CN102644007B - Low temperature power type hydrogen storage alloy for nickel-metal hydride battery - Google Patents
Low temperature power type hydrogen storage alloy for nickel-metal hydride battery Download PDFInfo
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- CN102644007B CN102644007B CN201210143770.2A CN201210143770A CN102644007B CN 102644007 B CN102644007 B CN 102644007B CN 201210143770 A CN201210143770 A CN 201210143770A CN 102644007 B CN102644007 B CN 102644007B
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Abstract
The invention discloses a low temperature power type hydrogen storage alloy for a nickel-metal hydride battery. An alloy general formula is MlNiaCobMncAld, wherein a, b, c and d show molar ratio, the number range is 3.9<=a<=4.8, 0.3<=b<=0.6, 0<=c<=0.1, 0.1<=d<=0.4, 5.0<=a+b+c+d<=5.3. The Ml is composed of La and one of elements of Ce, Pr, Nd, Sm, Gd, Dy, Y and Zr, the La content is 40-80wt% of the Ml, and corresponding La is 10-26wt% of the content of the alloy. The alloy has excellent low temperature performance and high discharge voltage, simultaneously Mn content in the alloy composition is low, and the low temperature power type hydrogen storage alloy has excellent self discharge performance.
Description
Technical field
The present invention relates to a kind of low temperature power-type Ni-H battery hydrogen storage alloy.
Background technology
In recent years, due to the development of mobile electronic device and the revolution of traffic power source, the research and development of high tension battery have become the emphasis of various countries development, wherein, as the nickel metal hydride battery of civilian or Hybrid Vehicle, receive much concern and have realized commercialization; In addition, nickel metal hydride battery is also widely used in the optional power supply of many portable Military Electronics equipment.Yet this Application Areas is had higher requirement to the dynamic performance of nickel metal hydride battery and use temperature scope.In cold district and Military Application, require battery-40 ℃ of electric discharges, and current common nickel metal hydride battery is in temperature during lower than-20 ℃, it is comparatively obvious that discharge performance declines, and at-40 ℃, substantially cannot discharge.The low temperature performance of battery and the positive and negative electrode of battery, electrolytic solution, barrier film have certain relation, and wherein at low temperatures, the capacity loss of hydrogen storage alloy negative material is very fast, larger on the impact of nickel metal hydride battery low temperature performance; In addition, in low temperature field, can require equally battery to there is equally good dynamic performance, therefore develop the more aobvious key of well behaved power type hydrogen storage alloy negative material under low temperature.
Chinese patent 200510123747.7 announced a kind of low-temperature performance good without neodymium hydrogen storage alloy, its chemical general formula is La
xce
ypr
zni
mco
nmn
ual
v, x=0.16～0.5 wherein, y=0.12～0.81, z=0.03～0.59, m=3.7～3.8, n=0.55～0.6, u=0.25～0.45, v=0.1～0.25.At low temperatures functional of this alloy, alloy loading capacity reaches 260mAh/g at-40 ℃, and alloy loading capacity reaches 280 mAh/g at-30 ℃, but this low-temperature alloy does not relate to dynamic performance.
Chinese patent 200810027969.2 has been announced a kind of hydrogen storage alloy for low temperature Ni-MH power cell, and its chemical general formula is La
1-x-y-zce
xpr
ynd
zni
aco
bmn
cal
db
e, x=0.45～0.60 wherein, y=0.05～0.07, z=0.15～0.21, a=3.50～3.80, b=0.40～0.65, c=0.25～0.45, d=0.10～0.35, e=0.05～0.15.This alloy is introduced B element, makes the CeCo of the formation high catalytic activity of alloy
4type B second-phase, thus heavy alloyed low-temperature performance and heavy-current discharge performance carried.But B element is volatile, in industrial application, there is larger difficulty, though and second-phase must form the large electric current that is conducive to alloy, likely make the corrosion of nickel metal hydride battery in storage, use procedure increase the weight of, thereby cause the self-discharge performance of alloy to decline to some extent.
Therefore, develop a kind of self-discharge performance superior, industrialization easily low temperature power-type Ni-H battery is especially aobvious important with hydrogen storage alloy.
Summary of the invention
The present invention relates to a kind of low temperature power-type Ni-H battery hydrogen storage alloy, make alloy there is good low temperature, power and self-discharge performance.
