CN109950061A - A kind of supercapacitor nickeliferous nano-graphene carbon ball porous composite electrode material and its preparation method and application - Google Patents
A kind of supercapacitor nickeliferous nano-graphene carbon ball porous composite electrode material and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of supercapacitor nickeliferous nano-graphene carbon ball porous composite electrode materials and its preparation method and application, belong to composite material and preparation method thereof and application field, to solve, a large amount of waste polyurethane foams have caused a series of environmental problem and existing electrode for super capacitor material specific capacitance is low with specific power, the problems such as at high cost, method provided by the invention is using the polyurethane foam discarded in industry and life as carbon base body, it is applied to supercapacitor using the nickeliferous nano-graphene carbon ball porous composite electrode material that hydro-thermal method and carbonizatin method prepare high specific capacitance.The preparation method simple process, raw material is sufficient, low in cost, has reached and has prepared the carbon-based composite electrode material with high specific capacitance, is treasured, the purpose to reduce environmental pollution with time-varying waste polyurethane foam.
Description
Technical field
The present invention relates to composite material and preparation method thereof, in particular to a kind of supercapacitor waste polyurethane is carbon-based nickeliferous
The preparation method and application of graphene carbon ball porous composite electrode material.
Background technique
Supercapacitor, the energy-storage travelling wave tube environmentally friendly as one kind emerging in recent years is with its high-energy-density, high ratio
Power, quick charge, long circulation life have a wide range of applications in various fields.Electrode material is most crucial as supercapacitor
Component decide its performance.Currently, be applied to supercapacitor material there are three types of: carbon-based material, conducting polymer, transition
Metallic compound.However, unitary electrode material always has the defect in structure to a certain degree and performance.
Although in recent years, it is numerous research made great progress in terms of electrode material for super capacitor, carbon
Material is still occupied an important position with its excellent cyclical stability.But carbon material there are specific capacitance it is low with specific power lack
It falls into, and higher cost.Therefore, it develops with excellent electrochemical performance, raw material is sufficient, cheap and preparation is simple carbon-based multiple
Composite electrode material is still project most crucial in supercapacitor research.
Polyurethane is that a kind of main chain contains carbamate groups (- NHCONH-) constitutional repeating unit and application is very extensive
Thermoplastic polymer.Currently, polyurethanes product is numerous in the world, including coating, adhesive and elastomer etc..Wherein, gather
Urethane foam is one of most important polyurethane products in industry and daily life, almost permeates each department of national economy, special
It is not especially universal in the fields use such as insulation, refrigeration, building, transport, furniture, bed accessory.Studies have shown that only the whole world in 2014 is poly-
The output of urethane foam is up to 5,800,000 tons, and China accounts for 1,600,000 tons.Due to polyurethane foam can not self degradation, industry and
The a large amount of waste polyurethane foams generated in life have caused a series of environmental problem.Therefore, exploring one can recycle
Using the approach of waste polyurethane foam, to reach reduction environmental pollution, the purpose for creating economic benefit that turns waste into wealth also becomes
One project studied extensively.
Summary of the invention:
A series of environmental problem and existing supercapacitor electricity consumption are caused to solve a large amount of waste polyurethane foams
The problems such as pole material specific capacitance is low with specific power, at high cost, the present invention provide a kind of simple process, raw material it is sufficient, it is low in cost,
Turn waste into wealth and the preparation method of the electrode for super capacitor of high specific capacitance.
The present invention with discarded polyurethane foam be it is carbon-based, using hydro-thermal method in the alkaline environment that hydrolysis of urea generates general
Graphene oxide and nickel hydroxide are coated on skeleton, are finally carbonized in nitrogen atmosphere high temperature, graphene oxide is gone back by heat
Original work are nickel oxide with graphene, nickel hydroxide pyrolytic is reduced to, and the macromolecular and small molecule in polyurethane foam are melted
And it is formed under the action of intermolecular force and surface tension and there is fine and close duct between nanoscale carbon ball and carbon ball, most
Nickeliferous nano-graphene carbon ball porous composite electrode material is prepared eventually.The graphene and nickel oxide wherein coated each serves as control
System melting polyurethane sized molecules formation rule carbon ball and the effect for promoting material carbonization.
