CN111826647A - Magnesium alloy with protective film on surface, processing method and application - Google Patents
Magnesium alloy with protective film on surface, processing method and application Download PDFInfo
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- CN111826647A CN111826647A CN202010630318.3A CN202010630318A CN111826647A CN 111826647 A CN111826647 A CN 111826647A CN 202010630318 A CN202010630318 A CN 202010630318A CN 111826647 A CN111826647 A CN 111826647A
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- magnesium alloy
- stannate
- treatment
- corrosion
- pretreatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
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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
- H01M4/36—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
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/466—Magnesium based
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/30—Deferred-action cells
- H01M6/32—Deferred-action cells activated through external addition of electrolyte or of electrolyte components
- H01M6/34—Immersion cells, e.g. sea-water cells
Abstract
The invention discloses a magnesium alloy with a protective film on the surface, a processing method and application thereof, wherein a stannate processing liquid consisting of 0.15-0.25mol/L stannate, 0.08-0.12mol/L pyrophosphate, 0.10-0.15mol/L sodium hydroxide or potassium hydroxide and 0.06-0.10mol/L acetate is adopted to form a film structure converted from stannate on the surface of the magnesium alloy, and the film has the performance of reducing the corrosion reaction rate of the magnesium alloy and not influencing the self-corrosion potential, thereby realizing the improvement of the battery discharge efficiency on the premise of reducing the reaction activity of the magnesium alloy and slowing down the self-corrosion rate.
Description
Technical Field
The invention belongs to the technical field of metal surface treatment, and particularly relates to a magnesium alloy with a protective film on the surface, a treatment method and application.
Background
The magnesium alloy has small density, high specific strength and high electrochemical activity when used as a battery anode, and has wide application prospect in the development of seawater batteries. However, the high corrosion sensitivity of magnesium alloy leads to the reduction of the discharge efficiency and the service life of the battery, and the popularization and the application of the magnesium alloy are limited to a great extent. At present, the reaction activity of the magnesium alloy is mainly adjusted by adding alloy elements to improve the discharge efficiency of the magnesium alloy, and the method brings about the corrosion problem of the magnesium alloy, so that the surface of the magnesium alloy needs to be further protected by adopting a certain surface treatment technology to improve the corrosion resistance of the surface of the magnesium alloy. But this treatment method adversely affects the discharge characteristics of the battery.
Disclosure of Invention
Aiming at the problem that the prior art cannot simultaneously protect the magnesium alloy and be used as a battery anode material, the invention provides the magnesium alloy with a stannate conversion film on the surface, a treatment method and application.
The technical purpose is achieved, the technical effect is achieved, and the invention is realized through the following technical scheme:
a method for processing magnesium alloy comprises placing cleaned magnesium alloy with polished smooth surface in stannate processing liquid to form a stannate conversion film on the surface of the magnesium alloy; wherein the stannate treatment liquid consists of 0.15-0.25mol/L stannate, 0.08-0.12mol/L pyrophosphate, 0.10-0.15mol/L sodium hydroxide or potassium hydroxide and 0.06-0.10mol/L acetate.
As a further improvement of the invention, the magnesium alloy is immersed in stannate treatment liquid with the temperature of 60-80 ℃ for treatment for 10-30 min.
As a further development of the invention, the stannate, pyrophosphate or acetate is selected from strong alkali salts.
Based on the method, the invention also prepares the magnesium alloy with the stannate conversion film on the surface.
As a further improvement of the invention, the stannate conversion film is a dense film layer composed of particles with uniformly distributed particle sizes.
The magnesium alloy prepared based on the foregoing is applied to a battery anode material.
Preferably, the magnesium alloy is applied to anode materials of seawater batteries.
