CN1564342A - Magnesium dry battery integral magnesium cylinder and manufacturing method thereof - Google Patents
Magnesium dry battery integral magnesium cylinder and manufacturing method thereof Download PDFInfo
- Publication number
- CN1564342A CN1564342A CNA2004100177493A CN200410017749A CN1564342A CN 1564342 A CN1564342 A CN 1564342A CN A2004100177493 A CNA2004100177493 A CN A2004100177493A CN 200410017749 A CN200410017749 A CN 200410017749A CN 1564342 A CN1564342 A CN 1564342A
- Authority
- CN
- China
- Prior art keywords
- magnesium
- cylinder
- solution
- alloy
- dry battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention discloses a magnesium dry battery integral magnesium cylinder and a manufacturing method thereof. The inner surface of the magnesium cylinder is used as an active substance of a battery cathode, the outer surface of the magnesium cylinder is a current collector of the battery cathode, and the magnesium cylinder is also a container of the battery and is characterized in that the surface of the magnesium cylinder is provided with a layer of passivation protective film formed by surface treatment. The passivation film is formed by immersing a magnesium cylinder in a fluoride solution or a chromate solution, a vanadate solution, a phosphate solution, or the like. The magnesium barrel material is a high-purity magnesium alloy taking magnesium as a substrate, wherein the magnesium content in the magnesium alloy is more than 92wt%, and the magnesium alloy also contains 1-5 wt% of aluminum, 0.5-2 wt% of zinc, 0-0.3 wt% of manganese, 0-0.05 wt% of indium and 0-0.1 wt% of rare earth. The product has the advantages of difficult self-corrosion and long service life. The method has the characteristics of high processing efficiency, low energy consumption and low production cost, and is suitable for industrial production.
Description
Technical Field
The invention relates to a magnesium dry battery integral magnesium cylinder and a manufacturing method thereof, in particular to a magnesium dry battery integral magnesium cylinder with excellent corrosion resistance and a manufacturing method thereof.
Background
The traditional cylindrical zinc-manganese battery has been used for more than a hundred years, is characterized by convenient use and low price, and is still a battery which is the most widely used and has the largest yield in primary batteries. However, harmful elements such as mercury, cadmium, lead and the like in the zinc-manganese battery material have a serious influence on the environment; another disadvantage of the zinc-manganese battery is that the battery has low storage capacity, large resource waste and poor discharge performance, and is not suitable for the requirements of modern electronic and electric appliances. In recent years, it has been found that a lithium manganese battery using lithium as a negative electrode active material achieves a great improvement in the performance of a primary battery, but lithium is an rare metal which is rare and rare, so that the cost of the lithium battery is greatly increased, and there are unsafe factors that limit its widespread use.
Magnesium is a metal with light weight, safety, no toxicity, low price and easily obtained material (the storage amount in the crust of the earth accounts for the seventh place), has more negative electrode potential and smaller electrochemical equivalent and can become an ideal material in the production of batteries.
In recent years, research on magnesium batteries has made a substantial progress, and laminated magnesium dry batteries using magnesium as a negative electrode have been used in military equipment. Chinese patent application No. 00811017.4 describes a magnesium-based primary battery (non-rechargeable type) and a secondary battery (rechargeable type), which relates to a cathode made of magnesium metal in a sintered form. Chinese patent application No. 02146143.0 describes a rechargeable magnesium battery negative electrode composed of a magnesium alloy. The magnesium alloy negative electrodes are all sheet electrodes formed by sintering powder. In addition, the Chinese patent application 02111675X discloses a magnesium alloy solid-state punch forming process which is a forming process developed by the applicant and suitable for producing a cylindrical magnesium dry battery cathode integral magnesium cylinder. Chinese patent applications 03134338.4 and 03142626.3 also disclose some techniques related to magnesium dry battery negative electrode materials and processing.
