CN115763789A - Flexible water-based zinc ion battery, positive electrode material and preparation method thereof - Google Patents
Flexible water-based zinc ion battery, positive electrode material and preparation method thereof Download PDFInfo
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 11
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- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 18
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 claims abstract description 16
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 9
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- 239000011149 active material Substances 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003990 capacitor Substances 0.000 abstract description 8
- 229910052725 zinc Inorganic materials 0.000 abstract description 8
- 239000011701 zinc Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 230000002950 deficient Effects 0.000 abstract 1
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
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- 150000008064 anhydrides Chemical class 0.000 description 1
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Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a flexible water-based zinc ion battery, a positive electrode material and a preparation method thereof, and belongs to the field of water-based zinc ion capacitor batteries. The invention aims at the problems that the cathode of the zinc ion battery is deficient and the metal zinc sheet as the anode can not achieve long circulation and the like. The method comprises the following steps: dissolving 3,4,9, 10-perylenetetracarboxylic dianhydride and ethylenediamine in N-methylpyrrolidone, carrying out condensation reflux reaction for at least 6h, cooling to room temperature, washing, carrying out suction filtration, and carrying out vacuum drying to obtain powder; and uniformly mixing the obtained powder with ethylenediamine and graphene oxide, carrying out hydrothermal reaction, washing, and carrying out freeze drying to obtain the cathode material. The water-based zinc ion battery assembled by the cathode material has good flexibility, and can realize a wearable effect.
Description
Technical Field
The invention belongs to the field of water-based zinc ion capacitor batteries, and particularly relates to a preparation method of a flexible water-based zinc ion battery anode material and a flexible water-based zinc ion battery.
Background
Because the environmental problem is increasingly severe, the development of green energy is a research which needs to be solved urgently, and the threat of the traditional existence on the ecological environment balance is abandoned firstly. As is well known, most lithium ion batteries have the problems of toxic, flammable and explosive organic electrolyte and the like, which restrict the ecological balance of people and bring much trouble to the life of people. And a green energy storage device is established to solve the problem that the life and the environment of human beings are harmed due to the continuous consumption of fossil fuels and the large emission of greenhouse gases. In the process of searching for a battery material which can meet the requirements of a large-scale energy storage system, has high cycle stability, high energy density and low cost, the water-based battery can definitely and completely meet all the requirements of people. The water-based battery is formed by taking water resources with abundant reserves as a solvent and taking inorganic salt as an electrolyte.
Although the aqueous electrolyte has high ionic conductivity and fast electron transport, the decomposition voltage of water is 1.23V, the voltage interval is small, and side reactions such as hydrogen evolution and oxygen evolution are easy to occur. Therefore, it is important to find an electrode material which has high solubility in water and can prevent side reactions. Among metal ions such as lithium, sodium, magnesium, and zinc, zinc ion is an important element that is indispensable in the development history of aqueous batteries, because of problems such as the size of the ionic radius and stability in air.
The development prospect of the water-based zinc ion battery in the water-based battery is very considerable, but metal zinc as a negative electrode material in the water-based battery is easy to cause dendrite on a zinc sheet in the long-cycle process, so that the long-cycle performance of the battery is seriously influenced.
Due to the harmfulness of organic electrolyte to human bodies, pollution to the environment and the like, a nontoxic, harmless and environment-friendly wearable battery capable of replacing a traditional battery is urgently needed to be found.
Disclosure of Invention
The invention provides a preparation method of a flexible water system zinc ion battery anode material and a flexible water system zinc ion battery aiming at the problems of the shortage of a zinc ion battery cathode, the incapability of achieving long circulation when a metal zinc sheet is used as an anode and the like, and aims to solve the problems of the zinc ion battery at the present stage.
In order to realize the technical problem, the invention adopts the following technical scheme:
the invention aims to provide a preparation method of a flexible water-based zinc ion battery positive electrode material, which is realized by the following steps:
dissolving 3,4,9, 10-perylene tetracarboxylic dianhydride and ethylenediamine in N-methyl pyrrolidone, carrying out condensation reflux reaction for at least 6h, cooling to room temperature, washing, carrying out suction filtration, and carrying out vacuum drying to obtain powder;
and step two, uniformly mixing the powder obtained in the step one with ethylenediamine and graphene oxide, performing hydrothermal reaction, washing, and performing freeze drying to obtain the cathode material.
Further limiting, in step one, 3,4,9, 10-perylenetetracarboxylic dianhydride and ethylenediamine were dissolved in N-methylpyrrolidone in a ratio of 1.
