CN110061210B - Preparation method and application of modified bagasse/sulfur composite material - Google Patents
Preparation method and application of modified bagasse/sulfur composite material Download PDFInfo
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- CN110061210B CN110061210B CN201910298345.2A CN201910298345A CN110061210B CN 110061210 B CN110061210 B CN 110061210B CN 201910298345 A CN201910298345 A CN 201910298345A CN 110061210 B CN110061210 B CN 110061210B
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- 241000609240 Ambelania acida Species 0.000 title claims abstract description 79
- 239000010905 bagasse Substances 0.000 title claims abstract description 79
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 42
- 239000011593 sulfur Substances 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 238000000498 ball milling Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 11
- 238000012216 screening Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 9
- 239000007774 positive electrode material Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 239000002893 slag Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 238000005520 cutting process 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
- 239000012153 distilled water Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical group N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims 3
- 238000007873 sieving Methods 0.000 claims 2
- 239000010406 cathode material Substances 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 239000005077 polysulfide Substances 0.000 description 7
- 229920001021 polysulfide Polymers 0.000 description 7
- 150000008117 polysulfides Polymers 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 206010042674 Swelling Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000012938 design process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
- H01M10/0422—Cells or battery with cylindrical casing
- H01M10/0427—Button cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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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- 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
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to a preparation method and application of a modified bagasse/sulfur composite material. The method comprises the following steps: firstly, preparing a bagasse precursor; secondly, preparing modified bagasse; thirdly, preparing the modified bagasse/sulfur composite material: and (3) putting the modified bagasse and the nano-sulfur powder prepared in the second step into a ball mill for ball milling for 2-4 h, then putting a mixture obtained by ball milling into a reaction kettle with polytetrafluoroethylene as a substrate, heating and preserving heat for 10-20 h, and keeping the reaction temperature at 100-300 ℃ to obtain the modified bagasse/sulfur composite lithium-sulfur battery cathode material. The modified bagasse/sulfur composite material provided by the invention is a lithium-sulfur battery cathode material with great market prospect.
Description
Technical Field
The invention relates to the technical field of lithium-sulfur battery positive electrode materials, in particular to a preparation method of a low-cost high-adsorbability biomass lithium-sulfur battery positive electrode material, and specifically relates to a preparation method of a modified bagasse/sulfur composite material for a lithium-sulfur battery positive electrode.
Background
According to the statistical data of the ministry of public security, the new energy automobile holding amount in China reaches 153 two thousands of years by 2017, and the number is expected to become 500 two thousands of years by 2020. The lithium ion battery is taken as a main power supply of a new energy automobile, and wins the favor of developers with the advantages of low pollution, high energy density (100-180 Wh/kg), good cycle performance and the like. But it still has the disadvantages of high manufacturing cost and difficulty in recycling the waste batteries; on the other hand, according to investigation, the endurance of the conventional electric vehicle prepared by using the lithium ion battery as a power supply is generally 200-400 km, and the expectation of people on the electric vehicle with high endurance is difficult to meet. Therefore, the development of low-cost, pollution-free and high-energy-density battery systems has become an industry hotspot. The lithium-sulfur battery prepared by taking lithium as a negative electrode and sulfur as a positive electrode has the characteristics of high theoretical specific capacity of 1672mAh/g, high theoretical energy density of 2600Wh/kg, rich sulfur in the earth crust, low price and no pollution, and is a battery system with great prospect.
However, lithium sulfur batteries also have problems to be solved, such as elemental sulfur and the discharge product lithium sulfide being an electronic insulator; the anode material has serious volume expansion (80 percent of volume expansion) in the discharge reaction process, and is easy to cause material pulverization; lithium polysulfide as a discharge intermediate product is easily dissolved in electrolyte to cause capacity attenuation of the battery; lithium polysulfide dissolved in the electrolyte migrates back and forth between the positive electrode and the negative electrode under the action of an electric field and concentration difference, and a solid lithium sulfide film is formed on the surface of the negative electrode, so that the contact between the lithium negative electrode and the electrolyte is blocked, and the coulomb efficiency of the battery is reduced.
