CN111916761B - Flexible stretchable zinc-air battery based on foam-based metal electrode and preparation - Google Patents
Flexible stretchable zinc-air battery based on foam-based metal electrode and preparation Download PDFInfo
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- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
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Abstract
The invention belongs to the field of intelligent energy storage devices, and particularly relates to a flexible stretchable zinc-air battery based on a foam metal electrode and a preparation method thereof. The invention prepares a zinc anode and an air cathode with three-dimensional structures by respectively electroplating zinc and nickel on a metal foam or polymer foam substrate, cross-links a polymer electrolyte membrane on the electrodes and separates the anode and the cathode, and then seals the edges to obtain the flexible zinc-air battery with a sandwich structure. And (3) cutting the flexible zinc-air battery into a specific stretchable shape to obtain the flexible stretchable zinc-air battery. The flexible stretchable zinc-air battery not only can be charged and discharged, but also has good bendable, curled, twisted and stretchable characteristics, keeps stable charging and discharging performance after deformation, and has good application prospect in the field of wearable devices.
Description
Technical Field
The invention belongs to the technical field of intelligent energy storage devices, and particularly relates to a flexible stretchable zinc-air battery based on a sponge-based metal electrode and a preparation method thereof.
Background
In recent years, flexible and stretchable electronic devices are receiving wide attention, can be applied to high and new technical fields such as intelligent wearing, robots, artificial organs and the like, and are considered to be one of scientific research directions with the most development potential. Energy storage devices such as flexible and stretchable supercapacitors, lithium ion batteries, lithium sulfur batteries, alkaline batteries, and the like have been developed. Zinc-air battery with high energy density (1086Wh kg)–1) The advantages of low cost, safety, environmental protection and the like are widely concerned. At present, some scientific research work on the preparation of flexible zinc-air batteries is advanced, and the flexible zinc-air batteriesBatteries hold promise for powering some wearable and portable electronic devices. In general, flexible zinc-air batteries consist of a zinc metal anode, a polymer electrolyte and a flexible air cathode (typically a foamed nickel material). One-dimensional linear zinc-air cells and two-dimensional sandwich zinc-air cells have been developed. Due to the influence of rigidity and difficulty in deformation of zinc and nickel metal materials, most of the developed zinc-air batteries can only perform simple bending deformation or small stretching deformation and cannot perform complex deformation such as large stretching deformation, and the application of the flexible stretchable zinc-air batteries in the wearable field is severely limited.
Zinc anodes conventionally used as flexible zinc-air cells use pure zinc flakes, zinc powder or zinc plating on copper flakes. The zinc electrodes described above are two-dimensional structured electrodes, and although they are flexible in bending, they have a small specific surface area because metallic zinc cannot be used sufficiently. The three-dimensional solid zinc block electrode has no flexibility. The metal zinc material with the three-dimensional structure has higher specific surface area, which is beneficial to improving the electrochemical performance of the zinc-air battery. The zinc-plated foam electrode can be obtained by depositing metal zinc on the flexible foam thin substrate, and meanwhile, the zinc-plated foam electrode can also be subjected to bending deformation. In this way, the metal foam is relatively flexible and compatible with the polymer electrolyte, and prevents the assembled battery from cracking and delamination and damage when deformed. The soft foam metal electrode also facilitates further shape processing of the electrode to prepare the flexible stretchable zinc-air battery with a special shape.
Disclosure of Invention
Aiming at the technical problems, the invention provides a flexible stretchable zinc-air battery based on a foam-based metal electrode. Specifically, a zinc anode and an air cathode with three-dimensional structures are prepared by respectively electroplating zinc and nickel on a metal foam or polymer foam substrate with three-dimensional structures.
The purpose of the invention is realized by the following technical scheme:
the invention provides a flexible stretchable zinc-air battery based on a foam-based metal electrode, which comprises the foam-based metal electrode and an electrolyte film; the metal foam electrode comprises a metal foam anode and a metal foam cathode; the electrolyte membrane is disposed between a metal foam anode and a metal foam cathode;
the foam-based metal anode is a zinc-plated foam electrode, and the foam-based metal cathode is a nickel-plated foam electrode.
Preferably, the zinc-plated foam electrode comprises a copper/nickel-plated foam layer and a zinc-plated layer arranged on the outer side of the copper/nickel-plated foam layer, wherein the copper/nickel-plated foam layer is selected from any one of a copper foam thin film layer, a nickel foam thin film layer and a copper/nickel-plated sponge layer;
the electrolyte film is selected from polyvinyl alcohol basic hydrogel or polyacrylic acid basic hydrogel.
Preferably, the preparation method of the copper/nickel-plated sponge layer comprises the following steps:
a1, cutting the sponge film into small pieces, and drying completely after ultrasonic cleaning;
a2, adhering the dried sponge film to a rubber film, and then curing to obtain an adhered sponge-rubber film;
a3, placing the bonded sponge-rubber film in SnCl2Vacuum soaking in hydrochloric acid solution for 10-60min, taking out, and then adding PdCl2Vacuum soaking in hydrochloric acid solution for 10-60min, taking out, and freeze drying to obtain surface activated sponge-rubber film;
a4, soaking the sponge-rubber film with the activated surface in an electroless copper plating solution or a nickel plating solution to deposit metal copper or nickel on the surface to form a copper plating layer or a nickel plating layer, thus obtaining the copper/nickel plated sponge layer.
