CN211665430U - Active carbon fiber felt for hydrogen storage - Google Patents
Active carbon fiber felt for hydrogen storage Download PDFInfo
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- CN211665430U CN211665430U CN201921250714.2U CN201921250714U CN211665430U CN 211665430 U CN211665430 U CN 211665430U CN 201921250714 U CN201921250714 U CN 201921250714U CN 211665430 U CN211665430 U CN 211665430U
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Abstract
The utility model provides an active carbon fiber felt for hydrogen storage, which comprises an active carbon fiber felt matrix and a metal layer attached to the surface of the active carbon fiber felt matrix; the surface aperture of the activated carbon fiber felt substrate is not less than 0.6 nm. Compare in the carbon fiber felt body or the activated carbon fiber felt body that do not have metallization treatment, the utility model discloses an activated carbon fiber felt that surface contains the metal level obtains promoting by a wide margin to the absorption of hydrogen and hydrogen storage characteristic.
Description
Technical Field
The utility model relates to a store up hydrogen and use carbonaceous material field, concretely relates to store up hydrogen and use active carbon fiber felt.
Background
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be taken as an acknowledgement or any form of suggestion that this information constitutes prior art that is already known to a person skilled in the art.
The application of hydrogen energy becomes the main development direction of the current novel energy revolution, the storage of the hydrogen energy becomes the scientific problem which needs to be solved urgently at present, wherein solid hydrogen storage materials are paid attention by researchers due to the characteristics of higher safety and less energy consumption, and the solid hydrogen storage materials researched and developed at present mainly comprise alloy metal materials, carbon materials, composite chemical hydrogen compound materials, metal organic framework compound materials and the like. The carbonaceous material has the excellent characteristics of large hydrogen absorption amount, light weight, strong anti-poisoning performance and the like, and the physical adsorption hydrogen storage capacity of the carbonaceous material is considered to be the most promising development prospect in the field of new energy storage at present, wherein the carbon material which is developed relatively comprises hydrogen storage adsorption carbonaceous materials such as activated carbon fibers, carbon nanotubes, graphene and the like. However, the inventors have found that these materials still have disadvantages, such as high cost of the hydrogen storage medium despite large hydrogen storage capacity, slow desorption rate, short cycle life, and unsuitability for large-scale storage and transportation.
Disclosure of Invention
The activated carbon fiber shows stronger adsorption characteristic due to the excellent porous surface characteristic, and becomes a hydrogen storage adsorption material which is economical and applicable, has high hydrogen storage capacity, quick desorption, can be recycled and has longer service life. The utility model provides an active carbon fiber felt for hydrogen storage, it contains active carbon fiber felt base member and deposits the metal level on active carbon fiber felt base member surface, can be applied to hydrogen energy storage and/or absorption field. The utility model discloses an activated carbon fiber felt can exert the adsorption characteristic of the monofilament fiber surface micropore structure of activated carbon felt simultaneously and store up the intrinsic hydrogen storage characteristic of hydrogen metal, the hydrogen storage capacity that can more effectively improve.
Specifically, the utility model discloses have as follows technical scheme:
the utility model provides an active carbon fiber felt for hydrogen storage, which comprises an active carbon fiber felt matrix and a metal layer deposited on the surface of the active carbon fiber felt matrix; the surface aperture of the activated carbon fiber felt substrate is not more than 0.7nm, or not more than 0.65nm, or not more than 0.6nm, or 0.6-0.7 nm.
The activated carbon fiber felt substrate takes pre-oxidized fiber felt as a raw material.
Or the activated carbon fiber felt substrate is an activated carbon fiber felt-shaped three-dimensional structure body which comprises at least two layers of net tires and needled fibers, wherein the net tires are alternately laminated, and the needled fibers are needled and penetrated between the alternately laminated net tires to connect and fix the adjacent laminated layers.
The net body is a pre-oxidized fiber net body, and pre-oxidized fibers are used as raw materials.
