CN109860628B - Preparation method and application of a planar flexible all-solid-state zinc-air battery - Google Patents
Preparation method and application of a planar flexible all-solid-state zinc-air battery Download PDFInfo
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- 238000010438 heat treatment Methods 0.000 claims description 10
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
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- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
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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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- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
本发明公开了一种平面型柔性全固态锌空气电池的制备方法，包括以下步骤：负载催化剂正极及锌负极的制备：固态凝胶电解质的制备；平面型柔性全固态锌空气电池的组装。本发明制得的固态凝胶电解质具有更高的吸水能力，更高的离子电导率和更好的机械性能，在进一步提高电池器件的循环稳定性、物理柔性和化学安全性；采用共面电极设计不仅有效地减少了离子传输距离，导致电解质离子迅速扩散，对器件的电化学性能起到了积极作用，同时也是有利于器件的小型化和集成，允许更多兼容微电子领域内的可用空间。
The invention discloses a preparation method of a flat flexible all-solid zinc-air battery, comprising the following steps: preparation of a positive electrode of a supported catalyst and a negative electrode of zinc; preparation of a solid gel electrolyte; and assembly of a flat flexible all-solid zinc-air battery. The solid gel electrolyte prepared by the invention has higher water absorption capacity, higher ionic conductivity and better mechanical properties, and further improves the cycle stability, physical flexibility and chemical safety of battery devices; the coplanar electrode is adopted The design not only effectively reduces the ion transport distance, leading to the rapid diffusion of electrolyte ions, which has a positive effect on the electrochemical performance of the device, but also facilitates the miniaturization and integration of the device, allowing more available space in the compatible microelectronics field.
Description
Technical Field
The invention relates to the field of flexible all-solid-state zinc-air batteries, in particular to a planar flexible all-solid-state zinc-air battery and a preparation method and application of a solid gel electrolyte thereof.
Background
In recent years, the continuous accumulation of nanotechnology power sources has promoted the rapid development of wearable microelectronic devices, which have the advantages of flexibility, miniaturization, light weight, and the like, such as inductive skin for robots, smart clothing for health monitors, flexible displays for entertainment and decoration, and the like. For these maintenance-free wearable applications, the power supply should have high energy density, be compact, and especially have good physical flexibility and integration capability, avoiding discomfort and inconvenience to the wearer. In addition, safety is also a key to power supply applications in view of the close contact with the human body in daily use. Currently, supercapacitors and thin film lithium ion batteries are the most commonly used energy supply devices for flexible electronic devices. However, the lower energy density and inherent safety issues of supercapacitors and thin film lithium ion batteries severely limit their commercial applications.
The Zinc Air Batteries (ZABs) have abundant earth content, energy density of about 1086Wh/kg, are novel batteries with low cost, abundant resources, environmental protection, safety, reliability and high energy density, have the advantages of cleanness and sustainable energy power generation, and are considered to be one of the first-choice technologies for next-generation electric energy conversion and large-scale storage. Therefore, the design and preparation of all-solid-state rechargeable flexible zinc-air batteries have become one of the research hotspots of novel wearable energy storage systems. At present, miniaturized all-solid-state rechargeable flexible ZABs are still in the initial development stage and face the problems of low open-circuit voltage, insufficient energy density, insufficient cycling stability, poor integration capability and the like.
From the perspective of energy storage devices, there are a lack of overall considerations, such as the solid-state electrolyte and electrode configuration employed. Currently, the most commonly used polyvinyl alcohol/potassium hydroxide (PVA/KOH) gel solid electrolyte, but has low ionic conductivity and poor water retention due to low supported KOH concentration. Ultimately, low open circuit voltages and poor cycling stability of the device result. In addition, all-solid-state rechargeable ZABs reported recently mainly adopt a sandwich electrode configuration, electrodes constructed in a sandwich design are easily separated from each other under repeated bending deformation, resulting in rapid degradation of electrochemical performance, and electrode layout is not favorable for device miniaturization, integration and compatibility with more microelectronic fields.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention provides a method for manufacturing a planar flexible all-solid-state zinc-air battery and an application thereof.
