KR20180071867A - Passivation layer for electrochemical device, method for manufacturing the same, and electrochemical device including the same - Google Patents

Abstract

The present invention provides a protective film for an electrochemical device which suppresses dendrite growth of lithium and improves deterioration of an electrode due to oxygen and moisture to improve performance and reliability of an electrochemical device while providing excellent ion conductivity. According to an embodiment of the present invention, the protective film for an electrochemical device comprises: a substrate; a metal protective film in contact with one surface of the substrate; and an electrolyte layer located in at least one of an inner part and a surface of the substrate and the metal protective film.

Description

TECHNICAL FIELD The present invention relates to a protective film for an electrochemical device, a method of manufacturing the same, and an electrochemical device including the same,

The present invention relates to a protective film for an electrochemical device, a method for producing the same, and an electrochemical device including the same.

Lithium has an excellent energy storage capacity in energy storage technology. Therefore, lithium is widely used in a lithium-ion battery, a lithium-sulfur battery, and a lithium-air battery.

Conventionally, a separator having a barrier function is used to prevent performance degradation of the lithium electrode due to moisture or outside air (especially oxygen). Such a separator has a role of suppressing deterioration of lithium metal and dendrite growth, but there is a problem that the volume of the battery including the lithium metal increases. Further, the contact between the separator and the lithium electrode was not stable, and an electrolyte having ion conductivity had to be added.

There is a demand for a protective film capable of preventing the deterioration of lithium metal while suppressing the growth of dendrite while retaining ionic conductivity in an electrochemical device.

The present invention provides a protective film for an electrochemical device for improving the performance and reliability of an electrochemical device by suppressing dendrite growth of lithium and improving deterioration of electrodes due to oxygen and moisture while providing excellent ion conductivity.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are not intended to limit the invention to the precise form disclosed. It can be understood.

According to an embodiment of the present invention, a protective film for an electrochemical device includes: a substrate; A metal protective film in contact with one surface of the substrate; And an electrolyte layer positioned on at least one of the inside and the surface of the substrate and the metal protective layer.

The electrolyte layer may be located on the surface and inside of the substrate, and on the surface and inside of the metal protective film.

The metal protective layer may include at least one of an organic compound and an inorganic compound.

The organic compound may be selected from the group consisting of graphene oxide (GO), reduced graphene oxide (rGO), polyethylene oxide (PEO), polyacrylonitrile (PAN), polymethylmethacrylate And at least one selected from the group including polyvinylidene fluoride (PVDF).

The inorganic compound may be at least one selected from the group consisting of LiPON, a hydride compound, a thio-LISICON compound, a NASICON compound, a LISICON compound and a perovskite compound And at least one selected from the group comprising < RTI ID = 0.0 >

The substrate may be formed of a material selected from the group consisting of polyethylene (PE), polypropylene (PP), polydimethylsiloxane (PDMS), poly methylmethacrylate (PMMA), polyimide, polycarbonate ), Polyetherimide, polyethersulfone, polyethylene terephthalate, polyethylene naphthalate, polysulfone, polyvinyildene fluoride, and poly (vinylidene fluoride) Polyacrylonitrile, polyacrylonitrile, polyacrylonitile, polyisoprene, polyetherimide (PEI), polyethylene oxide (PEO), polypropylene oxide (PPO), polyvinyl pyrrolidone , Polyvinyl alcohol (PVP), polyacrylate, polyvinyl alcohol, polystyrene (PS), and poly Which may include at least one selected from the group consisting of acrylamide (polyacrylamide).

The electrolyte layer may include at least one selected from the group consisting of ethoxylated trimethylolpropane triacrylate (ETPTA), carboxyethyl acrylate, trimethylolpropane-ethoxylate triacrylate, acrylic acid polyglycolic acid, polyacrylic acid, carboxymethyl cellulose, alginate, polyvinyl chloride, agarose, polyethylene glycol diacrylate, But are not limited to, ethylene glycol diacrylate, trimethylolpropane-ethocylate triacrylate, bisphenol A ethoxylate dimethacrylate, carboxyethylacrylate, , Methyl cyano Acrylates such as methyl cyanoacrylate, ethyl cyanoacrylate, ethyl cyano ethoxyacrylate, cyano acrylic acid, hydroxyethyl methacrylate, Hydroxypropyl acrylate, derivatives thereof, and mixtures thereof. The term " a "

The thickness of the metal protective film is about 0.1? To about 100 < / RTI >

The method for manufacturing a protective film for an electrochemical device according to an embodiment includes the steps of applying a first solution containing an organic compound or an inorganic compound on a substrate to form a metal protective film, And impregnating the second solution containing the polymer to form an electrolyte layer.

