) and other elements (aluminium (Al), cobalt (Co), manganese (Mn), zinc (Zn) etc.) of B composition are compared atomic radius.At A
5B
19In the type structure,, then produce the problem of the gap smaller between the metallic atom that constitutes elementary cell if increase the ratio of nickel (Ni).And, when the gap smaller between metallic atom, in metal lattice, entering metallic atom and become difficult, thereby form unsettled metal hydride, hydrogen balance presses liter.
Therefore, when will adopt with the hydrogen-storage alloy of the gap smaller between this metallic atom as the nickel-hydrogen dattery of negative electrode active material be used for big electric current discharge and recharge purposes the time, can quicken the micronizing of hydrogen-storage alloy, reduce persistence.In addition, press, thereby carry out the reduction reaction promotion self-discharge of hydrogen, as the degradation of battery at the nickel positive pole by the rising hydrogen balance.Its result is, existing problems when this alkaline cell being required the power supply of the purposes of power output performance (characteristics of output power is high), enduring quality (persistence is high) and self-discharge performance use as hybrid-power electric vehicle (HEV) or pure electric automobile (PEV) etc.
The present invention solves for addressing the above problem, its purpose is, the alloy structure of hydrogen-storage alloy is provided, especially by A composition element is specific and can have and far exceed the hydrogen-storage alloy of the characteristics of output power of scope in the past, and with the alkaline cell of this hydrogen-storage alloy as negative electrode active material.
For achieving the above object, hydrogen-storage alloy of the present invention is characterised in that, comprises the A composition of being made up of rare earth element of representing with Ln and magnesium; With the B composition of forming by the element that comprises nickel, aluminium at least; The alloy principal phase of hydrogen-storage alloy is A
5B
19The type structure is simultaneously with general formula Ln
1-xMgxNi
Y-a-bAl
aM
b(in the formula, M is at least a kind the element that is selected among Co, Mn, the Zn, 0.1≤x≤0.2,3.6≤y≤3.9,0.1≤a≤0.2,0≤b≤0.1) expression; Rare earth element Ln is made up of two elements at the most, wherein comprises La at least; And at 40 ℃ hydrogen adsorptive capacity H/M (atomic ratio) is that 0.5 o'clock absorption hydrogen equilibrium pressure (Pa) is 0.03～0.17MPa.
In the hydrogen-storage alloy, the rare earth element (Ln) that constitutes the A composition helps the occlusion of hydrogen to discharge.In this case, when increasing the number of elements of rare earth element (Ln), the interaction parameter between the formation element during alloy casting in liquid phase increases, and generates the two-phase of segregation grade in an imperial examination easily.In generation being had the alkaline cell of hydrogen-storage alloy as negative electrode active material of segregation grade in an imperial examination two-phase, follow repeated charge-discharge cycles, the micronizing of hydrogen-storage alloy is quickened.But when the number of elements of regulation rare earth element (Ln), the La that atomic radius is bigger during comprising rare earth element (Ln) when being at most two elements, constitutes the mutual parameter minimizing in liquid phase between element interior when alloy casting.Therefore, be easy to suppress the generation of segregation grade in an imperial examination two-phase, inhibition follows the micronizing of the hydrogen-storage alloy of charge and discharge cycles to become possibility.
Owing to known that adopting the quasi-steady structure is A
5B
19The type structure has significantly showed this inhibition effect, so the alloy principal phase is A
5B
19The type structure is being expressed as Ln with general formula
1-xMg
xNi
Y-a-bAl
aM
bWhen (in the formula, M is at least a kind the element that is selected among Co, Mn, the Zn), need to satisfy the condition of 0.1≤x≤0.2,0.1≤a≤0.2,0≤b≤0.1,3.6≤y≤3.9.This be because, at A with the quasi-steady structure
5B
19The type structure is during as the alloy principal phase, even satisfy the condition of 0.1≤x≤0.2,0.1≤a≤0.2,0≤b≤0.1, the metering of B composition also is about 3.5 and do not approved in than scope in the past metering than y, only just becomes possibility in the metering more than 3.6, below 3.9 in than scope (3.6≤y≤3.9).
