CN110970628B - Nano carbon fiber and metal composite electrode and application thereof - Google Patents
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Abstract
The invention discloses a nano carbon fiber/metal composite electrode for a flow battery and a preparation method thereof. The electrode material is prepared by taking a mixture of a high molecular polymer and a metal salt as a precursor, preparing nano-fibers by an electrostatic spinning method, carbonizing at a high temperature, and oxidizing and etching the surface of the nano-fibers, wherein the diameter of the nano-fibers is 100-1000nm, the diameter of metal particles is 2-100nm, the metal particles are distributed on the surfaces of the nano-fibers, one part of the metal particles is embedded in the nano-fibers, and the other part of the metal particles is exposed on the surfaces of the nano-fibers. The carbon nanofiber/metal composite electrode prepared by the preparation method has good electrocatalytic activity and electrochemical reversibility when being used for a flow battery, and has the advantages of simple preparation method, few working procedures, easily available raw materials, low price and the like.
Description
Technical Field
The invention relates to the field of flow batteries, in particular to an electrode material for a flow battery and a preparation method thereof.
Background
Energy and environment are two major problems facing mankind in the 21 st century. With the continuous development of economy, the demand of human beings on energy is increasing. It is estimated that human energy demand will double as much as today by 2050 and triple as much as it will be by the end of this century. On one hand, the traditional fossil energy is limited in reserves and cannot meet the requirements of social development, and on the other hand, the excessive consumption of the fossil energy brings about a serious environmental problem. In order to solve the dual problems of energy shortage and environmental pollution, the utilization and development of renewable energy sources are very important. However, renewable energy sources such as wind energy and solar energy are influenced by natural environments such as day and night alternation and season alternation, and the electric energy output has the characteristics of discontinuity, instability and uncontrollable, thereby bringing serious impact to the safe and stable operation of a power grid. In order to relieve the impact of renewable energy power generation on a power grid and improve the receiving capacity of the power grid on the renewable energy power generation, a large-capacity energy storage device needs to be equipped to effectively realize amplitude modulation and frequency modulation, smooth output, planned tracking power generation and improvement of the controllability, and the popularization and application of renewable energy sources are promoted.
The all-vanadium redox flow battery has the advantages that the output power and the capacity are mutually independent, and the system design is flexible; the energy efficiency is high, the service life is long, the operation stability and reliability are high, and the self-discharge is low; the method has the advantages of large freedom degree of site selection, no pollution, simple maintenance, low operation cost, high safety and the like, and has wide development prospect in the aspect of large-scale energy storage.
Currently, the main limitation restricting the commercialization of all-vanadium flow batteries is the cost problem. To reduce the cost, two main solutions are provided: one is to reduce the cost of each key material, such as the cost of ion exchange membrane, electrolyte and electrode bipolar plate; one is to increase the power density of the battery. Because the power density of the battery is improved, the same galvanic pile can be used for realizing larger power output, the occupied area and the space of the energy storage system can be reduced, the environmental adaptability and the mobility of the system are improved, and the application field of the flow battery is expanded. To increase the power density of a battery, the operating current density is increased. However, an increase in operating current density results in a decrease in voltage efficiency and energy efficiency. In order to increase the operating current density of the cell without reducing energy efficiency, it is necessary to reduce the cell polarization, i.e., ohmic polarization, electrochemical polarization, and concentration polarization, as much as possible and to reduce the voltage loss.
