KR20210063858A - Composite solid electrolyte comprising crosslinked polymer and manufacturing method for the same - Google Patents

Abstract

The present invention relates to a composite solid electrolyte including a crosslinked polymer and a method for manufacturing the same. One aspect of the present invention provides a composite solid electrolyte including a crosslinked polymer, including: an organic electrolyte; inorganic nanoparticles; a first photocrosslinking agent; a second photocrosslinking agent; and a photopolymerization initiator.

Description

Composite solid electrolyte containing cross-linked polymer and method for manufacturing same {COMPOSITE SOLID ELECTROLYTE COMPRISING CROSSLINKED POLYMER AND MANUFACTURING METHOD FOR THE SAME}

The present invention relates to a composite solid electrolyte comprising a crosslinked polymer and a method for preparing the same.

Recently, as interest in flexible/wearable electronic devices such as smart watches, roll-up displays, and foldable phones has increased, the need for developing a flexible secondary battery that can be applied to flexible/wearable electronic devices is emerging.

In general, a secondary battery is composed of a positive electrode consisting of a positive electrode active material and a positive electrode current collector, a negative electrode consisting of a negative electrode active material and a negative electrode current collector, and a separator interposed between the positive electrode and the negative electrode, and the electrolyte is a medium for transporting ions between the positive electrode and the negative electrode function as

Currently, liquid electrolytes are mainly used as electrolytes for secondary batteries, but liquid electrolytes may leak when deformation occurs by applying an external force, and there is a possibility of explosion because they contain volatile or combustible solvents.

Accordingly, in recent years, research and development of solid electrolytes that increase safety have been actively conducted. In particular, it is required to develop a solid electrolyte material with high ionic conductivity and high efficiency for application to flexible secondary batteries. It is becoming.

SUMMARY OF THE INVENTION The present invention is to solve the above problems, and an object of the present invention is to provide a solid electrolyte having excellent ionic conductivity, electrochemical stability and thermal stability while having flexibility, and a method for manufacturing the same.

However, the problem to be solved by the present invention is not limited to the problems mentioned above, and other problems that are not mentioned will be clearly understood by those skilled in the art from the following description.

One aspect of the present invention, an organic electrolyte; inorganic nanoparticles; a first photocrosslinking agent; a second photocrosslinking agent; and a photopolymerization initiator, to provide a composite solid electrolyte comprising a cross-linked polymer.

According to an embodiment, the organic electrolyte may include a dissociable salt, an organic solvent, or a mixture thereof, and the concentration of the dissociable salt in the organic solvent may be 0.1 M to 5.0 M.

According to an embodiment, the dissociable salt is TEABF ₄ , Li(CF ₃ SO ₂ ) ₂ N, Li(FSO ₂ ) ₂ N, LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiAsF ₆ , LiC ₄ F ₉ SO ₃ , LiClO ₄ , LiAlO ₂ , LiAlCl ₄ , LiN(C _x F _2x ⁺¹ SO ₂ )(C _y F _2y ⁺¹ SO ₂ ), where x and y are natural numbers, LiCl, LiI, LiB(C ₂ O ₄ ) ₂ (lithium bis(oxalato) borate; LiBOB) and combinations thereof may be included.

According to an embodiment, the organic solvent is an imidazolium-based compound, a pyrrolidinium-based compound, a quaternary ammonium-based compound, a quaternary phosphonium-based compound, a carbonate-based solvent, an ester-based solvent, an ether-based solvent, a ketone-based compound It may include one or more selected from the group consisting of solvents, alcohol solvents, aprotic solvents, and combinations thereof.

According to one embodiment, the inorganic nanoparticles, SiO ₂ , Al ₂ O ₃ , TiO ₂ , BaTiO ₃ , Li ₂ O, LiF, LiOH, Li ₃ N, BaO, Na ₂ O, Li ₂ CO ₃ , CaCO ₃ , LiAlO _{2 , SrTiO 3} , SnO ₂ , CeO ₂ , MgO, NiO, CaO, ZnO, ZrO ₂ and SiC may be included.

