CN116239100B - Rosin-based nitrogen-doped porous hard carbon material and preparation method and application thereof - Google Patents
Rosin-based nitrogen-doped porous hard carbon material and preparation method and application thereof Download PDFInfo
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- CN116239100B CN116239100B CN202310301037.7A CN202310301037A CN116239100B CN 116239100 B CN116239100 B CN 116239100B CN 202310301037 A CN202310301037 A CN 202310301037A CN 116239100 B CN116239100 B CN 116239100B
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 100
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 88
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 title claims abstract description 88
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 88
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 45
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 235000002639 sodium chloride Nutrition 0.000 claims description 15
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000003763 carbonization Methods 0.000 claims description 10
- 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
- 239000007789 gas Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 235000010333 potassium nitrate Nutrition 0.000 claims description 7
- 239000004323 potassium nitrate Substances 0.000 claims description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000001103 potassium chloride Substances 0.000 claims description 6
- 235000011164 potassium chloride Nutrition 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000011780 sodium chloride Substances 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
- 239000004471 Glycine Substances 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 56
- 239000003792 electrolyte Substances 0.000 abstract description 49
- 238000009792 diffusion process Methods 0.000 abstract description 11
- 238000004146 energy storage Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 10
- 239000011148 porous material Substances 0.000 abstract description 10
- 150000002500 ions Chemical class 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 8
- 238000001035 drying Methods 0.000 abstract description 7
- 238000009830 intercalation Methods 0.000 abstract description 6
- 230000002687 intercalation Effects 0.000 abstract description 6
- 238000009831 deintercalation Methods 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 4
- 230000001737 promoting effect Effects 0.000 abstract description 4
- 230000002829 reductive effect Effects 0.000 abstract description 4
- 238000004904 shortening Methods 0.000 abstract description 4
- 238000006276 transfer reaction Methods 0.000 abstract description 4
- 230000002427 irreversible effect Effects 0.000 abstract description 3
- 239000011232 storage material Substances 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 description 15
- 238000001179 sorption measurement Methods 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000011734 sodium Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 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 5
- 238000000227 grinding Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000006183 anode active material Substances 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- XXYVTWLMBUGXOK-UHFFFAOYSA-N [Na].FS(=N)F Chemical compound [Na].FS(=N)F XXYVTWLMBUGXOK-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000007773 negative electrode 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the technical field of energy storage materials, and provides a rosin-based nitrogen-doped porous hard carbon material, and a preparation method and application thereof. The method comprises the following steps: mixing rosin, a nitrogen source, metal salt, alkali metal hydroxide and a solvent, and sequentially drying and carbonizing to obtain the nitrogen-doped porous hard carbon material based on rosin. When the porous hard carbon material prepared by the invention is used as a sodium ion mixed capacitance electrode material, the graded open pore structure is beneficial to shortening the diffusion distance of ions and promoting the intercalation or deintercalation of ions; the doping of nitrogen element is beneficial to improving the conductivity of the material, provides rich active sites for charge transfer reaction, and can remarkably improve the electrochemical performance of the obtained sodium ion battery; when the porous hard carbon material is assembled into a sodium ion battery through the ether-based electrolyte, irreversible loss of electrolyte and effective sodium ions is reduced, so that the battery shows excellent initial coulombic efficiency, rate capability and cycle performance.
Description
Technical Field
The invention relates to the technical field of energy storage materials, in particular to a rosin-based nitrogen-doped porous hard carbon material, and a preparation method and application thereof.
Background
In recent years, clean renewable energy sources such as solar energy, wind energy, sea, etc. have been rapidly developed, and large-scale electric energy storage systems are considered as important solutions for collecting such unstable and intermittent energy. Lithium ion batteries occupy overwhelming predominance in the energy storage market of portable electronic products and electric automobiles, but due to the scarcity of lithium in the crust, the price of lithium is continuously rising, and the lithium is limited in the field of large-scale energy storage. Sodium ion batteries are one of the most promising candidate materials for lithium ion batteries because of their low cost, abundant sodium reserves, and many similarities to lithium ion batteries in electrochemical terms.
With the development of scientific technology, the development and application of the positive electrode material of the sodium ion battery have greatly progressed. However, the negative electrode material still has a barrier due to Na + Is larger in ion radius and Na + The thermodynamic incompatibility between the graphite layers, graphite which can be used commercially in lithium ion batteries, is not suitable for sodium ion batteries. The hard carbon is one of the most promising candidate compounds, and has the advantages of high specific capacity, abundant resources, simple synthesis process and the like. The microstructure of hard carbon is often described as a combination of graphene sheet fragments crumpling and twisting, with "short-range ordered" and "long-range disordered" states, relative to the regular structure of graphite. However, analysis of sodium storage mechanism is challenging due to the complex hard carbon structure. In hard carbon, active sites with the ability to store sodium ions mainly include adsorption on the surface of open pores, adsorption on defects of graphene sheets, intercalation between graphene layers, and filling of closed pores. In general, the hard carbon discharge curve exhibits a slope region at high potential and a plateau region at low potential, corresponding to a capacitance control process (surface adsorption and defect) and a diffusion control process (intercalation and filling), respectively. Due to thermodynamic incompatibility and structural recombinationThe long diffusion path of sodium ions becomes a rate determining step in the charge-discharge process, which always results in poor rate performance of hard carbon. Meanwhile, long-term platform area plating with sodium at low potential may cause dendrite growth of metallic sodium on the surface of hard carbon anode, resulting in safety problem of battery. Therefore, it is of great importance to provide a hard carbon anode material with high reversible capacity and high rate performance.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a rosin-based nitrogen-doped porous hard carbon material, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a rosin-based nitrogen-doped porous hard carbon material, which comprises the following steps:
mixing rosin, a nitrogen source, metal salt, alkali metal hydroxide and a solvent, and carbonizing to obtain the rosin-based nitrogen-doped porous hard carbon material.
Preferably, the nitrogen source comprises one or more of glycine, urea, thiourea and dimethylimidazole;
the metal salt comprises one or more of lithium chloride, sodium chloride, potassium chloride, sodium nitrate, potassium nitrate, sodium bicarbonate, potassium bicarbonate and calcium nitrate;
the alkali metal hydroxide comprises one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide;
the solvent comprises ethanol and/or water.
Preferably, the mass volume ratio of the rosin to the nitrogen source to the solvent is 1-20 g: 1-50 g: 50-500 mL.
Preferably, the mass ratio of the rosin, the metal salt and the alkali metal hydroxide is 1:1 to 10:0.5 to 2.
Preferably, the carbonization is performed under a protective gas, wherein the protective gas is argon and/or nitrogen, and the flow rate of the protective gas is 40-100 mL/min.
Preferably, the heating rate of the carbonization is 1-10 ℃/min, the target temperature of the carbonization is 600-900 ℃, and the heat preservation time after reaching the target temperature is 0.5-5 h.
The invention also provides the rosin-based nitrogen-doped porous hard carbon material obtained by the preparation method.
The invention also provides application of the rosin-based nitrogen-doped porous hard carbon material in sodium ion batteries.
The beneficial effects of the invention are as follows:
(1) The nitrogen-doped porous hard carbon-based anode active material with a hierarchical porous structure is prepared, when the nitrogen-doped porous hard carbon-based anode active material is used as a sodium ion mixed capacitance electrode material, the high specific surface area of the nitrogen-doped porous hard carbon-based anode active material can provide an electric double layer capacitance, and doped heterogeneous elements can provide a pseudo-capacitance to increase charge storage of the porous hard carbon material; the synthesis method is simple, the whole process is nontoxic and harmless, the activator can be recycled in the washing process, and the cost is low.
(2) The nitrogen-doped porous hard carbon material prepared by the method has ultrahigh specific surface area, and the graded open pore structure is beneficial to shortening the diffusion distance of ions and promoting the intercalation or deintercalation of ions; the doping of nitrogen element is beneficial to improving the conductivity of the hard carbon material, provides rich active sites for charge transfer reaction, and can remarkably improve the electrochemical performance of the obtained sodium ion battery.
(3) When the rosin-based nitrogen-doped porous hard carbon material prepared by the invention is assembled into a sodium ion battery through the ether-based electrolyte, the irreversible loss of electrolyte and effective sodium ions is reduced, so that the battery shows excellent initial coulombic efficiency, rate capability and cycle performance. Therefore, the rosin-based nitrogen-doped porous hard carbon material prepared by the invention has good application prospect in the existing energy conversion and storage device.
Drawings
FIG. 1 is a representation of the surface morphology of the rosin-based nitrogen-doped porous hard carbon material of example 1;
FIG. 2 is a representation of the internal morphology of the rosin-based nitrogen-doped porous hard carbon material of example 1;
FIG. 3 is a graph showing the isothermal adsorption and desorption of nitrogen (Relative Pressure-relative pressure, quantity Adsorbed-adsorption amount) of the rosin-based nitrogen-doped porous hard carbon material obtained in example 1;
FIG. 4 is a graph of Pore size distribution (Pore Width, dV/dW Pore Volume) of the rosin-based nitrogen-doped porous hard carbon material obtained in example 1;
FIG. 5 is an X-ray diffraction pattern (Binding energy, intensity) of the rosin-based nitrogen-doped porous hard carbon material obtained in example 1;
FIG. 6 is a Raman spectrum graph (Raman shift, intensity) of the rosin-based nitrogen-doped porous hard carbon material obtained in example 1;
FIG. 7 is a graph of the X-ray photoelectron spectrum (binding energy, density) of the rosin-based nitrogen-doped porous hard carbon material obtained in example 1;
FIG. 8 is a graph showing the rate performance (cycle number, specific capacity) of the rosin-based nitrogen-doped porous hard carbon material obtained in example 1 as a negative electrode of a sodium ion battery in an ether-based and an ester-based electrolyte;
FIG. 9 is a graph showing the first charge and discharge curves (specific-Potential, voltage) of the rosin-based nitrogen-doped porous hard carbon material obtained in example 1 as a negative electrode of a sodium ion battery in an ether-based electrolyte and an ester-based electrolyte, respectively, at a current density of 0.05A/g;
FIG. 10 is a graph (Specific capacity-specific capacity, voltage-Voltage) of the rosin-based nitrogen-doped porous hard carbon material of example 1 as a negative electrode of a sodium ion battery in an ether-based electrolyte at different current densities;
FIG. 11 is a graph of a comparison of the first cycle voltammogram (Voltage, current-Current) of the rosin-based nitrogen-doped porous hard carbon material of example 1 as a negative electrode of a sodium ion battery at a sweep rate of 0.2 mV/s;
FIG. 12 is a graph of the diffusion control and capacitance control duty cycle (scanning-rate, percent) of the rosin-based nitrogen-doped porous hard carbon material obtained in example 1 as a negative electrode of a sodium ion battery in an ether-based electrolyte;
FIG. 13 is a graph of diffusion control and capacitance control duty cycle (scanning-rate, percent) of the rosin-based nitrogen-doped porous hard carbon material obtained in example 1 as a negative electrode of a sodium ion battery in an ester-based electrolyte;
FIG. 14 is a graph showing the Cycle performance (Cycle number-Cycle number, specific capacity, coulomb efficiency) of the rosin-based nitrogen-doped porous hard carbon material obtained in example 1 as a negative electrode of a sodium ion battery in an ether-based electrolyte at a current density of 5A/g;
FIG. 15 is a graph showing the Cycle performance (Cycle number-Cycle number, specific capacity, coulomb efficiency) of the rosin-based nitrogen-doped porous hard carbon material obtained in example 1 as a negative electrode of a sodium ion battery in an ester-based electrolyte at a current density of 5A/g;
FIG. 16 is a graph showing the rate performance of the rosin-based nitrogen-doped porous hard carbon material obtained in example 2 as a negative electrode of a sodium ion battery in an ether-based electrolyte (cyclumber-number of cycles, specific capacity-specific capacity);
fig. 17 is a graph of the rate capability (cyclumber-number of cycles, specific capacity-specific capacity) of the rosin-based nitrogen-doped porous hard carbon material obtained in example 3 as a negative electrode of a sodium ion battery in an ether-based electrolyte.
Detailed Description
The invention provides a preparation method of a rosin-based nitrogen-doped porous hard carbon material, which comprises the following steps:
mixing rosin, a nitrogen source, metal salt, alkali metal hydroxide and a solvent, and carbonizing to obtain the rosin-based nitrogen-doped porous hard carbon material.
In the invention, the nitrogen source comprises one or more of glycine, urea, thiourea and dimethylimidazole;
the metal salt comprises one or more of lithium chloride, sodium chloride, potassium chloride, sodium nitrate, potassium nitrate, sodium bicarbonate, potassium bicarbonate and calcium nitrate;
the alkali metal hydroxide comprises one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide;
the solvent comprises ethanol and/or water.
In the present invention, when the solvent contains both ethanol and water, the volume ratio of water to solvent is preferably 50 to 100:100, more preferably 60 to 90:100, more preferably 70 to 80:100.
in the invention, the mass volume ratio of the rosin, the nitrogen source and the solvent is preferably 1-20 g: 1-50 g:50 to 500mL, more preferably 3 to 18g: 5-45 g:100 to 450mL, more preferably 5 to 16g: 15-35 g: 200-350 mL.
In the present invention, the mass ratio of the rosin, the metal salt and the alkali metal hydroxide is preferably 1:1 to 10:0.5 to 2, more preferably 1:2 to 9:0.7 to 1.8, more preferably 1: 3-8: 0.9 to 1.6.
In the invention, the mixing mode is stirring or grinding, the stirring is carried out in a closed container, and the rotating speed of the stirring is preferably 100-1500 r/min, more preferably 300-1300 r/min, and even more preferably 600-1000 r/min; the temperature of the stirring is preferably 20 to 30 ℃, more preferably 22 to 28 ℃, and even more preferably 24 to 26 ℃; the stirring time is preferably 1 to 12 hours, more preferably 3 to 10 hours, and still more preferably 5 to 8 hours; the time for the grinding is preferably 0.5 to 2 hours, more preferably 1 to 1.5 hours, still more preferably 1.2 to 1.3 hours; the particle size after grinding is preferably 100 μm or less, more preferably 80 μm or less, and still more preferably 50 μm or less.
In the present invention, the obtained mixed system is dried and then carbonized.
In the invention, the drying mode is one or more of low-temperature freeze drying, heating evaporation drying, spray drying and vacuum drying; the drying may be carried out by means conventional in the art.
In the present invention, the carbonization is performed under a shielding gas, which is argon and/or nitrogen, and the flow rate of the shielding gas is preferably 40 to 100mL/min, more preferably 50 to 90mL/min, and still more preferably 60 to 80mL/min.
In the present invention, the heating rate of the carbonization is preferably 1 to 10 ℃/min, more preferably 2 to 9 ℃/min, still more preferably 3 to 8 ℃/min; the target temperature for carbonization is preferably 600 to 900 ℃, more preferably 700 to 800 ℃, and even more preferably 720 to 780 ℃; the holding time after reaching the target temperature is preferably 0.5 to 5 hours, more preferably 1.5 to 4 hours, and still more preferably 2.5 to 3 hours.
In the invention, after carbonization is finished, the obtained sample is naturally cooled, and then impurity removal, suction filtration separation, washing and drying are sequentially carried out, so that the rosin-based nitrogen-doped porous hard carbon material is obtained.
In the present invention, the target temperature of natural cooling is preferably 20 to 30 ℃, more preferably 22 to 28 ℃, and even more preferably 24 to 26 ℃; the impurity removing reagent is hydrochloric acid solution, the mass fraction of the hydrochloric acid solution is preferably 1-5%, more preferably 2-4%, more preferably 2.5-3.5%, the sample is naturally cooled and then placed in the hydrochloric acid solution to be stirred, impurities and water-soluble salts on the surface of the sample are washed away, the stirring rotating speed is preferably 800-1000 r/min, more preferably 850-950 r/min, more preferably 870-930 r/min; the impurity removal temperature is preferably 25-100 ℃, more preferably 35-90 ℃, and even more preferably 50-75 ℃; the washing reagent is water, and the number of times of washing is preferably 2 times or more, more preferably 3 times or more, and still more preferably 4 times or more; the drying temperature is preferably 80 to 100 ℃, more preferably 85 to 95 ℃, and even more preferably 87 to 93 ℃.
The invention also provides the rosin-based nitrogen-doped porous hard carbon material obtained by the preparation method.
The invention also provides application of the rosin-based nitrogen-doped porous hard carbon material in sodium ion batteries.
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
Mixing 2g of rosin, 2g of urea, 10g of potassium chloride, 3g of potassium hydroxide, 35mL of ethanol and 65mL of water, and stirring for 2 hours at the temperature of 25 ℃ and the rotating speed of 1000r/min to obtain a mixed system; and then performing low-temperature freeze drying, heating to 800 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere (the flow rate of nitrogen is 80 mL/min) after the end of low-temperature freeze drying, preserving heat for 2 hours, naturally cooling the obtained sample to 25 ℃, then placing the sample in hydrochloric acid solution with mass fraction of 3%, stirring at a temperature of 30 ℃ and a rotating speed of 900r/min, washing impurities and water soluble salts on the surface of the sample, performing suction filtration separation, washing with water for 3 times after the end of suction filtration separation, and finally drying at 70 ℃ to obtain the rosin-based nitrogen-doped porous hard carbon material.
The rosin-based nitrogen-doped porous hard carbon material obtained in the embodiment is subjected to morphological structural characterization. Observing the surface morphology structure of the material by a Scanning Electron Microscope (SEM) to obtain a surface morphology structure characterization diagram of the rosin-based nitrogen-doped porous hard carbon material, as shown in figure 1; as can be seen from fig. 1, the rosin-based nitrogen-doped porous hard carbon material prepared in this embodiment is a cambered surface sheet material, and the surface of the material has protrusions with a bubble structure, and the cross section of the material can be seen that the protrusions with a bubble structure are hollow. Observing the internal morphology of the material by a Transmission Electron Microscope (TEM) to obtain an internal morphology characterization diagram of the rosin-based nitrogen-doped porous hard carbon material, as shown in FIG. 2; as can be seen from fig. 2, the rosin-based nitrogen-doped porous hard carbon material prepared in this example is shown to contain a nano-scale pore structure in the disordered graphene sheet layer. Obtaining a nitrogen adsorption and desorption isothermal curve of the rosin-based nitrogen-doped porous hard carbon material through 77K nitrogen adsorption and desorption test materials, wherein the curve is shown in figure 3; as can be seen from fig. 3, the nitrogen adsorption and desorption isothermal graph of the rosin-based nitrogen-doped porous hard carbon material prepared in this embodiment accords with the characteristic of the type I isothermal line, so that the adsorption of nitrogen in the nitrogen-doped porous hard carbon material is mainly microporous adsorption; pore size distribution graphs of rosin-based nitrogen-doped porous hard carbon materials, as shown in fig. 4; as can be seen from fig. 4, the rosin-based nitrogen-doped porous hard carbon material prepared in this example has a large number of nanopores below 4nm, and can provide a large specific surface area. Determining the phase structure of the material by X-ray diffraction and Raman spectrum analysis to obtain an X-ray diffraction pattern of the rosin-based nitrogen-doped porous hard carbon material, as shown in FIG. 5; raman spectrum graphs of rosin-based nitrogen-doped porous hard carbon materials, as shown in fig. 6; as can be seen from fig. 5 and 6, the X-ray diffraction curve and the raman spectrum curve are both typical hard carbon curves, which are beneficial to enhancing the wettability of the electrolyte, shortening the diffusion distance of ions, promoting the intercalation or deintercalation of ions, and providing rich active sites for charge transfer reaction. Characterizing the carbon, oxygen and nitrogen element composition of the material by X-ray photoelectron spectroscopy (XPS) to obtain an X-ray photoelectron spectrum of the rosin-based nitrogen-doped porous hard carbon material, as shown in figure 7; as can be seen from fig. 7, the rosin-based nitrogen-doped porous hard carbon material prepared in this example was successfully doped with nitrogen element. According to the structural analysis, the rosin-based nitrogen-doped porous hard carbon material prepared by the embodiment has a nanoscale porous structure, and the successful doping of nitrogen element improves the electrochemical performance of the electrode material, so that the storage and conversion of charges are facilitated.
The rosin-based nitrogen-doped porous hard carbon material prepared in the embodiment, the conductive agent Li-90 and polyvinylidene fluoride are mixed according to the mass ratio of 7:1.5:1.5, then adding the mixture into a proper amount of N-methyl pyrrolidone, fully mixing again, and uniformly dripping the obtained mixture onto a stainless steel sheet with the thickness of 100 mu m; placing the cathode sheet into a vacuum drying oven, and performing vacuum drying at 100 ℃ to obtain a cathode sheet; and assembling the negative plate, the glass fiber diaphragm and the sodium metal wafer in a glove box filled with argon, and respectively adopting an ether-based electrolyte and an ester-based electrolyte to obtain two sodium ion batteries. The electrolyte in the two electrolytes is sodium difluorosulfimide (the concentration is 1 mol/L), the ether-based electrolyte takes diethylene glycol dimethyl ether as a solvent, and the ester-based electrolyte takes ethylene carbonate and diethyl carbonate (the volume ratio is 1:1) as solvents. And then using a Chenhua CHI660E electrochemical workstation and a Xinwei CT-4008T to test a cyclic voltammetry curve and a constant current charge-discharge curve of the two assembled sodium ion batteries respectively at room temperature. Obtaining a multiplying power performance diagram of the rosin-based nitrogen-doped porous hard carbon material obtained in the embodiment in ether-based and ester-based electrolytes as a negative electrode of a sodium ion battery, as shown in fig. 8; as can be seen from fig. 8, the rosin-based nitrogen-doped porous hard carbon material exhibits a large difference in rate performance among the two electrolytes, probably because the porous hard carbon material is associated with the formation of a thicker SEI layer with the ester-based electrolyte. In the ether-based electrolyte, the porous hard carbon material has ultra-high reversible capacities of 367mAh/g, 347mAh/g, 337mAh/g, 315mAh/g, 291mAh/g, 265mAh/g, 242mAh/g, 225mAh/g, 212mAh/g and 183mAh/g at current densities of 0.05A/g, 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g, 4A/g, 5A/g and 10A/g. The rosin-based nitrogen-doped porous hard carbon material obtained in the present example with a current density of 0.05A/g was used as the first-turn charge-discharge curve of the negative electrode of the sodium ion battery in the ether-based and ester-based electrolytes, respectively, as shown in fig. 9; as can be seen from fig. 9, the sodium ion battery discharge curve in the ester-based electrolyte exhibited a capacity plateau at 0.2-1V during the first-turn discharge, whereas there was no plateau in the ether-based electrolyte. The charge-discharge curve diagram of the rosin-based nitrogen-doped porous hard carbon material obtained in this example as the negative electrode of sodium ion battery in ether-based electrolyte at different current densities is shown in fig. 10; as can be seen from fig. 10, the charge-discharge curve shows an inclined curve at each current density, and no obvious plateau area exists, which illustrates that the sodium storage mechanism of the rosin-based nitrogen-doped porous hard carbon material obtained in the embodiment is mainly adsorption; the first cycle voltammogram of the rosin-based nitrogen-doped porous hard carbon material obtained in this example as the negative electrode of sodium ion battery at a sweep rate of 0.2mV/s is shown in FIG. 11; as can be seen from fig. 11, the cyclic voltammogram shows a very high reduction peak in the ester-based electrolyte at about 0.4V, while the ether-based electrolyte does not, which is a voltage interval formed by the SEI, indicating that the ether-based electrolyte does not generate an excessively thick SEI layer and does not shield the adsorption energy storage sites on the surface of the porous carbon material. The rosin-based nitrogen-doped porous hard carbon material obtained in the embodiment is used as a negative electrode of a sodium ion battery to control the diffusion and capacitance in an ether-based electrolyte, and the ratio chart is shown in fig. 12; the rosin-based nitrogen-doped porous hard carbon material obtained in the embodiment is used as a negative electrode of a sodium ion battery to control the diffusion and capacitance in an ester-based electrolyte, as shown in fig. 13; as can be seen from fig. 12 and 13, the main energy storage mechanism of the rosin-based nitrogen-doped porous hard carbon material in the ether-based electrolyte is capacitive adsorption energy storage, while the energy storage mechanism in the ester-based electrolyte is more diffusion-controlled energy storage mechanism. Because the rosin-based nitrogen-doped porous hard carbon material has the characteristics of ultrahigh specific surface area, numerous defects, effective doping of nitrogen elements and the like, the ether-based electrolyte can more effectively exert the electrochemical performance of the rosin-based nitrogen-doped porous hard carbon material. The cycle performance of the rosin-based nitrogen-doped porous hard carbon material obtained in this example as a negative electrode of a sodium ion battery in an ether-based electrolyte at a current density of 5A/g is shown in fig. 14; the cycle performance of the rosin-based nitrogen-doped porous hard carbon material obtained in this example as a negative electrode of sodium ion battery in an ester-based electrolyte at a current density of 5A/g is shown in fig. 15; as can be seen from fig. 14 and 15, the battery using the ester-based electrolyte showed only a reversible capacity of 24.4mAh/g after 12000 cycles at a current density of 5A/g, while the battery using the ether-based electrolyte showed an ultra-high reversible capacity of 150.5mAh/g after 12000 cycles, indicating that the rosin-based nitrogen-doped porous hard carbon material had excellent cycle stability.
Example 2
The other conditions in example 1 were controlled to be unchanged, and 2.4g of potassium nitrate, 2g of rosin, 2g of urea, 10g of potassium chloride and 0.6g of potassium hydroxide were added to carry out grinding for 1 hour, and the particle size after grinding was 45 μm to obtain a mixed system; finally, the rosin-based nitrogen-doped porous hard carbon material is obtained.
In the embodiment, potassium nitrate and potassium hydroxide can form a eutectic, so that the activation temperature of the activator is reduced, and simultaneously, the potassium nitrate and the potassium hydroxide can have good activation effect; potassium nitrate and carbon are subjected to oxidation-reduction reaction at high temperature to decompose and release nitrogen oxides, so that a gas etching effect is achieved; the potassium hydroxide plays a role in alkali etching.
The rosin-based nitrogen-doped porous hard carbon material prepared in this example was assembled by the same assembly method as in example 1, wherein the electrolyte was an ether-based electrolyte. The assembled sodium ion battery was subjected to constant current charge-discharge curve testing at room temperature using new wei CT-4008T. The ratio performance diagram of the rosin-based nitrogen-doped porous hard carbon material obtained in the embodiment as a negative electrode of a sodium ion battery in an ether-based electrolyte is obtained, and is shown in fig. 16. As can be seen in FIG. 16, the porous hard carbon material has high reversible capacities of 262mAh/g, 240mAh/g, 218mAh/g, 194mAh/g, 174mAh/g, 156mAh/g, 143mAh/g, 133mAh/g, 126mAh/g, 111mAh/g at current densities of 0.05A/g, 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g, 4A/g, 5A/g, 10A/g, respectively.
Example 3
The other conditions in example 2 were controlled to be unchanged, and 10g of potassium chloride was replaced with 10g of sodium chloride to obtain a mixed system; finally, the rosin-based nitrogen-doped porous hard carbon material is obtained.
The rosin-based nitrogen-doped porous hard carbon material prepared in this example was assembled by the same assembly method as in example 1, wherein the electrolyte was an ether-based electrolyte. The assembled sodium ion battery was subjected to constant current charge-discharge curve testing at room temperature using new wei CT-4008T. Obtaining a multiplying power performance diagram of the rosin-based nitrogen-doped porous hard carbon material obtained in the embodiment in an ether-based electrolyte as a negative electrode of a sodium ion battery, as shown in fig. 17; as can be seen in FIG. 17, the porous hard carbon material has high reversible capacities of 273mAh/g, 266mAh/g, 250mAh/g, 233mAh/g, 215mAh/g, 197mAh/g, 182mAh/g, 171mAh/g, 163mAh/g, 142mAh/g at current densities of 0.05A/g, 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g, 3A/g, 4A/g, 5A/g, 10A/g, respectively.
As can be seen from the above examples, the present invention provides a nitrogen-doped porous hard carbon-based anode active material having a hierarchical porous structure, which can provide an electric double layer capacitance with a high specific surface area when used as a sodium ion mixed capacitance electrode material; the graded open pore structure is beneficial to shortening the diffusion distance of ions and promoting the intercalation or deintercalation of ions; the doping of nitrogen element is beneficial to improving the conductivity of the hard carbon material, provides rich active sites for charge transfer reaction, and can remarkably improve the electrochemical performance of the obtained sodium ion battery; when the rosin-based nitrogen-doped porous hard carbon material prepared by the invention is assembled into a sodium ion battery through the ether-based electrolyte, the irreversible loss of electrolyte and effective sodium ions is reduced, so that the battery shows excellent initial coulombic efficiency, rate capability and cycle performance. Therefore, the rosin-based nitrogen-doped porous hard carbon material prepared by the invention has good application prospect in the existing energy conversion and storage device.
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. A method for preparing a rosin-based nitrogen-doped porous hard carbon material, comprising the steps of:
mixing rosin, a nitrogen source, metal salt, alkali metal hydroxide and a solvent, and carbonizing to obtain the rosin-based nitrogen-doped porous hard carbon material;
the mass volume ratio of the rosin to the nitrogen source to the solvent is 1-20 g: 1-50 g: 50-500 mL;
the mass ratio of the rosin to the metal salt to the alkali metal hydroxide is 1:1 to 10:0.5 to 2;
the heating rate of the carbonization is 5-10 ℃/min, the target temperature of the carbonization is 800-900 ℃, and the heat preservation time after reaching the target temperature is 0.5-5 h.
2. The method of claim 1, wherein the nitrogen source comprises one or more of glycine, urea, thiourea, and dimethylimidazole;
the metal salt comprises one or more of lithium chloride, sodium chloride, potassium chloride, sodium nitrate, potassium nitrate, sodium bicarbonate, potassium bicarbonate and calcium nitrate;
the alkali metal hydroxide comprises one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide;
the solvent comprises ethanol and/or water.
3. The method according to claim 2, wherein the carbonization is performed under a shielding gas, the shielding gas is argon and/or nitrogen, and the flow rate of the shielding gas is 40-100 mL/min.
4. A rosin-based nitrogen-doped porous hard carbon material obtained by the production method of any one of claims 1 to 3.
5. The use of the rosin-based nitrogen-doped porous hard carbon material of claim 4 in a sodium ion battery.
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