CN107838419A - One kind is modified AB using bis-Schiff base surface3The method of type hydrogen storage alloy - Google Patents

One kind is modified AB using bis-Schiff base surface3The method of type hydrogen storage alloy Download PDF

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Publication number
CN107838419A
CN107838419A CN201711255100.9A CN201711255100A CN107838419A CN 107838419 A CN107838419 A CN 107838419A CN 201711255100 A CN201711255100 A CN 201711255100A CN 107838419 A CN107838419 A CN 107838419A
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alloy
bis
schiff base
phenylenediamine
type
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CN201711255100.9A
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黄红霞
王成
肖阳
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Guilin University of Technology
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Guilin University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/145—Chemical treatment, e.g. passivation or decarburisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/383—Hydrogen absorbing alloys
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses one kind AB is modified using the bromosalicylaldehyde contracting p-phenylenediamine of bis-Schiff base 53The method of type hydrogen storage alloy.Vacuum induction melting method prepares AB3Type La0.94Mg0.06Ni3.49Co0.73Mn0.12Al0.20Alloy, after alloy pig crushes, with 300 revs/min of ball milling 60min of rotating speed, screen out the alloy powder of 300 mesh.It is as follows to prepare bis-Schiff base process：2.5mmol p-phenylenediamine is taken, after being dissolved in 15mL absolute ethyl alcohols, is added in reaction bulb, is placed in 50 DEG C of water-baths.The solution that the bromosalicylaldehydes of 5mmol 5 are dissolved in 30mL absolute ethyl alcohols, drop Bi Fanying 3.5h is slowly added dropwise.With washes of absolute alcohol product, by product low temperature drying.Alloy is 95%~99%, and bis-Schiff base is 1%~5%, sum of the two 100%, by both uniformly mixing, the hydrogen bearing alloy of the obtained bromosalicylaldehyde contracting p-phenylenediamine of bis-Schiff base 5 modification.Using the bis-Schiff base with resistance to corrosion to AB3Type alloy carries out surface modification, and electrode maximum discharge capacity and discharge stability increase.The inventive method process conditions are simple, and low energy consumption, production equipment is simple, beneficial to industrialized production.

