CN101212047A - Hydrogen storage alloy and its preparation method - Google Patents
Hydrogen storage alloy and its preparation method Download PDFInfo
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- CN101212047A CN101212047A CNA2006101673841A CN200610167384A CN101212047A CN 101212047 A CN101212047 A CN 101212047A CN A2006101673841 A CNA2006101673841 A CN A2006101673841A CN 200610167384 A CN200610167384 A CN 200610167384A CN 101212047 A CN101212047 A CN 101212047A
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- 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
Abstract
The invention relates to a hydrogen storage alloy; the alloy has the ingredients expressed in the general expression: AxByMaNb, wherein x = 1, 2 is less than or equal to y is less than or equal to 5, 0 < a + b is less than or equal to 0.5, a > 0, b > 0, and 1 is less than or equal to b/a is less than or equal to 3. The A is one or a plurality of rare-earth elements and magnesiums. The B is one or a plurality of vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, tin, aluminum, molybdenum, silicon and boron. The M is titanium and/or zirconium. The N is nickel. The AxBy is the hydrogen-absorption phase of the hydrogen storage alloy. The MaNb is non hydrogen-absorption phase of the alloy. The hydrogen-absorption phase and the non-hydrogen-absorption phase are distributed with intervals. The battery manufactured by using the hydrogen storage alloy powder according to the method in the invention has the advantages of good performance of circulation, high discharging capacity and long service life.
Description
Technical field
The invention relates to a kind of hydrogen-storage alloy gold and preparation method thereof.
Summary of the invention
In recent years, because the development of mobile electronic device and the revolution of traffic power source, the research and development of the high-energy battery energy have become the focus of countries in the world academia and Industrial Revolution.Ni-MH battery is because of energy height, good, pollution-free, the memory-less effect of fail safe, price suits and is subjected to extensive attention, be one of main supplying cell type of digital camera, for example common No. five (AA type) nickel-hydrogen secondary cells promptly are nickel-hydrogen secondary cells (Ni/MH) of using always.
The Ni/MH secondary rechargeable battery is in order to satisfy the demand of electronic product at present, and just the direction towards high power capacity and high cycle performance develops.But, when therefore being immersed in the highly basic electrolyte, usually facing serious chemical corrosion and electrochemical corrosion problem, thereby cause cycle performance to descend as the hydrogen-storage alloy of negative material because the electrolyte of Ni-MH battery is generally strong electrolyte.
The problem that battery capacity that causes in order to solve the negative pole alloy corrosion and cycle performance descend, prior art are generally by changing the component and the preparation technology of hydrogen-storage alloy, to improve the performance of hydrogen-storage alloy.For example disclose a kind of no cobalt electrode material that is used for Metal hydrogen-storing/nickel-based battery among the CN 1585165A, described material alloys composition is (Mm
xMg
(1-x)) (Ni
yAlmR
(1-y-m))
n, 0.4≤x in the formula＜1; 0.5≤y≤1; 0＜m≤0.2; 3.3≤n≤3.7, Mm is at least a rare earth element or their mixing; R is a kind of or their mixing in Mn, Ti, Zr, Cr, V, Si, the Sn element.
But prior art is generally avoided dephasign by making hydrogen-storage alloy only have the metal principal phase as far as possible, improves battery performance.Use the initial stage at battery, only have battery, discharge capacity and the good cycle of the hydrogen-storage alloy of metal principal phase.But along with increasing of cycle-index, discharge capacity of the cell descends very fast, and cycle performance is variation also.Therefore, battery is still very short useful life.
Summary of the invention
To the objective of the invention is that the discharge capacity of the cell that contains existing hydrogen-storage alloy is low, the shortcoming of cycle performance difference in order overcoming, a kind of hydrogen-storage alloy powder to be provided, comprise nickel-hydrogen secondary cell discharge capacity height, good cycle that this alloy divides, long service life.
Prior art is generally avoided dephasign by making hydrogen-storage alloy only have the metal principal phase as far as possible, improves battery performance, points out to obtain purer Ce such as the specification of CN 1585165A
2Ni
7The single phase of type avoids generating AB
3Type and AB
5The dephasign of type.The present inventor is surprised to find that the main cause that causes the cycle performance of battery difference is that the corrosive nature of alkali resistance electrolyte solution is poor because the alloy principal phase is suction hydrogen principal phase; If but in raw metal except that the metal that adds the principal phase proportioning, add in addition as in zirconium, titanium and the transition metal one or more, the dephasign of the non-suction hydrogen that can outside the alloy principal phase, form, this dephasign does not influence the suction hydrogen effect of alloy principal phase, and the corrosive nature of alkali resistance electrolyte solution is good simultaneously.
