CN106025239A - Two-dimensional nitrogen-doped hierarchical pore carbon nano-sheet as well as preparation method and application thereof to lithium/sulfur battery - Google Patents
Two-dimensional nitrogen-doped hierarchical pore carbon nano-sheet as well as preparation method and application thereof to lithium/sulfur battery Download PDFInfo
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- H01M4/00—Electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract
The invention discloses a two-dimensional nitrogen-doped hierarchical pore carbon nano-sheet as well as a preparation method and application thereof to a lithium/sulfur battery. The method takes zinc salt and a water-soluble nitrogen-containing organic ligand as raw materials and two-dimensional lamellar MOF is synthesized in a water solution in one step; the two-dimensional nitrogen-doped hierarchical pore carbon nano-sheet is obtained through processes including carbonization, activation and the like. The carbon nano-sheet disclosed by the invention has micro-pores and also has micropores and macropores; the specific surface area is 200m<2>g/l to 5000m<2>g/l and the pore volume is 0.1cm<3>g/l to 4.5cm<3>g/l; the carbon nano-sheet disclosed by the invention is used as a positive electrode material of the lithium/sulfur battery, the sulfur fixing effect is obvious and the electron and ion conductivity is good, so that the obtained battery has very good circulating performance and rate performance; the first-turn discharge capacity at 0.2C can reach 1226mAh/g and the capacity rentention rate reaches 74.1 percent after 50 times of circulation. The preparation process is simple and has energy-saving and environment-friendly effects; large-scale preparation is easy to realize.
Description
Technical field
The invention belongs to electrochemical field, relate to a kind of two dimension N doping grading-hole carbon nanosheet, preparation method
And application, particularly relate to a kind of two dimension N doping grading-hole carbon nanosheet, preparation method and at lithium sulfur electricity
Application in pond.
Background technology
Along with electric automobile and the development of super-thin electronic equipment, the specific energy of secondary cell is proposed more by people
High requirement.At present, commercial Li-ion actual energy density based on deintercalation mechanism is less than 200Wh
kg-1, far from the demand meeting people.Lithium-sulfur cell as a kind of new electrochemical energy storage secondary cell,
In discharge process, there are two electron reactions in sulfur and lithium metal, can discharge 1675mAh g in theory-1
Specific capacity and 2600Wh kg-1Theoretical specific energy, meanwhile, active substance sulfur has aboundresources, become
This is low, low toxicity, advantages of environment protection.Therefore, lithium-sulfur cell is considered as alternative lithium ion battery
One of novel secondary battery, has a good application prospect.
Positive electrode is the important component part in lithium-sulfur cell, and it plays structure electrodes conduct network and solid sulfur
Effect.But the electron transmission pattern of " point cantact " of the carbon powder material of routine and the most single aperture
Distribution has had a strong impact on the transmission of its electronics and ion, thus limits performance and the high rate performance of its capacity.
Two dimension N doping grading-hole carbon nanosheet can solve as above problem well.Its two-dimensional orientation structure is conducive to
Build the electric transmission network of three-dimensional " face contact ", greatly improve the electric conductivity of electrode；Therefore, with
Two dimension N doping grading-hole carbon nanosheet can provide " high for electronics and ion for lithium sulfur battery anode material
Speed " passage such that it is able to meet the requirement to electronics and ion transport under the conditions of high magnification.
Traditionally, the preparation method of two dimension N doping grading-hole carbon nanosheet generally uses template, is usually
Under the synergism of various template, synthesize two-dimensional nano lamella porous material, subsequently it is carried out nitrogen-atoms and mix
Miscellaneous；Can also use and first nitrogenous carbon matrix precursor be injected in porous masterplate, allow presoma be polymerized in hole
With the complex that carbonization obtains masterplate-carbon, then masterplate etch obtains product.CN 103700859 B is open
A kind of graphene-based N doping multi-stage porous carbon nanometer sheet/sulfur composite for lithium-sulphur cell positive electrode, the party
Using graphene oxide and nano silicon as bimodulus version in method, it is 5～8nm by graphene oxide and particle diameter
Silicon dioxide presses the mass ratio mixing of 1:2, adds pyrroles, and graphene oxide with the mass ratio of pyrroles is
1:20-50, mixing, add 50ml hydrochloric acid and Ammonium persulfate., Ammonium persulfate. addition with the mass ratio of pyrroles is
1:3, after continuing reaction 12h, filters, washing, is dried, nitrogen atmosphere 700～900 DEG C of roasting 2h, it is thus achieved that
Black powder join 20% hydrofluoric acid solution stirring, filter, dry, it is thus achieved that product and hydroxide
Sodium is with mass ratio as 1:1～4 mixes in ethanol, ultrasonic, is evaporated ethanol, is transferred to 800 DEG C of roastings in tube furnace
Burn 1～5h, wash, filter and be dried, obtain graphene-based multi-stage porous nitrogen-doped carbon nanometer sheet, the knot of product
Structure is the Graphene class sandwich type as carbon nanosheet intermediate layer.But, above-mentioned prior art uses mould
It is complicated generally to there is technological process in the method for version, during consumption energy consumption, and the shortcoming being unfavorable for large-scale production.
Summary of the invention
The problems referred to above existed for prior art, present invention aim at providing the N doping classification of a kind of two dimension
Hole carbon nanosheet, preparation method and the application in lithium-sulfur cell thereof, the method for the invention can realize in situ
N doping, without any template, thus the later stage is without removing masterplate, and the sheet that presoma is nitrogenous
The preparation of shape metallic organic framework is easy, prepares in room temperature in aqueous, mild condition, energy-saving ring
Protecting, whole preparation process is simple to operate, can realize preparing on a large scale；The two-dimentional N doping classification prepared
Hole carbon nanosheet is used as the positive electrode of lithium-sulfur cell and has extraordinary captured sulfur result and electronics, ion transmission
Characteristic, makes lithium-sulfur cell have good cycle performance and high rate performance, and the first circle discharge capacity at 0.2C can
Reach 1226mA h g-1, after 50 times circulate, capability retention reaches 74.1%.