The step of applying the first solution on the substrate may be performed by a method such as casting method, tape casting method, dip coating method, bar coating method, spray coating method, At least one of sputtering, spin coating, sputtering of PVD, and atomic layer deposition (ALD) of chemical vapor deposition (CVD) may be used.

The first solution may comprise from about 0.1 wt% to 99 wt% of organic or inorganic compounds.

The second solution may comprise from about 0.1 to about 99 wt% of the gel polymer.

An electrochemical device according to one embodiment includes a positive electrode; cathode; And at least one of the positive electrode and the negative electrode includes a metal, and the metal is at least one of lithium, magnesium, and aluminum, A protective film for an electrochemical device according to any one of claims 18 to 19.

At least one of the anode and the cathode and the protective film may be crosslinked.

The electrochemical device may be any one of a lithium battery, a supercapacitor, a zinc metal-air battery, an aluminum metal-air battery, a lithium-air battery or a magnesium-air battery.

The electrochemical device may be a secondary battery.

The protective film for an electrochemical device according to the present invention has excellent ion conductivity, suppresses the growth of dendrite of lithium, improves deterioration of electrodes due to oxygen and moisture, and improves the performance and reliability of the device.

1 is a schematic cross-sectional view of a protective film for an electrochemical device according to an embodiment.
2 is an image in which a metal protective film is formed on a substrate.
3 is a cross-sectional image showing a metal protective film formed on a substrate.
4 is a schematic diagram of an electrochemical device according to one embodiment.
5 is a graph of performance evaluation of an electrochemical device according to one embodiment and a comparative example.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention, and the manner of achieving them, will be apparent from and elucidated with reference to the embodiments described hereinafter in conjunction with the accompanying drawings. However, it is to be understood that the present invention is not limited to the disclosed embodiments, but may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. It is intended that the disclosure of the present invention be limited only by the terms of the appended claims. Like reference numerals refer to like elements throughout the specification.

Thus, in some embodiments, well-known techniques are not specifically described to avoid an undesirable interpretation of the present invention. Unless defined otherwise, all terms (including technical and scientific terms) used herein may be used in a sense commonly understood by one of ordinary skill in the art to which this invention belongs. Whenever a component is referred to as "including" an element throughout the specification, it is to be understood that the element may include other elements, not the exclusion of any other element, unless the context clearly dictates otherwise. Also, singular forms include plural forms unless the context clearly dictates otherwise.

1, a protective layer 100 for an electrochemical device according to an embodiment of the present invention includes a substrate 110, a metal protective layer 130 that contacts one surface of the substrate 110, and an electrolyte layer 150 .

The substrate 110 may be formed of a material selected from the group consisting of polyethylene (PE), polypropylene (PP), polydimethylsiloxane (PDMS), poly methylmethacrylate (PMMA), polyimide, polycarbonate polyether sulfone, polycarbonate, polyetherimide, polyethersulfone, polyethylene terephthalate, polyethylene naphthalate, polysulfone, polyvinylidene fluoride, And polyolefins such as polyacrylonitile, polyisoprene, polyetherimide (PEI), polyethylene oxide (PEO), polypropylene oxide (PPO), polyvinylpyrrolidone polyvinyl pyrrolidone (PVP), polyacrylate, polyvinyl alcohol, polystyrene (PS), and poly May include at least one selected from the group consisting of acrylamide (polyacrylamide). However, it is not limited to, it can be used any substrate 110 suitable for the formation of the protective film (100).

The metal protective film 130 may be placed in contact with one surface of the substrate 110. The thickness of the metal overcoat 130 may range from about 0.1 to about 100? Lt; / RTI >

The metal protective film 130 may face a negative electrode or a positive electrode of a metal material (for example, lithium), and may function as a barrier for suppressing the growth of lithium dendrites. The lithium dendrite can have a mechanical strength of about 6 MPa and the mechanical strength of the metal protective film can be about 6 Mpa or more. The metal protective layer 130 according to one embodiment has excellent mechanical strength and can inhibit the growth of lithium dendrites.