The invention provides a kind of hydrogen-storage alloy, wherein, this alloy has general formula A
xB
yM
aN
bShown composition, x=1 in the formula, 2≤y≤5,0＜a+b≤0.5, a＞0, b＞0, and 1≤b/a≤3, A is one or more in rare earth element, magnesium and the calcium, B is selected from one or more in vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, tin, aluminium, molybdenum, silicon and the boron, M is titanium and/or zirconium, and N is a nickel; A
xB
yBe absorption hydrogen principal phase, M
aN
bBe the non-suction hydrogen of alloy phase, inhale hydrogen and distribute separately with non-suction hydrogen.
The present invention also provides above-mentioned hydrogen storage preparation method, and this method comprises smelting metal raw material and cool metal melt, and wherein, this method comprises smelting metal raw material and cool metal melt, it is characterized in that the composition general molecular formula A of described raw metal
xB
yM
aN
bShown composition, x=1 in the formula, 2≤y≤5,0＜a+b≤0.5, a＞0, b＞0, and 1≤b/a≤3, A is one or more in rare earth element, magnesium, the calcium, B is selected from one or more in vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, tin, aluminium, molybdenum, silicon and the boron, M is titanium and/or zirconium, and N is a nickel.
The present invention since in raw metal except that the metal that adds the principal phase proportioning, add in addition as in zirconium, titanium and the transition metal one or more, make and produce non-suction hydrogen phase in the alloy and suction hydrogen principal phase and non-suction hydrogen are distributed (as shown in Figure 1) separately because the performance of non-suction hydrogen potential resistance to electrolyte contamination solution mutually is good, thereby keep battery to have excellent cycle performance, prolong the useful life of battery.For example, 500 circulation back capacity sustainment rates that adopt the battery that hydrogen-storage alloy of the present invention makes are more than 80%, and the battery that prior art makes only is about 70%.
Description of drawings
Fig. 1 is the metallograph of embodiment 1 hydrogen-storage alloy;
Fig. 2 is the metallograph of Comparative Examples 1 hydrogen-storage alloy.
Embodiment
Hydrogen-storage alloy provided by the invention has general formula A
xB
yM
aN
bShown composition, x=1 in the formula, 2≤y≤5,0＜a+b≤0.5, a＞0, b＞0, and 1≤b/a≤3, A is one or more in rare earth element and the magnesium, B is selected from one or more in vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, tin, aluminium, molybdenum, silicon and the boron, M is titanium and/or zirconium, and N is a nickel; A
xB
yBe absorption hydrogen principal phase, M
aN
bBe the non-suction hydrogen of alloy phase, inhale hydrogen principal phase and non-suction hydrogen and distribute separately.
Hydrogen-storage alloy of the present invention is except that having the absorption hydrogen principal phase, also have the non-suction hydrogen of alloy phase, as shown in Figure 1, black is the non-suction hydrogen phase of hydrogen-storage alloy of the present invention mutually among the figure, and white is the alloy principal phase of hydrogen-storage alloy of the present invention mutually, and described suction hydrogen principal phase and non-suction hydrogen distribute separately.Like this, non-suction hydrogen can be protected mutually and inhale the corrosion that hydrogen was not subjected to or was subjected to less alkaline electrolyte solution mutually, inhales hydrogen and can finish to invertibity the hydrogen sucting discharging hydrogen process mutually, thereby improve the cycle performance of the battery that comprises this hydrogen-storage alloy.Preferred 3.0≤y≤5.0,0.05≤a+b≤0.3,1.5≤b/a≤2.5.
Suction hydrogen principal phase of the present invention must not be a kind of single metal principal phase, but can have in the existing various metal principal phase one or more, preferably has PuNi
3Type crystal structure thing phase, Ce
2Ni
7Type crystal structure thing phase, Sm
5Co
19Type crystal structure thing phase, Ce
5Co
19Type crystal structure thing phase and CaCu
5Type crystal structure thing one or more in mutually.
