CN105449230B - A kind of LaCoO3/ N-rGO compounds and its methods for making and using same - Google Patents
A kind of LaCoO3/ N-rGO compounds and its methods for making and using same Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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 LaCoO3/ N redox graphenes (rGO) compound and its methods for making and using same, preparation method are：LaCoO is prepared by sol-gal process respectively first3Graphene oxide (GO) is prepared with improved Hummers methods, then LaCoO is prepared by wet chemistry method in the presence of ammonium hydroxide3/ N rGO compounds；The preparation method is simple, at low cost, is conducive to industrialized production；Prepared LaCoO3/ N rGO compounds as can charge and discharge metal fuel battery hydrogen reduction (ORR) and oxygen (OER) bifunctional catalyst is precipitated, activity height, stability is good, relative to commercial 20wt%Pt/C, LaCoO3/ rGO and LaCoO3, there is better comprehensive performance, show good application prospect.
Description
Technical field
The present invention relates to the LaCoO that (OER) double-function catalyzing is precipitated in a kind of hydrogen reduction (ORR) and oxygen3/ N- oxygen reduction fossils
Black alkene (rGO) compound and its methods for making and using same, belong to electro-catalysis technical field.
Background technology
Continuous growth with human kind sustainable development to green, regenerative resource demand, countries in the world are just sought urgently
Look for the energy stores and conversion equipment efficient and economical with exploitation.Can charge and discharge metal fuel battery since it has high theory
Energy density, it is environmental-friendly, safe the features such as, be known as " green energy resource geared to the 21st century ".
Although however, in recent years can charge and discharge metal fuel battery technology receive much attention, its practical application is not in addition to
Outside the aeronautical field for counting cost, the requirement of business promotion can't be reached, the main reason is that your high-cost gold used
Belong to Pt bases and Ir sills respectively as itself ORR and OER catalyst.Therefore, develop cheap non-precious metal catalyst become can
The widely commercialized top priority of charge and discharge metal fuel battery.Realizing can ORR and OER catalyst in charge and discharge metal fuel battery
Integration, can greatly simplify can charge and discharge metal fuel battery preparation process, foreground is very tempting.In past more than ten year
In, some scientists all over the world are dedicated to ORR the and OER bifunctional catalysts of developing low-cost, efficient and long stability.
Regrettably, there is no so far suitably can practical application bifunctional catalyst.Precious metals pt sill is still considered
It is the best bifunctional catalyst of current comprehensive performance.
Perovskite composite oxide biomolecule expressions are AMO3(A represents rare earth atom, and M indicates transition metal atoms),
However under normal circumstances all there is the oxygen lattice defect of vacancy form in the based composite oxide, accurate expression formula should be
AMO3-x(0.5 ﹤ x ﹤ 0.2 of ﹣).The type and quantity of Lattice Oxygen can be changed by being formed by oxygen lattice defect usually, be helped speed up
Oxygen migration, thus there is higher ORR and OER catalytic activity.Currently, for perovskite composite oxide, main research
Still it concentrates in the exploitation to its ORR catalytic performance, the exploitation of its OER catalytic performance is rarely reported.As can charge and discharge gold
Belong to fuel cell ORR and OER catalyst, most important two defects are low mass activities to perovskite composite oxide at present
And conductivity.Reduce its physical size and it is compound with the substance of bigger serface high conductivity be to solve the two defects and raising
The effective way of its comprehensive performance.
In recent years, rGO is become with its excellent electric conductivity, stability and thermal conductivity and high theoretical specific surface area
A dazzling nova in field of new materials, its Electronic Performance can be further increased by carrying out N doping vario-properties to it.
Invention content
The present invention is for single LaCoO in the prior art3, conductivity low as ORR and OER catalyst activities is low and stablizes
Property poor defect, the first purpose is to be to provide a kind of ORR and OER synthesis catalytic performance to be far above LaCoO3/rGO、
LaCoO3And the novel LaCoO close to 20wt%Pt/C commercial catalysts3/ N-rGO compounds.
Second object of the present invention is to be to provide a kind of ORR and OER synthesis catalytic performance to be far above LaCoO3/rGO、
LaCoO3And the novel LaCoO close to 20wt%Pt/C commercial catalysts3Inexpensive, the easy-operating system of/N-rGO compounds
Preparation Method.
