CN103647053B - The method of alumina coating is prepared on a kind of nickel electrode surface - Google Patents
The method of alumina coating is prepared on a kind of nickel electrode surface Download PDFInfo
- Publication number
- CN103647053B CN103647053B CN201310687991.0A CN201310687991A CN103647053B CN 103647053 B CN103647053 B CN 103647053B CN 201310687991 A CN201310687991 A CN 201310687991A CN 103647053 B CN103647053 B CN 103647053B
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- nickel electrode
- alumina coating
- electrode surface
- nickel
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- 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
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/26—Processes of manufacture
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
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- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/045—Electrochemical coating; Electrochemical impregnation
- H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
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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
Abstract
The invention discloses the method that alumina coating is prepared on a kind of nickel electrode surface, utilize heat-treating methods at nickel electrode Surface Creation pre-made film, and the special micelle particle that aluminum nitrate is formed in alcohol has stronger absorption property, the surface of pre-made film can be adsorbed on, thus form complete barrier layer on nickel electrode surface.The present invention adopts pre-made film and cathode micro arc to be oxidized the method combined, nickel electrode with pre-made film is placed in alcoholic solution based on aluminum nitrate as negative electrode, by the technological means process of differential arc oxidation, finally form alchlor rete on nickel electrode surface.Alumina coating prepared by the present invention and nickel electrode matrix have very high bond strength and excellent corrosion resistance, alleviate that active material causes because the corrosion of nickel electrode is expanded loose, the problem such as come off, extend the useful life of battery, reduce its production cost, thus to the popularization of Ni-MH battery, there is good positive role.
Description
Technical field
The invention belongs to the conservation treatment technical field of Ni-MH battery nickel electrode, more specifically say, relate to the method that alchlor is prepared on a kind of nickel electrode surface.
Background technology
Ni-MH battery (NIMH) is one of the most widely used environmental protection battery in modern electronic product, the advantages such as it has, and specific energy density is high, monomer capacity is large, flash-over characteristic steady, highly versatile.But compared to nickel-cadmium cell, the price of the battery of ni-mh is much high again, thus how to reduce the loss of Ni-MH battery, extends its useful life, for the meaning that the popularization tool of Ni-MH battery is very real.
Ni-MH battery in use performance can decay gradually, and causes the reason of battery failure numerous.In actual applications, the corrosion of the nickel electrode of Ni-MH battery is expanded is a kind of more common reason causing Ni-MH battery to lose efficacy.
Inside due to Ni-MH battery is an alkaline environment, Ni-MH battery is in charge and discharge process, there is the change of a series of Chemical Physics in surface reactive material, corrosive liquid penetrates into metallic nickel electrode surface, causes the corrosion of nickel electrode and expands, causing surface reactive material pulverulent bulk, come off or contact bad, internal resistance is raised, battery capacity declines, and the capacitance loss of battery and the shortening of battery life, finally make the inefficacy that battery is too early.
Summary of the invention
The object of the invention is to overcome in the Ni-MH battery of prior art because nickel electrode is corroded the caused loss of battery capacity and the situation of the lost of life, a kind of nickel electrode surface is provided to prepare the method for alumina coating, to strengthen the resistance to corrosion of nickel electrode in Ni-MH battery electrolyte, prevent coming off of surface reactive material, thus extend the useful life of Ni-MH battery.
For realizing above object, the method for alumina coating is prepared on nickel electrode surface of the present invention, it is characterized in that, comprises the following steps:
(1), acetone ultrasonic cleaning 3min ~ 10min is put into by after the oxide layer on nickel electrode sand papering removing surface;
(2), by the nickel electrode after step (1) process, the environment being placed in 200 DEG C ~ 600 DEG C in atmospheric environment heats 3h ~ 9h, generates pre-made film;
(3), by aluminum nitrate concentration, to be 10g/L ~ 30g/L and additive concentration be that 0.5g/L ~ 10g/L is dissolved in alcohol configures electrolyte;
(4), the nickel electrode after step (2) process is put into the stainless steel trough body that step (3) preparation electrolyte is housed, negative electrode, stainless steel trough body is done for anode with metallic nickel, pulse mao power source is adopted to power, carry out differential arc oxidation process, alumina coating can be prepared on nickel electrode surface.
Wherein, additive described in step (3) is a kind of or wherein several combination in cerous nitrate, yttrium nitrate, erbium nitrate.
The object of the present invention is achieved like this:
Differential arc oxidization technique is a kind of technology at valve metal and alloy surface growth in situ ceramic coating thereof.In micro-arc oxidation process, the valve metal samples such as Al, Mg, Ti are put into electrolyte, after energising, very thin one deck barrier layer can be generated immediately in metal surface, and to form complete dielectric film be the necessary condition of carrying out differential arc oxidation process.Then metallic nickel is often difficult to generate complete barrier layer in micro-arc oxidation process.
