Synthesis of metal selenide-carbon materials from MOF based materials

Abstract

Synthesis of Metal Selenide-Carbon Materials from MOF Based Materials The invention relates to the synthesis of pure or multi-metal derivatives of ZIF-11 or ZIF-12 or amorphous-ZIF structures in high yields, followed by calcination under inert conditions to produce one or more metal-selenides in composite nanostructure, dispersed on a carbon matrix surface or embedded in this matrix, and the use of these composite materials as electrodes in Li-ion batteries, Na-ion batteries, K-ion batteries, supercapacitors, or fuel cells.

Description

[0001] Synthesis of Metal Selenide-Carbon Materials from MOF Based Materials

[0002] Field of the Invention

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

[0004] State of the Art

[0005] Nowadays, transition metal selenides (TMSe) are known as a preferred electrode material in many energy storage systems due to their large surface area, excellent electronic conductivity (1 x10'3Snr1) and high electrochemical activity. Selenite-based electrodes exhibit high cycle stability by forming polyselenide intermediates during charge / discharge. In recent years, many single, binary, or multiple composite metal selenide materials have been produced. These materials are especially important materials used as electrodes in Li-ion and Na-ion batteries, supercapacitors, and fuel cells.

[0006] In terms of energy storage devices, metal selenides with high energy density and high conductivity have the potential to replace conventional electrode materials, but they need to be developed due to their weak structural stability. When metal selenides are used as electrodes, this structural instability leads to low activity and low cycle life. In addition, the volume expansion of metals in the structure of different types of metal selenides used in electrode materials during charge-discharge and structural degradation due to this is known as the main problem of these electrode materials.

[0007] Document CN106654221A, encountered in the known state of the art, relates to a three-dimensional porous carbon-coated zinc selenide material for lithium ion battery anodes and a method of preparing the material. This document belongs to the technical field of materials and energy, and it is about three-dimensional porous carbon-coated zinc selenide material for lithium ion battery anodes and the preparation method of the material. In this document, the use of metal selenite and carbon structures is mentioned. However, the synthesis of single, double, or three different metal-selenides embedded or dispersed on the surface in a composite porous carbon structure obtained by pyrolysis from metal organic structures (ZIF-11 , ZIF-12 or amorphous ZIF) subject to this invention and their use as electrodes in Li-ion batteries, Na-ion batteries, K-ion batteries, supercapacitors or fuel cells is not mentioned. The ZIF-8 structure in the invention CN106654221A is a material that can be synthesized with very low yield. In addition, only the zinc selenide structure was obtained and only used in Li-ion batteries. As a result, there is no similarity between the ZIF-8 structure and the materials subject to our invention in terms of synthesis, composition, and application.

[0008] Document CN115893329A relates to a method of preparation of selenium-doped cobalt ditelluride electrode material. In this document, a method of preparation of selenium-doped cobalt ditelluride electrode material applicable to the technical field of sodium ion batteries is mentioned. However, the ZIF-67 structure used in the invention CN115893329A is a high cost material due to its low efficient synthesis. In addition, although the ZIF structures (ZIF-11 , ZIF-12 or amorphous ZIF) subject to our invention are different, these materials contain one or more different metal selenide structures. For this reason, it does not bear any similarity with the related patent work.

[0009] As a result, improvements are being made in the materials used as electrodes in Li-ion batteries, Na-ion batteries, K-ion batteries, supercapacitors, or fuel cells; therefore, new structures are needed to reduce or eliminate the disadvantages mentioned above and to provide solutions to existing systems.

[0010] Aim of the Invention

[0011] The present invention relates to composite porous and nitrogen atom-containing carbon materials comprising one or two or three different metal selenide structures that meet the above-mentioned requirements, minimize or eliminate all disadvantages and bring some additional advantages. The main object of the invention is to synthesize electrode materials that can be used as electrodes in Li-ion batteries, Na-ion batteries, K-ion batteries, supercapacitors, or fuel cells by using composite porous and nitrogen atom containing carbon materials containing one, two or three different metal selenide structures.

[0012] An aim of the invention is to provide high capacity, high charge-discharge cycle performance, and low capacitive drop value in energy storage and conversion systems (as anodes and cathodes of Li-ion batteries, Na-ion batteries, K-ion batteries, supercapacitors, fuel cells, etc.) with both designable carbon properties and the possibility of synthesis of two or three different metal selenide structures with these materials.

