In-situ synthesized manganese dioxide battery active material and preparation method thereof
By synthesizing the active materials of manganese dioxide batteries in situ, using foam carbon, manganese phosphate heterojunction and polyaniline coating, the existing positive electrode materials have poor electrochemical properties and low Coulomb efficiency have been solved, and the efficient electron transport and electrochemical performance of the materials have been improved.
Patent Information
- Application Number
- CN202311435962.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-10-31
- Publication Date
- 2025-05-06
AI Technical Summary
The existing positive electrode materials of zinc-ion batteries in water system have problems such as poor electrochemical properties, low Coulomb efficiency and deterioration of electrode structure, which limit the development of batteries.
Manganese dioxide battery active material is synthesized by in-situ, using foam carbon as a conductive substrate, and a microwave heating method is used to synthesize manganese dioxide nanosheets, and a manganese phosphate heterojunction and polyaniline coating are generated on its surface to improve the conductivity and ion transfer rate of the material.
It significantly improves the electron transmission efficiency and electrochemical performance of manganese dioxide active materials, extends the cycle life of the battery and improves the Coulomb efficiency.
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Figure CN119943868A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to the field of zinc ion batteries, and in particular to an in-situ synthesized manganese dioxide battery active material and a preparation method thereof. Background Art
[0002] In the related technologies, aqueous zinc-ion batteries, as a new type of safe aqueous battery, use compounds such as manganese, vanadium, and Prussian blue as positive electrodes. They have the advantages of being non-toxic and low-cost, and have potential application prospects in the fields of new energy vehicles and smart wearables in the future. However, most of these positive electrode materials show poor electrochemical properties and low coulombic efficiency. The strong electrostatic interaction between zinc ions and positive electrode materials causes problems such as electrode structure degradation and slow electron transfer rate, which seriously restricts the development of aqueous zinc-ion batteries. Summary of the invention
[0003] The present application aims to solve at least one of the technical problems existing in the prior art. To this end, the present application proposes an in-situ synthesis of manganese dioxide battery active material and a preparation method thereof, which can improve the electron transmission efficiency of the battery active material.
[0004] According to the preparation method of in-situ synthesized manganese dioxide battery active material in the first aspect of the present application, S1: foam carbon, potassium permanganate, concentrated sulfuric acid and deionized water are added to a high-pressure reaction vessel in sequence, stirred evenly, and the heat source is maintained at a temperature of 160° C. for 6 to 16 hours to obtain a first reaction solution; S2: phosphoric acid is added to the first reaction solution, and the heat source is maintained at a temperature of 160° C. to 180° C. for 6 to 16 hours to obtain a second reaction solution; S3: aniline is added to the second reaction solution, and the temperature is maintained at 2° C. to 3° C. for 5 to 12 hours to obtain a third reaction solution; S4: the third reaction solution is filtered, washed, and dried to obtain the in-situ synthesized manganese dioxide battery active material.
[0005] The in-situ synthesis of manganese dioxide battery active materials according to the embodiments of the present application has at least the following beneficial effects: The manganese dioxide nanosheet material synthesized in situ on carbon foam has a complex conductive carbon network, which greatly improves the conductivity of the manganese dioxide active material. The manganese phosphate heterojunction can also form an ion channel between manganese dioxide and the electrolyte, increase the reaction kinetics of zinc ions, and improve the ion transfer rate. Aniline has good ion permeability, which helps to fully penetrate the ions in the electrolyte and ensure the exposure of the active sites of the electrode material, thereby facilitating the embedding and de-embedding of zinc ions, and ultimately giving it excellent electrochemical properties. After the acid dissociation of phosphoric acid, the conductivity of polyaniline is improved. This makes the electron transfer efficiency of the in situ synthesized manganese dioxide battery active material good.
[0006] According to some embodiments of the present application, the molar ratio of concentrated sulfuric acid, foamed carbon and potassium permanganate is 1:2 to 5:2.
[0007] According to some embodiments of the present application, in S2, the mass ratio of phosphoric acid to potassium permanganate is 3 to 7:2.
[0008] According to some embodiments of the present application, in S3, the mass ratio of aniline to potassium permanganate is 3 to 7:7.
