CN117163946B - Nitrogen-oxygen doped porous carbon and preparation method and application thereof - Google Patents
Nitrogen-oxygen doped porous carbon and preparation method and application thereof Download PDFInfo
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- CN117163946B CN117163946B CN202311450781.XA CN202311450781A CN117163946B CN 117163946 B CN117163946 B CN 117163946B CN 202311450781 A CN202311450781 A CN 202311450781A CN 117163946 B CN117163946 B CN 117163946B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 56
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 23
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- -1 nitrogen-containing organic compound Chemical class 0.000 claims description 20
- 238000003763 carbonization Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 229920002678 cellulose Polymers 0.000 claims description 14
- 239000001913 cellulose Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- 159000000003 magnesium salts Chemical class 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000010306 acid treatment Methods 0.000 claims description 9
- 238000004108 freeze drying Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 229920000609 methyl cellulose Polymers 0.000 claims description 7
- 239000001923 methylcellulose Substances 0.000 claims description 7
- 235000010981 methylcellulose Nutrition 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 3
- 229920002749 Bacterial cellulose Polymers 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000005016 bacterial cellulose Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 229920002301 cellulose acetate Polymers 0.000 claims description 3
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 3
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 239000005539 carbonized material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003575 carbonaceous material Substances 0.000 abstract description 45
- 239000011148 porous material Substances 0.000 abstract description 14
- 239000003792 electrolyte Substances 0.000 abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 10
- 238000005187 foaming Methods 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- 230000009286 beneficial effect Effects 0.000 abstract description 8
- 230000003592 biomimetic effect Effects 0.000 abstract description 7
- 230000033558 biomineral tissue development Effects 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 7
- 238000009792 diffusion process Methods 0.000 abstract description 6
- 238000004146 energy storage Methods 0.000 abstract description 4
- 230000001737 promoting effect Effects 0.000 abstract description 4
- 238000009831 deintercalation Methods 0.000 abstract description 3
- 230000002708 enhancing effect Effects 0.000 abstract description 3
- 238000009830 intercalation Methods 0.000 abstract description 3
- 230000002687 intercalation Effects 0.000 abstract description 3
- 238000004904 shortening Methods 0.000 abstract description 3
- 238000006276 transfer reaction Methods 0.000 abstract description 3
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 230000001939 inductive effect Effects 0.000 abstract description 2
- 239000011232 storage material Substances 0.000 abstract description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 25
- 239000011734 sodium Substances 0.000 description 18
- 230000008569 process Effects 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 9
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 9
- 239000000347 magnesium hydroxide Substances 0.000 description 9
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000007547 defect Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000002411 adverse Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000002427 irreversible effect Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 3
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical group O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical group [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- 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 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910021201 NaFSI Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229940091250 magnesium supplement Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides nitrogen-oxygen doped porous carbon, and a preparation method and application thereof, and belongs to the technical field of energy storage materials. The invention provides a method for inducing foaming by biomimetic mineralization coupling seeds for the first time to obtain a porous carbon material with a hierarchical porous structure and nitrogen-oxygen doping, wherein the porous carbon material has a hierarchical open pore structure and a high specific surface area, which is beneficial to shortening the ion diffusion distance, promoting the intercalation/deintercalation of ions and providing rich active sites for charge transfer reaction, and is a basis for obtaining good electrochemical performance; the introduction of the nitrogen and oxygen elements is beneficial to enhancing the wettability of electrolyte, improving the conductivity and providing additional energy storage sites, so that the porous carbon material has excellent multiplying power performance and cycle performance in the sodium ion half cell and has high energy density and power density in the sodium ion full cell.
Description
Technical Field
The invention relates to the technical field of energy storage materials, in particular to nitrogen-oxygen doped porous carbon, and a preparation method and application thereof.
