JPWO2010090253A1 - Sheet illumination device - Google Patents

Abstract

The present invention provides a sheet-like secondary battery having a high capacity that does not cause degradation of performance or fire even when irradiated with sunlight or the like, and that can provide a stable output even at extremely low temperatures in cold regions. Provided is a sheet-like lighting device in which a solar cell and a sheet-like surface light emitter are laminated. This sheet-like lighting device is a sheet-like lighting device in which a sheet-like solar cell is laminated on one surface of a sheet-like secondary battery having an electrolyte, and a sheet-like surface light emitter is laminated on the other surface, The volatile organic solvent contained in the electrolyte of the sheet secondary battery is 0% or more and less than 10% of the total mass of the electrolyte, and the electrolyte contains an ionic liquid.

Description

  In the present invention, a sheet-like solar cell that absorbs solar energy, a sheet-like secondary battery that accumulates the energy, and a sheet-like surface light emitter that emits light by power supplied from the sheet-like secondary battery are sequentially stacked. The present invention relates to an integrated sheet illumination device.

  A lighting device including a solar battery and a secondary battery is widely used as a highly convenient lighting device that can be driven for a long time, particularly at a construction site or a disaster site where it is difficult to secure a power source.

  Further, a blind device composed of a slat formed by laminating a solar cell on one surface and an organic EL surface light emitter on the other surface around a sheet-like polymer secondary battery has been proposed (for example, Patent Document 1). reference). The blind device arranges a solar cell on the light shielding surface of the slat, converts the solar energy into electric energy at the time of light shielding, stores it in the sheet-like polymer secondary battery, and supplies the voltage to the sheet-like organic EL surface light emitter. So, we use the solar energy effectively to illuminate the room. The sheet-like polymer secondary battery of the present invention is obtained by replacing the electrolyte solution of a conventional lithium ion secondary battery with a polymer gel electrolyte obtained by impregnating a polymer with an electrolyte solution composed of an electrolyte salt and an organic solvent. It is a secondary battery that does not easily leak. For this reason, safety is maintained only by sealing with a metal film. Thereby, the thickness of the battery is reduced, and the degree of freedom in shape is increased.

  However, in order to maintain the performance of the battery, it contains a large amount of volatile organic solvent such as ethylene carbonate (10% by mass or more of the total mass of the battery electrolyte) (see, for example, Patent Document 2). In addition, a sealing material such as a highly flexible resin film cannot provide sufficient sealing performance. In particular, in the case of exposure to sunlight at all times during the day, such as blind devices, if the solvent evaporates and leaks to the outside due to heat storage, not only the performance of the secondary battery deteriorates, but also the cause of health damage to the human body, the worst In the case of, it was found to cause a fire.

  Therefore, inevitably, the sealing film must be a metallic material with low solvent permeability, thick, low flexibility, and low transparency. It was found that there are significant restrictions on the workability, the installation location, and the degree of freedom of carrying.

  In addition, the sheet-like lighting device is considered to be useful from the viewpoint of energy saving as an application for lighting a vehicle interior at night using energy stored in the daytime, for example, pasted on a window glass such as a sunroof of a car. . The lighting device is stable for a long time under exposure to a very severe temperature environment of about 50 ° C. to 70 ° C. during the daytime when exposed to direct sunlight in the summer, and about −30 ° C. to −40 ° C. during the winter night in a cold region. Output is required. However, in conventional polymer secondary battery electrolytes, the output fluctuated due to the volatilization of the solvent in the summer and the deterioration of the ionic conductivity in the winter.

JP 2001-82058 A JP 11-329500 A

  The purpose of the present invention is not to cause performance degradation or fire even when irradiated by sunlight or the like, and to a high capacity sheet-like secondary battery that can obtain a stable output even at extremely low temperatures in cold regions. It is providing the sheet-like illuminating device by which the sheet-like solar cell and the sheet-like surface light-emitting body were laminated | stacked.

  The above object of the present invention can be achieved by the following configuration.

  1. A sheet-like lighting device in which a sheet-like solar cell is laminated on one surface of a sheet-like secondary battery having an electrolyte and a sheet-like surface light emitter is laminated on the other surface, and the electrolyte of the sheet-like secondary battery The sheet-shaped lighting device characterized in that the volatile organic solvent contained in is not less than 0% and less than 10% of the total mass of the electrolyte, and the electrolyte contains an ionic liquid.

  2. 2. The sheet-like lighting device according to 1 above, wherein the ionic liquid is represented by the following general formula (1).

(Wherein, R ₁ to R ₄ represents an alkyl group which may have a substituent, may be any two groups of R ₁ to R ₄ form a ring together with the nitrogen atom .X is N (SO ₂ F) ₂ , BF ₃ Y or N (CN) ₂ is represented, and Y represents an alkyl group or a perfluoroalkyl group.
3. 3. The sheet-like lighting device according to 1 or 2, wherein the electrolyte of the sheet-like secondary battery contains inorganic fine particles.

