CN110010904A - A kind of composite material and preparation method and purposes with electrocatalytic oxidation reducing property - Google Patents
A kind of composite material and preparation method and purposes with electrocatalytic oxidation reducing property Download PDFInfo
- Publication number
- CN110010904A CN110010904A CN201910160463.7A CN201910160463A CN110010904A CN 110010904 A CN110010904 A CN 110010904A CN 201910160463 A CN201910160463 A CN 201910160463A CN 110010904 A CN110010904 A CN 110010904A
- Authority
- CN
- China
- Prior art keywords
- composite material
- cnt
- preparation
- present
- comparative example
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
-
- 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
- H01M4/9041—Metals or alloys
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of composite material and preparation method and purposes with electrocatalytic oxidation reducing property, belong to electrocatalysis material technical field.Metal is uniformly attached between BN lamella in the composite material and sheet surfaces, CNT play fixed function to metal and BN.A kind of composite material with electrocatalytic oxidation reducing property provided by the invention has efficient electrocatalytic oxidation reducing property, and stable cycle performance.Cost of material used by preparation method of the invention is relatively low, W-response mild condition, and post-processing is simple, and less energy consumption, cost is relatively low.
Description
Technical field
The invention belongs to electrocatalysis material technical field more particularly to a kind of composite woods with electrocatalytic oxidation reducing property
Material and its preparation method and application.
Background technique
Power and production movable basis of the energy as society's advance, play very important work in human lives
With the development and utilization of the energy greatly advances the development of world economy and human society.As the modern life needs the energy
The increase asked, energy crisis is increasingly prominent, and environmental pollution is also got worse.Compared with traditional energy, fuel cell it is obvious excellent
Gesture is exactly that whole process does not generate pernicious gas, can alleviate Present Situation of Air Pollution, is the clean energy of a kind of green that we have been look for
Source.
The Cathodic oxygen reduction of fuel cell is a key factor for restricting fuel cell development.The electrochemistry of oxygen is also
Original reaction invertibity it is very low, even if some common higher elctro-catalysts of catalytic activity (such as Pt, Pd) above, hydrogen reduction is anti-
The exchange current density answered is also only 10-9~10-10A/cm2, therefore, oxygen reduction reaction always with very high overpotential, causes
The working efficiency of battery reduces.Novel cathode catalyst degradation cathode overpotential is studied, improves fuel battery cathod catalyst also
Former activity is to improve the hot subject of fuel battery performance.It is at present largely price for the effective catalyst of oxygen reduction reaction
Expensive rare metal, limits its large-scale commercial application.Therefore, it is valuable to research and develop low-cost effective catalyst substitution
Metallic catalyst be comply with social development there is an urgent need to.In recent years, 2 years especially nearest, base metal class catalyst is ground
Study carefully and constantly make a breakthrough, such catalyst is considered as the hope that fuel cell realizes large-scale commercial application.
Currently, the main elctro-catalyst for fuel cell is platinum, there is good oxygen reduction activity in a fuel cell
It is thus widely used with durability, but since the surface Pt is easy in conjunction with CO, CO will lead to Pt and be poisoned and lose its reproducibility,
And platinum is as a kind of noble metal, and it is valuable rare, and also utilization rate is extremely low, so that fuel cell is at high cost, largely
On hinder the promotion and application of fuel cell.With the continuous development of power generation, more and more people make great efforts your non-gold
Belong to the cathod catalyst field for being introduced into fuel cell.Therefore, numerous researchers are making great efforts to look for solve this problem
Other metallic catalysts are sought to substitute the use of Pt/C.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide one kind to have electrocatalytic oxidation reproducibility
Can composite material and preparation method and purposes, overcome the catalyst cost existing in the prior art for fuel cell compared with
It is high, easily poisoned by CO, the defects of electrocatalytic oxidation reducing property is unstable, using being restricted.
To achieve the goals above or other purposes, the present invention is achieved by the following technical solutions.
A kind of preparation method of the composite material with electrocatalytic oxidation reducing property, comprising the following steps:
(1) CNT, BN are added in ethylene glycol, ultrasonic disperse processing；
(2) metal salt, urea is added to reaction system obtained by step (1) under stirring, continues to stir；
(3) heating reflux reaction is carried out after standing the reaction system in step (2), post-processing is carried out after reaction and obtains
Obtain composite material；
Wherein, metal salt is selected from FeCl3·6H2O、CoCl2·6H2O、NiCl2·6H2Any one of O or any two.
Wherein, the BN is the hexagonal boron nitride obtained by general commercial means, and BN is laminated structure, is had good
Electrical insulating property, thermal conductivity, chemical corrosion resistance and lubricity.BN partial size employed in the present invention is 20~700nm.
The CNT is the carbon nanotube obtained by general commercial means.Preferably, the partial size of the CNT is not less than
200nm。
Further, CNT, metal salt, BN molar ratio be 1:2:1.
When metal salt is selected from FeCl3·6H2O、CoCl2·6H2O、NiCl2·6H2In O any two when, then two kinds of metals
The molar ratio of salt is 1:1.
That is, when metal salt is FeCl3·6H2O、CoCl2·6H2When the mixture of O, CNT, FeCl3·6H2O、CoCl2·
6H2O, the molar ratio of BN is 1:1:1:1.
When metal salt is FeCl3·6H2O、NiCl2·6H2When the mixture of O, CNT, FeCl3·6H2O、NiCl2·6H2O、
The molar ratio of BN is 1:1:1:1.
When metal salt is CoCl2·6H2O、NiCl2·6H2When the mixture of O, CNT, CoCl2·6H2O、NiCl2·6H2O、
The molar ratio of BN is 1:1:1:1.
Further, the molar ratio of metal salt and urea is 1:(6~10).
