CN110957147A - Flexible electrode material, preparation method and application thereof, and supercapacitor - Google Patents
Flexible electrode material, preparation method and application thereof, and supercapacitor Download PDFInfo
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- CN110957147A CN110957147A CN201911232317.7A CN201911232317A CN110957147A CN 110957147 A CN110957147 A CN 110957147A CN 201911232317 A CN201911232317 A CN 201911232317A CN 110957147 A CN110957147 A CN 110957147A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
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- 239000002184 metal Substances 0.000 claims abstract description 56
- 150000003839 salts Chemical class 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 35
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- 239000002243 precursor Substances 0.000 claims abstract description 18
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 37
- 238000001354 calcination Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 26
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- 239000012298 atmosphere Substances 0.000 claims description 10
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- 230000035484 reaction time Effects 0.000 claims description 9
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- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 8
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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 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 7
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 7
- 229940044175 cobalt sulfate Drugs 0.000 claims description 7
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 235000002867 manganese chloride Nutrition 0.000 claims description 7
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- 235000007079 manganese sulphate Nutrition 0.000 claims description 7
- 239000011702 manganese sulphate Substances 0.000 claims description 7
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
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- 238000004519 manufacturing process Methods 0.000 claims 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
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- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000011245 gel electrolyte Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
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- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
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- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- 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
-
- 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
- H01G11/46—Metal oxides
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to the field of energy storage materials, and particularly provides a flexible electrode material, a preparation method and application thereof, and a super capacitor. The preparation method of the flexible electrode material comprises the following steps: sequentially mixing the nano sponge with aqueous solution of metal salt and OH-containing solution‑The precipitating agents are mixed and then react to obtain a precursor, and finally the precursor is calcined to obtain the flexible electrode material. The method has simple process and low time cost, can obtain the three-dimensional nitrogen-doped carbon/metal oxide composite flexible electrode material, and the obtained electrode material has good toughness and electrochemical performance.
Description
Technical Field
The invention relates to the field of energy storage materials, in particular to a flexible electrode material, a preparation method and application thereof and a super capacitor.
Background
Energy storage devices mainly include batteries and supercapacitors, and supercapacitors are favored because of their long cycle life and high power density. In recent years, the flexible wearable electronic device has the characteristics of portability, flexibility, intelligence, high efficiency and the like, and has a huge market prospect. Among a plurality of flexible wearable electronic devices, the flexible super capacitor stimulates the research enthusiasm of domestic and foreign researchers. However, most of the electrode materials at present have difficulty in meeting the requirements of flexible supercapacitors, and devices with good electrochemical performance and mechanical performance are difficult to obtain. Therefore, the exploration of a novel electrode material with ideal capacitance performance and good flexibility has important theoretical significance and practical application value.
CN109809375A discloses a method for preparing a carbon nitride three-dimensional electrode, the synthesis process of the invention needs to add an additional porous three-dimensional matrix, and the capacitance performance of the obtained electrode material is still unsatisfactory due to the limited specific capacitance of carbon nitride. CN110136982A discloses a preparation method of a polypyrrole/metal oxide/carbon material ternary composite electrode material, the method firstly synthesizes imidazole-based organic ligands, then carries out hydrothermal treatment to obtain a multi-metal MOFs/carbon material composite material, carries out high-temperature calcination to obtain a metal oxide/carbon composite material, finally disperses the obtained material into pyrrole, and obtains the ternary composite electrode material by an electrochemical polymerization deposition method, but the preparation process of the method is complicated and the time cost is high.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of a flexible electrode material, which has the advantages of simple process and low time cost, can obtain the three-dimensional nitrogen-doped carbon/metal oxide composite flexible electrode material, and has good toughness and electrochemical performance.
A second object of the present invention is to provide a flexible electrode material.
It is a third object of the present invention to provide a supercapacitor.
The fourth purpose of the invention is to provide an application of the flexible electrode material in preparing a super capacitor.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
in a first aspect, the present invention provides a method for preparing a flexible electrode material, comprising the following steps:
sequentially mixing the nano sponge with aqueous solution of metal salt and OH-containing solution-Mixing the precipitants, reacting to obtain a precursor, and finally mixingAnd calcining the precursor to obtain the flexible electrode material.
As a further preferable technical solution, the metal salt includes at least one of a nickel salt, a cobalt salt or a manganese salt;
preferably, the nickel salt comprises at least one of nickel chloride, nickel sulfate or nickel nitrate;
preferably, the cobalt salt comprises at least one of cobalt chloride, cobalt sulfate or cobalt nitrate;
preferably, the manganese salt comprises at least one of manganese chloride, manganese sulfate or manganese nitrate;
preferably, the concentration of the aqueous solution of the metal salt is 0.005 to 0.015 mol/L.
