CN106517133B - Ultra-thin layer of charcoal of nitrating three-dimensional co-continuous porous structure and its preparation method and application - Google Patents
Ultra-thin layer of charcoal of nitrating three-dimensional co-continuous porous structure and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of ultra-thin layer of charcoal preparation method and applications of nitrating three-dimensional co-continuous porous structure.Preparation method includes shrimp shell pre-treatment, and using urea, melamine or pyrroles as nitrogen source, using treated shrimp shell as raw material, under inert gas flow, it first carbonizes the high temperature pyrolysis together with alkaline matter again in advance through low temperature, the ultra-thin layer of charcoal of nitrating three-dimensional co-continuous porous structure is obtained finally by acid processing.The ultra-thin layer of charcoal of nitrating three-dimensional co-continuous porous structure prepared by the preparation method has unique Nano ultrathin Char Residues Structure, there is high specific surface area, total hole volume, and simple for process, cost is relatively low, environmental-friendly, has preferable physical and chemical performance.Present invention can apply to ultracapacitor, secondary cell, gas absorptions, and a new way is opened for the biomass new material that taps a new source of energy.
Description
Technical field
It is more more particularly, to a kind of nitrating three-dimensional co-continuous the invention belongs to biomass carbon materials preparation and application field
Ultra-thin layer of charcoal of pore structure and its preparation method and application.
Background technology
With the worsening shortages of non-renewable energy resources and increasingly severe environmental pollution, people are to regenerative resource and green
Color new energy will be increasingly dependent on.Biomass energy is to be only second to the fourth largest source of coal, oil and natural gas, has high storage
Can, renewable, free of contamination feature, showing appreciation for somebody for people is constantly subjected in terms of preparing carbon material using biomass, electrochemistry,
The fields such as sewage disposal, the absorption of pernicious gas have a wide range of applications, especially in electrochemical field, using biomass as raw material
The carbon material of preparation has the advantages that high specific surface area, high stability, good electric conductivity and energy large-scale commercial production.
With Daxing exploitation of the China coast one with aquatic products industry, tourist industry, the waste of the marine products such as shrimp shell increases year by year,
Cause the waste of resource and the pollution of environment.Containing abundant carbon source in shrimp shell, have unique lamellar structure, and derive from a wealth of sources,
Of low cost, environmental-friendly, preparing porous carbon as raw material using shrimp shell has unique advantage.
Biomass mainly has 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, occur using with presoma
Redox reaction carry out pore-forming character；Chemical activation method is to use alkali (KOH, NaOH, K2CO3) or H3PO4、ZnCl2Etc. chemical substances
Chemical attack is carried out to presoma, reacting increase specific surface area by pyrolytic polycondensation in activation process forms abundant gap knot
Structure；Template is to introduce a kind of material with orderly hole, in a template by presoma infiltration, makes to react in its hole, profit
With itself restriction effect of mould material, the carbon material of the ordering with single aperture is prepared.Above-mentioned three kinds of methods respectively have
Advantage and disadvantage：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 unique advantage, but present template is mostly based on some expensive templates, preparation process
Complexity, cost are higher.The porous carbon materials containing relatively orderly hole of Development of Novel are a huge challenges.
Ultracapacitor is a kind of novel electrochemical energy energy storage device, there is high energy density than traditional capacitor,
There is high power density than battery, and service life cycle is long, at low cost, is applied to numerous areas.It is answered in ultracapacitor
With under the continuous expansion driving in field, height ratio capacity is developed, 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.Since porous carbon material derives from a wealth of sources, chemistry is steady
Fixed and service life cycle is long, especially has high-specific surface area and Gao Kongrong, and relative to carbon materials such as carbon nanotube, graphenes
Material has many advantages, such as at low cost, abundant raw material, therefore it is used to become current research heat as the electrode material of ultracapacitor
Point.
