CN110336032A - Preparation method of nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon and application of nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon in lithium-sulfur battery - Google Patents

Preparation method of nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon and application of nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon in lithium-sulfur battery Download PDF

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CN110336032A
CN110336032A CN201910618473.0A CN201910618473A CN110336032A CN 110336032 A CN110336032 A CN 110336032A CN 201910618473 A CN201910618473 A CN 201910618473A CN 110336032 A CN110336032 A CN 110336032A
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porous carbon
doping
cobalt
dimensional porous
preparation
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CN110336032B (en
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刘双科
吴文植
洪晓斌
王丹琴
郑春满
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National University of Defense Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method of a nanometer cobalt loaded nitrogen doped three-dimensional porous carbon and application thereof in a lithium-sulfur battery. According to the preparation method provided by the invention, the precursor is prepared by taking cobalt salt as a source, 2-methylimidazole as a carbon source and a nitrogen source and an inorganic nanosphere as a template through a stirring and solvent evaporation method, so that the yield of the precursor is close to 100%, the yield of the final product, namely the nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon can be effectively improved, and the preparation method is favorable for large-scale production and preparation; the three-dimensional porous carbon prepared by the preparation method can be applied to lithium-sulfur batteries, and the sulfur capacity and the electrochemical performance of the lithium-sulfur batteries are effectively improved.

Description

The preparation method of the three-dimensional porous carbon of N doping of a kind of nanometer cobalt load and its in lithium sulphur Application in battery
Technical field
The present invention relates to nano-carbon material and its preparation technical field, especially a kind of N doping of nanometer cobalt load is three-dimensional The preparation method of porous carbon and its application in lithium-sulfur cell.
Background technique
Lithium-sulfur cell has high theoretical specific capacity (1672mAh/g) and high-energy density (2600Wh/kg) and sulphur list The advantages that matter is resourceful, cheap, environmentally friendly is considered as most promising next-generation high-energy density secondary Power supply.But following problems existing for lithium-sulfur cell constrain the performance of its performance: (1) sulphur positive conductive it is poor (at room temperature only 5 × 10-30S/cm), the utilization rate of sulphur and the high rate performance of battery are seriously reduced；(2) long-chain polysulfide lithium (Li in discharge process2Sx, x =3~8) it is dissolved in ethers electrolyte, forms " shuttle " effect, lead to lower coulombic efficiency and reversible capacity；(3) it recycles The biggish volume change of sulphur anode causes battery structure to destroy in the process.
In order to overcome disadvantage mentioned above, a kind of most common strategy is that there is high conductivity, the absorption of strong polysulfide ion to make for building With the porous carbon composite sulfur anode with abundant pore structure.MOFs (metal organic frame, Metal Organic Frameworks) Material has high-specific surface area, microcellular structure abundant and a large amount of active metal sites, in gas storage, catalysis, absorption, changes It learns the fields such as the energy, bio-sensing and receives more and more attention.Since the last few years, porous carbon hydridization derived from MOFs Material with microcellular structure abundant, good catalysis and suction-operated due to being applied to lithium-sulfur cell and carrying sulfenyl body material Material.Such as Dong (DOI:10.1039/C6EE00104A) is by the methanol solution of the methanol solution of cobalt nitrate and 2-methylimidazole It carries out hybrid reaction and prepares metal-organic framework ZIF-67, be then heat-treated ZIF-67 under high temperature inert atmosphere, acid Nano Co-N doped micropore carbon (Co-N-GC) is obtained after etching as sulfur-donor, it is found that it is good the Co-N-GC material not only has Good electronic conductivity, and can effectively adsorb polysulfide ion and play catalysis sulphur conversion, so as to effectively change Capacity, high rate performance and the cycle performance of kind material.But nano metal-microporous carbon that this simple carbonization MOFs is obtained has Following deficiency: (1) yield is too low (about 20%) during synthesizing ZIF-67, leads to finally obtained nano Co-N doped micropore carbon Material is difficult to that preparation is mass produced；(2) predominantly microcellular structure, shortage are situated between in the nano Co-N doped micropore carbon material prepared Hole, macroporous structure, it is difficult to accommodate a large amount of sulphur and buffer the volume change of sulphur anode in charge and discharge process, be unfavorable for preparing high energy Metric density, high-performance lithium-sulfur cell.Therefore, a kind of being rich in derived from mesoporous, macroporous structure MOFs with high yield is prepared Porous carbon hybrid material is prepared on a large scale for improving the chemical property of lithium sulphur anode and realization under high-sulfur carrying capacity with ten Divide important meaning and application value.