  4). The sheet-like lighting device according to any one of 1 to 3, wherein the sheet-like solar cell is an organic thin-film solar cell.

  5). The sheet-like lighting device according to any one of 1 to 4, wherein the sheet-like surface light emitter is an organic EL surface light emitter.

  According to the present invention, a sheet-like secondary battery having a high capacity that does not cause deterioration in performance or fire even when receiving heat storage by sunlight or the like, and that can obtain a stable output even at extremely low temperatures in cold regions. It was possible to provide a sheet-like lighting device in which a solar cell and a sheet-like surface light emitter were laminated.

It is sectional drawing of the sheet-like illuminating device of this invention. It is a top view for demonstrating the principal part structure of the sheet-like secondary battery which concerns on this invention. It is a longitudinal cross-sectional view of a sheet-like secondary battery. It is a top view of the sheet-like illuminating device which arrange | positioned the circuit for light-emitting a sheet-like surface light-emitting body on a sheet-like secondary battery.

  As a result of intensive studies in view of the above problems, the present inventor has found that in a sheet-like lighting device in which a sheet-like secondary battery having an electrolyte, a sheet-like solar battery, and a sheet-like surface light emitter are laminated, the sheet-like secondary Even if the volatile organic solvent contained in the battery electrolyte is reduced to less than 10% of the electrolyte, and the electrolyte contains an ionic liquid, even if it is irradiated with sunlight or the like, performance deterioration or fire A sheet-like lighting device in which a sheet-like solar cell and a sheet-like surface light emitter are stacked on a high-capacity sheet-like secondary battery that can produce stable output even at extremely low temperatures in cold regions. It is as soon as it has been found and can be realized.

  This effect is obtained because the electrolyte contains a small amount of volatile organic solvent, so the volatile solvent does not release to the outside even if it receives heat storage from sunlight, etc., and does not cause performance deterioration or fire. In addition, it is believed that stable output can be obtained because the ionic conductivity of the electrolyte does not deteriorate even at extremely low temperatures in cold regions.

[Sheet illumination device]
The sheet illumination device of the present invention will be described with reference to FIG.

  FIG. 1 is a cross-sectional view of the sheet illumination device of the present invention cut in a direction perpendicular to the sheet surface. Centering on the sheet-like secondary battery 2, one surface thereof is bonded to the sunlight non-light-receiving surface of the sheet-like solar cell 1, and the other surface is bonded to the non-light-emitting surface of the sheet-like surface light emitter 3. .

  As a method for bonding the members, any conventionally known method can be used as long as it forms a uniform and smooth bonded surface. An adhesion method capable of re-peeling between members can also be suitably used.

[Sheet-type secondary battery]
Next, the sheet-like secondary battery according to the present invention will be described in detail.

  The sheet-like secondary battery greatly reduces the amount of volatile organic solvent from the electrolyte solution of the conventional lithium ion secondary battery, and by using ionic liquid and inorganic fine particles, without impairing battery performance, It is a storage battery optimal for the sheet-like lighting device of the present invention which is safe and highly flexible.

〔Electrolytes〕
The electrolyte as used in the present invention refers to a mixture containing other metals, compounds, etc., regardless of whether it is an electrolyte or a non-electrolyte, an electrolyte (broadly defined electrolyte). The electrolyte generally refers to a substance that dissolves in water or an organic solvent and the solution exhibits ion conductivity.

(Volatile organic solvent)
The electrolyte used for the sheet-like secondary battery according to the present invention has a volatile organic solvent content of 0% by mass or more and less than 10% by mass. More preferably, it is 0 mass% or more and less than 5 mass%, Most preferably, it is 0 mass% or more and less than 3 mass%. Specific examples of the volatile organic solvent used in the present invention include those having a boiling point of 250 ° C. or less under atmospheric pressure. Aprotic organic solvents are typical examples, and specific examples include propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate, γ-butyllactone, sulfolane, 1,2-dimethoxyethane, 1,2-diethoxyethane. 2-methyltetrahydrofuran, 3-methyl-1,3-dioxolane, methyl propionate, methyl butyrate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate and the like. In particular, from the viewpoint of voltage stability, it is preferable to use cyclic carbonates such as propylene carbonate, ethylene carbonate, butylene carbonate and vinylene carbonate, and chain carbonates such as dimethyl carbonate, diethyl carbonate and dipropyl carbonate. Moreover, such a non-aqueous solvent may be used individually by 1 type, and may be used in mixture of 2 or more types.

