KR101852808B1 - A battery using solution containing sodium and attachable battery - Google Patents

Abstract

The present invention relates to a secondary battery using a sodium-containing solution. The secondary battery comprises a first anode which absorbs a sodium-containing solution, a charging reaction occurs through ionization of sodium, And a second anode which receives electrons and sodium ions from a cathode and a cathode supplied from the anode and in which a discharge reaction takes place.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a secondary battery and a skin-

More particularly, the present invention relates to a secondary battery and a skin-attached secondary battery using a sodium-containing solution capable of charging and discharging. More particularly, the present invention relates to a secondary battery and a skin- The present invention relates to a secondary battery and a skin-attachment type secondary battery using a sodium-containing solution in which a discharge reaction occurs by discharging sodium ions.

BACKGROUND ART [0002] A secondary battery is a battery capable of charging and discharging, and is widely used in high-tech electronic devices such as a mobile phone, a notebook computer, and a camera. Typical examples of the secondary battery include a lithium secondary battery that generates electrical energy by changing the chemical potential when the lithium ions are intercalated / deintercalated in the positive and negative electrodes.

In the case of a lithium secondary battery, a material capable of reversible intercalation / deintercalation of lithium ions is used as a positive electrode and a negative electrode active material, and an organic electrolyte solution Or by filling the polymer electrolyte.

Lithium required for the production of secondary batteries is present only on a limited amount on the earth, and generally it is necessary to obtain high cost and high energy because it is obtained from difficult processes such as minerals and salts.

Therefore, there is a need for a next-generation secondary battery which can replace lithium and which can support the performance of electronic devices in recent years and which is free from charge and discharge restrictions.

A secondary battery and a skin-attached secondary battery using a sodium-containing solution that can be charged and discharged by using a sodium-containing solution instead of lithium.

The secondary battery using the sodium-containing solution according to the present invention is characterized in that the secondary battery using the sodium-containing solution is located in the first anode and the electrolyte which absorbs the sodium-containing solution and undergoes the charging reaction through ionization of sodium, A negative electrode supplied from one positive electrode, and a second positive electrode receiving a supply of electrons and sodium ions from the negative electrode and causing a discharge reaction.

And a separation membrane positioned between the first anode and the cathode and between the second anode and the cathode to allow the sodium ions to pass therethrough.

The first anode and the second anode may each include a cathode current collector and a catalyst layer provided on the surface of the cathode current collector.

The catalyst in the catalyst layer may be selected from the group consisting of an oxygen reduction catalyst, an oxygen evolution catalyst, a Bi-functional catalyst, a Cl ₂ evolution reaction, Combinations thereof.

The second anode may be provided in a solvent other than air, water or water, and the resultant product resulting from the oxidation reaction in the second anode may be discharged to a solvent other than the air, water or water.

The second anode includes a cathode current collector, and does not include a cathode active material on the cathode current collector.

The second anode may not store the sodium ions supplied from the cathode during the discharge reaction.

Wherein the electrolyte contains at least one of a non-aqueous organic solvent and a sodium salt as an organic electrolyte, and the non-aqueous organic solvent includes a carbonate-based, ester-based, ether-based, ketone-based, alcoholic or aprotic solvent, sodium salt is _{NaClO 4, NaBF 4, NaPF 6} , NaAsF 6, NaTFSI, NaCF 3 SO 3, Na [(C 2 F 5) 3 PF 3] (NaFAP), Na [B (C 2 O 4) 2] ( NaBOB), Na may include _{[N (SO 2 F) 2} ] (NaFSI), NaBeti (NaN [SO 2 C 2 F 5] 2) or a combination thereof.

The sodium containing solution comprises at least one of sweat, salt water, seawater or a solution containing sodium recovered from waste, and the concentration of the sodium containing solution may be at least 0.04 mol.

Wherein the negative electrode includes a negative electrode current collector having a negative electrode active material layer on its surface and the negative electrode active material layer includes a negative electrode active material, a conductive material and a binder, and the negative electrode active material is an organic material, an alloy material, Or the like.

The separation membrane may be a polymer-based separation membrane, and may include a porous polymer separation membrane, a nonwoven system separation membrane, an inorganic composite separation membrane, or a combination thereof.