Preferably, in the step A1, the sponge film is a polyurethane sponge film with the thickness of 0.1-1 mm;
in the step A2, the rubber film is an Ecoflex rubber film with the thickness of 0.5-1.5 mm;
the Ecoflex rubber film is prepared by mixing Ecoflex-0030 silicone rubber A, B liquid according to the weight ratio of 1: mixing and stirring the raw materials in a weight ratio of 1 to obtain an Ecoflex precursor solution, pouring the Ecoflex precursor solution into a mould, putting the mould into an oven at 50-80 ℃ for 1h, and performing crosslinking and curing to obtain the Ecoflex precursor solution;
in step A3, the SnCl2Hydrochloric acid dissolutionThe concentration of the solution is 30-100 mM; the PdCl2The concentration of the hydrochloric acid solution is 1-5 mM;
in the step A4, the soaking temperature is 30-40 ℃ and the soaking time is 2-8 h.
Preferably, the preparation method of the galvanized foam electrode comprises the following steps: and (3) forming a two-electrode electroplating system by using the copper/nickel plated foam layer as a cathode and the zinc plate as an anode, and electroplating for 20-120min under the condition that the current is 20-200mA to form a zinc coating.
Preferably, the nickel-plated foam electrode comprises a nickel-plated foam layer and a catalyst layer arranged outside the nickel-plated foam layer; the nickel-plated foam layer is selected from any one of a nickel foam film layer and a nickel-plated sponge layer.
Preferably, the preparation method of the nickel-plated sponge layer comprises the following steps: forming a two-electrode electroplating system by using the copper/nickel foam plating layer as a cathode and a nickel plate as an anode, and electroplating for 20-120min under the condition that the current is 20-200mA to form a nickel plating layer;
the preparation method of the copper/nickel-plated foam layer comprises the following steps:
b1, cutting the sponge film into small pieces, and drying completely after ultrasonic cleaning;
b2, adhering the dried sponge film to the rubber film, and then curing to obtain an adhered sponge-rubber film;
b3, placing the bonded sponge-rubber film in SnCl2Vacuum soaking in hydrochloric acid solution for 10-60min, taking out, and then adding PdCl2Vacuum soaking in hydrochloric acid solution for 10-60min, taking out, and freeze drying to obtain surface activated sponge-rubber film;
and B4, soaking the sponge-rubber film with the activated surface in an electroless copper plating solution or a nickel plating solution to deposit metal copper or metal nickel on the surface to form a copper plating layer or a nickel plating layer, thus obtaining the copper/nickel plated sponge layer.
In the step B1, the sponge film is a polyurethane sponge film with the thickness of 0.1-1 mm;
in the step B2, the rubber film is an Ecoflex rubber film, and the thickness of the rubber film is 0.5-1.5 mm;
the Ecoflex rubber film is prepared by mixing Ecoflex-0030 silicone rubber A, B liquid according to the weight ratio of 1: mixing and stirring the raw materials in a weight ratio of 1 to obtain an Ecoflex precursor solution, pouring the Ecoflex precursor solution into a mold, forming holes by adopting a template method, then putting the mold into an oven at 50-80 ℃ for 1 hour, and performing crosslinking and curing to obtain the Ecoflex precursor solution;
in step B3, the SnCl2The concentration of the hydrochloric acid solution is 30-100 mM; the PdCl2The concentration of the hydrochloric acid solution is 1-5 mM;
in the step B4, the soaking temperature is 30-40 ℃ and the soaking time is 2-8 h.
Preferably, the preparation method of the catalyst layer includes the steps of:
coating catalyst slurry on the surface of the nickel-plated foam layer, and drying to form a catalyst layer;
the catalyst adopted in the catalyst slurry is metal oxide or noble metal, and the dosage of the catalyst is 0.1-5mgcm-2。
The prior foam nickel zinc plating is used for a common zinc-air battery with liquid electrolyte to prevent the generation of zinc electrode dendrite. The galvanized electrode in the patent is used for the flexible zinc-air battery with the solid electrolyte, and the battery performance is relatively higher because the electrode adopting the foam structure has larger specific surface area compared with the electrode with the compact plane. In addition, the electrode prepared by electroplating metal on the polymer sponge (polyurethane sponge) is more preferable, the electrode is softer than commercial nickel foam, copper foam, zinc foil and the like, the electrode bending deformation capacity is enhanced, and the battery prepared by the electrode can be bent and deformed flexibly.
Preferably, the polyvinyl alcohol alkaline hydrogel is prepared by adopting PVA/TEAOH/KOH precursor liquid; the polyacrylic acid alkaline hydrogel is prepared by adopting PAA/CMC/KOH precursor liquid.
