CN108288715A - A kind of BN/Ag/CNT composite material and preparation methods and purposes - Google Patents
A kind of BN/Ag/CNT composite material and preparation methods and purposes Download PDFInfo
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- CN108288715A CN108288715A CN201810087656.XA CN201810087656A CN108288715A CN 108288715 A CN108288715 A CN 108288715A CN 201810087656 A CN201810087656 A CN 201810087656A CN 108288715 A CN108288715 A CN 108288715A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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Abstract
The invention discloses a kind of BN/Ag/CNT composite material and preparation methods and purposes, belong to electrocatalysis material technical field.Ag is uniformly attached between BN lamellas in the BN/Ag/CNT composite materials and sheet surfaces, CNT play fixed function to Ag and BN.The preparation method W-response mild condition of the present invention does not use organic solvent, and safety and environmental protection, post-processing is simple, and flow is short, less energy consumption, and cost is relatively low.Obtained BN/Ag/CNT composite materials have efficient electrocatalytic oxidation reducing property and preferable electrochemical stability.
Description
Technical field
The invention belongs to electrocatalysis material technical fields, and in particular to a kind of BN/Ag/CNT composite materials and its preparation side
Method and purposes.
Background technology
With the development of economy, the horizontal of life is continuously improved, and demand of the people to the energy is higher and higher.Improve the energy
Utilization ratio is no longer sole criterion, is more and more paid close attention to by people using the spatter property energy.
Fuel cell be it is a kind of cleaning, efficiently, can continuous wave high power electric discharge device.Chemical energy can be directly translated into
Electric energy, without combustion process, because without being limited by Carnot cycle.In addition, another advantage of fuel cell is hardly to arrange
Pollution gas is put, the discharge capacity of carbon dioxide is fewer by 40% or so than power generation normally.These of fuel cell are unique
Advantage makes it be acknowledged as the generation technology of the following clean and safe more than nuclear energy.The appearance of fuel cell and later hair
Exhibition, it will generate more far-reaching influence in various aspects such as transportation, commercial powers.Fuel cell power generation principle and original
Battery is similar, and the key of fuel battery performance is that its cathode material.The major obstacle of cell reaction is cathode material
The oxygen reduction reaction of upper generation, hydrogen reduction reversibility of heat conduction process is smaller, and reduction is more difficult.Pt/C catalyst use at this stage compared with
It is more, there is good oxygen reduction activity and durability to be thus widely used in a fuel cell, but due to higher cost and
It is easy to be poisoned by CO, this kind of material is made to receive many limitations in application aspect.Numerous researchers are to solve this problem
Making great efforts to look for other metallic catalysts to substitute the use of Pt/C.
Hexagonal boron nitride appearance is white fluffy sprills, and soft texture has smooth feeling, similar to the property of graphite, sheet
Structure, therefore have the title of " white graphite ".Hexagonal boron nitride has good electrical insulating property, thermal conductivity, chemical resistance and lubrication
Property.Boron nitride can be widely used in oil, chemical industry, machinery, electronics, electric power, weaving, nuclear industry, space flight and other Ministry of Industry
Door.Currently, rarely have the synthesis and its application study in a fuel cell about boron nitride-metal-carbon pipe composite material,
The also rare report of the test of related chemical property.
Invention content
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of BN/Ag/CNT composite materials
And its preparation method and application, overcome the catalyst cost existing in the prior art for fuel cell higher, easily malicious by CO
Change, electrocatalytic oxidation reducing property it is unstable, the defects of using being restricted.
To achieve the goals above or other purposes, the present invention is achieved by the following technical solutions.
A kind of BN/Ag/CNT composite materials, in the BN/Ag/CNT composite materials Ag be uniformly attached between BN lamellas and
Sheet surfaces, CNT play fixed function to Ag and BN.
The BN/Ag/CNT composite materials of the present invention, metallic silver are uniformly adhered to the sheet surfaces and piece of BN (boron nitride)
Between layer, and the CNT (carbon nanotube) in composite material can further fix Argent grain with BN, form cage structure, together
When carbon nanotube also improve the electric conductivity of material.
Preferably, the molar ratio of BN, Ag and CNT are 1:2:1.
The present invention also provides a kind of method preparing BN/Ag/CNT composite materials described above, used in the method
BN, silver nitrate, CNT are starting material, and ethylene glycol is dispersant, concentrated ammonia liquor is complexing agent, and sodium borohydride is reducing agent, is made
Standby BN/Ag/CNT composite materials.
