CN101859900B - Preparation method of quick quenching Ti-V-base composite hydrogen storage alloy electrode - Google Patents
Preparation method of quick quenching Ti-V-base composite hydrogen storage alloy electrode Download PDFInfo
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Abstract
The invention discloses a preparation method of a quick quenching Ti-V-base composite hydrogen storage alloy electrode. The method comprises the following steps: 1 Ti-V-base composite hydrogen storage alloy is smelted and concreted quickly, 2 according to the routine mechanical alloying method, a high energy ball mill is used to mill Ti-V-base composite hydrogen storage alloy powder and AB 5 mischmetal hydrogen storage alloy powder, and 3 the Ti-V-base/AB5 composite alloy powder, acetylene black and cobaltous oxide are mixed and milled evenly, to which binder is added and mixed evenly and the mixture is coated on a Ni net to prepare a Ti-V-base/AB5 composite alloy cathode piece. The invention has the advantages of simple preparation technology step, low cost, short flow and convenient operation. The prepared quick quenching Ti-V-base composite hydrogen storage alloy electrode has good electrochemical performance and integrates the good electrochemical recycle performance of the Ti-V-base alloy electrode and the good electrochemical catalytic activity of the commodity AB 5 powder.
Description
Technical field
The invention belongs to the hydrogen storage material applied technical field, especially relate to a kind of preparation method of quick quenching Ti-V-base composite hydrogen storage alloy electrode.
Background technology
The principal phase structure is the Ti-V radical sosoloid alloy of body-centered cubic structure, because of theoretical hydrogen storage content up to 1018mAh/g, be about three times of LaNi5, manifested its applications well prospect as the Ni-MH cell negative electrode material.It is theoretical capacity density maximum in all known nickel-hydrogen battery negative pole materials, but has the shortcomings such as electrochemistry cycle performance and catalytic activity be relatively poor, has limited the application development of Ti-V radical sosoloid alloy aspect electrochemistry.
In recent years, scientists adopted quick setting method, made the electrochemistry cycle performance of Ti-V radical sosoloid alloy obtain significant the improvement.According to the literature, under nearly 200 electrochemistry circulation, the capability retention of rapidly solidified alloy electrode is more than 90%.Although adopt flash set technology to make the maximum discharge capacity of Ti-V base alloy electrode be reduced to 225mAh/g, electro-chemical activity and high-rate discharge ability have also reduced, but quick setting method is very significant to the improvement of Ti-V base alloy electrochemistry cycle performance.
The single Ti-V base alloy electrode of the electrochemistry cycle performance excellence that only makes by the fusing quick-quenching method because maximum discharge capacity reduces, has been lost its due advantage.And AB5 type powder can be used as the electro-chemical activity that electrochemical catalyst activates Ti-V base alloy, thereby effectively improves the maximum discharge capacity of Ti-V base alloy.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned deficiency of the prior art, a kind of preparation method of quick quenching Ti-V-base composite hydrogen storage alloy electrode is provided, its step of preparation process is simple, cost is low, flow process is short and easy to operate, result of use good, the chemical property of prepared quick quenching Ti-V-base composite hydrogen storage alloy electrode is good, combines the electrochemistry cycle performance of quick quenching Ti-V-base alloy electrode excellence and the characteristics of commodity AB5 type powder good electrical chemical catalysis activity.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of preparation method of quick quenching Ti-V-base composite hydrogen storage alloy electrode is characterized in that the method may further comprise the steps:
Step 1, the melting of Ti-V base composite hydrogen storage alloy and rapid solidification: at first, under protective atmosphere, adopt apparatus for melting metal that pending Ti-V base composite hydrogen storage alloy is carried out melting, described apparatus for melting metal is vacuum arc melting device or magnetic suspension induction melting furnace; Simultaneously, the quick solidification apparatus that adopts described apparatus for melting metal to carry carries out rapid solidification to the liquid Ti-V base composite hydrogen storage alloy after the melting; Subsequently, under protective atmosphere, the Ti-V base composite hydrogen storage alloy after adopting heat-treatment furnace to rapid solidification is heat-treated, and heat treatment temperature is that 700～1300 ℃ and heat treatment time are 1～20h; Afterwards, after heat treatment Ti-V base composite hydrogen storage alloy is carried out crushing grinding, obtain Ti-V base composite hydrogen storage alloy powder;
Step 2, Ti-V base/AB5 type complex alloy powder preparation: according to the conventional mechanical alloyage process, and adopt high energy ball mill that the base composite hydrogen storage alloy powder of Ti-V described in the step 1 and AB5 type mixed rare-earth hydrogen-bearing alloy powder are carried out ball milling, and prepare Ti-V base/AB5 type complex alloy powder, add mass percent that AB5 type mixed rare-earth hydrogen-bearing alloy powder accounts for described Ti-V base/AB5 type complex alloy powder be 5～30% and Ball-milling Time be 10min～40h;
Step 3, Ti-V base/AB5 type composite alloy negative plate is made: with the base of the Ti-V described in the step 2/AB5 type complex alloy powder, acetylene black and cobalt protoxide mixed grinding evenly and obtain compound; Simultaneously in the mixed grinding process, be 5～10% binding agent to the inner mass concentration that adds of described compound, and mix well rear acquisition mixed slurry; Afterwards, it is online with Ni that mixed slurry after mixing well evenly is coated in battery, and just obtain formed sheet after the battery that is coated with mixed slurry successively folded flanging, vacuumize and mold pressing with the Ni net, after being welded lug, described formed sheet just obtains again Ti-V base/AB5 type composite alloy negative plate; Weight ratio between described Ti-V base/AB5 type complex alloy powder and acetylene black and cobalt protoxide is 20～50: 1, the weight ratio of described binding agent and described compound is 0.8～1.5: 2, and described binding agent is carboxymethyl cellulose, polyvinyl alcohol or light the third methylcellulose.
When the liquid Ti-V base composite hydrogen storage alloy to after the melting described in the above-mentioned steps one carried out rapid solidification, employing was got rid of the band method and is carried out rapid solidification, and got rid of band linear velocity 5-40m/s.
Strong base solution described in the above-mentioned steps four is that concentration is the KOH solution of 5～7mol/L.
Described in the above-mentioned steps one pending Ti-V base composite hydrogen storage alloy is carried out melting the time, described protective atmosphere is pure argon atmosphere.
When the Ti-V base composite hydrogen storage alloy to behind the rapid solidification described in the above-mentioned steps one was heat-treated, the vacuum degree in the described heat-treatment furnace was not higher than 10
-2Pa.
Heat-treatment furnace described in the above-mentioned steps one is program control single tube sintering furnace.
The present invention compared with prior art has the following advantages:
1, step of preparation process is simple, cost is low, flow process is short and easy to operate.
2, result of use is good, the chemical property of prepared quick quenching Ti-V-base composite hydrogen storage alloy electrode is good, the present invention combines the electrochemistry cycle performance of quick quenching Ti-V-base alloy electrode excellence and the characteristics of commodity AB5 type powder good electrical chemical catalysis activity, the quick quenching Ti-V-base composite hydrogen storage alloy electrode electrochemistry capacitance of preparation is high and up to 350mAh/g～550mAh/g, cycle performance and activity function are good, have good comprehensive electrochemical.
