CN111244479B - N-Ni(Se)2CC self-supporting air electrode, preparation method thereof and flexible zinc-air battery - Google Patents

N-Ni(Se)2CC self-supporting air electrode, preparation method thereof and flexible zinc-air battery Download PDF

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CN111244479B
CN111244479B CN202010068800.2A CN202010068800A CN111244479B CN 111244479 B CN111244479 B CN 111244479B CN 202010068800 A CN202010068800 A CN 202010068800A CN 111244479 B CN111244479 B CN 111244479B
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CN111244479A (en
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彭生杰
熊一星
李林林
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Nanjing University of Aeronautics and Astronautics
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Abstract

The invention relates to N-Ni (Se)2A/CC self-supporting air electrode, a preparation method thereof and a flexible zinc-air battery belong to the technical field of zinc-air batteries. N-Ni (Se) of the present invention2The preparation method of the/CC self-supporting electrode comprises the following steps: the carbon substrate loaded with the nickel selenide is subjected to heat preservation for 1-3 hours at the temperature of 500 ℃ in the atmosphere of ammonia gas to obtain the nickel selenide carbon substrate; the carbon substrate is any one of carbon cloth, carbon paper and conductive metal foam. N-Ni (Se) of the present invention2The preparation method of the/CC self-supporting electrode comprises the steps of carrying out high-temperature treatment on a carbon substrate loaded with nickel selenide in an ammonia atmosphere, doping nitrogen elements into the nickel selenide loaded on the carbon substrate to generate the nitrogen-doped nickel selenide composite electrode material, regulating and controlling an electronic structure of a metal center by using nitrogen doping, improving intrinsic catalytic activity and improving the performance of a zinc-air battery adopting the self-supporting electrode.

Description

N-Ni(Se)2CC self-supporting air electrode, preparation method thereof and flexible zinc-air battery
Technical Field
The invention relates to N-Ni (Se)2A/CC self-supporting air electrode, a preparation method thereof and a flexible zinc-air battery belong to the technical field of zinc-air batteries.
Background
Electrochemical cells are devices that convert chemical energy into electrical energy through electrochemical reactions, such as metal-air cells, including zinc-air cells and aluminum-air cells. The metal-air battery is considered as a novel fuel battery, and the metal is equivalent to a fuel used as a negative active material of the battery and performs an oxidation-reduction reaction with oxygen in the air to realize conversion of chemical energy and electric energy. Compared with hydrogen, metals have the characteristics of easier storage, transportation, recovery and safety. And the metal-air fuel cell has many advantages that the traditional hydrogen fuel cell does not have, such as abundant fuel (zinc, etc.), inexhaustible energy supply of the metal-air cell, etc.
With the rapid development of portable wearable devices, the high energy density characteristic of metal-air batteries has attracted extensive attention. In particular, the flexible all-solid-state zinc-air battery takes zinc as a negative electrode, an air electrode as a positive electrode and hydrogel as a solid electrolyte, can realize bending and folding, and has wide application space. In the oxidation-reduction reaction of the zinc-air battery, the oxygen reaction of the anode has a slower electrochemical kinetic process, the overpotential of the zinc-air battery is seriously influenced, and the anode oxygen reaction catalyst can improve the problem. At present, noble metal catalysts such as platinum, iridium and rhodium base have excellent catalytic performance, but the large-scale commercial application of the noble metal catalysts is seriously influenced by the defects of high price, rare reserves, easy poisoning and activity loss and the like.
The nickel-based catalyst is widely applied to the field of electrocatalysis due to abundant reserves and low price. For example, the Chinese patent with application publication number CN105609794A discloses an air electrode catalyst of a zinc-air battery, the chemical general formula of which is Al2xFe2-2xNi4yTi2-2yO7Wherein x is more than or equal to 0.1 and less than or equal to 0.5, and y is more than or equal to 0.5 and less than or equal to 1. The catalyst is used as an air electrode catalyst of a zinc-air battery, can reduce the polarization of an oxygen reduction process, and is low in price. However, the catalyst is an oxide, so that the resistance is high, and the cycle performance of the zinc-air battery prepared by the nickel-based catalyst needs to be improved.
Disclosure of Invention
It is an object of the present invention to provide a N-Ni (Se)2The preparation method of the/CC self-supporting electrode is used for improving the cycle performance of the zinc-air battery.