According to an embodiment, the first photocrosslinking agent is a vinyl ether-based compound, an allyl ether-based compound, a propenyl ether-based compound, an alkene-based compound, an acrylate-based compound, an unsaturated ester-based compound, a maleimide-based compound, acrylo It may include one or more selected from the group consisting of nitrile-based compounds, styrene-based compounds, diene-based compounds, N-vinyl amide-based compounds, allyl triazine, and mixtures thereof.

According to an embodiment, the second photocrosslinking agent comprises at least one selected from the group consisting of an alkyl 3-mercaptopropionate-based compound, an alkylthioglycolate-based compound, an alkylthiol-based compound, and mixtures thereof. it could be

According to an embodiment, the photopolymerization initiator is benzophenone, thioxanthone, camphorquinone, acetophenone, benzyl, benzyl ketal, anthraquinone, benzoyl peroxide, benzoylphosphine oxide, acylphosphine oxide, triazine, oxime ester , may be one comprising at least one selected from the group consisting of aminophenyl ketone and hydroxyphenyl ketone.

According to one embodiment, based on 100 parts by weight of the organic electrolyte, the inorganic nanoparticles may be included in an amount of 1 to 100 parts by weight.

According to one embodiment, with respect to 100 parts by weight of the organic electrolyte, the first and second optical communication agent may be included in an amount of 1 to 100 parts by weight.

According to an embodiment, with respect to 100 parts by weight of the first optical crosslinking agent, the second optical crosslinking agent may be included in an amount of 10 parts by weight to 1,000 parts by weight.

According to an embodiment, in the composite solid electrolyte, cross-linked polymers form a network structure in the organic electrolyte, and inorganic nanoparticles are distributed between the cross-linked polymers.

Another aspect of the present invention comprises the steps of preparing an organic solution in which an organic electrolyte is dissolved; dissolving inorganic nanoparticles, a first photocrosslinking agent, a second photocrosslinking agent, and a photopolymerization initiator in the organic solution to form a mixed solution; forming an electrolyte layer on a substrate using the mixed solution; and irradiating ultraviolet light to the electrolyte layer; provides a method for producing a composite solid electrolyte comprising a cross-linked polymer.

According to an embodiment, the step of irradiating the ultraviolet rays may be irradiating a wavelength of 250 nm to 450 nm for 5 seconds to 5 minutes.

Another aspect of the present invention provides a flexible electronic device comprising the composite solid electrolyte or the composite solid electrolyte manufactured by the manufacturing method.

The composite solid electrolyte according to the present invention is flexible, exhibits high ionic conductivity even at high temperatures, and has excellent electrochemical stability and thermal stability.

In addition, in the method for manufacturing a composite solid electrolyte according to the present invention, a polymer crosslinked in the organic electrolyte is mixed with an organic electrolyte and inorganic nanoparticles, a first optical agent, a second optical agent, and a photopolymerization initiator and irradiated with ultraviolet rays. By distributing inorganic nanoparticles between cross-linked polymers and forming a network structure, it is possible to secure both mechanical properties and flexibility of the composite solid electrolyte.

1 is a schematic diagram showing the structure of a composite solid electrolyte according to an embodiment of the present invention.
2 is a photograph showing the composite solid electrolyte (Example 1 (a) and Example 2 (b)) prepared according to an embodiment of the present invention.
3 is a graph showing a current density value according to a voltage measured using a composite solid electrolyte prepared according to an embodiment of the present invention.
4 is a graph showing the change in weight over time of the composite solid electrolyte according to the present invention and the conventional liquid electrolyte generally used.

Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. However, since various changes may be made to the embodiments, the scope of the patent application is not limited or limited by these embodiments. It is to be understood that all changes, equivalents, or substitutes to the embodiments are included in the scope of the rights.

