CN106099126A - A kind of flower-like structure cobalt sulfide/carbon composite and preparation method thereof - Google Patents
A kind of flower-like structure cobalt sulfide/carbon composite and preparation method thereof Download PDFInfo
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- CN106099126A CN106099126A CN201610402101.0A CN201610402101A CN106099126A CN 106099126 A CN106099126 A CN 106099126A CN 201610402101 A CN201610402101 A CN 201610402101A CN 106099126 A CN106099126 A CN 106099126A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01M4/8825—Methods for deposition of the catalytic active composition
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- 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
Abstract
A kind of flower-like structure cobalt sulfide/carbon composite and preparation method thereof, belongs to fuel cell electro-catalyst and preparing technical field thereof.Flower-like structure cobalt sulfide/carbon composite is by the flower-shaped carbon of diameter 15 microns and the Co of particle diameter 5 70 nanometer9S8Composition, Co9S8Weight/mass percentage composition is 30 80 %；Wherein, flower-shaped carbon is 0.5 3 microns by interconnective radial dimension, and thickness is the carbon nanosheet composition of 5 20 nanometers, Co9S8Granule is supported on carbon nanosheet equably.Flower-like structure cobalt sulfide/carbon composite preparation method: the anion of organic molecule is inserted between stratiform cobaltous hydroxide layer by hydro-thermal reaction to obtain intercalation configuration presoma, obtaining flower-like structure cobalt sulfide/carbon composite through high-temperature calcination after mixing with sulfur powder, method advantage is that environment-protecting asepsis, technique are simple, production cost is low again.
Description
Technical field
The invention belongs to fuel cell electro-catalyst and preparing technical field thereof, particularly relate to a kind of flower-like structure sulfuration
Cobalt/carbon composite and preparation method thereof.
Background technology
Fuel cell causes researcher due to its high power density, high-energy conversion efficiency and advantages of environment protection
Extensive concern, is expected to be widely applied to electric vehicle and portable electric appts as efficient cleaner power sources.At fuel cell
In, the slow dynamic process of Cathodic oxygen reduction seriously constrains the commercialization of fuel cell.Although Pt base catalyst
Show the oxygen reduction catalytic activity of excellence, but owing to Pt metal price is expensive, reserves are few and the reason such as poor stability hinders
Its extensive application in commercialization fuel cell.Therefore, exploitation is the most urgent based on non-noble metal efficient electric catalyst.
Metal sulfide has broad application prospects as oxygen reduction electro-catalyst, but its poor electric conductivity and relatively
Big particle size limits the performance of its performance.Therefore, metal sulfide is carried out with the material with carbon element with multilevel hierarchy again
Conjunction can be effectively improved its electric conductivity and stop the reunion of granule, and then promotes the lifting of its catalytic performance.Vulcanize at metal
In the preparation method of thing and carbon composite thereof, it will usually relate to the poisonous and hazardous gaseous sulfur such as hydrogen sulfide, sulfur dioxide source, and
Mostly technology and equipment is relative complex, production cost is higher, needs the simple and environmentally-friendly nontoxic metal sulfide of development technology badly and prepares
Method.
Summary of the invention
The mesh of the present invention is to provide a kind of flower-like structure cobalt sulfide/carbon composite, and this composite is by a diameter of 1-5
The flower-shaped carbon of m and the Co that particle diameter is 5-70 nm9S8Granule forms；Wherein, flower-shaped carbon is 0.5-3 by interconnective radial direction
M, thickness is the carbon nanosheet composition of 5-20 nm, Co9S8Granule is supported on carbon nanosheet equably, Co9S8At composite
In weight/mass percentage composition be 30-80%.
Present invention also offers the preparation method of above-mentioned flower-like structure cobalt sulfide/carbon composite, will organic molecule
Anion inserted between stratiform cobaltous hydroxide layer by hydro-thermal reaction to obtain intercalation configuration presoma, then with the mixing of sulfur powder after warp
High-temperature calcination obtains flower-like structure cobalt sulfide/carbon composite, specifically includes following processing step.