The present invention also provides above-mentioned hydrogen storage preparation method, and this method comprises smelting metal raw material and cool metal melt, wherein, and the composition general molecular formula A of described raw metal
xB
yM
aN
bShown composition, x=1 in the formula, 2≤y≤5,0＜a+b≤0.5, a＞0, b＞0, and 1≤b/a≤3, A is one or more in rare earth element, magnesium, the calcium, B is selected from one or more in vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, tin, aluminium, molybdenum, silicon and the boron, M is titanium and/or zirconium, and N is a nickel.Preferred 3.0≤y≤5.0,0.05≤a+b≤0.3,1.5≤b/a≤2.5.
The improvements of hydrogen storage preparation method of the present invention are the raw metal composition, and other steps are known in this field.
For example described cooling can be undertaken by this area mode such as ingot casting, gas atomization or melt quenching commonly used.The present invention does not limit the speed of cooling is special, and under the preferable case, the speed of described cooling is 10
3-10
4℃/second.
Preparation method of the present invention also comprises cooled metal bath is heated in inert gas atmosphere.The temperature of described heating is 500-1000 ℃, the time 0.5-48 of heating hour.The temperature of preferred described heating is at 600-900 ℃, and the time of heating is 0.5-24 hour.The temperature of described melting is 1100-2500 ℃, and smelting time is 5-30 minute.
Described melting can use high-frequency electromagnetic oven commonly used to carry out in vacuum or inert gas atmosphere.Described inert gas atmosphere is selected from one or more in nitrogen, helium, neon, argon gas, xenon and the radon gas.For being fit to the requirement of cell preparation, can also carry out fragmentation to the hydrogen-storage alloy that obtains, described fragmentation can be adopted this area Mechanical Crushing or hydrogen crushing furnace fragmentation commonly used.The hydrogen crushing furnace principle is to utilize RE permanent magnetic alloy inhaling hydrogen and putting alloy itself is produced in the hydrogen process intercrystalline cracking and characteristic that transcrystalline circle ruptures causes alloy pulverization, thereby obtains the alloy powder of certain particle size.Hydrogen-storage alloy particle diameter 10-100 micron after the fragmentation.
Below by embodiment method provided by the invention is described further.
Embodiment 1
Present embodiment illustrates hydrogen-storage alloy powder provided by the invention and preparation method thereof.
Purity is mixed at 2 weight portion La more than 99%, 1 weight portion Mg, 9.4 weight portion Ni and 0.2 weight portion Zr, the gained raw metal is placed alumina crucible, then crucible is placed Efco-Northrup furnace (Shenyang NORTEL stove), be evacuated to 1.0 * 10 in the stove
-4Handkerchief, applying argon gas to 0.2 MPa then.Described metal is heated to 1500 ℃ of fusings through high frequency induction current, and melting is after 10 minutes, gained metal solution is poured in the water cooled copper mould cools off, and the speed of cooling is 1000 ℃/second.
Alloy pig is placed stainless cylinder of steel, be evacuated to 1.0 * 10
-3Handkerchief, applying argon gas to 0.2 MPa is warming up to 850 ℃, is incubated 12 hours, is cooled to room temperature then and promptly obtains hydrogen-storage alloy of the present invention.
The section of preparation hydrogen-storage alloy of the present invention, polish section with sand paper, be polished to the minute surface no marking, adopt 4 weight % nitric acid alcohol (ethanol solution of nitric acid) to corrode, corrode after 10 minutes, after cleaning with absolute ethyl alcohol, dry up ethanol, under 800 times, the corrosion section is carried out metallographic observation with BX51M model light microscope (Olympus, Japan).Shown in the metallograph of Fig. 1 hydrogen-storage alloy of the present invention, distribute separately in the alloy principal phase of white hydrogen storage alloy phase and the non-suction hydrogen of black phase alloy.The polishing section of the metal of present embodiment hydrogen-storage alloy is placed under the JSM-6390LV electron microscope, respectively the alloy principal phase of hydrogen-storage alloy is carried out (EDS) component analysis of X ray energy dispersion spectrum as can be known mutually with non-suction hydrogen, the hydrogen-storage alloy principal phase of present embodiment is a PuNi3 type structure, and the general formula of the hydrogen-storage alloy of present embodiment is La
2/3Mg
1/3Ni
3Zr
0.2/3Ni
0.4/3
Comparative Examples 1
Hydrogen-storage alloy that this Comparative Examples explanation prior art provides and preparation method thereof.
