CN112158872A - In-situ synthesis method of zinc-aluminum hydrotalcite-graphene nanocomposite - Google Patents

In-situ synthesis method of zinc-aluminum hydrotalcite-graphene nanocomposite Download PDF

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CN112158872A
CN112158872A CN202011058044.1A CN202011058044A CN112158872A CN 112158872 A CN112158872 A CN 112158872A CN 202011058044 A CN202011058044 A CN 202011058044A CN 112158872 A CN112158872 A CN 112158872A
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zinc
graphene
hydrotalcite
aluminum
naoh
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黎学明
谢玉婷
罗晓玉
杨文静
杨磊
雷颖
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Chongqing University
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Abstract

In-situ synthesis method of zinc-aluminum hydrotalcite-graphene nanocomposite, zinc/aluminum metal nitrate is dispersed in graphene suspension, and mixed with NaOH and Na2CO3Mixing with alkali solution, heating in water bath at 65 deg.C, stirring for 30min, and transferring to hydrothermal systemAnd reacting for 24 hours at 150 ℃ in a reaction kettle, filtering, washing and drying in vacuum to obtain the zinc-aluminum hydrotalcite-graphene nano composite material. The hydrotalcite material with the layered structure has good stability in the alkaline electrolyte, so that the deformation and dendrite phenomena of a zinc electrode can be inhibited, and the application of hydrotalcite in a zinc-based secondary battery is guaranteed; meanwhile, due to the excellent electron transfer property of the graphene, the conductivity of the hydrotalcite is improved, so that the material is strong in corrosion resistance and the electrode reaction is accelerated.