Pre-oxidation fibrofelt can select single kind pre-oxidation fibre or composite fiber, the tensile strength of the monofilament fiber in the pre-oxidation fibrofelt is not less than 200MPa, the tensile modulus is not less than 1.0GPa, the fiber density is not less than 1.3g/cm3The carbon content of the fiber is not less than 65 wt%; the pre-oxidized fiber felt has a density of not less than 0.05g/m3Further, it is not less than 0.07g/m3Preferably 0.07-0.085g/m3。
The utility model discloses in, the preoxidized fiber felt is polyacrylonitrile preoxidized fiber and/or viscose base preoxidized fiber (also called viscose base carbon fiber).
In the utility model, the gram weight of the single-layer net tire is 10-50g/m2。
The utility model discloses in, the acupuncture fibre runs through range upon range of net child with the direction acupuncture of perpendicular to stromatolite face. The needling density is 10-40 needles/cm2。
In the utility model, the thickness of the metal layer is 1 μm-100 μm. The metal is a single metal or an alloy. The metal layer may be a single metal layer such as a nickel metal layer, a magnesium metal layer, a copper metal layer, a cobalt metal layer, or a binary alloy metal layer or a ternary alloy metal layer, such as a nickel-cobalt alloy.
The present invention is not limited to the method for preparing the activated carbon fiber mat for hydrogen storage, and the present invention provides some preparation methods as follows as examples:
in some embodiments, an activated carbon fiber felt-like three-dimensional structure with a proper pore structure is prepared, then a proper treatment current density and a proper surface metallization treatment time are selected on the surface of the activated carbon fiber felt according to the requirement of metallization treatment thickness, ultrasonic vibration operation is simultaneously carried out on the carbon fiber felt in the treatment process, the uniformity and stability of the treatment process are ensured, and finally a three-dimensional chopped felt-like carbon fiber structure with a uniform metallization surface layer, namely the activated carbon fiber felt for hydrogen storage, is formed.
The pore structure of the activated carbon fiber felt is processed and activated, and the high-performance pre-oxidized fiber felt is used as a raw material for activation treatment. The activation process adopts a process of synchronously carrying out carbonization and activation, the prepared pre-oxidized felt is fed into a hearth of an activation furnace at room temperature, then nitrogen is introduced into the hearth, carbonization and heating are carried out at different heating rates, water vapor is introduced after a certain temperature is reached, constant-temperature activation is carried out for a certain time after a preset temperature is reached, finally the pre-oxidized fiber felt is cooled to a certain temperature under the protection of nitrogen, and then the pre-oxidized fiber felt is naturally cooled to room temperature, so that the activation and carbonization treatment of the pre-oxidized fiber felt are completed.
The high-performance pre-oxidized fiber felt can be selected from polyacrylonitrile pre-oxidized fiber or viscose pre-oxidized fiber, the tensile strength of monofilament fiber in the pre-oxidized fiber felt is more than 200MPa, such as 260-300MPa, the tensile modulus is more than 1.0GPa, such as 1.4-1.6GPa, and the density of a fiber body is 1.3g/cm3Above, the carbon content of the fiber is not less than 65%, for example, 55 to 75% by weight.
The carbonization process in the activation process adopts high-purity nitrogen, the purity of the nitrogen is more than 99.99999 percent, and the introduction pressure is not lower than 0.2 MPa; the heating rate of heating carbonization is controlled within the range of 5-15 ℃/min, the final carbonization temperature is controlled within the range of 1000-1500 ℃, the rate of introducing water vapor at the carbonization temperature is controlled within the range of 3-15g/min, the final activation time is controlled within the range of 20-50min, and after the activation treatment is finished, the cooling temperature under the protection of nitrogen is controlled within the range of 150-200 ℃. The surface aperture of the monofilament fiber of the finally obtained activated carbon fiber felt is controlled to be not more than 0.7nm, or not more than 0.65nm, or not more than 0.6nm, or in the range of 0.6-0.7 nm.