[0009] According to some embodiments of the present application, in S2, the phosphoric acid is a phosphoric acid solution with a mass fraction of 85%.
[0010] According to some embodiments of the present application, in S1 and S2, the heat source is a microwave heating device.
[0011] According to some embodiments of the present application, the high-pressure reaction vessel is a glass fiber autoclave.
[0012] According to some embodiments of the present application, in S1, concentrated sulfuric acid, foamed carbon, potassium permanganate and deionized water are added to a glass fiber autoclave, magnetically stirred for 30 minutes, kept at 160° C. for 6 hours, and naturally cooled to obtain a first reaction liquid.
[0013] According to some embodiments of the present application, the washing in S4 is washing with deionized water and anhydrous ethanol alternately for 3 times, and the drying is vacuum drying at 60° C. to 95° C. in a vacuum drying oven for 12 to 24 hours.
[0014] According to some embodiments of the present application, an in-situ synthesized manganese dioxide battery active material prepared by the above-mentioned method for preparing the in-situ synthesized manganese dioxide battery active material is provided.
[0015] Additional aspects and advantages of the present application will be given in part in the description below, and in part will become apparent from the description below, or will be learned through the practice of the present application. BRIEF DESCRIPTION OF THE DRAWINGS
[0016] The present application is further described below in conjunction with the accompanying drawings and embodiments, wherein: Figure 1 A schematic diagram of the process of preparing an in-situ synthesis manganese dioxide battery active material according to an embodiment of the present application; Figure 2 This is a schematic diagram of an emission scanning electron microscope (SEM) of an in-situ synthesis of manganese dioxide battery active material according to an embodiment of the present application; Figure 3 for Figure 2 A partial enlarged schematic diagram of the transmission scanning electron microscope (SEM); Figure 4 for Figure 3A partial enlarged schematic diagram of the transmission scanning electron microscope (SEM); Figure 5 for Figure 4 A partial enlarged schematic diagram of the transmission scanning electron microscope (SEM); Figure 6 for Figure 5 A partial enlarged schematic diagram of the transmission scanning electron microscope (SEM); Figure 7 A schematic diagram of the cycle performance and coulombic efficiency of a battery assembled with the in-situ synthesized manganese dioxide battery active material prepared in an embodiment of the present application as the positive electrode material; Figure 8 A schematic diagram of the charge and discharge curves of a battery assembled with the in-situ synthesized manganese dioxide battery active material prepared in an embodiment of the present application as the positive electrode material. Implementation
[0017] The embodiments of the present application are described in detail below, and examples of the embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present application, and cannot be understood as limiting the present application.
[0018] In the description of this application, "several" means more than one, "more" means more than two, "greater than", "less than", "exceed", etc. are understood to exclude the number itself, and "above", "below", "within", etc. are understood to include the number itself. If there is a description of "first" or "second", it is only used for the purpose of distinguishing technical features, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features or implicitly indicating the order of the indicated technical features.
[0019] In the description of the present application, the description with reference to the terms "one embodiment", "some embodiments", "illustrative embodiments", "examples", "specific examples", or "some examples" means that the specific features, structures, materials, or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present application. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described may be combined in any one or more embodiments or examples in a suitable manner.
[0020] The following is a further description of the present invention, rather than a limitation of the present invention. Example
[0021] like Figure 1 As shown, this embodiment prepares an in-situ synthesized manganese dioxide battery active material, and the specific process is: (1) 0.48 g of foamed carbon, 6.24 g of potassium permanganate, 2 mL of 98% concentrated sulfuric acid solution and 100 mL of ionized water were sequentially poured into a glass fiber autoclave and magnetically stirred for 30 minutes. The glass fiber autoclave was placed in a microwave muffle furnace and the parameters were set to 160°C. The temperature was kept for 6 hours and cooled naturally to obtain a manganese dioxide suspension, i.e., the first reaction solution. The concentrated sulfuric acid solution was added after potassium permanganate to avoid the reaction between the concentrated sulfuric acid and the foamed carbon.
