CN1812169A - Titanyl and vanadium radical sosoloid alloy hydride electrode material and preperative method - Google Patents
Titanyl and vanadium radical sosoloid alloy hydride electrode material and preperative method Download PDFInfo
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- CN1812169A CN1812169A CNA2006100123280A CN200610012328A CN1812169A CN 1812169 A CN1812169 A CN 1812169A CN A2006100123280 A CNA2006100123280 A CN A2006100123280A CN 200610012328 A CN200610012328 A CN 200610012328A CN 1812169 A CN1812169 A CN 1812169A
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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
This invention is a kind of producing method of nickel-metal hydride cell cathode material used in wide-temperature region. The chemical components are Ti<SUB>0.25-x</SUB>Zr<SUB>x</SUB>V<SUB>0.35</SUB>Cr<SUB>0.10</SUB>Ni<SUB>0.3</SUB>, Ti<SUB>0.17</SUB>Zr<SUB>0.08</SUB>V<SUB>0.35</SUB>Cr<SUB>0.10</SUB>Ni<SUB>0.3</SUB>A<SUB>y</SUB> and Ti<SUB>0.17</SUB>Zr<SUB>0.08</SUB>V<SUB>0.35</SUB>Cr<SUB>0.10</SUB>Ni<SUB>0.3-y</SUB>A<SUB>y</SUB>, in which 0.05<=x<=0.15, 0<=y<=0.15; A is Co, Al, Mn, Fe or B. This hydrogen storing alloy electrode has steady electrochemistry ability in wide component range. It has high discharging capacity in both home temperature and high temperature. The highest discharging capacity are 380mAh/g and 275mAh/g in home temperature and 70DEG C respectively.
Description
Technical field
The invention belongs to the preparation method of titanium in the ni-MH battery-vanadium radical sosoloid alloy hydride electrode.
Background technology
Ni-MH battery compare with the Ni-Cd battery have high power capacity, have extended cycle life, memory-less effect, anti-over-charging-discharge capability by force and with characteristics such as Environmental compatibility is good, therefore, be called as green battery.With MmNi
5(Mm represents mishmetal) is the AB of representative
5Type negative pole and Ni (OH)
2/ NiOOH is the anodal ni-MH battery of forming, and except the power supply as mobile communication, laptop computer and video camera etc., has more tempting prospect as the power supply of electric automobile.At present, the more storage alloy material for hydrogen of research mainly comprises AB
5, AB
2, magnesium base and vanadium radical sosoloid alloy.Though AB
5The extensive use of type negative material, but its electrochemistry capacitance theoretical value is lower, is about 372mAh/g.Zr base AB
2The discharge capacity height of type alloy electrode, but have the problem that activates difficulty and multiplying power discharging property difference.The discharge capacity height of magnesium base alloy and V-based solid solution, but because V and the seriously corroded of magnesium in alkali lye cause the discharge capacity of alloy electrode to decay rapidly.
U.S. Pat 5135589, US6270719 and Chinese patent 01117766 have successively been reported heterogeneous AB
nWhen (n=2-6) alloy system was with low discharging current, its discharge capacity was considerably beyond AB
5The discharge capacity of alloy electrode, therefore, this type of alloy is expected to be applied in the Ni-MH secondary cell.
Chinese patent 02116369 provides a kind of AB
5Type high temperature hydrogen-occlussion alloy electrode.In current density is that the electric current of 40mA/g carries out charge and discharge cycles, cut-ff voltage is under the condition of 0.5V (three-electrode system), this alloy electrode ℃ has higher discharge capacity from room temperature to 70, the discharge capacity of its room temperature is 315mAh/g, and the high energy of 70 ℃ discharge capacity reaches about 265mAh/g.But in view of AB
5The theoretical discharge capacity of type alloy electrode is lower, and therefore further improving this type of alloy at room temperature discharge capacity will be restricted.