The electrode is used as one of the key components of the all-vanadium redox flow battery, and the structure and the physical and chemical properties of the electrode greatly influence the performance of the redox flow battery. The electrode material of the all-vanadium redox flow battery in the prior art is mainly carbon felt or graphite felt, which has good stability and a three-dimensional network structure, but the electrocatalytic activity is not high enough. The electrocatalytic activity of the electrode directly determines the intrinsic reaction rate of the electrochemical reaction, and greatly influences the working current density and energy efficiency of the battery. Therefore, in order to obtain high working current density and energy efficiency, a proper activation method is adopted to improve the electrocatalytic activity of the graphite felt as much as possible. The patent documents disclosed so far mainly include methods for reducing electrochemical polarization of flow batteries: (1) the method is to perform oxidation modification treatment on electrode materials such as graphite felt, carbon paper and the like, modify oxygen-containing functional groups on the surface of carbon fibers, improve the electrocatalytic activity of an electrode, and reduce the electrochemical polarization of a battery, for example, the method disclosed in patents CN 101465417a and CN 101182678A for performing electrochemical oxidation on graphite felt. (2) Electrode materials such as Graphite felt, carbon paper, etc. are metallized by modifying the surface of the carbon Fiber with metal ions, such as Sun, et al (Sun, B.T.; Skyllas-Kazacos, M.chemical Modification and Electrochemical Behavior of Graphite Fiber in Acidic vacuum solution. electric chemistry. acta 1991,36, 513-)2+、Te4+、In3+And Ir3+Etc. found Ir3+The method has the most effect on improving the electrocatalytic activity of the electrode material, but is not suitable for large-scale application due to the high cost of the electrode caused by the use of noble metals. (3) Preparing the electrode material with high specific surface area. The nano carbon fiber electrode material was prepared by an electrospinning method as disclosed in patent CN 102522568A.
Disclosure of Invention
The invention aims to provide a carbon nanofiber/metal composite electrode for an all-vanadium redox flow battery and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a nano carbon fiber and metal composite electrode is prepared by taking a mixture of a high molecular polymer and a metal salt as a precursor, preparing composite nano fibers by an electrostatic spinning method, pre-oxidizing, performing high-temperature carbonization treatment, and performing oxidation treatment, wherein the diameter of the nano carbon fiber is 100-1000nm, the diameter of metal particles is 2-100nm, the metal particles are distributed on the surface of the nano carbon fiber, one part of the metal particles are embedded in the nano carbon fiber, the other part of the metal particles are exposed on the surface of the nano carbon fiber, and the mass fraction of the metal in the composite electrode is 1-50%; preferably, the mass fraction of the metal in the composite electrode is 5% to 20%, more preferably 10% to 20%.
The high molecular polymer is one or more than two of polyacrylonitrile, polylactic acid, polyvinylidene fluoride and polymethyl methacrylate;
the metal is one or two of bismuth and lead.
In order to ensure that metal particles are exposed and distributed on the surface of the carbon nanofiber, the specific preparation method of the carbon nanofiber/metal composite electrode comprises the following steps:
dissolving or dispersing metal salt in a solvent, and performing ultrasonic dispersion for 0.5-2h to fully dissolve or disperse the metal salt;
dissolving high molecular polymer in the solvent containing metal salt, and stirring at 40-85 deg.C for 10-30 hr to dissolve completely to obtain spinning solution;
the spinning solution is made into a polymer fiber membrane through electrostatic spinning, and the specific process is as follows: placing 3-20mL of the solution in a syringe, keeping the distance between the needle point of the syringe and a receiving plate at 5-20cm, and spinning by selecting the conditions of 10-30KV voltage, 10-30 ℃ and 10-40% relative humidity of the needle point of the syringe and the receiving plate;
pre-oxidizing the obtained polymer fiber membrane in air at the temperature of 200-350 ℃ for 1-3h, then carrying out carbonization heat treatment at the temperature of 800-2000 ℃ for 1-3h in an inert atmosphere, reducing metal salt into a metal simple substance, and cooling to room temperature to obtain the carbon nanofiber/metal composite electrode material;
and oxidizing the carbon nanofiber/metal composite electrode material in air at 350-500 ℃ for 1-3h, and oxidizing to remove the graphite sheet layer coated on the surface of the metal particles, so that the metal particles are exposed on the surface of the fibers.
The high molecular polymer is one or more than two of polyacrylonitrile, polylactic acid, polyvinylidene fluoride and polymethyl methacrylate;
the metal salt is one or more than two of bismuth sulfate, bismuth nitrate, bismuth phosphate, bismuth chloride, bismuth formate, bismuth acetate, bismuth subsalicylate, lead nitrate and lead chloride;
the solvent is one or more of N, N-dimethylformamide, absolute ethyl alcohol, tetrahydrofuran and dichloromethane;
the mass fraction of the high molecular polymer in the spinning solution is 5-30%;
the mass fraction of the metal salt and the high molecular polymer in the spinning solution is 1-60%, preferably 5-30%;
the inert gas is nitrogen or argon.