The terms used in the examples are used for illustrative purposes only and should not be construed as limiting. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present specification, terms such as "comprise" or "have" are intended to designate the presence of features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, but one or more other features. It is to be understood that the presence or addition of elements or numbers, steps, actions, components, parts, or combinations thereof does not preclude in advance.

Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the embodiment belongs. Terms as defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related technology, and should not be interpreted as an ideal or excessively formal meaning unless explicitly defined in the present application. Does not.

In addition, when it is determined that detailed descriptions of related known technologies may unnecessarily obscure the subject matter of the embodiments in describing the embodiments, detailed descriptions thereof will be omitted.

Hereinafter, the composite solid electrolyte of the present invention and a method for manufacturing the same will be described in detail with reference to Examples and drawings. However, the present invention is not limited to these examples and drawings.

One aspect of the present invention, an organic electrolyte; inorganic nanoparticles; a first photocrosslinking agent; a second photocrosslinking agent; and a photopolymerization initiator, to provide a composite solid electrolyte including a crosslinked polymer.

The composite solid electrolyte according to the present invention can secure high-temperature stability through an organic electrolyte, improve mechanical properties of the electrolyte through inorganic nanoparticles, and prevent internal short circuit between the positive electrode and the negative electrode, and include a first photocrosslinking agent Through the solidification of the electrolyte, the mechanical properties of the electrolyte can be increased, and the mechanical flexibility of the electrolyte can be increased through the second photocrosslinking agent.

The composite solid electrolyte according to the present invention may be formed in the form of an opaque gel, and may be prepared to form a film or layer depending on the shape of the electrochemical device.

According to an embodiment, the organic electrolyte may include a dissociable salt, an organic solvent, or a mixture thereof, and the concentration of the dissociable salt in the organic solvent may be 0.1 M to 5.0 M.

The organic electrolyte is a key component in ensuring ionic conductivity, and according to one embodiment, the organic electrolyte may have a boiling point of 200° C. or higher, thereby ensuring high-temperature stability.

According to an embodiment, the dissociable salt is TEABF ₄ , Li(CF ₃ SO ₂ ) ₂ N, Li(FSO ₂ ) ₂ N, LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiAsF ₆ , LiC ₄ F ₉ SO ₃ , LiClO ₄ , LiAlO ₂ , LiAlCl ₄ , LiN(C _x F _2x ⁺¹ SO ₂ )(C _y F _2y ⁺¹ SO ₂ ), where x and y are natural numbers, LiCl, LiI, LiB(C ₂ O ₄ ) ₂ (lithium bis(oxalato) borate; LiBOB) and combinations thereof may be included.

According to an embodiment, the organic solvent is an imidazolium-based compound, a pyrrolidinium-based compound, a quaternary ammonium-based compound, a quaternary phosphonium-based compound, a carbonate-based solvent, an ester-based solvent, an ether-based solvent, a ketone-based compound It may include one or more selected from the group consisting of solvents, alcohol solvents, aprotic solvents, and combinations thereof.

The organic electrolyte may be included by selecting from a group of materials having ion conductive properties.

According to one embodiment, the inorganic nanoparticles, SiO ₂ , Al ₂ O ₃ , TiO ₂ , BaTiO ₃ , Li ₂ O, LiF, LiOH, Li ₃ N, BaO, Na ₂ O, Li ₂ CO ₃ , CaCO ₃ , LiAlO _{2 , SrTiO 3} , SnO ₂ , CeO ₂ , MgO, NiO, CaO, ZnO, ZrO ₂ and SiC may be included.

The inorganic nanoparticles can prevent an internal short circuit between the positive electrode and the negative electrode by improving the mechanical properties of the electrolyte.

According to an embodiment, the first photocrosslinking agent is a vinyl ether-based compound, an allyl ether-based compound, a propenyl ether-based compound, an alkene-based compound, an acrylate-based compound, an unsaturated ester-based compound, a maleimide-based compound, acrylo It may include one or more selected from the group consisting of nitrile-based compounds, styrene-based compounds, diene-based compounds, N-vinyl amide-based compounds, allyl triazine, and mixtures thereof.

