CN116314730A - Biomass-based carbon electrode material for sodium ion battery - Google Patents
Biomass-based carbon electrode material for sodium ion battery Download PDFInfo
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- CN116314730A CN116314730A CN202310577973.0A CN202310577973A CN116314730A CN 116314730 A CN116314730 A CN 116314730A CN 202310577973 A CN202310577973 A CN 202310577973A CN 116314730 A CN116314730 A CN 116314730A
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- based carbon
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- sodium ion
- carbon electrode
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- 239000002028 Biomass Substances 0.000 title claims abstract description 111
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 55
- 239000007772 electrode material Substances 0.000 title claims abstract description 42
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 38
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 78
- 235000017048 Garcinia mangostana Nutrition 0.000 claims abstract description 36
- 240000006053 Garcinia mangostana Species 0.000 claims abstract description 36
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 150000002148 esters Chemical class 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 11
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 24
- 239000012153 distilled water Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- 238000004321 preservation Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 239000012300 argon atmosphere Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 11
- 239000011593 sulfur Substances 0.000 abstract description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 8
- 229910052708 sodium Inorganic materials 0.000 abstract description 8
- 239000011734 sodium Substances 0.000 abstract description 8
- 238000003860 storage Methods 0.000 abstract description 6
- 230000002441 reversible effect Effects 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 abstract description 5
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000005087 graphitization Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- -1 pentaerythritol tetra (mercaptoacetic acid) ester Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000013558 reference substance Substances 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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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
-
- 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
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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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
- H01M2004/027—Negative 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
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Abstract
The invention discloses a biomass-based carbon electrode material for a sodium ion battery, which is characterized in that firstly, a mangosteen shell is treated and burned to obtain a biomass-based carbon material, then the prepared biomass-based carbon material is subjected to oxidation treatment, and finally, the oxidized biomass-based carbon material and pentaerythritol tetra (thioglycollic acid) ester are subjected to hydrothermal reaction to obtain the biomass-based carbon electrode material, and the stacked block structure of the mangosteen shell biological-based carbon obtained after calcination also influences sodium storage behavior and performance, so that on the basis, functional sulfur elements are introduced into the mangosteen shell biological-based carbon, and the mangosteen shell biological-based carbon has good reversible capacity and cyclic stability in an electrical test; the prepared biomass-based carbon material electrode is charged and discharged for 150 times under the condition of 1A/g, the initial specific capacitance is 374mAh/g, the specific capacitance after 150 times of circulation is 312mAh/g, the initial specific capacitance is 83.4%, and the capacity retention rate is more than 80%.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a biomass-based carbon electrode material for a sodium ion battery.
Background
With the rapid development of society, the increasing depletion of traditional fossil energy sources represented by petroleum has forced renewable energy sources to be a need for sustainable development of society. Lithium ion batteries have been successfully commercialized for reliable safety due to high energy density, good power density. However, lithium ion batteries are difficult to use in large-scale energy storage facilities due to uneven distribution of lithium resources and price factors of part of transition metal elements. Due to the abundance of sodium resources and the similar mechanism of sodium ions like lithium ions in electrochemical energy storage, researchers have recently seen a hot trend toward sodium ion batteries. However, the lack of suitable negative electrode materials limits the commercial use of sodium ion batteries due to the inability of sodium ions to intercalate graphite in conventional ester electrolytes.
The sodium ion battery can be regarded as a 'rocking chair battery', the working principle of the sodium ion battery is similar to that of a traditional lithium ion battery, the basic structure of the sodium ion battery is composed of positive and negative electrode materials, electrolyte and a diaphragm, the positive electrode mainly refers to a sodium ion intercalation compound, the negative electrode mainly comprises carbon materials, metals, metal oxides and the like, no metal sodium exists, and only sodium ions exist. The sodium ion battery realizes charge and discharge by utilizing the process of inserting and extracting sodium ions between the anode and the cathode: when the battery is charged, sodium ions are detached from the positive electrode and are embedded into the negative electrode through the electrolyte and the diaphragm, and electric energy is converted into chemical energy; on the contrary, when the battery is discharged, sodium ions are deintercalated from the negative electrode and are re-embedded into the positive electrode through the electrolyte and the diaphragm, and chemical energy is converted into electric energy.