Summary of the invention
The purpose of this invention is to provide a kind of titanium-vanadium radical sosoloid alloy hydride electrode material and preparation method thereof.For the alloy electrode of obtained performance excellence, design, synthetic heterogeneous alloy are particularly important.Ti, Zr, V all can form stable hydride with hydrogen, and Cr, Ni, Co, Al, Mn, Fe or B play an important role to the reaction anticorrosive, that quicken alloy electrode that improves alloy electrode, the present invention is optimized processing to the component of alloy, obtained three kinds of good electrode materials of chemical property, it is characterized in that: their element is composed as follows: Ti
0.25-xZr
xV
0.35Cr
0.10Ni
03, Ti
0.17Zr
0.08V
0.35Cr
0.10Ni
0.3A
y, Ti
0.17Zr
0.08V
0.35Cr
0.10Ni
0.3-yA
y, 0.05≤x≤0.15,0≤y≤0.15 wherein, A selects Co for use, Al, Mn, Fe or B, 0.05≤x≤0.15,0≤y≤0.15.
The preparation method of titanium of the present invention-vanadium radical sosoloid alloy hydride electrode is:
A. after the raw material of component being pressed above-mentioned composition mixing, melting in non-consumable arc furnace;
B. be evacuated to 0.1-1 * 10 before the melting earlier
-2Pa feeds argon gas through processed then to 0.2-0.5MPa, and melt back alloy 3 times is even to guarantee alloy compositions;
C. the following alloyed powder of granularity 300 orders is got in alloy cooling back mechanical crushing, grinding, mixes with carbonyl nickel powder in 1: 5 ratio, is cold-pressed into the disk electrode sheet of Φ=10mm under the pressure of 10MPa～20MPa;
D. with sintering Ni (OH)
2/ NiOOH is anodal, and 6mol KOH solution is electrolyte, is assembled into the sandwich style simulated battery, and anodal capacity is greater than capacity of negative plates more than 5 times.During test, with the current charges of 120mA/g, the current discharge of 60mA/g, cut-ff voltage are 0.8V.Control probe temperature with water bath with thermostatic control, 1 ℃ of temperature-controlled precision.
The invention has the beneficial effects as follows: make full use of easy generation of multicomponent solid solution alloy and have second phase of catalytic action, have very high theoretical discharge capacity and characteristics such as easily-activated, alloy compositions is optimized, develop room temperature discharge capacity height, easily-activated alloy electrode, this type of alloy electrode still can keep very high power capacity when 70 ℃ of high temperature simultaneously, becomes the negative material that is suitable at the ni-MH battery of wide warm area application.
Description of drawings
Fig. 1 is Ti
0.25-xZr
xV
0.35Cr
0.10Ni
0.3The discharge capacity of alloy electrode and the relation between the cycle-index, x=0.05 wherein, 0.08,0.15;
Fig. 2 is Ti
0.17Zr
0.08V
0.35Cr
0.10Ni
0.3The discharge capacity of alloy electrode concerns with variation of temperature.
As can be seen from Figure 1, Ti
0.25-xZr
xV
0.35Cr
0.10Ni
0.3Alloy electrode is easy to activation, and wherein the discharge capacity during 0.05≤x≤0.15,30 ℃ changes between 300 to 340mAh/g.When x 0.08 when between 0.15, changing, the discharge capacity of alloy electrode does not have big variation.Fig. 2 shows, Ti
0.17Zr
0.08V
0.35Cr
0.10Ni
0.3The discharge capacity of matrix alloy electrode reduces slowly along with the increase of temperature, still has higher discharge capacity in the time of 70 ℃.Another characteristics of this series alloy are, alloy electrode charging back room temperature was placed after 14 days, and its charged conservation rate is more than 90%.
Embodiment
Embodiment 1:
Press Ti
0.25-xZr
xV
0.35Cr
0.10Ni
0.3Chemical formula proportioning metal, x=0.05 wherein, melting in the non-consumable vacuum melting furnace.Be evacuated to 0.1 * 10 earlier before the melting
-2Pa feeds argon gas through processed then to 0.2MPa, and melt back alloy 3 times is even to guarantee alloy compositions.The following alloyed powder 0.15g of 300 orders is got in alloy cooling back Mechanical Crushing, grinding, adds 0.75g carbonyl Ni powder, under the pressure of 14MPa, be cold-pressed into the disk electrode sheet of Φ=10mm, in the KOH of 6M solution, with the 120mA/g current charges, the 60mA/g discharge, discharge cut-off voltage 0.8V.
