CN113380553A - Co3S4/Co(CO3)0.5(OH)·0.11H2O-grade nanowire array electrode material - Google Patents
Co3S4/Co(CO3)0.5(OH)·0.11H2O-grade nanowire array electrode material Download PDFInfo
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Abstract
The invention discloses a Co3S4/Co(CO3)0.5(OH)·0.11H2A method for preparing and activating an O-grade nanowire array electrode material is characterized in that foamed nickel is used as a substrate, cobalt nitrate is used as a cobalt source, urea is used as a nucleating agent, thiourea is used as a sulfur source, and a hydrothermal method is adopted to obtain Co with a grade array structure3S4/Co(CO3)0.5(OH)·0.11H2O composite electrode material: namely, nanowires with the diameter of about 20nm are intertwined to form nanowires with the diameter of about 100nm, and the nanowires are uniformly grown on the foamed nickel to form an array structure. The special hierarchical array structure composed of a plurality of nanowiresMore active sites are provided than an array consisting of nanowires with the diameter of only 100 nanometers, which is beneficial to obtaining larger capacity; the structure is more stable than the structure of an array only consisting of nanowires with the diameter of 20 nanometers, and the structure is not easy to collapse in the circulating process. Moreover, through the charge and discharge treatment under certain conditions, the ion transmission resistance of the sample is obviously reduced, and the capacity is further increased.
Description
Technical Field
The invention belongs to the field of super capacitors, and particularly relates to Co3S4/Co(CO3)0.5(OH)·0.11H2Preparation of O-grade nanowire array electrode material and method for improving capacity by activation.
Background
Co(CO3)0.5(OH)·0.11H2O is due to the CO content3 2-The ions enable the surface of the material to have hydrophilicity, can reduce the polarization phenomenon in the charging and discharging process, and has good potential in the application of super capacitors. However, due to the microstructure and conductivity, Co (CO)3)0.5(OH)·0.11H2O is usually used only for the synthesis of CoO, Co3O4And the precursor of the Co-based oxide is rarely directly used for the electrode material of the super capacitor. Although carbon-coated modification is an effective way to improve conductivity, carbon-coated modification generally requires high temperature treatment, and Co (Co)3)0.5(OH)·0.11H2CO in O material3 2-And OH-cannot withstand high temperature treatment. On the other hand, Co (CO) is reported in the literature at present3)0.5(OH)·0.11H2O, although more or less nanostructured, leaves much room for improvement in electrochemically active sites for electrochemical reactions to occur at the atomic scale.
Disclosure of Invention
The object of the invention is to target at Co (CO)3)0.5(OH)·0.11H2The problems of low O conductivity and limited electrochemical active sites, provides a Co3S4/Co(CO3)0.5(OH)·0.11H2Preparation of O-grade nanowire array electrode material and method for improving capacity by activation. The innovation points are as follows: (1) the obtained sample is a special hierarchical array structure, the hierarchical array structure formed by the nanowires with the diameter of about 20nm intertwined together provides more active sites than the array formed by the nanowires with the diameter of only 100nm, and is beneficial to obtaining larger capacity than the array formed by the nanowires with the diameter of only 20nmThe structure of the array formed by the rice noodles is more stable and is not easy to collapse in the circulating process. (2) Co3S4/Co(CO3)0.5(OH)·0.11H2Co in O composite3S4And Co (CO)3)0.5(OH)·0.11H2A molar ratio of O of about 1:9, a low content of Co3S4The overall conductivity of the material can be obviously improved. (3) On the basis of a special array structure, a large number of sheet structures are formed on the surface of the original smooth nanowire through further charge and discharge treatment under certain conditions, active sites are further increased, and ion transmission rate is reduced.
The technical scheme of the invention is as follows: co is prepared by using foamed nickel as a substrate and adopting a hydrothermal method3S4/Co(CO3)0.5(OH)·0.11H2O-grade nanowire array, and then carrying out charge and discharge treatment under certain conditions.
