WO2022142774A1 - 一种碳基二维复合电极材料及其制备方法 - Google Patents
一种碳基二维复合电极材料及其制备方法 Download PDFInfo
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- WO2022142774A1 WO2022142774A1 PCT/CN2021/130530 CN2021130530W WO2022142774A1 WO 2022142774 A1 WO2022142774 A1 WO 2022142774A1 CN 2021130530 W CN2021130530 W CN 2021130530W WO 2022142774 A1 WO2022142774 A1 WO 2022142774A1
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- 239000002131 composite material Substances 0.000 title claims abstract description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 33
- 239000007772 electrode material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 24
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000002086 nanomaterial Substances 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 239000002135 nanosheet Substances 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 9
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 8
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims abstract description 7
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 150000002505 iron Chemical class 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 159000000014 iron salts Chemical class 0.000 claims description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 238000000137 annealing Methods 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 7
- 238000010276 construction Methods 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000005501 phase interface Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 239000002105 nanoparticle Substances 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 230000032258 transport Effects 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000007833 carbon precursor Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/12—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
Definitions
- the invention belongs to the technical field of electrode material preparation, and particularly relates to a carbon-based two-dimensional composite electrode material and a preparation method thereof.
- Lithium-ion batteries have been widely used in many aspects of daily life, and their applications have been successfully extended from portable electronics to electric vehicles due to their high energy density.
- sodium-ion batteries have shown great market potential in large-scale energy storage systems due to their abundant storage resources and low cost.
- the preparation of electrode materials with excellent electrochemical performance, abundant reserves, and low cost is a major challenge for Li-ion and Na-ion batteries.
- Iron sulfide is considered to be a promising electrode material due to its abundant reserves, low cost, and environmental friendliness.
- the electrochemical performance of iron sulfide is poor, which hinders its commercial application.
- nanostructured materials can well buffer the large volume change during cycling, thereby alleviating the pulverization phenomenon of electrode materials, and enhancing the reaction kinetics by shortening the transport paths of electrons and ions, thereby improving the cycling performance and rate performance.
- nanomaterials tend to undergo severe aggregation during charging and discharging, which largely weakens the advantages of nanoelectrode materials. Recent studies have shown that combining nanomaterials with carbonaceous materials can effectively alleviate the problem of nanomaterial aggregation.
- the introduced carbon material can also improve the ionic/electronic conductivity and act as a buffer material to slow down the pulverization problem of the electrode material.
- Graphene has become the most widely used carbonaceous material in composite electrode materials due to its excellent electrical conductivity and flexible two-dimensional structure.
- the traditional methods for synthesizing nanomaterials and graphene composites are mechanical mixing or hydrothermal/solvothermal with graphene as the substrate material.
- the common disadvantage of composite materials synthesized by the above method is that the interaction between active components and graphene is weak, resulting in poor structural stability.
- the technical problem to be solved by the present invention is that because the graphite negative electrode belongs to the intercalation material, the theoretical specific capacity is low, which is insufficient to meet people's demand for the energy density of lithium ion batteries; in addition, graphite is an inert material in sodium ion batteries, and the capacity is extremely low Therefore, it is necessary to develop anode materials with higher specific capacity.
- metal-based anode materials with alloying or conversion reactions have high theoretical specific capacity due to multi-electron reactions in the energy storage process, and have received extensive attention in recent years.
- iron sulfide is considered to be a very promising electrode material due to its high specific capacity, abundant reserves, low cost, and environmental friendliness. Due to the slow chemical reaction and other reasons, the electrochemical performance of iron sulfide is poor, which hinders its commercial application.
- the present invention prepares an ultra-thin iron sulfide and carbon nanosheet composite electrode material through a combination of a simple hydrothermal method and heat treatment.
- the integrated composite structure construction strategy not only simplifies the synthesis process of the entire electrode material, but also significantly increases the contact firmness between iron sulfide and 2D carbon nanosheets, greatly reduces the interface resistance, and promotes the electronic and ion transport speed at different phase interfaces, so the iron sulfide and carbon two-dimensional composite nanostructures show excellent cycle performance and extraordinary rate performance.
