KR20140091247A - Lithium air battery - Google Patents

Abstract

The present invention relates to a lithium air battery which prevents a catalyst layer from being delaminated even by combining oxygen which touches an electrolyte in the air with a membrane which allows lithium ions to pass through the catalyst layer of an anode used as an active material; and restrains the evaporation of an aqueous electrolyte solvent using a polyolefin-based fine porous layer, thereby preventing the performance of deterioration due to the repetitive charge/discharge process of the lithium air battery and the lifetime extended.

Description

Lithium air battery

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium-ion battery, and more particularly, to a lithium-ion battery capable of preventing performance deterioration caused by repetition of charging and discharging and prolonging its service life.

In recent years, the development of technologies for converting automobile energy sources from gasoline and light oil to electrical energy has been attracting attention, in light of an increase in carbon dioxide emissions due to the consumption of fossil fuels and a rapid change in crude oil prices. Electric vehicles have been put into practical use. For long-distance driving, it is required to increase the capacity and energy density of lithium-ion batteries, which are storage batteries. However, current lithium ion batteries have a disadvantage in that it is difficult to travel long distances because of limited battery capacity. Therefore, a lithium ion battery having a larger capacity and a higher energy density than the lithium ion battery is theoretically attracting attention.

Generally, a lithium-air battery includes a cathode capable of adsorbing and releasing lithium ions, and an anode including oxygen-reducing catalyst with oxygen in the air as a cathode active material, and a lithium ion conductive medium is provided between the anode and the cathode do. That is, the lithium air battery is a battery having a positive electrode using oxygen in the air as an active material, and is capable of charging and discharging the battery by performing oxidation-reduction reaction of oxygen in the positive electrode.

These lithium-ion batteries have a theoretical energy density of 3000Wh / kg or more, which corresponds to approximately 10 times the energy density of lithium-ion batteries. In addition, lithium air cells are environmentally friendly and can provide improved safety over lithium-ion batteries.

However, as the conventional lithium-ion battery is repeatedly charged and discharged, the catalyst layer of the anode is detached, the solvent of the water-based electrolyte used between the solid electrolyte and the anode is evaporated to deteriorate the performance of the lithium- There is a problem that this is shortened.

A related art related to this is disclosed in US Patent Publication (US 2012/0028164), "Lithium Air Battery ".

US 2012/0028164 A1 (2012.02.02)

SUMMARY OF THE INVENTION The present invention has been conceived in order to solve the above-mentioned problems, and it is an object of the present invention to provide a lithium ion battery in which deterioration of a catalyst layer constituting an anode of a lithium air battery is prevented, evaporation of an aqueous electrolyte solvent is suppressed, And the life of the battery can be prolonged.

A lithium air battery of the present invention comprises: a first electrode portion including lithium metal; A second electrode part including a gas diffusion layer having one side in contact with air, a catalyst layer formed on the other side of the gas diffusion layer, and a membrane coupled to the catalyst layer to allow lithium ions to pass therethrough, the second electrode part being spaced apart from the first electrode part; And an electrolyte unit disposed between the first electrode unit and the second electrode unit. .

The electrolyte unit may include a separation membrane which is in contact with one side of the first electrode unit and contains an organic electrolyte, a solid electrolyte which is in close contact with one side of the separation membrane, and an aqueous electrolyte which is provided between the solid electrolyte and the second electrode.

The second electrode portion may further include a polyolefin-based microporous membrane coupled to one side of the gas diffusion layer.

The lithium air battery of the present invention comprises a first housing having a space portion opened at an upper side thereof and an air accommodating portion disposed at an upper portion of the first housing to seal the space portion of the first housing and open downward, The first electrode portion is received in the space portion of the first housing, and the second electrode portion is received in the air receiving portion of the second housing, and the second electrode portion is received in the air receiving portion of the second housing, Wherein the first electrode part and the second electrode part are coupled to each other to be spaced apart from the first electrode part, the gas diffusion layer is disposed on the second electrode part, and the membrane is disposed on the lower side, and the electrolyte part is provided in the space part of the first housing, And is provided between the first electrode portion and the second electrode portion.

The electrolyte portion may include a separation membrane which is in close contact with the upper portion of the first electrode portion and contains an organic electrolyte, a solid electrolyte closely adhered to the upper portion of the separation membrane, an aqueous electrolyte provided between the solid electrolyte and the second electrode portion, And a receptacle formed on the upper side of the first electrode and having a receiving hole penetrating the upper and the lower, wherein the receptacle closely adheres the solid electrolyte, the separation membrane, and the first electrode portion to the space portion.

The housing unit may further include a third housing having a fixing hole formed between the first housing and the second housing and passing through the fixing hole and fixing the second electrode unit to the fixing hole.

Also, the membrane is formed of a porous membrane containing a sulfonic acid group.

In addition, the membrane is formed of a porous polyperfluorosulfonic acid (PFSA) resin.

The membrane may be formed to be in close contact with the catalyst layer by heating and pressing a polyperfluorosulfonic acid (PFSA) resin, or may be formed by a dip-coating method using a polyperfluorosulfonic acid (PFSA) And is formed in close contact with the catalyst layer.

The lithium-air battery of the present invention comprises a porous polyolefin microporous membrane, which is in contact with an electrolyte and uses oxygen in the air as an active material, and a membrane capable of passing lithium ions through the electrolyte membrane. , Evaporation of the aqueous electrolyte solvent is suppressed, performance deterioration due to repetition of charging and discharging of the lithium ion battery can be prevented, and life can be prolonged.