3, reasonable in design, with AB5 type alloy as surface modifying material, adopt Mechanical Alloying to carry out itself and quick quenching Ti-V-base alloy compound: because AB5 type alloy surface modifying particle itself has good electrocatalysis characteristic, can substitute and have little time the second-phase catalysis phase separated out in the melt spun alloy, activate the electrochemical hydrogenation and dehydrogenation performance of quick quenching Ti-V based solid solution principal phase, thus the maximum discharge capacity of Effective Raise quick quenching Ti-V-base alloy; And it can also provide express passway for hydrogen atom spreads as conductive current collector, thereby the performances such as the electro-chemical activity of Effective Raise quick quenching Ti-V-base alloy and dynamics; Simultaneously, because the electrochemistry cycle performance of AB5 alloy own is excellent, the characteristics of quick quenching Ti-V-base alloy electrochemistry cycle performance excellence are continued, obtain the composite hydrogen occluding alloy that performance obviously is better than single type.Therefore, when adopting the inventive method to prepare quick quenching Ti-V-base composite hydrogen storage alloy electrode, adopt first vacuum arc melting or magnetic suspension Induction Melting Technology to carry out the melting of alloy, employing rapid solidification belt-rejecting technology prepares TiV base alloy and machinery is broken into powder, and is by Mechanical Alloying that quick quenching Ti-V base alloy powder and commodity AB5 type powder is compound; This composite alloy and acetylene black and CoO mixed grinding is even, and mix well with a certain amount of binding agent, fast quenching TiV base/AB5 composite alloy negative plate is made in the compacting oven dry, with this alloy anode sheet and Ni (OH)
2Positive plate is positioned in the KOH solution and soaks, then at its chemical property of secondary cell device for detecting performance test.
In sum, step of preparation process of the present invention is simple, cost is low, flow process is short and easy to operate, result of use good, the chemical property of prepared quick quenching Ti-V-base composite hydrogen storage alloy electrode is good, combines the electrochemistry cycle performance of quick quenching Ti-V-base alloy electrode excellence and the characteristics of merchant's mouthful AB5 type powder good electrical chemical catalysis activity.
Below by drawings and Examples, technical scheme of the present invention is described in further detail.
Description of drawings
Fig. 1 is process chart of the present invention.
Embodiment
The preparation method of a kind of quick quenching Ti-V-base composite hydrogen storage alloy electrode as shown in Figure 1 may further comprise the steps:
Step 1, the melting of Ti-V base composite hydrogen storage alloy and rapid solidification: at first, under protective atmosphere, adopt apparatus for melting metal that pending Ti-V base composite hydrogen storage alloy is carried out melting, described apparatus for melting metal is vacuum arc melting device or magnetic suspension induction melting furnace; Simultaneously, the quick solidification apparatus that adopts described apparatus for melting metal to carry carries out rapid solidification to the liquid Ti-V base composite hydrogen storage alloy after the melting; Subsequently, under protective atmosphere, the Ti-V base composite hydrogen storage alloy after adopting heat-treatment furnace to rapid solidification is heat-treated, and heat treatment temperature is for being that 700～1300 ℃ and heat treatment time are 1～20h; Afterwards, after heat treatment Ti-V base composite hydrogen storage alloy is carried out crushing grinding, obtain Ti-V base composite hydrogen storage alloy powder.
In the actual fabrication process, when the liquid Ti-V base composite hydrogen storage alloy after the melting was carried out rapid solidification, employing was got rid of the band method and is carried out rapid solidification, and got rid of band linear velocity 5-40m/s.Simultaneously, can also adopt other quick setting method liquid towards Ti-V base composite hydrogen storage alloy to carry out rapid solidification.
Step 2, Ti-V base/AB5 type complex alloy powder preparation: according to the conventional mechanical alloyage process, and adopt high energy ball mill that the base composite hydrogen storage alloy powder of Ti-V described in the step 1 and AB5 type mixed rare-earth hydrogen-bearing alloy powder are carried out ball milling, and prepare Ti-V base/AB5 type complex alloy powder, add mass percent that AB5 type mixed rare-earth hydrogen-bearing alloy powder accounts for described Ti-V base/AB5 type complex alloy powder be 5～30% and Ball-milling Time be 10min～40h.