Description

One kind is modified AB using bis-Schiff base surface3The method of type hydrogen storage alloy
Technical field
It is more particularly to a kind of to utilize bis-Schiff base 5- bromine water poplars the invention belongs to materials chemistry and electrochemical research field Aldehyde contracting p-phenylenediamine is to AB3Type hydrogen storage alloy La0.94Mg0.06Ni3.49Co0.73Mn0.12Al0.20The method for carrying out surface modification.
Background technology
Ni-mh (Ni-MH) battery is considered to have high-power output, high rate capability, long lifespan, good reliability, nothing Poison, memory-less effect, the preferable clean energy resource of low cost and other advantages.In the research process of Ni-MH battery, novel anode material Always focus of attention.Compared to traditional hydrogen bearing alloy, La-Mg-Ni bases AB3The hydrogen bearing alloy of type is as the negative of Ni-MH battery During electrode, because with perfect activity function and excellent discharge capacity so as to more competitive.But La-Mg-Ni bases AB3Type Hydrogen bearing alloy in element M g easily corrode in strong alkaline electrolytes, generate MgO and Mg (OH)2, directly result in and consume The active material of electrode, and accelerate the efflorescence of alloy to aoxidize.Alkali process is the effective of improvement hydrogen-bearing alloy electrode chemical property Method.Alkali process refers generally to alloyed powder being positioned in alkaline solution, changes alloy surface composition, forms rich nickel dam, so that Alloy can be with the discharge capacity of fast activating and raising alloy electrode.Present invention addition bis-Schiff base 5- bromosalicylaldehyde contractings are to benzene Diamines is to La-Mg-Ni bases AB3Type alloy carries out surface and is modified to make it have more preferable corrosion resistance and more excellent in Ni-MH battery Good chemical property, it is a kind of new effective method.
The content of the invention
It is modified it is an object of the invention to provide one kind using bis-Schiff base 5- bromosalicylaldehyde contracting p-phenylenediamine surface La0.94Mg0.06Ni3.49Co0.73Mn0.12Al0.20The method of hydrogen bearing alloy.
The thinking of the present invention：By the use of bis-Schiff base 5- bromosalicylaldehyde contracting p-phenylenediamine as modifying agent, with AB3Type alloy La0.94Mg0.06Ni3.49Co0.73Mn0.12Al0.20Modified alloy is prepared by the method for addition, to improve the corrosion resistance of electrode And chemical property.
Concretely comprise the following steps：
(1) AB is prepared by vacuum induction melting method3Type La0.94Mg0.06Ni3.49Co0.73Mn0.12Al0.20Precursor alloy, close After ingot mechanical crushing, with 300 revs/min of rotating speed ball milling 60 minutes, 300 purposes are screened out La0.94Mg0.06Ni3.49Co0.73Mn0.12Al0.20Alloy powder.
(2) 2.5mmol p-phenylenediamine is taken, after being dissolved in 15mL absolute ethyl alcohols, is added in three-necked flask, is placed in 50 DEG C of water-baths In pot.5mmol 5- bromosalicylaldehydes are taken, 30mL absolute ethyl alcohols is dissolved in, is then slowly dropped in three-necked flask, after a few minutes i.e. There is faint yellow floccule, react 3.5h.With washes of absolute alcohol product, finally by product low temperature drying to constant weight, it is made double Schiff bases 5- bromosalicylaldehyde contracting p-phenylenediamine.
(3) by La made from step (1)0.94Mg0.06Ni3.49Co0.73Mn0.12Al0.20Alloying pellet powder 95%~99% With step (2) made from bis-Schiff base 5- bromosalicylaldehyde contractings p-phenylenediamine 1%~5%, sum of the two be 100% mass ratio Uniformly mixed, the AB that bis-Schiff base 5- bromosalicylaldehyde contracting p-phenylenediamine surface is modified is made3Type hydrogen storage alloy electrode.
The inventive method process conditions are simple, and low energy consumption, production equipment is simple, beneficial to industrialized production, because schiff bases have Certain resistance to corrosion, using bis-Schiff base 5- bromosalicylaldehyde contracting p-phenylenediamine to AB3Type La0.94Mg0.06Ni3.49Co0.73Mn0.12Al0.20Alloy carries out surface modification, and maximum discharge capacity and discharge stability have carried High hydrogen-bearing alloy electrode.
Embodiment
Embodiment 1：
(1) AB is prepared by vacuum induction melting method3Type La0.94Mg0.06Ni3.49Co0.73Mn0.12Al0.20Precursor alloy, close After ingot mechanical crushing, with 300 revs/min of rotating speed ball milling 60 minutes, 300 purposes are screened out La0.94Mg0.06Ni3.49Co0.73Mn0.12Al0.20Alloying pellet powder.
(2) 2.5mmol p-phenylenediamine is taken, after being dissolved in 15mL absolute ethyl alcohols, is added in three-necked flask, is placed in 50 DEG C of water-baths In pot.5mmol 5- bromosalicylaldehydes are taken, 30mL absolute ethyl alcohols is dissolved in, is then slowly dropped in three-necked flask, after a few minutes i.e. There is faint yellow floccule, react 3.5h.With washes of absolute alcohol product, finally by product low temperature drying to constant weight, it is made double Schiff bases 5- bromosalicylaldehyde contracting p-phenylenediamine.