Background
Clean, renewable and easily stored energy sources are highly appreciated due to the overuse of coal and oil and the increasing environmental pollution. At present, lithium Ion Batteries (LIB) are widely applied, but are limited by the reserve of Li in the crust, and the cost of the LIB is high, so that the LIB becomes a main factor for limiting the larger-scale application of the LIB. Recently, other alternative battery technologies, such as Sodium Ion Batteries (SIBs), have not been broken. SIB and LIB are similar in working principle, but Na is more abundant in reserves on the earth, lower in cost and wider in source. Although solvated Na + Specific solvation of Li + Has higher ionic conductivity, but the redox potential of LIB (-3.04V vs. standard hydrogen electrode) is lower than that of SIB (-2.71V vs. standard hydrogen electrode), which means that SIB has poor voltage and energy density. In addition, due to Na + Is larger (Na + ：0.102nm vs. Li + :0.076 nm), leading to Na + The diffusion rate in the SIB anode material is slow, and the volume change is large. In addition, the positive electrode materials of SIBs, such as sodium vanadium phosphate, require a suitable negative electrode material to match their high operating potential, which is a challenge.
The negative electrode material is an important part of SIB, and mainly comprises carbon material, metal compound and conductive high polymerThree types. The use of metal compounds in SIBs is limited due to their high cost and poor cycling stability. Carbon materials have low cost, high conductivity and cycling stability, and have become the main negative electrode material of SIBs. Constructing a carbon material having a thin wall and a layered porous structure with a high specific surface area can shorten Na + Diffusion distance of Na is favorable to + Transport kinetics, buffer volume expansion, carbon layer spacing expansion, providing stronger Na + Adsorbing and breaking pi conjugated structure to obtain reversible capacitance Na + Storage creates defects, thereby improving specific capacity, initial coulombic efficiency, and cycling stability. It should be noted that a high specific surface area may be beneficial, but is not required: the open micropores influence the initial coulombic efficiency, the open macropores are beneficial to the stability of the carbon material in the circulation process, and the closed nanopores are beneficial to the expansion of the platform capacity. Therefore, starting from the microstructure, the controllable preparation of the porous carbon is realized by using a simple process, and the development of the porous carbon cathode is greatly promoted.
However, the existing porous carbon negative electrode has the defects of low initial coulombic efficiency, small specific capacity and poor cycle performance in the ester-based electrolyte.
Disclosure of Invention
The invention aims to provide nitrogen-oxygen doped porous carbon, a preparation method and application thereof, and aims to overcome the defects of low initial coulomb efficiency, small specific capacity and poor cycle performance of the traditional porous carbon cathode in an ester electrolyte.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of nitrogen-oxygen doped porous carbon, which comprises the following steps:
mixing cellulose substances, magnesium salt, strong alkali, nitrogen-containing organic compound and water, and sequentially performing freeze drying and carbonization treatment on the obtained mixture to obtain carbonized products;
and sequentially carrying out acid treatment and separation on the carbonized product to obtain the nitrogen-oxygen doped porous carbon.
Preferably, the cellulose material comprises methyl cellulose, hydroxypropyl cellulose, bacterial cellulose or cellulose acetate.
Preferably, the strong base comprises potassium hydroxide, sodium hydroxide or lithium hydroxide; the nitrogen-containing organic compound includes urea, melamine, glycine, or dimethylimidazole.
Preferably, the mass ratio of the cellulose substance to the magnesium salt to the alkali to the nitrogen-containing organic compound is (1-5): 1-5.
Preferably, the freeze drying temperature is-70 to-20 ℃ and the time is 48-120 hours.
Preferably, the carbonization treatment is performed under a protective gas, wherein the protective gas is argon or nitrogen; the flow rate of the protective gas is 40-100 mL min -1 。
Preferably, the carbonization treatment temperature is 500-1000 ℃, and the heat preservation time is 0.5-5 h; the heating rate of the carbonized material to the temperature of the carbonization treatment is 1-10 ℃ min -1 。
Preferably, the acid used for the acid treatment is hydrochloric acid; the concentration of the hydrochloric acid is 0.5-5 mol/L.
The invention provides the nitrogen-oxygen doped porous carbon prepared by the preparation method.
The invention provides application of the nitrogen-oxygen doped porous carbon in sodium ion batteries.
Compared with the prior art, the invention has the following advantages:
(1) The invention provides a method for preparing a nitrogen-oxygen doped porous carbon material by biomimetic mineralization coupling seed induced foaming for the first time. Firstly, utilizing the polyhydroxy characteristic of cellulose substances, inducing the nucleation and growth of magnesium hydroxide generated by the reaction of strong alkali and magnesium salt at hydroxyl sites to form a uniform organic-inorganic hybrid structure, and providing a precursor synthesis concept of biomimetic mineralization; secondly, by utilizing different solubilities between magnesium hydroxide and nitrogen-containing organic compounds (such as urea), and taking magnesium hydroxide as a seed, the nitrogen-containing organic compounds (such as urea and foaming agents) are deposited around the magnesium hydroxide under the freezing condition, and the nitrogen-containing organic compounds play a role of foaming in the carbonization and calcination process, so that the synthetic concept of seed induced foaming is further provided; thirdly, decomposing in the calcining process of magnesium hydroxide, removing by acid treatment after calcining, decomposing and foaming the nitrogenous organic compound in the calcining process, and finally obtaining the porous carbon material with a hierarchical porous structure and doped with nitrogen and oxygen.
(2) The nitrogen-oxygen doped porous carbon material prepared by the method has a graded open pore structure and a high specific surface area, which is beneficial to shortening the ion diffusion distance, promoting the intercalation/deintercalation of ions, providing rich active sites for charge transfer reaction, and is a basis for obtaining good electrochemical performance, so that the porous carbon material has excellent multiplying power performance and cycle performance in a sodium ion half cell and has high energy density and power density in a sodium ion full cell.
(3) The nitrogen-oxygen element is introduced into the porous carbon material, which is beneficial to enhancing the wettability of electrolyte, improving conductivity and providing additional energy storage sites.
(4) The nitrogen-oxygen doped porous carbon material prepared by the invention is used for a negative electrode material of a sodium ion battery, has excellent initial coulombic efficiency, rate capability and cycle performance when being tested by an ether electrolyte, and has good application prospect in the existing energy conversion and storage device.
(5) The whole synthesis system of the invention uses water as solvent, and raw materials are nontoxic and easy to obtain, and the cost is low.
Drawings
FIG. 1 is a scanning electron micrograph (20 μm) of a nitrogen-oxygen doped porous carbon material prepared in example 1;
FIG. 2 is a scanning electron micrograph (20 μm) of the oxygen-doped porous carbon material prepared in comparative example 1;
FIG. 3 is a scanning electron micrograph (20 μm) of the nitrogen-oxygen doped porous carbon material prepared in comparative example 2;
FIG. 4 is a scanning electron micrograph (30 μm) of an oxygen doped porous carbon material prepared in comparative example 3;
FIG. 5 is a preparation of example 1The nitrogen-oxygen doped porous carbon material serving as the negative electrode of the sodium ion battery is 0.2 mV s -1 Cyclic voltammograms at a scanning rate, wherein 1 is the 1 st cycle of cyclic voltammograms, 2 is the 2 nd cycle of cyclic voltammograms, and 3 is the 3 rd cycle of cyclic voltammograms;
FIG. 6 is a graph showing that the oxygen-doped porous carbon material prepared in comparative example 1 was used as a negative electrode of a sodium ion battery at 0.2 mVs -1 Cyclic voltammograms at a scanning rate, wherein 1 is the 1 st cycle of cyclic voltammograms, 2 is the 2 nd cycle of cyclic voltammograms, and 3 is the 3 rd cycle of cyclic voltammograms;
FIG. 7 shows that the nitrogen-oxygen doped porous carbon material prepared in comparative example 2 is used as the negative electrode of sodium ion battery at 0.2 mV s -1 Cyclic voltammograms at a scanning rate, wherein 1 is the 1 st cycle of cyclic voltammograms, 2 is the 2 nd cycle of cyclic voltammograms, and 3 is the 3 rd cycle of cyclic voltammograms;
FIG. 8 is a graph showing that the oxygen-doped porous carbon material prepared in comparative example 3 was used as a negative electrode of a sodium ion battery at 0.2 mV s -1 Cyclic voltammograms at a scanning rate, wherein 1 is the 1 st cycle of cyclic voltammograms, 2 is the 2 nd cycle of cyclic voltammograms, and 3 is the 3 rd cycle of cyclic voltammograms;
FIG. 9 shows that the porous carbon material prepared in example 1 and comparative examples 1 to 3 was used as a negative electrode of sodium ion battery at 0.05A g -1 A charge-discharge curve comparison graph under current density;
FIG. 10 is a graph showing the comparison of the rate performance of porous carbon materials prepared in example 1 and comparative examples 1-3 as negative electrodes of sodium ion batteries at different current densities;
FIG. 11 shows the nitrogen-oxygen doped porous carbon material prepared in example 1 as a negative electrode of a sodium ion battery at 10A g -1 Cycling performance plot at current density;
fig. 12 is an energy-power density diagram of a sodium ion full cell assembled with a nitrogen-oxygen doped porous carbon material prepared in example 1 as a negative electrode and sodium vanadium phosphate as a positive electrode.
Detailed Description
The invention provides a preparation method of nitrogen-oxygen doped porous carbon, which comprises the following steps:
mixing cellulose substances, magnesium salt, strong alkali, nitrogen-containing organic compound and water, and sequentially performing freeze drying and carbonization treatment on the obtained mixture to obtain carbonized products;
and sequentially carrying out acid treatment and separation on the carbonized product to obtain the nitrogen-oxygen doped porous carbon.
In the present invention, the required raw materials or reagents are commercially available products well known to those skilled in the art unless specified otherwise.
The invention mixes cellulose substance, magnesium salt, alkali, nitrogenous organic compound and water, and the obtained mixture is sequentially subjected to freeze drying and carbonization treatment to obtain carbonized products.
In the present invention, the cellulose-based substance includes methyl cellulose, hydroxypropyl cellulose, bacterial cellulose, or cellulose acetate.
In the present invention, the magnesium salt is preferably magnesium chloride hexahydrate.
In the present invention, the strong base preferably includes potassium hydroxide, sodium hydroxide or lithium hydroxide.
In the present invention, the nitrogen-containing organic compound preferably includes urea, melamine, glycine, or dimethylimidazole.
In the invention, the mass ratio of the cellulose substance to the magnesium salt to the alkali to the nitrogen-containing organic compound is preferably (1-5): (1-5), more preferably (1.5-3.5): (1.5-4.0): (1.5-3.0): (1.5-4.0), and even more preferably 2:3.486:1.924:2.
In the invention, the process of mixing the cellulose substance, the magnesium salt, the strong alkali, the nitrogen-containing organic compound and the water is preferably to dissolve the cellulose substance and the magnesium salt in part of the water, and perform first stirring to obtain a first mixed solution; dissolving strong alkali and a nitrogenous organic compound in the residual water, and carrying out second stirring to obtain a second mixed solution; and (3) dropwise adding the second mixed solution into the first mixed solution, and carrying out third stirring to obtain a mixture.
In the invention, the volume ratio of the part of water to the residual water is (50-500): 20-200, more preferably (100-300): 30-150, and still more preferably 150:50; the time of the first stirring is preferably 6-12 hours, more preferably 8-10 hours; the second stirring time is preferably 0.5-5 h, more preferably 2-3 h; the third stirring time is preferably 12-48 hours, more preferably 24-36 hours.
In the third stirring process, cellulose substances induce the magnesium hydroxide generated by the reaction of strong alkali and magnesium salt to nucleate and grow up at hydroxyl sites, so that a uniform organic-inorganic hybrid structure is formed.
In the invention, the temperature of freeze drying is preferably-70 to-20 ℃, more preferably-60 to-30 ℃, and the time is preferably 48 to 120 hours, more preferably 72 to 100 hours. During the freeze-drying process, the nitrogen-containing organic compound is deposited around the magnesium hydroxide formed with the magnesium hydroxide as a "seed".
In the present invention, the carbonization treatment is preferably performed in a tube furnace, and the carbonization treatment is preferably performed under a protective gas, and the protective gas is preferably argon or nitrogen; the flow rate of the protective gas is preferably 40-100 mL min -1 More preferably 60 to 80mL min -1 。
In the invention, the temperature of the carbonization treatment is preferably 500-1000 ℃, more preferably 600-900 ℃, further preferably 700-800 ℃, and the heat preservation time is preferably 0.5-5 h, more preferably 1-4 h, further preferably 2-3 h; the heating rate to the carbonization treatment temperature is preferably 1-10 ℃ min -1 More preferably 5 to 8 ℃ min -1 。
During the carbonization treatment, the magnesium hydroxide is calcined and decomposed into magnesium oxide, and the nitrogen-containing organic compound is decomposed into NH 3 And volatilize the foaming action.
After the carbonized product is obtained, the carbonized product is subjected to acid treatment and separation in sequence, and the nitrogen-oxygen doped porous carbon is obtained.
In the present invention, the acid used for the acid treatment is preferably hydrochloric acid; the concentration of the hydrochloric acid is preferably 0.5-5 mol/L, more preferably 2-3 mol/L; the invention has no special limitation on the dosage of the hydrochloric acid, and ensures sufficient quantity. According to the invention, magnesium oxide is decomposed into magnesium ions through acid treatment, so that magnesium element is removed through subsequent water washing.
The carbonized product is preferably stirred and washed (impurities are removed) in hydrochloric acid and excessive deionized water in sequence, and then suction filtration separation, washing and drying are sequentially carried out to obtain nitrogen-oxygen doped porous carbon; the method is not particularly limited, and the hydrochloric acid and deionized water are stirred and washed, and impurities are removed by washing according to a process well known in the art; the extraction separation and washing are not particularly limited, and can be performed according to a process well known in the art; the drying temperature is preferably 60-120 ℃, more preferably 80-100 ℃, and the drying time is not particularly limited and can be adjusted according to actual requirements.
According to the invention, nitrogen (N) and oxygen (O) are introduced into the carbon material through surface modification, so that local bonding environment and electron distribution are effectively changed, thereby improving conductivity, improving surface wettability of the carbon material, improving surface accessibility of electrolyte ion transmission, expanding carbon layer spacing, creating defects and functional active sites to improve reaction activity, promoting diffusion control process and capacitance control process, and further improving initial coulomb efficiency, multiplying power performance and cycle life of the porous carbon cathode.
The invention provides the nitrogen-oxygen doped porous carbon prepared by the preparation method.
The invention provides application of the nitrogen-oxygen doped porous carbon in sodium ion batteries. The method of application of the present invention is not particularly limited, and may be applied according to methods well known in the art.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
2 g methylcellulose and 3.486 g magnesium chloride hexahydrate were dissolved in 150 mL deionized water and stirred for 6h (solution a); 1.924 g potassium hydroxide and 2 g urea were dissolved in 50 mL deionized water and stirred for 0.5 h (B solution); dropwise adding the solution B into the solution A, stirring for 24-h, and then freeze-drying at-60 ℃ for 72-h; the dried mixture was stirred at 40 mL min -1 Under the protection of nitrogen atmosphere at 5 DEG Cmin -1 Heating to 800 ℃ at a heating rate, carbonizing and preserving heat for 2 h; and stirring the carbonized sample in 2M hydrochloric acid and enough deionized water in sequence to wash out impurities, and then sequentially carrying out suction filtration, separation, washing and drying (100 ℃) on the obtained product to obtain the nitrogen-oxygen doped porous carbon material.
Comparative example 1
The only difference from example 1 is that: the raw materials are only methylcellulose, magnesium chloride hexahydrate and potassium hydroxide.
Comparative example 2
The only difference from example 1 is that: the raw materials are only methyl cellulose and urea.
Comparative example 3
The only difference from example 1 is that: the raw material is only methyl cellulose.
Characterization and testing
The morphology structure of the nitrogen-oxygen doped porous carbon material is observed through a Scanning Electron Microscope (SEM), the specific surface area and the pore volume of the nitrogen-oxygen doped porous carbon material are tested through 77K nitrogen adsorption and desorption, and the nitrogen-oxygen element content of the nitrogen-oxygen doped porous carbon material is characterized through X-ray photoelectron spectroscopy (XPS).
Fig. 1 is an SEM image of the nitrogen-oxygen doped porous carbon material prepared in example 1, and it can be seen that the structure is a porous structure of a bubble sheet. The nitrogen-oxygen heteroatom content, specific surface area and pore volume of the nitrogen-oxygen doped porous carbon material are listed in table 1, which shows that the nitrogen-oxygen doped porous carbon material has a porous structure and heteroatom doping, is beneficial to enhancing the wettability of electrolyte, shortening the ion diffusion distance, promoting the intercalation/deintercalation of ions and providing rich active sites for charge transfer reaction.
Fig. 2 is an SEM picture of the oxygen-doped porous carbon material prepared in comparative example 1, and it can be seen that the structure thereof is a porous structure. The oxygen atom content, specific surface area and pore volume of the oxygen-doped porous carbon material are shown in table 1, which shows that no "seed-induced foaming activation" participates in the reaction process, and the specific surface area and oxygen content are reduced compared with those of example 1, thereby adversely affecting the electrochemical performance.
Fig. 3 is an SEM picture of the nitrogen-oxygen doped porous carbon material prepared in comparative example 2, and it can be seen that the structure thereof is an irregular block-shaped porous structure. The nitrogen-oxygen heteroatom content, specific surface area and pore volume of the nitrogen-oxygen doped porous carbon material are listed in table 1, which shows that no biomimetic mineralization participates in the reaction process, and the specific surface area and pore volume are smaller than those of example 1, thereby having adverse effects on electrochemical performance.
Fig. 4 is an SEM picture of the oxygen-doped porous carbon material prepared in comparative example 3, and it can be seen that the structure thereof is an irregular block-shaped porous structure. The oxygen atom content, specific surface area and pore volume of the oxygen doped porous carbon material are listed in table 1, which shows that no "biomimetic mineralization" and no "seed induced foaming activation" are involved in the reaction process, and the specific surface area and pore volume are small compared with example 1, thereby adversely affecting the electrochemical performance.
TABLE 1 Performance data for Nitrogen-oxygen doped porous carbons prepared in example 1 and comparative examples 1-3
Application example 1
The nitrogen-oxygen doped porous carbon material (active material), the conductive agent (Li 90) and the binder (polyvinylidene fluoride) prepared in the example 1 are mixed according to the mass ratio of 7:1.5:1.5, added into N-methyl pyrrolidone for full grinding, uniformly dripped on a stainless steel sheet, and put into an oven at 80 ℃ for drying to prepare the negative plate. Assembling a negative plate, a glass fiber diaphragm and a sodium metal wafer into a sodium ion battery in a glove box filled with argon, wherein the electrolyte is an ether electrolyte: sodium bis (fluorosulfonyl imide) (NaFSI) is used as a solute, diethylene glycol dimethyl ether is used as a solvent, and the concentration is 1M; and using a Chenhua CHI660E electrochemical workstation and Xinwei CT-4008T to test a cyclic voltammetry curve and a constant current charge-discharge curve of the assembled sodium ion battery at room temperature, wherein the test results are shown in figures 5 and 9-12.
FIG. 5 shows that the nitrogen-oxygen doped porous carbon anode prepared in example 1 was prepared at 0.2 mV s -1 Initial 3 cycles of Cyclic Voltammetry (CV) plot at time. As shown in FIG. 5, the CV curve is around 0.01V in cathode peak and Na + With carbon-embedded layers or pore-fillingThe method comprises the steps of carrying out a first treatment on the surface of the While cathode peaks above 0.01V capture Na by carbon defects + (irreversible), SEI layer formation, and electrolyte decomposition. The area of the 1 st turn CV curve is larger than that of the 2 nd and 3 rd turns CV curves, so the Initial Coulombic Efficiency (ICE)<100%. However, the CV curves of circles 2 and 3 almost overlap, indicating that the nitrogen-oxygen doped porous carbon anode has good structural stability.
The nitrogen-oxygen doped porous carbon anode prepared in example 1 was at 0.05 Ag -1 The constant current charge-discharge curve at current density and the rate capability at different current densities are shown in fig. 9, fig. 10 and table 2. As shown in FIGS. 9-10, the nitrogen-oxygen doped porous carbon anode is 0.05 Ag -1 The ICE at this time was 90.2%. At the same time, it is between 0.05 and 2A g -1 The specific capacities are 537.4 and 335.3 mAh g respectively -1 Has excellent multiplying power performance.
TABLE 2 Performance data for porous carbon materials prepared in example 1 and comparative examples 1-3
As shown in FIG. 11, the nitrogen-oxygen doped porous carbon anode was at 10 Ag -1 180.6 mAh g after 5 times of circulation under current density -1 Indicating that it has excellent cycle performance.
As shown in fig. 12 and table 2, the full cell consisting of the nitrogen-oxygen doped porous carbon anode and the sodium vanadium phosphate cathode had 223.2 Wh kg -1 And 2756.5W kg -1 Is a maximum power density of (c).
Application example 2
The electrode preparation method, the sodium ion battery assembly and the testing method of the application example are basically the same as the application example 1, and the difference is that: the active material was an oxygen-doped porous carbon material prepared in comparative example 1. The test results are shown in fig. 6 and fig. 9 to 10.
FIG. 6 is a graph showing that the oxygen-doped porous carbon anode prepared in comparative example 1 was at 0.2 mV s -1 Initial 3 cycles of Cyclic Voltammetry (CV) plot at time. As shown in FIG. 6, the CV curve is around 0.01V in cathode peak and Na + Embedded carbon layers or pore filling;while cathode peaks above 0.01V capture Na by carbon defects + (irreversible), SEI layer formation, and electrolyte decomposition. The area of the 1 st turn CV curve is larger than that of the 2 nd and 3 rd turns CV curves, so the Initial Coulombic Efficiency (ICE)<100%. However, the CV curves of circles 2 and 3 overlap almost, indicating that the oxygen-doped porous carbon anode has good structural stability.
The oxygen-doped porous carbon anode prepared in comparative example 1 was at 0.05 ag -1 The constant current charge-discharge curve at current density and the rate capability at different current densities are shown in fig. 9, fig. 10 and table 2. The oxygen doped porous carbon cathode is 0.05 Ag -1 ICE at 67.2%. At the same time, it is between 0.05 and 2A g -1 The specific capacities are 488.6 and 285.1 mAh g respectively -1 The porous carbon anode has good rate capability, which indicates that no seed-induced foaming activation participates in the synthesis process, and the specific surface area and oxygen content of the oxygen-doped porous carbon anode are relatively low, so that the electrochemical performance is adversely affected.
Application example 3
The electrode preparation method, the sodium ion battery assembly and the testing method of the application example are basically the same as the application example 1, and the difference is that: the active material was the nitrogen-oxygen doped porous carbon material prepared in comparative example 2. The test results are shown in fig. 7 and fig. 9 to 10.
FIG. 7 is a graph showing that the nitrogen-oxygen doped porous carbon anode prepared in comparative example 2 was at 0.2 mV s -1 Initial 3 cycles of Cyclic Voltammetry (CV) plot at time. As shown in FIG. 7, the CV curve is around 0.01V in cathode peak and Na + Embedded carbon layers or pore filling; while cathode peaks above 0.01V capture Na by carbon defects + (irreversible), SEI layer formation, and electrolyte decomposition. The area of the 1 st turn CV curve is larger than that of the 2 nd and 3 rd turns CV curves, so the Initial Coulombic Efficiency (ICE)<100%. However, the CV curves of circles 2 and 3 almost overlap, indicating that the nitrogen-oxygen doped porous carbon anode has good structural stability.
The nitrogen-oxygen doped porous carbon anode prepared in comparative example 2 was 0.05 ag -1 The constant current charge-discharge curve at current density and the rate capability at different current densities are shown in fig. 9, fig. 10 and table 2. The nitrogen-oxygen doped porous carbon cathode is 0.05A g -1 ICE at 60.0%. At the same time, it is between 0.05 and 2A g -1 The specific capacities are 284.6 and 92.3 mAh g respectively -1 The anode has poor multiplying power performance, which indicates that no biomimetic mineralization participates in the synthesis process, and the specific surface area and pore volume of the nitrogen-oxygen doped porous carbon anode are relatively low, so that the electrochemical performance is adversely affected.
Application example 4
The electrode preparation method, the sodium ion battery assembly and the testing method of the application example are basically the same as the application example 1, and the difference is that: the active material was an oxygen-doped porous carbon material prepared in comparative example 3. The test results are shown in fig. 8-10.
FIG. 8 is a graph of the oxygen doped porous carbon anode of comparative example 3 at 0.2 mV s -1 An initial 3-turn Cyclic Voltammetry (CV) curve. Cathode peak with CV curve around 0.01V and Na + Embedded carbon layers or pore filling; while cathode peaks above 0.01V capture Na by carbon defects + (irreversible), SEI layer formation, and electrolyte decomposition. The area of the 1 st turn CV curve is larger than that of the 2 nd and 3 rd turns CV curves, so the Initial Coulombic Efficiency (ICE)<100%. However, the CV curves of circles 2 and 3 overlap almost, indicating that the oxygen-doped porous carbon anode has good structural stability.
The oxygen-doped porous carbon anode prepared in comparative example 3 was 0.05 ag -1 The constant current charge-discharge curve at current density and the rate capability at different current densities are shown in fig. 9, fig. 10 and table 2. The oxygen doped porous carbon cathode is 0.05 Ag -1 ICE at 47.7%. At the same time, it is between 0.05 and 2A g -1 The specific capacities are 212.8 and 68.9 mAh g respectively -1 The oxygen-doped porous carbon anode has poor multiplying power performance, which indicates that no biomimetic mineralization and no seed-induced foaming activation participate in the synthesis process, and the specific surface area and pore volume of the oxygen-doped porous carbon anode are relatively low, so that the electrochemical performance is adversely affected.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (5)
1. The preparation method of the nitrogen-oxygen doped porous carbon is characterized by comprising the following steps of:
mixing cellulose substances, magnesium salt, strong alkali, nitrogen-containing organic compound and water, and sequentially performing freeze drying and carbonization treatment on the obtained mixture to obtain carbonized products;
sequentially carrying out acid treatment and separation on the carbonized product to obtain nitrogen-oxygen doped porous carbon;
the cellulose substance comprises methyl cellulose, hydroxypropyl cellulose, bacterial cellulose or cellulose acetate;
the strong base comprises potassium hydroxide, sodium hydroxide or lithium hydroxide; the nitrogen-containing organic compound comprises urea, melamine, glycine or dimethylimidazole;
the mass ratio of the cellulose substances to the magnesium salt to the alkali to the nitrogen-containing organic compound is (1-5);
the temperature of freeze drying is-70 to-20 ℃ and the time is 48-120 hours;
the carbonization treatment temperature is 500-1000 ℃, and the heat preservation time is 0.5-5 h; the heating rate of the carbonized material to the temperature of the carbonization treatment is 1-10 ℃ min -1 。
2. The production method according to claim 1, wherein the carbonization treatment is performed under a protective gas, the protective gas being argon or nitrogen; the flow rate of the protective gas is 40-100 mL min -1 。
3. The method according to claim 1, wherein the acid used for the acid treatment is hydrochloric acid; the concentration of the hydrochloric acid is 0.5-5 mol/L.
4. The nitrogen-oxygen doped porous carbon prepared by the preparation method of any one of claims 1 to 3.
5. Use of the nitrogen-oxygen doped porous carbon of claim 4 in a sodium ion battery.
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| CN108455597A (en) * | 2018-05-12 | 2018-08-28 | 中国科学院新疆理化技术研究所 | A kind of method and application preparing N doping porous carbon using cotton seed hulls as raw material |
| CN111892047A (en) * | 2020-05-25 | 2020-11-06 | 北京化工大学 | Vanadium nitride hybrid and nitrogen-doped porous carbon material and preparation method and application thereof |
| CN112850708A (en) * | 2021-03-05 | 2021-05-28 | 中国海洋大学 | Preparation method and application of nitrogen-doped porous carbon material with high specific surface area |
| CN115367726A (en) * | 2021-05-19 | 2022-11-22 | 北京化工大学 | Oxygen-doped titanium nitride hybridized and nitrogen-doped porous carbon material and preparation method and application thereof |
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| CN108455597A (en) * | 2018-05-12 | 2018-08-28 | 中国科学院新疆理化技术研究所 | A kind of method and application preparing N doping porous carbon using cotton seed hulls as raw material |
| CN111892047A (en) * | 2020-05-25 | 2020-11-06 | 北京化工大学 | Vanadium nitride hybrid and nitrogen-doped porous carbon material and preparation method and application thereof |
| CN112850708A (en) * | 2021-03-05 | 2021-05-28 | 中国海洋大学 | Preparation method and application of nitrogen-doped porous carbon material with high specific surface area |
| CN115367726A (en) * | 2021-05-19 | 2022-11-22 | 北京化工大学 | Oxygen-doped titanium nitride hybridized and nitrogen-doped porous carbon material and preparation method and application thereof |
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