Description

In-situ synthesis method of zinc-aluminum hydrotalcite-graphene nanocomposite
Technical Field
The invention relates to a synthesis method of a zinc negative electrode material.
Background
Energy issues have become an increasingly important issue in the twenty-first century, drawing considerable attention from researchers in various fields. The appearance of the chemical power supply improves the energy problem to a great extent, but the current commercialized chemical power supplies such as lead-acid batteries, nickel-cadmium batteries and the like have heavy metal elements, which cause serious pollution to the environment; lithium ion batteries are also limited in their application in certain fields due to their safety issues. Meanwhile, the contradiction between the increasing demand of people on energy and the limited energy provided by a chemical power supply urgently needs scientific researchers to provide a novel high-efficiency green secondary battery.
The zinc-based battery takes the zinc electrode as the negative electrode of the battery, other electrodes as the positive electrode and the alkaline solution as the electrolyte, and has the characteristics of rich raw material resources, good safety, high energy density, small environmental pollution problem and the like. The active materials of the zinc electrode are mainly two types, one is metallic zinc powder, and the other is ZnO. The electrodes made of metallic zinc powder correspond to the zinc electrodes in the charged state, and the electrodes made of ZnO correspond to the zinc electrodes in the discharged state. Metallic zinc powder is generally used in primary zinc-based batteries and ZnO is used in zinc-based secondary batteries.
In the alkaline electrolyte, the self-discharge of zinc is serious, the problems of deformation, crystallization and the like can occur, and the cycle performance of the battery is seriously influenced. The over-potential of hydrogen deposition on metallic zinc is relatively large, so the self-dissolving speed of zinc in alkaline electrolyte solution is inherently lowNot very large. The actual zinc-based storage battery adopts the porous zinc electrode, so that the real contact area of zinc is rapidly increased, and although the self-dissolving speed of zinc is not very high, the self-discharge amount of zinc in the whole single battery is very obvious due to the increase of the contact area. In addition, the discharge products ZnO and Zn (OH)2There is some solubility in KOH solution so that both species can migrate in solution. The dissolution and deposition of zinc can not be carried out in the same place, so that the distribution of zinc in the electrode is changed, and the zinc content of each part of the electrode is not uniform; in addition, the density of zinc discharge product zincate is relatively high, and zinc is easy to deposit at the bottom of the battery, so that the concentration difference of the zincate at the upper part and the lower part of the battery is obvious, and a concentration difference battery is formed. In order to maintain balance, the zinc electrode is dissolved at the top to generate zincate, and the zincate is dissolved at the bottom to generate zinc, the zinc is deposited, the zinc distribution in the zinc electrode is further uneven, and the deformation and dendrite of a zinc cathode are caused, the utilization rate of an electrode active substance is greatly reduced due to the phenomenon, the cycle performance of the battery is influenced, and the cycle life is shortened. Meanwhile, the zinc-based secondary battery uses ZnO as an active substance, the ZnO is a semiconductor material, the conductivity of the ZnO is inferior to that of metal zinc powder, the conductivity of a zinc electrode is poor in the initial stage, and the internal resistance of the battery is high. Therefore, it is very important to research methods for improving the cycle life of the zinc-based secondary battery, such as preparation of active materials of a zinc electrode, additives, and the like.
In order to suppress deformation and dendrite of the zinc electrode during charge and discharge, a small amount of Polytetrafluoroethylene (PTFE) additive may be added to the active ingredient. During the charging and discharging processes, PTFE can form a three-dimensional network structure, and can fix an active substance in the three-dimensional network structure, so that the deformation and dendritic crystal phenomena of a zinc electrode are relieved. The performance of the zinc electrode can also be improved by adding some additives into the zinc electrode, and the additives are usually made of metal materials with larger hydrogen evolution overpotential, such as indium, bismuth, tin, thallium and the like, so that the materials can be better contacted with a current collector, the internal resistance of the battery is reduced, and the charge and discharge performance of the battery is improved. In order to solve the problem of poor conductivity of the zinc-based secondary battery taking ZnO as an active substance, a small amount of Zn powder can be added into ZnO to reduce the internal resistance of the battery, so that the initial charging efficiency of the battery is obviously improved, and the electrochemical properties of the battery, such as cycling stability, charging and discharging performance and the like, are improved. The carbon-coated ZnO can also improve the conductivity of the zinc electrode to a great extent, and further improve the performance of the zinc electrode, so that the battery has excellent cycle life.
The hybrid orbit of the carbon nano tube has a conjugated structure, so that the hybrid orbit has good electron transfer property, and when the hybrid orbit is applied to Zn-Al-LDHs, the one-dimensional carbon nano tube and the two-dimensional hydrotalcite layered structure form a compound with a three-dimensional conductive network, so that the hybrid orbit has very good conductivity. For the application of graphene to the lithium ion battery, research shows that with the addition of the graphene, the conductivity of the lithium ion battery is improved, and the performance of the lithium ion battery cathode material is further improved.
Although the method for improving the zinc negative active material can improve the cycle performance of the zinc-based secondary battery to a certain extent, the cycle stability is poor. By means of the application of the graphene in the lithium ion battery, if the graphene is applied to the zinc-aluminum hydrotalcite, the conductivity of a zinc cathode can be greatly improved, the characteristic of poor conductivity of the hydrotalcite is improved, and the electrochemical performance and the cycling stability of the zinc-based secondary battery are improved.
Disclosure of Invention
The invention aims to provide a preparation method of an improved zinc anode active material.
According to a first aspect of the present invention, there is provided an in-situ synthesis method of a zinc-aluminum hydrotalcite-graphene nanocomposite material, comprising:
preparing or providing a graphene oxide suspension, wherein the content of graphene is 3.53 g/L;
adding Zn (NO)3)2·6H2O and Al (NO)3)3·9H2Adding O into the graphene suspension respectively, and performing ultrasonic treatment to completely dissolve the metal nitrate, wherein Zn (NO)3)2·6H2O concentration of 0.02mol/L, Al (NO)3)3·9H2The concentration of O is 0.01 mol/L;
NaOH and Na were added at a rate of 0.05mL/s2CO3Dropping into graphene suspension containing metal nitrate, wherein the dropping amount of NaOH is 30.2g/L, and Na is added2CO3The dropping amount of (2) is 20 g/L;
dropping NaOH and Na2CO3Reacting the graphene suspension for 30min under the conditions of heating in a water bath at 65 ℃ and stirring to obtain slurry;
