CN117486212A - Honeycomb nitrogen-doped porous carbon material and application thereof in sodium-electricity negative electrode - Google Patents
Honeycomb nitrogen-doped porous carbon material and application thereof in sodium-electricity negative electrode Download PDFInfo
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- CN117486212A CN117486212A CN202311510384.7A CN202311510384A CN117486212A CN 117486212 A CN117486212 A CN 117486212A CN 202311510384 A CN202311510384 A CN 202311510384A CN 117486212 A CN117486212 A CN 117486212A
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000003763 carbonization Methods 0.000 claims abstract description 22
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 20
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000005539 carbonized material Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 230000001413 cellular effect Effects 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- 239000012190 activator Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 6
- 230000008014 freezing Effects 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000005715 Fructose Substances 0.000 claims description 3
- 229930091371 Fructose Natural products 0.000 claims description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000005720 sucrose 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 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000009831 deintercalation Methods 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 3
- 229910021385 hard carbon Inorganic materials 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 238000009830 intercalation Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 230000008859 change Effects 0.000 abstract description 2
- 239000002149 hierarchical pore Substances 0.000 abstract description 2
- 230000002687 intercalation Effects 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract description 2
- 239000007773 negative electrode material Substances 0.000 description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 6
- 235000013855 polyvinylpyrrolidone Nutrition 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 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-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
- 238000003917 TEM image Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- 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
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a honeycomb nitrogen-doped porous carbon material and application thereof in a negative electrode of a sodium ion battery, and belongs to the technical field of battery electrode materials. The nitrogen-doped porous carbon material is prepared by using the one-step carbonization method, is simple, convenient and energy-saving, saves cost, is more green and environment-friendly, has low price of experimental raw materials, is easy to obtain, and has long-term property in preparation of the material. The raw material is hard carbon with large capacity and long service life. The porous carbon material with the hierarchical pore structure is formed by removing impurities through acid washing and then enriching the pore structure. The nitrogen-doped porous carbon material is applied as a sodium-electricity negative electrode, and the presence of more mesopores and macropores is beneficial to improving the effective surface area and has obvious effect on improving the rate performance. And the large holes and the mesopores are more, so that the influence on the volume change of intercalation and deintercalation of sodium ions is small, the stability is improved, and the method has important application significance in the technical field of sodium ion batteries.
Description
Technical Field
The invention belongs to the technical field of battery electrode materials, and particularly relates to a honeycomb nitrogen-doped porous carbon material and application thereof in a sodium-electricity negative electrode.
Background
Along with the rapid development of new energy fields, research on more efficient energy storage technologies is a common focus of researchers, and lithium ion batteries have been widely applied to the fields of mobile equipment, electric automobiles, energy storage power stations and the like by virtue of higher energy density and energy conversion efficiency. However, the problems of scarce lithium resources, low recovery rate, high price and the like greatly limit future application of the lithium ion battery.
Compared with lithium element, sodium element has abundant crust content and low price, the deintercalation mechanism in the ion battery is similar to that of the lithium ion battery, and the sodium ion battery has higher safety and is more beneficial to actual mass production and application. However, due to the larger atomic size of sodium, the volumetric strain during cycling is also larger and smaller interlayer spacing affects the stability of sodium ion transport.
In the sodium ion battery, a carbon-based negative electrode material, a titanium-based negative electrode material, a conversion reaction-type negative electrode material, an intermetallic compound negative electrode material, and the like are generally used as the negative electrode material. The carbon-based negative electrode material has the advantages of wide source, low price and easy preparation, the hard carbon material in the carbon-based negative electrode material has stable structure, large capacity and long service life in the circulating process, and becomes the first choice of the negative electrode material of the sodium ion battery, but the current carbon negative electrode material still has the problem of poor rate performance, and the application range of the carbon-based negative electrode material is limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a honeycomb nitrogen-doped porous carbon material and application thereof in a sodium ion battery negative electrode, and the honeycomb nitrogen-doped porous carbon material has excellent multiplying power performance and excellent cycle performance as a sodium ion battery negative electrode material.
The aim of the invention can be achieved by the following technical scheme:
a cellular nitrogen-doped porous carbon material prepared by the steps of:
s1, dissolving a carbon source, a nitrogen source and an activator in water, and freezing the solution by using liquid nitrogen;
s2, putting the material frozen by liquid nitrogen in the step S1 into a freeze dryer, and freeze-drying to obtain a freeze-dried precursor;
s3, introducing inert gas serving as protective gas into the tubular furnace, adding the freeze-dried precursor for carbonization, and naturally cooling the furnace body to room temperature after carbonization to obtain carbonized materials;
s4, soaking the carbonized material in dilute hydrochloric acid until the PH value is 7, and washing with deionized water to obtain a washed material;
s5, placing the material washed in the step S4 into a vacuum drying oven, and drying at 60 ℃ for 8 hours to obtain the honeycomb nitrogen-doped porous carbon material.
Further, in the step S1, the mass ratio of the carbon source, the nitrogen source and the activator is 1:1:2-5.
Further, in step S1, the carbon source is one of glucose, fructose, sucrose, and starch.
Further, in step S1, the nitrogen source is PVP (polyvinylpyrrolidone).
Further, the activating agent in the step S1 is one of sodium bicarbonate, sodium carbonate, potassium carbonate and potassium bicarbonate.
Further, in the step S2, the freeze drying temperature is-80-0 ℃ and the time is 24-48 h.
Further, in step S3, the inert gas is one of nitrogen and argon.
Further, in the step S3, the carbonization temperature is 700-1000 ℃, the carbonization time is 1-3 h, and the heating speed of the tube furnace is 1-10 ℃/min.
Further, in the step S4, the concentration of the dilute hydrochloric acid is 1-6 mol/L.
The invention has the beneficial effects that:
the honeycomb nitrogen-doped porous carbon material is prepared by using a one-step carbonization method, and compared with a method requiring secondary carbonization after potassium hydroxide activation, the honeycomb nitrogen-doped porous carbon material is simpler, more convenient and energy-saving, saves cost and is more environment-friendly. The experimental raw materials are low in price and easy to obtain, and the preparation of the material has long-term property. The raw material is hard carbon, and has large capacity and long service life. The pure nitrogen-doped carbon material is obtained after the impurities are removed by acid washing, and the pore structure is further enriched, so that the porous carbon material with the hierarchical pore structure is formed. The nitrogen-doped porous carbon material is applied as a sodium-electricity negative electrode, and the presence of more mesopores and macropores is beneficial to improving the effective surface area and has obvious effect on improving the rate performance. And the large holes and the mesopores are more, the influence on the volume change of intercalation and deintercalation of sodium ions is small, the stability is improved, and the method has important application significance in the battery electrode material technology, especially in the field of sodium ion batteries.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is an X-ray diffraction pattern of a material prepared in example 1 of the present invention.
Fig. 2 is a scanning electron microscope image of a honeycomb nitrogen-doped porous carbon material prepared in example 1 of the present invention.
Fig. 3 is a transmission electron microscope image of the honeycomb nitrogen-doped porous carbon material prepared in example 1 of the present invention.
Fig. 4 is a high-magnification transmission electron microscope image of the honeycomb nitrogen-doped porous carbon material prepared in example 1 of the present invention.
Fig. 5 shows the rate performance of the sodium ion batteries prepared in examples 1-4 of the present invention at different current densities. (Current Density Unit: A/g)
Fig. 6 shows the cycling performance of the sodium ion batteries prepared in examples 1-4 of the present invention after multiple charge and discharge cycles.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
S1, dissolving 0.2g of glucose, 0.2g of PVP and 0.8g of sodium bicarbonate in 20mL of water, and freezing the solution by using liquid nitrogen;
s2, putting the material frozen by liquid nitrogen in the step S1 into a freeze dryer, freeze drying at-60 ℃ for 48 hours, and taking out to obtain a freeze-dried precursor;
s3, introducing nitrogen into the tube furnace as protective gas, adding the freeze-dried precursor for carbonization, wherein the carbonization temperature is 700 ℃, the carbonization time is 2 hours, and naturally cooling the furnace body to room temperature after carbonization, so as to obtain carbonized materials;
s4, soaking the carbonized material in dilute hydrochloric acid (the concentration is 1 mol/L) until the PH is 7, and washing with deionized water to obtain a washed material;
s5, placing the material washed in the step S4 into a vacuum drying oven, and drying at 60 ℃ for 8 hours to obtain the honeycomb nitrogen-doped porous carbon material.
Example 2
S1, dissolving 0.2g of fructose, 0.2g of PVP and 0.4g of sodium carbonate in 20mL of water, and freezing the solution by using liquid nitrogen;
s2, putting the material frozen by liquid nitrogen in the step S1 into a freeze dryer, freeze drying at-30 ℃ for 48 hours, and taking out to obtain a freeze-dried precursor;
s3, introducing nitrogen into the tube furnace as protective gas, adding the freeze-dried precursor for carbonization, wherein the carbonization temperature is 700 ℃, carbonizing for 2 hours, and naturally cooling the furnace body to room temperature to obtain carbonized materials;
s4, soaking the carbonized material in dilute hydrochloric acid (the concentration is 3 mol/L) until the PH is 7, and washing with deionized water to obtain a washed material;
s5, placing the material washed in the step S4 into a vacuum drying oven, and drying at 60 ℃ for 8 hours to obtain the honeycomb nitrogen-doped porous carbon material.
Example 3
S1, dissolving 0.2g of sucrose, 0.2g of PVP and 0.6g of potassium carbonate in 20mL of water, and freezing the solution by using liquid nitrogen;
s2, putting the material frozen by liquid nitrogen in the step S1 into a freeze dryer, freeze drying at-20 ℃ for 48 hours, and taking out to obtain a freeze-dried precursor;
s3, introducing argon into a tube furnace as a protective gas, adding a freeze-dried precursor for carbonization, wherein the carbonization temperature is 900 ℃, carbonizing for 3 hours, and naturally cooling the furnace body to room temperature to obtain a carbonized material;
s4, soaking the carbonized material in dilute hydrochloric acid (the concentration is 5 mol/L) until the PH is 7, and washing with deionized water to obtain a washed material;
s5, placing the material washed in the step S4 into a vacuum drying oven, and drying at 60 ℃ for 8 hours to obtain the honeycomb nitrogen-doped porous carbon material.
Example 4
S1, dissolving 0.2g of starch, 0.2g of PVP and 1g of potassium bicarbonate in 20mL of water, and freezing the solution by using liquid nitrogen;
s2, putting the material frozen by liquid nitrogen in the step S1 into a freeze dryer, freeze drying at-80 ℃ for 48 hours, and taking out to obtain a freeze-dried precursor;
s3, introducing argon into a tube furnace as a protective gas, adding a freeze-dried precursor for carbonization, wherein the carbonization temperature is 1000 ℃, carbonizing for 2 hours, and naturally cooling the furnace body to room temperature to obtain a carbonized material;
s4, soaking the carbonized material in dilute hydrochloric acid (the concentration is 6 mol/L) until the PH is 7, and washing with deionized water to obtain a washed material;
s5, placing the material washed in the step S4 into a vacuum drying oven, and drying at 60 ℃ for 8 hours to obtain the honeycomb nitrogen-doped porous carbon material.
The lattice spacing, total specific surface area, total pore volume, and average pore diameter of the honeycomb nitrogen-doped porous carbon materials prepared in examples 1 to 4 were measured as shown in table 1:
TABLE 1
As can be seen from Table 1, in examples 1 to 4, the amount of the activator used has a larger effect on the total specific surface area and the total pore volume, and the more the amount of the activator used, the larger the total specific surface area and the total pore volume, which can effectively enhance the adsorption-intercalation ability of the carbon material, and the carbonization condition has less effect on the honeycomb nitrogen-doped porous carbon material.
The properties of the honeycomb nitrogen-doped porous carbon material produced in example 1 are described below with reference to the accompanying drawings:
fig. 1 is an XRD pattern of example 1, from which it can be seen that there are two bulges at 24 ° and 43 °, corresponding to (002) and (100) crystal planes, respectively, indicating that the impurity-free carbon material was successfully prepared.
Fig. 2 is an SEM image of example 1, from which it can be seen that the material is lamellar, with a uniform pore structure on the surface.
Fig. 3 is a TEM image of example 1, and it can be seen that the honeycomb nitrogen-doped porous carbon material is composed of a sheet having an interconnected pore structure, and the pores are very developed as in the result of fig. 2.
Fig. 4 is an HRTEM image of example 1, where the lattice spacing of the cellular nitrogen-doped porous carbon material was measured to be 0.403nm, and the material had a larger lattice spacing, so that sodium ions received less resistance during diffusion, which is significant for the increase of energy storage density.
Taking the honeycomb nitrogen-doped porous carbon materials prepared in the examples 1-4 as the negative electrode of a sodium ion battery respectively, mixing the honeycomb nitrogen-doped porous carbon materials, carbon black and polyvinylidene fluoride in a mass ratio of 8:1:1, adding deionized water and N-methylpyrrolidone, grinding in a mortar to prepare uniform slurry, coating the uniform slurry on copper foil, drying in a vacuum drying oven at 60 ℃, cutting the pole piece into a wafer with the diameter of 12mm, taking the wafer as the negative electrode of the sodium ion battery, taking the sodium piece as the positive electrode of the sodium ion battery, and carrying out the assembly of the battery in a glove box filled with argon (the moisture content is lower than 0.01ppm, and the oxygen content is lower than 0.01 ppm); naPF with electrolyte of 1mol/L 6 Dissolved in dimethyl carbonate/ethylene carbonate (DMC: ec=1:1 vol), additive is 5% fluoroethylene carbonate.
The performance of the sodium ion batteries prepared in examples 1-4 is described below with reference to the accompanying drawings:
fig. 5 shows the rate performance of examples 1-4, and it can be seen from the graph that example 1 has the highest capacity, the specific capacitance at 0.1A/g is 271mAh/g, and the current density at 5A/g is 171mAh/g, indicating that it has good rate performance.
FIG. 6 shows the cycling performance of examples 1-4 at a current density of 0.1A/g, with example 1 having the highest capacity and stable performance after seven hundred charge and discharge cycles.
As can be seen from Table 1 and FIGS. 1 to 6, the prepared cellular nitrogen-doped porous carbon material has no impurity, has large sodium capacity, small specific surface area, large lattice spacing, good rate capability and strong stability, and has important application significance in the technical field of sodium ion batteries.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (10)
1. A cellular nitrogen-doped porous carbon material, characterized by being prepared by the steps of:
s1, dissolving a carbon source, a nitrogen source and an activator in water, and freezing the solution by using liquid nitrogen;
s2, putting the material frozen by liquid nitrogen in the step S1 into a freeze dryer, and freeze-drying to obtain a freeze-dried precursor;
s3, introducing inert gas serving as protective gas into the tubular furnace, adding the freeze-dried precursor for carbonization, and naturally cooling the furnace body to room temperature after carbonization to obtain carbonized materials;
s4, soaking the carbonized material in dilute hydrochloric acid until the PH value is 7, and washing with deionized water to obtain a washed material;
s5, placing the material washed in the step S4 into a vacuum drying oven, and drying at 60 ℃ for 8 hours to obtain the honeycomb nitrogen-doped porous carbon material.
2. The cellular nitrogen-doped porous carbon material according to claim 1, wherein the mass ratio of the carbon source, the nitrogen source and the activator in step S1 is 1:1:2-5.
3. The cellular nitrogen-doped porous carbon material of claim 1, wherein the carbon source in step S1 is one of glucose, fructose, sucrose, and starch.
4. The cellular nitrogen-doped porous carbon material of claim 1, wherein the nitrogen source in step S1 is PVP.
5. The cellular nitrogen-doped porous carbon material of claim 1, wherein the activator in step S1 is one of sodium bicarbonate, sodium carbonate, potassium bicarbonate.
6. The cellular nitrogen-doped porous carbon material according to claim 1, wherein the temperature of freeze-drying in step S2 is-80-0 ℃ for 24-48 hours.
7. The cellular nitrogen-doped porous carbon material of claim 1, wherein the inert gas in step S3 is one of nitrogen and argon.
8. The honeycomb nitrogen-doped porous carbon material according to claim 1, wherein the carbonization temperature in the step S3 is 700-1000 ℃, the carbonization time is 1-3 h, and the heating rate of the tube furnace is 1-10 ℃/min.
9. The cellular nitrogen-doped porous carbon material according to claim 1, wherein the concentration of the dilute hydrochloric acid in the step S4 is 1-6 mol/L.
10. A honeycomb nitrogen-doped porous carbon material, which is characterized by being applied to a negative electrode of a sodium ion battery.
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| CN107331867A (en) * | 2017-07-05 | 2017-11-07 | 中国矿业大学 | Nitrogen-doped porous carbon material preparation method as sodium-ion battery negative pole |
| CN110127696A (en) * | 2019-06-11 | 2019-08-16 | 吉林化工学院 | A kind of preparation method and applications of biomass-based nitrogen-doped porous carbon material |
| CN110155980A (en) * | 2019-05-20 | 2019-08-23 | 北京化工大学 | A kind of preparation method of the three-dimensional porous carbon material of honeycomb |
| CN110642238A (en) * | 2019-10-16 | 2020-01-03 | 河北省科学院能源研究所 | Graphene-like nitrogen-doped porous carbon material and preparation method and application thereof |
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| CN107331867A (en) * | 2017-07-05 | 2017-11-07 | 中国矿业大学 | Nitrogen-doped porous carbon material preparation method as sodium-ion battery negative pole |
| CN110155980A (en) * | 2019-05-20 | 2019-08-23 | 北京化工大学 | A kind of preparation method of the three-dimensional porous carbon material of honeycomb |
| CN110127696A (en) * | 2019-06-11 | 2019-08-16 | 吉林化工学院 | A kind of preparation method and applications of biomass-based nitrogen-doped porous carbon material |
| CN110642238A (en) * | 2019-10-16 | 2020-01-03 | 河北省科学院能源研究所 | Graphene-like nitrogen-doped porous carbon material and preparation method and application thereof |
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