Synthesis of multi-metallic nanoparticle carbon materials from zeolitic imidazolate frameworks (ZIFS)

Abstract

The invention relates to the high-efficiency synthesis of pure or multi-metallic derivatives of ZIF-11 or ZIF-12 or Amorph-ZIF structures, and subsequently the production of composite nano-structured materials with nano metal particles dispersed or embedded on a wide carbon surface through calcination under inert conditions, and the use of these composite nanomaterials as electrodes in Li-ion batteries, Li-S batteries, Na-ion batteries, K-ion batteries, supercapacitors, and fuel cells.

Description

[0001] Synthesis of Multi-Metallic Nanoparticle Carbon Materials from Zeolitic Imidazolate Frameworks (ZIFs)

[0002] Field of the Invention

[0003] The invention relates to the synthesis of pure or multi-metal derivatives of ZIF-11 , ZIF- 12 or amorphous-ZIF structures with high efficiency and subsequent calcination under inert conditions to produce composite nano-structured nano-metal particle materials dispersed or embedded on a large carbon surface and the use of these composite nano-materials as electrodes in Li-ion batteries, Li-S batteries, Na-ion batteries, K-ion batteries, supercapacitors, and fuel cells.

[0004] State of the Art

[0005] Nowadays, transition metal nanoparticles, especially cobalt, nickel, and copper nanoparticles, are useful materials for a number of potential applications such as data storage, medical imaging, energy storage and conversion systems, sensors, and especially heterogeneous catalysis due to their properties such as availability, low cost, unique physicochemical properties, and easy handling. Compared to monometallic nanoparticles, bimetallic and trimetallic alloy nanoparticles of these transition metals exhibit different properties in many application areas due to their controlled composition and strong metal-metal interactions. However, in order for transition metal nanoparticles to exhibit high activity, they must be spread or embedded (surrounded) on a large conductive surface that is not subject to degradation. Otherwise, aggregation occurs and loss of activity occurs. Aggregated materials bring various problems, such as loss of activity and low electrochemical performance, depending on the purpose for which they are used.

[0006] Document CN105024060A, which is encountered in the known state of the art, relates to anode material used in lithium ion batteries and its preparation method. In this document, the anode material Li2ZnTi3O8@C-N, which is used especially for lithium ion batteries, and the method of preparation thereof are mentioned. This invention relates to the synthesis of composite porous carbon nanostructures obtained by pyrolysis from metal organic polymer structures (ZIF-11 or ZIF-12 or amorphous ZIF) and their use as electrodes in Li-ion batteries, Li-S batteries, Na-ion batteries, K-ion batteries, supercapacitors and fuel cells. However, in document CN105024060A, there is no mention of a structure that contains at least two of the metal nanoparticles such as Co, Zn, Cu, Mn, Sn, Ni and Fe embedded and / or dispersed in a carbon network at the same time. The Li2ZnTisO8@C-N structure has no similarity with the materials subject to our invention in terms of synthesis, composition and application. In addition, unlike the invention CN105024060A, the main purpose of the invention is to use the obtained materials as anode or cathode electrode material in Li-ion batteries, Li-S batteries, Na- ion batteries, K-ion batteries, supercapacitors, and fuel cells.

[0007] Document LIS2017279109A1 relates to lithium metal oxide composites and methods for their preparation and use. In this document, it is mentioned that lithium metal oxide composites comprising lithium metal oxide coated with a metal oxide shell are provided, and the metal oxide shell may comprise a plurality of metal oxide particles dispersed in a porous carbon matrix. However, the present invention does not involve the formation of any metal oxide, but at least two different types of metal nanoparticles embedded in a carbon structure at the same time. Our invention is completely different from the materials in the document LIS2017279109A1 , and the materials in the related invention are completely different in terms of synthesis, content, and application.

[0008] As a result, improvements are being made with respect to the materials used as electrodes in Li-ion batteries, Na-ion batteries, K-ion batteries, supercapacitors, or fuel cells, and for this reason, it is subject to new structures that will minimize or eliminate the disadvantages mentioned above and provide solutions to existing systems.

[0009] Aim of the Invention

[0010] The present invention relates to materials in which at least two different metal nanoparticles, meeting the aforementioned requirements, minimizing or eliminating all disadvantages, and providing additional advantages, are combined within a porous and conductive carbon structure.

[0011] The main purpose of the invention is to provide the synthesis of a porous composite carbon nanomaterial that can be used as an electrode in Li-ion batteries, Na-ion batteries, K-ion batteries, supercapacitors, or fuel cells, using ZIF-11, ZIF-12, or Amorphous-ZIF structures.