Some researches show that, it is porous ultra-thin carbon-coating prepared by carbon source using natural biologic material, it is environmental-friendly, and its own
The uniqueness of biological template structure shows the advantage of application performance, and forms carbon matrix and hole based on biomass porous carbon
Bicontinuous structure, and can be expanded in length, width, thickness three dimension scale, there are the physical properties such as better conduction.Cause
This, it is the key that prepare different performance and the porous carbon of purposes to select different carbon source biological templates and treatment process.Such as Li
Sun et al. uses coconut husk as more in [Journal of Materials Chemistry A 2013,1,6462-6470]
The presoma of hole charcoal, in catalyst Fe Cl3With activator Zncl2The lower high temperature pyrolysis of effect simultaneously acid treated obtains porous carbon
Material, BET specific surface area 1874m2/ g, total hole volume 1.21cm3/ g, specific capacitance 268F/g, and answered as electrode material
With on ultracapacitor.And the general specific surface area of carbon-based material is in 2180-3100m2/ g, but existing multiporous biological matter
Carbon, because reasons, the specific capacitance such as material composition and structure are relatively low (250F/g)；The practical specific capacitance of existing graphene also limits
System is in 300F/g.
Invention content
Present invention aims at a kind of new ultra-thin layer of charcoal of nitrating three-dimensional co-continuous porous structure of offer and preparation method thereof
And application, the higher disadvantage of complex process, cost in template preparation process can be overcome, in conjunction with biomass template, Physical
With the advantage of chemical method, while it being easier to make for nitrogen atom doping, finally preparing a kind of has that pattern is special, chemical property
The ultra-thin layer of charcoal of superior novel nitrating three-dimensional co-continuous porous structure.
To achieve the goals above, according to one aspect of the present invention, the present invention provides a kind of nitrating three-dimensional co-continuous
The ultra-thin layer of charcoal preparation method of porous structure, step include：
(1) first shrimp shell raw material is cleaned by ultrasonic with deionized water, then ultrasonic immersing is cleaned in alkaline solution, it will after cleaning
Shrimp shell is dried；
(2) the drying shrimp shell for obtaining step (1) is 1 in mass ratio with nitrogen-containing material：0.01~5 ratio mixing, is used
The mixing of deionized water heating stirring is until moisture evaporating completely；
(3) mixture obtained by step (2) is ground to powdered, Low Temperature Thermal is then carried out under the protection of inert gas
Solution；
(4) by the substance obtained after step (3) low temperature pyrogenation and alkaline matter in mass ratio 1：0.5~3 ratio grinding
It is uniformly mixed, carries out high temperature pyrolysis under inert gas protection；
(5) lixiviating is mixed in the substance obtained after high temperature pyrolysis and excessive diluted acid by step (4), then spend from
Supernatant is outwelled after sub- water centrifuge washing to neutrality.
(6) step (5) products therefrom is dried to obtain the ultra-thin layer of charcoal of nitrating three-dimensional co-continuous porous structure.
Further, in step (1), alkaline solution is sodium hydroxide, potassium hydroxide a kind of or is 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
It is 50 DEG C to mix mixing temperature, rotating speed 300r/min.
Further, low temperature pyrogenation temperature is at 400-550 DEG C in step (3), and step (4) high temperature pyrolysis temperature is in 600-
1000℃。
Further, in step (3), (4), inert gas is nitrogen or argon gas；Heating rate is 10 DEG C/min, gas stream
Speed is 100-200mL/min.
Further, in step (4), alkaline matter is one kind in sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate
Or in which two or more mixture.
Further, in step (5), diluted acid can be one kind that mass concentration is the hydrochloric acid of 10-20%, nitric acid, sulfuric acid
Or their mixture, speed of agitator 500r/min；Centrifugation time each 5min, centrifugal rotational speed 1000r/min.
Further, ultra-thin carbon layers having thicknesses are in 1-100nm, BET specific surface area 1000-2300m2/ g, total hole volume
For 0.5-1.63cm3/ g, average pore size 2-4nm, nitrogen mass content are 1-11wt%.