Another object of the present invention is to provide N-Ni (Se) prepared by the above preparation method2a/CC self-supporting electrode. It is another object of the present invention to provide a method of using the aboveA flexible zinc-air cell supporting an electrode.
The technical scheme adopted by the invention for solving the technical problems is as follows:
N-Ni (Se)2The preparation method of the/CC self-supporting electrode comprises the following steps: the carbon substrate loaded with the nickel selenide is subjected to heat preservation for 1-3 hours at the temperature of 500 ℃ in the atmosphere of ammonia gas to obtain the nickel selenide carbon substrate; the carbon substrate is any one of carbon cloth, carbon paper and conductive metal foam.
N-Ni (Se) of the present invention2The preparation method of the/CC self-supporting electrode comprises the step of carrying out high-temperature treatment on a carbon substrate loaded with nickel selenide in an ammonia atmosphere to ensure that nitrogen elements are doped into the nickel selenide loaded on the carbon substrate to generate the nitrogen-doped nickel selenide composite electrode material. The nitrogen doping can be utilized to regulate and control the electronic structure of the metal center, the catalytic activity is improved, and the efficiency of the zinc-air battery adopting the self-supporting electrode is improved.
N-Ni (Se) of the present invention2N-Ni (Se) prepared by preparation method of CC self-supporting electrode2the/CC self-supporting electrode has larger aperture, uniform and consistent pore structure and smaller resistance, and is beneficial to improving the cycle performance of the zinc-air battery. Further, N-Ni (Se)2In the/CC self-supporting electrode, the catalyst is compounded with the conductive substrate, so that the overall conductivity and stability of the air electrode can be improved, and the cycle performance of the zinc-air battery is further improved.
In the preparation method, the temperature is kept at 300-plus-500 ℃ for 1-3h, and the temperature is raised to 300-plus-500 ℃ at the heating rate of 1-5 ℃/min and kept for 1-3 h.
The carbon matrix loaded with the nickel selenide is prepared by a method comprising the following steps:
1) mixing a nickel source, a carbon matrix and an organic solvent, and carrying out hydrothermal reaction for 6-10h at 55-65 ℃ to obtain a reacted mixed solution; the nickel source is any one of nickel nitrate, nickel acetate and nickel chloride;
2) uniformly mixing the solution reacted in the step 1) with persulfate and ammonia water, and then carrying out hydrothermal reaction for 10-20h at the temperature of 150-2a/CC material; the persulfate is potassium persulfate or sodium persulfate;
3) the Ni (OH) prepared in the step 2)2the/CC material was placed in an atmosphere tube furnace and heated in Ni (OH)2Placing a selenium source at the upstream of the CC material, and then carrying out a selenization reaction at the temperature of 500 ℃ for 1-3h in an inert atmosphere to obtain the material; the selenium source is selenium.
When the carbon substrate loaded with the nickel selenide is prepared, a nano array of a nickel hydroxide precursor is grown on the conductive substrate through hydrothermal reaction, and then the carbon substrate loaded with the nickel selenide is prepared through selenylation reaction in inert atmosphere, so that the nickel selenide loaded on the carbon substrate is uniformly arranged in an array and has a uniform pore structure.
The organic solvent in the step 1) is obtained by mixing ethanol and n-butanol in a volume ratio of 1-2: 1. The using amount of the mixed solvent in the step 1) is 12-18mL of the mixed solvent for every 1g of the nickel source. The carbon substrate in the step 1) is respectively cleaned by ultrasonic in acetone, ethanol and water for 1-3min before use.
The usage amount of the persulfate in the step 2) is 0.2-0.3mol per 1g of the nickel source.
The usage amount of the ammonia water in the step 2) is 5-10mL of ammonia water for each 1g of nickel source. The mass fraction of ammonia in the ammonia water is 25-28%.
Ni (OH) produced in the step 2)2Drying the/CC material at 55-65 ℃ for 1-2 h.
The heating rate of the step 3) to 300-500 ℃ is 1-5 ℃/min.
The upstream in step 3) means a position upstream in the direction of the flow of the atmosphere gas in the atmosphere tube furnace. The inert atmosphere in the step 3) is argon or nitrogen. The usage amount of the selenium source in the step 3) is 0.06-1g of selenium source per 1g of nickel source.
