CN106517133A - Nitrogen-doped three-dimensional bicontinuous porous structure ultrathin carbon layer and preparation method and application thereof - Google Patents
Nitrogen-doped three-dimensional bicontinuous porous structure ultrathin carbon layer and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a nitrogen-doped three-dimensional bicontinuous porous structure ultrathin carbon layer and a preparation method and application thereof. The preparation method comprises the steps that shrimp shell pretreatment is conducted, by taking urea or melamine or pyrrole as a nitrogen source and taking shrimp shells subjected to treatment as a raw material, under inert gas flow, low-temperature pre-carbonization is conducted, then, high-temperature pyrolysis is conducted with alkaline matter, acid treatment is conducted at last, and the nitrogen-doped three-dimensional bicontinuous porous structure ultrathin carbon layer is obtained. The nitrogen-doped three-dimensional bicontinuous porous structure ultrathin carbon layer prepared through the method has a unique nano ultrathin carbon layer structure, a high specific surface area and a total pore volume, is simple in technology, low in cost, friendly to environment, and has good physical and chemical properties. The nitrogen-doped three-dimensional bicontinuous porous structure ultrathin carbon layer can be applied to a supercapacitor, a secondary battery and gas absorption, and a new way for developing new energy biomass materials is opened up.
Description
Technical field
The invention belongs to biomass carbon materials preparation and application field, more more particularly, to a kind of nitrating three-dimensional co-continuous
Ultra-thin layer of charcoal of pore structure and its preparation method and application.
Background technology
With worsening shortages and the increasingly severe environmental pollution of non-renewable energy resources, people are to regenerative resource and green
Color new forms of energy will become increasingly dependent on.Biomass energy is the fourth-largest energy for being only second to coal, oil and natural gas, with high storage
Can, renewable, free of contamination feature, be constantly subjected to showing appreciation for somebody for people in terms of material with carbon element is prepared using biomass, electrochemistry,
The fields such as sewage disposal, the absorption of pernicious gas have a wide range of applications, particularly in electrochemical field, with biomass as raw material
The material with carbon element of preparation has the advantages that high specific surface area, high stability, good electric conductivity and energy large-scale commercial production.
As the discarded object of the marine products such as the exploitation of Daxing of the China coast one with aquatic products industry, tourist industry, shrimp shell increases year by year,
Cause the waste of resource and the pollution of environment.Containing abundant carbon source in shrimp shell, possess the lamellar structure of uniqueness, and wide material sources,
It is with low cost, environmental friendliness, preparing porous carbon with shrimp shell as raw material has the advantage of uniqueness.
Biomass mainly have physical activation method, chemical activation method and template as the method that carbon source prepares porous carbon materials
Method.Physically activated is temperature between 700 DEG C -1000 DEG C, with H2O、CO2With air as activator, utilize and occur with presoma
Redox reaction carry out pore-forming character；Chemical activation method is with alkali (KOH, NaOH, K2CO3) or H3PO4、ZnCl2Etc. chemical substance
Chemical attack is carried out to presoma, specific surface area is increased by pyrolytic polycondensation reaction in activation process and is formed abundant space knot
Structure；Template is to introduce a kind of material with orderly hole, presoma is infiltrated in a template so as to react in hole, profit
With itself restriction effect of mould material, the material with carbon element of the ordering with single aperture is prepared.Above-mentioned three kinds of methods respectively have
Pluses and minuses：Physical is simple with chemical method, but disordered state is presented for hole and adjustability is poor；Template is because aperture can be controlled
Size and hole state and there is the advantage of uniqueness, but present template is more based on some expensive templates, preparation technology
It is complicated, relatively costly.The porous carbon materials containing relatively orderly hole of Development of Novel are huge challenges.
Ultracapacitor is a kind of new electrochemical energy energy storage device, has high energy density than traditional capacitor,
There are high power density, and service life cycle length, low cost than battery, be applied to numerous areas.Should in ultracapacitor
Under being driven with the continuous expansion in field, developing height ratio capacity, the electrode material of high stability has become the hot subject in the world.Often
Electrode material has metal oxide, conducting polymer and porous carbon material.Due to porous carbon material wide material sources, chemistry surely
Fixed and service life cycle is long, especially with high-specific surface area and high pore volume, and relative to carbon materials such as CNT, Graphenes
Material has the advantages that low cost, abundant raw material, therefore becomes current research heat with its electrode material as ultracapacitor
Point.
