CN112299388A - Ordered microporous carbon, preparation method thereof and application thereof in sodium ion capacitor - Google Patents
Ordered microporous carbon, preparation method thereof and application thereof in sodium ion capacitor Download PDFInfo
- Publication number
- CN112299388A CN112299388A CN202010993341.9A CN202010993341A CN112299388A CN 112299388 A CN112299388 A CN 112299388A CN 202010993341 A CN202010993341 A CN 202010993341A CN 112299388 A CN112299388 A CN 112299388A
- Authority
- CN
- China
- Prior art keywords
- microporous carbon
- ordered microporous
- ordered
- nitrogen
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 90
- 239000003990 capacitor Substances 0.000 title claims abstract description 46
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 42
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000011148 porous material Substances 0.000 claims abstract description 19
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 52
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 20
- 239000002808 molecular sieve Substances 0.000 claims description 18
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000003763 carbonization Methods 0.000 claims description 14
- 239000010406 cathode material Substances 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 12
- 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 claims description 11
- 239000010405 anode material Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- 239000007773 negative electrode material Substances 0.000 claims description 9
- 238000005530 etching Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims description 6
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- 238000009830 intercalation Methods 0.000 claims description 6
- 230000002687 intercalation Effects 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 239000007772 electrode material Substances 0.000 claims description 4
- -1 ethylene, propylene, butylene, acetylene Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 239000006258 conductive agent Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000003325 tomography Methods 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 6
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 238000004146 energy storage Methods 0.000 description 12
- 229910009361 YP-50F Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 5
- 238000005087 graphitization Methods 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000003273 ketjen black Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002429 nitrogen sorption measurement Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Images
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
-
- 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
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses ordered microporous carbon, a preparation method thereof and application thereof in a sodium ion capacitor, and belongs to the technical field of electrochemistry. The invention is based on the homologous ordered microporous carbon material, and the ordered microporous carbon and the nitrogen-doped ordered microporous carbon are obtained by regulating and controlling the preparation process, have extremely high specific surface area, uniform pore size distribution, wide interlamellar spacing and a large number of active sites, and show high specific capacity and good cycle performance. The homologous ordered microporous carbon materials are respectively used as the anode and the cathode, and the sodium ion capacitor with high energy density, high power density, long cycle life and low self-discharge rate is obtained. Meanwhile, the homologous ordered microporous carbon is obtained by adopting the same synthesis process and different synthesis conditions, the process is simple, the repeatability is high, and the wide application prospect is provided for the practicability of the sodium ion capacitor.
Description
The technical field is as follows:
the invention relates to the technical field of electrochemistry, in particular to ordered microporous carbon, a preparation method thereof and application thereof in a sodium ion capacitor.
Background art:
lithium ion batteries and electrochemical capacitors are representative of high energy density and high power density energy storage devices, respectively, and are considered to be the most potential energy storage devices. The lithium ion battery has poor cycle stability and low power density due to slow bulk phase reaction and volume expansion of electrode materials; while electrochemical capacitors have high power density and cycle performance, they have low energy density due to the limitation of surface charge or reactive energy storage mechanism, and cannot be used as main energy storage devices. Therefore, a hybrid capacitor device having a higher energy density has been receiving attention from domestic and foreign researchers, and has been studied in recent years.
The disadvantages of low abundance and high price of lithium sources on earth make the wider application of lithium ion batteries and lithium ion hybrid capacitors still face great challenges. The sodium source reserves are abundant, and sodium ion hybrid capacitor comprises the negative pole of battery type and electric capacity type positive pole, has the characteristics of battery type and electric capacity type energy storage device concurrently, can have high energy density, high power density and long cycle life simultaneously, is regarded as the green energy storage device of new generation. However, the electric double-layer energy storage mechanism of the positive electrode of the sodium ion capacitor provides lower capacity, while the bulk redox reaction mechanism of the negative electrode makes the kinetics slower. Compared with a lithium ion capacitor, the dynamic problem of the sodium ion capacitor is more prominent due to the larger ionic radius of sodium ions, and the energy density and the power density of the sodium ion capacitor are required to be further improved.
