CN109686951A - A kind of S@NPC/CNT composite material and preparation method and application - Google Patents
A kind of S@NPC/CNT composite material and preparation method and application Download PDFInfo
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- CN109686951A CN109686951A CN201811602372.6A CN201811602372A CN109686951A CN 109686951 A CN109686951 A CN 109686951A CN 201811602372 A CN201811602372 A CN 201811602372A CN 109686951 A CN109686951 A CN 109686951A
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- H—ELECTRICITY
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- 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
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Abstract
The invention discloses a kind of S@NPC/CNT composite material and preparation method and applications, the S@NPC/CNT composite material is obtained by NPC/CNT composite material through carrying sulphur, the NPC/CNT composite material is made of N doping porous carbon and carbon nanotube intertexture, and the N doping porous carbon is the carbon material as derived from Zn/Co- bimetallic organic backbone.To contain zinc and/or cobalt transition metal salt, organic ligand, carbon material methanol and water mixed liquid in stirring, dry, calcining, acid processing and etc. obtain the carbon material of above-mentioned N doping, it is prepared for the high S@NPC/CNT composite material for carrying sulphur finally by melting diffusion method, which shows the sulfur content of superelevation.In addition, the invention also discloses the methods, and application of the carbon material of the high N doping for carrying sulphur in lithium-sulfur cell is made.The composite material is used for the positive electrode of lithium-sulfur cell, battery obtained to have very high area capacity and good chemical property.The present invention provides effective method to prepare the carbon material of the high N doping of sulfur content with high performance.
Description
Technical field
The invention belongs to energy storage material preparation fields；More particularly to a kind of S@NPC/CNT composite material and preparation method
And application.
Background technique
With the development of electric car and portable electronic device, theoretical specific volume (1675 m of lithium-sulfur cell Yin Qigao
Ah/g) and high theoretical energy density (~2 600Wh/kg) and cause the extensive concern of people, having very much in future can
Common power-supply device can be become.Lithium-sulfur cell due to its raw material sources it is extensive, it is low in cost and have theoretical capacity height with
And advantages of environment protection, it is considered as one of most potential high energy density cells technology of new generation.However in lithium sulphur electricity
In the business application in pond, it is still faced with many problems.It is primarily present following 3 problems:
(1) low conductivity of sulphur reduces the utilization rate of active material.
(2) in charge and discharge process, the dissolution in the electrolytic solution of more lithium sulfides and generate " shuttle effect ", cause low coulomb to be imitated
Rate.
(3) large volume expansion (~80%) caused by the mutual conversion between sulphur and more lithium sulfides causes the destruction of electrode
And lead to the reduction of positive electrode cycle performance.
Due to the high-specific surface area of carbon material, regulatable aperture and excellent electric conductivity, carbon nano-fiber, graphene,
The composite material of graphene oxide, carbon hollow ball or porous carbon and sulphur was all extensively studied.Addition carbon material not only increases
The electric conductivity of insulator sulphur, but also the diffusion for electrolyte and ion provides pore structure.However, non-in carbon material
Weak interaction between polar bond and polysulfide can not effectively inhibit the dissolution of polysulfide.
Usually, when improving the load sulfur content of material and being up to 70% or more, it can be good at the application for realizing lithium-sulfur cell.
Carbon material derived from metal organic framework (MOFs) is novel porous crystalline material, since the presence of its porous structure can incite somebody to action
Sulphur fetters wherein, so that active material not easily runs off in charge and discharge process.In addition, the gold in charge and discharge process, in MOFs
Category center can and sulphur be coordinated, shuttle effect is further avoided by chemical action, thus improve battery cycle life and
Stability.
There are still certain in being applied to lithium-sulfur cell for carbon material derived from metal organic framework (MOFs) in the prior art
Defect, for example a kind of cobalt nitride/porous carbon sheet/carbon cloth is disclosed in the Chinese patent of Publication No. 201810700910.9
The preparation method of self-supporting lithium sulfur electrode positive electrode, this preparation method are presoma using metal organic framework compound,
Carbon cloth is carrier, and metal organic framework compound is vertical uniform to be grown on carbon cloth flexible, is managed by carbonization nitridation etc.
The nanometer carbon plate particle studded to cobalt nitride, and the porous nano carbon plate is carried on the fiber surface of carbon cloth in a manner of vertical-growth
On.But the positive electrode, there are still the problem for carrying sulfur content deficiency, materials'use stablizes bad situation in the process.
Summary of the invention
In order to solve the positive electrode low sulfur content of existing lithium-sulfur cell, the problems such as polysulfide dissolution and capacitance loss,
The first purpose of this invention is the provision of a kind of high-specific surface area, the high S@NPC/CNT composite material for carrying sulphur.