Summary of the invention
The present invention provides a kind of preparation method of the three-dimensional porous carbon of N doping of nanometer cobalt load and its in lithium-sulfur cell Application realize the large-scale production preparation of three-dimensional porous carbon, the three-dimensional porous carbon is not for overcoming deficiency in the prior art Only there is microcellular structure abundant, also there is mesoporous, macroporous structure, form classifying porous three-dimensional network conduction carbon structure, effectively Improve the sulphur carrying capacity and chemical property of lithium-sulfur cell.
To achieve the above object, the present invention proposes a kind of preparation method of the three-dimensional porous carbon of N doping of nanometer cobalt load, The following steps are included:
(1) ultrasonic disperse in methanol is added in inorganic matter nanosphere, cobalt salt stirring and dissolving is then added, adds 2- methyl Imidazolemethanol solution, obtains precursor solution；
(2) precursor solution is stirred to react, then heating stirring is evaporated solvent, obtains gray purple precursor End；
(3) gray purple precursor powder is placed under inertia reducing atmosphere and is heat-treated, obtain black powder；
(4) black powder is placed in acidic aqueous solution and is washed, after filtering, drying, obtain the N doping of nanometer cobalt load Three-dimensional porous carbon material.
To achieve the above object, the present invention also proposes a kind of three-dimensional porous carbon of N doping of nanometer cobalt load, the nanometer In the porous carbon base body of N doping that the three-dimensional porous carbon of N doping of cobalt load is dispersed in three-dimensional honeycomb shape by nano cobalt granule And it is formed；The size of the nano cobalt granule is 5~50nm, and the aperture of the porous carbon is 100~500nm.
To achieve the above object, the present invention also proposes a kind of three-dimensional porous carbon of N doping of nanometer cobalt load in lithium-sulfur cell In application, the N doping that a kind of load of nanometer cobalt is prepared using the three-dimensional porous carbon of N doping of nanometer cobalt load is three-dimensional Porous carbon/sulphur composite material；The three-dimensional porous carbon of N doping of the nanometer cobalt load is prepared by preparation method described above It arrives, the mass fraction of sulphur is 40~90wt% in the composite material.
