Patent Application
20240157437
The present invention belongs to the field of smelting of rare metal functional materials, and particularly relates to a tantalum powder for manufacturing a high-reliability capacitor and a producing method thereof.
Tantalum electrolytic capacitor (hereinafter referred to as tantalum capacitor) has the advantages of high capacity, small volume, strong self-healing capability, high reliability and the like, and is widely applied to high-tech fields of communication, computers, automotive electronics, medical instruments, radars, aerospace, automatic control devices and the like. Tantalum powder is a key material for manufacturing tantalum capacitor, and only by using tantalum powder for capacitors with excellent withstand voltage, tantalum capacitor with good reliability can be produced, and the requirements of high-reliability of electronic devices and electronic circuits can be continuously met.
At present, industrial preparation methods of capacitor-grade tantalum powder mainly include sodium-reduction potassium fluorotantalate method, magnesium-reduction tantalum oxide method, tantalum ingot hydrogenation method and the like. No matter which method is used for preparing tantalum powder, in order to improve the electrical property of tantalum powder, the prepared tantalum raw powder needs to be subjected to subsequent treatments such as high-temperature high-vacuum heat treatment, oxygen reduction by reduction with metal magnesium. The high-temperature high-vacuum heat treatment process can remove gas impurities and a part of low-melting-point metal impurities adsorbed in the wet impurity removal process, and the reduction with metal magnesium can reduce the oxygen content of tantalum powder and improve the distribution of oxygen in tantalum powder; and the subsequent treatment can also cause tantalum metal particles to be aggregated and sintered, thereby improving the structure of tantalum metal particles and improving the electrical property of tantalum powder. In order to improve the withstand voltage of tantalum powder, general methods include increasing the sintering temperature, prolonging the sintering time and so on, but the increase of the sintering temperature and the prolongation of the sintering time may cause a loss of specific capacitance.
CN102120258B discloses a method for heat treatment of tantalum powder, which comprises the steps of firstly subjecting original tantalum powder to high-temperature vacuum heat treatment to obtain aggregated tantalum powder, and then mixing the heat-treated aggregated tantalum powder with a reducing agent for deoxidation heat treatment, and finally performing acid washing for impurity removal to obtain the tantalum powder suitable for the electrolytic capacitor. The tantalum powder prepared by the method has low oxygen content and good electrical property, but the tantalum powder particles prepared by the method have the problems of large loss, poor withstand voltage and the like. CN101189089B discloses a method for high-temperature vacuum heat treatment of metal powder by microwave energy, but the tantalum powder prepared by the method also has the problems of large leakage current and low breakdown voltage, and the equipment used has the disadvantages of high maintenance cost and low processing capacity.
In the prior art, there is still a self-propagating high-temperature synthesis method (SHS) for producing tantalum powder. However, this method requires a temperature of at least 2000° C. or more, and the reaction is too fast, which is not only difficult to control, but also has high requirements on process equipment. In addition, the tantalum powder obtained is not uniform and does not meet the need for manufacturing highly reliable capacitors.
In short, the tantalum powder prepared by the above methods has the defects of low breakdown voltage and the like, and is not suitable for manufacturing high-reliability capacitors.
An object of the present invention is to provide tantalum powder for capacitors with high breakdown voltage and capable of meeting the requirements of manufacturing high-reliability capacitors. Another object is to provide a method for preparing the tantalum powder, which is characterized in that after the tantalum powder is subjected to oxygen reduction and activation treatment in molten salt by using metal magnesium, excessive metal magnesium is separated, and then the tantalum powder is sintered in the molten salt.
An object of the present invention is to provide a method for producing tantalum powder for capacitors. Compared with the tantalum powder for capacitors of the same grade produced by other methods, the tantalum powder for capacitors produced by the method has a high specific capacitance under high-voltage energization conditions, and a high breakdown voltage, and the withstand voltage of the tantalum powder for capacitors is significantly improved.
The present invention relates to a method for producing tantalum powder, comprising the steps of:
Preferably, the mass ratio of the tantalum powder to the alkali metal and/or alkaline earth metal halide in step (1) is 1:0.5-10.0, more preferably 1:0.5-3.0, and still more preferably 1:1.5-2.5. The metal magnesium is added in an amount of 1-5%, preferably 1.5-3% by weight of the tantalum powder. It is understood that the amount of the metal magnesium added is excessive for oxygen reduction, so magnesium overflow may also occur during the separation of magnesium.