- a preparation method of a carbon-based two-dimensional composite electrode material respectively adding sodium dodecylbenzenesulfonate, polyvinylpyrrolidone, thiourea, sulfur to the iron salt solution.
- the two-dimensional composite material precursor is obtained after hydrothermal treatment after substitution of acetamide.
- sodium dodecyl sulfonate and polyvinylpyrrolidone act as surfactants and carbon sources, while thiourea and thioacetamide provide sulfur sources.
- iron ions and sulfur sources form iron sulfide, which is embedded in the In the 2D carbon precursor framework formed by the polymerization of small organic molecules.
- the precursor material is iron sulfide nanoparticles embedded in ultra-thin two-dimensional organic polymers with smooth surface and flexibility; the two-dimensional composite material precursor is heat-treated to obtain a two-dimensional composite nano-material of iron sulfide and carbon.
- the iron sulfide quantum dots are aggregated and crystallized, and the two-dimensional organic polymer is carbonized at high temperature.
- the iron sulfide nanoparticles or hexagonal nanosheets are embedded on the surface of the flexible and ultra-thin two-dimensional carbon nanosheets.
- the iron salt is one or more mixtures of iron salts such as iron chloride, iron nitrate, iron sulfate, iron acetate, etc., and all iron salts are applicable.
- the solvent for dissolving the iron salt is a mixed solvent of deionized water and alcohol.
- the concentration of the iron salt solution to 0.01-0.12 mol/L, the particle size of iron sulfide and the content in the composite material can be effectively adjusted.
- the addition amounts of sodium dodecyl sulfonate, polyvinylpyrrolidone, thiourea and thioacetyl are respectively 0.05-0.2g/50-90ml solvent, 0.1-0.5g/50-90ml solvent, 2-6mmol/ 50 ⁇ 90ml solvent, 2-6mmol/50 ⁇ 90ml solvent, different addition concentrations can effectively control the structure and components of the composite material, such as the thickness of the two-dimensional composite material, the content of iron, etc.
- the hydrothermal treatment step is: heating the mixed solution of iron salts after adding polyvinylpyrrolidone, thiourea, and thioacetamide at 150-250° C.
- the temperature is lower than this interval and a two-dimensional composite structure cannot be formed, and the temperature is high. In this range, the hydrothermal kettle cannot withstand it, and it has certain dangers.
- the product after hydrothermal treatment is cooled and centrifuged, washed with deionized water and ethanol to obtain a two-dimensional composite material precursor, which is completely dried and used for later use.
- the heat treatment step is: heating and annealing the prepared two-dimensional composite material precursor at 400°C and above in an inert atmosphere, and the carbon precursor material cannot be effectively carbonized below this temperature.
- iron sulfide quantum dots and iron sulfide hexagonal nanosheets are embedded in micron-scale ultra-thin carbon nanosheets.
- the carbon 2D nanosheets are thin and flexible, which not only prevents the aggregation problem of iron sulfide nanomaterials during charging and discharging, but also improves the transport speed of ions and electrons during cycling.
- the iron sulfide nanoparticles are beneficial for releasing the stress caused by the volume change, which in turn does not cause material powdering problems.
- the two-dimensional structure of this composite electrode material and the small size of iron sulfide nanoparticles not only provide a sufficiently large specific surface area to contact the electrolyte, but also greatly reduce the diffusion paths of lithium/sodium ions and electrons, greatly reducing the Promotes electrochemical reaction kinetics.
- the two-dimensional precursor material obtained after the hydrothermal treatment of the present invention is that iron sulfide nanoparticles are embedded in ultra-thin two-dimensional organic polymers with smooth surface and flexibility;
- the quantum dots are polymerized and crystallized, and the two-dimensional organic polymer is carbonized at high temperature.