The surface of monofilament fiber of the activated carbon fiber felt is metallized to obtain a deposited metal layer, the used metal treatment liquid is prepared into the treatment liquid of conventional single metal or alloy metal, an ultrasonic generating treatment device is prepared in a treatment liquid assembling container, and the carbon felt is subjected to ultrasonic vibration in the whole treatment process.
In some embodiments, the metal treatment fluid requires preheating, which can be achieved by heating in a water bath to a temperature of 50-60 ℃. The treatment can improve the treatment activity and optimize the treatment effect. In some embodiments, after the metal treatment fluid is preheated to the above temperature, an activated carbon fiber felt matrix is added for metallization.
The ultrasonic wave generating device adopts a parallel arrangement mode of a plurality of ultrasonic probes, the ultrasonic probes control the frequency and the ultrasonic power of the ultrasonic probes through an ultrasonic wave generating source, wherein the ultrasonic frequency and the ultrasonic power can be flexibly adjusted according to requirements, the ultrasonic frequency which can be emitted by the ultrasonic probes can be selected within the range of 16.5-40KHz, the ultrasonic power can be selected within the range of 1000-4000W, and the voltage of the ultrasonic generator is 220V.
The treatment process strictly controls and selects treatment current density and treatment time according to requirements, wherein the treatment current density is controlled to be 0.1-10A/dm2The treatment time is controlled to be about 5-150 minutes. And after a treatment power supply is switched on, the treatment liquid finally forms activated carbon fiber felt monofilament fiber surface deposits with uniform coatings in the ultrasonic vibration process, and after the deposits form a deposition treatment layer, the deposits are washed and dried in a drying oven to obtain the activated carbon fiber felt with the metal layer attached to the surface. The thickness of the treated layer can be controlled by adjusting factors such as current, treatment time and the like, and the thickness of the treated metal layer is controllable between 1 and 100 mu m.
Obtain the processing layer of different compositions through selecting different treatment fluid kinds and technology, the utility model discloses a method be used for the processing of the processing layer of present various metals, and the metal level can make monometallics such as nickel, magnesium, copper, also can be various binary and ternary alloy etc..
And, the activated carbon fiber felt of the present invention can also be selected from commercial products using pre-oxidized fiber felt as a raw material, such as polyacrylonitrile pre-oxidized fiber felt, or activated carbon fiber felt prepared from pre-oxidized fiber according to the following method.
In some embodiments of the present invention, the activated carbon fiber felt comprises at least two layers of web plies that are alternately stacked, and needled fibers that are needled through between the alternating layers of web plies to connect and secure adjacent plies; in some embodiments, the activated carbon fiber mat has a density of not less than 0.05g/m3And further 0.05 to 0.09g/m3Preferably 0.07-0.085g/m3。
In some embodiments of the present invention, pre-oxidized fibers may be first used as a raw material, and a web-forming process may be used to comb the web-formed batt; then, the net tire is laminated by adopting a hybrid lamination process and needled into a felt, and the needling density in the thickness direction and the needling fiber hybrid proportion are controlled in the needling process; finally, the flow and the temperature of the activation medium can be controlled in the activation process through the activation process, so that the surface aperture (not more than 0.7nm) of the monofilament fiber of the activated carbon fiber felt is controlled, and the activated carbon fiber felt material with controllable surface pore structure characteristics is prepared.
The net is combed to ensure that the gram weight of the single-layer net tire is 10-50g/m2In the range of further 10 to 45g/m2E.g. 10g/m2、40g/m2Or 45g/m2. When different types of fiber hybrid carded webs are adopted, the carded web mixing proportion can be flexibly adjusted according to requirements, for example, when different pre-oxidized fiber hybrid carded webs are used, for example, polyacrylonitrile pre-oxidized fibers and viscose-based pre-oxidized fibers are mixed, the mixing proportion (mass ratio) can be flexibly adjusted, for example, the mixing proportion is 1: 1-99 or 1-99: 1, e.g. 1: 1. 1: 5 or 4: 1.