Further, for ethylene glycol as solvent, institute's additive amount is excessive in the present invention.Preferably, second needed for 1mol CNT
The dosage of glycol should be not less than 4L.It is highly preferred that the molal volume of CNT and ethylene glycol ratio is 1mol:10L.
Further, the ultrasonic disperse time is 30min~60min in step (1)；Come into full contact with BN and CNT in system.
Further, continue to stir 10min~20min in step (2), each raw material is made sufficiently to dissolve and be uniformly mixed.
Further, after reaction system being stood 15min~25min in step (3), heating reflux reaction, reaction are carried out
Time is 6h~8h.
Further, post-processing includes washing, drying in step (3).
Further, it is cooled to room temperature after reaction in step (3), and using distilled water, ethyl alcohol successively to reaction
System carries out centrifuge washing.Preferably, using successively centrifuge washing 3~5 times of distilled water, ethyl alcohol.Preferably, when centrifuge washing,
Centrifugal rotational speed is 8000~9000r/min, is centrifuged 5~10min of duration.
Preferably, it when drying process, being carried out using vacuum oven, drying temperature is 90 DEG C, vacuum degree 0.08Mpa,
Drying time is 9~12h.
The present invention also provides the composite woods obtained by a kind of preparation method described above with electrocatalytic oxidation reducing property
Material.
Metal is uniformly attached between BN lamella in the composite material and sheet surfaces, CNT play metal and BN and fix
Effect.
Third aspect present invention also provides composite material conduct in a fuel cell prepared by a kind of above-mentioned preparation method
The purposes of catalyst.
In the present invention, metal simple-substance is uniformly adhered between the sheet surfaces and lamella of BN (boron nitride), and CNT (carbon
Nanotube) then metal and BN are fixed as rope, form chondritic of the partial size between 50~400nm.
Hexagonal boron nitride employed in the present invention has the layer structure of similar graphite, and the addition of metal can be more uniform
Be attached between nitridation boron surface and lamella, and the addition of carbon nanotube can fix metal and boron nitride as rope
Together, chondritic is formed, while improving the electric conductivity of composite material.
The absorption property of BN is utilized to utilize second two by adsorption of metal ions between the lamella of BN and surface in the present invention
Alcohol is reduced into metal simple-substance as solvent and reducing agent, by metal ion, and metal simple-substance is made to be attached to the sheet surfaces and piece of BN
Between layer, and the addition of CNT can make CNT that BN and metal simple-substance be fixed as rope, while increase composite material
Electric conductivity.
In short, there is efficient electro-catalysis the present invention provides a kind of composite material with electrocatalytic oxidation reducing property
Hydrogen reduction performance, and stable cycle performance.Cost of material used by preparation method of the invention is relatively low, W-response item
Part is mild, and post-processing is simple, and less energy consumption, cost is relatively low.
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) map of BN/Ni/CNT composite material obtained by embodiment 1；
Fig. 2 is the transmission electron microscope map (TEM) of BN/Ni/CNT composite material obtained by embodiment 1；
Fig. 3 is X-ray diffraction (XRD) map of BN/Fe/CNT composite material obtained by embodiment 3；
Fig. 4 is the transmission electron microscope map (TEM) of BN/Fe/CNT composite material obtained by embodiment 3；
Fig. 5 is X-ray diffraction (XRD) map of BN/Co/CNT composite material obtained by embodiment 5；
Fig. 6 is the transmission electron microscope map (TEM) of BN/Co/CNT composite material obtained by embodiment 5；
Fig. 7 is X-ray diffraction (XRD) map of BN/FeCo/CNT composite material obtained by embodiment 6；
Fig. 8 is the transmission electron microscope map (TEM) of BN/FeCo/CNT composite material obtained by embodiment 6；
Fig. 9 is X-ray diffraction (XRD) map of BN/FeNi/CNT composite material obtained by embodiment 7；
Figure 10 is the transmission electron microscope map (TEM) of BN/FeNi/CNT composite material obtained by embodiment 7；
Figure 11 is X-ray diffraction (XRD) map of BN/CoNi/CNT composite material obtained by embodiment 8；
Figure 12 is the transmission electron microscope map (TEM) of BN/CoNi/CNT composite material obtained by embodiment 8；
Figure 13 is Pt/C composite material in O2Cyclic voltammetry curve in the 0.1M KOH solution of saturation, sweeps speed: 5mV s-1；
Figure 14 is BN/Ni/CNT composite material following in the 0.1M KOH solution that oxygen is saturated obtained by embodiment 1
Ring volt-ampere curve figure, wherein sweep speed is 5mV s-1；
Figure 15 is BN/Fe/CNT composite material following in the 0.1M KOH solution that oxygen is saturated obtained by embodiment 3
Ring volt-ampere curve figure, wherein sweep speed is 5mV s-1；
Figure 16 is BN/Co/CNT composite material following in the 0.1M KOH solution that oxygen is saturated obtained by embodiment 5
Ring volt-ampere curve figure, wherein sweep speed is 5mV/s；
Figure 17 is BN/FeCo/CNT composite material obtained by embodiment 6 in the 0.1M KOH solution that oxygen is saturated
Cyclic voltammetry curve figure, wherein sweep speed is 5mV s-1；
Figure 18 is BN/FeNi/CNT composite material obtained by embodiment 7 in the 0.1M KOH solution that oxygen is saturated
Cyclic voltammetry curve figure, wherein sweep speed is 5mV s-1；
Figure 19 is BN/CoNi/CNT composite material obtained by embodiment 8 in the 0.1M KOH solution that oxygen is saturated
Cyclic voltammetry curve figure, wherein sweep speed is 5mV s-1；
