CN102181751B - Low-self-discharge hydrogen storage alloy and preparation method thereof - Google Patents
Low-self-discharge hydrogen storage alloy and preparation method thereof Download PDFInfo
- Publication number
- CN102181751B CN102181751B CN2011100327490A CN201110032749A CN102181751B CN 102181751 B CN102181751 B CN 102181751B CN 2011100327490 A CN2011100327490 A CN 2011100327490A CN 201110032749 A CN201110032749 A CN 201110032749A CN 102181751 B CN102181751 B CN 102181751B
- Authority
- CN
- China
- Prior art keywords
- self
- storage alloy
- low
- hydrogen storage
- alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a hydrogen storage alloy, particularly a low-self-discharge hydrogen storage alloy and a preparation method thereof. The low-self-discharge hydrogen storage alloy has the advantages of high charge retention rate, favorable activation property, high discharge capacity and long service life. The low-self-discharge hydrogen storage alloy is an AB5-tye alloy of which the general formula is La[a]Ce[1-a]Ni[b]Co[c]Mn[d]Al[e], wherein the elements of the hydrogen storage part only include La and Ce alloys; and a, b, c, d and e represent mol ratios, 0.81<=a<=0.85, 3.72<=b<=3.92, 0.58<=c<=0.72, 0.3<=d<=0.4, 0.15<=e<=0.25, and 4.9<=b+c+d+e<=5.1. Under the protection of inert gas, raw materials, which satisfy the low-self-discharge hydrogen storage alloy of which the general formula is La[a]Ce[1-a]Ni[b]Co[c]Mn[d]Al[e], is smelted, and cooled by a solidifying method, thereby obtaining the low-self-discharge hydrogen storage alloy.
Description
Technical field
The present invention relates to a kind of hydrogen-storage alloy, especially relate to a kind of low-self-discharge hydrogen storage alloy and preparation method thereof.
Background technology
Along with the raising of human environmental consciousness, because ni-mh has the characteristics such as environment friendly and pollution-free, preferably security, so secondary cell Ni/MH is widely used aspect civilian.But because primary alkaline battery has and namely buys the i.e. characteristics of usefulness, and nickel metal hydride battery is often because hang tag in reasons such as supermarket, convenience stores for a long time, the carried charge that dispatches from the factory is exhausted substantially, needing again, charging re-uses, become the main factor that the restriction nickel metal hydride battery substitutes a Civil battery, therefore develop the low self-discharge nickel metal hydride battery, so that battery can namely be bought i.e. usefulness, become the in recent years market mainstream.Hydrogen-storage alloy is the critical material that determines the Ni/MH battery performance.Hydrogen-storage alloy is a kind of novel functional materials, and hydrogen atom can be stored in the space of its crystal, and this storage has reversibility, therefore is widely used in secondary cell.The hydrogen atom that hydrogen-storage alloy can be stored, if synthesize at normal temperatures and pressures hydrogen, its volume is more than 1000 times of this hydrogen-storage alloy, that is to say that its suction hydrogen density surpasses liquid hydrogen and solid state hydrogen density, both light, safety demonstrates incomparable superiority again.
That be used widely in nickel metal hydride battery at present, is rare earth AB
5The type alloy, representing composition is MmNi
3.55Al
0.4Mn
0.3Co
0.75, wherein Mm contains La, and Ce, Pr, Nd, this alloy have the advantages such as activation is fast, high-rate discharge ability is good, the life-span is long.Studies show that, La in the alloy is the strongest element of hydrogen storage capacity, simultaneously also be to reduce the fastest element of equilibrium hydrogen pressure, but its life-span is the poorest, Ce then is best element of life-span, and Pr, Nd is between the two, now in the commercialization in order to be in harmonious proportion La, the performance of Ce alloy, what show extremely is to carry out Pr, and Nd doses, but after these two kinds of elements dose, the reducing effect of putting the hydrogen platform to hydrogen-storage alloy is obvious not as La, cause the alloy equilibrium hydrogen pressure in the present commercialization alloy under 45 ℃, all to be higher than 0.22 (atH/M=0.4dehydrogenation), caused the battery year self-discharge rate that is made into generally higher, be not suitable as the low self-discharge pond.