The outer surface of the integral magnesium cylinder is used as a current collector of the magnesium dry battery cathode, does not participate in electrochemical reaction, but is influenced by the external climate environment. However, the surface of the whole magnesium cylinder after stamping forming is generally adhered with lubricant, oxide or other metal impurities, and the impurities can not be completely removed even after cleaning. Since magnesium has high electrochemical activity and acts as an anode for almost all other metals, although magnesium forms an oxide protective film in a dry room temperature environment to reduce surface corrosion, the oxide protective film gradually dissolves to be converted into magnesium hydroxide at an ambient relative humidity of 80% or more, and thus self-corrosion occurs, which seriously affects the service life of a battery and the safe use of the battery. Experiments prove that the white pits appear on the surface of the integral magnesium cylinder after 3 months in an indoor exposure atmosphere environment. Further, the oxide film in this crystalline state has a large insulation resistance, and affects conductivity. Therefore, solving the self-corrosion problem of the whole magnesium cylinder is very key to the popularization and the application of the magnesium dry battery.
Disclosure of Invention
The invention aims to solve the technical problem of providing a magnesium dry battery integral magnesium cylinder which is not easy to generate self-corrosion and has long service life.
Another object of the present invention is to provide a method for manufacturing the above-mentioned magnesium dry battery integral magnesium cylinder.
The technical scheme adopted by the invention for solving the technical problems is as follows: the magnesium dry battery integral magnesium cylinder is characterized in that the surface of the magnesium cylinder is provided with a layer of passivation protective film formed by surface treatment.
The passivation protective film is a magnesium fluoride passivation protective film formed on the surface of the magnesium cylinder by soaking the magnesium cylinder in a fluoride solution, or an oxide passivation protective film formed on the surface of the magnesium cylinder by soaking the magnesium cylinder in a chromate solution, a vanadate solution or a phosphate solution. The fluoride may be selected from magnesium fluoride or ammonium bifluoride. In consideration of the use of the monolithic magnesium cylinder in a dry environment and the requirement of surface conductivity, the concentration of the fluoride solution, chromate solution, vanadate solution or phosphate solution used for the surface passivation treatment is preferably 0.01 to 0.1M.
The manufacturing method of the integral magnesium cylinder of the magnesium dry battery comprises three stages of alloying preparation of raw materials, punch forming and surface passivation treatment, and the specific process is as follows:
preparing alloying; placing alloy components of the magnesium cylinder in a heating furnace to be melted under the protection atmosphere or the covering of a fusing agent, controlling the furnace temperature at 600-750 ℃, and then obtaining a magnesium alloy cake with required thickness and diameter by casting, plate rolling, cake punching and surface cleaning;
punching and forming; performing recoil pressing on the magnesium alloy cake at the temperature of between 150 and 400 ℃ to obtain a magnesium cylinder blank, and then performing incision, trimming and surface cleaning to obtain a magnesium cylinder finished product;
surface passivation treatment; and soaking the magnesium cylinder finished product in passivation treatment liquid to form a layer of passivation protective film on the surface of the magnesium cylinder finished product.
The passivation treatment solution is fluoride solution, chromate solution, vanadate solution or phosphate solution, the concentration of the solution is 0.01-0.1M, and the soaking treatment time is 1-10 minutes. The fluoride is selected from magnesium fluoride or ammonium bifluoride, and the chromate, vanadate and phosphate are generally selected from potassium or sodium salts thereof.
As for the material adopted by the integral magnesium cylinder, the integral magnesium cylinder is a high-purity magnesium alloy taking magnesium as a matrix, the magnesium alloy contains more than 92wt% of magnesium, 1-5 wt% of aluminum, 0.5-2 wt% of zinc, 0-0.3 wt% of manganese, 0-0.05 wt% of indium and 0-0.1 wt% of rare earth, and the content of iron, less than 0.005wt% of nickel and less than 0.002wt% of nickel and less than 0.03wt% of copper and silicon in harmful substances accidentally brought in the magnesium alloy. Preferably, the total content of manganese, indium and rare earth in the magnesium alloy is 0.01-0.5 wt%.