In this case, by in rare earth element (Ln), comprising the bigger La of atomic radius, the hydrogen storage amount H/M (atomic ratio) in the time of 40 ℃ be storage hydrogen balance in 0.5 o'clock to press (Pa) be that 0.03～0.17MPa is possible, can improve the self-discharge performance.This be because, when equilibrium pressure during greater than 0.17MPa, the hydrogen concentration on hydrogen-storage alloy surface increases, owing to help anodal reduction reaction, therefore use etc. under hot environment in the long-term purposes of placing at hybrid-power electric vehicle, pure electric automobile, the capacity that self-discharge causes reduces obviously.On the other hand, when (Pa) pressed in the storage hydrogen balance less than 0.03MPa, because of starting resistor decline characteristics of output power reduces.
Based on above-mentioned situation, for bringing into play characteristics of output power and guaranteeing enduring quality simultaneously and the self-discharge performance, need use the hydrogen-storage alloy that meets the following conditions: the alloy principal phase is A
5B
19The type structure is with general formula Ln
1-xMg
xNi
Y-a-bAl
aM
b(in the formula, M is at least a kind the element that is selected among Co, Mn, the Zn, 0.1≤x≤0.2,3.6≤y≤3.9,0.1≤a≤0.2,0≤b≤0.1) expression; Rare earth element Ln is made up of two elements at the most, wherein comprises La at least; And at 40 ℃ hydrogen storage amount H/M (atomic ratio) is that to press (Pa) be 0.03～0.17MPa in storage hydrogen balance in 0.5 o'clock.
Hope is more than 74% with the nickel mol ratio ((y-a-b)/(y+1)) of the hydrogen-storage alloy that aforementioned formula is represented.In addition, wish with general formula Ln
1-xMg
xNi
Y-a-bAl
aM
bThe nickel substituted element M of the hydrogen-storage alloy of expression does not comprise cobalt (Mn) and manganese (Mn).In addition, rare earth element is preferably (Ln) and is lanthanum (La) and samarium (Sm) two elements, perhaps is lanthanum (La) and neodymium (Nd) two elements.In addition, because the hydrogen-storage alloy of above-mentioned composition has persistence, the volume cumulative frequency of the powder of being made up of hydrogen-storage alloy is that 50% particle diameter (D50) can be below the 20 μ m, can obtain higher characteristics of output power.
In the present invention, because special provision the alloy structure and the A composition element of hydrogen-storage alloy, so can obtain having and far exceed the hydrogen-storage alloy of the characteristics of output power of scope (auxiliary power output) in the past, by this hydrogen-storage alloy is used as negative electrode active material, can bring into play characteristics of output power and guarantee enduring quality simultaneously and the self-discharge performance.
Description of drawings
[Fig. 1] is for roughly representing the sectional drawing of alkaline cell of the present invention.
[symbol description] 11. hydrogen-occlussion alloy electrodes; 11c. core body exposed division; 12. nickel electrode; 12c. core body exposed division; 13. distance piece; 14. negative electrode collector; 15. positive electrode collector; 16. it is anodal with lead-in wire; 17. urceolus; 17a. annular groove portion; 17b. opening ora terminalis; 18. seal body; 18a. hush panel; 18b. positive electrode cap; 18c. valve plate; 18d. spring; 19a. insulating washer; 19b. vibrationproof ring.
Embodiment
Below describe embodiments of the present invention in detail, but the present invention is not limited to this, can suitably change in the scope that does not change its main points.Fig. 1 is for roughly representing the sectional drawing of alkaline cell of the present invention.
