KR20210106329A - Complex fiber, solid state electrolyte comprising the same, and metal-air battery comprising the same - Google Patents

Abstract

A solid electrolyte is provided. The solid electrolyte may include a membrane including cellulose and more than 30 wt% and less than 70 wt% of chitosan bound to the cellulose of the membrane.

Description

Composite fiber, a solid electrolyte including the same, and a metal-air battery including the same

The present application relates to a composite fiber, a solid electrolyte including the same, and a metal-air battery including the same.

As mid-to-large high-energy applications such as electric vehicles and energy storage systems (ESS) are growing rapidly beyond the existing rechargeable batteries for small devices and home appliances, the market value of the secondary battery industry is only about 22 billion dollars in 2018 However, it is expected to grow to about $118 billion by 2025. As such, in order for secondary batteries to be used as medium and large-sized energy storage media, price competitiveness, energy density, and stability that are significantly improved compared to the current level are required.

According to these technical needs, research on secondary batteries using solid electrolytes is being actively conducted.

For example, in International Patent Publication WO2014200198A1, a composite electrode layer and a composite electrolyte layer are integrated into a composite electrode-composite electrolyte composite, wherein the composite electrode layer includes a current collector and an electrode mixture layer formed on the current collector, and the electrode mixture layer a silver electrode active material, a conductive material, a crosslinked polymer matrix, a dissociable salt, and an organic solvent, wherein the composite electrolyte layer includes a crosslinked polymer matrix, inorganic particles, a dissociable salt, and an organic solvent, the electrode mixture layer and Disclosed is a composite electrode-composite electrolyte composite in which the composite electrolyte layer is superimposed and physically bonded.

For another example, in Korean Patent No. 10-1734301, a first metal precursor made of a Li precursor, a second metal precursor made of an Al precursor, a third metal precursor made of a Ti precursor, and a P precursor are reacted with a chelate former A first step of producing a sol by heating the sol, a second step of producing a gel by heating the sol, a third step of heating the gel to thermally decompose, and a heat treatment by contacting the pyrolyzed gel with air A fourth step, a fifth step of cooling the powder obtained through the fourth step, a sixth step of mixing 0.2 to 1 wt% _{of a sintering aid Bi 2} O _{3 in the powder cooled in the fifth step, and the sixth step} while molding the mixed powder obtained in the pressure contact with the air and is included the step 7, and the relative density of sintered body (%) and sintering at 850 ℃ 90.0 to 99.7, the ion conductivity (S cm ^-1) is 7.9 Х 10 ^-4 to 9.9 Х 10 ^{-4 A} method for producing a solid electrolyte for a lithium battery is disclosed.

One technical problem to be solved by the present application is to provide a solid electrolyte having high reliability and high ionic conductivity and a metal-air battery including the same.

Another technical problem to be solved by the present application is to provide a long-life solid electrolyte and a metal-air battery including the same.

Another technical problem to be solved by the present application is to provide a solid electrolyte having a flexible and high mechanical stability and a metal-air battery including the same.

Another technical problem to be solved by the present application is to provide a metal-air battery with improved charge/discharge capacity and lifespan.

Another technical problem to be solved by the present application is to provide a composite fiber and a membrane for a solid electrolyte, and a method for manufacturing the same.

The technical problem to be solved by the present application is not limited to the above.

In order to solve the above technical problem, the present application provides a solid electrolyte.

According to an embodiment, the solid electrolyte may include a membrane including cellulose, and chitosan bonded to the cellulose of the membrane and greater than 30wt% and less than 70wt%.

According to one embodiment, the chitosan may be 50wt%.

According to an embodiment, when the chitosan content is 50 wt%, the ratio of C-N bonds in the C1s spectrum as a result of XPS analysis may have a maximum value.

According to one embodiment, the cellulose may include bacterial cellulose.

According to an embodiment, according to the ratio of the chitosan, crystallinity, ionic conductivity, and swelling ratio may be controlled.

According to one embodiment, as the ratio of the chitosan increases, it may include that the crystallinity is gradually reduced.

In order to solve the above technical problem, the present application provides a method of manufacturing a solid electrolyte.

According to an embodiment, the method for preparing the solid electrolyte includes preparing a chitosan derivative, generating chitosan bound to cellulose from the chitosan derivative, and preparing a solid electrolyte using the cellulose to which the chitosan is bound. It may include a manufacturing step.

According to an embodiment, according to the ratio of the chitosan derivative, crystallinity, ionic conductivity, and swelling ratio may be controlled.

According to one embodiment, the cellulose may include bacterial cellulose.

According to one embodiment, the step of generating the chitosan bound to the cellulose may include preparing a culture medium having the chitosan derivative, and injecting and culturing a bacterial strain in the culture medium.

According to an embodiment, the method for preparing the solid electrolyte may further include preparing the first composite fiber by oxidizing the surface of the cellulose to which the chitosan is bound using an oxidizing agent.

According to one embodiment, the method for producing the solid electrolyte comprises the steps of binding bromine to the surface of the cellulose to which the chitosan is bound, and substituting a first functional group containing nitrogen with bromine to prepare a second composite fiber. may include more.

According to an embodiment, the method for preparing the solid electrolyte includes preparing a first composite fiber by oxidizing the surface of the cellulose to which the chitosan is bound using an oxidizing agent, and bromine on the surface of the cellulose to which the chitosan is bound. The method may further include the steps of preparing a second conjugated fiber by bonding to the bromine and substituting a first functional group containing nitrogen with bromine, and crosslinking the first conjugated fiber and the second conjugated fiber.

In order to solve the above technical problem, the present application provides an intermediate product of a solid electrolyte.

According to an embodiment, the intermediate product of the solid electrolyte includes a base composite fiber comprising chitosan and bacterial cellulose combined with chitosan, wherein the base composite fiber is dispersed in a first solvent, a first intermediate product, a surface a second intermediate product in which the oxidized base conjugate fibers are dispersed in a second solvent, a third intermediate product in which the base conjugate fibers surface bonded with bromine are dispersed in a third solvent, or a first intermediate product whose surface has quaternary N The base conjugate fiber combined with a functional group may include at least one of a fourth intermediate product dispersed in a fourth solvent.

The solid electrolyte according to an embodiment of the present application may include a membrane including cellulose, and chitosan bound to the cellulose of the membrane. The solid electrolyte may be provided in the form of a membrane in which the base composite fibers constitute a network. The solid electrolyte may contain a large amount of OH ions and moisture by the chitosan, and may have high ionic conductivity.

Accordingly, the charge/discharge capacity and lifespan characteristics of the metal-air battery including the solid electrolyte may be improved.

In addition, the solid electrolyte may be prepared by injecting a bacterial strain into a culture medium having a chitosan derivative and culturing. Accordingly, the content of the chitosan in the solid electrolyte can be improved, and the content of the chitosan can be easily controlled.

Accordingly, ionic conductivity, swelling ratio, and water impregnation rate of the solid electrolyte may be improved.

