CN115863619A - Preparation method of zinc aluminate graphene composite material and preparation method of lead-acid battery cathode - Google Patents
Preparation method of zinc aluminate graphene composite material and preparation method of lead-acid battery cathode Download PDFInfo
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Abstract
The application provides a preparation method of a zinc aluminate graphene composite material and a preparation method of a lead-acid battery cathode. Secondly, zinc aluminate spinel, as an inorganic material, is difficult to be uniformly dispersed in graphene oxide without adding a coupling agent, but the reactivity of carboxyl functional groups, hydroxyl functional groups and carbonyl functional groups on the surface of graphene oxide is effectively enhanced under an alkaline environment of pH8.0-9.0, and zinc aluminate is effectively enhanced by [ AlO3 ]] 2‑ Negative charge group and graphene oxide surfaceThe surface is established with covalent bond connection with stronger connection effect, so that zinc aluminate is uniformly dispersed in graphene oxide, and the zinc aluminate graphene composite material has better stability in the application of electrode materials, so that the zinc aluminate graphene composite material has better cycling stability when being applied to a negative electrode of a lead-acid battery.
Description
Technical Field
The invention relates to the field of batteries, in particular to a preparation method of a zinc aluminate graphene composite material and a preparation method of a lead-acid battery cathode.
Background
Lead-acid batteries are one of the most mature energy storage batteries in application at present, and the improvement of the technology and the battery materials is the key point in the research field of batteries nowadays. The graphene material is a two-dimensional layered material, and the graphene material is compounded with the positive and negative electrode materials of the lead-acid battery, so that the cycle stability and the battery capacity of the battery can be improved, and the graphene material has good mechanical properties and a double-capacitance effect. The materials capable of generating the capacitance effect comprise metal oxide materials and conductive polymer materials besides graphene carbon materials. The metal oxide material realizes energy storage through Faraday quasi-capacitance generated by redox reaction of metal ions, and spinel oxides such as cobaltate, manganate, nickelate and the like are compounds with better capacitance performance, and meanwhile, the spinel material has the advantages of rich raw materials, low preparation cost and the like. However, in the redox reversible transformation process of the spinel oxide material, the lattice structure changes greatly, and the spinel oxide material can be applied to a lead-acid battery, although the capacity of the battery can be improved, the cycle stability is obviously reduced, so that the existing spinel oxide material applied to the lead-acid battery cannot give consideration to the improvement of the capacity and the cycle performance of the battery.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of a zinc aluminate graphene composite material and a preparation method of a lead-acid battery cathode, wherein the zinc aluminate graphene composite material can improve the battery capacity and has better cycle stability.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a zinc aluminate graphene composite material comprises the following steps:
preparing zinc aluminate powder;
preparing a zinc aluminate graphene composite material;
the specific steps for preparing the zinc aluminate graphene composite material are as follows:
preparing the zinc aluminate powder, the graphene oxide powder and absolute ethyl alcohol into mixed powder;
adding the mixed powder into deionized water to obtain a mixed solution;
adjusting the pH of the mixed solution to make the pH of the mixed solution between 8.0 and 9.0;
carrying out ultrasonic operation on the mixed solution;
homogenizing the mixed solution after ultrasonic treatment;
carrying out vacuum drying operation on the mixed solution after homogenizing operation to obtain the zinc aluminate graphene composite material;
wherein, in the mixed solution, under an alkaline environment with a pH of 8.0-9.0, after the carboxyl functional group, the hydroxyl functional group and the carbonyl functional group on the surface of the graphene oxide are activated, the carboxyl functional group, the hydroxyl functional group and the carbonyl functional group on the surface of the graphene oxide are all mixed with the [ AlO ] of the zinc aluminate 3 ] 2- And combining groups, so that after a covalent bond force is built between the zinc aluminate and the graphene oxide, the zinc aluminate and the graphene oxide are uniformly dispersed into the graphene oxide.
In one embodiment, the specific steps for preparing the zinc aluminate powder are as follows:
dissolving soluble aluminum salt and soluble zinc salt in the absolute ethyl alcohol to obtain mixed salt solution;
adding polyethylene glycol into the mixed salt solution, and heating and stirring to obtain a mixed gel solution;
and sintering the mixed gel liquid to obtain the zinc aluminate powder.
In one embodiment, the soluble aluminum salt is one or both of aluminum nitrate and aluminum chloride.
In one embodiment, the soluble zinc salt is at least one of zinc nitrate, zinc acetate, zinc chloride, zinc bromide, and zinc propionate.
In one embodiment, the temperature of the sintering operation is 500 ℃ to 900 ℃.
In one embodiment, the time of the sintering operation is 5h-8h.
In one embodiment, the homogenizing operation is performed at a pressure of 20MPa to 40MPa.
In one embodiment, the homogenizing operation is performed for 30min-60min.
In one embodiment, the temperature of the vacuum drying is 120 ℃ to 160 ℃.