(Ionic liquid)
The electrolyte according to the present invention is characterized by containing an ionic liquid. In the present invention, an ionic liquid is a salt of an organic cation that can be liquefied at room temperature (around 25 ° C.), has a very low vapor pressure, does not substantially volatilize, is flame retardant, and has an ionic conductivity. Is a group of compounds excellent in The melting point of the ionic liquid according to the present invention is preferably 100 ° C. or less, more preferably 80 ° C. or less, particularly preferably 60 ° C. or less, and most preferably 30 ° C. or less.

  In the case of room temperature molten salts, these compounds can often be added to the electrolyte with little solvent, and can often be added alone to the electrolyte. Even if it is solid at room temperature (around 25 ° C.), it can be used in the electrolyte as a liquid state by adding a very small amount of solvent, other additives, and the like. Also, without adding a solvent or additives, etc., the method of infiltrating on the electrode by heating and dissolving, infiltrating on the electrode using a low boiling point solvent (methanol, acetonitrile, methylene chloride, etc.), and then heating the solvent It can be used by being incorporated in a battery by a method of removing by the above.

  The ionic liquid according to the present invention preferably has a structure represented by general formulas (Ya) to (Yc) described in Japanese Patent Application Laid-Open No. 2003-257476. Among them, the structure represented by the general formula (Yb) is preferable, and specific examples include Y21-1 to Y21-3.

  As the ionic liquid according to the present invention, the compound represented by the general formula (1) is more preferable.

In the general formula (1), R _{1 to} R ₄ represent an alkyl group which may have a substituent. Specific examples of the alkyl group include methyl, ethyl, i-propyl, hydroxyethyl, stearyl, dodecyl, and eicosyl. , Docosyl, oleyl and the like. Any two groups out of R _{1 to} R ₄ may form a ring together with the nitrogen atom. Examples of the ring formed include non-aromatic heterocycles such as a pyrrolidine ring, a piperidine ring, and a morpholine ring. Can be mentioned. They may have a substituent. Among R _{1 to} R ₄ , it is preferable that any two of them form a piperidine or pyrrolidine ring together with a nitrogen atom. X represents N (SO ₂ F) ₂ , BF ₃ Y, N (CN) ₂ , and Y represents an alkyl group or a perfluoroalkyl group. As the alkyl group, methyl, ethyl, i-propyl, hydroxyethyl , Stearyl, dodecyl, eicosyl, docosyl, oleyl and the like, and the perfluoroalkyl group represents trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl and the like. X is preferably N (SO ₂ F) ₂ .

  Hereinafter, although the specific example of a compound represented by General formula (1) of this invention is shown, this invention is not limited to these.

  The electrolyte according to the present invention contains at least one ionic liquid, but may be used in combination of two or more. Further, other electrolyte salts such as WO95 / 18456 pamphlet or J.P. Phys. Chem. B, 103, 4164 (1999) or the like may be added. The blending amount of the ionic liquid in the electrolyte composition is preferably 1 to 90% by mass, and particularly preferably 30 to 80% by mass.

The electrolyte according to the present invention preferably contains a metal ion salt as the electrolyte salt. Typical metal ion salts include LiCF ₃ SO ₃ , LiPF ₆ , LiClO ₄ , LiI, LiBF ₄ , LiCF ₃ CO ₂ , LiSCN, LiN (SO ₂ CF ₃ ) ₂ , NaI, NaCF ₃ SO ₃ , NaClO. ₄ , NaBF ₄ , NaAsF ₆ , KCF ₃ SO ₃ , KSCN, KPF ₆ , KClO ₄ , KAsF _{6 and the} like. More preferred is the Li salt. These may be used alone or in combination. The blending amount of the metal ion salt in the electrolyte composition is preferably 5 to 40% by mass, and particularly preferably 10 to 30% by mass.

  In the present invention, the electrolyte is used by gelling (solidifying) the above-mentioned molten salt electrolyte or electrolyte by a technique such as addition of a polymer, addition of an oil gelling agent, polymerization including polyfunctional monomers, or a crosslinking reaction of the polymer. You can also.

  In the case of gelation by polymer addition, compounds described in “Polymer Electrolyte Reviews-1 and 2” (JR MacCallum and CA Vincent co-edit, ELSEVIER APPLIED SCIENCE) can be used. In particular, polyacrylonitrile and polyvinylidene fluoride can be preferably used. In the case of gelation by adding an oil gelling agent, J.A. Chem. Soc. Japan, Ind. Chem. Sec. 46, 779 (1943), J. Am. Am. Chem. Soc. 111, 5542 (1989), J. Am. Chem. Soc. , Chem. Commun. 1993, 390, Angew. Chem. Int. Ed. Engl. , 35, 1949 (1996), Chem. Lett. 1996, 885, J. et al. Chem. Soc. , Chem. Commun. , 1997, 545 can be used, but preferred compounds are those having an amide structure in the molecular structure.