Step 3, Ti-V base/AB5 type composite alloy negative plate is made: with the base of the Ti-V described in the step 2/AB5 type complex alloy powder, acetylene black and cobalt protoxide (being CoO) mixed grinding evenly and obtain compound; Simultaneously in the mixed grinding process, be 5～10% binding agent to the inner mass concentration that adds of described compound, and mix well rear acquisition mixed slurry; Afterwards, it is online with Ni that mixed slurry after mixing well evenly is coated in battery, and just obtain formed sheet after the battery that is coated with mixed slurry successively folded flanging, vacuumize and mold pressing with the Ni net, after being welded lug, described formed sheet just obtains again Ti-V base/AB5 type composite alloy negative plate; Weight ratio between described Ti-V base/AB5 type complex alloy powder and acetylene black and cobalt protoxide is 20～50: 1, the weight ratio of described binding agent and described compound is 0.8～1.5: 2, and described binding agent is carboxymethyl cellulose, polyvinyl alcohol or light the third methylcellulose.
Subsequently, carry out electrode activation: with the base of the Ti-V described in the step 3/AB5 type composite alloy negative plate and Ni (OH)
2It is that the strong base solution of 5～7mol/L soaks and activated in 2～24 hours that positive plate is put into concentration simultaneously, and after the activation at described Ni (OH)
2Just form secondary cell after the energising on positive plate and Ti-V base/AB5 type composite alloy negative plate.
Embodiment 1
In the present embodiment, when quick quenching Ti-V-base composite hydrogen storage alloy electrode was prepared, its preparation process was as follows:
Step 1, the melting of Ti-V base composite hydrogen storage alloy and rapid solidification: at first, under pure argon atmosphere, adopt the vacuum arc melting device that pending Ti-V base composite hydrogen storage alloy is carried out melting; Simultaneously, the quick solidification apparatus that adopts described vacuum arc melting device to carry carries out rapid solidification to the liquid Ti-V base composite hydrogen storage alloy after the melting, gets rid of band linear velocity 25m/s; Subsequently, under protective atmosphere, the Ti-V base composite hydrogen storage alloy after adopting heat-treatment furnace to rapid solidification is heat-treated, and heat treatment temperature is that 700 ℃ and heat treatment time are 20h; Afterwards, after heat treatment Ti-V base composite hydrogen storage alloy is carried out crushing grinding, obtain Ti-V base composite hydrogen storage alloy powder.Described pending Ti-V base composite hydrogen storage alloy is TiV
2.1Ni
0.4Zr
0.06Cu
0.03Cr
0.1In the present embodiment, when carrying out alloy melting, carry out at water jacketed copper crucible.
In the present embodiment, when pending Ti-V base composite hydrogen storage alloy was carried out melting, used protective atmosphere was pure argon atmosphere, actually also can carry out melting at other protective atmosphere when carrying out melting.When the Ti-V base composite hydrogen storage alloy behind the rapid solidification was heat-treated, the vacuum degree in the described heat-treatment furnace was not higher than 10
-2Pa (when specifically heat-treating, is evacuated to 10 with the vacuum degree in the heat-treatment furnace first
-2During Pa, begin to pass into protective atmosphere and heat-treat), and described heat-treatment furnace is program control single tube sintering furnace, also can adopt the heat-treatment furnace of other type to heat-treat simultaneously.
Step 2, Ti-V base/AB5 type complex alloy powder preparation: according to the conventional mechanical alloyage process, and adopt high energy ball mill that the base composite hydrogen storage alloy powder of Ti-V described in the step 1 and AB5 type mixed rare-earth hydrogen-bearing alloy powder are carried out ball milling, and prepare Ti-V base/AB5 type complex alloy powder, add mass percent that AB5 type mixed rare-earth hydrogen-bearing alloy powder accounts for described Ti-V base/AB5 type complex alloy powder be 20% and Ball-milling Time be 30min, ratio of grinding media to material is 10: 1.Described AB5 type mixed rare-earth hydrogen-bearing alloy powder is LaNi
3.55Co
0.75Mn
0.4Al
0.3Powder.