Compared with prior art, the beneficial effects of the present invention are as follows:
The preparation method of the three-dimensional porous carbon of N doping of nanometer cobalt load provided by the invention is prepared first containing organic/inorganic substance The precursor solution of nanometer ball template, cobalt salt and 2-methylimidazole, then using cobalt salt and 2-methylimidazole as cobalt source and carbon source, with Inorganic matter nanosphere prepares presoma as template, then high temperature cabonization and reduction treatment is carried out to presoma, finally by acid Wash away the three-dimensional porous carbon of N doping that nanometer cobalt load is obtained except inorganic matter nanometer ball template and part metals cobalt.Of the invention Preparation method is not directly using the ZIF-67 of low-yield as presoma, and using inorganic matter nanosphere as template, with cobalt (Co) salt As cobalt source, using 2-methylimidazole as carbon source and nitrogen source, in methanol solution cobalt salt reacted with 2-methylimidazole generate ZIF67 And be wrapped in inorganic matter nanometer ball surface, then presoma is made using stirring evaporation solvent method, presoma yield close to 100%, The yield of the three-dimensional porous carbon of N doping of nanometer cobalt load can be effectively improved, to be conducive to large-scale production preparation.It should Preparation method is using inorganic matter nanosphere as the mould for forming mesoporous (aperture is between 2~50nm) and macropore (aperture is greater than 50nm) Plate, so that the three-dimensional porous carbon of N doping of final nanometer cobalt load obtained not only has micropore abundant (aperture is less than 2nm) Structure also has mesoporous, macroporous structure, and it is mesoporous to increasing mesoporous quantity to be formed to remove the cobalt of part by pickling, not by The cobalt of pickling removal can increase the absorption polysulfide performance of material, and the material finally prepared has classifying porous three-dimensional network conductive carbon Structure, and inorganic matter nanosphere can avoid the growth and reunion of nanometer cobalt in heat treatment sintering process, improve nanometer cobalt Be evenly distributed degree and catalysis characteristics, effectively improve the sulphur carrying capacity and chemical property of lithium-sulfur cell.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with The structure shown according to these attached drawings obtains other attached drawings.
Fig. 1 is the scanning electron microscope (SEM) of the three-dimensional porous carbon of N doping of nanometer cobalt load in the embodiment of the present invention 1 Figure；
Fig. 2 is scanning electron microscope (SEM) figure of the partial enlargement in Fig. 1；
Fig. 3 is X-ray diffraction (XRD) figure of the three-dimensional porous carbon of N doping of nanometer cobalt load in the embodiment of the present invention 1；
Fig. 4 a is the three-dimensional porous carbon of N doping/sulphur composite material scanning electricity of nanometer cobalt load in the embodiment of the present invention 1 Sub- microscope (SEM) figure；
Fig. 4 b is nitrogen doped micropore carbon/sulphur composite material scanning electron microscope of nanometer cobalt load in comparative example 1 (SEM) figure；
Fig. 5 is that the three-dimensional porous carbon of the N doping/sulphur composite material and comparative example that nanometer cobalt loads in embodiment 1 is respectively adopted The charge-discharge performance comparison diagram for the lithium-sulfur cell that nitrogen doped micropore carbon/sulphur composite material that nanometer cobalt loads in 1 is assembled into.
The embodiments will be further described with reference to the accompanying drawings for the realization, the function and the advantages of the object of the present invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that described embodiment is only a part of the embodiments of the present invention, instead of all the embodiments.Base Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts it is all its His embodiment, shall fall within the protection scope of the present invention.
It in addition, the technical solution between each embodiment of the present invention can be combined with each other, but must be general with this field Based on logical technical staff can be realized, it will be understood that when the combination of technical solution appearance is conflicting or cannot achieve this The combination of technical solution is not present, also not the present invention claims protection scope within.
Without specified otherwise, used drug/reagent is commercially available.
The present invention proposes a kind of preparation method of the three-dimensional porous carbon of N doping of nanometer cobalt load, comprising the following steps:
(1) ultrasonic disperse in methanol is added in inorganic matter nanosphere, cobalt salt stirring and dissolving is then added, adds 2- methyl Imidazolemethanol solution, obtains precursor solution；
Preferably, the concentration of inorganic matter nanosphere is 5~50g/L in the precursor solution；In the precursor solution The concentration of cobalt salt is 0.01~0.1mol/L；The molar ratio of the cobalt salt and 2-methylimidazole is 1:(0.5~10) to be formed ZIF67 presoma.Mesoporous and macropore quantity is controlled by the additional amount of control cobalt salt and inorganic matter nanosphere, passes through control The ratio of cobalt salt and inorganic matter nanosphere controls the wall thickness of three-dimensional porous carbon in product.
Preferably, the inorganic matter nanosphere is SiO2、TiO2, ZnO, raw material is cheap, is easy to get, while The book of Changes pickling Removal；The particle size of the inorganic matter nanosphere is 50~500 nm, to as the template for forming mesoporous and macropore.