The metal protective film 130 may include any one of an organic compound and an inorganic compound.

The organic compound may be selected from the group consisting of graphene oxide (GO), reduced graphene oxide (rGO), polyethylene oxide (PEO), polyacrylonitrile (PAN), polymethylmethacrylate And at least one selected from the group including polyvinylidene fluoride (PVDF). Preferably, the metal overcoat 130 may be graphene oxide (GO). Since graphene oxide (GO) is lighter than common metals, the performance of lithium secondary batteries can be improved by graphene oxide (GO) having a high energy density per unit weight. In addition, since the mechanical strength of graphene oxide (GO) is about 30 MPa more than the lithium dendrite having the mechanical strength of about 6 Mpa, dendrite formation can be effectively suppressed.

The inorganic compound may be at least one selected from the group consisting of LiPON, a hydride compound, a thio-LISICON compound, a NASICON compound, a LISICON compound and a perovskite compound And at least one selected from the group comprising < RTI ID = 0.0 >

According to one aspect, the hydride-based compound is selected from the group consisting of LiBH ₄ -LI, Li ₃ N, Li ₂ NH, Li ₂ BNH ₆ , Li _{1 .8} N _{0 .4} Cl _{0 .6} , LiBH ₄ , Li ₃ P-LiCl, Li ₄ SiO ₄ , Li ₃ PS _4, and Li ₃ SiS ₄ .

According to one side, the thio receiving cone (thio-LISICON) based compound is a _{Li 10 GeP 2 S 12, Li} 3 .25 Ge 0 .25 P 0 .75 S 4 and _{Li 2 S-GeS-Ga 2} S 3 And at least one selected from the group consisting of

According to one side, the tank top cone (NASICON) based compound is _{Li 1 .3 Al 0 .3 Ge 1} .7 (PO 4) 3, Li 1 .3 Al 0 .3 Ti 1 .7 (PO 4) 3 and LiTi _{0 .5} may be one containing at least one selected from the group consisting of _{Zr 1 .5 (PO 4) 3} .

According to one aspect, the LISICON-based compound may include Li ₁₄ Zn (GeO ₄ ) ₄ .

According to one aspect of the present invention, the perovskite-based compound may include Li _x La _{1 -x} TiO ₃ (0 <x <1) and Li ₇ La ₃ Zr ₂ O ₁₂ , , Li _{0 .35} La _{0 .55} TiO ₃ , Li _{0 .5} La _{0 .5} TiO ₃ And Li ₇ La ₃ Zr ₂ O ₁₂ .

The electrolyte layer 150 may be located on at least one of the surface and the interior of the substrate 110, and the surface and interior of the metal overcoat 130. For example, the electrolyte layer 150 may be located both on the surface and inside of the substrate 110, and on the surface and inside of the metallic protective film 130. The electrolyte layer 150 may be disposed inside the substrate 110 and the metal protective film 130 while surrounding the substrate 110 and the metal protective film 130.

The electrolyte layer 150 may include at least one selected from the group consisting of ethoxylated trimethylolpropane triacrylate (ETPTA), carboxyethyl acrylate, trimethylolpropane-ethocylate triacrylate, but are not limited to, acrylic acid, poly acrylic acid, carboxymethyl cellulose, alginate, polyvinyl chloride, agarose, polyethylene glycol diacrylate, Trimethylene glycol diacrylate, trimethylolpropane-ethocylate triacrylate, bisphenol A ethocylate dimethacrylate, carboxyethyl acrylate (also referred to as &quot; carboxyethylacrylate), methyl cyano But are not limited to, methyl cyanoacrylate, ethyl cyanoacrylate, ethyl cyano ethoxyacrylate, cyano acrylicacid, hydroxyethyl methacrylate, Hydroxypropyl acrylate, derivatives thereof, and mixtures thereof. The term &quot; a &quot; The electrolyte layer 150 may contain about 1 to 99 wt% of the above-mentioned gel polymer.

The electrolyte layer 150 may have cross-linking to the surface of a cathode or an anode to be described later. At least one of the cathode and the anode, the metal protective layer 130, and the substrate 110 may be interlaced by the electrolyte layer 150.