Figure 20 is 1 resulting materials of comparative example in O2Cyclic voltammetry curve in the 0.1M KOH solution of saturation, sweeps speed: 5mV s-1；
Figure 21 is 2 resulting materials of comparative example in O2Cyclic voltammetry curve in the 0.1M KOH solution of saturation, sweeps speed: 5mV s-1；
Figure 22 is 3 resulting materials of comparative example in O2Cyclic voltammetry curve in the 0.1M KOH solution of saturation, sweeps speed: 5mV s-1；
Figure 23 is 5 resulting materials of comparative example in O2Cyclic voltammetry curve in the 0.1M KOH solution of saturation, sweeps speed: 5mV s-1；
Figure 24 is 6 resulting materials of comparative example in O2Cyclic voltammetry curve in the 0.1M KOH solution of saturation, sweeps speed: 5mV s-1；
Figure 25 is 7 resulting materials of comparative example in O2Cyclic voltammetry curve in the 0.1M KOH solution of saturation, sweeps speed: 5mV s-1；
Figure 26 is 9 resulting materials of comparative example in O2Cyclic voltammetry curve in the 0.1M KOH solution of saturation, sweeps speed: 5mV s-1；
Figure 27 is 10 resulting materials of comparative example in O2Cyclic voltammetry curve in the 0.1M KOH solution of saturation, sweeps speed: 5mV s-1；
Figure 28 is 11 resulting materials of comparative example in O2Cyclic voltammetry curve in the 0.1M KOH solution of saturation, sweeps speed: 5mV s-1；
Figure 29 is 13 resulting materials of comparative example in O2Cyclic voltammetry curve in the 0.1M KOH solution of saturation, sweeps speed: 5mV s-1；
Figure 30 is 14 resulting materials of comparative example in O2Cyclic voltammetry curve in the 0.1M KOH solution of saturation, sweeps speed: 5mV s-1；
Figure 31 is 15 resulting materials of comparative example in O2Cyclic voltammetry curve in the 0.1M KOH solution of saturation, sweeps speed: 5mV s-1；
Figure 32 is 17 resulting materials of comparative example in O2Cyclic voltammetry curve in the 0.1M KOH solution of saturation, sweeps speed: 5mV s-1；
Figure 33 is 18 resulting materials of comparative example in O2Cyclic voltammetry curve in the 0.1M KOH solution of saturation, sweeps speed: 5mV s-1；
Figure 34 is 19 resulting materials of comparative example in O2Cyclic voltammetry curve in the 0.1M KOH solution of saturation, sweeps speed: 5mV s-1；
Figure 35 is 21 resulting materials of comparative example in O2Cyclic voltammetry curve in the 0.1M KOH solution of saturation, sweeps speed: 5mV s-1；
Figure 36 is 22 resulting materials of comparative example in O2Cyclic voltammetry curve in the 0.1M KOH solution of saturation, sweeps speed: 5mV s-1；
Figure 37 is 23 resulting materials of comparative example in O2Cyclic voltammetry curve in the 0.1M KOH solution of saturation, sweeps speed: 5mV s-1；
Figure 38 is the time current curve graph of BN/Ni/CNT composite material obtained by embodiment 1 and Pt/C composite material；
Figure 39 is the time current curve graph of BN/Fe/CNT composite material obtained by embodiment 3 and Pt/C composite material.
Figure 40 is the time current curve graph of BN/Co/CNT composite material obtained by embodiment 5 and Pt/C composite material.
Figure 41 is the time current curve of BN/FeCo/CNT composite material obtained by embodiment 6 and Pt/C composite material
Figure.
Figure 42 is the time current curve of BN/FeNi/CNT composite material obtained by embodiment 7 and Pt/C composite material
Figure.
Figure 43 is the time current curve of BN/CoNi/CNT composite material obtained by embodiment 8 and Pt/C composite material
Figure.
Specific embodiment
Illustrate embodiments of the present invention below by way of particular specific embodiment, those skilled in the art can be by this explanation
Other advantages and efficacy of the present invention can be easily understood for content disclosed by book.The present invention can also be by addition different specific
Embodiment is embodied or practiced, and the various details in this specification can also not carried on the back based on different viewpoints and application
From carrying out various modifications or alterations under spirit of the invention.
It should be noted that in the absence of conflict, the feature in following embodiment and embodiment can be combined with each other.Also
It should be appreciated that term used in the embodiment of the present invention is in order to describe specific specific embodiment, rather than in order to limit
Protection scope of the present invention.The test method of actual conditions is not specified in the following example, usually according to normal condition, or presses
According to condition proposed by each manufacturer.
When embodiment provides numberical range, it should be appreciated that except non-present invention is otherwise noted, two ends of each numberical range
Any one numerical value can be selected between point and two endpoints.Unless otherwise defined, the present invention used in all technologies and
The grasp and record of the invention of scientific term and those skilled in the art to the prior art, can also use and this hair
Any method, equipment and the material of the similar or equivalent prior art of bright method as described in the examples, equipment, material is realized
The present invention.
BN employed in the embodiment of the present invention is the hexagonal boron nitride obtained by general commercial means, institute in the present invention
The BN partial size used is 20~700nm.CNT is the common carbon nanotube obtained by general commercial means, it is preferable that described
The partial size of CNT is not less than 200nm.
Embodiment 1
A kind of BN/Ni/CNT composite material, W metal is uniformly attached between BN lamella and sheet surfaces, CNT to Ni and
BN plays fixed function, forms partial size in the chondritic of 100~300nm.Wherein, the molar ratio of BN, Ni and CNT are 1:2:1.
