CN117913301A - Method for modifying battery carbon cloth electrode by metal carbide nano material - Google Patents
Method for modifying battery carbon cloth electrode by metal carbide nano material Download PDFInfo
- Publication number
- CN117913301A CN117913301A CN202410306606.1A CN202410306606A CN117913301A CN 117913301 A CN117913301 A CN 117913301A CN 202410306606 A CN202410306606 A CN 202410306606A CN 117913301 A CN117913301 A CN 117913301A
- Authority
- CN
- China
- Prior art keywords
- carbon cloth
- battery
- metal carbide
- electrode
- modifying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004744 fabric Substances 0.000 title claims abstract description 144
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 127
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 36
- 239000002184 metal Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000007772 electrode material Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229920000297 Rayon Polymers 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 239000002964 rayon Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 2
- 230000014759 maintenance of location Effects 0.000 claims 1
- 239000011301 petroleum pitch Substances 0.000 claims 1
- 150000001721 carbon Chemical class 0.000 abstract description 19
- 239000003792 electrolyte Substances 0.000 abstract description 15
- 238000006722 reduction reaction Methods 0.000 abstract description 9
- 239000001257 hydrogen Substances 0.000 abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 8
- -1 hydrogen ions Chemical class 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 28
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 4
- 238000000840 electrochemical analysis Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 229910001430 chromium ion Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 230000022131 cell cycle Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Landscapes
- Inert Electrodes (AREA)
Abstract
The invention discloses a method for modifying a battery carbon cloth electrode by using a metal carbide nano material, which comprises the following steps of pretreating carbon cloth; preparing metal carbide nano material modified carbon cloth; calcining the modified carbon cloth to obtain a metal carbide nano material modified battery carbon cloth electrode; the metal carbide nanomaterial modified carbon cloth electrode has the advantages of simple operation method, low raw material cost and convenience in large-scale production, provides rich high catalytic activity sites for the oxidation and reduction reaction of battery electrolyte, promotes the oxidation and reduction reaction of the battery electrolyte by utilizing the formed worm-hole-shaped nanopores, improves the conductivity of the carbon cloth electrode, optimizes the growth environment of a catalyst, can improve the precipitation potential of hydrogen ions, reduces the hydrogen evolution amount of negative electrolyte, greatly improves the efficiency and performance of the battery, and has extremely strong commercial popularization potential.
Description
Technical Field
The invention relates to the technical field of energy storage, in particular to a method for modifying a battery carbon cloth electrode by modifying a metal carbide nano material.
Background
Because of the intermittent and random characteristics of renewable energy sources such as wind energy, solar energy and the like, the large-scale integration of the power grid brings serious impact to the safe and stable operation of the power grid. Therefore, a large-scale energy storage technology, particularly a long-term energy storage technology, is urgently needed to realize peak clipping and valley filling of a power grid, so that the capacity of the power grid for generating power by renewable energy sources is improved, and the problems of wind abandoning, light abandoning and the like are solved. The iron-chromium flow battery has the advantages of high safety, long cycle life, recyclable electrolyte, high life cycle cost performance, environmental friendliness and the like, is one of the preferred technologies for large-scale storage, and has a wide application prospect. Iron-chromium flow batteries are considered the first real flow battery to utilize low cost and abundant iron and chromium chloride as redox active materials, making them one of the most cost effective energy storage systems. The iron-chromium flow battery is composed of electrodes, a membrane, electrolyte, an electrolyte storage and supply unit, a management control unit and the like. In recent years, research is mainly focused on key materials (electrolyte, electrode, ion conducting membrane and the like) of an iron-chromium flow battery, battery structures and the like so as to improve the energy efficiency, energy density, stability and other performances of the battery.