The magnesium alloy material is used for replacing a zinc alloy material, so that the influence of mercury, cadmium and lead in the battery on the environment can be eliminated, and the battery has the advantages of light weight and resource conservation. The substitution of the magnesium material for the zinc material also shows excellent electrical properties, in particular:
battery capacity C = mass of active species fully reacted/Q active species electrochemical equivalent, and
battery energy w = battery capacity C × battery electromotive force E;
are theoretically superior to zinc actives. For example, the electrochemical equivalent of the zinc active material is 1.22, while the electrochemical equivalent of the magnesium active material is 0.4537, i.e. the same mass of magnesium active material is 2.71 times that of zinc; for another example, the oxidation-reduction potential of zinc in acidic solution is-0.763V, while magnesium is-2.38V, 1.617V higher than that of zinc. The oxidation-reduction potential of zinc in alkaline solution is-1.245V, while magnesium is-2.69V, 1.445V higher than the zinc potential, showing high power yield with magnesium as the active material; magnesium has conductivity close to that of aluminum, is better than zinc, and has lower resistivity. The inner surface of the integral magnesium cylinder is used as an active material of a battery cathode, and the components of the alloy have very important functions on the discharge performance and the storage performance of the battery, and are also related to whether the integral magnesium cylinder can be successfully machined. Magnesium is the main active material, and the battery capacity is large when the content of magnesium is high, but the pure magnesium is not beneficial to mechanical processing. Therefore, a suitable magnesium content in the magnesium alloy should be greater than 92wt%, with the addition of other modifying components.
The magnesium alloy added with the aluminum can improve the strength and hardness of the magnesium alloy, improve the ductility, facilitate plastic deformation, refine the alloy structure by the co-melting of the aluminum and the magnesium, improve the acid-base corrosion resistance of the alloy, and form a passivation film on the surface to play a role in protection. Aluminum is a metal with high hydrogen evolution overpotential, and the damage of hydrogen to the magnesium cathode can be reduced when the magnesium electrode is oxidized. The content of aluminum is preferably 1 to 5wt%, and when the content of aluminum is too large, the electrical properties of the magnesium dry battery, such as a decrease in capacity, a delay in discharge voltage, and the like, may be deteriorated.
The magnesium is added with zinc, so that the ductility of the alloy can be improved, the strength of the alloy at room temperature can be improved by adding the zinc and the aluminum together, the harmful corrosion of iron and nickel to the alloy can be overcome, the uneven crystal grains of the aluminum in the magnesium can be reduced by the existence of the zinc, the phenomenon of battery leakage caused by the uneven corrosion of the whole magnesium cylinder can be avoided, the content of the zinc is preferably 0.5-2 wt%, and the magnesium alloy plate is easy to cause brittleness when too much zinc is added, so that the mechanical processing is not facilitated.
The magnesium is further added with modified metal elements such as manganese, indium, rare earth and the like, so that the discharge performance and the storage performance of the magnesium dry battery can be improved, and the processing performance of the whole magnesium cylinder can be improved. The addition of manganese can improve the yield strength of the alloy and the corrosion resistance to salt water, and can also reduce the self-corrosion of iron impurities in the magnesium electrode. Preferably, the manganese content is 0.1 to 0.3wt%, and if the manganese content is more than 0.5wt%, the alloy structure is affected and the corrosion resistance of the alloy is reduced. The indium can inhibit the generation of hydrogen, reduce the hydrogen evolution corrosion of the magnesium cathode, and reduce the surface contact resistance of the magnesium electrode, and the addition amount is preferably 0.01 to 0.05 weight percent because the indium is expensive. The rare earth lanthanum or cerium is added, so that the alloy structure can be further refined, the machinability of the alloy is improved, and the surface quality and the corrosion resistance of the magnesium cylinder are improved.