Preparation method includes the following steps:
(1) 0.005mol carbon nanotube (CNT) and 0.005mol boron nitride (BN) is added in the ethylene glycol of 50mL, is surpassed
Sound disperses 30min；
(2) it is added with stirring 0.01mol NiCl2·6H2O, 0.06mol urea continues to stir 10min, keeps solid abundant
It dissolves and is uniformly mixed solution；
(3) after standing 20min, reaction system progress heating reflux reaction 6h is cooled to room temperature after reaction, point
Not Yong secondary distilled water and ethyl alcohol centrifuge washing solid, respectively wash 3 times, wherein centrifuge speed 8000r/min, centrifugation
Duration 5min.The solid finally obtained is poured into beaker, is sealed with sealing film, and stabs several ventholes on film, is put into true
In empty drying box, 90 DEG C of temperature is kept, the pressure of 0.08Mpa is 9 hours dry, is cooled to room temperature after drying, it grinds,
Obtain target solids composite material BN/Ni/CNT.
Gained BN/Ni/CNT composite material is subjected to XRD, TEM characterization, as a result as shown in Figure 1 and Figure 2.
From figure 1 it appears that having the characteristic diffraction peak of BN, Ni and CNT in figure, and occur without other impurity peaks,
Proof products obtained therefrom is BN/Ni/CNT composite material.
In Fig. 2, it is chondritic of the partial size in 100~300nm that Fig. 2 a, which can be seen that gained BN/Ni/CNT composite material,.
Fig. 2 b can be seen that Ni simple substance and uniformly be attached on the lamella of BN, and CNT fixes the BN for being attached with Ni as rope.
Embodiment 2
That the preparation method is the same as that of Example 1 is identical for BN/Ni/CNT composite material in the present embodiment, unlike the first embodiment,
Step (3) is heated to reflux 8h.Resulting materials structure is similar to Example 1.
Embodiment 3
A kind of BN/Fe/CNT composite material, metal Fe is uniformly attached between BN lamella and sheet surfaces, CNT to Fe and
BN plays fixed function, forms partial size in the chondritic of 100~300nm.Wherein, the molar ratio of BN, Fe and CNT are 1:2:1.Its
Preparation method the following steps are included:
(1) 0.005mol carbon nanotube (CNT) and 0.005mol boron nitride (BN) is added in the ethylene glycol of 50mL, is surpassed
Sound disperses 30min；
(2) it is added with stirring 0.01mol FeCl3·6H2O, 0.06mol urea continues to stir 10min, keeps solid abundant
It dissolves and is uniformly mixed solution；
(3) after standing 20min, reaction system progress heating reflux reaction 6h is cooled to room temperature after reaction, point
Not Yong secondary distilled water and ethyl alcohol centrifuge washing solid, respectively wash 3 times, wherein centrifuge speed 8000r/min, centrifugation
Duration 5min.The solid finally obtained is poured into beaker, is sealed with sealing film, and stabs several ventholes on film, is put into true
In empty drying box, 90 DEG C of temperature is kept, the pressure of 0.08Mpa is 9 hours dry, is cooled to room temperature after drying, it grinds,
Obtain target solids composite material BN/Fe/CNT.
Gained BN/Fe/CNT composite material is subjected to XRD, TEM characterization, as a result as shown in Figure 3, Figure 4.
From figure 3, it can be seen that having the characteristic diffraction peak of BN, Fe and CNT in figure, and occur without other impurity peaks,
Proof products obtained therefrom is BN/Fe/CNT composite material.
In Fig. 4, it is chondritic of the partial size in 100~300nm that Fig. 4 a, which can be seen that gained BN/Fe/CNT composite material,.
Fig. 4 b can be seen that Fe simple substance and uniformly be attached on the lamella of BN, and CNT fixes the BN for being attached with Fe as rope.
Embodiment 4
The preparation method of BN/Fe/CNT composite material is identical with embodiment 3 in the present embodiment, as different from Example 3,
Step (3) is heated to reflux 8h.Resulting materials structure is similar to Example 3.
Embodiment 5
A kind of BN/Co/CNT composite material, metal Co is uniformly attached between BN lamella and sheet surfaces, CNT to Co and
BN plays fixed function, forms partial size in the chondritic of 100~200nm, the partial size of Co simple substance is in 1~5nm.Wherein, BN, Co with
The molar ratio of CNT is 1:2:1.Preparation method includes the following steps:
(1) 0.005mol carbon nanotube (CNT) and 0.005mol boron nitride (BN) is added in the ethylene glycol of 50mL, is surpassed
Sound disperses 30min；
(2) it is added with stirring 0.01mol CoCl2·6H2O, 0.06mol urea continues to stir 10min, keeps solid abundant
It dissolves and is uniformly mixed solution；
(3) after standing 20min, reaction system progress heating reflux reaction 6h is cooled to room temperature after reaction, point
Not Yong secondary distilled water and ethyl alcohol centrifuge washing solid, respectively wash 3 times, wherein centrifuge speed 8000r/min, centrifugation
Duration 5min.The solid finally obtained is poured into beaker, is sealed with sealing film, and stabs several ventholes on film, is put into true
In empty drying box, 90 DEG C of temperature is kept, the pressure of 0.08Mpa is 9 hours dry, is cooled to room temperature after drying, it grinds,
Obtain target solids composite material BN/Co/CNT.
Gained BN/Co/CNT composite material is subjected to XRD, TEM characterization, as a result as shown in Figure 5, Figure 6.
From figure 5 it can be seen that having the characteristic diffraction peak of BN, Co and CNT in figure, and occur without other impurity peaks,
Proof products obtained therefrom is BN/Co/CNT composite material.
In Fig. 6, it is chondritic of the partial size in 200nm that Fig. 6 a, which can be seen that gained BN/Co/CNT composite material,.Fig. 6 b
As can be seen that Co simple substance is uniformly attached on the lamella of BN, CNT fixes the BN for being attached with Co as rope.
