CN111924825B - Porous carbon material and method for preparing porous carbon material by using catalytic cracking diesel oil - Google Patents
Porous carbon material and method for preparing porous carbon material by using catalytic cracking diesel oil Download PDFInfo
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- CN111924825B CN111924825B CN202010934084.1A CN202010934084A CN111924825B CN 111924825 B CN111924825 B CN 111924825B CN 202010934084 A CN202010934084 A CN 202010934084A CN 111924825 B CN111924825 B CN 111924825B
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
Abstract
The invention discloses a porous carbon material and a method for preparing the porous carbon material by utilizing catalytic cracking diesel, wherein the method comprises the following steps: and (3) carrying out contact reaction on the catalytic cracking diesel oil and the porous structure template agent so that the catalytic cracking diesel oil grows on the surface of the porous structure template agent to form carbon with a porous structure. The catalytic cracking diesel oil is subjected to condensation reaction on the surface of the porous structure template agent, particularly the catalytic cracking diesel oil contains bicyclic and above aromatic hydrocarbon substances, so that carbon directionally grows on the surface of the porous structure template agent to cover the surface of the porous structure template agent, and the porous carbon material can be obtained after the porous structure template agent is removed. The method has simple process, the formed porous carbon material has excellent electrochemical performance, and hydrogen can be generated in the reaction process, thereby being beneficial to improving the economic benefit; meanwhile, S, N heteroatom in the catalytic cracking diesel oil can be subjected to in-situ S, N doping in the process of preparing the porous carbon material, so that the electrochemical performance of the porous carbon material is improved.
Description
Technical Field
The invention relates to the technical field of petroleum processing, in particular to a porous carbon material and a method for preparing the porous carbon material by using catalytic cracking diesel oil.
Background
The catalytic cracking processing capacity of China is about 40 percent of the primary processing capacity of crude oil, so that the catalytic cracking diesel oil has a large proportion in a diesel oil pool of China, reaches more than 30 percent, and becomes a main secondary processing diesel oil component. However, the global crude oil has more obvious heavy-weight trend, the proportion of sulfur-containing crude oil and high-sulfur crude oil is increased, most of domestic western oil fields and part of offshore crude oil is heavy sulfur-containing crude oil, and in addition, the operating severity of an FCC (fluid catalytic cracking) device is continuously improved for increasing the yield of gasoline or increasing the yield of propylene, so that the quality of catalytic diesel oil is increasingly poor, the contents of sulfur, nitrogen and aromatic hydrocarbon are higher, the cetane number is lower, particularly the content of aromatic hydrocarbon is higher than 80%, the aromatic hydrocarbon content mainly comprises a naphthalene compound containing bicyclic aromatic hydrocarbon, and the catalytic diesel oil is used for producing automotive diesel oil after hydrofining or cracking, and has harsh process conditions, high hydrogen consumption, high product density, cetane number and polycyclic aromatic hydrocarbon content which are difficult to meet new national standard requirements. In recent years, the upgrading of the quality of automotive fuel oil in China is accelerated, and the national VI diesel oil standard originally implemented in 2020 has been implemented in advance in 2019. The polycyclic aromatic hydrocarbon component is more strictly controlled, the polycyclic aromatic hydrocarbon mass fraction of national VI diesel oil is reduced from originally not more than 11 percent to not more than 7 percent, the use of the catalytic diesel oil with high aromatic hydrocarbon content is limited to a certain extent, and the processing route selection of the catalytic diesel oil is limited along with the further reduction of the diesel-gasoline ratio of consumption. Therefore, finding a suitable catalytic diesel high-added-value utilization way has become a research hotspot of researchers. At present, the utilization method for improving the added value of the catalytic cracking diesel oil mainly focuses on the fields of hydrofining, hydrocracking and the like, and the problems of harsh process conditions, high energy consumption, poor product quality, low added value and the like generally exist in hydrofining and hydrocracking engineering.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The present invention aims to provide a porous carbon material and a method for preparing the porous carbon material by using catalytic cracking diesel oil, so as to improve the problems.
The invention is realized by the following steps:
in a first aspect, the present invention provides a method for preparing a porous carbon material by using catalytic cracking diesel, comprising: and (3) carrying out contact reaction on the catalytic cracking diesel oil and the porous structure template agent so that the catalytic cracking diesel oil grows on the surface of the porous structure template agent to form carbon with a porous structure.
Optionally, the temperature of the contact reaction is 700-850 ℃; the reaction pressure is 0.1-0.2 MPa.