1 is a conceptual view showing a lithium air battery of the present invention.
2 and 3 are an assembled perspective view and an exploded perspective view of a lithium ion battery according to an embodiment of the present invention;
4 is a sectional view taken along line AA 'in Fig.
5 is a photograph showing the surface of a catalyst layer in which platinum and a binder are mixed in an initial state.
FIG. 6 is a photograph of the catalyst layer of FIG. 5 when the charge / discharge cycle of the catalyst layer has elapsed 200 times. FIG.
7 is a photograph showing a cross section of a catalyst layer and a gas diffusion layer in which platinum and a binder are mixed in an initial state.
8 is a cross-sectional view showing a state in which particles of the catalyst layer are removed when the charge / discharge cycle of the catalyst layer of FIG. 7 has elapsed 200 times.
9 is a photograph of the surface of the polyolefin-based microporous membrane.
10 is a cross-sectional photograph of the microporous membrane of FIG.
11 is a graph showing the charging / discharging cycle of a lithium-ion battery to which a polyolefin-based microporous membrane and a porous air-cathode without a Nafion membrane are applied.
FIG. 12 is a graph showing the charging / discharging cycle of a lithium-ion battery in which a porous anode is applied to a polyolefin-based microporous membrane, to which a Nafion membrane is not applied.
13 is a graph showing a charge / discharge cycle of a lithium-ion battery (sample 1) using a porous air-cathode having both a Nafion membrane and a polyolefin-based microporous membrane.
FIG. 14 is a graph of charge / discharge energy of sample 1;
15 is a graph of charge / discharge energy efficiency of sample 1;
16 is a graph showing a charge / discharge cycle of a lithium-ion battery (sample 2) using a porous air-cathode having both a Nafion membrane and a polyolefin-based microporous membrane.
17 is a charge / discharge energy graph of sample 2;
18 is a graph of charge-discharge energy efficiency of sample 2;
19 is a photograph showing a comparison of the discoloration degree after several cycles of the aqueous electrolyte in the case of the lithium air battery in which the anode without the Nafion membrane is applied and the aqueous electrolyte in the case of the lithium air battery in which the anode with the Nafion membrane is applied.
FIG. 20 is a graph showing a 421 charge / discharge cycle of a lithium-ion battery using a porous air-cathode in which both a Nafion membrane and a polyolefin-based microporous membrane are used.
FIG. 21 is a graph of charge / discharge energy of the lithium ion battery of FIG. 20; FIG.
FIG. 22 is a graph showing charge / discharge energy efficiency of the lithium ion battery of FIG. 20;

Hereinafter, the lithium-ion battery of the present invention will be described in detail with reference to the accompanying drawings.

FIG. 1 is a conceptual view illustrating a lithium-ion battery of the present invention, and FIGS. 2 to 4 are an assembled perspective view, an exploded perspective view, and a cross-sectional view of a lithium-ion battery according to an embodiment of the present invention.

As shown in the figure, a lithium ion battery 1000 according to the present invention includes a first electrode unit 200 including a lithium metal 210; A catalyst layer 312 formed on the other side of the gas diffusion layer 311 and a membrane 313 connected to the catalyst layer 312 through which lithium ions pass, A second electrode part 300 spaced apart from the first electrode part 200; And an electrolyte unit 400 provided between the first electrode unit 200 and the second electrode unit 300; .

First, the lithium ion battery 1000 of the present invention comprises a first electrode unit 200, a second electrode unit 300, and an electrolyte unit 400.

The first electrode unit 200 includes a lithium metal 210 capable of storing and discharging lithium ions, and may further include a binder. As the lithium metal 210, for example, a lithium metal, a lithium metal based alloy, a lithium intercalating compound, or the like may be used, and it is preferable to use a lithium alloy to improve durability against moisture and the like. Examples of the binder include polyvinylidene fluoride (PVdF) and polytetrafluoroethylene (PTFE). The content of the binder is not particularly limited and may be, for example, 30% by weight or less, 10% by weight.

The second electrode unit 300 includes a gas diffusion layer 311, a catalyst layer 312, and a membrane 313, one side of which is in contact with air, and the second electrode unit 300 is composed of a first And is spaced apart from the electrode unit 200. 1, the second electrode unit 300 is configured such that a membrane 313 is disposed on a surface facing the first electrode unit 200, and a catalyst layer 312 is formed on one side of the gas diffusion layer 311 And the membrane 313 is coupled to one side of the catalyst layer 312 to form the second electrode unit 300. Thus, the air is diffused through the gas diffusion layer 311 and is capable of causing a redox reaction with lithium ions and oxygen in the air in the catalyst layer 312.

At this time, the second electrode unit 300 may include an electrically conductive material having oxygen and air in which oxygen and lithium ions can move, as an active material, and the catalyst layer 312 may be formed by mixing platinum (Pt) Or may be formed by coating or coating. That is, the catalyst, the conductive material and the binder are mixed and then press-formed on the gas diffusion layer (or the carbon paper) 311 or into an organic solvent such as acetone, methyl ethyl ketone, N-methyl- A catalyst, a conductive material and a binder are mixed and dissolved or dispersed to prepare a slurry, which is then applied onto the gas diffusion layer 311 by gravure coating, blade coating, comma coating, dip coating or the like, The catalyst layer 312 can be formed by volatilization and pressing.

As the conductive material, for example, conductive materials such as carbon materials and metal fibers, metal powders such as copper, silver, nickel and aluminum, and organic conductive materials such as polyphenylene derivatives can be used. As the carbon material, carbon black, graphite, activated carbon, carbon nanotubes, carbon fibers and the like can be used, and a synthetic resin containing an aromatic ring compound and mesoporous carbon obtained by calcining a petroleum pitch can be used.

In the electrolyte unit 400, the electrolyte unit 400 is provided between the first electrode unit 200 and the second electrode unit 300 so that lithium ions can be moved.

The first electrode unit 200 including the lithium metal 210 becomes an anode and the second electrode unit 300 becomes a cathode and the first electrode unit 200 And the second electrode unit 300. The lithium ion battery 1000 includes the electrolyte unit 400. [

At this time, when the lithium ion battery 1000 is charged and discharged, air is diffused through the gas diffusion layer 311 of the second electrode unit 300, oxygen and lithium ions in the air are oxidized and reduced in the catalyst layer 312 When charging and discharging are repeated, cracks are generated in the catalyst layer 312 and particles (platinum, binder, and conductive materials) forming the catalyst layer 312 can be separated from the gas diffusion layer 311 toward the electrolyte unit 400. As a result, the performance of the lithium-ion battery may deteriorate and the lifetime thereof may be shortened.

The lithium ion battery 1000 of the present invention has a membrane 313 through which lithium ions pass through the catalyst layer 312 of the second electrode unit 300 and can prevent particles of the catalyst layer 312 from being separated Therefore, even if charging and discharging are repeated, the performance of the lithium-ion battery can be prevented from deteriorating and the life can be prolonged.

5 and 6 are electron micrograph (SEM) photographs showing the surface of a catalyst layer in which platinum and a binder are mixed in an initial state and a charge / discharge cycle of 200 passes, and FIGS. 7 and 8 are photographs (SEM) photograph showing a cross section of the gas diffusion layer and the catalyst layer when the cycle has passed 200 times.

That is, after the charge and discharge are repeated as shown in FIG. 6, cracks are generated in the catalyst layer 312, and as a result, a part of the catalyst layer 312 (oval shaped display portion) is removed from the gas diffusion layer 311 (Pt) catalyst contained in the electrolyte portion measured by inductively coupled plasma emission spectroscopy (ICP) as shown in Table 1 below, It can be seen that the platinum catalyst is separated from the catalyst layer by repetition.