The first photocrosslinking agent may form a polymer matrix through a crosslinking reaction to solidify the electrolyte and increase mechanical properties of the electrolyte.

According to one embodiment, the second photocrosslinking agent, an alkyl 3-mercaptopropionate-based compound, an alkylthio glycolate-based compound, an alkylthiol-based compound, and at least one selected from the group consisting of mixtures thereof. it could be

The second photocrosslinking agent may increase the degree of crosslinking of the electrolyte and increase mechanical flexibility.

According to an embodiment, the photopolymerization initiator is benzophenone, thioxanthone, camphorquinone, acetophenone, benzyl, benzyl ketal, anthraquinone, benzoyl peroxide, benzoylphosphine oxide, acylphosphine oxide, triazine, oxime ester , may be one comprising at least one selected from the group consisting of aminophenyl ketone and hydroxyphenyl ketone.

The photopolymerization initiator may serve as an initiator to initiate crosslinking of the photocrosslinking agents in the electrolyte by receiving ultraviolet rays.

According to one embodiment, based on 100 parts by weight of the organic electrolyte, the inorganic nanoparticles may be included in an amount of 1 to 100 parts by weight.

Preferably, based on 100 parts by weight of the organic electrolyte, 10 parts by weight to 100 parts by weight of the inorganic nanoparticles may be included, and more preferably, the inorganic nanoparticles are added to 100 parts by weight of the organic electrolyte. It may be included in an amount of 10 parts by weight to 50 parts by weight.

If, based on the organic electrolyte, when the inorganic nanoparticles are included below the above range, the internal short circuit prevention function between the positive electrode and the negative electrode may be reduced due to deterioration of mechanical properties, and the inorganic nanoparticles exceed the above range , the ionic conductivity may be reduced.

According to one embodiment, with respect to 100 parts by weight of the organic electrolyte, the first and second optical communication agent may be included in an amount of 1 to 100 parts by weight.

Preferably, based on 100 parts by weight of the organic electrolyte, 5 to 100 parts by weight of the first optical agent and the second optical agent may be included, and more preferably, 100 parts by weight of the organic electrolyte. With respect to, it may be to include 10 parts by weight to 50 parts by weight of the first optical agent and the second optical agent, and even more preferably, based on 100 parts by weight of the organic electrolyte, the first optical agent and the agent 2 It may be to include 10 parts by weight to 30 parts by weight of the optical agent.

If, based on the organic electrolyte, when the total weight of the first and second optical agents is less than the above range, the polymer network according to the crosslinking reaction is not sufficiently formed, so that mechanical properties are lowered, or the flow Due to the characteristics, leakage may occur, and if the above range is exceeded, the ionic conductivity may be reduced.

According to one embodiment, with respect to 100 parts by weight of the first optical crosslinking agent, the second optical crosslinking agent may be included in an amount of 10 parts by weight to 1,000 parts by weight.

Preferably, with respect to 100 parts by weight of the first optical crosslinking agent, 10 parts by weight to 500 parts by weight of the second optical crosslinking agent may be included, and more preferably, with respect to 100 parts by weight of the first optical crosslinking agent, 100 parts by weight to 500 parts by weight of the second optical crosslinking agent may be included, and more preferably, 100 parts by weight to 300 parts by weight of the second optical crosslinking agent with respect to 100 parts by weight of the first optical crosslinking agent. may be doing

If, based on the first light crosslinking agent, when the second light crosslinking agent is included in less than the above range, flexibility may be reduced, and if the second light crosslinking agent exceeds the above range, the mechanical properties of the gel cutting agent are lowered This may cause a problem in that the film shape cannot be maintained.

According to an embodiment, a ratio of the weight of the photopolymerization initiator dissolved in the organic solution: the weight of the first photocrosslinking agent and the weight of the second photocrosslinking agent may be 0.5: 100 to 5: 100.

