CN1205680C - Heat treatment method for Ti base AB 2 type laves phase hydrogen storage electrode alloy - Google Patents
Heat treatment method for Ti base AB 2 type laves phase hydrogen storage electrode alloy Download PDFInfo
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- CN1205680C CN1205680C CNB011177675A CN01117767A CN1205680C CN 1205680 C CN1205680 C CN 1205680C CN B011177675 A CNB011177675 A CN B011177675A CN 01117767 A CN01117767 A CN 01117767A CN 1205680 C CN1205680 C CN 1205680C
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- alloy
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- storage electrode
- hydrogen
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 73
- 239000000956 alloy Substances 0.000 title claims abstract description 73
- 238000010438 heat treatment Methods 0.000 title claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 15
- 239000001257 hydrogen Substances 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 14
- 229910001068 laves phase Inorganic materials 0.000 title claims abstract description 12
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 239000000725 suspension Substances 0.000 claims abstract description 5
- 238000003723 Smelting Methods 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 12
- 239000011521 glass Substances 0.000 abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 230000005518 electrochemistry Effects 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 230000004087 circulation Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052987 metal hydride Inorganic materials 0.000 description 3
- 229910000967 As alloy Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910003307 Ni-Cd Inorganic materials 0.000 description 1
- 229910002640 NiOOH Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention discloses a hot treatment method for Ti-base AB 2 type laves-phase hydrogen storage electrode alloy, which comprises the steps: firstly, smelting Ti, Zr, V, Mn, Cr and Ni in a vacuum magnetic suspension smelting oven, and then sealing the cast hydrogen storage electrode alloy in a vacuum silicon glass tube to be annealed in an annealing oven and finally quenched. When the Ti-base hydrogen storage electrode alloy is treated in the heat treatment method of the present invention, the discharge capacity of an alloy electrode is greatly raised, but cyclical stability is hardly influenced and activate performance is also improved to improve the comprehensive electrochemical properties of the Ti-base hydrogen-storage electrode alloy.
Description
The present invention relates to secondary cell, especially relate to a kind of nickel-metal hydrides (Ni-MH) secondary battery cathode material Ti base AB
2The heat treatment method of type Laves phase hydrogen storage electrode metal.
In recent years, because nickel-metal hydrides (Ni-MH) secondary cell, with respect to the Ni-Cd secondary cell, have the capacity height, have extended cycle life, memory-less effect, anti-over-charging, cross advantage such as the strong and non-environmental-pollution of exoergic power and become the focus of lot of domestic and foreign scholar's research.
The anodal general nickel electrode that adopts of nickle-metal hydride secondary battery, negative material then is selected from hydrogen-storage alloy.Theoretically, the hydrogen-storage alloy that can be used as the Ni-MH secondary battery cathode material comprises rare earth based AB
5Type alloy, titanium base AB
2Type alloy, zirconium base AB
2Type alloy, magnesium base alloy and vanadium radical sosoloid alloy.Wherein, people are to rare earth based AB
5The research of type alloy is the most ripe, and it has good comprehensive electrochemical such as easily-activated, that the high current charge-discharge ability strong, have extended cycle life, and has realized industrialization.But, rare earth based AB
5The finite capacity of type hydrogen-storage alloy, and along with the research to this hydrogen-storage alloy reaches its maturity, its capacity also moves closer to its theoretical electrochemistry capacity, more and more is difficult to satisfy the demand of people to high energy density cells.
In the research of high capacity hydrogen storage alloy, zirconium base AB
2The type alloy owing to have the capacity height, having extended cycle life has caused people's attention, but the suitable difficulty of the initial stage of this alloy activation, and large current discharging capability is not ideal enough and be difficult to practicability.The initial electrochemical discharge capacity of magnesium base alloy and vanadium radical sosoloid alloy is quite high, but owing to their too fast capacity that causes of circulation decline in electrolyte descend rapidly, also do not have good solution at present, so can't realize practicability within the short-term yet.
Titanium base AB
2The type hydrogen-storage alloy has higher electrochemical discharge capacity.U.S. Pat 5922146 discloses titanium base AB
2The electrochemical discharge capacity of type hydrogen-occlussion alloy electrode can reach more than the 400mAh/g, has surmounted rare earth based AB greatly
5The discharge capacity of type hydrogen-occlussion alloy electrode.And titanium base AB
2The type hydrogen-occlussion alloy electrode has good cyclical stability, good high magnification characteristic and advantage such as activation capacity and low price and has demonstrated powerful application prospect in electrolyte.
But, from present achievement in research, titanium base AB
2The cyclical stability of type hydrogen-occlussion alloy electrode can't reach the requirement of industrialization, and for this reason, we add more Cr element in the B side.Discover that the cyclical stability of electrode has obtained tangible improvement, but but be accompanied by the decline of electrode discharge capacity.Usually, the discharge capacity of hydrogen-occlussion alloy electrode and cyclical stability are a pair of contradiction, tend to be accompanied by the decline of discharge capacity when cyclical stability improves, and the lifting of discharge capacity tend to the cost that drops to cyclical stability.