The invention has the beneficial effects that: by adopting the method, a film layer structure converted from stannate is formed on the surface of the magnesium alloy, and the film layer has the performance of reducing the corrosion reaction rate of the magnesium alloy and not influencing the self-corrosion potential, so that the discharge efficiency of the battery is improved on the premise of reducing the reaction activity of the magnesium alloy and slowing down the self-corrosion rate.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a stannate conversion film layer prepared on the surface of a magnesium alloy in example 1;
FIG. 2 is a scanning electron micrograph of a stannate conversion coating prepared on a magnesium alloy surface according to example 2;
FIG. 3 is a scanning electron micrograph of a stannate conversion coating formed on a magnesium alloy surface according to example 3;
FIG. 4 is an AC impedance plot of various example magnesium alloys versus magnesium alloys without stannate pretreatment in a 3.5 wt.% NaCl solution;
FIG. 5 is a graph of magnesium alloys of various embodiments versus magnesium alloys without stannate pretreatment at 10mA/cm in 3.5 wt.% NaCl solution2Half-cell discharge curve of discharge;
FIG. 6 shows different embodiments of a seawater cell comprising an anode made of magnesium alloy without stannate pretreatment and foamed nickel in 3.5 wt.% NaCl solution at 10mA/cm2Discharge curve of the discharge.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The following detailed description of the principles of the invention is provided in connection with the accompanying drawings.
Example 1
(1) Magnesium alloy surface pretreatment: and sequentially polishing the magnesium alloy by using No. 240, No. 600 and No. 1000 abrasive paper, cleaning by using deionized water, ultrasonically cleaning by using absolute ethyl alcohol and drying by using cold air for later use.
(2) Preparing a treatment solution: dissolving 0.15mol/L sodium stannate, 0.08 mol/L sodium pyrophosphate, 0.10mol/L sodium hydroxide and 0.06 mol/L sodium acetate in deionized water to prepare stannate pretreatment liquid. The magnesium alloy is firstly dissolved in the alkaline treatment solution to release Mg2+, and stannic acid is combined with ions and Mg2+ with positive charges on the surface of the magnesium alloy to form a MgSnO 3.3H 2O conversion film. The sodium pyrophosphate and the sodium acetate are used for adjusting and controlling the pH value of the solution to be between 12 and 13 and adjusting the nucleation rate of the stannate product on the surface of the magnesium alloy.
(3) Coating treatment: and soaking the magnesium alloy sample in stannate treatment liquid for 10 min at the treatment temperature of 80 ℃. Then taking out and washing with deionized water, and drying with cold air.
After stannate treatment, a gray film layer is generated on the surface of the magnesium alloy. As shown in the SEM image obtained by the present embodiment shown in fig. 1, it can be seen from the SEM image that the surface of the magnesium alloy is covered with a film layer composed of similar round particles, the diameter of the particles is between 1 μm and 2 μm, the particle size is uniform, and the film layer is relatively dense.
Example 2
(1) Magnesium alloy surface pretreatment: and sequentially polishing the magnesium alloy by using No. 240, No. 600 and No. 1000 abrasive paper, cleaning by using deionized water, ultrasonically cleaning by using absolute ethyl alcohol and drying by using cold air for later use.
(2) Preparing a treatment solution: dissolving 0.20 mol/L sodium stannate, 0.10mol/L sodium pyrophosphate, 0.12mol/L sodium hydroxide and 0.08 mol/L sodium acetate in deionized water to form stannate pretreatment solution.
(3) Coating treatment: and soaking the magnesium alloy sample in stannate treatment liquid for 20 min at the treatment temperature of 70 ℃. Then taking out and washing with deionized water, and drying with cold air.
After stannate treatment, a gray film layer is generated on the surface of the magnesium alloy. As shown in fig. 2, the SEM image obtained in this example shows that the surface of the magnesium alloy is covered with a conversion coating layer, which is composed of round particles, has a particle size of 2-3 μm, is uniform in particle size, and has a dense coating structure.
Example 3
(1) Magnesium alloy surface pretreatment: and sequentially polishing the magnesium alloy by using No. 240, No. 600 and No. 1000 abrasive paper, cleaning by using deionized water, ultrasonically cleaning by using absolute ethyl alcohol and drying by using cold air for later use.
(2) Preparing a treatment solution: dissolving 0.25mol/L sodium stannate, 0.12mol/L sodium pyrophosphate, 0.15mol/L sodium hydroxide and 0.10mol/L sodium acetate in deionized water to form stannate pretreatment solution.
(3) Coating treatment: and soaking the magnesium alloy sample in stannate treatment liquid for 30min at the treatment temperature of 60 ℃. Then taking out and washing with deionized water, and drying with cold air.
