CN113548679A - Preparation method of nano cobalt hexacyanocobaltate/nitrogen-doped porous carbon composite material - Google Patents
Preparation method of nano cobalt hexacyanocobaltate/nitrogen-doped porous carbon composite material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 24
- 239000010941 cobalt Substances 0.000 title claims abstract description 24
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 22
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001868 cobalt Chemical class 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000003763 carbonization Methods 0.000 claims abstract description 5
- 235000018102 proteins Nutrition 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000003760 magnetic stirring Methods 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 11
- 238000004108 freeze drying Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 108010073771 Soybean Proteins Proteins 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000005018 casein Substances 0.000 claims description 5
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical group NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims description 5
- 235000021240 caseins Nutrition 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 239000008247 solid mixture Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229940001941 soy protein Drugs 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 description 10
- 239000003990 capacitor Substances 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 4
- 235000019710 soybean protein Nutrition 0.000 description 4
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- C01C3/00—Cyanogen; Compounds thereof
- C01C3/08—Simple or complex cyanides of metals
- C01C3/11—Complex cyanides
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- 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
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- 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
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Abstract
The invention discloses a preparation method of a nano cobalt hexacyanocobaltate/nitrogen-doped porous carbon composite material, which adopts biological protein with rich natural resources as a raw material, strong base solution as a medium, tris (2-hydroxyethyl) isocyanurate (THEIC) as a cyano-group providing source and cobalt salt as a raw material, and prepares nano Co by pyrolyzing a precursor mixture at a high temperature in one step3[Co(CN)6]2Compared with the traditional solution chemical compounding method, the binding force between two components in the composite material is enhanced, and the charge transfer capacity between the two components is improved, in addition, the biological protein is protein rich in nitrogen element, and forms a self-doped nitrogen-doped porous carbon material after carbonization, so that the wettability of the material in aqueous electrolyte is improved, and Co is doped with nitrogen in the aqueous electrolyte3[Co(CN)6]2The particles are nano-sized and uniformly embedded on the nitrogen-doped porous carbon with high specific surface area, and the conductivity and the reaction rate of the particles are greatly improved in the charging and discharging processes.
Description
Technical Field
The invention belongs to the technical field related to energy storage device electrode material synthesis, and particularly relates to a preparation method of a nano cobalt hexacyanocobaltate/nitrogen-doped porous carbon composite material.
Background
Due to high power density, energy density and excellent cycle service life, the super capacitor is the most promising energy storage device in the field of energy storage. The electrode material of the electric double layer super capacitor is a high specific surface area carbon material and has been widely applied, however, the limited specific surface area of the carbon material causes the energy density of the electric double layer super capacitor not to be high; the pseudo-capacitance electrode material stores and releases energy by means of reversible redox reaction with electrolyte, and shows high energy density when used as a super capacitor electrode material, typical pseudo-capacitance materials comprise transition metal oxides, sulfides, nitrides, phosphides and the like, and although the materials have high specific capacity, the materials have poor conductivity and have the problems of poor rate performance and the like caused by slow reaction speed. At present, the research focus in the field is to effectively compound a pseudocapacitance material or a battery type material and a carbon material, improve the charge transmission efficiency of the material in the charge and discharge process, and simultaneously nano-convert the size of the material to improve the density of active sites so as to improve the reaction rate.
The potassium ion hybrid super capacitors (PIHCs) take a battery type material and a capacitance type carbon material as positive and negative electrodes, and show pseudo capacitance characteristics when the reaction rate of the battery type electrode material is high. The PIHCs has low reduction potential, is green and environment-friendly, has rich potassium resource reserve in the crust, has excellent power density of a capacitor while keeping higher energy density of battery behavior, and is the first choice of large-scale electrochemical energy storage. Cobalt hexacyanocobaltate Co in recent years 3[Co(CN)6]2Is widely reported as a high-performance ionic battery electrode material, and the storage K of the high-performance ionic battery electrode material+Is high and is therefore also a desirable battery-type electrode material in PIHCs. The bottleneck of the current potassium ion hybrid capacitor is the slow reaction and poor cycle stability of the battery type electrode material, and the main solution is to compound the battery type electrode material with a carbon material with high specific surface area and conductivity and to perform nanocrystallization of the material.
The existing cobalt hexacyanocobaltate preparation technology has the following problems: preparation of Co reported in the patent literature3[Co(CN)6]2The method is mostly realized by a solution chemical method, and the composition of the carbon material and the carbon material is also realized by solution chemical synthesis. The disadvantages of these methods are: 1) the solution chemical method is adopted to compound with the carbon material, the combination capability of the two materials is weaker, the contact resistance between the two components is large, and the particle agglomeration size is not easy to control. 2) Carbon materials have poor wettability in aqueous media without being specially modified. 3) The carbonization-followed-compounding method has complicated process steps, and increases unnecessary cost of the nanocomposite. Thereby greatly limiting the application of such nanocomposites in electrochemistry.
Disclosure of Invention
The invention aims to provide a preparation method of a nano cobalt hexacyanocobaltate/nitrogen-doped porous carbon composite material, which aims to solve the problems of poor material binding capacity, poor carbon material wettability and complex process in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a nano cobalt hexacyanocobaltate/nitrogen-doped porous carbon composite material comprises the following steps:
the method comprises the following steps: weighing a proper amount of biological protein, adding the biological protein into 0.1-2.0 mol/L strong alkali aqueous solution, and stirring and dissolving until the biological protein is uniform and free of precipitate;
step two: dropwise adding a cobalt salt water solution with a certain volume and concentration into the uniform solution obtained in the first step under the conditions of magnetic stirring and heating until the water solution is uniform and has no precipitate;
step three: weighing a certain amount of THEIC, adding into the uniform aqueous solution obtained in the second step under magnetic stirring and heating conditions until the aqueous solution is uniform and has no precipitate;
step four: pre-freezing the mixture aqueous solution obtained in the third step, and freeze-drying the mixture aqueous solution in a freeze dryer to obtain a solid mixture of the biological protein, the strong base, the cobalt salt and the THEIC;
step five: placing the solid mixture in the fourth step into a tubular furnace, heating to a certain temperature in the atmosphere of nitrogen or argon, preserving the temperature for a period of time, carbonizing, naturally cooling to room temperature, and taking out a residual solid sample;
step six: grinding the residual solid sample obtained in the fifth step, soaking the ground residual solid sample in a certain volume of HCl solution for a period of time under the condition of water bath, washing the soaked residual solid sample by using deionized water and a centrifugal separation method until the solution is neutral, and then drying the washed solution in vacuum to obtain a black powdery material, namely nano Co 3[Co(CN)6]2The nitrogen is doped with the porous carbon composite material.
Preferably, the biological protein of step one is casein, soy protein and the like, preferably casein or soy protein.
Preferably, the strong alkali aqueous solution in the step one is an alkaline solution like NaOH and KOH, preferably NaOH and KOH, the concentration of the strong alkali aqueous solution is 0.5-2.0 mol/L, preferably 0.6-1.0 mol/L, and the mass ratio of the strong alkali to the bioprotein is 0.5-2.0, preferably 1.0.
Preferably, the cobalt salt in the second step is one of nitrate, sulfate, phosphate, chloride, acetate and oxalate of cobalt.
Preferably, the concentration of the aqueous solution of the cobalt salt in the second step is 10-100 mmol/L, and the mass ratio of the cobalt salt to the biological protein is 5-20.
Preferably, the mass ratio of the THEIC to the biological protein in the third step is 0.1-1.0, preferably 0.2-0.5.
Preferably, the heating temperature in the second step and the third step is 40-80 ℃.
Preferably, the freeze-drying temperature in step four is not higher than-30 ℃.
Preferably, the carbonization temperature in the fifth step is 600-900 ℃, and the heat preservation time is 1-3 h.
Preferably, the concentration of the HCl solution in the sixth step is 0.5-3.0 mol/L, and the mass ratio of HCl to strong base is 1.0-3.0; the water bath temperature is 60-80 ℃, the soaking time is not less than 6h, the vacuum drying temperature is 60-150 ℃, and the drying time is not less than 6 h.
Compared with the prior art, the invention provides a preparation method of a nano cobalt hexacyanocobaltate/nitrogen-doped porous carbon composite material, which has the following beneficial effects:
1. the invention adopts biological protein with rich natural resources as raw material, strong alkaline solution as medium, tris (2-hydroxyethyl) isocyanurate (THEIC) as cyano-group providing source and cobalt salt as raw material, and prepares nano Co by pyrolyzing precursor mixture at high temperature in one step3[Co(CN)6]2Compared with the traditional solution chemical compounding method, the binding force between two components in the composite material is enhanced, and the charge transfer capacity between the two components is improved, in addition, the biological protein is protein rich in nitrogen element, and forms a self-doped nitrogen-doped porous carbon material after carbonization, so that the wettability of the material in aqueous electrolyte is improved, and Co is doped with nitrogen in the aqueous electrolyte3[Co(CN)6]2The particles are nano-sized and uniformly embedded on the nitrogen-doped porous carbon with high specific surface area, the conductivity and the reaction rate of the particles are greatly improved in the charging and discharging processes, and the precursor bioprotein doped with the porous carbon is rich in nitrogen elements and resources;
2. the invention adopts a one-step high-temperature pyrolysis synthesis method to simplify the nanometer Co taking biological protein as a carbon precursor 3[Co(CN)6]2The preparation process of the nitrogen-doped porous carbon composite material reduces the preparation cost of the material;
3. in-situ synthesis of nano Co in high-temperature carbonization process3[Co(CN)6]2The combination between the two components is firmer, the contact resistance is reduced, and the stability of the material in electrochemical application is improved;
4. the invention shows excellent performance in the application of the potassium ion hybrid super capacitor.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention without limiting the invention in which:
FIG. 1 shows the nano Co provided by the present invention3[Co(CN)6]2A flow chart of preparation steps of the nitrogen-doped porous carbon composite material;
FIG. 2 shows the nano Co of example 13[Co(CN)6]2XRD pattern of nitrogen doped porous carbon composite material;
FIG. 3 shows the nano Co of example 23[Co(CN)6]2Scanning electron microscope images of the/nitrogen-doped porous carbon composite material;
FIG. 4 shows the nano-Co of example 3 according to the present invention3[Co(CN)6]2Cyclic voltammetry curves of nitrogen-doped porous carbon composite materials in 1M KCl solution at different scanning speeds.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A method for synthesizing a nano cobalt hexacyanocobaltate/nitrogen-doped porous carbon composite material comprises the following steps:
r (1): putting 60mL of 1.0mol/L NaOH solution into a 100mL beaker, adding 3g of casein while heating by magnetic stirring, keeping the temperature at 45 ℃, and stirring until the casein is completely dissolved;
r (2): under the conditions of magnetic stirring and 45 ℃ temperature keeping, sucking 10mL of prepared 70mmol/L Co (NO3)2 solution by a dropper, dropwise adding the solution into the solution obtained in the step R (1), and continuously stirring until the solution is uniform;
r (3): adding 0.3g of THEIC into the mixed solution in R (2), and dissolving to a uniform state (no precipitate) under magnetic stirring;
r (4): then putting the mixed solution in the uniform state into a vacuum freeze dryer, and freeze-drying for 30h at the temperature of minus 82 ℃;
r (5): putting the mixture powder obtained after freeze drying into a vacuum tube furnace, heating to 650 ℃ in the atmosphere of nitrogen, preserving heat for 2 hours, and naturally cooling to room temperature;
r (6): taking out the solid residue after pyrolysis, grinding, soaking for 12h by 30mL of 1mol/L HCl solution under the condition of 80 ℃ water bath, finally washing for 3 times by using deionized water and a centrifugal separation method, and drying for 12h under vacuum at 80 ℃ to obtain a black powdery material.
Example 2
A method for synthesizing a nano cobalt hexacyanocobaltate/nitrogen-doped porous carbon composite material comprises the following steps:
s (1): putting 60mL of 0.8mol/L KOH solution into a 100mL beaker, adding 3g of soybean protein while heating by magnetic stirring, keeping the temperature at 40 ℃, and stirring until the soybean protein is completely dissolved;
s (2): under the conditions of magnetic stirring and temperature keeping at 40 ℃, 15mL of the prepared 50mmol/L CoCl2 solution is sucked by a dropper and added into the solution obtained in the step (1) drop by drop, and the stirring is continued until the solution is uniform;
s (3): adding 0.4g of THEIC into the mixed solution in S (2), and dissolving to a uniform state (no precipitate) under magnetic stirring;
s (4): then putting the mixed solution in the uniform state into a vacuum freeze dryer, and freeze-drying for 48 hours at the temperature of minus 55 ℃;
s (5): putting the mixture powder obtained after freeze drying into a vacuum tube furnace, heating to 600 ℃ in an argon atmosphere, preserving heat for 2 hours, and naturally cooling to room temperature;
s (6): taking out the solid residue after pyrolysis, grinding, soaking in 50mL of 1.5mol/L HCl solution at 80 ℃ for 12h, washing for 3 times by using deionized water and a centrifugal separation method, and vacuum drying at 80 ℃ for 12h to obtain a black powdery material.
Example 3
A method for synthesizing a nano cobalt hexacyanocobaltate/nitrogen-doped porous carbon composite material comprises the following steps:
t (1): putting 50mL of 1.0mol/L NaOH solution into a 100mL beaker, adding 4g of soybean protein while heating by magnetic stirring, keeping the temperature at 50 ℃, and stirring until the soybean protein is completely dissolved;
t (2): under the conditions of magnetic stirring and temperature keeping at 50 ℃, 15mL of the prepared 50mmol/L CoC2O2 solution is sucked by a dropper and added into the solution obtained in the step T (1) drop by drop, and the stirring is continued until the solution is uniform;
t (3): adding 0.6g of THEIC into the mixed solution in T (2), and dissolving to a uniform state (no precipitate) under magnetic stirring;
t (4): then putting the mixed solution in the uniform state into a vacuum freeze dryer, and freeze-drying for 48 hours at the temperature of minus 80 ℃;
t (5): putting the mixture powder obtained after freeze drying into a vacuum tube furnace, heating to 800 ℃ in the atmosphere of nitrogen, preserving heat for 2 hours, and naturally cooling to room temperature;
t (6): taking out the solid residue after pyrolysis, grinding, soaking in 50mL of 1.8mol/L HCl solution at 60 ℃ for 18h, washing for 3 times by using deionized water and a centrifugal separation method, and drying in vacuum at 90 ℃ for 20h to obtain a black powdery material.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A preparation method of a nano cobalt hexacyanocobaltate/nitrogen-doped porous carbon composite material is characterized by comprising the following steps of:
the method comprises the following steps: weighing a proper amount of biological protein, adding the biological protein into 0.1-2.0mol/L strong alkali aqueous solution, and stirring and dissolving until the biological protein is uniform and has no precipitate;
step two: dropwise adding a cobalt salt water solution with a certain volume and concentration into the uniform solution obtained in the first step under the conditions of magnetic stirring and heating until the water solution is uniform and has no precipitate;
step three: weighing a certain amount of THEIC, adding into the uniform aqueous solution obtained in the second step under magnetic stirring and heating conditions until the aqueous solution is uniform and has no precipitate;
step four: pre-freezing the mixture aqueous solution obtained in the third step, and freeze-drying the mixture aqueous solution in a freeze dryer to obtain a solid mixture of the biological protein, the strong base, the cobalt salt and the THEIC;
step five: placing the solid mixture in the fourth step into a tubular furnace, heating to a certain temperature in the atmosphere of nitrogen or argon, preserving the temperature for a period of time, carbonizing, naturally cooling to room temperature, and taking out a residual solid sample;
Step six: grinding the residual solid sample obtained in the fifth step, soaking the ground residual solid sample in a certain volume of HCl solution for a period of time under the condition of water bath, washing the soaked residual solid sample by using deionized water and a centrifugal separation method until the solution is neutral, and then drying the washed solution in vacuum to obtain a black powdery material, namely nano Co3[Co(CN)6]2The nitrogen is doped with the porous carbon composite material.
2. The preparation method of the nano cobalt hexacyanocobaltate/nitrogen-doped porous carbon composite material according to claim 1, characterized in that: the biological protein in the step one is casein or soy protein.
3. The preparation method of the nano cobalt hexacyanocobaltate/nitrogen-doped porous carbon composite material according to claim 1, characterized in that: the strong alkali aqueous solution in the first step is NaOH or KOH aqueous solution, the strong alkali aqueous solution is 0.5-2.0 mol/L, and the mass ratio of the strong alkali to the biological protein is 0.5-2.0.
4. The preparation method of the nano cobalt hexacyanocobaltate/nitrogen-doped porous carbon composite material according to claim 1, characterized in that: and the cobalt salt in the second step is one of nitrate, sulfate, phosphate, chloride, acetate and oxalate of cobalt.
5. The preparation method of the nano cobalt hexacyanocobaltate/nitrogen-doped porous carbon composite material according to claim 1, characterized in that: the concentration of the cobalt salt water solution in the second step is 10-100 mmol/L, and the mass ratio of the cobalt salt to the biological protein is 5-20.
6. The preparation method of the nano cobalt hexacyanocobaltate/nitrogen-doped porous carbon composite material according to claim 1, characterized in that: and the mass ratio of the THEIC to the biological protein in the step three is 0.1-1.0.
7. The preparation method of the nano cobalt hexacyanocobaltate/nitrogen-doped porous carbon composite material according to claim 1, characterized in that: the heating temperature in the second step and the third step is 40-80 ℃.
8. The preparation method of the nano cobalt hexacyanocobaltate/nitrogen-doped porous carbon composite material according to claim 1, characterized in that: and step four, the freeze drying temperature is not higher than-30 ℃.
9. The preparation method of the nano cobalt hexacyanocobaltate/nitrogen-doped porous carbon composite material according to claim 1, characterized in that: and fifthly, the carbonization temperature is 600-900 ℃, and the heat preservation time is 1-3 h.
10. The preparation method of the nano cobalt hexacyanocobaltate/nitrogen-doped porous carbon composite material according to claim 1, characterized in that: sixthly, the concentration of the HCl solution is 0.5-3.0 mol/L, and the mass ratio of HCl to strong base is 1.0-3.0; the water bath temperature is 60-80 ℃, the soaking time is not less than 6h, the vacuum drying temperature is 60-150 ℃, and the drying time is not less than 6 h.
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