N-Ni (Se) prepared by the preparation method2a/CC self-supporting electrode.
A flexible zinc-air battery comprises a flexible package shell, and a positive electrode, a negative electrode and an electrolyte which are arranged in the flexible package shell, wherein the positive electrode is the N-Ni (Se)2a/CC self-supporting electrode.
In the flexible zinc-air battery, the shell is an aluminum-plastic film shell. The negative electrode is a zinc sheet. The electrolyte is an acrylic hydrogel. Further preferably, the flexible zinc-air battery is an all-solid-state zinc-air battery.
The invention has the beneficial effects that:
N-Ni (Se) of the present invention2The preparation method of the/CC self-supporting electrode comprises the steps of growing a transition metal composite catalyst on a substrate in situ, doping nitrogen elements to obtain N-Ni (Se)2the/CC self-supporting electrode has a uniform pore structure, forms a nitrogen-doped nickel selenide nano array, has low resistance, low cost and excellent performance, and can be applied to a zinc-air battery. N-Ni (Se) of the present invention2N-Ni (Se) prepared by preparation method of CC self-supporting electrode2the/CC self-supporting electrode material has regular and compact appearance, the thickness of about 170nm, the transverse length of about 1.4 mu m, the aperture of about 20-100nm, uniformity, low resistance and obvious flexibility characteristic. The flexible zinc-air battery assembled based on the self-supporting electrode is an all-solid-state zinc-air battery with a sandwich structure, has good charge-discharge potential difference and stability, also has mechanical flexibility, and has a good application prospect.
Drawings
FIG. 1 shows N-Ni (Se) in example 1 of the present invention2SEM image of/CC free-standing electrode;
FIG. 2 shows N-Ni (Se) in example 1 of the present invention2TEM image of/CC free-standing electrode;
FIG. 3 shows N-Ni (Se) in example 1 of the present invention2XRD pattern of/CC self-supporting electrode;
fig. 4 is a power performance curve of the flexible zinc-air cell in example 1 of the present invention;
fig. 5 is a cycle performance curve of the flexible zinc-air battery in example 1 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention easier to understand, the present invention will be described in detail with reference to specific embodiments.
Example 1
Of the present embodimentN-Ni(Se)2The preparation method of the/CC self-supporting air electrode comprises the following steps:
1) putting carbon cloth with the size of 1cm x 2cm into acetone, performing ultrasonic treatment for 2min, taking out, putting into ethanol, performing ultrasonic treatment for 2min, then putting into deionized water, performing ultrasonic treatment for 2min, and taking out.
18mL of ethanol and 9mL of n-butanol were mixed uniformly to obtain a mixed solvent, and then 1.5g of nickel acetate tetrahydrate (Ni (CHCOO)2·4H2O), then preserving the heat at 60 ℃, stirring for 30min, then transferring to a reaction kettle, adding the treated carbon cloth, carrying out hydrothermal reaction at 60 ℃ for 8h, and obtaining Ni (CHCOO)2a/CC mixed solution.
2) Adding 0.36mol of potassium persulfate (K) into the mixed solution after the reaction in the step 1)2S2O8) And 9mL of ammonia water, and uniformly mixing to obtain a blue mixed solution; then carrying out hydrothermal reaction at 180 ℃ for 12 h. After the reaction, the carbon cloth is taken out, washed by ethanol and deionized water in sequence, and then put into a drying oven to be dried for 2 hours at the temperature of 60 ℃ to obtain Ni (OH)2the/CC samples.
3) The Ni (OH) prepared in the step 2)2the/CC sample was loaded into a magnetic boat, and 0.1g of selenium powder was added to the magnetic boat, which was then put into an atmosphere tube furnace to make Ni (OH)2the/CC sample and the selenium powder are respectively positioned at the downstream and the upstream of the atmosphere gas flow. Then argon is introduced into the tubular furnace, the temperature of the tubular furnace is raised to 400 ℃ at the heating rate of 1 ℃/min, the tubular furnace is kept for 1h under the protection of argon, and then the temperature is naturally reduced to the room temperature to obtain Ni (Se)2the/CC samples.
