CN107946606A - Nitrogen co-doped mesoporous carbon fiber of iron and preparation method thereof and apply in a fuel cell - Google Patents
Nitrogen co-doped mesoporous carbon fiber of iron and preparation method thereof and apply in a fuel cell Download PDFInfo
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- CN107946606A CN107946606A CN201711439385.1A CN201711439385A CN107946606A CN 107946606 A CN107946606 A CN 107946606A CN 201711439385 A CN201711439385 A CN 201711439385A CN 107946606 A CN107946606 A CN 107946606A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8817—Treatment of supports before application of the catalytic active composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention belongs to field of fuel cell technology; disclose nitrogen co-doped mesoporous carbon fiber of a kind of iron and preparation method thereof and apply in a fuel cell; the preparation method of the nitrogen co-doped mesoporous carbon fiber of iron using calcine Carapax Eriocheir sinensis, iron chloride, cyanamide, phenolic resin, block copolymer is raw material; it is uniformly mixed by being ultrasonically treated; treat that solvent volatilizees after placing room temperature; under nitrogen protection, pyrolysis obtains the nitrogen co-doped mesoporous carbon fiber of iron after removing template；According to volume ratio：Carapax Eriocheir sinensis, ferric trichloride, cyanamide, block copolymer P123, phenol resin solution：Ethanol/water=volume ratio 1:1.Low in raw material price of the present invention, is easy to get, and the discarded object of dining table is effectively changed into useful material；The preparation of hard template is avoided, is also effectively reduced cost；The nitrogen co-doped mesoporous carbon fiber of iron has large surface area and loose structure, has preferable hydrogen reduction catalytic effect.
Description
Technical field
The invention belongs to field of fuel cell technology, more particularly to a kind of nitrogen co-doped mesoporous carbon fiber of iron and its preparation side
Method and apply in a fuel cell.
Background technology
The cathode ORR of fuel cell is the key factor of fuel battery performance, in catalyst surface ORR with direct four electronics
Or two electronics branch mode carry out.Business cathod catalyst should have preferable stability, be catalyzed after through a long time use
Activity is almost without reduction.Catalyst should also have preferable methanol tolerance interference performance.ORR catalyst based on platinum is current
Common cathode material, ORR is shown higher catalytic activity and less overpotential based on the catalyst of platinum.In cathode
ORR often has slower electron transfer rate, needs to be catalyzed using further amounts of platinum when designing cathode platinum catalyst
ORR.Methanol molecules reach cathode easily through proton exchange membrane from anode, make cathode platinum catalyst that methanol oxidation occur anti-
Should, reduce the output power of battery and the utilization rate of methanol.Platinum catalyst has the disadvantages that at present：Nature content is rare,
Of high cost, stability and anti-interference are poor, limit the development of commercial fuel battery.Cathode ORR catalyst is fuel cell
Critical material, develop inexpensive, high performance base metal ORR catalyst to solving current platinum shortage of resources, reducing fuel
Battery cost, the development for promoting fuel cell studies and industrialization have directive significance.The nitrogen co-doped carbon material of iron has oxygen
There are preferable ORR catalytic effects.The nitrogen co-doped carbon material of particularly porous iron, due to its larger specific surface area and porous knot
Structure.Larger specific surface area is conducive to the exposure of active site.Loose structure is conducive to the transmission of material.Prepare at present
The nitrogen co-doped mesoporous carbon of iron uses hard template method, such as mesoporous silicon template SBA-15, monodispersed silicon template etc. mostly.These
Template needs to prepare in advance.For example, mesoporous silicon template needs to prepare using micella self-assembly method in advance, step is more complicated, no
It is only of high cost, and preparation time is longer, if material that can be cheap and easy to get prepares meso-porous carbon material very great Cheng as template
Degree reduces experimental cost and experimental period.The commercial catalysts of business hydrogen reduction at present are Pt/C, and cost is higher, and nature is deposited
Reserves are low, and through a long time can be reduced using the activity of Pt in addition, leverage the stability of catalyst and the performance of battery.Adopt
By the use of the carbon material of iron N doping as oxygen reduction catalyst, cost is relatively low, and stability is preferable.Method for preparing catalyst is simple：With
The past nitrogen co-doped mesoporous carbon of iron for preparing is needed using hard template, it is necessary to prepare template in advance, and cost is higher and step is numerous
It is trivial.The Cathodic oxygen reduction (oxygen reduction reaction, ORR) of fuel cell is the pass of fuel battery performance
Key factor, alloy platinum material are currently used ORR catalyst.Reduction of the ORR catalyst based on platinum for oxygen has higher
Catalytic activity and less overpotential, but often show slower electron transfer rate in platinum catalyst surface ORR.Cause
This, needs to be catalyzed ORR using further amounts of platinum when designing cathode material.Platinum as a kind of noble metal, cost it is higher and from
Right boundary amount of storage is less, and fuel cell cost will be greatly increased as cathode ORR catalyst using it.The stability of platinum catalyst
It is poor, under the electrochemical surface area of platinum catalyst can gradually subtract after prolonged use, it largely have impact on its electrification
Learn activity.