The basic principle of iron-chromium flow battery is that iron ions and chromium ion electrolyte undergo oxidation-reduction reaction on positive and negative electrode materials. Therefore, the electrode material is a key material affecting the performance of the battery. For commercial applications, low cost, easy preparation, high performance, long life, and large scale preparation are the basis for commercial use of electrode materials. The currently used flow battery electrodes are mainly carbon felt, graphite felt and carbon cloth. Carbon felt and graphite felt are three-dimensional network structures composed of carbon fibers with large surface areas, and high porosity is beneficial to mass transfer of electrolyte flow. The carbon cloth fiber is arranged in relatively orderly mode, and the pore distribution is wide. The carbon cloth is carbon fiber cloth, the fiber arrangement is relatively orderly, and the pore distribution is relatively wide. Carbon cloth has higher air permeability and lower curvature, higher permeability, lower flow resistance and lower pumping loss than carbon paper of the same porosity and fiber diameter, and thus carbon cloth electrodes are also popular modified materials in recent years.
Redox reaction pairs of the iron-chromium flow battery are iron ions and chromium ions, a cathode hydrogen evolution problem and a weak chromium ion activity problem are easy to occur at an electrode, and the electrode material modification of the iron-chromium flow battery is a new challenge.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, promote better commercialized development of an iron-chromium flow battery, and provide a method for modifying a carbon cloth electrode of a battery by using a metal carbide nanomaterial, which comprises the following steps of carbon cloth pretreatment; preparing metal carbide nano material modified carbon cloth; calcining the modified carbon cloth to obtain a metal carbide nano material modified battery carbon cloth electrode; the metal carbide nanomaterial modified carbon cloth electrode has the advantages of simple operation method, low raw material cost and convenience in large-scale production, provides rich high catalytic activity sites for the oxidation and reduction reaction of battery electrolyte, promotes the oxidation and reduction reaction of the battery electrolyte by utilizing the formed worm-hole-shaped nanopores, improves the conductivity of the carbon cloth electrode, optimizes the growth environment of a catalyst, can improve the precipitation potential of hydrogen ions, reduces the hydrogen evolution amount of negative electrolyte, greatly improves the efficiency and performance of the battery, and has extremely strong commercial popularization potential.
In order to achieve the technical effects, the following technical scheme is adopted:
a method for modifying a carbon cloth electrode of a battery by using a metal carbide nano material comprises the following steps:
Step S1: pretreatment of carbon cloth:
Cleaning the carbon cloth by using one or more solutions of deionized water, ethanol and methanol, and drying; carrying out high-temperature heat treatment on the cleaned carbon cloth to finish pretreatment;
step S2: preparing metal carbide nano material modified battery carbon cloth:
preparing a metal carbide nanomaterial precursor solution; immersing the pretreated carbon cloth obtained in the step S1 into a precursor solution, and treating the pretreated carbon cloth by using one or more methods of an immersion method or a hydrothermal method;
Step S3: calcining modified battery carbon cloth
And (3) taking out the carbon cloth treated in the step (S2), drying, and calcining at a high temperature under a protective atmosphere to perform carbothermic reduction to obtain the battery carbon cloth modified and modified by the metal carbide nano material.
Further, in the step S1, the carbon cloth is cleaned by adopting an ultrasonic mode, the cleaning time is 5-30 min, the drying is performed by adopting an oven, the drying temperature is 25-120 ℃, and the specific mode of high-temperature heat treatment of the carbon cloth is as follows: and (3) placing the cleaned carbon cloth into a muffle furnace to keep an air atmosphere for high-temperature heat treatment.
Further, the carbon cloth used in the step S1 is polyacrylonitrile PNV-based carbon cloth, rayon-based carbon cloth or petroleum asphalt-based carbon cloth.
Further, the temperature of the carbon cloth subjected to high-temperature heat treatment in the step S1 is 100-1000 o ℃, and the heat preservation time is 1-30 h.
Further, the concentration of the metal carbide nanomaterial precursor solution in the step S2 is 0.01-5 mol/L.