Preferably, the cobalt salt is at least one of cobalt nitrate, cobalt chloride, cobalt acetate.Common cobalt salt is selected, that is, is had Conducive to the progress of reaction, raw material are easy to obtain again.
(2) precursor solution is stirred to react, then heating stirring is evaporated solvent, obtains gray purple precursor End；
Preferably, the temperature being stirred to react is 10~40 DEG C, and mixing time is 0.5~2h.In the mistake being stirred to react Cheng Zhong, using inorganic matter nanosphere as template, using cobalt (Co) salt as cobalt source, using 2-methylimidazole as carbon source and nitrogen source, Forerunner's precursor reactant generates ZIF67 and is wrapped in inorganic matter nanometer ball surface in methanol solution.
Preferably, the temperature of the heating stirring is 70~90 DEG C, until heating stirring to solvent is volatilized completely, suitably Temperature is conducive to evaporate solvent, while avoiding damage to the original structure of material.
(3) gray purple precursor powder is placed under inertia reducing atmosphere and is heat-treated, obtain black powder；Under high temperature Presoma is carbonized, while the cobalt ions in presoma is reduced to metallic cobalt.
Preferably, the inertia reducing atmosphere is Ar and H2Gaseous mixture, Ar and H2Percent by volume be (70~95): Cobalt ions in presoma is reduced to metallic cobalt under reducing atmosphere by (5~30)；The temperature of the heat treatment is 500~1000 DEG C, the time is 0.5~10h, so that presoma carbonization is completely, while cobalt ions being promoted to be reduced to metallic cobalt.
(4) black powder is placed in acidic aqueous solution and is washed, after filtering, drying, obtain the N doping of nanometer cobalt load Three-dimensional porous carbon material.The metallic cobalt and inorganic matter nanosphere template that partial reduction comes out are removed in pickling, form product mesoporous And macropore.
Preferably, acid is hydrofluoric acid (HF) and hydrochloric acid (HCl) or sulfuric acid (H in the acidic aqueous solution2SO4) or nitric acid (HNO3) mixed acid；Sour mass fraction is 5~30wt% in the acidic aqueous solution.Common acid reagent is selected, was both held It easily obtains, and reduces cost.Select suitable acid content not only and can effectively remove inorganic matter nanosphere template and part metals cobalt but also It is cost-saved.
The nanometer that a kind of preparation method of the three-dimensional porous carbon of N doping of nanometer cobalt load as described above is prepared In the porous carbon base body of N doping that the three-dimensional porous carbon of N doping of cobalt load is dispersed in three-dimensional honeycomb shape by nano cobalt granule And it is formed；The size of the nano cobalt granule is 5~50nm, and the aperture of the porous carbon is 100~500nm, can be applicable to lithium In sulphur battery.
The present invention also proposes a kind of three-dimensional porous carbon of N doping of nanometer cobalt load, the N doping three of the nanometer cobalt load It is formed in the porous carbon base body of N doping that dimension porous carbon is dispersed in three-dimensional honeycomb shape by nano cobalt granule；The nanometer cobalt The size of particle is 5~50nm, and the aperture of the porous carbon is 100~500nm.
The present invention also proposes a kind of application of the three-dimensional porous carbon of N doping of nanometer cobalt load in lithium-sulfur cell, utilizes institute The three-dimensional porous carbon of N doping of nanometer cobalt load is stated to prepare a kind of three-dimensional porous carbon of N doping/sulphur composite wood of nanometer cobalt load Material；The three-dimensional porous carbon of N doping of the nanometer cobalt load is prepared by preparation method described above, the composite material The mass fraction of middle sulphur is 40~90wt%.
Embodiment 1
The present embodiment provides a kind of preparation methods of the three-dimensional porous carbon of N doping of nanometer cobalt load, comprising the following steps:
(1) 15ml tetraethyl orthosilicate is added to 10ml ammonium hydroxide, 200ml ethyl alcohol, 100ml water group under magnetic stirring At in the mixed solvent, stir 2h at 30 DEG C, products therefrom filtration washing dried, obtain the dioxy of partial size 300nm or so SiClx nanosphere powder.
(2) SiO for the 3.0g white for taking step (1) to obtain2Ultrasonic disperse 2h in 100ml methanol is added in nanosphere powder, Then 0.8g Co (NO is added3)2Stirring and dissolving adds the methanol solution of 100ml methylimidazole containing 1.0g2-, obtains forerunner Liquid solution.
(3) precursor solution is stirred to react at 30 DEG C 1h, then stirs solvent evaporated at 80 DEG C, obtains gray purple Precursor powder；
(4) gray purple precursor powder is placed in tube furnace in high-purity Ar/10%H2It is sintered at 900 DEG C under atmosphere 2h obtains black powder；
(5) mixing for black powder being placed in the HF aqueous solution of 100ml 10% and the HCl aqueous solution of 100ml 20% is molten 12h is stirred in liquid, washes off SiO2Nanometer ball template and part metals cobalt, are filtered, washed, dry, and obtain the nitrogen of nanometer cobalt load Adulterate three-dimensional porous carbon material.
Fig. 1 is the SEM figure of the three-dimensional porous carbon of N doping of nanometer cobalt load in the embodiment of the present invention 1, and Fig. 2 is in Fig. 1 The SEM of partial enlargement schemes, and as seen from Figure 1, the three-dimensional porous carbon of N doping of nanometer cobalt load shows three-dimensional honeycomb shape Network structure, the diameter of honeycomb hole are 300nm or so；As seen from Figure 2, the N doping of nanometer cobalt load is three-dimensional porous Carbon is dispersed in honeycomb carbon structure by nanometer cobalt and is constituted, and white granular is nanometer cobalt, having a size of from about for 10nm.
Fig. 3 is that the XRD diagram of the three-dimensional porous carbon of N doping of nanometer cobalt load in the embodiment of the present invention 1 is received as seen from the figure Rice cobalt load the three-dimensional porous carbon of N doping XRD spectrum in occur (002) diffraction maximum of graphite and metallic cobalt (111), (200) diffraction maximum shows that there are graphitized carbons and metallic cobalt in the three-dimensional porous carbon of N doping of nanometer cobalt load.
A kind of three-dimensional porous carbon material of N doping/sulphur composite material of nanometer cobalt load, preparation process are as follows:
The three-dimensional porous carbon material of N doping and 0.4g elemental sulfur for the nanometer cobalt load for taking 0.1g the present embodiment to be prepared Powder is ground, and after mixing, is placed in full of N2155 DEG C of heat preservation 10h in the tube furnace of protection take out after furnace cooling and obtain The three-dimensional porous carbon material of N doping/sulphur composite material of nanometer cobalt load.Sulfur content is 84% in the composite material.
Fig. 4 a is the three-dimensional porous carbon of N doping/sulphur composite material SEM figure of nanometer cobalt load in the present embodiment；Fig. 4 b is Nitrogen doped micropore carbon/sulphur composite material SEM figure that nanometer cobalt loads in comparative example 1.By Fig. 4 a it is found that manufactured in the present embodiment The three-dimensional porous carbon material of N doping/sulphur composite material of nanometer cobalt load has the three-dimensional porous carbon of N doping loaded with nanometer cobalt Similar three-dimensional honeycomb carbon network structure, surface do not have the appearance of bulky grain sulphur, show that sulphur has uniformly penetrated into porous carbon materials, This has benefited from its micropore abundant, mesoporous, macroporous structure；And by Fig. 4 b it is found that the nitrogen of nanometer cobalt load prepared by comparative example 1 Doped micropore carbon/irregular particle of the sulphur composite material by partial size in 100nm~1 μm forms, and bulky grain obviously occurs Sulphur, this shows to be classified pore structure due to lacking, and sulphur is difficult to fully penetrate into carbon skeleton.
Fig. 5 is that the three-dimensional porous carbon of the N doping/sulphur composite material and comparative example that nanometer cobalt loads in embodiment 1 is respectively adopted The charge-discharge performance comparison diagram for the lithium-sulfur cell that nitrogen doped micropore carbon/sulphur composite material that nanometer cobalt loads in 1 is assembled into, The charge and discharge for the lithium-sulfur cell that A is assembled into figure for the three-dimensional porous carbon of N doping/sulphur composite material of nanometer cobalt load in embodiment 1 Electric cycle performance, B is the lithium that is assembled into of the three-dimensional porous carbon of N doping/sulphur composite material of nanometer cobalt load in comparative example 1 in figure The charge-discharge performance of sulphur battery.As seen from the figure, the three-dimensional porous carbon/sulphur of N doping of nanometer cobalt load provided in this embodiment Composite material is higher than the nitrogen doped micropore carbon/sulphur composite material discharge capacity for the nanometer cobalt load that comparative example 1 provides, circulation Stability is more preferable.
Embodiment 2
The present embodiment provides a kind of preparation methods of the three-dimensional porous carbon of N doping of nanometer cobalt load, comprising the following steps:
(1) 15ml tetraethyl orthosilicate 5ml ammonium hydroxide, 200ml ethyl alcohol, 20ml water is added under magnetic stirring to form In the mixed solvent, stir 2h at 30 DEG C, products therefrom filtration washing dried, obtain the titanium dioxide of partial size 100nm or so Silicon nanosphere powder.
(2) SiO for the 3.0g for taking step (1) to obtain2Ultrasonic disperse 2h in 100ml methanol is added in nanosphere powder, then 0.8g Co (NO is added3)2Stirring and dissolving adds the methanol solution of 2-methylimidazole of the 100ml containing 1.0g, obtains presoma Reaction solution.
(3) step (2) is obtained into presoma reaction solution and is stirred to react 0.5h at 40 DEG C, then stirred and steam at 90 DEG C Dry solvent obtains gray purple precursor powder；
(4) the gray purple precursor powder that step (3) obtains is placed in tube furnace in high-purity Ar/20%H2Under atmosphere It is sintered 0.5h at 1000 DEG C, obtains black powder；
(5) black powder that step (4) obtains is placed in the HF aqueous solution of 100ml 5% and the HCl/water of 100ml 30% 12h is stirred in the mixed solution of solution, washes off SiO2Nanometer ball template and part metals cobalt, filtration washing is dry, obtains nanometer The three-dimensional porous carbon material of N doping of cobalt load.
The three-dimensional porous carbon of N doping of nanometer cobalt load shows the network structure of three-dimensional honeycomb shape, honeycomb hole it is straight Diameter size is 100nm or so, and the three-dimensional porous carbon of N doping of nanometer cobalt load is dispersed in institute's structure in honeycomb carbon structure by nanometer cobalt At, nanometer cobalt having a size of for 5~50nm.
A kind of three-dimensional porous carbon material of N doping/sulphur composite material of nanometer cobalt load, preparation process are as follows:
Take 0.1g nanometer cobalt manufactured in the present embodiment load the three-dimensional porous carbon material of N doping and 0.4g simple substance sulphur powder into Row grinding, after mixing, is placed in full of N2155 DEG C of heat preservation 10h in the tube furnace of protection take out after furnace cooling and are received The three-dimensional porous carbon material of N doping/sulphur composite material of rice cobalt load.
Embodiment 3
The present embodiment provides a kind of preparation methods of the three-dimensional porous carbon of N doping of nanometer cobalt load, comprising the following steps:
(1) by 5ml tetraethyl titanate be added under magnetic stirring 2ml ammonium hydroxide, 400ml ethyl alcohol, 5ml water composition it is mixed In bonding solvent, 30min is stirred at 30 DEG C, is then transferred to 100 DEG C of reaction 2h in water heating kettle, products therefrom filtration washing is dried It is dry, obtain the TiO of partial size 200nm or so2Nanosphere powder.
(2) TiO for the 3.0g white for taking step (1) to obtain2Ultrasonic disperse 2h in 100ml methanol is added in nanosphere powder, Then 0.8gCo (NO is added3)2Stirring and dissolving adds the methanol solution of 2-methylimidazole of the 100ml containing 1.0g, obtains forerunner Precursor reactant solution.
(3) step (2) is obtained into presoma reaction solution and is stirred to react 2.0h at 20 DEG C, then stirred and steam at 70 DEG C Dry solvent obtains gray purple precursor powder；
(4) the gray purple precursor powder that step (3) obtains is placed in tube furnace in high-purity Ar/15%H2Under atmosphere It is sintered 10h at 500 DEG C, obtains black powder；
(5) black powder that step (4) obtains is placed in the HF aqueous solution of 100ml 15% and the HNO of 100ml 20%3 12h is stirred in the mixed solution of aqueous solution, washes off TiO2Nanometer ball template and part metals cobalt, filtration washing is dry, is received The three-dimensional porous carbon material of N doping of rice cobalt load.
The three-dimensional porous carbon of N doping of nanometer cobalt load shows the network structure of three-dimensional honeycomb shape, honeycomb hole it is straight Diameter size is 200nm or so, and the three-dimensional porous carbon of N doping of nanometer cobalt load is dispersed in institute's structure in honeycomb carbon structure by nanometer cobalt At, nanometer cobalt having a size of for 5~50nm.
A kind of three-dimensional porous carbon material of N doping/sulphur composite material of nanometer cobalt load, preparation process are as follows:
Take 0.1g nanometer cobalt manufactured in the present embodiment load the three-dimensional porous carbon material of N doping and 0.4g simple substance sulphur powder into Row grinding, after mixing, is placed in full of N2155 DEG C of heat preservation 10h in the tube furnace of protection take out after furnace cooling and obtain nanometer The three-dimensional porous carbon material of N doping/sulphur composite material of cobalt load.
Comparative example 1
This comparative example provides a kind of nitrogen doped micropore carbon/sulphur nano-complex preparation method of nanometer cobalt load, and step is such as Under:
(1) by 0.8g Co (NO3)2It is separately added into stirring and dissolving in 100ml methanol with 1.0g 2-methylimidazole, by two kinds Solution mixes under magnetic stirring, obtains presoma reaction solution.
(2) step (1) is obtained into presoma reaction solution at 30 DEG C and is stirred to react 1h, be then allowed to stand reaction and adopt afterwards for 24 hours With ethyl alcohol filtration washing and drying, purple powder is obtained；
(3) the purple precursor powder that step (2) obtains is placed in tube furnace in high-purity Ar/15%H2Under atmosphere in It is sintered 2h at 900 DEG C, obtains black powder；
(4) black powder that step (3) obtains is placed in the HCL aqueous solution of 100ml 20% and stirs 12h, wash off part Metallic cobalt, filtration washing is dry, obtains the nitrogen doped micropore carbon material of nanometer cobalt load.
(5) the nitrogen doped micropore carbon material for taking 0.1g nanometer cobalt to load is ground with 0.4g simple substance sulphur powder, is uniformly mixed Afterwards, it is placed in full of N2155 degree of heat preservation 10h in the tube furnace of protection take out after furnace cooling and obtain the N doping of nanometer cobalt load Microporous carbon/sulphur composite material.The sulfur content of the composite material is 83%.
The above description is only a preferred embodiment of the present invention, is not intended to limit the scope of the invention, all at this Under the inventive concept of invention, using equivalent structure transformation made by description of the invention and accompanying drawing content, or directly/use indirectly It is included in other related technical areas in scope of patent protection of the invention.

Claims (10)

1. a kind of preparation method of the three-dimensional porous carbon of N doping of nanometer cobalt load, which comprises the following steps:
(1) ultrasonic disperse in methanol is added in inorganic matter nanosphere, cobalt salt stirring and dissolving is then added, adds 2-methylimidazole Methanol solution obtains precursor solution；
(2) precursor solution is stirred to react, then heating stirring is evaporated solvent, obtains gray purple precursor powder；
(3) gray purple precursor powder is placed under inertia reducing atmosphere and is heat-treated, obtain black powder；
(4) black powder is placed in acidic aqueous solution and is washed, after filtering, drying, the N doping for obtaining nanometer cobalt load is three-dimensional Porous carbon materials.
2. a kind of preparation method of the three-dimensional porous carbon of N doping of nanometer cobalt load as described in claim 1, which is characterized in that In the step (1), the concentration of inorganic matter nanosphere is 5~50g/L in the precursor solution；Cobalt in the precursor solution The concentration of salt is 0.01~0.1mol/L；The molar ratio of the cobalt salt and 2-methylimidazole is 1:(0.5~10).
3. a kind of preparation method of the three-dimensional porous carbon of N doping of nanometer cobalt load as claimed in claim 1 or 2, feature exist In the inorganic matter nanosphere is SiO2、TiO2,ZnO；The particle size of the inorganic matter nanosphere is 50~500nm.
4. a kind of preparation method of the three-dimensional porous carbon of N doping of nanometer cobalt load as claimed in claim 1 or 2, feature exist In the cobalt salt is at least one of cobalt nitrate, cobalt chloride, cobalt acetate.
5. a kind of preparation method of the three-dimensional porous carbon of N doping of nanometer cobalt load as described in claim 1, which is characterized in that In the step (2), the temperature being stirred to react is 10~40 DEG C, and the reaction time is 0.5~2h.
6. a kind of preparation method of the three-dimensional porous carbon of N doping of nanometer cobalt load as described in claim 1, which is characterized in that In the step (2), the temperature of heating stirring is 70~90 DEG C, is stirred until solvent volatilizees completely.
7. a kind of preparation method of the three-dimensional porous carbon of N doping of nanometer cobalt load as described in claim 1, which is characterized in that In the step (3), the inertia reducing atmosphere is Ar and H2Gaseous mixture, Ar and H2Percent by volume be (70~95): (5 ~30)；The temperature of the heat treatment is 500~1000 DEG C, and the time is 0.5~10h.
8. a kind of preparation method of the three-dimensional porous carbon of N doping of nanometer cobalt load as described in claim 1, which is characterized in that In the step (4), acid is the mixed acid of hydrofluoric acid and hydrochloric acid or sulfuric acid or nitric acid in the acidic aqueous solution；The acid water Sour mass fraction is 5~30wt% in solution.
9. a kind of three-dimensional porous carbon of N doping of nanometer cobalt load, which is characterized in that the N doping of the nanometer cobalt load is three-dimensional Porous carbon is by forming in the porous carbon base body of N doping that nano cobalt granule is dispersed in three-dimensional honeycomb shape；The nanometer cobalt The size of grain is 5~50nm, and the aperture of the porous carbon is 100~500nm.
10. a kind of application of three-dimensional porous carbon of N doping of nanometer cobalt load in lithium-sulfur cell, which is characterized in that described in utilization The three-dimensional porous carbon of N doping of nanometer cobalt load prepares the three-dimensional porous carbon of N doping/sulphur composite wood of nanometer cobalt load a kind of Material；The three-dimensional porous carbon of N doping of the nanometer cobalt load is prepared by preparation method according to any one of claims 1 to 9 It arrives, the mass fraction of sulphur is 40~90wt% in the composite material.
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