The polymer-based membrane NaAlO (CN) _2, perovskite and alumina, amorphous ionic conductive material, pear kongye solid electrolyte, sodium sulfide-based solid electrolyte, sodium oxide-based solid electrolyte or a derivative thereof or a mixture, or SiO ₂ Li ₂ O ₃ , Li ₂ O ₃ , TiO ₂ , BaTiO ₃ , Li ₂ O, LiF, LiOH, Li ₃ N, BaO, Na ₂ O, Li ₂ CO ₃ , CaCO ₃ , LiAlO ₂ , SrTiO ₃ , CeO ₂ , , CaO, ZnO, ZrO ₂ , SiC, derivatives thereof, or mixtures thereof.

At the first anode, the charging reaction of the following Reaction 1 or Reaction 2 may occur.

[Reaction Scheme 1]

4NaCl (aq) → 4Na ++ 2Cl 2 (g) + 4e -

[Reaction Scheme 2]

4 NaCl (aq) + 2H ₂ O? 4 Na ⁺ + 4 HCl (aq) + O ₂ (g) + 4 e ^-

At the second anode, a discharge reaction of the following Reaction Formula 3 or Reaction Formula 4 may occur.

 [Reaction Scheme 3]

_{^{4Na + + 2O 2 + 4e -}} → 2Na 2 O 2

[Reaction Scheme 4]

^{_{4Na + + O 2 + 2H 2}} O + 4e - → 4NaOH

The first anode, the cathode, the second anode, and the separator may be in the form of a nonwoven fabric having a three-dimensional network structure.

The first anode includes: a porous nonwoven fabric including a plurality of polymer fibers; And a conductive material, and the conductive material may be uniformly filled between the polymer fibers.

The negative electrode includes a porous nonwoven fabric including a plurality of polymer fibers, active material particles, and a conductive material, and the active material particles and the conductive material may be uniformly filled between the polymer fibers to form pores.

The second anode includes a porous nonwoven fabric including a plurality of polymer fibers, active material particles, and a conductive material, and the active material particles and the conductive material are uniformly filled between the polymer fibers and pores are formed.

Wherein the separation membrane comprises a porous nonwoven fabric including a plurality of polymer fibers, and the nonwoven fabric may be at least one selected from the group consisting of polyethylene terephthalate, polyimide, polyamide, polysulfone, polyvinylidene fluoride, polyacrylonitrile, polyethylene, , Polyetherimide, polyvinyl alcohol, polyethylene oxide, polyacrylic acid, polyvinylpyrrolidone, agarose, alginate, polyvinylidene hexafluoropropylene, derivatives thereof, or mixtures thereof.

The separator may be impregnated with the electrolyte, the electrolyte may be a polymer electrolyte, and the polymer electrolyte may include a polymer electrolyte composed of a network polymer, inorganic particles, a dissociable salt, and a liquid electrolyte composed of an organic solvent.

Wherein the polymer matrix comprises a linear polymer and a crosslinking monomer, wherein the linear polymer is selected from the group consisting of polyvinylidene fluoride, polyvinylidene fluoride hexafluoropropylene, polymethylmethacrylate, polystyrene, polyvinyl acetate, polyethylene oxide, Derivatives thereof, or mixtures thereof.

The crosslinking monomer may include an acrylate-based monomer, a derivative thereof, or a mixture thereof.

The second anode may be replaceable.

The skin-attachment type secondary battery according to the present invention is characterized in that the secondary battery except for the second anode is provided and has a skin adherent layer adhered to the skin, and a second anode arranged to align the position of the secondary electrode of the skin- And may include a replaceable replaceable layer.

The first adhesive layer and the second adhesive layer include polymer fibers, and the polymer may include polyacrylates, hydrogel-based polymers, saccharides, proteins, glycoproteins, mixtures thereof, or additives .

The replaceable layer includes a first adhesive layer for bonding with the skin attachment layer, and the skin attachment layer may comprise a second adhesive layer for attachment to the skin.

The secondary battery except the second anode provided on the skin adhesion layer may be electrically connected to the generator through a connection circuit.