(1) by divalent cobalt ion Co2+Soluble-salt and hexamethylenetetramine mixing, be dissolved in carbon dioxide removal go from
In sub-water, preparation obtains mixed solution；Under nitrogen protection by above-mentioned mixed solution and organic molecule anion A–Solubility
Salt mixes, and proceeds in hydrothermal reaction kettle at 80-120o8-24 h is reacted at a temperature of C；The suspension obtained after reaction is filtered,
It is 7-7.5 with deionized water and washing with alcohol filter cake to filtrate pH value, then by filter cake at 60-80oC is dried 8-20 h, obtains
The cobalt hydroxide that organic molecule is anion intercalated.Wherein, described divalent cobalt ion Co2+The nitrate that soluble-salt is cobalt,
One or more in sulfate, oxalates or chloride；Divalent cobalt ion Co in described mixed solution2+Concentration be 25-125
Mmol/L, described hexamethylenetetramine and described Co2+The ratio of amount of material be 2:1；Described organic molecule anion A-'s
Soluble-salt is one or more in sodium m-aminobenzene sulfonate, sodium sulfanilate, orthanilic acid sodium, and organic little
Molecular anion A–With Co2+The ratio of amount of material be 3-15:1.
(2) by cobalt hydroxide anion intercalated for the organic molecule of preparation in step (1) and sulfur powder according to mass ratio it is
The ratio mixing of 1-4:1, under an inert atmosphere, by said mixture with 2-10oC/min ramp is to 700-1000oC forges
Burn 2-10 h, naturally cool to room temperature, i.e. obtain flower-like structure of the present invention cobalt sulfide/carbon composite.Wherein, described indifferent gas
Atmosphere is the one in nitrogen or argon.
X-ray diffraction (XRD) figure of Fig. 1 shows that product of the present invention is Co9S8With the complex of material with carbon element, there is not it
His impurity phase, and crystal formation is good；Scanning electron microscope (SEM) photo of Fig. 2 shows that product of the present invention is the flower-shaped of a diameter of 1-5 m
Carbon, this flower-shaped carbon is 0.5-3 m by interconnective radial direction, and thickness is the carbon nanosheet composition of 5-20 nm, Co9S8Granule is uniform
Be supported on carbon nanosheet；The SEM photograph that Fig. 3 amplifies further is it can be seen that constitute and uniformly bear on the carbon nanosheet of flower-shaped carbon
Carry the Co that particle diameter is 5-70 nm9S8Nano-particle；Fig. 4 is the pore-size distribution test result of product of the present invention, there is 3-50 nm
Mesoporous；Fig. 5 is the thermal gravimetric analysis results of product of the present invention, through being calculated Co9S8Mass percent content is 77.2%.
Fig. 6 is under different rotating speeds, the linear sweep voltammetry curve test result of product of the present invention, it is seen that electric current density along with
The increase of rotating speed and increase, this is owing to diffusion length shortens caused at high speed, additionally, composite of the present invention has height
Half wave potential and Limited diffusion current density, show its have excellence hydrogen reduction (ORR) electrocatalysis characteristic.
Distinguishing feature and the advantage of the present invention are: the invention provides a kind of flower-like structure cobalt sulfide/carbon composite,
In this composite, flower-shaped carbon is made up of interconnective carbon nanosheet, Co9S8Nano-particle is supported on carbon nanosheet equably
On.Flower-shaped carbon provides high-specific surface area, quick material transmission channels and good electric conductivity, Co9S8Nano-particle uniformly divides
It is dispersed on carbon nanosheet, effectively controls Co9S8The particle diameter of nano-particle also prevents it from reuniting, and therefore this composite has excellent
Different hydrogen reduction ORR electro catalytic activity；The anion of organic molecule is inserted stratiform hydroxide by hydro-thermal reaction by the present invention
To obtain intercalation configuration presoma between cobalt layers, then it is combined through high-temperature calcination acquisition flower-like structure cobalt sulfide/carbon after the mixing of sulfur powder
Material, method advantage is that environment-protecting asepsis, technique are simple, production cost is low.
Accompanying drawing explanation
The flower-like structure Co that Fig. 1 provides for the embodiment of the present invention 19S8The XRD spectra of/carbon composite；Wherein, abscissa
For angle 2 θ, unit is: degree (o)；Vertical coordinate is diffracted intensity, and unit is: absolute unit (a.u).
The flower-like structure Co that Fig. 2 provides for the embodiment of the present invention 19S8The SEM photograph of/carbon composite.
The flower-like structure Co that Fig. 3 provides for the embodiment of the present invention 19S8The SEM photograph that/carbon composite amplifies.