The electrolyte formed by PVA/TEAOH/KOH precursor liquid has the characteristic of good water-retaining property. The good water retention property plays an important role in stabilizing the battery performance of the zinc-air battery, and the battery can work normally for a longer time. The good water retentivity also means that the electrolyte is not easily dried, and the electrolyte is not easily subjected to bending and stretching deformation when dried. If the electrolyte formed by the conventional PVA/KOH precursor liquid is used instead, the water retention is not good, the drying is easy, the service life of the battery is shortened, and the battery is not easy to deform. An electrolyte-packaged cell formed using a PVA/KOH precursor solution may take approximately 1 day, while an electrolyte-packaged cell formed using a PVA/TEAOH/KOH precursor solution of the present invention may take 2-3 days.
The invention makes the electrolyte fill the surface of the sponge by a method of crosslinking the electrolyte on the electrode in situ, and fully contacts the electrode and the electrolyte.
The invention also provides a preparation method of the stretchable flexible zinc-air battery based on the foam-based metal electrode, which comprises the following steps:
the foam metal anode and the foam metal cathode are assembled in a laminated mode, and an electrolyte film is arranged between the two electrodes to form a flexible zinc-air battery with a sandwich structure;
and cutting the flexible zinc-air battery with the sandwich structure to form a paper-cut structure, and curing and sealing the edges to obtain the flexible stretchable zinc-air battery.
Compared with the prior art, the invention has the following beneficial effects:
the invention uses zinc-plated and nickel-plated electrodes as anode and air cathode, polymer electrolyte film is crosslinked in situ on the electrodes and separates the cathode and anode, then edge sealing is carried out, and the flexible zinc-air battery with sandwich structure is obtained. The electrode can be prepared in a large area, and the flexible zinc-air battery can also be prepared in a large area. The flexible zinc-air battery has good bending, curling and twisting deformation capabilities. And (3) cutting the flexible zinc-air battery into a specific fence structure or a serpentine grain structure to obtain the flexible and stretchable zinc-air battery. This flexible tensile zinc-air battery keeps charging and discharging stable performance after warping, has fine application prospect in wearable device field.
The preparation method is simple, has low cost, and can massively prepare the soft metal material with large area.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a schematic diagram of the preparation of a high polymer foam-based flexible zinc electrode according to the present invention;
fig. 2 is a cyclic charge and discharge curve of the flexible stretchable zinc-air battery prepared in the present invention;
fig. 3 is a curved display view of a flexible stretchable zinc-air battery prepared in the present invention; wherein, fig. 3a is a flexible stretchable zinc-air battery with a sandwich structure; fig. 3b is a flexible stretchable zinc-air cell in serpentine shape; fig. 3c is a flexible stretchable zinc-air cell in the shape of a fence;
fig. 4 is a charge and discharge polarization curve of the flexible zinc-air cell in a fence shape at tensile strains of 0, 50% and 100%.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the concept of the invention. All falling within the scope of the present invention.
The following examples provide a flexible stretchable zinc-air battery based on a metal foam electrode comprising a metal foam electrode and an electrolyte film; the metal foam electrode comprises a metal foam anode and a metal foam cathode; the electrolyte membrane is disposed between a metal foam anode and a metal foam cathode;
the foam-based metal anode is a zinc-plated foam electrode, and the foam-based metal cathode is a nickel-plated foam electrode.
The zinc-plated foam electrode comprises a copper/nickel-plated foam layer and a zinc-plated layer arranged on the outer side of the copper/nickel-plated foam layer, wherein the copper/nickel-plated foam layer is selected from any one of a foam copper thin film layer, a foam nickel thin film layer and a copper/nickel-plated sponge layer;
the electrolyte film is selected from polyvinyl alcohol basic hydrogel or polyacrylic acid basic hydrogel.
The preparation method of the copper/nickel-plated sponge layer comprises the following steps:
a1, cutting the sponge film into small pieces, and drying completely after ultrasonic cleaning;
a2, adhering the dried sponge film to a rubber film, and then curing to obtain an adhered sponge-rubber film;
a3, placing the bonded sponge-rubber film in SnCl2Vacuum soaking in hydrochloric acid solution for 10-60min, taking out, and then adding PdCl2Vacuum soaking in hydrochloric acid solution for 10-60min, taking out, and freeze drying to obtain surface activated sponge-rubber film;
a4, soaking the sponge-rubber film with the activated surface in an electroless copper plating solution or a nickel plating solution to deposit metal copper or nickel on the surface to form a copper plating layer or a nickel plating layer, thus obtaining the copper/nickel plated sponge layer.
In the step A1, the sponge film is a polyurethane sponge film with the thickness of 0.1-1 mm;
in the step A2, the rubber film is an Ecoflex rubber film, and the thickness of the rubber film is 0.5-1.5 mm;
the Ecoflex rubber film is prepared by mixing Ecoflex-0030 silicone rubber A, B liquid according to the weight ratio of 1: mixing and stirring the raw materials in a weight ratio of 1 to obtain an Ecoflex precursor solution, pouring the Ecoflex precursor solution into a mould, putting the mould into an oven at 50-80 ℃ for 1h, and performing crosslinking and curing to obtain the Ecoflex precursor solution;
in step A3, the SnCl2The concentration of the hydrochloric acid solution is 30-100 mM; the PdCl2The concentration of the hydrochloric acid solution is 1-5 mM;
in the step A4, the soaking temperature is 30-40 ℃ and the soaking time is 2-8 h.