  An example of gelling the electrolytic solution is described in JP-A No. 11-185863, and an example of gelling the molten salt electrolyte is described in JP-A No. 2000-58140, which can also be applied to the present invention.

(Inorganic fine particles)
The electrolyte according to the present invention preferably contains inorganic fine particles. Any inorganic fine particles can be used as long as they are inert to the electrolyte. Among these, inorganic oxides are preferable, and examples thereof include titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, tantalum, aluminum, silicon, and boron. And oxides of phosphorus or magnesium. These oxides may be amorphous oxide glass or crystalline oxide. Among these, oxides of titanium, silicon, and aluminum are more preferable. Further preferred are silica particles. Silica (silicon dioxide) includes natural silica and synthetic silica. Synthetic silica is classified into high-temperature silica, wet silica, and fused solid silica according to its production method, and any silica may be used in the present invention. it can. Furthermore, you may contain dissimilar elements, such as sodium and aluminum. Silica particles may be treated with a surface treatment agent such as halogenated silanes, alkoxysilanes, silazanes, siloxanes and the like.

  These silica particles are known to form network aggregates in solution due to hydrogen bonds between silanol groups present on the surface, thereby thickening or gelling the liquid. Even when added to a molten salt electrolyte having a high salt concentration, the same effect can be seen and a gel electrolyte can be formed. The average primary particle diameter of the inorganic fine particles is preferably 5 to 200 nm, and more preferably 5 to 50 nm. The addition amount of the inorganic fine particles is preferably 0.5 to 30% by mass, and more preferably 1 to 10% by mass.

[Other configurations of sheet-like secondary battery]
The sheet-like secondary battery according to the present invention is produced by combining the electrolyte and a conventionally known positive electrode active material, negative electrode active material, electrode mixture, separator, and positive and negative electrode current collectors. JP-A 2003-257476, 2003-257476, 2007-207675, 2008-257963, and the like can be referred to for details of the members and a method for manufacturing the sheet-like secondary battery.

[Sheet solar cell]
Next, the sheet-like solar cell according to the present invention will be described.

  A sheet-like solar cell converts light energy directly into electrical energy. As the sheet-like solar cell, a silicon-based solar cell such as an amorphous silicon solar cell or a crystalline silicon solar cell or an organic solar cell can be used, and an organic thin-film solar cell is particularly preferable. An organic thin film solar cell is a solar cell using an organic thin film semiconductor in which a conductive polymer, fullerene, or the like is combined. Compared to a dye-sensitized solar cell, which is the same organic solar cell, there is no need to use an electrolyte solution, and this is advantageous in terms of flexibility and improved life. Moreover, since it is easy to form on a general plastic substrate, it can be said that it is optimal as a sheet-like solar cell for the sheet-like lighting device of the present invention. Moreover, the sheet-like solar cell according to the present invention includes a terminal for storing the converted electric energy in the sheet-like secondary battery.

  Examples of the organic thin film solar cell preferably used in the present invention include those described in the following patent documents and non-patent documents.

JP 2005-236278 A, WO 2007/076427 pamphlet, JP 2008-71937 A, M.C. Hiramoto, H. et al. Fujiwara, M .; Yokoyama, Appl. Phys. Lett. 58, 1062, (1986); Peumans, S .; R. Forrest, Appl. Phys. Lett. 79, 126, (2001); Xue, S .; Uchida, B .; P. Rand, S .; R. Forrest, Appl. Phys. Lett. 85, 5757, (2004); Ma, C.I. Yang, X .; Gong, K .; Lee, A.M. J. et al. Heeger, Adv. Funct. Mater. , 15, 1617, (2005); Y. Kim, S .; H. Kim, H .; H. Lee, K.M. Lee, W.M. Ma, X. Gong, A .; J. et al. Heeger, Adv. Mater. , 18, 572 (2006); MATERIAL STAGE vol. 2, no. 9 2002 p. 37-42 Junichi Nakamura et al. “Utilization of Organic Thin Film Solar Cell-Donor-Acceptor Interaction”; Applied Physics Vol. 71, No. 4 (2002) p. 425-428 Akinori Kuno “Current Status and Prospects of Organic Solar Cells”
[Sheet-like surface light emitter]
Next, the sheet-like surface light emitter according to the present invention will be described in detail.

  As the sheet-like surface light emitter, a chip-type LED (light emitting diode) element surface-mounted or an EL (electroluminescence) element using an inorganic or organic thin film for the electroluminescent layer is preferably used. The sheet-like surface light emitter of the present invention is particularly preferably an organic EL element (organic EL surface light emitter). The organic EL element to be used is extremely thin and bendable, and emits high luminance. Therefore, it can be said that the organic EL element is an optimum light emitter for the sheet-like lighting device of the present invention that is safe and highly flexible. The sheet-like surface light emitter according to the present invention is provided with a terminal 21 connected to a control unit 22 of FIG. 4 to be described later and a terminal for receiving a voltage supply from the terminal 21 ′.

