CN114759172A - Preparation method of graphene/zinc oxide negative electrode material for zinc-based battery - Google Patents

Preparation method of graphene/zinc oxide negative electrode material for zinc-based battery Download PDF

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CN114759172A
CN114759172A CN202110496404.4A CN202110496404A CN114759172A CN 114759172 A CN114759172 A CN 114759172A CN 202110496404 A CN202110496404 A CN 202110496404A CN 114759172 A CN114759172 A CN 114759172A
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zinc oxide
graphene
negative electrode
zinc
electrode material
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吴嘉豪
李政文
黎少伟
肖笛青
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Guangzhou Zhuoyue Power Technology Co ltd
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Guangzhou Zhuoyue Power Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite

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Abstract

The invention discloses a preparation method of a graphene/zinc oxide negative electrode material for a zinc-based battery, wherein zinc oxide is doped with a metal compound by a hydrothermal method, so that the capacitance and the cycle performance of the zinc oxide-based negative electrode material are greatly improved; in addition, the hydrothermal reaction has the advantages of high uniformity, uniform doping and the like, so that the electrical property of the prepared doped modified oxidability is more excellent. The invention modifies the surface of the electrolyte by oxidizing gas to form fluorine/chlorine compounds on the surface of the electrolyte, has better compatibility with the electrolyte, reduces the occurrence probability of side reaction and improves the cycle performance of the electrolyte.

Description

Preparation method of graphene/zinc oxide negative electrode material for zinc-based battery
Technical Field
The invention relates to the technical field of battery materials, in particular to a preparation method of a graphene/zinc oxide negative electrode material for a zinc-based battery.
Background
With the increasing environmental pollution and the gradual depletion of fossil energy, the demand for new renewable energy sources for sustainable development is continuously increasing. The rechargeable zinc-based battery is the first choice of energy storage equipment such as electric vehicles, emergency energy sources and energy storage power stations due to the excellent characteristics of the rechargeable zinc-based battery, and is an ideal potential power supply system of future space technology and high-end energy storage systems.
The zinc oxide as the common negative electrode material of the zinc-based battery has the advantages of easily obtained raw materials, low price and environmental friendliness, and is the most widely researched negative electrode material of the zinc-based battery. However, zinc oxide has the disadvantages of poor stability in an alkaline environment, high solubility and deformation, easy formation of dendrites in the charging and discharging processes, and poor conductivity, so that the zinc oxide serving as a zinc-based battery negative electrode material has the disadvantages of low specific capacity and poor cycling stability. Therefore, research in this field is currently focused on research, development and preparation techniques of novel zinc-based battery negative electrode materials with high capacity, high power, long service life and low cost.
Graphene is a carbon material having a single atomic layer thickness, has high conductivity, flexibility, and the like, and is an excellent carbon material for modifying an electrode material. Graphene is widely applied to modification of positive and negative electrode materials of lithium ion batteries, and is rarely applied to modification of zinc batteries. Since the graphene has the properties of high specific surface area, excellent chemical and thermal stability, good electrical conductivity and thermal conductivity, excellent mechanical properties and the like, the material needs to be further applied in the zinc-based battery to obtain the negative electrode material for the zinc-based battery with excellent performance and low price.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for preparing a graphene/zinc oxide negative electrode material for a zinc-based battery, comprising the steps of:
s1: adding graphene into deionized water, adding an additive, and then putting into an ultrasonic cleaning machine for ultrasonic treatment for 1-2 hours to obtain a uniformly dispersed graphene suspension;
s2: adding modified zinc oxide into the graphene suspension, and uniformly stirring and dispersing to obtain a mixed solution;
s3: transferring the uniformly dispersed mixed solution into a hydrothermal reaction kettle, reacting for 5-25h at the temperature of 100-240 ℃, cooling to room temperature, alternately cleaning for 2-3 times by using water and ethanol, and drying to obtain the graphene/zinc oxide composite material;
s4: and (5) calcining the composite material obtained in the step (S3) in an inert atmosphere, wherein the calcining temperature is 300-700 ℃, the calcining time is 2-4h, and cooling to room temperature after the calcining is finished to obtain the graphene/zinc oxide negative electrode material.