The invention is realized by the following technologies:
a preparation method of a planar flexible all-solid-state zinc-air battery comprises the following steps:
(1) preparing a catalyst-loaded positive electrode and a zinc negative electrode:
adding 2.0-6.0mL of ammonia water and 30.0-50.0mL of ethanol into 30.0-50.0mL of deionized water, stirring to obtain a mixed solution, adding 0.1-1g of ferric ammonium sulfate and 0.5-1.5g of dopamine hydrochloride into the mixed solution, stirring, and precipitating; centrifuging, washing, freeze-drying the precipitate to obtain a precursor,
heating the precursor to 850-950 ℃ in nitrogen, and preserving heat for 1-4h for carbonization to obtain the N-doped core-shell structure Fe/Fe3C @ C nanocluster electrocatalyst, and coating the prepared electrocatalyst on carbon cloth; cutting a zinc sheet and a carbon cloth loaded with a catalyst by using an inserting finger cutting die to manufacture an inserting finger type zinc cathode and a carbon cloth anode;
(2) preparation of solid gel electrolyte
Dissolving 3-5g Acrylamide (AM) and 3-8mL Acrylic Acid (AA) in 40-60mL deionized water to form a clear solution; subsequently adding 0.02-0.06g N, N ' -methylenebis (acrylamide) and 0.01-0.07ml of N, N, N ', N ' -tetramethylethylenediamine as a crosslinking agent; deoxidizing the mixture by using nitrogen for 10-40min, adding an initiator ammonium persulfate, quickly stirring, then placing the homogeneous solution in a cubic container, and heating at 52-75 ℃ for 1-5h to obtain an acrylamide-acrylic acid copolymer (marked as P- (AM-co-AA)) gel film; drying the synthesized P- (AM-co-AA) gel film, and then adding 3-7M KOH and 0.1-0.4M Zn (CH)2COO)2The mixed solution is soaked for 18 to 30 hours to form the P- (AM-co-AA)/6M KOH solid polymer alkaline electrolyte.
(3) Assembly of planar flexible all-solid-state zinc-air battery
Mounting the obtained finger-inserted anode and cathode electrodes on a solid alkaline gel electrolyte membrane supported by a bottom organic silica gel packaging layer; covering a top silica gel packaging layer with air holes on the coplanar interdigital anode/cathode electrode, and firmly adhering together by using semi-cured silica gel as glue to obtain the planar flexible all-solid-state rechargeable zinc-air battery.
In the step (1), the heating rate of the precursor in nitrogen is 5 ℃/min.
In the step (2), the initiator ammonium persulfate is added and the rapid stirring time is 10 s.
In the step (2), the synthesized P- (AM-co-AA) gel film is dried in a drying furnace at 80 ℃ for 12 hours, and water is removed.
A preparation method of a planar flexible all-solid-state zinc-air battery comprises the following steps:
(1) preparing a catalyst-loaded positive electrode and a zinc negative electrode:
adding 0.2g of ferric ammonium sulfate and 1.0g of dopamine hydrochloride into a mixed solution consisting of 4.5mL of ammonia water, 40.0mL of ethanol and 40.0mL of deionized water, stirring, precipitating, centrifuging, washing, and then, freeze-drying the precipitate to obtain a precursor;
heating the precursor to 900 ℃ at the speed of 5 ℃/min in nitrogen, preserving heat for 2h for carbonization, and obtaining the N-doped core-shell structure Fe/Fe3C @ C nanocluster electrocatalyst, and coating the prepared electrocatalyst on carbon cloth; and cutting the zinc sheet and the carbon cloth loaded with the catalyst by using an inserting finger cutting die to manufacture an inserting finger type zinc cathode and a carbon cloth anode.
(2) Preparation of solid gel electrolyte
Dissolving 4.5g Acrylamide (AM) and 5mL Acrylic Acid (AA) in 50mL deionized water to form a clear solution; 0.05g N, N ' -methylenebis (acrylamide) and 0.05ml of N, N, N ', N ' -tetramethylethylenediamine were subsequently added as crosslinking agents; deoxidizing the mixture by using nitrogen for 30min, adding an initiator ammonium persulfate, rapidly stirring for 10s, then placing the homogeneous solution in a cubic container, and heating for 3h at 60 ℃ to obtain an acrylamide-acrylic acid copolymer (marked as P- (AM-co-AA)) gel film; drying the synthesized P- (AM-co-AA) gel film in a drying oven at 80 deg.C for 12h to remove water, and adding 6M KOH and 0.2M Zn (CH)2COO)2The mixed solution is soaked for 24 hours to form the P- (AM-co-AA)/6M KOH solid polymer alkaline electrolyte.
(3) Assembly of planar flexible all-solid-state zinc-air battery
Mounting the obtained finger-inserted anode and cathode electrodes on a solid alkaline gel electrolyte membrane supported by a bottom organic silica gel packaging layer; covering a top silica gel packaging layer with air holes on the coplanar interdigital anode/cathode electrode, and firmly adhering together by using semi-cured silica gel as glue to obtain the planar flexible all-solid-state rechargeable zinc-air battery.