Second object of the present invention is to provide a kind of preparation method of S@NPC/CNT composite material.
Third object of the present invention, which is to provide, is applied to lithium for above-mentioned S@NPC/CNT composite material as positive electrode
Sulphur battery, gained lithium-sulfur cell have good cycle performance and capacity retention ratio.
To achieve the goals above, the invention provides the following technical scheme:
A kind of S@NPC/CNT composite material of the present invention, the S@NPC/CNT composite material are passed through by NPC/CNT composite material
It carries sulphur to obtain, the NPC/CNT composite material is made of N doping porous carbon and carbon nanotube intertexture, the N doping porous carbon
For the carbon material as derived from metal organic framework, the metal in the metal organic framework is zinc and/or cobalt.
For the problem that low sulfur content in the prior art, polysulfide dissolution and capacitance loss, the offer that the present invention initiates
A kind of high S@NPC/CNT composite material for carrying sulfur content, sulfur-donor NPC/CNT composite material have N doping porous carbon and carbon
The structure that nanotube interweaves, wherein N doping porous carbon is the carbon material as derived from metal organic framework, which can bring
Therefore bigger ratio table product has the characteristics that high load sulphur, contain a large amount of meso-hole structure simultaneously, not only can effectively prevent more
The dissolution of sulfide, additionally aids the quick transmission between electronics and lithium ion, and the electric conductivity of reinforcing material is in addition nonpolar
Polarity difference between nitrogen and polarity polysulfide is conducive to prevent the dissolution and diffusion of polysulfide, effectively reduces and filling
Shuttle effect in discharge process.
Carbon nanotube is added in the carbon plate of N doping, relative to other carbon materials, such as carbon cloth, graphene etc.,
Carbon nanotube is more advantageous to the stability of carbon plate structure and the storage of sulphur, prevents material recurring structure during charge and discharge from collapsing
The phenomenon that.
S@NPC/CNT composite material provided by the invention can be solved effectively existing such as lithium as lithium sulfur battery anode material
Sulphur positive electrode poorly conductive, the problems such as utilization efficiency is not high, the carbon material of N doping obtained contains high effective load sulphur
Amount, this can significantly improve the electric conductivity of lithium sulfur battery anode material and during charge and discharge cycles sulphur in positive electrode
Stability；In addition, the chemical properties such as the initial discharge capacity of lithium-sulfur cell, cycle performance, multiplying power property also can be improved.
As a further preference, the metal organic framework is Zn/Co- bimetallic organic backbone.
Inventors have found that the zeolite structured MOF that is, zinc and/or cobalt are synthesized with imidazoles precursor reactant derives material by ZIFs
The structure that material, derivative carbon material and carbon nanotube interweave, can obtain the S@NPC/CNT composite wood of excellent electrochemical performance
The structure that material, especially carbon material derived from Zn/Co- bimetallic organic backbone and carbon nanotube interweave, the S@finally obtained
NPC/CNT composite material chemical property is best.In addition in preparation, metallic cobalt, zinc salt can be with miaows under conditions of room temperature
Azoles body quickly forms metal-organic solution deposition, but also preparation process is more controllable and simplifies.And other metals form the condition of MOF
It is more stringent, it may be possible to adulterate or be adsorbed onto the duct MOF.
Preferred scheme, the load sulfur content of the S@NPC/CNT composite material are 75%~95%.
As a further preference, the load sulfur content of the S@NPC/CNT composite material is 85%~95%.
Preferred scheme, the specific surface area of the S@NPC/CNT composite material are 250~400 ㎡/g.
This mainly has benefited from micro- meso-hole structure present in material, and the S@NPC/CNT composite material pore size is 1~
50nm。
A kind of preparation method of S@NPC/CNT composite material of the present invention, metal salt is added in methanol-water mixed solution and is obtained
Mixed liquor is obtained, organic ligand, carbon nanotube acquisition feed liquid are then sequentially added in mixed liquor, after being stirred to react, through solid-liquid point
From, it is dry after obtain ZIFs//CNT composite material, ZIFs/CNT composite material obtains NPC/CNT composite wood through calcining, pickling
Expect, up to S@NPC/CNT composite material after NPC/CNT composite material load sulphur；The metal salt is zinc salt and/or cobalt salt.
Existing different functional groups electrostatic phase interaction between zinc, cobalt transition metal salt ion and carbon nanotube in the present invention
With so that after organic ligand stirring a period of time is added in methanol-water mixed solution, it can it is compound to obtain ZIFs//CNT
Material.Through ZIFs//CNT composite material through high-temperature calcination, organic ligand is converted into the carbon plate of two-dimensional N doping, then uses acid etching
Carve after transition metal ions up to NPC/CNT composite material, gained NPC/CNT composite material have Gao Bibiao product and
A large amount of meso-hole structure obtains the high S@NPC/CNT composite material for carrying sulphur after carrying sulphur.