[0013] Another aim of the invention is to facilitate electron and ion conductivity during the charge-discharge process with conductive, flexible, porous, and nitrogen-containing carbon networks prepared by using Zeolitic Imidazolate Frameworks (ZIF) or single or multi Metal Organic Framework (MOF) as templates and to minimize the volume expansion in metals thanks to the flexible structure of the carbon network material, to ensure that the electrochemical performance of these materials remains high, solid electrolyte interface (SEI) layer is formed in the batteries and the cycle life is long.

[0014] The present invention to realize all the advantages mentioned above and to be understood from the detailed description below;

[0015] The structural and characteristic features and all advantages of the invention will be more clearly understood from the detailed description given below. For this reason, the evaluation should also be made by considering the explanations.

[0016] Detailed Description of the Invention

[0017] In this detailed description, the preferred embodiments of the synthesis of the composite porous and nitrogen atom-containing carbon materials comprising one or two or three different metal selenide structures of the invention are described solely for the purpose of a better understanding of the subject matter and in a non-limiting manner. By doping metal selenides with porous and nitrogen atom containing carbon materials, disadvantages such as volume expansion of metal selenides and formation of unstable SEI layer can be minimized. In addition, the synthesis of two or more different types of metal selenides is possible with ZIF and MOFs, which are the source of the conductive, flexible, nitrogen-containing, and porous carbon structure obtained in this invention, and the electrochemical performances of these metal selenides can be increased or values close to their theoretical values can be obtained experimentally due to the synergistic effect of the metals with each other. At this point, the use of MOF or ZIF in the preparation of transition metal selenide carbon (TMSe-carbon) composite provides high performance in energy storage and conversion systems (as anodes and cathodes of Li-ion batteries, Na-ion batteries, K-ion batteries, supercapacitors, fuel cells, etc.) due to its designable carbon properties and the possibility of using two or multiple metals. The conductive carbon network prepared by using ZIF or MOF structures as a template facilitates electron and ion conductivity and minimizes the volume expansion in metals thanks to the flexible structure of the carbon network material, allowing the electrochemical performance of these materials to remain high, the formation of a stable SEI layer, and the formation of low capacitive drop and high cycle life.

[0018] The invention relates to the synthesis and synthesis method of single or two or three different metal selenide-carbon materials from ZIF or MOF-based (single or multimetal) materials. Within the scope of the invention, especially ZIF-11 , ZIF-12, and amorphous ZIF structures are discussed.

[0019] The ZIF-11 structure preferably contains 66.6% ligand and 33.3% Zn(OAc)2.2H2O. In addition, NH4OH, methanol, and toluene are used in the synthesis. Selenium is also used for the synthesis process. Selenium can be used in different ratios in the formation of TMSe. Copper, cobalt, iron, manganese, tin, and nickel salts are added to this structure to obtain multi-metal materials. The ratio of these salts is adjusted according to the amount of zinc in the ZIF structure. The ZIF-12 structure preferably contains 66.6% benzimidazole and 33.3% Co(OAc)2.4H2O. In addition, NH4OH, methanol, and toluene are used in the synthesis. Selenium is also used for the synthesis process. Selenium can be used in different ratios in the formation of TMSe. One or two of the salts of copper, zinc, iron, manganese, tin and nickel are added to this structure to obtain multi-metal materials. The ratio of these salts is adjusted according to the amount of cobalt in the ZIF structure. The amorphous ZIF structure preferably contains 66.6% benzimidazole and its derivatives and 33.3% cobalt, zinc, and nickel salts. In addition, NH4OH, methanol, and toluene are used in the synthesis. Selenium is also used for the synthesis process. Selenium can be used in different ratios in the formation of TMSe. One or two of the salts of copper, cobalt, zinc, iron, manganese, tin, and nickel are added to this structure to obtain multi-metal material. The ratio of these salts is adjusted according to the amount of basic ZIF metal in the ZIF structure.

[0020] Benzimidazole and its derivatives are one of the main 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 Amorphous-ZIF. These salts have low toxicity and are inexpensive. Copper, iron, tin, manganese, and nickel salts to be used for bimetallic ZIF synthesis are cheap compounds. NH4OH is an easily available base used to increase the reactivity of the ligand. Methanol and toluene are solvents used in ZIF synthesis reactions. They can be purified by distillation and used repeatedly. Metallic selenium is an element used in the synthesis of TMSe.

[0021] The synthesis of metal selenide-carbon nanoparticle material is mainly achieved through three method steps:

[0022] - Synthesis of ZIF structure (ZIF-11, ZIF-12 or Amorphous-ZIF),

[0023] - Addition (doping) of different types of metals to ZIF-11, ZIF-12 or amorphous ZIF structure for the synthesis of multi-metal ZIF,

[0024] - Selenium treatment and carbonization (calcination).