A lead-acid battery negative electrode comprising the steps of:
providing the zinc aluminate graphene composite material prepared by the preparation method of the zinc aluminate graphene composite material according to any one of the embodiments;
mixing the zinc aluminate graphene composite material, lead powder, sulfuric acid and water into paste mixed slurry;
and coating the paste mixed slurry on a negative electrode alloy grid to obtain the negative electrode of the lead-acid battery.
Compared with the prior art, the invention has at least the following advantages:
according to the preparation method of the zinc aluminate graphene composite material, zinc aluminate powder is prepared at first, the zinc aluminate belongs to one of aluminate spinel oxides, and the spinel oxide can improve the capacity of a lead-acid battery when being applied to the negative electrode of the lead-acid battery. Secondly, zinc aluminate spinel, as an inorganic material, is difficult to be uniformly dispersed in graphene oxide without adding a coupling agent, but the reactivity of carboxyl functional groups, hydroxyl functional groups and carbonyl functional groups on the surface of graphene oxide is effectively enhanced under an alkaline environment of pH8.0-9.0, and zinc aluminate is effectively enhanced by [ AlO ] 3 ] 2- The negative charge group and the surface of the graphene oxide establish covalent bond connection with strong connection effect, so that zinc aluminate is uniformly dispersed in the graphene oxide, and the zinc aluminate graphene composite material has better stability in the application of electrode materials, and has better cycle stability when being applied to the negative electrode of a lead-acid battery.
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In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic flow chart illustrating a method for preparing a zinc aluminate graphene composite according to an embodiment;
FIG. 2 is a schematic flow chart of a part of the steps of the preparation method of the zinc aluminate graphene composite material shown in FIG. 1;
FIG. 3 is a schematic flow chart of a portion of the steps of the method for preparing the zinc aluminate graphene composite material shown in FIG. 1;
FIG. 4 is an SEM image of a zinc aluminate graphene composite;
FIG. 5 is a TEM image of a zinc aluminate graphene composite;
fig. 6 is an infrared spectrum of the graphene oxide raw material and zinc aluminate graphene oxide composite powder.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
It will be understood that when an element is referred to as being "secured to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "left," "right," and the like as used herein are for illustrative purposes only and do not denote a single embodiment.
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. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The preparation method of the zinc aluminate graphene composite material provided by the application comprises the following steps: preparing zinc aluminate powder; preparing a zinc aluminate graphene composite material; the specific steps for preparing the zinc aluminate graphene composite material are as follows: preparing the zinc aluminate powder, the graphene oxide powder and absolute ethyl alcohol into mixed powder; adding the mixed powder into deionized water to obtain a mixed solution; carrying out pH adjustment operation on the mixed solution so as to enable the pH of the mixed solution to be between 8.0 and 9.0; carrying out ultrasonic operation on the mixed solution; homogenizing the mixed solution after ultrasonic treatment; carrying out vacuum drying operation on the mixed solution after homogenizing operation to obtain the zinc aluminate graphene composite material; wherein, in the mixed solution, under an alkaline environment with a pH of 8.0-9.0, after the carboxyl functional group, the hydroxyl functional group and the carbonyl functional group on the surface of the graphene oxide are activated, the carboxyl functional group, the hydroxyl functional group and the carbonyl functional group on the surface of the graphene oxide are all mixed with the [ AlO3 ] of the zinc aluminate] 2- And (3) combining groups, so that after the zinc aluminate and the graphene oxide build a covalent bond force, the zinc aluminate and the graphene oxide are uniformly dispersed into the graphene oxide.
According to the preparation method of the zinc aluminate graphene composite material, firstly, zinc aluminate powder is prepared, the zinc aluminate belongs to one of aluminate spinel oxides, and the spinel oxide can improve the capacity of a battery when being applied to a negative electrode of a lead-acid battery. Secondly, zinc aluminate spinel, as an inorganic material, is difficult to be uniformly dispersed in graphene oxide without adding a coupling agent, but the reactivity of carboxyl functional groups, hydroxyl functional groups and carbonyl functional groups on the surface of the graphene oxide is effectively enhanced under the alkaline environment of pH8.0-9.0Zinc aluminate through [ AlO ] 3 ] 2- The negative charge group and the surface of the graphene oxide establish covalent bond connection with strong connection effect, so that the zinc aluminate is uniformly dispersed in the graphene oxide, and the zinc aluminate graphene composite material has better stability in the application of electrode materials, and thus the zinc aluminate graphene composite material has better cycle stability when being applied to the negative electrode of a lead-acid battery.
Referring to fig. 1, 3, and 6, in order to better understand the preparation method of the zinc aluminate graphene composite material of the present application, the preparation method of the zinc aluminate graphene composite material is further explained as follows:
the preparation method of the zinc aluminate graphene composite material of the embodiment comprises the following steps:
s100, preparing zinc aluminate powder.
