CN117977023A - Alkaline zinc-based battery - Google Patents
Alkaline zinc-based battery Download PDFInfo
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- CN117977023A CN117977023A CN202410151080.4A CN202410151080A CN117977023A CN 117977023 A CN117977023 A CN 117977023A CN 202410151080 A CN202410151080 A CN 202410151080A CN 117977023 A CN117977023 A CN 117977023A
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- 239000011701 zinc Substances 0.000 title claims abstract description 79
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- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 70
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 239000011737 fluorine Substances 0.000 claims abstract description 4
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
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- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
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- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 210000001787 dendrite Anatomy 0.000 abstract description 15
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011241 protective layer Substances 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 18
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
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- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to an alkaline zinc-based battery, comprising a positive electrode, a negative electrode and electrolyte, wherein the positive electrode comprises silver oxide and/or silver; the cathode comprises a zinc substrate and a carbon coating, wherein the carbon coating comprises functionalized carbon quantum dots, and the functionalized carbon quantum dots are carbon dots doped with at least one of nitrogen, sulfur and fluorine; the electrolyte comprises an aqueous potassium hydroxide solution or an aqueous sodium hydroxide solution; the carbon coating is arranged on the surface of the zinc substrate to serve as a negative electrode, and serves as an artificial interface protective layer, so that the problem that zinc dendrites are generated due to direct contact between the strong alkaline electrolyte and the zinc foil can be effectively solved, meanwhile, zinc ions are guided to be uniformly deposited on the surface of the negative electrode by utilizing various functional groups on the surface of the functionalized carbon point in the carbon coating, and the rate capability and the cycle performance of the battery are improved.
Description
Technical Field
The invention relates to the technical field of zinc-based batteries, in particular to an alkaline zinc-based battery.
Background
Currently, the global energy consumption problem is increasing, and it is difficult to meet the increasing energy demand only by using traditional energy sources such as petroleum, natural gas, coal and the like, not to mention the damage caused by fossil fuels. The ecological challenges of resource shortages are more pronounced. This demand has stimulated intensive research into the development of renewable energy technologies such as wind and solar. However, the unpredictability and transience of these energies severely limit their application. Therefore, developing high performance energy storage devices is a reasonable choice for efficient use of clean energy. In order to achieve economical, high energy density, high safety and environmentally friendly batteries, important research efforts have focused on converting primary (non-rechargeable, including water-based) batteries into secondary (rechargeable) batteries. The advantages of high safety, abundant zinc reserves, low cost and high energy density are benefited, and the water-based zinc ion battery has great research and development space as an energy storage system with great prospect, and is particularly suitable for the fixed energy storage field represented by peak clipping and valley filling, standby power supply and the like. Under the effects of various factors such as cost, core advantages, fixed energy storage requirement and the like, the water-based zinc battery becomes a low-cost, high-power and absolute safe energy storage device in the rear lithium battery age, and becomes a promising alternative.
Zinc-based batteries are classified into zinc ion batteries using neutral or weak acid electrolytes and alkaline zinc-based batteries using extremely high concentration alkaline solution electrolytes according to the pH of the electrolyte.
In alkaline zinc-based batteries, zinc anodes face a great challenge: (1) As the electrochemical reaction proceeds, a Zn oxide passivation layer may form on the unreacted Zn surface due to supersaturation of zincate ions caused by low concentration of OH - in the electrolyte or uneven Zn deposition, and hinder ion conversion at the electrode/electrolyte interface, resulting in low utilization rate and poor charge/discharge capability of the Zn electrode, particularly in a sealed battery in which the amount of electrolyte is limited, hydrogen gas precipitated from the Zn anode consumes the electrolyte and increases the internal pressure of the battery, and may result in low coulombic efficiency of the battery; in addition, in alkaline solution, zn can be deposited at any position in the charging process, so that the electrode morphology is changed and dendrite growth after continuous circulation is caused, and Zn dendrite can even puncture through a diaphragm, so that the battery is short-circuited. In addition, dendrites generated by alkaline zinc-based batteries are greatly different from zinc ion batteries, when the concentration of zincate in electrolyte reaches the limit solubility or the pH value is reduced, the zincate is converted into an insulating precipitate ZnO, and the generated ZnO further induces the growth of Zn dendrites, so that the battery is finally disabled.