[0022] (2) The glass fiber autoclave was opened, 12 mL of 85% by mass phosphoric acid solution was added thereto, the glass fiber autoclave was sealed, and the parameters of the microwave muffle furnace were set to 160° C., the temperature was kept for 6 hours, and the suspension was naturally cooled to obtain a manganese phosphate heterojunction doped manganese dioxide suspension, i.e., the second reaction solution.
[0023] (3) The glass fiber autoclave was opened, 2.5 g of aniline was added, and the system temperature was maintained at 2-3° C. in a low-temperature reaction bath. The reaction was carried out for 5 hours to polymerize the aniline into polyaniline and coat the surface of the manganese dioxide. The obtained liquid was the third reaction liquid.
[0024] (4) The third reaction liquid was filtered and washed alternately with deionized water and anhydrous ethanol for three times. The obtained solid was placed in a vacuum drying oven at 60° C. and vacuum dried for 24 hours to obtain an in-situ synthesized manganese dioxide battery active material. Example
[0025] This embodiment prepares an in-situ synthesis of manganese dioxide battery active material, the specific process is: (1) 0.5 g of foamed carbon, 6.24 g of potassium permanganate, 2 mL of 98% concentrated sulfuric acid solution and 100 mL of ionized water were sequentially poured into a glass fiber autoclave and magnetically stirred for 30 min. The glass fiber autoclave was placed in a microwave muffle furnace and the parameters were set to 160 °C. The temperature was kept for 8 h and the mixture was naturally cooled to obtain a manganese dioxide suspension, i.e., the first reaction solution.
[0026] (2) The glass fiber autoclave was opened, 14 mL of 85% by mass phosphoric acid solution was added thereto, the glass fiber autoclave was sealed, and the parameters of the microwave muffle furnace were set to 165° C., the temperature was kept for 8 h, and the suspension was naturally cooled to obtain a manganese phosphate heterojunction-doped manganese dioxide suspension, i.e., the second reaction solution.
[0027] (3) The glass fiber autoclave was opened, 3 g of aniline was added, and the system temperature was maintained at 2-3°C in a low-temperature reaction bath. The reaction was carried out for 6 hours to polymerize the aniline into polyaniline and coat the surface of the manganese dioxide. The obtained liquid was the third reaction liquid.
[0028] (4) The third reaction liquid was filtered and washed alternately with deionized water and anhydrous ethanol for three times. The obtained solid was placed in a vacuum drying oven at 70° C. and vacuum dried for 20 hours to obtain an in-situ synthesized manganese dioxide battery active material. Example
[0029] This embodiment prepares an in-situ synthesis of manganese dioxide battery active material, the specific process is: (1) 0.7 g of foamed carbon, 6.24 g of potassium permanganate, 2 mL of 98% concentrated sulfuric acid solution and 100 mL of ionized water were sequentially poured into a glass fiber autoclave and magnetically stirred for 30 minutes. The glass fiber autoclave was placed in a microwave muffle furnace and the parameters were set to 160 °C. The temperature was kept for 10 hours and naturally cooled to obtain a manganese dioxide suspension, i.e., the first reaction solution.
[0030] (2) The glass fiber autoclave was opened, 16 mL of 85% by mass phosphoric acid solution was added thereto, the glass fiber autoclave was sealed, and the parameters of the microwave muffle furnace were set to 170° C., the temperature was kept for 10 h, and the suspension was naturally cooled to obtain a manganese phosphate heterojunction-doped manganese dioxide suspension, i.e., the second reaction solution.
[0031] (3) The glass fiber autoclave was opened, 3.5 g of aniline was added, and the system temperature was maintained at 2-3° C. in a low-temperature reaction bath. The reaction was carried out for 8 hours to polymerize the aniline into polyaniline and coat the surface of the manganese dioxide. The obtained liquid was the third reaction liquid.