After stannate treatment, a gray film layer is generated on the surface of the magnesium alloy. As shown in fig. 3, the SEM image obtained in this example shows that the conversion coating on the surface of the magnesium alloy is composed of round particles, the particle size is 2-3 μm, the particle size is uniform, and the coating is dense.
And (3) performance testing:
the corrosion performance and the discharge performance of the magnesium alloy without stannate pretreatment and the magnesium alloy treated by different examples were tested.
FIG. 4 is an AC impedance plot of various embodiments of magnesium alloys versus magnesium alloys without stannate pretreatment in a 3.5 wt.% NaCl solution. As can be seen from FIG. 4, the Nyquist plot shows a capacitive arc in the high frequency region and an inductive arc in the low frequency region, which indicates that the corrosion process of the magnesium alloy is relatively rapid. However, the volume resistance arc radius of the map is increased after the stannate treatment, which shows that the stannate conversion film layer can slow down the dissolution rate of the magnesium alloy.
FIG. 5 shows various embodiments of magnesium alloys without stannate pretreatmentMagnesium alloy at 10mA/cm in 3.5 wt.% NaCl solution2Half cell discharge curve of discharge. As can be seen from FIG. 5, the discharge potential of the magnesium alloy sample after the stannate pretreatment is lower than that of the untreated magnesium alloy, indicating that the film formed by the stannate pretreatment can reduce the discharge potential of the magnesium alloy as the anode. The magnesium alloy before and after the stannate treatment was combined with a nickel foam cathode to form a seawater cell, which was tested for discharge curve in a 3.5 wt.% NaCl solution.
FIG. 6 shows different embodiments of a seawater battery composed of an anode made of magnesium alloy without stannate pretreatment and foamed nickel in 3.5 wt.% NaCl solution at 10mA/cm2Discharge curve of the discharge. As can be seen from FIG. 6, the output voltage of the seawater battery made of the magnesium alloy without stannate pretreatment is 0.22V; the output voltage of the seawater battery formed by the magnesium alloy sample after stannate pretreatment is 0.33V, and the output voltage of the seawater battery is obviously improved.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. A method of processing a magnesium alloy, characterized by: the method comprises the steps of placing the magnesium alloy which is cleaned and has a polished smooth surface in stannate treatment liquid, and forming a stannate conversion film layer on the surface of the magnesium alloy; wherein the stannate treatment liquid consists of 0.15-0.25mol/L stannate, 0.08-0.12mol/L pyrophosphate, 0.10-0.15mol/L sodium hydroxide or potassium hydroxide and 0.06-0.10mol/L acetate.
2. The method of claim 1, wherein: comprises immersing the magnesium alloy in stannate treatment liquid at 60-80 deg.C for 10-30 min.
3. The method of claim 1, wherein: the stannate, pyrophosphate or acetate is selected from strong alkali salts.
4. A magnesium alloy having a stannate conversion film on the surface thereof prepared by the method according to any one of claims 1 to 3.
5. The magnesium alloy of claim 4, wherein: the stannate conversion film is a film layer with a compact structure and composed of particles with uniformly distributed particle sizes.
6. The magnesium alloy according to claim 4 is applied to a battery anode material.
7. Use according to claim 6, characterized in that: the magnesium alloy is applied to the anode material of the seawater battery.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113789508A (en) * | 2021-08-17 | 2021-12-14 | 北京科技大学 | Chemical conversion solution for magnesium alloy surface conductive corrosion-resistant treatment and preparation method thereof |
-
2020
- 2020-07-03 CN CN202010630318.3A patent/CN111826647A/en active Pending
Non-Patent Citations (4)
| Title |
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| 吴丹等: ""以锡酸钠为主盐的AZ91D镁合金化学转化处理工艺"", 《腐蚀与防护》 * |
| 王建利等: ""GW93镁合金表面锡酸盐化学转化膜工艺研究"", 《稀有金属材料与工程》 * |
| 苏晓强: ""溶氧型海水电池正负极材料性能的研究"", 《中国知网》 * |
| 蔡志强等: ""AZ91D镁合金锡酸盐转化膜的制备及其性能研究"", 《电镀与环保》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113789508A (en) * | 2021-08-17 | 2021-12-14 | 北京科技大学 | Chemical conversion solution for magnesium alloy surface conductive corrosion-resistant treatment and preparation method thereof |
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Application publication date: 20201027 |