In the magnesium alloy material of the above composition, the corrosion resistance and machinability of the entire magnesium barrel are deteriorated by the harmful impurities occasionally introduced at the time of raw material addition and during the production operation. The most harmful impurities are iron, nickel, copper, silicon, etc., which, when present between the crystal lattices, tend to form internal galvanic cells under the action of the electrolyte and are self-corroding and must be effectively controlled. In view of the technical standards of the current raw materials, considering the influence degree of impurities on the magnesium dry battery and the comprehensive consideration of all factors of the production cost, and referring to the practical effect of the integral zinc cylinder of the zinc-manganese battery, the harmful impurity components of the integral magnesium cylinder of the invention are preferably that iron is not more than 0.005wt%, nickel is not more than 0.002wt%, and copper and silicon are not more than 0.03wt%.
The stamping forming is to arrange the magnesium alloy cake in a concave-convex mould, and form a high-temperature and high-pressure effect by means of strong impact force, so that the magnesium alloy is rapidly molded into an integral magnesium cylinder along the gap of the concave-convex mould under the action of three-dimensional pressure. Because the magnesium alloy layer is in a close-packed hexagonal crystal structure, the magnesium alloy layer has small slip coefficient at room temperature and poor plastic processing performance, and cannot be formed by cold extrusion like an integral zinc cylinder. However, when the magnesium alloy is heated to 150 ℃ or above, the plasticity is improved, and the magnesium alloy can be rapidly formed by one-step stamping by matching with a high-temperature-resistant lubricant.
Magnesium alloys suitably have a pressing temperature in the range of 150 to 400 c, preferably 165 to 375 c, generally related to the alloy composition and deformation speed, and also related to the die structure and product shape. When the automatic feeding is adopted and the stamping speed is increased, the die absorbs a large amount of heat, the heating temperature of the blank can be reduced to 165 ℃, and when the deformation rate of the product is large or the work hardening requirement is low, the heating temperature of the blank needs to be properly increased, but the heating temperature is not too high, such as higher than 400 ℃, the product quality deterioration can be caused or the stamping insecurity can be increased. In addition, in the initial stage of stamping, the die is preheated to 165-265 ℃ to prevent the upper opening of the magnesium cylinder from cracking during stamping forming.
Magnesium alloys have a larger coefficient of thermal expansion than zinc alloys, and in order to ensure that the dimensions of the hot stamped products are within specified tolerances, the dimensions of the stamping die must be multiplied by a temperature compensation coefficient. Other factors that affect the stamping tolerances of magnesium alloys include the size, shape, aspect ratio, and precision of the stamping machinery and dies. When the length-diameter ratio of the integral magnesium cylinder of the magnesium dry battery is punched and formed to be 2-6: 1, the typical tolerance is obtained according to the experiment: the diameter tolerance is plus 0.05mm, the wall thickness tolerance is plus 0.03mm, and the bottom thickness tolerance is plus or minus 0.10mm.
The forming of the integral magnesium cylinder is suitable for a reverse stamping process, when the blank made of the magnesium alloy composition is used for stamping forming at the temperature of 165-375 ℃, the deformation rate is controlled to be lower than 96%, and the ratio of the length (or height) to the diameter is controlled to be within the range of 2-6: 1. When the ratio of length (or height) to diameter is less than 2: 1, the drawing and stamping efficiency may be higher; and when the ratio is more than 6: 1, the quality during the back-impact pressing molding is difficult to ensure, phenomena such as bending of the magnesium cylinder, uneven wall thickness, difficult demoulding and the like are easy to occur, and the forward stamping process is more favorable.
The integral magnesium cylinder is an active substance of the cathode of the magnesium dry battery, the discharge capacity of the cathode is usually larger than that of the anode in consideration of the durability and the safety of the magnesium dry battery, when the discharge of the battery is terminated, the proper wall thickness of the cylinder body still needs to be kept to prevent the battery from leaking and perforating, and the wall thickness is required to be 0.25-1.00 mm generally. When the thickness is too thin, the mechanical strength of the magnesium can is insufficient and the durability is poor, and when too thick, the material is wasted, the cost is increased, and the capacity of the positive electrode material is reduced, which is disadvantageous to the battery capacity.