1 is a flowchart illustrating a method of manufacturing a solid electrolyte according to an embodiment of the present application.
2 is a view showing a base composite fiber according to an embodiment of the present application.
3 is a view showing a first composite fiber according to an embodiment of the present application.
4 is a view showing a second composite fiber according to an embodiment of the present application.
5 is a diagram illustrating a solid electrolyte including a base composite fiber according to an embodiment of the present application.
6 is a view illustrating a metal-air battery including a solid electrolyte according to an embodiment of the present application.
7 is a view for explaining a first composite fiber and a manufacturing method thereof according to Experimental Example 1-2 of the present application.
8 is a view for explaining a second composite fiber and a method of manufacturing the same according to Experimental Examples 1-3 of the present application.
9 is a view for explaining a method of manufacturing a solid electrolyte according to Experimental Examples 1-4 of the present application.
10 is a view for explaining the principle of ion movement of the solid electrolyte according to Experimental Examples 1-4 of the present application.
11 is a hydrogen NMR analysis result of the first composite fiber, the second composite fiber, and the solid electrolyte prepared according to Experimental Examples 1-2 to 1-4 of the present application.
12 is an XRD analysis result of the solid electrolyte, bacterial cellulose, general bacterial cellulose, and cellulose prepared according to Experimental Examples 1-4 to Experimental Examples 1-7 of the present application.
13 is an FT-IR analysis result for the solid electrolyte, bacterial cellulose, and general bacterial cellulose prepared according to Experimental Examples 1-4 to 1-6 of the present application.
14 is an SEM photograph of a solid electrolyte prepared according to Experimental Examples 1-4 of the present application.
15 is a TGA and DSC analysis result of the solid electrolyte prepared according to Experimental Examples 1-4 of the present application.
16 to 19 are graphs of XPS analysis results of solid electrolytes and bacterial cellulose according to Experimental Examples 1-4 and 1-5 of the present application.
20 is an ionic conductivity measurement result for explaining the basic resistance test result of the solid electrolyte prepared according to Experimental Examples 1-4 of the present application.
21 is an XRD analysis result for explaining the basic resistance test result of the solid electrolyte prepared according to Experimental Examples 1-4 of the present application.
22 is a photograph for explaining the basic resistance test result of the solid electrolyte according to Experimental Examples 1-4 of the present application.
23 is a stress-strain graph according to the moisture impregnation rate of the solid electrolyte according to Experimental Examples 1-4 of the present application.
24 is a graph showing the results of measuring ionic conductivity according to mechanical deformation of the solid electrolyte according to Experimental Examples 1-4 of the present application.
25 is a graph of measuring the storage modulus of the solid electrolyte according to Experimental Examples 1-4 of the present application.
26 is a photograph for explaining the mechanical stability of the solid electrolyte according to Experimental Examples 1-4 of the present application.
27 is a graph measuring various ion transfer rates of the solid electrolyte according to Experimental Examples 1-4 of the present application.
28 is an XRD analysis result of solid electrolytes according to Experimental Examples 2-1 to 2-5 of the present application.
29 illustrates measurements of ionic conductivity according to temperature of solid electrolytes according to Experimental Examples 2-1 to 2-5 of the present application.
30 to 32 are XPS analysis results of solid electrolytes according to Experimental Examples 3-1 to 3-5 and bacterial cellulose according to Experimental Examples 1-5 of the present application.
33 is a graph analyzing element ratios of solid electrolytes according to Experimental Examples 3-1 to 3-5 of the present application and bacterial cellulose according to Experimental Examples 1-5.
34 is a result of analyzing the composition ratio of C1s spectra of solid electrolytes according to Experimental Examples 3-1 to 3-5 of the present application and bacterial cellulose according to Experimental Examples 1-5.
35 is a result of analyzing the composition ratio of N1s spectra of solid electrolytes according to Experimental Examples 3-1 to 3-5 of the present application and bacterial cellulose according to Experimental Examples 1-5.
36 is an XRD analysis result of the solid electrolyte according to Experimental Examples 3-1 to 3-5 of the present application, chitosan according to Experimental Examples 3-6, and bacterial cellulose according to Experimental Examples 1-5 of the present application.
37 is a solid electrolyte according to Experimental Example 3-1 to Experimental Example 3-5 of the present application, chitosan according to Experimental Example 3-6, bacterial cellulose according to Experimental Example 1-5, and general according to Experimental Example 1-6 The ionic conductivity according to the temperature of bacterial cellulose was measured.
38 is a solid electrolyte according to Experimental Example 3-1 to Experimental Example 3-5 of the present application, chitosan according to Experimental Example 3-6, bacterial cellulose according to Experimental Example 1-5, and general according to Experimental Example 1-6 The swelling ratio according to the temperature of bacterial cellulose was measured.
39 is a solid electrolyte according to Experimental Example 3-1 to Experimental Example 3-5 of the present application, chitosan according to Experimental Example 3-6, bacterial cellulose according to Experimental Example 1-5, and general according to Experimental Example 1-6 The moisture impregnation rate according to the temperature of bacterial cellulose was measured.
40 is a graph for explaining a result of measuring the voltage of the solid electrolyte according to Experimental Examples 1-4 of the present application.
41 is a graph for explaining the charge/discharge capacity of a metal-air battery including a solid electrolyte according to Experimental Examples 1-4 of the present application.
42 is a graph of measuring voltage values according to the number of times of charging and discharging of a metal-air battery including a solid electrolyte according to Experimental Examples 1-4 of the present application.
43 is a graph for explaining a change in charge/discharge characteristics according to external temperature conditions of a metal-air battery including a solid electrolyte according to Experimental Examples 1-4 of the present application.
44 is a view for explaining the capacity preservation characteristics according to the number of charge and discharge in low-temperature and high-temperature environments of the metal-air battery including the solid electrolyte according to Experimental Examples 1-4 of the present application.
45 is a graph for explaining the charge/discharge characteristics according to the external temperature of the metal-air battery including the solid electrolyte according to Experimental Examples 1-4 of the present application.
46 is a graph for explaining a change in charge/discharge characteristics according to a charge/discharge cycle according to an external temperature of a metal-air battery including a solid electrolyte according to Experimental Examples 1-4 of the present application.
47 is a block diagram of an electric vehicle according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the technical spirit of the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided so that the disclosed content may be thorough and complete, and the spirit of the present invention may be sufficiently conveyed to those skilled in the art.

In this specification, when a component is referred to as being on another component, it may be directly formed on the other component or a third component may be interposed therebetween. In addition, in the drawings, thicknesses of films and regions are exaggerated for effective description of technical content.

In addition, in various embodiments of the present specification, terms such as first, second, third, etc. are used to describe various components, but these components should not be limited by these terms. These terms are only used to distinguish one component from another. Accordingly, what is referred to as a first component in one embodiment may be referred to as a second component in another embodiment. Each embodiment described and illustrated herein also includes a complementary embodiment thereof. In addition, in the present specification, 'and/or' is used to mean including at least one of the elements listed before and after.

In the specification, the singular expression includes the plural expression unless the context clearly dictates otherwise. In addition, terms such as "comprise" or "have" are intended to designate that a feature, number, step, element, or a combination thereof described in the specification is present, and one or more other features, numbers, steps, configuration It should not be construed as excluding the possibility of the presence or addition of elements or combinations thereof. In addition, in the following description of the present invention, if it is determined that a detailed description of a related well-known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted.

1 is a flowchart for explaining a method of manufacturing a solid electrolyte according to an embodiment of the present application, FIG. 2 is a view showing a base composite fiber according to an embodiment of the present application, and FIG. 3 is an embodiment of the present application is a view showing a first composite fiber according to the present application, FIG. 4 is a view showing a second composite fiber according to an embodiment of the present application, and FIG. 5 is a solid electrolyte including a base composite fiber according to an embodiment of the present application It is the drawing shown.

1 to 5, the chitosan derivative is prepared (S110).

The chitosan derivative may be a mixture of a chitosan precursor in a solvent. According to one embodiment, the chitosan derivative, chitosan chloride and a solvent, may be a solubilizing agent added. Accordingly, the chitosan chloride can be easily dissolved in a solvent, and the chitosan derivative can be easily provided in a medium to be described later, so that cellulose to which chitosan is bound can be easily prepared.

For example, the solvent may be aqueous acetic acid, and the solvent is glycidyltrimethylammonium chloride, (2-Aminoethyl)trimethylammonium chloride, (2-Chloroethyl)trimethylammonium chloride, (3-Carboxypropyl)trimethylammonium chloride, or (Formylmethyl)trimethylammonium chloride It may include at least one of them.

The chitosan has excellent thermal and chemical stability, has high ionic conductivity, and can contain OH ions without loss for a long period of time. In addition, as will be described later, when used in a metal-air battery, it may have high compatibility with a zinc anode and a compound structure of copper, phosphorus, and sulfur.

From the chitosan derivative, chitosan bound to cellulose is produced (S120). The step of generating the cellulose to which the chitosan is bound is a step of preparing a culture medium having the chitosan derivative, and injecting and culturing a bacterial strain in the culture medium, the cellulose 112 to which the chitosan 114 is bound It may include the step of producing the base composite fiber 110 including the. In this case, the cellulose 112 may be bacterial cellulose.

According to one embodiment, the cellulose 112 to which the chitosan 114 is bound may be prepared by culturing the bacterial pellicle in the culture medium, and then desalting the bacterial pellicle. The bacterial pellicle prepares a culture medium containing the chitosan derivative together with raw materials for yeast and bacterial culture (eg, pineapple juice, peptone, disodium phosphate, citric acid), and after injecting the strain, culture can be manufactured. For example, the strain may be Acetobacter Xylinum.

After washing and drying the cultured bacterial pellicle, desalting with an acidic solution (eg, HCl), neutralizing and removing the solvent. The base complex comprising the cellulose 112 to which the chitosan 114 is bound. Fiber 110 may be manufactured. In the desalting process, the remaining Na, K, or cell shielding and debris are removed, and the cellulose 112 to which the chitosan 114 of high purity is bound can be prepared.

In addition, the chitosan 114 may be chemically bonded to the cellulose 112 . Accordingly, in the cellulose 112 to which the chitosan 114 is bound, a stretching vibration corresponding to C-N may be observed during XPS analysis.

According to an embodiment, the surface of the cellulose 112 to which the chitosan 114 is bonded using an oxidizing agent, that is, the surface of the base composite fiber 110 is oxidized, so that the first composite fiber 110a is manufactured. can

Specifically, the step of preparing the first composite fiber 110a includes adding the base composite fiber 110 to an aqueous solution containing an oxidizing agent to prepare a source solution, adjusting the pH of the source solution to basic Step, adjusting the pH of the source solution to neutral, and washing and drying the pulp in the source solution may include manufacturing the first composite fiber (110a).

For example, the aqueous solution containing the oxidizing agent may be a TEMPO aqueous solution. Or, for another example, the aqueous solution containing the oxidizing agent is 4-Hydroxy-TEMPO, (Diacetoxyiodo)benzene, 4-Amino-TEMPO, 4-Carboxy-TEMPO, 4-Methoxy-TEMPO, TEMPO methacrylate, 4-Acetamido It may include at least one of -TEMPO, 3-Carboxy-PROXYL, 4-Maleimido-TEMPO, 4-Hydroxy-TEMPO benzoate, or 4-Phosphonooxy-TEMPO.

The source solution may further include a sacrificial reagent and an additional oxidizing agent for the oxidation reaction of the base composite fiber 110 . For example, the sacrificial reagent may include at least one of NaBr, sodium iodide, sodium bromate, sodium bromite, sodium borate, sodium chlorite, or sodium chloride, and the additional oxidizing agent is, NaClO, potassium hypochlorite, Lithium at least one of hypochlorite, sodium chlorite, sodium chlorate, Perchloric acid, Potassium perchlorate, Lithium perchlorate, Tetrabutylammonium perchlorate, Zinc perchlorate, hydrogen peroxide, or sodium peroxide.

According to an embodiment, in the step of adjusting the pH of the source solution to be basic, the pH of the source solution may be adjusted to 10. Accordingly, the oxidation reaction may be easily induced while minimizing the precipitate, and the oxidation degree of the first composite fiber 110a may be improved as compared to a reaction condition of pH 8 to 9.

