KR20170121693A - Fibrous electrode structure with integrated separator, fibrous battery including the same, and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a membrane-integrated fibrous electrode structure, a fibrous battery including the same, and a method for manufacturing the fibrous electrode structure. The fibrous electrode structure includes: a conductive fiber including a carbon component; an active material layer covering the outer surface of the conductive fiber; and a membrane formed on the active material layer. As such, the present invention is capable of improving an interfacing property between a membrane and an active material and between the active material and a conductive fiber by coating the active material with the membrane and then drying the material. The membrane-integrated fibrous electrode structure is capable of improving an interfacing property while achieving high energy density.

Description

TECHNICAL FIELD [0001] The present invention relates to a separator-integrated fibrous electrode structure, a fibrous cell comprising the fibrous electrode structure, and a fabrication method of the fibrous electrode structure including a fibrous electrode structure including an integrated separator,

An active material layer covering the outer surface of the conductive fiber, and a separator formed on the active material layer, a fibrous electrode including the separator, a fibrous cell comprising the separator, and a method for manufacturing the fibrous electrode structure .

With the advent of new applications such as wellness-oriented healthcare, telemedicine-based medical care, state-of-the-art military systems, and portable smart electronics devices, demand for wearable smart electronic devices is increasing. Such a wearable electronic device is realized by being integrated with a wearable energy storage device capable of driving the same, but development of a wearable battery is delayed, while electronic devices such as smart glass and sensors are already in the product development stage. At present, the wearable device is a flexible and attachable step, and it goes far to a fabric type device which is a high dimensional form of fiberization or fiber, so that a real wearable device can be realized.

On the other hand, fabric batteries are widely applicable to smart wearable devices such as wearable electronic devices such as smart glass and portable electronic devices as wearable energy storage devices capable of driving wearable / portable devices. Unlike conventional battery research, which focuses on conventional electrochemical performance, wearable fabric batteries are required to develop customized technologies as various indexes of batteries are required. Wearable fabric batteries have focused on achieving safety and high energy density with physical flexibility (bending), stretching - (stretchable).

In the case of the cable type developed with the conventional fabric battery, since the positive and negative electrodes are formed on one cable wire and the contact area thereof is limited, it is difficult to achieve high energy density. Also, the use of a metal cable was heavy, and drapeability as a fiber was poor. Also, a cathode and anode fiber based wearable battery in which an active material is coated on a CNT sheet and a twisted electrode is formed in a fiber form has been reported. However, expensive equipment is used in the synthesis of a CNT sheet, resulting in a process cost. As shown in FIG. 2, the fiber-type battery was fabricated by winding the anode fiber and the anode fiber at regular intervals, but the distance between the two electrodes was too large to increase the energy density.

Therefore, it is required to develop a fibrous electrode having improved adhesion by interfacial control between each material while achieving high energy density.

One aspect of the present invention is to provide a separator-integrated fibrous electrode structure capable of realizing high energy density and improved interfacial characteristics.

Another aspect of the present invention is to provide a fibrous battery including the separator-integrated fibrous electrode structure.

Another aspect of the present invention is to provide a method for producing the separator-integrated fibrous electrode structure.

In one aspect of the invention,

A conductive fiber comprising a carbon component;

An active material layer covering an outer surface of the conductive fiber; And

A separator covering the outer surface of the active material layer;

Wherein the separator-integrated fibrous electrode structure is provided.

In another aspect of the present invention,

A bioadhesive is introduced into at least one of the conductive fiber and the active material layer, between the active material layer and the separator, and inside the active material layer,

The bioadhesive comprises a fibrous electrode structure comprising a phage displaying a peptide capable of binding to a carbon material.

According to one embodiment, the phage may be a phage that has been genetically engineered to have binding capacity for the carbonaceous material.

According to one embodiment, the bioadhesive may be in the form of a sheet.

According to one embodiment, the internal structure of the sheet may have a percolated network structure.

According to one embodiment, the grip can be a filamentous grip.

In another aspect of the present invention, there is provided a fibrous battery including the above-described separator integral fibrous electrode structure.

According to one embodiment, the fibrous cell comprises a bipolar electrode comprising at least one fibrous electrode structure; And a cathode electrode comprising at least one fibrous electrode structure, wherein the anode electrode and the cathode electrode may be twisted, overlapped or woven together.

In another aspect of the present invention,

Providing a conductive fiber comprising a carbonaceous material;

Forming an active material layer on an outer surface of the conductive fiber; And

Forming a separator on an outer surface of the active material layer;

And a method of manufacturing a separator-integrated fibrous electrode structure.

Also,

Further comprising the step of introducing a bioadhesive comprising a phage displaying a peptide capable of binding to a carbon material, at least one of the conductive fiber and the active material layer, between the active material layer and the separator, and / or inside the active material layer A method of manufacturing a fibrous electrode structure is provided.

According to one embodiment, the step of forming the active material layer and the step of forming the separation membrane may be a continuous process in which the conductive fibers are continuously passed through the active material-containing vessel and the separation membrane-containing vessel.

According to one embodiment, the method may further include a step of pressing after forming the fibrous separator.

The separator integrated fibrous electrode structure can realize a high energy density and improve the interfacial characteristics.

The separator-integrated fibrous electrode structure can be continuously coated on the conductive fibers by dispersing the active material in a solvent.

In addition, the method of manufacturing the fibrous electrode structure can improve the interface between the conductive fiber and the active material, and the interface between the active material and the separator by coating the separator on the active material and drying the separator.

1 is a conceptual diagram of a separator-integrated fibrous electrode structure according to one embodiment and a fibrous cell including the same.
2 is a schematic view of a conventional fibrous cell.
FIG. 3 is a schematic view illustrating a coating process of the carbon fiber-active material-separator according to one embodiment.
4 is a conceptual diagram of a pressing process according to one embodiment.
5 is a conceptual diagram of a fibrous cell comprising a pressing process according to one embodiment.
FIG. 6 is a graph showing the results of analysis of adhesion characteristics of a carbon nanotube film on a substrate by applying a bioadhesive according to one embodiment.
7 is a SEM image of a fibrous electrode structure coated with an active material according to an embodiment of the present invention.
FIG. 8 is a graph showing charge / discharge characteristics of a bipolar electrode structure using a bio-adhesive according to one embodiment. FIG.
9 is a graph showing charge / discharge characteristics of a bipolar electrode structure using a bioadhesive according to an embodiment after bending.
10 is a graph showing charge / discharge characteristics of a negative electrode fibrous electrode structure using a bioadhesive according to one embodiment.
FIG. 11 is a graph showing the charging / discharging characteristics of a full-cell separator integrated type cell according to one embodiment.
FIG. 12 is a graph showing voltage holding ratios at 1000 bending of a separator integrated type full-cell according to one embodiment. FIG.
FIG. 13A is a photograph of a bending evaluation of a full-cell full-cell using a bioadhesive according to an embodiment, and FIG. 13B is a graph showing charging / discharging characteristics of the entire fibrous cell after bending.
FIGS. 14A and 14B are SEM images showing an effect of improving the interfacial characteristics of a fibrous electrode structure coated with a cathode active material using a bioadhesive agent according to one embodiment. FIG.
15A and 15B are SEM images showing cross sections of the fibrous electrode structure before and after the pressing according to an embodiment, respectively.
16A and 16B are graphs showing characteristics of charging / discharging improvement of the positive electrode structure according to one embodiment of the present invention.

Hereinafter, a fibrous electrode structure according to one embodiment, a fibrous cell including the same, and a method of manufacturing the same will be described in detail with reference to the drawings.