net child mixes stromatolite can adopt the net child of different grammes per square metre to mix in order to adjust different intraformational fibrous density gradient. The lamination needling is performed in the direction perpendicular to the lamination surface (i.e. along the Z-axis direction), and the needling density is controlled to be 10-40 needles/cm2Within the range of (A) and (B),the needle punched fiber is selected from pre-oxidized fiber, the needle punched fiber can be single type pre-oxidized fiber such as polyacrylonitrile pre-oxidized fiber or viscose pre-oxidized fiber or can be composite fiber, the composite fiber can be mixed of different pre-oxidized fibers, and the mixing ratio can be flexibly adjusted. For example, the needle-punched fibers may be a mixture of polyacrylonitrile pre-oxidized fibers and viscose-based pre-oxidized fibers, and the mixing ratio (mass ratio) of the polyacrylonitrile pre-oxidized fibers and the viscose-based pre-oxidized fibers may be 1 to 99: 1 or 1: 1-99, in the technical scheme of the utility model, the proportion is 1-10: 1, in particular 3 to 8: the technical objects of the present invention are more easily achieved at 1 hour, such as 3: 1. 4: 1 or 8: 1.
in some embodiments of the present invention, the activation carbonization can be achieved by a carbonization activation heating device (such as the device shown in fig. 1), which comprises a heat preservation furnace chamber, a heater and a temperature control device, wherein high-purity nitrogen is introduced into the whole heat preservation furnace chamber through a flow inlet, and the gas flow is controlled by a flow controller; meanwhile, activating steam is introduced through a flow inlet, and the flow rate of the activating steam is controlled by a flow controller.
For example, in some manufacturing methods exemplified by the present invention, the carbonization activation treatment is based on the above-described carbonization activation heating apparatus, which includes: sending the prepared pre-oxidized fiber felt (namely the carbon fiber felt) into a heat preservation hearth 1 at room temperature, then introducing nitrogen into the hearth through a flow inlet 4, controlling the introduction pressure of the nitrogen to be not lower than 0.2MPa through a flow controller 5, controlling a heater 2 to heat to 1000-plus-one temperature at the heating rate of 5-15 ℃/min through a temperature control device 3, then introducing activating steam through a flow inlet 6, controlling the flow of the steam to be 3-15g/min through a flow controller 7, carbonizing at the temperature of 1000-plus-one temperature of 1500 ℃ for 20-50min, and then continuously cooling to 150-plus-one temperature of 200 ℃ in a nitrogen atmosphere; and then naturally cooling to room temperature to complete the activation and carbonization treatment of the fiber felt, thereby obtaining the activated carbon fiber felt.
In the embodiment of the utility model, the metal treatment liquid is evenly deposited on the surface of the monofilament fiber of the activated carbon fiber felt in the ultrasonic vibration process to form a metal deposition treatment layer; washing the formed metal deposition treatment layer with water and drying to obtain a metal layer, wherein the metal layer is attached to the surface of the activated carbon fiber felt substrate; in some embodiments of the present invention, the metal layer has a thickness controllable in a range of 1 μm to 100 μm.
In an embodiment of the present invention, the metallization treatment of the present invention, the metal treatment liquid used to prepare the treatment liquid can be conventional single metal or alloy metal, such as nickel, copper, cobalt, magnesium or a combination thereof.
In an embodiment of the invention, the process of surface metallization is performed in a metallization surface treatment device, wherein a metal treatment device, an ultrasound generating device and an electrode are arranged.
The utility model discloses an in some embodiments, ultrasonic generator adopts the parallel mode of arranging of a plurality of ultrasonic probe, and ultrasonic probe passes through ultrasonic wave generating source control ultrasonic probe's frequency and ultrasonic power, and wherein ultrasonic frequency and power can be adjusted in a flexible way, and wherein ultrasonic probe's ultrasonic frequency is optional in 16.5-40KHz scope, and ultrasonic power is optional in 1000 supplyes 4000W scopes, and ultrasonic generator's voltage is 220V.