In this embodiment, aluminate is used as one of compounds capable of effectively improving the capacitive performance in the spinel oxide, and zinc aluminate is selected as a main material for improving the capacitive performance, so that the battery capacity of the lead-acid battery can be effectively improved when the zinc aluminate graphene composite material is applied to a negative electrode of the lead-acid battery.
S200, preparing the zinc aluminate graphene composite material.
The specific steps for preparing the zinc aluminate graphene composite material are as follows:
s201, preparing the zinc aluminate powder, the graphene oxide powder and the absolute ethyl alcohol into mixed powder.
In this example, zinc aluminate powder and graphene oxide powder were poured into a mortar, and were wetted with absolute ethanol, and ground for 30min to obtain a mixed powder. Namely, the zinc aluminate powder and the graphene oxide powder are better mixed together under the wetting of absolute ethyl alcohol.
S202, adding the mixed powder into deionized water to obtain a mixed solution.
In this example, deionized water was used as the solvent, and the mixed powder was dissolved in deionized water to form a mixed solution, wherein the mass fraction of the powder was 0.5-2%.
S203, carrying out pH adjustment operation on the mixed solution so as to enable the pH of the mixed solution to be between 8.0 and 9.0.
In this embodiment, the pH of the mixed solution is adjusted by ammonia water, so that the pH of the mixed solution is between 8.0 and 9.0, and since the graphene oxide is a two-dimensional layered material, a covalent bond connection with a strong connection effect is established between the zinc aluminate and the graphene oxide surface, so that the zinc aluminate can be uniformly dispersed in the graphene oxide, and the circulation stability of the zinc aluminate graphene composite material when applied to the negative electrode of a lead-acid battery is good.
Further, in order to ensure sufficient contact between zinc aluminate and graphene oxide, the mass ratio of the zinc aluminate powder to the graphene oxide powder is 1: (1.5-3). Possess sufficient oxidation graphite alkene promptly and do contact zinc aluminate to guarantee zinc aluminate and oxidation graphite alkene's abundant contact, thereby promoted the compound effect of zinc aluminate and oxidation graphite alkene effectively, and then make zinc aluminate homodisperse in oxidation graphite alkene, further promoted the battery capacity and the circulation stability of zinc aluminate graphite alkene combined material when being applied to lead acid battery.
And S204, carrying out ultrasonic operation on the mixed solution.
In this embodiment, after the mixed solution is subjected to ultrasonic oscillation for 30min, zinc aluminate can be dispersed in graphene oxide more uniformly, so that the battery cycling stability of the zinc aluminate graphene composite material when the zinc aluminate graphene composite material is applied to a negative electrode of a lead-acid battery is effectively improved.
S205, homogenizing the mixed solution after ultrasonic treatment.
In this embodiment, put the mixed liquid after the supersound to carrying out the homogeneity operation in the isotropic symmetry, make zinc aluminate and graphene oxide obtain abundant contact in the mixed liquid through the homogeneity operation for zinc aluminate homodisperse is in graphene oxide, thereby has promoted the compound effect of zinc aluminate and graphene oxide effectively, and then has promoted zinc aluminate graphene composite's stability effectively.
Further, the mixed solution after the homogenization was subjected to high-speed centrifugation at 10000 rpm. The composite effect of the zinc aluminate and the graphene oxide is better under the action of high-speed centrifugation, namely, the zinc aluminate is more uniformly dispersed in the graphene oxide, so that the battery cycle stability of the zinc aluminate graphene composite material when the zinc aluminate graphene composite material is applied to a negative electrode of a lead-acid battery is further improved.
S206, carrying out vacuum drying operation on the mixed solution after the homogenizing operation to obtain the zinc aluminate graphene composite material.
In this example, the mixed solution was dried by a vacuum drier to obtain a zinc aluminate graphene composite material.
Wherein, in the mixed solution, under an alkaline environment with a pH of 8.0-9.0, after the carboxyl functional group, the hydroxyl functional group and the carbonyl functional group on the surface of the graphene oxide are activated, the carboxyl functional group, the hydroxyl functional group and the carbonyl functional group on the surface of the graphene oxide are all mixed with the [ AlO ] of the zinc aluminate 3 ] 2- And (3) combining groups, so that after the zinc aluminate and the graphene oxide build a covalent bond force, the zinc aluminate and the graphene oxide are uniformly dispersed into the graphene oxide. .
It should be noted that, zinc aluminate spinel, which is an inorganic material and graphene oxide is a two-dimensional layered material, is difficult to uniformly disperse in graphene oxide without adding a coupling agent, but the reactivity of functional groups on the surface of graphene oxide is enhanced in an alkaline environment at ph8.0 to 9.0, and zinc aluminate spinel passes through [ AlO [ ] 3 ] 2- Covalent bond relation with a strong connecting effect is established between the groups and the surface of the graphene oxide, and the zinc aluminate is uniformly dispersed in the graphene oxide, so that the zinc aluminate graphene composite material has better stability in the application of electrode materials, and further, the battery has better cycle stability when the zinc aluminate graphene composite material is applied to the negative electrode of a lead-acid battery.