Examples of the organic EL element preferably used in the present invention include those described in the following patent documents and non-patent documents. JP-A-2004-31341, JP-A-2005-44732, JP-A-2006-228457, WO2006 / 092964, JP-A-2006-228456, JP-A-2006-202717, and JP-A-2007-115629. No. 2007-173088, No. 2007-257855, No. 2007-324063, No. 2008-181937, No. 2008-27709, No. 2008-277462, J. Pat. KIDO, et. al. , Science 1995, 267, 1332; A. Baldo, et. , Al. , “Very high-efficiency green light-emitting devices based on electrophoresis”, Appl. Phys. Lett. , 75, p. 4, 1999; Matsumoto et al. , SID03 DIGEST, vol. XXXIV, BOOKII, p. 979; Tung, et. , Al. , “Ah high efficiency phosphorescent white OLED for LCD backlight and display applications”, SID Symposium Digest, 35, p. 48-51, 2004; Shinichi Saito: White organic EL caster lights, FPD International Seminar 2004 Proceedings, E-1 (October 2004) 45; S. Weaver, et. , Al. "Advanceds in Blue Phosphorescent Organic Light-Emitting Devices", SID Symposium Digest, 37, p. 127-130, 2006; W. D'Andrade, et. , Al. "Phosphorescent white organic light-emitting diodes for displays and lighting", Processeds of The 13th International Display Workshops, p. 469-472, 2006; Tomoyuki Nakayama, et. , Al. , KONICA MINOLTA TECHNOLOGY REPORT VOL. 5 (2008)
[Detailed configuration example of sheet-like lighting device]
FIG. 2 is a plan view for explaining a main configuration of the sheet-like secondary battery 2 employed in the present invention, and FIG. 3 is a longitudinal sectional view taken along line AA in FIG.

  The sheet-like secondary battery 2 is formed by sealing a battery element formed by laminating and arranging a sheet-like positive electrode 14 and a sheet-like negative electrode 15 via an electrolyte layer 11 according to the present invention with an exterior film 16. The sheet-like positive electrode 14 is composed of a positive electrode current collector and a positive electrode active material. The sheet-like positive electrode 14 is provided with a positive electrode terminal 12 having one end connected to a positive electrode current collector. Subsequently, the sheet-like negative electrode 15 is composed of a negative electrode current collector and a negative electrode active material. The sheet-like negative electrode 15 is provided with a negative electrode terminal 13 having one end connected to a negative electrode current collector. The exterior film 16 is a film that encapsulates a battery element composed of a laminate of the sheet-like positive electrode 14, the sheet-like negative electrode 15, and the electrolyte layer 11. After enclosing the battery element, the outer film 16 is thermally welded at its peripheral edge to seal the battery element.

  In addition, the positive electrode terminal 12 and the negative electrode terminal 13 are extended and extended from the outer film 16 as they are, and are sealed and led out in parallel with the outer film 16. The positive electrode terminal bent portion 12 a and the negative electrode terminal bent portion are respectively provided. 13a is formed. When the sheet-like lighting device of the present invention is manufactured, the positive terminal bent portion 12a and the negative terminal bent portion 13a are bent and arranged approximately 180 degrees on the surface to be bonded to the sheet-like surface light emitter 3.

  Therefore, the sheet-like secondary battery 2 is arranged on the same plane as the surface where the derived positive electrode terminal 12 and negative electrode terminal 13 are bonded to the sheet-like surface light emitter 5, and the voltage provided in the sheet-like surface light emitter 3. It is connected to a terminal for supply, and voltage / current can be supplied to the sheet-like surface light emitter 3.

  In order to maintain the performance of the battery, the exterior film 16 is required to have a sealing performance capable of blocking liquid leakage, entry of outside air, and the like, and a flexibility property that can be flexibly deformed according to the installation environment. . The material is preferably a film made of polypropylene, polyethylene, ionomer resin or the like having excellent heat-fusibility. The thickness of the laminate film is preferably about 20 to 250 μm, and varies depending on the type, but is more preferably in the range of 80 to 200 μm from the viewpoint of heat-fusibility, film strength, and film physical properties.

  Next, FIG. 4 shows a plan view when a circuit for causing the sheet-like surface light emitter 3 to emit light is disposed on the sheet-like secondary battery 2.

  The circuit for causing the sheet-like surface light emitter 3 (not shown) to emit light includes a wire 6, a terminal 21 for supplying voltage to the sheet-like surface light emitter 3, a terminal 21 ′, and an input from the switch 7. And a control unit 22 that controls the voltage output to the surface light emitter 3.