There are some researches show, the ultra-thin carbon-coating of porous prepared for carbon source using natural biologic material, environmental friendliness, and its own
The uniqueness of biological template structure shows the advantage of application performance, and forms carbon matrix with hole based on biomass porous carbon
Bicontinuous structure, and can expand in length, width, thickness three dimension scale, with physical properties such as more preferable conductions.Cause
This, selects different carbon source biological templates with the key that handling process is the porous carbon for preparing different performance and purposes.Such as Li
Sun et al. coconut husks used in [Journal of Materials Chemistry A 2013,1,6462 6470] are used as more
The presoma of hole charcoal, in catalyst Fe Cl3With activator Zncl2The lower high temperature pyrolysis of effect simultaneously acid treated obtain porous carbon
Material, its BET specific surface area are 1874m2/ g, total hole volume 1.21cm3/ g, specific capacitance 268F/g, and should as electrode material
On ultracapacitor.And the general specific surface area of carbon-based material is in 2180-3100m2/ g, but existing multiporous biological matter
Carbon, because the reason such as material composition and structure, specific capacitance relatively low (250F/g)；The actual specific capacitance of existing Graphene is also limited
System is in 300F/g.
The content of the invention
Present invention aim at providing a kind of new ultra-thin layer of charcoal of nitrating three-dimensional co-continuous loose structure and preparation method thereof
And application, complex process, relatively costly shortcoming in template preparation process can be overcome, with reference to biomass template, Physical
With the advantage of chemical method, while be easier to make for nitrogen atom doping, finally prepare and a kind of have that pattern is special, chemical property
The superior ultra-thin layer of charcoal of new nitrating three-dimensional co-continuous loose structure.
To achieve these goals, according to one aspect of the present invention, the invention provides a kind of nitrating three-dimensional co-continuous
The ultra-thin layer of charcoal preparation method of loose structure, its step include：
(1) first shrimp shell raw material deionized water is cleaned by ultrasonic, then the ultrasonic immersing cleaning in alkaline solution, will after cleaning
Shrimp shell is dried；
(2) shrimp shell that is dried for obtaining step (1) is 1 with nitrogen-containing material in mass ratio：0.01～5 ratio mixing, uses
The mixing of deionized water heating stirring is until moisture evaporating completely；
(3) mixture obtained by step (2) is ground to into powder, then carries out Low Temperature Thermal under the protection of inert gas
Solution；
(4) by the material obtained after step (3) low temperature pyrogenation and alkaline matter in mass ratio 1：0.5～3 ratio grinding
It is well mixed, carries out high temperature pyrolysis under inert gas shielding；
(5) by step (4) by the material obtained after high temperature pyrolysis with excess diluted acid mix lixiviating, then spend from
Sub- water centrifuge washing outwells supernatant to neutrality.
(6) step (5) products therefrom is dried to obtain into the ultra-thin layer of charcoal of nitrating three-dimensional co-continuous loose structure.
Further, in step (1), alkaline solution is NaOH, potassium hydroxide a kind of or for two kinds of solution
Mixed solution；Liquid quality fraction is 10%.
Further, in step (1), drying temperature is 80-150 DEG C.
Further, in step (2), nitrogen source is urea, melamine, pyrroles's one of which or their mixture, is stirred
Mixing temperature is mixed for 50 DEG C, rotating speed is 300r/min.
Further, in step (3) low temperature pyrogenation temperature at 400-550 DEG C, step (4) high temperature pyrolysis temperature is in 600-
1000℃。
Further, step (3), in (4), inert gas is nitrogen or argon gas；Programming rate be 10 DEG C/min, gas stream
Speed is 100-200mL/min.
Further, in step (4), alkaline matter is NaOH, potassium hydroxide, sodium carbonate, the one kind in potassium carbonate
Or mixture more than two of which.
Further, in step (5), diluted acid can be the hydrochloric acid that mass concentration is 10-20%, nitric acid, one kind of sulfuric acid
Or their mixture, speed of agitator 500r/min；The each 5min of centrifugation time, centrifugal rotational speed is 1000r/min.
Further, in 1-100nm, its BET specific surface area is 1000-2300m to ultra-thin carbon layers having thicknesses2/ g, total hole volume
For 0.5-1.63cm3/ g, average pore size are 2-4nm, and nitrogen mass content is 1-11wt%.
Further, the ultra-thin layer of charcoal of nitrating three-dimensional co-continuous loose structure is gentle for ultracapacitor, secondary cell
Body adsorbs.
