CN101289576B - Composite material of conducting high polymers/alloy for nickel-hydrogen battery and preparation thereof - Google Patents
Composite material of conducting high polymers/alloy for nickel-hydrogen battery and preparation thereof Download PDFInfo
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- CN101289576B CN101289576B CN2007100110497A CN200710011049A CN101289576B CN 101289576 B CN101289576 B CN 101289576B CN 2007100110497 A CN2007100110497 A CN 2007100110497A CN 200710011049 A CN200710011049 A CN 200710011049A CN 101289576 B CN101289576 B CN 101289576B
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Abstract
The invention relates to conductive high molecular polymer/alloy composite material for nickel-hydrogen batteries and a preparation method thereof. The composite material is compositely formed by a metal AB3 alloy and a conductive high molecular polymer, and is a material that the conductive high molecular polymer is coated on the surface of the metal alloy; the mixture ratio of the metal AB3 alloy is La 0.7 Mg 0.3-x Ti x Ni y Co 3.5-y, wherein, x is equal to 0-0.15, and y is equal to 2.0-3.5; and the mass mixture ratio of the metal alloy and the conductive high molecular polymer is 100:1-4. The composite material can be prepared according to the following steps: 1) an organic monomer with conductivity is evoked by acid conditions and oxidant to polymerize to obtain the conductive high molecular polymer; 2) the metal alloy is prepared through a high-temperature smelting furnace, and then undergoes ball milling with the conductive high molecular polymer to obtain the even composite material. The preparation method has simple process and low cost, and can effectively improve the stability of charge/discharge circulation of alloy electrodes by compounding the conductive high molecular polymer and the metal alloy, thereby providing effective protection for alloy electrodes. The material is suitable for applications such as the protection of electrode materials, fuel batteries and so on.
Description
Technical field
The present invention relates to the alloy composite materials that uses for nickel-hydrogen battery, specifically a kind of use for nickel-hydrogen battery conducting high polymers thing/alloy composite materials and preparation thereof will have the conducting high polymers thing that improves the electrode cyclical stability and the advanced composite material that is used for nickel metal hydride battery of the compound preparation of metal alloy.
Background technology
Metal alloy is a kind of as electrode materials, has a wide range of applications in fuel cell field.The typically used of this material is on nickel metal hydride battery, reaction on the positive and negative electrode of nickel metal hydride battery belongs to solid transformation mechanism, electrode materials itself does not relate to any dissolving and deposition process, and metal hydride cell only has hydrogen atom to participate in transmitting and electrochemical reaction, cause the battery cathode utilization ratio higher, be fit to very much do the negative pole of nickel metal hydride battery.But nickel metal hydride battery is for the maximum discharge capacity of alloy electrode, and charge and discharge cycles stability all has certain requirement, improves the charge-discharge performance of alloy electrode, is one of research purpose of alloy electrode material; In addition, alloy electrode alloy pulverization and the phenomenon that is corroded occur easily in charge and discharge cycles process repeatedly, thereby influences the performance of alloy electrode, and this also is the research purpose of alloy electrode material.
The AB that past is commonly used
3Alloy electrode is though loading capacity is than the AB of suitability for industrialized production
5The alloy electrode loading capacity is big, but but is subjected to the restriction of cyclical stability difference, can't replace AB veritably
5Alloy electrode, and be used for large-scale industrial production.
The conducting high polymers thing is widely used in the modification of nano material because light weight has certain electroconductibility.It is reported, modify certain conducting high polymers thing on the nano material after, the conducting high polymers thing can by with the key of nanoparticle and, strengthen the performances such as photoelectricity, magnetics of nanoparticle itself, and nanoparticle played the certain protection effect.1991, people such as Uemura coated LaNi by the research polystyrene
5Hydrogen storage alloy finds, polystyrene has and reduces to inhale the effect of putting hydrogen process interalloy efflorescence degree.This point has very important meaning and value to polymkeric substance at aspects such as alloy material hydrogen storage property and chemical properties.Tinge is by discovering LmNi
4Small-particle can be distributed in the polyethylene under 160 ℃, and in the suction hydrogen process of matrix material, the diffusion of hydrogen in polymkeric substance is the controlled step of inhaling the hydrogen process.Schmidt has carried out theoretical analysis to the matrix material of polymkeric substance/alloy.Think that polymkeric substance role in the alloy hydrogen absorption and desorption process is because polymkeric substance can be connected to alloy hydride by hydrogen bond, Fan Dehuali, thereby influence the process of alloy hydrogen absorption and desorption.This guide of theory is that next step development of polymkeric substance/alloy composite materials has provided theoretical foundation.In all conductive polymerss, polyaniline has many uniquenesses, good characteristics, such as: environmental stability; Preparation easily; Cheap etc.People such as Reddy are by arriving AB with Polyaniline Doped
2In the alloy, analyzed polyaniline to the absorption hydrogen effect of kinetics.The adding of discovering a small amount of polyaniline just can improve Zr base AB
2The dynamic (dynamical) performance of absorption hydrogen.
