CN110589795A - Manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network and preparation method and application thereof - Google Patents
Manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network and preparation method and application thereof Download PDFInfo
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 116
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 60
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims description 12
- 229920001817 Agar Polymers 0.000 claims abstract description 17
- 239000008272 agar Substances 0.000 claims abstract description 17
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000004108 freeze drying Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 229940071125 manganese acetate Drugs 0.000 claims description 9
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000004964 aerogel Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000003837 high-temperature calcination Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 239000000017 hydrogel Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 abstract description 16
- 239000011593 sulfur Substances 0.000 abstract description 16
- 239000003575 carbonaceous material Substances 0.000 abstract description 11
- 229920001021 polysulfide Polymers 0.000 abstract description 11
- 239000005077 polysulfide Substances 0.000 abstract description 11
- 150000008117 polysulfides Polymers 0.000 abstract description 11
- 239000002131 composite material Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 239000000499 gel Substances 0.000 abstract description 4
- 238000003763 carbonization Methods 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 238000009835 boiling Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 230000008595 infiltration Effects 0.000 abstract description 2
- 238000001764 infiltration Methods 0.000 abstract description 2
- 230000000670 limiting effect Effects 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 description 9
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002429 nitrogen sorption measurement Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- 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
-
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
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Abstract
The invention takes a natural hydrogel-agar as a raw material, the agar is dissolved in boiling water, the agar forms a gel formed by hydrogen bonds in and among agar molecules after being cooled, moisture is removed by a freeze-drying technology, then the agar molecules are carbonized at high temperature to form a carbon material, metal ions are successfully introduced into a carbon substrate in the process of forming the gel, and the manganese dioxide nano particle modified three-dimensional porous carbon network composite material is successfully prepared after high-temperature carbonization. When the synthesized material is applied to a lithium-sulfur battery anode host material, the sulfur carrying amount of the synthesized material is up to 76.3%, the hierarchical porous (macroporous, mesoporous, microporous) network structure has a good limiting effect on polysulfide, the porous network structure is favorable for the infiltration of electrolyte, in addition, manganese dioxide nanoparticles have a good adsorption effect on polysulfide, and the shuttle effect of the lithium-sulfur battery is effectively inhibited. The material selected by the invention has low price, is simple and easy to obtain, and has better application prospect in the aspect of future energy storage.
Description
Technical Field
The invention belongs to the field of materials science, relates to a lithium-sulfur battery positive electrode material, and particularly relates to a three-dimensional hierarchical porous carbon network modified by transition metal oxide manganese dioxide nanoparticles and a preparation method thereof.
Background
Lithium Sulfur Batteries (LSBs) have a capacity of up to 1675mA h g-1Theoretical specific capacity of, and 2600W h kg-1Has become one of the most promising second generation energy storage devices. In addition, sulfur is abundant in the earth, low in cost and low in toxicity, and thus has attracted extensive attention of researchers. However, the lithium-sulfur battery still has many problems that limit its practical application, such as: (1) the conductivity of both sulfur and lithium sulfide was poor (25 ℃ C.,. apprxeq.5X 10-30S m)-1) When used directly as a positive electrode material, the battery reaction hardly proceeds; (2) during charge and discharge cycles, the volume of the electrode material will expand severely (-80%), leading to electrode material pulverization, resulting in poor contact between the active material and the current collector, further hindering reaction kinetics; (3) intermediate polysulfide (Li)2SnN is more than or equal to 4 and less than or equal to 8) is easy to dissolve in electrolyte, so that shuttle effect is caused, and the coulomb efficiency of the battery is reduced; (4) the sulfur host material has a lower sulfur loading.