The invention has the beneficial effects that:
1. the basic component of the nano carbon fiber/metal composite electrode material provided by the invention is the nano carbon fiber, and the nano carbon fiber/metal composite electrode material has high specific surface area and thus high electrocatalytic activity.
2. According to the carbon nanofiber/metal composite electrode material provided by the invention, as the surface of the carbon nanofiber is exposed and distributed with the nano metal particles as the electrocatalyst, the electrocatalytic activity and the electrochemical reversibility of the electrode material are greatly improved, the charge transfer resistance is reduced, and the voltage efficiency and the energy efficiency of the all-vanadium redox flow battery can be improved.
3. The carbon nanofiber/metal composite electrode material provided by the invention has the advantages that the surface of the carbon nanofiber is exposed and distributed with nano Pb and/or Bi metal particles, and the nano Pb and/or Bi metal particles can inhibit the generation of hydrogen evolution side reaction when being used for a negative electrode due to the high hydrogen evolution overpotential of the metal particles.
4. The preparation method provided by the invention can directly obtain the film-shaped material, has simple preparation method and few working procedures, can be directly used for electrodes, and has the advantages of easily obtained raw materials, low price and easy large-scale production.
Drawings
FIG. 1 is an SEM picture of the nano carbon fiber/metal electrode material obtained in example 1;
FIG. 2 is a cyclic voltammogram of a pair of V (II)/V (III) pairs of the filamentous nanocarbon/metal electrode material prepared in example 1 and comparative example, scan rates: 10 mV/s.
Detailed Description
The present invention is further described below with reference to examples, but the practice of the present invention is not limited thereto.
Example 1
0.5g of Bi (NO) is weighed3)3·5H2Dissolving O in 20g N, N-dimethylformamide, ultrasonic dispersing for 1 hr to dissolve completely, adding 2g polyacrylonitrile powder, and standing at 70 deg.CStirring for 24h to fully dissolve. Then, 5mL of the above solution was put in a syringe and spun under the conditions of 10KV voltage, 25 ℃ and 10% relative humidity, with the distance between the tip of the syringe and the receiving plate being 5 cm. And pre-oxidizing the obtained polymer fiber/metal salt composite membrane in air at 300 ℃ for 2h, then sintering the composite membrane at 1200 ℃ for 2h in an argon atmosphere, reducing the metal salt in the composite membrane into metal, then cooling the metal salt to room temperature, oxidizing the composite membrane in air at 450 ℃ for 2h, and oxidizing to remove the graphite sheet layer coated on the surface of the Bi nano particles to obtain the carbon nanofiber/Bi composite electrode material. As shown in fig. 1, SEM images of the filamentous nanocarbon/Bi composite electrode material show that the filamentous nanocarbon is formed by interlacing filamentous nanocarbon, wherein the diameter of the filamentous nanocarbon is about 200nm, a large number of nano-scale metal particles are distributed on the surface of the filamentous nanocarbon, the diameter of the metal particles is about 40nm, and the mass fraction of Bi is 20%.
In order to test the electrochemical activity of the vanadium ion redox couple on the surface of the carbon nanofiber/metal composite electrode material, cyclic voltammetry tests were respectively performed on the carbon nanofiber/Bi composite electrode materials prepared in example 1 and the comparative example. The carbon nanofiber/Bi composite electrode material is used as a working electrode, a non-porous graphite plate is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and an adopted electrochemical testing instrument is a CHI604e type electrochemical workstation of Shanghai Chenghua company. The preparation concentration is 0.05M V (II) +0.05M V (III) +3M H2SO4The electrochemical activity of the V (II)/V (III) pair on the surface of the carbon nanofiber/Bi composite electrode material is researched, the scanning range is-0.8V to-0.2V, and the scanning speed is 10 mV/s. The cyclic voltammetry curve of the carbon nanofiber/Bi composite electrode material in this embodiment is shown in fig. 2, and it can be known from electrochemical oxidation, reduction peak position and peak current magnitude of V (ii)/V (iii), compared with the comparative example, the carbon nanofiber/Bi composite electrode material prepared in this embodiment has better electrocatalytic activity and electrochemical reversibility, which is mainly due to the fact that the graphite sheet layer coated on the surface of the Bi nanoparticle is etched in the subsequent oxidation treatment step, so that the Bi nanoparticle is exposed on the surface of the fiber, and plays a role in catalyzing the V (ii)/V (iii) redox reaction.