Further, the ultra-thin layer of charcoal of nitrating three-dimensional co-continuous porous structure is gentle for ultracapacitor, secondary cell
Body adsorbs.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, effect of the invention：This
Invention is from the fourth largest source biomass, using discarded shrimp shell as raw material, using urea, melamine, pyrroles as nitrogen source, lazy
Property the lower first low temperature of gas flow protection carbonize in advance, then using KOH as activator high temperature pyrolysis, in carbonisation, shrimp shell itself
High polymer pyrolytic, KOH and carbon source occur chemical reaction and also will produce small-molecule substance, such as CO2、H2、H2O etc., makes material internal
Pressure increase, the lamella texture structure that powerful air-flow keeps shrimp shell natural struts, formed have three-dimensional co-continuous, containing abundant
The lamellar structure of pore structure.The preparation method is not only simple for process, avoids previous preparation template and by presoma into template
The difficulty of infiltration, and it is of low cost, derive from a wealth of 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 porous structure of the present invention exists simultaneously big
Hole (being more than 50nm), mesoporous (2-50nm) and micropore (being less than 2nm), it is high that this abundant gap structure is conducive to raising acquisition
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 continuous poriferous ultra-thin layer of charcoal of structure, including development preparation method and related application.This method is simple for process, and cost is controllably relatively
It is low, using the ultra-thin layer of charcoal of nitrogen atom doping three-dimensional co-continuous porous structure, optimize lamellar structure, introduce fake capacitance, improves material
Specific capacity, to effectively improve the capacitance of ultracapacitor, and also have in secondary cell and gas absorption etc. excellent
Performance.
Description of the drawings
Fig. 1 is the process flow chart that the present invention is implemented.
Table 1 is the specific surface area of the ultra-thin layer of charcoal of novel nitrating three-dimensional co-continuous porous 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 novel nitrating three-dimensional co-continuous porous structure prepared in embodiment 1.
Fig. 2 (a) is the XPS spectrum of the ultra-thin layer of charcoal of novel nitrating three-dimensional co-continuous porous 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 novel nitrating three-dimensional co-continuous porous structure prepared in embodiment 1
Mirror TEM image, Fig. 3 (b) are high power TEM images.
Fig. 4 is the CV cyclic voltammetry curves under different scanning rates in application examples 1.
Fig. 5 is the CC charging and discharging curves under different current densities in application examples 1.
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 under different scanning rates in application examples 2.
Fig. 8 is the CC charging and discharging curves under different current densities in application examples 2.
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.
Figure 11 (a) is the cyclic curve of the lithium-sulfur rechargeable battery when current density is 0.1C of application examples 5, and Figure 11 (b) works 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 novel nitrating three-dimensional co-continuous porous 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 novel nitrating three-dimensional co-continuous porous structure prepared in application examples 6.
Figure 14 is that the t-Plot thickness of the ultra-thin layer of charcoal of novel nitrating three-dimensional co-continuous porous structure prepared in application examples 6 is bent
Line
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
It does not constitute a conflict with each other and can be combined with each other.
Embodiment 1：
New fresh shrimp shell is spent into the ultrasonic immersing in the NaOH solution that mass fraction is 10% after ionized water is cleaned by ultrasonic 3 times
1h is put into 80 degree of dry 12h in air drying cabinet after outwelling solution.Take dry shrimp shell 8g, 40g urea (shrimp shell and urea quality
Than being 1:5) it is placed in beaker, 100ml deionized waters is added, magnetic agitation makes urea be completely dissolved, and 50 DEG C of heating are until water
Divide evaporating completely.Then grind into powder is put into crucible in mortar, under the protection of nitrogen (flow velocity 100mL/min),
400 DEG C are warming up to the rate of 10 DEG C/min in tube furnace, and keeps 1h, pre- charing is carried out and obtains presoma.By Low Temperature Thermal
Substance 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
600 DEG C are warming up to the rate of 10 DEG C/min under gas (flow velocity 100mL/min) protection, and keeps 1h, cooled to room temperature.