Preferably, the magnesium in step 1) is magnesium particles. The particle size of the magnesium particles is not limited. However, after a great deal of research, the inventors find that magnesium particles with the particle size of 150-4000 μm are more suitable for this technology. The magnesium particles with the particle size range are not only beneficial to the safety during storage and transportation of the metal magnesium, but also beneficial to the uniform mixing. If the magnesium particles are too fine, the activity is too strong, and spontaneous combustion and ignition are easy to occur; if the magnesium particles are too coarse, uniform mixing is not so easy, and the performance optimization of the tantalum powder is not so easy.
The inert gas generally refers to rare gases such as helium, neon, and argon. Although nitrogen is sometimes used as an inert gas due to its stable properties, it is not suitable as an inert protective gas in the present invention because the temperature of step (2) is relatively high and the activity of nitrogen is very strong at this high temperature. However, after a great deal of research, the inventors has surprisingly found that the nitrogen doping of the tantalum powder can be achieved by the way when a small amount of nitrogen is contained in the inert gas without damaging the inert protective atmosphere. From the viewpoint of achieving a better nitrogen doping effect of the tantalum powder, the inert gas in step (2) may preferably contain 0.5 to 10% of nitrogen.
Preferably, the alkali metal or alkaline earth metal halide in step (1) is one or more of NaCl, KCl, KF, KI, and/or MgCl2. The alkali metal halide may be sodium chloride and/or potassium chloride, preferably a mixture of sodium chloride and potassium chloride, more preferably a mixture of sodium chloride and potassium chloride in a ratio of 1:1-10, most preferably about 1:1. The alkali metal and/or alkaline earth metal halide is preferably in particulate form. The particle size thereof is not limited, but the inventors find that the particles of 70-4000 μm are more suitable for this technology, and the tantalum powder obtained by reduction has better withstand voltage.
Preferably, one or more compounds containing B, P and/or N elements can be added as additive(s) in step (1) to dope the tantalum powder. Based on the amount of effective element, the B element is preferably added in an amount of 1-100 ppm, more preferably 20-60 ppm; the P element is preferably added in an amount of 10-200 ppm, more preferably 30-90 ppm; the N element is preferably added in an amount of 300-2500 ppm, more preferably 500-1200 ppm. It should be understood that although the compound(s) is (are) added here, the effective elements are B, P, and/or N, so the amounts referred to here are calculated as B, P and/or N.
The main object of step (2) is to effect oxidation reduction and/or activation of tantalum powder.
Preferably, in step (2), the heating furnace is heated to 750-1000° C. More preferably, the heating furnace is heated to 850-1000° C.
Preferably, in step (3), the temperature of the heating furnace is 650-800° C. More preferably, the temperature is 650-720° C. Preferably, in this step, the interior of the heating furnace is vacuumized to 5 Pa or less, preferably 0.5 Pa or less.
Preferably, in step (4), the heating furnace is heated to 900-1050° C.
The inert gas in step (2) may be the same as or different from the inert gas in step (4). Preferably, in steps (2) and/or (4), a positive voltage is maintained in the furnace.
Preferably, the method of the present invention further comprises, after step (6), subsequent treatment such as high-temperature high-vacuum heat treatment, oxygen reduction, acid washing and the like to obtain tantalum powder suitable for manufacturing high-reliability tantalum capacitors. These treatments are all processes known in the art. In other words, these treatments may employ any processes known in the art. For example, the high-temperature high-vacuum heat treatment and passivation may be performed by using processes provided in the patents CN201110039272.9, CN201120077798.1, CN201120077680.9, CN201120077305.4 and the like, the oxygen reduction may be performed by using processes provided in the patents CN201420777210.7 and CN201420777210.7, and the acid washing may be performed by using processes provided in the patents CN201210548101.3, CN201280077499.5, CN201210548008.2 and the like.
Instead of doping the N, P and/or B elements in step (1), a step of doping these elements separately may also be included in the present invention, for example, after step (6). Of course, raw materials containing these elements may be used as they are. These elements may also be added in the high-temperature high-vacuum heat treatment step described previously. It is particularly preferable to add the P element. The addition of the P element can improve the specific capacitance, and the effect of improving the specific capacitance is the same whenever the P element is added as long as the total amount of P doped is controlled well.