Example 2
0.4g of Pb (NO) was weighed3)2Dissolving in 20g N, N-dimethylformamide, ultrasonic dispersing for 1 hr to dissolve completely, adding 3g polymethyl methacrylate powder, and stirring at 50 deg.C for 24 hr to dissolve completely. Then 10mL of the above solution was put in a syringe and spun under a voltage of 15KV at 25 ℃ and a relative humidity of 20% at a distance of 5cm from the tip of the syringe to the receiving plate. Pre-oxidizing the obtained polymer fiber/metal salt composite membrane in air at 280 ℃ for 2h, then sintering the composite membrane at 1400 ℃ for 2h in an argon atmosphere, reducing the metal salt in the composite membrane into metal Pb, then cooling the composite membrane to room temperature, oxidizing the composite membrane in air at 400 ℃ for 2h, and oxidizing to remove graphite sheets coated on the surfaces of Pb nanoparticles to obtain the carbon nanofiber/Pb composite electrode material. The diameter of the carbon nanofiber in the obtained carbon nanofiber membrane is about 100nm, the diameter of the metal particles is about 20nm, and the mass fraction of Pb is 20%.
Example 3
0.1g of bismuth subsalicylate is weighed and dispersed in 20g N, N-dimethylformamide, ultrasonic dispersion is carried out for 1h to ensure that the bismuth subsalicylate is uniformly dispersed, then 2g of polyacrylonitrile powder is added, and the mixture is stirred for 24h at the temperature of 60 ℃ to ensure that the polyacrylonitrile powder is fully dissolved and uniformly mixed with the bismuth subsalicylate. Then 10mL of the above solution was put in a syringe and spun under the conditions of 10KV voltage, 25 ℃ and 10% relative humidity, with the distance between the tip of the syringe and the receiving plate being 5 cm. Pre-oxidizing the obtained polymer fiber/metal salt composite membrane in air at 280 ℃ for 2h, then sintering the composite membrane at 1400 ℃ for 2h under the atmosphere of argon, reducing the metal salt in the composite membrane into metal Bi, then cooling to room temperature, oxidizing the composite membrane in air at 500 ℃ for 1h, and oxidizing to remove the graphite sheet layer coated on the surface of the Bi nano particles to obtain the carbon nanofiber/Bi composite electrode material. The diameter of the carbon nanofiber in the obtained carbon nanofiber membrane is about 200nm, the diameter of the metal particles is about 10nm, and the mass fraction of Bi is 8%.
Comparative example
0.5g of Bi (NO) is weighed3)3·5H2Dissolving O in 20g N, N-dimethylformamide, ultrasonic dispersing for 1 hr to dissolve completely, adding 2g polyacrylonitrile powder, stirring at 70 deg.CFully dissolve it for 24 h. Then, 5mL of the above solution was put in a syringe and spun under the conditions of 10KV voltage, 25 ℃ and 10% relative humidity, with the distance between the tip of the syringe and the receiving plate being 5 cm. And pre-oxidizing the obtained polymer fiber/metal salt composite membrane in air at 300 ℃ for 2h, then sintering the composite membrane at 1200 ℃ for 2h in an argon atmosphere, reducing the metal salt in the composite membrane into metal, and then cooling the composite membrane to room temperature to obtain the carbon nanofiber/Bi composite electrode material.