Then by the 15% dilute hydrochloric acid magnetic agitation of mass fraction 2 times of 400ml of the substance after high temperature pyrolysis, each 30min removes it
In inorganic constituents.Then use deionized water centrifuge washing 4 times to neutral.Finally products therefrom is put into vacuum drier and is done
The ultra-thin layer of charcoal of novel nitrating three-dimensional co-continuous porous structure is obtained after dry 48h.It is surveyed using BET specific surface area method of testing
Examination, 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).For ultra-thin carbon layers having thicknesses about in 10nm, hole is in three-dimensional co-continuous porous structure,
Hole has macropore, mesoporous and micropore (see Fig. 3, table 1).
Table 1
Table 2
Embodiment 2：
New fresh shrimp shell is spent into the ultrasonic immersing in the NaOH solution that mass fraction is 10% after ionized water is cleaned by ultrasonic 3 times
1h is put into 80 degree of dry 12h in air drying cabinet after outwelling liquid.Take dry shrimp shell 15g, 0.15g melamines (shrimp shell and trimerization
Cyanamide mass ratio 1:0.01) 80ml deionized waters, are added, magnetic agitation makes melamine be completely dissolved, and 50 DEG C of heating until
Moisture evaporating completely.Then in mortar grind into powder be put into pulverized in crucible after be put into crucible, in argon in tube furnace
450 DEG C are warming up to the rate of 10 DEG C/min under the protection of gas (flow velocity 100mL/min), and keeps 1h, progress carbonizes in advance
Presoma is obtained to pre- charing is carried out.By the substance and sodium hydroxide in mass ratio 1 after low temperature pyrogenation:1 ratio ground and mixed
It is uniformly put in crucible, is placed in tube furnace and is heated up with the rate of 10 DEG C/min under argon gas (flow velocity 100mL/min) protection
To 750 DEG C, and 1h is kept, cooled to room temperature.Then the substance 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 use deionized water centrifuge washing 4 times to neutral.
Products therefrom is finally put into vacuum drier dry 48h.Above-mentioned institute's prepared material BET specific surface area is 1060.23m2/ g, always
Pore volume 0.51cm3/ g, average pore size 2.5nm, XPS photoelectron spectrum map analysis test nitrogen element content be 1.25%, SEM,
TEM image shows three-dimensional apertures distributed architecture.
Embodiment 3：
New fresh shrimp shell is spent into the ultrasonic immersing in the KOH solution that mass fraction is 10% after ionized water is cleaned by ultrasonic 3 times
2h is put into 80 degree of dry 12h in air drying cabinet after outwelling solution.It is 1 to take dry shrimp shell, pyrroles's mass ratio:5, it is placed in beaker
In, 100ml deionized waters are added, magnetic agitation makes pyrroles be completely dissolved, and 50 DEG C of heating are until moisture evaporating completely.Then exist
Grind into powder is put into crucible in mortar, under the protection of nitrogen (flow velocity 200mL/min), in tube furnace with 10 DEG C/
The rate of min is warming up to 500 DEG C, and keeps 1h, carries out pre- charing and obtains presoma.By the substance 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 at nitrogen (flow velocity 200mL/min)
850 DEG C are warming up to the rate of 10 DEG C/min under shield, and keeps 1h, cooled to room temperature.Then by the object after high temperature pyrolysis
Deionized water centrifuge washing is used in combination 4 times into matter 15% dilute sulfuric acid magnetic agitation of excessive mass fraction 2 times, each 30min
Property, products therefrom is finally put into vacuum drier dry 48h.Its BET specific surface area reaches 1800m2/ g, total hole volume
1.45cm3/ g, its nitrogen element content of average pore size 2.5nm, XPS photoelectron spectrum map analysis are 10%.