(3) by La made from step (1)0.94Mg0.06Ni3.49Co0.73Mn0.12Al0.20Alloying pellet powder is made with step (2) The bis-Schiff base 5- bromosalicylaldehyde contracting p-phenylenediamine obtained is with 99%：1% mass ratio is uniformly mixed, that is, double Schiffs are made Modified AB3Type hydrogen storage alloy.
Embodiment 2：
(1) AB is prepared by vacuum induction melting method3Type La0.94Mg0.06Ni3.49Co0.73Mn0.12Al0.20Precursor alloy, close After ingot mechanical crushing, with 300 revs/min of rotating speed ball milling 60 minutes, 300 purposes are screened out La0.94Mg0.06Ni3.49Co0.73Mn0.12Al0.20Alloying pellet powder.
(2) 2.5mmol p-phenylenediamine is taken, after being dissolved in 15mL absolute ethyl alcohols, is added in three-necked flask, is placed in 50 DEG C of water-baths In pot.5mmol 5- bromosalicylaldehydes are taken, 30mL absolute ethyl alcohols is dissolved in, is then slowly dropped in three-necked flask, after a few minutes i.e. There is faint yellow floccule, react 3.5h.With washes of absolute alcohol product, finally by product low temperature drying to constant weight, it is made double Schiff bases 5- bromosalicylaldehyde contracting p-phenylenediamine.
(3) by La made from step (1)0.94Mg0.06Ni3.49Co0.73Mn0.12Al0.20Alloying pellet powder is made with step (2) The bis-Schiff base obtained is with 97%：3% mass ratio is uniformly mixed, that is, the AB that bis-Schiff base is modified is made3Type hydrogen storage is closed Gold.
Embodiment 3：
(1) AB is prepared by vacuum induction melting method3Type La0.94Mg0.06Ni3.49Co0.73Mn0.12Al0.20Precursor alloy, close After ingot mechanical crushing, with 300 revs/min of rotating speed ball milling 60 minutes, 300 purposes are screened out La0.94Mg0.06Ni3.49Co0.73Mn0.12Al0.20Alloying pellet powder.
(2) 2.5mmol p-phenylenediamine is taken, after being dissolved in 15mL absolute ethyl alcohols, is added in three-necked flask, is placed in 50 DEG C of water-baths In pot.5mmol 5- bromosalicylaldehydes are taken, 30mL absolute ethyl alcohols is dissolved in, is then slowly dropped in three-necked flask, after a few minutes i.e. There is faint yellow floccule, react 3.5h.With washes of absolute alcohol product, finally by product low temperature drying to constant weight, it is made double Schiff bases 5- bromosalicylaldehyde contracting p-phenylenediamine.
(3) by bis-Schiff base made from alloying pellet powder made from step (1) and step (2) with 95%：5% quality Ratio is uniformly mixed, that is, the AB that bis-Schiff base 5- bromosalicylaldehyde contracting p-phenylenediamine surface is modified is made3Type hydrogen storage alloy.
It is real above respectively using X-ray diffractometer, LAND5.3B battery test systems and CHI660E electrochemical workstations Alloy made from example is applied to be tested, it is as a result as follows：
1) before and after adding bis-Schiff base, alloy is by LaNi5、La2Ni7Two kinds of phase structures composition, peak position also basic phase Together, illustrate that 5- bromosalicylaldehyde contracting p-phenylenediamine bis-Schiff bases can not change the phase structure of alloy, be only attached to the surface of alloy.
2) after adding bis-Schiff base, the maximum discharge capacity of electrode brings up to 370mAh/g (1% pair of Schiff from 346mAh/g Alkali), discharge capacitance brings up to 80% (5% bis-Schiff base) from 70%.
3) after the bis-Schiff base for adding different quality containing, exchange current density brings up to 154mA/ from 122mA/g respectively G, 165mA/g and 189mA/g.The limiting current density value of electrode increased, wherein adding 5% bis-Schiff base electrode from original The 892mA/g of beginning increases 1412mA/g.The corrosion potential of three alloy electrodes also adds, and shows the anti-of alloy electrode Corrosive power also increases.
4) after with the addition of bis-Schiff base, the electrochemical impedance of electrode surface is obviously reduced, wherein adding the electricity of 1% schiff bases Pole surface impedance is minimum.
The present invention is in hydrogen bearing alloy La0.94Mg0.06Ni3.49Co0.73Mn0.12Al0.20It is middle addition mass fraction be 1%, 3%, 5% 5- bromosalicylaldehyde contracting p-phenylenediamine bis-Schiff bases, investigate the electric property of the electrode of bis-Schiff base containing different proportion.Before processing The phase structure of alloy does not change afterwards.Because schiff bases have certain resistance to corrosion, the electrode maximum for adding schiff bases is put Capacitance is respectively increased to 370mAh/g, 361mAh/g, 365mAh/g from 346mAh/g, and the discharge capacity after 50 circulations is kept Rate is respectively increased to 78%, 78%, 80% from original 70%.Meanwhile the dynamic performance of electrode also makes moderate progress.