In general, by the contemplated above technical scheme of the present invention compared with prior art, the effect of the present invention：This
Invention from the fourth-largest energy organism matter, with the shrimp shell discarded as raw material, with urea, melamine, pyrroles as nitrogen source, lazy
Property the lower elder generation's low temperature of gas flow protection carbonize in advance, then with KOH as activator high temperature pyrolysis, in carbonisation, shrimp shell itself
High polymer pyrolytic, there is chemical reaction and can also produce small-molecule substance, such as CO in KOH and carbon source2、H2、H2O etc., makes material internal
Pressure increase, the lamella texture structure that powerful air-flow makes shrimp shell natural struts, formed it is with three-dimensional co-continuous, containing abundant
The lamellar structure of pore structure.The preparation method not only process is simple, it is to avoid conventional preparation template and by presoma in template
The difficulty of infiltration, and with low cost, wide material sources.The material has higher specific surface area, higher N doping amount, and shows
Go out very excellent chemical property.A kind of ultra-thin layer of charcoal of nitrating three-dimensional co-continuous loose structure of the present invention, while exist big
Hole (more than 50nm), mesoporous (2-50nm) and micropore (less than 2nm), it is high that this abundant gap structure is conducive to raising to obtain
Secondary cell chemical property and capacitance.
In the present invention, we have developed a kind of novel porous carbon structure using biomass shrimp shell, and a kind of nitrating is three-dimensional double
The ultra-thin layer of charcoal of continuous poriferous structure, including development preparation method and related application.The method process is simple, cost are controllable relatively
It is low, using the ultra-thin layer of charcoal of nitrogen atom doping three-dimensional co-continuous loose structure, optimize lamellar structure, introduce fake capacitance, improve material
Specific capacity, so as to effectively improve the capacitance of ultracapacitor, and also have excellent at aspects such as secondary cell and gas absorptions
Performance.
Description of the drawings
Fig. 1 is the process chart that the present invention is implemented.
Table 1 is the specific surface area of the ultra-thin layer of charcoal of new nitrating three-dimensional co-continuous loose structure prepared in embodiment 1, hole body
Product hole and size test result.
Table 2 is the XPS analysis result of the ultra-thin layer of charcoal of new nitrating three-dimensional co-continuous loose structure prepared in embodiment 1.
Fig. 2 (a) is the XPS spectrum of the ultra-thin layer of charcoal of new nitrating three-dimensional co-continuous loose structure prepared in embodiment 1, (b)
It is nitrogen spectrum.
Fig. 3 (a) is the low power transmission electricity of the ultra-thin layer of charcoal of new nitrating three-dimensional co-continuous loose structure prepared in embodiment 1
Mirror TEM image, Fig. 3 (b) are high power TEM images.
Fig. 4 is the CV cyclic voltammetry curves in application examples 1 under different scanning rates.
Fig. 5 is the CC charging and discharging curves in application examples 1 under different current densities.
Fig. 6 is CC charging and discharging curves when current density is 0.5A/g in application examples 1.
Fig. 7 is the CV cyclic voltammetry curves in application examples 2 under different scanning rates.
Fig. 8 is the CC charging and discharging curves in application examples 2 under different current densities.
Fig. 9 is CC charging and discharging curves when current density is 0.5A/g in application examples 2.
Figure 10 is capacity curve of 4 electrode material for super capacitor of application examples under different discharge current densities.
The cyclic curve of Figure 11 (a) lithium-sulfur rechargeable batteries that are application examples 5 when current density is 0.1C, Figure 11 (b) work as electricity
The cyclic curve of lithium-sulfur rechargeable battery when current density is 0.5C.
Figure 12 is that the nitrogen adsorption desorption of the ultra-thin layer of charcoal of new nitrating three-dimensional co-continuous loose structure prepared in application examples 6 is bent
Line.
Figure 13 is the pore size distribution figure of the ultra-thin layer of charcoal of new nitrating three-dimensional co-continuous loose structure prepared in application examples 6.
Figure 14 is that the t-Plot thickness of the ultra-thin layer of charcoal of new nitrating three-dimensional co-continuous loose structure prepared in application examples 6 is bent
Line
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, it is below in conjunction with drawings and Examples, right
The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only to explain the present invention, and
It is not used in the restriction present invention.As long as additionally, technical characteristic involved in invention described below each embodiment
Do not constitute conflict each other can just be mutually combined.
Embodiment 1：
New fresh shrimp shell deionized water is cleaned by ultrasonic into the ultrasonic immersing in the NaOH solution that mass fraction is 10% after 3 times
1h, is put in air drying cabinet 80 degree and is dried 12h after outwelling solution.Take and be dried shrimp shell 8g, 40g urea (shrimp shell and urea quality
Than for 1:5) it is placed in beaker, adds 100ml deionized waters, magnetic agitation to be completely dissolved urea, and 50 DEG C of heating is until water
Divide evaporating completely.Then in mortar, grind into powder is put in crucible, under the protection of nitrogen (flow velocity is 100mL/min),
With the ramp of 10 DEG C/min to 400 DEG C in tube furnace, and 1h is kept, carry out pre- charing and obtain presoma.By Low Temperature Thermal
Material after solution and potassium hydroxide in mass ratio 1:1 ratio ground and mixed is uniformly put in crucible, is placed in tube furnace in nitrogen
With the ramp of 10 DEG C/min to 600 DEG C under gas (flow velocity is 100mL/min) protection, and 1h is kept, naturally cool to room temperature.