[0012] One of the aims of the invention is to minimize the aggregation problem of metal nanoparticles by forming them within a flexible and highly conductive porous carbon network derived from a metal-organic frameworks (MOFs) with a large surface area, thereby helping to preserve the activities of the metal nanoparticles or the theoretical electrochemical performance values experimentally, depending on the intended use of these electrode materials.

[0013] The present invention, in order to realize all the advantages mentioned above and understood from the detailed description below, is a nanoparticle material obtained from zeolitic imidazolate frameworks (ZIFs) used as an electrode in Li-ion batteries, Na-ion batteries, K-ion batteries, supercapacitors, or fuel cells; a structure containing salts of metal-organic frameworks (MOFs) of the mentioned zeolitic imidazolate frameworks (ZIFs) has been obtained.

[0014] The structural and characteristic features of the invention and all its advantages will be more clearly understood through the detailed explanation provided below, along with the figures and references to these figures. Therefore, the evaluation should be conducted taking these forms and detailed explanations into account.

[0015] Detailed Description of the Invention

[0016] In this detailed explanation, the preferred structures of the synthesis of multi-metal nanoparticle porous composite carbon material, which is the subject of the invention, are described solely for the purpose of better understanding the subject and without creating any restrictive effect.

[0017] Metal-organic framework (MOFs) materials are composed of organic linkers and metal connection points. By changing the components and synthesis conditions, it is possible to synthesize numerous MOF compounds with different chemical and physical properties. The presence of metal nodules as electroactive regions in these materials allows for their use in numerous fields due to their chemical and physical durability. The porous nature of MOF structures and the ability to modify their pore properties, along with the capability to tailor the characteristics of MOF materials for specific applications through various synthesis methods and applications, make MOF materials highly significant. The dispersion of metal nanoparticles on the support material plays an important role in the effective utilization of electroactive regions. At this point, the formation of metal nanoparticles on a flexible and highly conductive network derived from a MOF structure with a large surface area minimizes the aggregation problem, thereby contributing to the enhancement of activity or electrochemical performance depending on the intended use of the material.

[0018] The invention relates to the synthesis and synthesis method of multi-metal nanoparticle carbon materials from zeolitic imidazolate frameworks (ZIFs). Within the scope of the invention, ZIF-11 , ZIF-12, and amorphous-ZIF structures have been specifically addressed.

[0019] The ZIF-11 structure preferably contains 66.6% ligand and 33.3% Zn(OAc)2.2H2O by content. Additionally, NH4OH, methanol, and toluene are used in the synthesis. Copper, cobalt, manganese, tin, and nickel salts are added to this structure to obtain a multi-metallic material. The ratio of these salts is adjusted according to the amount of zinc in the ZIF structure.

[0020] The ZIF-12 structure preferably contains 66.6% benzimidazole and 33.3% CO(OAC)2.4H2O by composition. Additionally, NH4OH, methanol, and toluene are used in the synthesis. Copper, zinc, iron, manganese, tin, and nickel salts are added to this structure to obtain a multi-metallic material. The ratio of these salts is adjusted according to the amount of cobalt in the ZIF structure.

[0021] The amorphous ZIF structure preferably contains 66.6% benzimidazole and its derivatives and 33.3% cobalt, zinc, and nickel salts. Additionally, NH4OH, methanol, and toluene are used in the synthesis. Copper, cobalt, zinc, iron, manganese, tin, and nickel salts are added to this structure to obtain a multi-metallic material. The ratio of these salts is adjusted according to the amount of base ZIF metal in the ZIF structure.

[0022] Benzimidazole and its derivatives are one of the key components of ZIF structures. CO(OAC)2.4H2O, Zn(OAc)2.2H2O, and Ni(OAc)2.4H2O salts are the metal sources used in the synthesis of ZIF-11 , ZIF-12, and Amorph-ZIF. The toxicity of these salts is low, and they are inexpensive. NH4OH is a base used to increase the reactivity of the ligand and is readily available. Methanol and toluene are solvents used in ZIF synthesis reactions. They can be purified through distillation and reused repeatedly. The salts of Cu, Co, Zn, Fe, Mn, Sn, and Ni to be used for the synthesis of multi-metallic ZIFs are readily available compounds.

[0023] The synthesis of multi-metal nanoparticle carbon material is primarily achieved through three method steps:

[0024] - Synthesis of the ZIF structure (ZIF-11, ZIF-12, or Amorphous-ZIF),

[0025] - Addition (doping) of various types of metals to the ZIF-11 , ZIF-12, or amorphous-ZIF structure for multi-metal ZIF synthesis,

[0026] - Carbonization (calcination).