As a further preferable technical solution, the ratio of the nanosponges to the aqueous solution of the metal salt is (0.05-0.15) g: (40-60) mL;
preferably, the mixing of the nanosponges with the aqueous solution of metal salt comprises: putting the nano sponge into the aqueous solution of metal salt, and carrying out ultrasonic treatment for 25-35 min.
As a further preferred embodiment, the OH group is contained-The precipitating agent of (a) comprises an aqueous solution of an ammonia-containing reagent and optionally a viscosity increasing agent;
preferably, the aqueous solution of an ammonia-containing reagent comprises at least one of an aqueous solution of ammonium bicarbonate, an aqueous solution of ethylenediamine, or aqueous ammonia;
preferably, the viscosifier comprises an alcohol;
preferably, the dynamic viscosity of the alcohol is higher than 2mpa.s at 25 ℃;
preferably, the alcohol comprises at least one of ethylene glycol, isopropanol, glycerol, polyethylene glycol or polyvinyl alcohol;
preferably, it contains OH-The precipitant has a dynamic viscosity of 1-13 mPas at 30-80 ℃.
As a further preferable technical scheme, the nano sponge comprises an aqueous solution of nano sponge and metal salt and OH-The pH of the mixed precipitant is 9-12, preferably 10;
preferably, the OH is introduced by means of a peristaltic pump-The precipitant is added into the mixture of the nano sponge and the aqueous solution of the metal salt to realize the precipitation of the nano sponge,Aqueous solution of metal salt and OH-containing solution-Mixing the precipitant;
preferably, the discharge speed of the peristaltic pump is 0.001-1 mL/min.
As a further preferred technical solution, the reaction comprises carrying out the reaction by a solvothermal method;
preferably, the solvothermal process comprises a microwave-assisted solvothermal process;
preferably, the reaction temperature is 30-80 ℃, and the reaction time is 1-24 h;
preferably, the calcination temperature is 600-1000 ℃, and the calcination time is 0.1-10 h;
preferably, the calcination is carried out under an inert atmosphere;
preferably, the inert atmosphere is provided primarily by nitrogen and/or inert gas;
preferably, the degree of vacuum at the time of calcination is zero.
As a further preferred technical solution, the solvothermal method includes a microwave-assisted solvothermal method;
preferably, the reaction temperature is 30-80 ℃ and the reaction time is 1-24 h.
As a further preferable technical scheme, the calcination temperature is 600-1000 ℃, and the calcination time is 0.1-10 h;
preferably, the calcination is carried out under an inert atmosphere;
preferably, the inert atmosphere is provided primarily by nitrogen and/or inert gas;
preferably, the degree of vacuum at the time of calcination is zero.
In a second aspect, the invention provides a flexible electrode material prepared by the method.
In a third aspect, the invention provides a supercapacitor comprising the above flexible electrode material.
In a fourth aspect, the invention provides an application of the flexible electrode material in preparing a supercapacitor.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the flexible electrode material provided by the invention adopts nano sponge and metal saltAnd containing OH-The precipitant is used as raw material, the nano sponge is firstly mixed with the aqueous solution of metal salt to ensure that the nano sponge fully adsorbs metal cations, and then the nano sponge is mixed with OH-containing solution-The precipitant is mixed and reacted to obtain a precursor, and in the reaction process, the aqueous solution of the metal salt and the OH-containing solution-The precipitator reacts to form metal hydroxide, so that the obtained precursor is metal hydroxide/nano sponge precursor, after calcination, the nano sponge is converted into nitrogen-doped carbon material with a three-dimensional framework structure, the metal hydroxide is converted into metal oxide, and finally the three-dimensional nitrogen-doped carbon/metal oxide composite flexible electrode material is obtained.
The method has simple process and low time cost, the three-dimensional framework structure of the nano sponge can be well maintained after being calcined, and the obtained three-dimensional nitrogen-doped carbon material provides a perfect platform for uniform loading of metal oxide and overcomes the defect of easy agglomeration commonly existing in the traditional metal oxide preparation method; the obtained flexible electrode material has better mechanical property, can be combined with alkaline gel electrolyte, does not need any conductive additive and adhesive, is assembled into a flexible super capacitor, and meets the requirements of future electronic device wearability; in addition, the electrode material organically combines the carbon material with the double electric layer capacitance and the metal oxide with the pseudo capacitance, overcomes the defect of poor capacitance performance of a single carbon material or metal oxide, and has excellent electrochemical performance, so that the electrode material has good application prospect in the field of flexible energy storage devices.