As a preferred technical scheme, the mass-to-volume ratio of the graphene to the deionized water is 1-2 mg: 1 ml.
As a preferred technical scheme, the weight percentages of the modified zinc oxide, the graphene and the additive are (70-90): (5-25): (1-10).
As a preferable technical scheme, the weight percentages of the modified zinc oxide, the graphene and the additive are (75-85): (10-20): (3-8).
As a preferable technical scheme, the weight percentage of the modified zinc oxide, the graphene and the additive is 80: 15: 5.
as a preferable technical scheme, the modified zinc oxide is obtained by doping and modifying a metal compound.
As a preferred technical scheme, the preparation method of the modified zinc oxide comprises the following steps: dissolving zinc oxide in an acetic acid solution, adding a metal compound, uniformly dispersing, adding a precipitator, transferring to a reaction kettle, reacting for 20-32h, filtering, drying, transferring to a tubular furnace, heating to 180-340 ℃, reacting for 0.5-1h in an oxidizing gas atmosphere, cooling to room temperature, and discharging to obtain the modified zinc oxide.
As a preferable technical scheme, the addition amount of the metal compound is 5-10% of the addition mass of the zinc oxide.
As a preferable technical scheme, the particle size of the zinc oxide is 15-100 nm.
As a preferable technical scheme, the thickness of the graphene is 4-20nm, and the diameter of the graphene is 5-10 μm.
Advantageous effects
1. Zinc oxide is doped with a metal compound by a hydrothermal method, so that the capacitance and the cycle performance of the zinc oxide-based negative electrode material are greatly improved; in addition, the hydrothermal reaction has the advantages of high uniformity, uniform doping and the like, so that the electrical property of the prepared doped modified oxidability is more excellent.
2. The surface of the electrolyte is modified by oxidizing gas, and fluorine/chlorine compounds are formed on the surface of the electrolyte, so that the electrolyte has better compatibility with the electrolyte, the occurrence probability of side reaction of the electrolyte is reduced, and the cycle performance of the electrolyte is improved.
3. The graphene/zinc oxide negative electrode material can effectively improve the utilization rate of active substance zinc, reduce the generation of zinc dendrites and reduce the hydrogen evolution amount of the battery in the charging process.
4. The modified zinc oxide particles in the graphene/zinc oxide negative electrode material are uniformly dispersed in the graphene with the three-dimensional network, and the graphene/zinc oxide negative electrode material has the advantages of good conductivity, large specific surface area, good stability and the like.
Detailed Description
The present invention will be more readily understood by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
In order to solve the problems, the invention provides a graphene/zinc oxide negative electrode material for a zinc-based battery, which comprises, by weight, 70-90 wt% of modified zinc oxide, 5-25 wt% of graphene and 1-10 wt% of an additive.
In some preferred embodiments, the preparation raw materials comprise 75-85 wt% of modified zinc oxide, 10-20 wt% of graphene and 3-8 wt% of additives in percentage by weight.
In some preferred embodiments, the preparation raw materials comprise, by weight, 80 wt% of modified zinc oxide, 15 wt% of graphene and 5 wt% of additives.
In some preferred embodiments, the modified zinc oxide is obtained by doping modification of a metal compound.
In some preferred embodiments, the metal compound includes one of a metal compound a and a metal compound B.
In some preferred embodiments, the metal compound a is at least one of gallium sulfate, gallium carbonate, potassium phosphate, gallium chloride, and gallium acetate.
In some more preferred embodiments, the metal compound a is at least one of gallium sulfate, gallium chloride, and gallium acetate.
In some more preferred embodiments, the metal compound a is gallium acetate.
In some preferred embodiments, the metal compound B is at least one of vanadium hydroxide, vanadium oxide, vanadium sulfate, vanadium acetate, and vanadium nitrate.
In some preferred embodiments, the metal compound B is at least one of vanadium oxide, vanadium sulfate, vanadium acetate.
In some preferred embodiments, the metal compound B is vanadium acetate.
In some more preferred embodiments, the modified zinc oxide is doped and modified from the metal compound a.