Compared with the existing integral magnesium cylinder, the integral magnesium cylinder after passivation treatment is placed for 2 years under the same condition, the surface corrosion phenomenon is not found, the corrosion resistance is obviously enhanced, and the service life and the use safety of the integral magnesium cylinder are prolonged. Compared with the existing integral zinc cylinder, the battery has the advantages of light weight, resource saving and excellent electrical property, and the influence of mercury, cadmium and lead in the battery on the environment is eliminated. The method has the characteristics of high processing efficiency, low energy consumption and low production cost, and the prepared product has the advantages of high dimensional precision and good surface quality and is suitable for industrial production.
In particular toDescription of the preferred embodiment
The present invention will be described in further detail with reference to examples.
Example one
The alloy components of the integral magnesium cylinder are that metal magnesium is used as a matrix, 1.0wt% of aluminum, 0.5wt% of zinc, 0.1wt% of manganese, no more than 0.005wt% of harmful impurity metal iron, no more than 0.002wt% of nickel, and no more than 0.03wt% of copper and silicon.
According to the proportion, magnesium, aluminum, zinc and manganese are placed in a heating melting furnace, the furnace temperature is controlled at 600-750 ℃, and the magnesium alloy plate or the coiled strip with the thickness of 6.1mm is obtained by melting in the presence of protective atmosphere or magnesium flux coverage and then casting and rolling the plate. Putting the plate or the coiled belt into a blanking die, selecting a punch head with a male die and a female die with the outer diameter of 13.0mm and the inner diameter of 13.22 mm, blanking and blanking to obtain a magnesium alloy cake with the diameter of 13.2mm and the thickness of 6.1 mm; removing oil stains, oxides and burrs on the surface of the magnesium alloy cake by mechanical polishing or chemical cleaning, then coating a high-temperature-resistant lubricant on the surface of the magnesium alloy, and then performing back-impact forming. The recoil press forming is completed by heating the magnesium alloy cake coated with the high-temperature-resistant lubricant to 265 ℃ and then placing the magnesium alloy cake in a concave-convex die, wherein the outer diameter of the convex die is 13.00mm, the inner diameter of the concave die is 13.63mm, the gap between the bottom dead points of the concave-convex die is 0.65mm, the deformation rate of the magnesium alloy is controlled to be less than 96 percent, and the whole magnesium cylinder blank with the outer diameter of 13.6mm, the height of 57.9 mm, the wall thickness of 0.30mm and the bottom thickness of 0.60mm is obtained by one-step stamping.
And cutting off redundant fractures on the integral magnesium cylinder blank to obtain an integral magnesium cylinder with the diameter of 13.6mm multiplied by 47.5mm, and then carrying out surface passivation treatment on the integral magnesium cylinder. In this embodiment, the surface passivation process includes: and soaking the whole magnesium cylinder in 0.05M of dilute chromate solution for 2 minutes, taking out and drying to obtain a finished product.
The parts not described in the present embodiment are the same as the conventional art.
Example two
The alloy components of the integral magnesium cylinder are that metal magnesium is used as a matrix, 5.0wt% of aluminum, 2.0wt% of zinc, 0.01wt% of indium, 0.05wt% of rare earth lanthanum, less than or equal to 0.005wt% of harmful impurity metal iron, less than or equal to 0.002wt% of nickel, and less than or equal to 0.03wt% of copper and silicon.
The pressing temperature was 375 ℃. The surface passivation treatment adopts 0.01M magnesium fluoride solution, and the soaking time is 10 minutes. The rest is the same as the first embodiment.
EXAMPLE III
The magnesium metal is taken as a matrix, 2.5wt% of aluminum, 0.5wt% of zinc, 0.1wt% of manganese, 0.05wt% of rare earth lanthanum, less than or equal to 0.005wt% of harmful impurity metal iron, less than or equal to 0.002wt% of nickel, and less than or equal to 0.03wt% of copper and silicon.
The pressing temperature was 165 ℃. The surface passivation treatment adopts 0.1M ammonium bifluoride solution, and the soaking time is 1 minute. The rest is the same as the first embodiment.