The discharge reaction at the second anode may take place only when the skin adhesion layer and the replaceable layer are combined.

According to this embodiment, by using a solution containing sodium, which is easy to obtain such as sweat, as a resource, it is possible to manufacture a secondary battery using a sodium-containing solution which can be more easily charged and discharged.

In addition, since the anode in which the charging reaction occurs and the anode in which the discharging reaction takes place, the anode in which the discharging reaction takes place can be replaced, and the resultant discharge resultant is discharged to the solvent other than air, water, A battery can be manufactured.

In addition, it is flexible and can be attached to the skin, so that it can be worn and the sodium-containing solution can be easily absorbed.

1 is a configuration diagram of a secondary battery using a sodium-containing solution according to the present embodiment.
2 is a structural view of each material constituting the secondary battery using the sodium-containing solution according to the present embodiment.
3 is a schematic view briefly showing a configuration of a skin-attachment type secondary battery according to the present embodiment.
4 is a graph showing charge / discharge curves of a secondary battery using a sodium-containing solution using a 0.04M NaCl solution at a charge capacity of 250 mAh / g according to the present embodiment.
FIG. 5 is a graph showing a cycling stability curve of a secondary battery using a sodium-containing solution using a 0.04M NaCl solution at a charge capacity of 250 mAh / g according to the present embodiment.

Hereinafter, a secondary battery and a skin-attachment type secondary battery using the sodium-containing solution according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings. The present invention is capable of various modifications and various forms, and specific embodiments are illustrated in the drawings and described in detail in the text. It is to be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but on the contrary, is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. Like reference numerals are used for like elements in describing each drawing. In the accompanying drawings, the dimensions of the structures are enlarged to illustrate the present invention in order to clarify the present invention.

The terms first, second, etc. may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component.

The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, the terms "comprises", "having", and the like are used to specify that a feature, a number, a step, an operation, an element, a part or a combination thereof is described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, components, parts, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

1 is a schematic view of a secondary battery using a sodium-containing solution according to an embodiment of the present invention.

Hereinafter, one embodiment of the present invention will be described with reference to FIG.

The secondary battery 100 using the sodium-containing solution according to an embodiment of the present invention may include a first anode 110, a cathode 130 positioned in the electrolyte, and a second anode 120.

The first anode 110 absorbs the sodium containing solution and the charging reaction can occur through sodium ionization.

For example, if the first cathode (110) absorbs the sodium-containing solution 4NaCl (aq) → 4Na ++ 2Cl 2 (g) + 4e - or 4NaCl (aq) + 2H ₂ O → 4HCl + 4Na ⁺ (aq) + O ₂ (g) + 4e ^- , so that sodium ions and electrons are generated.

At this time, the generated sodium ions and electrons can move to the cathode 130 located in the electrolyte through the electrolyte.

In addition, the sodium ion moved to the cathode 130 may move to the second anode 120 through the electrolyte to generate a discharge reaction.

Also, in the case of the second anode 120, it may be provided in a solvent other than air, water, or water, and the resultant discharge result may be discharged to a solvent other than air, water, or water.

The first positive electrode 110 and the second positive electrode 120 according to the present invention each comprise a positive electrode collector and the positive electrode collector includes carbon paper, carbon fiber, carbon cloth, carbon felt, metal thin film or a combination thereof And when the porosity ranges from 1 nm to 250 탆, it is possible to constitute an electrode having a large surface area to induce a more active electrode reaction.

In addition, the reactivity can be further improved by including a catalyst layer on the surface of the positive electrode collector, and the catalyst in the catalyst layer can be selected from the group consisting of an oxygen reduction catalyst, an oxygen evolution catalyst, a Bi- functional catalyst, a Cl ₂ evolution reaction, or a combination thereof.

That is, the structure may be a structure that effectively discharges sodium ions in the cathode 130 through a catalyst to generate electricity, and the structure is not limited thereto.

4Na ⁺ + 2O ₂ + 4e ^- → 2Na ₂ O ₂ or 4Na ⁺ + O ₂ + 2H ₂ O + 4e in which sodium ions react with oxygen or water molecules in the second anode 120 in which sodium ions are transferred ^- > 4NaOH. ≪ ^{/ RTI} >

In addition, the second anode 120 of the secondary battery using the sodium-containing solution according to another embodiment of the present invention may have a structure in which the cathode active material does not exist on the cathode current collector.