Embodiment 4：
New fresh shrimp shell is spent into the ultrasonic immersing in the NaOH solution that mass fraction is 10% after ionized water is cleaned by ultrasonic 3 times
1h is put into 80 degree of dry 12h in air drying cabinet.It is 1 to take dry shrimp shell, urea quality ratio:2, it is placed in beaker, is added
100ml deionized waters, magnetic agitation make urea be completely dissolved, and 50 DEG C of heating are until moisture evaporating completely.Then in mortar
Grind into powder is put into crucible, under the protection of nitrogen (flow velocity 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 substance and sodium carbonate in mass ratio 1 after low temperature pyrogenation:1 ratio ground and mixed is equal
It is even to be put in crucible, it is placed in tube furnace and is warming up to the rate of 10 DEG C/min under nitrogen (flow velocity 100mL/min) protection
950 DEG C, and 1h is kept, cooled to room temperature.Then by the 10% dilute salt of excessive mass fraction of the substance after high temperature pyrolysis
Sour magnetic agitation 2 times, each 30min is used in combination deionized water centrifuge washing 4 times to neutrality, products therefrom is finally put into vacuum
Dry 48h in drying machine.Its BET specific surface area reaches 2050m2/ g, total hole volume 1.61cm3/ g, average pore size 2.6nm, XPS
Its nitrogen element content of photoelectron spectrum map analysis is 12%.
Embodiment 5：
New fresh shrimp shell is spent into the ultrasonic immersing in the KOH solution that mass fraction is 10% after ionized water is cleaned by ultrasonic 3 times
2h is put into 80 degree of dry 12h in air drying cabinet.It is 1 to take dry shrimp shell, urea quality ratio:5, it is placed in beaker, is added
100ml deionized waters, magnetic agitation make urea be completely dissolved, and 50 DEG C of heating are until moisture evaporating completely.Then in mortar
Grind into powder is put into crucible, under the protection of nitrogen (flow velocity 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 substance and activator KOH in mass ratio 1 after low temperature pyrogenation:2 ratio ground and mixed
It is uniformly put in crucible, is placed in tube furnace and is heated up with the rate of 10 DEG C/min under nitrogen (flow velocity 200mL/min) protection
To 1000 DEG C, and 1h is kept, cooled to room temperature.Then the substance after high temperature pyrolysis is dilute with excessive mass fraction 20%
Hydrochloric acid, dilute sulfuric acid, dust technology mixture, magnetic agitation 2 times, each 30min are used in combination deionized water centrifuge washing 4 times to neutral,
Products therefrom is finally put into vacuum drier dry 48h.Its BET specific surface area reaches 1960m2/ g, total hole volume 1.95cm3/
G, its nitrogen element content of average pore size 3.2nm, XPS photoelectron spectrum map analysis are 10.4%
Application example 1
By the nitrating ultra-thin layer of charcoal of three-dimensional co-continuous porous structure obtained in embodiment 1 electrolyte be 0.5molL-
1H2SO4Three-electrode system in carry out electro-chemical test, wherein reference electrode is Ag/AgCl, and auxiliary electrode is platinum electrode.It will
The material is configured to the solution of 10mg/mL, wherein deionized water and isopropanol ratios 1:4, binder nafion mass accounts for activity
The 5% of material is used as working electrode by solution drop coating on vitreous carbon after dry.CV is carried out under voltage 0-1.1V ranges to follow
Ring volt-ampere is tested, and CV curves show rectangular shape, even if surface sweeping rate increases to 500mvs-1, curve, which remains unchanged, is presented square
Shape shape is 2mvs when sweeping speed-1、5mv·s-1、10mv·s-1、20mv·s-1、50mv·s-1、100mv·s-1With
200mv·s-1When, it is respectively 464.08Fg that specific capacity is measured in 0~1.1v voltage ranges-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 188.22Fg-1.When carrying out CC charge-discharge tests, when current density is 0.5Ag-1、
1A·g-1、2A·g-1、5A·g-1、10A·g-1、20A·g-1When, specific capacity is respectively 498.63Fg-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
So it is maintained at 181.81Fg-1, show material with good capacitance behavior and multiplying power with good high rate performance (see Fig. 4,
Fig. 5, Fig. 6).