To achieve these goals, solution of the present invention is:
A low temperature power-type Ni-H battery hydrogen storage alloy, its alloy general formula is: MlNi
aco
bmn
cal
d, in formula, a, b, c, d represent mol ratio, its numerical range is: 3.9≤a≤4.8,0.3≤b≤0.6,0 < c≤0.1,0.1≤d≤0.4,5.0≤a+b+c+d≤5.3; Ml is comprised of with at least a kind that is selected from Ce, Pr, Nd, Sm, Gd, Dy, Y, Zr element La, and wherein La content accounts for 40～80wt% in Ml, and corresponding La content in alloy accounts for 10～26wt%.
Hydrogen storage alloy of the present invention is AB
5type alloy, has CaCu
5type structure is the over-stoichiometric ratio of B side between 5.0 and 5.3 simultaneously.The put hydrogen balance pressure of alloy of the present invention at 45 ℃ is not less than 0.25MPa, and H/M=0.4(H/M represents the hydrogen atom mole number of every mole of alloy absorption), thus the low temperature of alloy and dynamic performance are improved.
In general formula, the scope of Ni is 3.9≤a≤4.8, if Ni content, lower than 3.9, can fall low-alloyed dynamic performance, if the content of Ni is greater than 4.8, can increase the cost of alloy.
In general formula, the scope of Co is 0.3 < b≤0.6, if Co content lower than 0.3, the cycle performance of alloy can worsen, if the content of Co is greater than 0.6, can fall low-alloyed dynamic performance.
In general formula, the scope of Mn is 0 < c≤0.1, if the content of Mn higher than 0.1, Mn the separate out amount of alloy in battery increases, the self-discharge aggravation of alloy.
In general formula, the scope of Al is 0.1≤d≤0.4, if the content of Al lower than 0.1, the cycle performance of alloy can worsen, if Al content is higher than 0.4, alloy volume lowering, high rate performance variation.
In general formula, the scope of alloy metering ratio is 5.0≤a+b+c+d≤5.3, if stoichiometric ratio lower than 5.0, the cycle life of alloy can reduce, if stoichiometric ratio higher than 5.3, the comprehensive comparison of alloy is poor.
Adopt after such scheme, the invention has the advantages that:
There is following relation in the equilibrium potential of hydrogen storage alloy and equilibrium hydrogen decomposition pressure:
E=-0.932-0.029logp
H2?（VS，Hg/HgO，20℃，6?mol?KOH）
In order to carry threshold voltage in heavy alloyed electric discharge, the present invention adopts the method that raising alloy is put hydrogen balance pressure to improve threshold voltage in electric discharge, by composition, adjust and suitable heat treatment has higher than the hydrogen balance of putting of conventional hydrogen storage alloy alloy to press, thereby there is the dynamic performance higher than conventional alloy; In addition, height is put hydrogen balance and is pressed and to make alloy putting hydrogen platform and can meet the needs that discharge under low-temperature condition, thereby makes alloy under low-temperature condition, has good chemical property.Too high equilibrium hydrogen pressure easily brings the increase of alloy self-discharge, and the present invention is by falling low-alloyed Mn content, make hydrogen storage alloy in battery system Mn content separate out minimizing, thereby make the self-discharge performance of alloy suitable with conventional hydrogen storage alloy.In addition, in alloy, not containing other element except Ml, Ni, Co, Mn, Al, recycling performance is good.
Accompanying drawing explanation
Fig. 1 is the PCT performance chart of alloy of the present invention.
Embodiment
Describe embodiments of the invention below in detail, but the present invention is not limited thereto, in the scope that does not change the claims in the present invention, suitably adjust, can implement the present invention equally.
" % " in embodiment is " wt% ".
1) alloy preparation method:
Preparation La (purity > 99.5%), Mm (La:30%, Ce:50%, Pr:5%, Nd:15%; La+Ce+Pr+Nd > 99%), Ni (purity > 99.5%), Co (purity > 99.5%), Mn (purity > 99.5%), Al (purity > 99.5%) amount to 5kg.Feed metal is put into Al by the order of Al, Mn, Ni, Co, La, Mm from the bottom to top
2o
3in crucible.First be evacuated to 3Pa, then baker, prepurging, applying argon gas is to 0.05MPa, and progressively regulating power 4kw, 6kw, each melting of 8kw, 10kw are 5 minutes, and controlling temperature is 1500 ℃ ± 30 ℃, then refining 3 minutes; Applying argon gas is to 0.05MPa, melt cast (linear velocity is 5ms through water-cooled copper roller
-1) cooling fast, obtain the alloy sheet that thickness is 0.1～0.3mm.Quenched alloy carries out 960 ℃ of insulations thermal treatment in 6.5 hours in argon shield gas, obtains heat treatment state alloy.Make subsequently granularity and be less than 140 object powdered alloys.