That is, the sodium ions transferred from the cathode 130 at the time of discharging are not separately stored in the second anode 120.

Therefore, the anode 120 where the discharge reaction takes place and the anode 110 where the charging reaction occurs can be different from each other, and the anode 120 where the discharge reaction takes place can be designed to be replaceable.

The negative electrode 130 according to an embodiment of the present invention includes a negative electrode current collector having a negative electrode active material layer on its surface and the negative electrode active material layer includes a negative electrode active material, a conductive material, and a binder. The negative electrode active material is an organic material, , A carbon-based material, or a sodium intercalation material.

The separation membrane 140 according to an embodiment of the present invention is a polymer-based separation membrane 140. The separation membrane 140 includes a first anode 110 and a cathode 130 where a charging reaction occurs, 2 located between the anodes 120 to prevent an electrical short between the electrodes and to serve as a path for sodium ions to flow during the charge and discharge reactions.

The separator 140 may include a porous polymer membrane, a nonwoven membrane separator, an inorganic composite separator membrane, or a combination thereof. The separator membrane 140 may include NaAlO (CN) ₂ , perovskite, Al ₂ O ₃ , TiO ₂ , BaTiO ₃ , Li ₂ O, LiF, or the like, or a mixture thereof, or a mixture thereof, or a mixture of _two or more selected from the group consisting of alumina, amorphous ion conductive material, nacicon solid electrolyte, sodium sulfide solid electrolyte, sodium oxide solid electrolyte, _{, LiOH, Li 3 N, BaO} , Na 2 O, Li 2 CO 3, CaCO 3, LiAlO 2, SrTiO 3, CeO 2, MgO, NiO, CaO, ZnO, ZrO 2, SiC, derivatives thereof or mixtures thereof . ≪ / RTI >

The electrolyte according to an embodiment of the present invention may include at least one of the non-aqueous organic solvent or the sodium salt as the organic electrolyte 150.

More specifically, the non-aqueous solvent serves as a medium through which ions involved in the electrochemical reaction of the battery can move, and may include carbonate-based, ester-based, ether-based, ketone-based, alcohol-based or aprotic solvents .

Examples of the carbonate solvent include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), methyl ethyl carbonate (MEC) ), Propylene carbonate (PC), butylene carbonate (BC) and the like can be used. As the ester solvent, methyl acetate, ethyl acetate, n-propyl acetate, 1,1-dimethyl ethyl acetate, methyl propionate, ethyl Propiolate, propionate,? -Butyrolactone, decanolide, valerolactone, mevalonolactone, caprolactone and the like can be used.

As the ether-based solvent, dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran and the like can be used. As the ketone solvent, cyclohexanone and the like can be used. As the alcoholic solvent, ethyl alcohol, isopropyl alcohol and the like can be used. As aprotic solvent, R-CN (R is a linear, branched or cyclic hydrocarbon group of C2 to C20, An aromatic ring such as an aromatic ring or an ether linkage; amides such as dimethylformamide; dioxolanes such as 1,3-dioxolane; sulfolanes; and the like.

In addition, the non-aqueous organic solvent may be used alone or in combination of one or more. If the one or more of the non-aqueous organic solvents is used in combination, the mixing ratio may be appropriately adjusted according to the desired cell performance. Can be understood.

More specifically, in the case of a carbonate-based solvent, it is preferable to use a mixture of a cyclic carbonate and a chain carbonate. In this case, when the cyclic carbonate and the chain carbonate are mixed in a volume ratio of about 1: 1 to about 1: 9, the performance of the electrolytic solution may be excellent.

In addition, the non-aqueous organic solvent may further include an aromatic hydrocarbon-based organic solvent in the carbonate-based solvent. In this case, the carbonate-based solvent and the aromatic hydrocarbon-based organic solvent may be mixed in a volume ratio of about 1: 1 to about 30: 1.

The aromatic hydrocarbon-based organic solvent may be an aromatic hydrocarbon-based compound represented by the following formula (1).