For achieving the above object, the technical solution used in the present invention is as follows:
First aspect, the present invention provides the preparation method of a kind of two dimension N doping grading-hole carbon nanosheet, described
Method comprises the following steps:
By nitrogenous metallic organic framework (Metal-Organic Framework, MOFs) under atmosphere in
Carburizing temperature 910～2000 DEG C carry out carbonization, cooling, obtain two dimension N doping grading-hole carbon nanosheet；
Wherein, the nitrogenous metal ion in metallic organic framework is zinc ion.
Preferably, described nitrogenous metallic organic framework is the nitrogen containing metal organic backbone of two-dimensional sheet.
It is organic with nitrogenous by the metal ion of positively charged for using nitrogenous metallic organic framework MOF in the present invention
The complex with regular ordered arrangement structure that there is the heteroatomic coordination of lone pair electrons and formed on part,
Due to its Stability Analysis of Structures, in carbonisation, size and morphology change are the least.Therefore, it is possible to by preparation two
The nitrogen containing metal organic backbone of dimension lamellar, as presoma through a step carbonization, obtains two dimension N doping classification
Hole carbon nanosheet.Being additionally, since MOF self is poromerics, carries out a step carbon using it as presoma
Changing, microcellular structure still can be maintained, the micropore in the two-dimentional N doping grading-hole carbon nanosheet prepared
Ratio is high.
Preferably, the gas in described gas atmosphere is Ar, N2、H2Or NH3In any one or at least
The gaseous mixture of two kinds, preferably Ar, N2, H2With the gaseous mixture of Ar, or NH3With appointing in Ar gaseous mixture
Meaning one.
Preferably, the flow velocity of the gas in described gas atmosphere is 30～300mL min-1, such as, can be 30
mL min-1、40mL min-1、60mL min-1、70mL min-1、80mL min-1、100mL min-1、
120mL min-1、130mL min-1、150mL min-1、160mL min-1、175mL min-1、195mL
min-1、210mL min-1、225mL min-1、245mL min-1、260mL min-1、280mL min-1Or
300mL min-1Deng.
In the present invention, " intensification " refers to that program is warming up to carburizing temperature from room temperature, is warming up to described carbonization temperature
The heating rate of degree is preferably 1～10 DEG C of min-1, such as, can be 1 DEG C of min-1、3℃min-1、4℃
min-1、5℃min-1、6℃min-1、8℃min-1、9℃min-1Or 10 DEG C of min-1Deng, the most excellent
Elect 2 DEG C of min as-1。
Preferably, the rate of temperature fall lowered the temperature from described carburizing temperature is 1～10 DEG C of min-1, such as, can be 1 DEG C
min-1、2℃min-1、3℃min-1、4℃min-1、6℃min-1、8℃min-1、9℃min-1Or
10℃min-1Deng, preferably 2 DEG C min-1。
Carburizing temperature in the method for the invention is 910～2000 DEG C, can be such as 910 DEG C, 920 DEG C,
930℃、950℃、960℃、970℃、980℃、1000℃、1200℃、1300℃、1500℃、
1600 DEG C, 1700 DEG C, 1800 DEG C or 2000 DEG C etc., preferably 920 DEG C.Carburizing temperature 910～2000 DEG C
Under the conditions of, the metal ion in MOF complex is changed into corresponding metal or metal-oxide, and at carbon material
Under the effect of material, it is converted into zinc simple substance, distils the most completely, by the size limitation of synthesized material, zinc
Grain size generally number nanometer, to tens nanometer, i.e. obtains mesoporous after distillation；In carbonisation, nitrogenous have
Machine part decomposes and produces gas at catabolic process, and this dual function is conducive to the formation of macropore.
Preferably, the time of described carbonization is 1～10h, can be such as 1h, 2h, 3h, 4h, 4.5h,
5h, 6h, 7h, 7.5h, 8h, 8.3h, 9h or 10h etc., preferably 2h.
As the optimal technical scheme of the method for the invention, described two dimension N doping grading-hole carbon nanosheet
After preparation method is additionally included in cooling, the carbonized product obtained through carbonization is activated, washs and dries
Step, described activation be steam activation or KOH activation in any one.
Its specific surface area and pore volume can be improved further by carbonized product being carried out activation.
Preferably, described steam activation is: by carbonized product under water vapor conditions in 600～1000 DEG C of work
Change 0.5～5h.
During steam activation of the present invention, the temperature of activation is 600～1000 DEG C, such as, can be
600 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C, 950 DEG C or 1000 DEG C etc..
During steam activation of the present invention, the time of activation is 0.5～5h, such as, can be
0.5h, 1h, 1.2h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h or 5h etc..
Preferably, during described steam activation, the flow velocity of steam is 30～100mL min-1,
Can be such as 30mL min-1、50mL min-1、60mL min-1、70mL min-1、80mL min-1、
90mL min-1Or 100mL min-1Deng.
Preferably, the process of described KOH activation is to be mixed with carbonized product by KOH, is warming up to activation temperature
Spend and be incubated 0.5～5h, then lowering the temperature, the product obtained being put in acid to neutralize KOH.
Preferably, during described KOH activation, KOH with the mass ratio of carbonized product is
(1～10): 1, such as, can be 1:1,2:1,3:1,4:1,4.5:1,5:1,6:1,7:1,8:1 or 10:1
Deng.