The existing zinc cathode optimization method mainly comprises the steps of adopting three-dimensional structural design, interface coating, artificial solid electrolyte interface and the like for the zinc cathode. The interface coating is generally formed by coating a protective layer on the surface of the negative electrode to avoid direct contact between the zinc negative electrode and the strong alkaline electrolyte, such as by coating an alloy liquid phase intermediate layer of a liquid Ga-In alloy on the negative electrode In the prior art, to establish a liquid-liquid (alloy coating-electrolyte) interface between the zinc negative electrode and the electrolyte solution, thereby avoiding dendrites and corrosion products. However, since the liquid alloy is easy to form droplets on the zinc surface, a special process is required to keep the liquid coating on the zinc anode surface, thereby limiting the application development thereof.
Disclosure of Invention
Based on the technical problems in the prior art, the invention provides an alkaline zinc-based battery, wherein a carbon coating is arranged on the surface of a zinc substrate and used as a negative electrode, and the carbon coating is used as an artificial interface protective layer, so that the problem that zinc dendrites are generated due to direct contact of a strong alkaline electrolyte and zinc foil can be effectively solved, meanwhile, zinc ions are guided to be uniformly deposited on the surface of the negative electrode by utilizing various functional groups on the surface of a functionalized carbon point in the carbon coating, and the rate performance and the cycle performance of the battery are improved.
In order to achieve the above object, the technical scheme of the present invention is as follows:
An alkaline zinc-based battery comprising a positive electrode comprising silver oxide and/or silver, a negative electrode and an electrolyte; the cathode comprises a zinc substrate and a carbon coating, wherein the carbon coating comprises functionalized carbon quantum dots, and the functionalized carbon quantum dots are carbon dots doped with at least one of nitrogen, sulfur and fluorine; the electrolyte comprises an aqueous potassium hydroxide solution or an aqueous sodium hydroxide solution.
In some embodiments, the negative electrode is prepared by the following method:
And mixing the functionalized carbon quantum dots, a binder and a solvent to form slurry, coating the slurry on the surface of the zinc substrate, and drying to obtain the negative electrode.
In some embodiments, the functionalized carbon quantum dots and the binder have a mass ratio of 1 to 4:6-9.
In some embodiments, the binder is at least one of carboxymethyl cellulose, polytetrafluoroethylene, polyvinyl alcohol.
In some embodiments, the solvent is at least one of water, isopropanol, dimethyl sulfoxide.
In some embodiments, the zinc substrate has a thickness of 10-200 μm.
In some embodiments, the method of making the negative electrode is as follows:
S1, uniformly mixing the binder and the solvent, then adding the functionalized carbon quantum dots, and uniformly mixing to obtain slurry;
s2, polishing the surface of the zinc substrate, and wiping the surface with ethanol;
And S3, coating the slurry on the surface of the zinc substrate, and drying to obtain the negative electrode.
In some embodiments, in step S3, drying is performed at 60-100deg.C for a drying time of 8-12 hours; preferably, it is dried at 80℃for 10 hours.
In some embodiments, in step S1, after adding the functionalized carbon quantum dots, stirring is performed for 4-8 hours.
In some embodiments, the positive electrode further comprises a conductive agent including, but not limited to, a graphite-based conductive agent, a carbon-based conductive agent, a metal conductive agent.
In some embodiments, the alkaline zinc-based battery further comprises a separator, the separator being a glass fiber.
Compared with the prior art, the invention has the following beneficial effects:
The alkaline zinc-based battery provided by the invention comprises a positive electrode, a negative electrode and an electrolyte, wherein the negative electrode comprises a zinc substrate and a carbon coating, the carbon coating comprises functionalized carbon quantum dots doped with at least one of nitrogen, sulfur and fluorine, the hydrophobic characteristic of the functionalized carbon quantum dots is utilized to prevent the zinc substrate from being directly contacted with the strong alkaline electrolyte, so that the zinc substrate is prevented from being corroded or generating hydrogen evolution reaction, zinc dendrites or dendrites are effectively prevented from being generated, and the use cycle performance and the safety performance of the battery are improved; meanwhile, by utilizing the characteristic of multiple functional groups on the functionalized carbon quantum dots, zinc ions are uniformly deposited on the surface of the negative electrode in the battery cycle process, so that the rate capability of the alkaline zinc-based battery is obviously improved, and the cycle performance of the alkaline zinc-based battery is further improved.