Publication number be CN1073046A Patent Application Publication a kind of low self-discharge electrode metal be AB
2V-Ti, it comprises: take atomic percent as the basis, 14%～22% vanadium, 28%～39% nickel, 7%～15% titanium, 15%～34% zirconium, with at least a element that is selected from following group, comprise: 0.01%～3.6% manganese, and 0.01%～2.7% aluminium, wherein the atomic ratio of vanadium and zirconium is 1: in the scope of (2.26～0.68).Although this alloy is a kind of electrochemical hydrogen storage alloy that reduces self-discharge rate that has, and owing to vanadium titanium zirconium all is the expensive element of price comparison, adds AB
2The alloy activation is slow, and this alloy does not obtain the real marketization now.
Publication number be CN1015188A Patent Application Publication a kind of low self-discharge battery hydrogen-storage alloy, be not traditional AB
5Structure, this alloy contains A
2B
7Structure, chemical general formula are Nd
1-xMg
xNi
yAl
z, x wherein, y, z are atomic ratio, x: y: z=0.1～0.25: 3.1～3.6: 0.1～0.3 is although this alloy also has low characteristics of putting the hydrogen platform, because this alloy contains volatile Mg, production control is extremely difficult, and performance is comparatively unstable, and therefore the difficulty of the marketization is very high.
Summary of the invention
The object of the present invention is to provide a kind of charged conservation rate high, and have the low-self-discharge hydrogen storage alloy in good activation performance, high discharge capacity and life-span and preparation method thereof.
Low-self-discharge hydrogen storage alloy of the present invention is AB
5Type alloy, general formula are La
A,Ce
1-aNi
bCo
cMn
dAl
e, in the formula, storage hydrogen partial element only contains La, two kinds of alloys of Ce alloy, a, b, c, d, e represent mol ratio, and its numerical range is: 0.81≤a≤0.85,3.72≤b≤3.92,0.58≤c≤0.72,0.3≤d≤0.4,0.15≤e≤0.25,4.9≤b+c+d+e≤5.1.
Described low-self-discharge hydrogen storage alloy has high discharge capacity and low equilibrium hydrogen pressure.
The preparation method of low-self-discharge hydrogen storage alloy of the present invention may further comprise the steps:
Under protection of inert gas, the general formula that will meet described low-self-discharge hydrogen storage alloy is La
A,Ce
1-aNi
bCo
cMn
dAl
eThe raw material melting after, adopt clotting method to cool off, get low-self-discharge hydrogen storage alloy.
The temperature of described melting can be 940～1000 ℃, and the time of melting can be 6～7h.Described cooling, controlled refrigeration roller linear velocity 〉=2m/s makes the thickness≤0.3mm of the low-self-discharge hydrogen storage alloy of gained; Resulting low-self-discharge hydrogen storage alloy is to have under 45 ℃, and putting the hydrogen balance pressure is the hydrogen-storage alloy of 0.12～0.22atm (at H/M=0.4dehydrogenation).
Described low-self-discharge hydrogen storage alloy has CaCu
5The type structure is traditional AB
5Alloy, the stoichiometric ratio of B: A is 4.9～5.1 simultaneously; In the general formula of described low-self-discharge hydrogen storage alloy, A side element only contains La, two kinds of alloys of Ce, and do not contain the alloys such as Pr, Nd, Pm, Sm, Dy, Y, Zr and Ti.The scope of La is 0.81≤a≤0.85, if the content of La is lower than 0.81, then the equilibrium hydrogen pressure of alloy is too high, and capacity is low; If the content of La is higher than 0.85, then the life-span has largely and reduces.