Example four
2.5 percent of aluminum, 1.2 percent of zinc, 0.3 percent of manganese, 0.05 percent of rare earth lanthanum, 0.05 percent of indium, less than or equal to 0.005 percent of harmful impurity metallic iron, less than or equal to 0.002 percent of nickel, and less than or equal to 0.03 percent of copper and silicon.
The surface passivation treatment adopts 0.05M vanadate solution, and the soaking time is 4 minutes. The rest is the same as the first embodiment.
EXAMPLE five
2.8 percent of aluminum, 1.0 percent of zinc, 0.2 percent of manganese, 0.1 percent of rare earth lanthanum, 0.02 percent of indium, less than or equal to 0.005 percent of harmful impurity metallic iron, less than or equal to 0.002 percent of nickel, and less than or equal to 0.03 percent of copper and silicon.
The surface passivation treatment adopts 0.05M magnesium fluoride solution, and the soaking time is 4 minutes. The rest is the same as the first embodiment.
Comparative example one: r6 integral zinc cylinder
The alloy components of the integral zinc cylinder are that metal zinc is used as a basal body, lead is 0.4wt%, cadmium is 0.035wt%, iron is not more than 0.01wt%, copper is not more than 0.002wt%, and tin is not more than 0.003wt%. Other operations are the same as the prior art.
Comparative example two: integral magnesium cylinder without surface passivation treatment
The same as in the above example except that the final surface passivation treatment was not performed.
The above examples and comparative examples pass through the comparative test of electrolyte corrosion, the weight loss rate of the integral magnesium cylinder is superior to that of the integral zinc cylinder in high temperature and low temperature corrosion, and the machinability and the hardness are basically close, so that the equipment and the production process of the common zinc-manganese dry battery can be used. After the magnesium-manganese dry battery is assembled by the integral magnesium cylinder, the discharge capacity is increased by more than 2 times compared with that of a zinc-manganese dry battery with the same specification, the voltage is 0.4V higher, the magnesium-manganese dry battery can be suitable for a large-current discharge effect as an alkaline battery, and the requirement of a modern green environment-friendly battery is met.
The integral magnesium cylinder without surface passivation treatment is naturally placed for about 3 months under the indoor conventional condition, the surface corrosion phenomenon appears, and the integral magnesium cylinder with surface passivation treatment is placed under the same condition for 2 years, the surface corrosion phenomenon still does not appear, and the visible corrosion resistance is obviously improved.
Claims (10)
1. The integral magnesium cylinder for magnesium dry battery has inner surface as the active matter of the negative pole of the battery, outer surface as the current collector of the negative pole of the battery and the container of the battery.
2. The magnesium dry battery magnesium integral cylinder according to claim 1, wherein the passivation film is a magnesium fluoride passivation film formed on the surface of the magnesium cylinder by immersing the magnesium cylinder in a fluoride solution, or an oxide passivation film formed on the surface of the magnesium cylinder by immersing the magnesium cylinder in a chromate solution, a vanadate solution or a phosphate solution.
3. The magnesium dry battery magnesium monobloc can as set forth in claim 2, wherein said fluoride is magnesium fluoride or ammonium bifluoride.
4. The magnesium dry battery magnesium monobloc can as set forth in claim 2, wherein the concentration of said fluoride solution, chromate solution, vanadate solution or phosphate solution is 0.01 to 0.1M.
5. The magnesium dry battery integral magnesium cylinder according to any one of claims 1 to 4, wherein the magnesium cylinder material is a high purity magnesium alloy based on magnesium, the magnesium alloy contains more than 92wt% of magnesium, and further contains 1 to 5wt% of aluminum, 0.5 to 2wt% of zinc, and 0 to 0.3wt% of manganese, 0 to 0.05wt% of indium, 0 to 0.1wt% of rare earth, and the magnesium alloy contains less than 0.005wt% of iron, less than 0.002wt% of nickel, and less than 0.03wt% of copper and silicon, which are harmful substances incidentally introduced.