- the iron sulfide nanoparticles or hexagonal nanosheets are embedded on the surface of the flexible and ultra-thin two-dimensional carbon nanosheets.
- Carbon materials have nitrogen-sulfur co-doping properties.
- the carbon 2D nanosheets are thin and flexible, which not only prevents the aggregation problem of iron sulfide nanomaterials during the charge-discharge process, but also improves the ionic and electronic properties during cycling. transfer speed. These iron sulfide nanoparticles are beneficial for releasing the stress caused by the volume change, which in turn does not cause material pulverization problems.
- the two-dimensional structure of this composite electrode material and the small size of iron sulfide nanoparticles not only provide a sufficiently large specific surface area to contact the electrolyte, but also greatly reduce the diffusion paths of lithium/sodium ions and electrons, greatly reducing the Promotes electrochemical reaction kinetics.
- the integrated construction strategy significantly improves the robustness of the interfacial contact between iron sulfide and 2D carbon nanosheets, greatly reduces the interfacial impedance, and promotes the transport speed of electrons and ions at different phase interfaces. . Based on the above structural and compositional advantages, the iron sulfide and carbon two-dimensional composite nanostructures exhibit excellent cycling performance and extraordinary rate capability.
- Fig. 1 is the scanning electron microscope picture of two-dimensional composite electrode material of the present invention
- (a) is the precursor of the two-dimensional composite material; (b, c) are the two-dimensional composite material.
- a preparation method of a carbon-based two-dimensional composite electrode material comprising the following steps:
- iron salts such as ferric chloride and ferric nitrate are dissolved in 50ml mixed solvent of deionized water and alcohol to form a transparent solution.
- the type of alcohol and the ratio of alcohol solvent to deionized water can be adjusted. Adjustable.
- S5 The prepared two-dimensional composite material precursor is heated and annealed at above 400°C in an inert atmosphere to obtain a two-dimensional composite nanomaterial of iron sulfide and carbon.
- the specific heating rate, heating temperature and heating time are adjustable.
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- Inorganic Chemistry (AREA)
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Abstract
涉及一种碳基二维复合电极材料及其制备方法,属于电极材料制备技术领域,具体包括:向铁盐溶液中分别加入十二烷基磺酸钠、聚乙烯吡咯烷酮、硫脲、硫代乙酰胺后经水热处理后得到二维复合材料前驱体;对二维复合材料前驱体进行热处理,得到硫化铁和碳的二维复合纳米材料。一体化的复合结构构建策略不仅简化了整个电极材料的合成过程,同时显著地增加了硫化铁和二维碳纳米片之间接触的牢固性,极大减小了界面阻抗,促进了电子和离子在不同相界面的传输速度,从而该硫化铁和碳二维复合纳米结构表现出了优异的循环性能和超常的倍率性能。
Description
本发明属于电极材料制备技术领域,具体涉及一种碳基二维复合电极材料及其制备方法。
锂离子电池已经被广泛的应用到日常生活的许多方面,由于其高能量密度,其应用已成功地从便携式电子产品扩展到电动汽车。作为锂离子电池的替代品,由于存储资源丰富、成本低廉,钠离子电池在大型储能系统中显示出了巨大的市场潜力。目前,制备具有优异电化学性能,丰富储量以及成本低廉的电极材料是锂离子电池和钠离子电池的主要挑战。硫化铁因其储量丰富、成本低、环境友好等优点,被认为是极有发展前途的电极材料。但由于充放电过程中体积变化大,动力学反应缓慢等原因导致硫化铁的电化学性能较差,阻碍了其商业化应用。
将电极材料制成纳米结构是解决硫化铁电化学性能差的可行方法。一般而言,纳米结构材料能够很好地缓冲循环过程中较大的体积变化,进而缓解电极材料的粉化现象,并通过缩短电子和离子的传输路径来增强反应动力学,从而改善循环性能和倍率性能。然而,纳米材料在充放电过程中往往会发生严重的聚集,这在很大程度上削弱了纳米电极材料的优点。最近的研究表明,将纳米材料与碳质材料结合,可以有效缓解纳米材料的聚集的问题。此外,引入的碳材料还可以提高离子/电子电导率,并作为缓冲材料来减缓电极材料的粉化问题。石墨烯因为其优异的导电性和柔韧的二维结构成为在复合电极材料中应用最广泛的碳质材料。合成纳米材料与石墨烯复合材料的传统方法是机械混合或以石墨烯作为基底材料进行水热/溶剂热。但用上述方法合成的复合材料常见缺点是:活性组分与石墨烯的相互作用较弱,导致结构稳定性较差。在充放电过程中,巨大的体积变化会使活性纳米材料不断从石墨烯上脱落,进而导致电池的容量衰减和倍率性能差的问题。此外,Hummers法合成石墨烯的附加程序也使复合材料整个制备过程变得更加复杂。
发明内容:
本发明要解决的技术问题是由于石墨负极属于插层材料,理论比容量较低,不足以满足人们对锂离子电池能量密度的需求;此外,石墨在钠离子电池中属于惰性材料,容量极低;因而,需要研发具有更高比容量的负极材料。而具有合金或转换反应的金属基负极材料因在储能过程中的多电子反应,具有较高的理论比容量,近年来受到人们的广泛关注。在众多的金属基转换材料中,硫化铁因其比容量高、储量丰富、成本低、环境友好等优点,被认为是极有发展前途的电极材料,但由于充放电过程中体积变化大,动力学反应缓慢等原因导致硫 化铁的电化学性能较差,阻碍了其商业化应用。