According to an embodiment, after the base composite fiber 110 and the sacrificial reagent are provided in an aqueous solution containing the oxidizing agent, the additional oxidizing agent may be provided. In addition, the additional oxidizing agent may be provided in drops. Accordingly, rapid oxidation of the base composite fiber 110 may be prevented, and as a result, the surface of the base composite fiber 110 may be uniformly and stably oxidized.

In addition, according to an embodiment, by binding bromine to the surface of the cellulose 112 to which the chitosan 114 is bonded and replacing the first functional group 116 containing nitrogen with bromine, the second composite fiber ( 110b) can be prepared.

The first functional group 116 may be represented by the following <Formula 1>, and the first functional group 116 may be combined with the chitosan 114 and/or the cellulose 112 . .

<Formula 1>

That is, the second composite fiber 110b may have a quaternary N.

Specifically, the manufacturing of the second composite fiber 110b includes dispersing the base composite fiber 110 in a first solvent and adding a bromine source to prepare a first source solution, the first source solution adding a coupling agent to and reacting to prepare a reaction suspension; filtering, washing and freeze-drying the reaction suspension to prepare a brominated base composite fiber; dispersing the brominated base composite fiber in a second solvent to prepare a reaction suspension 2 Preparing a source solution, adding and reacting the precursor of the first functional group 116 to the second source solution, filtering, washing, and freeze-drying the reacted solution to obtain the second composite fiber 110b It may include the step of manufacturing.

For example, the first solvent and the second solvent may be the same as each other, and may include at least one of N, N-dimethylacetamide, Acetamide, Acetonitrile, ethanol, ethylenediamine, diethyl ether, or benzaldehyde.

For example, the bromine source may include at least one of LiBr, sodium bromide, and potassium bromide.

For example, the coupling agent may include N-bromosuccinimide and triphenylphosphine. Bromine may be easily coupled to the surface of the base composite fiber 110 by the coupling agent. Specifically, bromine in N-bromosuccinimide may be combined with the base composite fiber 110, and triphenylphosphine may reduce a bromine precursor (bromosuccinimide or N-bromosuccinimide) to improve the reaction rate.

As described above, after obtaining the brominated base composite fiber in the reaction suspension, the brominated base composite fiber may be freeze-dried. Accordingly, loss of bromine in the brominated base composite fiber may be minimized, and secondary reaction of bromine with other elements may be minimized.

For example, the precursor of the first functional group 116 may include 1,4-Diazabicyclo[2.2.2]octane.

A solid electrolyte may be prepared using the cellulose 112 to which the chitosan 114 is bound (S130).

The solid electrolyte may be manufactured in the form of a membrane in which the base composite fiber 110 including the cellulose 112 to which the chitosan 114 is bonded constitutes a network, as shown in FIG. 5 . For this reason, the solid electrolyte may be provided with a plurality of pores therein, may have a high surface area, and may have excellent flexibility and mechanical properties.

The solid electrolyte may be in a state in which a crystalline phase and an amorphous phase are mixed. More specifically, in the solid electrolyte, the ratio of the amorphous phase may be higher than the ratio of the crystalline phase. Accordingly, the solid electrolyte may have high ion mobility.

According to an embodiment, the solid electrolyte may be manufactured by a gelatin process using the first composite fiber 110a and the second composite fiber 110b. In this case, the solid electrolyte includes the first conjugated fiber 110a and the second conjugated fiber 110b, wherein the first conjugated fiber 110a and the second conjugated fiber 110b are cross-linked to each other. can be By the first composite fiber 110a, the number of OH ions in the solid electrolyte may increase, ion conductivity may be improved, negative charge density may be increased, and swelling resistance may be improved. In addition, by the second composite fiber 110b, the molecular weight is increased to improve thermal stability, and ion exchange capacity is improved to have a high moisture impregnation rate and high swelling resistance, and the first Cross-linking strength with the composite fiber 110a may be improved, and may have high solubility (ion discerning selectivity) selectively in a specific solvent. Accordingly, charge/discharge characteristics and lifespan characteristics of the secondary battery including the solid electrolyte may be improved.

Specifically, preparing the solid electrolyte includes preparing a mixed solution by mixing the first conjugated fibers 110a and the second conjugated fibers 110b with a solvent, and adding a crosslinking agent and an initiator to the mixed solution. and reacting to prepare a suspension, casting the suspension on a substrate and drying to prepare a composite fiber membrane, and performing an ion exchange process on the composite fiber membrane.

For example, the solvent may include a mixed solvent of methylene chloride, 1,2-Propanediol, and acetone, the crosslinking agent may include glutaraldehyde, and the initiator may include N,N-Diethyl-N-methyl -N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide may be included.

Also, for example, the ion exchange process for the composite fiber membrane may include providing an aqueous KOH solution and an aqueous ZnTFSI solution to the composite fiber membrane. Due to this, the OH ion content in the solid electrolyte may be improved.

As described above, according to an embodiment of the present application, the solid electrolyte includes at least one of the base composite fiber 110 , the first composite fiber 110a , and the second composite fiber 110b . It may include the membrane (M).

In the solid electrolyte, the ratio of the chitosan 114 can be easily controlled according to the content of the chitosan derivative provided in the culture medium. According to the ratio of the chitosan 114, the crystallinity, ionic conductivity, and swelling ratio of the solid electrolyte may be controlled. Specifically, as the ratio of the chitosan 114 increases, the crystallinity of the solid electrolyte may be gradually reduced.

According to one embodiment, the content of the chitosan 114 may be more than 30wt% and less than 70wt%. If the content of the chitosan 114 is 30 wt% or less, or 70 wt% or more, the ionic conductivity of the solid electrolyte is significantly reduced, and the swelling ratio may be significantly increased.

However, according to the embodiment of the present application, the proportion of the chitosan 114 in the solid electrolyte may be more than 30 wt% and less than 70 wt%, and due to this, the solid electrolyte maintains high ionic conductivity characteristics, low swelling It can have a ratio value.

6 is a view illustrating a metal-air battery including a solid electrolyte according to an embodiment of the present application.

Referring to FIG. 6 , a metal-air battery according to an embodiment of the present application is provided. The metal-air battery may include a negative electrode 200 , a positive electrode 300 , and a solid electrolyte 100 between the negative electrode 200 and the positive electrode 300 .

The solid electrolyte 100 includes at least any one of the base composite fiber 110, the first composite fiber 110a, or the second composite fiber 110b described with reference to FIGS. 1 to 5 . It may be provided in the form of a membrane containing.

The negative electrode 200 may include zinc. Alternatively, the negative electrode 200 may include lithium.

According to an embodiment, the anode 300 may include Pt/C and RuO2. Alternatively, according to another embodiment, the anode 300 may include a compound structure of copper, phosphorus, and sulfur. In this case, the compound structure of copper, phosphorus, and sulfur is provided in a form in which a plurality of fibrillated fibers constitute a membrane, and may have a (101) crystal plane. A specific manufacturing process of the compound structure of copper, phosphorus, and sulfur will be described later with reference to FIG. 41 .

The solid electrolyte 100 included in the metal-air battery according to the embodiment of the present application may contain a large amount of OH ions and moisture, and may have high ionic conductivity. Accordingly, the charge/discharge capacity and lifespan characteristics of the metal-air battery may be improved, and growth of dendrites on the surface of the negative electrode 200 during the charge/discharge process of the metal-air battery may be minimized.

The solid electrolyte according to the embodiment of the present application may be distributed, delivered, traded, and stored as intermediate products of various types. Hereinafter, various types of intermediate products for preparing a solid electrolyte according to an embodiment of the present application will be described.

According to the first modification, by omitting the chitosan derivative and omitting the desalting process according to Experimental Examples 1-5 described below, in the case of bacterial cellulose that does not contain chitosan, it may be in a gel state immediately after synthesis, or after drying It may have a solid state (powder), or it may have a solution state provided in a solvent. The solvent may be, for example, DI water or an organic solvent (eg, methylene chloride, DMSO, DMF, THF, IPA).

According to the second modification, in the case of the chitosan derivative according to the embodiment of the present application described above, it may be in a gel state immediately after synthesis, or may have a solid state (powder) after drying, or a solution state provided in a solvent can have The solvent may be, for example, DI water or ethanol.

According to a third modification, in the case of the base composite fiber 110 comprising cellulose to which chitosan is bonded according to the embodiment of the present application described above, it may be in a gel state immediately after synthesis, or in a solid state ( powder) or may have a solution state provided in a solvent. The solvent may be, for example, DI water, DMSO, ethanol, methylene chloride, IPA, N,N,-DMF, or THF.

According to the fourth modification, in the case of the first composite fiber 110a in which the surface of the base composite fiber 110 is oxidized according to the embodiment of the present application described above, it may be in a gel state immediately after synthesis, or dried After being formed, it may have a solid state (powder), or it may have a solution state provided in a solvent. The solvent may be, for example, CHCl3 or DMSO.

According to the fifth modification, in the case of the brominated base composite fiber in which bromine is bonded to the surface of the base composite fiber 110 according to the embodiment of the present application described above, it may be in a gel state immediately after synthesis, or dried After being formed, it may have a solid state (powder), or it may have a solution state provided in a solvent. The solvent may be, for example, CHCl3, DMSO, or ethanol.

According to a sixth modification, in the case of the second composite fiber 110b having a quaternary N in which the first functional group according to the above-described embodiment of the present application is bonded to the surface of the base composite fiber 110, the synthesized It may be in a gel state immediately after drying, or may have a solid state (powder) after drying, or may have a solution state provided in a solvent. The solvent may be, for example, CHCl3 or DMSO.