Then by the 15% watery hydrochloric acid magnetic agitation of mass fraction 2 times of 400ml of the material after high temperature pyrolysis, each 30min removes which
In inorganic constituents.Then deionized water centrifuge washing 4 times is to neutral.Finally products therefrom is put in vacuum drier and is done
The ultra-thin layer of charcoal of new nitrating three-dimensional co-continuous loose structure is obtained after dry 48h.Which is surveyed using BET specific surface area method of testing
Examination, its BET specific surface area reach 2300m2/ g, total hole volume 1.63cm3/ g, average pore size are 2.84nm (being shown in Table 1).XPS photoelectrons
Its nitrogen element content of spectrum analysis is 11% (table 2).About in 10nm, hole is in three-dimensional co-continuous loose structure to ultra-thin carbon layers having thicknesses,
Hole has macropore, mesoporous and micropore, and (see Fig. 3, table is 1).
Table 1
Table 2
Embodiment 2：
New fresh shrimp shell deionized water is cleaned by ultrasonic into the ultrasonic immersing in the NaOH solution that mass fraction is 10% after 3 times
1h, is put in air drying cabinet 80 degree and is dried 12h after outwelling liquid.Take and be dried shrimp shell 15g, 0.15g melamines (shrimp shell and trimerization
Cyanamide mass ratio 1:0.01) 80ml deionized waters are added, magnetic agitation is completely dissolved melamine, and 50 DEG C of heating until
Moisture evaporating completely.Then in mortar, grind into powder is put into after pulverizing in being put into crucible in crucible, in argon in tube furnace
With the ramp of 10 DEG C/min to 450 DEG C under the protection of gas (flow velocity is 100mL/min), and 1h is kept, carry out pre- charing
Presoma is obtained to pre- charing is carried out.By the material after low temperature pyrogenation and NaOH in mass ratio 1:1 ratio ground and mixed
Uniformly it is put in crucible, is placed in tube furnace under argon gas (flow velocity is 100mL/min) protection with the ramp of 10 DEG C/min
To 750 DEG C, and 1h is kept, naturally cool to room temperature.Then it is the material after high temperature pyrolysis is dilute with the mass fraction 15% of 400ml
Nitric acid magnetic agitation 2 times, each 30min remove inorganic constituents therein.Then deionized water centrifuge washing 4 times is to neutral.
Finally products therefrom is put in vacuum drier and is dried 48h.Above-mentioned institute's prepared material BET specific surface area is 1060.23m2/ g, always
Pore volume 0.51cm3/ g, average pore size is 2.5nm, XPS photoelectron spectrums map analysis test nitrogen element content be 1.25%, SEM,
TEM image shows three-dimensional apertures distributed architecture.
Embodiment 3：
New fresh shrimp shell deionized water is cleaned by ultrasonic into the ultrasonic immersing in the KOH solution that mass fraction is 10% after 3 times
2h, is put in air drying cabinet 80 degree and is dried 12h after outwelling solution.Take shrimp shell, pyrroles's mass ratio is dried for 1:5, it is placed in beaker
In, add 100ml deionized waters, magnetic agitation to be completely dissolved pyrroles, and 50 DEG C of heating are until moisture evaporating completely.Then exist
In mortar, grind into powder is put in crucible, under the protection of nitrogen (flow velocity is 200mL/min), in tube furnace with 10 DEG C/
The ramp of min is to 500 DEG C, and keeps 1h, carries out pre- charing and obtains presoma.By material and potassium carbonate after low temperature pyrogenation
In mass ratio 1:3 ratio ground and mixed is uniformly put in crucible, is placed in tube furnace and is protected in nitrogen (flow velocity is 200mL/min)
With the ramp of 10 DEG C/min to 850 DEG C under shield, and 1h is kept, naturally cool to room temperature.Then by the thing after high temperature pyrolysis
The excessive 15% dilute sulfuric acid magnetic agitation of mass fraction of matter 2 times, each 30min, and deionized water centrifuge washing 4 times are into
Property, finally products therefrom is put in vacuum drier and is dried 48h.Its BET specific surface area reaches 1800m2/ g, total hole volume
1.45cm3/ g, average pore size are 2.5nm, and its nitrogen element content of XPS photoelectron spectrums map analysis is 10%.