30 ℃ are measured its discharge capacity down is 305mAh/g, and 70 ℃ discharge capacity is 250mAh/g.
Embodiment 2:
Press Ti
025-xZr
xV
0.35Cr
0.10Ni
0.3Chemical formula proportioning metal, x=0.08 wherein, all the other are identical with embodiment 1.30 ℃ are measured its discharge capacity down is 335mAh/g, and 70 ℃ discharge capacity is 275mAh/g.
Embodiment 3
Press Ti
0.25-xZr
xV
0.35Cr
0.10Ni
0.3Chemical formula proportioning metal, x=0.15 wherein, all the other are identical with embodiment 1.30 ℃ are measured its discharge capacity down is 340mAh/g, and 70 ℃ discharge capacity is 270mAh/g.
Embodiment 4:
Press Ti
0.17Zr
0.08V
0.35Cr
0.10Ni
0.3～chemical formula proportioning metal, wherein A=Mn, y=0.08, all the other are identical with embodiment 1.30 ℃ are measured its discharge capacity down is 340mAh/g, and 70 ℃ discharge capacity is 200mAh/g.
Embodiment 5:
Press Ti
0.17Zr
0.08V
0.35Cr
0.10Ni
0.3A
yFormula proportioning metal, wherein A=Co, y=0.05, all the other are identical with embodiment 1.30 ℃ are measured its discharge capacity down is 340mAh/g, and 70 ℃ discharge capacity is 180mAh/g.
Embodiment 6:
Press Ti
0.17Zr
0.08V
0.35Cr
0.10Ni
03A
yChemical formula proportioning metal, A=A1 wherein, y=0.15, all the other are identical with embodiment 1.30 ℃ are measured its discharge capacity down is 111mAh/g, and 70 ℃ discharge capacity is 155mAh/g.
Embodiment 7:
Press Ti
017Zr
0.08V
0.35Cr
0.10Ni
0.3A
yChemical formula proportioning metal, A=B wherein, y=0.05, all the other are identical with embodiment 1.30 ℃ are measured its discharge capacity down is 290mAh/g, and 70 ℃ discharge capacity is 230mAh/g.
Embodiment 8:
Press Ti
017Zr
0.08V
0.35Cr
0.10Ni
03A
yChemical formula proportioning metal, A=Fe wherein, y=0.08, all the other are identical with embodiment 1.30 ℃ are measured its discharge capacity down is 320mAh/g, and 70 ℃ discharge capacity is 215mAh/g.
Embodiment 9:
Press Ti
0.17Zr
0.08V
0.35Cr
0.10Ni
030-yA
yChemical formula proportioning metal, A=Co wherein, y=0.05, all the other are identical with embodiment 1.30 ℃ are measured its discharge capacity down is 330mAh/g, and 70 ℃ discharge capacity is 260mAh/g.
Embodiment 10:
Press Ti
0.17Zr
0.08V
0.35Cr
0.10Ni
0.30-yA
yChemical formula proportioning metal, A=Mn wherein, y=0.08, all the other are identical with embodiment 1.30 ℃ are measured its discharge capacity down is 380mAh/g, and 70 ℃ discharge capacity is 250mAh/g.
Embodiment 11:
Press Ti
0.17Zr
0.08V
0.35Cr
0.10Ni
0.30-yA
yChemical formula proportioning metal, A=A1 wherein, y=0.15, all the other are identical with embodiment 1.30 ℃ are measured its discharge capacity down is 270mAh/g, and 70 ℃ discharge capacity is 250mAh/g.
Embodiment 12:
Press Ti
0.17Zr
0.08V
0.35Cr
0.10Ni
0.30-yA
yChemical formula proportioning metal, A=Fe wherein, y=0.05, all the other are identical with embodiment 1.30 ℃ are measured its discharge capacity down is 355mAh/g, and 70 ℃ discharge capacity is 250mAh/g.