According to the seventh modification, in the case of a solid electrolyte in which the first composite fiber 110a and the second composite fiber 110b are crosslinked according to the above-described embodiment of the present application, the solid electrolyte may have a solid state (membrane), , or may have a solution state provided in a solvent. The solvent may be, for example, CHCl3 or DMSO.

Hereinafter, a method of manufacturing a base composite fiber, a first composite fiber, a second composite fiber, and a solid electrolyte according to a specific experimental example of the present application will be described.

7 is a view for explaining a first composite fiber and a manufacturing method thereof according to Experimental Example 1-2 of the present application, and FIG. 8 is a second composite fiber and a manufacturing method thereof according to Experimental Example 1-3 of the present application. FIG. 9 is a diagram for explaining a method of manufacturing a solid electrolyte according to Experimental Example 1-4 of the present application, and FIG. 10 is an ion migration principle of a solid electrolyte according to Experimental Example 1-4 of the present application. It is a drawing for explaining.

Preparation of base composite fiber (CBC) according to Experimental Example 1-1

Acetobacter xylinum was prepared as a bacterial strain, and a chitosan derivative was prepared. The chitosan derivative is a suspension of 1 g of chitosan chloride dissolved in 1% (v/v) aqueous acetic acid with 1M of glycidyltrimethylammonium chloride in N ₂ atmosphere at 65° C. for 24 hours. After treatment for a while, it was prepared by precipitation and filtration with ethanol several times.

Pineapple juice (2% w/v), yeast (0.5% w/v), peptone (0.5% w/v), disodium phosphate (0.27% w/v), citric acid (0.015% w/v), and the above A Hestrin-Schramm (HS) culture medium containing a chitosan derivative (2% w/v) was prepared and steam sterilized at 121° C. for 20 minutes. In addition, Acetobacter xylinum was activated in a pre-cultivation Hestrin-Schramm (HS) culture medium at 30° C. for 24 hours, and then maintained at pH 6 by adding acetic acid.

Then, Acetobacter xylinum was cultured in Hestrin-Schramm (HS) culture medium at 30 °C for 7 days.

The harvested bacterial pellicles were washed with deionized water to neutralize the pH of the supernatant and dehydrated in vacuum at 105°C. The resulting cellulose was demineralized with 1 N HCl for 30 minutes (mass ratio 1:15, w/v) to remove excess reagent, and then using deionized water several times until the supernatant became neutral pH. It was purified by centrifugation. Finally, after evaporating all solvents at 100° C., a base composite fiber (chitosan-bacterial cellulose (CBC)) was prepared.

Preparation of first composite fiber (oCBC) according to Experimental Example 1-2

The first composite fibers (TEMPO-oxidized CBCs (oCBCs)) on which the surface of the base composite fibers are oxidized are 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), as shown in FIG. 6 , By oxidation using sodium bromide (NaBr) and sodium hypochlorite (NaClO), hydroxymethyl and ortho-para directing acetamido-based composite fibers (CBC) were conjugated to the oxide of TEMPO. designed in this way.

Specifically, 2 g of the base composite fiber fibers dispersed in 2 mM TEMPO aqueous solution were reacted with NaBr (1.9 mM). 5 mM NaClO was used as an additional oxidizing agent.

The reaction suspension was stirred ultrasonically, and the reaction was allowed to proceed at room temperature for 3 hours. The pH of the suspension was maintained at 10 by continuous addition of 0.5M NaOH solution. Then, 1N HCl was added to the suspension to keep the pH neutral for 3 hours. The resulting oxidized pulp in the suspension was washed 3 times with 0.5 N HCl, and the supernatant was brought to neutral pH with deionized water.

The washed pulp was exchanged with acetone, toluene for 30 minutes and dried to evaporate the solvent, and finally, a first composite fiber (oCBC) fiber was obtained.

As can be seen from FIG. 7 , the surface of the base composite fiber may be oxidized.

Preparation of the second composite fiber (qCBC) according to Experimental Example 1-3

A second composite (Covalently quaternized CBC (qCBC)) in which a first functional group having nitrogen is bonded to the base composite fiber is, as shown in FIG. 8, a coupling agent using 1,4-Diazabicyclo[2.2.2]octane It was prepared by a method of conjugation of a brominated base conjugate fiber (CBC) and a quaternary amine group.

Specifically, 1 g of the base composite fiber dispersed in N,N-dimethylacetamide (35 ml) solution was reacted with a LiBr (1.25 g) suspension with stirring for 30 minutes. N-bromosuccinimide (2.1 g) and triphenylphosphine (3.2 g) were used as coupling agents. The two reaction mixtures were stirred for 10 minutes and reacted at 80° C. for 60 minutes.

The reaction suspension was then cooled to room temperature and added to deionized water, filtered, rinsed with deionized water and ethanol, and freeze-dried to obtain brominated base conjugate fiber (bCBC) fibers.

The brominated base composite fiber was dissolved in 100 ml of N,N-dimethylformamide and reacted with 1.2 g of 1,4-Diazabicyclo[2.2.2]octane.

Thereafter, the mixture was sonicated for 30 minutes and then reacted at room temperature for 24 hours. The resulting solution was mixed with diethyl ether, washed with diethyl ether/ethyl acetate 5 times, and freeze-dried to obtain a second composite fiber (Covalently quaternized CBC (qCBC)).

As can be seen from FIG. 8 , it can be confirmed that the first functional group having nitrogen is bonded to the surface of the base composite fiber.

Preparation of solid electrolytes (CBCs) according to Experimental Examples 1-4

As shown in FIG. 8 , the solid electrolyte was prepared by a gelatin process using the first conjugated fibers (oCBC) and the second conjugated fibers (qCBC). Specifically, the first composite fiber (oCBC) and the second composite fiber (qCBC) were mixed with methylene chloride and 1,2-Propanediol and acetone in the same weight ratio using ultrasound (8:1:1 v/v). /v%), 1wt% of glutaraldehyde as a crosslinking agent and 0.3wt% of N,N-Diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide as an initiator were added.

A vacuum chamber (200 Pa) was used to remove air bubbles from the gel suspension and cast on glass at 60° C. for 6 hours. The composite fiber membrane was peeled off while coagulated with deionized water, rinsed with deionized water, and vacuum dried.

Solid electrolytes (CBCs) were prepared by ion exchange with 1 M KOH aqueous solution and 0.1 M ZnTFSI at room temperature for 6 hours, respectively. Thereafter, in order to avoid reaction and carbonate formation with _{CO 2} , washing and immersion processes were performed with deionized water in an _{N 2 atmosphere.}

As can be seen in FIG. 9 , it can be confirmed that the first conjugated fibers (oCBC) and the second conjugated fibers (qCBC) are cross-linked with each other to constitute the solid electrolytes (CBCs).

In addition, referring to FIG. 10 , OH ions are hopping on the surfaces of the crosslinked first composite fibers (oCBC) and the second composite fibers (qCBC) of the solid electrolytes (CBCs). )) and may move through diffusion in the interior spaced apart from the surfaces of the first and second composite fibers. In addition, the solid electrolytes (CBCs) may have an amorphous phase as will be described later with reference to FIG. 12 , and thus may have high ionic conductivity compared to a crystalline structure.

Preparation of bacterial cellulose according to Experimental Examples 1-5

In the method for producing the base composite fiber of Experimental Example 1-1 described above, the chitosan derivative was omitted, and the desalting process was omitted to prepare bacterial cellulose that does not contain chitosan.

Preparation of general bacterial cellulose according to Experimental Example 1-6

Using a culture medium containing glucose (2wt%), peptone (0.5wt%), yeast (0.5wt%), disodium phosphate (0.2wt%), and citric acid (0.1wt%), omitting the chitosan derivative , and omitting the desalting process, bacterial cellulose was prepared in the same manner as in Experimental Example 1-1.

Cellulose preparation according to Experimental Examples 1-7

A sugar cane bagasse was prepared, and a solvent in which ethanol was mixed with deionized water, NaOH, and nitric acid was prepared. After washing by dispersing sugar cane bagasse in a solvent, it was filtered and washed several times with deionized water until a neutral pH was reached.

The washed sugarcane bagasse was dried at 100° C. for 3 hours, and polished through a stainless steel sieve of a 16 mesh IKA MF-10 mill to prepare fiber pulp.

The unit process of bleaching the fiber pulp with hydrogen peroxide (1%, pH 13.5) at 55 °C for 1 hour was repeated three times in total, and the residue was removed with NaOH solution for 3 hours in an atmospheric atmosphere, followed by washing with ethanol and acetone. and dried at 50° C. for 6 hours to prepare cellulose.

Experimental Example 1-1 to Experimental Example 1-7 may be organized as shown in [Table 1] below.

division structure Experimental Example 1-1 Base Composite Fiber (CBC): Chitosan + Bacterial Cellulose Experimental Example 1-2 First composite fiber (oCBC): surface oxidized chitosan + surface oxidized bacterial cellulose Experimental Example 1-3 Second composite fiber (qCBC): chitosan having a first functional group + bacterial cellulose having a first functional group Experimental Example 1-4 Crosslinking of first conjugated fibers (oCBC) and second conjugated fibers (qCBC) Experimental Example 1-5 Bacterial Cellulose Without Chitosan Experimental Example 1-6 Normal Bacterial Cellulose Experimental Example 1-7 cellulose

11 is a hydrogen NMR analysis result of the first composite fiber, the second composite fiber, and the solid electrolyte prepared according to Experimental Examples 1-2 to 1-4 of the present application.

Referring to FIG. 11 , hydrogen NMR was analyzed for the first composite fiber, the second composite fiber, and the solid electrolyte prepared according to the above-described Experimental Examples 1-2 to 1-4.