The present invention also relates to tantalum powder suitable for manufacturing high-reliability tantalum capacitors, which is characterized in that an anode block manufactured by using the tantalum powder is energized under high voltage conditions, and the energized block is tested for electrical performance. It is found that the energized block has a higher specific capacitance and shows a higher breakdown voltage in the breakdown voltage test.
There is no limitation on the tantalum powder raw material to be treated herein.
Moreover, the process of the present invention is simple and easy to control. For example, any step of the present invention does not involve the use of microwave, or the use of too high temperatures above 1300° C. Therefore, the equipment used is simpler, and the safety of the tantalum powder sintering process is better.
Without being bound to a general theory, through analysis of principle by combining the theory of powder liquid phase sintering, the inventors believe that the reason why the present invention achieves excellent effects resides in that: in step (2), with the rise of the temperature, the metal magnesium and the alkali metal or alkaline earth metal halide are melted and present as liquid phase, the liquid magnesium, for having higher reducibility, reduces oxygen on the tantalum powder, and increases the surface activity of tantalum powder particles; then, upon sintering in the liquid phase of the molten salt, the corners, projections of large particles in the tantalum powder and ultrafine tantalum powder particles are dissolved in the liquid phase. As the process continues, tantalum has a concentration in the liquid phase that exceeds the saturation concentration, and then preferentially deposits on certain sites in the large particles of tantalum and coalesces as a part of the large particles. As such, the tantalum powder has smooth particles, thick sintering neck and less ultrafine particles. Thereafter, the obtained tantalum powder is subjected to high-temperature high-vacuum sintering, oxygen reduction and acid washing treatment according to the prior art, thereby obtaining tantalum powder suitable for manufacturing high-voltage high-reliability capacitors.
The following FIGURE is provided for a better understanding of the present invention. The FIGURE is exemplary and not intended to limit the scope of the present invention.
The FIGURE illustrates that the obtained tantalum powder has more uniform distribution, smooth particles, thick sintering neck and less ultrafine particles.
In order to further illustrate the present invention, the preferred embodiments of the present invention are described in combination with the accompanying examples, from which the objects, features and advantages of the present invention can be clearly seen. The description is intended only to further illustrate the features and advantages of the present invention, not to limit the present invention. The examples were carried out under conventional conditions if the specific conditions are not specified. The reagents or instruments used are commercially available conventional products if the manufacturer is not specified.
For the purposes of the present specification, all numbers expressing amounts of ingredients, reaction conditions and the like in the specification and claims are to be understood as being modified in all instances by the term “about” unless otherwise indicated. Accordingly, the numerical parameters given in the following specification and attached claims are approximate values that may vary depending upon the desired properties sought to be obtained by the present invention, unless otherwise indicated. At the very least, and not intended to limit the application of the principle of equivalence in the scope of claims, each numerical parameter should be interpreted at least according to the number of reported significant digits and the usual rounding technique.
The content of impurities in the tantalum powder is analyzed according to the Chinese standard GB/T15076.1-15076.15, and the physical properties are tested according to the industry standard YS/T573-2015. The electrical performance of the tantalum powder is tested according to the Chinese standard GB/T3137.
5.0 kg of tantalum powder obtained by reducing potassium fluotantalate with sodium was mixed with 2.0% of metal magnesium particles by weight of the tantalum powder and simultaneously with 3.75 kg of potassium chloride (KCl). After uniformly mixing, the obtained mixture was loaded into a reaction vessel, and air in the reaction vessel was evacuated. Argon was introduced into the reaction vessel, and, under the condition of keeping positive pressure, the reaction vessel was put into a heating furnace for heating to a temperature of 900° C., followed by soaking for 4.0 h. Then, the reaction vessel was cooled to a temperature of 720° C., and vacuumized so that the pressure in the reaction vessel was lowered to 5.7 Pa, followed by soaking for 3 h, and vacuumizing was stopped. Then, argon was introduced into the reaction vessel, and, under the condition of keeping positive pressure, the reaction vessel was heated to 950° C., followed by soaking for 5 h. After the soaking was finished, the reaction vessel was cooled to room temperature, and passivation treatment was carried out. Thereafter, the obtained mixture of the halide and the tantalum powder was subjected to water washing, acid washing, filtering and drying, to obtain tantalum powder. The tantalum powder obtained was subjected to high-temperature high-vacuum heat treatment for 0.5 h at 1400° C. and under a pressure of less than 5.0×10−3 Pa, and then to oxygen reduction and acid cleaning to obtain tantalum powder.