1. hydrogen-storage alloy
With lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), magnesium (Mg), nickel (Ni), aluminium (Al), cobalt (Co), manganese (Mn), zinc metallic elements such as (Zn) by the mixed in molar ratio shown in the following table 1 after, these mixtures are dropped in the high-frequency induction stove of argon atmospheres and fuse.Then the metallic solution quenching is made it become alloy cast ingot below the thickness 0.5mm, make laminal hydrogen-storage alloy a～k.
In this case, be La with composition formula
0.8Ce
0.1Pr
0.05Nd
0.05Ni
4.2Al
0.3(Co, Mn)
0.7The alloy of expression is as hydrogen-storage alloy a, with Nd
0.9Mg
0.1Ni
3.2Al
0.2Co
0.1The alloy of expression is as hydrogen-storage alloy b, with La
0.3Nd
0.5Mg
0.2Ni
3.5Al
0.2The alloy of expression is as hydrogen-storage alloy c.In addition, with Nd
0.9Mg
0.1Ni
3.7Al
0.1The alloy of expression is as hydrogen-storage alloy d, with La
0.2Pr
0.2Nd
0.5Mg
0.1Ni
3.7Al
0.1The alloy of expression is as hydrogen-storage alloy e, La
0.2Nd
0.7Mg
0.1Ni
3.6Al
0.1Zn
0.1The alloy of expression is as hydrogen-storage alloy f.In addition, with La
0.2Nd
0.7Mg
0.1Ni
3.7Al
0.1The alloy of expression is as hydrogen-storage alloy g, with La
0.4Nd
0.5Mg
0.1Ni
3.7Al
0.1The alloy of expression is as hydrogen-storage alloy h, with La
0.5Sm
0.4Mg
0.1Ni
3.7Al
0.1The alloy of expression is as hydrogen-storage alloy i.Further, with La
0.4Sm
0.5Mg
0.1Ni
3.7Al
0.1The alloy of expression is as hydrogen-storage alloy j, La
0.8Mg
0.2Ni
3.8Al
0.1The alloy of expression is as hydrogen-storage alloy k, with La
0.6Sm
0.2Mg
0.2Ni
3.5Al
0.1The alloy of expression is as hydrogen-storage alloy 1.The results are summarized in the table more than inciting somebody to action, the result is as shown in table 1 below.
In following table 1, represented each hydrogen-storage alloy a～1 with general formula Ln
1-xMg
xNi
Y-a-bAl
aM
bThe value of x (stoichiometric proportion of Mg), a (stoichiometric proportion of Al), b (stoichiometric proportion of M) and y (stoichiometric proportion of B composition (Ni+Al+M)) during (in the formula, M is at least a kind the element that is selected among Co, Mn, the Zn) expression.In addition, the value of also having represented nickel mol ratio ((y-a-b)/(y+1)).
[table 1]
Then, to each the hydrogen-storage alloy a～k that obtains, adopt DSC (differential scanning calorimetry (DSC)) to measure fusing point (Tm).Then in the heat treatment of only carrying out certain hour (being 10 hours in this case) than the fusing point (Tm) of these hydrogen-storage alloys a～k under low 30 ℃ the temperature (Ta=Tm-30 ℃), ask the storage hydrogen balance of calculating each the hydrogen-storage alloy a～k after the heat treatment to press Pa (MPa) then, the result is as shown in table 2.At this moment, under 40 ℃ atmosphere, be that 0.5 o'clock the tripping of separating is pressed Pa (MPa) as the storage hydrogen balance with hydrogen storage amount (H/M), measure according to JIS H7201 (1991) " assay method of the pressure-composition of hydrogen-storage alloy (PCT curve) ".