The sodium ion battery cathode material mainly comprises other types of carbon-based materials, alloy materials, transition metal oxides/sulfides, partial organic compounds and the like, wherein the carbon-based materials are generally obtained by high-temperature decomposition of organic matters, have impurity groups remained, have large specific surface area and more irreversible side reactions, and cause the problems of low first coulomb efficiency, poor multiplying power performance, poor cycle performance and the like; for the sodium ion battery cathode material, the structure, the particle size, the graphitization degree and the non-graphitization degree of the carbon-based material have very close relations with the surface area and the sodium storage performance. For the sodium ion electrode material, the regular nano structure, the good conductive framework structure and the graphitization degree suitable for sodium ion battery storage are helpful for improving the sodium storage performance.
Disclosure of Invention
The invention aims to provide a biomass-based carbon electrode material for a sodium ion battery, which firstly adopts a biomass material with abundant resources as a carbon source, and compared with other biomass materials, the biomass material has clear rich layers of mangosteen shell fibers, is a good biological-based carbon source, and the stacked block structure of the mangosteen shell biological-based carbon obtained after calcination also influences sodium storage behavior and performance, so that on the basis, functional sulfur elements are introduced into the mangosteen shell biological-based carbon, and the carbon has good reversible capacity, cyclic stability and electrochemical performance in an electrical test.
The aim of the invention can be achieved by the following technical scheme:
a biomass-based carbon electrode material for sodium ion batteries is prepared by firstly treating mangosteen shells, burning the mangosteen shells to obtain a biomass-based carbon material, then oxidizing the prepared biomass-based carbon material, and finally performing hydrothermal reaction on the oxidized biomass-based carbon material and pentaerythritol tetra (mercaptoacetic acid) ester.
Further, the preparation method of the biomass-based carbon material comprises the following steps:
firstly, cleaning mangosteen shells with water and ethanol respectively, soaking the mangosteen shells in nitric acid solution with the mass fraction of 3-5%, washing the mangosteen shells with clear water, naturally airing the mangosteen shells, and then putting the mangosteen shells into an oven to be dried for 24-30 hours at 50-55 ℃;
secondly, grinding the dried mangosteen shells into small blocks, and presintering in an argon atmosphere to obtain presintering carbon materials;
thirdly, grinding the presintered carbon material into powder, cleaning and suction-filtering by adopting nitric acid solution with the mass fraction of 3-5%, cleaning and suction-filtering by using water, and drying in an oven at 50-55 ℃ for 8-10h;
and fourthly, adding the cleaned and dried presintered carbon powder material into a high-temperature tube furnace, and calcining in an argon atmosphere to obtain the biomass-based carbon material.
Further, in the first step, the soaking time is 6-8 hours.
Further, in the second step, the presintering temperature is 400-500 ℃, and the presintering time is 1-2h.
Further, in the fourth step, the calcination temperature is 1400-1450 ℃ and the calcination time is 2-3h.
Further, the prepared biomass-based carbon material is subjected to oxidation treatment, specifically:
4-5g biomass-based carbon material and 1-2g NaNO 3 Adding into a reaction bottle, placing the reaction bottle into ice salt bath, adding 98% concentrated sulfuric acid at 0-5deg.C, slowly stirring for 20-30min, and adding 0.6-0.8g KMnO 4 Slowly stirring for 20-30min, standing at room temperature, and continuously adding 5-6g KMnO 4 Slowly stirring for 1-2h, placing the reaction bottle in a water bath kettle, slowly stirring for 1-2h at the water bath temperature of 40-45 ℃, removing the reaction bottle from the water bath kettle, naturally cooling to room temperature, adding 300-500ml of distilled water into the reaction bottle, uniformly mixing, adding 10-15ml of hydrogen peroxide with the mass fraction of 25-30%, mixing and stirring for 10-15min, centrifuging in a centrifuge, washing the oxidized biomass-based carbon material with water, and finally drying to obtain the oxidized biomass-based carbon material.
Further, the modification treatment of the prepared oxidized biomass-based carbon material:
step one, adding 0.20-0.25g of oxidized biomass-based carbon material into a beaker, then adding 100-120ml of distilled water, putting into an ultrasonic instrument, and performing ultrasonic dispersion at room temperature;
step two, adding 0.15-0.18g pentaerythritol tetra (thioglycollic acid) ester into the solution in the step one, stirring and mixing for 20-30min, and then putting into an ultrasonic instrument for ultrasonic treatment;
pentaerythritol tetra (thioglycollic acid) ester contains a plurality of sulfhydryl groups, can be used as a sulfur source and can also be used as a reduction functional group, has low molecular weight, is in a liquid state at normal temperature, does not contain rigid groups, and is easier to disperse in a carbon-based material under ultrasound.
Step three, the solution obtained after the ultrasonic treatment in the step two is put into a hydrothermal reaction kettle, the reaction kettle is put into an explosion-proof oven for heat preservation reaction, after the reaction is finished, the hydrothermal reaction kettle is taken out, naturally cooled to room temperature, and then distilled water is adopted for washing;
and step four, freeze-drying the reaction product after the step three is cleaned for 2-3 days, and thus obtaining the biomass-based carbon electrode material.
Further, in the first step, the ultrasonic dispersion time is 2-3 hours.
Further, in the second step, the water bath temperature in the ultrasonic instrument is 50-55 ℃, and the ultrasonic time is 20-30min.
In the third step, the heat preservation temperature is 180-200 ℃ and the heat preservation time is 5-7h.
The invention has the beneficial effects that:
(1) The biomass-based carbon electrode material for the sodium ion battery provided by the invention adopts the biomass material with abundant resources as a carbon source, compared with other biomass materials, the mangosteen shell fiber has abundant levels and is a good biomass-based carbon source, the material is turned into wealth, the material is environment-friendly and recyclable, and the production cost is reduced;
(2) The stacked block structure of the mangosteen shell bio-based carbon obtained after calcination also affects the sodium storage behavior and performance, so on the basis, functional sulfur elements are introduced into the mangosteen shell bio-based carbon, and the mangosteen shell bio-based carbon has good reversible capacity and cycle stability in electrical tests; the prepared biomass-based carbon material electrode is charged and discharged for 150 times under the condition of 1A/g, the initial specific capacitance is 374mAh/g, the specific capacitance after 150 times of circulation is 312mAh/g, the initial specific capacitance is 83.4%, and the capacity retention rate is more than 80%.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of a biomass-based carbon material;
FIG. 2 is an SEM image of oxidized biomass-based carbon material;
FIG. 3 is an SEM image of a biomass-based carbon electrode material;
FIG. 4 is an SEM illustration of a biomass-based carbon electrode material and a corresponding EDS illustration;
note that: SEM analysis test used a FEI-aspect scanning electron microscope, FEI company, usa;
x-ray photoelectron spectroscopy, wherein the adopted instrument model is the Siemens flight ESCALAB 250Xi, the monochromized Al target is tested, and the energy is 1479.8eV to analyze all sample elements;
FIG. 5 is an SEM image of a biomass-based carbon electrode material prepared by oxidizing a biomass-based carbon material after a hydrothermal step;
FIG. 6 is a comparative graph of 150 cycles of charge and discharge at 1A/g for the biomass-based carbon electrode material electrode prepared in example 3 and the biomass-based carbon material reference electrode prepared in comparative example 1, respectively.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
A biomass-based carbon electrode material for sodium ion batteries is prepared by firstly treating mangosteen shells, burning the mangosteen shells to obtain a biomass-based carbon material, then oxidizing the prepared biomass-based carbon material, and finally performing hydrothermal reaction on the oxidized biomass-based carbon material and pentaerythritol tetra (mercaptoacetic acid) ester.
The preparation method of the biomass-based carbon material comprises the following steps:
firstly, cleaning mangosteen shells with water and ethanol respectively, soaking the mangosteen shells in 3-5% nitric acid solution for 6-8 hours, washing the mangosteen shells with clear water, naturally airing the mangosteen shells, and then putting the mangosteen shells into an oven to be dried for 24-30 hours at 50-55 ℃;
secondly, grinding the dried mangosteen shells into small blocks, and presintering for 1-2 hours at 400-500 ℃ in an argon atmosphere to obtain a presintered carbon material;
thirdly, grinding the presintered carbon material into powder, cleaning and suction-filtering by adopting nitric acid solution with the mass fraction of 3-5%, cleaning and suction-filtering by using water, and drying in an oven at 50-55 ℃ for 8-10h;
and fourthly, adding the cleaned and dried presintered carbon powder material into a high-temperature tube furnace, and calcining for 2-3 hours at 1400-1450 ℃ in an argon atmosphere to obtain the biomass-based carbon material.
The biomass-based carbon material is subjected to oxidation treatment, and specifically comprises the following steps:
4-5g biomass-based carbon material and 1-2g NaNO 3 Adding into a reaction bottle, placing the reaction bottle into ice salt bath, adding 98% concentrated sulfuric acid at 0-5deg.C, slowly stirring for 20-30min, and adding 0.6-0.8g KMnO 4 Slowly stirring for 20-30min, standing at room temperature, and continuously adding 5-6g KMnO 4 Slowly stirring for 1-2h, placing the reaction bottle in a water bath kettle, slowly stirring for 1-2h at the water bath temperature of 40-45 ℃, removing the reaction bottle from the water bath kettle, naturally cooling to room temperature, adding 300-500ml of distilled water into the reaction bottle, uniformly mixing, adding 10-15ml of hydrogen peroxide with the mass fraction of 25-30%, mixing and stirring for 10-15min, centrifuging in a centrifuge, washing the oxidized biomass-based carbon material with water, and finally drying to obtain the oxidized biomass-based carbon material.
Modification treatment of oxidized biomass-based carbon materials:
step one, adding 0.20-0.25g of oxidized biomass-based carbon material into a beaker, then adding 100-120ml of distilled water, putting into an ultrasonic instrument, and performing ultrasonic dispersion for 2-3 hours at room temperature;
step two, adding 0.15-0.18g pentaerythritol tetra (thioglycollic acid) ester into the solution in the step one, stirring and mixing for 20-30min, and then putting the mixture into an ultrasonic instrument for ultrasonic treatment, wherein the water bath temperature is 50-55 ℃ and the ultrasonic treatment time is 20-30min;
the structural formula of pentaerythritol tetrakis (thioglycollic acid) ester is shown as follows:
pentaerythritol tetra (thioglycollic acid) ester contains a plurality of sulfhydryl groups, can be used as a sulfur source and can also be used as a reduction functional group, has low molecular weight, is in a liquid state at normal temperature, does not contain rigid groups, and is easier to disperse in a carbon-based material under ultrasound.
Step three, the solution obtained after the ultrasonic treatment in the step two is put into a hydrothermal reaction kettle, the reaction kettle is put into an explosion-proof oven for heat preservation reaction, the heat preservation temperature is 180-200 ℃, the heat preservation time is 5-7 hours, after the reaction is finished, the hydrothermal reaction kettle is taken out, naturally cooled to room temperature, and then distilled water is adopted for washing;
and step four, freeze-drying the reaction product after the step three is cleaned for 2-3 days, and thus obtaining the biomass-based carbon electrode material.
The following is the example section
Example 1
Preparation of biomass-based carbon material:
firstly, cleaning 100g of mangosteen shells with water and ethanol respectively, soaking in a nitric acid solution with the mass fraction of 3% for 6 hours, washing with clear water, naturally airing, and then putting into an oven to be dried at 55 ℃ for 24 hours;
secondly, grinding the dried mangosteen shells into small blocks, and presintering for 1h at 500 ℃ in an argon atmosphere to obtain a presintering carbon material;
thirdly, grinding the presintered carbon material into powder, cleaning and suction-filtering by adopting nitric acid solution with the mass fraction of 5%, and finally cleaning and suction-filtering by using water, and drying in an oven at 55 ℃ for 10 hours;
and fourthly, adding the cleaned and dried presintered carbon powder material into a high-temperature tube furnace, and calcining for 2 hours at 1400 ℃ in an argon atmosphere to obtain the biomass-based carbon material.
As shown in SEM images of the biomass-based carbon material in fig. 1, the biomass-based carbon material sample has an irregular block structure containing a pore structure.
Example 2
Oxidation treatment of biomass-based carbon material:
5g of the biomass-based carbon material prepared in example 1 and 1.5g of NaNO 3 Adding into a reaction flask, placing the reaction flask into ice salt bath, adding 98% concentrated sulfuric acid at 0-5deg.C, slowly stirring for 30min, and adding 0.6g KMnO 4 Slowly stirring for 30min, standing the reaction flask at room temperature, and continuously adding 5g KMnO 4 Slowly stirring for 1h, placing the reaction bottle in a water bath kettle, slowly stirring for 2h at the water bath temperature of 45 ℃, removing the reaction bottle from the water bath kettle, naturally cooling to room temperature, adding 300ml of distilled water into the reaction bottle, uniformly mixing, adding 15ml of 30% hydrogen peroxide by mass fraction, mixing and stirring for 10min, putting into a centrifuge for centrifugation, washing the oxidized biomass-based carbon material with water, and finally drying to obtain the oxidized biomass-based carbon material.
As shown in fig. 2, the oxidized biomass-based carbon material contains a large number of pore structures due to oxidation reaction, and the surface of the material contains oxygen-containing functional groups, which may additionally contribute to a certain capacity.
Example 3
Modification treatment of biomass-based carbon materials:
step one, adding 0.25g of the oxidized biomass-based carbon material prepared in the example 2 into a beaker, then adding 100ml of distilled water, putting into an ultrasonic instrument, and performing ultrasonic dispersion for 2 hours at room temperature;
step two, adding 0.15g of pentaerythritol tetra (thioglycollic acid) ester into the solution in the step one, stirring and mixing for 20min, and then placing into an ultrasonic instrument, wherein the water bath temperature in the ultrasonic instrument is 55 ℃, and carrying out ultrasonic treatment for 30min;
step three, the solution obtained after the ultrasonic treatment in the step two is put into a hydrothermal reaction kettle, the reaction kettle is put into an explosion-proof oven, the temperature is kept for 5 hours at 200 ℃, after the reaction is finished, the hydrothermal reaction kettle is taken out, naturally cooled to room temperature, and then distilled water is adopted for washing;
and step four, freeze-drying the reaction product after the step three is cleaned for 2 days, and thus obtaining the biomass-based carbon electrode material.
As shown in fig. 3, in the SEM image of the biomass-based carbon electrode material, the biomass-based carbon electrode material has a three-dimensional network structure, and the three-dimensional network structure is formed by reducing oxidized biomass-based carbon material in a hydrothermal reaction kettle sheet under the condition of high temperature and high pressure in the hydrothermal process, and different layers of biomass-based carbon material are mutually overlapped while oxygen-containing functional groups are reduced, so that a three-dimensional crosslinked network structure is formed.
As shown in fig. 4, the X-ray optical energy spectrum analysis of the biomass-based carbon electrode material shows that sulfur elements are uniformly distributed in the biomass-based carbon electrode material, which means that pentaerythritol tetra (thioglycollic acid) ester and oxidized biomass-based carbon material successfully introduce sulfur elements in the hydrothermal reaction, the mercapto group of pentaerythritol tetra (thioglycollic acid) ester is taken as a sulfur source, and is taken as a reducing functional group at the same time, so that the oxidized biomass-based carbon material can be assisted to reduce, and further the reducing effect is improved, and the atomic percentage contents of three elements C, O, S are 91.2%,4.8% and 4.0% respectively through the energy spectrum analysis.
Comparative example 1
Preparation of biomass-based carbon material reference:
step one, adding 0.25g of oxidized biomass-based carbon material into a beaker, then adding 100ml of distilled water, and putting into an ultrasonic instrument for ultrasonic dispersion for 2 hours at room temperature;
step two, raising the water bath temperature of the ultrasonic instrument to 55 ℃, and carrying out ultrasonic treatment for 30min;
step three, the solution obtained after the ultrasonic treatment in the step two is put into a hydrothermal reaction kettle, the reaction kettle is put into an explosion-proof oven, the temperature is kept for 5 hours at 200 ℃, after the reaction is finished, the hydrothermal reaction kettle is taken out, naturally cooled to room temperature, and then distilled water is adopted for washing;
and step four, freeze-drying the reaction product after the step three is cleaned for 2 days, and thus obtaining the biomass-based carbon electrode material reference substance.
As shown in fig. 5, the form of the biomass-based carbon electrode material prepared by the hydrothermal step of the oxidized biomass-based carbon material is generally not different from that of the oxidized biomass-based carbon material, the pore structure is slightly loose and fluffy, and the possible reason is that the pore structure is caused by high temperature and high pressure in the hydrothermal reaction kettle.
Performance testing
Assembly of sodium ion batteries
100mg of the biomass-based carbon electrode material prepared in example 3 and the biomass-based carbon material reference substance prepared in comparative example 1 are respectively weighed, 30mg of the conductive agent and 12mg of the adhesive are respectively prepared into electrode slices;
the electrolyte is 1M NaClO 4 Dissolved in Ethylene Carbonate (EC) and diethyl carbonate (DEC) (v: v=1:1);
assembling a cathode shell, an elastic sheet, a gasket, a sodium sheet, a diaphragm, an electrode sheet gasket and an anode shell into a half cell, and performing electrochemical test on the assembled half cell;
as shown in fig. 6, the biomass-based carbon electrode material electrode prepared in example 3 and the biomass-based carbon material reference electrode prepared in comparative example 1 were charged and discharged 150 times at 1A/g, respectively, the biomass-based carbon electrode material electrode prepared in example 3 had an initial specific capacitance of 374mAh/g, a specific capacitance of 312mAh/g after 150 cycles of 83.4% of the initial specific capacitance, and the biomass-based carbon material reference electrode prepared in comparative example 1 had an initial specific capacitance of 271mAh/g, a specific capacitance of 192mAh/g after 150 cycles of 70.8% of the initial specific capacitance. A possible reason is that the reversible electrochemical reaction between the electrochemically active sulfur-containing functional groups and sodium ions in the biomass-based carbon electrode material prepared in example 3 contributes a large portion of the capacity. The biomass-based carbon electrode material with the three-dimensional network structure and the chemically bonded sulfur-containing functional group have the advantages that the biomass-based carbon electrode material has larger reversible specific capacity and excellent rate capability under the combined action of the biomass-based carbon electrode material and the chemically bonded sulfur-containing functional group.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (10)
1. A biomass-based carbon electrode material for sodium ion batteries, characterized in that: firstly, treating mangosteen shells, firing to obtain biomass-based carbon materials, then oxidizing the prepared biomass-based carbon materials, and finally performing hydrothermal reaction on the oxidized biomass-based carbon materials and pentaerythritol tetra (thioglycollic acid) ester to obtain the biomass-based carbon electrode materials.
2. A biomass-based carbon electrode material for sodium ion batteries according to claim 1, characterized in that:
the preparation method of the biomass-based carbon material comprises the following steps:
firstly, cleaning mangosteen shells with water and ethanol respectively, soaking the mangosteen shells in nitric acid solution with the mass fraction of 3-5%, washing the mangosteen shells with clear water, naturally airing the mangosteen shells, and then putting the mangosteen shells into an oven to be dried for 24-30 hours at 50-55 ℃;
secondly, grinding the dried mangosteen shells into small blocks, and presintering in an argon atmosphere to obtain presintering carbon materials;
thirdly, grinding the presintered carbon material into powder, cleaning and suction-filtering by adopting nitric acid solution with the mass fraction of 3-5%, cleaning and suction-filtering by using water, and drying in an oven at 50-55 ℃ for 8-10h;
and fourthly, adding the cleaned and dried presintered carbon powder material into a high-temperature tube furnace, and calcining in an argon atmosphere to obtain the biomass-based carbon material.
3. A biomass-based carbon electrode material for sodium ion batteries according to claim 2, characterized in that: in the first step, the soaking time is 6-8 hours.
4. A biomass-based carbon electrode material for sodium ion batteries according to claim 2, characterized in that: in the second step, the presintering temperature is 400-500 ℃ and the presintering time is 1-2h.
5. A biomass-based carbon electrode material for sodium ion batteries according to claim 2, characterized in that: in the fourth step, the calcining temperature is 1400-1450 ℃ and the calcining time is 2-3h.
6. A biomass-based carbon electrode material for sodium ion batteries according to claim 2, characterized in that:
the prepared biomass-based carbon material is subjected to oxidation treatment, and specifically comprises the following steps:
4-5g biomass-based carbon material and 1-2g NaNO 3 Adding into a reaction bottle, placing the reaction bottle into ice salt bath, adding 98% concentrated sulfuric acid at 0-5deg.C, slowly stirring for 20-30min, and adding 0.6-0.8g KMnO 4 Slowly stirring for 20-30min, standing at room temperature, and continuously adding 5-6g KMnO 4 Slowly stirring for 1-2h, placing the reaction bottle in a water bath kettle, slowly stirring for 1-2h at the water bath temperature of 40-45 ℃, removing the reaction bottle from the water bath kettle, naturally cooling to room temperature, adding 300-500ml of distilled water into the reaction bottle, uniformly mixing, adding 10-15ml of hydrogen peroxide with the mass fraction of 25-30%, mixing and stirring for 10-15min, centrifuging in a centrifuge, washing the oxidized biomass-based carbon material with water, and finally drying to obtain the oxidized biomass-based carbon material.
7. A biomass-based carbon electrode material for sodium ion batteries as claimed in claim 6, wherein:
modification treatment of the prepared oxidized biomass-based carbon material:
step one, adding 0.20-0.25g of oxidized biomass-based carbon material into a beaker, then adding 100-120ml of distilled water, putting into an ultrasonic instrument, and performing ultrasonic dispersion at room temperature;
step two, adding 0.15-0.18g pentaerythritol tetra (thioglycollic acid) ester into the solution in the step one, stirring and mixing for 20-30min, and then putting into an ultrasonic instrument for ultrasonic treatment;
step three, the solution obtained after the ultrasonic treatment in the step two is put into a hydrothermal reaction kettle, the reaction kettle is put into an explosion-proof oven for heat preservation reaction, after the reaction is finished, the hydrothermal reaction kettle is taken out, naturally cooled to room temperature, and then distilled water is adopted for washing;
and step four, freeze-drying the reaction product after the step three is cleaned for 2-3 days, and thus obtaining the biomass-based carbon electrode material.
8. A biomass-based carbon electrode material for sodium ion batteries as claimed in claim 7, wherein: in the first step, the ultrasonic dispersion time is 2-3h.
9. A biomass-based carbon electrode material for sodium ion batteries as claimed in claim 7, wherein: in the second step, the water bath temperature in the ultrasonic instrument is 50-55 ℃, and the ultrasonic time is 20-30min.
10. A biomass-based carbon electrode material for sodium ion batteries as claimed in claim 7, wherein: in the third step, the heat preservation temperature is 180-200 ℃ and the heat preservation time is 5-7h.
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| CN116130584A (en) * | 2022-09-08 | 2023-05-16 | 陈本 | Sodium metal negative electrode with solid polymer protective coating, preparation method of sodium metal negative electrode and battery containing negative electrode |
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Patent Citations (6)
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| JPH11307126A (en) * | 1998-04-17 | 1999-11-05 | Ricoh Co Ltd | Secondary battery |
| CN106744798A (en) * | 2016-12-12 | 2017-05-31 | 华中科技大学 | A kind of method and its application that hard carbon is prepared using carbon containing biological mass shell |
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