Further limited, in the first step, the reflux is condensed at the temperature of 120-160 ℃.
Further defined, the drying in step one is carried out for at least 6 hours under vacuum at 60 ℃ to 160 ℃.
Further limiting, in the second step, 0.1-0.2g of the powder obtained in the first step is mixed with 0.05-0.1g of ethylenediamine and 1-3mmol/L of redox graphene uniformly.
Further defined, in the second step, the hydrothermal reaction is carried out for at least 14h at the temperature of between 90 and 180 ℃.
Further defined, freeze-drying in step two for at least 24 hours.
A positive electrode material prepared by any of the above-mentioned preparation methods.
A flexible water-based zinc ion battery comprises the positive electrode material prepared by any preparation method.
Further, the negative electrode material takes activated carbon as an active substance, polyvinylidene fluoride as a binder and acetylene black as a conductive agent.
The battery of the invention takes zinc sulfate aqueous solution as electrolyte.
The organic polymer developed by the invention can realize the embedding and the separation of zinc ions, has lower de-embedding potential and high specific capacity, and not only can save a conductive agent and a current collector after the organic polymer is compounded with aerogel, but also can ensure that the preparation method of the battery is more convenient and more environment-friendly, can improve the electrochemical performance of an electrode material, and has better cycle stability.
The invention applies the synthesized organic polymer aerogel to the anode material of the water-based zinc ion battery for the first time, shows a certain electrochemical performance and realizes the de-intercalation of zinc ions. The polymer 3,4,9, 10-perylenetetracarboxylic dianhydride belongs to an N-type anhydride conductive material, two carbonyl groups are respectively arranged at two ends of the integral structure of the material, the process of converting double bonds in the carbonyl groups into enol groups after the double bonds are broken can be determined through the change of charging and discharging, and the space of the two enol groups can be determined according to the sizes of the enol groups and magnesium ions, so that the embedding of one zinc ion can be just met.
The active carbon is used as a negative electrode in an aqueous zinc ion battery, can solve the dendrite phenomenon caused by long-term circulation of a zinc sheet, and has a breakthrough in the cycle performance of the battery. The water system zinc ion battery adopts inorganic zinc salt with low cost and water resource with rich reserves as electrolyte, abandons expensive lithium salt and flammable and explosive organic electrolyte, greatly reduces the cost, improves the economic benefit, improves the safety in the production process, and really meets the requirements of green environmental protection and high safety performance of the second generation energy storage battery. Therefore, it is very important to study the electrochemical reaction of 3,4,9,10-perylenetetracarboxylic dianhydride polymer aerogel in aqueous zinc salt electrolyte.
Compared with the prior art, the invention has the following beneficial effects:
the 3,4,9, 10-perylenetetracarboxylic dianhydride polymer aerogel is prepared by adopting a one-step hydrothermal method, the preparation process is simple and easy to repeat, the cost is low, the industrial production is convenient, and certain economic benefits are achieved. The free de-intercalation of zinc ions can be realized in the process of carbonyl double bond fracture, and meanwhile, the performance and the cycling stability of the electrode material are greatly improved by adding the aerogel.
The battery of the invention takes zinc sulfate aqueous solution as electrolyte. Compared with the traditional lead-acid and nickel-hydrogen batteries, the ionic conductivity of the aqueous electrolyte is far higher than that of the organic electrolyte, and the impedance of the electrolyte is smaller, so that the high-rate charge and discharge are facilitated, and the electrochemical stability is improved.
The positive electrode material does not need a current collector, a conductive agent and a binder, and is more environment-friendly and energy-saving.
The cheap inorganic zinc salt aqueous solution is used as the electrolyte, so that the defects of environmental pollution, flammability, explosiveness and the like caused by the use of the organic electrolyte are overcome, the requirement of environmental protection is met, and the safety factor in the production and use processes is improved. Through electrochemical test, the material of the invention is 50mAg -1 At a current density of 1.0mol L -1 ZnSO 4 The highest electrolyte can reach 300mAh g -1 . At 500mAg -1 At current density, 1.0mol L -1 ZnSO 4 The capacity retention rate of the electrolyte reaches 98 percent after 1000 cycles.
The 3,4,9, 10-perylene tetracarboxylic dianhydride polymer aerogel prepared by the method is used as a self-supporting material, and the one-step synthesis method has a simple preparation process and is very beneficial to industrialization.
The invention uses the active carbon to replace the metal zinc sheet, solves the problems of dendritic crystals and the like of the metal zinc sheet, and obtains very good long cycle performance.
The assembled water system zinc ion battery has good flexibility, and can realize a wearable effect.
For a better understanding of the nature and technical aspects of the present invention, reference should be made to the following detailed description of the invention, taken in conjunction with the accompanying drawings, which are provided for purposes of illustration and description, and are not intended to limit the invention.
Drawings
FIG. 1 is an SEM image of a 3,4,9,10-perylenetetracarboxylic dianhydride polymer aerogel prepared in example 1;
FIG. 2 is a diagram showing a flexible aqueous zinc ion capacitor cell using 3,4,9, 100-perylenetetracarboxylic dianhydride polymer aerogel prepared in example 1 as a positive electrode and activated carbon as a negative electrode;
FIG. 3 is a graph of the rate performance of a flexible aqueous zinc ion capacitor cell with different current densities, which is composed of 3,4,9, 10-perylenetetracarboxylic dianhydride polymer aerogel prepared in example 1 as a positive electrode and activated carbon as a negative electrode;
FIG. 4 is prepared as in example 1The current density of the flexible water-based zinc ion capacitor battery with 3,4,9, 10-perylenetetracarboxylic dianhydride polymer aerogel as the anode and active carbon as the cathode is 500mAg -1 1000 cycles of the cycle efficiency map.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will aid those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any manner. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1: the preparation method of the flexible anode material of the water-based zinc-ion battery in the embodiment is realized by the following steps:
step one, dissolving 3,4,9, 10-perylene tetracarboxylic dianhydride and ethylenediamine in N-methylpyrrolidone according to a ratio of 1.5, then carrying out condensation reflux reaction for 6h at 160 ℃, cooling to room temperature, washing with deionized water for 3 times, carrying out suction filtration, and carrying out vacuum drying for 6h at 100 ℃ to obtain powder;
and step two, uniformly mixing 0.1g of the powder obtained in the step one, 0.2 mu L of ethylenediamine and 10mL of 3mmol/L graphene oxide, carrying out hydrothermal reaction for 16h at 160 ℃, washing for 3 times by using deionized water, and freeze-drying for 24h to obtain the anode material, namely the columnar hydrogel.
SEM characterization picture of PPTCDI/rGO shown in figure 1. In fig. 1, there are typical foamed aerogel sheets, each of which is wrapped with a rod-shaped structure of PPTCDI negative electrode material. It can be clearly observed that the aerogel sheet is wrapped with rod-shaped PPTCDI, which indicates that PPTCDI/rGO is based on graphene aerogel and tightly wrapped with PPTCDI, indicating that the two materials are successfully compounded together.
The obtained electrode was subjected to a flexibility test, as shown in fig. 2; as can be seen from fig. 2, the "sandwich" structure can be folded in half by 90 °, demonstrating the better flexibility of the battery.
Figures 3 and 4 show the electrochemical performance of a flexible battery. FIG. 3 shows 50, 100, 300 and 500mAg -1 Constant current charging and discharging curves under different current densities, the discharging specific capacities are 248,187,123 and 95mAh g respectively -1 It was shown that the cell was at 1.0mol dm -3 ZnSO 4 The electrolyte has better rate capability. After 1000 cycles, the battery capacity is not obviously changed, which indicates that the flexible battery has better practicability.
Mixing active carbon (active substance), polyvinylidene fluoride (binder) and acetylene black (conductive agent) according to the weight ratio of 8:1:1 to 2cm × 0.5cm carbon cloth and dried at 80 ℃ to obtain a negative electrode material, and the positive electrode material prepared in example 1 was used to form a battery having a concentration of 1.0mol · L -1 And (3) taking a zinc sulfate aqueous solution as an electrolyte, and carrying out SME (surface plasmon resonance), constant-current charge and discharge and circulation stability test.
As shown in fig. 2, the aqueous zinc ion capacitor cell assembled in this example is flexible as can be seen from fig. 2.
The multiplying power performance chart of the assembled water-based zinc ion capacitor battery of the embodiment under different current densities is shown in fig. 3; as can be seen from fig. 3, the flexible battery is at 50, 100, 300 and 500mAg -1 Constant current charging and discharging curves under different current densities, the discharging specific capacities are 248,187,123 and 95mAh g respectively -1 It was shown that the cell was at 1.0mol dm -3 ZnSO 4 The electrolyte has better rate capability.
The current density of the aqueous zinc ion capacitor battery assembled in the embodiment is 500mAg -1 The 1000-turn cycle efficiency graph is shown in fig. 4; as can be seen from FIG. 4, the battery capacity does not change significantly after the battery is cycled for 1000 cycles, which indicates that the flexible battery has better practicability.
Example 2: the preparation method of the flexible anode material of the water-based zinc-ion battery in the embodiment is realized by the following steps:
step one, dissolving 3,4,9, 10-perylene tetracarboxylic dianhydride and ethylenediamine in a reaction condition of 1:1 in N-methylpyrrolidone, carrying out condensation reflux reaction for 6h at 150 ℃, cooling to room temperature, washing for 3 times by using deionized water, carrying out suction filtration, and carrying out vacuum drying for 6h at 140 ℃ to obtain powder;
and step two, dissolving 1mmg of the powder obtained in the step one in 10mL of 5mmol/mL of redox graphene, uniformly dispersing, adding ethylenediamine, carrying out hydrothermal reaction at 180 ℃ for 14h, washing with deionized water for 3 times, and carrying out freeze drying for 24h to obtain the negative electrode material, namely the columnar hydrogel.
Example 3: the preparation method of the positive electrode material of the flexible water-based zinc ion battery in the embodiment is realized by the following steps:
step one, dissolving 3,4,9, 10-perylene tetracarboxylic dianhydride and ethylenediamine in a reaction condition of 1:1 in N-methylpyrrolidone, condensing, refluxing and reacting for 8h at 150 ℃, cooling to room temperature, washing for 3 times by deionized water, filtering, and drying in vacuum for 6h at 120 ℃ to obtain powder;
and step two, dissolving 1mmg of the powder obtained in the step one in 10mL of 5mmol/mL of redox graphene, adding ethylenediamine after uniform dispersion, washing for 3 times by using deionized water, and freeze-drying for 24 hours to obtain the anode material and the columnar hydrogel.
Example 3: the preparation method of the flexible anode material of the water-based zinc-ion battery in the embodiment is realized by the following steps:
step one, dissolving 3,4,9, 10-perylene tetracarboxylic dianhydride and ethylenediamine in a proportion of 1:1 in the ratio of N-methyl pyrrolidone, condensing and refluxing at 160 ℃ for 8h, cooling to room temperature, washing with deionized water for 3 times, filtering, and vacuum drying at 120 ℃ for 6h to obtain powder;
and step two, dissolving 1mmg of the powder obtained in the step one in 10mL of 5mmol/mL of redox graphene, adding ethylenediamine after uniform dispersion, washing for 3 times by using deionized water, and freeze-drying for 24 hours to obtain the anode material and the columnar hydrogel.
Claims (10)
1. A preparation method of a flexible anode material of an aqueous zinc ion battery is characterized by comprising the following steps:
dissolving 3,4,9, 10-perylene tetracarboxylic dianhydride and ethylenediamine in N-methyl pyrrolidone, carrying out condensation reflux reaction for at least 6h, cooling to room temperature, washing, carrying out suction filtration, and carrying out vacuum drying to obtain powder;
and step two, uniformly mixing the powder obtained in the step one with ethylenediamine and graphene oxide, carrying out hydrothermal reaction, washing, and carrying out freeze drying to obtain the cathode material.
2. The method according to claim 1, wherein 3,4,9, 10-perylenetetracarboxylic dianhydride and ethylenediamine are dissolved in N-methylpyrrolidone in a ratio of 1.
3. The method according to claim 1, wherein the reflux is condensed at 120 to 180 ℃ in the first step.
4. The method of claim 1, wherein the drying in step one is performed at 60 ℃ to 160 ℃ under vacuum for at least 6 hours.
5. The preparation method according to claim 1, wherein in the second step, 0.1-0.2g of the powder obtained in the first step is mixed with 0.05-0.1g of ethylenediamine and 1-3mmol/L of redox graphene uniformly.
6. The method according to claim 1, wherein the hydrothermal reaction is carried out at 90 to 180 ℃ for at least 14 hours in the second step.
7. The method of claim 1, wherein the cylindrical hydrogel obtained in step two is freeze-dried for at least 24 hours.
8. A positive electrode material produced by the production method according to any one of claims 1 to 7.
9. An aqueous zinc-ion battery having flexibility, characterized by comprising the positive electrode material produced by the production method according to any one of claims 1 to 7.
10. The flexible aqueous zinc-ion battery according to claim 9, wherein the negative electrode material comprises activated carbon as an active material, polyvinylidene fluoride as a binder, and acetylene black as a conductive agent.
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| CN116014063A (en) * | 2023-03-27 | 2023-04-25 | 青岛理工大学 | Electrode of water-based zinc ion battery, preparation method and application thereof |
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