Embodiment 6
A kind of BN/FeCo/CNT composite material, metal Fe, Co are uniformly attached between BN lamella and sheet surfaces, and CNT pairs
Fe, Co and BN play fixed function, form partial size in the chondritic of 100~400nm.Wherein, the molar ratio of BN, Fe, Co and CNT
For 1:1:1:1.Preparation method includes the following steps:
(1) 0.005mol carbon nanotube (CNT) and 0.005mol boron nitride (BN) is added in the ethylene glycol of 50mL, is surpassed
Sound disperses 30min；
(2) it is added with stirring 0.005mol FeCl3·6H2O、0.005mol CoCl2·6H2O, 0.06mol urea, after
Continuous stirring 10min, dissolves solid sufficiently and is uniformly mixed solution；
(3) after standing 20min, reaction system progress heating reflux reaction 6h is cooled to room temperature after reaction, point
Not Yong secondary distilled water and ethyl alcohol centrifuge washing solid, respectively wash 3 times, wherein centrifuge speed 8000r/min, centrifugation
Duration 5min.The solid finally obtained is poured into beaker, is sealed with sealing film, and stabs several ventholes on film, is put into true
In empty drying box, 90 DEG C of temperature is kept, the pressure of 0.08Mpa is 9 hours dry, is cooled to room temperature after drying, it grinds,
Obtain target solids composite material BN/FeCo/CNT.
Gained BN/FeCo/CNT composite material is subjected to XRD, TEM characterization, as a result as shown in Figure 7, Figure 8.
It can be seen from figure 7 that having the characteristic diffraction peak of BN, Fe, Co and CNT in figure, and go out without other impurity peaks
It is existing, it was demonstrated that products obtained therefrom is BN/FeCo/CNT composite material.
In Fig. 8, it is spherical knot of the partial size in 100~400nm that Fig. 8 a, which can be seen that gained BN/FeCo/CNT composite material,
Structure.Find out in Fig. 8 b, Fe, Co simple substance are uniformly attached between the lamella of BN and sheet surfaces, and CNT will be attached with as rope
The BN of Fe, Co are fixed.
Embodiment 7
A kind of BN/FeNi/CNT composite material, metal Fe, Ni are uniformly attached between BN lamella and sheet surfaces, and CNT pairs
Fe, Ni and BN play fixed function, form partial size in the chondritic of 100~200nm.Wherein, the molar ratio of BN, Fe, Ni and CNT
For 1:1:1:1.Preparation method includes the following steps:
(1) 0.005mol carbon nanotube (CNT) and 0.005mol boron nitride (BN) is added in the ethylene glycol of 50mL, is surpassed
Sound disperses 30min；
(2) 0.005mol FeCl is continuously added under stirring3·6H2O、0.005mol NiCl2·6H2O, 0.06mol urinates
Element continues to stir 10min, dissolves solid sufficiently and is uniformly mixed solution；
(3) after standing 20min, reaction system progress heating reflux reaction 6h is cooled to room temperature after reaction, point
Not Yong secondary distilled water and ethyl alcohol centrifuge washing solid, respectively wash 3 times, wherein centrifuge speed 8000r/min, centrifugation
Duration 5min.The solid finally obtained is poured into beaker, is sealed with sealing film, and stabs several ventholes on film, is put into true
In empty drying box, 90 DEG C of temperature is kept, the pressure of 0.08Mpa is 9 hours dry, is cooled to room temperature after drying, it grinds,
Obtain target solids composite material BN/FeNi/CNT.
Gained BN/FeNi/CNT composite material is subjected to XRD, TEM characterization, as a result as shown in Figure 9, Figure 10.
It can be seen in figure 9 that having the characteristic diffraction peak of BN, Fe, Ni and CNT in figure, and go out without other impurity peaks
It is existing, it was demonstrated that products obtained therefrom is BN/FeNi/CNT composite material.
In Figure 10, it is partial size in the spherical of 100~200nm that Figure 10 a, which can be seen that gained BN/FeNi/CNT composite material,
Structure.As can be seen that Fe, Ni simple substance are uniformly attached between the lamella of BN and sheet surfaces in Figure 10 b, CNT is as rope
The BN for being attached with Fe, Ni is fixed.
Embodiment 8
A kind of BN/CoNi/CNT composite material, metal Co, Ni are uniformly attached between BN lamella and sheet surfaces, and CNT pairs
Co, Ni and BN play fixed function, form partial size in the chondritic of 50~100nm.Wherein, the molar ratio of BN, Co, Ni and CNT
For 1:1:1:1.Preparation method includes the following steps:
(1) 0.005mol carbon nanotube (CNT) and 0.005mol boron nitride (BN) is added in the ethylene glycol of 50mL, is surpassed
Sound disperses 30min；
(2) 0.005mol CoCl is continuously added under stirring2·6H2O、0.005mol NiCl2·6H2O, 0.06mol urinates
Element continues to stir 10min, dissolves solid sufficiently and is uniformly mixed solution；
(3) after standing 20min, reaction system progress heating reflux reaction 6h is cooled to room temperature after reaction, point
Not Yong secondary distilled water and ethyl alcohol centrifuge washing solid, respectively wash 3 times, wherein centrifuge speed 8000r/min, centrifugation
Duration 5min.The solid finally obtained is poured into beaker, is sealed with sealing film, and stabs several ventholes on film, is put into true
In empty drying box, 90 DEG C of temperature is kept, the pressure of 0.08Mpa is 9 hours dry, is cooled to room temperature after drying, it grinds,
Obtain target solids composite material BN/CoNi/CNT.
Gained BN/CoNi/CNT composite material is subjected to XRD, TEM characterization, as a result as shown in Figure 11, Figure 12.
It can be seen from fig. 11 that having the characteristic diffraction peak of BN, Co, Ni and CNT in figure, and go out without other impurity peaks
It is existing, it was demonstrated that products obtained therefrom is BN/CoNi/CNT composite material.
