CN1604362A - Method for preparing titanium-vanadium based solid solution hydride alloy electrode - Google Patents

Method for preparing titanium-vanadium based solid solution hydride alloy electrode Download PDF

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CN1604362A
CN1604362A CNA2004100112022A CN200410011202A CN1604362A CN 1604362 A CN1604362 A CN 1604362A CN A2004100112022 A CNA2004100112022 A CN A2004100112022A CN 200410011202 A CN200410011202 A CN 200410011202A CN 1604362 A CN1604362 A CN 1604362A
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alloy
alloy electrode
discharge capacity
solid solution
discharge
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CN1288773C (en
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赵敏寿
柴玉俊
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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    • 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
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    • Y02E60/10—Energy storage using batteries

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Abstract

This invention relates to a titanium to vanadium sosoloid hydrid alloy electrode process method , which comprises the following chemistry components: Ti#-[0.25-x]Zr#-[x]V#-[0.35]Cr#-[0.10]Ni#-[0.3],Ti#-[0.17]Zr#-[0.08]V#-[0.35]Cr#-[0.10]Ni#-[0.3]A#-[y Ti#-[0.17]Zr#-[0.08]V#-[0.35]Cr#-[0.10]Ni#-[0.3-y]A#-[y]. This invention has high discharging capacitance in home temperature or high temperature.

Description

The preparation method of titanium-vanadium base solid solution hydride alloy electrode
Technical field
The invention belongs to the preparation method of titanium-vanadium base solid solution hydride alloy electrode.
Background technology
Ni-MH battery is compared with the Ni-Cd battery has 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 nickel-hydrogen cell 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.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 discloses 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, under the condition of three-electrode system, cut-ff voltage is 0.5V, and 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 low, therefore further improves this type of alloy at room temperature discharge capacity and is restricted.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of titanium-vanadium base solid solution hydride alloy electrode.
In order to obtain the alloy electrode of room temperature and high-temperature behavior 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, adjusts the component of alloy, has obtained the electrode material of chemical property excellence, and it consists of, Ti 0.25-xZr xV 0.35Cr 0.10Ni 03, Ti 0.17Zr 0.08V 0.35Cr 0.10Ni 0.3A yOr Ti 0.17Zr 0.08V 0.35Cr 0.10Ni 0.3-yA y, 0.05≤x≤0.15,0≤y≤0.15 wherein.
The preparation process of titanium of the present invention-vanadium base solid solution hydride alloy electrode is as follows:
Press chemical constitution formula Ti 0.25-xZr xV 0.35Cr 0.10Ni 0.3, Ti 0.17Zr 0.08V 0.35Cr 0.10Ni 0.3A yOr Ti 0.17Zr 0.08V 0.35Cr 0.10Ni 0.3yA yProportioning alloy, wherein 0.05≤x≤0.15,0≤y≤0.15; A selects Co for use, Al, Mn, Fe or B, melting in non-consumable arc furnace.Be evacuated to 0.1-1x10 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.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.With sintering Ni (OH) 2Be positive pole, 6molKOH is an electrolyte, is assembled into the sandwich style simulated battery, and 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 present invention makes full use of easy generation of multicomponent solid solution alloy and has second phase of catalytic action, have high theoretical discharge capacity and characteristics such as easily-activated, alloy compositions is optimized, develop the high and easily-activated alloy electrode of room temperature discharge capacity, this type of alloy electrode still can keep very high power capacity when 700 high temperature simultaneously, becomes the negative material that is suitable at the nickel-hydrogen cell of room temperature and high temperature application.
Description of drawings
Accompanying drawing 1 is Ti 0.25-xZr xV 0.35Cr 0.10Ni 0.3The discharge capacity of alloy electrode and the relation curve between the cycle-index, x=0.05 wherein, 0.08,0.15.
Accompanying drawing 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.Cooling back Mechanical Crushing, grinding alloy are got the following alloyed powder 0.15g of 300 orders, add 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 0.25-xZr xV 0.35Cr 0.10Ni 0.3Chemical formula proportioning metal, x=0.08 wherein, all the other are identical with embodiment 1, and 30 ℃ are measured its discharge capacities 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, and 30 ℃ are measured its discharge capacities down is 340mAh/g, and 70 ℃ discharge capacity is 270mAh/g.
Embodiment 4:
Press Ti 0.17Zr 0.08V 0.35Cr 0.10Ni 0.3A yChemical formula proportioning metal, wherein A=Mn, y=0.08, all the other are identical with embodiment 1, and 30 ℃ are measured its discharge capacities down is 340mAh/g, and 70 ℃ discharge capacity is 200mAh/g.
Embodiment 5:
Press Ti 0.17Zr 0.08V 0.35Cr 0.0Ni 0.3A yFormula proportioning metal, wherein A=Co, y=0.05, all the other are identical with embodiment 1, and 30 ℃ are measured its discharge capacities down is 340mAh/g, and 70 ℃ discharge capacity is 180mAh/g.
Embodiment 6:
Press Ti 0.17Zr 0.08V 0.35Cr 0.10Ni 0.3A yChemical formula proportioning metal, wherein A=Al, y=0.15, all the other are identical with embodiment 1, and 30 ℃ are measured its discharge capacities down is 111mAh/g, and 70 ℃ discharge capacity is 155mAh/g.
Embodiment 7:
Press Ti 0.17Zr 0.08V 0.35Cr 0.10Ni 0.3A yChemical formula proportioning metal, wherein A=B, y=0.05, all the other are identical with embodiment 1, and 30 ℃ are measured its discharge capacities down is 290mAh/g, and 70 ℃ discharge capacity is 230mAh/g.
Embodiment 8:
Press Ti 0.17Zr 0.08V 0.35Cr 0.10Ni 0.3A yChemical formula proportioning metal, wherein A=Fe, y=0.08, all the other are identical with embodiment 1, and 30 ℃ are measured its discharge capacities down is 320mAh/g, and 70 ℃ discharge capacity is 215mAh/g.
Embodiment 9:
Press Ti 0.17Zr 0.08V 0.35Cr 0.10Ni 0.30-yA yChemical formula proportioning metal, wherein A=Co, y=0.05, all the other are identical with embodiment 1, and 30 ℃ are measured its discharge capacities 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, wherein A=Mn, y=0.08, all the other are identical with embodiment 1, and 30 ℃ are measured its discharge capacities 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, wherein A=Al, y=0.15, all the other are identical with embodiment 1, and 30 ℃ are measured its discharge capacities down is 170mAh/g, and 70 ℃ discharge capacity is 250mAh/g.
Embodiment 12:
Press Ti 0.17Zr 0.08V 0.35Cr 0.0Ni 0.30-yA yChemical formula proportioning metal, wherein A=Fe, y=0.05, all the other are identical with embodiment 1, and 30 ℃ are measured its discharge capacities 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, wherein A=B, y=0.08, all the other are identical with embodiment 1, and 30 ℃ are measured its discharge capacities down is 300mAh/g, and 70 ℃ discharge capacity is 220mAh/g.