Embodiment 1 disclosed method of CN 1585165A prepares hydrogen-storage alloy.The method that the hydrogen-storage alloy for preparing is made metallograph according to the embodiment of the invention 1, obtain metallograph as shown in Figure 2, as seen from Figure 2, this hydrogen-storage alloy, adularescent is inhaled the hydrogen phase, do not have the non-suction hydrogen of black phase, carry out the EDS component analysis as can be known according to the embodiment of the invention 1 described method, the hydrogen-storage alloy principal phase of Comparative Examples is a PuNi3 type structure.
Embodiment 2-6
Present embodiment illustrates the preparation method of hydrogen-storage alloy powder provided by the invention.
Prepare hydrogen-storage alloy according to embodiment 1 described method, difference is, the proportioning of raw metal, smelting temperature, cooling rate, heating time, heating-up temperature, concrete difference sees Table 1, and the master metal facies type that records each embodiment according to the method for embodiment 1 sees Table 2.
Table 1
| | Embodiment | 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Raw metal and weight portion thereof | La 2Mg 0.5Ca 0.5 Ni 9.4Zr 0.2 | Nd 9Mg 3 Ni 50.6Co 5 Zr 0.4 | Sm 6Pr 2Mg 2Ni 8.7 Co 2Zr 0.3 | Ce 6La 2Mg 2 Ni 8.7Co 2Zr 0.3 | La 0.7Ce 3Ni 7.3 Cu 1Al 1Co 6 Zr 0.7 | |
| Smelting temperature (℃) | 1100 | 1200 | 1200 | 1200 | 1500 | |
| Smelting time (minute) | 5 | 10 | 10 | 15 | 20 | |
| Cooling rate (℃/minute) | 10000 | 8000 | 5000 | 2000 | 1000 | |
| Heating time (hour) | 1 | 5 | 10 | 0.5 | 15 | |
| Heating-up temperature (℃) | 800 | 900 | 600 | 900 | 700 | |
| The master metal facies type | PuNi 3Type | Ce 2Ni 7Type | Sm 5Co 19Type | Ce 5Co 19Type | CaCu 5Type |
Table 2
| Embodiment | The hydrogen-storage alloy |
| Embodiment | |
| 2 | La 2/3Mg 1/6Ca 1/6Ni 3Zr 0.2/3Ni 0.4/3 |
| Embodiment 3 | Nd 3/4Mg 1/4Ni 2/3.5Co 1.5/3.5Zr 0.1/3Ni 0.2/3 |
| Embodiment 4 | Sm 3/5Pr 1/5Mg 1/5Ni 3/3.8Co 0.8/3.8Zr 0.1/3Ni 0.2/3 |
| Embodiment 5 | Ce 3/5La 1/5Mg 1/5Ni 3/3.8Co 0.8/3.8Zr 0.1/3Ni 0.2/3 |
| Embodiment 6 | La 2/3Ce 1/3Ni 3/5Cu 1/10Al 1/10Co 3/5Zr 0.2/3Ni 0.4/3 |
Battery performance test:
(1) Zheng Ji preparation
With the nickel hydroxide of 100 weight portions, the CoO of 5 parts of weight (cobalt protoxide), the carboxymethyl cellulose binder of 0.2 part of weight reaches 30 parts of weight deionized waters and fully stirs, and is mixed into pasty slurry.Get regular-type foam nickel, be made into 91 millimeters * 42 millimeters * 1.4 millimeters nickel foam substrate after pressure, the cut-parts, nickel strap 20 millimeters * 1.5 millimeters * 0.2 millimeter of the centre position of nickel foam substrate spot welding, nickel strap exposes 10 millimeters of nickel screens, fill the above-mentioned slurry that obtains, oven dry, roll-in make and are of a size of 91 millimeters * 42 millimeters * 1.4 millimeters positive pole then.Wherein, the content of positive electrode active materials is about 8 grams.
(2) preparation of negative pole
Get a kind of hydrogen-storage alloy among the 100 weight portion embodiment 1-6 or the hydrogen-storage alloy powder of Comparative Examples 1, carboxymethyl cellulose binder and 20 parts of weight deionized waters of 0.5 weight portion fully stir, and are mixed into pasty slurry.This slurry is coated on the Punching steel strip equably, oven dry, roll-in then, cuts to make and be of a size of 172 millimeters * 42.5 millimeters * 0.5 millimeter negative pole, wherein, the amount of negative active core-shell material is about 9 grams.