The preparation method of the galvanized foam electrode comprises the following steps: and (3) forming a two-electrode electroplating system by using the copper/nickel plated foam layer as a cathode and the zinc plate as an anode, and electroplating for 20-120min under the condition that the current is 20-200mA to form a zinc coating.
The nickel-plated foam electrode comprises a nickel-plated foam layer and a catalyst layer arranged outside the nickel-plated foam layer; the nickel-plated foam layer is selected from any one of a nickel foam film layer and a nickel-plated sponge layer.
The preparation method of the nickel-plated sponge layer comprises the following steps: forming a two-electrode electroplating system by using the copper/nickel foam plating layer as a cathode and a nickel plate as an anode, and electroplating for 20-120min under the condition that the current is 20-200mA to form a nickel plating layer;
the preparation method of the copper/nickel-plated foam layer comprises the following steps:
b1, cutting the sponge film into small pieces, and drying completely after ultrasonic cleaning;
b2, adhering the dried sponge film to the rubber film, and then curing to obtain an adhered sponge-rubber film;
b3, placing the bonded sponge-rubber film in SnCl2Vacuum soaking in hydrochloric acid solution for 10-60min, taking out, and then adding PdCl2Vacuum soaking in hydrochloric acid solution for 10-60min, taking out, and freeze drying to obtain surface activated sponge-rubber film;
and B4, soaking the sponge-rubber film with the activated surface in an electroless copper plating solution or a nickel plating solution to deposit metal copper or metal nickel on the surface to form a copper plating layer or a nickel plating layer, thus obtaining the copper/nickel plated sponge layer.
In the step B1, the sponge film is a polyurethane sponge film with the thickness of 0.1-1 mm;
in the step B2, the rubber film is an Ecoflex rubber film, and the thickness of the rubber film is 0.5-1.5 mm;
the Ecoflex rubber film is prepared by mixing Ecoflex-0030 silicone rubber A, B liquid according to the weight ratio of 1: mixing and stirring the raw materials in a weight ratio of 1 to obtain an Ecoflex precursor solution, pouring the Ecoflex precursor solution into a mold, forming holes by adopting a template method, then putting the mold into an oven at 50-80 ℃ for 1 hour, and performing crosslinking and curing to obtain the Ecoflex precursor solution;
in step B3, the SnCl2The concentration of the hydrochloric acid solution is 30-100 mM; the PdCl2The concentration of the hydrochloric acid solution is 1-5 mM;
in the step B4, the soaking temperature is 30-40 ℃ and the soaking time is 2-8 h.
Preferably, the preparation method of the catalyst layer includes the steps of:
coating catalyst slurry on the surface of the nickel-plated foam layer, and drying to form a catalyst layer;
the catalyst slurry is prepared byThe catalyst is metal oxide or noble metal, and the dosage of the catalyst is 0.1-5mgcm-2。
The flexible stretchable zinc-air battery can be prepared by adopting all the parameters.
Example 1
The embodiment provides a preparation method of a flexible stretchable zinc-air battery based on a foam-based metal electrode, which comprises the following steps:
(1) preparation of galvanized foam (anode) (as shown in figure 1):
1.1 Ecoflex-0030 Silicone rubber A, B fluid was mixed as 1: mixing and stirring the raw materials in a weight ratio of 1 to obtain an Ecoflex precursor solution, pouring the Ecoflex precursor solution into a glass mold with the depth of 1mm, putting the glass mold into an oven with the temperature of 60 ℃ for 1h, and crosslinking and curing the solution to obtain the Ecoflex rubber film.
1.2 cutting commercial polyurethane sponge film (1 mm thick) into small pieces, ultrasonic cleaning with acetone, ethanol and deionized water for 10min, and drying in 60 deg.C oven.
1.3 adhering a piece of dried polyurethane sponge film on the Ecoflex rubber film by using Ecoflex precursor liquid, curing for 30min at 60 ℃, and tightly adhering the polyurethane sponge film and the Ecoflex rubber film together.
1.4 bonding the polyurethane sponge/Ecoflex rubber film at 50mM SnCl2Vacuum soaking in hydrochloric acid solution for 30 min. After removal, the solution was again diluted with 3mM PdCl2Vacuum soaking in hydrochloric acid solution for 15 min. The sample was removed, freeze dried for 3h and the sample surface was thus activated.
1.5 soaking the surface-activated polyurethane sponge/Ecoflex rubber film in a commercial electroless copper plating solution (purchased from Shenzhen zirconium vanadium technology company), soaking for about 4h at 40 ℃, and depositing a layer of reddish brown metal copper on the surface of the polyurethane sponge. Carefully flushing with distilled water and drying by cold air to prepare the copper-plated sponge sample.
1.6 in a two-electrode electroplating system, using copper plating sponge as a cathode and a zinc plate as an anode to form a two-electrode electroplating system, and electroplating for 20-120min to obtain the zinc plating sea foam product. The electroplating solution is ZnSO4The aqueous solution has the formula：125g L–1ZnSO4、10g L–1Al2(SO4)3And 15g L–1Na2SO4Dissolved in water.
