CN105914353A - Morphology-controlled carbon quantum dot/nickel cobaltate composite electrode material and preparation method - Google Patents
Morphology-controlled carbon quantum dot/nickel cobaltate composite electrode material and preparation method Download PDFInfo
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Abstract
The invention belongs to the technical field of nanometer materials, and particularly relates to a morphology-controlled carbon quantum dot/nickel cobaltate composite electrode material and a preparation method. The preparation method specifically comprises the following steps of (1) dissolving carbon quantum dot powder, nickel nitrate hexahydrate, cobalt nitrate hexahydrate and urea into a mixed solvent of water and ethanol, mixing, putting into a polytetrafluoroethylene-lined reaction kettle, adding foam nickel, sealing, heating to react, cooling, taking out foam nickel, flushing and drying; (2) performing heat treatment on the dried foam nickel, so as to obtain the carbon quantum dot/nickel cobaltate composite electrode material using the foam nickel as a substrate. The preparation method has the advantages that by adjusting the feeding amount of carbon quantum dots, different morphologies of the composite material, such as urchin shape, corolla shape and waxberry shape are formed on the micro structure; the preparation method is simple, the implementing is easy, and the cost is low; the chemical and physical property of obtained material is stable, and the application prospect is good in the fields of electrochemical energy storage and catalyzing.
Description
Technical field
The invention belongs to technical field of nano material, specifically, relate to the carbon quantum dot/cobalt acid nickel of a kind of morphology controllable
Combination electrode material and preparation method.
Background technology
Carbon quantum dot, also known as carbon point or carbon nano dot, is class size Novel Carbon Nanomaterials below 10 nanometers.
As a kind of zero dimensional nanometer materials because excellent solvent dispersion performance, good electric conductivity, hypotoxicity, wide material sources and
Cheap and gradually paid attention to by academia or even industrial quarters.Up to the present, the application of carbon quantum dot is the most all limited to
In fields such as biomarker, senser element, display devices.Comparatively speaking the research in electrochemical energy storage field is also in primary rank
Section, until just starting to show up prominently for 2013.Research work shows, carbon quantum dot can effectively promote metal-oxide material
The high rate performance of material and cyclical stability.As a example by single cobalt acid nickel does positive electrode, it is electrolysis at potassium hydroxide aqueous solution
Liquid, when current density change is promoted to 30A/g from 1A/g, the conservation rate of its capacitance typically about 25% to about 45%,
5000 times loop attenuation just can be to more than 5%, by composite polymeric materials (such as polypyrrole), grapheme material and carbon nanometer
Tube materials etc. can improve the deficiency of cobalt acid nickel material to a certain extent, but effect is limited, and complex exists cost of material and holds high
Expensive, and the source shortcoming such as the most extensive.By contrast, there is not disadvantage mentioned above, and its high-graphitized kernel in carbon quantum dot,
Abundant surface functional group and excellent dispersibility can be effectively increased the wettability of the surface of material and the electronics that material is overall
Electric conductivity, thus high rate performance and the cycle performance of metal-oxide is substantially improved.
Summary of the invention
In order to overcome the deficiencies in the prior art, it is an object of the invention to propose one and change pattern " can be customized "
There is carbon quantum dot/cobalt acid nickel combination electrode material and the preparation method of height ratio capacity.Preparation method of the present invention is simple, passes through
Change the ingredient proportion of carbon quantum dot, can by the microscopic appearance of electrode material from Hemicentrotus seu Strongylocentrotus shape (non-composite), regulate to Mao Lizhuan,
Corolla shape and strawberry-like.
Technical scheme is specifically described as follows.
The present invention provides the preparation method of the carbon quantum dot/cobalt acid nickel combination electrode material of a kind of morphology controllable, specifically walks
Rapid as follows:
(1) mixed solvent that carbon quantum dot powder, Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and carbamide are formed in water and ethanol
Middle mixing, mixing is placed in polytetrafluoroethyllining lining reactor, adds nickel foam, reacts 7 after sealing at a temperature of 85 ~ 95 DEG C
~ 9 hours, cool down afterwards, take out nickel foam and rinse, dry；
(2) nickel foam after drying carries out heat treatment at a temperature of 240 ~ 260 DEG C, obtains the carbon quantum that nickel foam is substrate
Point/cobalt acid nickel combination electrode material.