Drawings
In fig. 1, a and b are contact angles of the bare zinc anode of comparative example 1 and an electrolyte; graph c and graph d are contact angles of the negative electrode and the electrolyte of example 1;
in fig. 2, a-c are optical microscopic views after cycling of a button cell battery prepared by the negative electrode sheet obtained in comparative example 1; d-f is an optical microscope image of the button cell prepared by the negative electrode sheet obtained in example 1 after cycling;
Fig. 3 is a charge-discharge cycle chart at current densities of 0.1A g -1 and 0.5A g -1 for the negative electrode preparation full cells obtained in example 1 and comparative example 1, example 1 and comparative example 1;
FIG. 4 is a charge-discharge cycle chart of the negative electrode preparation full cell obtained in example 1 and comparative example 1 at a current density of 1mA cm -2;
In fig. 5, g1 to g4 are scanning electron microscope images of the negative electrode sheet prepared in comparative example 1 after the full cell is assembled and subjected to charge-discharge cycles; and h1-h4 are scanning electron microscope diagrams of the cathode sheet prepared in the embodiment 1 after the full battery is assembled and charge-discharge cycle is carried out.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit or scope of the invention, which is therefore not limited to the specific embodiments disclosed below.
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.
Example 1
(One) preparation of functionalized carbon dots, comprising the following steps:
The molar ratio is 1:2 respectively weighing the phthalaldehyde and the phthalacetonitrile, mixing, fully grinding, then adding into a 1M sodium hydroxide aqueous solution, carrying out ultrasonic treatment, and carrying out hydrothermal reaction for 2 hours at 160 ℃; after the reaction is completed, cooling to room temperature, filtering, washing with deionized water, and drying to obtain a sample.
And detecting the obtained sample to obtain the carbon quantum dots with uniform distribution and average size of 1-10nm.
(II) a composite anode, the preparation method comprises the following steps:
s1, polishing the surface of zinc foil (the thickness is 50 mu m) by using 1200-mesh sand paper, cleaning by using deionized water and ethanol, and drying;
s2, adding 15mg of carboxymethyl cellulose into a size mixing bottle at normal temperature, adding a proper amount of solvent, and stirring for 1h until the binder is uniformly dispersed;
S3, placing the functionalized carbon quantum dots into a mortar, and forcedly grinding for 15-20min until the carbon dots are uniform in particles and have no massive particles;
s4, weighing 60mg of the functionalized carbon quantum dots in the step S3, slowly adding the functionalized carbon quantum dots into a slurry mixing bottle, adding the rest of solvent, and stirring for 6 hours until the viscosity of the mixed slurry is proper;
s5, coating the mixed slurry obtained in the step S4 on a zinc metal substrate through an automatic coating machine, adjusting the height to 25 mu m, then placing the zinc metal substrate into a vacuum drying oven, drying the zinc metal substrate at 80 ℃ for 10 hours, and cutting the zinc metal substrate into pole pieces with the diameter of 14mm for standby.
Comparative example 1
Preparation of zinc metal negative electrode:
And (3) polishing the surface of the zinc foil (with the thickness of 100 mu m) for 10min by adopting 1200-mesh sand paper, cleaning by using deionized water and ethanol, drying to obtain the metal zinc foil (with the thickness of 90 mu m) with smooth and clean surface and no zinc oxide, and cutting into pole pieces with the diameter of 14mm for standby.