Purpose of the present invention just is to propose a kind of effective treating method, promptly improves the discharge capacity of electrode under the prerequisite that does not influence the electrode cyclical stability, for the comprehensive electrochemical of improving hydrogen-occlussion alloy electrode provides the basic AB with the Ti of reference frame
2The heat treatment method of type Laves phase hydrogen storage electrode metal.
In order to achieve the above object, the present invention takes following measures:
Ti base AB
2The heat treatment method of type Laves phase hydrogen storage electrode metal comprises the following steps:
1) Ti base AB
2A side element ti in the type Laves phase hydrogen storage electrode metal, Zr and B side element V, Mn, Cr, Ni place melting in the vacuum magnetic suspension smelting furnace;
2) melted as cast condition hydrogen-storing alloy as electrode is placed on is evacuated to 10 in the quartz glass tube
-5-10
-6Holder is sealed up the quartz glass mouth of pipe then;
3) the vitreosil glass tube that hydrogen-storing alloy as electrode will be housed in annealing furnace is heated to 700-1200 ℃ and be incubated 1-48 hour;
4) hydrogen-storing alloy as electrode is carried out Quenching Treatment in rapid quenching WATER AS FLOW MEDIUM or oil.
The titanium base hydrogen-storing alloy as electrode that adopts heat treatment method of the present invention to handle, especially after the 1000 ℃ * 5h heat treatment, the discharge capacity of alloy electrode is greatly improved, and cyclical stability is not subjected to any influence, simultaneously, the activity function of alloy electrode also is improved, thereby has improved the comprehensive electrochemical of titanium base hydrogen-storing alloy as electrode.Simultaneously can also find that under the situation of not considering cyclical stability, titanium base hydrogen-storing alloy as electrode is after 1100 ℃ * 8h heat treatment, the discharge capacity and the activity function of alloy electrode further are improved.The heat treatment method of titanium base hydrogen-storing alloy as electrode of the present invention will (comprise rare earth based AB for improving other hydrogen-storing alloy as electrode
5Type alloy, zirconium base AB
2Type alloy, magnesium base alloy and vanadium radical sosoloid alloy) comprehensive electrochemical provide the reference frame of usefulness.
Below in conjunction with drawings and Examples the present invention is elaborated.
Fig. 1 is the discharge capacity of cast alloy electrode of the alloy electrode handled according to embodiment 1 and unprocessed mistake and the relation curve between the cycle-index;
Fig. 2 is the discharge capacity of cast alloy electrode of the alloy electrode handled according to embodiment 2 and unprocessed mistake and the relation curve between the cycle-index.
Ti base AB
2The heating-up temperature of the annealing furnace in the heat treatment method of type Laves phase hydrogen storage electrode metal is 1000-1100 ℃, and temperature retention time is 5h-8h.
Embodiment 1
According to Ti base AB
2The design mix of type Laves phase hydrogen storage electrode metal adopts vacuum magnetic suspension stove molten alloy, is designated as alloy X.Wherein, the purity of alloy constituent element Ti, Zr, V, Mn, Cr, Ni is all more than 99%.Respectively get alloy part X and enclose respectively in two vitreosil glass tubes, the vacuum degree in the quartz glass tube is 10
-5Holder is designated as pipe 1 and pipe 2.To manage respectively then 1 and pipe 2 put into annealing furnace and carry out heat tracing.Pipe 1 heating condition is 1000 ℃ * 5h, and the heating condition of pipe 2 is 1100 ℃ * 8h, treat that temperature retention time arrives after, immediately envelope there is the quartz glass tube of hydrogen-storing alloy as electrode to take out and put into water, simultaneously glass tube is broken into pieces, allowed alloy contact with water fully, i.e. Quenching Treatment.The test of chemical property is to carry out in an open type three-electrode system, and it comprises a work electrode (being hydrogen-occlussion alloy electrode), a sintering Ni (OH)
2/ NiOOH auxiliary electrode and a Hg/HgO reference electrode.Electrolyte adopts the 6NKOH aqueous solution, and probe temperature remains on 303K.All test electrodes all are to form by the even electrode slice that mixes 100mg hydrogen-storage alloy powder (300 order) and 200mg carbonyl nickel powder and be pressed into diameter 10mm, thickness 1mm under the pressure of 20Mpa.Electrode adopts the electric current of 60mA/g to charge and discharge, and wherein the charging interval is 10 hours, and the discharge stopping potential is-0.6V (with respect to the Hg/HgO reference electrode).