[0027] The synthesis method consists of the following detailed steps:

[0028] - Dissolving 2 mmol of benzimidazole or its derivative in a flask containing a methanol / toluene (150 mmol / 50 mmol) mixture,

[0029] - Adding 4 mmol of NH4OH to the mixture,

[0030] - To the resulting solution: o For ZIF-11, adding tin and / or copper and / or iron and / or manganese salts in the range of 0.1 mmol-1 mmol with Zn(OAc)2.2H2O. o For ZIF-12, adding tin and / or copper and / or iron and / or manganese salts in the range of 0.1 mmol-1 mmol with Co(OAc)2.4H2O. o For Amorph-ZIF, adding tin and / or copper and / or iron and / or manganese salts in the range of 0.1 mmol-1 mmol with Co(OAc)2.4H2O or Zn(OAc)2.2H2O or Ni(OAc)2.4H2O and stirring at room temperature for 3 hours.

[0031] - Filtering the resulting precipitate, washing with methanol, and drying in an oven at 70 o / ^

[0032] - Carbonizing the obtained precipitate at temperatures in the range of 400-900 °C for 3- 5 hours. As a result of the carbonization process, a nanomaterial is obtained, and the resulting material is used as an anode or cathode in Li-ion batteries, Na-ion batteries, K-ion batteries, supercapacitors, and fuel cells.

[0033] In the synthesis process, the ZIF synthesis time can range from 2 to 3 hours. The metal plating (addition) process can take 1-2 hours. The ZIF drying temperature can be applied in the range of 50-80 °C. The ZIF drying temperature should not exceed 80 °C. Calcination temperature can be applied between 400-900 °C. The synthesis time for the multi-metallic ZIF should not exceed 2 hours.

Claims

CLAIMS1. A composite porous carbon-based nanoparticle material obtained from zeolitic imidazolate frameworks (ZIFs), used as an electrode in Li-ion batteries, Na-ion batteries, K-ion batteries, supercapacitors, or fuel cells, characterized by the presence of metal-organic framework (MOF) salts within the aforementioned zeolitic imidazolate frameworks (ZIFs).

2. The nanoparticle material suitable for Claim 1 , characterized by the mentioned zeolitic imidazolate frameworks (ZIFs) ZIF-11, ZIF-12, and amorph-ZIF structures.

3. A nanoparticle material suitable for claim 1 or 2, characterized by containing at least two of the salts of copper, cobalt, manganese, tin, and nickel for the ZIF-11 structure.

4. It is a nanoparticle material suitable for Claim 1 or 2, characterized by containing at least two of the salts of copper, zinc, iron, manganese, tin, and nickel for the ZIF-12 structure.

5. A nanoparticle material suitable for Claim 1 or 2, characterized by containing at least two of the salts of copper, cobalt, zinc, iron, manganese, tin, and nickel for the Amorph- ZIF structure.

6. A composite porous carbon-based nanoparticle material synthesis method obtained from zeolitic imidazolate frameworks (ZIFs) used as electrodes in Li-ion batteries, Na- ion batteries, K-ion batteries, supercapacitors, or fuel cells, characterized by the following general steps:• Synthesis of the ZIF structure (ZIF-11, ZIF-12, or Amorph-ZIF),• Addition of various types of metals to the ZIF-11, ZIF-12, or Amorph-ZIF structure for multi-metal ZIF synthesis,• Carbonization (calcination) process steps.

7. The nanoparticle material synthesis method suitable for Claim 6, characterized by the following steps:• Dissolving 2 mmol of benzimidazole or its derivative in a flask containing a methanol / toluene (150 mmol / 50 mmol) mixture,Adding 4 mmol of NH4OH to the mixture,• Adding to the resulting solution; o For ZIF-11 , tin and / or copper and / or iron and / or manganese salts in the range of 0.1 mmol-1 mmol with Zn(OAc)2.2H2O, o For ZIF-12, tin and / or copper and / or iron and / or manganese salts in the range of 0.1 mmol-1 mmol with Co(OAc)2.4H2O, o For Amorph-ZIF, tin and / or copper and / or iron and / or manganese salts in the range of 0.1 mmol-1 mmol with Co(OAc)2.4H2O or Zn(OAc)2.2H2O or Ni(OAc)2.4H2O, and stirring at room temperature for 3 hours,• Filtering the resulting solid, washing with methanol, and drying in an oven at 70 °C,• Carbonizing the obtained solid at temperatures in the range of 400-900 °C for 3-5 hours.