Step 3, Ti-V base/AB5 type composite alloy negative plate is made: with the cobalt protoxide mixed grinding of the acetylene black of the Ti-V base described in the 0.5g step 2/AB5 type complex alloy powder, 0.012g and 0.018g evenly and obtain compound; Simultaneously in the mixed grinding process, be 6% polyvinyl alcohol to the inner 0.2g mass concentration that adds of described compound, and mix well rear acquisition mixed slurry; Afterwards, it is online with Ni that mixed slurry after mixing well evenly is coated in battery, and just obtain formed sheet after the battery that is coated with mixed slurry successively folded flanging, vacuumize and mold pressing with the Ni net, after being welded lug, described formed sheet just obtains again Ti-V base/AB5 type composite alloy negative plate.
Afterwards, carry out electrode activation: with the base of the Ti-V described in the step 3/AB5 type composite alloy negative plate and NiOH
2It is that the KOH solution of 6mol/L soaks and to activate in 24 hours that positive plate is put into concentration simultaneously, and after the activation at described Ni (OH)
2Just form secondary cell after the energising on positive plate and Ti-V base/AB5 type composite alloy negative plate.During actual the activation, also can adopt other strong base solution to soak.In the present embodiment, all the other method steps are all identical with the described quick quenching Ti-V-base composite hydrogen storage alloy electrode preparation method of Fig. 1.
Subsequently, chemical property at the prepared quick quenching Ti-V-base composite hydrogen storage alloy electrode of MP-58 secondary cell device for detecting performance test, charging and discharging currents density is 50mA/g during test, the electrochemistry capacitance of the quick quenching Ti-V-base composite hydrogen storage alloy electrode of preparation is up to 376mAh/g, capability retention under 100 circulations reaches 96%, activity function is good, has good comprehensive electrochemical.
Embodiment 2
In the present embodiment, as different from Example 1: step 1, when carrying out rapid solidification, get rid of band linear velocity 20m/s, and when heat-treating, heat treatment temperature is that 800 ℃ and heat treatment time are 15h; When carrying out ball milling in the step 2, add mass percent that AB5 type mixed rare-earth hydrogen-bearing alloy powder accounts for described Ti-V base/AB5 type complex alloy powder be 25% and Ball-milling Time be 60min; When making Ti-V base/AB5 type composite alloy negative plate in the step 3, with cobalt protoxide (the being CoO) mixed grinding of the acetylene black of the Ti-V base of 0.5g/AB5 type complex alloy powder, 0.015g and 0.02g evenly and obtain compound, simultaneously in the mixed grinding process, be that 7% polyvinyl alcohol is mixed well to the inner 0.2g concentration that adds of described compound; When carrying out electrode activation in the step 4, with Ti-V base/AB5 type composite alloy negative plate and Ni (OH)
2It is that the KOH solution of 5mol/L soaks and to activate in 20 hours that positive plate is put into concentration simultaneously.
In the present embodiment, all the other method steps are all identical with embodiment 1.At last, chemical property at the prepared quick quenching Ti-V-base composite hydrogen storage alloy electrode of MP-58 secondary cell device for detecting performance test, charging and discharging currents density is 50mA/g during test, the electrochemistry capacitance of the quick quenching Ti-V-base composite hydrogen storage alloy electrode of preparation is up to 410mAh/g, capability retention under 100 circulations reaches 94%, activity function is good, has good comprehensive electrochemical.
Embodiment 3
In the present embodiment, as different from Example 1: step 1, when carrying out rapid solidification, get rid of band linear velocity 30m/s, and when heat-treating, heat treatment temperature is that 800 ℃ and heat treatment time are 8h; When carrying out ball milling in the step 2, add mass percent that AB5 type mixed rare-earth hydrogen-bearing alloy powder accounts for described Ti-V base/AB5 type complex alloy powder be 30% and Ball-milling Time be 2h; When making Ti-V base/AB5 type composite alloy negative plate in the step 3, with cobalt protoxide (the being CoO) mixed grinding of the acetylene black of the Ti-V base of 0.5g/AB5 type complex alloy powder, 0.015g and 0.025g evenly and obtain compound, simultaneously in the mixed grinding process, be that 5% polyvinyl alcohol is mixed well to the inner 0.2g concentration that adds of described compound; When carrying out electrode activation in the step 4, with Ti-V base/AB5 type composite alloy negative plate and Ni (OH)
2It is that the KOH solution of 6mol/L soaks and to activate in 24 hours that positive plate is put into concentration simultaneously.