The colored circles in the analysis result of FIG. 11 correspond to hydrogen atoms corresponding to the same colored circles in FIG. 9 . That is, the NMR analysis result of the circles having the color in FIG. 9 can be confirmed in FIG. 11 . As can be seen in FIG. 11 , it can be seen that the first conjugated fibers and the second conjugated fibers are alternately and repeatedly cross-linked at the same ratio.

12 is an XRD analysis result of the solid electrolyte, bacterial cellulose, general bacterial cellulose, and cellulose prepared according to Experimental Examples 1-4 to Experimental Examples 1-7 of the present application.

Referring to FIG. 12 , XRD analysis was performed on the solid electrolyte, bacterial cellulose, general bacterial cellulose, and cellulose prepared according to Experimental Examples 1-4 to 1-7 described above.

12, it can be seen that the cellulose fibers of Experimental Examples 1-7 have high crystallinity, and have peak values corresponding to (200), (110), and (1-10) crystal planes to form hexagonal crystals. It can be seen that the structure has On the other hand, in the bacterial cellulose (C(I)) of Experimental Examples 1-6, the crystallinity was relatively decreased, and it can be seen that the 2θ value of the peak corresponding to the (200) crystal plane was decreased.

Bacterial cellulose of Experimental Example 1-5 prepared according to an example of the present application had significantly reduced crystallinity compared to the general cellulose fiber of Experimental Example 1-7, and the general cellulose fiber of Experimental Example 1-7 and the experiment It can be confirmed that it has peak values corresponding to the (020) and (110) crystal planes differently from the general bacterial cellulose of Example 1-6, and it can be confirmed that it has two peak values corresponding to the (1-10) crystal plane . In addition, it can be confirmed that the peak value corresponding to the (110) crystal plane is higher than the peak value corresponding to the other crystal planes (eg, (101), (1-10)).

In addition, it can be seen that the solid electrolyte of Experimental Examples 1-4 prepared according to an embodiment of the present application has a crystalline phase and an amorphous phase at the same time, and the ratio of the amorphous phase is remarkably high.

13 is an FT-IR analysis result of the solid electrolyte, bacterial cellulose, and general bacterial cellulose prepared according to Experimental Examples 1-4 to 1-6 of the present application.

Referring to FIG. 13 , FT-IR analysis was performed on solid electrolytes, bacterial cellulose, and general bacterial cellulose according to Experimental Examples 1-4 to 1-6 described above.

As can be seen in FIG. 13, compared with the general bacterial cellulose of Experimental Example 1-6, in the case of the bacterial cellulose of Experimental Example 1-5, the stretching vibrations of CO and OH were 1056 cm ^-1 and 2932 cm ^-1 It can be seen that it has moved to ^{1022 cm -1} and 2895 cm ^{-1 .} In addition, in the case of the solid electrolyte of Experimental Examples 1-4 according to the embodiment of the present application, CN ⁺ stretching vibration was ^{observed at 1458 cm -1} , confirming that the quaternization reaction occurred. Vibration at 2916cm ^-1 and 3320cm ^-1 corresponds to the OH stretching vibration, 1652cm ^-1 and 1750cm ^-1 are to correspond to the water, it is possible to confirm that there is sufficient water molecules present in the solid electrolyte is an amorphous, Experiment 1 The increase in the strength of the stretching vibration of CO in the solid electrolyte of -4 is due to the reaction of chitosan and bacterial cellulose. In addition, it can be seen that carbonate is not substantially present in the solid electrolyte of Experimental Examples 1-4, and thus it can be seen that it has an advantage compared to a commercialized PVA electrolyte.

14 is an SEM photograph of a solid electrolyte prepared according to Experimental Examples 1-4 of the present application.

Referring to FIG. 14 , an SEM photograph of the solid electrolyte prepared according to Experimental Examples 1-4 described above was taken.

As can be seen from FIG. 14 , it can be confirmed that a plurality of pores are present inside, and it can be confirmed that the chitosan-bound bacterial cellulose fibers are provided in fibrillated form and have a diameter of 5 to 10 nm.

The measured pore size is about 20-200 nm, and it can be seen that the bacterial cellulose fibers bound with chitosan in the solid electrolyte form a network with high pores and high surface area, so that it can have high strength against swelling.

15 is a TGA and DSC analysis result of the solid electrolyte prepared according to Experimental Examples 1-4 of the present application.

Referring to FIG. 15 , TGA and DSC analysis were performed on the solid electrolyte prepared according to Experimental Examples 1-4 as described above while increasing the temperature under a condition of 5° C./min in a nitrogen atmosphere.

As can be seen from FIG. 15 , it can be confirmed that the solid electrolyte according to Experimental Examples 1-4 of the present application has stable thermal stability up to about 225°C. That is, it can be seen that the solid electrolyte prepared according to the embodiment of the present invention has high temperature stability.

16 to 19 are graphs of XPS analysis results of solid electrolytes and bacterial cellulose according to Experimental Examples 1-4 and 1-5 of the present application.

16 to 19 , XPS analysis was performed on the solid electrolyte and bacterial cellulose prepared according to Experimental Examples 1-4 and 1-5 described above. FIG. 17 is a C1s spectra, FIG. 18 is an N1s spectra, and FIG. 19 is an O1s spectra.

In Fig. 17, 284.5 eV, 285.9 eV, 288 eV, and 289.7 eV correspond to C=C, CN, CO, and C-OH, respectively, and in Fig. 18, 399.9 eV, 401.3 eV, and 402.5 eV are respectively pyrrolic, Corresponds to quaternary, and oxidized N.

As can be seen in FIGS. 16 to 19 , the solid electrolyte of Experimental Example 1-4 having chitosan-bound bacterial cellulose compared to the bacterial cellulose of Experimental Example 1-5 in which chitosan is omitted is pyrrolic in the N1s spectrum as a result of XPS analysis. , quaternary, and it can be confirmed that it has peak values corresponding to oxidized N.

20 is an ionic conductivity measurement result for explaining the basic resistance test result of the solid electrolyte prepared according to Experimental Examples 1-4 of the present application.

Referring to FIG. 20, after immersing the solid electrolyte, PVA film, and anion exchange membrane A201 membrane (Tokuyama) prepared according to the above-described Experimental Example 1-4 in 1M KOH solution at 100° C., the time for 2500 hours The ionic conductivity was measured. The picture inserted in FIG. 20 was taken of the solid electrolyte (30cm x 30cm, 5um) prepared according to Experimental Examples 1-4 of the present application.

As can be seen from FIG. 20 , it can be confirmed that the solid electrolyte according to Experimental Examples 1-4 of the present application has substantially no change in ionic conductivity. On the other hand, it can be seen that the ionic conductivity of the A201 membrane and the PVA film is rapidly reduced. That is, even if the solid electrolyte according to the embodiment of the present application is used in a basic environment, it can be confirmed that the ionic conductivity has long-term reliability without change.

21 is an XRD analysis result for explaining the basic resistance test result of the solid electrolyte prepared according to Experimental Examples 1-4 of the present application.

Referring to FIG. 21 , as described with reference to FIG. 20 , the solid electrolyte of Experimental Example 1-4 was immersed in a KOH solution, and then XRD analysis was performed.

As can be seen from FIG. 21 , it can be confirmed that there is no substantial crystallographic change in the solid electrolyte even after being immersed in the basic solution for a long time. That is, even when the solid electrolyte according to the embodiment of the present application is used in a basic environment, it can be confirmed that the solid electrolyte has long-term reliability without crystallographic change.

22 is a photograph for explaining the basic resistance test result of the solid electrolyte according to Experimental Examples 1-4 of the present application.

Referring to FIG. 22, as described with reference to FIG. 20, the solid electrolyte of Experimental Example 1-4 was immersed in a KOH solution, and then a photograph was taken.

As can be seen from FIG. 22 , it can be confirmed that there is no substantial change in the appearance of the solid electrolyte membrane even after being immersed in the basic solution for a long time. That is, even when the solid electrolyte according to the embodiment of the present application is used in a basic environment, it can be confirmed that the solid electrolyte has long-term reliability without external change.

23 is a stress-strain graph according to the moisture impregnation rate of the solid electrolyte according to Experimental Examples 1-4 of the present application.

Referring to FIG. 23 , the stress-strain analysis according to the moisture impregnation rate of the solid electrolytes (CBCs) prepared according to Experimental Examples 1-4 described above was performed at room temperature and 40% relative humidity. Stress-strain analysis was also performed on the A201 membrane (water impregnation rate of 44wt%) under the same conditions.

As can be seen in FIG. 23 , it can be confirmed that the strain value for the applied stress is changed according to the moisture impregnation rate. Specifically, it can be seen that the yield strength decreases as the water impregnation rate increases.

In particular, it can be seen that the solid electrolyte according to the experimental example of the present application has a remarkably high water impregnation rate and remarkably high mechanical properties compared to the commercially available A201 membrane.

24 is a graph showing the results of measuring ionic conductivity according to mechanical deformation of the solid electrolyte according to Experimental Examples 1-4 of the present application.

Referring to FIG. 24 , the ionic conductivity was measured while bending the solid electrolytes (CBCs) and the A201 membrane prepared according to Experimental Examples 1-4 described above from 0° to 180°, and the ionic conductivity was measured after crumpling or winding.

As can be seen from FIG. 24 , it can be confirmed that the solid electrolyte prepared according to Experimental Examples 1-4 of the present application has no substantial change in ionic conductivity despite various mechanical deformations. On the other hand, it can be seen that the commercially available A201 membrane has a decrease in ionic conductivity according to the number of bending, and a sharp decrease in ionic conductivity when crumpled or wound.