Embodiment 4：
New fresh shrimp shell deionized water is cleaned by ultrasonic into the ultrasonic immersing in the NaOH solution that mass fraction is 10% after 3 times
1h, is put in air drying cabinet 80 degree and is dried 12h.Take shrimp shell, urea quality ratio is dried for 1:2, it is placed in beaker, adds
100ml deionized waters, magnetic agitation are completely dissolved urea, and 50 DEG C of heating are until moisture evaporating completely.Then in mortar
Grind into powder is put in crucible, under the protection of nitrogen (flow velocity is 100mL/min), with the speed of 10 DEG C/min in tube furnace
Rate is warming up to 550 DEG C, and keeps 1h.By the material after low temperature pyrogenation and sodium carbonate in mass ratio 1:1 ratio ground and mixed is equal
It is even to be put in crucible, it is placed in tube furnace under nitrogen (flow velocity is 100mL/min) protection with the ramp of 10 DEG C/min extremely
950 DEG C, and 1h is kept, naturally cool to room temperature.Then by the material after high temperature pyrolysis excessive 10% dilute salt of mass fraction
Products therefrom is finally put into vacuum to neutral by sour magnetic agitation 2 times, each 30min, and deionized water centrifuge washing 4 times
48h is dried in drying machine.Its BET specific surface area reaches 2050m2/ g, total hole volume 1.61cm3/ g, average pore size are 2.6nm, XPS
Its nitrogen element content of photoelectron spectrum map analysis is 12%.
Embodiment 5：
New fresh shrimp shell deionized water is cleaned by ultrasonic into the ultrasonic immersing in the KOH solution that mass fraction is 10% after 3 times
2h, is put in air drying cabinet 80 degree and is dried 12h.Take shrimp shell, urea quality ratio is dried for 1:5, it is placed in beaker, adds
100ml deionized waters, magnetic agitation are completely dissolved urea, and 50 DEG C of heating are until moisture evaporating completely.Then in mortar
Grind into powder is put in crucible, under the protection of nitrogen (flow velocity is 200mL/min), with the speed of 10 DEG C/min in tube furnace
Rate is warming up to 450 DEG C, and keeps 1h.By the material after low temperature pyrogenation and activator KOH in mass ratio 1:2 ratio ground and mixed
Uniformly it is put in crucible, is placed in tube furnace under nitrogen (flow velocity is 200mL/min) protection with the ramp of 10 DEG C/min
To 1000 DEG C, and 1h is kept, naturally cool to room temperature.Then will be the material after high temperature pyrolysis excessive mass fraction 20% dilute
Hydrochloric acid, dilute sulfuric acid, dust technology mixture, magnetic agitation 2 times, each 30min, and deionized water centrifuge washing 4 times to neutral,
Finally products therefrom is put in vacuum drier and is dried 48h.Its BET specific surface area reaches 1960m2/ g, total hole volume 1.95cm3/
G, average pore size are 3.2nm, and its nitrogen element content of XPS photoelectron spectrums map analysis is 10.4%
Application example 1
It is 0.5mol L- by the nitrating obtained in embodiment 1 three-dimensional co-continuous loose structure ultra-thin layer of charcoal in electrolyte
1H2SO4Three-electrode system in carry out electro-chemical test, wherein reference electrode is Ag/AgCl, and auxiliary electrode is platinum electrode.Will
The material is configured to the solution of 10mg/mL, wherein deionized water and isopropanol ratios 1:4, binding agent nafion mass accounts for activity
The 5% of material, by solution drop coating on vitreous carbon, as working electrode after being dried.CV is carried out under voltage 0-1.1V scopes to follow
Ring volt-ampere is tested, and CV curves show rectangular shape, even if surface sweeping speed increases to 500mv s-1, curve is still presented square
Shape shape, is 2mv s when speed is swept-1、5mv·s-1、10mv·s-1、20mv·s-1、50mv·s-1、100mv·s-1With
200mv·s-1When, specific capacity is measured in 0～1.1v voltage ranges is respectively 464.08F g-1、372.29F·g-1、
326.31F·g-1、298.66F·g-1、259.23F·g-1、234.36F·g-1、211.87F·g-1, when increasing to 500mv
s-1When, specific capacity remains at 188.22F g-1.When CC charge-discharge tests are carried out, when current density is 0.5A g-1、
1A·g-1、2A·g-1、5A·g-1、10A·g-1、20A·g-1When, specific capacity is respectively 498.63F g-1、370.91F·g-1、
310F·g-1、255.9F·g-1、233.63F·g-1、203.63F·g-1, when current density increases to 40A/g, specific capacity is still
181.81F g are maintained at so-1, show material have good capacitance behavior and multiplying power have good high rate performance (see Fig. 4,
Fig. 5, Fig. 6).