6. The magnesium dry battery integrated magnesium cylinder as set forth in claim 5, wherein the total content of manganese, indium and rare earth in the magnesium alloy is 0.01 to 0.5wt%.
7. A manufacturing method of an integral magnesium cylinder of a magnesium dry battery comprises three stages of raw material alloying preparation, punch forming and surface passivation treatment, and comprises the following specific processes:
preparing alloying; placing alloy components of the magnesium cylinder in a heating furnace to be melted under the protection atmosphere or the covering of a fusing agent, controlling the furnace temperature at 600-750 ℃, and then obtaining a magnesium alloy cake with required thickness and diameter by casting, plate rolling, cake punching and surface cleaning;
punching and forming; performing recoil pressing on the magnesium alloy cake at the temperature of between 150 and 400 ℃ to obtain a magnesium cylinder blank, and then performing incision, trimming and surface cleaning to obtain a magnesium cylinder finished product;
surface passivation treatment; and soaking the magnesium cylinder finished product in passivation treatment liquid to form a layer of passivation protective film on the surface of the magnesium cylinder finished product.
8. The method for manufacturing a magnesium dry battery integrated magnesium cylinder according to claim 7, wherein the passivation solution is a fluoride solution, a chromate solution, a vanadate solution or a phosphate solution, the concentration of the solution is 0.01 to 0.1M, the soaking time is 1 to 10 minutes, and the fluoride is magnesium fluoride or ammonium hydrogen fluoride.
9. The method for manufacturing a magnesium dry battery integrated magnesium tube as set forth in claim 7 or 8, wherein the magnesium tube has an alloy composition of: the magnesium alloy contains more than 92wt% of magnesium, 1-5 wt% of aluminum, 0.5-2 wt% of zinc, 0-0.3 wt% of manganese, 0-0.05 wt% of indium and 0-0.1 wt% of rare earth metal, and the content of iron in harmful substances accidentally brought in the magnesium alloy is less than 0.005wt%, the content of nickel is less than 0.002wt%, and the content of copper and silicon is less than 0.03wt%.
10. The method for manufacturing a magnesium dry battery integral magnesium tube as claimed in claim 9, wherein the deformation rate of the magnesium alloy during the reverse press forming process is less than 96%, and the ratio of the length to the diameter of the magnesium tube blank obtained by forming is 2-6: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100177493A CN1326258C (en) | 2004-04-16 | 2004-04-16 | Magnesium dry battery integral magnesium cylinder and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100177493A CN1326258C (en) | 2004-04-16 | 2004-04-16 | Magnesium dry battery integral magnesium cylinder and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1564342A true CN1564342A (en) | 2005-01-12 |
| CN1326258C CN1326258C (en) | 2007-07-11 |
Family
ID=34479139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100177493A Expired - Fee Related CN1326258C (en) | 2004-04-16 | 2004-04-16 | Magnesium dry battery integral magnesium cylinder and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1326258C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101859918A (en) * | 2010-05-21 | 2010-10-13 | 余建岳 | Method for converting off-grid discontinuous and unstable carbon-free electric energy into mobile storage electric energy |
| CN104404329A (en) * | 2014-12-19 | 2015-03-11 | 中北大学 | Magnesium alloy material with high corrosion resistance and preparation method of magnesium alloy material |
| CN104272516B (en) * | 2012-05-29 | 2016-11-09 | 丰田自动车工程及制造北美公司 | Indium-tin binary anode for rechargeable Magnesium ion battery |
| CN108103334A (en) * | 2017-12-28 | 2018-06-01 | 重庆仟和镁业科技有限公司 | The production technology of whole magnesium alloy battery case |
| CN112944049A (en) * | 2021-03-05 | 2021-06-11 | 中电建宁夏工程有限公司 | Complex-shaped anti-corrosion pipeline for special tunnel structure and forming method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317781C (en) * | 2002-08-06 | 2007-05-23 | 李华伦 | Magnesium dry cell |