Preferably, during described KOH activation, activation temperature is 600～900 DEG C, such as, can be
600 DEG C, 650 DEG C, 700 DEG C, 730 DEG C, 780 DEG C, 800 DEG C, 825 DEG C, 875 DEG C or 900 DEG C etc..
Preferably, the heating rate being warming up to described activation temperature is 1～10 DEG C of min-1。
Preferably, the rate of temperature fall lowered the temperature from described activation temperature is 2 DEG C of min-1。
Preferably, described KOH activation during, soak time is 0.5～5h, can be such as 0.5h,
1h, 1.5h, 2h, 2.3h, 2.8h, 3h, 3.5h, 4h, 4.5h or 5h etc..
Preferably, in the step of described washing, second alcohol and water is used to wash.
Preferably, the preparation process of nitrogenous metallic organic framework of the present invention comprises the following steps:
(1) zinc salt is dissolved in the water, obtains solution A；By soluble in water for nitrogenous organic ligand, obtain molten
Liquid B；
(2) solution A and solution B are mixed, stirring, obtain nitrogenous metallic organic framework.
Preferably, in the preparation process of described nitrogenous metallic organic framework, step (1) described zinc salt is water
Any one or the mixing of at least two in soluble zinc salt, preferably zinc nitrate, zinc acetate or zinc chloride
Thing.
Preferably, in the preparation process of described nitrogenous metallic organic framework, step (1) is described nitrogenous organic
Part is the nitrogenous organic ligand of water solublity, preferably imidazoles, 2-methylimidazole, 4-methylimidazole, pyrazoles,
Any one or the mixture of at least two in 3-methylpyrazole or piperazine.
Preferably, in the preparation process of described nitrogenous metallic organic framework, step (1) described solution A
In, the concentration of zinc salt is 0.01～0.3M, can be such as 0.01M, 0.02M, 0.05M, 0.1M,
0.13M, 0.15M, 0.2M, 0.25M or 0.3M etc..
Preferably, in the preparation process of described nitrogenous metallic organic framework, in step (1) described solution B,
The concentration of nitrogenous organic ligand is 0.02～3M, can be such as 0.02M, 0.04M, 0.07M, 0.1M,
0.14M、0.16M、0.2M、0.5M、0.8M、1M、1.25M、1.5M、2M、2.3M、
2.6M, 2.8M or 3M etc..
Preferably, in the preparation process of described nitrogenous metallic organic framework, in step (2) described solution A
Zinc salt and solution B in the mol ratio of nitrogenous organic ligand be 1:(7～10), can be such as 1:7,1:7.2,
1:7.5,1:8,1:8.5,1:9,1:9.5 or 1:10 etc..
Preferably, in the preparation process of described nitrogenous metallic organic framework, step (2) described mixing and stirring
Mix and the most at room temperature carry out.
Preferably, in the preparation process of described nitrogenous metallic organic framework, step (2) described stirring time
Between be 2～48h, can be such as 2h, 4h, 6h, 8h, 10h, 13h, 16h, 20h, 24h, 26h,
28h, 30h, 33h, 36h, 40h, 42h, 45h or 48h etc., preferably 24h.
Preferably, in the preparation process of described nitrogenous metallic organic framework, it is additionally included in step (2) stirring
After completing, carry out step (3): the step that the slurry obtained after having stirred is separated, washs and is dried
Suddenly.
Preferably, in the preparation process of described nitrogenous metallic organic framework, be separated into described in step (3) from
The separate mode that the heart or filtration etc. are commonly used in the art.
As the further preferred technical scheme of two dimension N doping grading-hole carbon nanosheet of the present invention, described
Method comprises the following steps:
(a), zinc salt is dissolved in the water, the concentration obtaining the zinc salt in solution A, and solution A is
0.01～0.3M；By soluble in water for nitrogenous organic ligand, obtain in solution B, and solution B nitrogenous organic joins
The concentration of body is 0.02～3M；
B (), solution A step (a) obtained and solution B mixing, stir 2～48h, separate, wash
Washing and be dried, obtain the nitrogen containing metal organic backbone of two-dimensional sheet, wherein, the nitrogen containing metal of two-dimensional sheet has
Metal ion in machine skeleton is zinc ion；
C (), the nitrogen containing metal organic backbone of the two-dimensional sheet being dried step (b) obtained are placed in tubular type
In stove, carry out carbonization 1～10h in carburizing temperature 910～2000 DEG C；Gas, described gas it is connected with in tube furnace
For Ar, N2, H2Gaseous mixture or NH with Ar3With Ar gaseous mixture, the flow velocity of described gas be 30～
300mL min-1, the heating rate being warming up to described carburizing temperature is 1～10 DEG C of min-1。
D (), the carbonized product (1～10) in mass ratio obtained with step (c) by KOH: 1 mixing, put
In nickel pipe tube furnace, with 10 DEG C of min-1Heating rate be warming up to 700 DEG C, constant temperature 2h, then with 2 DEG C
min-1Rate of temperature fall be cooled to room temperature (15～35 DEG C), then product is placed in the HCl of 10wt%,
Stand 24h；
(e), to step (d) activate after product wash and dry, obtain two dimension N doping classification
Hole carbon nanosheet.
Second aspect, the present invention provides the two-dimentional N doping classification that method as described in relation to the first aspect prepares
Hole carbon nanosheet, the surface length of side of described carbon nanosheet in 5～500 μm, can be such as 5 μm, 20 μm,
30μm、50μm、65μm、80μm、100μm、120μm、140μm、155μm、170μm、
200μm、220μm、240μm、260μm、285μm、300μm、325μm、350μm、380μm、
400 μm, 420 μm, 435 μm, 460 μm, 480 μm or 500 μm etc..