Preferably, the load of the air electrode prepared in the step (1) is 1mg/cm2。
Preferably, the thickness of the zinc cathode prepared in the step (1) is 0.01-0.05 mm;
preferably, the thickness of the solid gel electrolyte prepared in the step (2) is 0.5-5 mm.
Preferably, the all-solid-state zinc-air battery prepared by the method can be used singly or integrated with an electronic device.
Compared with the prior art, the invention has the following advantages:
(1) the solid gel electrolyte (SPE) prepared by the method has higher water absorption capacity, higher ionic conductivity and better mechanical property, and further improves the cycle stability, physical flexibility and chemical safety of a battery device;
(2) the organic silicon packaging layer can further slow down volatilization of SPE locking water, reduce degradation of SPE in long-term work, facilitate improvement of stability of a battery device and endow the battery device with unprecedented wear resistance;
(3) the coplanar electrode design not only effectively reduces the ion transmission distance, leads electrolyte ions to diffuse rapidly, plays a positive role in the electrochemical performance of the device, but also is beneficial to the miniaturization and integration of the device, and allows more compatible available space in the microelectronic field.
Drawings
FIG. 1 is an impedance curve of a solid gel electrolyte of the present invention;
fig. 2 is a schematic structural diagram of a planar flexible all-solid-state zinc-air battery of the present invention;
fig. 3 is a power density curve of a planar flexible all-solid-state zinc-air battery of the present invention;
fig. 4 is a capacity curve of a planar flexible all-solid-state zinc-air battery of the present invention;
fig. 5 is a cycle stability curve of the planar flexible all-solid-state zinc-air battery of the present invention;
fig. 6 is a series-parallel integrated power density curve of the planar flexible all-solid-state zinc-air battery of the present invention;
fig. 7 is a photograph showing the flexibility of the flat flexible all-solid-state zinc-air battery of the present invention;
fig. 8 is a flexible wearable photograph of a planar flexible all-solid-state zinc-air cell of the present invention.
Detailed Description
Example 1
A preparation method of a planar flexible all-solid-state zinc-air battery comprises the following steps:
step one, adding 0.2g of ferric ammonium sulfate and 1.0g of dopamine hydrochloride into a mixed solution consisting of 4.5mL of ammonia water, 40.0mL of ethanol and 40.0mL of deionized water, stirring, precipitating, centrifuging and cleaning the precipitate for multiple times by using the ethanol and the deionized water, and then performing freeze-drying on the precipitate to obtain a precursor, thus obtaining the N-doped core-shell structure Fe/Fe precursor3C @ C nanocluster electrocatalyst (labeled as N-Fe/Fe)3C @ C-NCs) and the prepared electrocatalyst was coated on a carbon cloth (load of 1mg cm)-2). And cutting the zinc sheet and the carbon cloth loaded with the catalyst by adopting an inserting finger cutting die with customized geometric parameters to manufacture an inserting finger type zinc cathode and a carbon cloth anode.
Step two, 4.5g of Acrylamide (AM) and 5mL of Acrylic Acid (AA) were dissolved in 50mL of DI to form a clear solution, 0.05g N, N ' -methylenebis (acrylamide) and 0.05mL of N, N, N ', N ' -tetramethylethylenediamine were added as a crosslinking agent, the mixture was stirred with a magnetic stirrer until the reactants were completely dissolved, and after deoxygenating the mixture with nitrogen for 30min, 0.01g of the initiator Ammonium Persulfate (APS) was added and stirred rapidly for 10 s. The homogeneous solution was then placed in a cubic container and heated at 60 ℃ for 3h to give poly (acrylamide-co-propylene)Ethylenic acid copolymer) (labeled P- (AM-co-AA)) gel film. Finally, the synthesized P- (AM-co-AA) gel film was dried in a drying oven at 80 ℃ for 12h to remove water, then in 20mL of 6M KOH and 0.2M Zn (CH)2COO)2The mixed solution is soaked for 24 hours to prepare the high-conductivity P- (AM-co-AA)/6M KOH solid gel alkaline electrolyte, as shown in figure 1;
and step three, mounting the obtained insertion-finger type positive electrode and negative electrode on a solid alkaline gel electrolyte membrane supported by a bottom organic silica gel packaging layer. And then, covering a top silica gel packaging layer with air holes on the coplanar interdigitated anode/cathode electrode, and firmly adhering together by using semi-cured silica gel as glue, thereby successfully preparing and packaging a planar all-solid-state rechargeable zinc-air battery, as shown in fig. 2.