  The control unit 22 includes an electric wire 6 that transmits light emission and non-light emission signals of the sheet-like surface light emitter 3 input by the switch 7, a positive electrode terminal 12 and a negative electrode terminal 13 that are derived from the sheet-like secondary battery 2, and a sheet-like shape. A terminal 21 for supplying voltage to the surface light emitter 3 and a terminal 21 'are connected. The control unit 22 electrically connects the positive terminal 12 and the negative terminal 13 to the terminal 21 and the terminal 21 ′ in accordance with the light emission and non-light emission signals of the sheet-like surface light emitter 3 transmitted by the switch 7 via the electric wire 6, thereby forming a sheet-like shape. Light is emitted by supplying voltage from the secondary battery 2 to the sheet-like surface light emitter 3.

  The voltage supply from the sheet-like secondary battery 2 to the sheet-like surface light emitter 3 is automatically provided with a timer and the like, and a control means and a sensor for starting the voltage supply when a predetermined time is reached, in addition to the manual operation. It may be done automatically.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.

Example 1
(Preparation of electrolyte)
(Preparation of electrolyte E-18)
An ionic liquid (Y21-1, 51% by mass) and a metal ion salt (LiN (SO ₂ CF ₃ ) ₂ , 20% by mass) are dissolved in acetonitrile (500% by mass), and inorganic fine particles (S-1, 4) are dissolved. Mass%) and a gelling agent (PvDF, 20 mass%) in a volatile organic solvent (EC (ethylene carbonate) / PC (propylene carbonate) = 3 mass% / 2 mass%), and then depressurizing acetonitrile. Distilled off to prepare electrolyte E-18.

(Preparation of electrolytes E-1 to E-17, E-19 to E-45)
In the preparation of the electrolyte E-18, as shown in Tables 1 and 2, the types and amounts of the ionic liquid, the metal ion salt, the inorganic fine particles and the gelling agent were changed, and the electrolytes E-1 to E-17 were similarly prepared. , E-19 to E-45 were prepared.

PvDF: Polyvinylidene fluoride (Kureha KF Polymer, manufactured by Kureha Corporation)
S-1: Silica (AEROSIL 200, manufactured by Nippon Aerosil Co., Ltd., average particle size of about 12 nm)
S-2: Silica (AEROSIL RX200, manufactured by Nippon Aerosil Co., Ltd., average particle size of about 12 nm)
S-3: Silica (AEROSIL 30, manufactured by Nippon Aerosil Co., Ltd., average particle size of about 30 nm)

[Production of sheet-like secondary battery]
(Preparation of sheet-like positive electrode CA-1)
It is obtained by adding 43 parts by mass of LiCoO ₂ as a positive electrode active material, ₂ parts by mass of flaky graphite, 2 parts by mass of acetylene black, and 3 parts by mass of polyacrylonitrile as a binder, and kneading 100 parts by mass of acrylonitrile as a medium. The slurry was coated on an aluminum foil with a thickness of 20μm using an extrusion coater, dried and compression-molded with a calendar press, and then welded with an aluminum lead plate at the end, with a thickness of 95μm and a width. A sheet-like positive electrode CA-1 of 54 mm × length 49 mm was produced.

(Preparation of sheet-like negative electrode AN-1)
43 parts by mass of mesophase pitch-based carbon material (Petka) as a negative electrode active material, 2 parts by mass of acetylene black and 2 parts by mass of graphite as a conductive agent, and 3 parts by mass of polyacrylonitrile as a binder are added. Then, 100 parts by mass of N-methylpyrrolidone was kneaded as a medium to obtain a negative electrode mixture slurry. The negative electrode mixture slurry was applied to a copper foil having a thickness of 10 μm using an extrusion coater, dried and then compression-molded by a calendar press to produce a sheet-like negative electrode having a thickness of 46 μm, a width of 55 mm × a length of 50 mm. did. A nickel lead plate was welded to the end of the sheet-like negative electrode, and then heat treated at 230 ° C. for 1 hour in dry air having a dew point of −40 ° C. or lower. The heat treatment was performed using a far infrared heater.

