CN111834132A - Cobalt manganese sulfide material, preparation method and application thereof - Google Patents
Cobalt manganese sulfide material, preparation method and application thereof Download PDFInfo
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
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Abstract
The invention discloses a preparation method of a cobalt-manganese sulfide material, which takes soluble cobalt salt, soluble manganese salt and a vulcanizing agent as raw materials and prepares the cobalt-manganese sulfide material by a one-step hydrothermal method; the method has the advantages of simple process, easy realization of mass production and the like; the invention also discloses a cobalt manganese sulfide material, wherein the active substance of the material is cobalt manganese sulfide, the Co content of the cobalt manganese sulfide is 23-27%, the Mn content is 13-16%, and the S content is 32-38%; the invention also discloses application of the cobalt manganese sulfide material as a supercapacitor electrode material, wherein the material has high specific capacitance when being applied, and the current density is 1 A.g‑1The specific capacitance is 2475F g‑1。
Description
Technical Field
The invention relates to the technical field of metal sulfide materials, in particular to a cobalt manganese sulfide material, a preparation method thereof and a technology for using the material as a super capacitor electrode material.
Background
The overuse of fossil fuels by human production and life causes a great amount of greenhouse gases such as carbon dioxide and the like to be discharged, thereby causing a series of global environmental problems. To overcome these problems, many researchers have invested in the development and application of renewable clean energy sources (biofuels, wind energy, solar energy, tidal energy, hydrogen energy, etc.). However, due to the limitations of climate and geographical conditions, clean energy available to humans is very limited. Thus, storing the electrical energy generated by clean energy for subsequent use by electrochemical energy storage technology is considered to be one of the most promising ways. Electrochemical energy storage technologies such as lithium ion batteries and super capacitors have become the main energy source for commercial portable devices (smart phones, tablet computers, portable computers, video recorders), hybrid electric vehicles and plug-in hybrid electric vehicles (HEV/PHEV) due to their widespread use in the last few years. The super capacitor has attracted attention due to its advantages of fast charge and discharge speed, high energy storage density, long cycle life, wide working temperature limit, etc.
Due to the characteristics of high energy density, high charge-discharge rate, excellent cycle performance and the like, the electrochemical super capacitor is increasingly hot to research. The super capacitor mainly comprises: current collectors, electrolytes, electrodes, and separators. The structure and the characteristics of the electrode material of the supercapacitor are the key for determining the performance of the supercapacitor. Therefore, the research and development of high-performance supercapacitor electrode materials are of great significance.
Transition metal sulfide is one of the pseudocapacitance materials of the super capacitor, and has the advantages of more oxidation-reduction sites, excellent electrochemical performance, good conductivity and the like, so that the transition metal sulfide becomes a material which is researched more. However, the development and application of such materials are seriously hindered by the defects of poor rate capability, short cycle life and the like. Therefore, how to improve the electrochemical performance of the transition metal sulfide becomes a primary problem to be solved. In view of previous work, attempts are made to improve the conductivity of Co-Mn bimetallic sulfide and composite materials thereof by introducing metal cobalt ions into manganese sulfide, and improve the electrochemical performance of the Co-Mn bimetallic sulfide and composite materials thereof by utilizing the synergistic effect of bimetallic ions.
At present, the cobalt-manganese-based compounds, whether in powder form or in arrays, achieve a lot of high-quality results, but most of material systems are also concentrated on cobalt-manganese oxides and hydroxides, and the preparation of cobalt-manganese bimetallic sulfides is less reported. Cobalt manganese sulfide, one of the bimetallic sulfides, has higher specific capacitance, better conductivity and longer cycle life than the monometallic sulfide. In addition, compared with oxygen atoms, sulfur atoms have lower electronegativity, the generated sulfide has better structural stability and electrochemical performance, and the electrical conductivity and electrochemical activity of the electrode material can be enhanced by substituting the sulfur atoms for the oxygen atoms. Therefore, it is important to explore the preparation of cobalt manganese sulfide and its electrochemical characteristics.