Then, after the piece coarse crushing with above-mentioned each hydrogen-storage alloy a～1, carry out mechanical crushing in inert gas atmosphere, the particle diameter (D50) of preparation volume cumulative frequency 50% is hydrogen-storage alloy powder a～1 of 20 μ m.Then adopting with the Cu-Ka pipe is the X-ray diffraction determinator of x-ray source, adopts X-ray diffraction method to carry out the evaluation of the crystalline texture of hydrogen-storage alloy powder a～1.At this moment, carrying out X-ray diffraction under the condition of 1 °/min of sweep speed, tube voltage 40kV, tube current 300mA, 1 ° of scanning step (scan step), 20～50 ° of mensuration angles (2 θ) measures.According to obtaining XRD figure, adopt JCPDS card figure (card chart) to identify the crystalline texture of each hydrogen-storage alloy a～k.
Here, in the constituent ratio of each crystalline texture, A
5B
19The type structure is Ce
5Co
19Type structure, Pr
5Co
19And Sm
5Co
19The type structure, A
2B
7The type structure is Nd
2Ni
7Type structure and Ce
2Ni
7The type structure, AB
5The type structure is LaNi
5The type structure, the intensity level at the refraction angle of each structure that will obtain by JCPDS and 42～44 ° the strongest intensity level than each intensity rate, be applied in the XRD curve of gained, when obtaining the composition of each structure, obtain the result shown in the following table 2.
[table 2]
Can clear and definite following content by above-mentioned table 1 and table 2.That is, as alloy a, if the stoichiometric proportion of the condition of dissatisfied 0.1≤x≤0.2,0.1≤a≤0.2,0≤b≤0.1 and B composition (Ni+Al+M) then becomes AB greatly to 5.2 o'clock
5The type structure.In addition, as alloy b, even the stoichiometric proportion of B composition (Ni+Al+M) is little of 3.5 o'clock if satisfy the condition of 0.1≤x≤0.2,0.1≤a≤0.2,0≤b≤0.1, A then
2B
7The type structure is the alloy principal phase.
Relative with these, as alloy c～1, if satisfy the stoichiometric proportion of the condition of 0.1≤x≤0.2,0.1≤a≤0.2,0≤b≤0.1 and B composition (Ni+Al+M) be more than 3.6,3.9 when following, A then
5B
19The type structure is that the alloy principal phase is (at this moment, though A in the alloy 1
5B
19The composition of type structure is 46%, but also can claim the alloy principal phase), nickel mol ratio ((y-a-b)/(y+1)) is more than 74%, and the Ni ratio is increased.In addition, even if the stoichiometric proportion of B composition (Ni+Al+M) is more than 3.6, below 3.9, and when being element as the rare earth element among the alloy e (Ln), AB then
5The type structure forms segregation.
2. hydrogen-occlussion alloy electrode
Then, adopt above-mentioned hydrogen-storage alloy a～1, prepare hydrogen storage electrode 11 (a1～k1) as described below respectively.At this moment, at first CMC (carboxymethyl cellulose) being dissolved in the water (or purified water) and obtaining water-soluble sticker, is 1.5g/cm with the ratio of 0.5 quality % to wherein adding apparent density
3The nickel thin slice, and (it is mixing that a～k) carries out to sneak into hydrogen-storage alloy powder respectively.Then add and mix as water-insoluble sticker SBR (styrene butadiene latices) and water (or purified water), it is 3.1g/cm that adjustment viscosity makes serum density
3, prepare the hydrogen-storage alloy slurries respectively.In this case, adjust so that CMC (carboxymethyl cellulose) is 0.1 quality % with respect to 100 mass parts hydrogen-storage alloys, SBR (styrene butadiene latices) is 1.0 quality % with respect to 100 mass parts hydrogen-storage alloys.
Then, prepare the negative pole core body that the porous substrate (punch metal) by plating Ni mild steel material forms, being coated with the hydrogen-storage alloy slurries respectively to this negative pole core body, to make packing density be 5.0g/cm
3, dry back pressure rolling is to certain thickness.(in this case, negative terminal surface long-pending (minor axis length * major axis long * 2) is 800cm to be cut to certain size then
2), prepare hydrogen-occlussion alloy electrode 11 (a1～11) respectively.