In Formula (1), R ₁ to R ₆ are each independently hydrogen, halogen, a C ₁ to C ₁₀ alkyl group, a C ₁ to C ₁₀ haloalkyl group, or a combination thereof.

The aromatic hydrocarbon-based organic solvent is selected from the group consisting of benzene, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,3- 1,2,4-trifluorobenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2,4 - trichlorobenzene, iodobenzene, 1,2-diiodobenzene, 1,3-diiodobenzene, 1,4-diiodobenzene, 1,2,3-triiodobenzene, 1,2,4- Diisobutylenediamine, triiodobenzene, toluene, fluorotoluene, 1,2-difluorotoluene, 1,3-difluorotoluene, 1,4-difluorotoluene, 1,2,3-trifluorotoluene, 1 , 2,4-trifluorotoluene, chlorotoluene, 1,2-dichlorotoluene, 1,3-dichlorotoluene, 1,4-dichlorotoluene, 1,2,3-trichlorotoluene, 1,2,4- 1,2-diiodotoluene, 1,3-diiodotoluene, 1,4-diiodotoluene, 1,4-diiodotoluene, , 2,3-triiodotoluene, 1,2,4-triiodotoluene, xylene, or combinations thereof.

The non-aqueous electrolyte may further comprise vinylene carbonate or an ethylene carbonate-based compound represented by the following formula (2) to improve battery life.

In Formula 2, R ₇ and R ₈ are each independently hydrogen, a halogen group, a cyano group (CN), a nitro group (NO ₂ ) or a C ₁ to C ₅ fluoroalkyl group, and at least one of R ₇ and R ₈ is an alkyl group with a halogen group, a cyano group (CN), nitro group (NO2) or fluoroalkyl C ₁ to C _5.

Representative examples of the ethylene carbonate-based compound include difluoroethylene carbonate, chloroethylene carbonate, dichloroethylene carbonate, bromoethylene carbonate, dibromoethylene carbonate, nitroethylene carbonate, cyanoethylene carbonate, fluoroethylene carbonate and the like have. When the vinylene carbonate or the ethylene carbonate compound is further used, the amount of the vinylene carbonate or the ethylene carbonate compound can be appropriately controlled to improve the service life.

The sodium salt dissolves in the non-aqueous organic solvent to act as a source of sodium ions in the cell to enable operation of the basic secondary cell, and a substance that acts to promote the movement of sodium ions between the anode and the cathode 130 to be.

More specifically, it is preferable to use NaClO ₄ , NaBF ₄ , NaPF ₆ , NaAsF ₆ , NaTFSI, NaCF ₃ SO ₃ , Na [(C ₂ F ₅ ) ₃ PF ₃ ] (NaFAP, Na [B (C ₂ O ₄ ) ₂ ] NaBOB), Na may include _{[N (SO 2 F) 2} ] (NaFSI), NaBeti (NaN [SO 2 C 2 F 5] 2) or a combination thereof.

The concentration of the sodium salt may be from 0.001 to 10M, and more specifically, from 0.1 to 2.0M. When the concentration of the sodium salt is included in the range, the electrolyte can exhibit excellent electrolyte performance because it has appropriate conductivity and viscosity, and the sodium ion can effectively migrate.

The sodium containing solution comprises at least one of sweat, saline, sea water or a solution containing sodium recovered from waste, and more specifically, the concentration may be at least 0.04 moles.

2 is a schematic view of a secondary battery 200 using a sodium-containing solution according to another embodiment of the present invention.

Hereinafter, one embodiment of the present invention will be described with reference to FIG.

The secondary battery 200 using the sodium-containing solution according to an embodiment of the present invention includes a first anode 210, a cathode 230, a second anode 220, and a nonwoven fabric separator 240, And may be in the form of a nonwoven fabric of a three-dimensional network structure.

More specifically, the nonwoven fabric may be a porous fiber, and a structure in which the active material is contained in the matrix.

That is, the first anode 210, the cathode 230, the second anode 220, and the nonwoven fabric separator 240 may be integrated by electrospinning and filtration techniques to have excellent flexibility characteristics.