4) Mixing the Ni (Se) prepared in the step 3)2Putting the CC sample in a tubular furnace, introducing ammonia gas, heating the tubular furnace to 400 ℃ at the heating rate of 1 ℃/min, preserving the heat for 1h in the ammonia gas atmosphere, and naturally cooling to room temperature to obtain N-Ni (Se)2a/CC self-supporting electrode.
The flexible zinc-air battery comprises an aluminum plastic film flexible packaging shell, and also comprises a positive electrode, a negative electrode and an electrolyte which are arranged in the flexible packaging shell, wherein the positive electrode is N-Ni (Se) prepared by the method2(CC) self-supportingThe support electrode, the negative electrode are zinc sheets, and the electrolyte is acrylic acid hydrogel.
Example 2
The preparation method of the self-supporting air electrode of the embodiment comprises the following steps:
1) putting carbon cloth with the size of 1cm x 2cm into acetone, performing ultrasonic treatment for 2min, taking out, putting into ethanol, performing ultrasonic treatment for 2min, then putting into deionized water, performing ultrasonic treatment for 2min, and taking out.
18mL of ethanol and 9mL of n-butanol were mixed uniformly to obtain a mixed solvent, and then 1.5g of nickel acetate tetrahydrate (Ni (CHCOO)2·4H2O), then preserving the heat at 60 ℃, stirring for 30min, then transferring to a reaction kettle, adding the treated carbon cloth, carrying out hydrothermal reaction at 60 ℃ for 8h, and obtaining Ni (CHCOO)2a/CC mixed solution.
2) Adding 0.36mol of potassium persulfate (K) into the mixed solution after the reaction in the step 1)2S2O8) And 9mL of ammonia water (stored at 0 ℃ before use), and uniformly mixing to obtain a blue mixed solution; then carrying out hydrothermal reaction at 180 ℃ for 12 h. After the reaction, the carbon cloth is taken out, washed by ethanol and deionized water in sequence, and then put into a drying oven to be dried for 2 hours at the temperature of 60 ℃ to obtain Ni (OH)2the/CC samples.
3) The Ni (OH) prepared in the step 2)2the/CC sample was loaded into a magnetic boat, and 0.1g of selenium powder was added to the magnetic boat, which was then put into an atmosphere tube furnace to make Ni (OH)2the/CC sample and the selenium powder are respectively positioned at the downstream and the upstream of the atmosphere gas flow. Then argon is introduced into the tube furnace, the temperature of the tube furnace is raised to 400 ℃ at the heating rate of 5 ℃/min, the tube furnace is kept warm for 3h under the protection of argon, and then the temperature is naturally reduced to room temperature to obtain Ni (Se)2the/CC samples.
4) Mixing the Ni (Se) prepared in the step 3)2Putting the CC sample in a tubular furnace, introducing ammonia gas, heating the tubular furnace to 300 ℃ at the heating rate of 3 ℃/min, preserving the heat for 3 hours in the ammonia gas atmosphere, and naturally cooling to room temperature to obtain N-Ni (Se)2a/CC self-supporting electrode.
Flexible zinc hollow of the embodimentThe gas battery comprises an aluminum plastic film flexible packaging shell, and also comprises a positive electrode, a negative electrode and an electrolyte which are arranged in the flexible packaging shell, wherein the positive electrode is N-Ni (Se) prepared by the method2the/CC self-supporting electrode, the negative electrode are zinc sheets, and the electrolyte is acrylic acid hydrogel.
Example 3
The preparation method of the self-supporting air electrode of the embodiment comprises the following steps:
1) putting carbon cloth with the size of 1cm x 2cm into acetone, performing ultrasonic treatment for 2min, taking out, putting into ethanol, performing ultrasonic treatment for 2min, then putting into deionized water, performing ultrasonic treatment for 2min, and taking out.
18mL of ethanol and 9mL of n-butanol were mixed uniformly to obtain a mixed solvent, and then 1.5g of nickel acetate tetrahydrate (Ni (CHCOO)2·4H2O), then preserving the heat at 60 ℃, stirring for 30min, then transferring to a reaction kettle, adding the treated carbon cloth, carrying out hydrothermal reaction at 60 ℃ for 8h, and obtaining Ni (CHCOO)2a/CC mixed solution.