In the present embodiment, all the other method steps are all identical with embodiment 1.At last, chemical property at the prepared quick quenching Ti-V-base composite hydrogen storage alloy electrode of MP-58 secondary cell device for detecting performance test, charging and discharging currents density is 50mA/g during test, the electrochemistry capacitance of the quick quenching Ti-V-base composite hydrogen storage alloy electrode of preparation is up to 450mAh/g, capability retention under 100 circulations reaches 92%, activity function is good, has good comprehensive electrochemical.
Embodiment 4
In the present embodiment, as different from Example 1: step 1 adopts the magnetic suspension induction melting furnace that pending Ti-V base composite hydrogen storage alloy is carried out melting, get rid of band linear velocity 40m/s when carrying out rapid solidification, and when heat-treating, heat treatment temperature is that 900 ℃ and heat treatment time are 12h; When carrying out ball milling in the step 2, add mass percent that AB5 type mixed rare-earth hydrogen-bearing alloy powder accounts for described Ti-V base/AB5 type complex alloy powder be 15% and Ball-milling Time be 15h; When making Ti-V base/AB5 type composite alloy negative plate in the step 3, the weight ratio of Ti-V base/AB5 type complex alloy powder and acetylene black and cobalt protoxide is 20: 1, to add binding agent be concentration by 8% carboxymethyl cellulose and the weight ratio of adding binding agent and described compound be 0.8: 2; When carrying out electrode activation in the step 4, with Ti-V base/AB5 type composite alloy negative plate and Ni (OH)
2It is that the KOH solution of 6mol/L soaks and to activate in 15 hours that positive plate is put into concentration simultaneously.In the present embodiment, all the other method steps are all identical with embodiment 1.
Embodiment 5
In the present embodiment, as different from Example 1: step 1 adopts the magnetic suspension induction melting furnace that pending Ti-V base composite hydrogen storage alloy is carried out melting, get rid of band linear velocity 10m/s when carrying out rapid solidification, and when heat-treating, heat treatment temperature is that 1000 ℃ and heat treatment time are 10h; When carrying out ball milling in the step 2, add mass percent that AB5 type mixed rare-earth hydrogen-bearing alloy powder accounts for described Ti-V base/AB5 type complex alloy powder be 10% and Ball-milling Time be 25h; When making Ti-V base/AB5 type composite alloy negative plate in the step 3, the weight ratio of Ti-V base/AB5 type complex alloy powder and acetylene black and cobalt protoxide is 50: 1, to add binding agent be concentration by 10% carboxymethyl cellulose and the weight ratio of adding binding agent and described compound be 1.5: 2; When carrying out electrode activation in the step 4, with Ti-V base/AB5 type composite alloy negative plate and Ni (OH)
2It is that the KOH solution of 6mol/L soaks and to activate in 10 hours that positive plate is put into concentration simultaneously.In the present embodiment, all the other method steps are all identical with embodiment 1.
Embodiment 6
In the present embodiment, as different from Example 1: step 1 adopts the magnetic suspension induction melting furnace that pending Ti-V base composite hydrogen storage alloy is carried out melting, get rid of band linear velocity 8m/s when carrying out rapid solidification, and when heat-treating, heat treatment temperature is that 1100 ℃ and heat treatment time are 8h; When carrying out ball milling in the step 2, add mass percent that AB5 type mixed rare-earth hydrogen-bearing alloy powder accounts for described Ti-V base/AB5 type complex alloy powder be 5% and Ball-milling Time be 10min; When making Ti-V base/AB5 type composite alloy negative plate in the step 3, the weight ratio of Ti-V base/AB5 type complex alloy powder and acetylene black and cobalt protoxide is 30: 1, to add binding agent be concentration by light the third methylcellulose of 10% and the weight ratio of adding binding agent and described compound be 1.2: 2; When carrying out electrode activation in the step 4, with Ti-V base/AB5 type composite alloy negative plate and Ni (OH)
2It is that the KOH solution of 6mol/L soaks and to activate in 8 hours that positive plate is put into concentration simultaneously.In the present embodiment, all the other method steps are all identical with embodiment 1.