Claims (1)

1. the preparation method of titanium-vanadium base solid solution hydride alloy electrode is characterized in that, presses chemical constitution formula Ti 0.25-xZr xV 0.35Cr 0.10Ni 0.3, Ti 0.17Zr 0.08V 0.35Cr 0.10Ni 0.3A yOr Ti 0.17Zr 0.08V 0.35Cr 0.10Ni 0.3-yA yThe proportioning alloy, 0.05≤x≤0.1 5 wherein, 0≤y≤0.15; A selects Co for use, Al, and Mn, Fe or B, melting in non-consumable arc furnace is evacuated to 0.1-1 * 10 earlier before the melting -2Pa, feed argon gas through processed then to 0.2-0.5MPa, melt back alloy 3 times, alloy cooling back mechanical crushing, grinding, get the following alloyed powder of granularity 300 orders, mix with carbonyl nickel powder in 1: 5 ratio, under the pressure of 10MPa～20MPa, be cold-pressed into the disk electrode sheet of Φ=10mm, with sintering Ni (OH) 2Be positive pole, 6mol KOH is an electrolyte, is assembled into the sandwich style simulated battery, during test, and with the current charges of 120mA/g, the current discharge of 60mA/g, cut-ff voltage is 0.8V, controls probe temperature with water bath with thermostatic control, 1 ℃ of temperature-controlled precision.
CNB2004100112022A 2004-11-05 2004-11-05 Method for preparing titanium-vanadium based solid solution hydride alloy electrode Expired - Fee Related CN1288773C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103236529A (en) * 2013-04-23 2013-08-07 江苏科技大学 Cobalt-free hydrogen storing alloy electrode material and preparation method thereof
CN103456927A (en) * 2013-08-30 2013-12-18 攀枝花学院 Oxygen-containing vanadium titanium based hydrogen storage electrode alloy and preparation method thereof
CN105039765A (en) * 2015-07-31 2015-11-11 四川大学 Method for preparing V-Ti-Cr-Fe hydrogen storage alloy
CN108574091A (en) * 2018-04-12 2018-09-25 合肥国轩高科动力能源有限公司 A kind of new type lithium ion battery vanadium base hydride negative material and preparation method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103236529A (en) * 2013-04-23 2013-08-07 江苏科技大学 Cobalt-free hydrogen storing alloy electrode material and preparation method thereof
CN103236529B (en) * 2013-04-23 2016-07-06 江苏科技大学 A kind of non-cobalt hydrogen storage alloy electrode material and preparation method thereof
CN103456927A (en) * 2013-08-30 2013-12-18 攀枝花学院 Oxygen-containing vanadium titanium based hydrogen storage electrode alloy and preparation method thereof
CN103456927B (en) * 2013-08-30 2016-08-10 攀枝花学院 Containing vanadyl titanio hydrogen-storing alloy as electrode and preparation method thereof
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
CN108574091A (en) * 2018-04-12 2018-09-25 合肥国轩高科动力能源有限公司 A kind of new type lithium ion battery vanadium base hydride negative material and preparation method thereof

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