(3) assembling of battery
The negative pole that positive pole, dividing plate (grafted polypropylene diaphragm), (2) that (1) is obtained obtain stacks gradually the electrode group that is wound into scroll, the electrode that obtains is assembled in the AA shaped steel shell, (electrolyte is KOH and LiOH mixed aqueous solution to add electrolyte 1.1g/Ah, the LiOH that contains 30 weight %KOH and 15 grams per liters in the mixed aqueous solution), make nickel-hydrogen secondary cell after the sealing.
(4) negative pole weight ratio capacity
The battery that will be made by embodiment 1-6 and Comparative Examples 1 hydrogen-storage alloy was with the electric current constant current charge of 0.3C (630 milliamperes) 5 hours, shelve half an hour, be 1.0V extremely with 0.3C electric current constant-current discharge again by voltage, the discharge capacity first of record battery, the anodal weight ratio capacity of counting cell then.The result is as shown in table 2.
Wherein, the quality of discharge capacity/negative active core-shell material of negative pole weight ratio capacity=first.
(5) cycle performance test
Under 20 ℃, the battery B1 that will be made by embodiment 1-6 and Comparative Examples 1 hydrogen-storage alloy ends to-Δ V=10mV with the current charges of 1C, current discharge to cell voltage with 1C is 1.0V again, carry out charge and discharge cycles, repeat above step 500 time, obtain the capacity of 500 circulation backs of battery 1C current discharge, then capacity sustainment rate before and after the computation cycles to 1.0V.The result is as shown in table 3.
Capacity sustainment rate=(the 500th circulation back discharge capacity/cyclic discharge capacity) first * 100%
Table 3
| Hydrogen-storage alloy | Negative pole weight ratio capacity (MAH/gram) | Capacity sustainment rate (%) |
| Embodiment 1 | 380 | 80 |
| Comparative Examples 1 | 385 | 70 |
| |
390 | 81 |
| Embodiment 3 | 395 | 86 |
| Embodiment 4 | 391 | 84 |
| Embodiment 5 | 395 | 86 |
| Embodiment 6 | 300 | 82 |
As can be seen from Table 3, more than 80%, and only be 70% by 500 circulation back capacity sustainment rates of the obtained battery of hydrogen-storage alloy of embodiment of the invention 1-6 by 500 circulation backs of the obtained battery of the hydrogen-storage alloy of Comparative Examples 1 capacity sustainment rate.Therefore, the hydrogen-storage alloy powder that adopts the present invention to make can increase substantially the cycle performance of battery as the negative material of nickel-hydrogen secondary cell.
The obtained battery of hydrogen-storage alloy that all will be higher than in addition, Comparative Examples 1 by the anodal weight ratio capacity of the obtained battery of hydrogen-storage alloy of embodiment of the invention 1-6.
Claims (10)
1. a hydrogen-storage alloy is characterized in that, this alloy has general formula A
xB
yM
aN
bShown composition, x=1 in the formula, 2≤y≤5,0＜a+b≤0.5, a＞0, b＞0, and 1≤b/a≤3, A is one or more in rare earth element, magnesium and the calcium, B is selected from one or more in vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, tin, aluminium, molybdenum, silicon and the boron, M is titanium and/or zirconium, and N is a nickel; A
xB
yBe absorption hydrogen principal phase, M
aN
bBe the non-suction hydrogen of alloy phase, inhale hydrogen and distribute separately with non-suction hydrogen.
2. hydrogen-storage alloy according to claim 1, wherein, 3.0≤y≤5.0,0.05≤a+b≤0.3,1.5≤b/a≤2.5.
3. hydrogen-storage alloy according to claim 1, wherein, described suction hydrogen principal phase has PuNi
3Type crystal structure thing phase, Ce
2Ni
7Type crystal structure thing phase, Sm
5Co
19Type crystal structure thing phase, Ce
5Co
19Type crystal structure thing phase and CaCu
5Type crystal structure thing one or more in mutually.
4. hydrogen storage preparation method, this method comprises smelting metal raw material and cool metal melt, it is characterized in that the composition general molecular formula A of described raw metal
xB
yM
aN
bShown composition, x=1 in the formula, 2≤y≤5,0＜a+b≤0.5, a＞0, b＞0, and 1≤b/a≤3, A is one or more in rare earth element, magnesium, the calcium, B is selected from one or more in vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, tin, aluminium, molybdenum, silicon and the boron, M is titanium and/or zirconium, and N is a nickel.