Here, as hydrogen-occlussion alloy electrode a1, the electrode that has adopted hydrogen-storage alloy b is as hydrogen-occlussion alloy electrode b1 with the electrode that adopted hydrogen-storage alloy a.In addition, to adopt the electrode of hydrogen-storage alloy c as hydrogen-occlussion alloy electrode c1, the electrode that has adopted hydrogen-storage alloy d is as hydrogen-occlussion alloy electrode d1, the electrode that has adopted hydrogen-storage alloy e is as hydrogen-occlussion alloy electrode e1, the electrode that has adopted hydrogen-storage alloy f is as hydrogen-occlussion alloy electrode f1, the electrode that has adopted hydrogen-storage alloy g is as hydrogen-occlussion alloy electrode g1, and the electrode that has adopted hydrogen-storage alloy h is as hydrogen-occlussion alloy electrode h1.Further, to adopt the electrode of hydrogen-storage alloy i as hydrogen-occlussion alloy electrode i1, the electrode that has adopted hydrogen-storage alloy j is as hydrogen-occlussion alloy electrode j1, and the electrode that has adopted hydrogen-storage alloy k is as hydrogen-occlussion alloy electrode k1, and the electrode that has adopted hydrogen-storage alloy 1 is as hydrogen-occlussion alloy electrode 11.
3. nickel electrode
On the other hand, the about 85% porousness nickel sintered base plate of voidage is soaked in the mixed aqueous solution that proportion is 1.75 nickel nitrate and cobalt nitrate, in the pore of porousness nickel sintered base plate, maintains nickel salt and cobalt salt.Then, porousness nickel sintered plate is soaked in NaOH (NaOH) aqueous solution of 25 quality %, converts nickel salt and cobalt salt to nickel hydroxide and cobalt hydroxide respectively.
Then, after fully aqueous slkali is removed in washing, carry out drying, filling is the active material of principal component with the nickel hydroxide in the pore of porousness nickel sintered base plate.Carry out this active material filling operation repeatedly with certain number of times (for example 6 times), filling is based on the active material of nickel hydroxide and to make its packing density be 2.5g/cm in the pore of porousness sintered base plate
3Then, after drying at room temperature, be cut to certain size, preparation nickel electrode 12.
4. nickel-hydrogen dattery
Then, adopt the hydrogen-occlussion alloy electrode 11 and the nickel electrode 12 of preparation as mentioned above, between them, insert the distance piece 13 that the nonwoven fabrics by the polypropylene material forms, and be wound in the vortex shape, prepare whirlpool shape electrode group.Expose the core body exposed division 11c of hydrogen-occlussion alloy electrode 11 in like this bottom of the whirlpool shape electrode group of preparation, expose the core body exposed division 12c of nickel electrode 12 at an upper portion thereof.Then, welding negative electrode collector 14 on the core body exposed division 11c that exposes in the lower surface of the whirlpool shape electrode group that obtains, welding negative electrode collector 15 on the core body exposed division 12c of the nickel electrode of exposing in the upper surface of whirlpool shape electrode group 12 simultaneously is as electrode body.
Then, the gained electrode body is enclosed in the urceolus that bottom tube-like is arranged (outside of bottom surface is a negative outer terminal) 17 that has carried out nickel plating on the iron, negative electrode collector 14 is welded in the inner bottom surface of urceolus 17.On the other hand, positive electrode collector 15 is prolonged the current collection leading part 15a that, be welded in the bottom that has positive terminal concurrently and the seal body 18 of insulating washer 19 has been installed at peripheral part.Positive electrode cap 18a is installed, the pressure valve that configuration is made up of valve body 18b that is out of shape and spring 18c in this positive electrode cap 18a (not having diagram) under certain pressure on seal body 18.