The BN is the hexagonal boron nitride obtained by general commercial means.The CNT is to be obtained by general commercial means
The carbon nanotube obtained.
Specifically, include the following steps:
(1) silver nitrate is dissolved in deionized water, stirs lower dropwise addition concentrated ammonia liquor, obtains silver ammino ion solution;
(2) BN, CNT, ethylene glycol are added in silver ammino ion solution, ultrasonic disperse, obtain the mixing of stable homogeneous
Solution;
(3) the mixed solution and dripping sodium borohydride solution obtained to step (2) under stirring, it is post-treated after reaction
Obtain BN/Ag/CNT composite materials.
Further, in this method, raw material BN, silver nitrate, CNT molar ratio be 1:2:1.
Further, to ensure that silver ion is completely reduced, the dosage of sodium borohydride should be excessive.Preferably, reducing agent boron
The molar ratio of sodium hydride and silver nitrate should be greater than 1:8.
Further, when concentrated ammonia liquor is added dropwise under step (1) room temperature into the aqueous solution of silver nitrate, precipitation is generated first
AgOH, as the amount that concentrated ammonia liquor is added dropwise increases, gradually dissolving forms complex ([Ag (NH to AgOH3)2]OH);Therefore, step (1)
Middle dropwise addition concentrated ammonia liquor to precipitation is completely dissolved.
Further, the preparation method of sodium borohydride solution is in step (3):Using deionized water, prepare 0.5~
The sodium hydroxide solution of 2mol/L;Using sodium hydroxide solution as solvent, sodium borohydride is solute, prepares the hydroboration of 0.1mol/L
Sodium solution.
In the present invention, the formulation operations of sodium borohydride solution also can in advance be prepared when preparing composite material and starting, or
It is prepared again when step (3) use.Preferably, the sodium borohydride solution in the present invention is by the way of matching while using.
Further, the molal volume of BN and ethylene glycol ratio is (2.5mol in step (2):1L).
Further, the ultrasonic disperse time is 30min~60min in step (2).
Further, post-processing includes washing, dry, calcining in step (3).
Preferably, after reaction, the mixed solvent of reaction mixture absolute ethyl alcohol and deionized water is washed
For several times, the crude product after washing is dried in vacuo 5-7h at 70-100 DEG C.Product after drying is after grinding, in ar gas environment
Under, 1.5~3h is calcined at 750~850 DEG C, after calcining, is cooled to room temperature, and grinding obtains BN/Ag/CNT composite materials.
It is highly preferred that the crude product after washing is dried in vacuo 6h at 85 DEG C.Under ar gas environment, in tube furnace internal program
Temperature-raising method calcines 2h at 800 DEG C.
Another aspect of the present invention additionally provides a kind of BN/Ag/CNT composite materials described above in a fuel cell as urging
The purposes of agent.
And its BN/Ag/CNT composite materials obtained by method described above are in a fuel cell as the use of catalyst
On the way.
Hexagonal boron nitride employed in the present invention has the layer structure of similar graphite, although without electric conductivity,
With preferable absorption property, therefore, using the absorption property of BN, the surfaces BN of uniformly adhering to metallic silver in the present invention and
Between lamella, the addition of carbon nanotube can further fix metallic silver particles with BN, forms cage structure, improves simultaneously
The electric conductivity of composite material.
BN/Ag/CNT composite materials produced by the present invention are in the KOH solution for the 0.1M that oxygen is saturated, electrocatalytic oxidation reduction
Initial oxidation current potential in 0.99V or so, maximum hydrogen reduction electric current can reach 10-4mA/cm2The order of magnitude, there is efficient electricity
Catalytic oxidation-reduction performance.After the electro-chemical test of 16000s, the current density of BN/Ag/CNT composite materials of the invention is still
When up to starting 94% or so (and business Pt (20%)/C composite is only 77% left when starting under same experimental conditions
It is right), there is extraordinary electrochemical stability.
In preparation method of the present invention using deionized water as solvent, chlorion is avoided to entirely reacting
It influences;Using concentrated ammonia liquor as complexing agent, after stable silver ammino ion is generated with silver ion, using sodium borohydride as reduction
Agent, by silver ion reduction at elemental silver.Using ethylene glycol as dispersant, evengranular simple substance Argent grain can be obtained, finally make
The uniform elemental metals silver of grain is uniformly adhered between nitridation boron surface and lamella.Method using the present invention, W-response
Mild condition does not use organic solvent, and safety and environmental protection, post-processing is simple, and flow is short, less energy consumption, and cost is relatively low.