2) Adding 0.36mol of potassium persulfate (K) into the mixed solution after the reaction in the step 1)2S2O8) And 9mL of ammonia water (stored at 0 ℃ before use), and uniformly mixing to obtain a blue mixed solution; then carrying out hydrothermal reaction at 180 ℃ for 12 h. After the reaction, the carbon cloth is taken out, washed by ethanol and deionized water in sequence, and then put into a drying oven to be dried for 2 hours at the temperature of 60 ℃ to obtain Ni (OH)2the/CC samples.
3) The Ni (OH) prepared in the step 2)2the/CC sample was loaded into a magnetic boat, and 0.1g of selenium powder was added to the magnetic boat, which was then put into an atmosphere tube furnace to make Ni (OH)2the/CC sample and the selenium powder are respectively positioned at the downstream and the upstream of the atmosphere gas flow. Then argon is introduced into the tubular furnace, the temperature of the tubular furnace is raised to 400 ℃ at the heating rate of 2 ℃/min, the tubular furnace is kept for 2 hours under the protection of argon, and then the temperature is naturally reduced to the room temperature to obtain Ni (Se)2the/CC samples.
4) Mixing the Ni (Se) prepared in the step 3)2Placing the CC sample in a tubular furnace, introducing ammonia gas, and heating the tubular furnace to the temperature at the heating rate of 5 ℃/minKeeping the temperature at 500 ℃ for 3h in the ammonia atmosphere, naturally cooling to room temperature to obtain N-Ni (Se)2a/CC self-supporting electrode.
The flexible zinc-air battery comprises an aluminum plastic film flexible packaging shell, and also comprises a positive electrode, a negative electrode and an electrolyte which are arranged in the flexible packaging shell, wherein the positive electrode is N-Ni (Se) prepared by the method2the/CC self-supporting electrode, the negative electrode are zinc sheets, and the electrolyte is acrylic acid hydrogel.
Example 4
The preparation method of the self-supporting air electrode of the embodiment comprises the following steps:
1) putting carbon cloth with size of 1cm x 2cm into acetone, performing ultrasonic treatment for 3min, taking out, putting into ethanol, performing ultrasonic treatment for 3min, then putting into deionized water, performing ultrasonic treatment for 3min, and taking out.
Uniformly mixing 9mL of ethanol and 9mL of n-butanol to obtain a mixed solvent, adding 1.5g of nickel nitrate, keeping the temperature at 60 ℃, stirring for 30min, transferring to a reaction kettle, adding treated carbon cloth, and carrying out hydrothermal reaction at 65 ℃ for 6h to obtain Ni (NO)3)2a/CC mixed solution.
2) Adding 0.36mol of potassium persulfate (K) into the mixed solution after the reaction in the step 1)2S2O8) And 15mL of ammonia water (stored at 0 ℃ before use) are uniformly mixed to obtain a blue mixed solution; then carrying out hydrothermal reaction at 150 ℃ for 20 h. After the reaction, the carbon cloth is taken out, washed by ethanol and deionized water in sequence, and then put into a drying oven to be dried for 1h at the temperature of 65 ℃ to obtain Ni (OH)2the/CC samples.
3) The Ni (OH) prepared in the step 2)2the/CC sample was loaded into a magnetic boat, and 0.1g of selenium powder was added to the magnetic boat, which was then put into an atmosphere tube furnace to make Ni (OH)2the/CC sample and the selenium powder are respectively positioned at the downstream and the upstream of the atmosphere gas flow. Then argon is introduced into the tube furnace, the temperature of the tube furnace is raised to 500 ℃ at the heating rate of 5 ℃/min, the tube furnace is kept for 1h under the protection of argon, and then the temperature is naturally reduced to the room temperature to obtain Ni (Se)2the/CC samples.
4) Will step withStep 3) production of Ni (Se)2Putting the CC sample in a tubular furnace, introducing ammonia gas, heating the tubular furnace to 400 ℃ at the heating rate of 2 ℃/min, preserving the heat for 3 hours in the ammonia gas atmosphere, and naturally cooling to room temperature to obtain N-Ni (Se)2a/CC self-supporting electrode.
The flexible zinc-air battery comprises an aluminum plastic film flexible packaging shell, and also comprises a positive electrode, a negative electrode and an electrolyte which are arranged in the flexible packaging shell, wherein the positive electrode is N-Ni (Se) prepared by the method2the/CC self-supporting electrode, the negative electrode are zinc sheets, and the electrolyte is acrylic acid hydrogel.