The present invention is achieved by the following technical solutions, comprising the following steps:
Step 1: the preparation of graphene oxide.The present invention synthesizes graphene oxide using modified Hummer method, by flakey
Graphite is mixed with the concentrated sulfuric acid, is stirred at room temperature；It places into ice-water bath and stirs, and be slowly added to sodium nitrate, sufficiently after reaction, in batches
It is secondary to be slowly added to potassium permanganate, it is reacted in ice-water bath；Reaction system is transferred to and continues to be stirred to react at room temperature, water-bath adds later
Thermal response；Distilled water is added, ultrasound after being slowly stirred；Hydrogen peroxide is added dropwise dropwise to solution in golden yellow, and 10ml hydrochloric acid is added
Insoluble matter is dissolved, centrifugation takes dope.Dope is fitted into dialysis in filter membrane, until the pH of dialysate is 6.8-7.2, is being dried
Graphene oxide product is obtained after dry.
The mass volume ratio (g/mL) of the flaky graphite and the concentrated sulfuric acid is 1:23；The concentrated sulfuric acid is the sulphur of 98wt%
Acid.
It is described to be stirred at room temperature, mixing time 10-60min.
The mass ratio of the flaky graphite and sodium nitrate is 1:(0.2-2).
It is described that potassium permanganate is added in batches, it is divided into 3-5 batch, the flaky graphite quality and potassium permanganate gross mass
The ratio between be 1:(2-10)；It is reacted in the ice-water bath, time 2h；It is described to continue to be stirred to react at room temperature, reaction time 2h；
The heating in water bath for reaction, temperature are 35 DEG C, and the reaction time is for 24 hours；The quality of the flaky graphite and the distilled water of addition
Volume ratio (g/mL) is 1:250；It is described to be slowly stirred rear ultrasound, mixing time 20min, ultrasonic time 1h；The hydrochloric acid
Concentration is 37wt%；The drying, temperature are 60 DEG C, time 10h.
Step 2: it takes graphene oxide, urea and nickel nitrate ultrasonic in dehydrated alcohol and distilled water, obtains graphite oxide
Alkene mixed solution；Discarded polyurethane foam is crushed into obtain polyurethane foam fritter, is impregnated in dehydrated alcohol under room temperature, is dried
It is dry；By treated, polyurethane foam fritter is added in graphene oxide mixed solution, shifts stainless steel polytetrafluoroethylene (PTFE) water
Reaction is heated in hot kettle, product is taken out after reaction kettle is cooled to room temperature, is cleaned respectively with water and ethyl alcohol, is dried；Finally, will dry
Product after dry is wrapped in graphite paper, in horizontal pipe furnace carbonization treatment to get porous multiple to nickeliferous nano-graphene carbon ball
Composite electrode material；
The mass volume ratio (mg/g/mL) of the graphene oxide, urea and dehydrated alcohol is (25-150): 3:(20-
80), the urea and nickel nitrate mass ratio are 1:1-4:1, and the dehydrated alcohol and distilled water volume ratio are 2:3, the ultrasound
Time is 0.5-3h；It is described to crush discarded polyurethane foam, it specially pulverizes and sieves, obtains the polyurethane foam of partial size 2cm
Fritter, the immersion, time 12-24h, the drying, temperature are 60 DEG C, time 2-10h；The graphene oxide and poly-
The mass ratio (mg/g) of urethane foam piece is (25-150): (1-3), and the heating reaction, reaction temperature is 80-150 DEG C, instead
It is 8-24h between seasonable；The carbonization treatment, after being specially passed through 2h nitrogen in tube furnace, first with 10-30 in nitrogen atmosphere
℃·min-1Heating rate be heated to 300-400 DEG C, hereafter again with 2-20 DEG C of min-1Heating rate be heated to 600-
900 DEG C, and carbonization treatment 1-3h at this temperature.
The present invention also provides the supercapacitor of application above-mentioned preparation method preparation is porous with nickeliferous nano-graphene carbon ball
Combination electrode material.
In addition the present invention also provides the nickeliferous nano-graphene carbon ball porous composite electrode materials of above-mentioned supercapacitor
Using.
The application, specifically:
Supercapacitor is taken to be placed in mortar with nickeliferous nano-graphene carbon ball porous composite electrode material, every 15mg is super
1-20 drop distilled water and 1~2 drop polytetrafluoroethylene (PTFE) is added in the nickeliferous nano-graphene carbon ball porous composite electrode material of capacitor
It is ground to paste, painting scrapes in the nickel foam that soaked in absolute ethyl alcohol is dried afterwards for 24 hours, dries, will be coated with nickeliferous nano-graphite olefinic carbon
The composite porous nickel foam of ball is pressed into the thin slice with a thickness of 1-3mm on twin-roll machine, obtains electrode slice.