The charge and discharge cycles stability of electrode is the leading indicator of battery electrode performance, and under the identical loading capacity, charge and discharge cycles stability is high more, and electrode performance is good more.
Summary of the invention
The object of the present invention is to provide a kind of use for nickel-hydrogen battery conducting high polymers thing/alloy composite materials and preparation thereof, carry out conducting high polymers thing and metal alloy compound, make electrode with the material after compound, this electrode has charge and discharge cycles stability preferably in nickel metal hydride battery.Utilize conducting polymer that alloy is carried out the surface and coat, preparation technology is simple, and cost is low, is applicable to the application of aspects such as the protection of electrode materials and phase-changing energy storage material.
For achieving the above object, the technical solution adopted in the present invention is:
A kind of conducting high polymers thing/alloy composite materials that uses for nickel-hydrogen battery, it is by metal A B
3Alloy and conducting high polymers thing are composited, and matrix material is the material of conducting high polymers thing clad metal alloy surface; AB
3The proportioning of alloy is La
0.7Mg
(0.3-x)Ti
xNi
yCo
3.5-y, x=0～0.15, y=2～3.5; The quality proportioning of metal alloy and conducting high polymers thing is 100: 1～4.
Described conducting high polymers thing is generally polyaniline, polypyrrole or Polythiophene.
It can prepare as follows:
1) organic monomer (as aniline etc.) polymerization under acidic conditions, oxygenant cause that will have electroconductibility obtains the conducting high polymers thing; Detailed process is that organic monomer is through 2-4 distillation, organic monomer and H
+The mole proportioning be 1～1.5: 1; The mole proportioning of organic monomer and oxygenant is 1: 1-1.5; Stirring at room, reaction 8～12h filters through methyl alcohol, water washing, 60～80 ℃ of baking 12～24h; Described organic monomer is aniline, pyrroles or thiophene; Obtain polyaniline, polypyrrole or Polythiophene conducting high polymers thing (as: wherein polyaniline is the emeraldine salt form of conduction); Acid can be hydrochloric acid or sulfuric acid, and oxygenant can be ammonium persulphate or Anhydrous Ferric Chloride.
2) with metal alloy (as AB
3Deng) by after the high temperature melting furnace preparation,, obtain uniform matrix material with conducting high polymers thing ball milling 0.5-5h in ball mill.AB
3The proportioning of alloy is La
0.7Mg
(0.3-x)Ti
xNi
yCo
3.5-y, x=0～0.15, y=2～3.5; The quality proportioning of metal alloy and conducting high polymers thing is 100: 1～4, described conducting high polymers thing polyaniline, polypyrrole or Polythiophene.Matrix material is the material of conducting high polymers thing clad metal alloy surface.
Be specially: metal A B
3Alloy prepares by high temperature melting furnace, AB
3Under argon shield, melt back is 3～5 times in the high temperature melting furnace by the mole proportioning for alloy; AB
3After crossing the 100-300 mesh sieve, AB
3With the quality proportioning of polyaniline be 100: 1～4; Ratio of grinding media to material 15-20: 1, drum's speed of rotation is 200-300 rev/min, under argon shield, reaction times 1～2h.