[0025] The synthesis method consists of the following steps in more detail:

[0026] - Dissolving 2 mmol of benzimidazole or its derivative in a mixture of methanol / toluene (150 mmol / 50 mmol) in a flask,

[0027] - Addition of 4 mmol NH4OH to the mixture,

[0028] - To the resulting solution: o Zn(OAc)2.2H2O for ZIF-11 and salts of tin and / or copper and / or iron and / or manganese in the range 0.1 mmol-1 mmol, o For ZIF-12, Co(OAc)2.4H2O with tin and / or copper and / or iron and / or manganese salts in the range 0.1 mmol-1 mmol, o For amorphous-ZIF, Co(OAc)2.4H2O or Zn(OAc)2.2H2O or Ni(OAc)2.4H2O with tin and / or copper and / or iron and / or manganese salts in the range of 0.1 mmol-1 mmol and stirring at room temperature for 3 hours.

[0029] - The solid was filtered, washed with methanol and dried in an oven at 70 °C.

[0030] - The resulting solid is mixed with metallic selenium and carbonised at temperatures between 400-900 °C for 3-5 hours.

[0031] As a result of the carbonization process, nanomaterial is obtained, and the material obtained is used as anode or cathode in Li-ion batteries, Na-ion batteries, K-ion batteries, supercapacitors, heterogeneous catalysts, and fuel cells.

[0032] In the synthesis process, the ZIF synthesis time can be in the range of 2-3 hours. Metal doping time can be in the range of 1-2 hours. ZIF drying temperature can be applied in the range of 50-80 °C. The ZIF drying temperature must not exceed 80 °C. The ratio of Se / ZIF mixed for calcination can be between 1-3. The Se / ZIF ratio mixed for carbonization should not exceed 3. Carbonization temperature can be applied between 400-900 °C. Multimetallic ZIF synthesis time should not exceed 2 hours.

Claims

CLAIMS1. A carbon material according to claim 1 , characterized in that it is a composite porous and nitrogen atom-containing carbon material obtained from single or multi-metal ZIF or MOF structures and used as an electrode in a Li-ion battery, Na-ion battery, K-ion battery, supercapacitor or fuel cell.

2. The carbon material according to claim 1 , characterized in those said single or multimetal structures are ZIF-11 , ZIF-12 and amorphous-ZIF structures.

3. The carbon material, according to claims 1 or 2, characterized in that said single or multi-metal structure comprises at least two of copper, cobalt, manganese, tin and nickel salts for the ZIF-11 structure.

4. The carbon material according to claims 1 or 2, characterized in that said zeolitic imidazolate structure comprises at least two of the salts of copper, zinc, iron, manganese, tin and nickel for the structure ZIF-12.

5. The carbon material according to claims 1 or 2, characterized in that said zeolitic imidazolate structure comprises at least two of the salts of copper, cobalt, zinc, iron, manganese, tin and nickel for the amorphous-ZIF structure.

6. Carbon material synthesis method obtained from single or multi-metal ZIF or MOF structures, used as electrodes in Li-ion batteries, Na-ion batteries, K-ion batteries, supercapacitors or fuel cells.Synthesis of ZIF structure (ZIF-11 , ZIF-12 or Amorphous-ZIF),Addition (doping) of different types of metals to ZIF-11 , ZIF-12 or amorphous ZIF structure for the synthesis of multi-metal ZIF,-Selenium treatment and carbonization (calcination) comprising process steps.

7. A method of synthesizing carbon material according to claim 6, characterized in that; -Dissolving 2 mmol of benzimidazole or its derivative in a mixture of methanol / toluene (150 mmol / 50 mmol) in a flask,-Addition 4 mmol NH4OH to the mixture,To the resulting solution:-Zn(OAc)2.2H2O for ZIF-11 and tin and / or copper and / or iron and / or manganese salts in the range 0.1 mmol-1 mmol,-CO(OAC)2.4H2O for ZIF-12 and salts of tin and / or copper and / or iron and / or manganese in the range 0.1 mmol-1 mmol,To CO(OAC)2.4H2O or Zn(OAc)2.2H2O or Ni(OAc)2.4H2O for -Amorphous-ZIF and tin and / or copper and / or iron and / or manganese salts in the range of 0.1 mmol-1 mmol and stirring at room temperature for 3 hours.-Filtration the solid, washing with methanol, and drying in an oven at 70 °C. -The solid is mixed with metallic selenium and carbonized at temperatures between 400-900 °C for 3-5 hours.