Contact angles were measured with the pole pieces of example 1 and comparative example 1, respectively, and the measurement results are shown in fig. 1. As shown in fig. 2, the initial contact angle of bare zinc (Bare Zn) is known as 97.3 ° from fig. 1 (a), the initial contact angle of carbon dot modified zinc negative electrode (zn@cds) is known as 56.2 ° from fig. 1 (c), however, after thirty seconds, the contact angle of bare zinc (Bare Zn) is changed from 97.3 ° to 28.1 ° from fig. 1 (b), and the contact angle of functionalized carbon quantum dot modified zinc negative electrode (zn@cds) is changed from 56.2 ° to 51.1 ° from fig. 1 (d). It is shown that carbon-point modified zinc cathodes (zn@cds) form a good physical barrier that can prevent zinc to some extent from contacting the electrolyte.
Preparation of a battery:
Preparation of zinc symmetrical cell:
At room temperature, the electrode plates of the example 1 and the comparative example 1 are respectively taken as positive and negative electrodes, and potassium hydroxide is taken as electrolyte, and the symmetrical battery assembly of the two-electrode mold is completed in air.
Preparation of a full cell:
At room temperature, the battery assembly of the full battery was completed in air with the electrode sheets prepared in example 1 and comparative example 1 as a negative electrode, potassium hydroxide as an electrolyte, silver oxide as a positive electrode, and glass fiber as a separator, respectively.
Wherein:
The preparation process of the silver oxide comprises the following steps:
Preparing 2M concentration sodium hydroxide aqueous solution and 0.1M concentration nitrate aqueous solution, weighing according to the volume of the sodium hydroxide aqueous solution being twice that of the nitrate aqueous solution, adding the aqueous solution into a 100ml hydrothermal kettle, reacting for 2 hours at 160 ℃, naturally cooling to room temperature, respectively washing the products with ethanol and deionized water, and finally drying in a vacuum drying box for 10 hours to obtain Ag 2 O.
Preparation of silver oxide positive electrode:
According to the mass ratio of 7:2:1, respectively weighing 70mg of silver oxide, 20mg of carbon black conductive agent and 10mg of PVDF binder to an agate mortar, uniformly stirring, then dripping 20 drops of NMP to perform slurry stirring, grinding for 10min to uniform slurry, uniformly coating the slurry on the surface of a stainless steel mesh by using a scraper, then placing the stainless steel mesh in a vacuum drying oven at 100 ℃ for 10h, and then taking out a wafer with the diameter of 12 cm.
Performance testing
The prepared symmetrical battery is subjected to cycle performance test by using a blue electrochemical test system, and the current density of the symmetrical battery is 1.0mA cm -2; and (3) carrying out cycle performance test on the whole battery by using a blue-electricity electrochemical test system, wherein the voltage range of the zinc-silver oxide battery is as follows: 1.3-1.8V, and the current density is 0.1-0.5A g -1.
The pole pieces of example 1 and comparative example 1 were used as the positive and negative electrodes, potassium hydroxide was used as the electrolyte, glass fiber was used as the separator, after the whole battery was assembled and left to stand for 2 hours, charge and discharge cycles were performed at a current density of 1mA cm -2, after 80 cycles, the battery was disassembled, the pole pieces were washed with water and ethanol, the pole pieces were sampled, and photographing by an optical microscope was performed, and the results are shown in FIG. 2. Wherein the a-c diagrams of fig. 2 are photographs of the pole piece in comparative example 1, it can be seen from the a-c diagrams that the surface of the bare zinc anode is uneven, a large number of uneven zinc deposition particles are present, the three-dimensional height diagram shows the surface of the pole piece is uneven, and the highest scale is 31, which indicates that there is continuous zinc dendrite accumulation; the d-f graph is a photograph of the negative electrode sheet in example 1, and as can be seen from the d-f graph, the surface of the negative electrode sheet is flat, the highest scale is 19, no obvious dendrite formation exists, and zinc is uniformly deposited on the surface of the composite negative electrode.
Therefore, the carbon dot coating can be used as an artificial interface protective layer to effectively inhibit zinc dendrite formation, so that the risk of the dendrite penetrating through the diaphragm is greatly reduced, and the stability and the cycle life of the composite negative electrode are improved.
