CN113005377A - Processing method for improving discharge performance of magnesium anode - Google Patents
Processing method for improving discharge performance of magnesium anode Download PDFInfo
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Abstract
The invention discloses a processing method for improving the discharge performance of a magnesium anode, which comprises the following steps: performing friction stir processing on the magnesium alloy material, and then annealing to obtain a magnesium alloy anode material; the friction stir processing path is as follows: firstly, carrying out a first round of multi-pass friction stir processing along the X direction of the magnesium alloy material, and then carrying out a second round of multi-pass friction stir processing along the Y direction vertical to the X direction. The method of the invention omits the long-time homogenization treatment of the magnesium alloy ingot, reduces the burning loss of alloy elements caused by repeated heating in the plastic processing process, and the defects of thick and uneven alloy grain structure and difficult regulation and control in the hot processing process, and greatly saves the requirements of processing time and equipment conditions. The processing method of the invention can correct the alloy material structure, break the brittleness and the network phase, eliminate the microstructure defect of the casting, improve the structure uniformity and the compactness, and prepare the magnesium alloy anode material with ultra-fine grains.
Description
Technical Field
The invention relates to a processing method for improving the discharge performance of a magnesium anode; belongs to the technical field of the processing and preparation of novel anode materials of chemical power supplies.
Background
The magnesium metal has the characteristics of light weight, large theoretical capacity, negative potential, active chemical property and the like, and has a plurality of advantages when used as an anode material, for example, the magnesium alloy is applied to an air battery and a seawater battery which are introduced in the previous patent CN201610459776.9 'a magnesium alloy anode material and a preparation method thereof'. During the discharging process of the magnesium anode, because magnesium and alloy elements lose electrons to form hydroxide or oxide, the hydroxide or oxide covers the surface of the anode to generate passivation or polarization phenomena, and thus the discharging performance, namely the discharging activity, the current efficiency reduction, the voltage fluctuation and the like are seriously influenced. According to the existing reports of documents such as 'research progress of anode materials of magnesium-air batteries', power technology ', 2017, 41(2), 331-333' and the like, AZ31, AZ61, AZ91, AM50, AM60, Mg-Li, AP65, MTA75, Mg-Hg-Ga, Mg-Al-Sn alloys and the like can be used as magnesium anodes through blending of alloy elements. Patent CN201810067334.9 "a method for preparing magnesium alloy anode material" discloses a method for preparing magnesium alloy anode by homogenizing annealing treatment to improve discharge performance. Patent CN200710143645.0 discloses a method for manufacturing anode material of magnesium air fuel cell, which obtains magnesium anode with fine crystal grains by accelerating cooling rate. Patent CN200810127885.6 discloses a "production method of positive magnesium alloy plate for torpedo battery", which uses cast state to realize rapid solidification of metal and rolls it into magnesium positive alloy without regiospecific gravity segregation and with fine initial crystal grains. Patent CN03142626.3 discloses "magnesium battery anode plate", which is a compact magnesium alloy anode plate organized by a continuous casting or continuous casting-rolling method. Patent CN201010501387.0 discloses an anode of magnesium alloy fuel cell and its preparation method, which utilizes extrusion forming and gas phase quenching technology to obtain magnesium anode plate with fine structure grains. Patent CN201810261893.3 discloses a magnesium alloy anode material and a preparation method thereof, which utilizes homogenization treatment and hot rolling to process and obtain a magnesium anode of multi-component alloy. Patent CN201910630914.9 discloses a normal temperature plastic deformation-rapid consolidation magnesium alloy anode material and a preparation method and application thereof, which utilizes the process of alloy raw material nano grinding and plasma sintering to avoid the growth of crystal grains in the traditional solidification and hot rolling process and optimize the discharge effect. Patent CN202010830558.8 "a magnesium alloy anode material for seawater battery and its preparation method" discloses a method for preparing a high-efficiency magnesium anode by crushing a second phase by equal