Invention effect:
1. present invention preparation passes through a series of graphene oxide, urea, nitric acid using waste polyurethane foam as carbon base body
The adjustment of heating rate and carbonization treatment time, is prepared during quality, hydrothermal temperature and the time of nickel, carbonization treatment
Nickeliferous nano-graphene carbon ball porous composite electrode material.Simple process and low cost turns waste into wealth, and can reduce discarded
Environmental pollution caused by polyurethane.
2. nickeliferous nano-graphene carbon ball porous composite electrode material, the ruler of nickeliferous graphene carbon ball prepared by the present invention
It is very little to be maintained at 80nm-200nm, porous structure by different level is presented between carbon ball, pore size is maintained at 50nm-250nm, the knot
Not only there is structure biggish specific surface area to provide more reaction sites, but also with different levels cellular structure for redox reaction
While providing more multichannel for electrolyte ion transmission and this transmission channel can be shortened.
3. graphene oxide passes through heat in nickeliferous nano-graphene carbon ball porous composite electrode material prepared by the present invention
Reduction is reduced into graphene, can not only control polyurethane foam carbonization into regular carbon ball, and can increase combination electrode
The electric conductivity of material.
4. in nickeliferous nano-graphene carbon ball porous composite electrode material prepared by the present invention, nitrogen, oxygen, nickel content difference
Up to 14.02 wt%, 7.82wt% and 2.91wt%, and in the material respectively with nitrogen-containing functional group, oxygen-containing functional group, oxidation
The form of nickel exists, and three can be with OH in electrolyte-Reversible redox reaction occurs for (electrolyte is 6M KOH solution),
Generate faraday's capacitor.
5. by cyclic voltammetry, the electrode material shows apparent oxidation peak and reduction peak, can with outstanding
Inverse property, and specific capacitance is up to 1127.3Fg-1, it is suitble to do the positive electrode of supercapacitor.
In short, the invention patent utilizes hydro-thermal method and carbon using the polyurethane foam discarded in industry and life as carbon base body
The nickeliferous nano-graphene carbon ball porous composite electrode material that change method prepares high specific capacitance is applied to supercapacitor.The preparation
Method and process is simple, and raw material is sufficient, low in cost, has reached and has prepared the carbon-based composite electrode material with high specific capacitance, together
Time-varying waste polyurethane foam is treasured, the purpose to reduce environmental pollution.
Detailed description of the invention:
Scanning electron microscope under nickeliferous 2000 times of nano-graphene carbon ball porous composite electrode material of the preparation of Fig. 1 embodiment 1
Figure；
Scanning electricity under nickeliferous 40000 times of nano-graphene carbon ball porous composite electrode material of the preparation of Fig. 2 embodiment 1
Mirror figure；
Nickeliferous nano-graphene carbon ball porous composite electrode material EDX test chart prepared by Fig. 3 embodiment 1；
Nickeliferous nano-graphene carbon ball porous composite electrode material XRD test chart prepared by Fig. 4 embodiment 1；
Electrode cycle volt-ampere test chart prepared by Fig. 5 embodiment 7.
Specific embodiment:
Embodiment 1 prepares a kind of nickeliferous nano-graphene carbon ball porous composite electrode material:
Step 1: the preparation of graphene oxide.The present invention synthesizes graphene oxide using modified Hummer method, by 2g scale
Shape graphite and the 46ml concentrated sulfuric acid are mixed to join the three-necked bottle of 1000ml, and 30min is stirred at room temperature.It places into ice-water bath and stirs,
And it is slowly added to 1g sodium nitrate, sufficiently after reaction, point 5 batches are slowly added to the potassium permanganate of 6g, the reaction was continued 2h.By three-necked bottle
It is transferred to room temperature to continue to be stirred to react 2h, is then transferred to after 35 DEG C of water-baths that the reaction was continued later for 24 hours.The distilled water of 500ml is added
Enter into three-necked bottle, is slowly stirred ultrasound 1h after 20min.Then, hydrogen peroxide is added dropwise dropwise to solution in golden yellow, and is added
10ml dissolving with hydrochloric acid insoluble matter, centrifugation, takes dope.Dope is fitted into dialysis in filter membrane, until the PH ≈ 7 of dialysate,
Graphene oxide product is obtained after drying 10h at 60 DEG C in baking oven.