Further, as shown in FIG. 6, the wave number of the zinc aluminate graphene composite powder is 3407cm in comparison with that of the graphene oxide material -1 The peak and wave number of the hydroxyl group vibration of (2) is 1727cm -1 Has a peak vibration of carbonyl group and a wave number of 1622cm -1 The vibration intensity of the carboxyl vibration peak is obviously weakened, namely the carboxyl functional group,The hydroxyl functional group and the carbonyl functional group are substituted by zinc aluminate salt, so that the zinc aluminate is uniformly and stably compounded in the graphene oxide.
Further, as shown in fig. 4 and 5, in one embodiment, the zinc aluminate graphene composite material is subjected to scanning electron microscope analysis and transmission electron microscope analysis. According to the scanning electron microscope image and the transmission electron microscope image, the zinc aluminate is dispersed in the graphene oxide, so that the zinc aluminate graphene composite material has the capacity of improving the battery capacity and the cycle performance of the battery, namely the battery capacity and the cycle performance of the zinc aluminate graphene composite material are better when the zinc aluminate graphene composite material is applied to a negative electrode of a lead-acid battery.
As shown in fig. 2, in one embodiment, the specific steps for preparing the zinc aluminate powder are as follows:
s101, dissolving soluble aluminum salt and soluble zinc salt in the absolute ethyl alcohol to obtain a mixed salt solution.
In this example, absolute ethanol was used as a solvent, and a soluble aluminum salt and a soluble zinc salt were sufficiently dissolved in absolute ethanol to obtain a mixed salt solution. Wherein, the content ratio of the aluminum element to the zinc element is 2.
And S102, adding polyethylene glycol into the mixed salt solution, and heating and stirring to obtain a mixed gel solution.
In the embodiment, the polyethylene glycol plays a role in flocculation in the system, so that the zinc aluminate is changed into gel, namely, after the polyethylene glycol accounting for 2-5% of the total mass of the mixed salt solution is added into the mixed salt solution and stirred at high speed for 2-6h, the temperature is increased to 80 ℃, and stirring is continued until the solution becomes gel, so as to obtain the mixed gel solution.
S103, sintering the mixed gel liquid to obtain the zinc aluminate powder.
In this example, the mixed gel liquid was dried and ground, and then placed in a muffle furnace for sintering operation to obtain zinc aluminate powder.
Furthermore, the zinc aluminate spinel is a cubic crystal formed by alternately arranging aluminum octahedrons and zinc tetrahedrons, zinc positive divalent ions at the center position of the tetrahedrons in the crystal are easy to escape to form zinc vacancies with negative electricity, so that the zinc aluminate graphene composite material is favorable for accumulating negative charges and improving the overall capacity of a battery when applied to a negative electrode of a lead-acid battery, and meanwhile, the crystal does not deform in the charge accumulation and release processes, and can play a role in supporting and protecting the negative electrode of the lead-acid battery, thereby being favorable for improving the circulation stability of the negative electrode material.
In one embodiment, the soluble aluminum salt is one or both of aluminum nitrate and aluminum chloride. It is noted that both aluminum nitrate and aluminum chloride are capable of providing aluminum ions for the preparation of zinc aluminate.
In one embodiment, the soluble zinc salt is at least one of zinc nitrate, zinc acetate, zinc chloride, zinc bromide, and zinc propionate. It should be noted that zinc nitrate, zinc acetate, zinc chloride, zinc bromide, and zinc propionate are all capable of providing zinc ions for the preparation of zinc aluminate.
In one embodiment, the temperature of the sintering operation is 500 ℃ to 900 ℃. It is noted that the zinc aluminate graphene composite material has a good sintering molding effect at 500-900 ℃.
In one embodiment, the time of the sintering operation is 5h-8h. The method has the advantages that the cleaning time is 5-8 h, the zinc aluminate graphene composite material is more fully sintered, and the forming effect is better.
In one embodiment, the homogenizing operation is performed at a pressure of 20MPa to 40MPa. It should be noted that, under the homogenization condition with a pressure of 20MPa to 40MPa, the binding property of the zinc aluminate and the graphene oxide of the mixed solution in the homogenization operation is effectively enhanced, that is, the zinc aluminate is dispersed in the graphene oxide more uniformly, so that the stability of the zinc aluminate graphene composite material in the application of the electrode material is further improved, and further, the battery cycle stability of the zinc aluminate graphene composite material when being applied to the negative electrode of the lead-acid battery is further improved.
In one embodiment, the homogenizing operation is performed for 30min-60min. It should be noted that, under the condition of homogenizing operation for 30min to 60min, the zinc aluminate and the graphene oxide can be sufficiently fused, that is, the zinc aluminate and the graphene oxide are sufficiently contacted, and at this time, the composite effect of the zinc aluminate and the graphene oxide is better.