In some preferred embodiments, the modified zinc oxide is prepared by the following steps: dissolving zinc oxide in an acetic acid solution, adding a metal compound A, uniformly dispersing, adding a precipitator, transferring to a reaction kettle, reacting for 20-32h, filtering, drying, transferring to a tubular furnace, heating to 180-340 ℃, reacting for 0.5-1h in an oxidizing gas atmosphere, cooling to room temperature, and discharging to obtain modified zinc oxide; wherein the mass ratio of zinc oxide: acetic acid solution: a metal compound A: precipitant 1: 5-10: 0.05-0.1: 0.05 to 0.1.
In some preferred embodiments, the modified zinc oxide is prepared by the following steps: dissolving zinc oxide in an acetic acid solution, adding a metal compound B, uniformly dispersing, adding a precipitator, transferring to a reaction kettle, reacting for 20-32h, filtering, drying, transferring to a tubular furnace, heating to 180-340 ℃, reacting for 0.5-1h in an oxidizing gas atmosphere, cooling to room temperature, and discharging to obtain modified zinc oxide; wherein the mass ratio of zinc oxide: acetic acid solution: a metal compound B: precipitant 1: 5-10: 0.05-0.1: 0.05 to 0.1.
In some preferred embodiments, the precipitant is one of ammonia, ammonium carbonate, and urea.
In some preferred embodiments, the oxidizing gas is chlorine trifluoride.
In some preferred embodiments, the zinc oxide has a particle size of 15 to 100 nm.
In some preferred embodiments, the graphene has a thickness of 4 to 20nm and a diameter of 5 to 10 μm.
In some preferred embodiments, the additive is dispersant KYC-913.
The invention provides a preparation method of a graphene/zinc oxide negative electrode material for a zinc-based battery, which comprises the following steps:
s1: adding the graphene with the weight percentage into a certain amount of deionized water, adding an additive, and putting the mixture into an ultrasonic cleaning machine for ultrasonic treatment for 1-2 hours to obtain a uniformly dispersed graphene suspension; wherein the mass-volume ratio of the graphene to the deionized water is 1-2 mg: 1 ml;
s2: adding the modified zinc oxide in the weight percentage into the graphene suspension, and uniformly stirring and dispersing to obtain a mixed solution;
s3: transferring the uniformly dispersed mixed solution into a hydrothermal reaction kettle, reacting for 5-25h at the temperature of 100-240 ℃, cooling to room temperature, alternately cleaning for 2-3 times by using water and ethanol, and drying to obtain the graphene/zinc oxide composite material;
S4: and (5) calcining the composite material obtained in the step (S3) in an inert atmosphere, wherein the calcining temperature is 300-700 ℃, the calcining time is 2-4h, and cooling to room temperature after the calcining is finished to obtain the graphene/zinc oxide negative electrode material.
The third aspect of the invention provides an application of a graphene/zinc oxide negative electrode material for a zinc-based battery, wherein the negative electrode material is used in the zinc-based battery;
wherein, the negative pole of the battery is prepared by the following method: the graphene/zinc oxide negative electrode material, the adhesive and the conductive agent are mixed, coated on a tin-plated copper mesh, and dried in vacuum to obtain the graphene/zinc oxide negative electrode.
Examples
The technical solution of the present invention is described in detail by the following examples, but the scope of the present invention is not limited to the examples. Unless otherwise specified, all the raw materials in the present invention are commercially available.
Example 1
Example 1 provides a graphene/zinc oxide negative electrode material for a zinc-based battery, and the preparation raw materials comprise, by weight, 70 wt% of modified zinc oxide, 25 wt% of graphene and 5 wt% of an additive.
The preparation method of the modified zinc oxide comprises the following steps: dissolving zinc oxide in an acetic acid solution, adding a metal compound A, uniformly dispersing, adding ammonia water, transferring to a reaction kettle, reacting for 20 hours, filtering, drying, transferring to a tubular furnace, heating to 180 ℃, reacting for 1 hour in the atmosphere of chlorine trifluoride, cooling to room temperature, and discharging to obtain modified zinc oxide; wherein the mass ratio of zinc oxide: acetic acid solution: a metal compound A: precipitant 1: 5: 0.05: 0.05.