Described matrix material is used for the charge-discharge performance test to NiH electrode,
Described matrix material is made electrode, and carry out electro-chemical test, the electro-chemical test of described high molecular polymer/metal alloy matrix material carries out in LAND system (the LAND system is that Wuhan Jin Nuo Electronics Co., Ltd. produces), and specific operation process is
1) electrode is done conductive agent with the Ni powder, and Ni band is made lead, and the matrix material that makes with after the Ni powder mixes, is made electrode; The mass ratio of described matrix material and Ni powder is 1: 3, and the mixture of matrix material and Ni powder depresses to tinsel at 30MPa, and tinsel is pressed in the centre of two nickel foam, links to each other with battery clamp by the Ni band, can make electrode;
The reference electrode of battery is the Hg/HgO electrode; Ni (OH) just very
2/ NiOOH; Negative pole is prepared electrode.Electrolytic solution is the 6M potassium hydroxide aqueous solution; Electrode charge and discharge is set to, and constant current charge 300mA/g fills 3h, and constant-current discharge 100mA/g is discharged to voltage less than 0.6V.
2) electrode of preparation is made negative pole, in the LAND system, carry out the charge-discharge performance test; Electrode and pure metal alloy electrode ratio, discharge capacitance (C that described metal alloy is made after compound with the conducting high polymers thing
50/ C
Max) bring up to 66.3% by 57.7%.
The present invention has following advantage:
1. improved the charge and discharge cycles stability of alloy electrode effectively.The conducting high polymers thing is coated to the surface of metal alloy through ball milling method, in the charge and discharge cycles process of electrode, the efflorescence degree that has stoped alloying pellet effectively, increased the passive film of alloy surface, stop the further oxidation of alloy to a great extent, thereby improved the charge and discharge cycles stability of alloy electrode.
2. technological process is simple.The present invention utilizes planetary ball mill, conducting high polymers thing and metal alloy is compound to together simple, the easy row of method; Conducting high polymers thing synthetic method is also fairly simple, and room temperature can prepare, and the conducting high polymers thing that is adopted has extraordinary environmental stability, at room temperature, preserves in the air and gets final product.
3. cost of material is cheap.The various raw materials that prepare this conducting high polymers thing are inorganic raw material except that organic monomer, cheap, be easy to get; And can obtain the effect that metal alloy electrodes charge and discharge cycles stability improves a lot with the amount of less conducting high polymers thing, meet industrial production requirement.
The applicant first prelibation by with conducting high polymers thing and the compound chemical property that improves metal alloy electrodes of metal alloy.In all conducting high polymers things, the polyaniline that the applicant selects for use has many uniquenesses, good characteristics, such as: environmental stability, preparation easily, cheap etc.When the polyaniline that adds 3wt% to AB
3In the time of in the alloy, the stability that charge and discharge cycles is 20 times is than simple AB
3Alloy electrode is high by 7%.The stability that charge and discharge cycles is 50 times is than simple AB
3Alloy electrode is high by 8.6%.
Preparation technology of the present invention is simple, cost is low, by with conducting high polymers thing and the compound charge and discharge cycles stability that can improve alloy electrode effectively of metal alloy, thereby provides a kind of effective protection for alloy electrode.This material is applicable to the application of aspects such as the protection of electrode materials and fuel cell.
Description of drawings
Fig. 1 is the AB of specific embodiments of the invention 1
3The charge and discharge cycles curve of/PANI composite electrode;
Fig. 2 is the AB of specific embodiments of the invention 1
3The electrochemical impedance spectroscopy of/PANI composite electrode (the fifth cycle 50%DOD);
Embodiment
Embodiment 1
The aniline monomer of getting behind the 0.5ml second distillation is dissolved in the 10mL deionized water, the hydrochloric acid 2.6mL that adds 2mol/L again, after stirring about 30min, drip the aqueous solution (the 2.56g ammonium persulphate is dissolved in the 11mL water) of ammonium persulphate, the mean droplet acceleration is 20drop/min, after all dripping, restir reaction 12h, (polyaniline removes unreacted aniline monomer through methanol wash to the product that obtains after methyl alcohol, water washing are filtered, polyaniline has better electric conductivity), in 60 ℃ of vacuum drying ovens, cure 24h, standby.
AB
3Alloy is according to La
0.7Mg
(0.3-x)Ti
xNi
yCo
3.5-yThe proportioning of (x=0.02～0.06, y=2.9～3.2) is put into high temperature melting furnace with each metal, logical argon shield, and the intensification melting 3 times repeatedly, obtains the uniform AB of melting
3Alloy is with AB
3Alloy block smashes, and grinds, and crosses 300 mesh sieves, and is standby.