As can be seen from fig. 3, 4 and 5, compared with most of all solid zinc-air batteries based on conventional polyvinyl alcohol alkaline gel electrolyte reported at present, the planar flexible all solid zinc-air battery prepared by the method of the present invention has a larger specific capacity (736mAh g)-1) And better cycling stability (120 cycles/40 hours, 5mA cm)-2) And higher open circuit voltage (1.43V).
An integration of a planar flexible all-solid-state zinc-air battery is shown in fig. 6 and 7, and the preparation of a single battery is the same as that of example 1; the difference is that the single battery device is integrated, outputs larger voltage and current and is compatible with other electronic devices.
Step one, the same as the preparation method of example 1, the zinc sheet and the carbon cloth supporting the catalyst were cut to produce a plurality of insertion-finger-shaped zinc cathodes and carbon cloth anodes.
Step two, a plurality of solid gel electrolytes were prepared in the same manner as in example 1.
And step three, mounting the obtained three finger-inserted type positive/negative electrodes on a solid alkaline gel electrolyte membrane supported by a bottom organic silica gel packaging layer. And then, covering a top silica gel packaging layer with air holes on the coplanar interdigitated anode/cathode electrode, and firmly adhering together by using semi-cured silica gel as glue, thereby successfully preparing and packaging three planar all-solid-state rechargeable zinc-air batteries.
The integration of the planar flexible all-solid-state zinc-air battery can realize random series-parallel connection according to actual needs, thereby realizing the multiplication of voltage and current and meeting the actual needs.
Application of planar flexible all-solid-state zinc-air battery 2
An integration of a planar flexible all-solid-state zinc-air battery with an electronic device, see fig. 8, the preparation of a single battery is the same as in example 1; multiple battery integration is the same as application 2; the difference is that the battery is integrated with other electronic devices.
Step one, the same as the preparation method of example 1, the zinc sheet and the carbon cloth supporting the catalyst were cut to produce a plurality of insertion-finger-shaped zinc cathodes and carbon cloth anodes.
Step two, a plurality of solid gel electrolytes were prepared in the same manner as in example 1.
And step three, mounting the three obtained finger-inserting type positive electrodes, negative electrodes and dial electronic devices on a solid alkaline gel electrolyte membrane supported by a bottom organic silica gel packaging layer. And then, covering a top silica gel packaging layer with air holes on the coplanar interdigital anode/cathode electrode, and firmly adhering together by using semi-cured silica gel as glue, thereby successfully preparing and packaging three planar all-solid-state zinc-air batteries to drive one watch.
The integration of the planar flexible all-solid-state zinc-air battery prepared by the method and the dial can be successfully driven, normally timed and worn.
The foregoing is merely illustrative of the principles of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (9)
1. A preparation method of a planar flexible all-solid-state zinc-air battery is characterized by comprising the following steps:
(1) preparing a catalyst-loaded positive electrode and a zinc negative electrode:
adding 2.0-6.0mL of ammonia water and 30.0-50.0mL of ethanol into 30.0-50.0mL of deionized water, stirring to obtain a mixed solution, adding 0.1-1g of ferric ammonium sulfate and 0.5-1.5g of dopamine hydrochloride into the mixed solution, stirring, and precipitating; centrifuging, washing, freeze-drying the precipitate to obtain a precursor,
heating the precursor to 850-950 ℃ in nitrogen, and preserving heat for 1-4h for carbonization to prepare the N-doped core-shell structure Fe/Fe3C @ C nanocluster electrocatalyst, and coating the prepared electrocatalyst on carbon cloth; cutting a zinc sheet and carbon cloth loaded with a catalyst by using an interdigital cutting die to manufacture an interdigital zinc cathode and a carbon cloth anode;
(2) preparation of solid gel electrolyte
Dissolving 3-5g acrylamide and 3-8mL acrylic acid in 40-60mL deionized water to form a clear solution; subsequently adding 0.02-0.06g N, N ' -methylenebis (acrylamide) and 0.01-0.07ml of N, N, N ', N ' -tetramethylethylenediamine as a crosslinking agent; deoxidizing the mixture by using nitrogen for 10-40min, adding an initiator ammonium persulfate, quickly stirring, then placing the homogeneous solution in a cubic container, and heating at 52-75 ℃ for 1-5h to obtain an acrylamide-acrylic acid copolymer P- (AM-co-AA) gel film; drying the synthesized P- (AM-co-AA) gel film, and then adding 3-7M KOH and 0.1-0.4M Zn (CH)2COO)2The mixed solution is soaked for 18 to 30 hours to form P- (AM-co-AA)/KOH solid polymer alkaline electrolyte;
(3) assembly of planar flexible all-solid-state zinc-air battery
Mounting the obtained interdigital anode and cathode electrodes on a solid alkaline gel electrolyte membrane supported by an organic silica gel packaging layer at the bottom; and covering a top silica gel packaging layer with air holes on the coplanar interdigital anode/cathode electrode, and firmly adhering together by using semi-cured silica gel as glue to obtain the planar flexible all-solid-state rechargeable zinc-air battery.