In one embodiment, the temperature of the vacuum drying is 120 ℃ to 160 ℃. It is noted that the drying effect of the zinc aluminate graphene composite material at 120-160 ℃ is better.
The application also provides a lead-acid battery cathode, which comprises the following steps:
providing the zinc aluminate graphene composite material prepared by the preparation method of the zinc aluminate graphene composite material according to any one of the embodiments;
mixing the zinc aluminate graphene composite material, lead powder, sulfuric acid and water into paste mixed slurry;
coating the pasty mixed slurry on a negative electrode alloy grid to obtain a negative electrode of the lead-acid battery;
the preparation method of the zinc aluminate graphene composite material specifically comprises the following steps:
preparing zinc aluminate powder;
preparing a zinc aluminate graphene composite material;
the specific steps for preparing the zinc aluminate graphene composite material are as follows:
preparing the zinc aluminate powder, the graphene oxide powder and absolute ethyl alcohol into mixed powder;
adding the mixed powder into deionized water to obtain a mixed solution;
adjusting the pH of the mixed solution to make the pH of the mixed solution between 8.0 and 9.0;
carrying out ultrasonic operation on the mixed solution;
homogenizing the mixed solution after ultrasonic treatment;
carrying out vacuum drying operation on the mixed solution after homogenizing operation to obtain the zinc aluminate graphene composite material;
wherein the mixed solution contains carboxyl functional groups and hydroxyl functional groups on the surface of the graphene oxide under an alkaline environment with the pH value of 8.0-9.0After the energy group and the carbonyl functional group are activated, the carboxyl functional group, the hydroxyl functional group and the carbonyl functional group on the surface of the graphene oxide are all matched with the [ AlO ] of the zinc aluminate 3 ] 2- And combining groups, so that after a covalent bond force is built between the zinc aluminate and the graphene oxide, the zinc aluminate and the graphene oxide are uniformly dispersed into the graphene oxide.
In this embodiment, the zinc aluminate graphene composite material with better stability is used as one of the components of the coating material, so that the cycle stability of the lead-acid battery can be effectively improved. Meanwhile, the zinc aluminate graphene composite material adopts zinc aluminate spinel as a main component, and spinel oxide can be used for the capacity of the battery in the application and lead-acid battery, so that the capacity and the cycling stability of the battery in the application and lead-acid battery cathode of the zinc aluminate graphene composite material are improved.
In another embodiment, a method for preparing a zinc aluminate graphene composite material comprises the following steps:
preparing zinc aluminate powder;
preparing a zinc aluminate graphene composite material;
the specific steps for preparing the zinc aluminate graphene composite material are as follows:
preparing the zinc aluminate powder, the graphene oxide powder, the graphene powder and absolute ethyl alcohol into mixed powder;
adding the mixed powder into deionized water to obtain a mixed solution;
adjusting the pH of the mixed solution to make the pH of the mixed solution between 8.0 and 9.0;
carrying out ultrasonic operation on the mixed solution;
homogenizing the mixed solution after ultrasonic treatment;
carrying out vacuum drying operation on the mixed solution after homogenizing operation to obtain the zinc aluminate graphene composite material;
wherein, in the mixed solution, under an alkaline environment with a pH value of 8.0-9.0, after the carboxyl functional group, the hydroxyl functional group and the carbonyl functional group on the surface of the graphene oxide are activated, the surface of the graphene oxideWith the carboxyl, hydroxyl and carbonyl functions of the zinc aluminate [ AlO ] 3 ] 2- And (3) combining groups, so that after the zinc aluminate and the graphene oxide build a covalent bond force, the zinc aluminate and the graphene oxide are uniformly dispersed into the graphene oxide.
The conductivity of the graphene oxide is inferior to that of graphene, but functional groups such as carboxyl, hydroxyl and carbonyl on the surface of the graphene oxide can well adsorb zinc aluminate spinel, and the graphene oxide form pi-pi adsorption through the functional groups such as the carboxyl, the hydroxyl and the carbonyl, so that the conductivity of the graphene oxide can be improved. Specifically, the sheet diameter size of graphene oxide in the mixed solution is 500 nm-900 nm, and the sheet diameter size of graphene is less than 200nm, so that the conductive function modifying gene with the smaller sheet diameter size of graphene can be adsorbed on the graphene oxide with the larger sheet diameter size. Therefore, the conductivity of the obtained zinc aluminate graphene composite material is further improved, and the battery capacity of the zinc aluminate graphene composite material is further improved when the zinc aluminate graphene composite material is applied to a lead-acid battery.
The following examples are given by way of illustration, but it is to be understood that the following examples are not intended to be exhaustive of all possible and that the materials used in the following examples are commercially available without specific recitation.