In the embodiment of the present invention, the current density is controlled to be 0.1-10A/dm2The treatment time is controlled to be about 5-150 minutes. After the treatment power supply is switched on, the metal treatment liquid forms activated carbon fiber felt monofilament surface sediments with uniform coatings in the metal treatment device through an ultrasonic vibration process, and the activated carbon fiber felt with the metal layer attached to the surface is obtained. After the deposition treatment layer is formed, optionally, washing with water and drying in an oven are carried out to obtain the activated carbon fiber felt with the metal layer attached to the surface.
The thickness of the metal layer can be controlled by adjusting factors such as current, processing time and the like, and the thickness of the processed metal layer is controllable between 1 and 100 mu m.
In the embodiment of the utility model, the utility model discloses can obtain the processing layer of different compositions through selecting different treatment fluid kinds and technology, the method can be used to the processing on the processing layer of present various metals, the metal level can be single metal level such as nickel, magnesium, copper, cobalt, also can be various binary and ternary alloy etc. for example nickel cobalt alloy.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application. Embodiments of the present invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is a schematic diagram of a carbonization activation heating device for activating a carbon fiber felt, which comprises a heat preservation hearth 1, a heater 2 and a temperature control device 3, wherein high-purity nitrogen is introduced into the whole heat preservation hearth 1 through a flow inlet 4, and the nitrogen flow is controlled by a flow controller 5; meanwhile, the activating steam is introduced through a flow inlet 6, and the flow of the steam is controlled by a flow controller 7.
Fig. 2 is a schematic view of a metallized surface treatment apparatus comprising a metal treatment apparatus 1 ' (a treatment liquid is placed in the metal treatment apparatus 1 '), an ultrasonic generation apparatus 2 ' and an electrode 3 ', wherein 4 ' is a treatment sample.
Detailed Description
The present invention will be further described with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
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. The reagent or raw material used by the utility model can be purchased and obtained through a conventional way, if no special description is provided, the reagent or raw material used by the utility model can be used according to the conventional way in the field or the product specification. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.
The polyacrylonitrile pre-oxidized fiber, the viscose pre-oxidized fiber (i.e., viscose carbon fiber) or the felt body thereof used in the following examples are conventional commercially available varieties, and the specifications are optional, and the needle-punched fiber may be a single pre-oxidized fiber (e.g., polyacrylonitrile pre-oxidized fiber, viscose pre-oxidized fiber) or a composite fiber (e.g., a composite fiber in which polyacrylonitrile pre-oxidized fiber and viscose pre-oxidized fiber are mixed) in the manner exemplified in this example.
Alternatively, the activated carbon fiber mat may be prepared by carbonizing and activating a pre-oxidized fiber mat (also referred to as a carbon fiber mat body in the following specific examples) as a raw material in the following exemplary method. For example, in an exemplary embodiment, the pre-oxidized fiber mat is activated to obtain an activated carbon fiber mat, and the activation process may be based on the carbonization activation heating device shown in fig. 1, and may be performed according to the following activation procedures, for example: sending a pre-oxidized fiber felt (namely a carbon fiber felt) into a heat preservation hearth 1 at room temperature, then introducing nitrogen into the hearth through a flow inlet 4, controlling the introduction pressure of the nitrogen to be not lower than 0.2MPa through a flow controller 5, controlling a heater 2 to heat up to 1000-15 ℃/min through a temperature control device 3 to 1500 ℃, then introducing activating steam through a flow inlet 6, controlling the flow of the steam to be 3-15g/min through a flow controller 7, carbonizing at the temperature of 1000-15 ℃ for 20-50min, and then continuously cooling to 150-200 ℃ in a nitrogen atmosphere; and naturally cooling to room temperature to obtain the activated carbon fiber felt as the activated carbon fiber felt matrix. The surface pore size is controlled to be not more than 0.7nm, or not more than 0.65nm, or not more than 0.6nm, or in the range of 0.6-0.7 nm.