Table 1 shows the mass (mg / kg) of platinum contained per unit weight of the aqueous electrolyte solution analyzed by ICP after repetition of charging and discharging for lithium air batteries having platinum mass fractions of 10 wt% and 40 wt% Lt; / RTI >

catalyst Water-based electrolyte (platinum 10wt%) Water-based electrolyte (platinum 40wt%) Platinum (Pt) 33.7 51.1

Thus, according to the present invention, the catalyst layer 312 can be prevented from being detached by the membrane 313 coupled to the catalyst layer 312, so that deterioration of performance of the lithium ion battery can be prevented and the service life can be prolonged.

The electrolyte unit 400 includes a separator 410 adhered to one side of the first electrode unit 200 and containing an organic electrolyte, a solid electrolyte 420 adhered to one side of the separator 410, And an aqueous electrolyte (450) provided between the electrolyte (420) and the second electrode unit (300).

Thus, the electrochemical characteristics and the charge / discharge performance of the lithium air battery can be improved. Since the membrane 313 is disposed between the aqueous electrolyte 450 and the catalyst layer 312 of the second electrode unit 300 and the membrane 313 is coupled to the catalyst layer 312, 312 can be prevented from being detached and the catalyst layer 312 can be prevented from being mixed into the aqueous electrolyte 450.

Here, the organic electrolyte, the solid electrolyte 420 and the water-based electrolyte 450 will be described in more detail in the following embodiments of the lithium-ion battery according to the present invention.

The second electrode unit 300 further includes a polyolefin-based microporous membrane 314 coupled to one side of the gas diffusion layer 311.

That is, the polyolefin-based microporous membrane 314 is bonded to one side of the gas diffusion layer 311 to inhibit the evaporation of the solvent of the water-based electrolyte 450, thereby preventing the performance of the lithium-ion battery from deteriorating And can prolong the life span.

A lithium ion battery 1000 according to an embodiment of the present invention includes a first housing 110 having a space portion 111 opened at an upper side thereof and a second housing 110 disposed at an upper portion of the first housing 110, 1 A second housing 120 which encloses a space 111 of the housing 110 and has an air receiving portion 122 opened to the lower side and a vent hole 121 communicating with the air receiving portion 122, A housing part (100) comprising: A first electrode unit 200 including a lithium metal 210 accommodated in a space 111 of the first housing 110; The gas diffusion layer 311 is disposed on the upper side and the lower side of the gas diffusion layer 311 is disposed on the lower side of the gas diffusion layer 311. The gas diffusion layer 311 is disposed below the air receiving part 122 of the second housing 120 and is spaced apart from the first electrode part 200, A second electrode part 300 on which a catalyst layer 312 is formed and a membrane 313 through which lithium ions pass is formed on the lower side of the catalyst layer 312; An electrolyte unit 400 provided in the space 111 of the first housing 110 and disposed between the first electrode unit 200 and the second electrode unit 300; .

2 to 4, a lithium ion battery 1000 according to an embodiment of the present invention includes a first electrode unit 200, a second electrode unit 300, and an electrolyte (Not shown).

The housing part 100 includes a first housing 110 and a second housing 120. The first housing 110 has a disk shape and a space portion 111 is formed therein, and the space portion 111 is formed so that an upper side thereof is opened. The second housing 120 is formed in a circular plate shape and is disposed on the upper portion of the first housing 110 so that the space portion 111 of the first housing 110 is hermetically sealed. At this time, the second housing 120 is formed with the air receiving portion 122 at the lower side and the vent hole 121 is formed so as to communicate with the air receiving portion 122, And can be introduced into and discharged from the accommodating portion 122. One or a plurality of the vent holes 121 may be formed, and the vent holes 121 may be formed in various shapes to allow air to flow in and out of the air receiving portion 122.

A first fixing part 127 for coupling with the first housing 110 is formed on one side of the second housing 120 and a first coupling part 128 is inserted into the first fixing part 127 The second housing 120 and the first housing 110 may be combined. The first fixing part 127 of the second housing 120 according to the first embodiment of the present invention is formed as a through hole and the first engaging part 128 is formed of a bolt, 1 fixing part 127 is formed at a position corresponding to the fixing part 127 so that the first engaging part 128 penetrates the first fixing part 127 and is coupled to the engaging hole 112 The first housing 110 and the second housing 120 may be coupled. At this time, the first housing 110 and the second housing 120 may be combined in various forms such as fitting, welding, or riveting in addition to screw coupling.

The first electrode unit 200 includes a lithium metal 210 and the lithium metal 210 is accommodated in the space 111 of the first housing 110.

The second electrode unit 300 is connected to the open lower side of the air receiving part 122 of the second housing 120 so as to be hermetically closed so that the gas diffusion layer 311 is located on the upper side, And the membrane 313 may be coupled to the lower side thereof. Thus, the air contained in the air receiving portion 122 is diffused through the gas diffusion layer 311, and is capable of causing a redox reaction with lithium ions and oxygen in the air in the catalyst layer 312.

The electrolyte part 400 is provided in the space part 111 of the first housing 110 and disposed on the upper part of the first electrode part 200. That is, the electrolyte unit 400 is provided between the first electrode unit 200 and the second electrode unit 300 so that lithium ions can be moved.

That is, the first electrode unit 200 including the lithium metal 210 becomes an anode, the second electrode unit 300 becomes a cathode, and the first electrode unit 200, And an electrolyte unit 400 is provided between the first electrode unit 300 and the second electrode unit 300 to constitute a lithium air battery.

The lithium ion battery 1000 according to an exemplary embodiment of the present invention can be charged and discharged to the electrolyte layer 400 by the membrane 313 coupled to the lower side of the catalyst layer 312 of the second electrode unit 300, It is possible to prevent the particles of the lithium ion battery 312 from falling off, thereby preventing the performance of the lithium ion battery from deteriorating and extending the service life.

The electrolyte unit 400 includes a separator 410 adhered to the upper side of the first electrode unit 200 and containing an organic electrolyte, a solid electrolyte 420 adhered to the upper side of the separator 410, And an aqueous electrolyte 450 disposed between the solid electrolyte 420 and the second electrode unit 300. Thus, the electrochemical characteristics and the charge / discharge performance of the lithium air battery can be improved.