Then, after the upper periphery portion of urceolus 17 forms 17a, behind the injection electrolyte, be formed on the 17a of annular groove portion on urceolus 17 tops, placing the insulating washer 19 that is installed on seal body 18 peripheral parts.Then, by opening ora terminalis 17b sealing with urceolus 17, preparation nickel-hydrogen dattery 10 (A～L).In this case, inject the alkaline electrolyte of being made up of the potassium hydroxide (KOH) of 30 quality % in urceolus 17, making average cell capacity (Ah) is 2.5g (2.5g/Ah).
Here, to adopt the battery of hydrogen-occlussion alloy electrode a1 as battery A, the battery that adopts hydrogen-occlussion alloy electrode b1 is as battery B, the battery that adopts hydrogen-occlussion alloy electrode c1 is as battery C, the battery that adopts hydrogen-occlussion alloy electrode c1 is as battery C, the battery that adopts hydrogen-occlussion alloy electrode d1 is as battery D, the battery that adopts hydrogen-occlussion alloy electrode e1 is as battery E, the battery that adopts hydrogen-occlussion alloy electrode f1 is as battery F, the battery that adopts hydrogen-occlussion alloy electrode g1 is as battery G, the battery that adopts hydrogen-occlussion alloy electrode h1 is as battery H, the battery that adopts hydrogen-occlussion alloy electrode i1 is as battery I, the battery that adopts hydrogen-occlussion alloy electrode j1 is as battery J, and the battery that adopts hydrogen-occlussion alloy electrode k1 is as battery K, and the battery that adopts hydrogen-occlussion alloy electrode l1 is as battery L.
5. battery testing
(1) characteristics of output power evaluation
At first, adopt the battery A～L of preparation as mentioned above, in 25 ℃ of temperature atmosphere, to 120% of SOC (State Of Charge, state-of-charge), stop 1 hour with the charging current for charging of 1It.Then, after placing 24 hours under 70 ℃ the temperature atmosphere, under 45 ℃ temperature atmosphere, discharging with the discharging current of 1It makes cell voltage reach 0.3V, circulates repeatedly 2 times, and each above-mentioned battery A～L is activated.
After activation finishes, in 25 ℃ of temperature atmosphere, to 50% of SOC (StateOf Charge, state-of-charge), stop 1 hour with the charging current for charging of 1It.Then, after 20 seconds, stopping 30 minutes with charge rate charging arbitrarily under-10 ℃ the temperature atmosphere.Then, after 10 seconds, under 25 ℃ temperature atmosphere, stopping 30 minutes with discharge rate discharge arbitrarily under-10 ℃ the temperature atmosphere.Like this under-10 ℃ the temperature atmosphere with the charging of charge rate arbitrarily 20 seconds, stop 30 minutes, stop 30 minutes under with discharge rate discharge arbitrarily 10 seconds, temperature atmosphere at 25 ℃, carry out repeatedly.
At this moment, charge rate increases charging current according to the order of 0.8It → 1.7It → 2.5It → 3.3It → 4.2It arbitrarily, discharge rate increases discharging current according to the order of 1.7It → 3.3It → 5.0It → 6.7It → 8.3It arbitrarily, under each discharge rate, each electric current is measured the cell voltage (V) of each the battery A～L through 10 seconds the time respectively, obtain discharge V-I figure curve of approximation.
Here, electric current when the voltage on the V-I figure curve of approximation of trying to achieve is 0.9V is as the flash-over characteristic index, obtain discharge power output (10 ℃ of auxiliary power outputs), to adopt-10 ℃ of auxiliary power outputs of battery B of hydrogen-storage alloy b as benchmark (100), to obtain than (relative battery B) with its relative ratio conduct-10 ℃ auxiliary power output, its result is shown in following table 3.
(2) mensuration of the micronizing amount of hydrogen-storage alloy powder (the change of granularity amount before and after the activation).