(2) Preparation of nickel-plated foam (air cathode):
2.1 Ecoflex-0030 Silicone rubber A, B fluid was mixed as 1: mixing and stirring the raw materials in a weight ratio of 1 to obtain Ecoflex precursor liquid, pouring the Ecoflex precursor liquid into a glass mold with the depth of 1mm, carrying out pore-forming by a template-simulating method, putting the obtained product into an oven with the temperature of 60 ℃ for 1 hour, and carrying out crosslinking and curing to obtain the perforated Ecoflex rubber film.
2.2-2.5 in the same manner as in the above-mentioned steps 1.2 to 1.5, a dried polyurethane sponge film was stuck on a perforated Ecoflex rubber film, and surface Pd activation and electroless copper plating were carried out to prepare a copper-plated sponge sample.
2.6 in a two-electrode electroplating system, using the copper-plated sponge as a cathode and the nickel plate as an anode to form a two-electrode electroplating system, and electroplating for 20-120min to obtain the nickel-plated sponge sample. The electroplating solution is NiSO4Aqueous solution, plating solution formula 300g L-1NiSO4,10g L-1NaCl and 35g L-1H3BO3Dissolved in water and adjusted to Ph 4.
2.7 coating catalyst slurry on Ni-plated sponge sample, catalyst can be Co3O4Oxides such as MnO2, Pt and RuO2The dosage of the catalyst is 0.1 to 5mg cm-2Oven at 60 deg.C until completely dried. Co used in the present example3O4The catalyst slurry is prepared by the following steps: 3mg of commercial Co3O4The nanopowder and 7mg of XC-72 carbon black powder were added to the mixed solution (0.6mL of deionized water, 0.4mL of isopropanol, and 100. mu.l of Nafion) and sonicated to form a homogeneous suspension. And thereby a catalyst-supported nickel plated foam is produced.
(3) Preparation of solid electrolyte-polyvinyl alcohol alkaline (PVA for short) hydrogel:
3g of PVA powder with the molecular weight of 195,000 is dissolved in tetraethylammonium hydroxide (TEAOH for short) solution with the purity of 35 wt.% and deionized water, the volume ratio of the TEAOH solution in the mixed solution is 25-80 percent, and the total volume of the mixed solution is 24 mL. Magnetically stirring at 90 deg.C for 90 min. 6mL of KOH solution with a concentration of 1-6M was added rapidly, followed by magnetic stirring at 90 ℃ for 25 min. Obtaining the hydrogel precursor liquid. The just-formulated PVA/TEAOH/KOH precursor solution was poured over the galvanized foam. Standing for about 2min, freezing in a refrigerator at-4 deg.C to-15 deg.C for 3h, taking out, and thawing to obtain transparent polymer electrolyte.
(4) Preparing the flexible zinc-air battery with the sandwich structure:
assembling the zinc-plated foam anode prepared in the step (1), the nickel-plated foam air cathode prepared in the step (2) and the solid electrolyte prepared in the step (3), wherein the solid electrolyte is arranged between the anode and the air cathode to form a sandwich structure; and then, carrying out heat sealing by using an aluminum plastic film or a poly PET film, and punching holes when the film is sealed at one side of the air cathode to obtain the flexible zinc-air battery with a sandwich structure, as shown in figure 3 a. The cyclic charge and discharge curves are shown in fig. 2, and the results show that: the charging and discharging voltage of the assembled flexible zinc-air battery is about 1.2V and 2.0V, which is similar to the charging and discharging voltage of the common zinc-air battery.
Then the flexible zinc-air battery with the sandwich structure is cut into special stretchable shapes such as snake-shaped lines, fences and the like. And (3) coating the Ecoflex-0030 silicon rubber precursor on the sheared edge of the battery, and conveying the battery into an oven to be cured and sealed, so as to obtain the serpentine-grain and fence-like flexible and stretchable zinc-air battery, as shown in fig. 3b and 3 c. The charge and discharge polarization curves of the barrier-shaped flexible stretchable zinc-air battery at tensile strains of 0%, 50% and 100% are shown in fig. 4, and the curves are similar in shape as a result. Indicating that they are similar in voltage at the same current density. The flexible stretchable zinc-air battery is proved to have stable battery performance even under stretching deformation.
Example 2
The embodiment provides a preparation method of a flexible stretchable zinc-air battery based on a foam-based metal electrode, which comprises the following steps:
(1) preparation of galvanized foam (anode):
1.1 Ecoflex-0030 Silicone rubber A, B fluid was mixed in a ratio of 1: mixing and stirring the raw materials in a weight ratio of 1 to obtain an Ecoflex precursor solution, pouring the Ecoflex precursor solution into a glass mold with the depth of 1mm, putting the glass mold into an oven with the temperature of 60 ℃ for 1h, and crosslinking and curing the solution to obtain the Ecoflex rubber film.
1.2 cutting commercial polyurethane sponge film (1 mm thick) into small pieces, ultrasonic cleaning with acetone, ethanol and deionized water for 10min, and drying in 60 deg.C oven.