The second electrode unit 300 may further include a polyolefin-based microporous membrane 314 coupled to the upper side of the gas diffusion layer 311 so that the polyolefin-based microporous membrane 314 contacts the aqueous electrolyte Evaporation can be suppressed. In addition, the polyolefin-based microporous membrane has a very small pore size (about 10 nm) and is hydrophobic, so that the polyolefin-based microporous membrane is effective in suppressing the evaporation of water, which is a solvent of the aqueous electrolyte 450.

The electrolyte unit 400 may further include a receptor 430 formed on the solid electrolyte 420 and formed with a receiving hole 431 passing through the upper and lower portions of the solid electrolyte 420, The separation membrane 410, and the first electrode unit 200 to the space portion.

4, the upper edge of the receptacle 430 is pressed by the second housing 120 and the solid electrolyte 420, the separation membrane 410, and the first electrode unit 200 Can be closely fixed to the bottom surface of the space portion 111. At this time, the receptacle 430 is formed with a receiving hole 431 so as to pass through the upper and lower portions at the central portion thereof so that the water-based electrolyte 450 contacts the solid electrolyte 420 through the receiving hole 431, .

Thus, the lithium ion battery 1000 according to an embodiment of the present invention has reduced contact resistance between the electrolyte unit 400, the first electrode unit 200, and the first housing 110, thereby improving the efficiency and performance of the lithium ion battery. And the life of the lithium-ion battery is prolonged.

The lithium metal 210 and the electrolytic unit 400 may be disposed on the lower side of the lithium metal 210. The lithium metal 210 may be disposed in the space 111 of the first housing 110, A current collector 220 may be provided under the lithium metal 210 to closely contact the first housing 110 and the first housing 110. The current collector 220 may be formed of a resilient net, 210 and the electrolyte unit 400 can be brought into contact with each other in the most favorable state. That is, the current collector 220, the lithium metal 210, and the electrolyte unit 400, which are received in the space 111 of the first housing 110, are brought into close contact with each other by the engagement of the second housing 120, Can be further reduced. The material of the current collector 220 may be copper, stainless steel, nickel, or the like.

The electrolyte unit 400 may further include a first sealing unit 440 that allows the first electrode unit 200 to be received in the space 111 and to seal the first electrode unit 200.

This is because the first sealing portion 440 is disposed on the rim of the electrolyte portion 400 and the first electrode portion 200 is connected to the electrolyte portion 400 by the engagement of the first housing 110 and the second housing 120. [ And is configured to be sealed in the space portion 111 by the first sealing portion 400 and the first sealing portion 440. That is, the aqueous electrolyte 450 can be prevented from flowing into the first electrode unit 200, thereby preventing the corrosion of the lithium metal 210, thereby improving the performance and lifetime of the lithium ion battery.

A first sealing part 440 such as an O-ring is formed on the lower edge of the solid electrolyte 420 and the upper edge of the receptor 430 of the electrolyte part 400, The sealing force for sealing the first electrode unit 200 in the space 111 can be improved. The separation membrane 410 containing the organic electrolyte may also be sealed by the solid electrolyte 420 and the first sealing portion 440.

The housing part 100 is provided with a fixing hole 131 which is interposed between the first housing 110 and the second housing 120 and passes through the fixing hole 131, And a third housing 130 to which the unit 300 is fixed.

3 and 4, the third housing 130 is interposed between the first housing 110 and the second housing 120 to be in close contact with each other. At this time, after the first electrode unit 200 and the electrolyte unit 400 are received in the space 111 of the first housing 110, the third housing 130 is coupled from above to connect the electrolyte unit 400, The electrode unit 200 and the bottom surface of the space 111 of the first housing 110 may be closely contacted with each other and the first housing 110 and the third housing 130 may be coupled to each other by a bolt, Can be screwed to each other by the coupling hole 112 in which the female screw thread 133 formed on the first housing 110 and the female screw thread formed on the first housing 110 are formed. A second fixing part 132 is formed in the third housing 130 as a through hole so as to allow the second coupling part 133 to pass therethrough. The second fixing part 132 is formed so that the upper side is inclined, The coupling portion 133 is formed of a plate head bolt so that an upper head portion of the second coupling portion 133 is formed so as not to protrude above the upper surface of the third housing 130, The housing 120 can be easily tightly coupled.

The second housing 120 is tightly coupled to the upper portion of the third housing 130 and the through hole 134 is formed in the third housing 130 so that the first engaging portion 128 is engaged with the first fixing portion 127 and the through hole 134 and can be screwed into the coupling hole 112 of the first housing 110.

At this time, a fixing hole 131 is formed in the third housing 130, and the rim of the second electrode unit 300 is tightly fixed between the upper edge of the fixing hole 131 and the second housing 120. At this time, the upper edge of the fixing hole 131 may be formed to be inclined as shown in the drawing, and the edge of the second electrode unit 300 may be fixed at the step. The fixing hole 131 can receive the water-based electrolyte 450 so that ions can move between the first electrode unit 200 and the second electrode unit 300.

As a result, the first housing 110, the second housing 120, and the third housing 130 can be firmly coupled to each other, and the adhesion between the first electrode unit 200 and the electrolyte unit 400 can be improved And the second electrode unit 300 can be easily coupled and fixed.

That is, in the lithium ion battery 1000 according to an embodiment of the present invention, the housing part 100 is composed of the first housing 110, the second housing 120, and the third housing 130, And has an advantage in that the airtightness is excellent and durability is improved as compared with a conventional lithium air battery having a large space portion.

The membrane 313 may be formed of a porous membrane containing a sulfonic acid group, more preferably a porous perfluorosulfonic acid (PFSA) (trade name Nafion) resin As shown in FIG. The membrane 313 may be heated and pressed to be adhered to the catalyst layer. Also, the membrane 313 may be formed by a dip-coating method using a polyperfluorosulfonic acid (PFSA) resin solution. The polyfluoro sulfonic acid (PFSA) membrane is a proton (H ⁺ , hydrogen ion) -conducting (conductivity: 0.1 S / cm), a hydrophilic sulfonyl group in the molecular structure and a hydrophobic group fluorine It consists of hydrophobic fluorinated backbones. Therefore, a proton conductive property has a property of allowing the passage of Li ⁺ ions, absorbing water required for the reaction between oxygen and water to smoothly operate the lithium-air, and to protect the Pt catalyst layer It is a suitable membrane.

That is, the membrane 313 may be formed of a material capable of moving lithium ions while preventing particles of the catalyst layer 312 from falling off, which is most preferable in view of the performance of the lithium air battery.

In addition, the membrane 313 may be heated and pressed to be in close contact with the catalyst layer 312. That is to say, the membrane 313 is heated and pressed to the catalyst layer 312 at a high temperature to improve the bonding force between the catalyst layer 312 and the membrane 313, so that the removal of the catalyst layer 312 particles Can be blocked.