The conventional lithium electrode was prepared by attaching a lithium foil on a planar current collector, preparing a separator having a protective film to prevent lithium dendrite, and sequentially stacking the electrolyte and injecting an electrolyte solution. However, there has been a problem that the separator containing the protective film and the lithium foil are separated from each other in accordance with the volume change of the electrode during charging and discharging.

However, the substrate 110 including the metal protective layer 130 according to an embodiment of the present invention may be directly coupled to at least one of the cathode and the anode by the electrolyte layer 150, The safety and performance of the battery can be improved.

Hereinafter, a method for manufacturing a protective film for an electrochemical device will be described. Is one of the methods for producing the above-described protective film. Therefore, the description of the final properties of the protective film produced by the above method will be omitted, and the characteristics of each step will be described.

A metal protective layer 130 is formed by applying a first solution of an organic compound or an inorganic compound onto the substrate 110 and drying the applied first solution.

The step of applying the first solution on the substrate may be performed by a method such as casting method, tape casting method, dip coating method, bar coating method, spray coating method, At least one of sputtering, spin coating, sputtering of PVD, and atomic layer deposition (ALD) of chemical vapor deposition (CVD) may be used.

At this time, when the substrate 110 includes pores, the first solution may be uniformly positioned on the surface of the substrate 110 while being impregnated into pores in the substrate 110.

The organic compound may be selected from the group consisting of graphene oxide (GO), reduced graphene oxide (rGO), polyethylene oxide (PEO), polyacrylonitrile (PAN), polymethylmethacrylate And at least one selected from the group including polyvinylidene fluoride (PVDF).

The inorganic compound may be at least one selected from the group consisting of LiPON, a hydride compound, a thio-LISICON compound, a NASICON compound, a LISICON compound and a perovskite compound And at least one selected from the group comprising &lt; RTI ID = 0.0 &gt;

The content of any one of the organic compound and the inorganic compound contained in the first solution may be about 0.1 to about 99 wt%.

The metal overcoat 130 formed on the substrate 110 is in contact with one side of the substrate 110 and is in the range of about 0.1 to about 100? As shown in FIG. As an example, the metal overcoat may have a thickness of about 800 nm.

Next, the substrate 110 and the metal protective film 130 are impregnated with the second solution.

The second solution forms the electrolyte layer 150 and is composed of ethoxylated trimethylolpropane triacrylate (ETPTA), carboxyethyl acrylate, trimethylolpropaneethoxylate triacrylate trimethylolpropane-ethocylate triacrylate, acrylic acid, poly acrylic acid, carboxymethyl cellulose, alginate, polyvinyl chloride, agarose, polyethylene glycol di But are not limited to, polyethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane-ethocylate triacrylate, bisphenol ethoxylate dimethacrylate ), Carboxyethyl acrylate acrylates such as methyl cyanoacrylate, ethyl cyanoacrylate, ethyl cyano ethoxyacrylate, cyano acrylic acid, hydroxyethyl methacrylate, Hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, derivatives thereof, and mixtures thereof.

The above-mentioned gel polymer may be contained in an amount of about 0.1 to about 99 wt% with respect to the second solution. For example, the above-described gel polymer may be included in an amount of about 5 wt% with respect to the second solution.

Then, a photo-crosslinking process (for example, UV crosslinking process) is performed on the substrate 110 and the metal protective film 130 impregnated with the second solution to form an electrolyte layer 150. Thus, the protective film 100 for an electrochemical device is manufactured.

Further, before the step of performing the photo-crosslinking step, the electrode can be brought into contact with the electrode of the electrochemical element to be described later, and then the photo-crosslinking step can be carried out. According to this, the protective film 100 and the electrode (cathode or anode) can be crosslinked.

The electrochemical device according to one embodiment includes a positive electrode, a negative electrode, and a protective layer disposed between the positive and negative electrodes. The protective layer may be the above-described protective layer, and the positive electrode and the negative electrode may be the same as conventional techniques.

The electrochemical device may be a lithium battery, a supercapacitor, a zinc metal-air battery, an aluminum metal-air battery, a lithium-air battery, or a magnesium-air battery.