Example 1
Mixing soluble aluminum salt and soluble zinc salt according to the content ratio of aluminum element to zinc element 2, dissolving in absolute ethyl alcohol to obtain mixed salt solution, adding polyethylene glycol accounting for 2% of the total mass of the mixed salt solution, stirring at a high speed for 2 hours, raising the temperature to 80 ℃, continuously stirring until the solution becomes gel-like to obtain mixed gel solution, drying and grinding the mixed gel solution, and then placing in a muffle furnace for sintering at 500 ℃ for 8 hours to obtain zinc aluminate powder. Mixing zinc aluminate powder and graphene oxide powder according to a mass ratio of 1.5, adding absolute ethyl alcohol for wetting, grinding for 30min to obtain a mixture, adding the mixed powder into deionized water to obtain a mixed solution, adding ammonia water to adjust the pH of the mixed solution to 8.0, carrying out ultrasonic oscillation on the mixed solution for 30min, then homogenizing for 30min under the pressure of 20MPa by using a homogenizer, carrying out high-speed centrifugation at the rotation speed of 10000rpm after the homogenization operation, washing for 2 times by using deionized water, and finally carrying out vacuum drying at 120 ℃ to obtain the zinc aluminate graphene composite material.
Example 2
Mixing soluble aluminum salt and soluble zinc salt according to the content ratio of aluminum element to zinc element 2, dissolving in absolute ethyl alcohol to obtain mixed salt solution, adding polyethylene glycol accounting for 2% of the total mass of the mixed salt solution, stirring at a high speed for 4 hours, raising the temperature to 80 ℃, continuously stirring until the solution becomes gel-like to obtain mixed gel solution, drying and grinding the mixed gel solution, and then placing in a muffle furnace for sintering at 700 ℃ for 6 hours to obtain zinc aluminate powder. Mixing zinc aluminate powder and graphene oxide powder according to a mass ratio of 1.5, adding absolute ethyl alcohol for wetting, grinding for 30min to obtain a mixture, adding the mixed powder into deionized water to obtain a mixed solution, adding ammonia water to adjust the pH of the mixed solution to 8.5, carrying out ultrasonic oscillation on the mixed solution for 30min, homogenizing for 45min under the pressure of 30MPa by using a homogenizer, carrying out high-speed centrifugation at the rotation speed of 10000rpm after the homogenization operation, washing for 3 times by using deionized water, and finally carrying out vacuum drying at 140 ℃ to obtain the zinc aluminate graphene composite material.
Example 3
Mixing soluble aluminum salt and soluble zinc salt according to the content ratio of aluminum element to zinc element 2, dissolving in absolute ethyl alcohol to obtain mixed salt solution, adding polyethylene glycol accounting for 2% of the total mass of the mixed salt solution, stirring at a high speed for 6 hours, raising the temperature to 80 ℃, continuously stirring until the solution becomes gel-like to obtain mixed gel solution, drying and grinding the mixed gel solution, and then placing in a muffle furnace for sintering at 900 ℃ for 5 hours to obtain zinc aluminate powder. Mixing zinc aluminate powder and graphene oxide powder according to a mass ratio of 1.5, adding absolute ethyl alcohol for wetting, grinding for 30min to obtain a mixture, adding the mixed powder into deionized water to obtain a mixed solution, adding ammonia water to adjust the pH of the mixed solution to 9.0, carrying out ultrasonic oscillation on the mixed solution for 30min, then homogenizing for 60min under the pressure of 40MPa by using a homogenizer, carrying out high-speed centrifugation at the rotating speed of 10000rpm after the homogenization operation, washing for 3 times by using deionized water, and finally carrying out vacuum drying at 160 ℃ to obtain the zinc aluminate graphene composite material.
Comparative example 1
Mixing soluble aluminum salt and soluble zinc salt according to the content ratio of aluminum element to zinc element 2, dissolving in absolute ethyl alcohol to obtain mixed salt solution, adding polyethylene glycol accounting for 2% of the total mass of the mixed salt solution, stirring at a high speed for 2 hours, raising the temperature to 80 ℃, continuously stirring until the solution becomes gel-like to obtain mixed gel solution, drying and grinding the mixed gel solution, and then placing in a muffle furnace for sintering at 500 ℃ for 8 hours to obtain zinc aluminate powder. Mixing zinc aluminate powder and graphene oxide powder according to a mass ratio of 1.5, adding absolute ethyl alcohol for wetting, grinding for 30min to obtain a mixture, adding the mixed powder into deionized water to obtain a mixed solution, adding ammonia water to adjust the pH of the mixed solution to 5.0, carrying out ultrasonic oscillation on the mixed solution for 30min, then homogenizing for 30min under the pressure of 20MPa by using a homogenizer, carrying out high-speed centrifugation at the rotation speed of 10000rpm after the homogenization operation, washing for 2 times by using deionized water, and finally carrying out vacuum drying at 120 ℃ to obtain the zinc aluminate graphene composite material.