centrifuging and washing the obtained slurry for multiple times at the rotating speed of 5000rpm until the pH value is about 7; carrying out hydrothermal reaction on the centrifugal product at 150 ℃ for 24 h; and
and taking out the hydrothermal reaction product, filtering, washing and drying in vacuum to obtain the composite material.
According to the invention, the graphene oxide is preferably prepared by a Hummer modification method.
According to a second aspect of the present invention, there is provided a secondary battery comprising a zinc anode prepared from the composite material synthesized by the above method.
The invention has the following advantages:
(1) due to the existence of zinc element in the zinc-aluminum hydrotalcite, the zinc-aluminum hydrotalcite can be used as a negative active material to be applied to a zinc-based secondary battery, the hydrotalcite has alkalinity, the electrolyte of the zinc-based secondary battery is an alkaline solution, the stability of hydrotalcite materials in the alkaline electrolyte is guaranteed, the layered structure of the hydrotalcite inhibits the deformation and dendrite phenomenon of a zinc electrode to a certain extent, and the cycling stability of the battery is improved;
(2) the hydrotalcite is compounded with graphene with excellent conductivity, and the conductivity of the hydrotalcite is improved by utilizing the excellent electron transfer property of the graphene;
(3) the zinc-aluminum hydrotalcite-graphene nano composite material prepared by the in-situ synthesis method has the advantages of simple preparation process and strong binding force, and can effectively improve the reaction activity of the material.
In conclusion, the zinc cathode active material adopts the zinc-aluminum hydrotalcite, so that the deformation and dendrite phenomena of ZnO directly used as the active material are improved; then, an in-situ synthesis method is adopted, and the problem of improving the conductivity of the zinc-aluminum hydrotalcite is solved by utilizing the excellent electron transfer property of the graphene material (which is attributed to the fact that the graphene partially blocks the contact of an active substance and an alkaline electrolyte in the compound prepared by the in-situ growth method); finally, the zinc-aluminum hydrotalcite-graphene nano composite material is made into an electrode, so that the electrochemical performance of the active material is improved, and the cycle stability of the secondary zinc-based battery is improved.
Drawings
FIGS. 1(a) and 1(b) are an SEM magnified view and a detailed view, respectively, of a composite material of the present invention having a 2:1 molar ratio of zinc to aluminum;
FIGS. 2(a) - (e) are SEM images of composite materials with zinc to aluminum molar ratios of 1:1 to 5:1, respectively;
FIG. 3 is an XRD pattern of composites of different graphene content;
FIG. 4 is an AC impedance plot for composites of different graphene content;
fig. 5 is a Tafel plot for composites of different graphene content.
Detailed Description
Example 1
Preparing graphene oxide by adopting a Hummer improved method; adding Zn (NO)3)2·6H2O and Al (NO)3)3·9H2O is added into 3.53mg/mL graphene suspension respectively, so that Zn (NO) is obtained3)2·6H2O and Al (NO)3)3·9H2The content of O suspended in the solution is 0.02mol/L and 0.01mol/L respectively (the molar ratio of zinc to aluminum is 2:1), and the metal nitrate is completely dissolved by ultrasonic treatment for 10 min; separately, 1.51g of NaOH and 1g of Na were weighed2CO3Dissolving in a 100mL beaker filled with 50mL of ultrapure water by ultrasonic treatment for 10min to obtain a mixed alkali solution; adding the mixed alkali liquor into the graphene suspension containing the metal nitrate at the speed of 0.05ml/s (about 1 drop/s), and reacting for 30min, wherein the process is completed under the condition of heating and stirring in a water bath at 65 ℃; centrifuging the obtained slurry for many times at the rotating speed of 5000rpm until the pH value is approximately equal to 7; transferring the centrifugal product to a 100mL hydrothermal reaction kettle, adding a proper amount of ultrapure water, and carrying out hydrothermal reaction at 150 ℃ for 24 h. And taking out a product in the hydrothermal reaction kettle, filtering, washing, and drying in vacuum at 70 ℃ to obtain the zinc-aluminum hydrotalcite-graphene nano composite material.
The morphology of the sample was observed by Scanning Electron Microscopy (SEM).
As shown in fig. 1(a) and 1(b), the zinc-aluminum hydrotalcite-graphene nanocomposite material with a zinc-aluminum molar ratio of 2:1 prepared by the method has a hexagonal sheet structure, a thickness within a range of tens of nanometers, and relatively uniform distribution.
Comparative example 1
Similar to example 1, except that the molar ratio of zinc to aluminum was varied from 1:1 to 5:1, respectively. The morphology of the sample was also observed using a Scanning Electron Microscope (SEM).
As shown in fig. 2(a) to 2(e), when the ratio of zinc to aluminum is 2:1, the size of the nano-flake is large and a hexagonal plate structure is present. When the ratio of zinc to aluminum is 1:1, 3:1, 4:1 and 5:1, the size of the nano flake is small, the thickness of the flake is thin, but the size distribution is uneven, and an obvious hexagonal structure cannot be seen.
Comparative example 2
The other example is the same as example 1, except that the content of graphene is changed to 0.71mg/mL to 2.84 mg/mL.
As shown in fig. 3, the XRD patterns of hydrotalcite/graphene composites with different graphene contents show a series of narrow, strong, symmetrical peaks at 11.77 °, 23.58 °, 34.76 °, 39.38 °, 46.97 ° and 61.83 °. These peaks correspond to Zn, respectively3Al2(OH)10(CO3)2·xH2The (003), (006), (012), (015), (018), (113) crystal plane of O is Zn3Al2(OH)10(CO3)2·xH2Characteristic peak of O. The zinc-aluminum hydrotalcite is proved to be successfully synthesized and has a good crystal structure; and some small and wide diffraction peaks appear around 25 ° at 2 θ, which are characteristic peaks of graphene, and are marked by ellipses in fig. 3, and the diffraction peaks become more and more obvious as the content of graphene increases. This demonstrates that graphene is synthesized.
The active material was prepared as an electrode and tested for electrochemical properties.
As shown in fig. 4, as the content of graphene increases, the charge transfer resistance rapidly decreases; when a small amount of graphene is added, the charge transfer resistance of the hydrotalcite/graphene compound synthesized by the in-situ growth method stillCompared with the hydrotalcite/graphene compound synthesized by a mechanical mixing method with a large amount of graphene, the charge transfer resistance of the hydrotalcite/graphene compound is low. With the continuous increase of the added graphene amount, the charge transfer resistance of the hydrotalcite/graphene composite is rapidly reduced, and when the graphene content is 3.55mg/mL, the composite resistance is only 42.57 omega cm2Compared with pure steatite material, the resistance is reduced by about 4.5 times.
As shown in fig. 5, as the content of graphene increases, the graphene wraps the hydrotalcite material more perfectly, the proportion of blocking the contact of the active substance and the alkaline electrolyte increases, the contact of the hydrotalcite material and the electrolyte is less, the corrosion tendency of the active substance is weaker, and the corrosion potential continuously moves towards the positive direction. The corrosion current density also increases with increasing graphene content due to increased graphene content, resulting in increased conductivity of the composite, facilitated electron transfer, increased speed of electrochemical reaction, and increased corrosion current density.