In conclusion problem existing in the prior art is：The nitrogen co-doped mesoporous carbon of the iron for preparing before, which exists to prepare, to be walked
Rapid more complicated, of high cost, preparation time is longer.If without the nitrogen co-doped mesoporous carbon of the iron prepared under template existence condition
There is micropore mostly, be unfavorable for the mass transport process of catalytic specie.Therefore find template cheap and easy to get and prepare efficient iron nitrogen and be total to
The mesoporous carbon of doping, it is possible to reduce experimental cost.
The content of the invention
In view of the problems of the existing technology, the present invention provides a kind of nitrogen co-doped mesoporous carbon fiber of iron and its preparation side
Method and apply in a fuel cell.
The present invention is achieved in that a kind of preparation method of the nitrogen co-doped mesoporous carbon fiber of iron, with the Carapax Eriocheir sinensis of calcining,
Iron chloride, cyanamide, phenolic resin, block copolymer, ethanol/water are raw material, are uniformly mixed by being ultrasonically treated, after placing room temperature
Treat that solvent volatilizees, under nitrogen protection, pyrolysis obtains the nitrogen co-doped mesoporous carbon fiber of iron after removing template；
The Carapax Eriocheir sinensis, iron chloride, cyanamide, phenolic resin, block copolymer, the additive amount of ethanol/water are respectively：Crab
Shell 1g, ferric trichloride 0.1-0.3g, cyanamide 1g, block copolymer 0.5g, phenol resin solution 0.2g, ethanol/water 40mL；Its
In, ethanol/water=1 by volume:1.Block copolymer is block copolymer P123.
Further, the Carapax Eriocheir sinensis remove cellulose in Carapax Eriocheir sinensis and other are organic when 350 degree of calcinings 3 are small in atmosphere
Thing.
Further, the Carapax Eriocheir sinensis, ferric trichloride, cyanamide, block copolymer P123, phenol resin solution are in ethanol/water
Mixed solution in, be ultrasonically treated, formed mixed dispersion liquid.
Further, the mixed dispersion liquid is transferred in culture dish, when room temperature volatilization 24 is small.
Further, the pasty solid after volatilization places the polymerization for the phenolic resin for triggering low molecular weight in an oven.
Further, the mixture after polymerization is scraped from culture dish, when 900 degrees Celsius of calcinings 3 are small under nitrogen protection, phenol
Urea formaldehyde is carbonized to obtain mesoporous carbon at high temperature.
Further, the mesoporous carbon for obtaining having the iron of fibrillar meshwork structure nitrogen co-doped using dilute hydrochloric acid removing Carapax Eriocheir sinensis is fine
Dimension.
Prepared by the preparation method another object of the present invention is to provide a kind of nitrogen co-doped mesoporous carbon fiber of iron
Mesoporous carbon fiber.