Application example 2
It is 2mol L by the nitrating obtained in embodiment 1 three-dimensional co-continuous loose structure ultra-thin layer of charcoal in electrolyte- 1Li2SO4Three-electrode system carry out electro-chemical test, wherein reference electrode is Ag/AgCl, and auxiliary electrode is platinum electrode.Will
The material is configured to the solution of 10mg/mL, wherein deionized water and isopropanol ratios 1:4, binding agent PVDF
(polyvinylidene fluoride) quality accounts for the 5% of active material, by solution drop coating on vitreous carbon, conduct after being dried
Working electrode.It is 2mv s that CV cyclic voltammetries are carried out under voltage -1.6～1.2V scopes when speed is swept-1、5mv·s-1、
10mv·s-1、20mv·s-1、50mv·s-1、100mv·s-1When, electric capacity is respectively 496.14F g-1、357.48F·g-1、
288.41F·g-1、239.72F·g-1、195.73F·g-1、166.29F·g-1, when sweeping speed and increasing to 200mv/s, specific capacity
Remain at 141.99F g-1.When CC charge-discharge tests are carried out, when current density is 0.5A g-1、1A·g-1、2A·g-1、
5A·g-1、10A·g-1、20A·g-1When, specific capacity is respectively 339F g-1、208F·g-1、160.4F·g-1、117.4F·
g-1、89.6F·g-1、38.55F·g-1.Its voltage window widens 2.8V, and still keeps higher specific capacity.(see Fig. 7, figure
8th, Fig. 9).
Application example 3
The nitrating obtained in embodiment 1 three-dimensional co-continuous loose structure ultra-thin layer of charcoal is applied to into electrode of super capacitor,
The material is configured to into the solution of 10mg/mL, wherein deionized water and isopropanol ratios 1:4, binding agent nafion ratios are
5%, using solution drop coating on graphite carbon paper as electrode slice, using two electrode slices identical in quality as negative electrode and anode, electricity
Solution liquid is 0.5mol L-1H2SO4, barrier film is celgard3501, is assembled into button capacitor.When current density is in 0.5A/g,
Specific capacity reaches 417.5F g-1.When current density increases to 40A g-1, still remain in 224F g-1, follow through 5000 times
After ring, when current density is in 0.5A g-1When, specific capacity remains within 376F g-1(90% capability retention).(see
Figure 10)
Application example 4
The nitrating obtained in embodiment 1 three-dimensional co-continuous loose structure ultra-thin layer of charcoal is applied to into lithium-sulfur rechargeable battery, is glued
Knot agent is sodium carboxymethylcellulose (CMC-Na) and butadiene-styrene rubber (SBR), CMC-Na：SBR：The ultra-thin charcoal of nitrating three-dimensional porous structure
Layer：Elemental sulfur：The mass ratio of Super-P is 5:5:24:56:10, ground slurry carries out smear, and 80 DEG C of vacuum drying 12h are laggard
, used as positive electrode, used as negative pole, electrolyte is from addition 2wt%LiNO for lithium metal for row compressing tablet31M1,3- dioxolanes
(DOL) mixed solution (DEM, the DOL volume of/glycol dimethyl ether (DME) base two (trifluoromethane sulfonic acid) imine lithium (LiTFSI)
Than for 1:1), barrier film selects Celgard2400, the assembled battery under argon gas protection in glove box.In charging and discharging currents density it is
During 0.1C, first discharge specific capacity is about 1160mAh/g, and after 100 circulations, specific discharge capacity is still maintained at about
565mAh/g；When charging and discharging currents density is 0.5C, first discharge specific capacity is for about 1050mAh/g, is circulated through 100 times
Afterwards, specific discharge capacity is still maintained at about 438mAh/g (see Figure 11).