Optionally, the mass ratio of the catalytic cracking diesel oil to the porous structure template agent is 1: 3 to 10.
Optionally, the catalytic cracking diesel oil is subjected to contact reaction with a porous structure template agent under the action of a carrier gas; further preferably, the volume ratio of the carrier gas to the catalytic cracking diesel oil is 20-50: 1; more preferably, the carrier gas is one or more of nitrogen, hydrogen, argon and water vapor.
Optionally, the contact time of the catalytic cracking diesel oil and the porous structure template agent is 10-15 seconds.
Optionally, the porous structure template is selected from MgO and alpha-Fe with porous structure2O3Or catalytically cracking spent catalyst.
Optionally, the porous structure template is microspheres with the particle size distribution of 50nm-1000nm, and the specific surface area is 150-230m2/g。
Optionally, the catalytic cracking diesel has an aromatic hydrocarbon content of greater than 85 wt%, a bicyclic or higher aromatic hydrocarbon content of greater than 70%, a sulfur content of less than 8000 μ g/g, and a nitrogen content of less than 350 μ g/g.
Alternatively, the contacting reaction is carried out in a fluidized bed reactor.
Optionally, the porous structure template is placed in a fluidized bed, and then catalytic cracking diesel oil is brought into contact reaction with the porous structure template through carrier gas.
Optionally, the method further comprises removing the porous structure templating agent from the resulting product after the contacting reaction.
Optionally, the porous structure template is removed by an acidic solution, preferably, the acidic solution is a hydrochloric acid solution, and more preferably, the concentration of the hydrochloric acid solution is 1-6 mol/L.
In a second aspect, the invention also provides a porous carbon material prepared by the method for preparing the porous carbon material by using the catalytic cracking diesel oil.
In a third aspect, the present invention also provides an electrode material comprising a porous carbon material, optionally an electrode substrate, the porous carbon material being disposed on a surface of the electrode substrate, optionally the electrode substrate being nickel foam.
The invention has the following beneficial effects: the catalytic cracking diesel oil is subjected to condensation reaction on the surface of the porous structure template agent, particularly the catalytic cracking diesel oil contains bicyclic and above aromatic hydrocarbon substances, carbon generated by the reaction directionally grows on the surface of the porous structure template agent to cover the surface of the porous structure template agent, and then the porous carbon material can be obtained after the porous structure template agent is removed. The preparation method is simple in process, the formed porous carbon material is excellent in electrochemical performance, and a part of hydrogen can be generated in the reaction process, so that the economic benefit is improved; meanwhile, S, N heteroatom in the catalytic cracking diesel oil can be subjected to in-situ S, N doping in the process of preparing the porous carbon material, so that the electrochemical performance of the porous carbon material is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic diagram of a reaction flow for preparing a porous carbon material by using catalytic cracking diesel according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of a reaction mechanism for preparing a porous carbon material by using catalytic cracking diesel according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The porous carbon material and the method for preparing the porous carbon material by using the catalytic cracking diesel oil provided by the invention are specifically described below.
Some embodiments of the present invention provide a method for preparing a porous carbon material using catalytic cracking diesel, comprising: and (3) carrying out contact reaction on the catalytic cracking diesel oil and the porous structure template agent so that the catalytic cracking diesel oil grows on the surface of the porous structure template agent to form carbon with a porous structure.
The inventor finds that the catalytic cracking diesel oil can take a porous structure template agent as a template, and the porous structure template agent is subjected to in-situ condensation reaction on the surface of the porous structure template agent, particularly, the two or more aromatic hydrocarbon substances in the catalytic cracking diesel oil, carbon generated by the reaction directionally grows on the surface of the porous structure template agent to cover the surface of the porous structure template agent, and after the reaction is finished, the porous structure template agent is removed, so that the porous carbon material can be obtained. The reaction scheme and mechanism are shown in fig. 1 and fig. 2.
In particular, in order to enable the catalytic cracking diesel oil to be subjected to contact reaction on the surface of the porous structure template agent sufficiently and uniformly, the contact reaction is carried out in a fluidized bed reactor in some embodiments. The specific operation mode is as follows: the porous structure template agent is placed in a fluidized bed, and then catalytic cracking diesel oil is brought into contact with the porous structure template agent by carrier gas to react. So that the catalytic cracking diesel can continuously and uniformly grow carbon on the surface of the porous structure template agent in a directional manner to form a porous carbon material with better quality.
In order to make the reaction proceed smoothly and uniformly, in some embodiments, the temperature of the contact reaction is 700 ℃ to 850 ℃, for example, the reaction temperature may be 700 ℃, 720 ℃, 740 ℃, 750 ℃, 760 ℃, 770 ℃, 780 ℃, 790 ℃, 800 ℃, 810 ℃, 820 ℃, 830 ℃, 840 ℃, or 850 ℃ and the like; the reaction pressure is 0.1 to 0.2MPa, for example, the reaction pressure may be 0.1MPa, 0.12MPa, 0.14MPa, 0.15MPa, 0.17MPa, 0.18MPa, or 0.2 MPa.
In some embodiments, the mass ratio of the catalytic cracking diesel oil to the porous structure template agent is 1: 3-10, for example, the mass ratio of the catalytic cracking diesel oil to the porous structure template agent is 1: 3,1: 4,1: 5,1: 6,1: 7,1: 8 or 1: 9, etc. The mass ratio can make the porous carbon generated by the reaction have better pore structure, and the phenomenon that the generated carbon is insufficient to form the porous structure because of too little catalytic cracking diesel oil and the formed pore structure is covered by insufficient reaction or overgrowth because of too much catalytic cracking diesel oil can be avoided.
Further, the catalytic cracking diesel oil is continuously brought into the fluidized bed by the carrier gas to react with the porous structure template agent, so that the catalytic cracking diesel oil can fully and uniformly grow on the surface of the porous structure template agent until the required carbon material with the porous structure is formed. In order to optimize the loading capacity of the carrier gas and not cause the reaction time of the catalytic cracking diesel oil and the porous structure template agent to be too short, in some embodiments, the volume ratio of the carrier gas to the catalytic cracking diesel oil is 20-50: 1. wherein the carrier gas includes, but is not limited to, one or more of nitrogen, hydrogen, argon, and water vapor.
Further, in order to ensure a better reaction effect, the contact time of the catalytic cracking diesel oil and the porous structure template agent is 10-15 seconds.
The pore structure of the porous carbon material is determined by the specific structure of the porous structure template, and thus, in order to obtain a porous structure carbon material having a better pore structure and excellent electrochemical properties, in some embodiments, the porous structure template is selected from porous structures of MgO, α -Fe2O3Or catalytically cracking spent catalyst. Further, the porous structure template is preferably a particle size fractionThe cloth is 50nm-1000nm of microspheres, the specific surface area is 150-2Per g, more preferably, the porous structure template is microspheres with the particle size distribution of 300nm-1000nm and the specific surface area of 230m2(ii) in terms of/g. Through the selection of the specific type, shape and specific surface area of the porous structure template, the formed porous carbon material can have better electrochemical performance.
Further, in order to ensure the reaction effect of the condensation reaction of the catalytic cracking diesel oil to form porous carbon and the electrochemical performance of the product, in some embodiments, the aromatic hydrocarbon content of the catalytic cracking diesel oil is greater than 85 wt%, the aromatic hydrocarbon content of the double rings and above is greater than 70%, the sulfur content is less than 8000 mug/g, and the nitrogen content is less than 350 mug/g.
In some embodiments, the method of preparing a porous carbon material further comprises removing the porous structure templating agent from the resulting product after the contacting reaction.
Specifically, in some embodiments, the porous structure template is removed by an acidic solution, in a preferred embodiment, the acidic solution is a hydrochloric acid solution, and further, the concentration of the hydrochloric acid solution may be 1 to 6 mol/L.
Some embodiments of the invention also provide a porous carbon material prepared by the method for preparing the porous carbon material by using catalytic cracking diesel oil.
Also provided in some embodiments of the invention is an electrode material comprising a porous carbon material. In some embodiments, the electrode material further comprises an electrode substrate, and the porous carbon material is disposed on a surface of the electrode substrate, and in preferred embodiments, the electrode substrate includes, but is not limited to, nickel foam.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a method for preparing a porous carbon material by using catalytic cracking diesel, which specifically comprises the following steps: placing the porous structure template agent in a fluidized bed, introducing carrier gas loaded catalytic cracking diesel oil into the fluidized bed together to perform contact reaction with the porous structure template agent, and removing the porous structure template agent by stirring and soaking in 2mol/L hydrochloric acid solution to obtain the porous carbon material.
Wherein the content of dicyclic and above aromatic hydrocarbon of the catalytic cracking diesel oil is 72 percent, the content of sulfur is 6500 mu g/g, the content of nitrogen is 320 mu g/g, the porous structure template agent is porous MgO, the porous structure template agent is microspheres with the particle size distribution of 50nm-200nm, and the specific surface area is 150m2(ii) in terms of/g. The reaction temperature is 700 ℃, the reaction pressure is 0.1Mpa, the mass ratio of the porous structure template agent to the catalytic diesel oil is 3:1, the carrier gas is nitrogen, the volume ratio of the carrier gas to the catalytic cracking diesel oil is 20:1, and the contact time of the catalytic cracking diesel oil and the porous structure template agent is controlled for 15 s.
Example 2
The embodiment provides a method for preparing a porous carbon material by using catalytic cracking diesel, which specifically comprises the following steps: placing the porous structure template agent in a fluidized bed, introducing carrier gas loaded catalytic cracking diesel oil into the fluidized bed together to perform contact reaction with the porous structure template agent, and removing the porous structure template agent by stirring and soaking in 3mol/L hydrochloric acid solution to obtain the porous carbon material.
Wherein the content of dicyclic and above aromatic hydrocarbon of the catalytic cracking diesel oil is 78 percent, the content of sulfur is 6800 mu g/g, the content of nitrogen is 330 mu g/g, the porous structure template agent is porous MgO, the porous structure template agent is microspheres with the particle size distribution of 50nm-200nm, and the specific surface area is 150m2(ii) in terms of/g. The reaction temperature is 700 ℃, the reaction pressure is 0.1Mpa, the mass ratio of the porous structure template agent to the catalytic diesel oil is 3:1, the carrier gas is nitrogen, the volume ratio of the carrier gas to the catalytic cracking diesel oil is 20:1, and the contact time of the catalytic cracking diesel oil and the porous structure template agent is controlled for 15 s.
Example 3
The embodiment provides a method for preparing a porous carbon material by using catalytic cracking diesel, which specifically comprises the following steps: placing the porous structure template agent in a fluidized bed, introducing carrier gas loaded catalytic cracking diesel oil into the fluidized bed together to perform contact reaction with the porous structure template agent, and removing the porous structure template agent by stirring and soaking in 4mol/L hydrochloric acid solution to obtain the porous carbon material.
Wherein the content of dicyclic and above aromatic hydrocarbon in the catalytic cracking diesel oil is 85 percent, and the content of sulfur in the catalytic cracking diesel oil is7300 μ g/g, nitrogen content of 340 μ g/g, porous MgO as template agent, microspheres with particle size distribution of 50-200 nm and specific surface area of 150m2(ii) in terms of/g. The reaction temperature is 700 ℃, the reaction pressure is 0.1Mpa, the mass ratio of the porous structure template agent to the catalytic diesel oil is 3:1, the carrier gas is nitrogen, the volume ratio of the carrier gas to the catalytic cracking diesel oil is 20:1, and the contact time of the catalytic cracking diesel oil and the porous structure template agent is controlled for 15 s.
Example 4
The difference between the embodiment and the embodiment 2 is that the porous structure template agent is microspheres with the particle size distribution of 100nm-300nm and the specific surface area of 180m2/g。
Example 5
The difference between the embodiment and the embodiment 2 is that the porous structure template agent is microspheres with the particle size distribution of 300nm-1000nm and the specific surface area of 230m2/g。
Example 6
This example differs from example 4 only in that the porous structure template is porous alpha-Fe2O3。
Example 7
The difference between the example and the example 4 is that the reaction temperature is 750 ℃, the reaction pressure is 0.15Mpa, the mass ratio of the porous structure template agent to the catalytic diesel oil is 5:1, the carrier gas is nitrogen, the volume ratio of the carrier gas to the catalytic cracking diesel oil is 25:1, and the contact time of the catalytic cracking diesel oil and the porous structure template agent is 12 s.
Example 8
The difference between the example and the example 4 is that the reaction temperature is 800 ℃, the reaction pressure is 0.18Mpa, the mass ratio of the porous structure template agent to the catalytic cracking diesel oil is 7:1, the carrier gas is nitrogen, the volume ratio of the carrier gas to the catalytic cracking diesel oil is 35:1, and the contact time of the catalytic cracking diesel oil and the porous structure template agent is 13 s.
Example 9
The difference between the example and the example 4 is that the reaction temperature is 850 ℃, the reaction pressure is 0.2Mpa, the mass ratio of the porous structure template agent to the catalytic cracking diesel oil is 10:1, the carrier gas is nitrogen, the volume ratio of the carrier gas to the catalytic diesel oil is 50:1, and the contact time of the catalytic cracking diesel oil and the porous structure template agent is 10 s.
Example 10
This example differs from example 8 only in that the carrier gas was argon.
Example 11
This example differs from example 8 only in that the carrier gas is hydrogen.
Example 12
This example differs from example 8 only in that the carrier gas is water vapor.
Test examples
The specific surface area of the porous carbon material prepared in examples 1 to 12 was measured, and data on hydrogen generation during the reaction was collected. In addition, the porous carbon material and the binder PVDF are uniformly mixed according to the mass ratio of 9:1, the uniformly mixed slurry is uniformly coated on the polar fluid foamed nickel on a coating machine, finally, a disc with the diameter of 12mm is cut out, the disc is dried in a vacuum oven at 120 ℃ for 12 hours, the charge and discharge performance of the electrode material is tested under the current density of 20A/g under a three-electrode system, the specific capacitance of the electrode material is calculated according to the charge and discharge performance, and the performance indexes of the porous carbon materials of the above examples and comparative examples are further obtained, and are shown in Table 1.
TABLE 1
In summary, the method for preparing the porous carbon material by using the catalytic cracking diesel oil has the following advantages: on one hand, a part of hydrogen is generated in the process of generating carbon by the reaction of the catalytic cracking diesel oil, which is beneficial to improving the economic benefit of the processing of the catalytic cracking diesel oil; on the other hand, S, N heteroatoms in the catalytic cracking diesel oil can form an in-situ S, N doped porous energy storage carbon material in the process of preparing porous carbon, and the doping of S, N is favorable for improving the electrochemical performance of the porous energy storage carbon material. Compared with the prior art, the method provided by the embodiment of the invention enables the catalytic cracking diesel oil with lower added value to be prepared into the porous carbon material with high added value and simultaneously to produce hydrogen; simultaneously, a new process method for carrying out high value-added utilization on the catalytic cracking diesel oil is also provided.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. 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 (15)
1. A method for preparing a porous carbon material by using catalytic cracking diesel oil is characterized by comprising the following steps: carrying out contact reaction on the catalytic cracking diesel oil and a porous structure template agent so that the catalytic cracking diesel oil grows on the surface of the porous structure template agent to form carbon with a porous structure;
the temperature of the contact reaction is 700-850 ℃; the reaction pressure is 0.1-0.2 Mpa, and the mass ratio of the catalytic cracking diesel oil to the porous structure template agent is 1: 3-10, the catalytic cracking diesel oil is in contact reaction with the porous structure template agent under the action of carrier gas, and the volume ratio of the carrier gas to the catalytic cracking diesel oil is 20-50: 1; the contact time of the catalytic cracking diesel oil and the porous structure template agent is 10-15 seconds.
2. The method of claim 1, wherein the carrier gas is one or more of nitrogen, hydrogen, argon, and water vapor.
3. The method according to claim 1, wherein the porous structure templating agent is selected from the group consisting of porous-structured MgO, α -Fe2O3Or catalytically cracking spent catalyst.
4. The method as claimed in claim 1, wherein the porous structure template is microspheres with a particle size distribution of 50nm-1000nm and a specific surface area of 150-230m2/g。
5. The method according to any one of claims 1 to 4, wherein the catalytically cracked diesel has an aromatic content of greater than 85 wt%, a bicyclic and higher aromatic content of greater than 70%, a sulfur content of less than 8000 μ g/g, and a nitrogen content of less than 350 μ g/g.
6. The process according to any one of claims 1 to 4, wherein the contact reaction is carried out in a fluidized bed reactor.
7. The method of claim 6, wherein the porous structure template is placed in a fluidized bed, and then the catalytic cracking diesel oil is brought into contact reaction with the porous structure template through carrier gas.
8. The method according to any one of claims 1 to 4, further comprising removing the porous structure template from the obtained product after the contact reaction.
9. The method of claim 8, wherein the porous structure templating agent is removed by an acidic solution.
10. The method of claim 9, wherein the acidic solution is a hydrochloric acid solution.
11. The method of claim 10, wherein the hydrochloric acid solution has a concentration of 1 to 6 mol/L.
12. A porous carbon material prepared by the method of any one of claims 1 to 11.
13. An electrode material, characterized in that it comprises a porous carbon material according to claim 12.
14. The electrode material according to claim 13, further comprising an electrode substrate, wherein the porous carbon material is provided on a surface of the electrode substrate.
15. The electrode material of claim 14, wherein the electrode substrate is nickel foam.
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