Third object of the present invention is to provide a kind of as can charge and discharge metal fuel battery ORR and OER are difunctional urges
The novel LaCoO of agent3The application of/N-rGO compounds, in alkaline medium, comprehensive catalytic performance is far above LaCoO3/rGO、
LaCoO3And close to 20wt%Pt/C commercial catalysts.
A kind of LaCoO3/ N-rGO compounds, the compound are by cubic phase LaCoO3It is supported on two-dimensional N doping
It is formed on rGO；LaCoO in the compound3, N and rGO mass percent range be respectively 65% -95%,
0.5% -5% and 3% -30%.
LaCoO in the compound3, N and rGO the range of mass percent be respectively preferably 80% -90%, 1% -
3% and 8% -18%.
A kind of LaCoO3The preparation method of/N-rGO compounds, the LaCoO3/ N-rGO compounds are with LaCoO3With
GO is presoma, and during solvent hot preparation, nitrating type graphene is formed under the conditions of solvent heat by the way that ammonium hydroxide is added, and
Form LaCoO3/ N-rGO compounds.
LaCoO in the compound3, N and rGO the range of mass percent be respectively 65% -95%, 0.5% -
5% and 3% -30%.
LaCoO in the compound3, N and rGO the range of mass percent be respectively preferably 80% -90%, 1% -
3% and 8% -18%.
Specifically with LaCoO3It is presoma with GO suspension, the ammonium hydroxide of 0.5-5mL is added in 10-60min of ultrasonic disperse,
It in 140-220 DEG C of 5-15h of solvent thermal reaction, is centrifuged, deionized water washing and freeze-drying, obtains described
LaCoO3/ N-rGO compounds.
Above-mentioned preparation method is preferably such as under type：
Weigh 24.3mg LaCoO3Particle is added in 2mL GO alcohol suspensions, while 60mL absolute ethyl alcohols, room is added
After the lower ultrasound 30min of temperature at 80 DEG C heating stirring 5h, be transferred to after being cooled to room temperature in 80mL autoclaves, and be added dropwise
2mL ammonium hydroxide, solvent thermal reaction 10h under the conditions of 180 DEG C, is cooled to room temperature, finally by centrifugation, deionized water washing, freezing
It is dried to obtain LaCoO3/ N-rGO compounds.
Above-mentioned LaCoO3LaCoO is prepared by sol-gel method in the preparation method of/N-rGO compounds3：
Weigh 0.01mol La (NO3)3·6H2O、0.01mol Co(NO3)3·6H2O and 0.02mol EDTA are dissolved into
In 100mL deionized waters, and 0.03mol citric acids are added, then by the way that NH is added dropwise3·H2It is 8 that O solution, which modulates solution ph,
The solution is stirred continuously in 80 DEG C of water-baths until obtaining the gel of light red；The gel is calcined in 280 DEG C of Muffle furnaces
1h calcines 2h at 800 DEG C after grinding, obtains LaCoO3Particle.
Above-mentioned LaCoO3GO is prepared using improved Hummers methods in the preparation method of/N-rGO compounds：
It weighs 1g crystalline flake graphites and 20g NaCl mixes and grind 15min, vacuum filtration mode is passed through using deionized water
Wash away NaCl；After wet graphite powder is gone to after 60 DEG C are dried in vacuo 30min in 250mL round-bottomed flasks, 23mL 98wt% are added
Concentrated sulfuric acid magnetic agitation for 24 hours, is again heated to 35 DEG C and 0.5g NaNO is added under stiring3, after 5min, suspension is transferred to ice
In bath, it is extremely slowly added into 3g KMnO under stiring4And control system temperature is less than 20 DEG C, then at 35 DEG C and the item of stirring
120min is heated under part, 98 DEG C of stirring 30min are heated to after being slowly added to 46mL deionized waters；When the mixture is cooled to room temperature
Continue to stir 30min, 140mL deionized waters and 10mL 30wt%H is then added2O2；Precipitation is through centrifuging, using 5wt%HCl respectively
Solution and deionized water are redispersed in ultrasound 60min in 1500mL absolute ethyl alcohols after washing 2 to 3 times, obtain brownish black GO and suspend
Liquid.
Above-mentioned LaCoO3The application process of/N-rGO compounds, the LaCoO3/ N-rGO compounds are used as can charge and discharge gold
Belong to fuel cell oxygen reduction and bifunctional catalyst is precipitated in oxygen.
Preparation method of the present invention is simple, at low cost, is conducive to industrialized production；Prepared LaCoO3/ N-rGO compounds
As can charge and discharge metal fuel battery ORR and OER bifunctional catalyst, activity is high, and stability is good, relative to commercial 20wt%
Pt/C、LaCoO3/ rGO and LaCoO3, there is better comprehensive performance, show good application prospect.
Description of the drawings
Fig. 1 is LaCoO in embodiment 1, comparative example 2 and comparative example 33/N-rGO、LaCoO3/ rGO and LaCoO3XRD
Figure, shows the LaCoO containing well-crystallized in three kinds of materials3, characteristic peak that rGO is not detected be since its peak intensity is small and
Content is relatively low；
Fig. 2 is LaCoO in embodiment 13The TEM of/N-rGO schemes, and shows the LaCoO of about 20nm3Particle is evenly dispersed in two
On the rGO lamellas of dimension；
Fig. 3 (a) is LaCoO in embodiment 13The XPS figures of C element, show LaCoO in/N-rGO3C element is in/N-rGO
Exist in the form of C=C, C-O and O=C-O；Fig. 3 (b) is LaCoO in embodiment 13The XPS figures of N element, show N in/N-rGO
It is successfully doped in rGO, and exists in the form of pyrroles's type N and pyridine type N；
Fig. 4 (a) is LaCoO in embodiment 1, comparative example 1, comparative example 2 and comparative example 33/ N-rGO, 20wt%Pt/C,
LaCoO3/ rGO and LaCoO3Linear sweep voltammetry figure, rotating speed 1600rpm, sweep speed 10mV/s, scanning voltage range
For 0.2V to -0.8V (vs.Hg/HgO)；Fig. 4 (b) is LaCoO in embodiment 1 and comparative example 13/ N-rGO and 20 wt%Pt/C
Chronoamperogram, rotating speed 400rpm；
Fig. 5 (a) is LaCoO in embodiment 1, comparative example 1, comparative example 2 and comparative example 33/ N-rGO, 20wt%Pt/C,
LaCoO3/ rGO and LaCoO3Linear sweep voltammetry figure, rotating speed 400rpm, sweep speed 100mV/s, scanning voltage range
For 0.2V to 1.0V (vs.Hg/HgO)；Fig. 5 (b) is LaCoO in embodiment 1, comparative example 1 and comparative example 23/N-rGO、
20wt%Pt/C and LaCoO3The 1st time of/rGO and the 500th time linear sweep voltammetry figure, rotating speed 400rpm.
Specific implementation mode
The present invention is more fully described with embodiment below, but is not intended to limit protection scope of the present invention.
Embodiment 1
LaCoO3The preparation of/N-rGO:
LaCoO is prepared by sol-gel method first3.Weigh 0.01mol La (NO3)3·6H2O、0.01mol Co
(NO3)3·6H2O and 0.02mol EDTA are dissolved into 100mL deionized waters, and 0.03mol citric acids are added.Then pass through drop
Add NH3·H2It is 8 that O solution, which modulates solution ph, which is stirred continuously in 80 DEG C of water-baths until obtaining the solidifying of light red
Glue.The gel is calcined into 1h in 280 DEG C of Muffle furnaces, 2h is calcined at 800 DEG C after grinding, obtains LaCoO3Particle.
GO is prepared using modified Hummers methods.It weighs 1g crystalline flake graphites and 20g NaCl mixes and grind 15min,
NaCl is washed away by vacuum filtration mode using deionized water.Wet graphite powder goes to 250mL after 60 DEG C are dried in vacuo 30min
After in round-bottomed flask, 23mL 98wt% concentrated sulfuric acids magnetic agitation is added for 24 hours, is again heated to 35 DEG C and 0.5g is added under stiring
NaNO3.After 5min, suspension is transferred in ice bath, is extremely slowly added into 3g KMnO under stiring4And control system temperature
Less than 20 DEG C, 120min is heated then at 35 DEG C and under conditions of stirring, is slowly added to be heated to 98 DEG C after 46mL deionized waters to stir
Mix 30min.Continue to stir 30min when the mixture is cooled to room temperature, 140mL deionized waters and 10mL 30wt% is then added
H2O2.Precipitation is redispersed in 1500mL absolute ethyl alcohols after centrifuging, washing 2 to 3 times with 5wt%HCl solution and deionized water respectively
Middle ultrasound 60min, obtains brownish black GO suspension.
Weigh 24.3mg LaCoO3Particle is added in 2mLGO alcohol suspensions, while 60mL absolute ethyl alcohols are added.Room
After the lower ultrasound 30min of temperature at 80 DEG C heating stirring 5h, be transferred to after being cooled to room temperature in 80mL autoclaves, and be added dropwise
2mL ammonium hydroxide, solvent thermal reaction 10h under the conditions of 180 DEG C.It is cooled to room temperature, finally by centrifugation, deionized water washing, freezing
It is dried to obtain LaCoO3/ N-rGO compounds.
Using X-ray diffractometer (XRD, Rigaku-D/Max 2550, Cu-K α, λ=, 40kV, 300mA)
Material phase analysis is carried out to product；Pattern is observed by transmission electron microscope (TEM, JEOL-2010,200kV)；It is penetrated using X-
Photoelectron spectra (XPS, ESCALAB 250Xi, Al-K α) determines the element composition of sample and the chemical energy state of element, uses
XPSPeak4.1 softwares carry out swarming and data processing.
Pass through the pole of rotating disk electrode (r.d.e) (RDE) through CHI760D electrochemical workstations test sample in three-electrode system
Current density of rationing the power supply evaluates its ORR and OER activity.The preparation of working electrode：Weigh 4mg sample dispersions in 1.92mL deionized waters/
Ethyl alcohol (2:1V/V) and in the mixed liquor of 0.08mL Nafion solutions (5wt%), ultrasonic 30min, liquid-transfering gun draws 5 μ L and suspends
Drop is added on the glass-carbon electrode of diameter 5mm, to be measured after 60 DEG C of dryings.During the test, it is platinum electrode, reference electricity to electrode
Extremely Hg/HgO electrodes.When evaluating the ORR activity of sample, electrolyte is the 0.1M KOH solutions of oxygen saturation, and rotating speed is
1600rpm, sweep speed 10mV/s, scanning voltage ranging from 0.2V to -0.8V (vs.Hg/HgO)；In the OER of evaluation sample
When active, electrolyte is 1M KOH solutions, and rotating speed 400rpm, sweep speed 100mV/s, scanning voltage ranging from 0.2V is extremely
1.0V(vs.Hg/HgO).By the stability of chronoamperometry comparative sample ORR catalysis, test voltage is -0.2V (vs.Hg/
HgO), rotating speed 400rpm, electrolyte are the 6M KOH solutions of oxygen saturation, and other conditions are evaluated with the above ORR current densities
Test.Pass through test limits current density after continuous scanning, the stability of comparative sample OER catalysis.
LaCoO3/ N-rGO compounds are -3.76mA/cm as the limiting current density of ORR catalyst2, it is catalyzed as OER
The limiting current density of agent is 73.9mA/cm2.In being evaluated in galvanometer, after 6000s is continuously run, electric current conservation rate is
82.4%.In the evaluation of OER catalytic stabilities, through 500 continuous scannings, limiting current density conservation rate is 83.3%.
Comparative example 1
With commercial 20wt%Pt/C for ORR and OER bifunctional catalysts.
The evaluation method of catalytic performance is the same as embodiment 1.
20wt%Pt/C is -3.88mA/cm as the limiting current density of ORR catalyst2, the pole as OER catalyst
Current density of rationing the power supply is 14.3mA/cm2.In chrono-amperometric evaluation, after 6000s is continuously run, electric current conservation rate is 60.1%.
In the evaluation of OER catalytic stabilities, through 500 continuous scannings, limiting current density conservation rate is 10.5%.
Comparative example 2
As described in Example 1, it is not added with 2mL ammonium hydroxide before solvent heat, prepares LaCoO3/ rGO compounds.
The evaluation method of catalytic performance is the same as embodiment 1.
LaCoO3/ rGO is -2.01mA/cm as the limiting current density of ORR catalyst2, the limit as OER catalyst
Current density is 31.8mA/cm2.In the evaluation of OER catalytic stabilities, through 500 continuous scannings, limiting current density is kept
Rate is 58.5%.
Comparative example 3
By preparing LaCoO in embodiment 13Method prepare LaCoO3。
The evaluation method of catalytic performance is the same as embodiment 1.
LaCoO3Limiting current density as ORR catalyst is about -1.52mA/cm2, the limit electricity as OER catalyst
Current density is 4.1mA/cm.
Claims (2)
1. a kind of LaCoO3/ N-rGO compounds, which is characterized in that
1)LaCoO3The preparation of/N-rGO:
LaCoO is prepared by sol-gel method first3, weigh 0.01mol La (NO3)3·6H2O、0.01mol Co(NO3)3·
6H2O and 0.02mol EDTA are dissolved into 100mL deionized waters, and 0.03mol citric acids are added；Then by the way that NH is added dropwise3·
H2It is 8 that O solution, which modulates solution ph, which is stirred continuously in 80 DEG C of water-baths until the gel of light red is obtained, by this
Gel calcines 1h in 280 DEG C of Muffle furnaces, calcines 2h at 800 DEG C after grinding, obtains LaCoO3Particle；
2) GO is prepared using modified Hummers methods, weighs 1g crystalline flake graphites and 20g NaCl mix and grind 15min, adopts
NaCl is washed away by vacuum filtration mode with deionized water；Wet graphite powder goes to 250mL round bottoms after 60 DEG C are dried in vacuo 30min
After in flask, 23mL 98wt% concentrated sulfuric acids magnetic agitation is added for 24 hours, is again heated to 35 DEG C and 0.5g NaNO is added under stiring3；
After 5min, suspension is transferred in ice bath, is extremely slowly added into 3g KMnO under stiring4And control system temperature is less than
20 DEG C, 120min is heated then at 35 DEG C and under conditions of stirring, 98 DEG C of stirrings are heated to after being slowly added to 46mL deionized waters
30min；Continue to stir 30min when the mixture is cooled to room temperature, 140mL deionized waters and 10mL 30wt% is then added
H2O2；Precipitation is redispersed in 1500mL absolute ethyl alcohols after centrifuging, washing 2 to 3 times with 5wt%HCl solution and deionized water respectively
Middle ultrasound 60min, obtains brownish black GO suspension；
3) 24.3mg LaCoO are weighed3Particle is added in 2mLGO alcohol suspensions, while 60mL absolute ethyl alcohols are added；At room temperature
After ultrasonic 30min at 80 DEG C heating stirring 5h, be transferred to after being cooled to room temperature in 80mL autoclaves, and 2mL ammonia is added dropwise
Water, solvent thermal reaction 10h under the conditions of 180 DEG C；It is cooled to room temperature, finally by centrifugation, deionized water washing, is freeze-dried
To LaCoO3/ N-rGO compounds.
2. a kind of LaCoO described in claim 13The application process of/N-rGO compounds, which is characterized in that the LaCoO3/
N-rGO compounds are used as can the hydrogen reduction of charge and discharge metal fuel battery and oxygen precipitation bifunctional catalyst.
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| CN105692720B (en) * | 2016-04-20 | 2017-04-26 | 西安建筑科技大学 | Preparation method of spinous yttrium cobaltate microballs |
| CN105870467B (en) * | 2016-05-17 | 2019-01-29 | 中南大学 | A kind of hydrogen reduction La (OH)3/ redox graphene composite catalyst and its preparation method and application |
| CN107086130B (en) * | 2017-04-21 | 2019-07-02 | 南京信息工程大学 | A kind of graphene/DyCoO3Composite material and preparation method and application |
| CN107376928A (en) * | 2017-08-04 | 2017-11-24 | 南京邮电大学 | A kind of one-step synthesis method α Fe2O3The method of/Bi compounds |
| CN109126804B (en) * | 2018-08-24 | 2021-05-28 | 广东工业大学 | Boron-doped LaCoO3Bifunctional catalyst, preparation method and application thereof |
| CN109351357B (en) * | 2018-10-16 | 2020-09-22 | 华中科技大学 | Universal method for effectively improving catalytic performance of perovskite catalyst |
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