Here, the aqueous electrolyte 450 is prepared by dissolving a salt of Lithium Acetate dihydrate (C ₂ H ₃ LiO ₂ , Sigma-Aldrich), Lithium Chloride (LiCl, Sigma-Aldrich), Lithium hydroxide (LiOH, Sigma- In DI Water may be used. The aqueous electrolyte 450 may be selected from an ionic liquid, that is, a compound represented by the following formula (1), and a mixture thereof.

[Chemical Formula 1]

X ⁺ Y ^-

[In the above formula (1)

X ⁺ is an imidazolium ion, a pyrazolinium ion, a pyridinium ion, a pyrrolidium ion, an ammonium ion, a phosphonium ion or a sulfonium ion; Y ^- is _{(CF 3 SO 2) 2 N} -, (FSO 2) SN -, BF 4 -, PF 6 -, AlCl 4 -, halogen -, CH 3 CO 2 -, CF 3 CO 2 -, CH 3 SO _{^{4 -, CF 3 SO 3 -}} , (CF 3 SO 2) N -, NO 3 -, SbF 6 -, MePhSO 3 -, (CF 3 SO 2) 3 C - or ^{_{(R ") 2 PO 2 -}} ( wherein R "is C1-C5 alkyl).

The cation (X ⁺ ) in the above formula (1) can be illustrated by the following Table 2.

Cation structure
(X ⁺ ) Structure name Cation structure
(X ⁺ ) Structure name 임디azolium ion

약화물

피리드inium ion

ammonium ion

포파온늄 이온

ulfonium ion

피razolium ion

Wherein R ¹ to R ²⁰ and R are (C ¹ -C 20) alkyl, (C 2 -C 20) alkenyl or (C 2 -C 20) alkynyl, wherein said alkyl, alkenyl and alkynyl are each independently selected from the group consisting of hydroxy, _{SO 3 H, -COOH, (C1} -C5) alkyl, (C1-C5) ^{alkoxy, Si (R 21) (R} 22) (R 23) (R 21, R 22 and R ²³ are independently from each other hydrogen or ( (C1-C5) alkyl, (C1-C5) alkoxy).

The type of anion (Y ^- ) in the above formula (1) can be illustrated by the following Table 3.

Anion
(Y ^- ) Anion name Anion (Y ^- ) Anion name BF ₄ ^- tetrafluoroborate (CF ₃ SO ₂₎ N ^- bis [(trifluoromethyl) sulfonyl] amide PF ₆ ^- hexafluorophosphate NO ₃ ^- nitrate AlCl ₄ ^- aluminum chloride SbF ₆ ^- hexafluoroanimonate X ^- Halogen ^- (FSO ₂ ) ₂ N ^- Bis [fluorosulfonyl] imide CH ₃ CO ₂ ^- acetate MePhSO ₃ ^- tosylate CF ₃ CO ₂ ^- 트리프로오acetreate _{(CF 3 SO 2) 2 N} - bis (trifluoromethylsulfonyl) imide CH ₃ SO ₄ ^- 메틸사ulfate _{(CF 3 SO 2) 3 C} - tris (trifluoromethylsulfonyl) methide CF ₃ SO ₃ ^- trifluoromethylsulfate (OR) ₂ PO ₂ ^- 도화 부

Examples of the aqueous electrolyte include 1-methyl-3-ethylimidazolium bis (trifluoromethanesulfonyl) imide, 1-methyl-3-propylimidazolium bis (trifluoromethanesulfonyl) 1-methyl-3-allyl imidazolium bis (trifluoromethanesulfonyl) imide, 1-methyl-3-ethylimidazolium bis (fluorosulfonyl) imide, Methyl-3-allyl imidazolium bis (fluorosulfonyl) imide, 1-methyl-1-propylpyrrolidium bis (trifluoromethanesulfonyl) imide, Imide, 1-methyl-1-allyl pyrrolidium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidium (fluorosulfonyl) imide, Butyl-3-methylimidazoium chloride, 1-butyl-3-methylimidazolium dibutyl phosphate, 1-butyl- An Ami Butyl-3-methylimidazolium hexafluoroantimonate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazoliumhydrogen Butyl-3-methylimidazolium methylsulfate, 1-butyl-3-methylimidazolium tetrachloroaluminate, 1-butyl Methylimidazolium tetrachloroborate, 1-butyl-3-methylimidazolium thiocyanate, 1-dodecyl-3-methylimidazolium iodide, 1-ethyl-2,3 Methylimidazolium bromide, 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl- 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-butyl- Butyl-4-methylpyridinium hexafluorophosphate, benzyldimethyltetradecylammonium chloride, tetraheptylammonium chloride, tetrakis (decyl ) Ammonium bromide, tributylmethylammonium chloride, tetrahexylammonium iodide, tetrabutylphosphonium chloride, tetrabutylphosphonium tetrafluoroborate, triisobutylmethylphosphonium tosylate 1-butyl 1-butyl-1-methylpyrrolidium bromide, 1-butyl-1-methylpyrrolidinium tetrafluoroborate, 1-aryl-3-methylimidazolium bromide, 1 3-methylimidazoium chloride, 1-benzyl-3-methylimidazolium hexafluorophosphate, 1-benzyl-3-methylimidazoium bis (trifluoromethylsulfonyl) imide , chapter 1 3-methylimidazolium dibutyl phosphate, 1- (3-cyanopropyl) -3-methylimidazolium bis (trifluoromethylsulfonyl) amide, 1,3-dimethylimidazo Ethyl-2,3-dimethylimidazolium ethylsulfate, and the like, preferably 1-ethyl-3-methylimidazolium aluminum chloride, 1-butyl-4-methylpyridium hexa Butyl-1-methylpyrrolidium chloride, 1-butyl-3-methylimidazolium tetrachloride, tetrabutylphosphonium tetrafluoroborate, 1-butyl-4-methylpyridinium chloride, 1-butyl-4-methylpyridinium tetrafluoroborate, and the like.

The water-based electrolyte may preferably contain a cation represented by the following formula (2) or (3) in order to have a viscosity that exhibits a high ionic conductivity and excellent electrical characteristics.

(2)

(3)

[In the above formulas 2 to 3,

R ¹ to R ⁴ are (C ¹ -C 20) alkyl, (C 2 -C 20) alkenyl or (C 2 -C 20) alkynyl,

It said alkyl, alkenyl, and alkynyl is optionally substituted with hydroxy, _{amino, -SO 3 H, -COOH, (} C1-C5) alkyl, (C1-C5) ^{alkoxy, Si (R 21) (R} 22) (R 23) ( R ²¹ , R ²² and R ²³ are each independently of the other hydrogen or (C 1 -C 5) alkyl, (C 1 -C 5) alkoxy.