2) PCT(pressure-component-isothermal) Performance Detection:
The pressure component isothermal tester that adopts the U.S. to produce, sample first heats up after vacuum outgas, inhale again and put hydrogen activation 3 times, then test, probe temperature is 45 ℃, the residing temperature of instrument is 25 ℃ ± 1 ℃, then according to perfect gas formula N=p V/R T, from gas pressure change, calculates and inhales, puts hydrogen atoms molar weight.Repeat this process, draw pressure-component-isothermal curve.
3) chemical property detects
Electrochemical property test carries out in clip type open cell.First accurately take 0.2g hydrogen storing alloy powder and 0.8g carbonyl nickel powder, evenly mix, be cold-pressed into electrode slice spot-welded together with nickel strap, as alloy electrode to be measured.Supporting electrode is sintered type hydroxide nickel electrode, and electrolytic solution is 6molL
-1the KOH aqueous solution, test environment temperature remains on 25 ℃ ± 0.5 ℃.Testing tool is that a day secondary cell tester is held up in Guangzhou.Adopt 60mAg
-1constant current charge 450min, standing 5min, then 60mAg
-1constant-current discharge, stopping potential is 1.0V, standing 5min, successively circulation; Obtain the maximum discharge capacity (C of alloy
max, mAhg
-1) and activation number of times (N
a, inferior).1. normal temperature chemical property detects: adopt 300mAg
-1constant current charge 80min, standing 5min, then uses 300mAg
-1constant-current discharge, stopping potential is 1.0V, standing 5min, successively circulation; Obtain the 1C loading capacity (C of alloy
1C, mAhg
-1), and corresponding cycle index characterizes the cycle life (N, inferior) of alloy while being 80% with capability retention.2. low-temperature performance detects: battery, under 25 ℃ of conditions, is adopted to 60mAg
-1constant current charge 450min, then puts into battery 0 ℃, and-20 ℃ ,-30 ℃, in the cryostat of-40 ℃, to place 20 hours, last battery is with 300mAg
-1be discharged to terminal voltage 1.0V, measure the capacity of battery.
4) self-discharge performance detects:
Hydrogen storing alloy powder is ground to form and then makes D
50then the alloy powder that is 50 microns of left and right is pressed into the alloy powder of 9.8 grams on the collector of 128 * 43 * 0.3mm, wherein comprised the interpolation of conductive agent and tamanori, in like manner the ball nickel of anodal 7.8 grams is pressed on the collector of 100 * 43 * 0.62mm, then reel and install in the box hat of 50AA with sulfonated membrane, note 2.55 grams of alkali lye, sealing changes into, with 0.2C electric current, charge and discharge five weeks, record its 5th capacity and then use 0.2C current charges 6 hours, it is shelved 7 days at 45 ℃, with 0.2C electric current, discharged into 1.0V again, capacity by its capacity except record before 7 days, obtain its charged conservation rate, then 0.2C charges and discharge 2 weeks, record second week capacity, removed the capacity before shelving, being designated as the test of capacity restoration rate electrochemistry capacitance and cycle performance carries out holding up on day BS9300 tester, probe temperature is 25 ℃ of constant temperature.
Table 1: sample composition
| Sample | Design mix | B/ |
| Embodiment | ||
| 1 | La 0.63Ce 0.37Ni 4.37Co 0.45Mn 0.09Al 0.29 | 5.2 |
| Embodiment 2 | La 0.59Ce 0.30Pr 0.03Nd 0.09Ni 4.38Co 0.45Mn 0.07Al 0.3 | 5.2 |
| Comparative example 1 | La 0.62Ce 0.27Pr 0.03Nd 0.08Ni 4.07Co 0.45Mn 0.38Al 0.3 | 5.2 |
| Comparative example 2 | La 0.4Ce 0.44Pr 0.04Nd 0.12Ni 4.08Co 0.44Mn 0.32Al 0.26 | 5.1 |
| Comparative example 3 | La 0.66Ce 0.24Pr 0.03Nd 0.07Ni 4.16Co 0.46Mn 0.39Al 0.29 | 5.3 |
Respective electrical chemical property data are in Table 2:
From table 2, it is larger associated that threshold voltage in the electric discharge of alloy, low temperature performance and equilibrium hydrogen pressure exist, and equilibrium hydrogen pressure is higher, and in electric discharge, threshold voltage is higher, and low-temperature performance is better.This shows that the embodiment of the present invention 1,2 is all suitable with comparative example 2 at sparking voltage and low-temperature performance, is obviously better than comparative example 1 and comparative example 3.