Further, the solute of the precursor solution of the metal carbide nanomaterial in step S2 is one or more of titanium chloride, titanium fluoride, nickel chloride, nickel nitrate, copper chloride, copper sulfate, platinum chloride, platinum nitrate, tin chloride, nickel nitrate, zinc chloride and hydrates thereof, and the solvent for preparing the precursor is one or more of water, concentrated hydrochloric acid, sulfuric acid, nitric acid, sodium hydroxide, potassium hydroxide, ammonia water and ethylene glycol.
Further, in the step S2, when an impregnation method is adopted, the impregnation time is 0.1-24 h.
Furthermore, when the hydrothermal method is adopted in the step S2, the used instrument is a high-pressure hydrothermal kettle, the hydrothermal reaction temperature is 100-260 ℃, and the holding time is 1-24 h.
Further, in the step S3, the drying temperature of the carbon cloth is 50-100 ℃ and the drying time is 0.1-24 h; the carbothermic reduction is carried out by using a tube furnace, the calcination temperature is 600-2000 ℃, the protective atmosphere is one or more mixed gases of helium, nitrogen, argon, xenon and neon, the heating rate in the reaction process is 1-20 ℃/min, and the calcination temperature is kept at 0.5-12 h.
The battery carbon cloth electrode material is prepared by the method for modifying and modifying the battery carbon cloth electrode by the metal carbide nano material.
The beneficial effects of the invention are as follows:
1. According to the nanomaterial-modified carbon cloth electrode, carbide embedded in worm-shaped nanopores can be formed on the surface of the electrode through carbothermal reaction, the surface area of the electrode is increased through the worm-shaped nanopores, the redox area at the electrode is increased, and a richer effective area is provided for chemical reaction; the carbide inlaid in the vermicular nano-pores is an electrocatalyst with excellent battery reaction, increases the kinetics of oxidation-reduction reaction at the electrode and has great effect on inhibiting hydrogen evolution of the iron-chromium flow battery; the newly prepared carbon cloth electrode has a unique structure, and has the following advantages compared with the prior method for bonding the catalyst to the surface of the electrode: first, the electrocatalyst is embedded in the pores, avoiding being washed away in the flow environment; secondly, the electrocatalyst can be uniformly distributed to prevent agglomeration in the bonding process; third, the non-conductive nature of the polymeric binder is overcome, the cost of the binder process is overcome, the cost of electrode fabrication is reduced and the binder is avoided from covering the active surface of the electrocatalyst.
2. Compared with an unmodified material, the nano material for modifying the carbon cloth for the carbon cloth electrode of the iron-chromium flow battery prepared by the invention has higher energy efficiency, specific capacity, coulombic efficiency and more stable cycle performance in battery cycle, improves the conductivity of the carbon cloth electrode, optimizes the growth environment of a catalyst, improves the electrochemical performance of the prepared electrode material, and greatly improves the battery performance.
3. The method is simple in operation, low in raw material cost, suitable for large-scale market preparation and capable of promoting development of the iron-chromium flow battery.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described, the drawings in the description below are only embodiments of the present invention, and other drawings may be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is an electrochemical performance diagram of a nanomaterial-modified carbon cloth electrode prepared in example 1 of the present invention;
FIG. 2 is a graph showing the cycling performance of the carbon cloth modified in example 2 of the present invention at a current density of 140 mA/cm 2 when applied in an iron-chromium flow battery;
FIG. 3 is a graph showing the electrochemical performance of the nanomaterial-modified carbon cloth electrode prepared in example 3 of the present invention;
FIG. 4 is a graph showing the electrochemical performance of the nanomaterial-modified carbon cloth electrode prepared in example 4 of the present invention;
FIG. 5 is a graph showing the cycling performance of the carbon cloth modified in example 5 of the present invention at a current density of 140 mA/cm 2 when used in an iron-chromium flow battery;
FIG. 6 is a graph showing electrochemical performance of a nanomaterial-modified carbon cloth electrode prepared in example 6 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular forms also are intended to include the plural forms unless the context clearly indicates otherwise, and furthermore, it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, and/or combinations thereof.
