CN1702888A - AB5 type negative pole hydrogen storing material and preparation method thereof - Google Patents
AB5 type negative pole hydrogen storing material and preparation method thereof Download PDFInfo
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- CN1702888A CN1702888A CNA2005100835350A CN200510083535A CN1702888A CN 1702888 A CN1702888 A CN 1702888A CN A2005100835350 A CNA2005100835350 A CN A2005100835350A CN 200510083535 A CN200510083535 A CN 200510083535A CN 1702888 A CN1702888 A CN 1702888A
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Abstract
This invention provides one AB5 negative electrode hydrogen stock materials processed by quick fixed thin film , which comprises the following components: MmNi3.55-xPtxCo0.75Mn0.4Al0.3, wherein, 0<x <=0.065; Mm is rare earth mixture of La, Ce, Pr, Nd elements computed as weight of Mm; La is of 64.5-67.5%; Ce is of 22.0-24.0%; Pr is of2.5-3.5%; the Nd is of 7.0-9.0%. Wherein, the method cooling speed is decided through the control of the roller rotation speed of one to three m per second and product thickness.
Description
Technical field
The present invention relates to cell negative electrode material.Especially, the present invention relates to be used for the AB of Ni-MH battery
5Type cathode hydrogen storage material and preparation method thereof.
Background technology
Ni-MH battery is since last century, put goods on the market the nineties, because it is long that it has capacity height, life-span, characteristics such as memory-less effect, non-environmental-pollution, extensively receive an acclaim, occupation rate of market is more and more higher, cell types is also developed to other polytypes by AA, AAA common batteries, and product is widely used in electric tool, household electrical appliance, computer, building, space flight, communication and vehicle using motor etc., develops very rapid.
Because Ni-MH battery belongs to rechargeable battery, in use constantly repeated charge is used, therefore the number of times that battery can repeated charge, just cycle life just becomes one of key property of sign Ni-MH battery serviceability quality, people always wish that Ni-MH battery can have longer cycle life, and this mainly is the use cost that can reduce the user.For Ni-MH battery, its cycle life is relevant with many factors, therefore wherein the electrochemical hydrogenation and dehydrogenation cycle life of negative material is one of decisive factor of Ni-MH battery cycle life, and people have done many research work aspect the negative material cycle life improving.
For Ni-MH battery, used cathode hydrogen storage material mainly is mishmetal MmNi at present
5Generally about 300～330mAh/g, typical composition is MmNi for-type hydrogen storage alloy, alloy capacity
3.55Co
0.75Mn
0.4Al
0.3Wherein Mm is a mishmetal, main component is La, Ce, Pr, Nd, in this component prescription, cobalt occupies the percentage by weight (seeing Table 2) of 10wt%, this is because people are main relevant with two kinds of factors by the decline of discovering hydrogen storage material electrochemical hydrogenation and dehydrogenation cycle life, the one, oxidation, efflorescence besides, the reason of efflorescence comes from alloy and puts lattice dilatation and the contraction that causes in the hydrogen atom turnover alloy lattice gap in the hydrogen process in suction, it is found that through a large amount of research working as alloying component is MmNi
3.55Co
0.75Mn
0.4Al
0.3The time, can make the cycle life of alloy reach best in the homogenizing processing that is aided with again behind the vacuum induction melting about 1000 ℃ simultaneously, here no matter anti-oxidant still aspect the anti-efflorescence, cobalt all plays important effect, and reach optimum efficiency during for 10wt% at content, thereby become and improve the indispensable element of negative pole cycle life, manganese and aluminium also play a part certain in addition, the purpose that homogenizing is handled is component segregation and the distortion of lattice that causes in the casting cycle behind the elimination induction melting, because this component segregation and distortion of lattice can produce stress and concentrate in the alloy hydrogen absorption and desorption process, cause the fragmentation of alloy.More than obtaining of these achievements in research make the AB that is applicable to Ni-MH battery
5The cycle life of type cathode hydrogen storage material has reached more satisfactory level, and has obtained the commercialization use.Yet, further improve the AB that is applicable to Ni-MH battery
5The cycle life of type cathode hydrogen storage material is still the target that people pursue, so the researcher is devoted to adopt various new technologies such as quick quenching technique, atomization and rapid hardening thin strip process to research and develop the long-life AB that is applicable to Ni-MH battery
5The type cathode hydrogen storage material, the present invention adopts the rapid hardening thin strip process just, has prepared the long-life AB that is applicable to Ni-MH battery
5The type cathode hydrogen storage material.