Another object of the present invention is to provide a kind of fuel cell by the mesoporous carbon fiber manufacture.
The present invention has abundant pore passage structure using Carapax Eriocheir sinensis as template, Carapax Eriocheir sinensis, directly uses and uses as template
In preparing meso-porous carbon material, preparation method is simple, and cost is relatively low, it is not necessary to prepares template.The nitrogen co-doped carbon fiber of iron is to oxygen
Gas just has preferable hydrogen reduction catalytic effect, and half wave potential is similar with business Pt/C's, and there is preferable stability to be done with methanol tolerant
Immunity.The present invention, as template, prepares the nitrogen co-doped mesoporous carbon fiber of iron, preparation method letter using the relatively low Carapax Eriocheir sinensis of price
Single, fast, raw material are easy to get.
Low in raw material price of the present invention, is easy to get, and the discarded object of dining table is effectively changed into useful material；Avoid hard
The preparation of template, is also effectively reduced cost.Preparing the mesoporous silicon template of 1g at present needs to use 1mL tetraethyl orthosilicates,
When 35 degree of stirrings 24 are small, when then hydro-thermal preparation 48 is small, most SBA-15 templates, whole process time are obtained through 550 degree of calcinings afterwards
About 4 days.And Carapax Eriocheir sinensis, as dining table discarded object, generally all working processes are animal feed, and iron nitrogen is prepared as template
The mesoporous carbon fiber of codope, will shorten experimental period and cost；The nitrogen co-doped mesoporous carbon fiber of iron has large surface area
And loose structure, there is preferable hydrogen reduction catalytic effect.It is sudden and violent that larger specific surface area can increase iron N doping avtive spot
Dew, while loose structure is conducive to the mass transport process of material.In alkaline medium, the nitrogen co-doped mesoporous carbon origin of fibers electricity of iron
Position be -0.03V (vs.Ag/AgCl), and half wave potential is -0.143V (vs.Ag/AgCl), the limiting current density of 1600rpm is -
5.3mA cm-2.Under the conditions of same test, the Pt/C take-off potentials of equal load capacity are -0.02V (vs.Ag/AgCl), and half-wave is electric
Position is -0.144V (vs.Ag/AgCl), and the limiting current density of 1600rpm is -5.0mA cm-2.It is in addition, small through recycling 9
Shi Hou, the nitrogen co-doped mesoporous carbon fiber current attenuation 12% of iron, and business Pt/C decays to 35%.
Brief description of the drawings
Fig. 1 is the preparation method flow chart of the nitrogen co-doped mesoporous carbon fiber of iron provided in an embodiment of the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of (A) Carapax Eriocheir sinensis provided in an embodiment of the present invention；(B-D) the nitrogen co-doped mesoporous carbon of iron
The scanning electron microscope and projection electron microscope of fiber.
Fig. 3 is the nitrogen co-doped mesoporous carbon fiber catalytic oxidation-reduction reactive applications signal of iron provided in an embodiment of the present invention
Figure；
In figure：a:The nitrogen co-doped mesoporous carbon fiber of iron；b：Business platinum carbon；c:The mesoporous carbon fiber of N doping；d：It is mesoporous
Carbon fiber.
Fig. 4 be the nitrogen co-doped mesoporous carbon fiber catalytic oxidation-reduction of iron provided in an embodiment of the present invention (A) methanol tolerance with
(B) stability schematic diagram；
In figure：a:The nitrogen co-doped mesoporous carbon fiber of iron；b：Business platinum carbon.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
It is current to solving to develop cheap, high performance base metal ORR catalyst in order to reduce catalyst cost by the present invention
Platinum shortage of resources, reduce fuel cell cost, promote the development of fuel cell and industrialization to have directive significance.
The application principle of the present invention is explained in detail below in conjunction with the accompanying drawings.