Then, as the corrosion resistance index of hydrogen-storage alloy, measured the micronizing amount (granularity (the volume cumulative frequency is 50% particle diameter (D50) variable quantity) before and after the activation) of hydrogen-storage alloy powder.Here, the difference of the granularity after the granularity of micronizing amount after with firm pulverizing and the activation represents, is the index of the micronizing behavior of the hydrogen-storage alloy in the discharging and recharging when activation.In this case, the micronizing amount of battery B that adopted hydrogen-storage alloy b as benchmark (100), will be obtained than (relative battery B) as the micronizing amount with its relative ratio, its result is shown in following table 3.
Then, according to-10 ℃ of auxiliary power outputs of gained and the micronizing amount of hydrogen-storage alloy powder, as output persistence index, obtain the ratio (output persistence index=-10 ℃ auxiliary power output/micronizing amounts) of-10 ℃ of auxiliary power outputs with respect to the micronizing amount, its result is shown in following table 3.
[table 3]
Result according to above-mentioned table 3 can clear and definite following content.Promptly, compare with the battery B that adopts hydrogen-storage alloy b, adopted the battery C～L of hydrogen-storage alloy c～1, in other words, the condition of satisfied 0.1≤x≤0.2,0.1≤a≤0.2,0≤b≤0.1 and the stoichiometric proportion y of B composition (Ni+Al+M) are big more,-10 ℃ of auxiliary power outputs (low temperature power output) are big more, and when auxiliary power output had rising trend ,-10 ℃ of auxiliary power outputs also had trend of rising with respect to the ratio of micronizing amount.
But, even satisfying the condition of 0.1≤x≤0.2,0.1≤a≤0.2,0≤b≤0.1 and the stoichiometric proportion of B composition (Ni+Al+M) increases, if as battery D, adopting rare earth element (Ln) is not lanthanum (La) and when only comprising the hydrogen-storage alloy d of neodymium (Nd), then hydrogen balance presses (Pa) to increase, the micronizing amount also increases, and-10 ℃ of auxiliary power outputs also reduce with respect to the ratio of micronizing amount.Think this be because, when rare earth element (Ln) when being atomic radius less than the neodymium (Nd) of lanthanum (La), constitute the gap smaller between the metallic atom of elementary cell, hydrogen atom enters the metal lattice difficulty that becomes, thereby form unsettled metal hydride, hydrogen balance presses liter.Thereby think, like this with the hydrogen-storage alloy of the gap smaller between metallic atom as negative electrode active material be used for big electric current discharge and recharge purposes the time, quickened the micronizing of hydrogen-storage alloy, reduced persistence.
In addition, even satisfying the condition of 0.1≤x≤0.2,0.1≤a≤0.2,0≤b≤0.1 and the stoichiometric proportion of B composition (Ni+Al+M) increases, if as battery E, when rare earth element (Ln) is made up of lanthanum (La), praseodymium (Pr) and neodymium (Nd) element, then micronizing amount increases, and-10 ℃ of auxiliary power outputs also reduce with respect to the ratio of micronizing amount.This be because, when the number of elements of the rare earth element (Ln) that constitutes the A composition increased, the interaction parameter between the formation element during alloy casting in liquid phase increased, and generates the two-phase of segregation grade in an imperial examination easily.Thereby think that if the two-phase of segregation grade in an imperial examination generates, then quickened micronizing, the micronizing amount increases.
Result to above table 1～table 3 takes all factors into consideration as follows.That is, the alloy principal phase at the hydrogen-storage alloy of the B composition that comprises the A composition be made up of rare earth element of representing with Ln and magnesium and be made up of the element that comprises nickel, aluminium at least is A
5B
19The type structure is simultaneously with general formula Ln
1-xMg
xNi
Y-a-bAl
aM
b(in the formula, M is for being selected from Co, Mn, at least a kind element among the Zn) under Biao Shi the situation, when satisfied 0.1≤x≤0.2,0.1≤a≤0.2,0≤b≤0.1,3.6≤y≤3.9, and rare earth element (Ln) is made up of two elements at the most and when wherein comprising La at least, nickel mol ratio ((y-a-b)/(y+1)) is more than 74%, the nickel ratio increases, at 40 ℃ hydrogen storage amount H/M (atomic ratio) is that to press (Pa) be 0.03～0.17MPa for 0.5 o'clock storage hydrogen balance,-10 ℃ of auxiliary power outputs (low temperature output) increase, and-10 ℃ of auxiliary power outputs also increase with respect to the ratio of micronizing amount.