More preferably, the aqueous electrolyte may contain at least one compound selected from the following structures.

Water-based electrolyte is _{LiPF 6, LiTFSI (Lithium bis (} fluorosulfonly) imide), LiBF 4, LiClO 4, LiSbF 6, LiAsF 6, LiN (SO 2 C 2 F 5) 2, LiN (CF 3 SO 2) 2, LiN ( _{SO 3 C 2 F 5) 2} , LiCF 3 SO 3, LiC 4 F 9 SO 3, LiC 6 H 5 SO 3, LiSCN, LiAlO 2, LiAlCl 4, LiN (C x F 2x + 1 SO 2) (C y F _{2y + 1} SO ₂ ) (where x and y are natural numbers), LiCl, LiI, and LiB (C ₂ O ₄ ) ₂ , Li ₂ O ₂ may be present at a concentration of 0.025 to 1 mole in terms of increasing the ionic conductivity without interfering with the continuous reaction at the surface of the porous cathode.

The organic electrolyte contained in the separator 410 may be an organic solvent that does not contain water as a non-aqueous electrolyte. Examples of the non-aqueous organic solvent include carbonate, ester, ether, ketone, organosulfur, Based solvent, an organophosphorous-based solvent, or an aprotic solvent.

Examples of the carbonate solvent include dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC) MEC), ethylene carbonate (EC), propylene carbonate (PC), fluoroethylene carbonate (FEC), and butylene carbonate (BC) may be used. As ester solvents, methyl acetate, ethyl acetate, , Dimethylacetate, methyl propionate, ethyl propionate, gamma -butyrolactone, decanolide, valerolactone, mevalonolactone, caprolactone, etc. may 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.

Examples of the organic sulfur-based and organic phosphorus-based solvents include methanesulfonyl chloride and p-trichloro-n-dichlorophosphorylmonophosphazene, and aprotic solvents Include nitriles such as R'CN (wherein R 'is a linear, branched, or cyclic hydrocarbon group having 2 to 20 carbon atoms and may include a double bond aromatic ring or an ether bond), dimethylformamide Dioxolane such as amide of 1,3-dioxolane, and sulfolane of 1,3-dioxolane.

The non-aqueous organic solvents may be used singly or in combination of two or more. When two or more of them are used in combination, the mixing ratio may be suitably adjusted according to the performance of the desired battery, which is a range understood by those skilled in the art.

The non-aqueous organic solvent may include a lithium salt. The lithium salt may be dissolved in an organic solvent to act as a source of lithium ions in the battery. For example, the non-aqueous organic solvent may include, for example, Of lithium ions.

The lithium salt may be the same or different from the lithium salt contained in the aqueous electrolyte and may be LiPF ₆ , LiTFSI (lithium bis (fluorosulfonyl) imide), LiBF ₄ , LiSbF ₆ , LiAsF ₆ , LiN (SO ₂ C ₂ F ₅ ) _{2, Li (CF 3 SO 2} ) 2 N, LiC 4 F 9 SO 3, LiClO 4, LiAlO 2, LiAlCl 4, LiN (C x F 2x + 1 SO 2) (C y F 2y + 1 SO 2) ( (Wherein x and y are natural numbers), LiF, LiBr, LiCl, LiI and LiB (C ₂ O ₄ ) ₂ (lithium bis (oxalato) borate You can use more than one.

The concentration of the lithium salt can be used within the range of 0.1 to 2.0 moles. When the concentration of the lithium salt is within the above range, the electrolyte has appropriate conductivity and viscosity, and therefore, it can exhibit excellent electrolyte performance, and lithium ions can effectively move. The non-aqueous organic solvent may further include a metal salt in addition to the lithium salt. Examples of the non-aqueous organic solvent include AlCl ₃ , MgCl ₂ , NaCl, KCl, NaBr, KBr and CaCl ₂ .

The solid electrolyte 420 means a lithium ion conductive solid electrolyte membrane and can act as a protective layer to protect water contained in the aqueous electrolyte from reacting directly with lithium contained in the negative electrode. Examples of the lithium ion conductive solid electrolyte 420 include an inorganic material containing lithium ion conductive glass, lithium ion conductive crystal (ceramic or glass-ceramic), or a mixture thereof.

BRIEF DESCRIPTION OF THE DRAWINGS The invention will be better understood by reference to the following drawings and examples, which are for the purpose of illustrating the invention and are not intended to limit the scope of protection of the invention.

[Preparation Example 1] Preparation of Nafion coated air-cathode

Hot pressing method using Nafion membrane

Cut the Nafion perfluorinated membrane (N-115 or N-117, Sigma-Aldrich) using a punch somewhat larger than the diameter of the air cathode used (eg 1.7 cm in diameter for an air cathode with a diameter of 1.5 cm). The Pt (Pt) catalyst layer of the air cathode is brought into contact with the Nafion membrane and placed in a release film bag. Next, the prepared release film bag is maintained at a pressure of 100 kg / cm ² for 3 minutes using a hot press. The temperature of the hot press is maintained at 135 ^° C. At this time, pressure, temperature, and holding time can be changed to induce the microstructure change of the air cathode.

Dip coating method using Nafion resin solution

Nafion perfulorinated resin, aqueous dispersion (10 wt% in H ₂ O, Sigma-Aldrich) was added to the Petri dish according to the size of the air-cathode (100 mL for an air cathode with a diameter of 1.5 cm) Pt < / RTI > layer is fully submerged and maintained for 5 to 10 minutes. It is then dried in a laminar flow in a fume hood at room temperature for 24 hours. The Nafion resin used in this example can be a high concentration resin solution (for example, 30 wt% in H ₂ O), and the dipping and drying process can be carried out using the thickness of the Nafion film desired to be finally produced in the platinum catalyst layer of the air cathode Depending on the microstructure, it can be repeated one or two or more times.

[Preparation Example 2] Preparation of polyolefin-based composite microporous membrane (or separation membrane)

The polyolefin-based composite microporous membrane (or separation membrane) used for suppressing the evaporation of the electrolyte solution in the present lithium-air battery is a porous membrane containing a polymeric binder and inorganic particles. The polymeric binder uses a water-soluble polymer and a water- The content of the water-soluble polymer and the water-insoluble polymer can be controlled to optimize heat resistance, adhesion, and moisture content.