(Preparation of sheet-like secondary battery B-1)
Each of the sheet-like positive electrode CA-1 and the sheet-like negative electrode AN-1 was dehydrated and dried at 230 ° C. for 30 minutes in dry air having a dew point of −40 ° C. or less. In a dry atmosphere, a sheet-like positive electrode CA-1 having a width of 54 mm × a length of 49 mm, dehydrated and dried, and a non-woven fabric TAPYRUS P22FW-OCS manufactured by Tonen Tapirs Co., Ltd. having a thickness of 30 μm cut into a width of 60 mm × a length of 60 mm, Electrolyte E-1 was diluted with acetonitrile of the same mass as the electrolyte E-1, soaked into the positive electrode from the top of the nonwoven fabric, and then acetonitrile was distilled off under reduced pressure. After repeating this operation three times, a dehydrated and dried sheet-like negative electrode AN-1 having a width of 55 mm × length of 50 mm was laminated and heated to 80 ° C. under reduced pressure for 3 hours. Then, the exterior material which consists of a laminate film of polyethylene (50 micrometers)-polyethylene terephthalate (50 micrometers) was used, the edge was heat-sealed under vacuum, and it sealed, and produced the sheet-like secondary battery B-1.

(Preparation of sheet-like secondary batteries B-2 to B-45)
In producing the sheet-like secondary battery B-1, the electrolyte E-1 was replaced with the electrolytes E-2 to E-45, and sheet-like secondary batteries B-2 to B-45 were produced in the same manner.

[Production of sheet-like lighting device]
A circuit (FIG. 4) for causing the sheet-like surface light emitter to emit light was disposed in the sheet-like secondary batteries B-1 to B-45 produced as described above.

Next, a method described in Example 2 of JP-A-2005-236278 (system: C ₆₀ CO ₂ H and ZnP (CO ₂ H) ₂ system, the same shape and the same area as the above-prepared sheet-like secondary battery) Thus, a sheet-like organic thin film solar cell-1 was produced. Next, it connected to the said sheet-like secondary battery, and it enabled charging.

  Further, the connection surface was adhered using a 75 μm thick hot melt sheet (3BF TBF406). Next, the sheet-like organic EL surface light emitter-1 was prepared by the method described in Example 1 of Japanese Patent Application Laid-Open No. 2008-159741 (the organic EL element number 104 and the same shape and the same area as the above-prepared sheet-like secondary battery). The surface light emitter was connected to a circuit for emitting light, and light emission was enabled. Further, the connection surface was closely adhered using a 75-micron-thick hot melt sheet (3BF TBF406), and from each of the sheet-like secondary batteries B-1 to B-45 (respectively using the electrolytes E-1 to E-45). Sheet-like illumination devices L-1 to L-45 were produced.

[Evaluation of sheet illumination device]
The following evaluation was performed about the produced sheet-like illuminating device.

(Sunlight irradiation test)
The solar cell surface of the produced sheet-like lighting device is adhered to the inner surface of the ceiling surface of an airtight hexahedral glass test box (0.5 m ³ ) adjusted to a humidity of 50% and an internal temperature of 25 ° C. And was irradiated with sunlight for 5 hours continuously from noon on a fine day. Meanwhile, the average surface temperature of the solar battery surface of the sheet-like lighting device was recorded as 65 ° C. Thereafter, the light was shielded from a fully charged secondary battery (confirmed that it reached a charge end voltage of 3.7 V), and a voltage was supplied to the organic EL surface light emitter to continuously emit light. The time (τ _¼ ) until the voltage was lowered to ¼ of the initial emission luminance was measured. Thereafter, the secondary battery was completely discharged, and the above test was repeated continuously for 3 days from the next day. After the experiment, the air in the box was collected, and the amount of the solvent odor was sensory evaluated according to the following criteria.

Evaluation criteria ○: The odor of the solvent is not felt △: The odor of the solvent is slightly felt ×: The odor of the solvent is strongly felt (weather resistance test)
A sheet-like lighting device having a sheet-like secondary battery in a fully charged state (0.2 C, end-of-charge voltage of 3.7 V) is divided into an environmental room A (humidity 50%, room temperature 30 ° C.) and environmental room B (humidity 20%, After standing at room temperature-35 ° C. for 24 hours, continuous light emission was performed. The time (τ _¼ ) until the voltage was lowered to ¼ of the initial light emission luminance was measured.

  Table 3 shows the evaluation results.

  From Table 3, it can be seen that the sheet-like lighting device of the present invention has a high capacity and a small capacity drop, and therefore has high durability in repeated use. Moreover, since there is no generation | occurrence | production of the combustible vapor | steam from a secondary battery, it turns out that there is no danger, such as a fire.

  Further, it can be seen that the sheet-like lighting device of the present invention can obtain a stable output even at an extremely low temperature.

Example 2
In the illuminating device L-8 of Example 1, instead of the sheet-like organic thin-film solar cell-1, the following sheet-like organic thin-film solar cell-2 was produced and replaced with the same shape and the same area as the sheet-like secondary battery. .

  Similarly, the sheet-like organic EL surface light emitter-1 was obtained by applying the organic EL element No. 1 described in Example 1 of JP-A-2008-305613. In 221, a sheet-like lighting device L-201 was produced by replacing the glass substrate with a PEN film having a thickness of 120 μm and replacing the glass substrate with the same shape and area as the sheet-like secondary battery.