Embodiment 13:
Press Ti
0.17Zr
0.08V
0.35Cr
0.10Ni
0.30-yA
yChemical formula proportioning metal, A=B wherein, y=0.08, all the other are identical with embodiment 1.30 ℃ are measured its discharge capacity down is 300mAh/g, and 70 ℃ discharge capacity is 220mAh/g.
Claims (2)
1. titanium-vanadium radical sosoloid alloy hydride electrode material, it is characterized in that: this titanium-vanadium radical sosoloid alloy hydride electrode material is following three kinds of materials, and their element is composed as follows: Ti
0.25-xZr
xV
0.35Cr
0.10Ni
0.3, Ti
0.17Zr
0.08V
0.35Cr
0.10Ni
0.3A
yAnd Ti
0.17Zr
0.08V
0.35Cr
0.10Ni
0.3-yA
y, wherein, A selects Co for use, Al, Mn, Fe or B, 0.05≤x≤0.15,0≤y≤0.15.
2. method for preparing the titanium one vanadium radical sosoloid alloy hydride electrode material of claim 1, it is characterized in that: this method comprises the steps:
A. after the raw material of component being pressed above-mentioned composition mixing, melting in non-consumable arc furnace;
B. be evacuated to 0.1-1 * 10 before the melting earlier
-2Pa feeds argon gas through processed then to 0.2-0.5MPa, and melt back alloy 3 times is even to guarantee alloy compositions;
C. the following alloyed powder of granularity 300 orders is got in alloy cooling back mechanical crushing, grinding, mixes with carbonyl nickel powder in 1: 5 ratio, is cold-pressed into the disk electrode sheet of Ф=10mm under the pressure of 10MPa～20MPa;
D. with sintering Ni (OH)
2/ NiOOH is anodal, and 6mol KOH solution is electrolyte, is assembled into the sandwich style simulated battery, and anodal capacity is greater than capacity of negative plates more than 5 times; During test, with the current charges of 120mA/g, the current discharge of 60mA/g, cut-ff voltage are 0.8V.Control probe temperature with water bath with thermostatic control, 1 ℃ of temperature-controlled precision.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100123280A CN1812169A (en) | 2006-01-11 | 2006-01-11 | Titanyl and vanadium radical sosoloid alloy hydride electrode material and preperative method |
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|---|---|---|---|
| CNA2006100123280A CN1812169A (en) | 2006-01-11 | 2006-01-11 | Titanyl and vanadium radical sosoloid alloy hydride electrode material and preperative method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105039765A (en) * | 2015-07-31 | 2015-11-11 | 四川大学 | Method for preparing V-Ti-Cr-Fe hydrogen storage alloy |
| CN108913972A (en) * | 2018-07-04 | 2018-11-30 | 南通志乐新材料有限公司 | A kind of iron-based complex phase environmental protection hydrogen storage material |
| CN114725363A (en) * | 2022-04-13 | 2022-07-08 | 浙江水利水电学院 | V-based hydrogen storage alloy for nickel-metal hydride battery cathode and preparation method and application thereof |
-
2006
- 2006-01-11 CN CNA2006100123280A patent/CN1812169A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105039765A (en) * | 2015-07-31 | 2015-11-11 | 四川大学 | Method for preparing V-Ti-Cr-Fe hydrogen storage alloy |
| CN105039765B (en) * | 2015-07-31 | 2017-03-08 | 四川大学 | A kind of preparation method of V Ti Cr Fe hydrogen-storage alloy |
| CN108913972A (en) * | 2018-07-04 | 2018-11-30 | 南通志乐新材料有限公司 | A kind of iron-based complex phase environmental protection hydrogen storage material |
| CN108913972B (en) * | 2018-07-04 | 2019-10-01 | 南理工泰兴智能制造研究院有限公司 | A kind of vanadium base complex phase environmental protection hydrogen storage material |
| CN114725363A (en) * | 2022-04-13 | 2022-07-08 | 浙江水利水电学院 | V-based hydrogen storage alloy for nickel-metal hydride battery cathode and preparation method and application thereof |
| CN114725363B (en) * | 2022-04-13 | 2024-03-26 | 浙江水利水电学院 | V-base hydrogen storage alloy for nickel-hydrogen battery cathode and preparation method and application thereof |
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