Production Method 1

High-density polyethylene having a weight average molecular weight of 3.8 x 10 ⁵ was used for the production of a polyolefin-based microporous membrane. As the diluent, dibutyl phthalate and paraffin oil having a kinetic viscosity of 40 cSt were mixed at a ratio of 1: 2, and the content of polyethylene and diluent was 30 wt% and 70 wt%, respectively. The composition was extruded at 240 ° C using a biaxial compounder equipped with a T-die, passed through a section set at 170 ° C to induce phase separation of polyethylene and diluent present in a single phase, . The sheet produced by using the continuous biaxial stretching machine was stretched 6 times at a stretching temperature of 128 占 폚 in longitudinal / transverse direction, and the heat fixing temperature after stretching was 128 占 폚 and the heat fixing width was made at 1-1.2-1.1 . The final thickness of the prepared polyethylene microporous membrane was 16 탆, the gas permeability (gurley) was 130 sec, and the pore closing temperature was 140 캜.

Polyvinyl alcohol (2.6 wt%) having a melting point of 220 ° C. and a saponification degree of 98% and Acrylic latex having a Tg of -45 ° C. were mixed with 3.1 wt% (Rovene 6050) of solid content using the polyolefin microporous membrane prepared by the above- , And 47 wt% of Al ₂ O ₃ (average particle size of 0.4 μm) powder was dissolved in Deionized water. Die coating method was used to coat the cross section of the polyolefin-based microporous membrane, and then a certain amount of air was added in an oven at 60 ° C to remove / dry the solvent. Finally, a polyolefin-based composite microporous membrane having a thickness of 4.2 .mu.m was prepared.

FIG. 9 is a photograph of the surface of the polyolefin composite microporous membrane manufactured by the method, and FIG. 10 is a cross-sectional view thereof.

Production Method 2

High density polyethylene having a weight average molecular weight of 3.8 x 10 ⁵ was used for the production of a polyolefin microporous membrane, dibutyl phthalate and paraffin oil having a kinetic viscosity of 160 cSt were mixed in a ratio of 1: 2, And the content of the diluent was 25 wt% and 75 wt%, respectively. The composition was extruded at 240 ° C using a biaxial compounder equipped with a T-die, passed through a section set at 170 ° C to induce phase separation of polyethylene and diluent present in a single phase, . The sheet produced by using the continuous biaxial stretching machine was stretched 7 times at a stretching temperature of 128 占 폚 in longitudinal / transverse directions, a heat fixing temperature after stretching was 126 占 폚, and a heat fixing width of 1-1.2-1.2 . The final thickness of the prepared polyethylene microporous membrane was 9 탆, the gas permeability (Gurley) was 110 sec, and the pore closing temperature was 139 캜.

To the polyolefin-based microporous membrane described above, 0.5% by weight of a silanol-polyvinyl alcohol copolymer having a melting temperature of 225 ° C and a saponification degree of 97.5% and 1.5% by weight of Carboxylated Styrene butadiene latex having a Tg of -24 ° C (Rovene 4305) Was prepared by dissolving 22 wt% of plate-like Al ₂ O ₃ (average particle diameter 1.5 탆) powder of 10 to 20 in Deionized water. After coating on the cross section of the polyolefin microporous membrane using a micro-gravure coating method, the solvent was removed / dried by applying a constant air volume in an oven at 60 ° C, and finally a polyolefin composite microporous membrane .

Production Method 3

A polyolefin microporous membrane prepared using the above-mentioned Production Method 1 was used, and 0.6 wt% of polyvinyl alcohol having a melting point of 220 캜 and a saponification degree of 99% and 4.0 wt% of Acrylic latex having a Tg of -45 캜 (Rovene 6050) was prepared by dissolving 40wt% of Al ₂ O ₃ (average particle size 0.6 탆) powder in Deionized water. Die coating method was used to coat the cross-section of the polyolefin-based microporous membrane. Then, a certain amount of air was added in an oven at 60 ° C to remove / dry the solvent. Finally, a polyolefin-based composite microporous membrane having a coating thickness of 2.5 .mu.m was prepared.

[Example 1] Production of lithium air cell

LiCH ₃ COOH (Lithium Acetic Acid, molar mass = 102.02 g / mol, Sigma-Aldrich), LiCl (Lithium Chloride, molar mass = 42.39 g / mol, Sigma- 16.3g, 6.8g, and 3.8g were dissolved in 1 liter (liters, L) of DI water to prepare a 1M aqueous electrolyte solution, respectively, to prepare a second electrolyte. A lithium metal thin film was used as a cathode, and polypropylene (SKI, F305CHP, 525HV) was used as a separator disposed on the lithium metal thin film. A Nafion coated air-cathode was prepared as a porous cathode in the same manner as described in Preparation Example 1. A gas diffusion layer (Pt 10 wt%, Fuel Earth, EP1019) having a platinum catalyst layer was used as a basic air electrode. The polyolefin-based composite microporous membrane (SKI, F305CHP, 525HV) used for suppressing the evaporation of the electrolytic solution was prepared as in Production Example 2.

A lithium metal thin film cathode was provided on the stainless steel case and a 1 M LiTFSi in EC: DMC = 1: 1, 1 M LiTFSi in EC: PC = 1: 1 and 1 M LiPF ₆ in EC: DEC (OHARA, AG-01) was provided on the separator, and a receiver in which a water-based electrolyte prepared in the upper part was installed was installed. A positive electrode Was set so as to face the cathode. Next, a carbon paper washer was disposed on the anode, and the second housing 120 was fixed on the carbon paper washer. 1M LiCH ₃ COOH in DI water as an aqueous electrolyte and 1M LiTFSi in EC: DMC = 1: 1 as an organic electrolyte having good wettability with a separator were used, and the same materials as those described above were used for the remaining materials.

To evaluate the charge-discharge characteristics of the lithium-air cell manufactured by the above-described method, the battery was discharged and charged at a constant current mode of 0.25 mA / cm < ² > at 25 DEG C and 1 atm for 24 minutes.

[Example 2]

In Example 1, the evaporation of the water-based electrolyte was suppressed by using a polyolefin-based microporous membrane, and the results were compared. In addition, it uses a porous air electrode Nafion film is not applied in order to clearly compare the effects, atmosphere air (ambient air) is not moisture is 0.6ppm or less pure O ₂ gas vent of the (relative humidity 0%), the lithium air battery Discharge characteristics of a lithium air battery manufactured by flowing 5 to 10 ccm through the battery 121 was evaluated. The results of the charge-discharge test are shown in Figs. 11, 12 and 4. Fig. The lifetime of the lithium-ion battery manufactured by applying the polyolefin-based microporous membrane to the air-cathode is remarkably improved.