The metal compound A is gallium sulfate.
The particle size of the zinc oxide is 15nm (model: DK-ZnO-15, manufactured by Beijing Deke island gold technologies Co., Ltd.).
The graphene has a thickness of 4-20nm and a diameter of 5-10 μm (Beijing Deke island gold technologies Co., Ltd.).
The additive is dispersant KYC-913 (Keying).
The embodiment also provides a preparation method of the graphene/zinc oxide negative electrode material for the zinc-based battery, which comprises the following steps:
s1: adding the graphene with the weight percentage into a certain amount of deionized water, adding an additive, and putting the mixture into an ultrasonic cleaning machine for ultrasonic treatment for 1 hour to obtain a uniformly dispersed graphene suspension; wherein the mass-volume ratio of the graphene to the deionized water is 1 mg: 1 ml;
s2: adding the modified zinc oxide in the weight percentage into the graphene suspension, and uniformly stirring and dispersing to obtain a mixed solution;
s3: transferring the uniformly dispersed mixed solution into a hydrothermal reaction kettle, reacting for 25h at 100 ℃, cooling to room temperature, alternately cleaning for 2 times by using water and ethanol, and drying to obtain a graphene/zinc oxide composite material;
s4: and (5) calcining the composite material obtained in the step (S3) in an inert atmosphere, wherein the calcining temperature is 300 ℃, the calcining time is 4 hours, and after the calcining is finished, cooling to room temperature to obtain the graphene/zinc oxide negative electrode material.
Example 2
Embodiment 2 provides a graphene/zinc oxide negative electrode material for a zinc-based battery, which is prepared from 90 wt% of modified zinc oxide, 5 wt% of graphene and 5 wt% of an additive.
The preparation method of the modified zinc oxide comprises the following steps: dissolving zinc oxide in an acetic acid solution, adding a metal compound B, uniformly dispersing, adding ammonium carbonate, transferring into a reaction kettle, reacting for 32 hours, filtering, drying, transferring into a tubular furnace, heating to 340 ℃, reacting for 0.5 hour in the atmosphere of chlorine trifluoride, cooling to room temperature, and discharging to obtain modified zinc oxide; wherein the mass ratio of zinc oxide: acetic acid solution: a metal compound A: precipitant 1: 10: 0.1: 0.1.
the metal compound B is vanadium acetate.
The particle size of the zinc oxide is 100nm (model: DK-ZnO-100, Daidaku island technologies, Inc. of Beijing).
The graphene has a thickness of 4-20nm and a diameter of 5-10 μm (Beijing Deke island gold technologies Co., Ltd.).
The additive is dispersant KYC-913 (Keying).
The embodiment also provides a preparation method of the graphene/zinc oxide negative electrode material for the zinc-based battery, which comprises the following steps:
s1: adding the graphene with the weight percentage into a certain amount of deionized water, adding an additive, and putting the mixture into an ultrasonic cleaning machine for ultrasonic treatment for 2 hours to obtain a uniformly dispersed graphene suspension; wherein the mass-volume ratio of the graphene to the deionized water is 2 mg: 1 ml;
S2: adding the modified zinc oxide in percentage by weight into the graphene suspension, and uniformly stirring and dispersing to obtain a mixed solution;
s3: transferring the uniformly dispersed mixed solution into a hydrothermal reaction kettle, reacting for 5 hours at 240 ℃, cooling to room temperature, alternately cleaning for 3 times by using water and ethanol, and drying to obtain a graphene/zinc oxide composite material;
s4: and (5) calcining the composite material obtained in the step (S3) in an inert atmosphere at 700 ℃ for 2h, and cooling to room temperature after the calcination is finished to obtain the graphene/zinc oxide negative electrode material.
Example 3
Embodiment 3 provides a graphene/zinc oxide negative electrode material for a zinc-based battery, which is prepared from 75 wt% of modified zinc oxide, 22 wt% of graphene and 3 wt% of an additive.