In the embodiment of the present invention, the pre-oxidized fiber felt is prepared from a single pre-oxidized fiber felt such as polyacrylonitrile pre-oxidized fiber felt or viscose pre-oxidized fiber felt, the tensile strength of the monofilament fiber in the pre-oxidized fiber felt is not lower than 200MPa, such as 260-300MPa, the tensile modulus is not lower than 1.0GPa, such as 1.4-1.6GPa, and the density of the fiber body is not lower than 1.3g/cm3For example, 1.3 to 1.5g/cm3The carbon content of the fibers is not less than 65% by weight, for example, 55 to 75% by weight.
The pre-oxidized fiber felt (i.e. the carbon fiber felt body) prepared by taking the pre-oxidized fiber as the raw material is not limited in particular method; by way of example, a carbon fiber felt body according to the requirements of the present invention can be prepared by the following method:
taking pre-oxidized fibers as a raw material, and carding into a web body by adopting a carding process; and then, the net tire is laminated by adopting a hybrid lamination process and is needled into a felt, and the needling density in the thickness direction and the needling fiber hybrid proportion are controlled in the needling process. The gram weight of the single-layer net tire is 10-50g/m2In the range of further 10 to 45g/m2E.g. 10g/m2、40g/m2Or 45g/m2. Net child mixes stromatolite can adopt the net child of different grammes per square metre to mix in order to adjust different intraformational fibrous density gradient. The lamination needling is performed in the direction perpendicular to the lamination surface (i.e. along the Z-axis direction), and the needling density is controlled to be 10-40 needles/cm2Within the range.
The commercially available activated carbon fiber felt or activated carbon fiber felt prepared by the above-described exemplary method, which may be referred to as a metallization process, is used as a substrate to deposit a metal layer on the surface, and may be performed, for example, in a metallization surface treatment apparatus shown in FIG. 2, by introducing a metal treatment liquid into a metallization surface treatment apparatus 1', by introducing an activated carbon fiber felt to be treated, and by turning on a power supply to control the current density to 0.1-10A/dm2And turning on an ultrasonic generating device to carry out ultrasonic oscillation, controlling the time of the metallization treatment process to be about 5-150 minutes, and forming activated carbon fiber felt monofilament surface sediments with uniform coatings by the metal treatment liquid in the metal treatment device through the ultrasonic oscillation process in current to obtain the carbon fiber felt with the metal layer attached to the surface. After the deposition treatment layer is formed, optionally, washing with water and drying in an oven are performed. The thickness of the metal layer can be controlled by adjusting factors such as current, processing time and the like, and the thickness of the processed metal layer is controllable between 1 and 100 mu m.
The utility model discloses an active carbon fiber felt of surface containing metal level, the surface aperture of its active carbon fiber felt base member is for being not more than 0.7nm, or for being not more than 0.65nm or for being not more than 0.6nm, perhaps be 0.6-0.7nm, the metal layer thickness is controllable at 1 mu m-100 mu m scope, compare in the carbon fiber felt body that does not metallize or the active carbon fiber felt body absorption and the hydrogen storage characteristic of hydrogen and promote by a wide margin, the amplitude of lift can reach 5-20%.
Specifically, the utility model discloses still provide following more specific preparation example:
example 1
The carbon fiber felt activation treatment process comprises the following steps:
the tensile strength is 285MPa, the tensile modulus is 1.6GPa, and the density of the carbon felt is 0.08g/cm3Putting a polyacrylonitrile preoxidized fiber felt with 65 percent of carbon content into a heat-preservation hearth, introducing high-purity nitrogen with the pressure not lower than 0.2MPa and the purity of more than 99.99999 percent, and synchronously carbonizing and activating the polyacrylonitrile preoxidized fiber felt, firstly setting the carbonization temperature at 1000 ℃, increasing the temperature at the rate of 5 ℃/min, then introducing water vapor with the rate of 3g/min when the carbonization temperature is reached, after 20min of activation treatment, reducing the temperature to 150 ℃ under the protection of nitrogen, then naturally cooling the temperature to room temperature, and finally obtaining the activated carbon felt fiber felt, wherein the surface aperture of the activated carbon felt fiber felt is controlled within the range of 0.6nm and is used as a substrate for metallization treatment.