Discarded polyurethane foam: being crushed the small bulk of granulating partial size about 2cm by step 2, under room temperature in dehydrated alcohol
It impregnates for 24 hours, then dries 6h at 60 DEG C in an oven.Taking 100mg graphene oxide, 3g urea and 3g nickel nitrate, (mass ratio is
1:1) the ultrasound 1h in 60ml dehydrated alcohol and distilled water (2:3), obtains graphene oxide mixed solution.By 2g treated block
Shape waste polyurethane foam is added in graphene oxide mixed solution, is then transferred into the stainless steel polytetrafluoroethylene (PTFE) of 100ml
12h is reacted at a temperature of 120 DEG C in water heating kettle.Product is taken out after reaction kettle is cooled to room temperature, is cleaned respectively with water and ethyl alcohol
For several times, 10h is dried at 60 DEG C in an oven.Finally, the product after drying is wrapped in graphite paper, lead in horizontal pipe furnace
After entering 2h nitrogen, first with 20 DEG C of min in nitrogen atmosphere-1Heating rate be heated to 350 DEG C, hereafter again with 5 DEG C of min-1Heating rate be heated to 800 DEG C, and carbonization treatment 2h at this temperature, obtained product are nickeliferous nano-graphite olefinic carbon
Ball porous composite electrode material.
Fig. 1 is the scanning electricity under prepared by embodiment 1 nickeliferous 2000 times of nano-graphene carbon ball porous composite electrode material
Mirror figure；Fig. 2 is the scanning electron microscope under prepared by embodiment 1 nickeliferous 40000 times of nano-graphene carbon ball porous composite electrode material
Figure；Fig. 3 is nickeliferous nano-graphene carbon ball porous composite electrode material EDX test chart prepared by embodiment 1；Fig. 4 is embodiment 1
The nickeliferous nano-graphene carbon ball porous composite electrode material XRD test chart of preparation；It can be concluded that, prepared contains from result
The size of nickel graphene carbon ball is maintained at 80nm~200nm, and porous structure by different level is presented between carbon ball, and pore size is maintained at
Not only there is biggish specific surface area to provide more reaction sites for redox reaction for 50 nm~250nm, the structure, and
And with different levels cellular structure can for electrolyte ion transmission more multichannel is provided while and shorten this transmission channel.
In prepared nickeliferous nano-graphene carbon ball porous composite electrode material, nitrogen, oxygen, nickel content respectively be up to 14.02wt%,
7.82wt% and 2.91wt%, and exist in the form of nitrogen-containing functional group, oxygen-containing functional group, nickel oxide respectively in the material, three
Person can be with OH in electrolyte-Reversible redox reaction occurs for (electrolyte is 6M KOH solution), generates faraday's capacitor.
Embodiment 2: being adjusted to 2:1 for the ratio of urea and nickel nitrate unlike the first embodiment, and amount of urea remains as
3g。
Embodiment 3: being adjusted to 3:1 for the ratio of urea and nickel nitrate unlike the first embodiment, and amount of urea remains as
3g。
Embodiment 4: being adjusted to 4:1 for the ratio of urea and nickel nitrate unlike the first embodiment, and amount of urea remains as
3g。
Embodiment 5: hydrothermal reaction kettle reaction temperature is adjusted to 80 DEG C unlike step 2 in embodiment 1.It is other
Step is same as Example 1.
Embodiment 6: the hydrothermal reaction kettle reaction time is adjusted to 8h unlike step 2 in embodiment 1.Other steps
It is rapid same as Example 1.
The application of 7 gained composite material of embodiment:
It takes nickeliferous composite porous take of nano-graphene carbon ball made from 15mg embodiment 1 to be placed in mortar, 1 drop is added
Distilled water and 2 drop polytetrafluoroethylsolution solutions be ground to paste, painting scrapes in nickel foam on (soaked in absolute ethyl alcohol is for 24 hours), is drying
After being dried at 60 DEG C in case, the composite porous nickel foam of nickeliferous nano-graphene carbon ball will be coated with and be pressed on twin-roll machine
Thickness is about that 1 millimeter or so of thin slice is the nickeliferous composite porous electrode slice of nano-graphene carbon ball.Fig. 5 is embodiment 7
The electrode cycle volt-ampere test chart of preparation, as can be seen from the results, electrode shows apparent oxidation peak and reduction peak, has
Outstanding invertibity, and specific capacitance is up to 1127.3Fg-1, it is suitble to do the anode of supercapacitor.