The method of alumina coating is prepared on nickel electrode surface of the present invention, utilize heat-treating methods at nickel electrode Surface Creation pre-made film, and the special micelle particle that aluminum nitrate is formed in alcohol has stronger absorption property, the surface of pre-made film can be adsorbed on, thus form complete barrier layer on nickel electrode surface.The present invention adopts pre-made film and cathode micro arc to be oxidized the method combined, nickel electrode with pre-made film is placed in alcoholic solution based on aluminum nitrate as negative electrode, by the technological means process of differential arc oxidation, react under the acting in conjunction of electrochemistry, heat chemistry, plasma chemistry, finally form alchlor rete on nickel electrode surface.Alumina coating prepared by the present invention and nickel electrode matrix have very high bond strength and excellent corrosion resistance, alleviate that active material causes because the corrosion of nickel electrode is expanded loose, the problem such as come off, extend the useful life of battery, reduce its production cost, thus to the popularization of Ni-MH battery, there is good positive role.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram that embodiment 1 prepares alumina coating;
Fig. 2 is the surface scan Electronic Speculum figure that embodiment 1 prepares alumina coating;
Fig. 3 is the cross-sectional scans Electronic Speculum figure that embodiment 1 prepares alumina coating.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described, so that those skilled in the art understands the present invention better.Requiring particular attention is that, in the following description, when perhaps the detailed description of known function and design can desalinate main contents of the present invention, these are described in and will be left in the basket here.
Embodiment 1
In the present embodiment, the method that alumina coating is prepared on nickel electrode surface of the present invention comprises the following steps:
(1), first surperficial oxide layer is removed in No. 2000 sand paperings in the surface of nickel electrode (pure nickel that nickel mass content is greater than 99%), then put into acetone ultrasonic cleaning 5min;
(2), by the nickel electrode after process be placed in air, utilize Muffle furnace to be heated to 300 DEG C, insulation 6h, prepares pre-made film;
(3), by aluminum nitrate concentration be 20g/L and cerous nitrate concentration be that 1g/L takes aluminum nitrate and cerous nitrate, be dissolved in absolute ethyl alcohol, obtain electrolyte;
(4), the nickel electrode processed through step (2) is put into the stainless steel trough body that step (3) preparation electrolyte is housed, negative electrode, stainless steel trough body is done for anode with metallic nickel, adopt pulse mao power source to power, carry out differential arc oxidation process and prepare alumina coating on nickel electrode surface.
Differential arc oxidation be treated to pulse voltage be 300V ~ 600V, frequency is 50Hz ~ 2000Hz, duty ratio is 10% ~ 45%, electrolyte temperature is oxidized 10min ~ 90min under being the condition of 20 DEG C ~ 40 DEG C, prepares alumina coating on nickel electrode surface.
In the present embodiment, pulse voltage is 500V, frequency is 500Hz, duty ratio is 25%, electrolyte temperature is differential arc oxidation 60min under the condition of 30 DEG C, namely on nickel electrode matrix, prepares alumina coating.
Fig. 1 is the X-ray diffractogram that embodiment 1 prepares alumina coating.Coating forms primarily of alchlor as shown in Figure 1.
Fig. 2 is the surface scan Electronic Speculum figure that embodiment 1 prepares alumina coating.Alumina coating surface presentation goes out the surface topography of porous as shown in Figure 2, and this structure is conducive to the attachment of active material on surface.
Fig. 3 is the cross-sectional scans Electronic Speculum figure that embodiment 1 prepares alumina coating.Do not have obvious crackle and defect between alumina coating (Coating) and nickel electrode matrix (Substrate) as shown in Figure 3, alumina coating is combined well with nickel electrode matrix.Wherein, the resin (Resin) in Fig. 2 covers alumina coating (Coating) outward, conveniently can observe the outer surface of alumina coating (Coating) like this.
In the present embodiment, when other conditions are constant, adopt the different differential arc oxidation time, the surface roughness of coating and stretching bond strength are measured.Wherein, surface roughness (Ra) is that its result is as shown in table 1 with measured by contact pin type surface roughometer.
| The differential arc oxidation time (minute) | Surface roughness (micron) | Stretching bond strength (MPa) |
| 0 (before oxidation) | 0.67 | - |
| 10 | 1.49 | 45.2 |
| 20 | 2.36 | 50.3 |
| 40 | 5.55 | 38.7 |
| 60 | 6.78 | 35.6 |
| 80 | 6.91 | 31.2 |
| 90 | 6.27 | 30.7 |
Table 1
Table 1 be embodiment 1 gained alumina coating surface roughness and with the stretching bond strength of matrix and nickel electrode and the relation of differential arc oxidation time.As can be seen from Table 1, surface roughness increased gradually along with the differential arc oxidation time, but started to reduce after 80 minutes, and the bond strength that stretches is maximum at 20 minutes, progressively reduces subsequently.Thus, the differential arc oxidation time is advisable at 10min ~ 90min.