5. method according to claim 4, wherein, 3.0≤y≤5.0,0.05≤a+b≤0.3,1.5≤b/a≤2.5.
6. method according to claim 4, wherein, the speed of described cooling is 10
3-10
4℃/second.
7. method according to claim 1, wherein, described method also comprises cooled metal bath is heated in inert gas atmosphere.
8. method according to claim 7, wherein, the temperature of described heating is 500-1000 ℃, the time 0.5-48 of heating hour.
9. method according to claim 8, wherein, the temperature of described heating is at 600-900 ℃, the time of heating is 0.5-24 hour.
10. method according to claim 4, wherein, the temperature of described melting is 1100-2500 ℃, smelting time is 5-30 minute.
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| CN101212047B CN101212047B (en) | 2010-06-23 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103107314A (en) * | 2011-11-11 | 2013-05-15 | 北京有色金属研究总院 | Hydrogen storage alloy for cathode of long-service life low-self-discharge power battery and preparation process of hydrogen storage alloy |
| CN103540960A (en) * | 2013-09-30 | 2014-01-29 | 赣南师范学院 | Preparation method of rare-earth magnesium nickel based hydrogen storage alloy |
| CN107739936A (en) * | 2017-10-10 | 2018-02-27 | 安徽工业大学 | A kind of high entropy reversible hydrogen storage alloy of Mg bases and preparation method thereof |
| CN109524628A (en) * | 2017-09-18 | 2019-03-26 | 上海杉杉科技有限公司 | The method and lithium ion battery that technique preparation aoxidizes sub- silicium cathode material are broken using hydrogen |
| CN110129621A (en) * | 2019-06-12 | 2019-08-16 | 内蒙古科技大学 | Easily-activated hydrogen-storage alloy of high capacity and the preparation method and application thereof |
| CN112310391A (en) * | 2020-10-30 | 2021-02-02 | 桑顿新能源科技有限公司 | Positive electrode material precursor, positive electrode material and preparation method thereof, lithium ion battery positive electrode, lithium ion battery and electric equipment |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3397981B2 (en) * | 1996-06-11 | 2003-04-21 | 三洋電機株式会社 | Hydrogen storage alloy and manufacturing method |
| CN1330025C (en) * | 1999-12-27 | 2007-08-01 | 株式会社东芝 | Hydrogen-storage alloy, secondary battery, hybrid automobile and electric automobile |
| CN1173057C (en) * | 2001-12-26 | 2004-10-27 | 浙江大学 | Hydrogen-bearing mixed rare-earth alloy as electrodes of secondary nickel-metal oxide battery |
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2006
- 2006-12-31 CN CN2006101673841A patent/CN101212047B/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103107314A (en) * | 2011-11-11 | 2013-05-15 | 北京有色金属研究总院 | Hydrogen storage alloy for cathode of long-service life low-self-discharge power battery and preparation process of hydrogen storage alloy |
| CN103540960A (en) * | 2013-09-30 | 2014-01-29 | 赣南师范学院 | Preparation method of rare-earth magnesium nickel based hydrogen storage alloy |
| CN109524628A (en) * | 2017-09-18 | 2019-03-26 | 上海杉杉科技有限公司 | The method and lithium ion battery that technique preparation aoxidizes sub- silicium cathode material are broken using hydrogen |
| CN109524628B (en) * | 2017-09-18 | 2021-06-04 | 上海杉杉科技有限公司 | Method for preparing silicon monoxide negative electrode material by adopting hydrogen cracking process and lithium ion battery |
| CN107739936A (en) * | 2017-10-10 | 2018-02-27 | 安徽工业大学 | A kind of high entropy reversible hydrogen storage alloy of Mg bases and preparation method thereof |
| CN110129621A (en) * | 2019-06-12 | 2019-08-16 | 内蒙古科技大学 | Easily-activated hydrogen-storage alloy of high capacity and the preparation method and application thereof |
| CN112310391A (en) * | 2020-10-30 | 2021-02-02 | 桑顿新能源科技有限公司 | Positive electrode material precursor, positive electrode material and preparation method thereof, lithium ion battery positive electrode, lithium ion battery and electric equipment |
| CN112310391B (en) * | 2020-10-30 | 2021-09-17 | 桑顿新能源科技有限公司 | Positive electrode material precursor, positive electrode material and preparation method thereof, lithium ion battery positive electrode, lithium ion battery and electric equipment |
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|---|---|
| CN101212047B (en) | 2010-06-23 |
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