channel extrusion and dispersing the second phase. In patents CN201610373476.9 "a high current efficiency rare earth magnesium alloy anode material and its preparation method and application", CN201810098664.4 "a rare earth magnesium alloy anode material and its preparation method", and CN201610459776.9 discloses "a magnesium alloy anode material and its preparation method", homogenization treatment, hot extrusion, hot rolling and rare earth elements are used to improve the structure and improve the discharge effect. Patent CN202010479340.2 discloses a magnesium alloy anode material, a preparation method and application thereof, and a magnesium air battery, wherein the cast structure is directly refined by using a transition element Ge to obtain a magnesium anode which can meet industrial application requirements on electromotive force and anode utilization rate of the corresponding air battery. Patent CN201910670261.7 magnesium alloy anode material, its preparation method and application, magnesium air battery, utilizes rare earth element Er to directly refine as-cast structure crystal grains, and obtains high-performance magnesium anode with small hydrogen evolution and low energy loss. Patent CN201810332917.X magnesium alloy anode material preparation method and device discloses a powder metallurgy sintering process, and a magnesium alloy anode with a large specific surface is prepared, so that the discharge performance is improved. Therefore, trace alloy element modification and grain refinement are effective ways for improving the discharge activity of the magnesium anode alloy, more grain boundaries can be provided as discharge reaction channels, the self-corrosion rate is reduced, and the effective discharge area is increased.
Plastic working, nanocrystallization and densification are effective processing methods for the discharge performance of the magnesium anode. However, magnesium alloy has a six-row close-packed structure, plastic deformation at room temperature is mainly caused by basal plane slip, and prismatic plane slip and conical plane slip are seriously hindered. Although column slip also exists, basal plane slip and column slip can only provide four independent slip systems, and the requirement of the Misses criterion is difficult to meet. Therefore, the magnesium alloy has low plasticity and uneven forming at room temperature, and the plastic deformation process needs to preheat the alloy to obtain a good deformation effect. However, in the process of thermoplastic processing, the dynamic recrystallization and grain growth degree of the magnesium alloy are difficult to grasp, and the refining effect of the alloy structure is poor.
During the discharge process, magnesium atoms on the anode plate lose electrons to form magnesium ions, and the magnesium ions exist in the form of magnesium hydroxide or magnesium oxide, which is an electrochemical dissolution reaction. Generally, metal atoms have good bonding ability with atoms, and even magnesium hydroxide or magnesium oxide is easily coated on the surface of an anode during the dissolution process, so that a dynamically increased corrosion oxide layer is formed during the discharge process, and thus a dynamically increased internal resistance of a battery is formed. Because the potential of magnesium is low, the magnesium can generate self-corrosion reaction in neutral solution to release hydrogen, and the product layer can be pushed to a certain extent by the release of the hydrogen, so that the accumulation effect of the product layer is reduced. However, if the product layer is too thick and large, the hydrogen generated by the self-etching has a limited ability to drop, and the output voltage is severely reduced and unstable during the discharging process. The grain boundary is usually the weakest point of atom-to-atom bonding in the alloy, and can be regarded as an interface defect and a direct reaction channel between the electrolyte and the metal in the electrochemical reaction process.
The process in the prior art can refine grains and a second phase to a certain extent when the magnesium anode is subjected to plastic deformation. Although the stress and dislocation can be eliminated by recrystallization annealing, the crystal grains are recovered with annealing to form isometric crystals. However, such directional plastic deformation tends to cause the second phase in the alloy to exhibit a certain directionality, and the suppression capability in the grain recovery process of the alloy is limited.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a processing method for improving the discharge performance of a magnesium anode.
The invention adopts the stirring friction processing to process the as-cast magnesium alloy material, and then carries out low-temperature annealing treatment to prepare the high-performance magnesium anode material.