In the present invention, in step (1), the mol ratio of Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and carbamide is 1:2:12.
In the present invention, in step (1), Nickelous nitrate hexahydrate concentration range in mixed solvent is at 0.02 ~ 0.03mol/L
Between, adjust cabaltous nitrate hexahydrate and the concentration of carbamide the most accordingly.
In the present invention, in step (1), carbon quantum dot by with citric acid, ethylenediamine, Graphene, CNT, to benzene two
Phenol or carbamide are raw material, prepare through hydro-thermal method or electrochemical stripping method, the mean diameter of carbon quantum dot 2.5-3.5nm it
Between.
The carbon quantum dot of the present invention derives from different presomas, and the quantity of surface functional group is not quite similar with kind.With
Time the present invention in use carbon quantum dot, raw material sources non-toxic inexpensive and environmental protection.The carbon quantum dot of the present invention is on pattern
All show as being made up of the amorphous carbon two parts on graphited nucleus and surface.Its nanoparticle mean radius all exists
About 3nm.These nanoparticles contain substantial amounts of hydrophilic functional group in region, surface, including-NH ,-OH ,-COOH etc., it is possible to
Ensure the water solublity of they excellences.In a word, the kernel that the carbon quantum dot of the present invention is high-graphitized, abundant surface functional group and
Excellent dispersibility can be effectively increased the wettability of the surface of material and the electron conduction that material is overall, thus is substantially improved
The high rate performance of metal-oxide and cycle performance.
In the present invention, in step (1), carbon quantum dot powder mass body volume concentrations in mixed solvent is 0.1 ~ 2mg/
mL；
Preferably, carbon quantum dot powder mass body volume concentrations in mixed solvent is 0.25 ~ 1mg/mL.
In the present invention, in step (1), in mixed solvent, volume ratio 1:3 of second alcohol and water ~ 3:1.
In the present invention, in step (2), during heat treatment, first it is warmed up to 240 ~ 260 with the heating rate of 0.5 ~ 2 DEG C/min
DEG C, then it is incubated 1.5 ~ 3 hours.
The present invention also provides for carbon quantum dot/cobalt acid nickel combination electrode material that a kind of above-mentioned preparation method obtains.
Preferably, the carbon quantum dot that the present invention obtains/cobalt acid nickel combination electrode material is Mao Lizhuan, corolla shape or Fructus Myricae rubrae
Shape.The external diameter that its " hair chestnut " stings, the diameter of the just face granule of " petal " thickness and strawberry-like structure is respectively 70-80 nm,
25-35 nm and 20-30 nm, presents the trend successively decreased, and be contrasted is pure cobalt acid nickel material (Hemicentrotus seu Strongylocentrotus shape structure) " sea
Gallbladder " external diameter that stings then reaches 150nm.This demonstrates the chi that can effectively be shortened material components by composite carbon quantum dot
Very little, reduce ion and pass through path, and with the addition of different types of carbon quantum dot and present identical preparation result.
The beneficial effects of the present invention is:
1, preparation method of the present invention is simple, by change carbon quantum dot ingredient proportion will the microscopic appearance of electrode material from sea
Gallbladder shape (not composite carbon quantum dot), regulation is to Mao Lizhuan, corolla shape and strawberry-like；
2, by the carbon quantum dot obtained by composite carbon quantum dot/cobalt acid nickel electrode material, there is high power capacity, high magnification and longevity
Life etc.
Advantage.As a example by the composite that the carbon quantum dot prepared with ethylenediamine, citric acid and cobalt acid nickel are formed, with 3 mol/L
KOH aqueous solution is electrolyte, and under 1 A/g current density condition, specific discharge capacity can reach 2168 F/g, and electric current density carries
After rising to 30 A/g, the conservation rate of capacity remains to reach 75.2%, protects through 10000 circulation electric capacity under 5 A/g electric current densities
Holdup can reach 99.7%.
Accompanying drawing explanation
Fig. 1 is cobalt acid nickel material (A) and three kinds of carbon quantum dot/cobalt acid nickel composite materials (carbon quantum dot throwings in embodiment 1
Doses is 10,20 and 40 mg, respectively corresponding diagram B, C and D) high resolution scanning electromicroscopic photograph and structural model.
Fig. 2 be representative composite material in embodiment 1 (carbon quantum dot inventory is 20 mg, carbon quantum dot/cobalt acid nickel-
2) transmission electron microscope photo.
Fig. 3 is the X-ray diffraction knot of cobalt acid nickel material and three kinds of carbon quantum dot/cobalt acid nickel composite materials in embodiment 1
Really.
Fig. 4 be in embodiment 1 cobalt acid nickel material and three kinds carbon quantum dot/(carbon quantum dot feeds intake cobalt acid nickel composite material
Amount is 10,20 and 40 mg, respectively corresponding diagram A-D) cyclic voltammetry result, sweep speed for 2mV/s-100mV/s, current potential model
Enclose 0-0.65V vs. Hg/HgO.
Fig. 5 be representative composite material in embodiment 1 (carbon quantum dot inventory is 20 mg, carbon quantum dot/cobalt acid nickel-
2) with absorbent charcoal material (specific surface area 1300 m2/ g) assemble asymmetric capacitor system (electrolyte is 3 mol/L KOH,
Potential range 0-1.5V) energy density-power density curve and the super capacitor system that formed with other analog material
Contrast.
Detailed description of the invention
In order to be more fully understood that present disclosure, further illustrate this below in conjunction with specific embodiment and accompanying drawing
Bright.
Embodiment 1
(1) carbon quantum dot is prepared with ethylenediamine and citric acid for raw material
0.1g citric acid, 300 μ L ethylenediamines and 500 μ L water add 50mL polytetrafluoroethyllining lining reactor, 140 DEG C of reactions 4
Hour, add distilled water after being cooled to room temperature and form carbon quantum dot aqueous solution.This aqueous solution adds ethanol settle, obtain
Fluffy solid, collects solid precipitation, again uses alcohol flushing 2-3 time, puts into 40 DEG C of vacuum drying ovens and dries, obtains brown toner
End.
(2) preparation of carbon quantum dot/cobalt acid nickel composite material
1 mmol Nickelous nitrate hexahydrate (analytical pure), 2 mmol cabaltous nitrate hexahydrates (analytical pure) and different amounts of above-mentioned
Carbon amounts
Son select powder (W=10,20 and 40 mg) and is dissolved in 20ml water and 20ml ethanol forms pink and clarifies mixed liquor,
Then add 12 mmol carbamide (analytical pure), after stirring 10 minutes under room temperature, pour 50mL polytetrafluoroethyllining lining reactor into
In, add 1 clean nickel foam (1*2cm), be tamping latter 90 DEG C and react 8 hours.Bubble is taken out after reactor is cooled to room temperature
Foam nickel, rinses rear 60 DEG C of drying (12h) well.The foam nickel sheet being loaded with presoma dried is placed in tube furnace (or Muffle furnace)
In rise to 250 DEG C with the heating rate of 1 DEG C/min and keep after 2 hours, be cooled to room temperature and be i.e. prepared for nickel foam as substrate
It is loaded with different-shape carbon quantum dot/cobalt acid nickel composite material；Corresponding entitled carbon quantum dot/cobalt acid nickel-1, carbon quantum dot/cobalt acid
Nickel-2 and carbon quantum dot/cobalt acid nickel-3.Fig. 1 is that in embodiment 1, cobalt acid nickel material (A) and three kinds of carbon quantum dot/cobalt acid nickel are multiple
The high resolution scanning electromicroscopic photograph of condensation material (carbon quantum dot inventory is 10,20 and 40 mg, respectively corresponding diagram B, C and D) and knot
Structure model, inventory is that the corresponding title of the material that 10,20 and 40 mg obtain is respectively carbon quantum dot/cobalt acid nickel-1, carbon quantum
Point/cobalt acid nickel-2 and carbon quantum dot/cobalt acid nickel-3.Fig. 2 is the transmission electron microscope photo of carbon quantum dot in embodiment 1/cobalt acid nickel-2,
Wherein it can clearly be seen that 400 crystal faces (0.20 nanometer) of 002 crystal face of carbon quantum dot (0.34 nanometer) and cobalt acid nickel, 511
Crystal face (0.16 nanometer), 111 crystal faces (0.47 nanometer), 311 crystal faces (0.24 nanometer), staggered with carbon quantum dot point of cobalt acid nickel granule
Both cloth explanations are combined with each other well.Fig. 3 is that in embodiment 1, cobalt acid nickel material and three kinds of carbon quantum dot/cobalt acid nickel are multiple
The X-ray diffraction result of condensation material, corresponding to the standard card of cobalt acid nickel.Fig. 4 is cobalt acid nickel material and three kinds in embodiment 1
The cyclic voltammetry result of carbon quantum dot/cobalt acid nickel composite material, the speed of sweeping of every kind of sample is 2mV/s, 5mV/s, 10mV/
S, 20mV/s, 50mV/s and 100mV/s, (interior reference is that 1 mol/L KOH is water-soluble to potential range 0-0.65V vs. Hg/HgO
Liquid).Its oxidation-reduction potential interval (is 1 mol/L KOH water relative to interior reference at 0.2-0.3V and 0.35-0.45V respectively
Hydrargyrum/the mercury oxide reference electrode of solution).Fig. 5 is that (carbon quantum dot inventory is 20 to the representative composite material in embodiment 1
Mg, carbon quantum dot/cobalt acid nickel-2) and absorbent charcoal material (specific surface area 1300 m2/ g) assemble asymmetric capacitor system (electricity
Solve liquid be 3 mol/L KOH, potential range 0-1.5V) energy density-power density curve and with other analog material institute group
The super capacitor system contrast become.Can be seen that this cobalt acid nickel composite material phase prepared by easy inexpensive method
Cobalt acid nickel composite material prepared by the expensive material such as ratio uses noble metal, Graphene has higher specific energy and mass ratio
Power, demonstrates more superior application prospect.
Embodiment 2
(1) carbon quantum dot is prepared with p-phenylenediamine for raw material
First measure in the centrifuge tube that 50ml put into by 5ml ethanol, more respectively weigh 0.2g carbamide (analytical pure) and 0.2g not by
The p-phenylenediamine (analytical pure) of oxidation joins in centrifuge tube rapidly, and concussion, until being completely dissolved, forms rufous
Solution.Add 45ml deionized water, mix homogeneously, transfer to mixed liquor, in autoclave (150 ml), seal and preserve.
After first high temperature oven being preheated to 160 DEG C, then reactor is put into reaction 10 hours in baking oven, react complete, natural cooling
To room temperature.Gained solution, utilizes weak ammonia to carry out settling, purification, after obtaining pure carbon quantum dot solution, and 40 DEG C of vacuum drying
Obtain pitchy carbon quantum dot powder.
(2) preparation of carbon quantum dot/cobalt acid nickel composite material
0.8 mmol Nickelous nitrate hexahydrate (analytical pure), 1.6 mmol cabaltous nitrate hexahydrates (analytical pure) and different amounts of
Above-mentioned carbon quantum dot powder (W=10,20 and 40 mg) is dissolved in 10ml water and 30ml ethanol forms pink clarification mixing
Liquid, then adds 9.6 mmol carbamide (analytical pure), pours 50mL polytetrafluoroethyllining lining into anti-under room temperature after stirring 10 minutes
Answer in still, add 1 clean nickel foam (1*2cm), be tamping latter 85 DEG C and react 7 hours.Take after reactor is cooled to room temperature
Go out nickel foam, rinse rear 60 DEG C of drying (12h) well.The foam nickel sheet being loaded with presoma dried is placed in tube furnace (or horse
Not stove) in rise to 260 DEG C with the heating rate of 0.5 DEG C/min and keep after 2 hours, be cooled to room temperature and be i.e. prepared for nickel foam
It is loaded with different-shape carbon quantum dot/cobalt acid nickel composite material for substrate.
Embodiment 3
(1) carbon quantum dot is prepared with polyvinylpyrrolidone for raw material
First the polyvinylpyrrolidone (K-30, analytical pure) by 1g puts into the quartz boat of tube furnace, then arranges temperature and exists
Rising to 400 DEG C from room temperature in 100 minutes, calcining sample 3 hours, reaction naturally rings to room temperature, whole process after terminating
It is an exposure to air completes.Subsequently, the bulk sample grind into powder that will obtain for the first time, add 30mL ethanol and surpass
Sound settles.After this, taking ethanol liquid and be centrifuged purification (15000 revs/min), distillation etc. processes, and is finally obtained carbon
Point pressed powder.
(2) preparation of carbon quantum dot/cobalt acid nickel composite material
0.8 mmol Nickelous nitrate hexahydrate (analytical pure), 1.6 mmol cabaltous nitrate hexahydrates (analytical pure) and different amounts of
Above-mentioned carbon quantum dot powder (W=10,20 and 40 mg) is dissolved in 30ml water and 10ml ethanol forms pink clarification mixing
Liquid, then adds 9.6 mmol carbamide (analytical pure), pours 50mL polytetrafluoroethyllining lining into anti-under room temperature after stirring 10 minutes
Answer in still, add 1 clean nickel foam (1*2cm), be tamping latter 95 DEG C and react 9 hours.Take after reactor is cooled to room temperature
Go out nickel foam, rinse rear 60 DEG C of drying (12h) well.The foam nickel sheet being loaded with presoma dried is placed in tube furnace (or horse
Not stove) in rise to 250 DEG C with the heating rate of 1.5 DEG C/min and keep after 3 hours, be cooled to room temperature and be i.e. prepared for nickel foam
It is loaded with different-shape carbon quantum dot/cobalt acid nickel composite material for substrate.
Embodiment 4
(1) so that alpha-lipoic acid is prepared carbon quantum dot for raw material
First the NaOH of 0.1g is dissolved in 50mL water acquisition alkaline solution, the most again by the alpha-lipoic acid (analytical pure) of 0.5g
It is dissolved in this alkaline solution to obtain a pale yellow solution.Subsequently, proceed to be formed in stainless steel cauldron close by this solution
Place into after closure system and react respectively 19 hours inside the baking oven of 250 DEG C.Finally, the reaction solution of cooling is added weak ammonia
Settle, purification, be dried to obtain carbon quantum dot powder.
(2) preparation of carbon quantum dot/cobalt acid nickel composite material
1.2 mmol Nickelous nitrate hexahydrates (analytical pure), 2.4 mmol cabaltous nitrate hexahydrates (analytical pure) and different amounts of
Above-mentioned carbon quantum dot powder (W=10,20 and 40 mg) is dissolved in 10ml water and 30ml ethanol forms pink clarification mixing
Liquid, then adds 14.4 mmol carbamide (analytical pure), pours 50mL polytetrafluoroethyllining lining into anti-under room temperature after stirring 10 minutes
Answer in still, add 1 clean nickel foam (1*2cm), be tamping latter 95 DEG C and react 9 hours.Take after reactor is cooled to room temperature
Go out nickel foam, rinse rear 60 DEG C of drying (12h) well.The foam nickel sheet being loaded with presoma dried is placed in tube furnace (or horse
Not stove) in rise to 240 DEG C with the heating rate of 1 DEG C/min and keep after 2.5 hours, be cooled to room temperature and be i.e. prepared for nickel foam
It is loaded with different-shape carbon quantum dot/cobalt acid nickel composite material for substrate.
Embodiment 5
(1) carbon quantum dot is prepared with 3-cyclopentanepropanoiacid acid and ethylenediamine for raw material
First the 3-cyclopentanepropanoiacid acid (analytical pure) of 0.5g and the ethylenediamine (analytical pure) of 0.3g are dissolved in the water of 50mL formation thoroughly
Bright
Colourless solution, add 0.1g sodium hydroxide formed mixed-alkali solution.Subsequently, this solution is proceeded to rustless steel anti-
Answer to be formed in still and react respectively 19 hours inside the baking oven placing into 250 DEG C after enclosed system.Finally, the reaction by cooling is molten
Liquid adds ethanol settle, purification, be dried to obtain carbon quantum dot powder.
(2) preparation of carbon quantum dot/cobalt acid nickel composite material
1 mmol Nickelous nitrate hexahydrate (analytical pure), 2 mmol cabaltous nitrate hexahydrates (analytical pure) and different amounts of above-mentioned
Carbon quantum dot powder (W=10,20 and 40 mg) is dissolved in 20ml water and 20ml ethanol forms pink clarification mixed liquor,
Then add 12 mmol carbamide (analytical pure), after stirring 10 minutes under room temperature, pour 50mL polytetrafluoroethyllining lining reactor into
In, add 1 clean nickel foam (1*2cm), be tamping latter 95 DEG C and react 9 hours.Bubble is taken out after reactor is cooled to room temperature
Foam nickel, rinses rear 60 DEG C of drying (12h) well.The foam nickel sheet being loaded with presoma dried is placed in tube furnace (or Muffle furnace)
In rise to 250 DEG C with the heating rate of 2 DEG C/min and keep after 3 hours, be cooled to room temperature and be i.e. prepared for nickel foam as substrate
It is loaded with different-shape carbon quantum dot/cobalt acid nickel composite material.
Embodiment 6
(1) carbon quantum dot is prepared with graphite powder for raw material
1g Nano graphite powder (analytical pure) is scattered in 200mL nitric acid (12 mol/L), and continuous ultrasound 2h (100W, 40KHz),
Then mixture refluxes 48 hours.After being cooled to room temperature, centrifugal 30min obtains supernatant, heating evaporation remove moisture and
Part nitric acid, obtains red brown solid, is the most again dissolved in 50mL deionized water, dialyse 24 hours remove unnecessary acid with
Impurity, concentrates again, and adds weak ammonia and settle, and purification, lyophilization obtains brown-red powder.
(2) preparation of carbon quantum dot/cobalt acid nickel composite material
0.8 mmol Nickelous nitrate hexahydrate (analytical pure), 1.6 mmol cabaltous nitrate hexahydrates (analytical pure) and different amounts of
Above-mentioned carbon quantum dot powder (W=10,20 and 40 mg) is dissolved in 20ml water and 20ml ethanol forms pink clarification mixing
Liquid, then adds 12 mmol carbamide (analytical pure), pours the reaction of 50mL polytetrafluoroethyllining lining under room temperature after stirring 10 minutes into
In still, add 1 clean nickel foam (1*2cm), be tamping latter 95 DEG C and react 9 hours.Take out after reactor is cooled to room temperature
Nickel foam, rinses rear 60 DEG C of drying (12h) well.The foam nickel sheet being loaded with presoma dried is placed in tube furnace (or Muffle
Stove) in rise to 250 DEG C with the heating rate of 2 DEG C/min and keep after 3 hours, be cooled to room temperature and be i.e. prepared for nickel foam as base
The end be loaded with different-shape carbon quantum dot/cobalt acid nickel composite material.
Embodiment 7
(1) carbon quantum dot is prepared with citric acid for raw material
100g citric acid (analytical pure) powder calcines 48h in high pure nitrogen atmosphere tube type stove, and (calcining heat 800 DEG C, heat up speed
Rate
5 DEG C/min) remaining solid powder is dissolved in water after add weak ammonia settle, purification, be dried to obtain carbon quantum dot powder
End.
(2) preparation of carbon quantum dot/cobalt acid nickel composite material
1 mmol Nickelous nitrate hexahydrate (analytical pure), 2 mmol cabaltous nitrate hexahydrates (analytical pure) and different amounts of above-mentioned
Carbon quantum dot powder (W=10,20 and 40 mg) is dissolved in 20ml water and 20ml ethanol forms pink clarification mixed liquor,
Then add 12 mmol carbamide (analytical pure), after stirring 10 minutes under room temperature, pour 50mL polytetrafluoroethyllining lining reactor into
In, add 1 clean nickel foam (1*2cm), be tamping latter 85 DEG C and react 8 hours.Bubble is taken out after reactor is cooled to room temperature
Foam nickel, rinses rear 60 DEG C of drying (12h) well.The foam nickel sheet being loaded with presoma dried is placed in tube furnace (or Muffle furnace)
In rise to 260 DEG C with the heating rate of 1 DEG C/min and keep after 3 hours, be cooled to room temperature and be i.e. prepared for nickel foam as substrate
It is loaded with different-shape carbon quantum dot/cobalt acid nickel composite material.
Embodiment 8
(1) carbon quantum dot is prepared with SWCN for raw material
50mg SWCN (purity 90%) is scattered in 5mL concentrated nitric acid and 5mL dense perchloric acid mixed liquor, and mixing is all
It is transferred in reactor 100 DEG C after even react 24 hours, is cooled to room temperature and then adds 50mL deionized water and add dilute ammonia
Water settles, purification, is dried to obtain carbon quantum dot powder.
(2) preparation of carbon quantum dot/cobalt acid nickel composite material
0.8 mmol Nickelous nitrate hexahydrate (analytical pure), 1.6 mmol cabaltous nitrate hexahydrates (analytical pure) and different amounts of
Above-mentioned carbon quantum dot powder (W=10,20 and 40 mg) is dissolved in 20ml water and 20ml ethanol forms pink clarification mixing
Liquid, then adds 9.6 mmol carbamide (analytical pure), pours 50mL polytetrafluoroethyllining lining into anti-under room temperature after stirring 10 minutes
Answer in still, add 1 clean nickel foam (1*2cm), be tamping latter 95 DEG C and react 9 hours.Take after reactor is cooled to room temperature
Go out nickel foam, rinse rear 60 DEG C of drying (12h) well.The foam nickel sheet being loaded with presoma dried is placed in tube furnace (or horse
Not stove) in rise to 260 DEG C with the heating rate of 2 DEG C/min and keep after 1.5 hours, be cooled to room temperature and be i.e. prepared for nickel foam
It is loaded with different-shape carbon quantum dot/cobalt acid nickel composite material for substrate.
Embodiment 9
(1) so that polymine is prepared carbon quantum dot for raw material
First measure in the centrifuge tube that 5ml aq. polyethyleneimine (50%, analytical pure) puts into 50ml, add 0.5mg pair
Put into after Benzodiazepines (analytical pure) in 40 DEG C of calorstats aging 24 hours, after taking-up, insert 180 DEG C of reactions 12 in reactor
Hour, add DMF after adding 50ml pure water and settle, purification, it is dried to obtain carbon quantum dot powder.
(2) preparation of carbon quantum dot/cobalt acid nickel composite material
1 mmol Nickelous nitrate hexahydrate (analytical pure), 2 mmol cabaltous nitrate hexahydrates (analytical pure) and different amounts of above-mentioned
Carbon quantum dot powder (W=10,20 and 40 mg) is dissolved in 30ml water and 10ml ethanol forms pink clarification mixed liquor,
Then add 12 mmol carbamide (analytical pure), after stirring 10 minutes under room temperature, pour 50mL polytetrafluoroethyllining lining reactor into
In, add 1 clean nickel foam (1*2cm), be tamping latter 95 DEG C and react 9 hours.Bubble is taken out after reactor is cooled to room temperature
Foam nickel, rinses rear 60 DEG C of drying (12h) well.The foam nickel sheet being loaded with presoma dried is placed in tube furnace (or Muffle furnace)
In rise to 240 DEG C with the heating rate of 2.5 DEG C/min and keep after 2 hours, be cooled to room temperature and be i.e. prepared for nickel foam as substrate
Be loaded with different-shape carbon quantum dot/cobalt acid nickel composite material.
Embodiment 10
(1) carbon quantum dot is prepared with hydroquinone and ethylenediamine for raw material
0.1g hydroquinone (analytical pure), 300 μ L ethylenediamine (analytical pure) and 10 mL water add in 50mL politef
Lining
Reactor, 180 DEG C are reacted 12 hours, add distilled water diluting carbon quantum dot aqueous solution after being cooled to room temperature.This is water-soluble
Liquid adds ethanol settle, purification, be dried to obtain carbon quantum dot powder.
(2) preparation of carbon quantum dot/cobalt acid nickel composite material
1 mmol Nickelous nitrate hexahydrate (analytical pure), 2 mmol cabaltous nitrate hexahydrates (analytical pure) and different amounts of above-mentioned
Carbon quantum dot powder (W=10,20 and 40 mg) is dissolved in 10ml water and 30ml ethanol forms pink clarification mixed liquor,
Then add 12 mmol carbamide (analytical pure), after stirring 10 minutes under room temperature, pour 50mL polytetrafluoroethyllining lining reactor into
In, add 1 clean nickel foam (1*2cm), be tamping latter 80 DEG C and react 9 hours.Bubble is taken out after reactor is cooled to room temperature
Foam nickel, rinses rear 60 DEG C of drying (12h) well.The foam nickel sheet being loaded with presoma dried is placed in tube furnace (or Muffle furnace)
In rise to 250 DEG C with the heating rate of 2 DEG C/min and keep after 2.5 hours, be cooled to room temperature and be i.e. prepared for nickel foam as substrate
Be loaded with different-shape carbon quantum dot/cobalt acid nickel composite material.
The electrochemical energy storage performance test of the different samples prepared by embodiment 1-10 is shown in Table 1.
Table 1
Note: 1. test condition is three electrode test systems, the nickel foam being loaded with composite is Electrode, and platinized platinum is right
Electrode, hydrargyrum/mercuric oxide electrode (1 mol/L KOH aqueous solution is interior reference liquid) is reference electrode, and electrolyte is that 3M KOH is water-soluble
Liquid, test voltage scope 0-0.5V vs. Hg/HgO.2. asterisk is labeled as the more excellent sample of electrochemical energy storage performance.
Fig. 4 be in embodiment 1 cobalt acid nickel material and three kinds carbon quantum dot/(carbon quantum dot feeds intake cobalt acid nickel composite material
Amount is 10,20 and 40 mg, respectively corresponding diagram A-D) cyclic voltammetry result, sweep speed for 2mV/s-100mV/s, current potential model
Enclose 0-0.65V vs. Hg/HgO.
Representative composite material (carbon quantum dot inventory is 20 mg, carbon quantum dot/cobalt acid nickel-2) in embodiment 1 with
Absorbent charcoal material (specific surface area 1300 m2/ g) (electrolyte is 3 mol/L KOH, current potential for the asymmetric capacitor system that assembles
Scope 0-1.5V) energy density-power density curve and the super capacitor system contrast that formed with other analog material
See Fig. 5.Representative composite material (carbon quantum dot inventory is 20 mg) in embodiment 1 and absorbent charcoal material (specific surface area
1300 m2/ g) electrochemical performance data of full battery that assembles is as shown in table 2.
Table 2
| (electric current is close than electric capacity for quality Degree 1A/g) | High rate performance (electric current density 1A/ g-30A/g) | (electric current is close for maximum energy-density Degree 1A/g) | (electric current is close for maximum power density Degree 30A/g) | Cycle performance (electric current density 30A/g, circulation Number of times 5000 times) |
| 139 F/g | 61.1% | 43.2 Wh/kg | 4500.6 W/kg | 99.96% |
Claims (10)
1. the preparation method of the carbon quantum dot of a morphology controllable/cobalt acid nickel combination electrode material, it is characterised in that concrete steps
As follows:
(1) mixed solvent that carbon quantum dot powder, Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and carbamide are formed in water and ethanol
Middle mixing, mixing is placed in polytetrafluoroethyllining lining reactor, adds nickel foam, reacts 7 after sealing at a temperature of 85 ~ 95 DEG C
~ 9 hours, cool down afterwards, take out nickel foam and rinse, dry；
(2) nickel foam after drying carries out heat treatment at 240 ~ 260 DEG C, obtains carbon quantum dot/cobalt that nickel foam is substrate
Acid nickel combination electrode material.
Preparation method the most according to claim 1, it is characterised in that in step (1), Nickelous nitrate hexahydrate, six hydration nitre
The mol ratio of acid cobalt and carbamide is 1:2:12.
Preparation method the most according to claim 1, it is characterised in that in step (1), Nickelous nitrate hexahydrate is at mixed solvent
In concentration range between 0.02 ~ 0.03mol/L, adjust cabaltous nitrate hexahydrate and the concentration of carbamide the most accordingly.
Preparation method the most according to claim 1, it is characterised in that in step (1), carbon quantum dot by with citric acid,
Ethylenediamine, Graphene, CNT, hydroquinone or carbamide are raw material, prepare through hydro-thermal method or electrochemical stripping method, carbon
The mean diameter of quantum dot is between 2.5-3.5nm.
Preparation method the most according to claim 1, it is characterised in that in step (1), carbon quantum dot powder is at mixed solvent
In mass body volume concentrations be 0.1 ~ 2mg/mL.
Preparation method the most according to claim 1 or 5, it is characterised in that carbon quantum dot powder matter in mixed solvent
Amount volumetric concentration is 0.25 ~ 1mg/mL.
Preparation method the most according to claim 1, it is characterised in that in step (1), in mixed solvent, second alcohol and water
Volume ratio 1:3 ~ 3:1.
Preparation method the most according to claim 1, it is characterised in that in step (2), during heat treatment, first with 0.5 ~ 2 DEG C/
Minute heating rate be warmed up to 240 ~ 260 DEG C, then be incubated 1.5 ~ 3 hours.
9. carbon quantum dot/cobalt acid nickel combination electrode material that a preparation method according to claim 1 obtains.
Carbon quantum dot the most according to claim 9/cobalt acid nickel combination electrode material, it is characterised in that its be Mao Lizhuan,
Corolla shape or strawberry-like.
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