Preferred scheme, the zinc salt are selected from least one of zinc nitrate, zinc acetate, zinc chloride, and the cobalt salt is selected from
At least one of cobalt nitrate, cobalt acetate, cobalt chloride.
Preferred scheme, in mixed liquor, containing zinc salt and when salt, according to the molar ratio, zinc salt: cobalt salt=1:1~5.Make
To be further preferred, in the mixed liquor, according to the molar ratio, zinc salt: cobalt salt=1:1~2.
Preferred scheme, in the mixed solution of the first alcohol and water, the volume ratio of first alcohol and water is 1~7:1.
As further preferably, in the mixed solution of the first alcohol and water, the volume ratio of first alcohol and water is 2~4:1.
Preferred scheme, the organic ligand are selected from least one of 2-methylimidazole, benzimidazole.As further
It is preferred, the organic ligand be 2-methylimidazole.
As a further preference, the ratio between mole of the organic ligand and metal salt is 1~5:1.
When metal salt is selected from zinc salt and cobalt salt, the mole of metal salt is the integral molar quantity of zinc salt and cobalt salt.
The nitrogen-doped carbon content that the organic ligand of different amounts causes material final is different, influences the formation of porous structure,
To influence the specific surface area of material, the final performance for influencing composite material.
As further preferably, the ratio between mole of the organic ligand and metal salt is 1.4~2:1.
Preferred scheme, the carbon nanotube are selected from multi-walled carbon nanotube and/or single-walled carbon nanotube.
As a further preference, the diameter of the carbon nanotube is 20-40nm.
Carbon nanotube selected in the present invention includes single-walled carbon nanotube and multi-walled carbon nanotube.
As a further preference, the mass ratio of the carbon nanotube and organic ligand is 1:6~12.
As further preferably, the mass ratio of the carbon nanotube and organic ligand is 1:9~11.
Inventors have found that carbon nanotube used in amounts will be controlled effectively, the embedded quantity of sulphur can be significantly contributed to and led
Electrically, to influence the chemical property of material.Carbon nanotube dosage is excessively not easy to disperse, to cause the heap of material
Product, is unfavorable for the insertion of sulphur and the raising of material conductivity.
Preferred scheme, the temperature of the reaction are room temperature, and the reaction time is 3~8h.
Preferred scheme, the ZIFs//CNT composite material are calcined under protective atmosphere, the calcination temperature be 600~
900℃.The protective atmosphere is nitrogen atmosphere.
As further preferred, calcination temperature is 700~900 DEG C, and calcination time is 2~5h.
The acid solution of preferred scheme, the pickling is selected from least one of hydrochloric acid, sulfuric acid, nitric acid.
As a further preference, the acid solution of the pickling is selected from hydrochloric acid.
As a further preference, the concentration of hydrochloric acid is 1~5mol/L.
As further preferably, the concentration of hydrochloric acid is 1.5~2.5mol/L.
Calcined material removes dezincify cobalt transition metal ions through pickling processes, and acid used is hydrochloric acid, in sulfuric acid, nitric acid
One kind.Pickling is to remove dezincify cobalt transition metal ions as far as possible, and suitable acid strength can remove the transition of dezincify cobalt
While metal ion, the meso-hole structure of material script is not destroyed yet.
Preferred scheme, it is melting osmosis that the NPC/CNT composite material, which carries sulphur method,.
As a further preference, the NPC/CNT composite material carries sulphur process and is, by NPC/CNT composite material and sulphur
Powder mixing obtains mixture, grinds 15~30min, is then heated to 150~180 DEG C, keeps the temperature 10~15h, i.e. acquisition S@NPC/
CNT composite material.
As it is further preferably, in the mixture, the mass ratio of NPC/CNT composite material and sulphur powder be 1:7~
9。
Inventors have found that carrying mixed proportion in sulphur technical process, milling time and carrying sulphur temperature and time to sulfur content
Ratio can also generate certain influence.
A kind of application of S@NPC/CNT composite material of the present invention, using S@NPC/CNT composite material as positive electrode application
In lithium-sulfur cell.
The method that lithium ion battery is assembled into using the carbon material of the high N doping for carrying sulphur provided by the present invention are as follows: by one
The carbon material (S@NPC/CNT) and acetylene black, adhesive (such as PTFE) mixing of the high N doping for carrying sulphur of certainty ratio, warp
Drying cuts out film, tabletting, is assembled into battery, carries out charge-discharge test using blue electric battery test system (LAND CT2001A).