Table 2 alloy normal temperature chemical property and low-temperature performance
Alloy is made into battery, and its performance is as follows:
The battery performance of table 3 alloy
On equilibrium hydrogen pressure, see that embodiment 1,2 and comparative example are higher, corresponding charged conservation rate is also lower.The charged conservation rate of comparative example 1 is the highest, and comparative example 3 equilibrium hydrogen pressures are placed in the middle, and charged conservation rate is also placed in the middle.
And for equilibrium hydrogen pressure suitable embodiment 1,2 and comparative example 2, charged conservation rate changes along with the variation of Mn content.This idea that shows that the present invention improves self-discharge performance by reduction Mn content is verified.
In sum, embodiment 1,2, by improving equilibrium hydrogen pressure and reducing Mn constituent content in alloy, makes alloy threshold voltage in having higher electric discharge, preferably low-temperature performance and comparatively good self-discharge performance.
Claims (3)
1. a low temperature power-type Ni-H battery hydrogen storage alloy, is characterized in that alloy general formula is: MlNi
aco
bmn
cal
d, in formula, a, b, c, d represent mol ratio, its numerical range is: 3.9≤a≤4.8,0.3≤b≤0.6,0 < c≤0.1,0.1≤d≤0.4,5.0≤a+b+c+d≤5.3; Ml is comprised of with at least a kind that is selected from Ce, Pr, Nd, Sm, Gd, Dy, Y, Zr element La, and wherein La content accounts for 40～80wt% in Ml, and corresponding La content in alloy accounts for 10～26wt%.
2. a kind of low temperature power-type Ni-H battery hydrogen storage alloy as claimed in claim 1, is characterized in that: hydrogen storage alloy is AB
5type alloy, has CaCu
5type structure is the over-stoichiometric ratio of B side between 5.0 and 5.3 simultaneously.
3. a kind of low temperature power-type Ni-H battery hydrogen storage alloy as claimed in claim 1, is characterized in that: the put hydrogen balance pressure of hydrogen storage alloy at 45 ℃ is not less than 0.25MPa, H/M=0.4.
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| CN104532095B (en) * | 2014-08-28 | 2017-01-25 | 包头稀土研究院 | Yttrium-nickel rare earth-based hydrogen storage alloy |
| CN104263997A (en) * | 2014-09-19 | 2015-01-07 | 广东省工业技术研究院(广州有色金属研究院) | Praseodymium/neodymium-free hydrogen storage alloy |
| CN110714139A (en) * | 2018-07-13 | 2020-01-21 | 有研工程技术研究院有限公司 | Rare earth-nickel-based hydrogen storage alloy material and preparation method thereof |
| CN110265655B (en) * | 2019-06-27 | 2022-08-02 | 兰州金川科力远电池有限公司 | High-performance low-cost hydrogen storage alloy powder for nickel-hydrogen power battery and preparation method thereof |
| CN111180697A (en) * | 2019-12-31 | 2020-05-19 | 深圳拓量技术有限公司 | Nickel-hydrogen battery for ultralow temperature environment |
| CN111180718A (en) * | 2019-12-31 | 2020-05-19 | 深圳拓量技术有限公司 | Hydrogen storage alloy powder of nickel-hydrogen battery for ultralow temperature environment and preparation method thereof |
| CN111471910B (en) * | 2020-04-14 | 2021-12-03 | 包头稀土研究院 | AB3Gadolinium-containing hydrogen storage alloy, electrode, battery and preparation method thereof |
| CN111979449A (en) * | 2020-08-13 | 2020-11-24 | 兰州金川科力远电池有限公司 | Low-cost power type hydrogen storage alloy and preparation method thereof |
| CN113881872B (en) * | 2021-10-27 | 2022-05-20 | 厦门钨业股份有限公司 | Low-cobalt high-rate AB5 type hydrogen storage alloy and preparation method thereof |
| CN116445791A (en) * | 2023-04-04 | 2023-07-18 | 惠州星燚新材料技术有限公司 | Hydrogen storage alloy and preparation process thereof |
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Effective date of registration: 20230605 Address after: No. 300-2, Kejingshe, Xiamen Area, China (Fujian) Pilot Free Trade Zone, Xiamen City, Fujian Province, 361026 Patentee after: Xiamen Xiamen Tungsten Hydrogen Energy Technology Co.,Ltd. Address before: 361000 Ke Gang, Haicang District, Fujian, Xiamen Patentee before: XIAMEN TUNGSTEN Co.,Ltd. |