In specific implementation process, alumina coating can adopt different conditions to be prepared, specifically as shown in table 1.
Table 1
After tested, under above-mentioned condition, adopt differential arc oxidation be treated to pulse voltage be 300V ~ 600V, frequency is 50Hz ~ 2000Hz, duty ratio is 10% ~ 45%, electrolyte temperature is oxidized 10min ~ 90min under being the condition of 20 DEG C ~ 40 DEG C, all can prepare alumina coating on nickel electrode surface.The concentration and the oxidization time that are electrolyte have a certain impact to alumina coating.
Although be described the illustrative embodiment of the present invention above; so that those skilled in the art understand the present invention; but should be clear; the invention is not restricted to the scope of embodiment; to those skilled in the art; as long as various change to limit and in the spirit and scope of the present invention determined, these changes are apparent, and all innovation and creation utilizing the present invention to conceive are all at the row of protection in appended claim.
Claims (1)
1. a method for alumina coating is prepared on nickel electrode surface, it is characterized in that, comprises the following steps:
(1), acetone ultrasonic cleaning 3min ~ 10min is put into by after the oxide layer on nickel electrode sand papering removing surface;
(2), by the nickel electrode after step (1) process, the environment being placed in 200 DEG C ~ 600 DEG C in atmospheric environment heats 3h ~ 9h, generates pre-made film;
(3), by aluminum nitrate concentration, to be 10g/L ~ 30g/L and additive concentration be that 0.5g/L ~ 10g/L is dissolved in alcohol configures electrolyte;
(4), the nickel electrode after step (2) process is put into the stainless steel trough body that step (3) preparation electrolyte is housed, negative electrode, stainless steel trough body is done for anode with metallic nickel, pulse mao power source is adopted to power, carry out differential arc oxidation process, alumina coating can be prepared on nickel electrode surface;
In step (3), described additive is a kind of or wherein several combination in cerous nitrate, yttrium nitrate, erbium nitrate
In step (4), described differential arc oxidation be treated to pulse voltage be 300V ~ 600V, frequency is 50Hz ~ 2000Hz, duty ratio is 10% ~ 45%, electrolyte temperature is oxidized 10min ~ 90min under being the condition of 20 DEG C ~ 40 DEG C, prepares alumina coating on nickel electrode surface.
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| CN201310687991.0A CN103647053B (en) | 2013-12-16 | 2013-12-16 | The method of alumina coating is prepared on a kind of nickel electrode surface |
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| CN201310687991.0A CN103647053B (en) | 2013-12-16 | 2013-12-16 | The method of alumina coating is prepared on a kind of nickel electrode surface |
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| CN103647053B true CN103647053B (en) | 2015-10-21 |
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| CN104372394A (en) * | 2014-07-03 | 2015-02-25 | 西安工业大学 | Preparation method for oxide ceramic layer |
| CN111847596A (en) * | 2019-04-26 | 2020-10-30 | 无锡小天鹅电器有限公司 | Electrolytic electrode, preparation method thereof, electrolytic device and clothes treatment equipment |
| CN112342592A (en) * | 2020-10-23 | 2021-02-09 | 南昌航空大学 | Method for preparing ceramic film layer on surface of nickel-based alloy through micro-arc oxidation |
| CN112962132B (en) * | 2021-02-02 | 2022-02-18 | 山东省科学院新材料研究所 | Magnesium alloy ultrahigh-porosity micro-arc oxidation coating and preparation method and application thereof |
| CN113430615B (en) * | 2021-06-09 | 2022-02-15 | 华南理工大学 | Anodic aluminum oxide film and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101187047A (en) * | 2007-09-12 | 2008-05-28 | 哈尔滨工业大学 | Method for preparing Al2O3 film on medical use nickel-titanium alloy surface by micro-arc oxidation |
| CN101555597A (en) * | 2009-05-13 | 2009-10-14 | 大连理工大学 | Preparation method for preparing titanium oxide bioactive coating on the surface of nitinol alloy |
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| JP4836921B2 (en) * | 2007-10-25 | 2011-12-14 | 株式会社アルバック | Surface treatment method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101187047A (en) * | 2007-09-12 | 2008-05-28 | 哈尔滨工业大学 | Method for preparing Al2O3 film on medical use nickel-titanium alloy surface by micro-arc oxidation |
| CN101555597A (en) * | 2009-05-13 | 2009-10-14 | 大连理工大学 | Preparation method for preparing titanium oxide bioactive coating on the surface of nitinol alloy |
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