More specifically, the first anode 210 includes a porous nonwoven fabric including a plurality of polymer fibers and a conductive material. As the conductive material is uniformly filled between the polymer fibers, pores are formed to facilitate absorption of the sodium-containing solution can do.

The cathode 230 includes a porous nonwoven fabric including a plurality of polymer fibers, active material particles, and a conductive material, and the active material particles and the conductive material are uniformly filled between the polymer fibers and pores can be formed.

The second anode 220 includes a porous nonwoven fabric including a plurality of polymer fibers and a conductive material. Since the conductive material is uniformly filled in the polymer fibers and the pores are formed, the second anode 220 may have a three-dimensional structure, .

The separator 240 may include a porous nonwoven fabric including a plurality of polymer fibers and the nonwoven fabric may be a polyethylene terephthalate, a polyimide, a polyamide, a polysulfone, a polyvinylidene fluoride, a polyacrylonitrile, a polyethylene, a polypropylene, a poly Polyvinyl alcohol, polyethylene oxide, polyacrylic acid, polyvinylpyrrolidone, agarose, alginate, polyvinylidene hexafluoropropylene, derivatives thereof, or mixtures thereof.

The nonwoven fabric separator 240 is disposed between the first anode 210 and the cathode 230 and between the cathode 230 and the second anode 220 and is capable of passing sodium ions.

The electrolyte may be a polymer electrolyte 250, and may include a liquid electrolyte composed of a polymer matrix composed of a network polymer, inorganic particles, a dissociable salt, and an organic solvent.

More specifically, the polymer matrix may include linear polymers and crosslinking monomers.

Here, the linear polymer may include polyvinylidene fluoride, polyvinylidene fluoride hexafluoropropylene, polymethyl methacrylate, polystyrene, polyvinyl acetate, polyethylene oxide, derivatives thereof, or a mixture thereof.

In addition, the crosslinking monomer may include an acrylate-based monomer, a derivative thereof, or a mixture thereof.

3 is a schematic view of a skin-mounted secondary battery 300 using a sodium-containing solution according to another embodiment of the present invention.

Hereinafter, one embodiment of the present invention will be described with reference to FIG.

The second anode 220 of the skin-attachment-type secondary battery 300 according to an embodiment of the present invention may be replaceable, and may include a skin attachment layer to which the secondary battery 220 is attached except for the second anode 220, A second anode 220 arranged to align the position of the secondary battery 220 with the position of the secondary battery of the skin attachment layer, and may include a replaceable replaceable layer.
That is, the skin-mounted rechargeable battery 300 according to an embodiment of the present invention includes a skin attachment layer and a replaceable layer. On the surface of the skin adhesion layer, the configuration of the secondary battery except for the second anode 2200 such as the generator, the first anode 210, and the cathode 230 is provided.

More specifically, the skin adhesive layer comprises a first adhesive layer for attachment to the skin, and the replaceable layer may comprise a second adhesive layer for bonding to the skin adhesive layer.

More specifically, the first adhesive layer and the second adhesive layer include polymer fibers, and the polymer fibers may include polyacrylates, hydrogel-based polymers, saccharides, proteins, glycoproteins, mixtures or additives thereof.

Here, the polymer fiber may be in the form of a porous membrane, has a biocompatible property that adverse effects do not occur even when adhered to the skin, and may include wide contact and interaction points with the skin so as to be adhered to the skin. In addition, it can have a property of absorbing a water or sodium-containing solution well.

The secondary battery except for the second anode 220 provided on the skin adhesion layer is electrically connected to the generator through the connection circuit so that when the sodium-containing solution is absorbed by the first anode 210, electrons move to the generator through the connection circuit .

In addition, a discharge reaction may be possible if the skin attachment layer and the replaceable layer are coupled so that sodium ions and electrons can move to the second anode 220 included in the replaceable layer.

The second adhesive layer may be a material capable of absorbing the sodium-containing solution and having an adhesive strength so as not to be desorbed even under vigorous movements such as exercise.

Such a cell can replace lithium and use sodium as an energy source, which can be a next-generation alternative to a lithium secondary battery, and it is expected that the technology application field can be further expanded by enriching the energy source.