Get the AB that 1g crosses 300 mesh sieves
3Alloy mixes the 0.03g polyaniline, puts into agate jar, adds the about 16.5g of agate ball, and agate jar fills the argon gas of 1.5MPa, on planetary ball mill with the rotating speed ball milling 1h of 200rpm.Can obtain AB
3/ PANI matrix material.
With the AB that makes
3/ PANI matrix material is got 0.1g, mixes with the 0.3g nickel powder, depresses to disk about 1cm at 30MPa, presses two nickel foam on the disk two sides, and the edge of nickel foam carries out spot welding to be handled, and on edge joint weld a nickel strap, can do the negative pole of battery.
On the LAND battery test system that Jin Nuo Electronics Co., Ltd. in Wuhan produces, carry out the test of electrode charge and discharge performance, the reference electrode of described battery is the Hg/HgO electrode; Ni (OH) just very
2/ NiOOH; Negative pole is prepared electrode slice.Electrolytic solution is the 6M potassium hydroxide aqueous solution; Electrode charge and discharge is set to, and constant current charge 300mA/g fills 3h, and constant-current discharge 100mA/g is discharged to voltage less than 0.6V.By real-time monitoring of computer and automatic the collection and the record experimental data.
Table 1 is the AB of specific embodiments of the invention 1
3The chemical property of/PANI composite electrode (comprising maximum discharge capacity and discharge capacitance).
Table 1 AB
3The chemical property of/PANI composite electrode
| Sample | Maximum discharge capacity (mAhg -1) | Discharge capacitance C 20/C max(％) | Discharge capacitance C 50/C max(％) |
| AB 3 | 364.8 | 76.7 | 57.7 |
| AB 3-ball milled | 357.9 | 78.4 | 58.1 |
| AB 3/PANI(1 wt％) | 359.3 | 80.7 | 59.0 |
| AB 3/PANI(2 wt％) | 351.6 | 81.6 | 61.4 |
| AB 3/PANI(3 wt％) | 355.4 | 83.7 | 66.3 |
| AB 3/PANI(4 wt％) | 350.3 | 81.4 | 58.9 |
The electrochemical impedance match value of table 2 composite electrode
| Sample | Electrochemical impedance R ct(mΩ) |
| AB 3 | 93.47 |
| AB 3-ball milled | 144 |
| AB 3/PANI(1wt％) | 170.5 |
| AB 3/PANI(2wt％) | 187.4 |
| AB 3/PANI(3wt％) | 220.1 |
| Sample | Electrochemical impedance R ct(mΩ) |
| AB 3/PANI(4wt％) | 195.8 |
Difference from Example 1 is: the preparation of polypyrrole is to get 1mL through 4 distillatory pyrrole monomers, is injected in the acidic aqueous solution of ammonium persulphate of 100mL (wherein ammonium persulphate is 3.12g).12h is under agitation carried out in reaction, and the product that obtains cures 24h in 60 ℃ of vacuum drying ovens after methyl alcohol, water washing are filtered (polypyrrole removes unreacted aniline monomer through methanol wash, and polyaniline has better electric conductivity), standby.
AB
3Gold is according to La
0.7Mg
(0.3-x)Ti
xNi
yCo
3.5-yThe proportioning of (x=0～0.02, y=3.3～3.5), the melting preparation condition is identical with embodiment 1.With AB
3Alloy block smashes, and grinds, and crosses the 200-300 mesh sieve, gets intermediate product, and is standby.
Get the AB that 1g crosses the 200-300 mesh sieve
3Alloy mixes the polypyrrole of 0.01g, puts into agate jar, adds the about 20.2g of agate ball, and agate jar fills the argon gas of 1.5MPa, on planetary ball mill with the rotating speed ball milling 2h of 300rpm.Can obtain AB
3/ PPy matrix material.
Claims (4)
1. conducting high polymers thing/alloy composite materials that uses for nickel-hydrogen battery, it is characterized in that: it is by metal A B
3Alloy and conducting high polymers thing are composited, and matrix material is the material of conducting high polymers thing clad metal alloy surface; AB
3The proportioning of alloy is La
0.7Mg
(0.3-x)Ti
xNi
yCo
3.5-y, x=0～0.15, y=2.0～3.5; The quality proportioning of metal alloy and conducting high polymers thing is 100: 1～4; Wherein, described conducting high polymers thing is polyaniline, polypyrrole or Polythiophene.