Example 5
The preparation method of the self-supporting air electrode of the embodiment comprises the following steps:
1) putting carbon cloth with the size of 1cm x 2cm into acetone, performing ultrasonic treatment for 1min, taking out, putting into ethanol, performing ultrasonic treatment for 1min, then putting into deionized water, performing ultrasonic treatment for 1min, and taking out.
18mL of ethanol and 9mL of n-butanol were mixed uniformly to obtain a mixed solvent, and then 1.5g of nickel acetate tetrahydrate (Ni (CHCOO)2·4H2O), then preserving the heat at 60 ℃ and stirring for 30min, then transferring the mixture into a reaction kettle, adding the treated carbon cloth, and carrying out hydrothermal reaction at 55 ℃ for 10h to obtain Ni (CHCOO)2a/CC mixed solution.
2) Adding 0.36mol of potassium persulfate (K) into the mixed solution after the reaction in the step 1)2S2O8) And 9mL of ammonia water (stored at 0 ℃ before use), and uniformly mixing to obtain a blue mixed solution; then carrying out hydrothermal reaction at 200 ℃ for 10 h. After the reaction, the carbon cloth is taken out, washed by ethanol and deionized water in sequence, and then put into a drying oven to be dried for 2 hours at the temperature of 55 ℃ to obtain Ni (OH)2the/CC samples.
3) The Ni (OH) prepared in the step 2)2the/CC sample was loaded into a magnetic boat, and 1g of selenium powder was added to the magnetic boat, which was then placed in an atmospheric tube furnace to make Ni (OH)2the/CC sample and the selenium powder are respectively positioned at the downstream and the upstream of the atmosphere gas flow. Then argon gas is introduced into the tube furnace, and the temperature rise rate is 1 ℃/minHeating the tubular furnace to 300 ℃, preserving heat for 3h under the protection of argon, and then naturally cooling to room temperature to obtain Ni (Se)2the/CC samples.
4) Mixing the Ni (Se) prepared in the step 3)2Putting the CC sample in a tubular furnace, introducing ammonia gas, heating the tubular furnace to 350 ℃ at the heating rate of 1 ℃/min, preserving the heat for 3 hours in the ammonia gas atmosphere, and naturally cooling to room temperature to obtain N-Ni (Se)2a/CC self-supporting electrode.
The flexible zinc-air battery comprises an aluminum plastic film flexible packaging shell, and also comprises a positive electrode, a negative electrode and an electrolyte which are arranged in the flexible packaging shell, wherein the positive electrode is N-Ni (Se) prepared by the method2the/CC self-supporting electrode, the negative electrode are zinc sheets, and the electrolyte is acrylic acid hydrogel.
Test examples
(1) Taking the N-Ni (Se) prepared in example 12the/CC self-supporting electrode is respectively tested by a scanning electron microscope and a transmission electron microscope, and the measured images are respectively shown in figure 1 and figure 2.
As can be seen from FIGS. 1 and 2, N-Ni (Se)2the/CC self-supporting electrode material has regular and compact appearance, the thickness of about 170nm, the transverse length of about 1.4 mu m, the pore diameter of about 20-100nm, and uniformity.
(2) Taking the N-Ni (Se) prepared in example 12the/CC self-supporting electrode is subjected to XRD test, and the XRD pattern is shown in figure 3.
As can be seen from FIG. 3, the N-Ni (Se) of the present invention2the/CC self-supporting electrode material has obvious NiSe2Characteristic peaks of the profile.
(3) The flexible zinc-air battery of example 1 was subjected to charge and discharge tests, and the test results are shown in fig. 4 and 5, respectively. (the dotted line in FIG. 4 is a discharge curve, the solid line is a power curve, the test interval is 1.5 v-0.5 v, the discharge rate is 10 mv/s. both the discharge rate and the charge rate in FIG. 5 are 10 mA/min.)
As is clear from FIGS. 4 and 5, the present invention is applied to N-Ni (Se)2The flexible zinc-air battery with the/CC self-supporting electrode has good charge and discharge performance, and has no obvious attenuation after being circulated for 1800 times.