Application example 5
The nitrating obtained in embodiment 1 three-dimensional co-continuous loose structure ultra-thin layer of charcoal is applied to into the absorption of gas, is adopted
Gas adsorption method is tested, and ASAP2020 physical adsorption appearance of the tester for micromeritics companies of the U.S., in liquid nitrogen
At temperature (- 195 DEG C), relative pressure is that 0.01～1 scope carries out adsorption/desorption experiment to nitrogen, obtains Adsorption and desorption isotherms
Specific surface area can be can be calculated by BET method, and the result for measuring is 2300m2/ g, can be seen that curve from nitrogen adsorption desorption curve
Type is I types, illustrates that the material belongs to pore type.And nitrogen molecule belongs to micro-molecular gas, thus explanation material is for little point
Sub- gas has stronger suction-operated, can be used for the aspects such as absorption, the isolation and purification of gas.(see Figure 12, Figure 13, Figure 14)
The ultra-thin layer of charcoal ultracapacitor of nitrating three-dimensional co-continuous loose structure prepared by the present invention is used in electro-chemical test
0.5mol·L-1HCl solution be electrolyte solution, the test of chemical property is carried out using three-electrode system, wherein reference electricity
Extremely Ag/AgCl, auxiliary electrode are platinum electrode, and working electrode is material electrodes.In cyclic voltammetry, the performance of CV curves
Rectangular shape is gone out, even if surface sweeping speed increases to 500mv s-1, curve is still presented rectangular shape, is 2mv s when speed is swept-1、10mv·s-1、50mv·s-1With 200mv s-1When, specific capacity is measured in 0-1.1v voltage ranges be respectively 464.08F
g-1、326.31F·g-1、259.23F·g-1、211.87F·g-1, when increasing to 500mv s-1When, electric capacity is remained at
188.22F·g-1.In charge-discharge test, when current density is 0.5A g-1、1A·g-1、5A·g-1When, specific capacity is respectively
498.63F·g-1、370.91F·g-1、255.9F·g-1, when current density increases to 20A g-1When, specific capacity is remained in that
In 203.63F g-1, show that there is material good capacitance behavior and multiplying power to have good high rate performance.
The ultra-thin layer of charcoal of nitrating three-dimensional co-continuous porous prepared by the present invention is electrode assembling into button-shaped ultracapacitor, and
Carry out electrochemical property test.When current density is in 0.5A g-1, specific capacity reaches 417.5F g-1.When current density increases
To 40A g-1, still remain in 224F g-1, after 5000 circulations, when current density is in 0.5A g-1When, specific volume
Amount remains within 376F g-1(90% capability retention).Show that material has good capacitance characteristic and stability.
As it will be easily appreciated by one skilled in the art that the foregoing is only presently preferred embodiments of the present invention, not to
The present invention, all any modification, equivalent and improvement made within the spirit and principles in the present invention etc. is limited, all should be included
Within protection scope of the present invention.
Claims (10)
1. the ultra-thin layer of charcoal preparation method of a kind of nitrating three-dimensional co-continuous loose structure, it is characterised in that comprise the following steps：
(1) first shrimp shell raw material deionized water is cleaned by ultrasonic, then the ultrasonic immersing cleaning in alkaline solution, by shrimp shell after cleaning
Drying；
(2) shrimp shell that is dried for obtaining step (1) is 1 with nitrogen-containing material in mass ratio：0.01～5 ratio mixing, spend from
Sub- water heating stirring mixing is until moisture evaporating completely；
(3) mixture obtained by step (2) is ground to into powder, then carries out low temperature pyrogenation under the protection of inert gas；
(4) by the material obtained after step (3) low temperature pyrogenation and alkaline matter in mass ratio 1：0.5～3 ratio ground and mixed
Uniformly, high temperature pyrolysis are carried out under inert gas shielding；
(5) diluted acid by step (4) by the material obtained after high temperature pyrolysis with excess mixes lixiviating, then deionized water
Centrifuge washing outwells supernatant to neutrality.
(6) step (5) products therefrom is dried to obtain into the ultra-thin layer of charcoal of nitrating three-dimensional co-continuous loose structure.
2. the preparation method of the ultra-thin layer of charcoal of nitrating according to claim 1 three-dimensional co-continuous loose structure, it is characterised in that
In step (1), alkaline solution is NaOH, potassium hydroxide a kind of or for the mixed solution of two kinds of solution；Solution quality
Fraction is 10%.
3. the preparation method of the ultra-thin layer of charcoal of nitrating according to claim 1 and 2 three-dimensional co-continuous loose structure, its feature exist
In, in step (1), drying temperature is 80-150 DEG C.
4. the preparation method of the ultra-thin layer of charcoal of nitrating according to claim 1 three-dimensional co-continuous loose structure, it is characterised in that
In step (2), nitrogen source is urea, melamine, pyrroles's one of which or their mixture, and stirring mixing temperature is 50 DEG C,
Rotating speed is 300r/min.
5. the preparation method of the ultra-thin layer of charcoal of nitrating according to claim 1 three-dimensional co-continuous loose structure, it is characterised in that
In step (3), at 400-550 DEG C, step (4) high temperature pyrolysis temperature is at 600-1000 DEG C for low temperature pyrogenation temperature.
6. the preparation method of the ultra-thin layer of charcoal of nitrating three-dimensional co-continuous loose structure according to claim 1 or 5, its feature exist
In, in step (3), (4), inert gas is nitrogen or argon gas；Programming rate is 10 DEG C/min, and gas flow rate is 100-200mL/
min。
7. the preparation method of the ultra-thin layer of charcoal of nitrating according to claim 1 three-dimensional co-continuous loose structure, it is characterised in that
In step (4), alkaline matter is the mixed of more than NaOH, potassium hydroxide, sodium carbonate, the one kind in potassium carbonate or two of which
Compound.