Claims (1)

1. one kind is modified AB using bis-Schiff base 5- bromosalicylaldehyde contracting p-phenylenediamine surface3The method of type hydrogen storage alloy, its feature exist In concretely comprising the following steps：
(1) AB is prepared by vacuum induction melting method3Type La0.94Mg0.06Ni3.49Co0.73Mn0.12Al0.20Precursor alloy, alloy pig After mechanical crushing, with 300 revs/min of rotating speed ball milling 60 minutes, 300 purposes are screened out La0.94Mg0.06Ni3.49Co0.73Mn0.12Al0.20Alloy powder.
(2) 2.5mmol p-phenylenediamine is taken, after being dissolved in 15mL absolute ethyl alcohols, is added in three-necked flask, is placed in 50 DEG C of water-baths In.5mmol 5- bromosalicylaldehydes are taken, 30mL absolute ethyl alcohols is dissolved in, is then slowly dropped in three-necked flask, are after a few minutes Existing faint yellow floccule, reacts 3.5h.With washes of absolute alcohol product, finally by product low temperature drying to constant weight, it is made double uncommon Husband's alkali 5- bromosalicylaldehyde contracting p-phenylenediamine.
(3) by La made from step (1)0.94Mg0.06Ni3.49Co0.73Mn0.12Al0.20Alloying pellet powder 95%~99% and step Suddenly bis-Schiff base 5- bromosalicylaldehyde contractings p-phenylenediamine 1%~5% made from (2), the mass ratio that sum of the two is 100% are carried out Uniformly mixing, the AB that bis-Schiff base 5- bromosalicylaldehyde contracting p-phenylenediamine surface is modified is made3Type hydrogen storage alloy electrode.
CN201711255100.9A 2017-12-02 2017-12-02 One kind is modified AB using bis-Schiff base surface3The method of type hydrogen storage alloy Withdrawn CN107838419A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108456794A (en) * 2018-03-31 2018-08-28 桂林理工大学 It is a kind of to be modified AB using polypyrrole3The method of type hydrogen storage alloy
CN108539155A (en) * 2018-03-31 2018-09-14 桂林理工大学 It is a kind of to be modified AB using polyparaphenylene3The method of type hydrogen storage alloy

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JPH10172552A (en) * 1996-12-06 1998-06-26 Sanyo Electric Co Ltd Hydrogen storage alloy powder and its manufacture
CN102990082A (en) * 2012-12-17 2013-03-27 桂林理工大学 Method for preparing fluorescence nano gold sol by using PVP (Poly Vinyl Pyrrolidone) through reduction modification under hydrothermal condition
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CN107159879A (en) * 2017-05-24 2017-09-15 桂林理工大学 One kind is modified AB using bis-Schiff base surface3The method of type hydrogen storage alloy

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108456794A (en) * 2018-03-31 2018-08-28 桂林理工大学 It is a kind of to be modified AB using polypyrrole3The method of type hydrogen storage alloy
CN108539155A (en) * 2018-03-31 2018-09-14 桂林理工大学 It is a kind of to be modified AB using polyparaphenylene3The method of type hydrogen storage alloy

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