为解决上述问题,本发明通过一种简单的水热方法和热处理相结合的策略制备了一种超薄硫化铁和碳纳米片复合电极材料。其中,一体化的复合结构构建策略不仅简化了整个电极材料的合成过程,同时显著地增加了硫化铁和二维碳纳米片之间接触的牢固性,极大减小了界面阻抗,促进了电子和离子在不同相界面的传输速度,从而该硫化铁和碳二维复合纳米结构表现出了优异的循环性能和超常的倍率性能。
为达到上述目的,本发明通过以下技术方案实现,一种碳基二维复合电极材料的制备方法,向铁盐溶液中分别加入十二烷基苯磺酸钠、聚乙烯吡咯烷酮、硫脲、硫代乙酰胺后经水热处理后得到二维复合材料前驱体。其中十二烷基磺酸钠、聚乙烯吡咯烷酮起到表面活性剂和碳源的作用,硫脲和硫代乙酰胺提供硫源,在水热过程中铁离子和硫源形成硫化铁,并镶嵌在由有机小分子聚合形成的二维碳前驱体骨架中。该前驱体材料为硫化铁纳米颗粒镶嵌在表面光滑、具有柔韧性的超薄的二维有机聚合物;对二维复合材料前驱体进行热处理,得到硫化铁和碳的二维复合纳米材料,热处理过程中,硫化铁量子点聚合结晶析出,二维有机聚合物高温碳化,热处理结束之后得到的是硫化铁纳米颗粒或六边形纳米片镶嵌在柔韧超薄的二维碳纳米片表面。
进一步的,所述铁盐为氯化铁、硝酸铁、硫酸铁、醋酸铁等铁盐中的一种或一种以上的混合物,所有铁盐均适用。
进一步的,铁盐溶解的溶剂为去离子水和醇类混合溶剂。
进一步的,通过将铁盐溶液的浓度调控在0.01-0.12mol/L,可有效调控硫化铁的颗粒大小及在复合材料中的含量。
进一步的,十二烷基磺酸钠、聚乙烯吡咯烷酮、硫脲、硫代乙酰的添加量分别为0.05-0.2g/50~90ml溶剂,0.1~0.5g/50~90ml溶剂、2-6mmol/50~90ml溶剂、2-6mmol/50~90ml溶剂,不同的添加浓度可以有效控制复合材料的结构和组分,如二维复合材料的厚度,铁的含量等。
进一步的,水热处理步骤为:将加入聚乙烯吡咯烷酮、硫脲、硫代乙酰胺后的铁盐混合溶液,在150-250℃下加热,温度低于此区间无法形成二维复合结构,温度高于此区间水热釜无法承受,具有一定的危险性。
进一步的,水热处理后的产物,经冷却、离心分离后,用去离子水和乙醇洗涤得到二维复合材料前驱体,完全干燥后备用。
进一步的,热处理步骤为:将制备好的二维复合材料前驱体在惰性气氛中于400℃及以 上加热退火,低于此温度碳前驱体材料无法有效碳化。
上述技术方案中提及到的方法及中间流程,所有与之相似的方法、或由此技术衍生出来的方法均受本专利保护。上述提及到的方法中所有涉及的反应物比例、铁盐种类均可调节,且合成方法的规模如反应物的量,反应釜的容量等均可按比例放大生产制备,相关技术细节均受本专利保护。此外,本专利中涉及到的升温速率、加热温度和加热时间可调,相关技术均受本专利保护。
一种上述方法制备得到的碳基二维复合电极材料,硫化铁量子点和硫化铁六边形纳米片镶嵌在微米级超薄的碳纳米片中。
在这种复合材料中,碳二维纳米片薄而柔韧,不仅阻止了硫化铁纳米材料在充放电过程中的聚集问题,还提高了循环过程中的离子和电子的传输速度。硫化铁纳米颗粒有利于释放因体积变化引起的应力,进而不会引发材料粉化问题。这种复合电极材料的二维结构以及硫化铁纳米颗粒较小的尺寸不仅提供了足够大的比表面积与电解质接触,同时很大程度上减小了锂/钠离子和电子的扩散路径,极大地促进了电化学反应动力学。此外,氮硫共掺杂增加了电极材料的活性位点,对于容量及倍率性能的提升效果显著。所有由上述技术方案及与之相似的或由其衍生出的技术方案所合成出的类似的结构均受本专利保护。
本发明的有益效果在于:
(1)合成方法:本发明中提出的一体化的复合结构构建策略具有很高的创新性,极大简化了此类复合电极材料的制备过程。
(2)结构和成分特征:本发明水热之后获得的二维前驱体材料是硫化铁纳米颗粒镶嵌在表面光滑、具有柔韧性的超薄的二维有机聚合物中;热处理过程中,硫化铁量子点聚合结晶析出,二维有机聚合物高温碳化,热处理结束之后得到的是硫化铁纳米颗粒或六边形纳米片镶嵌在柔韧超薄的二维碳纳米片表面,在成份上,此二维碳材料具有氮硫共掺杂特性。