1.3 adhering a piece of dried polyurethane sponge film on the Ecoflex rubber film by using Ecoflex precursor liquid, curing for 30min at 60 ℃, and tightly adhering the polyurethane sponge film and the Ecoflex rubber film together.
1.4 bonding the polyurethane sponge/Ecoflex rubber film at 50mM SnCl2Vacuum soaking in hydrochloric acid solution for 30 min. After removal, the solution was again diluted with 3mM PdCl2Vacuum soaking in hydrochloric acid solution for 15 min. The sample was removed, freeze dried for 3h and the sample surface was thus activated.
1.5 soaking the surface-activated polyurethane sponge/Ecoflex rubber film in a commercial chemical nickel plating solution (purchased from Shenzhen zirconium vanadium technology company), soaking for about 4h at 40 ℃, and depositing a layer of reddish brown metallic nickel on the surface of the polyurethane sponge. Carefully flushing with distilled water and drying by cold air to prepare the nickel-plated sponge sample.
1.6 in a two-electrode electroplating system, using nickel-plated sponge as a cathode and a zinc plate as an anode to form a two-electrode electroplating system, and electroplating for 20-120min to obtain a zinc-plated foam sample. The electroplating solution is ZnSO4The formula of the aqueous solution is as follows: 125g L–1ZnSO4、10g L–1Al2(SO4)3And 15g L–1Na2SO4Dissolved in water.
(2) Preparation of nickel-plated foam (air cathode):
2.1 Ecoflex-0030 Silicone rubber A, B fluid was mixed as 1: mixing and stirring the raw materials in a weight ratio of 1 to obtain Ecoflex precursor liquid, pouring the Ecoflex precursor liquid into a glass mold with the depth of 1mm, carrying out pore-forming by a template-simulating method, putting the obtained product into an oven with the temperature of 60 ℃ for 1 hour, and carrying out crosslinking and curing to obtain the perforated Ecoflex rubber film.
2.2-2.4 the dried polyurethane sponge film was adhered to a perforated Ecoflex rubber film and subjected to surface activation in the same manner as in the aforementioned steps 1.2 to 1.4.
2.5 soaking the surface-activated polyurethane sponge/Ecoflex rubber film in a commercial chemical nickel plating solution at 40 ℃ for about 4 hours to deposit a layer of metallic nickel on the surface of the polyurethane sponge. Carefully flushing with distilled water and drying with cold air to obtain the nickel-plated sponge sample 1.
2.6 in a two-electrode electroplating system, using nickel-plated sponge as a cathode and a nickel plate as an anode to form a two-electrode electroplating system, and electroplating for 20-120min to obtain a nickel-plated sponge sample 2. The electroplating solution is NiSO4Aqueous solution, plating solution formula 300g L-1NiSO4,10g L-1NaCl and 35g L-1H3BO3Dissolved in water and adjusted to Ph 4.
2.7 coating catalyst slurry on Nickel plated sponge sample 2, the catalyst can be Co3O4Oxides such as MnO2, Pt and RuO2The dosage of the catalyst is 0.1 to 5mg cm-2Oven at 60 deg.C until completely dried. Co used in the present example3O4The catalyst slurry is prepared by the following steps: 3mg of commercial Co3O4The nanopowder and 7mg of XC-72 carbon black powder were added to the mixed solution (0.6mL of deionized water, 0.4mL of isopropanol and 100. mu.l of Nafion) and sonicated to form a uniform suspension. And thereby a catalyst-supported nickel plated foam is produced.
(3) Preparation of solid electrolyte-polyacrylic acid alkaline (PAA for short) hydrogel:
mixing N, N' -methylene bisacrylamide (MBA for short) and K2S2O8A cross-linking agent and an initiator for PAA chemical cross-linking. 25mg of MBA powder was dissolved in 5.5g of acrylic acid (AA for short) and sonicated to a clear solution. 0.1g of K2S2O8The powder was dissolved in 2.4g of deionized water and sonicated to a clear aqueous solution. A certain amount of sodium carboxymethylcellulose (CMC) powder is dissolved in 25ml of 8.4M KOH aqueous solution (ice bath at 0 ℃ in advance), and the solution is continuously stirred until the sodium carboxymethylcellulose is completely dissolved. The MBA/AA solution was poured into the CMC/KOH solution and stirred for 5min with ice bath and stirring. Then, the product is processedPouring into K2S2O8The aqueous solution was stirred for about 20 seconds to prepare a CMC/PAA/KOH precursor solution. CMC added in terms of relative electrolyte total weight (0 to 0.8 wt.%). Pouring the just prepared CMC/PAA/KOH precursor liquid on the galvanized foam, and waiting for 20s to form transparent polymer electrolyte through crosslinking and curing of the hydrogel precursor liquid.
(4) Preparing the flexible zinc-air battery with the sandwich structure:
a flexible zinc-air battery of a sandwich structure was prepared in the same manner as in example 1. Under the bending or stretching deformation condition, the battery performance of the assembled zinc-air battery is stable and has little change.