In Figure 12, it is spherical knot of the partial size in 50~100nm that Figure 12 a, which can be seen that gained BN/CoNi/CNT composite material,
Structure.As can be seen that Co, Ni simple substance are uniformly attached between the lamella of BN and sheet surfaces in Figure 12 b, CNT will as rope
The BN for being attached with Co, Ni is fixed.
Comparative example 1
It is added in the present embodiment using the similar preparation method of embodiment 1 different from embodiment 1 in the present embodiment
For water as solvent, ethylene glycol is reducing agent, and the additional amount of water and ethylene glycol is respectively 25ml.
Comparative example 2
Using the preparation method that embodiment 1 is similar in the present embodiment, different from embodiment 1, the present embodiment is not added
Urea.
Comparative example 3
It, will in the present embodiment different from embodiment 1 using the preparation method that embodiment 1 is similar in the present embodiment
NiCl2·6H2O and urea are substituted for NiSO4·6H2O。
Comparative example 4
Using the similar preparation method of embodiment 1 in the present embodiment, different from embodiment 1, urea in the present embodiment
Additive amount is 0.01mol.
Comparative example 5
It is added in the present embodiment using the similar preparation method of embodiment 3 different from embodiment 3 in the present embodiment
For water as solvent, ethylene glycol is reducing agent, and the additional amount of water and ethylene glycol is respectively 25ml.
Comparative example 6
The present embodiment is not added in the present embodiment using the similar preparation method of embodiment 3 different from embodiment 3
Urea.
Comparative example 7
It, will in the present embodiment different from embodiment 3 using the preparation method that embodiment 3 is similar in the present embodiment
FeCl3·6H2O and urea are substituted for Fe2(SO4)3。
Comparative example 8
Using the similar preparation method of embodiment 3 in the present embodiment, different from embodiment 3, urea in the present embodiment
Additive amount is 0.01mol.
Comparative example 9
It is added in the present embodiment using the similar preparation method of embodiment 5 different from embodiment 5 in the present embodiment
For water as solvent, ethylene glycol is reducing agent, and the additional amount of water and ethylene glycol is respectively 25ml.
Comparative example 10
The present embodiment is not added in the present embodiment using the similar preparation method of embodiment 5 different from embodiment 5
Urea.
Comparative example 11
It, will in the present embodiment different from embodiment 5 using the preparation method that embodiment 5 is similar in the present embodiment
CoCl2·6H2O and urea are substituted for CoSO4·7H2O。
Comparative example 12
Using the similar preparation method of embodiment 5 in the present embodiment, different from embodiment 5, urea in the present embodiment
Additive amount is 0.02mol.
Comparative example 13
It is added in the present embodiment using the similar preparation method of embodiment 6 different from embodiment 6 in the present embodiment
For water as solvent, ethylene glycol is reducing agent, and the additional amount of water and ethylene glycol is respectively 25ml.
Comparative example 14
The present embodiment is not added in the present embodiment using the similar preparation method of embodiment 6 different from embodiment 6
Urea.
Comparative example 15
It, will in the present embodiment different from embodiment 6 using the preparation method that embodiment 6 is similar in the present embodiment
FeCl3·6H2O and CoCl2·6H2O changes CoSO into4·7H2O and Fe2(SO4)3, and do not add urea.
Comparative example 16
Using the similar preparation method of embodiment 6 in the present embodiment, different from embodiment 6, urea in the present embodiment
Additive amount is 0.01mol.
Comparative example 17
It is added in the present embodiment using the similar preparation method of embodiment 7 different from embodiment 7 in the present embodiment
For water as solvent, ethylene glycol is reducing agent, and the additional amount of water and ethylene glycol is respectively 25ml.
Comparative example 18
The present embodiment is not added in the present embodiment using the similar preparation method of embodiment 7 different from embodiment 7
Urea.
Comparative example 19
It, will in the present embodiment different from embodiment 7 using the preparation method that embodiment 7 is similar in the present embodiment
FeCl3·6H2O and NiCl2·6H2O changes NiSO into4·6H2O and Fe2(SO4)3, and do not add urea.
Comparative example 20
Using the similar preparation method of embodiment 7 in the present embodiment, different from embodiment 7, urea in the present embodiment
Additive amount is 0.01mol.
Comparative example 21
It is added in the present embodiment using the similar preparation method of embodiment 8 different from embodiment 8 in the present embodiment
For water as solvent, ethylene glycol is reducing agent, and the additional amount of water and ethylene glycol is respectively 25ml.
Comparative example 22
The present embodiment is not added in the present embodiment using the similar preparation method of embodiment 8 different from embodiment 8
Urea.
Comparative example 23
It, will in the present embodiment different from embodiment 8 using the preparation method that embodiment 8 is similar in the present embodiment
CoCl2·6H2O and NiCl2·6H2O changes NiSO into4·6H2O and CoSO4·7H2O, and do not add urea.
Comparative example 24
Using the similar preparation method of embodiment 8 in the present embodiment, different from embodiment 8, urea in the present embodiment
Additive amount is 0.01mol.
Experimental example
Electrocatalytic oxidation reducing property
1, embodiment 1, embodiment 3, embodiment 5 to the composite material obtained of embodiment 8, and commercial Pt/C is multiple
Condensation material (general commercial means are bought) carries out the test of corresponding chemical property respectively, and electro-chemical test instrument is upper
The CHI 760E type electrochemical workstation of Hai Chenhua company.Electro-chemical test uses three-electrode system, with platinum filament be to electrode, with
Saturated calomel electrode (SCE) is reference electrode, using glass-carbon electrode as working electrode.In 0.1mol L when test-1In KOH solution with
Hg/Hg2Cl2It for reference electrode, carries out at room temperature, sweep speed is 5mV s-1, the amount of catalyst is on glass carbon working electrode
0.073mg。
Specifically, before each oxygen reduction reaction starts, all by electrolyte solution N2Saturation, from 0.2V to -0.8V with 5mV
s-1Sweep speed scan 20 circulations to guarantee the stabilizations of current-voltage signal.Electrolyte solution is passed through O2At least 30min is again
Carry out the test of chemical property.The scanning of working electrode at least 20 circulations before data recording.