Description of the drawings
Fig. 1 is scanning electron microscope (SEM) collection of illustrative plates of the BN/Ag/CNT composite materials obtained by embodiment 1, wherein a, b distinguish
For the SEM spectrum under different amplification, c is the mapping collection of illustrative plates of regional area in b;
Fig. 2 is X-ray diffraction (XRD) collection of illustrative plates of the BN/Ag/CNT composite materials obtained by embodiment 1;
Fig. 3 is embodiment 1, the 0.1M KOH solutions of comparative example 1, the oxygen saturation of composite material obtained by comparative example 2
In cyclic voltammetry curve figure, wherein sweep speed be 5mV s-1;
Fig. 4 is the time current curve graph of the BN/Ag/CNT composite materials and Pt/C composite materials obtained by embodiment 1.
Specific implementation mode
Illustrate that embodiments of the present invention, those skilled in the art can be by this explanations below by way of particular specific embodiment
Content disclosed by book understands other advantages and effect of the present invention easily.The present invention can also be by addition different specific
Embodiment is embodied or practiced, and the various details in this specification can also be based on different viewpoints and application, not carry on the back
Various modifications or alterations are carried out under spirit from the present 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 the term used in the embodiment of the present invention is 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 the 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, in the present invention all technologies for using and
Record of the scientific terminology with those skilled in the art to the grasp of the prior art and the present invention, can also use and this hair
Any method, equipment and the material of the similar or equivalent prior art of method, equipment described in bright embodiment, 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, and CNT is to pass through
The common carbon nanotube that general commercial means obtain.
In embodiments of the present invention, BN, Ag and CNT molar ratio of BN/Ag/CNT composite materials are 1:2:1.Metal Ag is equal
Even to be attached between BN lamellas and sheet surfaces, CNT plays fixed functions to Ag and BN.
The sodium borohydride solution preparation method of 0.1mol/L employed in the embodiment of the present invention is:Using deionized water,
Prepare the sodium hydroxide solution of 0.5~2mol/L;Using sodium hydroxide solution as solvent, sodium borohydride is solute, prepares 0.1mol/
The sodium borohydride solution of L.
Embodiment 1
A kind of BN/Ag/CNT composite materials, metal Ag is uniformly attached between BN lamellas and sheet surfaces, CNT to Ag and
BN plays fixed function, forms cage structure.Wherein, the molar ratio of BN, Ag and CNT are 1:2:1.
Preparation method includes the following steps:
(1) 30mL deionized waters are added in the small beaker of 100mL, while magnetic stirrer, are added
1.6987g(0.01mol)AgNO3, stir to dissolving, obtain colourless uniform liquid, concentrated ammonia liquor to generation is slowly added dropwise and precipitates again extremely
Precipitation dissolving, obtains silver ammino ion solution;
(2) add ethylene glycol 2mL, carbon nanotube 0.06g (0.005mol), hexagonal boron nitride into silver ammino ion solution
0.124g (0.005mol), ultrasound 30min makes to be uniformly mixed after stirring 2min;
(3) under room temperature, the sodium borohydride solution 30ml of 0.1mol/L is slowly added dropwise in magnetic agitation while, continues stirring extremely
Reaction terminates, gained crude product deionized water and absolute ethyl alcohol mixed solution (volume ratio 1:1) it washs five times, it then will be thick
Product is put into vacuum drying chamber and is dried in vacuo 6h at 85 DEG C, takes out, grinding, 800 DEG C of calcinings under argon gas atmosphere in tube furnace
2h obtains black powder, as has the BN/Ag/CNT composite materials of efficient electric catalytic oxidation-reduction performance.
BN/Ag/CNT composite materials are subjected to SEM, XRD characterization.
Gained SEM spectrum is as shown in Figure 1, wherein sheet is BN, and granular simple substance Ag, tubulose is CNT.From
As can be seen that elemental silver is in granular form in Fig. 1, uniform particle sizes are supported between the lamella of BN and sheet surfaces, and CNT is by simple substance
Silver further fixes, and forms stable cage structure.As can be seen from the figure elemental silver distributing very evenly in the material.