Example 1:
And ultrasonically cleaning the carbon cloth material by using deionized water for 10min, putting the carbon cloth material into an oven, and drying the carbon cloth material at 60 ℃ to remove impurity interference on the surface of the carbon cloth material. The carbon cloth was placed in a muffle furnace apparatus, subjected to 400 o C high temperature heat treatment in air, and kept at 4: 4 h. 0.9484 gTiCl 4 is dissolved in water to a constant volume of 5: 5mL, 5ml of 1 mol/L TiCl 4 aqueous solution is prepared, carbon cloth is immersed in TiCl 4 aqueous solution for 0.5: 0.5h, then dried at 60 ℃, the treated carbon cloth is placed in a high-temperature device of a tubular furnace, 1300 ℃ high-temperature heat treatment is carried out in nitrogen atmosphere, the heating rate in the reaction process is 4 ℃/min, and the heat preservation duration is 3 h.
The electrochemical test result of the obtained nano material modified carbon cloth electrode material is shown in figure 1, and the electrode oxidation peak and the reduction peak prepared in the figure also show more symmetrical and less separation, and show strong electrocatalytic activity.
Example 2:
And ultrasonically cleaning the carbon cloth material by using deionized water for 10min, putting the carbon cloth material into an oven, and drying the carbon cloth material at 60 ℃ to remove impurity interference on the surface of the carbon cloth material. The carbon cloth was placed in a muffle furnace apparatus, subjected to 400 o C high temperature heat treatment in air, and kept at 4: 4 h. 0.4742 gTiCl 4 is dissolved in water to a constant volume of 5mL, 5ml of 0.5 mol/L TiCl 4 aqueous solution is prepared, carbon cloth is immersed in TiCl 4 aqueous solution for 0.5h, then dried at 60 ℃, the treated carbon cloth is put into a high-temperature device of a tube furnace, 1300 ℃ high-temperature heat treatment is carried out in nitrogen atmosphere, the heating rate in the reaction process is 4 ℃/min, and the heat preservation duration is 3 h.
Fig. 2 is a graph of cell cycle performance at a current density of 140 mA/cm 2 for an iron-chromium flow battery with a blank control of raw carbon cloth, using the carbon cloth modified in accordance with an example of the present invention. It can be seen that at higher current densities, the resulting carbon cloth still maintains a very high energy efficiency.
Example 3:
And ultrasonically cleaning the carbon cloth material by using deionized water for 10 min, putting the carbon cloth material into an oven, and drying the carbon cloth material at 60 ℃ to remove impurity interference on the surface of the carbon cloth material. The carbon cloth was placed in a muffle furnace apparatus, subjected to 400 o C high temperature heat treatment in air, and kept at 4: 4 h. 0.23769 gNiCl 2·6H2 O was dissolved in water to a constant volume of 5mL, 5mL of a 0.2 mol/L aqueous solution of NiCl 2·6H2 O was prepared, and the diluted solution of NH 3·H2 O was added until the pH was 8. Immersing the carbon cloth in the solution for 0.5 h, then drying at 60 ℃, placing the treated carbon cloth in a high-temperature device of a tube furnace, performing 1300 ℃ high-temperature heat treatment in a nitrogen atmosphere, wherein the heating rate in the reaction process is 4 ℃/min, and the heat preservation duration is 3h.
The electrochemical test result of the obtained nanomaterial modified carbon cloth electrode material is shown in figure 3.