Preferably, the S@NPC/CNT material and acetylene black and PTFE (adhesive) 80:10:10 in mass ratio into
Row mixing.
Compared with the prior art, the invention has the benefit that
(1) what the present invention was pioneering provides a kind of high S@NPC/CNT composite material for carrying sulphur, by NPC/CNT composite wood
Material is obtained through carrying sulphur, NPC/CNT composite material due to the structure that interweaves with unique N doping porous carbon and carbon nanotube, from
And can the structure bigger ratio table product can be brought therefore to have the characteristics that high load sulphur, load sulfur content are up to 89% or more.Simultaneously
Containing a large amount of micro- meso-hole structure, not only can effectively prevent the dissolution of polysulfide, additionally aid electronics and lithium ion it
Between quick transmission, the electric conductivity of reinforcing material, in addition the difference between N doping porous carbon and polarity polysulfide is conducive to
The dissolution and diffusion for preventing polysulfide, effectively reduce the shuttle effect in charge and discharge process.
The preparation method of S@NPC/CNT composite material provided by the present invention, preparation method is simple, at low cost, controllability
Height is conducive to industrial amplification production.
(2) there will be high load sulphur S@NPC/CNT composite material as positive electrode applied to lithium-sulfur cell obtained by the present invention
In, it can be obviously improved the performance of lithium-sulfur cell, the charge and discharge at 0.5C, initial capacity is 1141.0 mAhg-1, and have
There is relatively good cycle performance, is still able to maintain 686.0mAhg after circulation 120 times-1Capacity.
Detailed description of the invention
[Fig. 1] embodiment 1 prepares the flow chart of the carbon material of the high N doping for carrying sulphur；
[Fig. 2] (a) is the thermogravimetric analysis figure of embodiment 1 and S@NPC/CNT, S@NPC and NPC/CNT in comparative example 1,
The loss amount that the load sulfur content that wherein the load sulfur content of S@NPC/CNT is 89%, S@NPC is 86% and NPC/CNT is about 10%.
(b) figure is the comparison XRD figure of S@NPC/CNT and elemental sulfur standard card；
[Fig. 3] is the SEM figure, TEM figure and HRTEM figure of NPC/CNT composite material made from embodiment 1.(a) (b) figure is
The SEM of NPC/CNT composite material schemes, and (c) (d) is the TEM figure of NPC/CNT composite material, and (e) (f) is NPC/CNT composite material
HRTEM figure；(g) N of (h) difference NPC/CNT2Adsorption desorption curve and graph of pore diameter distribution.Wherein, (g) figure can be seen that load
After sulphur, nitrogen adsorption capacity reduces, and illustrates that sulphur loads in porous material well；
[Fig. 4] is the XPS figure of NPC/CNT and S@NPC/CNT composite material made from embodiment 1；Wherein, (a) figure is
The XPS full figure of NPC/CNT and S@NPC/CNT, (b) figure is the C1s spectrogram of S@NPC/CNT composite material, and (c) figure is S@NPC/
The N1s spectrogram of CNT composite material, (d) figure is the S2p spectrogram of S@NPC/CNT composite material；
[Fig. 5] is the battery performance figure of embodiment 1 and comparative example 1.(a) it is 0.5C charge and discharge cycles figure, (b) is multiplying power
Performance map.Wherein (a) figure can be seen that S@NPC/CNT porous carbon materials chemical property is higher than S@CNT porous carbon materials
Performance.
Specific embodiment
Following embodiment is intended to further illustrate the contents of the present invention, rather than limits the protection model of the claims in the present invention
It encloses.
Embodiment 1
The preparation of S@NPC/CNT composite material and its performance test for being assembled into lithium-sulfur cell
Step (1): the preparation of Zn/Co- bimetallic ZIFs//CNT composite material
By the mixed solution that the cobalt nitrate of the zinc nitrate of 1.68mmol and 1.71mmol is put into methanol and water volume ratio is 3:1
In, it is placed on agitated dissolution on magnetic stirring apparatus, forms uniform pink colour solution.Then it is added into above-mentioned solution
The 2-methylimidazole of 6.09mmol and the carbon nanotube (particle size 20-40nm) of 50mg, stir 6h after, solution through filtering,
Methanol washing, is finally putting into drying box and is dried overnight for 70 DEG C, obtain ZnCo-ZIFs/CNTs material.
Step (2): the preparation of NPC/CNT material
After being fully ground of ZnCo-ZIFs/CNTs composite material of step (1) preparation, be put into porcelain boat, with 5 DEG C/
The heating rate of min keeps the temperature 3h at 900 DEG C in nitrogen atmosphere.After naturally cooling to room temperature, by product 2mol/L hydrochloric acid
Middle washing 3 times except dezincify cobalt metal ion.It is washed with deionized later and removes by-product that may be present, until solution is to neutral
Condition (pH=7) is finally putting into drying box and is dried overnight for 70 DEG C, obtains NPC/CNT material.