2. the preparation of the described matrix material of claim 1 is characterized in that: with metal A B
3Alloy and conducting high polymers thing ball milling 0.5-5h in ball mill obtains uniform matrix material; AB
3The proportioning of alloy is La
0.7Mg
(0.3-x)Ti
xNi
yCo
3.5-y, x=0～0.15, y=2.0～3.5; The quality proportioning of metal alloy and conducting high polymers thing is 100: 1～4, and described conducting high polymers thing is polyaniline, polypyrrole or Polythiophene.
3. according to the preparation of the described matrix material of claim 2, it is characterized in that: described conducting high polymers thing obtains organic monomer polymerization under acidic conditions, oxygenant cause, and detailed process is that organic monomer is through 2-4 distillation, organic monomer and H
+The mole proportioning be 1～1.5: 1; The mole proportioning of organic monomer and oxygenant is 1: 1～1.5; Stirring at room, reaction 8～12h filters through methyl alcohol, water washing, 60～80 ℃ of baking 12～24h; Described organic monomer is aniline, pyrroles or thiophene; Obtain polyaniline, polypyrrole or Polythiophene conducting high polymers thing, acid is hydrochloric acid or sulfuric acid, and oxygenant is ammonium persulphate or Anhydrous Ferric Chloride.
4. according to the preparation of the described matrix material of claim 2, it is characterized in that: described metal A B
3Alloy prepares by high temperature melting furnace, is specially AB
3Under argon shield, melt back is 3～5 times in the high temperature melting furnace by the mole proportioning for alloy; AB
3After crossing 100～300 mesh sieves, AB
3With the quality proportioning of polymkeric substance be 100: 1～4; Ratio of grinding media to material 15-20: 1, drum's speed of rotation is 200-300 rev/min, under argon shield, reaction times 1～2h.
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107293752A (en) * | 2017-06-20 | 2017-10-24 | 燕山大学 | A kind of plating polyaniline that evaporates improves the method for negative plate of nickel-hydrogen battery chemical property |
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|---|---|---|---|---|
| CN101728527B (en) * | 2009-12-01 | 2013-04-17 | 燕山大学 | Method for improving electrochemical properties of hydrogen storage alloy powder by using polyaniline |
| CN102810665A (en) * | 2012-07-30 | 2012-12-05 | 燕山大学 | Method for improving electrochemical performance of hydrogen storing alloy by using polypyrrole |
| CN104923776A (en) * | 2015-05-17 | 2015-09-23 | 桂林理工大学 | Method for surface modification of AB3 hydrogen storage alloy by using aniline |
| CN108424645A (en) * | 2018-04-04 | 2018-08-21 | 温州市赢创新材料技术有限公司 | A kind of fire prevention battery conductive material and preparation method thereof |
| CN109037658A (en) * | 2018-08-31 | 2018-12-18 | 重庆工商大学 | A kind of lithium iron phosphate positive material preparation method of polymer overmold |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1271025A (en) * | 2000-05-31 | 2000-10-25 | 南开大学 | Magnesium-base hydrogen storing alloy material |
| CN1554797A (en) * | 2003-12-21 | 2004-12-15 | 浙江大学 | Non crystal state hydrogen storage composite materal and its producing method |
| CN1554796A (en) * | 2003-12-21 | 2004-12-15 | 浙江大学 | Non crystal state hydrogen storge composite material and its producing method |
| CN1644737A (en) * | 2005-01-20 | 2005-07-27 | 南开大学 | Magnesium based hydrogen storing alloy composite material and production thereof |
-
2007
- 2007-04-20 CN CN2007100110497A patent/CN101289576B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1271025A (en) * | 2000-05-31 | 2000-10-25 | 南开大学 | Magnesium-base hydrogen storing alloy material |
| CN1554797A (en) * | 2003-12-21 | 2004-12-15 | 浙江大学 | Non crystal state hydrogen storage composite materal and its producing method |
| CN1554796A (en) * | 2003-12-21 | 2004-12-15 | 浙江大学 | Non crystal state hydrogen storge composite material and its producing method |
| CN1644737A (en) * | 2005-01-20 | 2005-07-27 | 南开大学 | Magnesium based hydrogen storing alloy composite material and production thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107293752A (en) * | 2017-06-20 | 2017-10-24 | 燕山大学 | A kind of plating polyaniline that evaporates improves the method for negative plate of nickel-hydrogen battery chemical property |
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