Since the structure and manufacturing method of the lithium secondary battery are well known in the art, a detailed description thereof will be omitted in order to avoid an ambiguous interpretation of the present invention.

Hereinafter, a protective film according to an embodiment will be described with reference to FIGS. 2 and 3. FIG. Fig. 2 is an image in which a metal protective film is formed on a substrate, and Fig. 3 is a cross-sectional image in which a metal protective film is formed on the substrate.

First, referring to FIGS. 2 and 3, an image obtained by coating a metal protective film 130 on a base material 110 made of polyethylene (PE). Specifically, the metal protective film 130 is a layer formed to a thickness of about 800 nm using a dispersion containing 0.5 wt% graphene oxide. As shown in FIG. 4, it was confirmed that a metal protective film was formed on the substrate stably with a thickness of 1 micrometer or less.

Hereinafter, the charging and discharging cycle characteristics of the electrochemical device according to one embodiment will be described with reference to FIGS. 4 and 5. FIG.

The electrochemical device according to one embodiment is an example in which the substrate and the metal protective film manufactured in FIGS. 2 and 3 are impregnated with the second solution, and the resultant is placed on the surface of a lithium metal (electrode) .

At this time, the second solution contains 5 wt% of ethoxylated trimethylolpropane triacrylate (ETPTA). The photo-crosslinking process is a UV photo-crosslinking process.

The two pairs of the protective film and the electrode thus prepared were superimposed as shown in FIG. 4 to prepare a secondary battery and evaluate the performance of the battery.

Referring to FIG. 5, it was confirmed that, in the case of a protective layer including a metal protective layer (graphen oxide) according to an embodiment, the shape of the polarization in the device is suppressed and stable reliability is shown compared to a protective layer containing only a substrate. That is, it is possible to provide an electrochemical device having mechanical strength and smooth ion mobility.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, You will understand.

It is therefore to be understood that the above-described embodiments are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be interpreted as being included in the scope of the present invention .

Claims (15)

materials;
A metal protective film in contact with one surface of the substrate; And
And an electrolyte layer disposed on at least one of an inner surface and a surface of the substrate and the metal protective layer,
The metal protective layer may be formed of at least one selected from the group consisting of graphene oxide (GO), reduced graphene oxide (rGO), polyethylene oxide (PEO), polyacrylonitrile (PAN), polymethylmethacrylate (PMMA) (PVDF) LiPON, a hydride-based compound, a thio-LISICON-based compound, a NASICON-based compound, a LISICON-based compound, and a perovskite- ) -Based compound, and the at least one compound selected from the group consisting of
The electrolyte layer may include at least one selected from the group consisting of ethoxylated trimethylolpropane triacrylate (ETPTA), carboxyethyl acrylate, trimethylolpropane-ethoxylate triacrylate, acrylic acid polyglycolic acid, polyacrylic acid, carboxymethyl cellulose, alginate, polyvinyl chloride, agarose, polyethylene glycol diacrylate, But are not limited to, ethylene glycol diacrylate, trimethylolpropane-ethocylate triacrylate, bisphenol A ethoxylate dimethacrylate, carboxyethylacrylate, , Methyl cyano Acrylates such as methyl cyanoacrylate, ethyl cyanoacrylate, ethyl cyano ethoxyacrylate, cyano acrylicacid, hydroxyethyl methacrylate, A hydroxypropyl acrylate, a derivative thereof, and a mixture thereof. The protective film for an electrochemical device according to claim 1,
The method of claim 1,
Wherein the electrolyte layer is located on the surface and inside of the substrate and on the surface and inside of the metal protective film.
The method of claim 1,
The substrate may be formed of a material selected from the group consisting of polyethylene (PE), polypropylene (PP), polydimethylsiloxane (PDMS), poly methylmethacrylate (PMMA), polyimide, polycarbonate ), Polyetherimide, polyethersulfone, polyethylene terephthalate, polyethylene naphthalate, polysulfone, polyvinyildene fluoride, and poly (vinylidene fluoride) Polyacrylonitrile, polyacrylonitrile, polyacrylonitile, polyisoprene, polyetherimide (PEI), polyethylene oxide (PEO), polypropylene oxide (PPO), polyvinyl pyrrolidone , Polyvinyl alcohol (PVP), polyacrylate, polyvinyl alcohol, polystyrene (PS), and poly Protective film for an electrochemical device comprising at least one selected from the group consisting of acrylamide (polyacrylamide).
The method of claim 1,
The thickness of the metal protective film is about 0.1? To about &lt; RTI ID = 0.0 &gt; 100. &lt; / RTI &gt;
Applying a first solution containing any one of an organic compound and an inorganic compound onto a substrate to form a metal protective film, and
Impregnating the substrate and the metal protective film with a second solution containing a gel polymer to form an electrolyte layer,
The first solution containing any one of the organic compound and the inorganic compound may be applied to a substrate such as a graphene oxide (GO), a reduced graphene oxide (rGO), a polyethylene oxide (PEO), a polyacrylonitrile ), Polymethylmethacrylate (PMMA), polyvinylidene fluoride (PVDF), LiPON, hydride-based compounds, thio-LISICON-based compounds, NASICON- At least one selected from the group consisting of LISICON-based compounds and perovskite-based compounds,
The gel polymer may be selected from the group consisting of ethoxylated trimethylolpropane triacrylate (ETPTA), carboxyethyl acrylate, trimethylolpropane-ethocylate triacrylate, acrylic acid polyglycolic acid, polyacrylic acid, carboxymethyl cellulose, alginate, polyvinyl chloride, agarose, polyethylene glycol diacrylate, But are not limited to, ethylene glycol diacrylate, trimethylolpropane-ethocylate triacrylate, bisphenol A ethoxylate dimethacrylate, carboxyethylacrylate, , Methyl cyano Acrylates such as methyl cyanoacrylate, ethyl cyanoacrylate, ethyl cyano ethoxyacrylate, cyano acrylicacid, hydroxyethyl methacrylate, And at least one selected from the group consisting of hydroxypropyl acrylate, derivatives thereof, and mixtures thereof.
The method of claim 5,
The step of applying the first solution on the substrate may be performed by a method such as casting method, tape casting method, dip coating method, bar coating method, spray coating method, Wherein at least one of a spin coating method, a spin coating method, a physical vapor deposition (PVD) sputtering method and a chemical vapor deposition (ALD) atomic layer deposition method is used.
The method of claim 5,
Wherein the electrolyte layer is located on the surface and inside of the substrate and on the surface and inside of the metal protective film.