Example 3
The embodiment provides a preparation method of a flexible stretchable zinc-air battery based on a foam-based metal electrode, which comprises the following steps:
(1) zinc plating on metal foam to prepare zinc plated foam (anode): a commercial foam copper film with the specification of 25-200 ppi is respectively subjected to ultrasonic cleaning for 10min by acetone, ethanol and deionized water, and then the obtained product is placed into an oven to be dried. Electroplating with two electrodes, zinc plate (0.2-2 cm in thickness) as anode, copper foam as cathode, electroplating current of 20-200mA, and electroplating time of 20-200 min to obtain the final product. The electrolyte is 250g L-1ZnSO of4、20g L-1Al of (2)2(SO4)3,45g L-1KAl (SO) of (2)4)2And 30g L-1Aqueous Na2SO4 solution.
(2) Commercial nickel foam was used as an air cathode. Coating catalyst slurry on commercial foam nickel metal film, wherein catalyst particle can be Co3O4、MnO2Etc. oxide, also Pt, RuO2The dosage of the catalyst is 0.1 to 5mg cm-2Oven at 60 deg.C until completely dried. The catalyst slurry used in this example was prepared as follows: 3mg of commercial Co3O4The nanopowder and 7mg of XC-72 carbon black powder were added to the mixed solution (0.6mL of deionized water, 0.4mL of isopropanol and 100. mu.l of Nafion) and sonicated to form a uniform suspension.
(3) Preparation of solid electrolyte-polyvinyl alcohol alkaline (PVA for short) hydrogel: the same procedure as in example 1 was followed.
(4) Preparing the flexible zinc-air battery with the sandwich structure: the same procedure was followed as in example 1. Under the bending or stretching deformation condition, the battery performance of the assembled zinc-air battery is stable and has little change.
Example 4
This example provides a method for preparing a flexible and stretchable zinc-air battery based on a metal foam electrode, which is substantially the same as the method for preparing the battery of example 3, except that: in this example, step (1) used a commercial nickel foam film instead of a commercial copper foam film.
In the embodiment, the battery performance of the assembled zinc-air battery is stable and has small change under the bending or stretching deformation condition.
The urethane sponge-based electrodes and batteries prepared in examples 1 and 2 above were more flexible, and were more easily bent and deformed by tension, than the electrodes and batteries made of copper nickel foam in examples 3 and 4.
According to the invention, by selecting a proper foam substrate structure and a proper electroplating time, the prepared zinc plating can obtain a metal foam electrode with a three-dimensional porous structure, and the metal deposition amount is controllable. The preparation method of the electrolyte in-situ crosslinking enables the electrolyte to be filled in the foam electrode, and increases the contact area between the electrode and the electrolyte. Therefore, the assembled flexible zinc-air battery has higher specific capacity and energy density and better cycling stability. The flexible zinc-air battery can be bent and has stable charging and discharging performance under the bending condition, and all the components are flexible. Although the metal foam electrode is stretched, the battery as a whole can take up more than 100% of the tensile deformation by cutting the battery shape into a special pattern.
The invention has many applications, and the above description is only a preferred embodiment of the invention. It should be noted that the above examples are only for illustrating the present invention, and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that various modifications can be made without departing from the principles of the invention and these modifications are to be considered within the scope of the invention.
Claims (8)
1. A flexible stretchable zinc-air battery based on a foam-based metal electrode is characterized by comprising the foam-based metal electrode and an electrolyte film; the metal foam electrode comprises a metal foam anode and a metal foam cathode; the electrolyte membrane is disposed between a metal foam anode and a metal foam cathode;
the foam-based metal anode is a zinc-plated foam electrode, and the foam-based metal cathode is a nickel-plated foam electrode;
the galvanized foam electrode comprises a copper/nickel plated foam layer and a galvanized layer arranged on the outer side of the copper/nickel plated foam layer, and the copper/nickel plated foam layer is a copper/nickel plated sponge layer;
the electrolyte film is selected from polyacrylic acid alkaline hydrogel;
the preparation method of the copper/nickel-plated sponge layer comprises the following steps:
a1, cutting the sponge film into small pieces, and drying completely after ultrasonic cleaning;
a2, adhering the dried sponge film to a rubber film, and then curing to obtain an adhered sponge-rubber film;
a3, placing the bonded sponge-rubber film in SnCl2Vacuum soaking in hydrochloric acid solution for 10-60min, taking out, and then adding PdCl2Vacuum soaking in hydrochloric acid solution for 10-60min, taking out, and freeze drying to obtain surface activated sponge-rubber film;
a4, soaking the sponge-rubber film with the activated surface in an electroless copper plating solution or a nickel plating solution to deposit metal copper or nickel on the surface to form a copper plating layer or a nickel plating layer, thus obtaining the copper/nickel plated sponge layer.
2. The flexible stretchable zinc-air battery based on metal foam electrodes according to claim 1, wherein in step a1, the sponge film is polyurethane sponge film with thickness of 0.1-1 mm;
in the step A2, the rubber film is an Ecoflex rubber film, and the thickness of the rubber film is 0.5-1.5 mm;
the Ecoflex rubber film is prepared by mixing Ecoflex-0030 silicone rubber A, B liquid according to the weight ratio of 1: mixing and stirring the raw materials in a weight ratio of 1 to obtain an Ecoflex precursor solution, pouring the Ecoflex precursor solution into a mould, putting the mould into a 50-80 ℃ oven for 1h, and performing crosslinking and curing to obtain the Ecoflex precursor solution;
in step A3, the SnCl2The concentration of the hydrochloric acid solution is 30-100 mM; the PdCl2The concentration of the hydrochloric acid solution is 1-5 mM;
in the step A4, the soaking temperature is 30-40 ℃ and the soaking time is 2-8 h.