If the photopolymerization initiator is included less than the weight sum of the first and second photocrosslinking agents based on the numerical range, there may be a problem that the crosslinking reaction does not occur sufficiently, and if it is excessively included, There may be a problem in that side reactions occur due to the reactive photopolymerization initiator.

According to an embodiment, in the composite solid electrolyte, cross-linked polymers form a network structure in the organic electrolyte, and inorganic nanoparticles are distributed between the cross-linked polymers.

The crosslinked polymers may be formed of at least one of a first photocrosslinking agent and a second photocrosslinking agent component.

The inorganic nanoparticles distributed between the cross-linked polymers function to not only improve the mechanical properties of the composite solid electrolyte, but also prevent an internal short circuit between the positive electrode and the negative electrode.

Another aspect of the present invention comprises the steps of preparing an organic solution in which an organic electrolyte is dissolved; dissolving inorganic nanoparticles, a first photocrosslinking agent, a second photocrosslinking agent, and a photopolymerization initiator in the organic solution to form a mixed solution; forming an electrolyte layer on a substrate using the mixed solution; and irradiating ultraviolet light to the electrolyte layer; provides a method for producing a composite solid electrolyte comprising a cross-linked polymer.

According to an embodiment, the step of irradiating the ultraviolet rays may be irradiating a wavelength of 250 nm to 450 nm for 5 seconds to 5 minutes.

If ultraviolet rays of excessive energy are irradiated for a long time outside the above conditions, the components of the composite solid electrolyte may be decomposed, and if ultraviolet rays of insufficient energy are irradiated for a short time outside the above conditions, the composite solid electrolyte will be There may be a problem of not being sufficiently crosslinked.

Another aspect of the present invention provides a flexible electronic device comprising the composite solid electrolyte or the composite solid electrolyte manufactured by the manufacturing method.

Hereinafter, the present invention will be described in more detail by examples and comparative examples.

However, the following examples are for illustrative purposes only, and the contents of the present invention are not limited to the following examples.

< Example 1>

Trimethylolpropane triacrylate as the first photocrosslinking agent, trimethylolpropane tris(3-mercaptopropionate) as the second photocrosslinking agent, and silica nanoparticles as inorganic nanoparticles are mixed in a weight ratio of 5:8:10, A crosslinking mixture was prepared by mixing 2,2-dimethoxy-2-phenyl acetophenone as a photopolymerization initiator so that the photopolymerization initiator: the first photocrosslinking agent and the second photocrosslinking agent have a weight ratio of 1:100.

The crosslinking mixture was dissolved in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, which is an organic electrolyte, in a weight ratio of 77:23 (organic electrolyte:crosslinked mixture), using a stirrer bar. A mixed solution was prepared by dispersing.

Then, the mixed solution was applied on the substrate to form an electrolyte layer, and ultraviolet rays of 365 nm wavelength were irradiated for 20 seconds to prepare a composite solid electrolyte.

< Example 2>

Trimethylolpropane triacrylate as the first photocrosslinking agent, pentaneerythritol tetrakis (3-mercaptopropionate) as the second photocrosslinking agent, and silica nanoparticles as inorganic nanoparticles in a weight ratio of 4: 7:25 were mixed, A crosslinking mixture was prepared by mixing 2,2-dimethoxy-2-phenyl acetophenone as a photopolymerization initiator so that the photopolymerization initiator: the first photocrosslinking agent and the second photocrosslinking agent have a weight ratio of 1:100.

Dissolve the crosslinking mixture in the organic electrolyte 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide in a weight ratio of 64:36 (organic electrolyte:crosslinking mixture), and use a stirrer bar to A mixed solution was prepared by dispersing.

Then, the mixed solution was applied on the substrate to form an electrolyte layer, and ultraviolet rays of 365 nm wavelength were irradiated for 20 seconds to prepare a composite solid electrolyte.

1 is a schematic diagram showing the structure of a composite solid electrolyte according to an embodiment of the present invention.