The preparation method of the modified zinc oxide comprises the following steps: dissolving zinc oxide in an acetic acid solution, adding a metal compound A, uniformly dispersing, adding urea, transferring to a reaction kettle, reacting for 24 hours, filtering, drying, transferring to a tubular furnace, heating to 200 ℃, reacting for 1 hour in the atmosphere of chlorine trifluoride, cooling to room temperature, and discharging to obtain modified zinc oxide; wherein the mass ratio of zinc oxide: acetic acid solution: a metal compound A: precipitant 1: 6: 0.06: 0.06.
The metal compound A is gallium chloride.
The particle size of the zinc oxide is 30nm (model: DK-ZnO-30, Beijing Deke island gold science and technology Co., Ltd.).
The graphene has a thickness of 4-20nm and a diameter of 5-10 μm (Beijing Dekojima technologies, Ltd.).
The additive is a dispersant KYC-913 (Keying).
The embodiment also provides a preparation method of the graphene/zinc oxide negative electrode material for the zinc-based battery, which comprises the following steps:
s1: adding the graphene with the weight percentage into a certain amount of deionized water, adding an additive, and putting the mixture into an ultrasonic cleaning machine for ultrasonic treatment for 1.5 hours to obtain a uniformly dispersed graphene suspension; wherein the mass-volume ratio of the graphene to the deionized water is 1.5 mg: 1 ml;
s2: adding the modified zinc oxide in the weight percentage into the graphene suspension, and uniformly stirring and dispersing to obtain a mixed solution;
s3: transferring the uniformly dispersed mixed solution into a hydrothermal reaction kettle, reacting at 120 ℃ for 20 hours, cooling to room temperature, alternately cleaning with water and ethanol for 3 times, and drying to obtain the graphene/zinc oxide composite material;
s4: and (5) calcining the composite material obtained in the step (S3) in an inert atmosphere, wherein the calcining temperature is 400 ℃, the calcining time is 3h, and after the calcining is finished, cooling to room temperature to obtain the graphene/zinc oxide negative electrode material.
Example 4
Embodiment 4 provides a graphene/zinc oxide negative electrode material for a zinc-based battery, which is prepared from 85 wt% of modified zinc oxide, 13 wt% of graphene and 2 wt% of an additive.
The preparation method of the modified zinc oxide comprises the following steps: dissolving zinc oxide in an acetic acid solution, adding a metal compound B, uniformly dispersing, adding urea, transferring to a reaction kettle, reacting for 30 hours, filtering, drying, transferring to a tubular furnace, heating to 280 ℃, reacting for 45 minutes in the atmosphere of chlorine trifluoride, cooling to room temperature, and discharging to obtain modified zinc oxide; wherein the mass ratio of zinc oxide: acetic acid solution: metal compound A: precipitant 1: 9: 0.08: 0.08.
the metal compound B is vanadium sulfate.
The particle size of the zinc oxide is 30nm (model: DK-ZnO-30, Daidaku island technologies, Inc. of Beijing).
The graphene has a thickness of 4-20nm and a diameter of 5-10 μm (Beijing Deke island gold technologies Co., Ltd.).
The additive is dispersant KYC-913 (Keying).
The embodiment also provides a preparation method of the graphene/zinc oxide negative electrode material for the zinc-based battery, which comprises the following steps:
s1: adding the graphene with the weight percentage into a certain amount of deionized water, adding an additive, and putting the mixture into an ultrasonic cleaning machine for ultrasonic treatment for 1.5 hours to obtain a uniformly dispersed graphene suspension; wherein the mass-volume ratio of the graphene to the deionized water is 1 mg: 1 ml;
S2: adding the modified zinc oxide in the weight percentage into the graphene suspension, and uniformly stirring and dispersing to obtain a mixed solution;
s3: transferring the uniformly dispersed mixed solution into a hydrothermal reaction kettle, reacting for 10 hours at 200 ℃, cooling to room temperature, alternately cleaning for 3 times by using water and ethanol, and drying to obtain a graphene/zinc oxide composite material;
s4: and (5) calcining the composite material obtained in the step (S3) in an inert atmosphere, wherein the calcining temperature is 600 ℃, the calcining time is 3h, and after the calcining is finished, cooling to room temperature to obtain the graphene/zinc oxide negative electrode material.