Based on the principle of friction stir welding, the friction stir processing technology is a novel large plastic deformation technology. The friction stir processing can locally process the workpiece without influencing the shape and the size of the workpiece, and the processing depth is from hundreds of micrometers to tens of millimeters. In the process, the microstructure of the material can be refilled, homogenized and densified simultaneously, the microstructure defects of a casting are eliminated, the brittleness and the network phase are broken, and the magnesium alloy with fine grains, ultra-fine grains and nano grains is prepared, wherein the grain size can reach 100-300nm, so that the performance of the material is improved. In addition, the working process may cause the alloy second phase to break up and dissolve, thereby achieving a solid solution effect in the working zone.
More importantly, in the invention, the process control of the invention further increases the number of grain boundaries and the length of the grain boundaries in the grain refinement process, thereby increasing channels in the discharge dissolution reaction process of the magnesium anode and actually increasing the reaction area of the electrolyte and the magnesium matrix. Because more crystal boundaries exist, the crystal grain dissolved product in the discharging process can be naturally divided by means of the interface defects of the crystal boundaries to form corrosion cracks and sections of the discharging product layer, so that the size of the stacked product layer block is reduced, the stacked product layer block is favorable for falling off, and the internal resistance of the battery during discharging is reduced. On the other hand, the second phase can promote the magnesium matrix to self-corrode to generate hydrogen gas as a cathode. If the second phase is refined, the local corrosion tendency of the magnesium anode can be reduced, the uniform corrosion effect of the surface of the magnesium anode is increased, the position and the quantity of hydrogen generated on the surface are increased, and the uniform shedding of the surface of the discharge product layer is facilitated. In addition, the grain refinement and the second phase refinement enable the matrix to be changed from local corrosion to uniform corrosion, the self corrosion resistance of the alloy can be improved, more matrixes can participate in the discharge dissolution reaction, the loss of the self-corrosion reaction is reduced, and the utilization efficiency of the magnesium anode is improved.
The invention utilizes the stirring friction processing, can obviously increase the number and the length of the crystal boundary, provides more channels for the electrochemical reaction and improves the electrochemical activity; the size of a stacking block of a discharge product is reduced, the product layer is easy to fall off, and the internal resistance of the battery in the discharge process is reduced; finally, the crystal grains are refined, and meanwhile, the self-corrosion loss and the undischarged loss can be reduced, so that the anode efficiency is improved.
Firstly, the high-speed rotation of the stirring head is utilized, so that the structure of the as-cast magnesium alloy material can be repaired, the defects of shrinkage porosity, shrinkage cavity and the like of air holes are eliminated, and the uniformity and compactness of the structure are improved; secondly, the brittleness and the network phase are broken, part of alloy phase is dissolved back to the matrix, and the residual alloy phase is further dispersed and distributed; finally, the alloy matrix is dynamically recrystallized under the action of stirring force and temperature, and the dispersed second phase can play a role in inhibiting recrystallization growth. In the invention, because of the action of the rotating circumferential force and the pressing force in the stirring process, the second phase in the alloy can be dispersed more randomly, the inhibition effect of the alloy during recovery and re-growth is better, the number and the random positions of self-corrosion driving points in the discharging process are increased, and the discharging effect is improved and promoted.
In the present invention, the diameter and length of the stirring pin are properly selected according to the thickness of the processed plate, and the rotation speed and the advancing speed of the stirring head are simultaneously matched with the processing path, so as to prepare the magnesium alloy anode plate with different thicknesses, ultra-fine crystal grains, a large number of crystal boundaries and enough crystal boundary lengths.
The processing method can directly process the as-cast magnesium alloy material into the high-performance magnesium anode, and can also carry out secondary processing on the magnesium alloy plate so as to improve the discharge performance of the anode, save long-time homogenization treatment of alloy cast ingots, reduce the defects of element burning loss in the alloy caused by repeated heating in the plastic processing process, coarse and uneven grain structure in the thermal processing process and difficult regulation, greatly save the processing time, and can be applied to all magnesium anode alloy materials which can be used for seawater batteries and air batteries.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention relates to a processing method for improving the discharge performance of a magnesium anode, which comprises the following steps: performing friction stir processing on the magnesium alloy material, and then annealing to obtain a magnesium alloy anode material; the friction stir processing path is as follows: firstly, carrying out a first round of multi-pass friction stir processing along the X direction of the magnesium alloy material, and then carrying out a second round of multi-pass friction stir processing along the Y direction vertical to the X direction.