Embodiment 7
In the present embodiment, as different from Example 1: step 1 adopts the magnetic suspension induction melting furnace that pending Ti-V base composite hydrogen storage alloy is carried out melting, get rid of band linear velocity 5m/s when carrying out rapid solidification, and when heat-treating, heat treatment temperature is that 1300 ℃ and heat treatment time are 1h; When carrying out ball milling in the step 2, add mass percent that AB5 type mixed rare-earth hydrogen-bearing alloy powder accounts for described Ti-V base/AB5 type complex alloy powder be 8% and Ball-milling Time be 40h; When making Ti-V base/AB5 type composite alloy negative plate in the step 3, the weight ratio of Ti-V base/AB5 type complex alloy powder and acetylene black and cobalt protoxide is 40: 1, to add binding agent be concentration by light the third methylcellulose of 10% and the weight ratio of adding binding agent and described compound be 1.0: 2; When carrying out electrode activation in the step 4, with Ti-V base/AB5 type composite alloy negative plate and Ni (OH)
2It is that the KOH solution of 6mol/L soaks and to activate in 5 hours that positive plate is put into concentration simultaneously.In the present embodiment, all the other method steps are all identical with embodiment 1.
Embodiment 8
In the present embodiment, as different from Example 1: step 1 adopts the magnetic suspension induction melting furnace that pending Ti-V base composite hydrogen storage alloy is carried out melting, get rid of band linear velocity 5m/s when carrying out rapid solidification, and when heat-treating, heat treatment temperature is that 1200 ℃ and heat treatment time are 5h; When carrying out ball milling in the step 2, add mass percent that AB5 type mixed rare-earth hydrogen-bearing alloy powder accounts for described Ti-V base/AB5 type complex alloy powder be 10% and Ball-milling Time be 32h; When making Ti-V base/AB5 type composite alloy negative plate in the step 3, the weight ratio of Ti-V base/AB5 type complex alloy powder and acetylene black and cobalt protoxide is 25: 1, to add binding agent be concentration by light the third methylcellulose of 10% and the weight ratio of adding binding agent and described compound be 0.9: 2; When carrying out electrode activation in the step 4, with Ti-V base/AB5 type composite alloy negative plate and Ni (OH)
2It is that the KOH solution of 6mol/L soaks and to activate in 2 hours that positive plate is put into concentration simultaneously.In the present embodiment, all the other method steps are all identical with embodiment 1.
The above; it only is preferred embodiment of the present invention; be not that the present invention is imposed any restrictions, every any simple modification, change and equivalent structure of above embodiment being done according to the technology of the present invention essence changes, and all still belongs in the protection range of technical solution of the present invention.