In the general formula of described low-self-discharge hydrogen storage alloy, the scope of Ni is 3.72≤b≤3.92, if the content of Ni less than or equal to 3.72, then can fall low-alloyed electrochemical activation performance, and the reduction capacity; If Ni content is higher than 3.92, consider 4.95≤b+c+d+e≤5.1, then can have influence on the adding of falling the more obvious element of equilibrium pressure, such as the adding of Co, what be difficult to guarantee like this hydrogen-storage alloy puts hydrogen balance pressure≤0.22atm (at H/M=0.4dehydrogenation).
In the general formula of described low-self-discharge hydrogen storage alloy, the scope of Co is 0.58≤c≤0.72, if Co is lower than 0.58, then the cycle performance of alloy can worsen, and puts hydrogen balance and presses higher; If the content of Co is greater than 0.72, then performance boost is few, increases simultaneously cost of alloy, reduces cost performance.
In the general formula of described low-self-discharge hydrogen storage alloy, the scope of Mn is 0.3≤d≤0.4, if the content of Mn less than 0.3, then the equilibrium hydrogen pressure of alloy can be too high, thereby cause inner pressure of battery high, self-discharge is large; If the content of Mn greater than 0.65, then causes the segregation of making processes easily, be made into battery Mn and separate out easily, worsen the cycle life of battery.
In the general formula of described low-self-discharge hydrogen storage alloy, the scope of Al is 0.15≤e≤0.25, if the content of Al is lower than 0.15, the capacity of alloy increases, but the obvious variation of cycle life.If the content of Al is higher than 0.25, the capacity of alloy can obviously reduce.
In the general formula of described low-self-discharge hydrogen storage alloy, the scope of alloy metering ratio is 4.9≤b+c+d+e≤5.1, if stoichiometric ratio is lower than 4.9, then the cycle life of alloy can reduce; If stoichiometric ratio is higher than 5.1, then alloy the obvious capacity that affects alloy, simultaneously also can cause equilibrium hydrogen pressure to uprise, self-discharge is large.
Hydrogen-storage alloy put hydrogen balance press be 0.12～0.22atm (at H/M=0.4dehydrogenation) if equilibrium pressure is higher than 0.22atm (at H/M=0.4dehydrogenation), then the self-discharge of alloy is just larger; If equilibrium pressure is lower than 0.22atm (atH/M=0.4dehydrogenation), then the discharge platform of alloy is on the low side, and loading capacity is less than normal.
With existing AB
5The alloy phase ratio, the present invention is on the basis of other alloy over-all propertieies such as guaranteed capacity and life-span, by rejecting Pr, the elements such as Nd are adjusted La, the Ce ratio, optimize melting, annealing process, realized reducing the gordian technique of the equilibrium hydrogen pressure of hydrogen-storage alloy under 45 ℃, achievement battery normal temperature lotus conservation rate is so that the competition of nickel metal hydride battery and primary cell is seized the first opportunity.Studies show that, be reduction equilibrium hydrogen pressure and the most effective element of raising hydrogen storage performance under the normal temperature at the B side La of storage protium, and Ce promotes the most effective element of life-span in the B side.Removing Pr, in the time of Nd, adjusting La, the Ce ratio by control hydrogen-storage alloy preparation technology, thereby obtains the alloy of high discharge capacity and low equilibrium hydrogen pressure.
Low-self-discharge hydrogen storage alloy provided by the present invention especially can be used for nickel metal hydride battery, but the self-discharge performance of decrease hydrogen-storage alloy in battery.
Description of drawings
Fig. 1 is that the embodiment of the invention 1, comparative example 1 and comparative example 2 are 45 ℃ of suction Hydrogen desorption isotherms (P-C-T figure) under the condition in temperature.In Fig. 1, X-coordinate is H/M, and ordinate zou is equilibrium hydrogen pressure P
H2(atm); Curve a is embodiment 1, and curve b is comparative example 1, and curve c is comparative example 2.