Drawings
FIG. 1a is a SEM photograph of the flexible electrode material obtained in example 1;
FIG. 1b is a SEM photograph of the flexible electrode material obtained in example 2;
FIG. 1c is a SEM photograph of the flexible electrode material obtained in example 3;
fig. 2a is a scanning photograph of a scanning area of the element surface to be measured of the flexible electrode material obtained in example 1;
FIG. 2b is a scanning photograph of the distribution of the element C in the region to be measured in FIG. 2 a;
FIG. 2c is a scanning photograph of the distribution of O element in the region to be measured in FIG. 2 a;
FIG. 2d is a scanning photograph of the distribution of N elements in the region to be measured in FIG. 2 a;
FIG. 2e is a scanning photograph of the distribution of Ni element in the region to be measured in FIG. 2 a;
FIG. 3 is a constant current charge and discharge curve of a supercapacitor assembled by the flexible electrode material of example 1;
FIG. 4 is a specific capacitance graph of a supercapacitor assembled from the flexible electrode material of example 1 at different current densities;
FIG. 5 is a graph of the cycling performance of a supercapacitor assembled with the flexible electrode material of example 1;
fig. 6 is a digital photograph of a supercapacitor assembled from the flexible electrode material of example 1.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer.
According to one aspect of the present invention, there is provided a method for preparing a flexible electrode material, comprising the steps of:
sequentially mixing the nano sponge with aqueous solution of metal salt and OH-containing solution-The precipitating agents are mixed and then react to obtain a precursor, and finally the precursor is calcined to obtain the flexible electrode material.
The method adopts nano sponge, aqueous solution of metal salt and OH-containing solution-The precipitant is used as raw material, the nano sponge is firstly mixed with the aqueous solution of metal salt to ensure that the nano sponge fully adsorbs metal cations, and then the nano sponge is mixed with OH-containing solution-The precipitant is mixed and reacted to obtain a precursor, and in the reaction process, the aqueous solution of the metal salt and the OH-containing solution-The precipitant reacts to form metal hydroxide, so that the obtained precursor is metal hydroxide/nano sponge precursor, and after calcination, the nano sponge is converted into nitrogen-doped carbon material with a three-dimensional framework structureAnd converting the metal hydroxide into metal oxide to finally obtain the three-dimensional nitrogen-doped carbon/metal oxide composite flexible electrode material.
The method has simple process and low time cost, the three-dimensional framework structure of the nano sponge can be well maintained after being calcined, and the obtained three-dimensional nitrogen-doped carbon material provides a perfect platform for uniform loading of metal oxide and overcomes the defect of easy agglomeration commonly existing in the traditional metal oxide preparation method; the obtained flexible electrode material has better mechanical property, can be combined with alkaline gel electrolyte, does not need any conductive additive and adhesive, is assembled into a flexible super capacitor, and meets the requirements of future electronic device wearability; in addition, the electrode material organically combines the carbon material with the double electric layer capacitance and the metal oxide with the pseudo capacitance, overcomes the defect of poor capacitance performance of a single carbon material or metal oxide, and has excellent electrochemical performance, so that the electrode material has good application prospect in the field of flexible energy storage devices.
The nano sponge is a special open-pore structure foam body developed by adopting a novel nano technology.
In a preferred embodiment, the metal salt comprises at least one of a nickel salt, a cobalt salt, or a manganese salt. The metal salts include, but are not limited to, nickel salts, cobalt salts, manganese salts, combinations of nickel and cobalt salts, combinations of cobalt and manganese salts, combinations of nickel and manganese salts, or combinations of nickel, cobalt and manganese salts, and the like. NiO, CoO, Co3O4And MnO2The material is a typical pseudo-capacitor material and is easy to deposit on a carbon material substrate in situ, so that the difficulty in preparing the flexible electrode material can be greatly reduced by adopting nickel, cobalt or manganese salt as a raw material.
Preferably, the nickel salt includes at least one of nickel chloride, nickel sulfate, or nickel nitrate. Nickel salts include, but are not limited to, nickel chloride, nickel sulfate, nickel nitrate, a combination of nickel chloride and nickel sulfate, a combination of nickel sulfate and nickel nitrate, a combination of nickel chloride and nickel nitrate, or a combination of nickel chloride, nickel sulfate, and nickel nitrate, and the like.
Preferably, the cobalt salt comprises at least one of cobalt chloride, cobalt sulfate or cobalt nitrate. Cobalt salts include, but are not limited to, cobalt chloride, cobalt sulfate, cobalt nitrate, a combination of cobalt chloride and cobalt sulfate, a combination of cobalt sulfate and cobalt nitrate, a combination of cobalt chloride and cobalt nitrate, or a combination of cobalt chloride, cobalt sulfate, and cobalt nitrate, and the like.
Preferably, the manganese salt comprises at least one of manganese chloride, manganese sulfate or manganese nitrate. Manganese salts include, but are not limited to, manganese chloride, manganese sulfate, manganese nitrate, a combination of manganese chloride and manganese sulfate, a combination of manganese sulfate and manganese nitrate, a combination of manganese chloride and manganese nitrate, or a combination of manganese chloride, manganese sulfate and manganese nitrate, and the like.