The technical method comprises the following steps:
(1) preparation of Co (CO)3)0.5(OH)·0.11H2O precursor: and (3) putting the foamed nickel with the area of 2cm multiplied by 4cm into a 1M hydrochloric acid solution, deionized water and absolute ethyl alcohol in sequence, ultrasonically cleaning for 15 minutes, then putting the cleaned foamed nickel into a 60-degree oven for drying, and weighing the mass of the foamed nickel after drying. Adding cobalt nitrate and urea into 40mL of deionized water, stirring until the cobalt nitrate and the urea are fully dissolved, pouring the prepared solution into an inner container of a reaction kettle, putting clean foamed nickel into the inner container, sealing the inner container by using a stainless steel outer sleeve, reacting for 4-6h at 90-100 ℃, taking out, sequentially ultrasonically cleaning for 2 min by using deionized water and absolute ethyl alcohol, and drying to obtain Co (CO)3)0.5(OH)·0.11H2And (4) O precursor. Wherein the molar ratio of the cobalt nitrate to the urea is 1: 7.5-1: 10, preferably 1: 10. Namely, the dosage of the cobalt nitrate and the dosage of the urea in each 40mL of deionized water are respectively 4mmol and 30-40 mmol, and preferably, the dosage of the cobalt nitrate and the dosage of the urea in each 40mL of deionized water are respectively 4mmol and 40 mmol.
(2) Preparation of Co3S4/Co(CO3)0.5(OH)·0.11H2O-grade nanowire array: preparing thiourea solution with a certain concentration, pouring the thiourea solution into the inner container of the reaction kettle, and obtaining the compound (1)The obtained precursor is put into an inner container, sealed by a stainless steel jacket and reacted for 6 to 8 hours at the temperature of 120 ℃ and 130 ℃. Taking out the sample after the reaction is finished, sequentially washing the sample for multiple times by using deionized water and absolute ethyl alcohol, and drying the sample to obtain Co3S4/Co(CO3)0.5(OH)·0.11H2And (4) O-grade nanowire arrays. Wherein the concentration of the thiourea solution is 0.05-0.1M, preferably 0.1M.
(3) Constant-current charge-discharge activation: preparing KOH solution with certain concentration as electrolyte, and using the Co obtained in the step (2)3S4/Co(CO3)0.5(OH)·0.11H2Using O-grade nanowire array as working electrode, platinum sheet as counter electrode, mercury/mercury oxide electrode as reference electrode, adopting cyclic charge-discharge technology in electrochemical workstation three-electrode system, and applying Co to the measured result under a certain current density3S4/Co(CO3)0.5(OH)·0.11H2And O, activating treatment. Wherein the concentration of KOH solution is 1M, the window of activation potential is 0-0.5V, and the current density is 20-30 mA/cm2Preferably 20mA/cm2The number of charging and discharging turns is 1000-3000 turns, preferably 2000 turns.
The technical scheme of the application adopts a hydrothermal method to obtain Co with a hierarchical array structure3S4/Co(CO3)0.5(OH)·0.11H2O composite electrode material: namely, nanowires with the diameter of about 20nm are intertwined to form nanowires with the diameter of about 100nm, and the nanowires are uniformly grown on the foamed nickel to form an array structure. The special-grade array structure formed by the multiple nanowires provides more active sites than an array formed by nanowires with the diameter of only 100 nanometers, and is beneficial to obtaining larger capacity; the structure is more stable than the structure of an array only consisting of nanowires with the diameter of 20 nanometers, and the structure is not easy to collapse in the circulating process. Moreover, through the charge and discharge treatment under certain conditions, the ion transmission resistance of the sample is obviously reduced, and the capacity is further increased.
Drawings
Fig. 1 is a comparison of an XRD pattern and a standard pattern of a sample prepared in example 1.
FIG. 2 shows Co in example 13S4/Co(CO3)0.5(OH)·0.11H2SEM image of O sample;
FIG. 3 is Co3S4/Co(CO3)0.5(OH)·0.11H2And (4) element distribution diagram corresponding to the O sample.