2. The method for preparing a planar flexible all-solid-state zinc-air battery according to claim 1, wherein in the step (1), the precursor is heated in nitrogen at a heating rate of 5 ℃ per minute.
3. The method for preparing a planar flexible all-solid-state zinc-air battery according to claim 1, wherein in the step (2), the initiator ammonium persulfate is added and the rapid stirring time is 10 s.
4. The method of preparing a planar flexible all-solid-state zinc-air battery according to claim 1, wherein the synthesized P- (AM-co-AA) gel film is dried in a drying oven at 80 ℃ for 12 hours to remove water in step (2).
5. The method for preparing a planar flexible all-solid-state zinc-air battery according to any one of claims 1 to 4, comprising the steps of:
(1) preparing a catalyst-loaded positive electrode and a zinc negative electrode:
adding 0.2g of ferric ammonium sulfate and 1.0g of dopamine hydrochloride into a mixed solution consisting of 4.5mL of ammonia water, 40.0mL of ethanol and 40.0mL of deionized water, stirring, precipitating, centrifuging, washing, and then, freeze-drying the precipitate to obtain a precursor;
heating the precursor to 900 ℃ at 5 ℃/min in nitrogen, preserving heat for 2h, and carbonizing to obtain the N-doped core-shell structure Fe/Fe3C @ C nanocluster electrocatalyst, and coating the prepared electrocatalyst on carbon cloth; cutting a zinc sheet and carbon cloth loaded with a catalyst by using an interdigital cutting die to manufacture an interdigital zinc cathode and a carbon cloth anode; (2) preparation of solid gel electrolyte
Dissolving 4.5g acrylamide and 5mL acrylic acid in 50mL deionized water to form a clear solution; 0.05g N, N ' -methylenebis (acrylamide) and 0.05ml of N, N, N ', N ' -tetramethylethylenediamine were subsequently added as crosslinking agents; deoxidizing the mixture for 30min by using nitrogen, adding initiator ammonium persulfate and rapidly stirringStirring for 10s, then placing the homogeneous solution in a cubic container, and heating at 60 ℃ for 3h to obtain an acrylamide-acrylic acid copolymer P- (AM-co-AA) gel film; drying the synthesized P- (AM-co-AA) gel film in a drying oven at 80 deg.C for 12h to remove water, and adding 6M KOH and 0.2M Zn (CH)2COO)2The mixed solution is soaked for 24 hours to form P- (AM-co-AA)/KOH solid polymer alkaline electrolyte;
(3) assembly of planar flexible all-solid-state zinc-air battery
Mounting the obtained interdigital anode and cathode electrodes on a solid alkaline gel electrolyte membrane supported by an organic silica gel packaging layer at the bottom; and covering a top silica gel packaging layer with air holes on the coplanar interdigital anode/cathode electrode, and firmly adhering together by using semi-cured silica gel as glue to obtain the planar flexible all-solid-state rechargeable zinc-air battery.
6. The method for preparing a planar flexible all-solid-state zinc-air battery according to claim 5, wherein the air electrode prepared in step (1) has a loading of 1mg/cm2And (2) the thickness of the zinc cathode prepared in the step (1) is 0.01-0.05 mm.
7. The method for preparing a planar flexible all-solid-state zinc-air battery according to claim 5, wherein the thickness of the solid gel electrolyte prepared in the step (2) is 0.5-5 mm.
8. Use of a planar flexible all-solid-state zinc-air cell prepared by the preparation method according to any one of claims 1 to 7, wherein the all-solid-state zinc-air cell is used singly.
9. Use of a planar flexible all-solid-state zinc-air cell prepared by the preparation method according to any one of claims 1 to 7, wherein the all-solid-state zinc-air cell is integrated with an electronic device.
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