[Sheet organic thin film solar cell-2]
(Production of flexible transparent substrate)
A 110 nm thick indium tin oxide (ITO) transparent conductive film (sheet resistance 13 Ω / □) deposited on a 120 μm thick PEN film substrate with a barrier layer using a normal photolithography technique and hydrochloric acid etching Then, patterning with a width of 5 cm in the center was performed to form a flexible transparent substrate with a transparent electrode.

(Preparation of sheet-like organic thin film solar cell-2)
After performing the washing and PEDOT layer forming process using the above flexible substrate, the substrate was measured under a nitrogen atmosphere in accordance with JIS B9920, the measured cleanliness was class 10, the dew point temperature was −80 ° C. or lower, and the oxygen concentration was 0. . Moved to 8 ppm glove box.

  In a glove box, a coating liquid for a bulk heterojunction layer was prepared as follows, and applied with a spin coater under conditions of 500 rpm and 60 seconds. After a bulk heterojunction layer was provided, the coating liquid was dried at room temperature for 30 minutes. .

(Bulk heterojunction layer coating solution)
Chlorobenzene 1.0 g
Plexcore OS2100 15mg made by Plextronics
Aldrich PCBM 15mg
The substrate provided up to the bulk heterojunction layer was moved to a vapor deposition machine without being exposed to the atmosphere, and the pressure was reduced to 4 × 10 ⁻⁴ Pa. In addition, lithium fluoride was put in a resistance heating boat made of tantalum, and aluminum was put in a resistance heating boat made of tungsten, and was attached in a vapor deposition machine.

  Subsequently, the resistance heating boat made of tantalum was energized and heated, and an electron injection layer of lithium fluoride was provided to 0.5 nm on the substrate. Subsequently, the tungsten tantalum heating boat was energized and heated, and a cathode having a thickness of 100 nm and a width of 5 cm was deposited at a deposition rate of 1 to 2 nm / second so as to be orthogonal to the transparent conductive film.

  The obtained sheet-like organic thin film solar cell-2 was sealed with an aluminum foil having a thickness of 30 μm using a sealant (manufactured by Nagase ChemteX Corporation, UV RESIN XNR5570-B1), Removed into the atmosphere.

  As a result of the same evaluation as in Example 1 for the sheet-like lighting device L-201, the solar irradiation test, the solvent odor, and the weather resistance test showed not only excellent performance similar to that of the present invention of Example 1, but also the same. Furthermore, as a result of performing the sunlight irradiation test 3 days after the following bending test, the sheet-like illumination device L-201 was superior to the sheet-like illumination devices L-4 and L-8 produced in Example 1 as described below. Showed performance.

(Bending test)
About sheet-like illuminating devices L-4, L-8, and L-201, the both ends of the length direction of FIG. A total of 300 runs were performed for 20 minutes.

(Results of 3 days of solar irradiation test)
Sheet illumination device τ _1/4 (hr)
L-4 Does not emit light L-8 13
L-201 24

DESCRIPTION OF SYMBOLS 1 Sheet-like solar cell 2 Sheet-like secondary battery 3 Sheet-like surface light-emitting body 4 Sheet-like illuminating device 6 Electric wire 7 Switch 11 Electrolyte layer 12 Positive electrode terminal 13 Negative electrode terminal 14 Sheet-like positive electrode 15 Sheet-like negative electrode 16 Exterior film 21, 21 ' Terminal for supplying voltage 22 Control unit

Claims (5)

  A sheet-like lighting device in which a sheet-like solar cell is laminated on one surface of a sheet-like secondary battery having an electrolyte and a sheet-like surface light emitter is laminated on the other surface, and the electrolyte of the sheet-like secondary battery The sheet-shaped lighting device characterized in that the volatile organic solvent contained in is not less than 0% and less than 10% of the total mass of the electrolyte, and the electrolyte contains an ionic liquid. The sheet-like lighting device according to claim 1, wherein the ionic liquid is represented by the following general formula (1).

(Wherein, R ₁ to R ₄ represents an alkyl group which may have a substituent, may be any two groups of R ₁ to R ₄ form a ring together with the nitrogen atom .X is N (SO ₂ F) ₂ , BF ₃ Y or N (CN) ₂ is represented, and Y represents an alkyl group or a perfluoroalkyl group.   The sheet-like lighting device according to claim 1 or 2, wherein the electrolyte of the sheet-like secondary battery contains inorganic fine particles.   The sheet-like lighting device according to any one of claims 1 to 3, wherein the sheet-like solar cell is an organic thin-film solar cell.   The sheet-like lighting device according to claim 1, wherein the sheet-like surface light emitter is an organic EL surface light emitter.