The method of claim 5,
The substrate may be formed of a material selected from the group consisting of polyethylene (PE), polypropylene (PP), polydimethylsiloxane (PDMS), poly methylmethacrylate (PMMA), polyimide, polycarbonate ), Polyetherimide, polyethersulfone, polyethylene terephthalate, polyethylene naphthalate, polysulfone, polyvinyildene fluoride, and poly (vinylidene fluoride) Polyacrylonitrile, polyacrylonitrile, polyacrylonitile, polyisoprene, polyetherimide (PEI), polyethylene oxide (PEO), polypropylene oxide (PPO), polyvinyl pyrrolidone , Polyvinyl alcohol (PVP), polyacrylate, polyvinyl alcohol, polystyrene (PS), and poly Method for manufacturing a protective film for an electrochemical device comprising at least one selected from the group consisting of acrylamide (polyacrylamide).
The method of claim 5,
Wherein the first solution comprises about 0.1 wt% to about 99 wt% of an organic compound or an inorganic compound.
The method of claim 5,
Wherein the second solution comprises about 0.1 to about 99 wt% of a gel polymer.
The method of claim 5,
The metal protective film has a thickness of about 0.1? To about 100 &lt; RTI ID = 0.0 &gt;.&Lt; / RTI &gt;
anode;
cathode; And
And a protective film located between the anode and the cathode,
Wherein at least one of the anode and the cathode comprises a metal,
Wherein the metal is at least one of lithium, magnesium, and aluminum,
The electrochemical device according to any one of claims 1 to 4, wherein the protective film comprises a protective film for an electrochemical device.
The method of claim 12,
Wherein at least one of the positive electrode and the negative electrode and the protective film are crosslinked.
The method of claim 12,
Wherein the electrochemical device is any one of a lithium battery, a supercapacitor, a zinc metal-air battery, an aluminum metal-air battery, a lithium-air battery or a magnesium-air battery.
The method of claim 12,
Wherein the electrochemical device is a secondary battery.

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