The friction stir processing path of the invention can obtain a structure with fine crystal grains, dispersed distribution of a second phase and enough number and length of crystal boundaries only by two mutually vertical processing procedures, if the processing procedure is carried out in one direction, a strong texture can be caused, the nonuniformity of the structure can be caused, even if the processing procedure is carried out for multiple times in the same processing path, the nonuniformity can not be improved, because the proportion of alloy elements in the magnesium alloy is more, the volume fraction of the texture can be reduced by the processing in two directions, and the texture can be recovered more uniformly by low-temperature treatment. In addition, because the number of the second phases in the alloy is relatively large, the second phases can be distributed more uniformly and dispersed by processing in two directions.
In the present invention, the X direction may be a longitudinal direction or a width direction. In the invention, the single-pass friction stir processing refers to the process that the stirring pin linearly moves forwards in the length direction or the width direction of the magnesium alloy material to complete the length or the width of the magnesium alloy material.
In a preferred scheme, the magnesium alloy material is an as-cast magnesium alloy or a magnesium alloy plate.
The cast magnesium alloy refers to a magnesium anode alloy with coarse grains and dendritic segregation of a second phase under the traditional casting condition, and the magnesium alloy plate refers to an alloy raw material with coarse grains and segregation under the die casting condition and the hot rolling condition.
In the present invention, the magnesium alloy composition is not excessively limited and all magnesium anode alloy materials that can be used in a sea water battery and an air battery are included. The processing method of the invention can improve the alloy structure, eliminate the structure defect and prepare the anode material containing ultra-fine grains, ultra-fine grains and nano-grains.
Preferably, the magnesium alloy in the magnesium alloy material is selected from at least one of pure magnesium, AZ31, AZ61, AM60, Mg-Al-Ca, AP65 and Mg-Al-Sn.
Preferably, the thickness of the magnesium alloy material is 4-20mm, and the surface roughness is 1.6-12.5 μm, preferably 6.3.
According to the preferable scheme, the magnesium alloy material is subjected to surface milling, surface acid washing and alkali washing, and then is washed to be neutral by deionized water, an acid solution used for acid washing is at least one of a nitric acid solution, a sulfuric acid solution, a phosphoric acid solution and a citric acid solution, a solvent of the acid solution is deionized water or ethanol, and the pH value of the acid solution is 4-6; the pH value of the alkali solution is 7-8.5. In the present invention, the alkali used for the alkali solution is not limited, and for example, sodium hydroxide, potassium hydroxide and the like can be used.
According to the method, the cast magnesium alloy is required to be cut into pieces with the thickness of 4-20mm, and the surface of the sheet in the thickness direction is milled to achieve certain smoothness, so that the surface roughness of the magnesium alloy material is 1.6-12.5 microns, and preferably 6.3 microns. And then the surface of the magnesium alloy material is cleaned with weak acid and weak base to remove the surface oxide layer and grease impurities.
According to the method, the tool for friction stir processing is a stirring head with a stirring pin, and the shape of the stirring pin is not particularly required.
In the preferred scheme, in the stirring head for friction stir processing, the length of the stirring pin is 85-98% of the thickness of the plate; the diameter of the stirring pin is 85% -100% of the thickness of the plate.
In the preferable scheme, in the friction stir processing process, the depth of the stirring pin pressed into the magnesium alloy material is more than 85% of the thickness of the magnesium alloy material and is less than or equal to 98% of the thickness of the magnesium alloy material.