Fig. 2 is the XRD spectrum of the BN/Ag/CNT composite materials of the present embodiment, can be seen that material from the diffraction maximum in figure
In in addition to there is no the appearance of other impurity peaks by BN, elemental silver, CNT, it was demonstrated that the purity of BN/Ag/CNT composite materials is very high.
Embodiment 2
That the preparation method is the same as that of Example 1 is identical for BN/Ag/CNT composite materials in the present embodiment, as different from Example 1,
Step is dried in vacuo 5h in (3) at 90 DEG C, after grinding, under ar gas environment, and 850 DEG C of calcining 1.5h in tube furnace.
Embodiment 3
That the preparation method is the same as that of Example 1 is identical for BN/Ag/CNT composite materials in the present embodiment, as different from Example 1,
Step is dried in vacuo 6h in (3) at 80 DEG C, after grinding, under ar gas environment, and 800 DEG C of calcining 3h in tube furnace.
Comparative example 1
In the small beaker of 100mL, while magnetic stirrer, 30mL deionized waters are added, 1.6987g is added
(0.01mol)AgNO3, stirring and dissolving forms colourless uniform liquid, and concentrated ammonia liquor is slowly added dropwise to generating precipitation again to precipitation dissolving.
Add ethylene glycol 2mL, carbon nanotube 0.06g (0.005mol), ultrasound 30min makes to be uniformly mixed after stirring 2min.Under room temperature, magnetic force
The sodium borohydride solution 30ml of 0.1mol/L is slowly added dropwise while stirring, continues stirring to reaction and terminates, gained crude product is used
Deionized water and absolute ethyl alcohol mixed solution (volume ratio 1:1) it washs five times, it is dry to be put into vacuum drying chamber vacuum at 85 DEG C
Dry 6h takes out, grinding, and 800 DEG C of calcining 2h under argon gas atmosphere, obtain black powder, as contrast material Ag/CNT in tube furnace
Composite material.
Comparative example 2
In the small beaker of 100mL, while magnetic stirrer, 30mL deionized waters are added, 1.6987g is added
(0.01mol)AgNO3, stirring and dissolving forms colourless uniform liquid, and concentrated ammonia liquor is slowly added dropwise to generating precipitation again to precipitation dissolving.
Add ethylene glycol 2mL, hexagonal boron nitride 0.124g (0.005mol), ultrasound 30min makes to be uniformly mixed after stirring 2min.Under room temperature,
The sodium borohydride solution 30ml of 0.1mol/L is slowly added dropwise while magnetic agitation, continues stirring and terminates to reaction, gained slightly produces
Product deionized water and absolute ethyl alcohol mixed solution (volume ratio 1:1) it washs five times, is put into vacuum drying chamber at 85 DEG C true
The dry 6h of sky takes out, grinding, and 800 DEG C of calcining 2h under argon gas atmosphere, obtain black powder, as contrast material in tube furnace
Ag/BN composite materials.
Experimental example
1, the composite material obtained in embodiment 1, comparative example 1, comparative example 2 is subjected to corresponding chemical property respectively
Test, electro-chemical test instrument be Shanghai Chen Hua company CHI 760E type electrochemical workstations.Electro-chemical test is adopted
It is to electrode, with saturated calomel electrode (SCE) for reference electrode, using glass-carbon electrode as work electricity with platinum filament with three-electrode system
Pole.In 0.1mol L when test-1With Hg/Hg in KOH solution2Cl2It for reference electrode, carries out at room temperature, sweep speed is 5mV s-1, the amount of catalyst is 0.073mg on glass carbon working electrode.
Specifically, before each oxygen reduction reaction starts, all by electrolyte solution N2Saturation, from 0.2V to -0.8V with
5mVs-1Sweep speed scan 20 cycle to ensure the stabilization of current-voltage signal.Electrolyte solution is passed through O2At least
30min carries out the test of chemical property again.The scanning of at least 20 cycles of working electrode before data recording.
