CN113205964A - ZIF-67@ LDHs electrode material applied to supercapacitor and preparation method thereof - Google Patents
ZIF-67@ LDHs electrode material applied to supercapacitor and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 55
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000463 material Substances 0.000 claims abstract description 32
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
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- 238000004090 dissolution Methods 0.000 claims abstract description 10
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 10
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 18
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 18
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 12
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- 238000010438 heat treatment Methods 0.000 claims description 5
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
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- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention discloses a ZIF-67@ LDHs electrode material applied to a super capacitor and a preparation method thereof. Comprises mixing trivalent metal ions M3+Divalent metal ion M2+Adding into deionized water, ultrasonic dissolving, and adding urea and ammonium fluoride (NH)4F) Before stirring is obtainedMoving the precursor solution into a high-pressure reaction kettle, then reacting at 120-140 ℃, cooling, then carrying out ultrasonic treatment, filtering, washing with deionized water, then adding into deionized water again, carrying out ultrasonic treatment, filtering, and drying to obtain the LDHs material; adding an LDHs material into a methanol solution, performing ultrasonic treatment for 40-60 min to obtain a mixed solution I, adding 2-methylimidazole into the methanol solution, performing ultrasonic dissolution to obtain a solution II, adding the solution II into the mixed solution I, performing magnetic stirring for 5-8 h, centrifuging, filtering, and washing with methanol and deionized water respectively to obtain the ZIF-67@ LDHs material.
Description
Technical Field
The invention belongs to the technical field of electrode materials of supercapacitors, and particularly relates to a ZIF-67@ LDHs electrode material applied to a supercapacitor and a preparation method thereof.
Background
In recent years, two-dimensional layered materials have attracted attention due to their novel physicochemical properties, and applications of such materials in the fields of electricity, light, catalysis, and the like have been reported on the basis of their specific structural characteristics. In the typical field of electronics, the geometric shape of a two-dimensional material is more operable, and is more directly compatible with device design and operation processing in the semiconductor industry, which can overcome the limitations of one-dimensional structures with essentially different diameters, different lengths, and even different electronic properties.
Layered double hydroxides (referred to as LDHs) are typical representatives of this class of materials, and the chemical formula of these materials can be expressed as: m2+ 1-xM3+ x(OH)2An- x/n·mH2O, wherein M2+＝Mg2+，Fe2+，Co2+，Ni2+，Zn2+Etc.; m3+＝Al3+，Fe3+，Co3+Etc.; a. then-＝CO3 2-，NO3-，Cl-，ClO4-And other functional organic anions. The structural formula shows that the material has wide adjustable denaturation, such as lamella metal cation type, M2+/M3+The ratio of (a) to (b), the type and proportion of interlayer guest anions, and the like.
Super capacitor is as a new energy storage device, is stronger than the battery in power density, simultaneously, has higher energy density than traditional condenser. The composition and structure of the electrode material are key factors in determining the performance of the supercapacitor. The LDHs become one of the widely researched pseudocapacitance materials due to the high theoretical specific capacitance, low cost and adjustable interlayer structure of the LDHs, and particularly, the stripped LDHs nanosheet can generate more active sites, so that the LDHs further receives attention. However, the LDHs as the electrode material of the super capacitor has a certain poor conductivity, the theoretical specific capacitance is difficult to be fully exerted, and the stripped single-layer LDHs nanosheet is easy to stack, so that the electrochemical performance of the LDHs is affected.
Disclosure of Invention
Aiming at the defects that LDHs serving as electrode materials of a super capacitor in the prior art have certain poor conductivity, the theoretical specific capacitance of the electrode materials is difficult to give full play, and stripped single-layer LDHs nanosheets are easy to stack, the invention aims to provide the ZIF-67@ LDHs electrode material applied to the super capacitor, wherein the electrode material has a core-shell structure, the core structure is a metal organic framework material ZIF-67, and the shell structure is layered double-metal hydroxide LDHs.
Further, the shell structure in the electrode material is layered double hydroxide CoAl-LDHs.
The invention also aims to provide a preparation method of the ZIF-67@ LDHs electrode material applied to the super capacitor, which comprises the following steps:
s1: adding trivalent metal ions M3+Divalent metal ion M2+Adding into deionized water, ultrasonic dissolving, and adding urea and ammonium fluoride (NH)4F) Stirring at room temperature for 30-50 min to obtain precursor solution containing urea and ammonium fluoride (NH)4F) The molar ratio of (1.22-2.4) to (0.69-1.32).
S2: and (3) moving the precursor solution into a high-pressure reaction kettle, then reacting for 6.5-10 h at 120-140 ℃, cooling, then carrying out ultrasonic treatment for 10-20 min, filtering, washing with deionized water, then adding into ethylene glycol dimethyl ether again, carrying out ultrasonic treatment for 30-45 min, and then filtering, and drying at 65-80 ℃ to obtain the LDHs material.
S3: adding the LDHs material obtained in the step S2 into a methanol solution, adding cobalt nitrate, performing ultrasonic treatment for 40-60 min, adding polyethylene glycol, stirring to obtain a mixed solution I, adding 2-methylimidazole into the methanol solution, performing ultrasonic dissolution to obtain a solution II, dropwise adding the solution II into the magnetically stirred mixed solution I, heating to 40-60 ℃ while dropwise adding, keeping the temperature, continuing to perform magnetic stirring, keeping the temperature and standing for 18-36 h after dropwise adding is completed, centrifuging, and washing with methanol and deionized water respectively to obtain the ZIF-67@ LDHs material.
Preferably, the trivalent metal ion M is3+Is Al3+Divalent metal ion M2+Is Co2+。
Preferably, M is as defined above3+、M2+The molar ratio of urea to urea is (0.55-1.15): 0.69-1.25): 1.
Preferably, the molar ratio of the cobalt nitrate to the 2-methylimidazole is (1-2) to (2.8-5.9).
Preferably, the concentration of the polyethylene glycol in the mixed solution I is 0.05-0.1 mol/L.
Preferably, in the step S3, when the solution II is dropwise added, the dropwise adding speed of the first half of the solution II is 4-8 mL/min, and the dropwise adding speed of the second half of the solution is 16-25 mL/min.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the ZIF-67@ LDHs electrode material, after 5000 cycles of circulation, the gas circulation stability can reach more than 97.1%, and the electrode material has excellent circulation stability, mainly because the core-shell structure of the electrode material can effectively prevent the electrode structure from collapsing in the charge-discharge circulation process, so that the electrode material has excellent circulation performance.
(2) In the prior art, the conductivity of the LDHs material is relatively low, the metal organic framework material ZIF-67 has good conductivity, and the electron transfer is limited, the ZIF-67@ LDHs electrode material with the core-shell structure is prepared by the preparation method, the specific surface area of the electrode material is increased, and meanwhile, the ion diffusion distance on the surface of the electrolyte active material ZIF-67 can be shortened by the nano sheets in the layers in the structure, and the conductivity of the electrode material is effectively improved.
(3) The preparation method disclosed by the invention is mild in reaction conditions, simple to operate, low in requirement on production equipment, and easy for large-scale mass production, adopts a non-toxic or low-toxic reagent in the production process, accords with the green development concept, modifies the LDHs material by using ethylene glycol dimethyl ether and polyethylene glycol, enables cobalt ions and the LDHs material to generate a certain complexing effect, and can well control the appearance of the electrode material by regulating the dropping speed of the dropping solution II to obtain the ZIF-67@ LDHs with the core-shell structure.
Drawings
FIG. 1 is a TEM spectrum of a ZIF-67@ LDHs electrode material prepared in example 1 of the present invention.
Detailed Description
The following embodiments of the present invention are described in detail, and the embodiments are implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, it should be noted that, for those skilled in the art, a plurality of modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Example 1
A preparation method of a ZIF-67@ LDHs electrode material applied to a super capacitor specifically comprises the following steps:
s1: mixing aluminum nitrate (Al (NO)3)3·9H2O) and cobalt nitrate (Co (NO)3)2·6H2O) is added into deionized water, ultrasonic dissolution is carried out, and then urea and ammonium fluoride (NH) are added4F) Stirring at room temperature for 30min to obtain precursor solution containing urea and ammonium fluoride (NH)4F) Is 1.22: 0.69.
S2: and (2) transferring the precursor solution into a high-pressure reaction kettle, then reacting for 6.5h at 120 ℃, cooling, then carrying out ultrasonic treatment for 10min, filtering, washing with deionized water, then adding into ethylene glycol dimethyl ether again, carrying out ultrasonic treatment for 30min, then filtering, and drying at 65 ℃ to obtain the LDHs material, wherein the molar ratio of aluminum nitrate, cobalt nitrate and urea is 0.55:0.69: 1.
S3: adding the LDHs material obtained in the step S2 into a methanol solution, adding cobalt nitrate, performing ultrasonic treatment for 40min, adding polyethylene glycol, stirring to obtain a mixed solution I, adding 2-methylimidazole into the methanol solution, performing ultrasonic dissolution to obtain a solution II, dropwise adding the solution II into the magnetically stirred mixed solution I, heating to 40 ℃ while dropwise adding, keeping the temperature, continuing to perform magnetic stirring, keeping the temperature and standing for 18h after dropwise adding is completed, centrifuging, and washing with methanol and deionized water respectively to obtain a ZIF-67@ LDHs material; wherein the molar ratio of the cobalt nitrate to the 2-methylimidazole is 1: 2.8; the concentration of the polyethylene glycol in the mixed solution I is 0.05 mol/L; when the solution II is dropwise added, the adding speed of the first half of the solution II is 4mL/min, and the adding speed of the second half of the solution is 16 mL/min.
Example 2
A preparation method of a ZIF-67@ LDHs electrode material applied to a super capacitor specifically comprises the following steps:
s1: mixing aluminum nitrate (Al (NO)3)3·9H2O) and cobalt nitrate (Co (NO)3)2·6H2O) is added into deionized water, ultrasonic dissolution is carried out, and then urea and ammonium fluoride (NH) are added4F) Stirring at room temperature for 50min to obtain precursor solution containing urea and ammonium fluoride (NH)4F) Is 2.4: 1.32.
S2: and (2) transferring the precursor solution into a high-pressure reaction kettle, then reacting for 10h at 140 ℃, cooling, then carrying out ultrasonic treatment for 20min, filtering, washing with deionized water, then adding into ethylene glycol dimethyl ether again, carrying out ultrasonic treatment for 45min, then filtering, and drying at 80 ℃ to obtain the LDHs material, wherein the molar ratio of aluminum nitrate to cobalt nitrate to urea is 1.15:1.25: 1.
S3: adding the LDHs material obtained in the step S2 into a methanol solution, adding cobalt nitrate, performing ultrasonic treatment for 60min, adding polyethylene glycol, stirring to obtain a mixed solution I, adding 2-methylimidazole into the methanol solution, performing ultrasonic dissolution to obtain a solution II, dropwise adding the solution II into the magnetically stirred mixed solution I, heating to 60 ℃ while dropwise adding, keeping the temperature, continuing to perform magnetic stirring, keeping the temperature and standing for 36h after dropwise adding is completed, centrifuging, and respectively washing with methanol and deionized water to obtain a ZIF-67@ LDHs material; wherein the molar ratio of the cobalt nitrate to the 2-methylimidazole is 2: 5.9; the concentration of the polyethylene glycol in the mixed solution I is 0.1 mol/L; when the solution II is dropwise added, the adding speed of the first half of the solution II is 8mL/min, and the adding speed of the second half of the solution is 25 mL/min.
Example 3
A preparation method of a ZIF-67@ LDHs electrode material applied to a super capacitor specifically comprises the following steps:
s1: mixing aluminum nitrate (Al (NO)3)3·9H2O) and cobalt nitrate (Co (NO)3)2·6H2O) is added into deionized water, ultrasonic dissolution is carried out, and then urea and ammonium fluoride (NH) are added4F) Stirring at room temperature for 40min to obtain precursor solution containing urea and ammonium fluoride (NH)4F) Is 1.96: 1.21.
S2: and (2) transferring the precursor solution into a high-pressure reaction kettle, then reacting for 8h at 130 ℃, cooling, then carrying out ultrasonic treatment for 15min, filtering, washing with deionized water, then adding into ethylene glycol dimethyl ether again, carrying out ultrasonic treatment for 40min, and then filtering, and drying at 70 ℃ to obtain the LDHs material, wherein the molar ratio of aluminum nitrate to cobalt nitrate to urea is 0.94:1.13: 1.
S3: adding the LDHs material obtained in the step S2 into a methanol solution, adding cobalt nitrate, performing ultrasonic treatment for 50min, adding polyethylene glycol, stirring to obtain a mixed solution I, adding 2-methylimidazole into the methanol solution, performing ultrasonic dissolution to obtain a solution II, dropwise adding the solution II into the magnetically stirred mixed solution I, heating to 50 ℃ while dropwise adding, keeping the temperature, continuing to perform magnetic stirring, keeping the temperature and standing for 28h after dropwise adding is completed, centrifuging, and respectively washing with methanol and deionized water to obtain a ZIF-67@ LDHs material; wherein the molar ratio of the cobalt nitrate to the 2-methylimidazole is 1.6: 3.9; the concentration of the polyethylene glycol in the mixed solution I is 0.08 mol/L; when the solution II is dropwise added, the adding speed of the first half of the solution II is 6mL/min, and the adding speed of the second half of the solution is 21 mL/min.
Comparative example 1
S1: mixing aluminum nitrate (Al (NO)3)3·9H2O) and cobalt nitrate (Co (NO)3)2·6H2O) is added into deionized water, ultrasonic dissolution is carried out, and then urea and ammonium fluoride (NH) are added4F) Stirring at room temperature for 30min to obtain precursor solution containing urea and ammonium fluoride (NH)4F) Is 1.22: 0.69.
S2: and (2) transferring the precursor solution into a high-pressure reaction kettle, then reacting for 6.5h at 120 ℃, cooling, then carrying out ultrasonic treatment for 10min, filtering, washing with deionized water, then adding into deionized water again, carrying out ultrasonic treatment for 30min, and then filtering, and drying at 65 ℃ to obtain the LDHs material, wherein the molar ratio of aluminum nitrate to cobalt nitrate is 0.55: 0.96.
Examples of the experiments
And (3) performance testing: the ZIF-67@ LDHs electrode material prepared in examples 1-3 and the electrode material prepared in comparative example 1 are used as the positive electrode of a super capacitor, 2mol/L KOH solution is used as electrolyte to assemble the super capacitor, wherein activated carbon, acetylene black and PVDF are mixed and ground according to the proportion of 80:10:10 and then coated on foamed nickel, and the mixture is dried at 80 ℃ to obtain a negative electrode material, and the specific capacity, rate capability and cycle performance of the electrode material are tested through constant current charge and discharge; the electrochemical test is a three-electrode system, and the charge transfer resistance R of the electrochemical test is tested by using an electrochemical workstation to perform cyclic voltammetry in 2mol/L KOH electrolyte at room temperaturectThe results are shown in table 1, wherein the ZIF-67@ LDHs electrode materials prepared in examples 1 to 3 and the electrode material in comparative example 1 are working electrodes, Hg/HgO is a reference electrode, Pt is an auxiliary electrode, and the test frequency is 100kHz to 0.01Hz, and the cycle stability is calculated by using the following formula:
table 1. test results:
from the table 1 above, it can be seen that the specific capacities of the electrode materials prepared in examples 1 to 3 are all above 1858F/g under the current density of 1A/g, compared with the electrode material prepared in comparative example 1, which has a higher specific capacity, the cycling stability of the electrode materials prepared in examples 1 to 3 after 5000 cycles is above 97% under the current density of 10A/g, and the cycling stability of the electrode material prepared in comparative example 1 only reaches 55.4%, which indicates that the electrode material of the present invention has more excellent conductivity and cycling stability.
Claims (8)
1. The ZIF-67@ LDHs electrode material is characterized by having a core-shell structure, wherein the core structure is a metal organic framework material ZIF-67, and the shell structure is a layered double hydroxide LDHs.
2. The ZIF-67@ LDHs electrode material applied to the supercapacitor according to claim 1, wherein the shell structure in the electrode material is layered double hydroxide CoAl-LDHs.
3. The preparation method of the ZIF-67@ LDHs electrode material applied to the supercapacitor according to claim 1, wherein the preparation method comprises the following steps:
s1: adding trivalent metal ions M3+Divalent metal ion M2+Adding into deionized water, ultrasonic dissolving, and adding urea and ammonium fluoride (NH)4F) Stirring at room temperature for 30-50 min to obtain precursor solution containing urea and ammonium fluoride (NH)4F) The molar ratio of (1.22-2.4) to (0.69-1.32);
s2: transferring the precursor solution into a high-pressure reaction kettle, then reacting for 6.5-10 h at 120-140 ℃, cooling, then carrying out ultrasonic treatment for 10-20 min, filtering, washing with deionized water, then adding into ethylene glycol dimethyl ether again, carrying out ultrasonic treatment for 30-45 min, and then filtering, and drying at 65-80 ℃ to obtain the LDHs material;
s3: adding the LDHs material obtained in the step S2 into a methanol solution, adding cobalt nitrate, performing ultrasonic treatment for 40-60 min, adding polyethylene glycol, stirring to obtain a mixed solution I, adding 2-methylimidazole into the methanol solution, performing ultrasonic dissolution to obtain a solution II, dropwise adding the solution II into the magnetically stirred mixed solution I, heating to 40-60 ℃ while dropwise adding, keeping the temperature, continuing to perform magnetic stirring, keeping the temperature and standing for 18-36 h after dropwise adding is completed, centrifuging, and washing with methanol and deionized water respectively to obtain the ZIF-67@ LDHs material.
4. The preparation method of the ZIF-67@ LDHs electrode material applied to the supercapacitor according to claim 3, wherein the trivalent metal ion M is3+Is Al3+Divalent metal ion M2+Is Co2+。
5. The preparation method of the ZIF-67@ LDHs electrode material applied to the supercapacitor according to claim 3, wherein M is3+、M2+The molar ratio of urea to urea is (0.55-1.15): 0.69-1.25): 1.
6. The preparation method of the ZIF-67@ LDHs electrode material applied to the supercapacitor according to claim 3, wherein the molar ratio of the cobalt nitrate to the 2-methylimidazole is (1-2): 2.8-5.9.
7. The preparation method of the ZIF-67@ LDHs electrode material applied to the supercapacitor according to claim 3, wherein the concentration of the polyethylene glycol in the mixed solution I is 0.05-0.1 mol/L.
8. The preparation method of the ZIF-67@ LDHs electrode material applied to the supercapacitor according to claim 3, wherein in step S3, when the solution II is dropwise added, the dropwise adding speed of the first half of the solution II is 4-8 mL/min, and the dropwise adding speed of the second half of the solution II is 16-25 mL/min.
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