Example 5
Embodiment 5 provides a graphene/zinc oxide negative electrode material for a zinc-based battery, which comprises, by weight, 80 wt% of modified zinc oxide, 15 wt% of graphene, and 5 wt% of an additive.
The preparation method of the modified zinc oxide comprises the following steps: dissolving zinc oxide in an acetic acid solution, adding a metal compound A, uniformly dispersing, adding urea, transferring to a reaction kettle, reacting for 26 hours, filtering, drying, transferring to a tubular furnace, heating to 250 ℃, reacting for 45 minutes in the atmosphere of chlorine trifluoride, cooling to room temperature, and discharging to obtain modified zinc oxide; wherein the mass ratio of zinc oxide: acetic acid solution: a metal compound A: precipitant 1: 8: 0.07: 0.07.
The metal compound A is gallium acetate.
The particle size of the zinc oxide is 30nm (model: DK-ZnO-30, Beijing Deke island gold science and technology Co., Ltd.).
The graphene has a thickness of 4-20nm and a diameter of 5-10 μm (Beijing Dekojima technologies, Ltd.).
The additive is a dispersant KYC-913 (Keying).
The embodiment also provides a preparation method of the graphene/zinc oxide negative electrode material for the zinc-based battery, which comprises the following steps:
s1: adding the graphene with the weight percentage into a certain amount of deionized water, adding an additive, and putting the mixture into an ultrasonic cleaning machine for ultrasonic treatment for 2 hours to obtain a uniformly dispersed graphene suspension; wherein the mass-volume ratio of the graphene to the deionized water is 2 mg: 1 ml;
s2: adding the modified zinc oxide in the weight percentage into the graphene suspension, and uniformly stirring and dispersing to obtain a mixed solution;
s3: transferring the uniformly dispersed mixed solution into a hydrothermal reaction kettle, reacting for 15h at 170 ℃, cooling to room temperature, alternately cleaning for 3 times by using water and ethanol, and drying to obtain a graphene/zinc oxide composite material;
s4: and (5) calcining the composite material obtained in the step (S3) in an inert atmosphere, wherein the calcining temperature is 500 ℃, the calcining time is 3h, and after the calcining is finished, cooling to room temperature to obtain the graphene/zinc oxide negative electrode material.
Comparative example 1
The modified zinc oxide was changed to a common nano zinc oxide having a particle size of 30nm (model: DK-ZnO-30, manufactured by Beijing Dekojima technologies Co., Ltd.), and the remainder was the same as in example 5.
Comparative example 2
Changing the specific surface area of the graphene to 50-80m2(ii)/g, particle size 1-5 μm (from Chengdu organic chemistry Co., Ltd., type: TNERGO-3, Proc. Natl. Acad. Sci., China), and the rest is the same as in example 5.
Comparative example 3
The specific surface area of the graphene is changed to 110-170m2(ii)/g, particle size > 50 μm (from Chengdu organic chemistry Co., Ltd., type: TNERGO-50, China academy of sciences), and the remainder of the process was the same as in example 5.
Comparative example 4
And (2) enabling the mass ratio of the metal compound A to the zinc oxide to be 0.5: 1, the rest of the same procedure as in example 5.
Comparative example 5
And (2) enabling the mass ratio of the metal compound A to the zinc oxide to be 0.01: 1, the rest of the same procedure as in example 5.
Performance testing
1. Cycle performance test
The zinc-based battery negative working electrode is prepared by the following steps:
(1) mixing a graphene/zinc oxide negative electrode material, a binder PTFE and acetylene black according to the weight ratio of 8: 1: 1, mixing uniformly, preparing into paste with deionized water, and uniformly coating on a brass net;
(2) drying in a vacuum oven at 80 ℃ for 12 hours;
(3) and cutting the brass net coated with the graphene/zinc oxide negative electrode material into wafers to prepare the working electrode.
The electrochemical performance of the electrode material was tested as follows:
(1) the simulated cell used a button CR2032 type system in which the positive electrode was spherical ni (oh) 2.