Comparative example 2
Mixing soluble aluminum salt and soluble zinc salt according to the content ratio of aluminum element to zinc element 2, dissolving in absolute ethyl alcohol to obtain mixed salt solution, adding polyethylene glycol accounting for 2% of the total mass of the mixed salt solution, stirring at a high speed for 2 hours, raising the temperature to 80 ℃, continuously stirring until the solution becomes gel-like to obtain mixed gel solution, drying and grinding the mixed gel solution, and then placing in a muffle furnace for sintering at 500 ℃ for 8 hours to obtain zinc aluminate powder. Mixing zinc aluminate powder and graphene oxide powder according to a mass ratio of 1.5, adding absolute ethyl alcohol for wetting, grinding for 30min to obtain a mixture, adding the mixed powder into deionized water to obtain a mixed solution, adding ammonia water to adjust the pH of the mixed solution to 6.0, carrying out ultrasonic oscillation on the mixed solution for 30min, homogenizing for 30min under the pressure of 20MPa by using a homogenizer, carrying out high-speed centrifugation at the rotating speed of 10000rpm after the homogenization operation, washing for 2 times by using deionized water, and finally carrying out vacuum drying at 120 ℃ to obtain the zinc aluminate graphene composite material.
Comparative example 3
Mixing soluble aluminum salt and soluble zinc salt according to the content ratio of aluminum element to zinc element 2, dissolving in absolute ethyl alcohol to obtain mixed salt solution, adding polyethylene glycol accounting for 2% of the total mass of the mixed salt solution, stirring at a high speed for 2 hours, raising the temperature to 80 ℃, continuously stirring until the solution becomes gel-like to obtain mixed gel solution, drying and grinding the mixed gel solution, and then placing in a muffle furnace for sintering at 500 ℃ for 8 hours to obtain zinc aluminate powder. Mixing zinc aluminate powder and graphene oxide powder according to a mass ratio of 1.5, adding absolute ethyl alcohol for wetting, grinding for 30min to obtain a mixture, adding the mixed powder into deionized water to obtain a mixed solution, adding ammonia water to adjust the pH of the mixed solution to 7.0, carrying out ultrasonic oscillation on the mixed solution for 30min, then homogenizing for 30min under the pressure of 20MPa by using a homogenizer, carrying out high-speed centrifugation at the rotation speed of 10000rpm after the homogenization operation, washing for 2 times by using deionized water, and finally carrying out vacuum drying at 120 ℃ to obtain the zinc aluminate graphene composite material.
Comparative example 4
Mixing soluble cobalt salt and soluble zinc salt according to the content ratio of aluminum element to zinc element 2, dissolving in absolute ethyl alcohol to obtain mixed salt solution, adding polyethylene glycol accounting for 3.5% of the total mass of the mixed salt solution, stirring at a high speed for 4 hours, raising the temperature to 80 ℃, continuously stirring until the solution becomes gel-like to obtain mixed gel solution, drying and grinding the mixed gel solution, and then placing the mixed gel solution in a muffle furnace for sintering at 700 ℃ for 6 hours to obtain zinc aluminate powder. Mixing zinc aluminate powder and graphene oxide powder according to a mass ratio of 1.
Comparative example 5
Mixing soluble manganese salt and soluble lithium salt according to the content ratio of aluminum element to zinc element 2:1, dissolving in absolute ethyl alcohol to obtain mixed salt solution, adding polyethylene glycol accounting for 3.5% of the total mass of the mixed salt solution, stirring at high speed for 4 hours, heating to 80 ℃, continuously stirring until the solution becomes gel-like to obtain mixed gel solution, drying and grinding the mixed gel solution, and then placing in a muffle furnace for sintering at 700 ℃ for 6 hours to obtain zinc aluminate powder. Mixing zinc aluminate powder and graphene oxide powder according to a mass ratio of 1.
Comparative example 6
Grinding the graphene oxide powder for 30min, adding the graphene oxide powder into deionized water for dispersing, adding ammonia water for adjusting the pH of the mixed solution to 8.5, carrying out ultrasonic oscillation on the mixed solution for 30min, then homogenizing the mixed solution for 45min under the pressure of 30MPa by using a homogenizer, carrying out high-speed centrifugation at the rotating speed of 10000rpm after the homogenization operation, washing the mixed solution for 3 times by using the deionized water, and finally carrying out vacuum drying at 140 ℃ to obtain the graphene material.
The materials prepared in the above examples 1 to 6 are respectively mixed with lead powder, sulfuric acid and water to form paste mixed slurry, and the paste mixed slurry is coated on a negative electrode alloy grid to obtain a negative electrode of the lead-acid battery, and the lead-acid battery is prepared.
The lead-acid battery was subjected to a charge-discharge cycle test at 0.1C, and the test results are shown in table 1.
TABLE 1
As can be seen from table 1:
as can be seen by comparing the data of examples 1-3 with the data of comparative examples 1-3, the composite effect of zinc aluminate and graphene is better under the alkaline environment with the pH value of 8.0-9.0, so that the zinc aluminate graphene composite material can improve the battery capacity and the cycling stability when being applied to a lead-acid battery.