Claims (9)
1. The application of the nano carbon fiber and metal composite electrode in the flow battery is characterized in that: the flow battery is an all-vanadium flow battery, the composite electrode takes a mixture of a high molecular polymer and a metal salt as a precursor, composite nano-fibers are prepared by an electrostatic spinning method, the mixture is subjected to high-temperature carbonization treatment after pre-oxidation, and then the composite electrode is prepared by oxidation treatment, wherein the diameter of the nano-carbon fibers is 1000nm, the diameter of metal particles is 2-100nm, the metal particles are distributed on the surface of the nano-carbon fibers, one part of the metal particles are embedded in the nano-carbon fibers, the other part of the metal particles are exposed on the surface of the nano-carbon fibers, and the mass fraction of the metal in the composite electrode is 1% -50;
the high molecular polymer is one or more than two of polyacrylonitrile, polylactic acid, polyvinylidene fluoride and polymethyl methacrylate;
the metal is one or two of bismuth and lead;
the preparation steps of the nano carbon fiber and metal composite electrode are as follows,
1) dissolving or dispersing metal salt in a solvent, and performing ultrasonic treatment for 0.5-2h to form a metal salt solution;
2) dissolving high molecular polymer in the metal-containing salt solution, and stirring at 40-85 deg.C for 10-30h to obtain spinning solution;
3) preparing a polymer fiber membrane from the spinning solution through electrostatic spinning;
4) pre-oxidizing the obtained polymer fiber membrane in air at the temperature of 200-350 ℃ for 1-3h, and then carrying out carbonization heat treatment at the temperature of 800-2000 ℃ for 1-3h under inert atmosphere;
5) and oxidizing the carbonized nano carbon fiber metal composite electrode in air at 400-500 ℃ for 1-3h, and removing the graphite sheet layer coated on the surface of the metal particles to expose the metal particles on the surface of the fiber.
2. Use according to claim 1, characterized in that: the mass fraction of the metal in the composite electrode is 5-20%.
3. Use according to claim 1, characterized in that: the mass fraction of the metal in the composite electrode is 10-20%.
4. Use according to claim 1, characterized in that: the high molecular polymer is one or more than two of polyacrylonitrile, polylactic acid, polyvinylidene fluoride and polymethyl methacrylate;
the metal salt is one or two of bismuth sulfate, bismuth nitrate, bismuth phosphate, bismuth chloride, bismuth formate, bismuth acetate, bismuth subsalicylate, lead nitrate and lead chloride.
5. Use according to claim 1, characterized in that: the mass fraction of the high molecular polymer in the spinning solution is 5-30%, and the mass fraction ratio of the metal salt to the high molecular polymer in the spinning solution is 1-60%.
6. Use according to claim 5, characterized in that: the mass fraction ratio of the metal salt to the high molecular polymer in the spinning solution is 5-30%.
7. Use according to claim 1, characterized in that: one or more than two of the solvents of N, N-dimethylformamide, absolute ethyl alcohol, tetrahydrofuran and dichloromethane.
8. Use according to claim 1, characterized in that: the inert gas is one or two of nitrogen or argon.
9. Use according to claim 1, characterized in that: the spinning solution is made into a polymer fiber membrane through electrostatic spinning, and the specific process is as follows: 3-20mL of the solution is placed in a syringe, the distance between the needle point of the syringe and a receiving plate is kept at 5-20cm, and spinning is carried out by selecting the conditions of 10-30KV voltage, 10-30 ℃ and 10-40% relative humidity of the needle point of the syringe and the receiving plate.
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| CN111477893A (en) * | 2020-05-11 | 2020-07-31 | 辽宁大学 | Electrospun carbon nanofiber composite material with functional components distributed in longitudinal gradient manner, preparation method of electrospun carbon nanofiber composite material and application of electrospun carbon nanofiber composite material in vanadium battery |
| CN111477894A (en) * | 2020-05-11 | 2020-07-31 | 辽宁大学 | High-activity hydrogen evolution inhibition type carbon nanofiber electrode material, preparation method thereof and application thereof in vanadium battery |
| CN111540915A (en) * | 2020-05-11 | 2020-08-14 | 辽宁大学 | Carbon nanofiber electrode material embedded with carbonaceous microspheres and preparation method and application thereof |
| CN112054215A (en) * | 2020-08-05 | 2020-12-08 | 深圳大学 | Composite electrode for redox flow battery based on all vanadium and preparation method thereof |
| CN112186161B (en) * | 2020-09-30 | 2021-05-18 | 青岛科技大学 | Semi-filled one-dimensional nano longitudinal hole composite fiber membrane flexible electrode material and preparation method thereof |
| CN113652648B (en) * | 2021-08-16 | 2023-03-28 | 武汉纺织大学 | Method for compounding metal material with carbon fiber net in desublimation manner in carbonization process |
| CN115632132B (en) * | 2022-10-25 | 2023-10-24 | 辽宁金谷炭材料股份有限公司 | Preparation method of composite electrode of iron-chromium flow battery |
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