In order to solve a series of problems of the lithium-sulfur battery, researchers improve the electrochemical performance of the lithium-sulfur battery by improving a sulfur positive electrode, and obtain certain results, chinese patent CN102969481A discloses a preparation method of a microporous carbon/sulfur composite material for the lithium-sulfur battery positive electrode, the method uses sucrose as a carbon source and nitrocellulose as an additive, a microporous carbon material is obtained by high-temperature carbonization, and the microporous carbon/sulfur composite material is prepared by mixing with sulfur powder, the material has good ionic conductivity and electronic conductivity, the carbon material with a microporous structure can inhibit the dissolution of lithium polysulfide which is a discharge intermediate product, and the cycle performance of the lithium-sulfur battery is improved, but the method still has the following defects: (1) the sulfur element is in poor contact with the electrolyte in the discharge process, the discharge reaction kinetics is slow, and high-power discharge is difficult to realize, (2) the carbonization reaction temperature involved in the preparation process is as high as 1000 ℃, the temperature in the sulfur doping process is as high as 400 ℃, and the preparation cost of the electrode material is increased; chinese patent CN103762345A discloses a method for preparing an active carbon/sulfur composite lithium-sulfur battery anode material, which mixes sulfur powder directly with porous active carbon and forms a composite material by a melting method, and the method has the characteristics of simple process and low cost, but the active carbon is a non-graphitized carbon material with poor conductivity, and the battery prepared by the method has no good rate capability; chinese patent CN106463703A discloses a method for preparing a boron-doped carbon/sulfur composite material for a lithium-sulfur battery positive electrode, which uses ordered mesoporous silica as a template, sugars as a carbon source, and boron-containing compounds as a boron source, and prepares the boron-doped carbon/sulfur composite material through hydrothermal reaction and high-temperature carbonization, the material has a good void structure and an excellent specific surface area, and with the doping of boron, a polar boron-carbon bond is generated in the carbon material, which can effectively adsorb lithium polysulfide, and the boron atom is an atom with a larger volume, and in the boron doping process, the carbon material can locally generate certain distortion, and the adsorption capacity of the carbon material can also be increased, but the method still has some disadvantages: (1) the preparation process is complicated, (2) the carbonization temperature involved in the preparation process is higher, which increases the manufacturing cost, and (3) the template used in the preparation process can not be reused, which can cause certain waste.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the preparation method of the modified bagasse/sulfur composite material for the lithium-sulfur battery positive electrode overcomes the defects that the preparation raw materials of the lithium-sulfur battery positive electrode material in the prior art are expensive (such as graphene, titanium dioxide, lanthanum hydroxide and the like), the preparation process is complex and the like.
The technical scheme of the invention is as follows:
a preparation method of a modified bagasse/sulfur composite material comprises the following steps:
step one, preparing a bagasse precursor:
taking bagasse, cutting up, and screening out crushed slag with the particle size of 1000 meshes-10 meshes; adding the crushed slag obtained by screening into 0.1-2 mol/L NaOH solution, standing and soaking for 5-24 h, and then adjusting the pH value to be neutral by using dilute hydrochloric acid; finally, centrifugally washing the bagasse precursor for 3-5 times by using distilled water to obtain a swelled bagasse precursor;
wherein, 0.5-2 g of bagasse is added into each 10mL of NaOH solution;
second step, preparing modified bagasse:
adding the bagasse precursor prepared in the first step into a NaOH solution with the pH value of 8-13; then dropping an acrylonitrile aqueous solution; ultrasonically dispersing for 10-60 min, then placing the mixed solution in a constant-temperature water bath, and uniformly stirring for 0.5-10 h at the temperature of 25-90 ℃; centrifugally washing the obtained solid product for 3-5 times by using deionized water; drying the bagasse in a drying oven at the temperature of 30-80 ℃ for 1-24 hours to obtain modified bagasse containing cyanogen groups;
wherein, 0.5-2 g of bagasse is added into each 100mL of NaOH solution, and 1-10 mL of acrylonitrile solution is added into each 100mL of NaOH solution; the concentration of the acrylonitrile aqueous solution is 0.5-2 mg/mL;
thirdly, preparing the modified bagasse/sulfur composite material:
placing the modified bagasse and the nano-sulfur powder prepared in the second step into a ball mill for ball milling for 2-4 h, then placing a mixture obtained by ball milling into a reaction kettle with polytetrafluoroethylene as a substrate, heating and preserving heat for 10-20 h, and keeping the reaction temperature at 100-300 ℃ to obtain a modified bagasse/sulfur composite lithium-sulfur battery positive electrode material;
wherein the mass ratio of the modified bagasse: nano sulfur powder is 1: 1-5;
the mass concentration of the dilute hydrochloric acid in the first step is 5-15 wt.%.
The screening process in the first step is completed in a vibration screening machine.
The application of the modified bagasse/sulfur composite material is used for a positive electrode material of a lithium-sulfur battery.
The lithium sulfur battery is preferably a button CR2025 half cell.
The above-mentioned method for preparing a modified bagasse/sulfur composite material for use in a positive electrode of a lithium-sulfur battery, wherein the raw materials involved are commercially available, and the equipment and processes used are well known to those skilled in the art.
Compared with the prior art, the method has the prominent substantive characteristics as follows:
1. the bagasse is a waste in the sugar industry, and the method recycles the waste, changes waste into valuable, and has the characteristic of environmental protection;
2. the preparation process of the modified bagasse/sulfur composite material is simple, and the preparation conditions are mild;
3. in the design process of the invention, the method innovatively and newly proposes that the bagasse modified by acrylonitrile is used as a sulfur-carrying material to prepare the lithium-sulfur battery cathode material. The bagasse mainly comprises lignin and cellulose, and a large amount of hydroxyl in the cellulose and the lignin can be exposed to form hydroxyl with reaction activity by pretreating the bagasse with NaOH; the reaction of acrylonitrile with the reactive hydroxyl groups causes the bagasse microstructure to be "propped open", resulting in bagasse having a cross-linked network structure with a large specific surface area, providing a site for efficient sulfur attachment and charge-discharge reactions. The modified bagasse has a large amount of cyano groups and carbon-nitrogen bonds, so that the adsorption capacity of the cathode material on a lithium polysulfide intermediate product is greatly improved, and the shuttle effect can be effectively inhibited.
Compared with the prior art, the method provided by the invention has the following remarkable improvements:
1. compared with CN102969481A in the prior art, the preparation method provided by the invention has the advantages of mild preparation conditions and simple preparation process.
2. Compared with the prior art CN103762345A, the modified bagasse in the cathode material provided by the invention can effectively adsorb lithium polysulfide as a discharge intermediate product, and inhibit the dissolution of the lithium polysulfide, so that the shuttle effect is inhibited from the source, taking example 1, under the current density of 0.1C, the first discharge specific capacity reaches 957mAh/g, the specific capacity can still keep 675mAh/g battery capacity decay rate of 0.29%/time after 100 cycles, the capacity of the battery can be better kept between 670-770 mAh/g after 20 cycles, and the capacity decay rate is only 0.13%/time.
3. Compared with CN106463703A in the prior art, the preparation method is simple.
In conclusion, the modified bagasse/sulfur composite material provided by the invention is a lithium-sulfur battery cathode material with great market prospect.
Drawings
Fig. 1 is a first charge-discharge curve, a second charge-discharge curve, a third charge-discharge curve and a 100 th charge-discharge curve at a current density of 0.1C when the bagasse/sulfur composite material prepared in example 1 was used as a positive electrode of a lithium-sulfur battery;
FIG. 2 is a graph of the cycling performance of the bagasse/sulfur composite prepared in example 1 as a positive electrode for a lithium sulfur battery at a current density of 0.1C;
fig. 3 is a graph of the rate performance of the bagasse/sulfur composite material prepared in example 1 as a positive electrode of a lithium sulfur battery.
Detailed Description
Example 1
First, bagasse precursor is prepared
Taking bagasse, cutting up, and screening out crushed slag with the particle size of 10-100 meshes; adding 2g of crushed slag obtained by screening into 20mL of 2mol/L NaOH solution; standing and soaking for 10h, and then adjusting the pH to be neutral by using dilute hydrochloric acid with the mass concentration of 15 wt.%; finally, repeatedly centrifuging and washing for 3 times by using distilled water, and centrifuging to obtain a swelled bagasse precursor;
the screening process is completed in a vibration screening instrument, the aperture of an upper layer screen is 10 meshes, the aperture of a lower layer screen is 100 meshes, and the particle size of the obtained screened product is 10-100 meshes;
the swelled bagasse precursor obtained by centrifugation is a product obtained by centrifugation at the rotating speed of 6000 rpm;
second step, preparation of modified bagasse
Preparing 100mL of NaOH solution with the pH value of 10, adding 1g of bagasse precursor prepared in the first step into the NaOH solution, then dripping 1mL of acrylonitrile aqueous solution with the concentration of 1mg/mL into the NaOH solution, ultrasonically dispersing the mixture for 30min, finally placing the mixed solution into a constant-temperature water bath kettle, stirring the mixed solution at a constant speed for 3h at the temperature of 80 ℃, repeatedly centrifuging and washing a reaction product for 3 times by using deionized water, and drying the reaction product in a drying oven at the temperature of 50 ℃ for 10h to obtain the modified bagasse containing cyanogen groups;
thirdly, preparing the modified bagasse/sulfur composite lithium-sulfur battery cathode material
According to the mass ratio of 1:1, respectively weighing the modified bagasse and the nano-sulfur powder prepared in the second step, placing the modified bagasse and the nano-sulfur powder into a ball mill for ball milling for 2 hours, wherein the rotating speed of the ball mill is 200rpm, then placing a mixture obtained by ball milling into a reaction kettle with polytetrafluoroethylene as a substrate for heating and heat preservation, wherein the reaction time is 10 hours, and the reaction temperature is 155 ℃, so as to prepare the modified bagasse/sulfur composite lithium-sulfur battery anode material;
fourthly, preparing a battery positive plate and assembling the battery
And (2) putting the prepared modified bagasse/sulfur composite material, a conductive agent and a binder into a mortar according to the mass ratio of 7: 2: 1, uniformly grinding, adding a proper amount of N-methyl pyrrolidone, grinding into slurry, uniformly scraping and coating the slurry on a carbon-containing aluminum foil, coating the carbon-containing aluminum foil to the thickness of 15 micrometers, drying at 55 ℃ for 24 hours, and pressing into a sheet by using a tablet press under the pressure of 5MPa to obtain the positive plate. The obtained modified bagasse/sulfur was used as a positive electrode, a metal Li sheet was used as a negative electrode, and an electrolyte (electrolyte components: 1M LiTFSI, 0.1M LiNO3, DME: DOL ═ 1:1 Vol%) was added to assemble a button CR2025 half cell in a glove box.
The prepared samples were subjected to electrochemical performance analysis (BTS-800, Newwei).
Fig. 1 shows the first discharge curve, the second charge-discharge curve, the third charge-discharge curve and the 100 th charge-discharge curve of the bagasse/sulfur composite material prepared in this example as the positive electrode of the lithium-sulfur battery at a current density of 0.1C. Under the current density of 0.1C, the first discharge specific capacity reaches 957mAh/g, and after 100 cycles, the specific capacity can still maintain 675 mAh/g.
Fig. 2 is a graph of the cycling performance of the bagasse/sulfur composite material prepared in this example as a positive electrode for a lithium sulfur battery at a current density of 0.1C. Under the current density of 0.1C, the initial discharge specific capacity reaches 957mAh/g, after 100 cycles, the specific capacity can still maintain 675mAh/g, and the battery capacity decay rate is 0.29%/time, and according to the figure, the battery prepared by the embodiment can better maintain the capacity between 670 and 770mAh/g after the 20 th cycle, and the capacity decay rate is about 0.13%/time.
Fig. 3 is a graph of rate performance of the bagasse/sulfur composite material prepared in this example as a positive electrode of a lithium-sulfur battery. As the current charge-discharge current density increased from 0.1C to 2C, the bagasse/sulfur composite discharge capacity ranged from 909mAh/g to 360 mAh/g. For the battery prepared from the composite material, when the current density is reduced from 2C to 0.1C, the discharge capacity can be mostly recovered, and excellent rate performance is shown.
Example 2
The other points are the same as example 1 except for the fourth step. The modified bagasse/sulfur composite material, the conductive agent and the binder are mixed according to the mass ratio of 6: 3: 1. compared with the embodiment 1, the battery prepared by the embodiment has the specific first discharge capacity of 980mAh/g under the current density of 0.1C, and the specific first discharge capacity is increased by 23 mAh/g; meanwhile, the cycling stability of the battery prepared in the embodiment is slightly improved (the capacity fading rate is about 0.27%/time in the previous one hundred cycles), but the sulfur content of the positive electrode material prepared in the embodiment is 30%, and is reduced by 5% in a same ratio.
Example 3
Otherwise, the same as example 1, except that the first step was omitted. The first discharge specific capacity of the battery prepared in the embodiment is about 500mAh/g at the current density of 0.1C, and the battery can not discharge basically at the current density of 1C.
Example 4
The procedure of example 1 was otherwise the same except that in the second step, the final mixed solution was subjected to a water bath for 10 hours. The first discharge specific capacity of the battery prepared in the embodiment is 950mAh/g at the current density of 0.1C, and the benefit is close to that obtained in the embodiment 1.
Through the above examples, it can be seen that bagasse is used as a raw material, and the bagasse is subjected to swelling treatment and modification treatment, and then is compounded with nano sulfur powder to form the lithium-sulfur battery positive electrode material. The lithium-sulfur battery prepared by the cathode material has excellent discharge specific capacity, cycle performance and rate capability. Meanwhile, the invention has the characteristics of environmental protection, simple process and mild process conditions;
the previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
The invention is not the best known technology.
Claims (4)
1. A preparation method of a modified bagasse/sulfur composite material is characterized by comprising the following steps:
step one, preparing a bagasse precursor:
taking bagasse, cutting up, and screening out crushed slag with the particle size of 1000 meshes-10 meshes; adding the crushed slag obtained by screening into 0.1-2 mol/L NaOH solution, standing and soaking for 5-24 h, and then adjusting the pH value to be neutral by using dilute hydrochloric acid; finally, centrifugally washing the bagasse precursor for 3-5 times by using distilled water to obtain a swelled bagasse precursor;
wherein, 0.5-2 g of bagasse is added into each 10mL of NaOH solution;
second step, preparing modified bagasse:
adding the bagasse precursor prepared in the first step into a NaOH solution with the pH value of 8-13; then dropping an acrylonitrile aqueous solution; ultrasonically dispersing for 10-60 min, then placing the mixed solution in a constant-temperature water bath, and uniformly stirring for 0.5-10 h at the temperature of 25-90 ℃; centrifugally washing the obtained solid product for 3-5 times by using deionized water; drying the bagasse in a drying oven at the temperature of 30-80 ℃ for 1-24 hours to obtain modified bagasse containing cyanogen groups;
wherein, 0.5-2 g of bagasse is added into each 100mL of NaOH solution, and 1-10 mL of acrylonitrile solution is added into each 100mL of NaOH solution; the concentration of the acrylonitrile aqueous solution is 0.5-2 mg/mL;
thirdly, preparing the modified bagasse/sulfur composite material:
placing the modified bagasse and the nano-sulfur powder prepared in the second step into a ball mill for ball milling for 2-4 h, then placing a mixture obtained by ball milling into a reaction kettle with polytetrafluoroethylene as a substrate, heating and preserving heat for 10-20 h, and keeping the reaction temperature at 100-300 ℃ to obtain a modified bagasse/sulfur composite lithium-sulfur battery positive electrode material;
wherein the mass ratio of the modified bagasse: nano sulfur powder is 1: 1-5;
the mass concentration of the dilute hydrochloric acid in the first step is 5-15%.
2. A process for the preparation of a modified bagasse/sulphur composite as claimed in claim 1, characterized in that the sieving process in the first step is carried out in a vibrating sieving machine.
3. Use of a modified bagasse/sulphur composite according to claim 1, characterised by being used as a positive electrode material for lithium sulphur batteries.
4. Use of a modified bagasse/sulphur composite according to claim 1, characterised in that the lithium sulphur battery is a button CR2025 half-cell.
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