As can be seen from comparing the data of example 3 with the data of comparative example 6, after the graphene oxide is modified by adding zinc aluminate, the cycle stability of the battery can be improved, and the battery capacity can also be improved.
As can be seen from the data of comparative example 3, comparative example 4, and comparative example 5, the zinc cobaltate graphene composite material has a small difference in the battery capacity improvement effect but a large difference in the cycle stability improvement effect when applied to a lead acid battery, compared to the zinc aluminate graphene composite material of the present application. And lithium manganate graphene composite material compares in the zinc aluminate graphene composite material of this application when being applied to lead acid battery, promotes the effect at battery capacity and is optimal, but the cycling stability is the worst too.
To sum up, the zinc aluminate graphene composite material of the application can have better battery capacity and better cycling stability when the lead-acid battery is applied.
Compared with the prior art, the invention has at least the following advantages:
according to the preparation method of the zinc aluminate graphene composite material, zinc aluminate powder is prepared at first, the zinc aluminate belongs to one of aluminate spinel oxides, and the spinel oxide can improve the capacity of a lead-acid battery when being applied to the negative electrode of the lead-acid battery. Secondly, zinc aluminate spinel, as an inorganic material, is difficult to be uniformly dispersed in graphene oxide without adding a coupling agent, but the reactivity of carboxyl functional groups, hydroxyl functional groups and carbonyl functional groups on the surface of graphene oxide is effectively enhanced under an alkaline environment of pH8.0-9.0, and zinc aluminate is effectively enhanced by [ AlO ] 3 ] 2- The negative charge group and the surface of the graphene oxide establish covalent bond connection with strong connection effect, so that zinc aluminate is uniformly dispersed in the graphene oxide, and the zinc aluminate graphene composite material has better stability in the application of electrode materials, and has better cycle stability when being applied to the negative electrode of a lead-acid battery.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of a zinc aluminate graphene composite material is characterized by comprising the following steps:
preparing zinc aluminate powder;
preparing a zinc aluminate graphene composite material;
the specific steps for preparing the zinc aluminate graphene composite material are as follows:
preparing the zinc aluminate powder, the graphene oxide powder and absolute ethyl alcohol into mixed powder;
adding the mixed powder into deionized water to obtain a mixed solution;
carrying out pH adjustment operation on the mixed solution so as to enable the pH of the mixed solution to be between 8.0 and 9.0;
carrying out ultrasonic operation on the mixed solution;
homogenizing the mixed solution after ultrasonic treatment;
carrying out vacuum drying operation on the mixed solution after homogenizing operation to obtain the zinc aluminate graphene composite material;
wherein, in the mixed solution, under an alkaline environment with a pH of 8.0-9.0, after the carboxyl functional group, the hydroxyl functional group and the carbonyl functional group on the surface of the graphene oxide are activated, the carboxyl functional group, the hydroxyl functional group and the carbonyl functional group on the surface of the graphene oxide are all mixed with the [ AlO ] of the zinc aluminate 3 ] 2- And combining groups, so that after a covalent bond force is built between the zinc aluminate and the graphene oxide, the zinc aluminate and the graphene oxide are uniformly dispersed into the graphene oxide.
2. The method for preparing the zinc aluminate graphene composite material according to claim 1, wherein the specific steps for preparing the zinc aluminate powder are as follows:
dissolving soluble aluminum salt and soluble zinc salt in the absolute ethyl alcohol to obtain mixed salt solution;
adding polyethylene glycol into the mixed salt solution, and heating and stirring to obtain a mixed gel solution;
and sintering the mixed gel liquid to obtain the zinc aluminate powder.
3. The method for preparing the zinc aluminate graphene composite material according to claim 2, wherein the soluble aluminum salt is one or both of aluminum nitrate and aluminum chloride.
4. The method for preparing the zinc aluminate graphene composite material according to claim 2, wherein the soluble zinc salt is at least one of zinc nitrate, zinc acetate, zinc chloride, zinc bromide and zinc propionate.
5. The method of claim 2, wherein the sintering operation is performed at a temperature of 500 ℃ to 900 ℃.
6. The method for preparing the zinc aluminate graphene composite material according to claim 5, wherein the sintering operation is performed for 5-8 hours.
7. The method of claim 1, wherein the homogenizing operation is performed at a pressure of 20MPa to 40MPa.
8. The method for preparing the zinc aluminate graphene composite material according to claim 7, wherein the time for the homogenizing operation is 30min to 60min.
9. The method for preparing the zinc aluminate graphene composite material according to claim 1, wherein the temperature of the vacuum drying is 120 ℃ to 160 ℃.
10. A lead-acid battery negative electrode is characterized by comprising the following steps:
providing the zinc aluminate graphene composite material prepared by the preparation method of the zinc aluminate graphene composite material according to any one of claims 1 to 9;
mixing the zinc aluminate graphene composite material, lead powder, sulfuric acid and water into paste mixed slurry;
and coating the paste mixed slurry on a negative electrode alloy grid to obtain the negative electrode of the lead-acid battery.
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