Metallization treatment: adopting sulfamate metal treatment liquid, 420g/L of nickel sulfamate, 5g/L of nickel chloride and 40g/L of boric acid, placing the prepared treatment liquid into a metal treatment device, heating the treatment liquid to 60 ℃ under the condition of water bath, then placing an activated carbon fiber felt into the metal treatment device, treating the activated carbon fiber felt by adopting an ultrasonic generating device, and switching on a power supply to adjust the current density to be 0.6A/dm in the treatment process2The treatment time is 120 minutes. The prepared metal nickel layer active carbon fiber felt with the thickness of about 1.2 mu m has greatly improved hydrogen adsorption and hydrogen storage characteristics.
Example 2
The carbon fiber felt activation treatment process comprises the following steps:
the tensile strength of 260MPa, the tensile modulus of 1.5GPa and the density of the carbon felt body of 0.07g/m are selected3Placing the viscose-based preoxidized fiber felt with 75% of carbon content into a heat-preservation hearth, and introducing 99.999% of high-purity viscose-based preoxidized fiber felt with the pressure not lower than 0.3MPaAnd (2) synchronously carrying out carbonization and activation treatment on over 9 percent of high-purity nitrogen, firstly setting the carbonization temperature at 1500 ℃, raising the temperature at 15 ℃/min, then introducing 15g/min of water vapor when the carbonization temperature is reached, reducing the temperature to 150 ℃ under the protection of nitrogen after the activation treatment for 26min, and then naturally cooling to room temperature to finally obtain the activated carbon fiber felt, wherein the surface aperture of the activated carbon fiber felt is controlled within the range of 0.6nm, and the activated carbon fiber felt is used as a substrate for metallization treatment.
Metallization treatment: adopting sulfamate metal treatment liquid, 420g/L of nickel sulfamate, 5g/L of nickel chloride and 40g/L of boric acid, placing the prepared treatment liquid into a metal treatment device, heating the treatment liquid to 50 ℃ under the condition of water bath, then placing an activated carbon fiber felt into the metal treatment device, treating the activated carbon fiber felt by adopting an ultrasonic generating device, and adjusting the current density to be 2A/dm2The treatment time was 80 minutes. The prepared metal nickel layer active carbon fiber felt with the thickness of about 20 mu m has greatly improved hydrogen adsorption and hydrogen storage characteristics.
Example 3
The carbon fiber felt activation treatment process comprises the following steps:
the tensile strength of 260MPa, the tensile modulus of 1.5GPa and the density of the carbon felt body of 0.07g/m are selected3Placing the viscose-based preoxidized fiber felt with 75% of carbon content into a heat-preservation hearth, introducing high-purity nitrogen with the pressure not lower than 0.4MPa and the purity of more than 99.99999%, and synchronously carbonizing and activating the viscose-based preoxidized fiber felt, firstly setting the carbonization temperature at 1400 ℃, increasing the temperature at the rate of 12 ℃/min, then introducing water vapor at the rate of 12g/min when the carbonization temperature is reached, after 30min of activation treatment, reducing the temperature to 110 ℃ under the protection of nitrogen, and then naturally cooling to room temperature to finally obtain the activated carbon felt fiber felt, wherein the surface aperture of the activated carbon felt fiber felt is controlled within the range of 0.65nm, and the activated carbon felt is used as a substrate for metallization treatment.