(2) Reversible capacity, coulombic efficiency and cycle performance of the electrode material are tested and analyzed by constant current charging and discharging in experiments. The charging and discharging system comprises: voltage range: 1.0-1.9V; the number of cycles is generally from 1 to 3000.
The cycle charge and discharge performance of the full cell composed of the materials of examples 1 to 5 and comparative examples 1 to 5 are shown in Table 1.
TABLE 1
Examples Reversible capacity/mAh/g Capacity retention ratio after 100 cycles%
Example 1 ＞400 87
Example 2 ＞400 86
Example 3 ＞400 91
Example 4 ＞400 93
Example 5 ＞400 96
Comparative example 1 ＜300 63
Comparative example 2 ＜300 74
Comparative example 3 ＜300 72
Comparative example 4 ＜300 70
Comparative example 5 ＜300 68
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (10)

1. A preparation method of a graphene/zinc oxide negative electrode material for a zinc-based battery comprises the following steps:
S1: adding graphene into deionized water, adding an additive, and then putting into an ultrasonic cleaning machine for ultrasonic treatment for 1-2 hours to obtain a uniformly dispersed graphene suspension;
s2: adding modified zinc oxide into the graphene suspension, and uniformly stirring and dispersing to obtain a mixed solution;
s3: transferring the uniformly dispersed mixed solution into a hydrothermal reaction kettle, reacting for 5-25h at the temperature of 100-240 ℃, cooling to room temperature, alternately cleaning for 2-3 times by using water and ethanol, and drying to obtain a graphene/zinc oxide composite material;
s4: and (5) calcining the composite material obtained in the step (S3) in an inert atmosphere at the temperature of 300-700 ℃ for 2-4h, and cooling to room temperature after the calcination is finished to obtain the graphene/zinc oxide negative electrode material.
2. The preparation method of the graphene/zinc oxide negative electrode material for the zinc-based battery according to claim 1, wherein the mass-to-volume ratio of the graphene to the deionized water is 1-2 mg: 1 ml.
3. The method for preparing the graphene/zinc oxide negative electrode material for the zinc-based battery according to claim 1, wherein the modified zinc oxide, the graphene and the additive are prepared from (70-90) by weight percent: (5-25): (1-10).
4. The method for preparing the graphene/zinc oxide negative electrode material for the zinc-based battery according to claim 3, wherein the weight percentages of the modified zinc oxide, the graphene and the additive are (75-85): (10-20): (3-8).
5. The preparation method of the graphene/zinc oxide negative electrode material for the zinc-based battery as claimed in claim 4, wherein the weight percentage of the modified zinc oxide, the graphene and the additive is 80: 15: 5.
6. the method for preparing the graphene/zinc oxide negative electrode material for the zinc-based battery according to claim 1, wherein the modified zinc oxide is obtained by doping and modifying a metal compound.
7. The preparation method of the graphene/zinc oxide negative electrode material for the zinc-based battery according to claim 1, wherein the preparation method of the modified zinc oxide comprises the following steps: dissolving zinc oxide in acetic acid solution, adding a metal compound, dispersing uniformly, adding a precipitator, transferring to a reaction kettle, reacting for 20-32h, filtering, drying, transferring to a tubular furnace, heating to 180-340 ℃, reacting for 0.5-1h in an oxidizing gas atmosphere, cooling to room temperature, and discharging to obtain the modified zinc oxide.
8. The method for preparing the graphene/zinc oxide negative electrode material for the zinc-based battery according to claim 7, wherein the addition amount of the metal compound is 5-10% of the addition amount of zinc oxide.
9. The method for preparing the graphene/zinc oxide negative electrode material for the zinc-based battery according to claim 8, wherein the particle size of the zinc oxide is 15-100 nm.
10. The method for preparing the graphene/zinc oxide negative electrode material for the zinc-based battery according to claim 1, wherein the graphene has a thickness of 4-20nm and a diameter of 5-10 μm.
CN202110496404.4A 2021-05-07 2021-05-07 Preparation method of graphene/zinc oxide negative electrode material for zinc-based battery Pending CN114759172A (en)

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