8. the preparation method of the ultra-thin layer of charcoal of nitrating according to claim 1 three-dimensional co-continuous loose structure, it is characterised in that
In step (5), diluted acid can be the hydrochloric acid that mass concentration is 10-20%, nitric acid, one kind of sulfuric acid or their mixture, stir
Mix rotating speed 500r/min；The each 5min of centrifugation time, centrifugal rotational speed is 1000r/min.
9. the ultra-thin layer of charcoal of a kind of nitrating three-dimensional co-continuous loose structure that according to claim 1 prepared by method, its feature exist
In in 1-100nm, its BET specific surface area is 1000-2300m to ultra-thin carbon layers having thicknesses2/ g, total hole volume are 0.5-1.63cm3/ g,
Average pore size is 2-4nm, and nitrogen mass content is 1-11wt%.
10. the purposes of the ultra-thin layer of charcoal of nitrating three-dimensional co-continuous loose structure that according to claim 1 prepared by method, its feature
It is that the ultra-thin layer of charcoal of nitrating three-dimensional co-continuous loose structure is used for ultracapacitor, secondary cell and gas absorption.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108002360A (en) * | 2017-11-30 | 2018-05-08 | 浙江海洋大学 | A kind of preparation based on shrimp and crab shells biomass carbon electrode material for super capacitor |
| CN108465815A (en) * | 2018-02-13 | 2018-08-31 | 东莞市联洲知识产权运营管理有限公司 | A kind of porous carbon-based transition metal porous material and preparation method thereof of three-dimensional co-continuous |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102887501A (en) * | 2011-07-21 | 2013-01-23 | 海洋王照明科技股份有限公司 | Method for preparing nitrating graphene |
| CN103058177A (en) * | 2013-01-05 | 2013-04-24 | 张家港市东大工业技术研究院 | Preparation method for realizing N-doped grapheme by high-energy microwave vacuum irradiation |
| CN103420353A (en) * | 2012-05-15 | 2013-12-04 | 北京化工大学 | Porous carbon material and preparation method and application thereof |
| CN105314629A (en) * | 2015-11-27 | 2016-02-10 | 燕山大学 | Method for directly preparing co-doping three-dimensional graphene electrode material through biomass carbon sources |
| CN105390672A (en) * | 2015-10-21 | 2016-03-09 | 天津大学 | Preparation method for three-dimensional nitrogen-doped mesoporous carbon ultra-thin nanosheet material |
-
2016
- 2016-10-09 CN CN201610880172.1A patent/CN106517133B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102887501A (en) * | 2011-07-21 | 2013-01-23 | 海洋王照明科技股份有限公司 | Method for preparing nitrating graphene |
| CN103420353A (en) * | 2012-05-15 | 2013-12-04 | 北京化工大学 | Porous carbon material and preparation method and application thereof |
| CN103058177A (en) * | 2013-01-05 | 2013-04-24 | 张家港市东大工业技术研究院 | Preparation method for realizing N-doped grapheme by high-energy microwave vacuum irradiation |
| CN105390672A (en) * | 2015-10-21 | 2016-03-09 | 天津大学 | Preparation method for three-dimensional nitrogen-doped mesoporous carbon ultra-thin nanosheet material |
| CN105314629A (en) * | 2015-11-27 | 2016-02-10 | 燕山大学 | Method for directly preparing co-doping three-dimensional graphene electrode material through biomass carbon sources |
Cited By (9)
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|---|---|---|---|---|
| CN108002360A (en) * | 2017-11-30 | 2018-05-08 | 浙江海洋大学 | A kind of preparation based on shrimp and crab shells biomass carbon electrode material for super capacitor |
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| CN108922794A (en) * | 2018-06-05 | 2018-11-30 | 江苏海基新能源股份有限公司 | A kind of preparation method of N doping biology base active carbon electrode material |
| CN110127662A (en) * | 2019-05-26 | 2019-08-16 | 天津大学 | A method of assist charing Small molecule organic solvents to prepare porous charcoal using alkali metal |
| CN110127662B (en) * | 2019-05-26 | 2022-02-01 | 天津大学 | Method for preparing porous carbon by using alkali metal-assisted carbonization small-molecule organic solvent |
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| CN111591988A (en) * | 2020-06-09 | 2020-08-28 | 山东大学 | Porous carbon prepared from nitrogen source modified enteromorpha and preparation method and application thereof |
| CN116632221A (en) * | 2023-07-24 | 2023-08-22 | 深圳海辰储能控制技术有限公司 | Negative electrode material, preparation method thereof, negative electrode plate, energy storage device and power utilization device |
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