Example 4:
And ultrasonically cleaning the carbon cloth material by using deionized water for 10min, putting the carbon cloth material into an oven, and drying the carbon cloth material at 60 ℃ to remove impurity interference on the surface of the carbon cloth material. The carbon cloth was placed in a muffle furnace apparatus, subjected to 400 o C high temperature heat treatment in air, and kept at 4: 4 h. 0.47538 gNiCl 2·6H2 O was dissolved in water to a constant volume of 5 mL,5 mL of a 0.4 mol/L aqueous solution of NiCl 2·6H2 O was prepared, and the diluted solution of NH 3·H2 O was added until the pH was 8. Immersing the carbon cloth in the solution for 0.5 h, then drying at 60 ℃, placing the treated carbon cloth in a high-temperature device of a tube furnace, performing 1300 ℃ high-temperature heat treatment in a nitrogen atmosphere, wherein the heating rate in the reaction process is 4 ℃/min, and the heat preservation duration is 3 h.
The electrochemical test result of the obtained nanomaterial modified carbon cloth electrode material is shown in fig. 4.
Example 5:
And ultrasonically cleaning the carbon cloth material by using deionized water for 10min, putting the carbon cloth material into an oven, and drying the carbon cloth material at 60 ℃ to remove impurity interference on the surface of the carbon cloth material. The carbon cloth was placed in a muffle furnace apparatus, subjected to 400 o C high temperature heat treatment in air, and kept at 4: 4 h. 0.61935 gTiF 4 is dissolved in water to a constant volume of 5mL, 5ml of 1 mol/L TiF 4 aqueous solution is prepared, carbon cloth is immersed in the TiF 4 aqueous solution for 0.5h, then dried at 60 ℃, the treated carbon cloth is placed in a high-temperature device of a tubular furnace, 1200 ℃ high-temperature heat treatment is carried out in a nitrogen atmosphere, the heating rate in the reaction process is 4 ℃/min, and the heat preservation duration is 0.5 h.
FIG. 5 is a graph of cell cycle performance at a current density of 140 mA/cm 2 for an example modified carbon cloth of the present invention applied in an iron-chromium flow battery. Wherein the blank control group is original carbon cloth. It can be seen that at higher current densities, the resulting carbon cloth still maintains a very high energy efficiency.
Example 6:
and ultrasonically cleaning the carbon cloth material by using deionized water for 10 min, putting the carbon cloth material into an oven, and drying the carbon cloth material at 60 ℃ to remove impurity interference on the surface of the carbon cloth material. The carbon cloth was placed in a muffle furnace apparatus, subjected to 400 o C high temperature heat treatment in air, and kept at 4: 4 h. 0.81789 gZnCl 2 is dissolved in water to 30mL, 30ml of ZnCl 2 water solution with the concentration of 0.2 mol/L is prepared, the precursor solution is poured into a polytetrafluoroethylene reaction kettle, the carbon cloth after heat treatment is put into the polytetrafluoroethylene reaction kettle, the cover is screwed, and then the carbon cloth is put into a metal shell. The reaction vessel was placed in a constant temperature forced air drying oven. And then carrying out hydrothermal treatment at the temperature of 180 ℃ for 12 h ℃, naturally cooling, then drying, putting the treated carbon cloth into high-temperature equipment of a tube furnace, carrying out 1500 ℃ high-temperature heat treatment in a nitrogen atmosphere, wherein the heating rate in the reaction process is 4 ℃/min, and the heat preservation duration is 3 h.
The electrochemical test result of the obtained nanomaterial modified carbon cloth electrode material is shown in fig. 6.
In summary, the invention discloses a method for modifying a carbon cloth electrode of a battery by using a metal carbide nanomaterial, which comprises the following steps of pretreating carbon cloth; preparing metal carbide nano material modified carbon cloth; calcining the modified carbon cloth to obtain a metal carbide nano material modified battery carbon cloth electrode; the metal carbide nanomaterial modified carbon cloth electrode has the advantages of simple operation method, low raw material cost and convenience in large-scale production, provides rich high catalytic activity sites for the oxidation and reduction reaction of battery electrolyte, promotes the oxidation and reduction reaction of the battery electrolyte by utilizing the formed worm-hole-shaped nanopores, improves the conductivity of the carbon cloth electrode, optimizes the growth environment of a catalyst, can improve the precipitation potential of hydrogen ions, reduces the hydrogen evolution amount of negative electrolyte, greatly improves the efficiency and performance of the battery, and has extremely strong commercial popularization potential.