The fibrous electrode structure according to one embodiment comprises a fibrous electrode structure,

A conductive fiber comprising a carbon component; An active material layer covering an outer surface of the conductive fiber; And a separation layer covering the outer surface of the active material layer.

Also, a bioadhesive is introduced into at least one of the conductive fiber and the active material layer, between the active material layer and the separator, and / or inside the active material layer, and the bioadhesive includes a phage displaying a peptide capable of binding to a carbon material .

FIG. 1 is a conceptual diagram of a separator-integrated fibrous electrode structure and a fibrous cell including the separator according to an embodiment. When a separator is coated on a conductive fiber-active material layer, a monolith electrode thread of each of the positive electrode and the negative electrode is It is possible to have a direct contact effect without concern for short circuits. In such a monolithic separator structure, direct contact between the anode chamber and the cathode chamber results in a narrow gap between the electrodes, which is advantageous for high energy density.

1, the bio-adhesive in the fibrous electrode structure according to an embodiment is introduced between the conductive fiber and the active material layer as an example.

Referring to FIGS. 4 and 15, the fibrous electrode may be in a flat shape through a pressing process.

The conductive fiber containing the carbon component serves as a current collector in the core of the fibrous electrode structure and may be, for example, a conductive carbon fiber, a carbon component-containing conductive polymer fiber, or a carbon component-containing conductive metal fiber. When the conductive fiber is a conductive polymer fiber or a conductive metal fiber, the surface of the fiber may have a binding ability to a carbon material or a phage displaying a peptide having binding ability to a carbon material.

The conductive metal fiber may be, for example, SUS fiber, Al, Cu, or Ni fiber. In addition, the above-mentioned "conductive polymer" is a conductive polymer capable of conducting electricity, and is a molecule capable of forming a fiber structure. The conductive polymer is a molecule that is conductive and capable of producing fibers. For example, the conductive polymer may be dissolved in a solvent and then subjected to electrospinning, wet spinning, conjugate spinning, melt blown spinning ) Or flash spinning, and the like. The term " fiber " The conductive polymer may be selected from the group consisting of polyacetylene, polypyrrole, polythiophene, polyethylene dioxythiophene, polyphenylene vinylene, polyphenylene, polysilane, polyfluorene, polyaniline and polysulfuronitrile .

The active material layer includes an active material.

In one embodiment, the active material layer may comprise a composite of an active material and a graphitic material. The active material has a nanometer size, and the strain due to external physical deformation can be minimized through a hybrid with a two-dimensional flexible material such as graphene.

When the active material layer is a positive electrode, for example, LiCoO ₂ , LiNiO ₂ , LiMn ₂ O ₄ , LiCoPO ₄ , LiFePO ₄ , LiMnPO _{4 ,} LiNi _x Mn _y Co _z O ₂ (Where, 0≤x≤1, 0≤y≤1, 0≤z≤1, only x + y + z = 1) , FeF 3, FeOF, BiF 3, BiOF, polyimide (PI), quinones (for example, benzoquinone, pyromellitic diimide, and the like. If the active material layer is a cathode, for example, _{carbon, Si, SiO 2, SnO 2} , Co 3 O 4, Li 4 Ti 5 O 12 (LTO), MoS 2, activated carbon, graphene, doped graphene, carbon Nanotubes, and modified carbon nanotubes.

The electrolyte layer may comprise a gel electrolyte, a solid electrolyte, a liquid electrolyte or a combination thereof. Further, the electrolyte layer may be one in which a lithium salt is dissolved. The gel electrolyte may comprise, for example, PEO, PVdF, PVdF-HFP, PMMA, PAN, PVAC or combinations thereof. The solid electrolyte may include, for example, PEO, PVdF, polypropylene oxide (PPO), polyethylene imine (PEI), polyethylene sulphide (PES), polyvinyl acetate (PVAc), or combinations thereof. The lithium salt, for example, _{LiCl, LiBr, LiI, LiClO 4} , LiBF 4, LiB 10 Cl 10, LiPF 6, LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiAlCl 4, CH 3 SO 3 Li, CF ₃ SO ₃ Li, (CF ₃ SO ₂ ) ₂ NLi, chloroborane lithium, lower aliphatic carboxylate lithium, lithium tetraphenylborate, or a combination thereof. In addition, the electrolyte layer may further include an additive for controlling physical strain characteristics.

The separator may be replaced with the gel electrolyte or the solid electrolyte layer. The gel electrolyte or solid electrolyte layer itself can function as a free-standing membrane.

Examples of the liquid electrolyte include ethylene carbonate (EC): dimethyl carbonate (DMC), diethylene carbonate (DEC), EC-DEC, EC-DEC-DMC, propylene carbonate (PC), butylene carbonate , Dimethyl ether (DME), 1,2-dimethoxyethane, diethylene glycol dimethylene ether (DEGDME), acetonitrile, dimethyl sulfoxide (DMSO), methyl acetate (MA), methyl formate (N-methyl-2-pyrrolidinone), tetrahydrofuran (THF), N-methyl-2-pyrrolidinone, gamma-butylolactone, 2- methyltetrahydrofuran, dimethylsulfoxide, , Methyl acetate, triester phosphate, trimethoxymethane, dioxolane derivatives, sulfolane, methylsulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, ether , Methyl pyrophosphate, ethyl propionate, or combinations thereof .

The liquid electrolyte may include, for example, ethylene carbonate (EC): dimethyl carbonate (DMC), EC-DEC, EC-DEC-DMC or a combination thereof.

The bioadhesive may include a phage displaying a peptide capable of binding to a carbon material, and a carbon material.

Bonding with an electrochemical device (for example, a conductive fiber) using the bioadhesive is carried out between an epitaxial protein of the phage or an electrochemical device (for example, a conductive fiber) containing a carbon material and a peptide displayed on the fragment Lt; / RTI >

In another embodiment, a phage displaying a peptide capable of binding to a carbon material is specifically bound to a carbon material, so that it is possible to impart additional functions by a non-destructive method that does not impair the properties of these carbon materials, It is introduced into the interface of each constitution of the device, and the adhesion property or the interface property can be improved. For example, when the bioadhesive is introduced between the conductive fiber and the active material layer, the active material may be further adhered to the conductive fiber to thickly coat the active material. For example, when the bioadhesive is introduced into the active material layer, the interface peeling of the active material layer can be prevented. As described above, the bioadhesive may improve the adhesion between the conductive fiber and the active material layer of the fibrous electrode structure, between the active material layer and the separator, or to improve the interfacial characteristics of the active material layer.

The carbon material may comprise a graphitic material. As used herein, the term "graphitic materials " refers to a material having a graphitic surface on which carbon atoms are arranged in a hexagonal shape. If the material contains a graphitic surface, , Chemical properties, and structural properties of the composition. The graphitic material may be, for example, a graphene sheet, a highly oriented pyrolytic graphite (HOPG) sheet, a single-walled carbon nanotube, a double-walled carbon nanotube, nanotubes, carbon nanotubes such as multi-walled carbon nanotubes, fullerenes, or combinations thereof. The graphitic material may be a metallic, semiconductive or hybrid material, for example, a mixture of a graphene sheet and a single-walled carbon nanotube.

The peptide binding to the carbon material may be a substance that binds non-destructively with the carbon material. The peptides may be screened through a library of peptides, for example, by phage display techniques. The phage display technique allows the peptide to be displayed on the outside of the phage genetically linked, inserted, or substituted into the phage's coat protein, and the peptide can be encoded by the genetic information in the virion. By screening the proteins of various variants by the displayed proteins and the DNA encoding them, they can be screened and called "biopanning". Briefly, the bio-panning technique involves reacting a displayed phage with a fixed target (e.g., a carbonaceous material), washing the unbound phage, and then destroying the binding interaction between the phage and the target, And a method for elution of a phage bound to the phage. A portion of the eluted phage can be left for DNA sequencing and peptide identification, and the remainder can be amplified in vivo and a sub-library for the next round can be generated and repeated.

The term " phage "or" bacteriophage "is used interchangeably and can refer to a virus that infects bacteria and replicates in bacteria. Phage or bacteriophage may be used to display peptides that selectively or specifically bind to the carbonaceous material. The phage may be one that has been genetically engineered such that a peptide capable of binding to the carbon material is displayed on the phage coat protein or fragment thereof. The term "genetic engineering" or "genetically engineered" in the context of the present invention is intended to encompass one or more genetic modifications to the phage to display peptides having avidity in the carbonaceous material, May refer to the act of introducing a genetic modification or a phage created thereby. The genetic modification includes introducing a foreign gene encoding the peptide. The phage may be a filamentous phage, for example, M13 phage, F1 phage, Fd phage, If1 phage, Ike phage, Zj / Z phage, Ff phage, Xf phage, Pf1 phage, or Pf3 It can be a phage.

The term "phage display" or "phage displayed on a peptide" in the present invention may refer to the display of a functional foreign peptide or protein on the surface of a phage or phagemid particle. The surface of the phage may refer to the envelope protein of the phage or a fragment thereof.

The functional foreign peptide may be present in association with the N-terminus of the envelope protein of the phage, or inserted into the envelope protein. Also, the phage may be linked to the N-terminus of the phage coat protein of the phage, or the C-terminus of the functional peptide may be inserted between consecutive amino acid sequences of the phage coat protein of the phage or the consecutive amino acid sequence of the coat protein Which is a part of the phage. The position of the consecutive amino acid sequence in which the peptide is inserted or substituted in the coat protein is selected from the N-terminal of the coat protein at positions 1 to 50, positions 1 to 40, positions 1 to 30, positions 1 to 20, Position 10, position 2 to 8, position 2 to 4, position 2 to 3, position 3 to 4, or position 2. In addition, the envelope protein may be p3, p6, p8 or p9.

The peptide having specific binding ability to the carbon material is X ₂ SX ₁ AAX ₂ X ₃ P (SEQ ID NO: 1), X ₂ X ₂ PX ₃ X ₂ AX ₃ P (SEQ ID NO: 2), SX ₁ AAX ₂ X ₃ P (SEQ ID NO: 3) and X ₂ PX ₃ X ₂ AX ₃ P (SEQ ID NO: 4). In addition, the peptide or peptide set may be a peptide or a peptide set comprising at least one selected from the group consisting of the amino acid sequences of SEQ ID NOS: 5 to 8. The N-terminal or C-terminal end of the amino acid sequence of the peptide or peptide set may be linked to the consecutive amino acid sequence of the phage coat protein. Thus, for example, the set of peptides or peptides may comprise a sequence of 5 to 60 amino acids, 7 to 55 amino acids, 7 to 40 amino acids, 7 to 30 amino acids, 7 to 20 amino acids, 7 to 10 amino acid sequences.

The peptide may be one which comprises a conservative substitution of the disclosed peptide. As used herein, the term "conservative substitution" refers to the replacement of a first amino acid residue with a second, different amino acid residue without altering the biophysical properties of the protein or peptide, Amino acid residues may mean having a side chain with similar biophysical properties. Similar biophysical properties may include the ability to provide or accept hydrophobic, charge, polar, or hydrogen bonds. Examples of conservative substitutions include, but are not limited to, basic amino acids (arginine, lysine and histidine), acidic amino acids (glutamic and aspartic acid), polar amino acids (glutamine and asparagine), hydrophobic amino acids (leucine, isoleucine, valine and methionine), hydrophilic amino acids Alanine, serine and threonine), aromatic amino acids (phenylalanine, tryptophan, tyrosine and histidine), and small amino acids (glycine, alanine, serine and threonine). In general, amino acid substitutions that do not alter specific activity are known in the art. Thus, for example, in the peptide X ₁ can be W, Y, F or H, X ₂ can be D, E, N or Q, and X ₃ can be I, L or V.

Thus, for example, if the C-terminus of any of SEQ ID NO: 1 to SEQ ID NO: 8 is not the trunk of the M13 phage, i.e., the end of the phage, but the 50 amino acid length p8 (SEQ ID NO: 19). For example, when the peptide of any one of SEQ ID NOS: 1 to 8 is an amino acid sequence (i.e., EGD) at position 2 to 4 of the coat protein p8 of M13 phage, position 2 to 3, position 3 to 4 Position, or in place of the amino acid sequence of position 2.

In other embodiments, the phage can be directionally arranged on the surface of the carbonaceous material using the structure of the filamentary form of the phage itself. For example, they may be aligned in a specific direction, in which case the binding force between the peptide located on the coat protein of the phage and the surface of the carbonaceous material may increase and be aligned on the same day. A phage aligned in a day can impart anisotropic functionalization to the surface of the carbonaceous material, which is different from isotropic or random functionalization only when the peptide alone is used. In addition to the above ordered alignment structure, a structure having a specific directionality such as a smectic structure, a layered structure such as a nematic structure, a spiral structure, and a lattice structure can be formed, Various functions can be given on the surface.

In another embodiment, the bioadhesive may be in the form of a sheet. As used herein, the term "sheet" may refer to a material having a certain width and thickness, and may be understood to include, for example, a film, web, membrane, or composite structure thereof. Area of the sheet, for example, from 0.0001 to 1000 cm ^2, from 0.0001 to 100 cm ^2, or from 1 to 20 cm ² may be, the thickness is, for example, 20 to 400 nm, 40 to 200, or 40 to 100 nm. The internal structure of the sheet may also be a percolated network structure. As used herein, the term " percolated network "may refer to a lattice structure consisting of randomly conducting or non-conducting connections.

The bioadhesive facilitates coating of the active material on the conductive fibers, prevents peeling of the active material at the interface of each layer, improves adhesion between the active material particles, and improves performance stability by external deformation of the fabric battery It is effective.

Accordingly, the fibrous electrode structure is improved in interfacial characteristics by introducing a bio-adhesive having a one-dimensional wire structure at the interface between the conductive fiber, the active material, the active material, the separator, and the active material particles in the active material layer, Is prevented.

According to one embodiment, the fibrous electrode structure is membrane-integrated. The separator may be a polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), microporous polytetrafluoroethylene, microporous polyethylene oxide, microporous polyester, microporous polyethylene, microporous polypropylene , A microporous ethylene-propylene copolymer, a microporous two-layered polypropylene / polyethylene, and a microporous three-layered polypropylene / polyethylene / polypropylene membrane. Also, a separation membrane coated with an aramid resin or a separation membrane coated with a resin including a polyamideimide and an alumina filler may be used as the separation membrane. By coating the separator on the conductive fiber-active material layer, a monolith electrode thread of each of the positive electrode and the negative electrode can be formed, so that there is an effect that direct contact is possible without concern for short circuit. Further, in such a structure, the distance between the electrodes can be narrowed by direct contact between the anode chamber and the cathode chamber, and a high linear energy density can be achieved by the multi-weaving method.

In addition, in the case of a separator-integrated fibrous electrode, physical contact between the conductive fibers and the active material and between the active material and the separator is improved in the process of coating and drying the separator on the active material.

The separator integral fibrous electrode may be further flattened by a pressing process. In the case of the flat shape, the contact property between the electrode and the active material is improved and a high energy density can be achieved. In addition, a flat yarn can be stacked on a plurality of cathodes and anodes to achieve a high linear energy density.

A fibrous cell according to another aspect comprises the fibrous electrode structure described above.

1, the fibrous battery includes a cathode electrode including at least one separator integral fibrous electrode structure, and a cathode electrode including at least one separator integral fibrous electrode structure, wherein the anode electrode and the cathode electrode May be twisted or woven together.

5, the fibrous battery includes a cathode electrode including at least one separator integral fibrous electrode structure, and a cathode electrode including at least one separator integral fibrous electrode structure, wherein the plurality of cathodes and the plurality of A positive electrode may be stacked to form a battery. In this case, there is an effect of increasing the linear energy density of the fibrous electrode.

The fibrous electrode structure is as described above.

The fibrous cell may have one anode electrode and one cathode electrode as one unit cell, and the plurality of unit cells may be twisted together to form a battery, and a plurality of cathodes and a plurality of anode electrodes may be twined to form a battery You may.

In one embodiment, the fibrous cell has a thin film type separation membrane coated on the surface of the conductive fiber-active material layer structure to enable direct contact between the anode electrode and the cathode electrode, thereby achieving high energy density.

The fibrous battery may be a secondary battery, for example, a lithium secondary battery. The constitution of the active material layer, the electrolyte layer, and the separator for constituting the lithium secondary battery is as described above.

Another aspect provides a method of manufacturing the fibrous electrode structure.

The method for fabricating the fibrous electrode structure includes the steps of: providing a conductive fiber containing a carbon component; Forming an active material layer on an outer surface of the conductive fiber; And forming a separation layer on an outer surface of the active material layer.

In one embodiment, a bioadhesive comprising a phage displaying a peptide capable of binding to a carbon material is provided on at least one of the conductive fiber and the active material layer, between the active material layer and the separator, and / or inside the active material layer And a step of introducing the data.

In one embodiment, when introducing the bioadhesive between the conductive fiber and the active material layer, the outer surface of the conductive fiber may be coated with a solution in which the bioadhesive is dispersed in a solvent. The coating can be any known coating method.

In another embodiment, when introducing the bioadhesive into the active material layer, the bioadhesive may be dispersed together when the active material is dispersed in a solvent to prepare a composition for forming the active material layer.

3, the step of forming the active material layer and the step of forming the separator may be a continuous process in which the conductive fibers are continuously passed through the active material-containing container and the electrolyte-containing container.

According to one embodiment, as shown in FIGS. 4 and 5, the method may further include a step of pressing after the step of forming the separation membrane. Through this process, it is possible to stack a plurality of fibrous electrodes.

According to the method for producing a fibrous electrode structure according to one embodiment, the active material can be dispersed in a solvent to continuously coat the conductive fibers.

EXAMPLES The following examples and comparative examples illustrate exemplary embodiments in more detail. It should be noted, however, that the examples and the comparative examples are intended to illustrate technical ideas and are not intended to limit the scope of the present invention.

Example  1. Fabrication of bio-adhesives for electrochemical devices and their adhesion and analysis of their ability to improve surface activity

1.1. Bio-adhesives (carbon materials Ability to bind  (A phage displaying a peptide having

(P8GB # 5), SWAADIP (SEQ ID NO: 7) displaying the phage (P8GB # 1), DNPIQAVP (SEQ ID NO: 6) displaying the DSWAADIP (SEQ ID NO: 5) , And NPIQAVP (SEQ ID NO: 8) were displayed in the following manner.

For the site-directed mutation of C in G1381 base pair of the M13KE vector (NEB, product # N0316S) (SEQ ID NO: 9), oligonucleotides of SEQ ID NOs: 10 and 11 Were used to construct the M13HK vector. The prepared M13HK vector was double-digested using restriction enzymes BspHI (NEB, product # R0517S) and BamHI restriction enzyme (NEB, product # R3136T), and was then digested with antarctic phosphatase Lt; / RTI > The dephosphorylated vector was incubated with double-cut DNA duplex at 16 overnight. The product was then purified and concentrated. Electrocompetent cells (XL-1 Blue, Stratagene) were transformed by electroporation into 2 μl of concentrated, coupled vector solution at 18 kV / cml and a total of 5 transformations were performed for library construction Respectively. Subsequently, the transformed cells were cultured for 60 minutes, and the fraction of the multiple transformants was transformed with X-gal / isopropyl-beta-D-1-thiogalactopyranoside (IPTG) / tetracycline (Tet) ≪ / RTI > to determine the library ' s diversity. Remaining cells were amplified in shaking incubator for 8 hours. Oligonucleotides of SEQ ID NOS: 12 and 13 were used to construct the phage display p8 peptide library.

The base sequence of the phage display p8 peptide library prepared according to one embodiment has 4.8 x 10 ⁷ pfu (plaque form unit) kinds of diversity and has a copy number of about 1.3 × 10 ⁵ per each sequence .

Then, a highly ordered pyrolytic graphite (HOPG) substrate (manufacturer: SPI product # 439HP-AB) having a diameter of 1 cm was prepared. At this time, a relatively large HOPG substrate having a grain size of 100 μm or less was used as the HOPG substrate. HOPG was stripped from the substrate prior to testing to obtain a fresh surface to minimize defects such as oxidation of the sample surface. Then, a phage display p8 peptide library of 4.8 × 10 ¹⁰ pfu (4.8 × 10 ⁷ kinds of replications, 1000 replications per each sequence) prepared above was prepared in a 100 μL Tris-Buffered Saline buffer solution HOPG surface for 1 hour at 100 rpm in a shaking incubator. After 1 hour, the solution was removed and then washed 10 times in TBS. The washed HOPG surface was reacted with Tris-HCl at pH 2.2 for 8 minutes as an acidic buffer to elute the non-selectively reacting peptide, and then the peptide was eluted in mid-log XL-1 blue E. coli. coli < / RTI > culture for 30 minutes. A portion of the eluted culture was left for DNA sequencing and peptide identification and the rest amplified to create a sub-library for the next round. The above procedure was repeated using the created sub-library. On the other hand, the plaques were analyzed for DNA to obtain p8 peptide sequences, and the obtained sequences were analyzed to obtain a phage displaying any of the peptides of SEQ ID NOS: 5 to 8 having strong binding ability to the carbon material.

1.2 Analysis of Improvement of Interfacial Adhesion by Bio Adhesive

The bioadhesive according to one embodiment is a bacterio phage having a one-dimensional linear structure, and has a characteristic of excellent adhesion to carbon materials in particular. Thus, in this example, the adhesive properties of P8GB # 1 M13 bacteriophage were analyzed.

Specifically, to test the adhesive properties of the bioadhesive, 5 × 10 ¹² M13 phages were mixed with 1.3 mg carbon nanotubes (CNT) and dispersed in water to prepare a mixed solution. Thereafter, a predetermined amount of the mixed solution was dropped on PET as a plastic substrate to produce a film. As a comparative example, a film was prepared by dropping a certain amount of a solution containing CNT on PET without M13 phage, and the result is shown in Fig.

6, when the bioadhesive according to Example 1.1 was not added, the CNT film peeled off from the PET substrate, whereas when the bioadhesive according to Example 1.1 was added, the CNT film adhered well to the PET substrate . As a result, it can be seen that the bioadhesive according to one embodiment can be usefully used in a bioadhesive for an electrochemical device.

1.3. Method of coating bioadhesive on conductive fibers .

To improve mechanical and electrical adhesion between conductive fibers and active materials, a solution of a monolayer carbon nanotube and a P8GB # 1 phage solution was coated on conductive fibers.

To this end, an aqueous solution was prepared by adding a surfactant, sodium cholate, to the distilled water at a concentration of 2% w / v. Then, carbon nanotubes (Nanointegris, SuperPure SWNTs, 1 mg / mL) was dialyzed for 48 hours to prepare a colloidal solution in which single-walled carbon nanotubes were stabilized with sodium cholate. Assuming that the average length of single-wall carbon nanotubes (CNTs) is 1 μm and the average diameter is 1.4 nm, the concentration of single-wall carbon nanotubes is as follows.

[Equation 1]

Number of single-walled carbon nanotubes (dog / ml) = concentration / / ml X 3 X 10 ¹¹ CNT

According to the above equation, the number of single-walled carbon nanotubes contained in the colloidal solution is (3 × 10 ¹⁴ ) / ml. The dangyeop 0.2 mL solution (3 × 10 ¹⁴ / mL) and the the p8GB # 1 phage solution ^{0.15 mL (1 × 10 14 /} mL) were mixed in 1% w / v sodium cholate solution, 10 mL of carbon nanotubes The carbon fibers were immersed for 24 hours, taken out and dried in the air.

Example 2. Fabrication and characterization of a fibrous electrode structure comprising a bioadhesive

2.1 Improvement of coating property of active material after introduction of bio-adhesive

The difference in coating properties depending on the presence or absence of the bioadhesive in the process of coating the cathode active material on the conductive fiber used as the core collector was examined as follows. In this embodiment, a carbon fiber bundle is used as a core collector, and a LiFePO ₄ -rGO hybrid composite is used as an active material using reduced graphene oxide (rGO) as a two-dimensional support to enhance the flexibility of the active material . Hybridization with graphene improves the flexibility of the active material, helps to make LiFePO ₄ nanoparticles, and improves the conductivity of the anode. The active material coating on the conductive fiber is coated with active material in a glass tube having a certain diameter using a die-coating method, and the conductive fiber is passed through the glass tube at a constant speed to form an active material coating. At this time, as shown in FIG. 3, the coating of the separator may proceed continuously after coating the active material.

The active material ink was prepared by mixing 10 wt% of polyvinylidene fluoride (PVDF) as a polymer binder with 70 wt% of the LiFePO ₄ -rGO particles and 20 wt% of the conductive carbon additive Super P carbon (SP) to form a solvent NMP (N-methyl- -pyrrolidone). The bio-adhesive was coated on the carbon fibers before coating the active material on the carbon fiber bundle, and coated in the same manner as in Example 1.3. At this time, differences in the coating properties of the active material were compared according to the presence or absence of the bioadhesive.

As shown in FIG. 7, when the bio-adhesive is present under the same die-coating condition, the active material is more adhered to the conductive fibers and thickly coated. This is a result of improving the wettability and adhesion of the active material ink to the fibers by using the bioadhesive.

2.2 Fabrication and Characterization of Fibrous Anode Electrode Structure

The active material layer was coated on the biofabricated conductive fiber, and then the separator was coated to examine the characteristics of the electrode structure. The separation membrane used in this embodiment can be replaced by a gel electrolyte. The gel electrolyte can also be applied to a fibrous anode. The gel electrolyte contains succinonitrile (SN) as a plasticizer in the form of poly (ethylene oxide) (PEO) and bis (trifluoromethane) sulfonimide lithium salt (LiTFSI). The gel electrolyte was coated by the die-coating method described above.

As a result, the thickness of the fibrous cathode electrode structure linear density 0.107 mAhcm when 100 μm, as shown in Figure 8 ^were confirmed was confirmed by having the ^first, having a stable charge and discharge characteristics even in repeated measurements. Charging and discharging was performed by applying a current of 0.68 mA to a 4-cm-long bipolar electrode. Also, as shown in FIG. 9, it was shown that the bipolar electrode structure can be charged and discharged even when bent to have a bending radius of 1 cm.

Here, charge and discharge conditions were carried out by applying a current of 0.27 mA to a 6.5-cm-long anodic fiber.

2.3 Fabrication and Characterization of Fibrous Cathode Electrode Structures

The active fiber layer coated with the bioadhesive coated on the above was coated with the porous separator to examine the characteristics of the negative electrode fibrous electrode structure. The porous separator can also be applied to the fibrous anode. The porous separator used in this embodiment is formed using a phase inversion phenomenon in a solution of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) -acetone-water. The porous separator was coated by the die-coating method described above.

As a result, when the negative electrode active material coating pipe diameter 1.8 mm linear density 0.72 mAhcm As shown in FIG. ¹⁰ was confirmed was confirmed by having the ^first, having a stable charge and discharge characteristics even in repeated measurements. Charging and discharging was performed by applying a current of 0.3 mA to a 3-cm-long bipolar electrode.

2.4 Fabrication and Characteristics of Fibrous Whole Cells

The fibrous cell was fabricated using the anode fiber structure and the cathode fiber structure coated with PVDF-HFP-based porous separator fabricated above. In order to further enhance the physical contact between the positive electrode fiber structure and the negative electrode fiber structure, the fibrous positive electrode and the negative electrode structure were contacted with each other, and then a PVDF-HFP porous separator was additionally coated to form a fibrous electrode-negative electrode separator integrated structure. An electrolyte solution of 1: 1 volume ratio of ethylene carbonate (EC): dimethyl carbonate (DMC) in which 1 M LiTFSI was dissolved was used as a liquid electrolyte. The fibrous battery structure was assembled in the form of a beaker cell, a pouch cell, and a tube cell. As a result, the amount, as shown in Figure 11, the negative electrode active material coated tube 2.0 mm when one complete fiber linear density cells 1.45 mAhcm ^- were identified by having a ^1, it was confirmed that even in repeated measurements having a stable charge and discharge characteristics. Charging and discharging was carried out by applying a current of 0.4 mA to a 4 cm long fibrous battery. As shown in Fig. 12, it was confirmed that the full-cell voltage maintaining ratio of the fibrous cell was 1.4 times as much as that of the negative electrode active material coating tube. 13A and 13B show that the same fibrous all-over-cell as used in FIG. 12 exhibits stable charge-discharge characteristics at a bending diameter of 10 mm.

Example 3 Bio-adhesive-based interface reinforced membrane coating for preventing peeling of active material

In one embodiment, the bioadhesive is in the form of a primary nanowire, which can be self-assembled to form a network structure. The self-assembled network has nano-sized pores so that Li ions can escape, but the active material can not pass through and acts as an interfacial strengthening film that can prevent peeling of the active material without interfering with the migration of Li ions .

Example 1.3 0.2 mL solution of dangyeop carbon nanotube according to (3 × 10 ¹⁴ / mL) and the the p8GB # 1 phage solution ^{0.15 mL (1 × 10 14 /} mL) a 1% w / v sodium cholate (sodium cholate solution, the mixture was placed in a tube of a semipermeable dialysis membrane (SpectrumLab, MWCO 12,000 ~ 14,000, product # 132 700), and the membrane tube was dialyzed against the third distilled water . After about 16 hours from the start of the dialysis, a thin electronic sheet was formed along the surface of the membrane tube. Then, the membrane tube was transferred into tertiary distilled water, and the membrane tube was twisted to obtain an electronic sheet in water. The electronic sheet has a network structure composed of a bioadhesive and a conductive carbon nanotube, so that the electronic sheet can function as an interfacial strengthening film when coated on an active material including a carbon material .

The electronic sheet obtained in water was lifted with carbon fibers coated with a cathode active material and dried in air to form an interfacial strengthening film. 14A and 14B show that the cathode active material coated on the conductive fiber is coated with the bioadhesive based interface reinforcing film, and the cathode active material is not easily separated from the cathode active material.

Example  4. Fibrous  Electrode Ray energy  For increasing density Fibrous  Electrode Pressing  fair

The electrode fibers coated with the active material and the separator were passed through a roll press apparatus. At least one portion of the upper or lower roll of the roll press apparatus is piled up with a material having elasticity (e.g., rubber), which has the effect of uniform pressure dispersion and minimization of destruction of the fiber electrode. 15A and 15B show cross sections of the electrode fibers before and after pressing. The pressing pressure applied in this embodiment was approximately 100 N, but the pressure was not an absolute value and may be varied depending on the manufacturing conditions of the electrode chamber. FIGS. 16A and 16B are graphs showing the charging / discharging improvement characteristics of the positive electrode structure before and after the application of the pressing process, respectively.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, . Accordingly, the scope of protection of the present invention should be determined by the appended claims.

<110> Korea Institute of Science and Technology          Hanyang university industry-university cooperation foundation <120> Fibrous electrode structure, fibrous battery including the same,          and manufacturing method thereof <130> PN110492 <160> 14 <170> Kopatentin 2.0 <210> 1 <211> 8 <212> PRT <213> Artificial Sequence <220> <223> peptide selectively binding to graphitic materials <220> <221> VARIANT <222> (3) <223> X is W, Y, F or H <220> <221> VARIANT <222> (1) <223> X is D, E, N, or Q <220> <221> VARIANT <222> (6) <223> X is D, E, N or Q <220> <221> VARIANT <222> (7) <223> X is I, L, or V <400> 1 Xaa Ser Xaa Ala Ala Xaa Xaa Pro   1 5 <210> 2 <211> 8 <212> PRT <213> Artificial Sequence <220> <223> peptide selectively binding to graphitic materials <220> <221> VARIANT <222> (1) <223> X is D, E, N, or Q <220> <221> VARIANT <222> (2) <223> X is D, E, N, or Q <220> <221> VARIANT <222> (4) <223> X is I, L, or V <220> <221> VARIANT <222> (5) <223> X is D, E, N, or Q <220> <221> VARIANT <222> (7) <223> X is I, L, or V <400> 2 Xaa Xaa Pro Xaa Xaa Ala Xaa Pro   1 5 <210> 3 <211> 7 <212> PRT <213> Artificial Sequence <220> <223> peptide selectively binding to graphitic materials <220> <221> VARIANT <222> (2) <223> X is W, Y, F, or H <220> <221> VARIANT <222> (5) <223> X is D, E, N, or Q <220> <221> VARIANT <222> (6) <223> X is I, L, or V <400> 3 Ser Xaa Ala Ala Xaa Xaa Pro   1 5 <210> 4 <211> 7 <212> PRT <213> Artificial Sequence <220> <223> peptide selectively binding to graphitic materials <220> <221> VARIANT <222> (1) <223> X is D, E, N, or Q <220> <221> VARIANT <222> (3) <223> X is I, L, or V <220> <221> VARIANT <222> (4) <223> X is D, E, N, or Q <220> <221> VARIANT <222> (6) <223> X is I, L, or V <400> 4 Xaa Pro Xaa Xaa Ala Xaa Pro   1 5 <210> 5 <211> 8 <212> PRT <213> Artificial Sequence <220> <223> peptide selectively binding to graphitic materials <400> 5 Asp Ser Trp Ala Ala Asp Ile Pro   1 5 <210> 6 <211> 8 <212> PRT <213> Artificial Sequence <220> <223> peptide selectively binding to graphitic materials <400> 6 Asp Asn Pro Ile Gln Ala Val Pro   1 5 <210> 7 <211> 7 <212> PRT <213> Artificial Sequence <220> <223> peptide selectively binding to graphitic materials <400> 7 Ser Trp Ala Ala Asp Ile Pro   1 5 <210> 8 <211> 7 <212> PRT <213> Artificial Sequence <220> <223> peptide selectively binding to graphitic materials <400> 8 Asn Pro Ile Gln Ala Val Pro   1 5 <210> 9 <211> 7222 <212> DNA <213> Artificial Sequence <220> <223> cloning vector M13KE <400> 9 aatgctacta ctattagtag aattgatgcc accttttcag ctcgcgcccc aaatgaaaat 60 atagctaaac aggttattga ccatttgcga aatgtatcta atggtcaaac taaatctact 120 cgttcgcaga attgggaatc aactgttata tggaatgaaa cttccagaca ccgtacttta 180 gttgcatatt taaaacatgt tgagctacag cattatattc agcaattaag ctctaagcca 240 tccgcaaaaa tgacctctta tcaaaaggag caattaaagg tactctctaa tcctgacctg 300 ttggagtttg cttccggtct ggttcgcttt gaagctcgaa ttaaaacgcg atatttgaag 360 tctttcgggc ttcctcttaa tctttttgat gcaatccgct ttgcttctga ctataatagt 420 cagggtaaag acctgatttt tgatttatgg tcattctcgt tttctgaact gtttaaagca 480 tttgaggggg attcaatgaa tatttatgac gattccgcag tattggacgc tatccagtct 540 aaacatttta ctattacccc ctctggcaaa acttcttttg caaaagcctc tcgctatttt 600 gt; aattcctttt ggcgttatgt atctgcatta gttgaatgtg gtattcctaa atctcaactg 720 atgaatcttt ctacctgtaa taatgttgtt ccgttagttc gttttattaa cgtagatttt 780 tcttcccaac gtcctgactg gtataatgag ccagttctta aaatcgcata aggtaattca 840 caatgattaa agttgaaatt aaaccatctc aagcccaatt tactactcgt tctggtgttt 900 ctcgtcaggg caagccttat tcactgaatg agcagctttg ttacgttgat ttgggtaatg 960 aatatccggt tcttgtcaag attactcttg atgaaggtca gccagcctat gcgcctggtc 1020 tgtacaccgt tcatctgtcc tctttcaaag ttggtcagtt cggttccctt atgattgacc 1080 gtctgcgcct cgttccggct aagtaacatg gagcaggtcg cggatttcga cacaatttat 1140 caggcgatga tacaaatctc cgttgtactt tgtttcgcgc ttggtataat cgctgggggt 1200 caaagatgag tgttttagtg tattcttttg cctctttcgt tttaggttgg tgccttcgta 1260 gtggcattac gtattttacc cgtttaatgg aaacttcctc atgaaaaagt ctttagtcct 1320 caaagcctct gtagccgttg ctaccctcgt tccgatgctg tctttcgctg ctgagggtga 1380 cgatcccgca aaagcggcct ttaactccct gcaagcctca gcgaccgaat atatcggtta 1440 tgcgtgggcg atggttgttg tcattgtcgg cgcaactatc ggtatcaagc tgtttaagaa 1500 attcacctcg aaagcaagct gataaaccga tacaattaaa ggctcctttt ggagcctttt 1560 ttttggagat tttcaacgtg aaaaaattat tattcgcaat tcctttagtg gtacctttct 1620 attctcactc ggccgaaact gttgaaagtt gtttagcaaa atcccataca gaaaattcat 1680 ttactaacgt ctggaaagac gacaaaactt tagatcgtta cgctaactat gagggctgtc 1740 tgtggaatgc tacaggcgtt gtagtttgta ctggtgacga aactcagtgt tacggtacat 1800 gggttcctat tgggcttgct atccctgaaa atgagggtgg tggctctgag ggtggcggtt 1860 ctgagggtgg cggttctgag ggtggcggta ctaaacctcc tgagtacggt gatacaccta 1920 ttccgggcta tacttatatc aaccctctcg acggcactta tccgcctggt actgagcaaa 1980 accccgctaa tcctaatcct tctcttgagg agtctcagcc tcttaatact ttcatgtttc 2040 agaataatag gttccgaaat aggcaggggg cattaactgt ttatacgggc actgttactc 2100 aaggcactga ccccgttaaa acttattacc agtacactcc tgtatcatca aaagccatgt 2160 atgacgctta ctggaacggt aaattcagag actgcgcttt ccattctggc tttaatgagg 2220 atttatttgt ttgtgaatat caaggccaat cgtctgacct gcctcaacct cctgtcaatg 2280 ctggcggcgg ctctggtggt ggttctggtg gcggctctga gggtggtggc tctgagggtg 2340 gcggttctga gggtggcggc tctgagggag gcggttccgg tggtggctct ggttccggtg 2400 attttgatta tgaaaagatg gcaaacgcta ataagggggc tatgaccgaa aatgccgatg 2460 aaaacgcgct acagtctgac gctaaaggca aacttgattc tgtcgctact gattacggtg 2520 ctgctatcga tggtttcatt ggtgacgttt ccggccttgc taatggtaat ggtgctactg 2580 gtgattttgc tggctctaat tcccaaatgg ctcaagtcgg tgacggtgat aattcacctt 2640 taatgaataa tttccgtcaa tatttacctt ccctccctca atcggttgaa tgtcgccctt 2700 ttgtctttgg cgctggtaaa ccatatgaat tttctattga ttgtgacaaa ataaacttat 2760 tccgtggtgt ctttgcgttt cttttatatg ttgccacctt tatgtatgta ttttctacgt 2820 ttgctaacat actgcgtaat aaggagtctt aatcatgcca gttcttttgg gtattccgtt 2880 attattgcgt ttcctcggtt tccttctggt aactttgttc ggctatctgc ttacttttct 2940 taaaaagggc ttcggtaaga tagctattgc tatttcattg tttcttgctc ttattattgg 3000 gcttaactca attcttgtgg gttatctctc tgatattagc gctcaattac cctctgactt 3060 tgttcagggt gttcagttaa ttctcccgtc taatgcgctt ccctgttttt atgttattct 3120 ctctgtaaag gctgctattt tcatttttga cgttaaacaa aaaatcgttt cttatttgga 3180 ttgggataaa taatatggct gtttattttg taactggcaa attaggctct ggaaagacgc 3240 tcgttagcgt tggtaagatt caggataaaa ttgtagctgg gtgcaaaata gcaactaatc 3300 ttgatttaag gcttcaaaac ctcccgcaag tcgggaggtt cgctaaaacg cctcgcgttc 3360 ttagaatacc ggataagcct tctatatctg atttgcttgc tattgggcgc ggtaatgatt 3420 cctacgatga aaataaaaac ggcttgcttg ttctcgatga gtgcggtact tggtttaata 3480 cccgttcttg gaatgataag gaaagacagc cgattattga ttggtttcta catgctcgta 3540 aattaggatg ggatattatt tttcttgttc aggacttatc tattgttgat aaacaggcgc 3600 gttctgcatt agctgaacat gttgtttatt gtcgtcgtct ggacagaatt actttacctt 3660 ttgtcggtac tttatattct cttattactg gctcgaaaat gcctctgcct aaattacatg 3720 ttggcgttgt taaatatggc gattctcaat taagccctac tgttgagcgt tggctttata 3780 ctggtaagaa tttgtataac gcatatgata ctaaacaggc tttttctagt aattatgatt 3840 ccggtgttta ttcttattta acgccttatt tatcacacgg tcggtatttc aaaccattaa 3900 atttaggtca gaagatgaaa ttaactaaaa tatatttgaa aaagttttct cgcgttcttt 3960 gtcttgcgat tggatttgca tcagcattta catatagtta tataacccaa cctaagccgg 4020 aggttaaaaa ggtagtctct cagacctatg attttgataa attcactatt gactcttctc 4080 agcgtcttaa tctaagctat cgctatgttt tcaaggattc taagggaaaa ttaattaata 4140 gcgacgattt acagaagcaa ggttattcac tcacatatat tgatttatgt actgtttcca 4200 ttaaaaaagg taattcaaat gaaattgtta aatgtaatta attttgtttt cttgatgttt 4260 gtttcatcat cttcttttgc tcaggtaatt gaaatgaata attcgcctct gcgcgatttt 4320 gtaacttggt attcaaagca atcaggcgaa tccgttattg tttctcccga tgtaaaaggt 4380 actgttactg tatattcatc tgacgttaaa cctgaaaatc tacgcaattt ctttatttct 4440 gttttacgtg caaataattt tgatatggta ggttctaacc cttccattat tcagaagtat 4500 aatccaaaca atcaggatta tattgatgaa ttgccatcat ctgataatca ggaatatgat 4560 gataattccg ctccttctgg tggtttcttt gttccgcaaa atgataatgt tactcaaact 4620 tttaaaatta ataacgttcg ggcaaaggat ttaatacgag ttgtcgaatt gtttgtaaag 4680 tctaatactt ctaaatcctc aaatgtatta tctattgacg gctctaatct attagttgtt 4740 agtgctccta aagatatttt agataacctt cctcaattcc tttcaactgt tgatttgcca 4800 actgaccaga tattgattga gggtttgata tttgaggttc agcaaggtga tgctttagat 4860 ttttcatttg ctgctggctc tcagcgtggc actgttgcag gcggtgttaa tactgaccgc 4920 ctcacctctg ttttatcttc tgctggtggt tcgttcggta tttttaatgg cgatgtttta 4980 gggctatcag ttcgcgcatt aaagactaat agccattcaa aaatattgtc tgtgccacgt 5040 attcttacgc tttcaggtca gaagggttct atctctgttg gccagaatgt tccttttatt 5100 actggtcgtg tgactggtga atctgccaat gtaaataatc catttcagac gattgagcgt 5160 caaaatgtag gtatttccat gagcgttttt cctgttgcaa tggctggcgg taatattgtt 5220 ctggatatta ccagcaaggc cgatagtttg agttcttcta ctcaggcaag tgatgttatt 5280 actaatcaaa gaagtattgc tacaacggtt aatttgcgtg atggacagac tcttttactc 5340 ggtggcctca ctgattataa aaacacttct caggattctg gcgtaccgtt cctgtctaaa 5400 atccctttaa tcggcctcct gtttagctcc cgctctgatt ctaacgagga aagcacgtta 5460 tacgtgctcg tcaaagcaac catagtacgc gccctgtagc ggcgcattaa gcgcggcggg 5520 tgtggtggtt acgcgcagcg tgaccgctac acttgccagc gccctagcgc ccgctccttt 5580 cgctttcttc ccttcctttc tcgccacgtt cgccggcttt ccccgtcaag ctctaaatcg 5640 ggggctccct ttagggttcc gatttagtgc tttacggcac ctcgacccca aaaaacttga 5700 tttgggtgat ggttcacgta gtgggccatc gccctgatag acggtttttc gccctttgac 5760 gttggagtcc acgttcttta atagtggact cttgttccaa actggaacaa cactcaaccc 5820 tatctcgggc tattcttttg atttataagg gattttgccg atttcggaac caccatcaaa 5880 caggattttc gcctgctggg gcaaaccagc gtggaccgct tgctgcaact ctctcagggc 5940 caggcggtga agggcaatca gctgttgccc gtctcactgg tgaaaagaaa aaccaccctg 6000 gcgcccaata cgcaaaccgc ctctccccgc gcgttggccg attcattaat gcagctggca 6060 cgacaggttt cccgactgga aagcgggcag tgagcgcaac gcaattaatg tgagttagct 6120 cactcattag gcaccccagg ctttacactt tatgcttccg gctcgtatgt tgtgtggaat 6180 tgtgagcgga taacaatttc acacaggaaa cagctatgac catgattacg ccaagcttgc 6240 atgcctgcag gtcctcgaat tcactggccg tcgttttaca acgtcgtgac tgggaaaacc 6300 ctggcgttac ccaacttaat cgccttgcag cacatccccc tttcgccagc tggcgtaata 6360 gcgaagaggc ccgcaccgat cgcccttccc aacagttgcg cagcctgaat ggcgaatggc 6420 gctttgcctg gtttccggca ccagaagcgg tgccggaaag ctggctggag tgcgatcttc 6480 ctgaggccga tactgtcgtc gtcccctcaa actggcagat gcacggttac gatgcgccca 6540 tctacaccaa cgtgacctat cccattacgg tcaatccgcc gtttgttccc acggagaatc 6600 cgacgggttg ttactcgctc acatttaatg ttgatgaaag ctggctacag gaaggccaga 6660 cgcgaattat ttttgatggc gttcctattg gttaaaaaat gagctgattt aacaaaaatt 6720 taatgcgaat tttaacaaaa tattaacgtt tacaatttaa atatttgctt atacaatctt 6780 cctgtttttg gggcttttct gattatcaac cggggtacat atgattgaca tgctagtttt 6840 acgattaccg ttcatcgatt ctcttgtttg ctccagactc tcaggcaatg acctgatagc 6900 ctttgtagat ctctcaaaaa tagctaccct ctccggcatt aatttatcag ctagaacggt 6960 tgaatatcat attgatggtg atttgactgt ctccggcctt tctcaccctt ttgaatcttt 7020 acctacacat tactcaggca ttgcatttaa aatatatgag ggttctaaaa atttttatcc 7080 ttgcgttgaa ataaaggctt ctcccgcaaa agtattacag ggtcataatg tttttggtac 7140 aaccgattta gctttatgct ctgaggcttt attgcttaat tttgctaatt ctttgccttg 7200 cctgtatgat ttattggatg tt 7222 <210> 10 <211> 41 <212> DNA <213> Artificial Sequence <220> <223> BamH I_SM_upper which is a primer used for site-directed mutation <400> 10 aaggccgctt ttgcgggatc ctcaccctca gcagcgaaag a 41 <210> 11 <211> 41 <212> DNA <213> Artificial Sequence <220> <223> BamH I_SM_lower which is a primer used for site-directed mutation <400> 11 tctttcgctg ctgagggtga ggatcccgca aaagcggcct t 41 <210> 12 <211> 90 <212> DNA <213> Artificial Sequence <220> <223> BamM13HK_P8_primer which is an extension primer used for          preparation <400> 12 ttaatggaaa cttcctcatg aaaaagtctt tagtcctcaa agcctctgta gccgttgcta 60 ccctcgttcc gatgctgtct ttcgctgctg 90 <210> 13 <211> 95 <212> DNA <213> Artificial Sequence <220> <223> M13HK_P8 which is a library oligonucleotide used for preparation <220> <221> variation <222> (1) <223> n is a, g, c or t <220> <221> variation <222> (1) <223> m is a or c <400> 13 aaggccgctt ttgcgggatc cnmnnmnnmnnmnnmn nmncagcagc gaaagacagc 60 atcggaacga gggtagcaac ggctacagag gcttt 95 <210> 14 <211> 50 <212> PRT <213> P8 protein of M13 phage <400> 14 Ala Glu Gly Asp Asp Pro Ala Lys Ala Ala Phe Asn Ser Leu Gln Ala   1 5 10 15 Ser Ala Thr Glu Tyr Ile Gly Tyr Ala Trp Ala Met Val Val Val Ile              20 25 30 Val Gly Ala Thr Ile Gly Ile Lys Leu Phe Lys Lys Phe Thr Ser Lys          35 40 45 Ala Ser      50