Preferably, the concentration of the aqueous solution of the metal salt is 0.005 to 0.015 mol/L. The "concentration of the aqueous solution of the metal salt" refers to the molar concentration of the metal salt in the aqueous solution of the metal salt. Typical but non-limiting concentrations are 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.011, 0.012, 0.013, 0.014, or 0.015 mol/L. When the concentration of the aqueous solution of the metal salt is within the range, metal ions can be uniformly and properly distributed in the nano sponge, if the concentration is too low, the content of the metal ions is too low, the capacitance of the obtained electrode material is reduced, and if the concentration is too high, the content of the metal ions is too high, and the specific capacitance of the electrode material is reduced.
In a preferred embodiment, the ratio of nanosponges to aqueous solution of metal salt is (0.05-0.15) g: (40-60) mL. The above ratio is typically, but not limited to, 0.05 g: 40mL, 0.05 g: 50mL, 0.05 g: 60mL, 0.1 g: 40mL, 0.1 g: 50mL, 0.1 g: 60mL, 0.15 g: 40mL, 0.15 g: 50mL or 0.15 g: 60mL, etc. When the ratio of the nano sponge to the metal salt is within the range, the nano sponge and the aqueous solution of the metal salt can be fully mixed, the scientificity of the content of the effective components of the nano sponge and the aqueous solution of the metal salt is ensured, the flexibility of the electrode material is further enhanced, and the specific capacitance of the electrode material is improved.
Preferably, the mixing of the nanosponges with the aqueous solution of metal salt comprises: putting the nano sponge into the aqueous solution of metal salt, and carrying out ultrasonic treatment for 25-35 min. The mixing efficiency of ultrasonic mixing is higher, typically but not limited to 25, 26, 27, 28, 29, 30, 31, 32, 33, 34 or 35 min. The ultrasonic time is too short, the mixing of the nano sponge and the aqueous solution of the metal salt is relatively not uniform, and the time cost is too high if the ultrasonic time is too long.
In a preferred embodiment, the OH group is contained-The precipitating agent of (a) comprises an aqueous solution of an ammonia-containing reagent and optionally a viscosity increasing agent. The aqueous solution of the ammonia-containing reagent is alkaline and relatively weak in alkalinity, and contains OH with reasonable concentration-And the reaction with metal ions is facilitated. The tackifier is mainly used for improving the viscosity of the precipitator, and when the precipitator has certain viscosity, the precipitator has a more uniform precipitation effect, so that the formed metal hydroxide is uniformly loaded on the nano sponge matrix.
The "ammonia-containing reagent" refers to a reagent capable of generating ammonia at a certain temperature.
Preferably, the aqueous solution of an ammonia-containing reagent comprises at least one of an aqueous solution of ammonium bicarbonate, an aqueous solution of ethylenediamine or aqueous ammonia. The aqueous solution of the ammonia-containing reagent includes, but is not limited to, an aqueous solution of ammonium bicarbonate, an aqueous solution of ethylenediamine, aqueous ammonia, a combination of an aqueous solution of ammonium bicarbonate and an aqueous solution of ethylenediamine, a combination of an aqueous solution of ethylenediamine and aqueous ammonia, a combination of an aqueous solution of ammonium bicarbonate and aqueous ammonia, or a combination of an aqueous solution of ammonium bicarbonate, an aqueous solution of ethylenediamine and aqueous ammonia, and the like. The aqueous solution of ammonium bicarbonate, the aqueous solution of ethylenediamine and the ammonia water have wide sources and low prices, and are beneficial to reducing the preparation cost of the electrode material.
Preferably, the viscosifier comprises an alcohol.
Preferably, the dynamic viscosity of the alcohol is higher than 2mpa.s at 25 ℃.
Preferably, the alcohol comprises at least one of ethylene glycol, isopropanol, glycerol, polyethylene glycol or polyvinyl alcohol. Alcohols include, but are not limited to, ethylene glycol, isopropanol, glycerol, polyethylene glycol, polyvinyl alcohol, combinations of ethylene glycol and isopropanol, glycerol and polyethylene glycol, polyethylene glycol and polyvinyl alcohol, ethylene glycol, isopropanol and glycerol, or glycerol, polyethylene glycol and polyvinyl alcohol, and the like. Ethylene glycol is a sweet, viscous liquid with a viscosity of about 25.66mPa · s (16 ℃); isopropanol is a colorless transparent liquid with a viscosity of about 2.431mPa · s; the glycerol is colorless, odorless and sweet, has a clear and viscous liquid appearance and has a viscosity of about 1500mPa & s (20 ℃); polyethylene glycol is colorless odorless viscous liquid; the polyvinyl alcohol is a white flaky, flocculent or powdery solid with a viscosity of about 3-70 mPas.
Preferably, it contains OH-The precipitant has a dynamic viscosity of 1-13 mPas at 30-80 ℃. The viscosity is typically, but not limited to, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13mPa · s. Experiments prove that when the viscosity of the precipitating agent is in the range, the precipitating agent has better precipitation uniformity for metal ions.
When OH is contained, it is noted that-When the precipitating agent (C) comprises the aqueous solution of the ammonia-containing reagent and the tackifier, the ratio of the aqueous solution of the ammonia-containing reagent and the tackifier is not limited as long as the aqueous solution of the ammonia-containing reagent and the tackifier can contain OH after being mixed-The viscosity of the precipitant is 1-13 mPas.
In a preferred embodiment, the nanosponges are in aqueous solution with metal salts and contain OH-The pH of the mixture of the precipitant (2) is 9 to 12, preferably 10. The above pH is typically, but not limited to, 9, 10, 11 or 12. When the pH value is 9-12 after mixing, the metal ions and OH in the mixed system-The proportion between the two is more scientific, all metal ions can be precipitated, and waste caused by excessive precipitator is avoided.
Preferably, the OH is introduced by means of a peristaltic pump-The precipitant is added into the mixture of the nano sponge and the aqueous solution of the metal salt to realize the nano sponge, the aqueous solution of the metal salt and the aqueous solution containing OH-Mixing the precipitant. Adding OH-containing solution by using a peristaltic pump-The precipitant can improve the uniformity of the metal oxide particle loading, thereby improving the uniformity of the flexible electrode material at each position and improving the uniformity of the electrochemical performance of the flexible electrode material.
Preferably, the discharge speed of the peristaltic pump is 0.001-1 mL/min. The discharge rate of the peristaltic pump is typically, but not limited to, 0.001, 0.005, 0.01, 0.02, 0.05, 0.08, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1 mL/min. When the discharge rate is within the above range, OH is contained-The precipitant can be slowly added into the nano sponge and the metalIn a mixture of aqueous salt solutions, to contain OH-The precipitant and the aqueous solution of the pre-metal salt are mixed more uniformly, so as to be beneficial to the uniformity of the subsequent precipitation process.
Optionally, in the presence of added OH-containing compounds-When the precipitating agent is used, OH is added in a stirring way-The precipitant and the mixture of the nano sponge and the aqueous solution of the metal salt are mixed uniformly, and the stirring speed can be selected from 100-1000 rpm.
In a preferred embodiment, the reaction comprises carrying out the reaction using a solvothermal method. The solvothermal method has high reaction speed and high reaction uniformity.
Preferably, the solvothermal process comprises a microwave-assisted solvothermal process. The microwave-assisted solvothermal method is characterized in that microwaves are introduced into a reaction system on the basis of the traditional solvothermal method, and the microwaves can generate a high-frequency electromagnetic field to intensify molecular motion in a material and enable the material to generate a heat effect in a short time instead of relying on heat conduction of the material, so that the method is more uniform and faster. Compared with the traditional solvothermal method, the microwave-assisted solvothermal method has the advantages that the prepared material is more uniform, the reaction temperature can be effectively reduced, the reaction time is shortened, and the low-temperature rapid preparation is realized.
Preferably, the reaction temperature is 30-80 ℃ and the reaction time is 1-24 h. The above reaction temperature is typically, but not limited to, 30, 40, 50, 60, 70 or 80 ℃. The above reaction time is typically, but not limited to, 1, 2, 5, 8, 10, 12, 14, 16, 18, 20, 22 or 24 hours. When the reaction temperature and the reaction time are within the above ranges, the metal salt and the precipitant can sufficiently react, and the metal hydroxide is uniformly loaded on the nano sponge.
It should be understood that for the solvothermal method, the nanosponges, the aqueous solution of the metal salt and the OH-containing solution are reacted before-The precipitator is sealed in a high-pressure reaction kettle.
In a preferred embodiment, the calcination temperature is 600-1000 ℃ and the calcination time is 0.1-10 h. The above calcination temperatures are typically, but not limited to, 600, 650, 700, 750, 800, 850, 900, 950 or 1000 ℃. The above calcination times are typically, but not limited to, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 hours. It is verified that when the calcination temperature and the calcination time are within the above ranges, the nanosponges can be completely converted into the nitrogen-doped carbon material having a three-dimensional framework structure, and the metal hydroxide is also completely converted into the metal oxide and uniformly supported on the surface of the three-dimensional framework material.
Preferably, the calcination is carried out under an inert atmosphere. The calcination is carried out in the inert atmosphere, so that the oxidation of the nano sponge by oxygen in the air can be avoided, and the smooth generation of the nitrogen-doped carbon material is ensured.
Preferably, the inert atmosphere is provided primarily by nitrogen and/or inert gas. The inert gas includes at least one of helium, neon, argon, krypton, or xenon.
Preferably, the degree of vacuum at the time of calcination is zero.
Optionally, after obtaining the precursor, firstly cleaning the precursor with water and absolute ethyl alcohol, purging with nitrogen for 20 minutes, then placing the precursor in a vacuum tube furnace, pumping the precursor until the vacuum degree in the furnace is less than-0.04 MPa, then introducing nitrogen and/or inert gas to make the vacuum degree in the furnace zero, and repeating the process of vacuumizing and introducing nitrogen and/or inert gas to make the vacuum degree in the furnace zero for three times. And finally calcining the mixture in an inert atmosphere with zero vacuum degree.
According to another aspect of the invention, a flexible electrode material prepared by the method is provided. The electrode material is prepared by the method, so that the electrode material has the advantages of simple preparation, low cost, good electrochemical performance and good flexibility.
According to another aspect of the present invention, there is provided a supercapacitor comprising the above flexible electrode material. The super capacitor comprises the flexible electrode material, so that the super capacitor has at least the advantages of low cost, good electrochemical performance and good flexibility.
It should be understood that the supercapacitor core consists of the above-mentioned flexible electrode material, and the invention is not particularly limited with respect to other components or parts, for example the electrolyte may be selected from alkaline PVA gels. PVA: polyvinyl alcohol, polyvinyl alcohol.
According to another aspect of the invention, the application of the flexible electrode material in the preparation of the super capacitor is provided. The flexible electrode material is applied to the preparation of the super capacitor, so that the preparation cost of the super capacitor can be effectively reduced, and the electrochemical performance and flexibility of the capacitor are enhanced.
The present invention will be described in further detail with reference to examples and comparative examples.
Example 1
A preparation method of a flexible electrode material comprises the following steps:
weigh 1.2g NiCl on an electronic balance2·6H2And O, dissolving in 40mL of deionized water, uniformly stirring, and then carrying out ultrasonic treatment for 30 minutes. 0.05g of nano sponge is weighed and soaked in the metal salt solution, and ultrasonic adsorption is carried out for 30 minutes. Preparing a precipitant solution with the viscosity of 5 mPas, mixing ethylene glycol, ammonia water (25-28 wt% ammonia-containing aqueous solution) and water in a ratio of 6: 3: 1, and uniformly mixing. And transferring the nano sponge and the metal salt solution into a polytetrafluoroethylene lining, injecting the prepared precipitator solution at a discharge speed of 0.5mL/min by using a peristaltic pump, and adjusting the pH value of a nano sponge and metal salt solution system to 10 under stirring. Then the system is sealed in a stainless steel high-pressure reaction kettle and reacts for 12 hours at 40 ℃ by adopting a microwave-assisted solvothermal method. After the reaction, the sample was taken out, washed with water and absolute ethanol, respectively, purged with nitrogen for 20 minutes, and then placed in a vacuum tube furnace. Pumping to a vacuum degree of less than-0.04 MPa in the furnace, introducing nitrogen to the vacuum degree of zero in the furnace, and repeating the process for three times. And finally calcining the mixture for 2 hours at 650 ℃ in a nitrogen atmosphere with zero vacuum degree to obtain the flexible electrode material.
Fig. 1a is an SEM photograph of the flexible electrode material obtained in this embodiment, and it can be seen that the obtained flexible electrode material includes a three-dimensional framework structure material and nanoparticles uniformly loaded on the surface of the framework structure, where the three-dimensional framework structure material is a nitrogen-doped carbon material, and the nanoparticles are a metal oxide.
Fig. 2a to fig. 2e are element surface scanning photographs of the flexible electrode material obtained in this embodiment, which respectively include a scanning photograph of a scanning area of an element surface to be measured of the electrode material and a scanning photograph of distribution of each element, and it can be seen that the target material is successfully synthesized by using the method, and oxygen and nickel are uniformly distributed on the nitrogen-doped carbon skeleton.
Example 2
Different from the embodiment 1, the precipitator solution in the embodiment is ammonia water (25-28 wt% ammonia-containing aqueous solution).
Fig. 1b is an SEM photograph of the flexible electrode material obtained in this example, and it can be seen that the distribution uniformity of the nanoparticles in the obtained flexible electrode material is inferior to that of example 1, and thus it can be known that a more uniform precipitation effect can be obtained by using the precipitant solution including the tackifier, so that the loading of the nanoparticles is more uniform.
Example 3
Different from the embodiment 1, the preparation method of the flexible electrode material adopts the traditional solvothermal method to perform reaction to obtain a precursor, and the reaction temperature is 80 ℃.
Fig. 1c is an SEM photograph of the flexible electrode material obtained in this example, and it can be seen that the distribution uniformity of the nanoparticles in the obtained flexible electrode material is worse than that of example 1, and thus it can be known that a more uniform precipitation effect can be obtained by using the microwave-assisted solvothermal method, the loading of the nanoparticles is more uniform, and the reaction temperature is lower.
Examples 4 to 6
A method for preparing a flexible electrode material, which is different from example 1 in that the precipitant solutions of examples 4 to 6 have viscosities of 1, 13 and 15mPa · s, respectively.
The viscosity of the precipitant solutions of examples 1, 4-5 are within the preferred range of the present invention.
Examples 7 to 9
A method for preparing a flexible electrode material, which is different from example 1 in that in examples 7 to 9, pH was adjusted to 9, 12 and 8, respectively.
The pH in examples 1, 7-8 is within the preferred range of the present invention.
Examples 10 to 11
Different from the preparation method of the flexible electrode material in the embodiment 1, in the embodiments 10 to 11, the reaction temperature is 60 ℃ and 25 ℃, and the reaction time is 8 h and 26h respectively.
The reaction temperature and reaction time of examples 1 and 10 are within the preferred ranges of the present invention.
Examples 12 to 13
Different from the preparation method of the flexible electrode material in the embodiment 1, in the embodiments 12 to 13, the calcining temperature is 750 ℃ and 550 ℃, and the calcining time is 1.5 h and 12h respectively.
The calcination temperature and calcination time of examples 1 and 12 are within the preferred ranges of the present invention.
Examples 14 to 15
The difference between the preparation method of the flexible electrode material and the embodiment 1 is that in the embodiments 14 to 15, NiCl is adopted2The concentration of the solution is 0.01 and 0.02mol/L respectively, and the nano sponge and the NiCl2The ratio of the solutions was 0.1 g: 50mL and 0.2 g: 35 mL.
NiCl in examples 1 and 142Concentration of solution and nano sponge and NiCl2The ratio of the solutions is within the preferred range of the present invention.
Examples 16 to 18
A method for preparing a flexible electrode material, which is different from that of example 1, in examples 16 to 18, 1.2g of CoCl is used as a metal salt2·6H2O, 1.5g of Co (NO)3)2·6H2O and 1.1g of MnSO4·4H2O。
Comparative example 1
The electrode material was prepared using the method of CN109809375A embodiment one.
Comparative example 2
An electrode material was prepared using the method of CN110136982A example 1.
Comparative example 3
Different from the embodiment 1, the preparation method of the flexible electrode material in the comparative example comprises the steps of firstly mixing a metal salt solution and a precipitator solution, and then soaking the nano sponge in the mixture of the metal salt solution and the precipitator solution, wherein the rest processes are the same as the embodiment 1.
The electrode materials obtained in the above examples and the comparative examples and the alkaline PVA gel electrolyte were assembled into supercapacitors, each supercapacitor was charged and discharged at a constant current, the specific capacitance of each supercapacitor at current densities of 1, 2, 5 and 10A/g was tested, the results are shown in table 1, and the cycle performance of the supercapacitor made with the electrode material of example 1 was tested.
TABLE 1
Fig. 3 is a constant current charging and discharging curve of a supercapacitor assembled by the flexible electrode material of example 1, and it can be seen that the discharging time is shortened along with the increase of the current density. Fig. 4 is a specific capacitance graph of a supercapacitor assembled by the flexible electrode material of example 1 at different current densities. Fig. 5 is a graph of the cycle performance of a supercapacitor assembled by the flexible electrode material of example 1, and it can be seen that the specific capacitance of the prepared sample can be well maintained at a current density of 1A/g, which indicates that the prepared sample has excellent cycle performance. Fig. 6 is a digital photo of a supercapacitor assembled by the flexible electrode material of example 1, which shows that the supercapacitor has good flexibility and is expected to be applied to the field of flexible energy storage devices.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (10)
1. The preparation method of the flexible electrode material is characterized by comprising the following steps of:
sequentially mixing the nano sponge with aqueous solution of metal salt and OH-containing solution-Is mixed with the precipitant and then reactedAnd finally, calcining the precursor to obtain the flexible electrode material.
2. The method for preparing the flexible electrode material according to claim 1, wherein the metal salt comprises at least one of a nickel salt, a cobalt salt or a manganese salt;
preferably, the nickel salt comprises at least one of nickel chloride, nickel sulfate or nickel nitrate;
preferably, the cobalt salt comprises at least one of cobalt chloride, cobalt sulfate or cobalt nitrate;
preferably, the manganese salt comprises at least one of manganese chloride, manganese sulfate or manganese nitrate;
preferably, the concentration of the aqueous solution of the metal salt is 0.005 to 0.015 mol/L.
3. The method for preparing a flexible electrode material according to claim 1, wherein the ratio of the nanosponges to the aqueous solution of the metal salt is (0.05-0.15) g: (40-60) mL;
preferably, the mixing of the nanosponges with the aqueous solution of metal salt comprises: putting the nano sponge into the aqueous solution of metal salt, and carrying out ultrasonic treatment for 25-35 min.