The tantalum powder was made into an anode block according to the anode block mass, pressed density, anode block sintering temperature, sintering time specified in Table 1, and other conditions as per the above-mentioned GB/T3137 requirements, energized at 150 V, and then tested for electrical properties as per the above-mentioned GB/T3137 requirements. The test results are listed in Table 1.
5.0 kg of tantalum powder obtained by reducing potassium fluotantalate with sodium was mixed with 2.0% of metal magnesium particles by weight of the tantalum powder and simultaneously with 2.0 kg of potassium chloride (KCl) and 2.0 kg of sodium chloride (NaCl). After uniformly mixing, the obtained mixture was loaded into a reaction vessel, and air in the reaction vessel was separated (i.e., evacuated). Argon was introduced into the reaction vessel, and, under the condition of keeping positive pressure, the reaction vessel was put into a heating furnace for heating to a temperature of 980° C., followed by soaking for 4.0 h. Then, the reaction vessel was cooled to a temperature of 680° C., and vacuumized so that the pressure in the reaction vessel was lowered to 5.7 Pa, followed by soaking for 6 h, and vacuumizing was stopped. Then, argon was introduced into the reaction vessel, and, under the condition of keeping positive pressure, the reaction vessel was heated to 900° C., followed by soaking for 3 h. After the soaking was finished, the reaction vessel was cooled to room temperature, and passivation treatment was carried out. Thereafter, the obtained mixture of the halide and the tantalum powder was subjected to water washing, acid washing, filtering and drying, to obtain tantalum powder with improved particle structure. The tantalum powder obtained was subjected to high-temperature high-vacuum heat treatment for 0.5 h at 1400° C. and under a pressure of less than 5.0×10−3 Pa, and then to oxygen reduction and acid cleaning to obtain tantalum powder.
The tantalum powder was made into an anode block according to the anode block mass, pressed density, anode block sintering temperature, sintering time specified in Table 1, and other conditions as per the above-mentioned GB/T3137 requirements, energized at 150 V, and then tested for electrical properties as per the above-mentioned GB/T3137 requirements. The test results are listed in Table 1.
5.0 kg of tantalum powder obtained by reducing potassium fluotantalate with sodium, comprising a compound comprising 50 ppm phosphorus, was mixed with 2.0% of metal magnesium particles by weight of the tantalum powder and simultaneously with 2.0 kg of potassium chloride (KCl) and 2.0 kg of sodium chloride (NaCl). After uniformly mixing, the obtained mixture was loaded into a reaction vessel, and air in the reaction vessel was separated. Argon was introduced into the reaction vessel, and, under the condition of keeping positive pressure, the reaction vessel was put into a heating furnace for heating to a temperature of 850° C., followed by soaking for 4.0 h. Then, the reaction vessel was cooled to a temperature of 720° C., and vacuumized so that the pressure in the reaction vessel was lowered to 5.7 Pa, followed by soaking for 3 h, and vacuumizing was stopped. Then, argon was introduced into the reaction vessel, and, under the condition of keeping positive pressure, the reaction vessel was heated to 920° C., followed by soaking for 5 h. After the soaking was finished, the reaction vessel was cooled to room temperature, and passivation treatment was carried out. Thereafter, the obtained mixture of the halide and the tantalum powder was subjected to water washing, acid washing, filtering and drying, to obtain tantalum powder with improved particle structure. The tantalum powder obtained was subjected to high-temperature high-vacuum heat treatment for 0.5 h at 1420° C. and under a pressure of less than 5.0×10−3 Pa, and then to oxygen reduction by reducing with magnesium and acid cleaning to obtain tantalum powder.
The tantalum powder was made into an anode block according to the anode block mass, pressed density, anode block sintering temperature, sintering time specified in Table 1, and other conditions as per the above-mentioned GB/T3137 requirements, energized at 150 V, and then tested for electrical properties as per the above-mentioned GB/T3137 requirements. The test results are listed in Table 1.