That is, it can be confirmed that the solid electrolyte according to the experimental example of the present application maintains stable performance without substantial change in ionic conductivity despite various mechanical deformations.

25 is a graph of measuring the storage modulus of the solid electrolyte according to Experimental Examples 1-4 of the present application.

Referring to FIG. 25 , the storage modulus was measured while changing the frequency at which an external force is applied to the solid electrolyte prepared according to Experimental Examples 1-4 described above. As can be seen from FIG. 25 , as the frequency increases, it can be seen that the storage elastic modulus of the solid electrolyte increases linearly.

26 is a photograph for explaining the mechanical stability of the solid electrolyte according to Experimental Examples 1-4 of the present application.

Referring to FIG. 26, after crumpling the solid electrolyte prepared according to Experimental Example 1-4 described above at room temperature (a, b, c in FIG. 26) and -20°C (d, e, f in FIG. 26), restoration Whether it was filmed As can be seen from FIG. 26 , it can be confirmed that, after crumpling, it is easily restored to a substantially original state at room temperature as well as at a low temperature. That is, it can be seen that the solid electrolyte according to Experimental Examples 1-4 of the present application is stably restored without substantial external change in various mechanical deformations at room temperature as well as in a low-temperature environment.

27 is a graph measuring various ion transfer rates of the solid electrolyte according to Experimental Examples 1-4 of the present application.

^{Referring to FIG. 27 , ion transfer rates for K +} , Zn ²⁺ , OH ⁻ , TFSI ⁻ , [Ch] ⁺ ions were calculated for the solid electrolyte prepared according to Experimental Examples 1-4. As shown in Figure 27, OH ^- it has been identified that has the highest transmission rate for the ion, OH ^- ions and then to it was confirmed to have high transmission rate for K ⁺ ion.

Specific ionic conductivity is shown in [Table 2] below.

Ion type Charge valence
(Z _i ) Ionic Conductivity
(m ² s ^-1 V ^-1 ) density
(M) move factor
(t _i ) K ⁺ One 6.88*10 ^-8 6 0.15 Zn ²⁺ 2 5.32*10 ^-8 0.2 0.014 OH ^- One 2.15*10 ^-7 6 0.75 TFSI ^- One 3.69*10 ^-8 0.4 0.006 [Ch] ⁺ One 7.56*10 ^-8 One 0.08

Preparation of a solid electrolyte according to Experimental Examples 2-1 to 2-5

A solid electrolyte was prepared in the same manner as in Experimental Example 1-4 described above, except that the ratio of the first composite fiber (oCBC) of Experimental Example 1-2 and the ratio of the second composite fiber (qCBC) of Experimental Example 1-3 were below. Solid electrolytes according to Experimental Examples 2-1 to 2-5 were prepared while controlling as shown in Table 3 of [Table 3].

division first composite fiber second composite fiber Experimental Example 2-1 10wt% 90wt% Experimental Example 2-2 30wt% 70wt% Experimental Example 2-3 50wt% 50wt% Experimental Example 2-4 70wt% 30wt% Experimental Example 2-5 90wt% 10wt%

28 is an XRD analysis result of solid electrolytes according to Experimental Examples 2-1 to 2-5 of the present application.

Referring to FIG. 28 , XRD analysis was performed on the solid electrolytes according to Experimental Examples 2-1 to 2-5 described above.

As can be seen in FIG. 28 , the solid electrolytes according to Experimental Examples 2-1 to 2-5 have peak values corresponding to (101) and (002) crystal planes, and the first composite fiber (oCBC) and the second composite fiber According to the ratio of the fiber (qCBC), the crystal structure is not substantially changed, but it can be seen that the 2θ value of the peak value corresponding to the (002) crystal plane slightly increases as the ratio of the second composite fiber increases.

29 illustrates measurements of ionic conductivity according to temperature of solid electrolytes according to Experimental Examples 2-1 to 2-5 of the present application.

Referring to FIG. 29 , the ionic conductivity of the solid electrolytes according to Experimental Examples 2-1 to 2-5 described above was measured according to temperature, and the ionic conductivity of the commercially available A201 membrane was measured and compared according to temperature. did.

As can be seen from FIG. 29 , as the temperature increased, the ionic conductivity of the solid electrolyte and the A201 membrane according to Experimental Examples 2-1 to 2-5 increased. In addition, it can be seen that the ionic conductivity of the solid electrolytes according to Experimental Examples 2-1 to 2-5 is significantly higher than that of the A201 membrane.

In addition, according to Experimental Example 2-3, the ionic conductivity of the solid electrolyte having the same ratio of the first composite fiber and the second composite fiber was determined in Experimental Example 2-1, Experimental Example 2-2, Experimental Example 2-4, and Experimental Example. It can be confirmed that it is significantly higher than the solid electrolytes according to Examples 2-5. As a result, controlling the proportion of the first composite fiber to be more than 30 wt% and less than 70 wt% and controlling the proportion of the second conjugate fiber to less than 70 wt% and more than 30 wt% is an efficient way to improve the ionic conductivity of OH ions It can be confirmed that

Preparation of a solid electrolyte according to Experimental Example 3-1 to Experimental Example 3-5

According to the above-described experimental example, a base composite fiber was prepared, but the base composite fiber having a different chitosan content was prepared by controlling the addition ratio of the chitosan derivative. Then, according to Experimental Examples 1-4 described above, a solid electrolyte was prepared using the base composite fibers having different chitosan contents.

Chitosan preparation according to Experimental Example 3-6

As a comparative example for the above-described Experimental Examples 3-1 to 3-5, pure chitosan was prepared.

The content of chitosan in the solid electrolyte according to Experimental Example 3-1 to Experimental Example 3-6 is shown in Table 4 below.

division proportion of chitosan Experimental Example 3-1 10wt% Experimental Example 3-2 30wt% Experimental Example 3-3 50wt% Experimental Example 3-4 70wt% Experimental Example 3-5 90wt% Experimental Example 3-6 100wt%

30 to 32 are XPS analysis results of solid electrolytes according to Experimental Examples 3-1 to 3-5 of the present application and bacterial cellulose according to Experimental Examples 1-5, and FIG. 33 is Experimental Example 3- of the present application. 1 to Experimental Example 3-5 is a graph analyzing the element ratio of the solid electrolyte and Experimental Example 1-5 according to Experimental Example 1-5, Figure 34 is a solid according to Experimental Example 3-1 to Experimental Example 3-5 of the present application It is a result of analyzing the composition ratio of C1s spectra of bacterial cellulose according to electrolyte and Experimental Example 1-5, and FIG. 35 is a solid electrolyte according to Experimental Examples 3-1 to 3-5 of the present application and Experimental Example 1-5 This is the result of analyzing the composition ratio of N1s spectra of bacterial cellulose.

30 to 35 , XPS analysis was performed on the solid electrolyte according to the above-described Experimental Examples 3-1 to 3-5, and the bacterial cellulose in which chitosan according to the above-described Experimental Example 1-5 was omitted, and , As shown in FIG. 33, the ratio of elements in the solid electrolyte was analyzed, the composition ratio of C1s spectra was analyzed as shown in FIG. 34, and the composition ratio of N1s spectra was analyzed as shown in FIG. 35 . 30 is a C1s spectrum, FIG. 31 is an O1s spectrum, and FIG. 32 is an N1s spectrum.

In the case of the solid electrolytes according to Experimental Examples 3-1 to 3-5, it can be confirmed that CN bonding is observed according to the bonding of chitosan and bacterial cellulose, compared to the bacterial cellulose of Experimental Example 1-5 in which chitosan is omitted. have.

In addition, as can be seen in FIGS. 30 and 34, as the ratio of chitosan increases from 0 to 50wt%, the ratio of CN increases, and as the ratio of chitosan increases from 50wt% to 90wt%, it can be seen that the CN ratio decreases. have. In other words, when the proportion of chitosan is more than 30 wt% and less than 70 wt%, it can be confirmed that the C-N ratio in the solid electrolyte is remarkably high.

In addition, as can be seen in FIGS. 32 and 35, the nitrogen peak was not detected in the bacterial cellulose of Experimental Examples 1-5 in which chitosan was omitted, and as the ratio of chitosan increased, the ratio of oxidized N was generally increased, but , it can be seen that the ratio of pyrrolic N increases as the ratio of chitosan increases from 0 to 50wt%, and decreases as the ratio of chitosan increases from 50wt% to 90wt%. In other words, when the proportion of chitosan is more than 30wt% and less than 70wt%, it can be confirmed that the ratio of pyrrolic N in the solid electrolyte is remarkably high.

In addition, as can be seen from FIG. 33, as the ratio of chitosan increases, the ratio of nitrogen increases, and according to Experimental Examples 3-5, when the ratio of chitosan is 90wt%, it was confirmed to have a nitrogen ratio of 6.63at%.

36 is an XRD analysis result of the solid electrolyte according to Experimental Examples 3-1 to 3-5 of the present application, chitosan according to Experimental Examples 3-6, and bacterial cellulose according to Experimental Examples 1-5 of the present application.

Referring to FIG. 36 , the solid electrolyte according to Experimental Example 3-1 to Experimental Example 3-5 described above, chitosan according to Experimental Example 3-6, and chitosan according to Experimental Example 1-5 were omitted in bacterial cellulose. XRD analysis was performed on the

As can be seen from FIG. 36, in the chitosan itself of Experimental Example 3-6, a specific peak was not observed, and the solid according to Experimental Example 3-1 to Experimental Example 3-6 compared to the bacterial cellulose of Experimental Example 1-5) It can be seen that the electrolyte has somewhat low crystallinity.