Researchers solve the problems encountered by the lithium-sulfur battery from different aspects, wherein a porous carbon material attracts people's attention, and a carbon-sulfur composite material is prepared to be used as a conductive framework of a positive electrode material and used for enhancing and improving the defect of poor sulfur conductivity; secondly, the porous carbon skeleton acts as a physical barrier to limit the "shuttling effect" of lithium polysulfides; due to the high conductivity, various redox reactions of the sulfur anode can be carried out, and redox intermediates can be efficiently captured; the porous structure has higher specific surface area, and can improve the loading of sulfur. Therefore, the rational design of the porous network carbon material with hierarchical porosity and internal crosslinking is always a research hotspot of the scientific community, wherein the pore size plays a crucial role in improving the electrochemical performance of the lithium-sulfur battery. The following are advantages and disadvantages of carbon materials of different pore sizes in lithium sulfur battery applications: the microporous carbon material (the aperture is less than 2nm) can effectively limit the shuttling of soluble lithium polysulfide and reduce the shuttling effect, but the aperture is too small, the aperture is easily blocked by a solid product and is not beneficial to the electrolyte permeation in the discharging process, and in addition, the loading capacity of sulfur is lower due to the too small aperture; macroporous carbon materials (pore size >50nm) can hold a large amount of sulfur, but the pores are too large to easily cause dissolution of lithium polysulfide; mesoporous carbon materials (2nm and less than or equal to 50nm) are considered as the most ideal strategy; however, the single use of mesoporous materials still cannot effectively inhibit the dissolution of lithium polysulfide and promote the permeation of electrolyte in electrode materials, so there is an urgent need to combine the advantages of materials with different pore diameters to synthesize porous materials with multiple scales to overcome the inherent limitations of porous materials with single scale. In recent years, many hierarchical porous carbon materials containing both macropores, micropores and mesopores have been used in lithium sulfur batteries, but still have some drawbacks such as rapid capacity fade due to a polarity difference between the carbon material and lithium polysulfide, shuttle effect of polysulfide not being effectively limited, and structural integrity of the positive electrode material during charge and discharge cannot be maintained.
Disclosure of Invention
The invention aims to provide a manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network and a preparation method thereof.
In order to achieve the aim, the invention provides a preparation method of a manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network, which is characterized by comprising the following steps of:
step 1: preparing a manganese acetate aqueous solution, adding agar powder, magnetically stirring for 30-60 min, raising the temperature to 100 ℃, continuously magnetically stirring until agar is completely dissolved, and heating at 100 ℃ for 1-3 h to obtain a colloidal solution;
step 2: ultrasonically defoaming the colloidal solution obtained in the step 1, naturally cooling to room temperature to form hydrogel, quickly freezing by using liquid nitrogen, and freeze-drying in a freeze dryer for 3 d;
and step 3: shearing the aerogel obtained after freeze-drying and dehydration in the step 2, placing the sheared aerogel in a tube furnace, and calcining the sheared aerogel at high temperature in an argon atmosphere;
and 4, step 4: and (3) mixing the sample obtained by high-temperature calcination in the step (3) with solid KOH according to the mass ratio of 1:3, grinding into powder, placing the powder in a tube furnace, activating at the high temperature of 500-700 ℃ for 1-2 h under the nitrogen atmosphere, washing, centrifugally collecting, placing the powder in a vacuum drying box, vacuum drying at the temperature of 60-80 ℃ for 8-12 h, and grinding to obtain the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network.
Preferably, the concentration of manganese acetate in the manganese acetate aqueous solution in the step 1 is 5-10mg/mL, and the mass-to-volume ratio of the agar powder to the manganese acetate aqueous solution is 0.01-0.05 g/mL.
Preferably, in the step 3, the specific conditions of the high-temperature calcination are as follows: keeping the temperature at 100 ℃ for 2h, keeping the temperature at 300 ℃ for 5h, keeping the temperature at 400 ℃ for 12h, keeping the temperature at 700 ℃ for 5h, and keeping the temperature rise rate at 1-5 ℃/min.
Preferably, the washing in the step 4 is washing with 0.1mol/L diluted HCl and deionized water respectively for several times, and finally washing with water to be neutral.
The invention also provides the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network prepared by the method, which is characterized in that the microstructure of the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network is a three-dimensional hierarchical porous carbon network structure with macropores, mesopores and micropores existing simultaneously.
Preferably, in the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network, the doping amount of C atoms is 85-95 wt%,
preferably, in the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network, the doping amount of O atoms is 2.5-5 wt%,
preferably, in the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network, the doping amount of Mn atoms is 2.5-5 wt%.
The invention also provides application of the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network prepared by the method in preparation of a lithium-sulfur battery anode host material.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention uses a natural hydrogel-agar as a raw material, the agar is dissolved in boiling water, the agar forms a gel by hydrogen bonds in and among molecules after being cooled, moisture is removed by a freeze-drying technology, then the agar is carbonized at high temperature to form a carbon material, metal ions are successfully introduced into a carbon substrate in the process of gel forming, and the three-dimensional porous carbon network composite material modified by metal oxide nano particles is successfully prepared after high-temperature carbonization. The synthetic method is simple and easy to implement, and has small harm to the environment, when the synthetic material is applied to the lithium-sulfur battery anode host material, the sulfur carrying amount is up to 76.3%, in addition, the hierarchical porous (macroporous, mesoporous, microporous) network structure has good limiting effect on polysulfide, the porous network structure is favorable for the infiltration of electrolyte, in addition, manganese dioxide nano particles also have good adsorption effect on polysulfide, and the shuttle effect of the lithium-sulfur battery is effectively inhibited.
(2) The invention has cheap and easily obtained raw materials, simple preparation method and no addition of any hard template, synthesizes the three-dimensional carbon-based composite material which is modified by the inorganic transition metal oxide nano particles and has hierarchical porosity, is suitable for large-scale production, reduces the cost, contributes to arousing the attention of people to energy crisis and has better prospect in the future energy storage direction.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) picture of a manganese dioxide nanoparticle-modified three-dimensional hierarchical porous carbon network of example 1;
FIG. 2a is a nitrogen sorption and desorption curve of the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network of example 1;
FIG. 2b is a plot of the pore size distribution of the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network of example 1;
FIG. 3a is a Raman (Raman) plot of the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network of example 1;
FIG. 3b is a thermogravimetric analysis (TGA) plot of the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network of example 1;
FIG. 3c is an X-ray diffraction (XRD) pattern of the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network of example 1;
FIG. 3d is a graph of infrared spectroscopic analysis (FT-IR) of the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network of example 1;
FIG. 4 is an X-ray photoelectron spectroscopy (XPS) plot of the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network of example 1;
FIG. 5 is a graph of the alternating current impedance (EIS) and Cyclic Voltammogram (CV) at a sweep rate of 0.1mV s-1 for the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network of example 4;
FIG. 6 is a graph of electrochemical performance of the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network of example 4, (a) cycling performance of the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network (HPCM/S) and HPC/S without manganese dioxide nanoparticle modification; (b) constant current charge and discharge curve of HPCM/S; (c) charging and discharging curves of HPCM/S and HPC/S at a current density of 0.2C; (d) multiplying power performance diagrams (e) of HPCM/S and HPC/S the charging and discharging curves of HPCM/S at current densities of 0.1C,0.2C,0.5C,1C,2C, respectively;
FIG. 7 is a schematic flow chart of the preparation process of the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network of the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
As shown in fig. 7, this embodiment provides a method for preparing a manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network, which specifically includes the following steps:
step 1: preparing 50mL of 5-10mg/mL manganese acetate aqueous solution, adding 1.5g of agar powder, magnetically stirring for 30min, raising the temperature to 100 ℃, simultaneously magnetically stirring until the agar is completely dissolved, and heating at 100 ℃ for 2h to obtain a colloidal solution;
step 2: ultrasonically defoaming the colloidal solution obtained in the step 1, naturally cooling to room temperature to form hydrogel, quickly freezing by using liquid nitrogen, and freeze-drying in a freeze dryer for 3 d;
and step 3: shearing the aerogel obtained after freeze-drying and dehydration in the step 2, placing the sheared aerogel in a tube furnace, calcining at high temperature in Ar atmosphere, preserving heat at 100 ℃ for 2h, preserving heat at 300 ℃ for 5h, preserving heat at 400 ℃ for 12h, preserving heat at 700 ℃ for 5h, and increasing the temperature rate at 2 ℃/min;
and 4, step 4: and (3) mixing a sample obtained by high-temperature calcination in the step (3) with solid KOH according to the mass ratio of 1:3 grinding the mixture into powder (200 meshes and 300 meshes) after mixing, placing the powder in a tube furnace, and N2And (2) activating at the high temperature of 700 ℃ for 2h in the atmosphere, then washing with 0.1mol/L diluted HCl and deionized water for several times respectively, washing with water to neutrality, centrifugally collecting, placing in a vacuum drying oven, and vacuum drying at the temperature of 60 ℃ for 12h to obtain the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network sample.
By combining a Scanning Electron Microscope (SEM) image in FIG. 1 and a nitrogen adsorption and desorption curve and a pore size distribution curve in FIG. 2, it can be seen that a carbon composite material modified by manganese dioxide nanoparticles and having a hierarchical porous carbon network structure with micropores, mesopores and macropores is indeed obtained after high-temperature carbonization and KOH activation;
from the Raman (Raman) diagram, the thermogravimetric analysis (TGA), the X-ray diffraction (XRD) diagram and the infrared spectroscopic analysis (FT-IR) diagram of FIG. 3; the method can obtain the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network which is rich in defects due to the porous structure and has the sulfur carrying capacity of 76.3 percent;
from XPS analysis of fig. 4, the material contained elements C, O, Mn, which was laterally verified to be a manganese dioxide nanoparticle modified carbon material.
Example 2
The sulfur loading is carried out on the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network obtained in the example 1, and the specific steps are as follows:
step 1: the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network sample obtained in example 1 and sublimed sulfur are mixed according to the mass ratio of 1:3 grinding in agate mortar for 20min, adding carbon disulfide (CS)2) To submerge the sample, continue grinding until carbon disulfide (CS)2) Completely volatilizing, and grinding for 20 min;
step 2: transferring the sample ground in the step 1 into a stainless steel reaction kettle with a polytetrafluoroethylene lining, heating to 155 ℃, keeping for 12 hours, and naturally cooling to room temperature to obtain a sample;
and step 3: and (3) grinding the sample obtained in the step (2) by using an agate mortar, and collecting to obtain the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network and sulfur composite material (HPCM/S).
Example 3
The manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network and sulfur composite material (HPCM/S) obtained in the embodiment 2 is prepared into an electrode plate of a lithium-sulfur battery, and the method specifically comprises the following steps:
step 1: grinding 0.07g of the manganese dioxide nanoparticle-modified three-dimensional hierarchical porous carbon network and sulfur composite material (HPCM/S) obtained in example 2, 0.02g of acetylene black and 0.01g of binder (PVDF) in an agate mortar for 30min, and then adding 0.25mL of N-methylpyrrolidone (NMP) to grind into slurry;
step 2: and (3) uniformly coating the slurry prepared in the step (1) on an aluminum foil by using a scraper, and carrying out vacuum drying at 60 ℃ for 12h to obtain the electrode material.
Example 4
The electrode material obtained in example 3 was subjected to electrochemical performance testing, which specifically comprises the following steps:
step 1: the electrode material obtained in example 3 was cut into electrode pieces 14mm in diameter, and a battery case of size 2032 was selected and assembled in a glove box,
step 2: after the assembled battery is allowed to stand for 12 hours, the electrochemical performance test is carried out by using a blue electricity system, and the performance graphs are shown in fig. 5 and 6.
FIG. 5 A.C. impedance (EIS) plot and sweep rate of 0.1mV s for a three-dimensional hierarchical porous carbon network modified with manganese dioxide nanoparticles-1The cyclic voltammetry Curve (CV) diagram shows that after the manganese dioxide nanoparticles are modified, the alternating current impedance values of all components are obviously reduced, and in the cyclic voltammetry curve, the current density of the three-dimensional hierarchical porous carbon network modified by the manganese dioxide nanoparticles is obviously improved under the same voltage, so that the three-dimensional hierarchical porous carbon network has more excellent electrochemical performance;
FIG. 6 is a graph of electrochemical performance of manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon networks (a) cycling performance of manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon networks (HPCM/S) and manganese dioxide nanoparticle free modified HPC/S; (b) constant current charge and discharge curve of HPCM/S; (c) charging and discharging curves of HPCM/S and HPC/S at a current density of 0.2C; (d) multiplying factor performance diagrams (e) for HPCM/S and HPC/S the charging and discharging curves for HPCM/S at current densities of 0.1C,0.2C,0.5C,1C,2C, respectively. Can exhibit excellent electrochemical properties. At a high current density of 1C, after 1000 circles of long circulation, the reversible capacity of the material still maintains 665mAh g-1The capacity fade rate per cycle was only 0.033%. In addition, HPCM has good rate capability with capacities of 1350, 1100, 920, 830 and 680mAhg at 0.1C,0.2C,0.5C,1C and 2C respectively-1When the current density is recovered to the low current density, the specific capacity can still be recovered to the initial value.
Claims (9)
1. A preparation method of a manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network is characterized by comprising the following steps:
step 1: preparing a manganese acetate aqueous solution, adding agar powder, magnetically stirring for 30-60 min, raising the temperature to 100 ℃, continuously magnetically stirring until agar is completely dissolved, and heating at 100 ℃ for 1-3 h to obtain a colloidal solution;
step 2: ultrasonically defoaming the colloidal solution obtained in the step 1, naturally cooling to room temperature to form hydrogel, quickly freezing by using liquid nitrogen, and freeze-drying in a freeze dryer for 3 d;
and step 3: shearing the aerogel obtained after freeze-drying and dehydration in the step 2, placing the sheared aerogel in a tube furnace, and calcining the sheared aerogel at high temperature in an argon atmosphere;
and 4, step 4: and (3) mixing the sample obtained by high-temperature calcination in the step (3) with solid KOH according to the mass ratio of 1:3, grinding into powder, placing the powder in a tube furnace, activating at the high temperature of 500-700 ℃ for 1-2 h under the nitrogen atmosphere, washing, centrifugally collecting, placing the powder in a vacuum drying box, vacuum drying at the temperature of 60-80 ℃ for 8-12 h, and grinding to obtain the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network.
2. The preparation method of the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network according to claim 1, wherein the concentration of manganese acetate in the manganese acetate aqueous solution in the step 1 is 5-10mg/mL, and the mass-to-volume ratio of the agar powder to the manganese acetate aqueous solution is 0.01-0.05 g/mL.
3. The preparation method of the manganese dioxide nanoparticle-modified three-dimensional hierarchical porous carbon network according to claim 1, wherein in the step 3, the specific conditions of high-temperature calcination are as follows: keeping the temperature at 100 ℃ for 2h, keeping the temperature at 300 ℃ for 5h, keeping the temperature at 400 ℃ for 12h, keeping the temperature at 700 ℃ for 5h, and keeping the temperature rise rate at 1-5 ℃/min.
4. The method for preparing the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network according to claim 1, wherein the washing in the step 4 is performed by washing with 0.1mol/L diluted HCl and deionized water for several times respectively, and finally washing with water until the network is neutral.
5. The manganese dioxide nanoparticle-modified three-dimensional hierarchical porous carbon network prepared by the method of any one of claims 1 to 4, characterized in that the microstructure thereof is a manganese dioxide nanoparticle-modified three-dimensional hierarchical porous carbon network structure with macropores, mesopores and micropores existing simultaneously.
6. The manganese dioxide nanoparticle-modified three-dimensional hierarchical porous carbon network of claim 5, wherein the doping amount of C atoms in the manganese dioxide nanoparticle-modified three-dimensional hierarchical porous carbon network is 85-95 wt%.
7. The manganese dioxide nanoparticle-modified three-dimensional hierarchical porous carbon network of claim 5, wherein the doping amount of O atoms in the manganese dioxide nanoparticle-modified three-dimensional hierarchical porous carbon network is 2.5-5 wt%.
8. The manganese dioxide nanoparticle-modified three-dimensional hierarchical porous carbon network of claim 5, wherein the doping amount of Mn atoms in the manganese dioxide nanoparticle-modified three-dimensional hierarchical porous carbon network is 2.5-5 wt%.
9. The application of the manganese dioxide nanoparticle modified three-dimensional hierarchical porous carbon network prepared by the method of any one of claims 1 to 4 in preparation of a lithium-sulfur battery positive host material.
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