3. The flexible stretchable zinc-air battery based on metal foam electrode according to claim 1, characterized in that the preparation method of the zinc coated foam electrode comprises the following steps: and (3) forming a two-electrode electroplating system by using the copper/nickel plated foam layer as a cathode and the zinc plate as an anode, and electroplating for 20-120min under the condition that the current is 20-200mA to form a zinc coating.
4. The flexible stretchable zinc-air battery based on foam-based metal electrodes according to claim 1, characterized in that the nickel-plated foam electrode comprises a nickel-plated foam layer and a catalyst layer disposed outside the nickel-plated foam layer; the nickel-plated foam layer is selected from any one of a nickel foam film layer and a nickel-plated sponge layer.
5. The flexible stretchable zinc-air battery based on metal foam electrodes according to claim 4, wherein the nickel-plated sponge layer is prepared by a method comprising the following steps: forming a two-electrode electroplating system by using the copper/nickel plated foam layer as a cathode and the nickel plate as an anode, and electroplating for 20-120min under the condition that the current is 20-200mA to form a nickel plated layer;
the preparation method of the copper/nickel-plated foam layer comprises the following steps:
b1, cutting the sponge film into small pieces, and completely drying after ultrasonic cleaning;
b2, adhering the dried sponge film to the rubber film, and then curing to obtain an adhered sponge-rubber film;
b3, placing the bonded sponge-rubber film in SnCl2Vacuum soaking in hydrochloric acid solution for 10-60min, taking out, and then adding PdCl2Vacuum soaking in hydrochloric acid solution for 10-60min, taking out, and freeze drying to obtain surface activated sponge-rubber film;
and B4, soaking the sponge-rubber film with the activated surface in an electroless copper plating solution or a nickel plating solution to deposit metal copper or metal nickel on the surface to form a copper plating layer or a nickel plating layer, thus obtaining the copper/nickel plated sponge layer.
6. Flexible stretchable zinc-air battery based on metal foam electrodes according to claim 5,
in the step B1, the sponge film is a polyurethane sponge film with the thickness of 0.1-1 mm;
in the step B2, the rubber film is an Ecoflex rubber film with the thickness of 0.5-1.5 mm;
the Ecoflex rubber film is prepared by mixing Ecoflex-0030 silicone rubber A, B liquid according to the weight ratio of 1: mixing and stirring the raw materials in a weight ratio of 1 to obtain an Ecoflex precursor solution, pouring the Ecoflex precursor solution into a mold, forming holes by adopting a template method, then putting the mold into a 50-80 ℃ oven for 1 hour, and performing crosslinking and curing to obtain the Ecoflex precursor solution;
in step B3, the SnCl2The concentration of the hydrochloric acid solution is 30-100 mM; the PdCl2The concentration of the hydrochloric acid solution is 1-5 mM;
in the step B4, the soaking temperature is 30-40 ℃ and the soaking time is 2-8 h.
7. The flexible stretchable zinc-air battery based on metal foam electrode according to claim 4, wherein the preparation method of the catalyst layer comprises the following steps:
coating catalyst slurry on the surface of the nickel-plated foam layer, and drying to form a catalyst layer;
the catalyst adopted in the catalyst slurry is metal oxide or noble metal, and the dosage of the catalyst is 0.1-5mg cm−2。
8. A method of making a stretchable flexible zinc-air cell based on metal foam electrodes according to claim 1 comprising the steps of:
the foam metal anode and the foam metal cathode are assembled in a laminated mode, and an electrolyte film is arranged between the two electrodes to form a flexible zinc-air battery with a sandwich structure;
and cutting the flexible zinc-air battery with the sandwich structure to form a paper-cut structure, and curing and sealing the edges to obtain the flexible stretchable zinc-air battery.
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| CN113290231B (en) * | 2021-05-31 | 2022-07-05 | 华中科技大学 | Method for compounding aluminum-magnesium bimetal by lost foam casting liquid-liquid and aluminum-magnesium bimetal |
| WO2023108312A1 (en) * | 2021-12-13 | 2023-06-22 | 中国科学院深圳先进技术研究院 | Gel electrolyte for flexible zinc-air battery, preparation method therefor, and application thereof |
| CN114188549B (en) * | 2021-12-13 | 2022-10-28 | 山东省科学院新材料研究所 | Preparation and application of nitrogen-sulfur-doped cellulose as flexible zinc-air battery electrode |
| CN114054822B (en) * | 2021-12-21 | 2024-07-19 | 湖南科技大学 | Self-adaptive milling composite cutter |
| CN114094241B (en) * | 2022-01-20 | 2022-04-26 | 北京大学 | Lithium-air battery based on carbon nanotube sponge positive electrode with controllable compression and gradient infiltration and assembling method thereof |
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