[0032] (4) The third reaction liquid was filtered and washed alternately with deionized water and anhydrous ethanol for three times. The obtained solid was placed in a vacuum drying oven at 80° C. and vacuum dried for 16 hours to obtain an in-situ synthesized manganese dioxide battery active material. Example
[0033] This embodiment prepares an in-situ synthesis of manganese dioxide battery active material, the specific process is: (1) 0.8 g of foamed carbon, 6.24 g of potassium permanganate, 2 mL of 98% concentrated sulfuric acid solution and 100 mL of ionized water were sequentially poured into a glass fiber autoclave and magnetically stirred for 30 min. The glass fiber autoclave was placed in a microwave muffle furnace and the parameters were set to 160 °C. The temperature was kept for 12 h and the mixture was naturally cooled to obtain a manganese dioxide suspension, i.e., the first reaction solution.
[0034] (2) The glass fiber autoclave was opened, 20 mL of 85% by mass phosphoric acid solution was added thereto, the glass fiber autoclave was sealed, and the parameters of the microwave muffle furnace were set to 175° C., the temperature was kept for 12 h, and the suspension was naturally cooled to obtain a manganese phosphate heterojunction-doped manganese dioxide suspension, i.e., the second reaction solution.
[0035] (3) The glass fiber autoclave was opened, 4 g of aniline was added, and the system temperature was maintained at 2-3°C in a low-temperature reaction bath. The reaction was carried out for 10 hours to polymerize the aniline into polyaniline and coat the surface of the manganese dioxide. The obtained liquid was the third reaction liquid.
[0036] (4) The third reaction liquid was filtered and washed alternately with deionized water and anhydrous ethanol for three times. The obtained solid was placed in a vacuum drying oven at 90° C. and vacuum dried for 14 hours to obtain an in-situ synthesized manganese dioxide battery active material. Example
[0037] This embodiment prepares an in-situ synthesis of manganese dioxide battery active material, the specific process is: (1) 1.2 g of foamed carbon, 6.24 g of potassium permanganate, 2 mL of 98% concentrated sulfuric acid solution and 100 mL of ionized water were sequentially poured into a glass fiber autoclave and magnetically stirred for 30 minutes. The glass fiber autoclave was placed in a microwave muffle furnace and the parameters were set to 160°C. The temperature was kept for 16 hours and naturally cooled to obtain a manganese dioxide suspension, i.e., the first reaction solution.
[0038] (2) The glass fiber autoclave was opened, 25 mL of 85% by mass phosphoric acid solution was added thereto, the glass fiber autoclave was sealed, and the parameters of the microwave muffle furnace were set to 180° C., the temperature was kept for 16 h, and the suspension was naturally cooled to obtain a manganese phosphate heterojunction-doped manganese dioxide suspension, i.e., the second reaction solution.
[0039] (3) The glass fiber autoclave was opened, 5 g of aniline was added, and the system temperature was maintained at 2-3°C in a low-temperature reaction bath. The reaction was carried out for 12 hours to polymerize the aniline into polyaniline and coat the surface of the manganese dioxide. The obtained liquid was the third reaction liquid.
[0040] (4) The third reaction liquid was filtered and washed alternately with deionized water and anhydrous ethanol for three times. The obtained solid was placed in a vacuum drying oven at 95° C. and vacuum dried for 12 hours to obtain an in-situ synthesized manganese dioxide battery active material.
[0041] Working principle: Microwave heating is used to control the temperature and time of the hydrothermal reaction. Foam carbon is a three-dimensional structural carbon material formed by a carbon atom network, and can have a large specific surface area and high adsorption capacity, which is beneficial to provide more reaction sites and electron transfer for manganese dioxide. Based on the conductive substrate of foam carbon, microwave radiation method is further used to synthesize manganese dioxide nanosheets on it in situ, and then the above product is added to a glass fiber autoclave and reacted in a closed container. By controlling the reaction temperature and time, the crystal form and morphology of manganese dioxide are affected, and the microstructure of the composite material is highly retained. In addition, the manganese dioxide nanosheet material synthesized in situ on foam carbon has a complex conductive carbon network, which greatly improves the conductivity of the manganese dioxide active material. The reaction mechanism is as follows: 4 KMnO 4 +4 C+2 H 2 SO 4 == 4 MnO 2 +3 CO 2 +2 K 2 SO 4 +2 H 2 O After that, an excess of phosphoric acid is added to the system, and by controlling the temperature and reaction time, a manganese phosphate heterojunction is generated on the surface of the manganese dioxide nanosheet. In this way, the manganese phosphate heterojunction provides a stable support site between the lattice layers of manganese dioxide, thereby maintaining the structural stability of manganese dioxide. At the same time, the manganese phosphate heterojunction can also form an ion channel between manganese dioxide and the electrolyte, increase the reaction kinetics of zinc ions, and improve the ion transfer rate.