The flower-like structure Co that Fig. 4 provides for the embodiment of the present invention 19S8The graph of pore diameter distribution of/carbon composite；Wherein, horizontal seat
Being designated as hole dimension, unit is: nanometer (nm)；Vertical coordinate is pore volume, and unit is: cubic centimetre/(gram nanometer) (cm3/
(g·nm))。
The flower-like structure Co that Fig. 5 provides for the embodiment of the present invention 19S8The thermal multigraph of/carbon composite；Wherein, abscissa is
Temperature, unit is: degree Celsius (oC), vertical coordinate is mass percent, and unit is: percent (%).
The flower-like structure Co that Fig. 6 provides for the embodiment of the present invention 19S8/ carbon composite is anti-in electrode surface generation hydrogen reduction
The linear sweep voltammetry curve answered；Wherein, abscissa is that current potential is: volt (V) relative to reversible hydrogen electrode, unit；Vertical coordinate
For electric current density, unit is: milliampere every square centimeter (mA/cm2)。
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with accompanying drawing and be embodied as
Example, is further elaborated to the present invention, but the present invention is not limited only to this.
Embodiment 1: first by the Co (NO of 5 mmol3)2·6H2The hexamethylenetetramine mixing of O and 10 mmol, is dissolved in 20
In the deionized water of mL carbon dioxide removal, preparation obtains mixed solution；Then by metanilic acid and 15 mmol of 15 mmol
NaOH be dissolved in the deionized water of 20 mL carbon dioxide removals and be neutralized reaction, obtain sodium m-aminobenzene sulfonate solution；At nitrogen
Under gas shielded, above-mentioned mixed solution and sodium m-aminobenzene sulfonate solution are mixed, after stirring, be transferred to the poly-of 50 mL
In the autoclave of tetrafluoroethene substrate, put in baking oven 100oC isothermal reaction 12 h, takes out autoclave natural
It is cooled to room temperature, is 7 with 500 mL deionized waters and 200 mL ethanol filtering and washing to filtrate pH value, then by filter cake 80oC forced air drying 8 h, obtains the cobalt hydroxide of metanilic acid root intercalation.
By cobalt hydroxide and the 0.05 g sulfur powder mix homogeneously of 0.2 g metanilic acid root intercalation of above-mentioned preparation, put
Enter porcelain boat and be placed on heating region in the middle of quartz tube furnace, be passed through the purity nitrogen deoxygenation more than 99%, after 30 min, with 5oC/
Min heating rate is heated to 900oC is also incubated 2 h；Then it is slowly dropped to room temperature, bottom porcelain boat, generates black calcined product,
I.e. obtain flower-like structure Co9S8/ carbon composite.
The XRD spectra of composite prepared by the present embodiment is as it is shown in figure 1, show that product of the present invention is Co9S8And material with carbon element
Complex, other impurity phases do not occur, and crystal formation are good；Fig. 2 is above-mentioned Co9S8The SEM photograph of/carbon composite, from figure
In can be seen that composite is the flower-shaped carbon of a diameter of 1-5 m, this flower-shaped carbon is 0.5-3 m by interconnective radial direction,
Thickness is the carbon nanosheet composition of 5-20 nm, Co9S8Granule is supported on carbon nanosheet equably；The SEM that Fig. 3 amplifies further
Photo, it can be seen that constitute uniform load on the carbon nanosheet of flower-shaped carbon, the Co that particle diameter is 5-70 nm9S8Nano-particle；Fig. 4 is
, there is the mesoporous of 3-50 nm in the pore-size distribution test result of product of the present invention；Fig. 5 is the thermal gravimetric analysis results of product of the present invention,
Through being calculated Co9S8Mass percent content is 77.2%.
Embodiment 2: first by the CoCl of 2.5 mmol2·6H2The hexamethylenetetramine mixing of O and 5 mmol, is dissolved in 20
In the deionized water of mL carbon dioxide removal, preparation obtains mixed solution；Then by p-aminobenzene sulfonic acid and 15 mmol of 15 mmol
NaOH be dissolved in the deionized water of 20 mL carbon dioxide removals and be neutralized reaction, obtain sodium sulfanilate solution；At nitrogen
Under gas shielded, above-mentioned mixed solution and sodium sulfanilate solution are mixed, after stirring, be transferred to the poly-of 50 mL
In the autoclave of tetrafluoroethene substrate, put in baking oven 100oC isothermal reaction 8 h, takes out autoclave the coldest
But to room temperature, it is 7 with 500 mL deionized waters and 200 mL ethanol filtering and washing to filtrate pH value, then by filter cake 70oC
Forced air drying 12 h, obtains the cobalt hydroxide of p-aminobenzene sulfonic acid root intercalation.
By cobalt hydroxide and the 0.1 g sulfur powder mix homogeneously of 0.2 g p-aminobenzene sulfonic acid root intercalation of above-mentioned preparation, put into
Porcelain boat is placed on heating region in the middle of quartz tube furnace, is passed through the purity nitrogen deoxygenation more than 99%, after 30 min, with 10oC/
Min heating rate is heated to 700oC is also incubated 10 h；Then it is slowly dropped to room temperature, bottom porcelain boat, generates black calcining produce
Thing, i.e. obtains flower-like structure Co9S8/ carbon composite.
Embodiment 3: first by the CoSO of 1 mmol4·7H2The hexamethylenetetramine mixing of O and 2 mmol, is dissolved in 20 mL
In the deionized water of carbon dioxide removal, preparation obtains mixed solution；Then by the metanilic acid of 15 mmol and 15 mmol
NaOH is dissolved in the deionized water of 20 mL carbon dioxide removals and is neutralized reaction, obtains sodium m-aminobenzene sulfonate solution；At nitrogen
Under protection, above-mentioned mixed solution and sodium m-aminobenzene sulfonate solution are mixed, after stirring, be transferred to poly-the four of 50 mL
In the autoclave of fluorothene substrate, put in baking oven 120oC isothermal reaction 8 h, takes out autoclave natural cooling
To room temperature, it is 7 with 500 mL deionized waters and 200 mL ethanol filtering and washing to filtrate pH value, then by filter cake 60oC drum
Air-dry dry 20 h, obtain the cobalt hydroxide of metanilic acid root intercalation.
By cobalt hydroxide and the 0.2 g sulfur powder mix homogeneously of 0.2 g metanilic acid root intercalation of above-mentioned preparation, put into
Porcelain boat is placed on heating region in the middle of quartz tube furnace, is passed through the purity argon deoxygenation more than 99%, after 30 min, with 2oC/
Min heating rate is heated to 1000oC is also incubated 2 h；Then it is slowly dropped to room temperature, bottom porcelain boat, generates black calcining produce
Thing, i.e. obtains flower-like structure Co9S8/ carbon composite.
Embodiment 4: first by the CoC of 1 mmol2O4Mix with the hexamethylenetetramine of 2 mmol, be dissolved in 20 mL and take off dioxy
Change preparation in the deionized water of carbon and obtain mixed solution；Then by orthanilic acid and the NaOH of 15 mmol of 15 mmol
It is dissolved in the deionized water of 20 mL carbon dioxide removals and is neutralized reaction, obtain orthanilic acid sodium solution；Protect at nitrogen
Lower above-mentioned mixed solution and orthanilic acid sodium solution are mixed, after stirring, be transferred to the polytetrafluoroethyl-ne of 50 mL
In the autoclave of alkene substrate, put in baking oven 80oC isothermal reaction 24 h, takes out autoclave and naturally cools to room
Temperature, is 7 with 500 mL deionized waters and 200 mL ethanol filtering and washing to filtrate pH value, then by filter cake 70oC air blast is done
Dry 20 h, obtain the cobalt hydroxide of orthanilic acid root intercalation.
By cobalt hydroxide and the 0.2 g sulfur powder mix homogeneously of 0.2 g orthanilic acid root intercalation of above-mentioned preparation, put into
Porcelain boat is placed on heating region in the middle of quartz tube furnace, is passed through the purity argon deoxygenation more than 99%, after 30 min, with 5oC/
Min heating rate is heated to 800oC is also incubated 5 h；Then it is slowly dropped to room temperature, bottom porcelain boat, generates black calcined product,
I.e. obtain flower-like structure Co9S8/ carbon composite.
In order to verify the flower-like structure Co that the above embodiment of the present invention provides further9S8The electrochemistry of/carbon composite
Can, choose above-described embodiment 1 gained flower-like structure Co9S8/ carbon composite, and test its as oxygen reduction catalyst oxygen also
Former reactivity.
By the flower-like structure Co of 2.95 mg9S8/ carbon composite be dispersed in 0.3 mL deionized water, 0.6 mL isopropanol and
0.1 mL mass percent is in the Nafion mixed solution of 5 %；Then ultrasonic for above-mentioned mixed liquor 30 min are obtained black to hang
Supernatant liquid；Take the dispersant liquid drop of 3.75 L with Al2O3On the glass-carbon electrode of polished diameter 3 mm, natural drying.In electrification
Learn and on work station, use three-electrode system to carry out electrochemical property test, use saturated calomel electrode and platinum line as reference electrode
With to electrode, for convenience, current potential is all converted into relative to reversible hydrogen electrode.The KOH electrolyte solution of 0.1 mol/L enters
Row cyclic voltammetry and rotating disk electrode (r.d.e) test.Before test, electrolyte solution leads to nitrogen or oxygen at least 30 min.Rotate
The test of the linear sweep voltammetry curve of disk electrode turns at 1.0-0.2 V (relative to reversible hydrogen electrode), 400 ~ 2500 rpm
Under speed, the speed of sweeping with 5 mV/s is carried out.Fig. 6 is under different rotating speeds, flower-like structure Co9S8The linear sweep voltammetry of/carbon composite
Curve test result, it is seen that electric current density increases along with the increase of rotating speed, this is owing to diffusion length shortens at high speed
Caused, additionally, flower-like structure Co9S8/ carbon composite has high half wave potential and Limited diffusion current density, shows that it has
There is the hydrogen reduction electrocatalysis characteristic of excellence.
Examples detailed above is the citing of the present invention, although disclosing highly preferred embodiment of the present invention and attached for the purpose of illustration
Figure, but it is not intended to limit the present invention, any those of ordinary skill in the art, without departing from the present invention and appended right
In the spirit and scope required, various replacements, to change and modifications be all possible.Therefore, the present invention should not be limited to optimal reality
Execute example and accompanying drawing disclosure of that.
Claims (6)
1. flower-like structure cobalt sulfide/carbon composite, it is characterised in that this composite is by the flower of a diameter of 1-5 micron
Shape carbon and the Co that particle diameter is 5-70 nanometer9S8Granule forms；Wherein, flower-shaped carbon is 0.5-3 micron by interconnective radial direction, thick
The carbon nanosheet composition that degree is 5-20 nanometer, Co9S8Granule is supported on carbon nanosheet equably, Co9S8In the composite
Weight/mass percentage composition is 30-80 %.
2. the preparation method of the flower-like structure cobalt sulfide/carbon composite described in a claim 1, it is characterised in that include
Following steps:
(1) by divalent cobalt ion Co2+Soluble-salt and hexamethylenetetramine mixing, be dissolved in the deionized water of carbon dioxide removal
Middle preparation obtains mixed solution；Under nitrogen protection by above-mentioned mixed solution and organic molecule anion A–Soluble-salt mix
Close, proceed in hydrothermal reaction kettle at 80-120oReact 8-24 hour at a temperature of C；The suspension obtained after reaction is filtered, uses
Deionized water and washing with alcohol filter cake are 7-7.5 to filtrate pH value, then by filter cake at 60-80oC is dried 8-20 hour, obtains
The cobalt hydroxide that organic molecule is anion intercalated；
(2) it is 1-4 by cobalt hydroxide anion intercalated for the organic molecule of preparation in step (1) and sulfur powder according to mass ratio:
The ratio mixing of 1, under an inert atmosphere, by said mixture with 2-10oC/ minute ramp is to 700-1000oC calcines 2-
10 hours, naturally cool to room temperature, i.e. obtain flower-like structure of the present invention cobalt sulfide/carbon composite.
Preparation method the most according to claim 2, it is characterised in that in step (1), described divalent cobalt ion Co2+'s
Soluble-salt is one or more in the nitrate of cobalt, sulfate, oxalates or chloride.
Preparation method the most according to claim 2, it is characterised in that in step (1), bivalence cobalt in described mixed solution
Ion Co2+Concentration be 25-125 mmol/L, described hexamethylenetetramine and described Co2+The ratio of amount of material be 2:1.
Preparation method the most according to claim 2, it is characterised in that in step (1), described organic molecule anion
A-Soluble-salt be one or more in sodium m-aminobenzene sulfonate, sodium sulfanilate, orthanilic acid sodium, and have
Machine small molecule anionic A–With Co2+The ratio of amount of material be 3-15:1.
Preparation method the most according to claim 2, it is characterised in that in step (2), described inert atmosphere be nitrogen or
One in argon.
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| CN106824228A (en) * | 2017-03-21 | 2017-06-13 | 合肥工业大学 | A kind of flower-shaped cobalt sulfide photochemical catalyst and preparation method thereof |
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| CN112563471A (en) * | 2020-12-10 | 2021-03-26 | 潍坊科技学院 | Preparation method of cobalt disulfide/carbon hollow nanoflower composite material and prepared composite material |
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