The carbon material is suitable for being used as a positive electrode material and a negative electrode material of a sodium ion capacitor due to the characteristics of high conductivity, adjustable morphology and pore structure, high chemical stability, light weight, no toxicity and the like. Based on the method, the specific surface area of the carbon material is improved and ion adsorption sites are increased aiming at the electric double-layer adsorption energy storage mechanism of the anode, and a large number of pore structures and uniform pore size distribution provide favorable channels for the rapid transmission of ions and provide possibility for obtaining the anode with high specific capacity. In addition, hetero atoms introduced into the carbon material can not only act with anions in the electrolyte to provide pseudo capacitance, but also influence the charge distribution in the material to further improve the conductivity of the material and the wettability of the electrolyte. Therefore, the carbon material with high specific surface area and ordered pore structure is prepared and doped with hetero atoms, and the cathode material with excellent performance can be obtained. Aiming at an intercalation energy storage mechanism of the negative electrode carbon material, the graphitization degree is improved, the interlamellar spacing is widened, the transmission in a sodium plasma phase is facilitated, and the negative electrode material with high specific capacity and reaction kinetics can be obtained. Through the matching of the anode and the cathode, the sodium ion capacitor with high energy density, high power density, long cycle life and low self-discharge rate can be finally realized.
The invention content is as follows:
the invention aims to provide ordered microporous carbon, a preparation method thereof and application thereof in a sodium ion capacitor. The high specific surface area of the nitrogen-doped ordered microporous carbon increases the adsorption sites of ions in the electrolyte, and the doping of nitrogen elements introduces pseudocapacitance to further increase the specific capacity of the material. The relatively high graphitization degree and the increased interlayer spacing of the ordered microporous carbon are beneficial to the intercalation behavior of sodium ions, and the reaction kinetics are improved. The sodium ion capacitor has the characteristics of high energy density, high power density, long cycle life and low self-discharge rate.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing ordered microporous carbon is characterized in that: the ordered microporous carbon comprises an ordered microporous carbon cathode material and an ordered microporous carbon anode material, and the preparation method of the ordered microporous carbon comprises the preparation methods of the ordered microporous carbon cathode material and the ordered microporous carbon anode material, and specifically comprises the following steps:
the preparation of the ordered microporous carbon negative electrode material comprises the following steps (a) to (c):
(a) dipping: at room temperature, dipping a molecular sieve template into a liquid carbon source, introducing nitrogen gas flow, stirring, filtering, and heating the obtained powder in an oil bath under the nitrogen atmosphere to polymerize the carbon source;
(b) CVD method: putting a sample in a fixed bed catalytic reactor, and introducing a mixed gas of hydrocarbon and nitrogen for carbonization treatment for a period of time;
(c) etching: under an acidic condition, removing the molecular sieve template by etching to obtain the ordered microporous carbon cathode material;
the preparation process of the ordered microporous carbon cathode material comprises the steps (a), (b1) and (c), wherein in the step (b1), a nitrogen source is introduced into a fixed bed catalytic reactor to continue carbonization treatment on a sample treated by the CVD method in the step (b); etching the obtained sample in the step (c) to obtain a nitrogen-doped ordered microporous carbon material, namely the ordered microporous carbon anode material;
in the step (a), the molecular sieve is a microporous molecular sieve which is reasonably selected according to the pore structure of the required microporous carbon and is suitable for FAU (X and Y type), EMT (Electron cyclotron emission tomography) and Beta type molecular sieves; the liquid carbon source is various alcohols or esters which are liquid at normal temperature, such as one or more of furfuryl alcohol, furan, vinyl acetate and the like; the impregnation time is 10-30h, and the impregnation process can be normal pressure, reduced pressure or pressurized impregnation.
In the step (a), the oil bath heating process is as follows: firstly heating to 80-100 ℃ for 10-30h, and then heating to 120-160 ℃ for 7-9 h.
In the step (b), the hydrocarbon used in the CVD method is one of methane, ethylene, propylene, butylene, acetylene and the like; in the mixed gas of the hydrocarbon and the nitrogen, the volume concentration of the hydrocarbon is 2-7%.
In the step (b), the carbonization conditions of hydrocarbon and nitrogen gas introduced in the CVD process are as follows: the heating rate is 5-10 ℃/min, the carbonization temperature is 600-700 ℃, and the total gas flow is 100-200 ml-min-1·g-1The heat preservation time is 2-4 h.
In the step (c), the etched molecular sieve can be etched by using a mixed solution of hydrochloric acid and hydrofluoric acid, and the volume ratio of the hydrochloric acid to the hydrofluoric acid in the mixed solution is (0.5-3): 10.
in the step (b1), in the preparation process of the nitrogen-doped ordered microporous carbon, the nitrogen source can be one of acetonitrile, ammonia gas and the like, and the carbonization conditions for introducing the nitrogen source are as follows: the heating rate is 5-10 ℃/min, the carbonization temperature is 800--1·g-1The heat preservation time is 0.5-2 h.
The above-mentionedThe prepared ordered microporous carbon has ordered microporous structure with concentrated pore diameter, the pore diameter is regulated and controlled within the range of 1.2-2nm, and the specific surface area can reach 3000-2·g-1And different hetero elements can be doped according to the difference of synthesis conditions.
Respectively taking the ordered microporous carbon negative electrode material and the ordered microporous carbon positive electrode material as a negative electrode material and a positive electrode material of the sodium ion capacitor, preparing positive and negative electrodes, and assembling the positive and negative electrodes into the sodium ion capacitor; wherein:
the manufacturing process of the electrode comprises the following steps: orderly microporous carbon (a positive electrode material or a negative electrode material), a binder and a conductive agent are mixed according to the proportion of (70-90): (5-15): (5-15) preparing materials according to the mass ratio, and coating, tabletting and slicing to obtain the anode or the cathode;
assembling a sodium ion capacitor: the electrolyte comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode and the negative electrode pre-embedded with sodium are as follows (10-30): 10 into a device;
the method for obtaining the sodium pre-intercalation cathode comprises the following steps: the electrode half cell is 0.05-0.1 A.g-1And performing charge-discharge circulation within the current density and voltage range of 0.01-3V, after 5-10 circles of circulation, stopping discharge to 0.01-1V, and disassembling the battery to obtain the cathode pre-embedded with sodium. The design principle of the invention is as follows:
the positive pole of the sodium ion capacitor depends on the electric double-layer adsorption energy storage, and the negative pole of the sodium ion capacitor depends on the sodium ion intercalation behavior energy storage. Micropores in the anode are the main positions for storing charges, adsorption active sites can be increased by increasing the proportion of the micropores, pseudo-capacitance can be introduced by doping heteroatoms, and the electrolyte wettability and electronic conduction of the material can be improved, so that the specific capacity of the anode is improved. The negative electrode is in Faraday reaction, and the electrochemical performance of the negative electrode is limited by slow dynamics, so that the interlayer spacing is widened, the graphitization degree of the material is improved, and the specific capacity and the reaction dynamics of the negative electrode can be improved. By combining the analysis, the nitrogen-doped ordered microporous carbon and the ordered microporous carbon material are suitable for anode and cathode materials, and the assembled sodium ion capacitor realizes high energy density, high power density, long cycle life and low self-discharge rate.
The invention has the following advantages and beneficial effects:
1. the ordered microporous carbon and nitrogen-doped ordered microporous carbon material prepared by the method has extremely high specific surface area, uniform pore diameter and high purity.
2. The nitrogen-doped ordered microporous carbon prepared by the method can provide a large number of ion adsorption sites and introduce pseudocapacitance, so that the nitrogen-doped ordered microporous carbon has high specific capacity and cycling stability.
3. The ordered microporous carbon prepared by the method has higher graphitization degree, widened interlayer spacing and higher specific surface area, and shows better reaction kinetics and high specific capacity.
4. The invention makes good use of the aperture characteristics of the molecular sieve and has universality for molecular sieves with different pore size specifications.
5. The anode and cathode materials are prepared by the same synthesis process, the synthesis conditions are different, the process is simple, the repeatability of different batches is high, and the production cost is greatly reduced.
Description of the drawings:
FIG. 1 is a scheme of the synthesis of Ordered Microporous Carbon (OMC) and nitrogen-doped ordered microporous carbon (N-OMC).
Fig. 2 is an X-ray diffraction pattern (XRD) of Ordered Microporous Carbon (OMC) and nitrogen-doped ordered microporous carbon (N-OMC).
FIG. 3 is a Transmission Electron Micrograph (TEM) of Ordered Microporous Carbon (OMC) and nitrogen-doped ordered microporous carbon (N-OMC) at different magnifications; wherein: (a) and (b) TEM images of OMC at different magnifications; (c) and (d) TEM images of N-OMC at different magnifications.
FIG. 4 is an X-ray energy scattering spectrum of carbon, nitrogen and oxygen elements of nitrogen-doped ordered microporous carbon (N-OMC).
FIG. 5 is a nitrogen sorption and desorption isotherm curve and pore size distribution curve for Ordered Microporous Carbon (OMC) and nitrogen-doped ordered microporous carbon (N-OMC); wherein: (a) nitrogen adsorption and desorption isothermal curve; (b) pore size distribution curve.
Fig. 6 is a Raman spectrum (Raman) of Ordered Microporous Carbon (OMC) and nitrogen-doped ordered microporous carbon (N-OMC).
FIG. 7 is a graph of electrochemical performance of nitrogen-doped ordered microporous carbon (N-OMC) electrodes; in the figure: (a) At 0.5 A.g-1A charge-discharge curve at current density; (b) at 1 A.g-1Specific capacity-cycle number of cycles and coulombic efficiency-cycle number curves for cycles at current density.
FIG. 8 is a graph of electrochemical performance of an Ordered Microporous Carbon (OMC) electrode; in the figure: (a) at 0.1 A.g-1A charge-discharge curve at current density; (b) at 1 A.g-1Specific capacity-cycle number of cycles and coulombic efficiency-cycle number curves for cycles at current density.
FIG. 9 shows cyclic voltammograms of sodium ion capacitors (OMC// N-OMC) at different scan rates.
FIG. 10 is a constant current charge and discharge curve of a sodium ion capacitor (OMC// N-OMC) at different current densities.
FIG. 11 shows sodium ion capacitors (OMC// N-OMC) at 1 A.g-1Cycling stability measured at current density.
FIG. 12 is a plot of energy-power density measured for a sodium ion capacitor (OMC// N-OMC).
FIG. 13 is a self-discharge test curve of a sodium-ion capacitor (OMC// N-OMC) versus a symmetric capacitor (YP-50F// YP-50F, XPF06// XPF 06).
The specific implementation mode is as follows:
the invention is illustrated below with reference to comparative examples and examples, but the content of the patent protection is not limited to the following examples.
Comparative example 1
The purchased activated carbon (XFNANO, XPF06), ketjen black and polytetrafluoroethylene binder were sequentially compounded, coated, tabletted, and sliced in a mass ratio of 8:1:1 (Φ ═ 10 mm). 2025 button cells were used for electrochemical performance testing of the electrode materials. Respectively taking active carbon pole pieces with the same mass and area as a positive pole and a negative pole, taking Whatman glass fiber (GF/C) as a diaphragm, and selecting 1mol/L sodium perchlorate (NaClO)4) The capacitor is assembled by dissolving the electrolyte in a mixed solvent of ethylene carbonate/acrylic carbonate (EC/PC) with a volume ratio of 1:1 and adding 5 wt% of fluoroethylene carbonate (FEC) as an additive (XPF06// XPF 06).
Comparative example 2
Mixing the obtained activated carbon (YP-50F), Ketjen black and polyThe tetrafluoroethylene adhesive is sequentially mixed, coated, tabletted and sliced (phi is 10mm) according to the mass ratio of 8:1: 1. 2025 button cells were used for electrochemical performance testing of the electrode materials. Respectively taking YP-50F pole pieces with the same mass and area as positive and negative electrodes, Whatman glass fiber (GF/C) as a diaphragm, and selecting 1mol/L sodium perchlorate (NaClO)4) The capacitor was assembled by dissolving the mixture of ethylene carbonate/acrylic carbonate (EC/PC) in a volume ratio of 1:1, and adding 5 wt% fluoroethylene carbonate (FEC) as an additive to the electrolyte solution (YP-50F// YP-50F).
Example 1
(1) NaY type molecular sieve (Zeolyst, CBV 100, 1318-02-1) was immersed in Furfuryl Alcohol (FA) at room temperature, stirred for 12h with a stream of nitrogen gas, and then filtered. The residual furfuryl alcohol on the surface of the NaY molecular sieve is washed three times by mesitylene. The powder was heated in an oil bath at 80 ℃ for 24h under nitrogen flow, and the temperature was raised to 150 ℃ for 8 h. (2) The obtained powder sample is put into a reaction tube of a fixed bed catalytic reactor for carbonization, heated to 700 ℃ at the heating rate of 5 ℃/min under the nitrogen atmosphere, and then 200 ml/min-1·g-1Introducing 2% propylene/nitrogen mixed gas at the total gas flow rate, and keeping the temperature for 4 h; then switching to nitrogen, heating to 900 ℃ at the heating rate of 5 ℃/min, and preserving heat for 3 h. (3) Removing the molecular sieve template by etching with a mixed acid solution of hydrochloric acid and hydrofluoric acid (the mixed acid solution is formed by mixing hydrochloric acid with the concentration of 36 wt.% and hydrofluoric acid with the concentration of 40 wt.% (0.5-3): 10 volume ratio), and obtaining ordered microporous carbon (marked as OMC) (shown in figure 1).
The method for doping the ordered microporous carbon with nitrogen is basically the same as that of the ordered microporous carbon, except that: in the second step, the powder is put into a reaction tube of a fixed bed catalytic reactor for carbonization, and after the powder is heated to 700 ℃ at the heating rate of 5 ℃/min under the nitrogen atmosphere, the powder is heated at 100 ml/min-1·g-1Introducing 2% propylene/nitrogen mixed gas at the total gas flow rate, and keeping the temperature for 2 h; switching to nitrogen, raising the temperature to 800 ℃ at a heating rate of 5 ℃/min, and then passing acetonitrile vapor through a bubbler along with 100 ml-min-1·g-1Introducing nitrogen gas flow into the reactor, keeping the temperature for 30min, and maintaining the temperature of the bubbling gas device at 0 ℃ through an ice bath; then in nitrogen atmosphereThe temperature of the reactor was then raised to 900 ℃ and maintained for 1 h. And finally, removing the molecular sieve template by etching treatment of a mixed acid solution of hydrochloric acid and hydrofluoric acid to obtain the nitrogen-doped ordered microporous carbon (marked as N-OMC) (shown as figure 1).
And (3) sequentially mixing, coating, tabletting and slicing the ordered microporous carbon (nitrogen-doped ordered microporous carbon), the Ketjen black and the polytetrafluoroethylene binder according to the mass ratio of 8:1:1 (phi is 10mm), so as to obtain the negative electrode pole piece and the positive electrode pole piece. Whatman glass fiber (GF/C) is used as a diaphragm, and 1mol/L sodium perchlorate (NaClO) is selected4) Dissolved in a mixed solvent of ethylene carbonate/acrylic acid carbonate (EC/PC) at a volume ratio of 1: 1. In a glove box filled with argon, sodium sheets are selected as a counter electrode and a reference electrode, and a negative electrode sheet (OMC) is assembled into a sodium half-cell at 0.1 A.g-1Circulating for 5 circles in the voltage range of 0.01-3V under the current density, and discharging to 0.1V vs. Na/Na+And cutting off to obtain the cathode pole piece pre-embedded with sodium. And assembling the positive electrode and the negative electrode into a sodium ion capacitor (OMC// N-OMC) according to the mass ratio (2.5: 1). The electrochemical test of the invention is carried out by adopting a Wuhan blue battery tester and a Bio-Logic VSP-300 electrochemical workstation.
The following are the basic characterization and performance tests on the samples prepared in the examples:
as shown in fig. 2, the OMC and N-OMC materials peaked at about 6.5 °, indicating an ordered pore structure. FIGS. 3(a) and (c) show that the OMC and N-OMC materials are similar in morphology, relative to the templated preparation; the microporous pores are clearly observed in fig. 3(b) and (d), and the graphitized regions of the OMC material are more distinct, with a lattice spacing of 0.38nm, which is greater than the conventional graphite interlayer spacing (0.34nm), indicating a wider interlayer spacing, which favors the intercalation behavior of sodium ions. Fig. 4 can observe the uniform distribution of carbon, nitrogen and oxygen elements in the N-OMC material, indicating successful doping of the nitrogen element. As shown in FIG. 5, both OMC and N-OMC materials have extremely high specific surface areas, 3421 and 2791m, respectively2·g-1N-OMC specific surface area is reduced compared to OMC materials due to nitrogen doping destroying some of the pore structure. In addition, it can be observed that both materials have a relatively uniform pore size distribution and are microporous in structure. As shown in the figureAs shown in FIG. 6, the results of Raman tests show that the OMC material has relatively high graphitization degree, which is consistent with TEM conclusions. As can be seen from FIG. 7(a), the constant current charging and discharging curve is linear in the voltage range of 2-4.3V, which shows that the N-OMC material has typical capacitance characteristics, and is 0.5 A.g-1The discharging specific capacity under current density can reach 105.4 mAh.g-1(ii) a It can be seen from fig. (b) that the material has good cycle stability, and thus, the N-OMC material exhibits excellent electrochemical properties as a positive electrode. As shown in FIG. 8, the OMC material has a current density of 0.1 A.g in the voltage range of 0.01-3V-1The specific discharge capacity can reach 434.7mAh g-1(ii) a At 1 A.g-1The specific capacity is still kept about 90% after 3000 cycles of circulation under the current density, and the material shows high specific capacity and excellent structural stability. As shown in fig. 9, the cyclic voltammetry of the sodium ion capacitor has no significant redox peak due to the different energy storage forms of the positive and negative electrodes. From fig. 10, it is observed that the constant current charge and discharge curve is triangular in shape, indicating the capacitance characteristic of the electrochemical behavior. As shown in fig. 11, the capacity retention rate of the sodium ion capacitor after 1800 cycles was 73%, indicating that the cycle performance was excellent. FIG. 12 is a graph of energy-power density of sodium ion capacitors, where the highest energy density of 119Wh kg can be observed-1The highest power density can reach 5807 W.kg-1The energy storage device exhibits high power density and high energy density. FIG. 13 is a graph of the self-discharge rate of a sodium-ion capacitor versus a symmetric capacitor (YP-50F// YP-50F, XPF06// XPF06), which shows that the sodium-ion capacitor assembled with the homogeneous microporous carbon material has a lower self-discharge rate.
Therefore, based on the above description, the present invention provides a method for preparing ordered microporous carbon, by controlling the preparation process, a homogeneous ordered microporous carbon anode and cathode material with excellent performance can be obtained, and the assembled sodium ion capacitor shows excellent electrochemical performance and has the characteristics of high energy density, high power density, long cycle stability and low self-discharge rate. The preparation method disclosed by the patent has good repeatability, is easy to regulate and control, is expected to expand production, and has a wide application prospect.
Furthermore, the above-described embodiments are merely illustrative descriptions of the present patent and are not to be construed as limitations of the present patent. Any improvements and modifications that may be made based on the principles and techniques of this patent are intended to be covered by this patent.
Claims (10)
1. A method for preparing ordered microporous carbon is characterized in that: the ordered microporous carbon comprises an ordered microporous carbon cathode material and an ordered microporous carbon anode material, and the preparation method of the ordered microporous carbon comprises the preparation methods of the ordered microporous carbon cathode material and the ordered microporous carbon anode material, and specifically comprises the following steps:
the preparation of the ordered microporous carbon negative electrode material comprises the following steps (a) to (c):
(a) dipping: at room temperature, dipping a molecular sieve template into a liquid carbon source, introducing nitrogen gas flow, stirring, filtering, and heating the obtained powder in an oil bath under the nitrogen atmosphere to polymerize the carbon source;
(b) CVD method: putting a sample in a fixed bed catalytic reactor, and introducing a mixed gas of hydrocarbon and nitrogen for carbonization treatment for a period of time;
(c) etching: under an acidic condition, removing the molecular sieve template by etching to obtain the ordered microporous carbon cathode material;
the preparation process of the ordered microporous carbon cathode material comprises the steps (a), (b1) and (c), wherein in the step (b1), a nitrogen source is introduced into a fixed bed catalytic reactor to continue carbonization treatment on a sample treated by the CVD method in the step (b); and (c) etching the obtained sample to obtain the nitrogen-doped ordered microporous carbon material, namely the ordered microporous carbon anode material.
2. The method of producing ordered microporous carbon according to claim 1, wherein: in the step (a), the molecular sieve is a microporous molecular sieve which is reasonably selected according to the pore structure of the required microporous carbon and is suitable for FAU (X and Y type), EMT (Electron cyclotron emission tomography) and Beta type molecular sieves; the liquid carbon source is various alcohols or esters which are liquid at normal temperature, such as one or more of furfuryl alcohol, furan, vinyl acetate and the like; the impregnation time is 10-30h, and the impregnation process can be normal pressure, reduced pressure or pressurized impregnation.
3. The method of producing ordered microporous carbon according to claim 1, wherein: in the step (a), the oil bath heating process is as follows: firstly heating to 80-100 ℃ for 10-30h, and then heating to 120-160 ℃ for 7-9 h.
4. The method of producing ordered microporous carbon according to claim 1, wherein: in the step (b), the hydrocarbon used in the CVD method is one of methane, ethylene, propylene, butylene, acetylene and the like; in the mixed gas of the hydrocarbon and the nitrogen, the volume concentration of the hydrocarbon is 2-7%.
5. The method of producing ordered microporous carbon according to claim 1, wherein: in the step (b), the carbonization conditions of hydrocarbon and nitrogen gas introduced in the CVD process are as follows: the heating rate is 5-10 ℃/min, the carbonization temperature is 600-700 ℃, and the total gas flow is 100-200 ml-min-1·g-1The heat preservation time is 2-4 h.
6. The method of producing ordered microporous carbon according to claim 1, wherein: in the step (c), the etched molecular sieve can be etched by using a mixed solution of hydrochloric acid and hydrofluoric acid, and the volume ratio of the hydrochloric acid to the hydrofluoric acid in the mixed solution is (0.5-3): 10.
7. the method of producing ordered microporous carbon according to claim 1, wherein: in the step (b1), in the preparation process of the nitrogen-doped ordered microporous carbon, the nitrogen source can be one of acetonitrile, ammonia gas and the like, and the carbonization conditions for introducing the nitrogen source are as follows: the heating rate is 5-10 ℃/min, the carbonization temperature is 800--1·g-1The heat preservation time is 0.5-2 h.
8. An ordered microporous carbon prepared according to the method of any one of claims 1 to 7, wherein: the ordered microporous carbon has ordered microporous structure with concentrated pore diameter, and the pore diameter is regulated and controlled within 1.2-2nm, and the ratioThe surface area can reach 3000-2·g-1And different hetero elements can be doped according to the difference of synthesis conditions.
9. Use of the ordered microporous carbon of claim 8 in a sodium ion capacitor, wherein: and respectively taking the ordered microporous carbon cathode material and the ordered microporous carbon anode material as a cathode material and an anode material of the sodium-ion capacitor.
10. Use of the ordered microporous carbon of claim 9 in a sodium ion capacitor, wherein: preparing the ordered microporous carbon negative electrode material and the ordered microporous carbon positive electrode material as active electrode materials into positive and negative electrodes, and assembling the positive and negative electrodes into a sodium ion capacitor; wherein:
the manufacturing process of the electrode comprises the following steps: orderly microporous carbon (a positive electrode material or a negative electrode material), a binder and a conductive agent are mixed according to the proportion of (70-90): (5-15): (5-15) preparing materials according to the mass ratio, and coating, tabletting and slicing to obtain the anode or the cathode;
assembling a sodium ion capacitor: the electrolyte comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode and the negative electrode pre-embedded with sodium are as follows (10-30): 10 into a device;
the method for obtaining the sodium pre-intercalation cathode comprises the following steps: the electrode half cell is 0.05-0.1 A.g-1And performing charge-discharge circulation within the current density and voltage range of 0.01-3V, after 5-10 circles of circulation, stopping discharge to 0.01-1V, and disassembling the battery to obtain the cathode pre-embedded with sodium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010993341.9A CN112299388A (en) | 2020-09-21 | 2020-09-21 | Ordered microporous carbon, preparation method thereof and application thereof in sodium ion capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010993341.9A CN112299388A (en) | 2020-09-21 | 2020-09-21 | Ordered microporous carbon, preparation method thereof and application thereof in sodium ion capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112299388A true CN112299388A (en) | 2021-02-02 |
Family
ID=74483311
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010993341.9A Pending CN112299388A (en) | 2020-09-21 | 2020-09-21 | Ordered microporous carbon, preparation method thereof and application thereof in sodium ion capacitor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112299388A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112919459A (en) * | 2021-03-18 | 2021-06-08 | 辽宁科技大学 | Method for preparing three-dimensional ordered microporous carbon at low temperature on large scale |
| CN112952037A (en) * | 2021-02-25 | 2021-06-11 | 武汉大学 | Pre-sodium-modified sodium ion battery positive electrode and pre-sodium-modification method and application thereof |
| CN114044509A (en) * | 2021-12-28 | 2022-02-15 | 中国石油大学(华东) | Preparation method of ordered microporous carbon with precise pore diameter |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002338211A (en) * | 2001-03-13 | 2002-11-27 | Inst Of Physical & Chemical Res | Thin film material of amorphous metal oxide |
| US20020187896A1 (en) * | 2001-04-30 | 2002-12-12 | Ryong Ryoo | Carbon molecular sieve and process for preparing the same |
| CN101531357A (en) * | 2008-12-29 | 2009-09-16 | 中国科学院上海硅酸盐研究所 | Method for preparing nitrogen-doped porous carbon material by two-step method and application thereof |
| CN109292749A (en) * | 2018-10-16 | 2019-02-01 | 辽宁科技大学 | A kind of porous carbon and preparation method thereof of complex ordered pore structure |
| CN109354006A (en) * | 2018-11-21 | 2019-02-19 | 温州大学 | A kind of preparation method of N doping mesoporous carbon |
| CN110335764A (en) * | 2019-07-30 | 2019-10-15 | 中南大学 | A kind of pre- sodium modification method for efficiently constructing sodium ion capacitor |
-
2020
- 2020-09-21 CN CN202010993341.9A patent/CN112299388A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002338211A (en) * | 2001-03-13 | 2002-11-27 | Inst Of Physical & Chemical Res | Thin film material of amorphous metal oxide |
| US20020187896A1 (en) * | 2001-04-30 | 2002-12-12 | Ryong Ryoo | Carbon molecular sieve and process for preparing the same |
| CN101531357A (en) * | 2008-12-29 | 2009-09-16 | 中国科学院上海硅酸盐研究所 | Method for preparing nitrogen-doped porous carbon material by two-step method and application thereof |
| CN109292749A (en) * | 2018-10-16 | 2019-02-01 | 辽宁科技大学 | A kind of porous carbon and preparation method thereof of complex ordered pore structure |
| CN109354006A (en) * | 2018-11-21 | 2019-02-19 | 温州大学 | A kind of preparation method of N doping mesoporous carbon |
| CN110335764A (en) * | 2019-07-30 | 2019-10-15 | 中南大学 | A kind of pre- sodium modification method for efficiently constructing sodium ion capacitor |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112952037A (en) * | 2021-02-25 | 2021-06-11 | 武汉大学 | Pre-sodium-modified sodium ion battery positive electrode and pre-sodium-modification method and application thereof |
| CN112919459A (en) * | 2021-03-18 | 2021-06-08 | 辽宁科技大学 | Method for preparing three-dimensional ordered microporous carbon at low temperature on large scale |
| CN114044509A (en) * | 2021-12-28 | 2022-02-15 | 中国石油大学(华东) | Preparation method of ordered microporous carbon with precise pore diameter |
| CN114044509B (en) * | 2021-12-28 | 2023-09-26 | 中国石油大学(华东) | Preparation method of ordered microporous carbon with accurate pore diameter |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | 3D uniform nitrogen-doped carbon skeleton for ultra-stable sodium metal anode | |
| Lu et al. | The effect of nitrogen and/or boron doping on the electrochemical performance of non-caking coal-derived activated carbons for use as supercapacitor electrodes | |
| CN107221654B (en) | Three-dimensional porous nest-shaped silicon-carbon composite negative electrode material and preparation method thereof | |
| CN112299388A (en) | Ordered microporous carbon, preparation method thereof and application thereof in sodium ion capacitor | |
| US10707026B2 (en) | Hydrogel derived carbon for energy storage devices | |
| Zhang et al. | Synergistic effects of B/S co-doped spongy-like hierarchically porous carbon for a high performance zinc-ion hybrid capacitor | |
| Wang et al. | Multi-forks hierarchical porous amorphous carbon with N-Doping for high-performance potassium-ion batteries | |
| Gong et al. | Anchoring high-mass iodine to nanoporous carbon with large-volume micropores and rich pyridine-N sites for high-energy-density and long-life Zn-I2 aqueous battery | |
| Quan et al. | Microporous carbon materials from bacterial cellulose for lithium− sulfur battery applications | |
| Tian et al. | Phoenix tree leaves-derived biomass carbons for sodium-ion batteries | |
| Qin et al. | Scalable synthesis of macroscopic porous carbon sheet anode for potassium-ion capacitor | |
| CN108711618A (en) | Method for improving cycle stability of lithium-sulfur battery positive electrode material | |
| CN109192532B (en) | Super capacitor electrode material and preparation method thereof | |
| Huang et al. | Microstructures and electrochemical properties of coconut shell-based hard carbons as anode materials for potassium ion batteries | |
| Tian et al. | Unveiling the role of oxygen doping in activated carbon cathode for potassium-ion capacitors | |
| Wang et al. | Rapid and Up‐Scalable Flash Fabrication of Graphitic Carbon Nanocages for Robust Potassium Storage | |
| Liu et al. | Ordered porous structure of nitrogen-self-doped carbon supporting Co3O4 nanoparticles as anode for improving cycle stability in lithium-ion batteries | |
| Chao et al. | Regulation of nitrogen configurations and content in 3D porous carbons for improved lithium storage | |
| CN112290025B (en) | Preparation method of electrode material based on carbonized kelp and lithium-sulfur battery | |
| CN112029095B (en) | Reticular polymer material for negative electrode of sodium-ion battery, preparation method of reticular polymer material and sodium-ion battery | |
| CN111313020B (en) | Preparation method of sulfur-doped nitrogen-rich carbon material, electrode and application of sulfur-doped nitrogen-rich carbon material in sodium/potassium ion battery | |
| CN114975957A (en) | Sulfur/glucose mesoporous carbon sphere lithium sulfur battery positive electrode material and preparation method thereof | |
| CN111661877B (en) | Preparation method of tungsten disulfide/carbon composite nanorod, product and application thereof | |
| Wang et al. | Sulfur-doped carbonized bacterial cellulose as a flexible binder-free 3D anode for improved sodium ion storage | |
| Dong et al. | Fabrication of Uniform Fe3O4 Nanocubes Derived from Prussian Blue and Enhanced Performance for Lithium Storage Properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210202 |
|
| RJ01 | Rejection of invention patent application after publication |