Application example 2
By the nitrating ultra-thin layer of charcoal of three-dimensional co-continuous porous structure obtained in embodiment 1 electrolyte be 2molL- 1Li2SO4Three-electrode system carry out electro-chemical test, wherein reference electrode be Ag/AgCl, auxiliary electrode is platinum electrode.It will
The material is configured to the solution of 10mg/mL, wherein deionized water and isopropanol ratios 1:4, binder PVDF
(polyvinylidene fluoride) quality accounts for the 5% of active material, by solution drop coating on vitreous carbon, conduct after drying
Working electrode.It is 2mvs that CV cyclic voltammetries are carried out under voltage -1.6~1.2V ranges when sweeping speed-1、5mv·s-1、
10mv·s-1、20mv·s-1、50mv·s-1、100mv·s-1When, capacitance is respectively 496.14Fg-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 141.99Fg-1.When carrying out CC charge-discharge tests, when current density is 0.5Ag-1、1A·g-1、2A·g-1、
5A·g-1、10A·g-1、20A·g-1When, specific capacity is respectively 339Fg-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
8, Fig. 9).
Application example 3
The ultra-thin layer of charcoal of nitrating three-dimensional co-continuous porous structure obtained in embodiment 1 is applied to electrode of super capacitor,
The material is configured to the solution of 10mg/mL, wherein deionized water and isopropanol ratios 1:4, binder nafion ratios are
5%, solution drop coating is regard as electrode slice on graphite carbon paper, using two electrode slices identical in quality as cathode and anode, electricity
Solution liquid is 0.5molL-1H2SO4, diaphragm celgard3501 is assembled into button capacitor.When current density is in 0.5A/g,
Specific capacity reaches 417.5Fg-1.When current density increases to 40Ag-1, still remain in 224Fg-1, followed by 5000 times
After ring, when current density is in 0.5Ag-1When, specific capacity remains within 376Fg-1(90% capacity retention ratio).(see
Figure 10)
Application example 4
The ultra-thin layer of charcoal of nitrating three-dimensional co-continuous porous structure obtained in embodiment 1 is applied to 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, grinding slurry carries out smear, and 80 DEG C of vacuum drying 12h are laggard
Row tabletting is as positive electrode, and for lithium metal as cathode, electrolyte selects addition 2wt%LiNO31M1,3- dioxolanes
(DOL) mixed solution (DEM, the DOL volume of two (trifluoromethane sulfonic acid) imine lithium (LiTFSI) of/glycol dimethyl ether (DME) base
Than being 1:1), diaphragm selects Celgard2400, the assembled battery under argon gas protection in glove box.It is in charging and discharging currents density
When 0.1C, first discharge specific capacity is about 1160mAh/g, and after 100 cycles, specific discharge capacity is still maintained at about
565mAh/g；When charging and discharging currents density is 0.5C, first discharge specific capacity is about 1050mAh/g, is recycled by 100 times
Afterwards, specific discharge capacity is still maintained at about 438mAh/g (see Figure 11).
Application example 5
The ultra-thin layer of charcoal of nitrating three-dimensional co-continuous porous structure obtained in embodiment 1 is applied to the absorption of gas, is used
Gas adsorption method is tested, and test equipment is the ASAP2020 physical adsorption appearances of micromeritics companies of the U.S., in liquid nitrogen
At temperature (- 195 DEG C), the range that relative pressure is 0.01~1 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 measured 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 illustrate material for small point
Sub- gas has stronger suction-operated, can be used for absorption, isolation and purification of gas etc..(see Figure 12, Figure 13, Figure 14)
The ultra-thin layer of charcoal ultracapacitor of nitrating three-dimensional co-continuous porous structure prepared by the present invention is used in electro-chemical test
0.5mol·L-1HCl solution be electrolyte solution, using three-electrode system carry out chemical property test, 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 rate increases to 500mvs-1, rectangular shape is still presented in curve, is 2mvs when sweeping speed-1、10mv·s-1、50mv·s-1And 200mvs-1When, it is respectively 464.08F that specific capacity is measured in 0-1.1v voltage ranges
g-1、326.31F·g-1、259.23F·g-1、211.87F·g-1, when increasing to 500mvs-1When, capacitance remains at
188.22F·g-1.In charge-discharge test, when current density is 0.5Ag-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 20Ag-1When, specific capacity still maintains
In 203.63Fg-1, show material with good capacitance behavior and multiplying power with good high rate performance.