Step (3): the preparation of S@NPC/CNT material
Step (2) is obtained into NPC/CNT material and distillation sulphur powder with the ratio mixed grinding of 1:9, by ground mixing
Object is transferred in the stainless steel cauldron of 50ml, is warming up to 157 DEG C of heat preservation 12h, is naturally cooled to room temperature to reaction kettle, finally
To S@NPC/CNT material.
The thermogravimetric analysis figure of Fig. 2 (a) shows that the load sulfur content of S@NPC/CNT material is up to 89%.The SEM and TEM of Fig. 3 schemes
All show the good weave in of carbon plate of carbon nanotube and N doping derived from metal-organic solution deposition in NPC/CNT material,
It forms containing a large amount of micro- mesoporous rock-steady structures.
Step (4): the preparation of lithium sulphur battery electrode film
The PTFE of S@NPC/CNT composite material and 10wt% acetylene black and 10wt% made from the present embodiment by 80wt%
0.2mm thickness, 0.8cm is being made by film, drying, sanction film, tabletting in (adhesive) mixing2Electrode wafer.
Step (5): the assembling and performance test of lithium-sulfur cell
Electrode wafer obtained by step (4) is operated in the glove box full of high-purity argon gas atmosphere, cathode is done with lithium piece,
2300 perforated membrane of Celgard is diaphragm, and the LiTFSI solution of 1M is electrolyte, is assembled into 2025 type button cells.Use Lan electricity electricity
Pond test macro (LAND CT2001A) carries out charge-discharge test between 1.5~2.8v.As shown in Figure 5, initial capacity is
1141.0mAhg-1, and there is relatively good cycle performance, the charge and discharge at 0.5C can still be protected after recycling 120 times
Hold 686.0mAhg-1Capacity.
Embodiment 2
The preparation of S@NPC/CNT composite material and its performance test for being assembled into lithium-sulfur cell
Step (1): the preparation of Zn/Co- bimetallic ZIFs//CNT composite material
By the mixed solution that the cobalt nitrate of the zinc nitrate of 1.68mmol and 1.71mmol is put into methanol and water volume ratio is 3:1
In, it is placed on agitated dissolution on magnetic stirring apparatus, forms uniform pink colour solution.Then it is added into above-mentioned solution
The 2-methylimidazole of 5.08mmol and the carbon nanotube of 40mg, after stirring 6h, solution is washed through filtering, methanol, is finally putting into dry
It is dried overnight for 70 DEG C in dry case, obtains ZnCo-ZIFs/CNTs material.
Step (2): the preparation of NPC/CNT material
After being fully ground of ZnCo-ZIFs/CNTs composite material of step (1) preparation, be put into porcelain boat, with 5 DEG C/
The heating rate of min is in nitrogen atmosphere, 900 DEG C of heat preservation 3h.After naturally cooling to room temperature, by product in the hydrochloric acid of 2mol/L
Washing 3 times except dezincify cobalt metal ion.It is washed with deionized later and removes by-product that may be present, until solution is to neutrality item
Part (pH=7) is finally putting into drying box and is dried overnight for 70 DEG C, obtains NPC/CNT material.
Step (3): the preparation of S@NPC/CNT material
Step (2) is obtained into NPC/CNT material and distillation sulphur powder with the ratio mixed grinding of 1:9, by ground mixing
Object is transferred in the stainless steel cauldron of 50ml, is warming up to 157 DEG C of heat preservation 12h, is naturally cooled to room temperature to reaction kettle, finally
To S@NPC/CNT material.
Step (4): the preparation of lithium sulphur battery electrode film
The PTFE of S@NPC/CNT composite material and 10wt% acetylene black and 10wt% made from the present embodiment by 80wt%
0.2mm thickness, 0.8cm is being made by film, drying, sanction film, tabletting in (adhesive) mixing2Electrode wafer.
Step (5): the assembling and performance test of lithium-sulfur cell
Electrode wafer obtained by step (4) is operated in the glove box full of high-purity argon gas atmosphere, cathode is done with lithium piece,
2300 perforated membrane of Celgard is diaphragm, and the LiTFSI solution of 1M is electrolyte, is assembled into 2025 type button cells.Use Lan electricity electricity
Pond test macro (LAND CT2001A) carries out charge-discharge test between 1.5~2.8v.After being assembled into battery, initial capacity
For 1102.5mAhg-1, the charge and discharge at 0.5C are still able to maintain 672.0mAhg after recycling 120 times-1Appearance
Amount.
Embodiment 3
The preparation of S@NPC/CNT composite material and its performance test for being assembled into lithium-sulfur cell
Step (1): the preparation of Zn/Co- bimetallic ZIFs//CNT composite material
By the mixed solution that the cobalt nitrate of the zinc nitrate of 1.68mmol and 1.71mmol is put into methanol and water volume ratio is 3:1
In, it is placed on agitated dissolution on magnetic stirring apparatus, forms uniform pink colour solution.Then it is added into above-mentioned solution
The 2-methylimidazole of 7.24mmol and the carbon nanotube of 60mg, after stirring 6h, solution is washed through filtering, methanol, is finally putting into dry
It is dried overnight for 70 DEG C in dry case, obtains ZnCo-ZIFs/CNT material.
Step (2): the preparation of NPC/CNT material
After being fully ground of ZnCo-ZIFs/CNT composite material of step (1) preparation, it is put into porcelain boat, with 5 DEG C/min
Heating rate in nitrogen atmosphere, 900 DEG C of heat preservation 3h.After naturally cooling to room temperature, product is washed in the hydrochloric acid of 2mol/L
3 times are washed except dezincify cobalt metal ion.It is washed with deionized later and removes by-product that may be present, until solution is to neutrallty condition
(pH=7), it is finally putting into drying box and is dried overnight for 70 DEG C, obtain NPC/CNT material.
Step (3): the preparation of S@NPC/CNT material
Step (2) is obtained into NPC/CNT material and distillation sulphur powder with the ratio mixed grinding of 1:9, by ground mixing
Object is transferred in the stainless steel cauldron of 50ml, is warming up to 157 DEG C of heat preservation 12h, is naturally cooled to room temperature to reaction kettle, finally
To S@NPC/CNT material.
Step (4): the preparation of lithium sulphur battery electrode film
The PTFE of S@NPC/CNT composite material and 10wt% acetylene black and 10wt% made from the present embodiment by 80wt%
0.2mm thickness, 0.8cm is being made by film, drying, sanction film, tabletting in (adhesive) mixing2Electrode wafer.
Step (5): the assembling and performance test of lithium-sulfur cell
Electrode wafer obtained by step (4) is operated in the glove box full of high-purity argon gas atmosphere, cathode is done with lithium piece,
2300 perforated membrane of Celgard is diaphragm, and the LiTFSI solution of 1M is electrolyte, is assembled into 2025 type button cells.Use Lan electricity electricity
Pond test macro (LAND CT2001A) carries out charge-discharge test between 1.5~2.8v.After being assembled into battery, initial capacity
For 1061.0mAhg-1, the charge and discharge at 0.5C are still able to maintain 668.5mAhg after recycling 120 times-1Appearance
Amount.
Embodiment 4
Using monometallic MOF as precursor preparation NPC/CNT composite material and its it is assembled into the performance test of lithium-sulfur cell
Step (1): the preparation of metallic zinc ZIF/CNT composite material
The zinc nitrate of 3.05mmol is put into methanol and water volume ratio is to be placed on magnetic stirring apparatus in the mixed solution of 3:1
Upper agitated dissolution.Then the 2-methylimidazole of 6.09mmol and the carbon nanotube of 50mg are added into above-mentioned solution, are stirred
After 6h, solution is washed through filtering, methanol, is finally putting into drying box and is dried overnight for 70 DEG C, obtains ZIF/CNT material.
Step (2): the preparation of NPC/CNT material
After being fully ground of ZIFs/CNTs composite material of step (1) preparation, it is put into porcelain boat, with 5 DEG C/min's
Heating rate is in nitrogen atmosphere, 900 DEG C of heat preservation 3h.After naturally cooling to room temperature, product is washed in the hydrochloric acid of 2mol/L
3 removing zinc metal ions.It is washed with deionized later and removes by-product that may be present, until solution is to neutrallty condition (pH
=7) it, is finally putting into drying box and is dried overnight for 70 DEG C, obtain NPC/CNT material.
Step (3): the preparation of S@NPC/CNT material
Step (2) is obtained into NPC/CNT material and distillation sulphur powder with the ratio mixed grinding of 1:9, by ground mixing
Object is transferred in the stainless steel cauldron of 50ml, is warming up to 157 DEG C of heat preservation 12h, is naturally cooled to room temperature to reaction kettle, finally
To S@NPC/CNT material.
Step (4): the preparation of lithium sulphur battery electrode film
The PTFE of S@NPC/CNT composite material and 10wt% acetylene black and 10wt% made from the present embodiment by 80wt%
0.2mm thickness, 0.8cm is being made by film, drying, sanction film, tabletting in (adhesive) mixing2Electrode wafer.
Step (5): the assembling and performance test of lithium-sulfur cell
Electrode wafer obtained by step (4) is operated in the glove box full of high-purity argon gas atmosphere, cathode is done with lithium piece,
2300 perforated membrane of Celgard is diaphragm, and the LiTFSI solution of 1M is electrolyte, is assembled into 2025 type button cells.Use Lan electricity electricity
Pond test macro (LAND CT2001A) carries out charge-discharge test between 1.5~2.8v.Its initial capacity is 1009.5mA
Hg-1, and there is relatively good cycle performance, the charge and discharge at 0.5C are still able to maintain 626.0mA after recycling 120 times
h·g-1Capacity.
Embodiment 5
Using monometallic MOF as precursor preparation NPC/CNT composite material and its it is assembled into the performance test of lithium-sulfur cell
Step (1): the preparation of metallic cobalt ZIF/CNT composite material
The cobalt nitrate of 3.05mmol is put into methanol and water volume ratio is to be placed on magnetic stirring apparatus in the mixed solution of 3:1
Upper agitated dissolution.Then the 2-methylimidazole of 6.09mmol and the carbon nanotube of 50mg are added into above-mentioned solution, are stirred
After 6h, solution is washed through filtering, methanol, is finally putting into drying box and is dried overnight for 70 DEG C, obtains ZIF/CNT material.
Step (2): the preparation of NPC/CNT material
After being fully ground of ZIFs/CNT composite material of step (1) preparation, it is put into porcelain boat, with the liter of 5 DEG C/min
Warm rate is in nitrogen atmosphere, 900 DEG C of heat preservation 3h.After naturally cooling to room temperature, product is washed 3 in the hydrochloric acid of 2mol/L
Secondary removing cobalt metal ion.It is washed with deionized later and removes by-product that may be present, until solution is to neutrallty condition (pH=
7) it, is finally putting into drying box and is dried overnight for 70 DEG C, obtain NPC/CNT material.
Step (3): the preparation of S@NPC/CNT material
Step (2) is obtained into NPC/CNT material and distillation sulphur powder with the ratio mixed grinding of 1:9, by ground mixing
Object is transferred in the stainless steel cauldron of 50ml, is warming up to 157 DEG C of heat preservation 12h, is naturally cooled to room temperature to reaction kettle, finally
To S@NPC/CNT material.
Step (4): the preparation of lithium sulphur battery electrode film
The PTFE of S@NPC/CNT composite material and 10wt% acetylene black and 10wt% made from the present embodiment by 80wt%
0.2mm thickness, 0.8cm is being made by film, drying, sanction film, tabletting in (adhesive) mixing2Electrode wafer.
Step (5): the assembling and performance test of lithium-sulfur cell
Electrode wafer obtained by step (4) is operated in the glove box full of high-purity argon gas atmosphere, cathode is done with lithium piece,
2300 perforated membrane of Celgard is diaphragm, and the LiTFSI solution of 1M is electrolyte, is assembled into 2025 type button cells.Use Lan electricity electricity
Pond test macro (LAND CT2001A) carries out charge-discharge test between 1.5~2.8v.Its initial capacity is 982.0mA
Hg-1, and there is relatively good cycle performance, the charge and discharge at 0.5C are still able to maintain 603.0mA after recycling 120 times
h·g-1Capacity.
Comparative example 1
The preparation of S@NPC composite material and its performance test for being assembled into lithium-sulfur cell
Step (1): the preparation of ZnCo-ZIFs material
By the mixed solution that the cobalt nitrate of the zinc nitrate of 1.68mmol and 1.71mmol is put into methanol and water volume ratio is 3:1
In, it is placed on agitated dissolution on magnetic stirring apparatus, forms uniform pink colour solution.Then it is added into above-mentioned solution
The 2-methylimidazole of 6.09mmol, after stirring 6h, solution is washed through filtering, methanol, be finally putting into drying box 70 DEG C it is dried
Night obtains ZnCo-ZIFs material.
Step (2): the preparation of NPC material
After being fully ground of ZnCo-ZIFs composite material of step (1) preparation, it is put into porcelain boat, with 5 DEG C/min's
Heating rate is in nitrogen atmosphere, 900 DEG C of heat preservation 3h.After naturally cooling to room temperature, product is washed in the hydrochloric acid of 2mol/L
3 times except dezincify cobalt metal ion.It is washed with deionized later and removes by-product that may be present, until solution is to neutrallty condition
(pH=7), it is finally putting into drying box and is dried overnight for 70 DEG C, obtain NPC/CNT material
Step (3): the preparation of S@NPC material
Step (2) is obtained into NPC material and distillation sulphur powder with the ratio mixed grinding of 1:9, ground mixture is turned
It moves on in the stainless steel cauldron of 50ml, is warming up to 157 DEG C of heat preservation 12h, naturally cools to room temperature to reaction kettle, finally obtain S@
NPC material.
Step (4): the preparation of lithium sulphur battery electrode film
The PTFE of S@NPC composite material made from the present embodiment by 80wt% and 10wt% acetylene black and 10wt% are (viscous
Mixture) mixing, 0.2mm thickness, 0.8cm is being made by film, drying, sanction film, tabletting2Electrode wafer.
Step (5): the assembling and performance test of lithium-sulfur cell
Step (4) resulting electrode wafer is operated in the glove box full of high-purity argon gas atmosphere, cathode is done with lithium piece,
2300 perforated membrane of Celgard is diaphragm, and the LiTFSI solution of 1M is electrolyte, is assembled into 2025 type button cells.With blue electricity
Battery test system (LAND CT2001A) carries out charge-discharge test between 1.5~2.8v.As shown in Figure 5, initial capacity
For 818.mAhg-1, and cycle performance is poor, the charge and discharge at 0.5C, only keeps 468.2mAhg after circulation 67 times-1
Capacity, and its high rate performance has a certain distance compared to the high rate performance of S NPC/CNT material described in embodiment 1.
Claims (10)
1. a kind of S@NPC/CNT composite material, it is characterised in that: the S@NPC/CNT composite material is by NPC/CNT composite material
It is carried sulphur to obtain, the NPC/CNT composite material is made of N doping porous carbon and carbon nanotube intertexture, and the N doping is porous
Carbon is the carbon material as derived from metal organic framework, and the metal in the metal organic framework is zinc and/or cobalt.
2. a kind of S@NPC/CNT composite material according to claim 1, it is characterised in that: the S@NPC/CNT composite wood
The load sulfur content of material is 75%~95%.
3. preparing a kind of method of S@NPC/CNT composite material as claimed in claim 1 or 2, it is characterised in that: by metal salt
It is added in methanol-water mixed solution and obtains mixed liquor, organic ligand is then sequentially added in mixed liquor, carbon nanotube is expected
Liquid, after being stirred to react, after being separated by solid-liquid separation, being dried obtain ZIFs//CNT composite material, ZIFs/CNT composite material through calcining,
Pickling obtains NPC/CNT composite material, and NPC/CNT composite material carries after sulphur up to S@NPC/CNT composite material；The metal salt
For zinc salt and/or cobalt salt.
4. a kind of preparation method of S@NPC/CNT composite material according to claim 3, it is characterised in that: the zinc salt
Selected from least one of zinc nitrate, zinc acetate, zinc chloride, the cobalt salt in cobalt nitrate, cobalt acetate, cobalt chloride at least
It is a kind of；In mixed liquor, containing zinc salt and when cobalt salt, according to the molar ratio, zinc salt: cobalt salt=1:1~5.
5. a kind of preparation method of S@NPC/CNT composite material according to claim 3, it is characterised in that: the methanol
In the mixed solution of water, the volume ratio of first alcohol and water is 1~7:1.
6. a kind of preparation method of S@NPC/CNT composite material according to claim 3, it is characterised in that: described organic
Ligand is selected from least one of 2-methylimidazole, benzimidazole；The ratio between mole of the organic ligand and metal salt be 1~
5:1。
The carbon nanotube is selected from multi-walled carbon nanotube and/or single-walled carbon nanotube, and the diameter of the carbon nanotube is 20-
The mass ratio of 40nm, the carbon nanotube and organic ligand is 1:6~12.
7. a kind of preparation method of S@NPC/CNT composite material according to claim 3, it is characterised in that: described
ZIFs//CNT composite material is calcined under protective atmosphere, and the calcination temperature is 600~900 DEG C.
8. a kind of preparation method of S@NPC/CNT composite material according to claim 3, it is characterised in that: the pickling
Acid solution be selected from least one of hydrochloric acid, sulfuric acid, nitric acid, preferably hydrochloric acid, the concentration of the hydrochloric acid is 1~5mol/L.
9. a kind of preparation method of S@NPC/CNT composite material according to claim 3, it is characterised in that: the NPC/
CNT composite material carries sulphur process, and NPC/CNT composite material is mixed with sulphur powder and obtains mixture, grinds 15~30min, so
After be heated to 150~180 DEG C, keep the temperature 10~15h, i.e. acquisition S@NPC/CNT composite material；In the mixture, NPC/CNT is multiple
Condensation material and the mass ratio of sulphur powder are 1:7~9.
10. a kind of application of S@NPC/CNT composite material according to claim 1 or 2, which is characterized in that by S@NPC/
CNT composite material is applied to lithium-sulfur cell as positive electrode.
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