The nitrogen co-doped mesoporous carbon fiber of iron provided in an embodiment of the present invention, with the Carapax Eriocheir sinensis of calcining, iron chloride, cyanamide, phenol
Urea formaldehyde, block copolymer, ethanol/water are raw material, are uniformly mixed by being ultrasonically treated, and treat that solvent volatilizees after placing room temperature,
Under nitrogen protection, pyrolysis obtains the nitrogen co-doped mesoporous carbon fiber of iron after removing template；
The Carapax Eriocheir sinensis, iron chloride, cyanamide, phenolic resin, block copolymer, the additive amount of ethanol/water are respectively：Crab
Shell 1g, ferric trichloride 0.1-0.3g, cyanamide 1g, block copolymer 0.5g, phenol resin solution 0.2g, ethanol/water 40mL；Its
In, ethanol/water=1 by volume:1.
As shown in Figure 1, the preparation method of the nitrogen co-doped mesoporous carbon fiber of iron provided in an embodiment of the present invention includes following step
Suddenly：
S101：Carapax Eriocheir sinensis in atmosphere 350 degree calcining 3 it is small when；
S102：In Carapax Eriocheir sinensis, ferric trichloride, cyanamide, block copolymer P123, phenol resin solution in ethanol/water (volume
Than 1:1) in mixed solution, it is ultrasonically treated, forms uniform mixed dispersion liquid；
S103：Mixed dispersion liquid is transferred in culture dish, when room temperature volatilization 24 is small；
S104：Pasty solid after volatilization places the polymerization for the phenolic resin for triggering low molecular weight in an oven；
S105：Mixture after polymerization is scraped from culture dish, when 900 degrees Celsius of calcinings 3 are small under nitrogen protection；
S106：Carapax Eriocheir sinensis (main composition-calcium carbonate) are removed using dilute hydrochloric acid and obtain the nitrogen co-doped mesoporous carbon fiber of iron.
The application principle of the present invention is further described with reference to specific embodiment.
Embodiment 1
The nitrogen co-doped mesoporous carbon fiber production method of iron of the embodiment of the present invention comprises the following steps：
Step 1：Carapax Eriocheir sinensis after the calcining of 1g are added in 20mL deionized waters and in 20mL alcohol mixed solutions,
It is ultrasonically treated 5 minutes (power of ultrasonic machine is 350W).
Step 2：By 0.1g ferric trichlorides, 1g cyanamides, (molecular weight is small for 0.5g block copolymer P123,0.2g phenolic resin
In 500) into Carapax Eriocheir sinensis dispersion liquid, being then sonicated 10 minutes, it is set to be sufficiently mixed uniformly.
Step 3：The mixture dispersion liquid is transferred in culture dish, when room temperature volatilization 24 is small.
Step 4：Obtained paste product height is placed in quartz ampoule, 900 degrees Celsius of calcinings 3 are small under nitrogen protection
When.
Step 5：To obtain black powder be immersed in dilute hydrochloric acid (1moL) 2 it is small when remove Carapax Eriocheir sinensis (main component be carbon
Hydrochlorate) and Fe nanometer particles, after speed centrifuges (7000 revs/min), then in vacuum with deionized water centrifuge washing three times
50-70 DEG C of drying 24 obtains iron nitrogen co-doped mesoporous carbon fiber when small.Fig. 2A is sweeping for the Carapax Eriocheir sinensis template used in embodiment 1
Retouch electron microscope, it can be seen that Carapax Eriocheir sinensis template has clearly pore passage structure.Scanning electron microscope (SEM) photograph is observed that iron from Fig. 2 B
Nitrogen co-doped mesoporous carbon fiber has fibre structure.Electron microscope is projected in Fig. 2 B and can be found that the nitrogen co-doped mesoporous carbon of iron is fine
Dimension table face has abundant pore passage structure.
Embodiment 2
The nitrogen co-doped mesoporous carbon fiber production method of iron of the embodiment of the present invention comprises the following steps：
Step 1：Carapax Eriocheir sinensis after the calcining of 1g are added in 20mL deionized waters and in 20mL alcohol mixed solutions,
It is ultrasonically treated 5 minutes (power of ultrasonic machine is 350W).