[0042] Then, aniline monomer is added to the system. The excess phosphoric acid in the previous step is used as a proton acid, and the manganese dioxide synthesized in the first step is used as an initiator to polymerize the aniline monomer. Aniline monomer forms cationic radicals after oxidation, on which two cations undergo free radical coupling to form dimers through dehydrogenation aromatization. Then, these dimers or newly generated monomers are oxidized to form cationic radicals, further forming aniline polymers with larger molecular weight. Finally, polyaniline on these macromolecular chains is deposited on the surface of manganese dioxide nanosheets. Porous polyaniline has good ion permeability, which helps to fully penetrate ions in the electrolyte and ensures the exposure of active sites of electrode materials, thereby facilitating the embedding and de-embedding of zinc ions, ultimately giving it excellent electrochemical properties. Polyaniline has excellent conductivity and flexibility, which can effectively slow down the volume expansion during charging and discharging, ensuring excellent electrochemical performance. At the same time, when phosphoric acid undergoes acid dissociation, protons will undergo protonation reaction with nitrogen atoms on polyaniline imine. This forms a polaron structure, and electrons can be delocalized on the conjugated large π bonds on the molecular skeleton, greatly improving the conductivity of polyaniline. The synergistic effect of the polyaniline and manganese phosphate heterojunction reduces the diffusion barrier of zinc ions in layered manganese dioxide, greatly improving the diffusion kinetics of zinc ions. In addition, polyaniline coating increases the hydrophobicity of the active material of the in-situ synthesized manganese dioxide battery, which can alleviate its decomposition and dissolution problems in aqueous electrolytes, thereby significantly enhancing the electrochemical stability of the positive electrode material and the cycle life of the battery. During the synthesis process, a single container is used, and the foam carbon skeleton is first used as a template to in-situ synthesize manganese dioxide nanosheets. Subsequently, phosphoric acid is introduced to introduce manganese phosphate heterojunctions on the manganese dioxide nanosheets. After that, phosphoric acid is used as a protonic acid and manganese dioxide is used as an initiator to polymerize aniline monomers into polyaniline, which is then coated on the surface of the material. There is no need to remove impurities from the phosphoric acid in the previous step. Therefore, the process steps are simple, the materials used are simple, and they can be reused in different links, saving process links and material preparation, which is beneficial to industrial production.
[0043] The in-situ synthesized manganese dioxide battery active material was tested, and the results were as follows Figures 2 to 8 shown.
[0044] The prepared in-situ synthesized manganese dioxide battery active material was mixed with carbon black conductive agent and binder (PVDF) in a mass ratio of 92:5:3, and N-methyl-2-pyrrolidone (NMP) was used as solvent. The above materials were stirred into a slurry and coated on titanium foil, and then dried in a drying oven at 130°C for 24 hours to obtain a pole piece. The above-prepared pole piece was used as the positive electrode, the copper foil coated with zinc powder was used as the negative electrode, the sulfonated PP film was used as the diaphragm, and 2 mol / L ZnSO4 was used as the electrolyte. The CR2025 button battery was assembled in an air atmosphere to test the electrochemical performance of the material. Using the LAND battery test system, the battery was activated at 1-1.9V, 0.05C, and then cycled at 1-1.9V, 1C, and 5C.
[0045] The obtained in-situ synthesized manganese dioxide battery active material was made into a working electrode according to the method provided by the present invention and the corresponding performance tests were carried out. The results are shown in Table 1.