According to the method, in the friction stir processing process, the stirring pin is slowly inserted into the magnesium alloy material at the same time of high speed, and the shaft shoulder of the stirring head is just contacted with the alloy surface, but no additional pressure is generated.
The preferable scheme is as follows: during the friction stir processing, the rotation speed of the stirring head is 300-3000r/min, and the advancing speed is 50-200 mm/min.
Further preferably, when the magnesium alloy material is selected from AZ31, the rotation speed of the stirring head is 1000-1500r/min and the advancing speed is 100-200mm/min during the friction stir processing.
Further preferably, when the magnesium alloy material is selected from AZ61, the rotation speed of the stirring head is 1500-2000r/min and the advancing speed is 100-150mm/min during the friction stir processing.
Further preferably, when the magnesium alloy material is selected from Mg-Al-Sn, the rotation speed of the stirring head is 1500-.
Further preferably, when the magnesium alloy material is selected from AP65, the rotation speed of the stirring head is 1500-3000r/min and the advancing speed is 60-150mm/min during the friction stir processing.
According to the performance of different magnesium alloy materials, the rotating speed and the advancing speed are controlled within the range, and the performance of the finally obtained magnesium alloy anode is optimal.
According to the preferable scheme, the path of the first round of friction stir processing is that a stirring needle advances along the X direction to complete the first friction stir processing, then a stirring head is parallelly deviated for a certain distance, the friction stir processing is repeated until the magnesium alloy material is integrally processed, and the lap joint rate (OR) of two adjacent processing is 30-100%; preferably 50%.
In the present invention, the method of determining the lap joint ratio is as follows: l is the distance between two machining center lines of adjacent channels, dpinThe lapping rate (OR) is (1-l/d) for the diameter of the stirring pinpin)×100％。
According to the preferable scheme, the path of the second round of friction stir processing is that a stirring needle advances along the Y direction to complete the first friction stir processing, then a stirring head is parallelly deviated for a certain distance, the friction stir processing is repeated until the magnesium alloy material is integrally processed, and the lap joint rate of two adjacent processing is 30-100%; preferably 50%.
The structure of the material can be densified, homogenized and refined through two rounds of stirring and friction processing, and more grain boundaries can be obtained.
In a preferred scheme, the annealing temperature is 100-200 ℃, and the annealing time is 1-4 h.
In the invention, low-temperature stress relief annealing is used, so that stress concentration generated in the stirring friction process is eliminated, the dislocation density is reduced, the random texture in the stirring process is weakened, more crystal boundaries are reserved, and the high-power-consumption high-power.
Principles and advantages
The magnesium anode material with excellent performance is obtained by the cooperation of stirring friction processing and annealing treatment for the first time. In the invention, the path and technological parameters of the friction stir processing are controlled; finally, a structure having ultra-fine grains, a dispersed distribution of the second phase structure, and a sufficient number and length of grain boundaries can be obtained.
The preparation method is simple and short in flow, omits long-time homogenization treatment of magnesium alloy ingots, reduces the burning loss of elements in the alloy caused by repeated heating in the plastic processing process, and the defects of thick and uneven alloy grain structure and difficulty in regulation and control in the hot processing process, and greatly saves the requirements on processing time and equipment conditions.
Drawings
FIG. 1 is a friction stir processing route diagram according to the present invention
FIG. 2 is a grain structure diagram of a magnesium anode fabricated in example 1.
Figure 3 microscopic alloy phase distribution plot for magnesium anodes processed according to example 1.
FIG. 4 is a transmission electron micrograph of the magnesium anode processed according to example 1.
Detailed Description
The embodiments of the present invention will be described in detail below with reference to the drawings and examples.
In the embodiment of the invention, the discharge performance of the alloy material is detected by using a traditional three-electrode testing device, silver chloride as a reference electrode, a platinum electrode as a counter electrode, a processed alloy as a working electrode and 3.5% sodium chloride solution as electrolyte, performing a half-cell test, and performing a test at a high current of 100mA/cm by using an electrochemical workstation2Under the condition and with small current of 10mA/cm2The purpose of the constant current discharge test under the condition is to meet the discharge application of batteries with different power levels.
Example 1
AZ61 cast alloy is used as raw material, processed into plates of 100mm multiplied by 6mm, and milled by surface processing to make the roughness 6.3 μm. The surface is cleaned by 0.0001mol/L nitric acid and then by 0.01mol/L sodium hydroxide to remove surface grease and oxygenAnd the layer is formed by horizontally fixing the alloy plate on a workbench of the friction stir processing equipment. The rotation speed of the stirring friction processing is 1500r/min, the advancing speed is 110mm/min, the shaft shoulder is 17mm, the diameter of the stirring needle is 6mm, the length is 5.8mm, the insertion depth is 5.8mm, and the inclination angle is 2.5 degrees. As shown in fig. 1, the process is performed by performing multiple times of friction stir processing along the length direction, i.e., the X direction; the distance between the two adjacent machining operations OR is 50 percent until the plate is all subjected to friction stir machining along the X direction. Further, in the width direction, i.e., the Y direction, the friction stir processing is performed for multiple times, and the OR interval between two adjacent processes is 50% until all processes are completed. Then, annealing treatment is carried out at low temperature of 150 ℃ for 2 hours. After the processing and the heat treatment of the embodiment, the grain structure of the alloy plate is shown in figure 2, the alloy plate has uniform and fine grains, compact structure and no obvious shrinkage porosity, shrinkage cavity and slag inclusion; the distribution of the micro alloy phase is shown in figure 3, and the second phase is distributed in a fine dispersion way; when observed using a transmission electron microscope, it was revealed to have ultrafine crystal grains of nanometer order. Through a constant current discharge test, the current is 100mA/cm at a large current2Under the condition, the discharge potential can reach-1.49V, and the current efficiency is 81.2%; at a small current of 10mA/cm2Under the condition, the discharge potential can reach-1.55V, and the current efficiency is 48.5 percent.
Example 2
AZ31 cast alloy is used as raw material, processed into plates of 100mm x 80mm x 4mm, and milled by surface processing to make the roughness 3.2 μm. And cleaning the surface by using 0.0001mol/L nitric acid, then cleaning by using 0.01mol/L sodium hydroxide, removing surface grease and an oxidation layer, and horizontally fixing the alloy plate on a workbench of the friction stir processing equipment. The rotation speed of the stirring friction processing is 1000r/min, the advancing speed is 100mm/min, the shaft shoulder is 14mm, the diameter of the stirring needle is 3.8mm, the length of the stirring needle is 3.8mm, the insertion depth is 3.8mm, and the inclination angle is 2.5 degrees. The processing route is similar to that of fig. 1, and the stirring friction processing in the X and Y directions is carried out successively, and the distance between two adjacent OR lines is 50%. Then, annealing treatment is carried out at low temperature of 140 ℃ for 3 hours. Through a constant current discharge test, the current is 100mA/cm at a large current2Under the condition, the discharge potential canThe voltage reaches-1.43V, and the current efficiency is 82.5 percent; at a small current of 10mA/cm2Under the condition, the discharge potential can reach-1.49V, and the current efficiency is 49.6 percent.
Example 3
The cast alloy AP65 is used as a raw material, processed into plates of 120mm multiplied by 100mm multiplied by 8mm, and milled by surface processing to ensure that the roughness is 6.3 mu m. And cleaning the surface by using 0.0001mol/L nitric acid, then cleaning by using 0.01mol/L sodium hydroxide, removing surface grease and an oxidation layer, and horizontally fixing the alloy plate on a workbench of the friction stir processing equipment. The rotation speed of the stirring friction processing is 2500r/min, the advancing speed is 100mm/min, the shaft shoulder is 19mm, the diameter of the stirring needle is 7.8mm, the length of the stirring needle is 7.8mm, the pressing depth is 7.8mm, and the inclination angle is 2.5 degrees. The processing route is similar to that of fig. 1, and the stirring friction processing in the X and Y directions is carried out successively, and the distance between two adjacent OR lines is 50%. Then, annealing treatment is carried out at low temperature of 160 ℃ for 1 hour. Through a constant current discharge test, the current is 100mA/cm at a large current2Under the condition, the discharge potential can reach-1.74V, and the current efficiency is 78.2%; at a small current of 10mA/cm2Under the condition, the discharge potential can reach-1.80V, and the current efficiency is 46.6%.
Example 4
Mg-6Al-1Sn as-cast alloy is used as a raw material and processed into a plate with the thickness of 80mm multiplied by 10mm, and the surface is milled to ensure that the roughness is 6.3 mu m. And cleaning the surface by using 0.0001mol/L nitric acid, then cleaning by using 0.01mol/L sodium hydroxide, removing surface grease and an oxidation layer, and horizontally fixing the alloy plate on a workbench of the friction stir processing equipment. The rotation speed of the stirring friction processing is 2000r/min, the advancing speed is 100mm/min, the shaft shoulder is 21mm, the diameter of the stirring needle is 9.8mm, the length of the stirring needle is 9.8mm, the pressing depth is 9.8mm, and the inclination angle is 2.5 degrees. The processing route is similar to that of fig. 1, and the stirring friction processing in the X and Y directions is carried out successively, and the distance between two adjacent OR lines is 50%. Then, annealing treatment is carried out at low temperature of 160 ℃, and the holding time is 1.5 hours. Through a constant current discharge test, the current is 100mA/cm at a large current2Under the condition, the discharge potential can reach-1.65V, and the current efficiency is 80.1%; at a small current of 10mA/cm2Under the condition, the discharge potential can reach-1.70V, and the current efficiency is 48.7 percent.
Comparative example 1
AZ61 cast alloy is used as raw material, processed into plates of 80mm multiplied by 10mm, and milled by surface processing to make the roughness 6.3 μm. And cleaning the surface by using 0.0001mol/L nitric acid, then cleaning by using 0.01mol/L sodium hydroxide, removing surface grease and an oxidation layer, and horizontally fixing the alloy plate on a workbench of the friction stir processing equipment. The rotation speed of the stirring friction processing is 500r/min, the advancing speed is 220mm/min, the shaft shoulder is 21mm, the diameter of the stirring needle is 9.8mm, the length of the stirring needle is 9.8mm, the pressing depth is 9.8mm, and the inclination angle is 2.5 degrees. The processing route is similar to that of fig. 1, and the stirring friction processing in the X and Y directions is carried out successively, and the distance between two adjacent OR lines is 10%. Then, annealing treatment is carried out at low temperature of 250 ℃ for 6 hours. Through a constant current discharge test, the current is 100mA/cm at a large current2Under the condition, the discharge potential can reach-1.38V, and the current efficiency is 76.2%; at a small current of 10mA/cm2Under the condition, the discharge potential is-1.46V, and the current efficiency is 42.3%.
Comparative example 2
AZ31 cast alloy is used as raw material, processed into plates of 100mm multiplied by 6mm, and milled by surface processing to make the roughness 3.2 μm. And cleaning the surface by using 0.0001mol/L nitric acid, then cleaning by using 0.01mol/L sodium hydroxide, removing surface grease and an oxidation layer, and horizontally fixing the alloy plate on a workbench of the friction stir processing equipment. The rotation speed of the stirring friction processing is 500r/min, the advancing speed is 250mm/min, the shaft shoulder is 14mm, the diameter of the stirring needle is 3.8mm, the length of the stirring needle is 3.8mm, the pressing depth is 3.8mm, and the inclination angle is 2.5 degrees. The processing route only carries out stirring friction processing in the X direction, and the distance between two adjacent OR lines is 20%. Then, annealing treatment is carried out at low temperature of 250 ℃ for 6 hours. Through a constant current discharge test, the current is 100mA/cm at a large current2Under the condition, the discharge potential can reach-1.34V, and the current efficiency is 77.3%; at a small current of 10mA/cm2Under the condition, the discharge potential can reach-1.43V, and the current efficiency is 44.1%.