So far, those skilled in the art will recognize that while embodiments of the present invention have been shown and described in detail herein, many other variations or modifications that are in accordance with the principles of the present invention may be directly ascertained or inferred from the present disclosure without departing from the spirit and scope of the present invention. Accordingly, the scope of the present invention should be understood and deemed to cover all such other variations or modifications.
Claims (10)
1. A method for modifying a carbon cloth electrode of a battery by using a metal carbide nanomaterial, which is characterized by comprising the following steps:
Step S1: pretreatment of carbon cloth:
Cleaning the carbon cloth by using one or more solutions of deionized water, ethanol and methanol, and drying; carrying out high-temperature heat treatment on the cleaned carbon cloth to finish pretreatment;
step S2: preparing metal carbide nano material modified battery carbon cloth:
preparing a metal carbide nanomaterial precursor solution; immersing the pretreated carbon cloth obtained in the step S1 into a precursor solution, and treating the pretreated carbon cloth by using one or more methods of an immersion method or a hydrothermal method;
Step S3: calcining modified battery carbon cloth
And (3) taking out the carbon cloth treated in the step (S2), drying, and calcining at a high temperature under a protective atmosphere to perform carbothermic reduction to obtain the battery carbon cloth modified and modified by the metal carbide nano material.
2. The method for modifying the carbon cloth electrode of the battery by using the metal carbide nano material as claimed in claim 1, wherein the carbon cloth is cleaned in an ultrasonic mode in the step S1, the cleaning time is 5-30 min, the drying is carried out by adopting an oven, the drying temperature is 25-120 ℃, and the specific mode of high-temperature heat treatment of the carbon cloth is as follows: and (3) placing the cleaned carbon cloth into a muffle furnace to keep an air atmosphere for high-temperature heat treatment.
3. The method for modifying a carbon cloth electrode of a battery with a metal carbide nanomaterial according to claim 1, wherein the carbon cloth used in the step S1 is polyacrylonitrile PNV-based carbon cloth, rayon-based carbon cloth, or petroleum pitch-based carbon cloth.
4. The method for modifying a carbon cloth electrode of a battery with a metal carbide nanomaterial according to claim 1, wherein the carbon cloth is subjected to high-temperature heat treatment in the step S1 at a temperature of 100-1000 o ℃ for a heat preservation time of 1-30 h.
5. The method for modifying a carbon cloth electrode of a battery with a metal carbide nanomaterial according to claim 1, wherein the concentration of the metal carbide nanomaterial precursor solution in the step S2 is 0.01-5 mol/L.
6. The method for modifying a carbon cloth electrode of a battery according to claim 1, wherein the solute of the precursor solution of the metal carbide nanomaterial in the step S2 is one or more of titanium chloride, titanium fluoride, copper chloride, copper sulfate, platinum chloride, platinum nitrate, tin chloride, nickel nitrate, zinc chloride and hydrates thereof, and the solvent for preparing the precursor is one or more of water, hydrochloric acid, sulfuric acid, nitric acid, sodium hydroxide, potassium hydroxide, ammonia water and ethylene glycol.
7. The method for modifying a carbon cloth electrode of a battery according to claim 1, wherein the dipping time is 0.1-24 h when the dipping method is adopted in the step S2.
8. The method for modifying a carbon cloth electrode of a battery with a metal carbide nanomaterial according to claim 1, wherein in the step S2, a hydrothermal method is adopted, an instrument used is a high-pressure hydrothermal kettle, the hydrothermal reaction temperature is 100-260 ℃, and the retention time is 1-24 h.
