CN105914353B - The carbon quantum dot of morphology controllable/cobalt acid nickel combination electrode material and preparation method - Google Patents
The carbon quantum dot of morphology controllable/cobalt acid nickel combination electrode material and preparation method Download PDFInfo
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- CN105914353B CN105914353B CN201610296455.1A CN201610296455A CN105914353B CN 105914353 B CN105914353 B CN 105914353B CN 201610296455 A CN201610296455 A CN 201610296455A CN 105914353 B CN105914353 B CN 105914353B
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention belongs to technical field of nano material, the carbon quantum dot/cobalt acid nickel combination electrode material and preparation method of specially a kind of morphology controllable.Preparation method of the invention is specific as follows: (1) carbon quantum dot powder, Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and urea being dissolved in the in the mixed solvent that water and ethyl alcohol are formed, mixing is placed in polytetrafluoroethyllining lining reaction kettle, and nickel foam is added, reaction is heated after sealing, and nickel foam flushing, drying are taken out after cooling；(2) nickel foam after drying is heat-treated to obtain using nickel foam as the carbon quantum dot of substrate/cobalt acid nickel combination electrode material.The present invention forms composite material in microstructure from sea urchin shape, the different pattern such as corolla shape to strawberry-like by adjusting the inventory of carbon quantum dot.Preparation method is simple by the present invention, low in cost；The chemical physical property of resulting materials is stablized, and has a good application prospect in electrochemical energy storage and catalytic field.
Description
Technical field
The invention belongs to technical field of nano material, specifically, are related to a kind of carbon quantum dot/cobalt acid nickel of morphology controllable
Combination electrode material and preparation method.
Background technique
Carbon quantum dot, also known as carbon dots or carbon nano dot are a kind of sizes in 10 nanometers of Novel Carbon Nanomaterials below.
As a kind of zero dimensional nanometer materials because of excellent solvent-dispersible energy, good electric conductivity, hypotoxicity, it is from a wealth of sources and
The cheap and gradually attention by academia or even industry.Up to the present, the application of carbon quantum dot is all limited to mostly
In biomarker, senser element, the fields such as display device.In comparison electrochemical energy storage field research also in primary rank
Section, just started to show up prominently until 2013.Research work shows that carbon quantum dot can effectively promote metal oxide material
The high rate performance and cyclical stability of material.It is electrolysis in potassium hydroxide aqueous solution so that single cobalt acid nickel does positive electrode as an example
Liquid, when current density change is promoted to 30A/g from 1A/g, the conservation rate of capacitance generally 25% or so to 45% or so,
5000 times loop attenuation can be to 5% or more, by composite polymeric materials (such as polypyrrole), grapheme material and carbon nanometer
Tube material etc. can improve the deficiency of cobalt acid nickel material to a certain extent, but effect is limited, and there are cost of material to hold high for compound
The disadvantages of expensive, and source is not extensive.In contrast, carbon quantum dot and disadvantage mentioned above is not present, and its high-graphitized kernel,
Surface functional group abundant and excellent dispersibility can effectively increase the electronics of the wettability of the surface and material entirety of material
Electric conductivity, so that the high rate performance and cycle performance of metal oxide be substantially improved.
Summary of the invention
For overcome the deficiencies in the prior art, it is an object of the invention to propose that one kind " can customize " to change pattern
Carbon quantum dot with height ratio capacity/cobalt acid nickel combination electrode material and preparation method.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 sea urchin shape (non-composite), be adjusted to Mao Lizhuan,
Corolla shape and strawberry-like.
Technical solution of the present invention is specifically described as follows.
The present invention provides a kind of carbon quantum dot/cobalt acid nickel combination electrode material preparation method of morphology controllable, specific to walk
It is rapid as follows:
(1) mixing for forming carbon quantum dot powder, Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and urea in water and ethyl alcohol
It is mixed in solvent, mixing is placed in polytetrafluoroethyllining lining reaction kettle, nickel foam is added, after sealing at a temperature of 85 ~ 95 DEG C
Reaction 7 ~ 9 hours, cools down later, takes out nickel foam and rinses, dries；
(2) nickel foam after drying is heat-treated at a temperature of 240 ~ 260 DEG C, obtains the carbon amounts that nickel foam is substrate
Sub- point/cobalt acid nickel combination electrode material.
In the present invention, in step (1), the molar ratio of Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and urea is 1:2:12.
In the present invention, in step (1), Nickelous nitrate hexahydrate in the mixed solvent concentration range in 0.02 ~ 0.03mol/L
Between, thus accordingly adjust the concentration of cabaltous nitrate hexahydrate and urea.
In the present invention, in step (1), carbon quantum dot by with citric acid, ethylenediamine, graphene, carbon nanotube, to benzene two
Phenol or urea are raw material, are prepared through hydro-thermal method or electrochemical stripping method, the average grain diameter of carbon quantum dot 2.5-3.5nm it
Between.
Carbon quantum dot of the invention derives from different presomas, and quantity and the type of surface functional group are not quite similar.Together
When the present invention used in carbon quantum dot, raw material sources non-toxic inexpensive and environmentally protective.Carbon quantum dot of the invention is both topographically
It all shows as being made of the amorphous carbon two parts on graphited nucleus and surface.Its nanoparticle mean radius all exists
3nm or so.These nanoparticles contain a large amount of hydrophilic functional group in surface region, can including-NH ,-OH ,-COOH etc.
Guarantee their excellent water solubilitys.In short, the kernel that carbon quantum dot of the invention is high-graphitized, surface functional group abundant and
Excellent dispersibility can effectively increase the electron conduction of the wettability of the surface and material entirety of material, to be substantially improved
The high rate performance and cycle performance of metal oxide.
In the present invention, in step (1), carbon quantum dot powder is 0.1 ~ 2mg/ in the mass-volume concentration of in the mixed solvent
mL；
Preferably, carbon quantum dot powder is 0.25 ~ 1mg/mL in the mass-volume concentration of in the mixed solvent.
In the present invention, in step (1), in the mixed solvent, volume ratio 1:3 ~ 3:1 of second alcohol and water.
In the present invention, in step (2), when heat treatment, 240 ~ 260 first are warming up to 0.5 ~ 2 DEG C/min of heating rate
DEG C, then keep the temperature 1.5 ~ 3 hours.
The present invention also provides a kind of carbon quantum dot that above-mentioned preparation method obtains/cobalt acid nickel combination electrode materials.
Preferably, the carbon quantum dot that the present invention obtains/cobalt acid nickel combination electrode material is in Mao Lizhuan, corolla shape or red bayberry
Shape.The diameter of the just face particle of the outer diameter of its " Mao Li " thorn, " petal " thickness and strawberry-like structure is respectively 70-80 nm,
25-35 nm and 20-30 nm, shows the trend successively decreased, and what is be contrasted is pure cobalt acid nickel material (sea urchin shape structure) " sea
The outer diameter of gallbladder " thorn then reaches 150nm.This, which shows, can effectively shorten the rulers of material components by compound carbon quantum dot
It is very little, reduce ion passage path, and be added to different types of carbon quantum dot and show identical preparation result.
The beneficial effects of the present invention are:
1, preparation method of the present invention is simple, by changing the ingredient proportion of carbon quantum dot i.e. by the microscopic appearance of electrode material
From sea
Gallbladder shape (not compound carbon quantum dot), is adjusted to Mao Lizhuan, corolla shape and strawberry-like；
2, by the obtained carbon quantum dot of compound carbon quantum dot/cobalt acid nickel electrode material have high capacity, high magnification and
Long-life etc.
Advantage.By taking the composite material formed with ethylenediamine, the carbon quantum dot of citric acid preparation and cobalt acid nickel as an example, with 3
Mol/L KOH aqueous solution is electrolyte, and specific discharge capacity can achieve 2168 F/g, electric current under 1 A/g current density condition
The conservation rate that density is promoted to capacity after 30 A/g remains to reach 75.2%, by 10000 circulations under 5 A/g current densities
Capacity retention can achieve 99.7%.
Detailed description of the invention
Fig. 1 is that (carbon quantum dot is thrown for cobalt acid nickel material (A) and three kinds of carbon quantum dots/cobalt acid nickel composite material in embodiment 1
Doses be 10,20 and 40 mg, respectively correspond figure B, C and D) high resolution scanning electromicroscopic photograph and structural model.
Fig. 2 be in embodiment 1 representative composite material (carbon quantum dot inventory be 20 mg, carbon quantum dot/cobalt acid nickel-
2) transmission electron microscope photo.
Fig. 3 is cobalt acid nickel material and three kinds of carbon quantum dots/cobalt acid nickel composite material X-ray diffraction knot in embodiment 1
Fruit.
Fig. 4 is cobalt acid nickel material and three kinds of carbon quantum dots in embodiment 1/(carbon quantum dot feeds intake cobalt acid nickel composite material
Amount be 10,20 and 40 mg, respectively correspond figure A-D) cyclic voltammetry as a result, sweep speed be 2mV/s-100mV/s, current potential model
Enclose 0-0.65V vs. Hg/HgO.
Fig. 5 be in embodiment 1 representative composite material (carbon quantum dot inventory be 20 mg, carbon quantum dot/cobalt acid nickel-
2) with absorbent charcoal material (1300 m of specific surface area2/ g) assembling asymmetric capacitor system (electrolyte be 3 mol/L KOH,
Potential range 0-1.5V) energy density-power density curve and with super capacitor system composed by other analog materials
Comparison.
Specific embodiment
In order to better understand the content of the present invention, this hair is further illustrated below with reference to specific embodiment and attached drawing
It is bright.
Embodiment 1
(1) carbon quantum dot is prepared using ethylenediamine and citric acid as raw material
0.1g citric acid, 300 μ L ethylenediamines and 500 μ L water addition 50mL polytetrafluoroethyllining lining reaction kettle, 140 DEG C
Reaction 4 hours is added distilled water and forms carbon quantum dot aqueous solution after being cooled to room temperature.Ethyl alcohol is added in this aqueous solution to be sunk
Drop obtains fluffy solid, collects solid precipitating, is rinsed 2-3 times with ethyl alcohol again, is put into 40 DEG C of vacuum drying oven drying, obtains palm fibre
Brown powder.
(2) carbon quantum dot/cobalt acid nickel composite material preparation
1 mmol Nickelous nitrate hexahydrate (analysis pure), 2 mmol cabaltous nitrate hexahydrates (analysis is pure) and different amounts of
Above-mentioned carbon amounts
Son point powder (W=10,20 and 40 mg) is dissolved in 20ml water and 20ml ethyl alcohol forms pink clarification mixing
Liquid is then added 12 mmol urea (analysis is pure), stirs pour into the reaction of 50mL polytetrafluoroethyllining lining after ten minutes at room temperature
In kettle, 1 clean nickel foam (1*2cm) is added, is reacted 8 hours for 90 DEG C after being tamping.It is taken out after reaction kettle is cooled to room temperature
Nickel foam, 60 DEG C of drying (12h) after rinsing well.The foam nickel sheet for being loaded with presoma of drying is placed in tube furnace (or Muffle
Furnace) in 1 DEG C/min of heating rate rise to 250 DEG C keep 2 hours after, be cooled to room temperature and be prepared for using nickel foam as base
Bottom 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 cobalt acid nickel material (A) and three kinds of carbon quantum dots/cobalt acid in embodiment 1
The high resolution scanning electromicroscopic photograph of nickel composite material (carbon quantum dot inventory is 10,20 and 40 mg, respectively corresponds figure B, C and D)
And structural model, the correspondence title for the material that inventory 10,20 and 40 mg are obtained is respectively carbon quantum dot/cobalt acid nickel -1, carbon
Quantum dot/cobalt acid nickel -2 and carbon quantum dot/cobalt acid nickel -3.Fig. 2 is carbon quantum dot in embodiment 1/cobalt acid nickel -2 transmission electron microscope
Photo, wherein it can clearly be seen that 002 crystal face (0.34 nanometer) and 400 crystal faces of cobalt acid nickel of carbon quantum dot (0.20 receives
Rice), 511 crystal faces (0.16 nanometer), 111 crystal faces (0.47 nanometer), 311 crystal faces (0.24 nanometer), cobalt acid nickel particle and carbon quantum
Dot interlace distribution illustrates that the two is combined with each other well.Fig. 3 be cobalt acid nickel material and three kinds of carbon quantum dots in embodiment 1/
The X-ray diffraction of cobalt acid nickel composite material is as a result, correspond to the standard card of cobalt acid nickel.Fig. 4 is cobalt acid nickel material in embodiment 1
And three kinds of carbon quantum dots/cobalt acid nickel composite material cyclic voltammetry as a result, every kind of sample sweep speed be 2mV/s,
5mV/s, 10mV/s, 20mV/s, 50mV/s and 100mV/s, (interior reference is 1 mol/ to potential range 0-0.65V vs. Hg/HgO
L KOH aqueous solution).Its oxidation-reduction potential section (is respectively 1 relative to interior reference in 0.2-0.3V and 0.35-0.45V
Mercury/mercury oxide reference electrode of mol/L KOH aqueous solution).Fig. 5 is representative composite material (the carbon quantum dot throwing in embodiment 1
Doses is 20 mg, carbon quantum dot/cobalt acid nickel -2) and absorbent charcoal material (1300 m of specific surface area2/ g) assembling asymmetric capacitor
Energy density-power density curve of body system (electrolyte be 3 mol/L KOH, potential range 0-1.5V) and to it is other similar
The comparison of super capacitor system composed by material.It can be seen that this cobalt acid nickel being prepared by easy inexpensive method is multiple
Condensation material, which is compared, uses noble metal, and the cobalt acid nickel composite material of the expensive materials such as graphene preparation has higher quality specific energy
With quality specific power, more superior application prospect is shown.
Embodiment 2
(1) carbon quantum dot is prepared by raw material of p-phenylenediamine
It first measures 5ml ethyl alcohol to be put into the centrifuge tube of 50ml, then weigh 0.2g urea (analysis is pure) and 0.2g respectively not having
Quilt
The p-phenylenediamine (analysis is pure) of oxidation is rapidly added in centrifuge tube, until being completely dissolved, formation is reddish brown for concussion
The solution of color.45ml deionized water is added, is uniformly mixed, mixed liquor is transferred in autoclave (150 ml), sealing
It saves.After high temperature oven is first preheated to 160 DEG C, then reaction kettle is put into baking oven and reacts 10 hours, end of reaction is natural
It is cooled to room temperature.Acquired solution is settled using weak aqua ammonia, is purified, after obtaining pure carbon quantum dot solution, 40 DEG C of vacuum
It is drying to obtain dark brown carbon quantum dot powder.
(2) carbon quantum dot/cobalt acid nickel composite material preparation
0.8 mmol Nickelous nitrate hexahydrate (analysis is pure), 1.6 mmol cabaltous nitrate hexahydrates (analysis is pure) and difference
The above-mentioned carbon quantum dot powder (W=10,20 and 40 mg) of amount is dissolved in 10ml water and 30ml ethyl alcohol forms pink clarification
Mixed liquor is then added 9.6 mmol urea (analysis is pure), stirs poured into 50mL polytetrafluoroethylene (PTFE) after ten minutes at room temperature
It serves as a contrast in reaction kettle, 1 clean nickel foam (1*2cm) is added, reacted 7 hours for 85 DEG C after being tamping.Reaction kettle is cooled to room temperature
After take out nickel foam, rinse well after 60 DEG C of drying (12h).The foam nickel sheet for being loaded with presoma of drying is placed in tube furnace
After rising to 260 DEG C of holdings 2 hours with 0.5 DEG C/min of heating rate in (or Muffle furnace), it is cooled to room temperature and is prepared for steep
Foam nickel is loaded with different-shape carbon quantum dot/cobalt acid nickel composite material for substrate.
Embodiment 3
(1) carbon quantum dot is prepared by raw material of polyvinylpyrrolidone
First the polyvinylpyrrolidone of 1g (K-30 is analyzed pure) is put into the quartz boat of tube furnace, then temperature is set
?
400 DEG C are risen to from room temperature in 100 minutes, calcining sample 3 hours, naturally rings to room temperature after reaction, entirely
Process, which is an exposure to, to be completed in air.Then, the bulk sample grind into powder that will be obtained for the first time, add 30mL ethyl alcohol into
Row ultrasonic sedimentation.After this, ethanol liquid is taken to carry out centrifugal purification (15000 revs/min), the processing such as distillation is final to obtain
Carbon dots solid powders.
(2) carbon quantum dot/cobalt acid nickel composite material preparation
0.8 mmol Nickelous nitrate hexahydrate (analysis is pure), 1.6 mmol cabaltous nitrate hexahydrates (analysis is pure) and difference
The above-mentioned carbon quantum dot powder (W=10,20 and 40 mg) of amount is dissolved in 30ml water and 10ml ethyl alcohol forms pink clarification
Mixed liquor is then added 9.6 mmol urea (analysis is pure), stirs poured into 50mL polytetrafluoroethylene (PTFE) after ten minutes at room temperature
It serves as a contrast in reaction kettle, 1 clean nickel foam (1*2cm) is added, reacted 9 hours for 95 DEG C after being tamping.Reaction kettle is cooled to room temperature
After take out nickel foam, rinse well after 60 DEG C of drying (12h).The foam nickel sheet for being loaded with presoma of drying is placed in tube furnace
After rising to 250 DEG C of holdings 3 hours with 1.5 DEG C/min of heating rate in (or Muffle furnace), it is cooled to room temperature and is prepared for steep
Foam nickel is loaded with different-shape carbon quantum dot/cobalt acid nickel composite material for substrate.
Embodiment 4
(1) to prepare carbon quantum dot as raw material to alpha-lipoic acid
First the NaOH of 0.1g is dissolved in 50mL water and obtains alkaline solution, then again by the alpha-lipoic acid of 0.5g (analysis is pure)
This alkaline solution is dissolved in obtain a pale yellow solution.Then, this solution is transferred to shape in stainless steel cauldron
19 hours are reacted respectively at the baking oven the inside for placing into 250 DEG C after enclosed system.Finally, cooling reaction solution is added dilute
Ammonium hydroxide is settled, and purifying is dried to obtain carbon quantum dot powder.
(2) carbon quantum dot/cobalt acid nickel composite material preparation
1.2 mmol Nickelous nitrate hexahydrates (analysis is pure), 2.4 mmol cabaltous nitrate hexahydrates (analysis is pure) and difference
The above-mentioned carbon quantum dot powder (W=10,20 and 40 mg) of amount is dissolved in 10ml water and 30ml ethyl alcohol forms pink clarification
Mixed liquor is then added 14.4 mmol urea (analysis is pure), stirs poured into 50mL polytetrafluoroethylene (PTFE) after ten minutes at room temperature
It serves as a contrast in reaction kettle, 1 clean nickel foam (1*2cm) is added, reacted 9 hours for 95 DEG C after being tamping.Reaction kettle is cooled to room temperature
After take out nickel foam, rinse well after 60 DEG C of drying (12h).The foam nickel sheet for being loaded with presoma of drying is placed in tube furnace
After rising to 240 DEG C of holdings 2.5 hours with 1 DEG C/min of heating rate in (or Muffle furnace), it is cooled to room temperature and is prepared for steep
Foam nickel is loaded with different-shape carbon quantum dot/cobalt acid nickel composite material for substrate.
Embodiment 5
(1) carbon quantum dot is prepared using 3- cyclopentanepropanoiacid acid and ethylenediamine as raw material
The ethylenediamine (analysis is pure) of the 3- cyclopentanepropanoiacid acid of 0.5g (analysis is pure) and 0.3g are first dissolved in shape in the water of 50mL
At transparent
Colourless solution, add 0.1g sodium hydroxide formed mixed-alkali solution.Then, this solution is transferred to stainless
It is placed into after formation enclosed system in steel reaction kettle inside 250 DEG C of baking oven and reacts 19 hours respectively.Finally, by cooling anti-
It answers addition ethyl alcohol in solution to be settled, purifies, be dried to obtain carbon quantum dot powder.
(2) carbon quantum dot/cobalt acid nickel composite material preparation
1 mmol Nickelous nitrate hexahydrate (analysis pure), 2 mmol cabaltous nitrate hexahydrates (analysis is pure) and different amounts of
Above-mentioned carbon quantum dot powder (W=10,20 and 40 mg) is dissolved in 20ml water and 20ml ethyl alcohol forms pink clarification mixing
Liquid is then added 12 mmol urea (analysis is pure), stirs pour into the reaction of 50mL polytetrafluoroethyllining lining after ten minutes at room temperature
In kettle, 1 clean nickel foam (1*2cm) is added, is reacted 9 hours for 95 DEG C after being tamping.It is taken out after reaction kettle is cooled to room temperature
Nickel foam, 60 DEG C of drying (12h) after rinsing well.The foam nickel sheet for being loaded with presoma of drying is placed in tube furnace (or Muffle
Furnace) in 2 DEG C/min of heating rate rise to 250 DEG C keep 3 hours after, be cooled to room temperature and be prepared for using nickel foam as base
Bottom is loaded with different-shape carbon quantum dot/cobalt acid nickel composite material.
Embodiment 6
(1) carbon quantum dot is prepared by raw material of graphite powder
1g nano graphite powder (analysis is pure) is scattered in 200mL nitric acid (12 mol/L), and continuous ultrasound 2h (100W,
40KHz),
Then mixture flows back 48 hours.After being cooled to room temperature, centrifugation 30min obtains supernatant, and heating evaporation removes water
Point and part nitric acid, obtain red brown solid, be then dissolved in 50mL deionized water again, dialysing 24 hours, it is extra to remove
Acid and impurity, are concentrated, and weak aqua ammonia is added and is settled again, purify, and freeze-drying obtains brown-red powder.
(2) carbon quantum dot/cobalt acid nickel composite material preparation
0.8 mmol Nickelous nitrate hexahydrate (analysis is pure), 1.6 mmol cabaltous nitrate hexahydrates (analysis is pure) and difference
The above-mentioned carbon quantum dot powder (W=10,20 and 40 mg) of amount is dissolved in 20ml water and 20ml ethyl alcohol forms pink clarification
Mixed liquor is then added 12 mmol urea (analysis is pure), stirs pour into 50mL polytetrafluoroethyllining lining after ten minutes at room temperature
In reaction kettle, 1 clean nickel foam (1*2cm) is added, is reacted 9 hours for 95 DEG C after being tamping.After reaction kettle is cooled to room temperature
Nickel foam is taken out, 60 DEG C of drying (12h) after rinsing well.By the foam nickel sheet for being loaded with presoma of drying be placed in tube furnace (or
Muffle furnace) in 2 DEG C/min of heating rate rise to 250 DEG C keep 3 hours after, be cooled to room temperature and be prepared for nickel foam
Different-shape carbon quantum dot/cobalt acid nickel composite material is loaded with for substrate.
Embodiment 7
(1) carbon quantum dot is prepared by raw material of citric acid
100g citric acid (analysis is pure) powder calcines 48h in high pure nitrogen atmosphere tube type furnace, and (800 DEG C of calcination temperature, rise
Warm rate
5 DEG C/min) it remaining solid powder is dissolved in after water weak aqua ammonia is added settles, it purifies, is dried to obtain carbon quantum
Point powder.
(2) carbon quantum dot/cobalt acid nickel composite material preparation
1 mmol Nickelous nitrate hexahydrate (analysis pure), 2 mmol cabaltous nitrate hexahydrates (analysis is pure) and different amounts of
Above-mentioned carbon quantum dot powder (W=10,20 and 40 mg) is dissolved in 20ml water and 20ml ethyl alcohol forms pink clarification mixing
Liquid is then added 12 mmol urea (analysis is pure), stirs pour into the reaction of 50mL polytetrafluoroethyllining lining after ten minutes at room temperature
In kettle, 1 clean nickel foam (1*2cm) is added, is reacted 8 hours for 85 DEG C after being tamping.It is taken out after reaction kettle is cooled to room temperature
Nickel foam, 60 DEG C of drying (12h) after rinsing well.The foam nickel sheet for being loaded with presoma of drying is placed in tube furnace (or Muffle
Furnace) in 1 DEG C/min of heating rate rise to 260 DEG C keep 3 hours after, be cooled to room temperature and be prepared for using nickel foam as base
Bottom is loaded with different-shape carbon quantum dot/cobalt acid nickel composite material.
Embodiment 8
(1) carbon quantum dot is prepared by raw material of single-walled carbon nanotube
50mg single-walled carbon nanotube (purity 90%) is scattered in 5mL concentrated nitric acid and the dense perchloric acid mixed liquor of 5mL, and mixing is equal
It is transferred in reaction kettle and reacts 24 hours after even for 100 DEG C, be cooled to room temperature and the addition of 50mL deionized water is then added
Weak aqua ammonia is settled, and purifying is dried to obtain carbon quantum dot powder.
(2) carbon quantum dot/cobalt acid nickel composite material preparation
0.8 mmol Nickelous nitrate hexahydrate (analysis is pure), 1.6 mmol cabaltous nitrate hexahydrates (analysis is pure) and difference
The above-mentioned carbon quantum dot powder (W=10,20 and 40 mg) of amount is dissolved in 20ml water and 20ml ethyl alcohol forms pink clarification
Mixed liquor is then added 9.6 mmol urea (analysis is pure), stirs poured into 50mL polytetrafluoroethylene (PTFE) after ten minutes at room temperature
It serves as a contrast in reaction kettle, 1 clean nickel foam (1*2cm) is added, reacted 9 hours for 95 DEG C after being tamping.Reaction kettle is cooled to room temperature
After take out nickel foam, rinse well after 60 DEG C of drying (12h).The foam nickel sheet for being loaded with presoma of drying is placed in tube furnace
After rising to 260 DEG C of holdings 1.5 hours with 2 DEG C/min of heating rate in (or Muffle furnace), it is cooled to room temperature and is prepared for steep
Foam nickel is loaded with different-shape carbon quantum dot/cobalt acid nickel composite material for substrate.
Embodiment 9
(1) to prepare carbon quantum dot as raw material to polyethyleneimine
It first measures 5ml aq. polyethyleneimine (50%, analyze pure) to be put into the centrifuge tube of 50ml, adds 0.5mg
It is right
Be put into 40 DEG C of insulating boxs aging 24 hours after benzenediol (analysis pure), be placed in after taking-up in reaction kettle 180 DEG C it is anti-
It answers 12 hours, addition n,N-Dimethylformamide is settled after 50ml pure water is added, and is purified, is dried to obtain carbon quantum dot powder
End.
(2) carbon quantum dot/cobalt acid nickel composite material preparation
1 mmol Nickelous nitrate hexahydrate (analysis pure), 2 mmol cabaltous nitrate hexahydrates (analysis is pure) and different amounts of
Above-mentioned carbon quantum dot powder (W=10,20 and 40 mg) is dissolved in 30ml water and 10ml ethyl alcohol forms pink clarification mixing
Liquid is then added 12 mmol urea (analysis is pure), stirs pour into the reaction of 50mL polytetrafluoroethyllining lining after ten minutes at room temperature
In kettle, 1 clean nickel foam (1*2cm) is added, is reacted 9 hours for 95 DEG C after being tamping.It is taken out after reaction kettle is cooled to room temperature
Nickel foam, 60 DEG C of drying (12h) after rinsing well.The foam nickel sheet for being loaded with presoma of drying is placed in tube furnace (or Muffle
Furnace) in 2.5 DEG C/min of heating rate rise to 240 DEG C keep 2 hours after, be cooled to room temperature be prepared for be with nickel foam
Substrate is loaded with different-shape carbon quantum dot/cobalt acid nickel composite material.
Embodiment 10
(1) carbon quantum dot is prepared using hydroquinone and ethylenediamine as raw material
50mL polytetrafluoroethyl-ne is added in 0.1g hydroquinone (analysis is pure), 300 μ L ethylenediamines (analysis is pure) and 10 mL water
Alkene liner
Reaction kettle, 180 DEG C are reacted 12 hours, and distilled water is added after being cooled to room temperature and dilutes carbon quantum dot aqueous solution.By this
Ethyl alcohol is added in aqueous solution to be settled, purifies, is dried to obtain carbon quantum dot powder.
(2) carbon quantum dot/cobalt acid nickel composite material preparation
1 mmol Nickelous nitrate hexahydrate (analysis pure), 2 mmol cabaltous nitrate hexahydrates (analysis is pure) and different amounts of
Above-mentioned carbon quantum dot powder (W=10,20 and 40 mg) is dissolved in 10ml water and 30ml ethyl alcohol forms pink clarification mixing
Liquid is then added 12 mmol urea (analysis is pure), stirs pour into the reaction of 50mL polytetrafluoroethyllining lining after ten minutes at room temperature
In kettle, 1 clean nickel foam (1*2cm) is added, is reacted 9 hours for 80 DEG C after being tamping.It is taken out after reaction kettle is cooled to room temperature
Nickel foam, 60 DEG C of drying (12h) after rinsing well.The foam nickel sheet for being loaded with presoma of drying is placed in tube furnace (or Muffle
Furnace) in 2 DEG C/min of heating rate rise to 250 DEG C keep 2.5 hours after, be cooled to room temperature be prepared for be with nickel foam
Substrate is loaded with different-shape carbon quantum dot/cobalt acid nickel composite material.
The electrochemical energy storage performance test of different samples prepared by embodiment 1-10 is shown in Table 1.
Table 1
Note: 1. test conditions are three electrode test systems, and the nickel foam for being loaded with composite material is Electrode, platinized platinum
For to electrode, mercury/mercuric oxide electrode (1 mol/L KOH aqueous solution is interior reference liquid) is reference electrode, and electrolyte is 3M KOH
Aqueous solution, test voltage range 0-0.5V vs. Hg/HgO.2. asterisk is labeled as the more excellent sample of electrochemical energy storage performance.
Fig. 4 is cobalt acid nickel material and three kinds of carbon quantum dots in embodiment 1/(carbon quantum dot feeds intake cobalt acid nickel composite material
Amount be 10,20 and 40 mg, respectively correspond figure A-D) cyclic voltammetry as a result, sweep speed be 2mV/s-100mV/s, current potential model
Enclose 0-0.65V vs. Hg/HgO.
Representative composite material (carbon quantum dot inventory be 20 mg, carbon quantum dot/cobalt acid nickel -2) in embodiment 1 with
Absorbent charcoal material (1300 m of specific surface area2/ g) assembling asymmetric capacitor system (electrolyte be 3 mol/L KOH, current potential
Range 0-1.5V) energy density-power density curve and with super capacitor system composed by other analog materials compare
See Fig. 5.Representative composite material (carbon quantum dot inventory is 20 mg) and absorbent charcoal material (specific surface area in embodiment 1
1300 m2/ g) assembling full battery electrochemical performance data it is as shown in table 2.
Table 2
| Quality specific capacitance (current density 1A/ g) | High rate performance (electric current Density 1A/g-30A/ g) | Maximum energy-density (current density 1A/ g) | Maximum power density (current density 30A/ g) | Cycle performance (current density 30A/g, cycle-index 5000 It is secondary) |
| 139 F/g | 61.1% | 43.2 Wh/kg | 4500.6 W/kg | 99.96% |
Claims (8)
1. a kind of carbon quantum dot of morphology controllable/cobalt acid nickel combination electrode material preparation method, which is characterized in that specific steps
It is as follows:
(1) mixed solvent for forming carbon quantum dot powder, Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and urea in water and ethyl alcohol
Middle mixing, mixing are placed in polytetrafluoroethyllining lining reaction kettle, add nickel foam, react 7 at a temperature of 85 ~ 95 DEG C after sealing
It ~ 9 hours, cools down later, takes out nickel foam and rinse, dry；
(2) nickel foam after drying is heat-treated at 240 ~ 260 DEG C, obtains carbon quantum dot/cobalt that nickel foam is substrate
Sour nickel combination electrode material；It is in Mao Lizhuan, corolla shape or strawberry-like；Wherein:
In step (1), carbon quantum dot powder is 0.25 ~ 1mg/mL in the mass-volume concentration of in the mixed solvent.
2. preparation method according to claim 1, which is characterized in that in step (1), Nickelous nitrate hexahydrate, six hydration nitre
The molar ratio of sour cobalt and urea is 1:2:12.
3. preparation method according to claim 1, which is characterized in that in step (1), Nickelous nitrate hexahydrate is in mixed solvent
In concentration range between 0.02 ~ 0.03mol/L thus accordingly adjustment cabaltous nitrate hexahydrate and urea concentration.
4. preparation method according to claim 1, which is characterized in that in step (1), carbon quantum dot by with citric acid,
Ethylenediamine, graphene, carbon nanotube, hydroquinone or urea are raw material, are prepared through hydro-thermal method or electrochemical stripping method, carbon
The average grain diameter of quantum dot is between 2.5-3.5nm.
5. preparation method according to claim 1, which is characterized in that in step (1), in the mixed solvent, second alcohol and water
Volume ratio 1:3 ~ 3:1.
6. preparation method according to claim 1, which is characterized in that in step (2), when heat treatment, first with 0.5 ~ 2 DEG C/
The heating rate of minute is warming up to 240 ~ 260 DEG C, then keeps the temperature 1.5 ~ 3 hours.
7. a kind of carbon quantum dot that preparation method according to claim 1 obtains/cobalt acid nickel combination electrode material.
8. carbon quantum dot according to claim 7/cobalt acid nickel combination electrode material, which is characterized in that it is in Mao Lizhuan, flower
Coronal or strawberry-like.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103497762A (en) * | 2013-06-26 | 2014-01-08 | 上海交通大学 | Method for synthesizing nitrogen doped carbon quantum dot based on one-step monocomponent hydro-thermal synthesis |
| CN103594246A (en) * | 2013-11-21 | 2014-02-19 | 东华大学 | Preparation method for electrode material of porous NiCo2O4 nanowire array supercapacitor |
| CN103840176A (en) * | 2014-02-27 | 2014-06-04 | 浙江大学 | Three-dimensional graphene-based combined electrode with Au nanoparticle-loaded surface, and preparation method and applications thereof |
| CN104143450A (en) * | 2014-07-10 | 2014-11-12 | 东华大学 | Method for preparing NiCo2O4 composite electrode material coated with conducting polymer |
-
2016
- 2016-05-06 CN CN201610296455.1A patent/CN105914353B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103497762A (en) * | 2013-06-26 | 2014-01-08 | 上海交通大学 | Method for synthesizing nitrogen doped carbon quantum dot based on one-step monocomponent hydro-thermal synthesis |
| CN103594246A (en) * | 2013-11-21 | 2014-02-19 | 东华大学 | Preparation method for electrode material of porous NiCo2O4 nanowire array supercapacitor |
| CN103840176A (en) * | 2014-02-27 | 2014-06-04 | 浙江大学 | Three-dimensional graphene-based combined electrode with Au nanoparticle-loaded surface, and preparation method and applications thereof |
| CN104143450A (en) * | 2014-07-10 | 2014-11-12 | 东华大学 | Method for preparing NiCo2O4 composite electrode material coated with conducting polymer |
Non-Patent Citations (1)
| Title |
|---|
| Porous NiCo2O4 spheres tuned through carbon quantum dots utilize;Yirong Zhu et al.;《Journal of Materials Chemistry A》;20141107;第3卷(第2期);第866页摘要，第867页右栏第2-3段，第870页左栏第2段 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112885612A (en) * | 2021-01-11 | 2021-06-01 | 湖南大学 | Sea urchin-shaped amorphous carbon/foamed nickel composite material, preparation method thereof and application thereof in super capacitor |
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