Test result is as shown in Figure 13 to Figure 19, wherein Figure 13 is business Pt/C composite material in O2The 0.1M of saturation
Cyclic voltammetry curve in KOH solution, it can be seen from the figure that embodiment 1, embodiment 3, embodiment 5 to embodiment 8 are obtained
Composite material in the 0.1M KOH solution that oxygen is saturated, have a good electrocatalytic oxidation reducing property, starting hydrogen reduction electricity
Position is close with business Pt/C composite material.Further comparison can find that the electricity of the BN/CoNi/CNT composite material of embodiment 8 is urged
Change hydrogen reduction performance to be significantly improved than the performance of composite material in embodiment 1,5, the BN/FeNi/CNT of embodiment 7 is multiple
The electrocatalytic oxidation reducing property of condensation material is significantly improved than the performance of composite material in embodiment 1,3, embodiment 6
The electrocatalytic oxidation reducing property of BN/FeCo/CNT composite material has than the performance of composite material in embodiment 3,5 significantly to be mentioned
Height shows that starting hydrogen reduction current potential and peak current density significantly improve；It is possible thereby to prove, composite material of the invention
In, it is compound due to BN, CNT and two kinds of metal simple-substances when using two kinds of metals, have and preferably act synergistically, electricity is urged
Change hydrogen reduction performance to significantly improve, and is apparently higher than the compound of BN, CNT and any metal material.
2, embodiment 2, embodiment 4 and comparative example 1 to comparative example 24 are equally subjected to chemical property survey by aforesaid operations
Examination has preferable electrocatalytic oxidation reproducibility the results show that the test result of embodiment 2, embodiment 4 is similar to Example 1
Energy.
And comparative example 1 to comparative example 3, comparative example 5-7, comparative example 9-11, comparative example 13-15, comparative example 17-19, comparison
The test result of example 21-23 as shown in Figure 20 to Figure 37, does not have electrocatalytic oxidation reducing property respectively.
Comparative example 4,8,12,16,20,24 although have certain electrocatalytic oxidation reducing property, be markedly less than embodiment 1,
3,5,6,7,8 and performance it is unstable.
Stability
By the composite material obtained of embodiment 1,3,5,6,7,8, with existing routine Pt/C composite material (general business
Means are bought), test its corresponding time current curve graph respectively under constant voltage.
Test result is as shown in Figure 38 to 43, it can be seen from the figure that composite material obtained by the embodiment of the present invention passes through
18000 seconds circulations are crossed, current density has almost no change；Under the same terms, business Pt/C composite material but occurs more bright
Aobvious cyclical stability reduces, it can thus be seen that the stability of composite material obtained by the embodiment of the present invention is more preferable.
In conclusion composite material electrocatalytic oxidation reducing property with higher provided by the present invention, and stable circulation
Property it is higher, compared to the Pt/C composite material of business, have more utility value.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (9)
1. a kind of preparation method of the composite material with electrocatalytic oxidation reducing property, which comprises the following steps:
(1) CNT, BN are added in ethylene glycol, ultrasonic disperse processing；
(2) metal salt, urea is added to reaction system obtained by step (1) under stirring, continues to stir；
(3) heating reflux reaction is carried out after standing the reaction system in step (2), post-processing is carried out after reaction and is answered
Condensation material；
Wherein, metal salt is selected from FeCl3·6H2O、CoCl2·6H2O、NiCl2·6H2Any one of O or any two.
2. preparation method according to claim 1, which is characterized in that the molar ratio of metal salt and urea is 1:(6~10).
3. preparation method according to claim 1, which is characterized in that CNT, metal salt, BN molar ratio be 1:2:1.
4. preparation method according to claim 1, which is characterized in that in step (1) the ultrasonic disperse time be 30min~
60min。
5. preparation method according to claim 1, which is characterized in that continue to stir 10min~20min in step (2).
6. preparation method according to claim 1, which is characterized in that in step (3) by reaction system stand 15min~
After 25min, heating reflux reaction is carried out, the reaction time is 6h~8h.
7. the composite material with electrocatalytic oxidation reducing property obtained by any one of claim 1 to 6 preparation method.
8. composite material according to claim 7, which is characterized in that metal is uniformly attached to BN lamella in the composite material
Between and sheet surfaces, CNT fixed functions are risen to metal and BN.