In the graded manganese cobalt sulfide for high-performance asymmetric super capacitor published in Power supply Magazine (Journal of Power Sources342 (2017) 629-637) by Liu vertical DE et al, a graded myelin-shaped MnCo directly growing on a foamed nickel substrate is realized by a two-step hydrothermal method2S4The array is mainly divided into two hydrothermal steps: the first step is to prepare a Co-Mn precursor. Soaking the pretreated foamed nickel in the mixed solution, and then carrying out a first-step hydrothermal reaction, namely NH4And F, activating the matrix, using urea as a precipitator and a template to enable the Co-Mn precursor nanosheets to uniformly grow on the foamed nickel matrix, and gradually converting the Co-Mn precursor into regular nanowires under the action of Oswald curing. The second step is to carry out the second hydrothermal reaction under the hydrothermal condition, and convert the Co-Mn precursor into myelin MnCo through the ion exchange reaction2S4. Mixing MnCo2S4After forming the working electrode, the test was carried out at 1A. g-1Has a current density of 2067F · g-1The specific capacitance of (c). When the current density is increased to 20A g-1When the specific capacitance is 1156F · g-1. Finally MnCo2S4The positive electrode and the graphene are used as negative electrodes, and the energy density and the power density are respectively 31.3 W.kg after the assembly-1And 800 W.kg-1And a cycle life test was performed with a capacity loss of about 11% after 5000 cycles compared to the first cycle.
However, since the above method requires a two-step hydrothermal preparation of MnCo grown on nickel foam2S4The morphology is also required to be controlled by an activating agent, a precipitating agent, a template agent and the like, the process is complex, and the requirement on energy is high; the prepared material shows a sheath-like structure which is easily broken when used as a supercapacitor material, resulting in a decrease in capacityThe electrochemical performance is general.
Disclosure of Invention
One objective of the present invention is to provide a method for preparing cobalt manganese sulfide material with simple process by using one-step hydrothermal method, in order to overcome the above-mentioned disadvantages of the prior art.
One object of the present invention is to provide a cobalt manganese sulfide material, which can be used to prepare a flaky cobalt manganese sulfide attached to nickel foam.
One object of the present invention is to provide an application of cobalt manganese sulfide material as an electrode material of a super capacitor, aiming at the above-mentioned defects of the prior art.
The technical scheme adopted by the invention for solving the technical problem is to provide a preparation method of a cobalt-manganese sulfide material, which is characterized by comprising the following steps of:
the method comprises the following steps: mixing soluble cobalt salt and soluble manganese salt in an alcohol-water solution to obtain a cobalt-manganese precursor solution; the molar ratio of the cobalt element, the manganese element, the alcohol and the water in the cobalt-manganese precursor solution is 1: 0.2-1: 100-500: 500-1500; the alcohol water solution is prepared by mixing one or more of ethanol, glycol and glycerol in water at any ratio; the number of moles of the alcohol is calculated as the number of moles of the alcohol molecule, and for example, the number of moles of 1mol of ethanol, 1mol of ethylene glycol, and 1mol of glycerol are the same.
Step two: mixing the cobalt-manganese precursor solution in the step one with a sulfide to obtain a cobalt-manganese sulfide precursor solution; the molar ratio of the cobalt element to the sulfur element in the cobalt-manganese sulfide precursor solution is 1: 0.5-2.5.
Step three: placing the cobalt manganese sulfide precursor solution and the foamed nickel in the second step into a reaction kettle together for hydrothermal reaction, cooling after the reaction, and washing and drying to obtain a cobalt manganese sulfide material; the temperature of the hydrothermal reaction is 170-190 ℃, and the reaction time is 3-24 h.
Preferably, the alcohol aqueous solution in step one is prepared by mixing ethylene glycol in water.
Preferably, the sulfide in step two is L-cysteine.
Preferably, in the first step, the molar ratio of the cobalt element, the manganese element, the alcohol and the water in the cobalt-manganese precursor solution is 1: (0.4-0.6): (100-500): (600-1000).
Preferably, in the second step, the molar ratio of the cobalt element to the sulfur element in the cobalt manganese sulfide precursor solution is 1: (1.25-1.75).
Preferably, in the third step:
the hydrothermal reaction temperature is 175-190 ℃, and the reaction time is 12-24 h;
the washing is as follows: firstly, washing for more than 3 times by using absolute ethyl alcohol, and then washing for more than 3 times by using deionized water;
the drying comprises the following steps: vacuum drying at 50-70 deg.C.
Preferably, the soluble cobalt salt in the first step is one or more of cobalt acetate tetrahydrate and cobalt nitrate hexahydrate which are mixed in any ratio; the soluble manganese salt is one or more of manganese acetate tetrahydrate and manganese nitrate tetrahydrate mixed in any ratio.
The technical scheme adopted by the invention for solving a technical problem is to provide a cobalt manganese sulfide material prepared by the preparation method, preferably, the active substance on the cobalt manganese sulfide material is cobalt manganese sulfide, the Co content of the cobalt manganese sulfide is 23-27%, the Mn content is 13-16%, and the S content is 32-38%; the prepared cobalt manganese sulfide has a lamellar structure.
The technical scheme adopted for solving the technical problem is to provide the application of the cobalt manganese sulfide material prepared by any preparation method in the technical scheme as the electrode material of the super capacitor.
The preparation method of the cobalt-manganese sulfide material provided by the invention has the following beneficial effects:
1. on the basis of the two-step hydrothermal method in the prior art, fundamental changes are made, and the cobalt manganese sulfide material which grows in situ by taking foamed nickel as a substrate is prepared by the one-step hydrothermal method, so that the energy consumption is greatly reduced, the experimental method is simple, the experimental process is easy to regulate and control, and the mass production is easy to realize.
2. The alcohol aqueous solution in the step one is prepared by mixing ethylene glycol in water. When metal ions are complexed by abundant functional groups on L-cysteine, the polarity of alcohol molecules and water molecules can induce cobalt manganese sulfide to grow, and finally the flaky cobalt manganese sulfide is formed on the foamed nickel substrate. In addition, the addition of the glycol containing two hydroxyl groups (-OH) in a single molecule in the reaction has obvious promotion effect on the performance of the final material, because the L-cysteine contains carboxyl groups (-COOH) and amino groups (NH)2) When the number of hydroxyl groups in a single alcohol molecule is small, the growth of the material cannot be sufficiently controlled by hydrogen bonding, and when the number of hydroxyl groups in a single alcohol molecule is too large, the growth of the material is inhibited.
3. The sulfide in step two is preferably L-cysteine. L-cysteine is rich in-NH2Functional groups such as-COOH and-SH have strong complexation effect on metal cations. Therefore, the L-cysteine can be used as an S source and a complexing agent in the reaction, so that the use of an auxiliary agent is reduced, and the foamed nickel substrate can be used for growing the cobalt manganese sulfide material to the maximum extent.
4. Step three, the drying is as follows: vacuum drying at 50-70 deg.C to prevent oxidation of the material.
The cobalt manganese sulfide material provided by the invention has the following beneficial effects:
the cobalt-manganese sulfide material prepared by a one-step hydrothermal method and growing in situ on the foamed nickel by taking the foamed nickel as a substrate directly grows on the foamed nickel in a mixed crystal form, a thin cobalt-manganese sulfide layer is formed on the surface of the foamed nickel, rapid electron transfer and full utilization of active substances are facilitated, the foamed nickel is taken as a conductive substrate to grow in situ in the electrode slice preparation process without a binder, a conductive agent, a stabilizer and the like, the active substances (cobalt-manganese sulfide) can be borne without the conductive agent and the binder, on the one hand, the specific gravity of the active substances can be furthest increased, and the utilization rate of the active substances is increased; on the other hand, the foamed nickel serving as a substrate can effectively improve the transfer rate of electrons, so that the rate capability of the electrode is improved. When the current density is 1 A.g-1The specific capacitance is 2475F g-1To do soWhen the current density is increased to 20A g-1The specific capacitance still has 1650F g-1. Therefore, we can see that the flaky cobalt manganese sulfide material grown in situ on the foamed nickel substrate has excellent rate performance and conductivity.
When the cobalt manganese sulfide material provided by the invention is applied as a supercapacitor electrode material, the cobalt manganese sulfide material has the following beneficial effects: exhibits an ultrahigh cycle stability of 10A. g-1At a current density of (d), capacity loss is about 20% after 3000 cycles; high specific capacitance 2475F g-1(ii) a At 132Wh kg-1Under the energy density, the power density can reach 14.4kw kg-1。
Drawings
FIG. 1 is a scanning electron microscope characterization result chart of a cobalt manganese sulfide material prepared in example 1 of the present invention.
FIG. 2 is a graph of the results of cyclic voltammetry tests on cobalt manganese sulfide materials prepared in example 1 of the present invention.
FIG. 3 is a graph of the result of constant current charge and discharge tests on cobalt manganese sulfide material prepared in example 1 of the present invention.
FIG. 4 is a graph of specific capacitance test results of cobalt manganese sulfide materials prepared in example 1 of the present invention at different current densities.
FIG. 5 is a graph of the long cycle performance test results for cobalt manganese sulfide materials prepared in example 1 of the present invention.
Detailed Description
The following are specific embodiments of the present invention and are further described with reference to the drawings, but the present invention is not limited to these embodiments.
Example 1
The method comprises the following steps: dissolving 0.36mol of ethylene glycol in 0.90mol of deionized water during stirring to form an alcohol water solution; respectively weighing 1mmol of cobalt acetate tetrahydrate and 0.5mmol of manganese acetate tetrahydrate, dissolving in an alcohol-water solution, heating to 70 ℃, and stirring for 30 minutes;
step two: after stirring, weighing 1.5mmol L-cysteine, adding into the mixture, and continuously stirring for 1 hour at 70 ℃;
step three: cutting a piece of 1 cm-1 cm foamed nickel, sequentially performing ultrasonic treatment in acetone, ethanol, diluted hydrochloric acid and deionized water for 15 minutes, and drying under a vacuum condition; weighing the mass of the pretreated nickel foam, then placing the nickel foam into the mixed solution obtained in the second step, transferring the nickel foam into a 100ml polytetrafluoroethylene reaction kettle, and preserving the heat for 18 hours at the temperature of 180 ℃; and after the reaction is finished, cooling to room temperature, respectively washing the foamed nickel for three times by using absolute ethyl alcohol and deionized water, drying in a vacuum oven at the temperature of 60 ℃, weighing the mass of the dried foamed nickel, and obtaining the difference value of the mass of the dried foamed nickel and the mass of the blank foamed nickel after pretreatment, namely the loading capacity of the active substance.
The cobalt-manganese sulfide material prepared by the method is subjected to morphology characterization by adopting a scanning electron microscope, a Gemini500 field emission scanning electron microscope of Zeiss company of Germany is adopted in an experiment to research the microscopic morphology of the cobalt-manganese sulfide material, and as a result, a thin cobalt-manganese sulfide layer is formed on the surface of the foamed nickel as shown in figure 1, which is beneficial to the rapid transfer of electrons and the full utilization of active substances.
The cobalt manganese sulfide electrode is used as a working electrode, the platinum sheet and the mercury-mercury oxide are respectively used as a counter electrode and a reference electrode, the three parts are put into a three-electrode system, 2M KOH is selected as electrolyte, and the three parts are measured by an electrochemical workstation (CHI 760E, Shanghai Chenghua) (cyclic voltammetry (CV, voltage window of 0-0.6V), constant current charge and discharge (GCD, cut-off voltage of 0-0.5V)), and the test results are shown in FIG. 2, FIG. 3 and FIG. 4. In 2M KOH electrolyte, 10 Ag is used in the potential interval of 0-0.5V-1Discharge current density vs. prepared MnCo2S4The electrode is subjected to constant current charge-discharge cycle test, the cycle stability performance of the material can be explored by comparing the specific capacity of the electrode material after 10000 cycles with the initial specific capacity, and the test result is shown in fig. 5. When calculating the specific capacitance of the electrode material, the calculation can be carried out by the following formula:
wherein，CsIs specific capacitance (F.g)-1) I is a discharge current (a), Δ t is a discharge time(s), m is an active material loading amount (g) of the working electrode, and Δ V is a discharge voltage window (V).
Example 2
The method comprises the following steps: dissolving 0.10mol of ethanol in 0.50mol of deionized water during stirring to form an alcohol-water solution; respectively weighing 1mmol of cobalt acetate tetrahydrate and 0.2mmol of manganese nitrate tetrahydrate, dissolving in an alcohol-water solution, heating to 70 ℃, and stirring for 30 minutes;
step two: after stirring, 0.5mmol L-cysteine is weighed and added, and stirring is continued for 1 hour at 70 ℃;
step three: cutting a piece of 1 cm-1 cm foamed nickel, sequentially performing ultrasonic treatment in acetone, ethanol, diluted hydrochloric acid and deionized water for 15 minutes, and drying under a vacuum condition; weighing the mass of the pretreated nickel foam, then placing the nickel foam into the mixed solution obtained in the second step, transferring the nickel foam into a 100ml polytetrafluoroethylene reaction kettle, and preserving the heat for 3 hours at the temperature of 170 ℃; and after the reaction is finished, cooling to room temperature, respectively washing the foamed nickel for three times by using absolute ethyl alcohol and deionized water, drying in a vacuum oven at 50 ℃, weighing the mass of the dried foamed nickel, and obtaining the difference value between the mass of the dried foamed nickel and the mass of the blank foamed nickel after pretreatment, namely the loading capacity of the active substance.
Example 3
The method comprises the following steps: dissolving 0.50mol of ethylene glycol in 1.50mol of deionized water during stirring to form an alcohol water solution; respectively weighing 1mmol of cobalt nitrate hexahydrate and 1mmol of manganese acetate tetrahydrate, dissolving in an alcohol-water solution, heating to 70 ℃, and stirring for 30 minutes;
step two: after stirring, weighing 2.5mmol L-cysteine, adding into the mixture, and continuously stirring for 1 hour at 70 ℃;
step three: cutting a piece of 1 cm-1 cm foamed nickel, sequentially performing ultrasonic treatment in acetone, ethanol, diluted hydrochloric acid and deionized water for 15 minutes, and drying under a vacuum condition; weighing the mass of the pretreated nickel foam, then placing the nickel foam into the mixed solution obtained in the second step, transferring the nickel foam into a 100ml polytetrafluoroethylene reaction kettle, and preserving the heat for 24 hours at 190 ℃; and after the reaction is finished, cooling to room temperature, washing the foamed nickel for three times by using absolute ethyl alcohol and deionized water, drying in a vacuum oven at 70 ℃, weighing the mass of the dried foamed nickel, and obtaining the difference value between the mass of the dried foamed nickel and the mass of the pretreated blank foamed nickel as the loading capacity of the active substance.
Example 4
The method comprises the following steps: dissolving 0.10mol of glycerol in 0.60mol of deionized water during stirring to form an alcohol water solution; respectively weighing 1mmol of cobalt nitrate hexahydrate and 0.4mmol of manganese nitrate tetrahydrate, dissolving in an alcohol-water solution, heating to 70 ℃, and stirring for 30 minutes;
step two: after stirring, weighing 1.25mmol L-cysteine, adding into the mixture, and continuously stirring for 1 hour at 70 ℃;
step three: cutting a piece of 1 cm-1 cm foamed nickel, sequentially performing ultrasonic treatment in acetone, ethanol, diluted hydrochloric acid and deionized water for 15 minutes, and drying under a vacuum condition; weighing the mass of the pretreated nickel foam, then placing the nickel foam into the mixed solution obtained in the second step, transferring the nickel foam into a 100ml polytetrafluoroethylene reaction kettle, and preserving the heat for 12 hours at the temperature of 175 ℃; and after the reaction is finished, cooling to room temperature, respectively washing the foamed nickel for three times by using absolute ethyl alcohol and deionized water, drying in a vacuum oven at the temperature of 60 ℃, weighing the mass of the dried foamed nickel, and obtaining the difference value of the mass of the dried foamed nickel and the mass of the blank foamed nickel after pretreatment, namely the loading capacity of the active substance.
Example 5
The method comprises the following steps: dissolving 0.50mol of ethylene glycol in 1.00mol of deionized water during stirring to form an alcohol-water solution; respectively weighing 1mmol of cobalt acetate tetrahydrate and 0.6mmol of manganese acetate tetrahydrate, dissolving in an alcohol-water solution, heating to 70 ℃, and stirring for 30 minutes;
step two: after stirring, weighing 1.75mmol L-cysteine, adding into the mixture, and continuously stirring for 1 hour at 70 ℃;
step three: cutting a piece of 1 cm-1 cm foamed nickel, sequentially performing ultrasonic treatment in acetone, ethanol, diluted hydrochloric acid and deionized water for 15 minutes, and drying under a vacuum condition; weighing the mass of the pretreated nickel foam, then placing the nickel foam into the mixed solution obtained in the second step, transferring the nickel foam into a 100ml polytetrafluoroethylene reaction kettle, and preserving the heat for 18 hours at the temperature of 180 ℃; and after the reaction is finished, cooling to room temperature, respectively washing the foamed nickel for three times by using absolute ethyl alcohol and deionized water, drying in a vacuum oven at the temperature of 60 ℃, weighing the mass of the dried foamed nickel, and obtaining the difference value of the mass of the dried foamed nickel and the mass of the blank foamed nickel after pretreatment, namely the loading capacity of the active substance.
Example 6
The method comprises the following steps: dissolving 0.12mol of ethanol, 0.12mol of ethylene glycol and 0.12mol of glycerol into 0.90mol of deionized water during stirring to form an alcohol-water solution; respectively weighing 0.5mmol of cobalt acetate tetrahydrate, 0.5mmol of cobalt nitrate hexahydrate, 0.25mmol of manganese acetate tetrahydrate and 0.25mmol of manganese nitrate tetrahydrate, dissolving in an alcohol-water solution, heating to 70 ℃, and stirring for 30 minutes;
step two: after stirring, weighing 1.5mmol L-cysteine, adding into the mixture, and continuously stirring for 1 hour at 70 ℃;
step three: cutting a piece of 1 cm-1 cm foamed nickel, sequentially performing ultrasonic treatment in acetone, ethanol, diluted hydrochloric acid and deionized water for 15 minutes, and drying under a vacuum condition; weighing the mass of the pretreated nickel foam, then placing the nickel foam into the mixed solution obtained in the second step, transferring the nickel foam into a 100ml polytetrafluoroethylene reaction kettle, and preserving the heat for 18 hours at the temperature of 180 ℃; and after the reaction is finished, cooling to room temperature, respectively washing the foamed nickel for three times by using absolute ethyl alcohol and deionized water, drying in a vacuum oven at the temperature of 60 ℃, weighing the mass of the dried foamed nickel, and obtaining the difference value of the mass of the dried foamed nickel and the mass of the blank foamed nickel after pretreatment, namely the loading capacity of the active substance.
Example 7
The method comprises the following steps: dissolving 0.16mol of ethanol and 0.2mol of ethylene glycol in 0.90mol of deionized water during stirring to form an alcohol aqueous solution; respectively weighing 0.3mmol of cobalt acetate tetrahydrate, 0.7mmol of cobalt nitrate hexahydrate and 0.5mmol of manganese acetate tetrahydrate, dissolving in an alcohol-water solution, heating to 70 ℃, and stirring for 30 minutes;
step two: after stirring, 1.5mmol of sodium sulfide is weighed and added, and stirring is continued for 1 hour at 70 ℃;
step three: cutting a piece of 1 cm-1 cm foamed nickel, sequentially performing ultrasonic treatment in acetone, ethanol, diluted hydrochloric acid and deionized water for 15 minutes, and drying under a vacuum condition; weighing the mass of the pretreated nickel foam, then placing the nickel foam into the mixed solution obtained in the second step, transferring the nickel foam into a 100ml polytetrafluoroethylene reaction kettle, and preserving the heat for 18 hours at the temperature of 180 ℃; and after the reaction is finished, cooling to room temperature, respectively washing the foamed nickel for three times by using absolute ethyl alcohol and deionized water, drying in a vacuum oven at the temperature of 60 ℃, weighing the mass of the dried foamed nickel, and obtaining the difference value of the mass of the dried foamed nickel and the mass of the blank foamed nickel after pretreatment, namely the loading capacity of the active substance.
Example 8
The method comprises the following steps: dissolving 0.25mol of ethanol and 0.2mol of glycerol into 0.90mol of deionized water during stirring to form an alcohol water solution; respectively weighing 1mmol of cobalt nitrate hexahydrate, 0.1mmol of manganese acetate tetrahydrate and 1.3mmol of manganese nitrate tetrahydrate, dissolving in an alcohol-water solution, heating to 70 ℃, and stirring for 30 minutes;
step two: after stirring, 1.5mmol of thiourea was weighed and added, and stirring was continued at 70 ℃ for 1 hour;
step three: cutting a piece of 1 cm-1 cm foamed nickel, sequentially performing ultrasonic treatment in acetone, ethanol, diluted hydrochloric acid and deionized water for 15 minutes, and drying under a vacuum condition; weighing the mass of the pretreated nickel foam, then placing the nickel foam into the mixed solution obtained in the second step, transferring the nickel foam into a 100ml polytetrafluoroethylene reaction kettle, and preserving the heat for 18 hours at the temperature of 180 ℃; and after the reaction is finished, cooling to room temperature, respectively washing the foamed nickel for three times by using absolute ethyl alcohol and deionized water, drying in a vacuum oven at the temperature of 60 ℃, weighing the mass of the dried foamed nickel, and obtaining the difference value of the mass of the dried foamed nickel and the mass of the blank foamed nickel after pretreatment, namely the loading capacity of the active substance.
Comparative example 1
Using a controlled variation method, using the experimental conditions of example 1 as basic conditions (unless otherwise specified, except for the variables, the experimental conditions were the same as those of example 1, by changing the solvent in the first step, a plurality of cobalt manganese sulfides as shown in Table 1 were prepared, byExperimental comparison is carried out to compare the three materials at 10 A.g-1The results of the specific capacitance at the current density are shown in table 1, and the test method and the specific capacitance calculation method are the same as those of example 1.
When metal ions are complexed with abundant functional groups on the L-cysteine, the polarity of alcohol molecules and water molecules can induce the cobalt manganese sulfide to grow, and finally the flaky cobalt manganese sulfide is formed on the foamed nickel. And we can see from table 1 that the addition of ethylene glycol containing two hydroxyl groups (-OH) in a single molecule has a significant effect on the performance of the material, since L-cysteine contains carboxyl groups (-COOH) and amino groups (NH)2) When the number of hydroxyl groups in a single alcohol molecule is small, the growth of the material cannot be sufficiently controlled by hydrogen bonding, and when the number is too large, the growth of the material is inhibited.
Comparative example 2
A variety of cobalt manganese sulfides as shown in Table 2 were prepared by controlled variable method under the basic conditions of the experiment in example 1 (unless otherwise specified, except for the variables, the same experiment as in example 1 was conducted by changing the amount of L-cysteine in the first step, and experimental comparisons were made to compare the results at 10A · g for three materials-1The specific capacitance at current density and the results are shown in Table 2, and the test method and the specific capacitance calculation method are the same as those of example 1
As can be seen from Table 2, under the condition of constant solution volume, the change of the amount of the L-cysteine has great influence on the electrochemical performance of the material. The specific capacitance of cobalt manganese sulfide is increased along with the increasing of the content of L-cysteine, and the performance reaches the best when the addition amount is 1.5mmol (namely Co: M n: L-cysteine = 1: 0.5: 1.5). This is because L-cysteine contains a mercapto group (-SH), a carboxyl group (-COOH) and ammonia in its moleculeRadical (-NH)2) When the content of L-cysteine is low, sufficient complexing sites cannot be provided for metal ions, so that the electrochemical performance of the material is poor. The performance of the cobalt manganese sulfide is gradually increased along with the increase of the content of the L-cysteine, however, when the content of the L-cysteine is excessive, the abundant functional groups on the molecules can cause intermolecular polymerization, and metal ions cannot be fully complexed, so that the electrochemical performance of the cobalt manganese sulfide is weakened.
Comparative example 3
A variety of cobalt manganese sulfides as shown in Table 3 were prepared by controlled variable method under the basic conditions of the experiment in example 1 (unless otherwise specified, except for the variables, the reaction time in the third step was changed as in example 1), and the results of experimental comparison were compared to each other at 10A g-1The results of the specific capacitance at the current density are shown in table 3, and the test method and the specific capacitance calculation method are the same as those of example 1.
As can be seen from Table 3, the electrochemical performance of S-Co-Mn is greatly improved with the increase of the reaction time. Due to the prolonged reaction time, the Ostwald ripening process is continuously carried out, the structural morphology of the material is damaged, 18 hours are known as the optimal reaction time, and when the reaction time exceeds 18 hours and is continuously prolonged, functional groups which do not participate in the reaction in the L-cysteine molecule can attract the complexed metal ions, so that the structure is damaged, active substances are lost, and the specific capacitance and the cycle performance of the material are reduced.
Comparative example 4
Using the controlled variable method, using the experimental conditions of example 1 as basic conditions (unless otherwise specified, except for the variables, the experimental conditions of example 1 were the same, by changing the vulcanizing agent in step two, i.e., without using L-cysteine, and using other vulcanizing agents instead, various cobalt manganese sulfides as shown in Table 4 were prepared, and by comparing the experimental results, the three materials were compared at 10A · g-1Electric currentThe results of the specific capacitance at density are shown in table 4, and the test method and the specific capacitance calculation method are the same as those of example 1.
As can be seen from Table 4, MnCo prepared by using L-cysteine as a vulcanizing agent2S4The performance is excellent because the L-cysteine molecule has a functional group (-NH) relative to other vulcanizing agents2-COOH and-SH) has strong chelating effect on metal cations, and the cobalt manganese sulfide serving as a structure directing agent and a sulfur source in the reaction has the effect of promoting the uniform growth of the cobalt manganese sulfide on a foam nickel matrix.
Comparative example 5
The cobalt manganese sulfide prepared in example 1 was compared with cobalt manganese sulfides prepared in other multi-step methods to compare specific capacitance.
[1] Foamed rGO/Ni in situ growth manganese cobalt sulfide materials with high capacity and their use in hybrid supercapacitors (Electrochimica Acta (2018)' 288,31-41)
[2] Hierarchical manganese cobalt sulfide (Journal of Power Sources342 (2017) 629-637) for high performance asymmetric supercapacitors
[3]Foamed nickel MnCo for high-performance asymmetric super capacitor2O4@ MnCo2S4Core/shell micro-nano structure material (Colloids and Surfaces a-physical and Engineering Aspects (2019) 570,73-80)
[4]De-templated synthesis of 3D layered damascene-like interconnect MnCo2S4Nano-sheet array material and its mixed energy storage device application (Carbon (2020) 161,299-308)
As shown in Table 5, when cobalt manganese sulfide directly grown on a foamed nickel substrate has a three-dimensional structure, the structure is cracked to reduce the capacity under the influence of the super capacitor or other external forces during the operation, and the flaky cobalt manganese sulfide prepared by the method has a two-dimensional structure, so that the capacity can be well avoided. In addition, the two-step or multi-step method is not suitable for industrial application due to large energy consumption and complex process.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of cobalt manganese sulfide material is characterized by comprising the following steps:
the method comprises the following steps: mixing soluble cobalt salt and soluble manganese salt in an alcohol-water solution to obtain a cobalt-manganese precursor solution; the molar ratio of the cobalt element, the manganese element, the alcohol and the water in the cobalt-manganese precursor solution is 1: 0.2-1: 100-500: 500-1500; the alcohol water solution is prepared by mixing one or more of ethanol, glycol and glycerol in water at any ratio;
step two: mixing the cobalt-manganese precursor solution in the step one with a sulfide to obtain a cobalt-manganese sulfide precursor solution; the molar ratio of the cobalt element to the sulfur element in the cobalt-manganese sulfide precursor solution is 1: 0.5-2.5;
step three: placing the cobalt manganese sulfide precursor solution and the foamed nickel in the second step into a reaction kettle together for hydrothermal reaction, cooling after the reaction, and washing and drying to obtain a cobalt manganese sulfide material; the temperature of the hydrothermal reaction is 170-190 ℃, and the reaction time is 3-24 h.
2. The method of claim 1, wherein the cobalt manganese sulfide material is prepared by:
the alcohol aqueous solution in the step one is prepared by mixing ethylene glycol in water.
3. The method of claim 1, wherein the cobalt manganese sulfide material is prepared by:
in the second step, the sulfide is L-cysteine.
4. The method of claim 1, wherein the cobalt manganese sulfide material is prepared by:
in the first step, the molar ratio of the cobalt element, the manganese element, the alcohol and the water in the cobalt-manganese precursor solution is 1: 0.4-0.6: 100-500: 600-1000.
5. The method of claim 1, wherein the cobalt manganese sulfide material is prepared by:
in the second step, the molar ratio of the cobalt element to the sulfur element in the cobalt manganese sulfide precursor solution is 1: 1.25-1.75.
6. The method for preparing cobalt manganese sulfide material according to claim 1, wherein the step three is:
the hydrothermal reaction temperature is 175-190 ℃, and the reaction time is 12-24 h;
the washing is as follows: firstly, washing for more than 3 times by using absolute ethyl alcohol, and then washing for more than 3 times by using deionized water;
the drying comprises the following steps: vacuum drying at 50-70 deg.C.
7. The method of claim 1, wherein the cobalt manganese sulfide material is prepared by:
in the step one, the soluble cobalt salt is one or more of cobalt acetate tetrahydrate and cobalt nitrate hexahydrate which are mixed in any ratio; the soluble manganese salt is one or more of manganese acetate tetrahydrate and manganese nitrate tetrahydrate mixed in any ratio.
8. Cobalt manganese sulphide material produced according to the method of any one of claims 1 to 7.
9. The cobalt manganese sulfide material of claim 8, wherein: the active substance on the cobalt manganese sulfide material is cobalt manganese sulfide, wherein the content of Co in the cobalt manganese sulfide is 23-27%, the content of Mn in the cobalt manganese sulfide is 13-16%, and the content of S in the cobalt manganese sulfide is 32-38%.
10. Use of cobalt manganese sulphide material according to claim 8 as supercapacitor electrode material.
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