9. The method for modifying a carbon cloth electrode of a battery with a metal carbide nanomaterial according to claim 1, wherein the carbon cloth is dried at a temperature of 50-100 ℃ for a time period of 0.1-24 h in the step S3; the carbothermic reduction is carried out by using a tube furnace, the calcination temperature is 600-2000 ℃, the protective atmosphere is one or more mixed gases of helium, nitrogen, argon, xenon and neon, the heating rate in the reaction process is 1-20 ℃/min, and the calcination temperature is kept at 0.5-12 h.
10. The carbon cloth electrode material of the battery prepared by the method for modifying and modifying the carbon cloth electrode of the battery by using the metal carbide nano material according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410306606.1A CN117913301B (en) | 2024-03-18 | 2024-03-18 | Method for modifying battery carbon cloth electrode by metal carbide nano material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410306606.1A CN117913301B (en) | 2024-03-18 | 2024-03-18 | Method for modifying battery carbon cloth electrode by metal carbide nano material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117913301A true CN117913301A (en) | 2024-04-19 |
| CN117913301B CN117913301B (en) | 2024-07-05 |
Family
ID=90690848
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410306606.1A Active CN117913301B (en) | 2024-03-18 | 2024-03-18 | Method for modifying battery carbon cloth electrode by metal carbide nano material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117913301B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017049466A1 (en) * | 2015-09-22 | 2017-03-30 | 许昌学院 | Composite electrode material, manufacturing method thereof, and use thereof in vanadium flow battery |
| CN107863536A (en) * | 2017-10-16 | 2018-03-30 | 香港科技大学 | Multiple dimensioned porous electrode applied to flow battery and its preparation method and application |
| CN110492054A (en) * | 2019-08-12 | 2019-11-22 | 中盐金坛盐化有限责任公司 | Modify method, electrode, battery and the energy-storage system of organic flow battery electrode |
| CN111514927A (en) * | 2019-02-04 | 2020-08-11 | 国家能源投资集团有限责任公司 | Metal carbide nano material catalyst and preparation method thereof |
| CN115832328A (en) * | 2023-02-08 | 2023-03-21 | 南方科技大学 | Porous carbon electrode, preparation method thereof and flow battery |
| WO2023045328A1 (en) * | 2021-09-26 | 2023-03-30 | 液流储能科技有限公司 | Method for purifying iron-chromium electrolyte, and iron-chromium electrolyte thereby obtained |
| CN115957604A (en) * | 2022-11-28 | 2023-04-14 | 北京工商大学 | Carbon nanotube modified carbon cloth electrode with adjustable structure and preparation method and application thereof |
| CN116031418A (en) * | 2023-02-20 | 2023-04-28 | 中海储能科技(北京)有限公司 | Method for modifying defects of carbon cloth electrode of iron-chromium flow battery |
| CN116111109A (en) * | 2021-11-11 | 2023-05-12 | 南方科技大学 | Carbon electrode composite material, preparation method thereof and secondary battery |
| CN116487618A (en) * | 2022-01-15 | 2023-07-25 | 中国石油化工股份有限公司 | Flow battery electrode and preparation method thereof |
-
2024
- 2024-03-18 CN CN202410306606.1A patent/CN117913301B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017049466A1 (en) * | 2015-09-22 | 2017-03-30 | 许昌学院 | Composite electrode material, manufacturing method thereof, and use thereof in vanadium flow battery |
| CN107863536A (en) * | 2017-10-16 | 2018-03-30 | 香港科技大学 | Multiple dimensioned porous electrode applied to flow battery and its preparation method and application |
| CN111514927A (en) * | 2019-02-04 | 2020-08-11 | 国家能源投资集团有限责任公司 | Metal carbide nano material catalyst and preparation method thereof |
| CN110492054A (en) * | 2019-08-12 | 2019-11-22 | 中盐金坛盐化有限责任公司 | Modify method, electrode, battery and the energy-storage system of organic flow battery electrode |
| WO2023045328A1 (en) * | 2021-09-26 | 2023-03-30 | 液流储能科技有限公司 | Method for purifying iron-chromium electrolyte, and iron-chromium electrolyte thereby obtained |