| CN100495773C (en) * | 2003-06-09 | 2009-06-03 | 李华伦 | Anode plate material for magnesium cell |
| CN1225050C (en) * | 2003-06-30 | 2005-10-26 | 西安亚太博轩科技有限责任公司 | Magnesium-manganese dry cell and its manufacturing technology |
-
2004
- 2004-04-16 CN CNB2004100177493A patent/CN1326258C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101859918A (en) * | 2010-05-21 | 2010-10-13 | 余建岳 | Method for converting off-grid discontinuous and unstable carbon-free electric energy into mobile storage electric energy |
| CN101859918B (en) * | 2010-05-21 | 2013-11-27 | 余建岳 | Method for converting off-grid discontinuous and unstable carbon-free electric energy into mobile storage electric energy |
| CN104272516B (en) * | 2012-05-29 | 2016-11-09 | 丰田自动车工程及制造北美公司 | Indium-tin binary anode for rechargeable Magnesium ion battery |
| CN104404329A (en) * | 2014-12-19 | 2015-03-11 | 中北大学 | Magnesium alloy material with high corrosion resistance and preparation method of magnesium alloy material |
| CN108103334A (en) * | 2017-12-28 | 2018-06-01 | 重庆仟和镁业科技有限公司 | The production technology of whole magnesium alloy battery case |
| CN112944049A (en) * | 2021-03-05 | 2021-06-11 | 中电建宁夏工程有限公司 | Complex-shaped anti-corrosion pipeline for special tunnel structure and forming method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1326258C (en) | 2007-07-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20170000761A (en) | Electrolytic Copper Foil, Current Collector Comprising The Same, Electrode Comprising The Same, Secondary Battery Comprising The Same, and Method for Manufacturing The Same | |
| CN101075691A (en) | Lithium ion battery | |
| KR20140057584A (en) | Rolled copper foil for secondary battery collector and production method therefor | |
| CN110038900B (en) | Processing method of aluminum foil layer for lithium ion battery flexible package aluminum-plastic composite film | |
| CN1326258C (en) | Magnesium dry battery integral magnesium cylinder and manufacturing method thereof | |
| JP2918434B2 (en) | Battery negative electrode zinc can | |
| JP2918446B2 (en) | Battery negative electrode zinc can | |
| CN1328803C (en) | Environment-friendly zinc-manganese battery cathode can | |
| CN100347884C (en) | Battery cathode material of air battery or alkaline nickel-hydrogen battery, preparation method and battery using material | |
| CN106025345B (en) | A kind of lithium ion battery | |
| CN1941461A (en) | Production of non-pump button battery and its battery | |
| CN111139378A (en) | Aluminum foil for high-strength high-conductivity current collector and preparation method thereof | |
| MXPA02011680A (en) | Surface treatment of metallic components of electrochemical cells for improved adhesion and corrosion resistance. | |
| CN101271973B (en) | Non-mercury alkaline zinc-manganese and zinc-silver button cell cathode and manufacturing method thereof | |
| WO1995029510A1 (en) | Negative electrode zinc-can for dry cell, its manufacture, and manganese dry cell using it | |
| CN112126821B (en) | Processing method for aluminum plastic film aluminum foil of power battery | |
| CN113798322A (en) | Preparation method of composite foil | |
| CN101299457B (en) | Method for treating surface of negative electrode cover of mercury-free alkaline zinc-manganese and zinc-silver button cell | |
| CN1225050C (en) | Magnesium-manganese dry cell and its manufacturing technology | |
| KR20100056263A (en) | Fabrication method of negative electrode for nickel/zinc secondary battery using surface-modified current collector and nickel/zinc secondary battery fabricated using the same | |
| CN102465218A (en) | Environment-friendly zinc-manganese alloy and zinc-manganese battery | |
| CN101533911B (en) | Application of aluminum based ternary alloy as anode material of Li-ion batteries | |
| CN100490216C (en) | Cell zinc tank preparing method | |
| CN1330421A (en) | Lattice plate of lead-acid accumulator and its preparing process | |
| CN113241445B (en) | Grid alloy for lead-carbon battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070711 Termination date: 20160416 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |