CN116013698B - Composite electrode material for super capacitor and preparation process thereof - Google Patents
Composite electrode material for super capacitor and preparation process thereof Download PDFInfo
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- CN116013698B CN116013698B CN202310308773.5A CN202310308773A CN116013698B CN 116013698 B CN116013698 B CN 116013698B CN 202310308773 A CN202310308773 A CN 202310308773A CN 116013698 B CN116013698 B CN 116013698B
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Abstract
The invention relates to the technical field of super capacitors and discloses a composite electrode material for a super capacitor and a preparation process thereof, wherein the composite electrode material is prepared from modified carboxymethyl cellulose, cobalt chloride and urea, and the cellulose-Co is formed by utilizing the principle that the modified carboxymethyl cellulose can generate a crosslinking reaction with cobalt ions and taking cobalt chloride as a heavy metal ion source to generate the crosslinking reaction under the stirring condition 2+ And (3) a cross-linking network, wherein urea is wrapped in the cross-linking network in a cross-linking reaction to prepare an electrode material precursor, the electrode material precursor is placed in a nitrogen-protected tubular furnace for calcination, a carbon source and a sulfur source provided by modified carboxymethyl cellulose are used, and urea provides a nitrogen source and an oxygen source to form the nitrogen-sulfur doped carbon-coated cobalt oxide composite electrode material.
Description
Technical Field
The invention relates to the technical field of super capacitors, in particular to a composite electrode material for a super capacitor and a preparation process thereof.
Background
The super capacitor has the characteristics of higher power density, similar to a secondary battery, capable of realizing charge cycle storage through repeated charge and discharge, and flexible structure and environmental friendliness, so that the super capacitor is paid attention to in the research of a novel energy storage device, in each component of the super capacitor, the performance of an electrode material plays a decisive role in each phase performance parameter of the super capacitor, so far, the research of relatively wide electrode materials mainly comprises carbonaceous materials, transition metal oxides and conductive polymers, the carbon materials have good porosity and high specific surface area and can generate good double-layer capacitance, but the carbon materials have low universal specific capacitance and are not suitable for the further development of the high-power super capacitor, the transition metal oxides can generate higher specific capacitance through oxidation-reduction reaction, but the poor conductivity and volume expansion phenomenon of the transition metal oxides are difficult to maintain the cycle stability of the super capacitor, the conductive polymers have similar action mechanisms with the metal oxides, the influence of repeated ion embedding and consumption in the charge and discharge process can easily generate mechanical degradation, so that the problem of poor cycle stability exists, and the development of the novel composite electrode material is an important factor in the research of the super capacitor.
The Chinese patent publication No. CN111508720B discloses a polyaniline-Co 3 O 4 Composite nanofiber supercapacitor electrode material and preparation method thereof, and porous hollow Co is prepared by using polyaniline nanofiber 3 O 4 Coating to prepare composite electrode material with excellent specific capacitance, but polyaniline and Co 3 O 4 The electrode material prepared by the combination still has the problems of unstable structure and poor cycle performance, so that the capacitance retention rate of the composite electrode material only reaches 74.2% -78.1%, therefore, the carbon material with stable structure can be used as one of the component parts in the electrode material, and meanwhile, the excellent conductivity of the carbon material is utilized to prepare the supercapacitor electrode material with excellent comprehensive performance.
Disclosure of Invention
The invention aims to provide a composite electrode material for a super capacitor and a preparation process thereof, wherein the composite electrode material doped with porous carbon coated metal oxide is prepared by preparing modified carboxymethyl cellulose, mixing and crosslinking carboxymethyl cellulose, cobalt chloride and urea and calcining at high temperature, so that the problems of poor electrochemical activity such as low specific capacitance or poor cycling stability and the like when a carbon material or a metal oxide is singly used as an electrode material are solved.
The aim of the invention can be achieved by the following technical scheme:
a composite electrode material for super capacitor is prepared from modified carboxymethyl cellulose, cobalt chloride and urea;
the modified carboxymethyl cellulose is prepared by the following steps:
dissolving carboxymethyl cellulose in dimethyl sulfoxide, adding a catalyst, heating to 50-60 ℃, continuously adding 2-thiophenecarboxyl chloride, keeping the temperature and stirring for 1-3h, stopping heating, pouring the reaction solution into ethanol, stirring until solid materials are separated out, filtering out a solid sample, washing 2-3 times by using ethanol, and vacuum drying to obtain the modified carboxymethyl cellulose.
Through the technical scheme, under the catalysis of the catalyst, active hydroxyl in the carboxymethyl cellulose structure can be subjected to condensation reaction with acyl chloride groups in the 2-thiophenecarboxyl chloride structure, and thiophene groups are introduced into the carboxymethyl cellulose structure to prepare the modified carboxymethyl cellulose.
Further, the catalyst is pyridine, and the addition amount of the pyridine is 5-10% of the total dosage of the carboxymethyl cellulose and the 2-thiophenecarboxyl chloride.
Further, the mass ratio of the carboxymethyl cellulose to the 2-thiophenecarboxyl chloride is 1:0.1-0.25.
Further, the preparation method comprises the following steps:
step I, adding the modified carboxymethyl cellulose into purified water, and mechanically stirring to obtain a modified carboxymethyl cellulose aqueous solution;
step II, injecting the modified carboxymethyl cellulose aqueous solution into a mixed solution containing cobalt chloride and urea, stirring for 24-36h at a stirring rate of 100-200r/min, filtering the materials, taking a solid sample, using purified water to wash the sample, and freeze-drying to obtain a precursor;
and III, transferring the precursor into a tube furnace, introducing nitrogen for protection, and roasting to obtain the composite electrode material.
Through the upper partAccording to the technical scheme, the characteristic that carboxyl in a modified carboxymethyl cellulose structure can be subjected to crosslinking reaction with high-valence metal ions is utilized, cobalt chloride is taken as a heavy metal ion source, and the crosslinking reaction is carried out under the stirring condition to form cellulose-Co 2+ And (3) a cross-linking network, wherein urea is wrapped in the cross-linking network in the cross-linking reaction to prepare an electrode material precursor, the electrode material precursor is placed in a nitrogen-protected tubular furnace for calcination, a carbon source and a sulfur source provided by modified carboxymethyl cellulose are provided, urea provides a nitrogen source and an oxygen source, and the composite electrode material of the nitrogen-sulfur doped carbon-coated cobalt oxide is prepared.
Further, in the step I, the percentage concentration of the aqueous solution of cellulose is 2% -5%.
Further, in the step II, the concentration of the cobalt chloride is 0.2-0.5mol/L, and the concentration of the urea is 1-1.5mol/L.
Further, in the step II, the volume ratio of the aqueous solution of cellulose to the mixed solution is 0.2-0.3:1.
Further, in the step III, the flow rate of the nitrogen is 1-1.5L/min.
Further, in the step III, during the roasting, the heating rate in the tube furnace is set to be 2-4 ℃/min, the temperature is raised to 700-800 ℃, and the roasting is performed for 1-3 hours.
The invention has the beneficial effects that:
1) The invention uses the principle that carboxymethyl cellulose can generate cross-linking reaction with high valence metal ion, uses cobalt chloride as a metal source, and prepares cellulose-Co under the condition of stirring 2+ A crosslinked network, the crosslinking reaction being capable of reacting Co 2+ Uniformly distributed in a cross-linked network, and then baked at high temperature, combined with oxygen source provided by urea to generate a composite electrode material with carbon uniformly coated with cobalt oxide, so as to avoid capacitance reduction caused by cobalt oxide agglomeration, and simultaneously, the composite electrode material can be combined with an electric double layer capacitor provided by carbon material and a pseudo capacitor provided by cobalt oxide to realize high conductivity and high specific capacitance of the electrode materialIn addition, the volume change phenomenon of the cobalt oxide in the charging and discharging process can be effectively slowed down by utilizing the coating of the carbon material on the cobalt oxide, and the problem of poor cycle performance of the electrode material caused by structural pulverization of the cobalt oxide in the continuous use process is avoided.
2) According to the invention, uniformly distributed thiophene groups are introduced into a carboxymethyl cellulose structure, urea is taken as a nitrogen source, nitrogen and sulfur elements are doped into a carbon material in one step through high-temperature calcination, the doping of the nitrogen elements can generate active structures such as graphite nitrogen and pyridine nitrogen in the carbon material structure, the conductivity of the carbon material can be enhanced, a certain pseudo-capacitance can be generated in the carbon material, further the carbon material can generate more excellent electrochemical performance, and as the thiophene groups are uniformly distributed in a carboxymethyl cellulose molecular chain, sulfur elements generated after calcination can be uniformly doped in the carbon material, the carbon layer is spread by utilizing the higher atomic radius of the sulfur elements, so that the carbon material generates higher specific surface area for charge storage, the capacitor is facilitated, meanwhile, gas is generated through urea pyrolysis, the carbon material is etched, so that the generated carbon material contains rich pore structures, the diffusion and transmission paths of electrolyte ions can be shortened, more charges can be stored in the carbon material, and the capacitance of the carbon material is further improved.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an electron microscope image of a composite electrode material prepared in example 2 of the present invention, wherein A is a scanning electron microscope image and B is a projection electron microscope image;
fig. 2 is a constant current charge-discharge cycle stability test chart of the electrode material prepared in example 2 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparation of modified carboxymethyl cellulose
Dissolving 5g of carboxymethyl cellulose in dimethyl sulfoxide, adding 0.3g of pyridine, heating to 60 ℃, continuously adding 0.8g of 2-thiophenecarboxyl chloride, keeping the temperature and stirring for 2 hours, stopping heating, pouring the reaction solution into ethanol, stirring until solid materials are separated out, filtering out a solid sample, washing for 3 times by using ethanol, and vacuum drying to obtain modified carboxymethyl cellulose; weighing 0.5g of carboxymethyl cellulose and modified carboxymethyl cellulose, respectively adding 25mL of sodium hydroxide solution with the concentration of 0.5mol/L, stirring at room temperature for 3d to form a mixed solution, adding 2 drops of phenolphthalein reagent into the mixed solution, titrating with hydrochloric acid with the concentration of 0.1mol/L until the color of the solution disappears, respectively recording the volume of the consumed hydrochloric acid solution, and calculating the grafting degree of the modified carboxymethyl cellulose by using the following formula:
，
wherein Y is the degree of grafting, M 1 Molecular weight, M, of carboxymethylcellulose sugar units 2 Molecular weight of 2-thiophenecarboxyl chloride, V 1 To titrate the hydrochloric acid volume consumed by the modified carboxymethyl cellulose, V 0 In order to titrate the volume of hydrochloric acid consumed by carboxymethyl cellulose, C is the concentration of hydrochloric acid, m is the quality of modified carboxymethyl cellulose, and the grafting degree Y of the modified carboxymethyl cellulose is 0.26 through testing.
Example 2
Preparation of composite electrode material
Step I, adding the modified carboxymethyl cellulose prepared in the embodiment 1 of the invention into purified water, and mechanically stirring to obtain a modified carboxymethyl cellulose aqueous solution with the percentage concentration of 4%;
step II, injecting 25mL of modified carboxymethyl cellulose aqueous solution into 100mL of mixed solution containing cobalt chloride with the concentration of 0.4mol/L and urea with the concentration of 1mol/L, stirring for 36h at the stirring rate of 150r/min, filtering the material, taking a solid sample, using purified water to wash the sample, and freeze-drying to obtain a precursor;
step III, transferring the precursor into a tube furnace, heating to 750 ℃ at a heating rate of 3 ℃/min under a nitrogen flow rate of 1L/min, and roasting for 2 hours to obtain a composite electrode material; the composite electrode material is tested by using an S-4800 Hitachi scanning electron microscope and a JEOL-2100 transmission electron microscope, and the test result is shown in figure 1, wherein A is a scanning electron microscope image, and the composite electrode material can be observed to contain a pore structure from A, because urea can be decomposed to generate gases at high temperature, and the gases are coated to etch the carbon material in the process of preparing the carbon material at high temperature, so that the carbon material forms a special shape with a porous structure; b is a transmission electron microscope, from which it can be seen that the cobalt oxide is relatively uniformly dispersed in the carbon material matrix due to the fact that the carboxymethyl cellulose is mixed with Co 2+ Under the stirring condition, a cross-linked network is formed, and the cross-linking reaction can lead Co to be formed 2+ Uniformly distributed in a cross-linked network, and then roasting at high temperature to obtain the composite electrode material with carbon uniformly coated with cobalt oxide.
Comparative example 1
Preparation of composite electrode material
Step I, adding the modified carboxymethyl cellulose prepared in the embodiment 1 of the invention into purified water, and mechanically stirring to obtain a modified carboxymethyl cellulose aqueous solution with the percentage concentration of 4%;
step II, injecting 25mL of modified carboxymethyl cellulose aqueous solution into 100mL of cobalt chloride aqueous solution with the concentration of 0.4mol/L, stirring for 36h at the stirring rate of 150r/min, filtering the materials, taking a solid sample, using purified water to wash the sample, and freeze-drying to obtain a precursor;
step III, transferring the precursor into a tube furnace, heating to 750 ℃ at a heating rate of 3 ℃/min under a nitrogen flow rate of 1L/min, and roasting for 2 hours to obtain a composite electrode material;
performance detection
a. Referring to SJ/T11792-2022, the electrode materials prepared in example 2 and comparative example 1 of the present invention were subjected to conductive property test, and the test results are shown in the following table:
，
as can be seen from the above table, the electrode material prepared in example 2 of the present invention has higher conductivity and exhibits better conductivity, and the electrode material prepared in comparative example 1 is not doped with nitrogen element because urea is not added during the preparation process of the electrode material, thus resulting in poor conductivity of the electrode material.
b. Mixing the electrode material prepared in the example 2 with carbon black and polytetrafluoroethylene (mass ratio of 7:2:1), fully stirring the mixture with ethanol to form viscous slurry, uniformly coating the slurry on a round current collector with the diameter of 10mm, keeping the mass at 1mg, drying, tabletting to obtain a working electrode, forming a three-electrode system with a saturated glycerol common electrode and a platinum electrode, using 1mol/L potassium hydroxide solution as electrolyte, and using a DH7000 electrochemical workstation for cyclic voltammetry test, wherein the test result is shown in figure 2; as can be seen from FIG. 2, the initial specific capacitance of the composite electrode material prepared in example 2 of the present invention at a current density of 1A/g is 766.3F/g, and after 4000 charge and discharge cycles, the specific capacitance of 647.9F/g is still maintained, and the coulomb efficiency is always maintained at 90% or more, thus exhibiting good cycle stability.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar alternatives may be made by those skilled in the art, without departing from the scope of the invention as defined by the principles of the invention.
Claims (8)
1. The composite electrode material for the super capacitor is characterized by being prepared from modified carboxymethyl cellulose, cobalt chloride and urea;
the modified carboxymethyl cellulose is prepared by the following steps:
dissolving carboxymethyl cellulose in dimethyl sulfoxide, adding a catalyst, heating to 50-60 ℃, continuously adding 2-thiophenecarboxyl chloride, keeping the temperature and stirring for 1-3 hours, stopping heating, pouring the reaction solution into ethanol, stirring until solid materials are separated out, filtering out a solid sample, washing 2-3 times by using ethanol, and vacuum drying to obtain modified carboxymethyl cellulose;
the catalyst is pyridine, and the mass of the added pyridine is 5-10% of the total mass of the carboxymethyl cellulose and the 2-thiophenecarboxyl chloride;
the preparation process of the composite electrode material comprises the following steps:
step I, adding the modified carboxymethyl cellulose into purified water, and mechanically stirring to obtain a modified carboxymethyl cellulose aqueous solution;
step II, injecting the modified carboxymethyl cellulose aqueous solution into a mixed solution containing cobalt chloride and urea, stirring for 24-36h at a stirring rate of 100-200r/min, filtering the materials, taking a solid sample, using purified water to wash the sample, and freeze-drying to obtain a precursor;
and III, transferring the precursor into a tube furnace, introducing nitrogen for protection, and roasting to obtain the composite electrode material.
2. The composite electrode material for a supercapacitor according to claim 1, wherein the mass ratio of the carboxymethyl cellulose to the 2-thiophenecarboxyl chloride is 1:0.1-0.25.
3. A process for preparing the composite electrode material for the supercapacitor according to claim 1, wherein the preparation process comprises the following steps:
step I, adding the modified carboxymethyl cellulose into purified water, and mechanically stirring to obtain a modified carboxymethyl cellulose aqueous solution;
step II, injecting the modified carboxymethyl cellulose aqueous solution into a mixed solution containing cobalt chloride and urea, stirring for 24-36h at a stirring rate of 100-200r/min, filtering the materials, taking a solid sample, using purified water to wash the sample, and freeze-drying to obtain a precursor;
and III, transferring the precursor into a tube furnace, introducing nitrogen for protection, and roasting to obtain the composite electrode material.
4. The process for preparing a composite electrode material for a supercapacitor according to claim 3, wherein in the step i, the percentage concentration of the aqueous solution of cellulose is 2% -5%.
5. The process for preparing a composite electrode material for a supercapacitor according to claim 3, wherein in the step ii, the concentration of cobalt chloride is 0.2 to 0.5mol/L, and the concentration of urea is 1 to 1.5mol/L.
6. The process for preparing a composite electrode material for a supercapacitor according to claim 3, wherein in the step ii, the volume ratio of the aqueous solution of cellulose to the mixed solution is 0.2-0.3:1.
7. The process for preparing a composite electrode material for a supercapacitor according to claim 3, wherein in the step III, the flow rate of the nitrogen gas is 1 to 1.5L/min.
8. The process for preparing a composite electrode material for a supercapacitor according to claim 3, wherein in the step III, the temperature rising rate in the tube furnace is set to be 2-4 ℃/min, the temperature is raised to be 700-800 ℃ and the baking is performed for 1-3 hours.
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| CN113707861A (en) * | 2021-08-26 | 2021-11-26 | 合肥工业大学 | Nitrogen-doped carbon layer-coated cobalt oxide nanosheet and preparation method and energy storage application thereof |
| CN114566395A (en) * | 2021-10-29 | 2022-05-31 | 哈尔滨工业大学 | Preparation method of biomass-derived nitrogen-sulfur double-doped metal oxide/carbon-based composite material |
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| DE102011057015A1 (en) * | 2011-12-23 | 2013-06-27 | Westfälische Wilhelms-Universität Münster | Cobalt oxide-carbon composite useful as anode material for lithium-based energy storage device, preferably e.g. lithium-ion battery, lithium polymer battery and lithium-ion capacitor, comprises carbon coated cobalt monoxide particles |
| CN107591250B (en) * | 2017-09-12 | 2019-06-28 | 桂林电子科技大学 | A kind of porous carbon composite and its preparation method and application of CoO- N doping |
| CN113353989A (en) * | 2021-05-24 | 2021-09-07 | 杭州绮泺新型材料有限公司 | Rambutan-shaped Co3O4-N, S doped porous carbon composite material and preparation method thereof |
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| CN113707861A (en) * | 2021-08-26 | 2021-11-26 | 合肥工业大学 | Nitrogen-doped carbon layer-coated cobalt oxide nanosheet and preparation method and energy storage application thereof |
| CN114566395A (en) * | 2021-10-29 | 2022-05-31 | 哈尔滨工业大学 | Preparation method of biomass-derived nitrogen-sulfur double-doped metal oxide/carbon-based composite material |
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