Claims (22)

A conductive fiber comprising a carbon component;
An active material layer covering an outer surface of the conductive fiber; And
A separation membrane formed on the active material layer;
Wherein the separator-integrated fibrous electrode structure comprises: The method according to claim 1,
A bioadhesive is introduced into at least one of the conductive fiber and the active material layer, between the active material layer and the separator, and inside the active material layer,
Wherein the bioadhesive comprises a phage displaying a peptide capable of binding to a carbon material. The method according to claim 1,
Wherein the conductive fiber comprising the carbon component comprises at least one of a conductive carbon fiber, a carbon component-containing conductive polymer fiber, and a carbon component-containing conductive metal fiber. The method of claim 3,
Wherein the conductive metal fibers are fibers made of SUS, Al, Cu, Ni or a combination thereof. The method according to claim 1,
Wherein the active material layer comprises a composite of an active material and a graphitic material. The method according to claim 1,
The active material layer is _{LiCoO 2, LiNiO 2, LiMn 2} O 4, LiCoPO 4, LiFePO 4, LiMnPO 4, LiNi x Mn y Co z O 2 ( where, 0≤x≤1, 0≤y≤1, 0≤z 1, x + y + z = 1), FeF ₃ , BiF ₃ , BiOF, FeOF polyimide (PI), quinone, and pyromellitic dimide. Fibrous electrode structure. The method according to claim 1,
The active material layer is _{carbon, Si, SiO 2, SnO 2} , Co 3 O 4, Li 4 Ti 5 O 12 (LTO), MoS 2, activated carbon, graphene, doped graphene, carbon nanotubes, and a modified carbon And at least one selected from the group consisting of nanotubes. The method according to claim 1,
Wherein the separation membrane comprises an electrolyte. 9. The method of claim 8,
Wherein the electrolyte is a lithium salt dissolved therein. 3. The method of claim 2,
Wherein said phage is a phage that is genetically engineered to have a binding capacity to a carbon material. 3. The method of claim 2,
Wherein the bioadhesive has a sheet form. 12. The method of claim 11,
Wherein the internal structure of the sheet has a percolated network structure. 3. The method of claim 2,
Wherein the grip is a filamentous grip. 14. A fibrous cell comprising the separator-integrated fibrous electrode structure according to any one of claims 1 to 13. An electrode comprising: a separator integral fibrous electrode structure according to any one of claims 1 to 13; And a cathode electrode comprising at least one separator integral fibrous electrode structure according to any one of claims 1 to 12,
Wherein the positive electrode and the negative electrode are twisted, overlapped or woven together. 16. The method of claim 15,
Wherein the fibrous battery is a lithium secondary battery. Providing a conductive fiber comprising a carbon component;
Forming an active material layer on an outer surface of the conductive fiber; And
Forming a separator on an outer surface of the active material layer;
A method of manufacturing a separator-integrated fibrous electrode structure, 18. The method of claim 17,
Further comprising the step of introducing a bioadhesive comprising a phage displaying a peptide capable of binding to a carbon material, at least one of the conductive fiber and the active material layer, between the active material layer and the separator, and / or inside the active material layer Wherein the method comprises the steps of: 18. The method of claim 17,
Wherein the bio-adhesive is introduced between the conductive fiber and the active material layer by coating the conductive fiber using a solution in which the bio-adhesive is dispersed in a solvent. 18. The method of claim 17,
Wherein the bioadhesive agent is introduced into the active material layer by dispersing the bioadhesive agent together in a composition for forming the active material layer. 18. The method of claim 17,
Wherein the step of forming the active material layer and the step of forming the separation membrane comprise a continuous process for continuously passing the conductive fiber through the active material containing container and the separation membrane containing container. 18. The method of claim 17,
Further comprising the step of pressing after the step of forming the separator.

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