Preferably, the thickness of described carbon nanosheet is 2～300nm, can be such as 2nm, 10nm,
15nm、20nm、25nm、30nm、40nm、50nm、60nm、80nm、100nm、125nm、
150nm, 170nm, 180nm, 200nm, 225nm, 245nm, 260nm, 280nm or 300nm
Deng.
Preferably, the specific surface area of described carbon nanosheet is 200～5000m2g-1, such as, can be 200m2
g-1、240m2g-1、270m2g-1、300m2g-1、325m2g-1、350m2g-1、380m2g-1、400m2
g-1、450m2g-1、500m2g-1、550m2g-1、625m2g-1、675m2g-1、750m2g-1、800m2
g-1、900m2g-1、1000m2g-1、1200m2g-1、1400m2g-1、1600m2g-1、1800m2g-1、
2000m2g-1、2200m2g-1、2500m2g-1、2700m2g-1、3000m2g-1、3300m2g-1、
3500m2g-1、3800m2g-1、4000m2g-1、4250m2g-14500m2g-1Or 5000m2g-1Deng.
Carbon nanosheet of the present invention includes micropore, mesoporous and macropore.
In the present invention, the aperture of described micropore be less than 2nm, can be such as 1.8nm, 1.7nm, 1.5nm,
1.4nm, 1.3nm, 1.2nm, 1nm, 0.8nm or 0.5nm etc..
In the present invention, described mesoporous aperture 2～50nm, can be such as 2nm, 5nm, 8nm,
10nm、13nm、15nm、20nm、22.5nm、25nm、30nm、33nm、35nm、38nm、
40nm, 43nm, 45nm, 48nm or 50nm etc..
In the present invention, the aperture of described macropore be more than 50nm, can be such as 60nm, 70nm, 80nm,
100nm、130nm、150nm、200nm、235nm、300nm、365nm、400nm、450nm、
500nm、560nm、600nm、645nm、700nm、800nm、900nm、950nm、
1000nm, 1200nm, 1500nm, 1700nm or 2000nm etc..
Preferably, the pore volume of described carbon nanosheet is 0.1～4.5cm3g-1, such as, can be 0.1cm3g-1、
0.5cm3g-1、1cm3g-1、1.5cm3g-1、2cm3g-1、2.5cm3g-1、2.8cm3g-1、3cm3g-1、
3.5cm3 4g-1、4.2cm3g-1Or 4.5cm3g-1Deng.
The third aspect, the present invention provides answering of the two-dimentional N doping grading-hole carbon nanosheet as described in second aspect
With, described carbon nanosheet is used as the positive electrode of lithium-sulfur cell.
Compared with the prior art, there is advantages that
(1) method of the present invention is by using nitrogenous two-dimensional sheet metallic organic framework as presoma, in nothing
Under conditions of needing any masterplate assosting effect, activate further after temperature programming carbonization or carbonization,
Be there is the two-dimentional N doping grading-hole carbon nanosheet of micropore, mesoporous and big pore size distribution simultaneously.The present invention's
Method is by the concentration of nitrogenous organic ligand in regulation presoma preparation process, the concentration of zinc salt, nitrogenous organic
The parameters such as the mol ratio of part and zinc salt, the carburizing temperature in down-stream intensification carbonisation and carbonization time
Etc. each parameter in parameter, and activation process, it is achieved to the hole in two dimension N doping grading-hole carbon nanosheet
The isoparametric regulation and control of footpath size, pore-size distribution, specific surface area and pore volume, thus improve the profit of active substance
By rate, improve it as captured sulfur result during lithium sulfur battery anode material and the combination property of lithium-sulfur cell.
(2) method of the present invention can realize situ Nitrogen Doping, without any template, thus the later stage also without
Removing template need to be removed；And the preparation of the nitrogen containing metal organic backbone of presoma two-dimensional sheet is easy, at aqueous solution
In in room temperature one-step synthesis, mild condition, it is not necessary to heat or add template, energy-conserving and environment-protective, this
The whole preparation technology of bright two dimension N doping grading-hole carbon nanosheet is simple, and material selection wide ranges can realize
Extensive preparation, has good application prospect.
(3) the two-dimentional N doping grading-hole carbon nanosheet of the present invention can be as the positive electrode of lithium-sulfur cell, its
Having micropore, mesoporous and macropore, specific surface area is 200～5000m2g-1, pore volume is 0.1～4.5cm3
g-1, owing to micropore has confinement effect, nitrogen-atoms and polysulfide can occur extensive chemical effect, both
The collaborative dissolving diffusion reducing polysulfide of effect, limits the shuttle of polysulfide to greatest extent, is situated between
Hole and macropore can provide infiltration and the transmission of lithium ion of bigger pore volume, beneficially electrolyte.This
Bright two-dimentional N doping grading-hole carbon nanosheet positive electrode is compared with conventional carbon powder material, due to its base
In the electron transmission pattern of " face contact ", be conducive to building three-dimensional electronic transmission network, thus improve electrode
Electric conductivity, therefore, such material with carbon element has electronics and the ion of good sulfur fixation, electric conductivity and excellence
Transmittability, has good cycle performance and high rate performance using it as the lithium-sulfur cell of electrode material,
The first circle discharge capacity of 0.2C is up to 1226mA h g-1, after 50 times circulate, capability retention reaches
74.1%.