Metallization treatment: preparing metal sulfate treatment liquid, namely 200g/L of copper sulfate and 70g/L of sulfuric acid, putting the prepared treatment liquid into a metal treatment device, heating the treatment liquid to 60 ℃ under the condition of water bath, then putting an activated carbon fiber felt into the metal treatment device, and carrying out ultrasonic treatment on the activated carbon fiber felt by using an ultrasonic generation deviceTreating, adjusting current density to 5A/dm2The treatment time was 40 minutes. The obtained activated carbon fiber felt with the metal copper layer with the thickness of about 100 mu m has greatly improved hydrogen adsorption and hydrogen storage characteristics.
Example 4
The carbon fiber felt activation treatment process comprises the following steps:
the tensile strength is 264MPa, the tensile modulus is 1.45GPa, and the density of the carbon felt is 0.085g/m3And placing the viscose-based preoxidized fiber felt with 67% of carbon content into a heat-preservation hearth, introducing high-purity nitrogen with the pressure not lower than 0.5MPa and the purity of more than 99.99999%, and synchronously carbonizing and activating the viscose-based preoxidized fiber felt, firstly setting the carbonization temperature at 1500 ℃, increasing the temperature at the rate of 8 ℃/min, then introducing water vapor with the rate of 10g/min when the carbonization temperature is reached, after 33min of activation treatment, reducing the temperature to 190 ℃ under the protection of nitrogen, and then naturally cooling to room temperature to finally obtain the activated carbon felt fiber felt, wherein the surface aperture of the activated carbon felt fiber felt is controlled within the range of 0.7nm, and the activated carbon felt is used as a substrate for metallization treatment.
Metallization treatment: adopting sulfamate metal treatment liquid, 600g/L of nickel sulfamate, 1.25g/L of cobalt sulfamate and 35g/L of nickel chloride, putting the prepared treatment liquid into a metal treatment device, heating the treatment liquid to 60 ℃ under the condition of water bath, then putting an activated carbon fiber felt into the metal treatment device, treating the activated carbon fiber felt by adopting an ultrasonic generating device, and adjusting the current density to be 3A/dm2The treatment time was 25 minutes. The metal nickel layer active carbon fiber felt with the thickness of about 2 mu m greatly improves the hydrogen adsorption and storage characteristics.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described in the foregoing embodiments, or equivalents may be substituted for elements thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An activated carbon fiber mat for hydrogen storage, characterized by comprising an activated carbon fiber mat substrate and a metal layer attached to the surface of the activated carbon fiber mat substrate.
2. The activated carbon fiber mat for hydrogen storage according to claim 1, wherein the surface pore size of the activated carbon fiber mat matrix is not more than 0.7nm, or not more than 0.65nm, or not more than 0.6 nm.
3. The activated carbon fiber mat for hydrogen storage according to claim 1, wherein the surface pore size of the activated carbon fiber mat matrix is 0.6 to 0.7 nm.
4. The activated carbon fiber mat for hydrogen storage according to claim 1, wherein the activated carbon fiber mat substrate comprises at least two layers of web bodies, the web bodies being alternately laminated; and the combination of (a) and (b),
and (3) needling fibers, wherein the needling fibers are penetrated through the alternate laminated layers of the net tire in a needling mode so as to connect and fix the adjacent laminated layers.
5. The activated carbon fiber mat for hydrogen storage according to claim 4, wherein the web is a pre-oxidized fiber web.
6. The activated carbon fiber mat for hydrogen storage according to claim 4, wherein the web is a single-layer web having a grammage of 10 to 50g/m2。
7. The activated carbon fiber mat for hydrogen storage according to claim 4, wherein the needle-punched fibers are needle-punched through the stacked web in a direction perpendicular to the stacking surface.
8. The activated carbon fiber mat for hydrogen storage according to claim 7, wherein the needling density is 10 to 40 needles/cm2。
9. The activated carbon fiber mat for hydrogen storage according to claim 1, wherein the metal layer has a thickness of 1 μm to 100 μm.
10. The activated carbon fiber mat for hydrogen storage according to claim 1, wherein the metal is a single metal or an alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201921250714.2U CN211665430U (en) | 2019-08-01 | 2019-08-01 | Active carbon fiber felt for hydrogen storage |
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