5.0 kg of tantalum powder obtained by reducing potassium fluotantalate with sodium, comprising a compound comprising 800 ppm nitrogen, was mixed with 2.0% of metal magnesium particles by weight of the tantalum powder and simultaneously with 2.0 kg of potassium chloride (KCl) and 2.0 kg of sodium chloride (NaCl). After uniformly mixing, the obtained mixture was loaded into a reaction vessel, and air in the reaction vessel was separated. Argon was introduced into the reaction vessel, and, under the condition of keeping positive pressure, the reaction vessel was put into a heating furnace for heating to a temperature of 920° C., followed by soaking for 4.0 h. Then, the reaction vessel was cooled to a temperature of 720° C., and vacuumized so that the pressure in the reaction vessel was lowered to 5.7 Pa, followed by soaking for 6 h, and vacuumizing was stopped. Then, argon was introduced into the reaction vessel, and, under the condition of keeping positive pressure, the reaction vessel was heated to 950° C., followed by soaking for 5 h. After the soaking was finished, the reaction vessel was cooled to room temperature, and passivation treatment was carried out. Thereafter, the obtained mixture of the halide and the tantalum powder was subjected to water washing, acid washing, filtering and drying, to obtain tantalum powder with improved particle structure. The tantalum powder obtained was subjected to high-temperature high-vacuum heat treatment for 0.5 h at 1400° C. and under a pressure of less than 5.0×10−3 Pa, and then to oxygen reduction and acid cleaning to obtain tantalum powder.
The tantalum powder was made into an anode block according to the anode block mass, pressed density, anode block sintering temperature, sintering time specified in Table 1, and other conditions as per the above-mentioned GB/T3137 requirements, energized at 150 V, and then tested for electrical properties as per the above-mentioned GB/T3137 requirements. The test results are listed in Table 1.
5.0 kg of tantalum powder obtained by reducing potassium fluotantalate with sodium, comprising a compound comprising 50 ppm boron, was mixed with 2.0% of metal magnesium particles by weight of the tantalum powder and simultaneously with 2.0 kg of potassium chloride (KCl) and 2.0 kg of sodium chloride (NaCl). After uniformly mixing, the obtained mixture was loaded into a reaction vessel, and air in the reaction vessel was separated. Argon was introduced into the reaction vessel, and, under the condition of keeping positive pressure, the reaction vessel was put into a heating furnace for heating to a temperature of 920° C., followed by soaking for 4.0 h. Then, the reaction vessel was cooled to a temperature of 720° C., and vacuumized so that the pressure in the reaction vessel was lowered to 5.7 Pa, followed by soaking for 6 h, and vacuumizing was stopped. Then, argon was introduced into the reaction vessel, and, under the condition of keeping positive pressure, the reaction vessel was heated to 950° C., followed by soaking for 5 h. After the soaking was finished, the reaction vessel was cooled to room temperature, and passivation treatment was carried out. Thereafter, the obtained mixture of the halide and the tantalum powder was subjected to water washing, acid washing, filtering and drying, to obtain tantalum powder with improved particle structure. The tantalum powder obtained was subjected to high-temperature high-vacuum heat treatment for 0.5 h at 1400° C. and under a pressure of less than 5.0×10−3 Pa, and then to oxygen reduction and acid cleaning to obtain tantalum powder.
The tantalum powder was made into an anode block according to the anode block mass, pressed density, anode block sintering temperature, sintering time specified in Table 1, and other conditions as per the above-mentioned GB/T3137 requirements, energized at 150 V, and then tested for electrical properties as per the above-mentioned GB/T3137 requirements. The test results are listed in Table 1.
5.0 kg of tantalum powder obtained by reducing potassium fluotantalate with sodium, comprising a compound comprising 50 ppm phosphorus, was directly subjected to high-temperature high-vacuum heat treatment for 0.5 h at 1400° C., and then to oxygen reduction and acid cleaning to obtain tantalum powder.
The tantalum powder was made into an anode block according to the anode block mass, pressed density, anode block sintering temperature, sintering time specified in Table 1, and other conditions as per the above-mentioned GB/T3137 requirements, energized at 150 V, and then tested for electrical properties as per the above-mentioned GB/T3137 requirements. The test results are listed in Table 1.