In addition, as the ratio of chitosan gradually increases, it can be confirmed that the crystallinity is reduced and has an amorphous phase like chitosan. In particular, when the ratio of chitosan is 70 wt% or more according to Experimental Example 3-4, the crystallinity is It can be seen that there is a sharp decline.

37 is a solid electrolyte according to Experimental Example 3-1 to Experimental Example 3-5 of the present application, chitosan according to Experimental Example 3-6, bacterial cellulose according to Experimental Example 1-5, and general according to Experimental Example 1-6 The ionic conductivity according to the temperature of bacterial cellulose was measured.

Referring to FIG. 37 , the solid electrolyte according to Experimental Example 3-1 to Experimental Example 3-5, chitosan according to Experimental Example 3-6, bacterial cellulose in which chitosan according to Experimental Example 1-5 is omitted, and Experimental Example 1- For general bacterial cellulose according to 6, the ionic conductivity was measured as a function of temperature.

As can be seen from Figure 37, as the temperature increases, the solid electrolyte of Experimental Examples 3-1 to 3-5, chitosan of Experimental Example 3-6, bacterial cellulose in which chitosan of Experimental Example 1-5 is omitted, and the experiment The ionic conductivity of the normal bacterial cellulose of Examples 1-6 was increased. In addition, it can be confirmed that the bacterial cellulose according to Experimental Example 1-5 of the present invention has a higher ionic conductivity compared to the general bacterial cellulose of Experimental Example 1-6 and chitosan of Experimental Example 3-6, Experimental Example 3 The ionic conductivity of the solid electrolytes according to -1 to Experimental Examples 3-5 was compared with the bacterial cellulose in which the chitosan of Experimental Example 1-5 was omitted, the general bacterial cellulose of Experimental Example 1-6, and the chitosan of Experimental Example 3-6 , it can be seen that it is remarkably high.

In addition, the ionic conductivity of the solid electrolyte having 50wt% chitosan according to Experimental Example 3-3 was the solid electrolyte according to Experimental Example 3-1, Experimental Example 3-2, Experimental Example 3-4, and Experimental Example 3-5. It can be seen that they are significantly higher than As a result, it can be confirmed that controlling the proportion of chitosan in the solid electrolyte to be more than 30 wt% and less than 70 wt% is an effective method for improving the ionic conductivity of OH ions.

38 is a solid electrolyte according to Experimental Example 3-1 to Experimental Example 3-5 of the present application, chitosan according to Experimental Example 3-6, bacterial cellulose according to Experimental Example 1-5, and general according to Experimental Example 1-6 The swelling ratio according to the temperature of bacterial cellulose was measured.

Referring to FIG. 38 , the solid electrolyte according to Experimental Example 3-1 to Experimental Example 3-5, chitosan according to Experimental Example 3-6, bacterial cellulose according to Experimental Example 1-5, and Experimental Example 1-6 For general bacterial cellulose according to the temperature, the swelling ratio was measured.

As can be seen in FIG. 38, as the temperature increases, the solid electrolyte according to Experimental Examples 3-1 to 3-5, chitosan of Experimental Example 3-6, bacterial cellulose in which chitosan of Experimental Example 1-5 is omitted, and The swelling ratio of normal bacterial cellulose of Experimental Examples 1-6 was increased. In addition, the bacterial cellulose according to Experimental Example 1-5 of the present application, as well as the general bacterial cellulose of Experimental Example 1-6, and chitosan of Experimental Example 3-6, Experimental Example 3-1, Experimental Example 3-2, Experiment It can be confirmed that the swelling ratio is low compared to Examples 3-4 and Experimental Examples 3-5.

In addition, the swelling ratio of the solid electrolyte having 50wt% chitosan according to Experimental Example 3-3, Experimental Example 3-1, Experimental Example 3-2, Experimental Example 3-4, and Experimental Example 3-5. Electrolytes, of course, can be confirmed to be significantly lower than the bacterial cellulose according to Experimental Examples 1-5 of the present application. As a result, it can be confirmed that controlling the proportion of chitosan in the solid electrolyte to be more than 30 wt% and less than 70 wt% is an effective way to reduce the swelling ratio.

39 is a solid electrolyte according to Experimental Example 3-1 to Experimental Example 3-5 of the present application, chitosan according to Experimental Example 3-6, bacterial cellulose according to Experimental Example 1-5, and general according to Experimental Example 1-6 The moisture impregnation rate according to the temperature of bacterial cellulose was measured.

Referring to FIG. 39 , the solid electrolyte according to Experimental Example 3-1 to Experimental Example 3-5 described above, chitosan according to Experimental Example 3-6, bacterial cellulose according to Experimental Example 1-5, and Experimental Example 1-6 The moisture impregnation rate was measured according to the temperature for general bacterial cellulose.

As can be seen from FIG. 39, as the temperature increases, the solid electrolyte according to Experimental Examples 3-1 to 3-5, chitosan of Experimental Example 3-6, and bacterial cellulose in which chitosan of Experimental Example 1-5 is omitted, experiment The water impregnation rate of the normal bacterial cellulose of Examples 1-6 was increased.

In the room temperature range, the moisture impregnation rate of the solid electrolyte having 50wt% chitosan according to Experimental Example 3-3 was, according to Experimental Example 3-1, Experimental Example 3-2, Experimental Example 3-4, and Experimental Example 3-5 As well as the solid electrolyte, it can be seen that the moisture impregnation rate is higher than that of the bacterial cellulose in which the chitosan of Experimental Examples 1-5 is omitted, the general bacterial cellulose of Experimental Examples 1-6, and the chitosan of Experimental Examples 3-6. As a result, it can be confirmed that controlling the proportion of chitosan in the solid electrolyte to be more than 30 wt% and less than 70 wt% is an effective method to improve the moisture impregnation rate.

40 is a graph for explaining a result of measuring the voltage of the solid electrolyte according to Experimental Examples 1-4 of the present application.

Referring to FIG. 40 , the solid electrolyte according to the above-described Experimental Example 1-4 was inserted between the zinc electrodes, and the voltage was measured at current density conditions of ^{5mAcm -2} , 10mAcm ^{-2 , and 20mAcm -2 , and in the same condition} Instead of the solid electrolyte according to Experimental Examples 1-4, an A201 membrane was inserted between the zinc electrodes to measure the voltage. The graph at the top of FIG. 40 shows voltage values at 999 cycles and 1000 cycles of successive cycles, and the picture at the bottom of FIG. 40 is an SEM picture of a zinc electrode after 1000 cycles.

As can be seen from FIG. 40 , when the A201 membrane was used, it did not operate after about 23 hours, but when the solid electrolyte according to Experimental Examples 1-4 of the present application was used, it was confirmed that the A201 membrane was stably operated up to 1000 times at a high current density. can

In addition, as can be seen from the SEM photograph below of FIG. 40 , even when a high-density current is applied for a long time, it can be confirmed that dendrites are not generated and stably driven.

41 is a graph for explaining the charge/discharge capacity of a metal-air battery including a solid electrolyte according to Experimental Examples 1-4 of the present application.

Referring to FIG. 41 , a metal-air battery was manufactured using the solid electrolyte according to Experimental Examples 1-4, a positive electrode having a compound structure of copper, phosphorus, and sulfur, and a patterned zinc negative electrode. Under the same conditions, a metal-air battery (Pt/C) was prepared using _{commercially available Pt/C and RuO 2} , instead of a compound structure of copper, phosphorus, and sulfur as an anode.

A positive electrode having a compound structure of copper, phosphorus, and sulfur was prepared by the following method.

Three suspensions of ethanol/ethylenediamine were prepared, dithiooxamide, tetradecylphosphonic acid/ifosfamide and copper chloride were added and stirred.

Then, the dithiooxamide solution and tetradecylphosphonic acid/ifosfamide were continuously and gradually injected into the copper chloride solution while stirring, and the mixture was stirred for 2 hours while adding ammonium hydroxide.

The resulting copper-dithiooxamide-tetradecylphosphonic acid-ifosfamide black suspension was refluxed at 120° C. for 6 hours, collected by centrifugation, washed with deionized water and ethanol, and dried in vacuo.

Then, the obtained copper-dithiooxamide-tetradecylphosphonic acid-ifosfamide precursor suspension was mixed with deionized water with Triton X-165 and sodium bisulfite in an ice bath. The reaction suspension was autoclaved and cooled to room temperature. The obtained black solid sponge was washed with deionized water and ethanol until the supernatant reached neutral pH.

The resulting product was transferred to a -70°C environment for 2 hours, immersed in liquid nitrogen, and freeze-dried under vacuum conditions to prepare a compound structure positive electrode material of copper, phosphorus and sulfur, positive electrode material (90wt%), super P carbon (5wt%), and PTFE (5wt%) was mixed with N-methyl-pyrrolidone containing 0.5wt% of Nafion solution to prepare a slurry. The slurry was coated on a stainless steel mesh and the solvent was evaporated. Thereafter, it was cut into a size of 6 cm x 1.5 cm and dried in a vacuum to prepare a positive electrode.

As can be seen in Figure 41, it can ^{be confirmed that it has excellent charge and discharge capacity under the conditions of 25mAcm -2} and 50mAcm ^-2 , when using the compound structure of copper, phosphorus, and sulfur prepared as described above, Pt / C and Compared with the case of using RuO ₂ , it can be confirmed that it has a significantly higher capacity.

42 is a graph of measuring voltage values according to the number of times of charging and discharging of a metal-air battery including a solid electrolyte according to Experimental Examples 1-4 of the present application.