Example

Electrochemical analysis

The secondary battery 100 using the sodium-containing solution used in the electrochemical analysis is composed of 0.04 mol of NaCl solution, the first anode 110, the second anode 120, the polymer-based separation membrane 140, the organic electrolyte 150 ) And a cathode (130).

More specifically, MWCNT / Co3O4 = 50 mg / 25 mg for the first anode 110, 50 mg / 25 mg for the cathode 130, MWCNT / Hard Carbon 50 mg / 25 mg for the cathode 120, Based separator 140 used NASICON (Na superionic conductor) and organic electrolyte 150 used 1.0 mol NaCF ₃ SO ₃ / TEGDME.

For the NaCl used as the energy source, a 0.04 molar NaCl solution was used based on 0.04 mol of the sodium ion concentration in the sweat.

The electrochemical performance test was carried out at a current of 0.1 mA, a charge time of 250 mAh / g, and a discharge at 0.5 V.

FIG. 4 is a graph showing charge-discharge curves of a secondary battery 100 using a sodium-containing solution using 0.04M NaCl. It can be seen how the charging / discharging voltage and the electric capacity of the secondary battery according to the present invention change.

The charging and discharging characteristics of the secondary battery according to the embodiment are such that the battery voltage gradually rises during charging and reaches the maximum voltage at about 1 hour after the charging. Thereafter, during secondary cell discharge, the battery voltage gradually decreases to reach a discharge voltage of 0.5V. Even if the number of times of charging and discharging is increased, it is measured that there is no change in the maximum voltage and the minimum voltage, so that the secondary battery according to the present invention has a stable capacity characteristic.

5 is a graph showing the cycling stability curve of the secondary battery 100 using sodium-containing solution using 0.04M NaCl.

The capacity change according to the number of charging and discharging cycles does not change as the number of cycles increases, and the Coulomb efficiency is also kept constant, so that the stable cycle characteristics of the secondary battery according to the present invention can be confirmed.

The description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features presented herein.

100: secondary battery using sodium-containing solution
150: organic electrolyte
110, 210: first anode
120, 220: a second anode
130, 230: cathode
140: polymer-based membrane
200: Secondary battery using sodium-containing solution
240: nonwoven fabric membrane
250: Polymer electrolyte
300: Skin-attached secondary battery

Claims (27)