The porous ultra-thin layer of charcoal of nitrating three-dimensional co-continuous prepared by the present invention be electrode assembling at button-shaped ultracapacitor, and
Carry out electrochemical property test.When current density is in 0.5Ag-1, specific capacity reaches 417.5Fg-1.When current density increases
To 40Ag-1, still remain in 224Fg-1, after 5000 cycles, when current density is in 0.5Ag-1When, specific volume
Amount remains within 376Fg-1(90% capacity retention ratio).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 merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all within the spirits and principles of the present invention made by all any modification, equivalent and improvement etc., should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of ultra-thin layer of charcoal preparation method of nitrating three-dimensional co-continuous porous structure, which is characterized in that include the following steps：
(1) first shrimp shell raw material is cleaned by ultrasonic with deionized water, then ultrasonic immersing is cleaned in alkaline solution, by shrimp shell after cleaning
Drying；
(2) the drying shrimp shell for obtaining step (1) is 1 in mass ratio with nitrogen-containing material：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 powdered, low temperature pyrogenation is then carried out under the protection of inert gas；
(4) by the substance 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 is carried out under inert gas protection；
(5) lixiviating is mixed in the substance obtained after high temperature pyrolysis and excessive diluted acid by step (4), then uses deionized water
Supernatant is outwelled after centrifuge washing to neutrality；
(6) step (5) products therefrom is dried to obtain the ultra-thin layer of charcoal of nitrating three-dimensional co-continuous porous structure.
2. the preparation method of the ultra-thin layer of charcoal of nitrating three-dimensional co-continuous porous structure according to claim 1, which is characterized in that
In step (1), alkaline solution is the mixed solution that is a kind of or being two kinds of solution of sodium hydroxide, potassium hydroxide；Solution quality
Score is 10%.
3. the preparation method of the ultra-thin layer of charcoal of nitrating three-dimensional co-continuous porous structure according to claim 1 or 2, 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 three-dimensional co-continuous porous structure according to claim 1, which is characterized in that
In step (2), nitrogen-containing material is urea, melamine, pyrroles's one of which or their mixture, and it is 50 to be stirred temperature
DEG C, rotating speed 300r/min.
5. the preparation method of the ultra-thin layer of charcoal of nitrating three-dimensional co-continuous porous structure according to claim 1, which is characterized in that
Low temperature pyrogenation temperature is at 400-550 DEG C in step (3), and step (4) high temperature pyrolysis temperature is at 600-1000 DEG C.
6. the preparation method of the ultra-thin layer of charcoal of nitrating three-dimensional co-continuous porous structure, feature exist according to claim 1 or 5
In in step (3), (4), inert gas is nitrogen or argon gas；Heating rate is 10 DEG C/min, gas flow rate 100-200mL/
min。
7. the preparation method of the ultra-thin layer of charcoal of nitrating three-dimensional co-continuous porous structure according to claim 1, which is characterized in that
In step (4), alkaline matter is sodium hydroxide, potassium hydroxide, sodium carbonate, one kind in potassium carbonate or in which two or more mixed
Close object.
8. the preparation method of the ultra-thin layer of charcoal of nitrating three-dimensional co-continuous porous structure according to claim 1, which is characterized in that
In step (5), diluted acid can be hydrochloric acid, nitric acid, one kind of sulfuric acid or their mixture that mass concentration is 10-20%, stir
Mix rotating speed 500r/min；Centrifugation time each 5min, centrifugal rotational speed 1000r/min.
9. the ultra-thin layer of charcoal of a kind of nitrating three-dimensional co-continuous porous structure that according to claim 1 prepared by method, feature exist
In ultra-thin carbon layer is in 1-100nm, BET specific surface area 1000-2300m2/ g, total hole volume 0.5-1.63cm3/ g,
Average pore size is 2-4nm, and nitrogen mass content is 1-11wt%.
10. the purposes for the ultra-thin layer of charcoal of nitrating three-dimensional co-continuous porous structure that according to claim 1 prepared by method, feature
It is, which is used for ultracapacitor, secondary cell and gas absorption.
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