Unit charge, discharge capacity cycle Running Time Polyolefin-based microporous membrane 0.18 mAh 7 7 (H): 45 (M): 43 (S) Not applicable 0.18 mAh 52 58 (H): 55 (M): 47 (S) Applied

[Example 3]

In Example 1, N-ion coating was performed using the N-117 Nafion membrane according to the hot pressing method of Preparation Example 1, and an air-cathode using a polyolefin microporous membrane was prepared and used in a lithium air battery. The results of 50 charge / discharge cycles of the lithium ion battery of the two samples (sample 1 and sample 2) are shown in FIGS. 13 to 18 and the discharge energy retention rate is shown in Table 5 and Table 6 It looked. The air-cathode with Nafion Membrane is stable and shows excellent battery performance. Also, as shown in FIG. 19, when the Nafion coating was applied, the platinum (Pt) catalyst layer was completely prevented from being peeled off completely, and no discoloration of the aqueous electrolyte due to the peeled platinum (Pt) catalyst layer occurred after 50 cycles of charging and discharging.

Sample 1: Discharge Energy Retention Rate after 50 Cycles Discharge energy [mWHr] cycle Discharge Energy Retention Rate [%] 0.54 One 103.7 0.56 50

Sample 2: Discharge Energy Retention Rate after 50 Cycles Discharge energy [mWHr] cycle Discharge Energy Retention Rate [%] 0.55 One 98.1 0.54 50

[Example 4]

In Example 1, Nafion coating was performed by the dip coating method of Production Example 1, and an air-cathode using a polyolefin-based microporous membrane was prepared and used in a lithium-air battery. The results of the 421 charge / discharge cycles of the lithium air cell, the charge / discharge energy change and the charge / discharge energy efficiency are shown in FIGS. 19 to 21, and the discharge energy retention rate is shown in Table 7. When applied with Nafion dip coating method, it showed excellent battery performance, especially very improved cycle life.

Discharge Energy Retention Rate after 421 cycles Discharge energy [mWHr] cycle Discharge Energy Retention Rate [%] 0.55 One 85.5 0.47 421

In the lithium air battery of the present invention, as shown in Examples 1 to 4, the Nafion coating prevents the platinum (Pt) catalyst layer from being slowly peeled off, and the polyolefin-based microporous membrane inhibits the evaporation of the aqueous electrolyte solvent, It can be seen that it is improved. It can be seen that an excellent cycle life of 421 cycles can be secured in an atmospheric environment, and a discharge energy retention rate is also very high.

In addition, when lithium metal is used as the cathode, it is difficult to secure a lifetime of several tens of cycles or more in the past due to the influence of water. However, the lithium air battery of the present invention is prevented from electrical short circuit, To ensure excellent cycle life.

The lithium-ion battery of the present invention employs an ionic liquid having anions such as FSI and TFSI as an aqueous electrolyte when the ionic liquid is used as an aqueous electrolyte, thereby reducing the deterioration due to the decomposition reaction with lithium, Respectively. In this case, a stabilization time of at least 4 hours to 12 hours is required even in a general half-cell, whereas the lithium-ion battery of the present invention has a short stabilization time of 30 minutes to 1 hour.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. It goes without saying that various modifications can be made.

1000: Lithium air battery
100: housing part
110: first housing
111: space part 112: engaging hole
120: second housing 121: vent hole
122: air receiving portion 127: first fixing portion
128:
130: third housing 131: fixing hole
132: second fixing portion 133: second coupling portion
134: Through hole
200: first electrode portion
210: lithium metal 220: collector
300: second electrode portion
311: gas diffusion layer 312: catalyst layer
313: Membrane 314: Polyolefin-based microporous membrane
400: electrolyte part
410: separator (organic electrolyte) 420: solid electrolyte
430: Receptor 431: Receiving hole
440: first closure 450: aqueous electrolyte

Claims (9)

A first electrode portion including a lithium metal;
A second electrode part including a gas diffusion layer having one side in contact with air, a catalyst layer formed on the other side of the gas diffusion layer, and a membrane coupled to the catalyst layer to allow lithium ions to pass therethrough, the second electrode part being spaced apart from the first electrode part; And
An electrolyte part provided between the first electrode part and the second electrode part; A lithium-ion battery.
The method according to claim 1,
The electrolyte unit may include a separator membrane which is in close contact with one side of the first electrode unit and contains an organic electrolyte, a solid electrolyte which is in close contact with one side of the separator membrane, and a lithium-air battery including an aqueous electrolyte provided between the solid electrolyte and the second electrode unit. .
The method according to claim 1,
And the second electrode portion further comprises a polyolefin-based microporous membrane coupled to one side of the gas diffusion layer.
The method according to claim 1,
The air conditioner according to any one of claims 1 to 3, wherein the air conditioner comprises: a first housing having a space portion opened on the upper side and an air receiving portion disposed on the upper portion of the first housing to seal the space portion of the first housing, And a housing portion including a second housing,
The first electrode portion is accommodated in a space portion of the first housing,
The second electrode part is coupled to the lower part of the air receiving part of the second housing and is spaced apart from the first electrode part. The second electrode part is coupled with the gas diffusion layer on the upper side and the membrane on the lower side,
Wherein the electrolyte portion is provided in a space portion of the first housing and is provided between the first electrode portion and the second electrode portion.
5. The method of claim 4,
The electrolyte part may include a separator membrane which is in close contact with the upper side of the first electrode part and contains an organic electrolyte, a solid electrolyte which is in close contact with the upper side of the separator, an aqueous electrolyte which is provided between the solid electrolyte and the second electrode part, And a receiver having a receiving hole penetrating the upper and lower portions,
Wherein the solid electrolyte, the separation membrane, and the first electrode portion are brought into close contact with the space portion.
5. The method of claim 4,
Wherein the housing part further comprises a third housing interposed between the first housing and the second housing and having a fixing hole penetrating the fixing part, the third housing being fixed to the fixing hole.
7. The method according to any one of claims 1 to 6,
Wherein the membrane is a porous membrane including a sulfonic acid group.
8. The method of claim 7,
Wherein the membrane is formed of a porous polyperfluorosulfonic acid (PFSA) resin.
9. The method of claim 8,
The membrane may be formed to be in close contact with the catalyst layer by heating and pressing a polyperfluorosulfonic acid (PFSA) resin, or may be formed by a dip-coating method using a polyperfluorosulfonic acid (PFSA) Lithium air battery formed closely.

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