[0046] Example <![CDATA[Initial discharge specific capacity / mAh g -1 > <![CDATA[50th discharge specific capacity / mAh g -1 > <![CDATA[100th discharge specific capacity / mAh g -1 > <![CDATA[The specific discharge capacity at the 200th cycle / mAh g -1 > <![CDATA[500th discharge specific capacity / mAh g -1 > <![CDATA[800th discharge specific capacity / mAh g -1 > 1000th discharge capacity / mAhg-1 Example 1 190 210 205 198 184 176 170 Example 2 188 205 203 194 178 173 166 Example 3 184 201 205 196 182 179 175 Example 4 187 209 203 197 189 171 163 Example 5 175 197 195 187 183 176 165 Table 1 shows the cycle performance of the batteries in different embodiments, indicating that the in-situ synthesized manganese dioxide battery active material has a long cycle stability for the positive electrode of zinc ion batteries.
[0047] The embodiments of the present application are described in detail above in conjunction with the accompanying drawings, but the present application is not limited to the above embodiments. Various changes can be made within the knowledge of ordinary technicians in the relevant technical field without departing from the purpose of the present application. In addition, the embodiments of the present application and the features in the embodiments can be combined with each other without conflict.
[0048] It should also be noted that the terms "include", "comprises" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, commodity or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, commodity or device. In the absence of more restrictions, the elements defined by the sentence "comprises a ..." do not exclude the existence of other identical elements in the process, method, commodity or device including the elements.
[0049] Although the present invention has been described in detail with reference to the aforementioned embodiments, it is still possible for those skilled in the art to modify the technical solutions described in the aforementioned embodiments, or to make equivalent substitutions for some of the technical features therein. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.
Claims
1. A method for preparing an in-situ synthesized manganese dioxide battery active material, characterized in that: include: S1: Add foamed carbon, potassium permanganate, concentrated sulfuric acid and deionized water into a high-pressure reaction vessel in sequence, stir evenly, maintain the temperature of the heat source at 160° C., and keep the temperature for 6 to 16 hours to obtain a first reaction solution; S2: adding phosphoric acid to the first reaction solution, maintaining the temperature of the heat source at 160° C. to 180° C., and keeping the temperature for 6 to 16 hours to obtain a second reaction solution; S3: adding aniline to the second reaction solution, and keeping the temperature at 2° C. to 3° C. for 5 to 12 hours to obtain a third reaction solution; S4: filtering, washing, and drying the third reaction liquid to obtain the in-situ synthesized manganese dioxide battery active material.
2. The method for preparing the in-situ synthesized manganese dioxide battery active material and its application according to claim 1, characterized in that: The molar ratio of the concentrated sulfuric acid, the foamed carbon and the potassium permanganate is 1:2 to 5:
2.
3. The method for preparing the in-situ synthesized manganese dioxide battery active material according to claim 1, characterized in that: In S2, the mass ratio of the phosphoric acid to the potassium permanganate is 3 to 7:
2.
4. The method for preparing the in-situ synthesized manganese dioxide battery active material according to claim 1, characterized in that: In S3, the mass ratio of the aniline to the potassium permanganate is 3 to 7:
7.
5. The method for preparing the in-situ synthesized manganese dioxide battery active material according to claim 1, characterized in that: In S2, the phosphoric acid is a phosphoric acid solution with a mass fraction of 85%.
6. The method for preparing in-situ synthesized manganese dioxide battery active material according to claim 1, characterized in that: In S1 and S2, the heat source is a microwave heating device.
7. The method for preparing in-situ synthesized manganese dioxide battery active material according to claim 1, characterized in that: The high-pressure reaction vessel is a glass fiber autoclave.
8. The method for preparing the in-situ synthesized manganese dioxide battery active material according to claim 7, characterized in that: In the S1, the concentrated sulfuric acid, the foamed carbon, the potassium permanganate and the deionized water are added into the glass fiber autoclave, magnetically stirred for 30 minutes, kept at 160° C. for 6 hours, and cooled naturally to obtain a first reaction solution.
9. The method for preparing an in-situ synthesized manganese dioxide battery active material according to any one of claims 1 to 8, characterized in that: The washing in S4 is washing with deionized water and anhydrous ethanol alternately for 3 times, and the drying is vacuum drying in a vacuum drying oven at 60° C. to 95° C. for 12 hours to 24 hours.
10. An in-situ synthesized manganese dioxide battery active material prepared according to the preparation method according to any one of claims 1 to 9.