A secondary battery comprising a first anode, a cathode, and a second anode,
A skin adhesion layer which is provided on the one surface with the first anode and the negative electrode and on which a first adhesive layer having adhesiveness is formed and absorbs the sodium-containing solution from the skin;
Further comprising:
Wherein the first anode comprises:
The sodium-containing solution absorbed in the skin adhesion layer is used as an active material to cause a charging reaction,
And the second anode includes:
Which causes a discharge reaction using sodium ions generated by the charge reaction and oxygen in the atmosphere,
Secondary battery.
The method according to claim 1,
The secondary battery includes:
A replaceable layer on which a second adhesive layer having an adhesive property is formed;
Further comprising:
And the second anode includes:
A second adhesive layer provided on the first adhesive layer and aligned with the first anode,
Secondary battery.
3. The method of claim 2,
Wherein a portion of said one surface of said second adhesive layer is bonded to a portion of said one surface of said skin adhesive layer,
Secondary battery.
3. The method of claim 2,
Wherein each of the first adhesive layer and the second adhesive layer comprises:
Comprising a biocompatible polymeric fiber,
Secondary battery.
5. The method of claim 4,
The biocompatible polymeric fibers may be prepared by,
Polyacrylates, hydrogel-based polymers, saccharides, proteins, glycoproteins, mixtures or additives thereof,
Secondary battery.
The method according to claim 1,
Wherein the second anode includes a cathode current collector,
A positive electrode active material not containing a positive electrode active material on the positive electrode current collector,
Secondary battery.
The method according to claim 1,
And the second anode includes:
Wherein the negative electrode does not store sodium ions supplied from the negative electrode during the discharging reaction,
Secondary battery.
The method according to claim 1,
The secondary battery includes:
A generator which is provided on the one surface of the skin adhesion layer and is electrically connected to the first anode and the cathode;
≪ / RTI >
Secondary battery.
The method according to claim 1,
Wherein each of the first anode and the second anode comprises:
Anode collector; And
A catalyst layer provided on a surface of the positive electrode collector;
/ RTI >
Secondary battery.
10. The method of claim 9,
The catalyst in the catalyst layer may be,
A catalyst comprising an oxygen reducing catalyst, an oxygen evolution reaction, a Bi-functional catalyst, a Cl ₂ evolution reaction, or a combination thereof.
Secondary battery.
The method according to claim 1,
The negative electrode,
An anode current collector having a negative electrode active material layer on its surface;
Lt; / RTI >
Wherein the negative electrode active material layer includes a negative electrode active material, a conductive material, and a binder,
The negative electrode active material,
An organic material, an alloy system, a carbon-based material, or a sodium intercalation material.
Secondary battery.
The method according to claim 1,
The secondary battery includes:
A separation membrane which is provided between the first anode and the cathode and between the second anode and the cathode to allow sodium ions and electrons generated by the charging reaction to pass therethrough;
≪ / RTI >
Secondary battery.
13. The method of claim 12,
The separation membrane includes:
Based separator comprising a porous polymer membrane, a non-woven membrane separator, an inorganic composite separator membrane, or a combination thereof,
Secondary battery.
13. The method of claim 12,
The separation membrane includes:
NaAlO (CN) _2, perovskite and alumina, amorphous ionic conductive material, pear kongye solid electrolyte, sodium sulfide-based solid electrolyte, sodium oxide-based solid electrolyte or a derivative thereof or a mixture, or SiO _2, Al ₂ O _3, TiO _{2, BaTiO 3, Li 2 O} , LiF, LiOH, Li 3 N, BaO, Na 2 O, Li 2 CO 3, CaCO 3, LiAlO 2, SrTiO 3, CeO 2, MgO, NiO, CaO, ZnO, ZrO 2 , SiC, derivatives thereof, or mixtures thereof.
Secondary battery.
13. The method of claim 12,
Wherein each of the first anode, the cathode, the second anode,
A non-woven form of a three-dimensional network structure,
Secondary battery.
The method according to claim 1,
Wherein the first anode comprises:
A porous nonwoven fabric comprising a plurality of polymer fibers; And
Conductive material;
/ RTI >
Wherein the conductive material is uniformly filled between the polymer fibers,
Secondary battery.
The method according to claim 1,
The negative electrode,
A porous nonwoven fabric comprising a plurality of polymer fibers;
Anode active material particles; And
Conductive material;
/ RTI >
Wherein the anode active material particles and the conductive material are uniformly filled and pores are formed between the polymer fibers,
Secondary battery.
The method according to claim 1,
And the second anode includes:
A porous nonwoven fabric comprising a plurality of polymer fibers; And
Conductive material;
/ RTI >
The conductive material is uniformly filled and pores are formed between the polymer fibers,
Secondary battery.
13. The method of claim 12,
The separation membrane includes:
A porous nonwoven fabric comprising a plurality of polymer fibers;
Lt; / RTI >
The porous non-
Polyvinyl pyrrolidone, polyethylene terephthalate, polyimide, polyamide, polysulfone, polyvinylidene fluoride, polyacrylonitrile, polyethylene, polypropylene, polyetherimide, polyvinyl alcohol, polyethylene oxide, polyacrylic acid, polyvinylpyrrolidone , Agarose, alginate, polyvinylidene hexafluoropropylene, derivatives thereof, or mixtures thereof.
Secondary battery.
13. The method of claim 12,
The secondary battery includes:
A polymer electrolyte impregnated with the separation membrane, the polymer electrolyte comprising a polymer matrix composed of a network polymer, inorganic particles, a dissociable salt, and an organic solvent;
≪ / RTI >
Secondary battery.
21. The method of claim 20,
The polymer matrix may comprise,
A linear polymer comprising polyvinylidene fluoride, polyvinylidene fluoride, polyvinylidene fluoride hexafluoropropylene, polymethylmethacrylate, polystyrene, polyvinyl acetate, polyethylene oxide, derivatives thereof, or mixtures thereof; And
A crosslinking monomer comprising an acrylate-based monomer, a derivative thereof, or a mixture thereof;
/ RTI >
Secondary battery. delete delete delete delete delete delete

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