4. The method for preparing a flexible electrode material according to claim 1, wherein the OH group is contained-The precipitating agent of (a) comprises an aqueous solution of an ammonia-containing reagent and optionally a viscosity increasing agent;
preferably, the aqueous solution of an ammonia-containing reagent comprises at least one of an aqueous solution of ammonium bicarbonate, an aqueous solution of ethylenediamine, or aqueous ammonia;
preferably, the viscosifier comprises an alcohol;
preferably, the dynamic viscosity of the alcohol is higher than 2mpa.s at 25 ℃;
preferably, the alcohol comprises at least one of ethylene glycol, isopropanol, glycerol, polyethylene glycol or polyvinyl alcohol;
preferably, it contains OH-The precipitant has a dynamic viscosity of 1-13 mPas at 30-80 ℃.
5. The method for preparing the flexible electrode material according to claim 1, wherein the nanosponges are mixed with an aqueous solution of a metal salt and OH-containing solution-The pH of the mixed precipitant is 9-12, preferably 10;
preferably, the OH is introduced by means of a peristaltic pump-The precipitant is added into the mixture of the nano sponge and the aqueous solution of the metal salt to realize the nano sponge, the aqueous solution of the metal salt and the aqueous solution containing OH-Mixing the precipitant;
preferably, the discharge speed of the peristaltic pump is 0.001-1 mL/min.
6. The method for preparing the flexible electrode material according to claim 1, wherein the reaction comprises performing the reaction by a solvothermal method;
preferably, the solvothermal process comprises a microwave-assisted solvothermal process;
preferably, the reaction temperature is 30-80 ℃ and the reaction time is 1-24 h.
7. The method for preparing the flexible electrode material according to any one of claims 1 to 6, wherein the calcination temperature is 600-1000 ℃, and the calcination time is 0.1-10 h;
preferably, the calcination is carried out under an inert atmosphere;
preferably, the inert atmosphere is provided primarily by nitrogen and/or inert gas;
preferably, the degree of vacuum at the time of calcination is zero.
8. A flexible electrode material prepared by the method of any one of claims 1 to 7.
9. A supercapacitor comprising the flexible electrode material of claim 8.
10. Use of the flexible electrode material of claim 8 in the manufacture of a supercapacitor.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111725490A (en) * | 2020-06-11 | 2020-09-29 | 武汉工程大学 | Nitrogen-doped carbon-coated superfine niobium pentoxide nanocomposite and preparation method thereof |
| CN114388737A (en) * | 2021-12-24 | 2022-04-22 | 西安理工大学 | Self-supporting electrode, preparation method thereof and lithium-sulfur battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109243856A (en) * | 2018-11-09 | 2019-01-18 | 天津工业大学 | A kind of preparation method of iron-cobalt-nickel oxide/carbon cloth composite and flexible electrode |
| CN109326460A (en) * | 2018-11-09 | 2019-02-12 | 天津工业大学 | A kind of preparation method of di-iron trioxide/carbon cloth composite and flexible electrode |
| CN109671575A (en) * | 2018-11-09 | 2019-04-23 | 江苏大学 | A kind of preparation method of cobalt oxide manganese nano flower-carbon sponge flexible composite |
| KR20190072301A (en) * | 2017-12-15 | 2019-06-25 | 주식회사 엘지화학 | Process for preparing manganese dioxide-carbon nanocomposite |
-
2019
- 2019-12-05 CN CN201911232317.7A patent/CN110957147B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190072301A (en) * | 2017-12-15 | 2019-06-25 | 주식회사 엘지화학 | Process for preparing manganese dioxide-carbon nanocomposite |
| CN109243856A (en) * | 2018-11-09 | 2019-01-18 | 天津工业大学 | A kind of preparation method of iron-cobalt-nickel oxide/carbon cloth composite and flexible electrode |
| CN109326460A (en) * | 2018-11-09 | 2019-02-12 | 天津工业大学 | A kind of preparation method of di-iron trioxide/carbon cloth composite and flexible electrode |
| CN109671575A (en) * | 2018-11-09 | 2019-04-23 | 江苏大学 | A kind of preparation method of cobalt oxide manganese nano flower-carbon sponge flexible composite |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111725490A (en) * | 2020-06-11 | 2020-09-29 | 武汉工程大学 | Nitrogen-doped carbon-coated superfine niobium pentoxide nanocomposite and preparation method thereof |
| CN111725490B (en) * | 2020-06-11 | 2023-07-14 | 武汉工程大学 | Nitrogen-doped carbon-coated superfine niobium pentoxide nanocomposite and preparation method thereof |
| CN114388737A (en) * | 2021-12-24 | 2022-04-22 | 西安理工大学 | Self-supporting electrode, preparation method thereof and lithium-sulfur battery |
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