Referring to FIG. 1 , it can be confirmed that, in the composite solid electrolyte according to the present invention, cross-linked polymers form a network structure inside the organic electrolyte, and inorganic nanoparticles are distributed between the cross-linked polymers.

2 is a photograph showing the composite solid electrolyte (Example 1 (a) and Example 2 (b)) prepared according to an embodiment of the present invention.

Referring to FIG. 2 , it can be seen that the composite solid electrolyte according to the present invention exhibits an opaque and flexible gel form.

< Experimental example 1> solid Ionic Conductivity of Electrolytes evaluation

After forming the composite solid electrolytes prepared in Examples 1 and 2 into a circular shape having a diameter of 18 mm, coin-shaped cells were manufactured and AC voltage according to frequency was applied to measure ionic conductivity.

The measured ionic conductivity values are shown in Table 1.

Example Ionic Conductivity (Scm ^-1 ) Example 1 4.59 x 10 ^-3 Example 2 3.85 x 10 ^-3

Referring to Table 1, it can be seen that the solid electrolyte according to the present invention exhibits excellent ionic conductivity.

< Experimental example 2> Electrochemical stability evaluation

Current density values according to voltage were measured using the composite solid electrolytes prepared in Examples 1 and 2 above.

3 is a graph showing a current density value according to a voltage measured using a composite solid electrolyte prepared according to an embodiment of the present invention.

Referring to FIG. 3 , it was confirmed that the composite solid electrolyte according to the present invention exhibited excellent electrochemical stability.

< Experimental example 3> Thermal stability evaluation

Using the composite solid electrolyte prepared in Example 1, the weight % value over time was measured at a temperature of 150 °C.

As a comparative example, a conventional liquid electrolyte (1 M tetraethylammonium tetrafluoroborate (TEABF ₄ ) in propylene carbonate) used in supercapacitors was used.

4 is a graph showing the change in weight over time of the composite solid electrolyte according to the present invention and the conventional liquid electrolyte generally used.

Referring to FIG. 4 , it can be confirmed that the weight of the liquid electrolyte according to the present invention does not decrease with time, unlike the conventional liquid electrolyte generally used in high temperature conditions, which decreases in weight with time.

Through this, it can be seen that the composite solid electrolyte according to the present invention has excellent thermal stability at high temperatures.

As described above, although the embodiments have been described by the limited drawings, a person of ordinary skill in the art can apply various technical modifications and variations based on the above. For example, even if the described techniques are performed in a different order from the described method, and/or the described components are combined or combined in a form different from the described method, or are replaced or substituted by other components or equivalents. Appropriate results can be achieved. Therefore, other implementations, other embodiments, and claims and equivalents fall within the scope of the following claims.

Claims (15)