5.0 kg of tantalum powder obtained by reducing tantalum oxide with magnesium was mixed with 2.3% of metal magnesium particles by weight of the tantalum powder and simultaneously with 5.0 kg of potassium chloride (KCl). After uniformly mixing, the obtained mixture was loaded into a reaction vessel, and air in the reaction vessel was separated. Argon was introduced into the reaction vessel, and, under the condition of keeping positive pressure, the reaction vessel was put into a heating furnace for heating to a temperature of 950° C., followed by soaking for 4.0 h. Then, the reaction vessel was cooled to a temperature of 720° C., and vacuumized so that the pressure in the reaction vessel was lowered to 5.7 Pa, followed by soaking for 2 h, and vacuumizing was stopped. Then, argon was introduced into the reaction vessel, and, under the condition of keeping positive pressure, the reaction vessel was heated to 900° C., followed by soaking for 6 h. After the soaking was finished, the reaction vessel was cooled to room temperature, and passivation treatment was carried out. Thereafter, the obtained mixture of the halide and the tantalum powder was subjected to water washing, acid washing, filtering and drying, to obtain tantalum powder.
The tantalum powder obtained was subjected to high-temperature high-vacuum heat treatment for 0.5 h at 1420° C. and under a pressure of less than 5.0×10−3 Pa, and then to oxygen reduction and acid cleaning to obtain tantalum powder. The tantalum powder was made into an anode block according to the anode block mass, pressed density, anode block sintering temperature, sintering time specified in Table 2, and other conditions as per the above-mentioned GB/T3137 requirements, energized at 200 V, and then tested for electrical properties as per the above-mentioned GB/T3137 requirements. The test results are listed in Table 2.
5.0 kg of flake tantalum powder comprising a compound comprising 1500 ppm nitrogen and a compound comprising 50 ppm boron was mixed with 2.8% of metal magnesium particles by weight of the tantalum powder and simultaneously with 5 kg of potassium chloride (KCl) and 2.5 kg of potassium fluoride (KF). After uniformly mixing, the obtained mixture was loaded into a reaction vessel, and air in the reaction vessel was separated. Argon was introduced into the reaction vessel, and, under the condition of keeping positive pressure, the reaction vessel was put into a heating furnace for heating to a temperature of 950° C., followed by soaking for 4.0 h. Then, the reaction vessel was cooled to a temperature of 700° C., and vacuumized so that the pressure in the reaction vessel was lowered to 5.7 Pa, followed by soaking for 6 h, and vacuumizing was stopped. Then, argon was introduced into the reaction vessel, and, under the condition of keeping positive pressure, the reaction vessel was heated to 950° C., followed by soaking for 5 h. After the soaking was finished, the reaction vessel was cooled to room temperature, and passivation treatment was carried out. Thereafter, the obtained mixture of the halide and the tantalum powder was subjected to water washing, acid washing, filtering and drying, to obtain tantalum powder.
The tantalum powder obtained was subjected to high-temperature high-vacuum heat treatment for 0.5 h at 1500° C. and under a pressure of less than 5.0×10−3 Pa, and then to oxygen reduction and acid cleaning to obtain tantalum powder. The tantalum powder was made into an anode block according to the anode block mass, pressed density, anode block sintering temperature, sintering time specified in Table 2, and other conditions as per the above-mentioned GB/T3137 requirements, energized at 270 V, and then tested for electrical properties as per the above-mentioned GB/T3137 requirements. The test results are listed in Table 2.
It can be seen from Table 1 and Table 2 that: the present invention has the following advantages compared to the prior art: tantalum powder produced according to the present invention is energized under high voltage conditions, and the energized block is tested for electrical performance, which demonstrates that the energized block has a higher specific capacitance and shows a higher breakdown voltage in the breakdown voltage test.
Therefore, the tantalum powder produced according to the present invention is more suitable for manufacturing high-reliability tantalum capacitors.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202111533324.8 | Dec 2021 | CN | national |
The present application is the National Stage of International Patent Application No. PCT/CN2022/114375, filed on Aug. 24, 2022, which claims priority to and all the benefits of Chinese Application No. 202111533324.8, filed on Dec. 15, 2021, which are hereby expressly incorporated herein by reference in their entirety.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2022/114375 | 8/24/2022 | WO |