Claims (10)
1. a kind of supercapacitor preparation method of nickeliferous nano-graphene carbon ball porous composite electrode material, feature exist
In: the following steps are included:
Step 1: the preparation of graphene oxide；The present invention synthesizes graphene oxide using modified Hummer method, by flaky graphite
It mixes, is stirred at room temperature with the concentrated sulfuric acid；It places into ice-water bath and stirs, and be slowly added to sodium nitrate, sufficiently after reaction, delay in batches
It is slow that potassium permanganate is added, it is reacted in ice-water bath；Reaction system is transferred to and continues to be stirred to react at room temperature, heating water bath is anti-later
It answers；Distilled water is added, ultrasound after being slowly stirred；Hydrogen peroxide is added dropwise dropwise to solution in golden yellow, and 10ml dissolving with hydrochloric acid is added
Insoluble matter, centrifugation, takes dope；Dope is fitted into dialysis in filter membrane, until the pH of dialysate is 6.8-7.2, after the drying
Obtain graphene oxide product；
Step 2: it takes graphene oxide, urea and nickel nitrate ultrasonic in dehydrated alcohol and distilled water, it is mixed to obtain graphene oxide
Close solution；Discarded polyurethane foam is crushed into obtain polyurethane foam fritter, is impregnated in dehydrated alcohol under room temperature, is dried；It will
Treated, and polyurethane foam fritter is added in graphene oxide mixed solution, is shifted in stainless steel polytetrafluoroethylene (PTFE) water heating kettle
Heating reaction, product is taken out after reaction kettle is cooled to room temperature, is cleaned respectively with water and ethyl alcohol, is dried；Finally, by after drying
Product is wrapped in graphite paper, horizontal pipe furnace carbonization treatment to get arrive nickeliferous nano-graphene carbon ball porous composite electrode
Material.
2. method according to claim 1, it is characterised in that: the quality volume of flaky graphite and the concentrated sulfuric acid described in step 1
It is 1:23 than (g/mL)；The concentrated sulfuric acid is the sulfuric acid of 98wt%.
3. method according to claim 1, it is characterised in that: the mass ratio of flaky graphite and sodium nitrate described in step 1 is
1:(0.2-2)；The ratio between the flaky graphite quality and potassium permanganate gross mass are 1:(2-10).
4. method according to claim 1, it is characterised in that: reacted in ice-water bath described in step 1, time 2h；The room
Continue to be stirred to react under temperature, reaction time 2h；The heating in water bath for reaction, temperature are 35 DEG C, and the reaction time is for 24 hours.
5. method according to claim 1, it is characterised in that: the matter of the distilled water of flaky graphite and addition described in step 1
Measuring volume ratio (g/mL) is 1:250；It is described to be slowly stirred rear ultrasound, mixing time 20min, ultrasonic time 1h；The salt
Acid concentration is 37wt%；The drying, temperature are 60 DEG C, time 10h.
6. method according to claim 1, it is characterised in that: graphene oxide, urea described in step 2 and dehydrated alcohol
Mass volume ratio (mg/g/mL) is (25-150): 3:(20-80), the urea and nickel nitrate mass ratio are 1:1-4:1, described
Dehydrated alcohol and distilled water volume ratio are 2:3, and the ultrasonic time is 0.5-3h.
7. method according to claim 1, it is characterised in that: graphene oxide described in step 2 and polyurethane foam fritter
Mass ratio (mg/g) is (25-150): (1-3), and the heating reaction, reaction temperature is 80-150 DEG C, reaction time 8-24h；
The carbonization treatment, after being specially passed through 2h nitrogen in tube furnace, first with 10-30 DEG C of min in nitrogen atmosphere-1Heating speed
Rate is heated to 300-400 DEG C, hereafter again with 2-20 DEG C of min-1Heating rate be heated to 600-900 DEG C, and at this temperature
Carbonization treatment 1-3h.
8. a kind of supercapacitor of any one of -7 the method preparations according to claim 1 is more with nickeliferous nano-graphene carbon ball
Hole combination electrode material.
9. a kind of supercapacitor according to any one of claims 8 answering with nickeliferous nano-graphene carbon ball porous composite electrode material
With.
10. applying according to claim 9, it is characterised in that: specifically: take supercapacitor with nickeliferous nano-graphite olefinic carbon
Ball porous composite electrode material is placed in mortar, the nickeliferous nano-graphene carbon ball porous composite electrode of every 15mg supercapacitor
1-20 drop distilled water is added in material and 1~2 drop polytetrafluoroethylene (PTFE) is ground to paste, and painting scrapes soaked in absolute ethyl alcohol dries afterwards for 24 hours
Nickel foam on, drying, the composite porous nickel foam of nickeliferous nano-graphene carbon ball will be coated with and be pressed on twin-roll machine
With a thickness of the thin slice of 1-3mm, electrode slice is obtained.
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