FIG. 4 is a graph comparing CV values of samples prepared in example 1.
FIG. 5 is a comparative EIS plot of samples prepared in example 1.
FIG. 6 Co prepared in example 13S4/Co(CO3)0.5(OH)·0.11H2SEM image of O after 2000 repeated charging and discharging.
FIG. 7 Co prepared in example 13S4/Co(CO3)0.5(OH)·0.11H2Comparison of GCD curves before and after 2000 repeated charging and discharging.
FIG. 8 shows Co prepared in example 13S4/Co(CO3)0.5(OH)·0.11H2Graph of cycling stability for O.
Detailed Description
In order to further understand the summary and features of the present invention, the following examples are given, but the scope of the present invention is not limited thereto.
The experimental procedures in the following examples are conventional unless otherwise specified.
Example 1
(1) Preparation of Co (CO)3)0.5(OH)·0.11H2O precursor: and (3) putting the foamed nickel with the area of 2cm multiplied by 4cm into a 1M hydrochloric acid solution, deionized water and absolute ethyl alcohol in sequence, ultrasonically cleaning for 15 minutes, then putting the cleaned foamed nickel into a 60-degree oven for drying, and weighing the mass of the foamed nickel after drying. Dissolving 4mmol of cobalt nitrate and 40mmol of urea in 40ml of deionized water, stirring until the cobalt nitrate and the urea are fully dissolved, pouring the mixture into an inner container of a reaction kettle, then putting clean foamed nickel into the inner container, sealing the inner container by using a stainless steel outer sleeve, reacting for 6 hours at 95 ℃, taking out the reaction kettle after cooling to room temperature, and ultrasonically cleaning for 2 minutes by using the deionized water and absolute ethyl alcohol in sequence.
(2) Preparation of Co3S4/Co(CO3)0.5(OH)·0.11H2O-grade nanowire array: preparing 0.1M thiourea solution, pouring the thiourea solution into an inner container of a reaction kettle, putting the precursor obtained in the step (1) into the inner container, sealing the inner container by a stainless steel outer sleeve, and reacting for 8 hours at 120 ℃. And after the reaction is finished, taking out the sample when the reaction kettle is cooled to room temperature, sequentially washing the sample by deionized water and absolute ethyl alcohol for multiple times, drying the sample, and weighing the mass of the sample. FIG. 1 is an XRD pattern of the precursor and the sample after sulfidation, which proves that the precursor is Co (CO)3)0.5(OH)·0.11H2O, after vulcanization, is Co3S4/Co(CO3)0.5(OH)·0.11H2And (3) an O composite material. FIG. 2 is Co3S4/Co(CO3)0.5(OH)·0.11H2SEM of O, indicating that the sample has a hierarchical nanowire array structure: namely, nanowires with the diameter of about 20nm are intertwined to form grade nanowires with the diameter of about 100nm, and then the nanowires with the diameter of about 100nm form an array structure on a foamed nickel substrate. FIG. 3 is Co3S4/Co(CO3)0.5(OH)·0.11H2The HAADF-STEM diagram and the corresponding element distribution diagram of the O sample show that S element is uniformly distributed in the sample and has low content, and Co is obtained by XPS detection3S4And Co (CO)3)0.5(OH)·0.11H2The molar ratio of O is about 1:9, indicating that in the composite structure, Co3S4The content of (A) is low.
FIG. 4 is a graph comparing CV curves of the precursor and the samples after the sulfidation treatment, Co3S4/Co(CO3)0.5(OH)·0.11H2The area enclosed by the curve of the O composite material is obviously specific to Co (CO)3)0.5(OH)·0.11H2O is much larger, indicating a significant increase in the capacity of the sample after vulcanization. FIG. 5 is an EIS comparison graph of the precursor and the vulcanized sample, wherein the internal resistance of the vulcanized sample is obviously reduced. Combined with XPS results, low Co content in composites3S4Can effectively reduce the internal resistance of the material, is beneficial to the electron transmission in the electrochemical process and obviously increases the capacity of the sample.
(3) Constant-current charge-discharge activation: preparing KOH solution with the concentration of 1M as electrolyte, and using the Co obtained in the step (2)3S4/Co(CO3)0.5(OH)·0.11H2Using O as a working electrode, a platinum sheet as a counter electrode and a mercury/mercury oxide electrode as a reference electrode, and adopting a constant-current charging and discharging technology in a three-electrode system of an electrochemical workstation to carry out Co-reaction3S4/Co(CO3)0.5(OH)·0.11H2And O, activating treatment. The window of the activation potential is 0-0.5V, and the current density is 20mA/cm2The number of charging and discharging turns is 2000. FIG. 6 is Co3S4/Co(CO3)0.5(OH)·0.11H2According to the SEM image of the O subjected to 2000 repeated charging and discharging, the original array structure of the sample is basically maintained, but the surface appearance of the nanowire is remarkably changed, a nanosheet structure appears, and the nanowire formed by the nanosheets has a larger surface area than a smooth nanowire and can provide more active sites for electrochemical reaction. FIG. 7 is Co3S4/Co(CO3)0.5(OH)·0.11H2The GCD curve contrast chart of the O sample after 2000 repeated charge and discharge times shows that the charge and discharge time of the activated sample is obviously longer than that of the unactivated sample, and the specific capacitance calculation formula is used
(the values of I, t, S and V are shown in the attached Table 1), the capacity value of the sample is obtained, and the capacity of the sample after activation is 1.76 times that of the sample without activation. Fig. 8 is a cycle stability chart after 2000 times of repeated charge and discharge activation, and after 9000 times of cycles, the capacity retention rate of the sample is still as high as 94.8%.
TABLE 1
| Sample (I) | I(mA) | t(s) | S(cm-2) | V(V) | C(Fcm-2) |
| Before |
20 | 33 | 0.8 | 0.5 | 1.65 |
| After 2000 cycles of |
20 | 58 | 0.8 | 0.5 | 2.90 |
Example 2
Compared with the example 1, in the step (3), the number of the charging and discharging circles of the electrochemical activation is 1000 circles, the rest steps are unchanged, and the capacity of the sample after the activation is 1.31 times that of the sample without the activation.
Example 3
Compared with the example 1, in the step (3), the number of the charging and discharging circles of the electrochemical activation is 3000, the rest steps are not changed, and the capacity of the sample after the activation is 1.75 times that of the sample without the activation.
Example 4
In step (3), the electrochemical activation current was 30mA/cm, as compared with example 12And the rest steps are unchanged, and the volume of the activated sample is 1.7 times that of the sample without activation.
Example 5
Compared with the example 1, in the step (3), the number of the charge and discharge cycles of the electrochemical activation is 100, the rest steps are not changed, the sample capacity after the activation under the condition is 0.35 times of the sample after the activation of the example 1, and the capacity of the sample is reduced when the number of the activation cycles is too small.
Example 6
Compared with the example 1, in the step (3), the electrochemical activation potential window is-1.2-0V, the rest steps are not changed, and the volume of the sample after activation under the condition is 0.47 times of that of the sample after activation in the example 1. Indicating that the sample volume decreased when the activation potential window was changed.
Claims (5)
1. Co3S4/Co(CO3)0.5(OH)·0.11H2The preparation method of the O-grade nanowire array electrode material is characterized by comprising the following steps of:
(1) preparation of Co (CO)3)0.5(OH)·0.11H2O precursor: adding cobalt nitrate and urea into deionized water, stirring to fully dissolve, pouring the prepared solution into a reaction kettle inner container, putting clean foamed nickel into the inner container, sealing with a stainless steel outer sleeve, reacting at 90-100 ℃ for 4-6h, taking out, ultrasonic cleaning with deionized water and absolute ethyl alcohol for 2 min, and drying to obtain Co (CO)3)0.5(OH)·0.11H2O precursor;
(2) preparation of Co3S4/Co(CO3)0.5(OH)·0.11H2O-grade nanowire array: preparing thiourea solution with a certain concentration, pouring the thiourea solution into a liner of a reaction kettle, putting the precursor obtained in the step (1) into the liner, sealing the liner by using a stainless steel jacket, reacting for 6-8h at the temperature of 120-3S4/Co(CO3)0.5(OH)·0.11H2An O-grade nanowire array;
(3) constant-current charge-discharge activation: preparing KOH solution with certain concentration as electrolyte, and using the Co obtained in the step (2)3S4/Co(CO3)0.5(OH)·0.11H2Using O-grade nanowire array as working electrode, platinum sheet as counter electrode, mercury/mercury oxide electrode as reference electrode, and adopting electrochemistryThe cyclic charge-discharge technology in the three-electrode system of the workstation is used for Co under a certain current density3S4/Co(CO3)0.5(OH)·0.11H2And O, activating treatment.
2. Co according to claim 13S4/Co(CO3)0.5(OH)·0.11H2The preparation method of the O-grade nanowire array electrode material is characterized in that the molar ratio of cobalt nitrate to urea in the step (1) is 1: 7.5-1: 10.
3. Co according to claim 13S4/Co(CO3)0.5(OH)·0.11H2The preparation method of the O-grade nanowire array electrode material is characterized in that the concentration of thiourea in the step (2) is 0.05-0.1M.
4. Co according to claim 13S4/Co(CO3)0.5(OH)·0.11H2The preparation method of the O-grade nanowire array electrode material is characterized in that the concentration of a KOH solution in the step (3) is 1-2M, the activation potential window is 0-0.5V, and the current density is 20-30 mA/cm2The number of charging and discharging is 1000-3000.
5. Co3S4/Co(CO3)0.5(OH)·0.11H2The O-grade nanowire array electrode material is characterized by being prepared by the preparation method of any one of claims 1-4, and the obtained electrode is Co3S4/Co(CO3)0.5(OH)·0.11H2O composite material of Co3S4And Co (CO)3)0.5(OH)·0.11H2The molar ratio of O is 1:9, the shape is a graded nanowire array, namely nanowires with the diameter of about 20nm are intertwined to form nanowires with the diameter of about 100nm, and the nanowires uniformly grow on the foamed nickel to form an array structure.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20110235240A1 (en) * | 2008-08-15 | 2011-09-29 | The Regents Of The University Of California | Hierarchical nanowire composites for electrochemical energy storage |
| CN106206067A (en) * | 2016-07-12 | 2016-12-07 | 安徽大学 | A kind of based on Co2(OH)2cO3the preparation method of nano-array flexible solid-state supercapacitor |
| CN106783234A (en) * | 2017-01-13 | 2017-05-31 | 安徽师范大学 | A kind of preparation method and application of cobalt sulfide/cobalt basic salt nano composite material |
| CN109174146A (en) * | 2018-07-24 | 2019-01-11 | 安徽师范大学 | One-dimensional basic cobaltous carbonate@dimensional Co Se/NF heterojunction structure composite material and preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110235240A1 (en) * | 2008-08-15 | 2011-09-29 | The Regents Of The University Of California | Hierarchical nanowire composites for electrochemical energy storage |
| CN106206067A (en) * | 2016-07-12 | 2016-12-07 | 安徽大学 | A kind of based on Co2(OH)2cO3the preparation method of nano-array flexible solid-state supercapacitor |
| CN106783234A (en) * | 2017-01-13 | 2017-05-31 | 安徽师范大学 | A kind of preparation method and application of cobalt sulfide/cobalt basic salt nano composite material |
| CN109174146A (en) * | 2018-07-24 | 2019-01-11 | 安徽师范大学 | One-dimensional basic cobaltous carbonate@dimensional Co Se/NF heterojunction structure composite material and preparation method and application |
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