9. composite material prepared by any one of claim 1 to 6 preparation method is used as catalyst in a fuel cell
Purposes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910160463.7A CN110010904B (en) | 2019-03-04 | 2019-03-04 | Composite material with electrocatalytic oxygen reduction performance and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910160463.7A CN110010904B (en) | 2019-03-04 | 2019-03-04 | Composite material with electrocatalytic oxygen reduction performance and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110010904A true CN110010904A (en) | 2019-07-12 |
| CN110010904B CN110010904B (en) | 2022-04-19 |
Family
ID=67166314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910160463.7A Active CN110010904B (en) | 2019-03-04 | 2019-03-04 | Composite material with electrocatalytic oxygen reduction performance and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110010904B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010093343A1 (en) * | 2009-02-10 | 2010-08-19 | Utc Power Corporation | Boron-doped diamond coated carbon catalyst support |
| CN102950015A (en) * | 2012-09-21 | 2013-03-06 | 燕山大学 | Method for preparing boron carbon nitride nanotube with high oxygen reduction catalytic activity |
| CN108281678A (en) * | 2018-01-30 | 2018-07-13 | 济南大学 | A kind of BN/Cu/CNT composite material and preparation methods and purposes |
| CN108288715A (en) * | 2018-01-30 | 2018-07-17 | 济南大学 | A kind of BN/Ag/CNT composite material and preparation methods and purposes |
| CN108306023A (en) * | 2018-01-30 | 2018-07-20 | 济南大学 | A kind of BN/CuAg/CNT composite material and preparation methods and purposes |
-
2019
- 2019-03-04 CN CN201910160463.7A patent/CN110010904B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010093343A1 (en) * | 2009-02-10 | 2010-08-19 | Utc Power Corporation | Boron-doped diamond coated carbon catalyst support |
| CN102950015A (en) * | 2012-09-21 | 2013-03-06 | 燕山大学 | Method for preparing boron carbon nitride nanotube with high oxygen reduction catalytic activity |
| CN108281678A (en) * | 2018-01-30 | 2018-07-13 | 济南大学 | A kind of BN/Cu/CNT composite material and preparation methods and purposes |
| CN108288715A (en) * | 2018-01-30 | 2018-07-17 | 济南大学 | A kind of BN/Ag/CNT composite material and preparation methods and purposes |
| CN108306023A (en) * | 2018-01-30 | 2018-07-20 | 济南大学 | A kind of BN/CuAg/CNT composite material and preparation methods and purposes |
Non-Patent Citations (6)
| Title |
|---|
| 《化工百科全书》编辑委员会: "《化工百科全书》", 30 November 1996 * |
| INDRAJIT M. PATIL等: "Carbon Nanotube/Boron Nitride Nanocomposite as a Significant Bifunctional Electrocatalyst for Oxygen Reduction and Oxygen Evolution Reactions", 《CHEMISTRY-A EUROPEAN JOURNAL》 * |
| SAURABH GHOSH等: "Novel properties of boron nitride nanotubes encapsulated with Fe, Co, and Ni nanoclusters", 《THE JOURNAL OF CHEMICAL PHYSICS 》 * |
| 新能源材料 第2版: "《新能源材料 第2版》", 30 June 2017 * |
| 解忧: "氮化硼纳米管填充、掺杂和吸附的结构、电子与磁性质", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 马建新，乔锦丽: "《基于非铂催化剂的质子交换膜燃料电池研究》", 31 August 2017 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110010904B (en) | 2022-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Si et al. | Fe, N‐codoped graphdiyne displaying efficient oxygen reduction reaction activity | |
| CN109256567B (en) | Preparation method of transition metal/nitrogen-doped bamboo-like carbon nanotube | |
| Iqbal et al. | Recent developments in graphene based novel structures for efficient and durable fuel cells | |
| CN108411324A (en) | The sulfur and nitrogen co-doped graphene-supported cobalt sulfide nickel catalytic material of one kind and preparation and application | |
| CN103094584B (en) | Nanometer sandwich structure fuel cell non-precious metal catalyst, membrane electrode and preparation method | |
| CN106207204A (en) | Nitrogen sulfur difunctional VPO catalysts of codope material with carbon element and its preparation method and application | |
| CN107604375A (en) | Difunctional VPO catalysts of the porous carbon complex of nitrogen cobalt codope and its preparation method and application | |
| CN108923050A (en) | A kind of carbon nano-structured elctro-catalyst of the nucleocapsid of high catalytic performance and preparation method thereof | |
| CN106992304A (en) | It is a kind of to nitrogenize the Preparation method and use that carbon-based composite oxygen reduction electro-catalyst modifies disk electrode | |
| CN109346734A (en) | A kind of preparation method of manganese bioxide/carbon nano tube complex fuel battery negative pole oxygen reduction catalyst | |
| CN112133929B (en) | Preparation method of ZIF-8-derived Au-N-C oxygen reduction electrocatalyst | |
| CN105576262A (en) | Nitrogen ferride/carbide co-doped composite material used for increasing high oxygen reduction activation of fuel cell cathode | |
| CN104525185A (en) | Carbon-based composite fuel cell cathode oxygen reduction catalyst and preparation method thereof | |
| Gong et al. | Prussian blue analogues derived electrocatalyst with multicatalytic centers for boosting oxygen reduction reaction in the wide pH range | |
| Ma et al. | Electrocatalytic Oxidation of Methanol over An Electrode with Ni‐MOF‐74 Catalyst | |
| CN114628696B (en) | Preparation method of porous carbon-supported cobalt-based bifunctional oxygen catalyst | |
| Norouzi et al. | Methanol electrooxidation on novel modified carbon paste electrodes with supported poly (isonicotinic acid)(sodium dodecyl sulfate)/Ni-Co electrocatalysts | |
| CN112054221B (en) | Preparation method and application of ZIF 8-graphene-based rhodium-loaded aerogel catalyst | |
| CN109560288A (en) | A kind of highly reactive form of oxygen reducing catalyst and preparation method and purposes | |
| Chen et al. | Interfacial coupling effect of CoO/CoMoO4 promotes alkaline hydrogen electrode for hydrogen energy storage system | |
| CN106299388A (en) | A kind of biomass alkaline fuel cell air cathode and preparation method and application | |
| CN111313045A (en) | Platinum-copper alloy nanowire and preparation method and application thereof | |
| Yisilamu et al. | Silk‐Derived N‐Doped Fe@ NPC as Efficient Bifunctional Electrocatalyst for Direct Methanol Fuel Cell (DMFC) | |
| CN110010904A (en) | A kind of composite material and preparation method and purposes with electrocatalytic oxidation reducing property | |
| CN101783409A (en) | Preparation method of membrane electrode with negative pole being carbon-carried transition metal chelate catalytic agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |