CN112768653A - Preparation method and application of flexible nickel-cobalt double hydroxide/metal organic frame/fabric electrode - Google Patents
Preparation method and application of flexible nickel-cobalt double hydroxide/metal organic frame/fabric electrode Download PDFInfo
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Abstract
The invention provides a preparation method of a flexible nickel-cobalt double hydroxide/metal organic frame/fabric flexible electrode, which comprises the following steps: (1) dissolving cobalt salt in deionized water at a concentration of 0.01-0.5mol L‑1(ii) a Dissolving organic compound in deionized water, stirring to obtain solution with concentration of 0.1-1mol L‑1. Mixing the two solutions in equal volume, adding the cleaned conductive fabric, performing hydrothermal reaction, washing and drying to obtain the conductive fabricMetal organic framework/fabric. (2) The nickel salt is dissolved in deionized water, and the concentration of the nickel salt is 0.01-0.5mol L‑1And (2) putting the sample obtained in the step (1) into the solution, reacting, washing and drying to obtain the nickel-cobalt double hydroxide/metal organic framework/fabric electrode. The invention provides an application of the fabric electrode in the field of nickel-zinc flexible batteries. The electrode has the characteristics of good flexibility, high specific capacity, good rate capability, good cycling stability and the like.
Description
Technical Field
The invention belongs to the field of nickel-cobalt double hydroxide nickel electrode materials and preparation and application thereof, and particularly relates to a preparation method and application of a flexible nickel-cobalt double hydroxide/metal organic frame/fabric electrode.
Background
With the rapid development of scientific technology in recent years, various wearable intelligent electronic devices rise and energy automobiles develop vigorously, and higher requirements are put forward on the performance of chemical power sources. It is of great importance to develop safe, efficient and flexible electrochemical energy storage devices. The nickel-zinc battery has attracted more and more attention in recent years due to the advantages of cheap and easily available raw materials, low production cost, environmental friendliness, high output voltage, high power density and the like. Compared with cadmium-nickel batteries and lead-acid batteries, the zinc-nickel batteries have the advantages of high specific energy and specific power, no environmental pollution, small pollution and the like; compared with metal hydride/nickel battery, it has high monomer working voltage, small self-discharge and low manufacturing cost; compared with lithium ion battery, the zinc-nickel battery has very good safety performance besides low price. However, the poor flexibility, low rate capacity and poor cycle stability of the nickel-zinc battery prepared by the traditional pure metal material become the main bottlenecks in energy supply of the wearable intelligent electronic device. Therefore, designing and preparing a high-performance flexible fabric nickel electrode is a key ring for promoting the application of nickel-zinc batteries in the field of wearable intelligent electronic equipment.
Among the numerous reported electrode materials, under the combined action of the nickel-cobalt double hydroxide, such as reasonable mesoporous pore size distribution, high specific surface area, multiple valence states of two elements of nickel and cobalt, synergistic effect of two elements and the like, the nickel-cobalt double hydroxide has very high specific capacitance, has excellent performance in various electrochemical energy storage devices, and is considered to be a high-performance electrode material. CN106952740B patent of chenya et al discloses a preparation method and application of a nickel-cobalt composite oxide electrode, wherein the electrode does not contain a binder, and the obtained electrode has the advantages of large overall energy density, small environmental impact, easy process control, energy conservation and the like. CN106449136B patent of Ponfaphenanthrene et al invented an alpha-nickel hydroxide cobalt electrode material, its preparation method and application, the preparation process is simple, cost is low, environment-friendly, efficiency is high, it is suitable for industrial scale-up production, the obtained composite electrode has the advantages of high specific capacity and excellent cycling stability. However, like other transition metal-based double hydroxides or hydroxides and other battery active materials, nickel cobalt has poor conductivity and poor rate capability due to the characteristics of semiconductors, and particularly, at a high rate, the kinetics of nickel cobalt is controlled by a diffusion control process and a phase change process, so that the structure of nickel cobalt is not stable enough, the active materials are lost, and the cycle performance of the energy storage device is poor directly. Therefore, how to effectively solve the problems of poor conductivity, unstable microstructure, poor rate capability, unstable cycle and the like of the nickel-cobalt layered double hydroxide becomes an urgent research for novel energy storage devices.
Compared with a nickel-based active material, some people change the electrochemical properties of an electrode through research on a bearing matrix, and the electrochemical properties such as a three-dimensional structure, a porous structure and the like are widely applied to electrochemical energy storage devices. The problems of poor conductivity, unstable microstructure, poor rate, unstable cycle and the like of nickel-cobalt layered double hydroxide are improved, and CN111816453A patent of Shenjuan et al discloses a three-dimensional silicon structure/nickel-cobalt hydroxide based composite electrode material and a preparation method thereofThe composite electrode obtained has high charge-discharge reversibility, high specific capacity, high multiplying power and excellent electrochemical performance. However, the three-dimensional silicon structure of the fabric lacks flexibility, and cannot well meet the energy supply requirement of intelligent clothes. CN110993365A of Heucheli et al discloses an electrode material of self-growing bimetallic MOF (organic metal framework) and its derivatives on foamed nickel, which uses bimetallic MOFs sheet as precursor to grow array-like multiple NiCo on foamed nickel substrate2S4Nanosheets. The specific surface area of the matrix is increased by porous materials MOFs, rich reaction sites are provided for the growth and oxidation reduction of active substances, and the specific capacity and the cycling stability of the electrode are increased. But the foam nickel substrate is still not flexible, and fusion is difficult to realize in the fields of wearable electronic equipment and intelligent clothing.
In the prior art, a nickel-cobalt flexible electrode is prepared on carbon cloth, for example, a patent with publication number CN109449011A discloses a preparation method of a nickel cobaltate flexible electrode with a needle-shaped network structure by using carbon fiber as a support, a carbon fiber precursor is prepared from a PAN solution by an electrostatic spinning method, and then the carbon fiber precursor is subjected to pre-oxidation treatment and carbonization treatment at low temperature to obtain flexible carbon fiber; then soaking the flexible carbon fiber in a mixed solution of nickel salt and cobalt salt, carrying out hydrothermal reaction by taking urea as a precipitator, and finally calcining to obtain the nickel cobaltate flexible electrode material with the needle-shaped network structure and taking the carbon fiber as a support body. The Chinese patent with application number 201810510211.8 discloses a nanometer nickel cobaltate carbon cloth electrode and a preparation method thereof, wherein the method comprises the steps of cutting carbon cloth and carrying out ultrasonic treatment to activate carbon fibers; and then growing nickel cobaltate on the carbon cloth in sequence by a hydrothermal method, electroplating by taking Ag/AgCl as a reference electrode, washing with water, washing with alcohol, and performing heat treatment to obtain the flexible electrode material. The Chinese patent with application number 201810154690.4 discloses a nanosheet array nickel cobaltate-carbon composite material and a preparation method thereof, the method comprises the steps of carrying out ultrasonic treatment on wet tissues, then adding the wet tissues, nickel nitrate, cobalt nitrate, urea and hexamethylenetetramine into an ethanol solution, carrying out hydrothermal treatment, and carbonizing to obtain the nanosheet array nickel cobaltate on the surface of carbon fibers. The Chinese invention patent with application number 201910083401.0 discloses a carbon cloth loaded nickel-cobalt-oxygen nanosheet composite material, a preparation method thereof and application of an electrode, wherein cobalt nitrate and nickel nitrate are dissolved in deoxidized deionized water and are stirred and dissolved in a gas protective atmosphere to obtain a mixed salt solution; uniformly stirring a sodium hydroxide solution and a mixed salt solution at room temperature, centrifuging to obtain a precipitate, and cleaning with deionized water and absolute ethyl alcohol; and drying the obtained precipitate in vacuum to obtain a precursor, and sintering to obtain the nickel-cobalt-oxygen nanosheet composite catalyst for the cathode of the air battery.
However, in the above method, the carbon cloth is used as a substrate, and although the flexibility of the electrode is improved to a certain extent, the carbon fibers themselves used for manufacturing the carbon cloth have problems such as high modulus and brittle fracture when the fibers are bent to a large extent, so that the mechanical flexibility of the carbon cloth is far from that of a fabric substrate, and the number of bending times, the bending degree and the like of the carbon cloth have a great influence on the electrode. In addition, the method can obtain the activated carbon fiber (such as electrostatic spinning, oxidation, high-temperature carbonization and the like) by carrying out multiple treatments, and has the disadvantages of complicated treatment process and high cost. The stability of the prepared electrode still needs to be improved.
In view of the above drawbacks, it is actually necessary to provide a method for preparing a flexible self-supporting working electrode with simple operation, low cost and good bonding force.
Disclosure of Invention
The nickel-cobalt double hydroxide/metal organic frame/fabric flexible electrode well solves the problems, and has the characteristics of good flexibility, high specific capacity, good rate capability, good cycling stability and the like. The metal organic framework is used as a precursor to enable active substances to be uniformly loaded and to be more orderly, a charge transmission path is shortened, electrochemical impedance is reduced, the problem of expansion of the nickel anode can be effectively solved, and stability is improved. And the electrode has no binder, so that the specific capacity of the electrode is further increased.
Aiming at the defects of the prior art, the invention provides a preparation method of a flexible nickel-cobalt double hydroxide/metal organic frame/fabric flexible electrode, and the electrode has the characteristics of good flexibility, high specific capacity, good rate capability and cycling stability and the like.
The invention provides a preparation method of a flexible nickel-cobalt double hydroxide/metal organic framework/fabric electrode, which comprises the following steps:
(1) dissolving cobalt salt in deionized water, stirring to obtain a solution with a concentration of 0.01-0.5mol L-1(ii) a Dissolving organic compound in deionized water, stirring to obtain solution with concentration of 0.1-1mol L-1. Mixing the above two solutions in equal volume, and stirring. And adding the cleaned conductive fabric, carrying out hydrothermal reaction, washing and drying to obtain the metal organic framework/fabric.
Preferably, the conductive fabric is one of silver-plated or nickel-plated polyester, nylon, aramid or polypropylene, and the substrate has good flexibility. The conductive fabric is one of a knitted, woven or non-woven fabric.
The conductive fabric is placed in absolute ethyl alcohol for ultrasonic cleaning for 10-30 min before an experiment, then is washed by deionized water, and is dried by an oven for standby.
Preferably, the cobalt salt is Co (NO)3)2·6H2O、CoSO4·6H2One of O and the other; the organic compound is 2-methylimidazole.
Preferably, the hydrothermal reaction is carried out at the temperature of 0-80 ℃ for 0.1-5 h.
(2) Dissolving nickel salt in deionized water, stirring to obtain a solution with a concentration of 0.01-0.5mol L-1. And (2) putting the sample obtained in the step (1) into the solution, reacting, washing and drying to obtain the nickel-cobalt double hydroxide/metal organic framework/fabric electrode.
Preferably, the nickel salt is Ni (NO)3）2·6H2O、NiSO4·6H2O is one of the compounds.
Preferably, the reaction temperature is 0-80 ℃, and the reaction time is 0.5-10 h.
The invention provides an application of a flexible nickel-cobalt double hydroxide/metal organic frame/fabric electrode in the field of nickel-zinc flexible batteries.
Advantageous effects
The invention discloses a preparation method of a flexible nickel-cobalt double hydroxide/metal organic frame/fabric electrode, which has the advantages that:
1) the invention adopts the organic metal frame carrier, which increases the specific surface area of the matrix, thereby improving the specific capacitance;
2) the adopted metal organic framework substrate promotes the nickel-cobalt double hydroxide to have good structural stability, and the structure is not easy to collapse after long-term cyclic use, so that the specific capacitance and the cyclic service life of the nickel-cobalt double hydroxide are improved (the capacity retention rate is 54 percent after 2000 cycles);
3) has more electrically active contact points and active sites, thereby improving the conductivity and specific capacitance, and the electrode of the invention has 0.2mA cm in 1M KOH-2The mass specific capacitance reaches 228.7mAh g under the current density-1。
Drawings
FIG. 1 is a SEM photograph of a sample prepared in example 1 (a)1，a2Is a nickel-plated fabric, b1，b2Is a metal organic framework/nickel-plated fabric, c1，c2Is a nickel cobalt double hydroxide/metal organic frame/nickel plated fabric).
Fig. 2 shows the flexibility (folding, twisting, etc.) of the electrode made in example 1.
Fig. 3 shows CV curves of nickel-plated fabric, metal-organic frame/nickel-plated fabric, and nickel-cobalt double hydroxide/metal-organic frame/fabric electrode in a 1M KOH solution three-electrode test, respectively.
Fig. 4 is a graph showing the charging and discharging curves of nickel-plated fabric, metal organic frame/nickel-plated fabric, and nickel-cobalt double hydroxide/metal organic frame/fabric electrode in a 1M KOH solution three-electrode test, respectively.
Figure 5 is a CV curve of a nickel cobalt double hydroxide/metal organic framework/fabric electrode at different scan rates in a 1M KOH solution three electrode test.
Fig. 6 is a charge-discharge curve of a nickel-cobalt double hydroxide/metal organic framework/fabric electrode under different current densities in a 1M KOH solution three-electrode test.
FIG. 7 is a charge-discharge cycle curve for a nickel-cobalt double hydroxide/metal organic framework/fabric electrode at 10mA/cm in a 1M KOH solution three-electrode test.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
A preparation method of a flexible nickel-cobalt double hydroxide/metal organic framework/fabric electrode comprises the following steps:
(1) putting the cut nickel-plated fabric (4 x 4 cm) into a beaker filled with absolute ethyl alcohol, ultrasonically stirring for 10-30 minutes, and then drying for later use;
(2) weigh 0.43g Co (NO)3)2·6H2Dissolving O and 0.99g 2-methylimidazole in 30mL of deionized water respectively, and uniformly stirring and mixing the two to form a solution A;
(3) putting the fabric obtained in the step (1) into the solution A, carrying out hydrothermal reaction for 1 hour at the temperature of 20 ℃, taking out, cleaning and drying to obtain a metal organic framework/fabric;
(4) weighing 0.17g of NiSO4·6H2And (3) dissolving O in 40mL of deionized water, uniformly stirring to obtain a solution B, putting the sample obtained in the step (3) into the solution B, carrying out hydrothermal reaction for 1.5 hours at the temperature of 20 ℃, taking out, cleaning and drying to obtain the nickel-cobalt double hydroxide/metal organic frame/fabric electrode.
The fabric electrode prepared in example 1 was excellent in performance. As shown in FIG. 1, a1Is a cleaned nickel cloth, b1Is a metal organic framework/fabric, c1Is a nickel cobalt double hydroxide/metal organic frame/fabric sample. In the corresponding SEM picture, the metal organic framework grows on the nickel-plated fabric uniformly and orderly, the nickel-cobalt double hydroxide grows on the metal organic framework uniformly and orderly, the metal organic framework is used as a precursor to enable active substances to be uniformly loaded, the active substances are more orderly, the charge transmission path is shortened, the electrochemical impedance is reduced, and the framework can effectively solve the problem of nickel anodeSwelling problem, and improved stability. And the electrode has no binder, so that the specific capacity of the electrode is further increased. As can be seen from FIG. 2, the electrode designed by the invention can be bent and has good flexibility.
At a concentration of 1mol L-1In the KOH solution, the electrochemical performance of the nickel-cobalt double hydroxide/metal-organic frame/fabric electrode prepared in the embodiment of the present invention is studied, and the specific process is as follows:
adopting a standard three-electrode system, taking a nickel-cobalt double hydroxide/metal organic frame/fabric electrode as a working electrode, putting the working electrode into a KOH solution, taking a mercury/mercury oxide electrode as a reference electrode, taking a platinum sheet electrode as a counter electrode, and sweeping the working electrode at 5/10/20/30/40/50/100mV s within the potential range of 0-0.6V-1Testing a linear sweep voltammetry curve; in the voltage range of 0-0.5 at 0.2/0.5/1/2/5/10mA cm-2The multiplying power charge-discharge test is carried out on the current density, and the electrode capacity, multiplying power performance and cycling stability of the current density are tested.
Fig. 3, 4 compare the electrochemical performance of the electrodes at different stages. It can be seen that the nickel-cobalt double hydroxide is successfully grown on the surface of the fabric and shows ultra-high electrochemical activity. The main properties of the electrode are provided by nickel cobalt double hydroxide, relative to the precursor.
Fig. 5, 6 and 7 show the electrochemical spectra of the electrode obtained in example 1, which has strong oxidation-reduction peak and high electrochemical activity. And has a large specific capacity (228.7 mAh g)-1) Good rate capability (capacity retention rate of 65% after 50 times of current increase) and stable cycle stability (capacity retention rate of 54% after 2000 cycles).
Example 2
A preparation method of a flexible nickel-cobalt double hydroxide/metal organic framework/fabric electrode comprises the following steps:
(1) putting the cut nickel-plated fabric (4 x 4 cm) into a beaker filled with absolute ethyl alcohol, ultrasonically stirring for 10-30 minutes, and then drying for later use;
(2) weigh 0.43g Co (NO)3)2·6H2O and 0.99g 2-methylimidazole were dissolved in 30mL each to removeMixing the two solutions uniformly to form a solution A;
(3) putting the fabric obtained in the step (1) into the solution A, carrying out hydrothermal reaction for 4 hours at the temperature of 20 ℃, taking out, cleaning and drying to obtain a metal organic framework/fabric;
(4) weighing 0.17g of NiSO4·6H2And (3) dissolving O in 40mL of deionized water, uniformly stirring to obtain a solution B, putting the sample obtained in the step (3) into the solution B, carrying out hydrothermal reaction for 1.5 hours at the temperature of 20 ℃, taking out, cleaning and drying to obtain the nickel-cobalt double hydroxide/metal organic frame/fabric electrode.
The metal organic framework prepared in example 2 has a relatively thick thickness and a loading capacity of more than 2mg cm-2The too thick lamella makes the nickel cobalt double hydroxide grow incompletely, is unfavorable for the quick conduction of electric charge and ions, and also makes its inside difficult to contact the electrolyte and take part in the reaction completely. The electrochemical performance was slightly inferior to that of example 1.
Example 3
A preparation method of a flexible nickel-cobalt double hydroxide/metal organic framework/fabric electrode comprises the following steps:
(1) putting the cut nickel-plated fabric (1 x 1 cm) into a beaker filled with absolute ethyl alcohol, ultrasonically stirring for 10-30 minutes, and then drying for later use;
(2) weigh 0.43g Co (NO)3)2·6H2Dissolving O and 0.99g 2-methylimidazole in 30mL of deionized water respectively, and uniformly stirring and mixing the two to form a solution A;
(3) putting the fabric obtained in the step (1) into the solution A, carrying out hydrothermal reaction for 4 hours at the temperature of 10 ℃, taking out, cleaning and drying to obtain a metal organic framework/fabric;
(4) weighing 0.17g of NiSO4·6H2And (3) dissolving O in 40mL of deionized water, uniformly stirring to obtain a solution B, putting the sample obtained in the step (3) into the solution B, carrying out hydrothermal reaction for 6 hours at the temperature of 20 ℃, taking out, cleaning and drying to obtain the nickel-cobalt double hydroxide/metal organic frame/fabric electrode.
The metal organic framework prepared in example 3 has a relatively thickThick, and the loading capacity exceeds 2mg cm-2The growth time of the nickel-cobalt double hydroxide is prolonged, but the electrolyte is not easy to contact with the internal active substance in the test process, so that the electrochemical performance of the nickel-cobalt double hydroxide is weakened.
Example 4
A preparation method of a flexible nickel-cobalt double hydroxide/metal organic framework/fabric electrode comprises the following steps:
(1) putting the cut nickel-plated fabric (1 x 1 cm) into a beaker filled with absolute ethyl alcohol, ultrasonically stirring for 10-30 minutes, and then drying for later use;
(2) weigh 0.22g Co (NO)3)2·6H2Dissolving O and 0.99g 2-methylimidazole in 30mL of deionized water respectively, and uniformly stirring and mixing the two to form a solution A;
(3) putting the fabric obtained in the step (1) into the solution A, carrying out hydrothermal reaction for 1 hour at the temperature of 20 ℃, taking out, cleaning and drying to obtain a metal organic framework/fabric;
(4) weighing 0.17g of NiSO4·6H2And (3) dissolving O in 40mL of deionized water, uniformly stirring to obtain a solution B, putting the sample obtained in the step (3) into the solution B, carrying out hydrothermal reaction for 1.5 hours at the temperature of 20 ℃, taking out, cleaning and drying to obtain the nickel-cobalt double hydroxide/metal organic frame/fabric electrode.
The metal organic frame prepared in example 4 is thinner, and the performance of the prepared nickel cobalt double hydroxide/metal organic frame/fabric electrode is improved, but the nickel cobalt double hydroxide/metal organic frame/fabric electrode is not optimal.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (7)
1. A preparation method of a flexible nickel-cobalt double hydroxide/metal organic frame/fabric electrode is characterized by comprising the following steps:
(1) cobalt salt is dissolved in deionized waterStirring in water to obtain a solution with a concentration of 0.01-0.5mol L-1(ii) a Dissolving organic compound in deionized water, stirring to obtain solution with concentration of 0.1-1mol L-1(ii) a Mixing the two solutions in equal volume, and stirring; adding the cleaned conductive fabric, performing hydrothermal reaction, washing and drying to obtain a metal organic framework/fabric;
(2) dissolving nickel salt in deionized water, stirring to obtain a solution with a concentration of 0.01-0.5mol L-1(ii) a And (2) putting the sample obtained in the step (1) into the solution, reacting, washing and drying to obtain the nickel-cobalt double hydroxide/metal organic framework/fabric electrode.
2. The method for preparing the flexible nickel-cobalt double hydroxide/metal-organic framework/fabric electrode according to claim 1, wherein the conductive fabric in the step (1) is one of silver-plated or nickel-plated polyester, nylon, aramid or polypropylene.
3. The method of claim 1, wherein the cobalt salt in step (1) is Co (NO)3)2·6H2O or CoSO4·6H2O; the organic compound is 2-methylimidazole.
4. The method for preparing the flexible nickel-cobalt double hydroxide/metal-organic framework/fabric electrode according to claim 1, wherein in the step (1), the hydrothermal reaction temperature is 0-80 ℃ and the reaction time is 0.1-5 h.
5. The method for preparing a flexible nickel cobalt double hydroxide/metal organic frame/fabric electrode as claimed in claim 1, wherein in the step (2), the nickel salt is Ni (NO)3)2·6H2O or NiSO4·6H2O。
6. A nickel cobalt double hydroxide/metal organic frame/fabric electrode prepared according to the preparation method of any one of claims 1 to 5.
7. Use of the nickel cobalt double hydroxide/metal organic frame/fabric electrode of claim 6 in a positive electrode material for a nickel zinc battery.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113903604A (en) * | 2021-10-12 | 2022-01-07 | 青岛科技大学 | Preparation method of electrode for spiny metal hydroxide through-growth MOF material |
| CN114430076A (en) * | 2022-01-25 | 2022-05-03 | 中国石油大学(华东) | Full MOF flexible nickel-iron battery and preparation method thereof |
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| CN113903604A (en) * | 2021-10-12 | 2022-01-07 | 青岛科技大学 | Preparation method of electrode for spiny metal hydroxide through-growth MOF material |
| CN113903604B (en) * | 2021-10-12 | 2023-12-26 | 青岛科技大学 | Preparation method of electrode of thorn-shaped metal hydroxide-MOF material |
| CN114430076A (en) * | 2022-01-25 | 2022-05-03 | 中国石油大学(华东) | Full MOF flexible nickel-iron battery and preparation method thereof |
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