Step 2：By 0.2g ferric trichlorides, 1g cyanamides, 0.5g block copolymers P123, (molecular weight is small for 0.2 phenolic resin
In 500) into Carapax Eriocheir sinensis dispersion liquid, being then sonicated 10 minutes, it is set to be sufficiently mixed uniformly.
Step 3：The mixture dispersion liquid is transferred in culture dish, when room temperature volatilization 24 is small.
Step 4：Obtained paste product height is placed in quartz ampoule, 900 degrees Celsius of calcinings 3 are small under nitrogen protection
When.
Step 5：To obtain black powder be immersed in dilute hydrochloric acid (1moL) 2 it is small when remove Carapax Eriocheir sinensis (main component be carbon
Hydrochlorate) and Fe nanometer particles, after speed centrifuges (7000 revs/min), then in vacuum with deionized water centrifuge washing three times
50-70 DEG C of drying 24 obtains iron nitrogen co-doped mesoporous carbon fiber when small.
Embodiment 3
The nitrogen co-doped mesoporous carbon fiber production method of iron of the embodiment of the present invention comprises the following steps：
Step 1：Carapax Eriocheir sinensis after the calcining of 1g are added in 20mL deionized waters and in 20mL alcohol mixed solutions,
It is ultrasonically treated 5 minutes (power of ultrasonic machine is 350W).
Step 2：By 0.3g ferric trichlorides, 1g cyanamides, (molecular weight is small for 0.5g block copolymer P123,0.2g phenolic resin
In 500) into Carapax Eriocheir sinensis dispersion liquid, being then sonicated 10 minutes, it is set to be sufficiently mixed uniformly.
Step 3：The mixture dispersion liquid is transferred in culture dish, when room temperature volatilization 24 is small.
Step 4：Obtained paste product height is placed in quartz ampoule, 900 degrees Celsius of calcinings 3 are small under nitrogen protection
When.
Step 5：To obtain black powder be immersed in dilute hydrochloric acid (1moL) 2 it is small when remove Carapax Eriocheir sinensis (main component be carbon
Hydrochlorate) and Fe nanometer particles, after speed centrifuges (7000 revs/min), then in vacuum with deionized water centrifuge washing three times
50-70 DEG C of drying 24 obtains iron nitrogen co-doped mesoporous carbon fiber when small.
By the nitrogen co-doped mesoporous carbon fiber applications of the iron for preparing of the present invention in oxygen reduction reaction, and with N doping mesoporous carbon
Fiber, business platinum carbon compare with mesoporous carbon fiber.Electrocatalysis characteristic comparison is carried out, is comprised the following steps that：
1) three electrode test system testing hydrogen reduction catalytic capabilities (and CHI730e electrochemical workstations), silver/chlorination are used
Silver be used as reference electrode, and platinum filament is used as to electrode, and as working electrode, (area is the glass-carbon electrode that material prepared is modified
0.24cm-2).Solution is 0.1mol L-1Sodium hydroxide solution.
2) by 3mg, the prepared material is scattered in 1mL Nafion solutions.Draw the 30 μ L dispersant liquid drops and be coated in glass
Carbon electrodes, (100W) is dried under infrared lamp.
3) three electrodes are placed in electrolytic cell, are passed through high purity oxygen gas, the hydrogen reduction catalytic capability of test material in the solution.
Fig. 4 for the electro-catalysis of business platinum carbon, mesoporous carbon fiber, the mesoporous carbon fiber of N doping and case study on implementation 2 to oxygen also
Former cyclic voltammogram.Compared to business platinum carbon, mesoporous carbon fiber and N doping mesoporous carbon, the nitrogen co-doped mesoporous carbon fiber of iron
Show lower overpotential and the catalytic current of bigger.The catalysis take-off potential meter half wave potential of hydrogen reduction is close to business platinum
Carbon, limiting current density are more than the platinum carbon catalyst of business.Compared with business platinum carbon, the nitrogen co-doped mesoporous carbon fiber of iron is also
With excellent stability and methanol tolerance interference performance figure (Fig. 4).
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should all be included in the protection scope of the present invention.
Claims (9)
- A kind of 1. preparation method of the nitrogen co-doped mesoporous carbon fiber of iron, it is characterised in that the nitrogen co-doped mesoporous carbon fiber of iron Preparation method using calcine Carapax Eriocheir sinensis, iron chloride, cyanamide, phenolic resin, block copolymer, ethanol/water as raw material, by super Sonication is uniformly mixed, and treats that solvent volatilizees after placing room temperature, and it is nitrogen co-doped to obtain iron under nitrogen protection, after pyrolysis removing template Mesoporous carbon fiber；The Carapax Eriocheir sinensis, iron chloride, cyanamide, phenolic resin, block copolymer, the additive amount of ethanol/water are respectively：Carapax Eriocheir sinensis 1g, ferric trichloride 0.1-0.3g, cyanamide 1g, block copolymer 0.5g, phenol resin solution 0.2g, ethanol/water 40mL；Wherein, Ethanol/water=1 by volume:1.
- 2. the preparation method of the nitrogen co-doped mesoporous carbon fiber of iron as claimed in claim 1, it is characterised in that the Carapax Eriocheir sinensis exist When 350 degree of calcinings 3 are small in air.
- 3. the preparation method of the nitrogen co-doped mesoporous carbon fiber of iron as claimed in claim 1, it is characterised in that the Carapax Eriocheir sinensis, Ferric trichloride, cyanamide, block copolymer P123, phenol resin solution are ultrasonically treated in the mixed solution of ethanol/water, are formed Mixed dispersion liquid.
- 4. the preparation method of the nitrogen co-doped mesoporous carbon fiber of iron as claimed in claim 1, it is characterised in that the mixing is scattered Liquid is transferred in culture dish, when room temperature volatilization 24 is small.
- 5. the preparation method of the nitrogen co-doped mesoporous carbon fiber of iron as claimed in claim 1, it is characterised in that the paste after volatilization Solid places the polymerization for the phenolic resin for triggering low molecular weight in an oven.
- 6. the preparation method of the nitrogen co-doped mesoporous carbon fiber of iron as claimed in claim 1, it is characterised in that the mixing after polymerization Thing is scraped from culture dish, when 900 degrees Celsius of calcinings 3 are small under nitrogen protection.
- 7. the preparation method of the nitrogen co-doped mesoporous carbon fiber of iron as claimed in claim 1, it is characterised in that removed using dilute hydrochloric acid Carapax Eriocheir sinensis are gone to obtain the nitrogen co-doped mesoporous carbon fiber of iron.
- A kind of 8. mesoporous carbon fiber prepared by preparation method of the nitrogen co-doped mesoporous carbon fiber of iron as claimed in claim 1.
- A kind of 9. fuel cell of the fuel battery cathode material of carbon fiber structure mesoporous as described in claim 8.
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| CN110416545A (en) * | 2019-08-07 | 2019-11-05 | 东北林业大学 | A method of Porous hollow carbon nano rod lithium ion battery negative material is prepared by template of Carapax Eriocheir sinensis |
| CN110562956A (en) * | 2019-09-04 | 2019-12-13 | 复旦大学 | Preparation method and application of ordered mesoporous carbon nanofiber array material |
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Cited By (4)
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| CN109860633A (en) * | 2019-02-13 | 2019-06-07 | 苏州擎动动力科技有限公司 | The preparation method and purposes of a kind of order mesoporous Catalytic Layer and membrane electrode |
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| CN110416545A (en) * | 2019-08-07 | 2019-11-05 | 东北林业大学 | A method of Porous hollow carbon nano rod lithium ion battery negative material is prepared by template of Carapax Eriocheir sinensis |
| CN110562956A (en) * | 2019-09-04 | 2019-12-13 | 复旦大学 | Preparation method and application of ordered mesoporous carbon nanofiber array material |
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Application publication date: 20180420 |