Embodiment
The present invention is further illustrated in connection with accompanying drawing for following examples.
Embodiment 1
Design mix is La
0.83Ce
0.17Ni
3.75Co
0.72Mn
0.38Al
0.21According to shown in the mass percent that forms prepare burden; the raw material for preparing is placed the vacuum induction quick quenching furnace; after vacuumizing again applying argon gas protect; then carry out inducing melting; cast in subsequently on the high speed rotating cooling roller of interior logical water coolant and cool off fast; cold roller speed line speed 〉=2m/s; obtain the low-self-discharge hydrogen storage alloy sheet of thickness≤0.3mm; the heating smelting temperature that adopts is 940～1000 ℃; and employing air-blast device; to guarantee that temperature is even; the heating smelting time is 6～7h, and the low-self-discharge hydrogen storage alloy sheet that obtains is put the hydrogen balance pressure-controlled at 0.15～0.22atm (at H/M=0.4dehydrogenation) under 45 ℃.Then make D
50It is the powdered alloy about 45 μ m.
Comparative example 1
Design mix is La
0.33Ce
0.48Pr
0.05Nd
0.15Ni
3.59Co
0.73Mn
0.31Al
0.17, except design mix was different from embodiment 1, other were with embodiment 1.
Comparative example 2
Design mix is La
0.64Ce
0.25Pr
0.03Nd
0.08Ni
3.7Co
0.74Mn
0.4Al
0.2, except design mix was different from embodiment 1, other were with embodiment 1.
Utilize inductively coupled plasma atomic emission spectrometry method (ICP-AES) to measure each component content in embodiment and the comparative example alloy.As shown in table 1, each constituent content is consistent with design in the alloy.
Table 1
| La | Ce | Pr | Nd | Ni | Co | Mn | Al | B/A | |
| Embodiment 1 | 26.88 | 5.61 | / | / | 51.50 | 9.92 | 4.76 | 1.33` | 5.06 |
| Comparative example 1 | 10.94 | 16.12 | 1.67 | 5.09 | 50.72 | 10.27 | 4.1 | 1.09 | 4.79 |
| Comparative example 2 | 20.82 | 8.49 | 0.92 | 2.68 | 50.64 | 10.04 | 5.13 | 1.30 | 4.99 |
The opening gram volume test of gained sample is as follows:
At first hydrogen-storage alloy powder is ground to form less than 140 purpose alloy powders, get the 0.2g hydrogen-storage alloy powder and the 0.8gNi powder mixes, under 20MPa pressure, be pressed into the disk of diameter 16mm as negative pole, again weighing after the disk deflashing calculates the actual content of hydrogen-storage alloy powder in the disk in the ratio of alloy powder and nickel powder.Electric welding nickel strap on the negative pole disk, the anodal sintering nickel hydroxide that adopts same point to weld.To resemble sandwich intermediate plate mode with two positive poles with the negative plate of barrier film parcel and fit together, fix with polyvinyl chloride (PVC) plate, immerse in the KOH electrolytic solution of 6mol/L, the open cell of composition negative pole decision capacity.
The test of electrochemistry capacitance and cycle performance is carried out holding up a day BS9300 tester, and maximum discharge capacity is specifically tested as follows: probe temperature is 25 ℃ of constant temperature, with 60mA/g charging 450min, leave standstill 5min, be discharged to 1.0V with 60mA/g again, leave standstill 5min, then repeat above-mentioned charge and discharge process 2 times; With 300mA/g charging 80min, leave standstill 5min, be discharged to 1.0V with 300mA/g again, leave standstill 5min after, then repeat above-mentioned charge and discharge process, wherein the maximum value that reaches of loading capacity is designated as the opening gram volume of alloy powder.
All samples self-discharge performance testing method is as follows:
Be made into the battery of AA2000 with the method for the routine battery material that alloy powder is relevant with other, improve because the present invention only relates to alloy, therefore other condition all will keep except the alloy powder model can be changed.
Hydrogen-storage alloy powder ground to form then make D
50Be that then alloy powder about 50 μ m is pressed into the alloy powder of 9.8g on the collector of 128mm * 43mm * 0.3mm, wherein comprised the interpolation of conductive agent and tamanori, in like manner the ball nickel of anodal 7.8g is pressed on the collector of 100mm * 43mm * 0.62mm, then reel with sulfonated membrane and install in the box hat of 50AA, annotate alkali lye 2.55g, sealing changes into, charged and discharged for 5 weeks with the 0.2C electric current, record its 5th capacity and then use 0.2C current charges 6h, with its normal temperature storage 1 year, with the 0.2C electric current it is discharged into 1.0V again, its capacity except in the capacity that records the year before, is namely got charged conservation rate of its year, then 0.2C charged and discharged for 2 weeks, record the 2nd all capacity, it except in capacity the year before, is designated as the capacity restoration rate; Electric current with 0.5C charges and discharge battery at last, is designated as battery life during cut-off capacity 1200mA when (60%), and electrochemistry capacitance and cycle performance test are carried out holding up a day BS9300 tester, and probe temperature is 25 ℃ of constant temperature.
The P-C-T performance test methods of all samples is as follows:
The pressure component equitemperature tester that adopts the U.S. to produce, sample heats up first after the vacuum outgas, inhale again and put hydrogen activation 3 times, then test, probe temperature is 318K, and namely 45 ℃, the residing temperature of instrument is 298K ± 1K, then according to perfect gas formula N=pV/RT, calculate suction, put the hydrogen atoms molar weight from gas pressure change.Repeat this process, draw pressure-component-isothermal curve.
Embodiment 1 and Comparative Examples 1,2 equilibrium hydrogen pressure and self-discharge performance are listed in table 2.
Table 2
Illustrate: it is average that charged conservation rate of year, capacity restoration rate and the life-span in the table 2 is 6 battery institutes.
By as seen from Table 1, embodiment 1 (La
0.83Ce
0.17Ni
3.75Co
0.72Mn
0.38Al
0.21) and comparative example 1 (La
0.33Ce
0.48Pr
0.05Nd
0.15Ni
3.59Co
0.73Mn
0.31Al
0.17) main difference be exactly a value of La of comparative example 1 less than 0.81 value, the Ce value is also up to 0.48, greater than the upper limit 0.19 of the present invention, the value of B/A is 4.80, is 4.90 requirement less than minimum value of the present invention.Comparative example 1 is the rich Ce prescription of commonly using on the market now.Can find by table 2, the equilibrium hydrogen pressure of comparative example 1 under 45 ℃ condition is that its charged conservation rate of 1.326atm (at H/M=0.4) is lower, year, charged conservation rate only had 58.97%, and embodiment 1 hydrogen pressure is 0.169atm (at H/M=0.4), and its year, charged conservation rate was up to more than 85%.
Comparative example 2 (La
0.64Ce
0.25Pr
0.03Nd
0.08Ni
3.7Co
0.74Mn
0.4Al
0.2) be common on the market rich La prescription, with embodiment 1 (La
0.83Ce
0.17Ni
3.75Co
0.72Mn
0.38Al
0.21) mainly be that this product has replaced La and Ce with PrNd, so that the 0.15～0.22atm (at H/M=0.4) less than requirement of the present invention falls in balance, this product Mn value is higher simultaneously, can cause like this this product that the Mn dissolving occurs in battery, has influence on the self-discharge performance of battery.
Embodiment 2
Design mix is La
0.83Ce
0.17Ni
3.75Co
0.72Mn
0.38Al
0.21, annealing temperature is 960 ℃, soaking time is 6.5h.
Comparative example 3
Except thermal treatment process is that 900 ℃ of insulation 6.5h are different from the embodiment 2, other are with embodiment 2.
Comparative example 4
Except thermal treatment process is that 1000 ℃ of insulation 6.5h are different from the embodiment 2, other are with embodiment 2.
Embodiment 2 and comparative example 3,4 hydrogen storage property, open cell performance, the year charged conservation rate of enclosed cell is listed in table 3.Table 3 data show, adopt the year charged conservation rate of embodiment 2 of 960 ℃ of insulation 6.5h suitable with embodiment 1, and this is that equilibrium hydrogen pressure owing to this alloy reaches 0.15～0.22atm of the present invention (atH/M=0.4).Comparative example 3,4 adopts respectively 900 ℃ of insulation 6.5h, 1000 ℃ of insulation 6.5h, is balanced hydrogen pressure all greater than 0.22atm (at H/M=0.4), and therefore a year charged conservation rate all is lower than embodiment 2.Wherein the small portion sintering appears in the product of comparative example 4, is an important factor that descends in its life-span, so the present invention is decided to be upper limit technological temperature with 1000 ℃.
Table 3
Claims (2)
1. a low-self-discharge hydrogen storage alloy is characterized in that being AB
5Type alloy, general formula are La
aCe
1-aNi
bCo
cMn
dAl
e, in the formula, storage hydrogen partial element only contains La, two kinds of alloys of Ce alloy, a, b, c, d, e represent mol ratio, and its numerical range is: 0.81≤a≤0.85,3.72≤b≤3.92,0.58≤c≤0.72,0.3≤d≤0.4,0.15≤e≤0.25,4.9≤b+c+d+e≤5.1;
Described a kind of low-self-discharge hydrogen storage alloy is prepared by following methods:
Under protection of inert gas, the general formula that will meet described low-self-discharge hydrogen storage alloy is La
aCe
1-aNi
bCo
cMn
dAl
eThe raw material melting after, adopt clotting method to cool off, get low-self-discharge hydrogen storage alloy; The temperature of described melting is 940～1000 ℃, and the time of melting is 6～7h; Described cooling is the cold roller linear velocity 〉=2m/s of control, makes the thickness≤0.3mm of the low-self-discharge hydrogen storage alloy of gained.
2. a kind of low-self-discharge hydrogen storage alloy claimed in claim 1 is characterized in that described low-self-discharge hydrogen storage alloy has CaCu
5Type structure, the stoichiometric ratio of B: A are 4.9～5.1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100327490A CN102181751B (en) | 2011-01-28 | 2011-01-28 | Low-self-discharge hydrogen storage alloy and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100327490A CN102181751B (en) | 2011-01-28 | 2011-01-28 | Low-self-discharge hydrogen storage alloy and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102181751A CN102181751A (en) | 2011-09-14 |
| CN102181751B true CN102181751B (en) | 2013-01-09 |
Family
ID=44568036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100327490A Active CN102181751B (en) | 2011-01-28 | 2011-01-28 | Low-self-discharge hydrogen storage alloy and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102181751B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102828069B (en) * | 2012-09-26 | 2015-05-20 | 鞍山鑫普电池材料有限公司 | Praseodymium-neodymium-free low-cost superlong life type hydrogen storage alloy and preparation method thereof |
| CN102888539B (en) * | 2012-10-25 | 2015-07-29 | 厦门钨业股份有限公司 | A kind of there is ultra-high capacity characteristic low cost AB5 type hydrogen-storage alloy and method for making and application |
| 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 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3454780B2 (en) * | 1997-06-27 | 2003-10-06 | 日立マクセル株式会社 | Alkaline storage battery |
| JP3369148B2 (en) * | 1997-06-27 | 2003-01-20 | 日立マクセル株式会社 | Alkaline storage battery |
| JPH11191412A (en) * | 1997-06-27 | 1999-07-13 | Hitachi Maxell Ltd | Alkaline storage battery |
| JP2000239767A (en) * | 1999-02-22 | 2000-09-05 | Shin Etsu Chem Co Ltd | Hydrogen storage alloy, and hydrogen storage alloy electrode |
| JP3881823B2 (en) * | 2000-06-09 | 2007-02-14 | 三井金属鉱業株式会社 | Hydrogen storage alloy and method for producing the same |
| JP4647910B2 (en) * | 2001-12-13 | 2011-03-09 | 株式会社三徳 | Hydrogen storage alloy powder, production method thereof, and negative electrode for nickel metal hydride secondary battery |
-
2011
- 2011-01-28 CN CN2011100327490A patent/CN102181751B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN102181751A (en) | 2011-09-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104532095B (en) | Yttrium-nickel rare earth-based hydrogen storage alloy | |
| CN101629255B (en) | Low-cost high-performance rare-earth-based AB5-type hydrogen storage alloy and preparation method thereof | |
| CN104518204B (en) | A kind of rare earth-yttrium-nickel base hydrogen storage alloy and the secondary cell containing the hydrogen bearing alloy | |
| CN101353733B (en) | Preparation of La-Mg-Ni system hydrogen occluding alloy | |
| CN104152749B (en) | A5B19 type rare earth-yttrium-nickel system hydrogen storage alloy added with zirconium and titanium elements | |
| CN110317974B (en) | Yttrium-nickel rare earth hydrogen storage alloy | |
| CN104513925B (en) | Yttrium-nickel rare earth family hydrogen storage alloy, and secondary battery containing hydrogen storage alloy | |
| CN104513915B (en) | Zirconium and titanium-doped AB3 type rare earth-yttrium-nickel family hydrogen storage alloy | |
| CN106654240B (en) | A kind of Ce2Ni7Single-phase superlattice hydrogen storage alloy electrode material of type and preparation method thereof | |
| CN101626076A (en) | High-capacity long-life low-cost rare earth and magnesium-based hydrogen storage alloy | |
| CN102104146B (en) | Cobalt-free AB3.5-type hydrogen storage alloy anode material used for nickel-hydrogen battery and preparation method thereof | |
| CN101613818B (en) | Low cost hydrogen storage alloy, preparation method and application thereof | |
| CN104513916B (en) | Zirconium and titanium-doped A2B7 type rare earth-yttrium-nickel family hydrogen storage alloy | |
| CN110257649A (en) | A kind of High-performance Single-Phase La0.6R0.15Mg0.25Ni3.5Electrode metal and preparation method thereof | |
| CN105274395B (en) | La-Mg-Ni hydrogen storage material | |
| CN102703764A (en) | Cu-contained rare earth system AB5-type hydrogen storage alloy and preparation method thereof | |
| CN107075617B (en) | A kind of lanthanon hydrogen storage alloy and application thereof | |
| CN102181751B (en) | Low-self-discharge hydrogen storage alloy and preparation method thereof | |
| CN113881872B (en) | Low-cobalt high-rate AB5 type hydrogen storage alloy and preparation method thereof | |
| CN102383011B (en) | Rare earth magnesium-based hydrogen storage alloy with low cost and long life and applications thereof | |
| CN101552337A (en) | Superlattice hydrogen storage alloy and preparation method thereof | |
| CN108588495B (en) | AB with high capacity and long service life4.5Hydrogen storage alloy and preparation method thereof | |
| CN111118341A (en) | Rare earth-samarium-nickel type hydrogen storage alloy, negative electrode, battery and preparation method | |
| CN102888545A (en) | Method for preparing magnesium-based hydrogen storage alloy | |
| CN100593577C (en) | BCC structure hydrogen-storing alloy with flat pressure platform |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230703 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: 361026 Ke Jing She, Haicang Investment Zone, Xiamen City, Fujian Province Patentee before: XIAMEN TUNGSTEN Co.,Ltd. |