Accompanying drawing explanation
Fig. 1 is dividing for raw material preparation two dimension N doping with zinc nitrate and 2-methylimidazole of the embodiment of the present invention 1
Level hole carbon nanosheet, use it to continue to fill sulfur to prepare lithium-sulfur cell and carry out the flow process signal of charge-discharge test
Figure；
Fig. 2 a and Fig. 2 b is the white solid powder that obtains of the step (1) of comparative example 1 and step (3) respectively
The SEM figure of the sample prepared；
Fig. 2 c and Fig. 2 d is the zinc metallic organic framework that obtains of the step (1) of embodiment 2 and step respectively
(3) the SEM figure of the two-dimentional N doping grading-hole carbon nanosheet after the activation obtained；
Fig. 3 is the adsorption desorption curve of the sample that comparative example 1 prepares with embodiment 1-3；
Fig. 4 is the graph of pore diameter distribution of the sample that comparative example 1 prepares with embodiment 1-3；
Fig. 5 is the partial enlarged drawing of the graph of pore diameter distribution of the sample that comparative example 1 prepares with embodiment 1-3；
Fig. 6 is the electricity of the lithium-sulfur cell that the sample prepared using comparative example 1 and embodiment 1-3 is assembled into as positive pole
Chemical impedance spectrogram (EIS)；
Fig. 7 is the electricity of the lithium-sulfur cell that the sample prepared using comparative example 1 and embodiment 1-3 is assembled into as positive pole
The fitting circuit figure of chemical impedance spectrogram (EIS)；
Fig. 8 is the Z ' and ω of the sample that comparative example 1 prepares with embodiment 1-3-1/2Graph of a relation；
Fig. 9 is that the lithium-sulfur cell that the sample prepared using comparative example 1 and embodiment 1-3 is assembled into as positive pole exists
The cyclical stability test figure of 0.2C；
Figure 10 is that the lithium-sulfur cell that the sample prepared using comparative example 1 and embodiment 1-3 is assembled into as positive pole exists
The high rate performance test figure of 0.2C, 0.5C, 1C and 2C.
Detailed description of the invention
Further illustrate technical scheme below in conjunction with the accompanying drawings and by detailed description of the invention.
The sample of comparative example 1 and the sample two dimension N doping grading-hole carbon of embodiment 1-3 that use the present invention are received
Rice sheet prepares battery and the method that carries out detecting is identical, specific as follows:
Take the sample in 0.2g comparative example or embodiment, and 0.025g commercialization carbon dust Super P is scattered in
2.36g N-Methyl pyrrolidone (NMP), after ultrasonic 20min, stirs 1h, adds 0.25g 10wt% and gathers
Vinylidene (PVDF) solution, solvent is NMP, stirs 5h, and regulation scraper is to 250 μm, thin at aluminum
Scratching film forming on film, 70 DEG C overnight cuts into a diameter of 10mm sequin after drying, after weighing,
60 DEG C vacuum drying 24h after, with scribble the sample in comparative example or embodiment sequin as positive pole (monolithic
Carry sulfur content and be about 1.5mg cm-2), lithium sheet is negative pole, and celgard 2325 is barrier film, with containing 1wt%
LiNO3Double (trifluoromethyl semi-annular jade pendant acyl) the imine lithium solution (LiTFSI) of 1M be electrolyte solution, solvent is 1,3-
The mixed liquor (volume ratio v/v=1:1) of dioxolanes (DOL) and dimethyl ether (DME), fills sulfur, assembled battery,
High rate performance charge-discharge test is carried out under 0.2C～2C multiplying power.
Comparative example 1
(1) weigh 2.606g zinc nitrate to be dissolved in 75mL methanol and obtain solution A, 5.736g 2-methyl miaow
Azoles is dissolved in 75mL methanol and obtains solution B, solution B is poured into rapidly in solution A, stirs 24h,
Centrifugal, washing, it is dried to obtain white solid powder；
(2) white solid powder is proceeded in tube furnace, with 1 DEG C of min-1Intensification temperature ramp extremely
920 DEG C, constant temperature 2h, then with 1 DEG C of min-1Rate of temperature fall be down to room temperature, obtain material with carbon element.
(3), after uniformly being mixed with 0.7g S by the material with carbon element that 0.3g step (2) obtains, it is dissolved in 10mL CS2
In, treat CS2After volatilization completely, being placed in tube furnace, be warming up to 155 DEG C, heating rate is 1 DEG C
Min-1, constant temperature 20h, obtain sample.
Fig. 2 a and Fig. 2 b is the white solid powder that obtains of the step (1) of comparative example 1 and step (3) respectively
The SEM figure of the sample prepared, this white powder is the polyhedron that diameter is about 100nm as seen from the figure,
The sample arrived after carbonization, in addition to surface occurs in that a lot of fold, its basic pattern and size
There is not significant change.
Making battery using the sample of this comparative example 1 as positive pole, and detect, the result obtained is: 0.2
Under C multiplying power, first circle specific discharge capacity is 936mA h g-1, after 50 circulations, specific capacity maintains 596mA h
g-1, capability retention is 63.6%；When multiplying power rises to 2C, specific discharge capacity is 133mA h g-1。
Embodiment 1
The preparation flow schematic diagram of the two-dimentional N doping grading-hole carbon nanosheet of the present embodiment 1 sees Fig. 1.
(1) weigh 0.330g zinc nitrate to be dissolved in 90mL water and obtain solution A (zinc nitrate in solution A
Concentration is 0.019M), 0.985g 2-methylimidazole is dissolved in 90mL methanol and obtains solution B (solution B
The concentration of middle 2-methylimidazole is 0.133M), solution B is poured into rapidly in solution A, stirs 24h, from
The heart, washing, it is dried to obtain white solid powder, i.e. zinc metallic organic framework；
(2) white solid powder is proceeded in tube furnace, with 1 DEG C of min-1Heating rate be warming up to
920 DEG C, constant temperature 2h, then with 1 DEG C of min-1Rate of temperature fall be down to room temperature, obtain finished product two dimension N doping and divide
Level hole carbon nanosheet.
Make battery using the sample two dimension N doping grading-hole carbon nanosheet of the present embodiment 1 as positive pole, go forward side by side
Row detection, the result obtained is:
Under 0.2C multiplying power, first circle specific discharge capacity is 1011mA h g-1, after 50 circulations, specific capacity maintains
710mA h g-1, capability retention is 70.2%；When multiplying power rises to 2C, specific discharge capacity is 303
mA h g-1。
Embodiment 2
(1) identical with the step of embodiment 1 (1)；
(2) identical with the step of embodiment 1 (1)；
(3) the two-dimentional N doping grading-hole carbon nanosheet preparing step (2) activates, specifically
Ground, weighs the two-dimentional N doping grading-hole carbon nanosheet that 1g embodiment 1 prepares and uniformly mixes with 4g KOH
Close, be placed in nickel pipe tube furnace, with 10 DEG C of min-1Heating rate be warming up to 700 DEG C, constant temperature 2h, then
With 2 DEG C of min-1Rate of temperature fall be down to room temperature, products therefrom is again placed in the HCl of 10wt%, quiet
After putting 24, washing and drying, the two-dimentional N doping grading-hole carbon nanosheet after being activated.
Fig. 2 c and Fig. 2 d is the zinc metallic organic framework that obtains of the step (1) of embodiment 2 and step respectively
(3) the SEM figure of the two-dimentional N doping grading-hole carbon nanosheet after the activation obtained, as seen from the figure,
The MOF that zinc metallic organic framework is lamellar structure that step (1) obtains, can see after carbonization and activation
Going out, the two-dimentional N doping grading-hole carbon nanosheet after the activation that step (3) obtains still maintains lamellar structure,
Zero pile structure of the sample that this lamellar structure obtains relative to comparative example 1, is conducive to building three-dimensional " face
Contact " electric transmission network, for electronics provide high-speed channel, greatly improve the electric conductivity of electrode.
Secondly, its lamellar structure is piled up the macropore formed and is conducive to the infiltration of electrolyte and the transmission of lithium ion, reduces
The ion transport resistance of electrode interior.
Two-dimentional N doping grading-hole carbon nanosheet after activating using the sample of the present embodiment 2 makes electricity as positive pole
Pond, and detect, the result obtained is:
Under 0.2C multiplying power, first circle specific discharge capacity is 1226mA h g-1, after 50 circulations, specific capacity maintains
909mA h g-1, capability retention is 74.1%；When multiplying power rises to 2C, first circle specific discharge capacity is
663mA h g-1。
Embodiment 3
(1) weighing 0.330g zinc nitrate to be dissolved in 90mL water and obtain solution A, 0.985g 2-methylimidazole is molten
Solution obtains solution B in 90mL methanol, solution B is poured into rapidly in solution A, stirs 24h, centrifugal,
Washing, is dried to obtain white solid powder；
(2) white solid powder is proceeded in tube furnace, with 1 DEG C of min-1Heating rate be warming up to
1100 DEG C, constant temperature 2h, then with 1 DEG C of min-1Rate of temperature fall be down to room temperature, obtain finished product two dimension N doping
Grading-hole carbon nanosheet.
(3) the two-dimentional N doping grading-hole material with carbon element obtaining step (2) activates, the method for activation
Identical with the method in the step of embodiment 2 (3) and condition with condition；
Make battery using the sample two dimension N doping grading-hole carbon nanosheet of the present embodiment 3 as positive pole, go forward side by side
Row detection, the result obtained is:
Under 0.2C multiplying power, first circle specific discharge capacity is 1144mA h g-1, after 50 circulations, specific capacity maintains
765mA h g-1, capability retention is 66.8%；When multiplying power rises to 2C, specific discharge capacity is 579
mA h g-1。
Fig. 3, Fig. 4 and Fig. 5 be respectively the sample that comparative example 1 prepares with embodiment 1-3 adsorption desorption curve and
Graph of pore diameter distribution and partial enlargement graph of pore diameter distribution, understand in conjunction with Fig. 3, Fig. 4, Fig. 5 and table 1, implement
The two-dimentional N doping grading-hole carbon nanosheet of example 1-3 is organic except the presoma zinc metal maintaining microcellular structure
Outside the microcellular structure of skeleton, in hundred nanometers it can be seen that there is the big pore size distribution of relatively horn of plenty, these structures are non-
Often be conducive to two dimension N doping grading-hole carbon nanosheet as electrode material for lithium-sulfur cell, on the one hand micropore
Can provide bigger specific surface, allow sulfur can contact with material with carbon element is more preferable, and on the other hand, micropore also may be used
To be hindered the dissolving of polysulfide to spread by powerful capillary force, it is achieved " Gu sulfur ".Macropore is permissible
There is provided bigger pore volume to be used for storing electrolyte, meet the transmission requirement to electronics under the conditions of high magnification.
Fig. 6, Fig. 7 and Fig. 8 are that the sample prepared using comparative example 1 and embodiment 1-3 assembles as positive pole respectively
Electrochemical impedance (EIS) spectrogram of the lithium-sulfur cell become, corresponding fitting circuit figure and Z ' and ω-1/2's
Graph of a relation, by Fig. 6, Fig. 7, Fig. 8 and Biao 2 it can be seen that the two-dimentional N doping multi-stage porous of embodiment 1-3
The lithium-sulfur cell that carbon nanosheet is prepared as positive electrode is made as positive pole relative to the sample of comparative example 1
Battery, has less electrochemical impedance and bigger ionic diffusion coefficient, and this is likely due to and is structure
In pile up hole define good ion transmission channel, it is ensured that the transmission of lithium ion, wherein, embodiment
2 electrochemical impedances with minimum and maximum ionic diffusion coefficient, this is possibly due to material in activation process
The specific surface of material improves, and avtive spot increases, and electrochemical impedance declines；And the two-dimentional N doping of embodiment 3
The specific surface area of grading-hole carbon nanosheet and the less reason of pore volume are probably: the step (2) of step 3
Carburizing temperature higher (1100 DEG C), can cause the degree of graphitization of material with carbon element to raise, and specific surface area declines.
Fig. 9 is that the lithium-sulfur cell that the sample prepared using comparative example 1 and embodiment 1-3 is assembled into as positive pole exists
The cyclical stability test figure of 0.2C, due to it can be seen that with the two-dimentional N doping grading-hole of embodiment 1-3
The first circle specific discharge capacity of the battery that carbon nanosheet is made as positive electrode is above the sample of comparative example 1 and makees
For the first circle specific discharge capacity of the battery that positive pole is made, the sample of comparative example 1 is granular zero dimension carbon material
Material, is hardly formed bigger accumulation hole, and the mass transfer causing electrode interior is poor, thus the sample of comparative example 1
Making battery as positive pole, its chemical property is poor.And embodiment 2 and the two-dimentional N doping of embodiment 3
The first circle specific discharge capacity of the battery that grading-hole carbon nanosheet is made as positive electrode is higher, at 1200mA
h g-1Left and right, this is mainly due to the two-dimentional N doping grading-hole carbon nanosheet of embodiment 2 and embodiment 3
Specific surface area and pore volume are relatively big, and sulfur is uniformly dispersed wherein, and sulfur is good with the contact of carbon nanosheet, sulfur
Utilization rate high.And, after 50 circulate, with the two-dimentional N doping grading-hole carbon nanometer of embodiment 2
The specific capacity of the battery that sheet is made still is up to 909mA h g-1, this on the one hand can due to its more micropore
Realizing solid sulfur by capillary force, on the other hand its surface can be formed by force with polysulfide containing N functional group
Interaction loose structure improve captured sulfur result further.The two-dimentional N doping grading-hole carbon of embodiment 1 is received
Although little than embodiment 3 of specific surface area of rice sheet, but the carbon nanosheet of embodiment 1 and embodiment 3 is made
The cyclical stability measured after making battery for positive pole remains basically stable, and this is likely due to the carbonization of embodiment 3
Temperature (1100 DEG C) is the highest with the carburizing temperature of embodiment 1 (920 DEG C), material with carbon element under hot conditions
Degree of graphitization improve, the nitrogen-containing functional group on surface reduces and causes, demonstrate further chemistry solid sulfur and
The synergism of the solid sulfur of physics.
Figure 10 is that the lithium-sulfur cell that the sample prepared using comparative example 1 and embodiment 1-3 is assembled into as positive pole exists
The high rate performance test figure of 0.2C, 0.5C, 1C and 2C, as seen from the figure, the sample of comparative example 1 is made
The high rate performance of the battery being assembled into for positive pole is worst, and the two-dimentional N doping grading-hole carbon of embodiment 1-3 is received
The preferable reason of high rate performance of the battery that rice sheet is assembled into as positive pole is: in the material of these two-dimensional structures
Macropore (see pore-size distribution Fig. 4) is distributed, and these ducts are conducive to Li+Transmission, it is possible to meet battery and exist
Requirement to lithium ion transport under the conditions of high magnification, high rate performance is improved.
Table 1 pore structure parameter
Table 2 kinetic parameter
The kinetic parameter of above-mentioned table 2 is that the data from Fig. 6 and Fig. 7 calculate.
In sum, we are by aqueous, and synthesis two dimension MOF material under room temperature condition, with synthesis
Two-dimentional MOF material as presoma, obtain after carbonization two dimension N doping grading-hole carbon nanosheet, and should
Both there is micropore in carbon nanosheet, and there is again mesoporous and macropore, specific surface area is 200～5000m2g-1, hole
Volume is 0.1～4.5cm3g-1, using the two dimension lithium made as positive electrode of N doping grading-hole carbon nanosheet
Sulfur battery has the chemical property of excellence, in the first circle discharge capacity of 0.2C up to 1226mA h g-1, warp
After 50 circulations, capability retention reaches 74.1%, has a good application prospect.
Applicant states, the present invention illustrates the method detailed of the present invention by above-described embodiment, but the present invention
It is not limited to above-mentioned method detailed, does not i.e. mean that the present invention has to rely on above-mentioned method detailed ability real
Execute.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, to product of the present invention
The equivalence of each raw material is replaced and the interpolation of auxiliary element, concrete way choice etc., all falls within the guarantor of the present invention
Within the scope of protecting scope and disclosure.
Claims (10)
1. the preparation method of a two-dimentional N doping grading-hole carbon nanosheet, it is characterised in that described method
Comprise the following steps:
Nitrogenous metallic organic framework is carried out carbonization in carburizing temperature 910～2000 DEG C under atmosphere, fall
Temperature, obtains two dimension N doping grading-hole carbon nanosheet；Wherein, the nitrogenous metal in metallic organic framework from
Son is zinc ion.
Method the most according to claim 1, it is characterised in that described nitrogenous metallic organic framework
Nitrogen containing metal organic backbone for two-dimensional sheet；
Preferably, the gas in atmosphere is Ar, N2、H2Or NH3In any one or at least two
The gaseous mixture planted, preferably Ar, N2, H2With the gaseous mixture of Ar, or NH3With appointing in Ar gaseous mixture
Meaning one；
Preferably, in described atmosphere, the flow velocity of gas is 30～300mL min-1。
Method the most according to claim 1 and 2, it is characterised in that described carburizing temperature is
920℃；
Preferably, the heating rate being warming up to described carburizing temperature is 1～10 DEG C of min-1, preferably 2 DEG C
min-1；
Preferably, the rate of temperature fall lowered the temperature from described carburizing temperature is 1～10 DEG C of min-1, preferably 2 DEG C
min-1；
Preferably, described carbonization time is 1～10h, preferably 2h.
4. according to the method described in any one of claim 1-3, it is characterised in that it is characterized in that, described
After method is additionally included in cooling, the step that the carbonized product obtained through carbonization is activated, washs and dries
Suddenly；
Preferably, described activation is any one in steam activation or KOH activation, described steam
The process of activation is that in 600～1000 DEG C, carbonized product is activated 0.5～5h under water vapor conditions, and described water steams
The flow velocity of gas is preferably 30～100mL min-1；
Preferably, the process of described KOH activation is to be mixed with carbonized product by KOH, is warming up to activation temperature
Spend and be incubated 0.5～5h, then lowering the temperature, the product obtained being put in acid to neutralize KOH；
Preferably, during described KOH activation, described KOH with the mass ratio of carbonized product is
(1～10): 1；
Preferably, during described KOH activation, activation temperature is 600～900 DEG C；
Preferably, during described KOH activation, be warming up to the heating rate of described activation temperature be 1～
10℃min-1；
Preferably, during described KOH activation, the rate of temperature fall lowered the temperature from described activation temperature is 2 DEG C
min-1；
Preferably, in the step of described washing, second alcohol and water is used to wash.
5. according to the method described in any one of claim 1-4, it is characterised in that described nitrogenous metal has
The preparation process of machine skeleton comprises the following steps:
(1) zinc salt is dissolved in the water, obtains solution A；By soluble in water for nitrogenous organic ligand, obtain molten
Liquid B；
(2) solution A and solution B are mixed, stirring, obtain nitrogenous metallic organic framework.
Method the most according to claim 5, it is characterised in that described nitrogenous metallic organic framework
Preparation process in, step (1) described zinc salt be in zinc nitrate, zinc acetate or zinc chloride any one or
The mixture of at least two；
Preferably, in the preparation process of described nitrogenous metallic organic framework, step (1) described solution A
In, the concentration of zinc salt is 0.01～0.3M；
Preferably, in the preparation process of described nitrogenous metallic organic framework, step (1) is described nitrogenous organic
Part is any one in imidazoles, 2-methylimidazole, 4-methylimidazole, pyrazoles, 3-methylpyrazole or piperazine
Plant or the mixture of at least two；
Preferably, in the preparation process of described nitrogenous metallic organic framework, step (1) described solution B
In, the concentration of nitrogenous organic ligand is 0.02～3M；
Preferably, in the preparation process of described nitrogenous metallic organic framework, step (2) described solution A
In zinc salt and the mol ratio of nitrogenous organic ligand in solution B be 1:(7～10)；
Preferably, the time of step (2) described stirring is 2～48h, preferably 24h；
Preferably, in the preparation process of described nitrogenous metallic organic framework, it is additionally included in step (2) stirring
After completing, carry out step (3): the step that the slurry obtained after having stirred is separated, washs and is dried
Suddenly.
7. according to the method described in any one of claim 1-6, it is characterised in that described method includes following
Step:
(a), zinc salt is dissolved in the water, the concentration obtaining the zinc salt in solution A, and solution A is
0.01～0.3M；By soluble in water for nitrogenous organic ligand, obtain in solution B, and solution B nitrogenous organic joins
The concentration of body is 0.02～3M；
B (), solution A step (a) obtained and solution B mixing, stir 2～48h, separate, wash
Washing and be dried, obtain the nitrogen containing metal organic backbone of two-dimensional sheet, wherein, the nitrogen containing metal of two-dimensional sheet has
Metal ion in machine skeleton is zinc ion；
C (), the nitrogen containing metal organic backbone of the two-dimensional sheet being dried step (b) obtained are placed in tubular type
In stove, carry out carbonization 1～10h in carburizing temperature 910～2000 DEG C；Gas, described gas it is connected with in tube furnace
For Ar, N2, H2Gaseous mixture or NH with Ar3With Ar gaseous mixture, the flow velocity of described gas be 30～
300mL min-1, the heating rate being warming up to described carburizing temperature is 1～10 DEG C of min-1；
D (), the carbonized product (1～10) in mass ratio obtained with step (c) by KOH: 1 mixing, put
In nickel pipe tube furnace, with 10 DEG C of min-1Heating rate be warming up to 700 DEG C, constant temperature 2h, then with 2 DEG C
min-1Rate of temperature fall be cooled to 15～35 DEG C, then product is placed in the HCl of 10wt%, stand
24h；
(e), to step (d) activate after product wash and dry, obtain two dimension N doping classification
Hole carbon nanosheet.
8. the two-dimentional N doping grading-hole carbon nanometer that method as described in any one of claim 1-7 prepares
Sheet, it is characterised in that the length of side of described carbon nanosheet is 5～500 μm；
Preferably, the thickness of described carbon nanosheet is 2～300nm；
Preferably, the specific surface area of described carbon nanosheet is 200～5000m2g-1。
Two dimension N doping grading-hole carbon nanosheet the most according to claim 8, it is characterised in that institute
State carbon nanosheet and include micropore, mesoporous and macropore；
Preferably, the aperture of described micropore is less than 2nm；
Preferably, described mesoporous aperture is 2～50nm；
Preferably, the aperture of described macropore is more than 50～2000nm；
Preferably, the pore volume in described carbon nanosheet is 0.1～4.5cm3g-1。
10. the purposes of the most two-dimentional N doping grading-hole carbon nanosheet, its feature
Being, described carbon nanosheet is used as the positive electrode of lithium-sulfur cell.
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