^{Referring to FIG. 42 , 50 mAcm -2} for a metal-air battery using a solid electrolyte, a compound structure positive electrode of copper, phosphorus, and sulfur according to Experimental Example 1-4 described above with reference to FIG. 41, and a patterned zinc negative electrode A voltage value according to the number of times of charging and discharging was measured under conditions and 25mA ^{-2 conditions.}

As can be seen from FIG. 42 , it can be confirmed that the battery is stably driven for about 600 charge/discharge times. That is, it can be confirmed that the solid electrolyte prepared according to the above-described embodiment of the present invention can be stably used as a solid electrolyte of a metal-air battery.

43 is a graph for explaining a change in charge/discharge characteristics according to external temperature conditions of a metal-air battery including a solid electrolyte according to Experimental Examples 1-4 of the present application.

Referring to FIG. 43 , a metal-air battery using solid electrolytes (CBCs), a compound structure positive electrode of copper, phosphorus, and sulfur according to Experimental Example 1-4 described with reference to FIG. 41, and a patterned zinc negative electrode Changes in charge/discharge characteristics were measured while changing the external temperature from -20°C to 80°C. Figure 43 (b) is a measurement of the rate performance at a ^{current density of 25 mAcm -2.}

As can be seen from FIG. 43 , it can be seen that the voltage value increases as the temperature increases, and it has a low charge/discharge overpotential. That is, it can be confirmed that the secondary battery including the solid electrolyte according to Experimental Examples 1-4 of the present application can be stably driven in high temperature and low temperature environments.

44 is a view for explaining the capacity preservation characteristics according to the number of charge and discharge in a low-temperature and high-temperature environment of the metal-air battery including the solid electrolyte according to Experimental Examples 1-4 of the present application.

Referring to FIG. 44 , a metal-air battery using solid electrolytes (CBCs), a compound structure positive electrode of copper, phosphorus, and sulfur according to Experimental Example 1-4 described with reference to FIG. 41, and a patterned zinc negative electrode A charge/discharge cycle was performed under 25mAcm-2 conditions while controlling the external temperature to -20°C and 80°C. In FIG. 44, black indicates that the charge/discharge cycle was performed at -20°C, and in FIG. 38, red indicates that the charge/discharge cycle was performed at 80°C.

As can be seen from FIG. 44 , it can be confirmed that the high retention characteristics of about 94.5% are maintained and the stable operation is performed even after 1,500 charge/discharge cycles at high and low temperatures.

45 is a graph for explaining the charge/discharge characteristics according to the external temperature of the metal-air battery including the solid electrolyte according to Experimental Examples 1-4 of the present application.

Referring to FIG. 45 , the exterior of a metal-air battery using solid electrolytes (CBCs), a compound structure positive electrode of copper, phosphorus, and sulfur according to Experimental Example 1-4 described above with reference to FIG. 41, and a patterned zinc negative electrode While controlling the temperature to -20 °C, 25 °C, and 80 °C, the charge/discharge voltage was measured under 25mAcm-2 conditions, and a Nyquist plot was shown.

As can be seen from FIG. 45, as the temperature increases, a surface protection layer (SEI) having a safe and low interfacial resistance is formed (FIG. ℃) (Fig. 45 (a)), only a slight deterioration in properties is observed in a low-temperature environment, and it can be confirmed that it has a high discharge capacity characteristic of 1Ah or more at low temperature, room temperature, and high temperature.

46 is a graph for explaining a change in charge/discharge characteristics according to a charge/discharge cycle according to an external temperature of a metal-air battery including a solid electrolyte according to Experimental Examples 1-4 of the present application.

Referring to FIG. 46 , the exterior of a metal-air battery using solid electrolytes (CBCs), a compound structure positive electrode of copper, phosphorus, and sulfur according to Experimental Example 1-4 described with reference to FIG. 41, and a patterned zinc negative electrode While controlling the temperature to -20 °C and 80 °C, charging and discharging were performed 1,500 times for 200 hours at ^{25mAcm -2 condition.} Figure 46 (a) is the result of charging and discharging at -20 ℃ condition, Figure 46 (b) is the result of performing charging and discharging at 80 ℃.

As can be seen from Figure 46, the charging and discharging characteristics are slightly deteriorated in a low-temperature environment of -20 ℃, but it can be confirmed that it is stably driven for a long time, and it can be confirmed that it is stably driven for a long time even in a high-temperature environment of 80 ℃ .

47 is a block diagram of an electric vehicle according to an embodiment of the present invention.

Referring to FIG. 47 , an electric vehicle 1000 according to an embodiment of the present invention includes a motor 1010 , a transmission 1020 , an axle 1030 , a battery pack 1040 , a power control unit 1050 , and a charging unit 1060 . may include at least one of

The motor 1010 may convert electrical energy of the battery pack 1040 into kinetic energy. The motor 1010 may provide the converted kinetic energy to the axle 1030 through the transmission 1020 . The motor 1010 may include a single motor or a plurality of motors. For example, when the motor 1010 includes a plurality of motors, the motor 1010 may include a front wheel motor that supplies kinetic energy to a front axle and a rear wheel motor that supplies kinetic energy to a rear axle.

The transmission 1020 may be located between the motor 1010 and the axle 1030, and may provide the axle 1030 by shifting the kinetic energy from the motor 1010 to suit the driving environment desired by the driver. have.

The battery pack 1040 may store electrical energy from the charging unit 1060 , and may provide the stored electrical energy to the motor 1010 . The battery pack 1040 may supply electric energy directly to the motor 1010 , or may supply electric energy through the power control unit 1050 .

In this case, the battery pack 1040 may include at least one battery cell. In addition, the battery cell may include, but is not limited to, the metal-air secondary battery including the solid electrolyte according to the embodiment of the present invention described above, and may include secondary batteries of various types. Meanwhile, the battery cell may be a term referring to individual batteries, and the battery pack may refer to a battery cell assembly in which individual battery cells are interconnected to have a desired voltage and/or capacity.

The power controller 1050 may control the battery pack 1040 . In other words, the power control unit 1050 may control the power from the battery pack 1040 to the motor 1010 to have a required voltage, current, waveform, and the like. To this end, the power control unit 1050 may include at least one of a passive power device and an active power device.

The charging unit 1060 may receive power from the external power source 1070 illustrated in FIG. 43 and provide it to the battery pack 1040 . The charging unit 1060 may control the overall charging state. For example, the charging unit 1060 may control charging on/off and charging speed.

As mentioned above, although the present invention has been described in detail using preferred embodiments, the scope of the present invention is not limited to specific embodiments and should be construed according to the appended claims. In addition, those skilled in the art should understand that many modifications and variations are possible without departing from the scope of the present invention.

100: solid electrolyte
110: base composite fiber
110a: first composite fiber
110b: second composite fiber
112: to cellulose
114: chitosan
116: first functional group
200: cathode
300: positive electrode

Claims (14)

a membrane comprising cellulose; and
A solid electrolyte bound to the cellulose of the membrane and comprising greater than 30 wt % and less than 70 wt % chitosan.
According to claim 1,
The chitosan is a solid electrolyte comprising 50 wt%.
According to claim 1,
When the chitosan is 50wt%, the XPS analysis result, the solid electrolyte comprising a ratio of CN bonds in the C1s spectrum has a maximum value.
According to claim 1,
The cellulose is a solid electrolyte comprising bacterial cellulose.
According to claim 1,
According to the ratio of the chitosan, crystallinity, ionic conductivity and swelling ratio comprising a controlled solid electrolyte.
6. The method of claim 5,
As the proportion of the chitosan increases, the solid electrolyte comprising a gradual decrease in crystallinity.
preparing a chitosan derivative;
From the chitosan derivative, generating chitosan bound to cellulose; and
Method for producing a solid electrolyte comprising the step of preparing a solid electrolyte using the cellulose to which the chitosan is bound.
8. The method of claim 7,
According to the ratio of the chitosan derivative, a method for producing a solid electrolyte comprising controlling crystallinity, ionic conductivity, and swelling ratio.
8. The method of claim 7,
The cellulose is a method for producing a solid electrolyte comprising bacterial cellulose.
10. The method of claim 9,
The step of generating the chitosan bound to the cellulose,
preparing a culture medium having the chitosan derivative; and
A method for producing a solid electrolyte comprising the step of injecting and culturing a bacterial strain in the culture medium.
8. The method of claim 7,
The method of manufacturing a solid electrolyte further comprising the step of preparing a first composite fiber by oxidizing the surface of the cellulose to which the chitosan is bound using an oxidizing agent.
8. The method of claim 7,
The method of manufacturing a solid electrolyte further comprising: binding bromine to the surface of the cellulose to which the chitosan is bound, and preparing a second composite fiber by substituting a first functional group containing nitrogen with bromine.
8. The method of claim 7,
oxidizing the surface of the cellulose to which the chitosan is bound using an oxidizing agent to prepare a first composite fiber;
preparing a second composite fiber by binding bromine to the surface of the cellulose to which the chitosan is bonded, and substituting a first functional group containing nitrogen with bromine; and
The method of manufacturing a solid electrolyte further comprising the step of crosslinking the first composite fiber and the second composite fiber.
Comprising a base composite fiber comprising chitosan and bacterial cellulose combined with the chitosan,
a first intermediate product in which the base composite fibers are dispersed in a first solvent;
A second intermediate product in which the surface of the oxidized base composite fiber is dispersed in a second solvent;
a third intermediate product in which the base composite fiber surface-bonded with bromine is dispersed in a third solvent, or
An intermediate product of a solid electrolyte comprising at least one of a fourth intermediate product in which the base conjugate fiber bonded to a first functional group having a quaternary N on its surface is dispersed in a fourth solvent.

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