Industrial applicability
In above-mentioned embodiment,, also can use praseodymium (Pr), cerium lanthanide series such as (Ce) in addition at samarium (Sm), neodymium (Nd) though be illustrated as the samarium (Sm) of lanthanum (La) rare earth element (Ln) in addition or the example of neodymium (Nd) to using.In addition, wish with general formula Ln
1-xMg
xNi
Y-a-bAl
aM
bThe nickel substituted element M of the hydrogen-storage alloy of expression does not comprise cobalt (Mn) and manganese (Mn), this be because, use with, pure electric automobile etc. under the high temperature environment in the long-term purposes of placing at hybrid vehicle, require self-discharge performance (self-discharge is few), if negative pole contains cobalt (Mn) and manganese (Mn), these element strippings when long-term the placement are separated out on distance piece again, cause the reduction of self-discharge performance.
Claims (6)
1. a hydrogen-storage alloy is characterized in that, it is formed by A composition and B composition, and described A composition is formed by rare earth element of representing with Ln and magnesium, and described B composition is formed by the element that comprises nickel, aluminium at least,
The alloy principal phase of described hydrogen-storage alloy is A
5B
19The type structure, simultaneously,
Described hydrogen-storage alloy is with general formula Ln
1-xMg
xNi
Y-a-bAl
aM
bExpression, in the formula, M is at least a kind the element that is selected among Co, Mn, the Zn, 0.1≤x≤0.2,3.6≤y≤3.9,0.1≤a≤0.2,0≤b≤0.1,
Described rare earth element Ln is made of and wherein comprises at least La at the most two elements, and is that to press (Pa) be 0.03～0.17MPa for 0.5 o'clock storage hydrogen balance at 40 ℃ hydrogen storage amount H/M (atomic ratio).
2. hydrogen-storage alloy according to claim 1 is characterized in that, with described general formula Ln
1-xMg
xNi
Y-a-bAl
aM
bThe nickel mol ratio ((y-a-b)/(y+1)) of the hydrogen-storage alloy of expression is more than 74%.
3. hydrogen-storage alloy according to claim 1 and 2 is characterized in that, becomes described general formula Ln
1-xMg
xNi
Y-a-bAl
aM
bThe M of the nickel substituted element of the hydrogen-storage alloy of expression does not comprise cobalt (Mn) and manganese (Mn).
4. according to each described hydrogen-storage alloy in the claim 1～3, it is characterized in that described rare earth element (Ln) is lanthanum (La) and samarium (Sm) two elements, or lanthanum (La) and neodymium (Nd) two elements.
5. according to each described hydrogen-storage alloy in the claim 1～4, it is characterized in that the volume cumulative frequency of the powder of described hydrogen-storage alloy is that 50% particle diameter (D50) is below the 20 μ m.
6. an alkaline cell is characterized in that, the hydrogen-occlussion alloy electrode that to have with each described hydrogen-storage alloy in the claim 1～5 in urceolus be negative electrode active material, positive pole, distance piece and alkaline electrolyte that these the two poles of the earth are isolated.
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| JP2008242207A JP5425433B2 (en) | 2007-12-27 | 2008-09-22 | Hydrogen storage alloy and alkaline storage battery using hydrogen storage alloy as negative electrode active material |
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| JP2009176712A (en) | 2009-08-06 |
| JP5425433B2 (en) | 2014-02-26 |
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