Test results are shown in figure 3, it can be seen from the figure that the BN/Ag/CNT composite materials of embodiment 1 are saturated in oxygen
0.1M KOH solutions in, have good electrocatalytic oxidation reducing property, initial oxidation current potential is in 0.99V or so;The Ag/ of comparative example 1
For CNT composite materials in the 0.1M KOH solutions that oxygen is saturated, electrocatalytic oxidation reducing property is general, and initial oxidation current potential exists
0.97V or so;The Ag/BN composite materials of comparative example 2 are in the 0.1M KOH solutions that oxygen is saturated, electrocatalytic oxidation reducing property one
As, initial oxidation current potential is in 0.90V or so.Compare the electricity it can be found that the BN/Ag/CNT composite materials of the embodiment of the present invention 1
The performance of composite material is significantly improved in catalytic oxidation-reduction performance test ratio 1,2, is in particular in starting hydrogen reduction
Current potential is than the corrigendum of comparative example material, peak point current bigger.It is possible thereby to prove, BN/Ag/CNT composite materials of the invention, it will
BN, Ag, CNT three are compound, there is preferable synergistic effect, electrocatalytic oxidation reducing property to significantly improve, and be apparently higher than and appoint
Meaning both it is compound.
2, the BN/Ag/CNT composite materials for being obtained embodiment 1, with existing conventional material Pt/C composite materials (one
As commercial means buy), test its corresponding time current curve graph respectively under constant voltage.
Test results are shown in figure 4, it can be seen from the figure that the BN/Ag/CNT composite materials of embodiment 1 pass through 16000
The cycle of second, the ultimate current of reaction are 94% or so of initial current, and business Pt/C is 77% or so under same case, thus
As can be seen that the stability of BN/Ag/CNT composite materials is more preferable.
In short, the BN/Ag/CNT composite materials of the present invention can be used as the use of the catalyst in fuel cell, have higher
Electrocatalytic oxidation reducing property and stability.Therefore, the present invention effectively overcomes some practical problems in the prior art to have
There is very high utility value and uses meaning.
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 can all carry out modifications and changes to above-described embodiment without violating the spirit and scope of the present invention.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 by the present invention claim be covered.
Claims (10)
1. a kind of BN/Ag/CNT composite materials, which is characterized in that Ag is uniformly attached to BN in the BN/Ag/CNT composite materials
Between lamella and sheet surfaces, CNT play fixed function to Ag and BN.
2. BN/Ag/CNT composite materials as described in claim 1, which is characterized in that the molar ratio of BN, Ag and CNT are 1:2:1.
3. a kind of method preparing any one of claim 1 to 2 BN/Ag/CNT composite materials, which is characterized in that the side
Use BN, silver nitrate, CNT for starting material in method, ethylene glycol is dispersant, concentrated ammonia liquor is complexing agent, and sodium borohydride is reduction
Agent.
4. method as claimed in claim 3, which is characterized in that include the following steps:
(1) silver nitrate is dissolved in deionized water, stirs lower dropwise addition concentrated ammonia liquor, obtains silver ammino ion solution;
(2) BN, CNT, ethylene glycol are added in silver ammino ion solution, ultrasonic disperse, obtain the mixed solution of stable homogeneous;
(3) the mixed solution and dripping sodium borohydride solution obtained to step (2) under stirring, after reaction post-treated acquisition
BN/Ag/CNT composite materials.
5. method as claimed in claim 4, which is characterized in that BN, silver nitrate, CNT molar ratio be 1:2:1.
6. method as claimed in claim 4, which is characterized in that concentrated ammonia liquor to precipitation is added dropwise in step (1) and is completely dissolved.
7. method as claimed in claim 4, which is characterized in that the preparation method of sodium borohydride solution is in step (3):Using going
Ionized water prepares the sodium hydroxide solution of 0.5~2mol/L;Using sodium hydroxide solution as solvent, sodium borohydride is solute, is prepared
The sodium borohydride solution of 0.1mol/L.
8. method as claimed in claim 4, which is characterized in that further include any one or multinomial of following characteristics:
The molal volume of BN and ethylene glycol ratio is 2.5mol in step (2):1L;
The ultrasonic disperse time is 30min~60min in step (2);
Post-processing includes washing, dry, calcining in step (3).
9. BN/Ag/CNT composite materials are in a fuel cell as the purposes of catalyst as described in any one of claim 1 to 2.
10. the BN/Ag/CNT composite materials conduct in a fuel cell as obtained by any one of claim 3 to 8 the method
The purposes of catalyst.
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CN110010904A (en) * | 2019-03-04 | 2019-07-12 | 济南大学 | A kind of composite material and preparation method and purposes with electrocatalytic oxidation reducing property |
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