Summary of the invention
The objective of the invention is with MmNi
3.55Co
0.75Mn
0.4Al
0.3Be the basis, when keeping its capacity, the improvement by composition adjustment and preparation technology obtains a kind of long-life AB that is applicable to Ni-MH battery
5The type cathode hydrogen storage material is to satisfy on the market demand to the long-life cathode hydrogen storage material product that is applicable to Ni-MH battery.
Specifically, the invention provides a kind of AB by the preparation of rapid hardening thin strip process
5The type cathode hydrogen storage material, this AB
5The atomic ratio composition of type cathode hydrogen storage material consists of Mm
1-xDy
xNi
3.55Co
0.75Mn
0.4Al
0.3, 0＜x≤0.065 wherein, Mm is the lucium of being made up of La, Ce, Pr, Nd element, and the weight with lucium Mm is benchmark, and the content of La is 64.5-67.5%, and the content of Ce is 22.0-24.0%, the content of Pr is 2.5-3.5%, and the content of Nd is 7.0-9.0%.The cooling rate of the rapid hardening thin strip process that wherein, is adopted is that 1-3m/s and product thickness are that 0.2～0.5mm determines by control chill roll surface of revolution linear velocity.
AB
5The type hydrogen storage alloy material be by the elements A of easy generation stable hydride (as Mm, Ca, Zr) intermetallic compound of forming with other element B (as Ni, Al, Mn, Si, Zn, Cr, Fe, Cu, Co etc.) belongs to CaCu
5The type hexagonal structure, for Ni-MH battery, used negative material mainly is mishmetal MmNi at present
5Generally about 300mAh/g, typical composition is MmNi for-type hydrogen storage alloy, alloy capacity
3.55Co
0.75Mn
0.4Al
0.3, wherein Mm is a mishmetal, main component is La, Ce, Pr, Nd.In order to improve the cycle life of material, the present invention adds a spot of heavy rare earth element dysprosium (Dy) in rare earth, adopts the rapid hardening thin strip process simultaneously on technology, has finally obtained to satisfy the long-life AB of actual use
5The type cathode hydrogen storage material by the optimization of composition and technology, is not changing under the situation of capacity and activity function substantially, the cycle life of material obviously can be improved.Therefore, AB proposed by the invention
5The type cathode hydrogen storage material becomes to be grouped into (atomic ratio): Mm
1-xDy
xNi
3.55Co
0.75Mn
0.4Al
0.3, 0＜x≤0.065 wherein, and that the composition of mishmetal Mm is formed is as shown in table 1.
Each constituent content in table 1 mishmetal
| Element | Percentage by weight (wt%) |
| ??La | ??64.5-67.5 |
| ??Ce | ??22.0-24.0 |
| ??Pr | ??2.5-3.5 |
| ??Nd | ??7.0-9.0 |
At AB of the present invention
5In the type cathode hydrogen storage material, the scope of preferred x is 0.026～0.052.
As AB of the present invention
5The example of type cathode hydrogen storage material, atomic ratio one-tenth is grouped into and can be:
Mm
0.987Dy
0.013Ni
3.55Co
0.75Mn
0.4Al
0.3；
Mm
0.974Dy
0.026Ni
3.55Co
0.75Mn
0.4Al
0.3；
Mm
0.961Dy
0.039NixCo
0.75Mn
0.4Al
0.3；
Mm
0.948Dy
0.052Ni
3.55Co
0.75Mn
0.4Al
0.3Or
Mm
0.935Dy
0.065Ni
3.55Co
0.75Mn
0.4Al
0.3Or the like.
Preferred AB of the present invention
5Type cathode hydrogen storage material atomic ratio consists of
Mm
0.974Dy
0.026Ni
3.55Co
0.75Mn
0.4Al
0.3；Mm
0.961Dy
0.039Ni
3.55Co
0.75Mn
0.4Al
0.3；
Mm
0.948Dy
0.052Ni
3.55Co
0.75Mn
0.4Al
0.3Deng, be preferably especially
Mm
0.961Dy
0.039Ni
3.55Co
0.75Mn
0.4Al
0.3。
Prepare AB of the present invention
5The rapid hardening thin strip process of type cathode hydrogen storage material is as follows:
To mol ratio is Mm: Dy: Ni: Co: Mn: Al=(1-x): x: 3.55: 0.75: 0.4: 0.3 raw material carries out melting, 0＜x≤0.065 wherein, Mm is the lucium of being made up of La, Ce, Pr, Nd element, and the weight with lucium Mm is benchmark, the content of La is 64.5-67.5%, the content of Ce is 22.0-24.0%, and the content of Pr is 2.5-3.5%, and the content of Nd is 7.0-9.0%;
The liquation that melting is obtained is directed to the water flowing cooling and with the chill roll surface of the linear resonance surface velocity rotation of 1-3m/s, and this chill roll is with the rapid cool to room temperature of melting liquation and be thrown in the sample divider, obtains the AB that thickness is 0.2～0.5mm
5The type cathode hydrogen storage material.Wherein, the surface of revolution linear velocity of chill roll and product thickness have determined the cooling rate of rapid hardening thin strip process of the present invention jointly.
In above-mentioned melting step, employing be to vacuumize the back and feed the vacuum induction melting of argon shield.
In above-mentioned rapid cooling step, can adopt bottom opening and place the crucible of chill roll top to compile the melting liquation, the hole of melting liquation below crucible is directed into the surface of chill roll.
In the step of above-mentioned rapid cooling, preferably adopt the copper roller as chill roll.
The linear resonance surface velocity of chill roll rotation is preferably 1m/s.
AB of the present invention
5The type cathode hydrogen storage material can be used for preparing nickel-hydrogen battery negative pole.Adopt AB of the present invention
5The type cathode hydrogen storage material has long charge and discharge circulation life as the Ni-MH battery of negative pole.
With use conventional vacuum induction melting, and handled 15 hours and the cathode hydrogen storage material that obtains is compared 980 ℃ of homogenizing, among the present invention with the cathode hydrogen storage material Mm of rapid hardening thin strip process preparation
1-xDy
xNi
3.55Co
0.75Mn
0.4Al
0.3(0＜x≤0.065) can improve the cycle life of alloy material significantly, and increase along with cooling rate (under the situation that product thickness is fixed, characterizing) by the chill roll rotating speed, the cycle life of alloy increases, but can cause activity function and charge discharge capacity that decline (still satisfying instructions for use) is arranged slightly, and the interpolation of heavy rare earth element dysprosium (Dy) can further improve the cycle life of alloy, also capacity is had some improvement simultaneously.The present invention is by selecting suitable cooling rate and adding a spot of heavy rare earth element dysprosium (Dy) simultaneously, not only can keep good activity function and charge discharge capacity, the cycle life of alloy is increased substantially (up to 40%), thereby reach long-life requirement.
Embodiment
Below in conjunction with embodiment the present invention is launched further description.But should be appreciated that following execution mode only is used for the present invention is illustrated and is not in order to limit scope of the present invention.
Percentage by weight according to each element of alloy in the table 2 is prepared burden, and adopts conventional smelting process and rapid hardening thin strip process that raw material is made AB respectively
5Type cathode hydrogen storage material, and the performance of the aspects such as activation number of times, heap(ed) capacity and cycle life of each product of comparison.
The composition that table 2 embodiment of the invention is compared with the prior art example compares (wt%)
| Composition | ??La | ??Ce | ??Pr | ??Nd | ??Dy | ??Ni | ??Co | ??Mn | ??Al | |
| The present invention | ??Mm 0.987Dy 0.013Ni 3.55Co 0.75Mn 0.4Al 0.3 | ??21.53 | ??7.50 | ??0.98 | ??2.61 | ??0.50 | ??49.30 | ??10.46 | ??5.20 | ??1.92 |
| ??Mm 0.974Dy 0.026Ni 3.55Co 0.75Mn 0.4Al 0.3 | ??21.23 | ??7.40 | ??0.97 | ??2.57 | ??1.00 | ??49.27 | ??10.45 | ??5.20 | ??1.91 | |
| ??Mm 0.961Dy 0.039Ni 3.55Co 0.75Mn 0.4Al 0.3 | ??20.93 | ??7.30 | ??0.95 | ??2.54 | ??1.50 | ??49.23 | ??10.44 | ??5.19 | ??1.91 | |
| ??Mm 0.948Dy 0.052Ni 3.55Co 0.75Mn 0.4Al 0.3 | ??20.64 | ??7.19 | ??0.94 | ??2.50 | ??2.00 | ??49.20 | ??10.44 | ??5.19 | ??1.91 | |
| ??Mm 0.935Dy 0.065Ni 3.55Co 0.75Mn 0.4Al 0.3 | ??20.34 | ??7.09 | ??0.92 | ??2.47 | ??2.50 | ??49.17 | ??10.43 | ??5.19 | ??1.91 | |
| Comparative Examples | ??MmNi 3.55Co 0.75Mn 0.4Al 0.3 | ??21.83 | ??7.61 | ??0.99 | ??2.65 | ??0.00 | ??49.34 | ??10.47 | ??5.20 | ??1.92 |
Sample for conventional melting; the alloy raw material for preparing is carried out melting and ingot casting in the induction furnace that vacuumizes afterwards and feed argon shield; then ingot casting being carried out homogenizing in the vacuum heat treatment furnace that vacuumizes afterwards and feed argon shield handles; treatment temperature is 980 ℃; temperature retention time is 15 hours, then takes out with the stove cool to room temperature.
For the rapid hardening sample; the alloy raw material for preparing is carried out melting in the induction furnace that vacuumizes afterwards and feed argon shield; then liquation is poured in the crucible of a bottom opening; this crucible is placed on water flowing cooling and copper roller rotating top; liquation passes through the surface of the orifice flow of crucible bottom to the copper roller; experimental requirement is respectively 1m/s, 2m/s and 3m/s with the rotational speed regulation of copper roller to its linear resonance surface velocity respectively; the water-cooled copper roller cools off the melting liquation rapidly and is thrown in the sample divider; obtain laboratory sample, sample thickness is between 0.2～0.5mm.
The test of electrochemistry capacitance at first becomes resulting hydrogen bearing alloy less than 200 purpose alloyed powders in grinding at room temperature, then will be less than 200 purpose negative alloy powders and nickel powder mixed by 1: 4, and add an amount of poly-vinyl alcohol solution as binding agent, be cold-pressed into diameter then and use [the Ni (OH) that used positive electricity is very identical with Ni-MH battery as negative electrode for the cake of (d=15mm)
2-NiOOH] electrode, the Capacity design of positive electrode is the capacity far above negative electrode, so that negative electrode material reaches fully saturated when charging, [Hg/HgO/6M KOH] is reference electrode.In the electrode performance test process, test for activity function and charge discharge capacity, 30 ℃ of current densities that adopt 60mA/g to the storage hydrogen negative material 400min that charges, paused 15 minutes in the charging back, then with the current density of 60mA/g discharge into the negative electrode current potential with respect to the electrode potential of reference electrode for till-0.5 volt, carry out the next round charge and discharge cycle again.Capacity of negative plates be along with the increase capacity that discharges and recharges number of times will reach a maximum gradually, and relatively stablely get off, and our amount of trying to please reached the required number of times that discharges and recharges of maximum and was the activation number of times this moment, and this maximum is the hydrogen storage capability of material under 30 ℃.
Test for cycle life, in order to shorten the testing time, charging and discharging currents density is chosen as 300mA/g, method of testing is as follows: at first adopt the current density of 60mA/g to activate by the method for top test capacity with the activation number of times at 30 ℃ specimen, after activation is good, 30 ℃ of current densities that adopt 300mA/g to the storage hydrogen negative material 75min that charges, paused 15 minutes in the charging back, then with the current density of 300mA/g discharge into the negative electrode current potential with respect to the electrode potential of reference electrode for till-0.5 volt, carrying out next round again fills, discharge cycles, in order to contrast conveniently, the cycle life of sample is defined as cycle-index when its capacity under this experiment condition drops to 160mAh/g, and its test result all is given in the table 3.
The comparison of the activity function of table 3 embodiment of the invention and Comparative Examples, electrochemistry capacitance and cycle life
| Composition | Copper roller linear resonance surface velocity | ||||||||||
| ??1m/s | ??2m/s | ??3m/s | ??1m/s | ??2m/s | ??3m/s | ??1m/s | ??2m/s | ??3m/s | |||
| The activation number of times | Heap(ed) capacity (mAh/g) | Cycle life | |||||||||
| The preparation of rapid hardening thin strip process | The present invention | ??Mm 0.987Dy 0.013Ni 3.55Co 0.75Mn 0.4Al 0.3 | ??4 | ??8 | ??16 | ??321 | ??316 | ??295 | ??947 | ??1050 | ??1151 |
| ??Mm 0.974Dy 0.026Ni 3.55Co 0.75Mn 0.4Al 0.3 | ??4 | ??8 | ??16 | ??323 | ??318 | ??297 | ??993 | ??1089 | ??1181 | ||
| ??Mm 0.961Dy 0.039Ni 3.55Co 0.75Mn 0.4Al 0.3 | ??4 | ??8 | ??16 | ??325 | ??320 | ??301 | ??1027 | ??1121 | ??1214 | ||
| ??Mm 0.948Dy 0.052Ni 3.55Co 0.75Mn 0.4Al 0.3 | ??4 | ??9 | ??18 | ??324 | ??318 | ??299 | ??1042 | ??1138 | ??1233 | ||
| ??Mm 0.935Dy 0.065Ni 3.55Co 0.75Mn 0.4Al 0.3 | ??6 | ??11 | ??20 | ??314 | ??305 | ??285 | ??1057 | ??1165 | ??1271 | ||
| Comparative Examples | ??MmNi 3.55Co 0.75Mn 0.4Al 0.3 | ??4 | ??8 | ??16 | ??320 | ??314 | ??293 | ??884 | ??987 | ??985 | |
| Conventional smelting method for preparing | The activation number of times | Heap(ed) capacity (mAh/g) | Cycle life | ||||||||
| ??MmNi 3.55Co 0.75Mn 0.4Al 0.3 | ??3 | ??328 | ??725 | ||||||||
| ??Mm 0.987Dy 0.013Ni 3.55Co 0.75Mn 0.4Al 0.3 | ??3 | ??328 | ??728 | ||||||||
| ??Mm 0.974Dy 0.026Ni 3.55Co 0.75Mn 0.4Al 0.3 | ??3 | ??328 | ??730 | ||||||||
| ??Mm 0.961Dy 0.039Ni 3.55Co 0.75Mn 0.4Al 0.3 | ??3 | ??331 | ??735 | ||||||||
| ??Mm 0.948Dy 0.052Ni 3.55Co 0.75Mn 0.4Al 0.3 | ??3 | ??331 | ??734 | ||||||||
| ??Mm 0.935Dy 0.065Ni 3.55Co 0.75Mn 0.4Al 0.3 | ??3 | ??323 | ??730 | ||||||||
Table 3 has provided respectively the Mm that handled 15 hours and prepared with the rapid hardening thin strip process with behind the conventional vacuum induction melting and 980 ℃ of homogenizing
1-xDy
xNi
3.55Co
0.75Mn
0.4Al
0.3(0＜x≤0.065) and MmNi
3.55Co
0.75Mn
0.4Al
0.3Electrochemistry capacitance, activity function and the The cyclic lifetime test results of under 300mA/g charging and discharging currents density, measuring that compound is measured under 30 ℃ and 60mA/g charging and discharging currents density.By data in the table as seen, can improve the cycle life of alloy significantly by the rapid hardening thin strip process, and increase along with cooling rate (under the situation that product thickness is fixed, characterizing) by copper roller rotating speed, the cycle life of alloy increases, but can cause activating number of times and increase charge discharge capacity decline (but still satisfying instructions for use), the interpolation of heavy rare earth element dysprosium (Dy) can further improve the cycle life of alloy, also capacity is had some improvement simultaneously.The hydrogen storage material Mm of the present invention for preparing during for 1m/s in copper roller linear velocity
1-xDy
xNi
3.55Co
0.75Mn
0.4Al
0.3The alloy and the Mm of the identical component of (0.026≤x≤0.052) and conventional method preparation
0.935Dy
0.065Ni
3.55Co
0.75Mn
0.4Al
0.3The alloy phase ratio, its capacity and activity function are similar substantially, but cycle life obviously increases, and are that 0.039 o'clock capacity is the highest with Dy content in this based material, especially, the hydrogen storage material Mm of the present invention for preparing during for 1m/s in copper roller linear velocity
0.961Dy
0.039Ni
3.55Co
0.75Mn
0.4Al
0.3Compare with conventional method the activation number of times substantially quite, heap(ed) capacity is close and cycle life has improved more than 40%.
In sum, in the technical scheme of the present invention by selecting suitable cooling rate and adding a spot of heavy rare earth element dysprosium (Dy) simultaneously, not only can keep good activity function and charge discharge capacity, therefore the cycle life of alloy is significantly improved (the raising degree is up to 40%), has reached the effect that has not only improved the life-span but also satisfied instructions for use.
Claims (11)
1. AB
5The type cathode hydrogen storage material is that 1-3m/s and product thickness are the rapid hardening thin strip process preparation of 0.2～0.5mm by control chill roll surface of revolution linear velocity, this AB
5The atomic ratio composition of type cathode hydrogen storage material consists of Mm
1-xDy
xNi
3.55Co
0.75Mn
0.4Al
0.3, 0＜x≤0.065 wherein, Mm is the lucium of being made up of La, Ce, Pr, Nd element, and the weight with lucium Mm is benchmark, and the content of La is 64.5-67.5%, and the content of Ce is 22.0-24.0%, the content of Pr is 2.5-3.5%, and the content of Nd is 7.0-9.0%.
2. AB according to claim 1
5The type cathode hydrogen storage material is characterized in that, described chill roll surface of revolution linear velocity is 1m/s.
3. AB according to claim 1 and 2
5The type cathode hydrogen storage material is characterized in that, x is 0.026～0.052.
4. AB according to claim 1 and 2
5The type cathode hydrogen storage material is characterized in that, described AB
5The atomic ratio composition of type cathode hydrogen storage material consists of:
Mm
0.987Dy
0.013Ni
3.55Co
0.75Mn
0.4Al
0.3；
Mm
0.974Dy
0.026Ni
3.55Co
0.75Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.75Mn
0.4Al
0.3；
Mm
0.948Dy
0.052Ni
3.55Co
0.75Mn
0.4Al
0.3Or
Mm
0.935Dy
0.065Ni
3.55Co
0.75Mn
0.4Al
0.3。
5. AB according to claim 4
5The type cathode hydrogen storage material is characterized in that, described AB
5The atomic ratio composition of type cathode hydrogen storage material consists of:
Mm
0.961Dy
0.039Ni
3.55Co
0.75Mn
0.4Al
0.3。
6. one kind prepares the described AB of claim 1
5The method of type cathode hydrogen storage material, this method are the rapid hardening thin strip process that comprises the following steps:
To mol ratio is Mm: Dy: Ni: Co: Mn: Al=(1-x): x: 3.55: 0.75: 0.4: 0.3 raw material carries out melting, 0＜x≤0.065 wherein, Mm is the lucium of being made up of La, Ce, Pr, Nd element, and the weight with lucium Mm is benchmark, the content of La is 64.5-67.5%, the content of Ce is 22.0-24.0%, and the content of Pr is 2.5-3.5%, and the content of Nd is 2.5-3.5%;
The liquation that melting is obtained is directed to the water flowing cooling and with the chill roll surface of the linear resonance surface velocity rotation of 1-3m/s, and this chill roll is with the rapid cool to room temperature of melting liquation and be thrown in the sample divider, obtains the AB that thickness is 0.2～0.5mm
5The type cathode hydrogen storage material.
7. method according to claim 6 is characterized in that, described chill roll is with the linear resonance surface velocity rotation of 1m/s.
8. according to claim 6 or 7 described methods, it is characterized in that, adopt the vaccum sensitive stove that vacuumizes the back and feed argon shield to carry out melting in the described melting step.
9. according to claim 6 or 7 described methods, it is characterized in that adopt bottom opening in the described rapid cooling step and place the crucible of chill roll top to compile the melting liquation, the hole of melting liquation below crucible is directed into the surface of chill roll.
10. any described AB of claim 1-5
5The application of type cathode hydrogen storage material in making nickel-hydrogen battery negative pole.
11. application according to claim 10 is characterized in that, described Ni-MH battery is the Ni-MH battery with long charge and discharge circulation life.
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|---|---|---|---|
| CNA2005100835350A CN1702888A (en) | 2005-07-08 | 2005-07-08 | AB5 type negative pole hydrogen storing material and preparation method thereof |
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108987738A (en) * | 2018-07-23 | 2018-12-11 | 合肥科晶材料技术有限公司 | A kind of technique preparing sodium stannum alloy cathode material and battery |
-
2005
- 2005-07-08 CN CNA2005100835350A patent/CN1702888A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108987738A (en) * | 2018-07-23 | 2018-12-11 | 合肥科晶材料技术有限公司 | A kind of technique preparing sodium stannum alloy cathode material and battery |
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