| CN116111109A (en) * | 2021-11-11 | 2023-05-12 | 南方科技大学 | Carbon electrode composite material, preparation method thereof and secondary battery |
| CN116487618A (en) * | 2022-01-15 | 2023-07-25 | 中国石油化工股份有限公司 | Flow battery electrode and preparation method thereof |
| CN115957604A (en) * | 2022-11-28 | 2023-04-14 | 北京工商大学 | Carbon nanotube modified carbon cloth electrode with adjustable structure and preparation method and application thereof |
| CN115832328A (en) * | 2023-02-08 | 2023-03-21 | 南方科技大学 | Porous carbon electrode, preparation method thereof and flow battery |
| CN116031418A (en) * | 2023-02-20 | 2023-04-28 | 中海储能科技(北京)有限公司 | Method for modifying defects of carbon cloth electrode of iron-chromium flow battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117913301B (en) | 2024-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111785978B (en) | Porous electrode for flow battery and preparation method thereof | |
| CN106560944B (en) | Porous carbon fiber paper electrode material used for all-vanadium redox flow battery and its preparation and application | |
| CN106549162B (en) | Composite electrode material, preparation method thereof and application of composite electrode material in all-vanadium redox flow battery | |
| CN105597791A (en) | Molybdenum selenide/porous carbon nanofiber composite material and preparation method and application thereof | |
| CN106784877B (en) | Preparation method of microbial fuel cell cathode composite material and microbial fuel cell reactor | |
| CN105742658A (en) | Preparation method of electrode material for all-vanadium flow battery | |
| CN105529471A (en) | Treatment method for all-vanadium redox flow battery electrode | |
| CN111740126A (en) | Chemical doping modification method for graphite felt electrode material of vanadium battery | |
| CN111211307B (en) | Flexible sulfur-nitrogen co-doped porous carbon fiber composite electrode material and preparation method and application thereof | |
| CN111628188B (en) | Electrode material for all-vanadium redox flow battery constructed by boron-doped aerogel and preparation method and application thereof | |
| CN104716338B (en) | Processing method of electrode used for liquid flow cell | |
| CN113512738B (en) | Ternary iron-nickel-molybdenum-based composite material water electrolysis catalyst, and preparation method and application thereof | |
| CN113839058A (en) | Carbon-based oxygen reduction reaction catalyst and preparation method thereof | |
| CN110034305B (en) | Activation method of graphite felt electrode material for iron-chromium flow battery | |
| CN117913301B (en) | Method for modifying battery carbon cloth electrode by metal carbide nano material | |
| CN116404174A (en) | Method for modifying graphite felt electrode by manganese dioxide nano particles and application | |
| CN115863666A (en) | Preparation method of graphite felt modified electrode for all-vanadium redox flow battery | |
| CN104716349B (en) | A kind of preparation method of high activity electrode material used for all-vanadium redox flow battery | |
| CN108878817A (en) | Reduce lithium selenium cell positive electrode, electrode slice and button cell that more selenides are lost | |
| CN104269223A (en) | Method for preparing electrode materials by using electroplating sludge and eggshell membranes | |
| CN114709427A (en) | Preparation method of nitrogen-sulfur co-doped hierarchical porous carbon catalyst with acid-alkali-oxygen-resistant reduction catalysis performance | |
| CN108539211B (en) | Preparation method of fluoride salt modified multifunctional electrode material for vanadium battery | |
| CN114974927B (en) | Preparation method of self-supporting electrode material of carbon nano array | |
| CN110620244A (en) | Glucose hydrothermal carbon and nitrogen co-doped graphite felt electrode and preparation method and application thereof | |
| CN117712399A (en) | Preparation method of nitrogen-oxygen co-doped biomass carbon catalyst modified carbon felt electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |