CN117208936A - Carbon-based Co-Fe Prussian blue composite material and preparation method and application thereof - Google Patents
Carbon-based Co-Fe Prussian blue composite material and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910020598 Co Fe Inorganic materials 0.000 title claims abstract description 35
- 229910002519 Co-Fe Inorganic materials 0.000 title claims abstract description 35
- 229960003351 prussian blue Drugs 0.000 title claims abstract description 35
- 239000013225 prussian blue Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000032683 aging Effects 0.000 claims abstract description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 22
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 14
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 14
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 13
- 239000010941 cobalt Substances 0.000 claims abstract description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 12
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010000 carbonizing Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 238000001035 drying Methods 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 14
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 12
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- -1 potassium ferricyanide Chemical compound 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 239000003990 capacitor Substances 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 239000000276 potassium ferrocyanide Substances 0.000 claims description 2
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 57
- 229910052593 corundum Inorganic materials 0.000 description 9
- 239000010431 corundum Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 102100023116 Sodium/nucleoside cotransporter 1 Human genes 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 102100021541 Sodium/nucleoside cotransporter 2 Human genes 0.000 description 2
- 102100021470 Solute carrier family 28 member 3 Human genes 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a carbon-based Co-Fe Prussian blue composite material, and a preparation method and application thereof, and belongs to the field of energy materials. The preparation method of the carbon-based Co-Fe Prussian blue composite material comprises the following steps: s1, mixing a cobalt source solution and a 2-methylimidazole solution, and then aging to obtain a solid which is a precursor; s2, carbonizing the precursor to obtain a carbon carrier containing carbon nanotubes and a metal source; s3, dispersing a carbon carrier containing carbon nano tubes and a metal source in an iron source solution, adding a hydrochloric acid solution, and then aging to obtain a solid which is the carbon-based Co-Fe Prussian blue composite material. The carbon-based Co-Fe Prussian blue composite material prepared by the method has high capacity and high conductivity, and can be used in a water system sodium ion supercapacitor.
Description
Technical Field
The invention relates to the field of energy materials, in particular to a carbon-based Co-Fe Prussian blue composite material, and a preparation method and application thereof.
Background
Nowadays, renewable electric energy storage systems play an important role in consumer electronics, electric automobiles, mainly comprising two energy storage devices, a battery and a capacitor; the former provides high energy density, and the latter provides high power density, long service life, and rapid charge and discharge capability. However, the conventional electric double layer capacitor has limited its application in energy storage due to its low energy density. To overcome this problem, many pseudocapacitive materials such as metal oxides, metal sulfides, and Prussian Blue Analogues (PBAs) based on redox reactions have emerged in the prior art with high theoretical specific capacitance and high energy density. Among them, PBAs is one of the most promising candidates for energy storage materials, and has the advantages of unique open framework structure, excellent redox activity, easy synthesis, low cost, and the like.
PBAs are generally denoted as A x M 1 [M 2 (CN) 6 ]- y nH 2 O, wherein A is an alkali metal, e.g. Na or K ion, M 1 And M 2 Is a transition metal such as Fe, ni, co, cu, mn and Zn, etc., so the electrochemical properties of PBAs can be tuned by tuning the different transition metal elements. However, PBAs generally have poor conductivity, which is detrimental to charge transfer. To improve its electrochemical performance, PBAs are often composited with carbon materials, such as CNT, GO, MXene, PPy and PANI. However, how to construct a reasonable composite structure to fully exploit the advantages of two materials is a technical problem.
Disclosure of Invention
The invention provides a carbon-based Co-Fe Prussian blue composite material, a preparation method and application thereof.
The invention firstly provides a preparation method of a carbon-based Co-Fe Prussian blue composite material, which comprises the following steps:
s1, mixing a cobalt source solution and a 2-methylimidazole solution, and then aging to obtain a solid which is a precursor;
s2, carbonizing the precursor to obtain a carbon carrier containing carbon nanotubes and a metal source;
s3, dispersing a carbon carrier containing carbon nano tubes and a metal source in an iron source solution, adding a hydrochloric acid solution, and then aging to obtain a solid which is the carbon-based Co-Fe Prussian blue composite material.
In the preparation method of the carbon-based Co-Fe Prussian blue composite material, in S1, the cobalt source is cobalt nitrate and/or cobalt chloride;
the cobalt source solution and the 2-methylimidazole solution are prepared from methanol as a solvent;
in S3, the iron source solution is potassium ferricyanide solution and/or potassium ferrocyanide solution.
In the preparation method of the carbon-based Co-Fe Prussian blue composite material, in S1, the concentration of the cobalt source solution is 0.03-0.09 mol/L; specifically, the concentration of the catalyst can be 0.03mol/L, 0.06mol/L or 0.09mol/L;
the concentration of the 2-methylimidazole solution is 1-1.4 mol/L; specifically, the concentration of the catalyst can be 1mol/L, 1.2mol/L or 1.4mol/L;
the volume ratio of the cobalt source solution to the 2-methylimidazole solution is 0.5-2:1; specifically, the ratio of the raw materials can be 1:1;
s3, the concentration of the iron source solution is 0.05-0.15 mol/L; specifically, the concentration of the catalyst can be 0.05mol/L, 0.1mol/L or 0.15mol/L;
the concentration of the hydrochloric acid solution is 0.05-0.15 mol/L; specifically, the concentration of the catalyst can be 0.05mol/L, 0.1mol/L or 0.15mol/L;
the mass volume ratio of the carbon carrier containing the carbon nano tube and the metal source to the iron source solution is 100-500 mg/100 mL; specifically, the concentration of the active ingredients can be 100 mg/100 mL;
the volume ratio of the hydrochloric acid solution to the iron source solution is 0.5-2:10; specifically, the ratio of the raw materials can be 1:10.
In the preparation method of the carbon-based Co-Fe Prussian blue composite material, in S1, aging is carried out at the room temperature in a dark place; the aging time is 12-36 hours;
s2, carbonizing in an inert atmosphere; the carbonization temperature is 700-900 ℃ and the carbonization time is 1-3 h;
the inert atmosphere is nitrogen atmosphere;
s3, dropwise adding the hydrochloric acid into the dispersion liquid, wherein the dropwise adding speed is 3-7 mL/h; specifically, the concentration can be 5mL/h;
the ageing is ageing at the dark room temperature; the aging time is 12-36 h.
In the preparation method of the carbon-based Co-Fe Prussian blue composite material, in S1, mixing and stirring the cobalt source solution and the 2-methylimidazole solution, and then aging; the stirring time is 10-30 min; centrifuging after ageing to obtain solid, washing the solid and drying to obtain the precursor;
specifically, the washing is performed by methanol;
in the step S2, the step of grinding the precursor is also carried out before carbonization;
s3, centrifuging after ageing to obtain a solid, washing the solid and drying to obtain the carbon-based Co-Fe Prussian blue composite material; specifically, the washing is performed by using water;
specifically, in S1 and S3, the rotational speed of the centrifugation can be 7000-9000 r/min, and the time can be 5-9 min;
the drying temperature can be 60-90 ℃ and the drying time can be 6-18 h.
The invention also provides the carbon-based Co-Fe Prussian blue composite material prepared by the preparation method.
The application of the carbon-based Co-Fe Prussian blue composite material in preparing the cathode of the water system sodium ion supercapacitor also belongs to the protection scope of the invention.
Finally, the invention provides a cathode of a water-based sodium ion supercapacitor, which is prepared from the carbon-based Co-Fe Prussian blue composite material.
The invention further provides a preparation method of the cathode of the water system sodium ion supercapacitor, which comprises the following steps: dispersing the carbon-based Co-Fe Prussian blue composite material, conductive carbon black and polyvinylidene fluoride in an ethanol solution to form viscous slurry; and then drying the slurry, pressing the slurry on a titanium mesh through a hot press, and drying the slurry again after pressing to obtain the cathode of the water system sodium ion supercapacitor.
In the preparation method of the cathode of the water-based sodium ion supercapacitor, the mass ratio of the carbon-based Co-Fe Prussian blue composite material to the conductive carbon black to the polyvinylidene fluoride is 7-8:1-2:1;
the temperature of the drying is 60-90 ℃ and the time is 1-3 h.
The room temperature described in the present invention is well known to those skilled in the art and is generally 15 to 35 ℃.
According to the invention, PBAs nano particles are deposited on the surface of the carbon substrate, so that PBAs are uniformly and tightly embedded on the surface of the carbon substrate, and the PBAs are firmly combined. The bonding mode fully exposes the active sites of PBAs, exerts excellent conductivity of the carbon substrate and provides a high-speed channel for charge transmission. Through the series of researches, a new thought and a new method are provided for developing the high-performance PBAs electrode.
The invention has the following advantages:
(1) The Prussian blue analogue has two metal active sites, so that the theoretical storage capacity of sodium ions is larger, and the Prussian blue analogue has capacity advantages;
(2) According to the invention, the carbon material with rich carbon nano tubes is taken as a substrate, and PBAs are grown in situ by an acid leaching method, so that the PBAs are tightly combined with the carbon substrate, and the prepared composite material has the advantages of the two materials and has high capacity and high conductivity;
(3) The preparation process is simple and feasible, has low cost and potential of mass production; meanwhile, the method can be popularized to the preparation of other Prussian blue analogues, and has certain universality.
Drawings
FIG. 1 is an SEM image of Co@CNT prepared in example 1;
FIG. 2 is an SEM image of CoHCF@CNT prepared in example 1;
FIG. 3 is a cyclic voltammogram of examples 1-3 and comparative examples 1-2 over a voltage range of 0.1 to 1.1V;
FIG. 4 is a graph showing the capacity of examples 1-3 and comparative examples 1-2.
Detailed Description
The following detailed description of the invention is provided in connection with the accompanying drawings that are presented to illustrate the invention and not to limit the scope thereof.
The experimental methods in the following examples are conventional methods unless otherwise specified.
The quantitative tests in the following examples were all set up in triplicate and the results averaged.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
In the following examples and comparative examples, the solvent of the potassium ferricyanide solution used was water.
Example 1
S1, dissolving cobalt nitrate into methanol to prepare a solution A, wherein the concentration of the cobalt nitrate is 0.06mol/L; 2-methylimidazole is dissolved in methanol to prepare a solution B, wherein the concentration of the 2-methylimidazole is 1.2mol/L;
s2, putting a rotor in an empty beaker, taking 200mL of each solution A, B, slowly pouring the solutions into the beaker, stirring for 20min, and then placing the solution in a dark place for ageing for 24h at room temperature;
s3, centrifuging the turbid liquid after aging for 7min at 8000r/min to separate a purple precipitate, washing with methanol, and drying at 80 ℃ for 12h to obtain a precursor ZIF-67;
s4, fully grinding a precursor ZIF-67, then placing the ground precursor ZIF-67 in a corundum crucible, placing the corundum crucible in a tube furnace, and carbonizing for 2 hours at 800 ℃ in a nitrogen atmosphere to obtain a carbon carrier containing rich carbon nanotubes and metal sources, wherein the carbon carrier is named as Co@CNT-1;
s5, dispersing 100mg of Co@CNT in 100mL of 0.1mol/L potassium ferricyanide solution to prepare a dispersion liquid C; 10mL of a 0.1mol/L hydrochloric acid solution was slowly added dropwise to dispersion C via a microsyringe at a rate of 5mL/h with continuous stirring. After the dripping is finished, the reaction solution is placed at a light-proof place for ageing for 24 hours at room temperature;
s6, centrifuging the turbid liquid after aging for 7min at 8000r/min, washing the obtained black precipitate by deionized water, drying at 80 ℃ for 12h, and grinding to obtain the target product carbon-based Co-Fe Prussian blue composite material, and naming the target product as CoHCF@CNT-1.
As shown in FIG. 1, an SEM image of Co@CNT-1 prepared in example 1 shows that dense carbon nanotubes are grown on the surface of ZIF-67 by high temperature carbonization, resulting from the catalysis of Co at high temperature, which imparts excellent conductivity to the carbon substrate. As shown in the SEM image of CoHCF@CNT-1 shown in FIG. 2, the CoHCF is uniformly covered on the surface of the carbon substrate, and compared with the physical mixing of the CoHCF and the CNT, the in-situ growth mode ensures that the connection between the CoHCF and the CNT is more compact, thus not affecting the exposure of an active site, but solving the problem of poor conductivity of the CoHCF.
Example 2
S1, dissolving cobalt nitrate into methanol to prepare a solution A, wherein the concentration of the cobalt nitrate is 0.03mol/L; 2-methylimidazole is dissolved in methanol to prepare a solution B, wherein the concentration of the 2-methylimidazole is 1mol/L;
s2, putting a rotor in an empty beaker, taking 200mL of each solution A, B, slowly pouring the solutions into the beaker, stirring for 10min, and then placing the solution in a dark place for ageing for 24h at room temperature;
s3, centrifuging the turbid liquid after aging for 5min at 7000r/min to separate a purple precipitate, washing with methanol, and drying at 80 ℃ for 12h to obtain a precursor ZIF-67;
s4, fully grinding a precursor ZIF-67, then placing the ground precursor ZIF-67 in a corundum crucible, placing the corundum crucible in a tube furnace, and carbonizing the corundum crucible for 3 hours at 700 ℃ in a nitrogen atmosphere to obtain a carbon carrier containing rich carbon nanotubes and metal sources, wherein the carbon carrier is named Co@CNT-2;
s5, 100mg of Co@CNT is dispersed in 100mL of 0.05mol/L potassium ferricyanide solution to prepare dispersion C. 10mL of a 0.05mol/L hydrochloric acid solution was slowly added dropwise to dispersion C via a microsyringe at a rate of 5mL/h with continuous stirring. After the dripping is finished, the reaction solution is placed at a light-proof place for ageing for 24 hours at room temperature;
s6, centrifuging the turbid liquid after aging for 5min at 7000r/min, washing the obtained black precipitate by deionized water, drying at 80 ℃ for 12h, and grinding to obtain the target product carbon-based Co-Fe Prussian blue composite material, and naming the target product as CoHCF@CNT-2.
Example 3
S1, dissolving cobalt nitrate into methanol to prepare a solution A, wherein the concentration of the cobalt nitrate is 0.09mol/L; 2-methylimidazole is dissolved in methanol to prepare a solution B, wherein the concentration of the 2-methylimidazole is 1.4mol/L;
s2, putting a rotor in an empty beaker, taking 200mL of each solution A, B, slowly pouring the solutions into the beaker, stirring for 30min, and then placing the solution in a light-proof place for ageing for 24h at room temperature;
s3, centrifuging the turbid liquid after aging for 9min at 9000r/min to separate a purple precipitate, washing with methanol, and drying at 80 ℃ for 12h to obtain a precursor ZIF-67;
s4, fully grinding a precursor ZIF-67, then placing the ground precursor ZIF-67 in a corundum crucible, placing the corundum crucible in a tube furnace, and carbonizing for 1h at 900 ℃ in nitrogen atmosphere to obtain a carbon carrier containing rich carbon nanotubes and metal sources, wherein the carbon carrier is named as Co@CNT-3;
s5, 100mg of Co@CNT is dispersed in 100mL of 0.15mol/L potassium ferricyanide solution to prepare dispersion C. 10mL of a 0.15mol/L hydrochloric acid solution was slowly added dropwise to dispersion C via a microsyringe at a rate of 5mL/h with continuous stirring. After the dripping is finished, the reaction solution is placed at a light-proof place for ageing for 24 hours at room temperature;
s6, centrifuging the turbid liquid after aging for 9min at 9000r/min, washing the obtained black precipitate by deionized water, drying at 80 ℃ for 12h, and grinding to obtain the target product carbon-based Co-Fe Prussian blue composite material, and naming the target product as CoHCF@CNT-3.
Comparative example 1
S1, dissolving cobalt nitrate into methanol to prepare a solution A, wherein the concentration of the cobalt nitrate is 0.06mol/L; 2-methylimidazole is dissolved in methanol to prepare a solution B, wherein the concentration of the 2-methylimidazole is 1.2mol/L;
s2, putting a rotor in an empty beaker, taking 200mL of each solution A, B, slowly pouring the solutions into the beaker, stirring for 20min, and then placing the solution in a dark place for ageing for 24h at room temperature;
s3, centrifuging the turbid liquid after aging for 7min at 8000r/min to separate a purple precipitate, washing with methanol, and drying at 80 ℃ for 12h to obtain a precursor ZIF-67;
s4, fully grinding a precursor ZIF-67, then placing the ground precursor ZIF-67 into a corundum crucible, placing the corundum crucible into a tube furnace, and carbonizing for 2 hours at 800 ℃ in a nitrogen atmosphere to obtain a carbon carrier containing rich carbon nanotubes and metal sources, wherein the carbon carrier is named as Co@CNT-4.
Comparative example 2
S1, dissolving cobalt nitrate into deionized water to prepare a solution A, wherein the concentration of the cobalt nitrate is 0.06mol/L; dissolving potassium ferricyanide in deionized water to prepare solution B, wherein the concentration of the potassium ferricyanide is 1.2mol/L;
s2, putting a rotor in an empty beaker, taking 200mL of each solution A, B, slowly pouring the solutions into the beaker, stirring for 20min, and then placing the solution in a dark place for ageing for 24h at room temperature;
s3, centrifuging the turbid liquid after aging for 7min at 8000r/min to separate pink precipitate, washing with deionized water, and drying at 80 ℃ for 12h to obtain CoHCF.
The electrochemical test method is as follows: dispersing the prepared composite material, conductive carbon black and polyvinylidene fluoride in an ethanol solution according to a mass ratio of 8:1:1 to form viscous slurry; drying, pressing on titanium mesh by hot press, drying again to obtain working electrode, using platinum wire as counter electrode, ag/AgCl as reference electrode, and adding 1M Na 2 SO 4 The electrochemical test is carried out in the aqueous solution, and the test instrument is a Chen Hua 760D electrochemical workstation. The cyclic voltammetry test is carried out in a voltage range of 0.1-1.1V for 5mV s -1 Is performed at a scanning speed of (2). The constant current charge and discharge test is 0.1 to the maximumWithin a voltage range of 1.1V, different current densities (1, 2,3,5,10A g) -1 ) And is performed as follows.
FIGS. 3 and 4 are cyclic voltammograms of examples 1-3 and comparative examples 1-2 of the present invention at voltage ranges of 0.1 to 1.1V and specific capacities at different current densities, and it is apparent from the figures that CoHCF@CNT-1 prepared under appropriate conditions exhibits the best current response and the largest specific capacity. As can be seen from comparative examples 1-3 and comparative example 2, after compounding with CNT, the sodium storage performance of coff is significantly improved due to the improvement of conductivity, which increases the electron/ion mobility rate of coff, indicating the rationality of the composite design.
Claims (10)
1. A preparation method of a carbon-based Co-Fe Prussian blue composite material comprises the following steps:
s1, mixing a cobalt source solution and a 2-methylimidazole solution, and then aging to obtain a solid which is a precursor;
s2, carbonizing the precursor to obtain a carbon carrier containing carbon nanotubes and a metal source;
s3, dispersing a carbon carrier containing carbon nano tubes and a metal source in an iron source solution, adding a hydrochloric acid solution, and then aging to obtain a solid which is the carbon-based Co-Fe Prussian blue composite material.
2. The method for preparing the carbon-based Co-Fe Prussian blue composite material according to claim 1, wherein the method comprises the following steps: in S1, the cobalt source is cobalt nitrate and/or cobalt chloride;
the cobalt source solution and the 2-methylimidazole solution are prepared from methanol as a solvent;
in S3, the iron source solution is potassium ferricyanide solution and/or potassium ferrocyanide solution.
3. The method for preparing the carbon-based Co-Fe Prussian blue composite material according to claim 1, wherein the method comprises the following steps: in S1, the concentration of the cobalt source solution is 0.03-0.09 mol/L;
the concentration of the 2-methylimidazole solution is 1-1.4 mol/L;
the volume ratio of the cobalt source solution to the 2-methylimidazole solution is 0.5-2:1;
s3, the concentration of the iron source solution is 0.05-0.15 mol/L;
the concentration of the hydrochloric acid solution is 0.05-0.15 mol/L;
the mass volume ratio of the carbon carrier containing the carbon nano tube and the metal source to the iron source solution is 100-500 mg/100 mL;
the volume ratio of the hydrochloric acid solution to the iron source solution is 0.5-2:10.
4. The method for preparing the carbon-based Co-Fe Prussian blue composite material according to claim 1, wherein the method comprises the following steps: in the S1, the aging is aging at the dark room temperature; the aging time is 12-36 hours;
s2, carbonizing in an inert atmosphere; the carbonization temperature is 700-900 ℃ and the carbonization time is 1-3 h;
s3, dropwise adding the hydrochloric acid into the dispersion liquid, wherein the dropwise adding speed is 3-7 mL/h;
the ageing is ageing at the dark room temperature; the aging time is 12-36 h.
5. The method for preparing the carbon-based Co-Fe Prussian blue composite material according to claim 1, wherein the method comprises the following steps: s1, mixing the cobalt source solution and the 2-methylimidazole solution, stirring, and then aging; centrifuging after ageing to obtain solid, washing the solid and drying to obtain the precursor;
s2, grinding the precursor before carbonization;
and S3, centrifuging to obtain a solid after ageing, washing the solid, and drying to obtain the carbon-based Co-Fe Prussian blue composite material.
6. The carbon-based Co-Fe Prussian blue composite material prepared by the preparation method of any one of claims 1 to 5.
7. The use of the carbon-based Co-Fe Prussian blue composite material of claim 6 in preparing a cathode of a water-based sodium-ion supercapacitor.
8. A water system sodium ion super capacitor cathode, which is characterized in that; the cathode is prepared from the carbon-based Co-Fe Prussian blue composite material of claim 6.
9. The method for preparing the cathode of the aqueous sodium-ion supercapacitor of claim 8, comprising the following steps: dispersing the carbon-based Co-Fe Prussian blue composite of claim 6, conductive carbon black, and polyvinylidene fluoride in an ethanol solution to form a viscous slurry; and then drying the slurry, pressing the dried slurry on a titanium mesh through a hot press, and drying the dried slurry again to obtain the sodium ion super capacitor cathode.
10. The method for preparing the cathode of the aqueous sodium-ion supercapacitor according to claim 9, wherein the method comprises the following steps: the mass ratio of the carbon-based Co-Fe Prussian blue composite material to the conductive carbon black to the polyvinylidene fluoride is 7-8:1-2:1;
the temperature of the drying is 60-90 ℃ and the time is 1-3 h.
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| CN117486235A (en) * | 2023-12-29 | 2024-02-02 | 内蒙古默锐能源材料有限公司 | Prussian blue positive electrode material with controllable grain size, preparation method and application |
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| CN117486235B (en) * | 2023-12-29 | 2024-04-09 | 内蒙古默锐能源材料有限公司 | Prussian blue positive electrode material with controllable grain size, preparation method and application |
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