Embodiment 2
According to Ti base AB
2The design mix of type Laves phase hydrogen storage electrode metal adopts vacuum magnetic suspension stove molten alloy, is designated as alloy Y.Wherein, the purity of alloy constituent element Ti, Zr, V, Mn, Cr, Ni is all more than 99%.Get alloy part Y and enclose in the vitreosil glass tube, the vacuum degree in the quartz glass tube is 10
-5Holder is put into annealing furnace with this pipe then and is carried out heat tracing, and heating condition is 1000 ℃ * 5h, after treating that temperature retention time arrives, immediately envelope there is the quartz glass tube taking-up of hydrogen-storing alloy as electrode and puts into water, simultaneously glass tube is broken into pieces, allow alloy contact with water fully, i.e. Quenching Treatment.The making of electrode slice and the test of chemical property are all identical with embodiment 1.
Comparing embodiment 1
The alloy X of melting does not do any processing among the selected part embodiment 1, makes electrode and carries out the test of electrochemistry cycle life according to embodiment 1 described method.
Comparing embodiment 2
The alloy Y of melting among the selected part embodiment 2 is not done any processing, makes electrode and carries out the test of electrochemistry cycle life according to embodiment 1 described method.
As can be seen from Figure 1, the high electrochemistry capacitance of alloy X under as-cast condition only has 289mAh/g, and after carrying out 1000 ℃ * 5h heat treatment, its high electrochemistry capacitance becomes 380mAh/g, improved 91mAh/g, and after 103 circulations, its capacity still is higher than the discharge capacity of cast alloy.After carrying out 1100 ℃ * 8h heat treatment, the high electrochemistry capacitance of alloy X is promoted to 408mAh/g, than cast alloy height 119mAh/g, but the cyclical stability variation.Simultaneously, can also be as seen from Figure 1, after heat treatment, the activity function of alloy X is improved: alloy needs 7 circulations just can reach maximum discharge capacity under the as-cast condition, carry out needing 6 circulations after the 1000 ℃ * 5h heat treatment, and carry out only needing 2 circulations after the 1100 ℃ * 8h heat treatment.
As can be seen from Figure 2, the high electrochemistry capacitance of cast alloy Y is 360mAh/g, and after carrying out 1000 ℃ * 5h heat treatment, its high electrochemistry capacitance becomes 400mAh/g, improved 40mAh/g, and heat treatment does not reduce the cyclical stability of alloy electrode.It can also be seen that simultaneously the activity function of alloy electrode is improved, promptly become 4 circulations after the heat treatment, shortened 4 cycle periods by 8 times under as-cast condition circulations.
Claims (1)
1. Ti base AB
2The heat treatment method of type Laves phase hydrogen storage electrode metal is characterized in that it comprises the following steps:
1) Ti base AB
2A side element ti in the type Laves phase hydrogen storage electrode metal, Zr and B side element V, Mn, Cr, Ni place melting in the vacuum magnetic suspension smelting furnace;
2) melted as cast condition hydrogen-storing alloy as electrode is placed on is evacuated to 10 in the quartz glass tube
-5-10
-6Holder is sealed up the quartz glass mouth of pipe then;
3) quartz glass tube that will be packaged with the as cast condition hydrogen-storing alloy as electrode in annealing furnace carries out vacuum annealing, and the heating-up temperature of said annealing furnace is 1000-1100 ℃, and temperature retention time is 5h-8h;
4) annealing is carried out Quenching Treatment with hydrogen-storing alloy as electrode after finishing in rapid quenching WATER AS FLOW MEDIUM or oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011177675A CN1205680C (en) | 2001-05-11 | 2001-05-11 | Heat treatment method for Ti base AB 2 type laves phase hydrogen storage electrode alloy |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011177675A CN1205680C (en) | 2001-05-11 | 2001-05-11 | Heat treatment method for Ti base AB 2 type laves phase hydrogen storage electrode alloy |
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| CN1385910A CN1385910A (en) | 2002-12-18 |
| CN1205680C true CN1205680C (en) | 2005-06-08 |
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| CNB011177675A Expired - Fee Related CN1205680C (en) | 2001-05-11 | 2001-05-11 | Heat treatment method for Ti base AB 2 type laves phase hydrogen storage electrode alloy |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103741049A (en) * | 2014-01-21 | 2014-04-23 | 湘潭大学 | Iron-based abrasion-resistant alloy based on Laves phase strengthening and preparation method thereof |
| CN104032104A (en) * | 2014-06-06 | 2014-09-10 | 上海大学 | Vacuum heat-treatment experimental method under conventional condition |
| CN107541614B (en) * | 2017-08-07 | 2019-01-15 | 华南理工大学 | A kind of deformation induces laves phase dispersion consolidatedization titanium alloy and preparation method thereof |
| CN107502783B (en) * | 2017-09-03 | 2019-06-04 | 河北国工新材料技术开发有限公司 | A kind of preparation method of titanium-based hydrogen storage alloy |
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Granted publication date: 20050608 Termination date: 20100511 |