Claims (5)

1. N-Ni (Se)2 The preparation method of the/CC self-supporting electrode is characterized by comprising the following steps: the method comprises the following steps: heating the carbon substrate loaded with the nickel selenide to 300-500 ℃ at the heating rate of 1-5 ℃/min in the ammonia atmosphere, and preserving the heat for 1-3 hours to obtain the nickel selenide carbon substrate; the carbon substrate is any one of carbon cloth and carbon paper;
the carbon matrix loaded with the nickel selenide is prepared by a method comprising the following steps:
1) mixing a nickel source, a carbon matrix and an organic solvent, and then carrying out solvothermal reaction for 6-10h at 55-65 ℃ to obtain a reacted mixed solution; the nickel source is any one of nickel nitrate, nickel acetate and nickel chloride;
2) uniformly mixing the solution reacted in the step 1) with persulfate and ammonia water, and then carrying out hydrothermal reaction for 10-20h at the temperature of 150-2 a/CC material; the persulfate is potassium persulfate or sodium persulfate;
3) the Ni (OH) prepared in the step 2)2 the/CC material was placed in an atmosphere tube furnace and heated in Ni (OH)2 Placing a selenium source at the upstream of the CC material, and then carrying out a selenization reaction at the temperature of 500 ℃ for 1-3h in an inert atmosphere to obtain the material; the selenium source is selenium;
the organic solvent in the step 1) is obtained by mixing ethanol and n-butanol in a volume ratio of 1-2: 1;
the usage amount of the persulfate in the step 2) is 0.2-0.3mol of persulfate per 1g of nickel source;
the using amount of the ammonia water in the step 2) is 5-10mL of ammonia water corresponding to each 1g of nickel source, and the mass fraction of ammonia in the ammonia water is 25-28%.
2. The N-Ni (Se) of claim 12 The preparation method of the/CC self-supporting electrode is characterized by comprising the following steps: ni (OH) produced in the step 2)2 Drying the/CC material at 55-65 ℃ for 1-2 h.
3. The N-Ni (Se) of claim 12 The preparation method of the/CC self-supporting electrode is characterized by comprising the following steps: the temperature rise in the step 3) is up to 300-500 DEG CThe rate is 1-5 deg.C/min.
4. N-Ni (Se) prepared by the preparation method of claim 12 a/CC self-supporting electrode.
5. The utility model provides a flexible zinc-air battery, includes flexible package shell and sets up anodal, negative pole, electrolyte in flexible package shell, its characterized in that: the positive electrode is N-Ni (Se) as defined in claim 42 a/CC self-supporting electrode.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104269565A (en) * 2014-08-18 2015-01-07 广州大学 Preparation method and use of multiwalled carbon nanotube (MWCNT)-loaded Ni0.85Se composite material
CN106025244A (en) * 2016-07-30 2016-10-12 复旦大学 Nickel selenide/graphene/carbon nanotube composite material and preparation method thereof
CN110400926A (en) * 2019-08-07 2019-11-01 福州大学 A kind of nitrogen-doped carbon cladding two-phase is interspersed type nickel cobalt bimetallic selenides electrode material and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130084474A1 (en) * 2010-03-18 2013-04-04 Randell L. Mills Electrochemical hydrogen-catalyst power system
CN108336373B (en) * 2017-12-27 2021-05-04 青岛科技大学 Preparation method of transition metal oxide nitrogen-phosphorus doped catalyst applied to zinc-air battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104269565A (en) * 2014-08-18 2015-01-07 广州大学 Preparation method and use of multiwalled carbon nanotube (MWCNT)-loaded Ni0.85Se composite material
CN106025244A (en) * 2016-07-30 2016-10-12 复旦大学 Nickel selenide/graphene/carbon nanotube composite material and preparation method thereof
CN110400926A (en) * 2019-08-07 2019-11-01 福州大学 A kind of nitrogen-doped carbon cladding two-phase is interspersed type nickel cobalt bimetallic selenides electrode material and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Controllable Synthesis of NixSe (0.5≤x≤1) Nanocrystals for Efficient Rechargeable Zinc-Air Batteries and Water Splitting;Xuerong Zheng et al.;《ACS Applied Materials & Interfaces》;20180404;第10卷;第13675-13684页 *
Energy-level engineered hollow N-doped NiS1.03 for Zn–Air batteries;Jingyan Zhang et al.;《Energy Storage Materials》;20191013;第25卷;第202-209页 *

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