Claims (3)

1. An in-situ synthesis method of a zinc-aluminum hydrotalcite-graphene nanocomposite material comprises the following steps:
preparing or providing a graphene oxide suspension, wherein the content of graphene is 3.53 g/L;
adding Zn (NO)3)2·6H2O and Al (NO)3)3·9H2Adding O into the graphene suspension respectively, and performing ultrasonic treatment to completely dissolve the metal nitrate, wherein Zn (NO)3)2·6H2O concentration of 0.02mol/L, Al (NO)3)3·9H2The concentration of O is 0.01 mol/L;
NaOH and Na were added at a rate of 0.05mL/s2CO3Dropping into graphene suspension containing metal nitrate, wherein the dropping amount of NaOH is 30.2g/L, and Na is added2CO3The dropping amount of (2) is 20 g/L;
dropping NaOH and Na2CO3Reacting the graphene suspension for 30min under the conditions of heating in a water bath at 65 ℃ and stirring to obtain slurry;
centrifuging and washing the obtained slurry for multiple times at the rotating speed of 5000rpm until the pH value is about 7;
carrying out hydrothermal reaction on the centrifugal product at 150 ℃ for 24 h; and
and taking out the hydrothermal reaction product, filtering, washing and drying in vacuum to obtain the composite material.
2. The method of claim 1, wherein the graphene oxide is prepared using a Hummer modification.
3. A secondary battery comprising a zinc anode prepared from the composite material synthesized by the method of claim 1 or 2.
CN202011058044.1A 2020-09-30 2020-09-30 In-situ synthesis method of zinc-aluminum hydrotalcite-graphene nanocomposite Pending CN112158872A (en)

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CN113745642A (en) * 2021-08-09 2021-12-03 信阳师范学院 Preparation method of shell structure aluminum-based material and application of shell structure aluminum-based material in lithium ion battery
CN115707749A (en) * 2022-09-30 2023-02-21 马鞍山拓锐金属表面技术有限公司 High-adhesion antirust agent and preparation method thereof

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Cited By (5)

* Cited by examiner, † Cited by third party
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CN113036194A (en) * 2021-03-09 2021-06-25 湖北工程学院 Preparation method of organic-inorganic composite alkaline polyelectrolyte membrane
CN113451562A (en) * 2021-07-02 2021-09-28 辽宁工程技术大学 Flexible positive electrode material of lithium-sulfur battery and preparation method thereof
CN113451562B (en) * 2021-07-02 2023-06-20 辽宁工程技术大学 Flexible positive electrode material of lithium-sulfur battery and preparation method thereof
CN113745642A (en) * 2021-08-09 2021-12-03 信阳师范学院 Preparation method of shell structure aluminum-based material and application of shell structure aluminum-based material in lithium ion battery
CN115707749A (en) * 2022-09-30 2023-02-21 马鞍山拓锐金属表面技术有限公司 High-adhesion antirust agent and preparation method thereof

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Application publication date: 20210101