(3)构效关系:在这种复合材料中,碳二维纳米片薄而柔韧,不仅阻止了硫化铁纳米材料在充放电过程中的聚集问题,还提高了循环过程中的离子和电子的传输速度。这些硫化铁纳米颗粒有利于释放因体积变化引起的应力,进而不会引发材料粉化问题。这种复合电极材料的二维结构以及硫化铁纳米颗粒较小的尺寸不仅提供了足够大的比表面积与电解质接触,同时很大程度上减小了锂/钠离子和电子的扩散路径,极大地促进了电化学反应动力学。此外,氮硫共掺杂增加了电极材料的活性位点,对于容量及倍率性能的提升效果显著。更重要的是,一体化的构建策略显著地提高了硫化铁和二维碳纳米片之间界面接触的牢固性,极大减小了界面阻抗,促进了电子和离子在不同相界面的传输速度。基于上述结构及成分上的优势,该 硫化铁和碳二维复合纳米结构表现出了优异的循环性能和超常的倍率性能。
图1是本发明二维复合电极材料的扫描电镜图片;
其中,(a)为二维复合材料前驱体;(b,c)为二维复合材料。
为使本发明实施例的目的、技术方案和优点更加清楚,下面对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1:
一种碳基二维复合电极材料的制备方法,包括以下步骤:
S1:4mmol铁盐如氯化铁、硝酸铁等溶于50ml去离子水与醇类的混合溶剂中形成透明溶液,醇类的种类及醇类溶剂和去离子水的比例可调,铁盐种类可调。
S2:将0.05g十二烷基磺酸钠,0.5g聚乙烯吡咯烷酮、5mmol硫脲、4mmol硫代乙酰胺分别加入上述溶液中,搅拌形成均匀溶液,其中十二烷基磺酸钠、聚乙烯吡咯烷酮、硫脲、硫代乙酰胺的比例上下可调。
S3:将上述溶液转移到100ml聚四氟乙烯内胆中,然后密封到不锈钢高压釜中,并在160-250℃下加热,具体加热温度和时间可调。
S4:所得产物自然冷却至室温后,离心分离,用去离子水和乙醇洗涤数次,得到黑色的二维复合材料前驱体,然后将其在真空箱中干燥数小时直至完全干燥。
S5:将制备好的二维复合材料前驱体在惰性气氛中于400℃以上加热退火,获得硫化铁和碳的二维复合纳米材料,具体的升温速率、加热温度和加热时间可调。
Claims (9)
- 一种碳基二维复合电极材料的制备方法,其特征在于包括:向铁盐溶液中分别加入十二烷基苯磺酸钠、聚乙烯吡咯烷酮、硫脲、硫代乙酰胺后经水热处理后得到二维复合材料前驱体;对二维复合材料前驱体进行热处理,得到硫化铁和碳的二维复合纳米材料。
- 如权利要求1所述的碳基二维复合电极材料的制备方法,其特征在于:所述铁盐为氯化铁、硝酸铁、硫酸铁、醋酸铁等铁盐中的一种或一种以上的混合物。
- 如权利要求1所述的碳基二维复合电极材料的制备方法,其特征在于:铁盐溶解的溶剂为去离子水和醇类混合溶剂。
- 如权利要求1所述的碳基二维复合电极材料的制备方法,其特征在于:铁盐溶液的浓度为0.01-0.12mol/L。
- 如权利要求1所述的碳基二维复合电极材料的制备方法,其特征在于:十二烷基磺酸钠、聚乙烯吡咯烷酮、硫脲、硫代乙酰的添加量分别为0.05-0.2g/50~90ml溶剂,0.1~0.5g/50~90ml溶剂、2-6mmol/50~90ml溶剂、2-6mmol/50~90ml溶剂。
- 如权利要求1所述的碳基二维复合电极材料的制备方法,其特征在于:水热处理步骤为:将加入十二烷基磺酸钠、聚乙烯吡咯烷酮、硫脲、硫代乙酰胺后的铁盐混合溶液,在150-250℃下加热。
- 如权利要求1所述的碳基二维复合电极材料的制备方法,其特征在于:水热处理后的产物,经冷却、离心分离后,用去离子水和乙醇洗涤得到二维复合材料前驱体,完全干燥后备用。
- 如权利要求1所述的碳基二维复合电极材料的制备方法,其特征在于:热处理步骤为:将制备好的二维复合材料前驱体在惰性气氛中于400℃及以上加热退火。
- 一种权利要求1-8中的制备方法得到的碳基二维复合电极材料,其特征在于:硫化铁量子点和硫化铁六边形纳米片镶嵌在微米级超薄的碳纳米片中。
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CN116395672A (zh) * | 2023-03-31 | 2023-07-07 | 西南交通大学 | 荧光碳点的制备方法、抑菌材料以及抑制革兰氏菌的方法 |
CN117486264A (zh) * | 2023-12-29 | 2024-02-02 | 洛阳理工学院 | 一种碳纳米片负载钴基异质结材料及其制备方法和应用 |
CN117486264B (zh) * | 2023-12-29 | 2024-04-02 | 洛阳理工学院 | 一种碳纳米片负载钴基异质结材料及其制备方法和应用 |
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