organic electrolytes;
inorganic nanoparticles;
a first photocrosslinking agent;
a second photocrosslinking agent; and
containing a photopolymerization initiator,
A composite solid electrolyte comprising a crosslinked polymer.
The method of claim 1,
The organic electrolyte includes a dissociable salt, an organic solvent, or a mixture thereof,
The concentration of the dissociable salt in the organic solvent is 0.1 M to 5.0 M,
A composite solid electrolyte comprising a crosslinked polymer.
The method of claim 2,
The dissociable salt is, TEABF ₄ , Li(CF ₃ SO ₂ ) ₂ N, Li(FSO ₂ ) ₂ N, LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiAsF ₆ , LiC ₄ F ₉ SO ₃ , LiClO ₄ , LiAlO ₂ , LiAlCl ₄ , LiN(C _x F _2x ^{+ 1} SO ₂ )(C _y F _2y ^{+ 1} SO ₂ ), where x and y are natural numbers, LiCl, LiI, LiB(C ₂ O ₄ ) ₂ ( Lithium bis (oxalato) borate (lithium bis (oxalato) borate; LiBOB) and a combination thereof comprising at least one selected from the group consisting of,
A composite solid electrolyte comprising a crosslinked polymer.
The method of claim 2,
The organic solvent is an imidazolium-based compound, a pyrrolidinium-based compound, a quaternary ammonium-based compound, a quaternary phosphonium-based compound, a carbonate-based solvent, an ester-based solvent, an ether-based solvent, a ketone-based solvent, an alcohol-based solvent, Which comprises at least one selected from the group consisting of aprotic solvents and combinations thereof,
A composite solid electrolyte comprising a crosslinked polymer.
The method of claim 1,
The inorganic nanoparticles are, SiO ₂ , Al ₂ O ₃ , TiO ₂ , BaTiO ₃ , Li ₂ O, LiF, LiOH, Li ₃ N, BaO, Na ₂ O, Li ₂ CO ₃ , CaCO ₃ , LiAlO ₂ , SrTiO ₃ , SnO ₂ , CeO ₂ , MgO, NiO, CaO, ZnO, ZrO ₂ and that comprising any one or more selected from the group consisting of SiC,
A composite solid electrolyte comprising a crosslinked polymer.
The method of claim 1,
The first photocrosslinking agent is a vinyl ether-based compound, an allyl ether-based compound, a propenyl ether-based compound, an alkene-based compound, an acrylate-based compound, an unsaturated ester-based compound, a maleimide-based compound, an acrylonitrile-based compound, a styrene-based compound compounds, diene-based compounds, N-vinyl amide-based compounds, allyl triazine and a mixture thereof comprising at least one selected from the group consisting of,
A composite solid electrolyte comprising a crosslinked polymer.
The method of claim 1,
The second photocrosslinking agent, which comprises at least one selected from the group consisting of an alkyl 3-mercaptopropionate compound, an alkylthio glycolate compound, an alkylthiol compound, and mixtures thereof,
A composite solid electrolyte comprising a crosslinked polymer.
The method of claim 1,
The photopolymerization initiator is benzophenone, thioxanthone, camphorquinone, acetophenone, benzyl, benzyl ketal, anthraquinone, benzoyl peroxide, benzoylphosphine oxide, acylphosphine oxide, triazine, oxime ester, aminophenyl ketone and hydr Which comprises at least one selected from the group consisting of hydroxyphenyl ketone,
A composite solid electrolyte comprising a crosslinked polymer.
The method of claim 1,
With respect to 100 parts by weight of the organic electrolyte, 1 part by weight to 100 parts by weight of the inorganic nanoparticles,
A composite solid electrolyte comprising a crosslinked polymer.
The method of claim 1,
With respect to 100 parts by weight of the organic electrolyte, 1 part by weight to 100 parts by weight of the first optical agent and the second optical agent,
A composite solid electrolyte comprising a crosslinked polymer.
The method of claim 1,
With respect to 100 parts by weight of the first optical crosslinking agent, the second optical crosslinking agent comprising 10 parts by weight to 1,000 parts by weight,
A composite solid electrolyte comprising a crosslinked polymer.
The method of claim 1,
The composite solid electrolyte is
Cross-linked polymers form a network structure in the organic electrolyte,
Inorganic nanoparticles are distributed between the cross-linked polymers,
A composite solid electrolyte comprising a crosslinked polymer.
preparing an organic solution in which an organic electrolyte is dissolved;
dissolving inorganic nanoparticles, a first photocrosslinking agent, a second photocrosslinking agent, and a photopolymerization initiator in the organic solution to form a mixed solution;
forming an electrolyte layer on a substrate using the mixed solution; and
Including; irradiating ultraviolet rays to the electrolyte layer;
A method for producing a composite solid electrolyte comprising a cross-linked polymer.
The method of claim 13,
In the step of irradiating the ultraviolet rays, 250 nm to 450 nm wavelength is irradiated for 5 seconds to 5 minutes,
A method for producing a composite solid electrolyte comprising a cross-linked polymer.
Claims 1 to 13, comprising the composite solid electrolyte of any one of claims 1 to 13 or the composite solid electrolyte prepared by the method of any one of claims 13 and 14,
Flexible electronic devices.

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