Claims (4)
1. the preparation method of a quick quenching Ti-V-base composite hydrogen storage alloy electrode is characterized in that the method may further comprise the steps:
Step 1, the melting of Ti-V base composite hydrogen storage alloy and rapid solidification: at first, under protective atmosphere, adopt apparatus for melting metal that pending Ti-V base composite hydrogen storage alloy is carried out melting, described apparatus for melting metal is vacuum arc melting device or magnetic suspension induction melting furnace; Simultaneously, the quick solidification apparatus that adopts described apparatus for melting metal to carry carries out rapid solidification to the liquid Ti-V base composite hydrogen storage alloy after the melting; Subsequently, under protective atmosphere, the Ti-V base composite hydrogen storage alloy after adopting heat-treatment furnace to rapid solidification is heat-treated, and heat treatment temperature is that 700～1300 ℃ and heat treatment time are 1～20h; Afterwards, after heat treatment Ti-V base composite hydrogen storage alloy is carried out crushing grinding, obtain Ti-V base composite hydrogen storage alloy powder;
Described in the step 1 pending Ti-V base composite hydrogen storage alloy is carried out melting the time, described protective atmosphere is pure argon atmosphere;
Step 2, Ti-V base/AB
5Type complex alloy powder preparation: according to the conventional mechanical alloyage process, and adopt high energy ball mill to the base composite hydrogen storage alloy powder of Ti-V described in the step 1 and AB
5The type mixed rare-earth hydrogen-bearing alloy powder carries out ball milling, and prepares Ti-V base/AB
5The type complex alloy powder, add AB
5The type mixed rare-earth hydrogen-bearing alloy powder accounts for described Ti-V base/AB
5The mass percent of type complex alloy powder be 5～30% and Ball-milling Time be 10min～40h;
Step 3, Ti-V base/AB
5Type composite alloy negative plate is made: with the Ti-V base/AB described in the step 2
5Type complex alloy powder, acetylene black and cobalt protoxide mixed grinding are evenly and obtain compound; Simultaneously in the mixed grinding process, be 5～10% binding agent to the inner mass concentration that adds of described compound, and mix well rear acquisition mixed slurry; Afterwards, it is online with Ni that mixed slurry after mixing well evenly is coated in battery, and just obtain formed sheet after the battery that is coated with mixed slurry successively folded flanging, vacuumize and mold pressing with the Ni net, after being welded lug, described formed sheet just obtains again Ti-V base/AB
5Type composite alloy negative plate; Described Ti-V base/AB
5Weight ratio between type complex alloy powder and acetylene black and cobalt protoxide is 20～50: 1, and the weight ratio of described binding agent and described compound is 0.8～1.5: 2, and described binding agent is carboxymethyl cellulose or polyvinyl alcohol;
Subsequently, carry out electrode activation: with the Ti-V base/AB described in the step 3
5Type composite alloy negative plate and Ni (OH)
2It is that the strong base solution of 5～7mol/L soaks and activated in 2～24 hours that positive plate is put into concentration simultaneously, and employed strong base solution is KOH solution.
2. according to the preparation method of a kind of quick quenching Ti-V-base composite hydrogen storage alloy electrode claimed in claim 1, it is characterized in that: when the liquid Ti-V base composite hydrogen storage alloy to after the melting described in the step 1 carries out rapid solidification, employing is got rid of the band method and is carried out rapid solidification, and gets rid of band linear velocity 5-40m/s.
3. according to the preparation method of claim 1 or 2 described a kind of quick quenching Ti-V-base composite hydrogen storage alloy electrodes, it is characterized in that: when the Ti-V base composite hydrogen storage alloy to behind the rapid solidification described in the step 1 was heat-treated, the vacuum degree in the described heat-treatment furnace was not higher than 10
-2Pa.
4. according to the preparation method of claim 1 or 2 described a kind of quick quenching Ti-V-base composite hydrogen storage alloy electrodes, it is characterized in that: the heat-treatment furnace described in the step 1 is program control single tube sintering furnace.
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| CN1522308A (en) * | 2001-04-27 | 2004-08-18 | 株式会社三德 | Method for producing cr-ti-v hydrogen storage alloys |
| CN101027802A (en) * | 2004-08-26 | 2007-08-29 | 株式会社杰士汤浅 | Hydrogen storage electrode and nickel hydrogen battery |
| CN101307395A (en) * | 2008-07-14 | 2008-11-19 | 西北有色金属研究院 | Method for preparing amorphous state NiB hydrogen occluding alloy electrode |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1522308A (en) * | 2001-04-27 | 2004-08-18 | 株式会社三德 | Method for producing cr-ti-v hydrogen storage alloys |
| CN101027802A (en) * | 2004-08-26 | 2007-08-29 | 株式会社杰士汤浅 | Hydrogen storage electrode and nickel hydrogen battery |
| CN101307395A (en) * | 2008-07-14 | 2008-11-19 | 西北有色金属研究院 | Method for preparing amorphous state NiB hydrogen occluding alloy electrode |
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