Claims (9)
1. A processing method for improving the discharge performance of a magnesium anode is characterized by comprising the following steps: the method comprises the following steps: stirring and rubbing the magnesium alloy material, and then annealing at low temperature to obtain a magnesium alloy anode material; the friction stir processing path is as follows: firstly, carrying out a first round of multi-pass friction stir processing along the X direction of the magnesium alloy material, and then carrying out a second round of multi-pass friction stir processing along the Y direction vertical to the X direction.
2. The processing method for improving the discharge performance of the magnesium anode according to claim 1, wherein the processing method comprises the following steps: the magnesium alloy in the magnesium alloy material is selected from at least one of pure magnesium, AZ31, AZ61, AM60, Mg-Al-Ca, AP65, Mg-Al-Sn and other alloys.
3. The processing method for improving the discharge performance of the magnesium anode according to claim 1, wherein the processing method comprises the following steps: the thickness of the magnesium alloy material is 4-20mm, and the surface roughness is 1.6-12.5 μm.
4. The processing method for improving the discharge performance of the magnesium anode according to claim 1, wherein the processing method comprises the following steps: in the stirring head for friction stir processing, the length of the stirring pin is 85-98% of the thickness of the plate; the diameter of the stirring pin is 85% -100% of the thickness of the plate;
in the friction stir processing process, the depth of the stirring pin pressed into the magnesium alloy material is more than 85% of the thickness of the magnesium alloy material and is less than or equal to 98% of the thickness of the magnesium alloy material.
5. The processing method for improving the discharge performance of the magnesium anode according to claim 1, wherein the processing method comprises the following steps: during the friction stir processing, the rotation speed of the stirring head is 300-3000r/min, and the advancing speed is 50-200 mm/min.
6. The processing method for improving the discharge performance of the magnesium anode according to claim 5, wherein the processing method comprises the following steps: when the magnesium alloy material is selected from AZ31, the rotating speed of the stirring head is 1000-1500r/min and the advancing speed is 100-200mm/min during the friction stir processing.
When the magnesium alloy material is selected from AZ61, the rotating speed of the stirring head is 1500-2000r/min and the advancing speed is 100-150mm/min during the friction stir processing.
When the magnesium alloy material is selected from Mg-Al-Sn, the rotation speed of the stirring head is 1500-2500r/min and the advancing speed is 60-180mm/min during the stirring and friction processing.
When the magnesium alloy material is selected from AP65, the rotation speed of the stirring head is 1500-3000r/min and the advancing speed is 60-150mm/min during the friction stir processing.
7. The processing method for improving the discharge performance of the magnesium anode according to claim 1, wherein the processing method comprises the following steps: the first round of friction stir processing is performed by enabling the stirring pin to move forward along the X direction to complete the first friction stir processing, enabling the stirring head to parallelly shift for a certain distance, and repeating the friction stir processing until the magnesium alloy material is integrally processed, wherein the lap joint rate of two adjacent processing is 30-100%.
8. The processing method for improving the discharge performance of the magnesium anode according to claim 1, wherein the processing method comprises the following steps: and the second round of friction stir processing is performed by enabling the stirring pin to move forward along the Y direction to finish the first friction stir processing, enabling the stirring head to parallelly deviate for a certain distance, and repeating the friction stir processing until the magnesium alloy material is integrally processed, wherein the lap joint rate of two adjacent processing steps is 30-100%.
9. The processing method for improving the discharge performance of the magnesium anode according to claim 1, wherein the processing method comprises the following steps: the annealing temperature is 100-200 ℃, and the annealing time is 1-4 h.
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