The electrode sheets of example 1 and comparative example 1 were used as the negative electrode, the silver oxide electrode sheet was used as the positive electrode, the potassium hydroxide was used as the electrolyte, and the glass fiber was used as the separator, and after the complete battery was assembled and left to stand for 2 hours, charge and discharge cycles were performed at current densities of 0.1A g -1 and 0.5A g -1, respectively, and the results are shown in a graph and b graph of fig. 3, respectively. As shown in fig. 3, the cycle life of the battery assembled by using example 1 as the negative electrode is far longer than that of the negative electrode of comparative example 1 under different current densities, which indicates that the carbon dot coating can be used as an artificial interface to uniformly deposit zinc ions, so as to reduce the risk of dendrite penetration.
The electrode sheets of example 1 and comparative example 1 were used as the positive and negative electrodes, respectively, potassium hydroxide was used as the electrolyte, and after the symmetrical battery assembly of the two-electrode mold was completed in air and left to stand for 2 hours, charge and discharge cycles were performed at a current density of 1mA cm -2, and the results are shown in FIG. 4. As shown in fig. 4, the battery assembled as the positive electrode and the negative electrode in comparative example 1 had a short circuit around 230 hours and could not be recycled, while the battery assembled as the positive electrode and the negative electrode in example 1 still had a normal cycle after more than 600 hours, which means that the carbon dot coating layer as an artificial interface could be used as a good barrier to inhibit the corrosion of the electrolyte and protect the zinc negative electrode.
And then respectively taking the pole pieces of the embodiment 1 and the comparative embodiment 1 as positive and negative electrodes, taking potassium hydroxide as electrolyte and taking glass fiber as a diaphragm, after the battery is assembled and stood for 2 hours, carrying out charge-discharge circulation under the current density of 1mA cm -2, disassembling the battery after 10 circles of circulation, cleaning the pole pieces with water and ethanol, preparing the pole pieces into samples, and shooting under a scanning electron microscope, wherein the result is shown in figure 5. In fig. 5, g1 to g4 are pictures of the pole piece in comparative example 1, and h1 to h4 are pictures of the pole piece of example 1. As can be seen from the diagrams g1-g4, the surface of the zinc sheet has larger bulges, and the whole corrosion condition is serious; from the h1-h4 graphs, the surfaces of the grade sheets are smooth and have no larger dendrite particles, which indicates that the corrosion of the zinc sheets is greatly relieved under the protection of the carbon dot coating.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (9)
1. An alkaline zinc-based battery comprising a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode comprises silver oxide and/or silver; the cathode comprises a zinc substrate and a carbon coating, wherein the carbon coating comprises functionalized carbon quantum dots, and the functionalized carbon quantum dots are carbon dots doped with at least one of nitrogen, sulfur and fluorine; the electrolyte comprises an aqueous potassium hydroxide solution or an aqueous sodium hydroxide solution.
2. The alkaline zinc-based battery of claim 1, wherein the negative electrode is prepared by the method of:
And mixing the functionalized carbon quantum dots, a binder and a solvent to form slurry, coating the slurry on the surface of the zinc substrate, and drying to obtain the negative electrode.
3. The alkaline zinc-based battery according to claim 2, wherein the mass ratio of the functionalized carbon quantum dots to the binder is 1-4:6-9.
4. The alkaline zinc-based battery of claim 2, wherein the binder is at least one of carboxymethyl cellulose, polytetrafluoroethylene, polyvinyl alcohol.
5. The alkaline zinc-based battery of claim 2, wherein the solvent is at least one of water, isopropyl alcohol, dimethyl sulfoxide.
6. The alkaline zinc-based battery of claim 2, wherein the zinc substrate has a thickness of 10-200 μιη.
7. The alkaline zinc-based battery of claim 2, wherein the negative electrode is prepared by the following method:
S1, uniformly mixing the binder and the solvent, then adding the functionalized carbon quantum dots, and uniformly mixing to obtain slurry;
s2, polishing the surface of the zinc substrate, and wiping the surface with ethanol;
And S3, coating the slurry on the surface of the zinc substrate, and drying to obtain the negative electrode.
8. The alkaline zinc-based battery according to claim 7, wherein in step S3, the drying is performed at 60 to 100 ℃ for 8 to 12 hours.
9. The alkaline zinc-based battery of any one of claims 1-8, further comprising a separator, the separator being glass fibers.
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