JPH1174002A - Secondary battery integrated with solar cell and watch - Google Patents
Secondary battery integrated with solar cell and watchInfo
- Publication number
- JPH1174002A JPH1174002A JP9236690A JP23669097A JPH1174002A JP H1174002 A JPH1174002 A JP H1174002A JP 9236690 A JP9236690 A JP 9236690A JP 23669097 A JP23669097 A JP 23669097A JP H1174002 A JPH1174002 A JP H1174002A
- Authority
- JP
- Japan
- Prior art keywords
- secondary battery
- solar cell
- negative electrode
- substrate
- positive electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 24
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 9
- 239000007773 negative electrode material Substances 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 238000012856 packing Methods 0.000 abstract description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 abstract description 6
- 229910002804 graphite Inorganic materials 0.000 abstract description 4
- 239000010439 graphite Substances 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- 229910018225 Li PF6 Inorganic materials 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 210000000707 wrist Anatomy 0.000 abstract 1
- 229910052744 lithium Inorganic materials 0.000 description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- -1 lithium transition metal compounds Chemical class 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 2
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 2
- 229910052912 lithium silicate Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 229940071182 stannate Drugs 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- WKFQMDFSDQFAIC-UHFFFAOYSA-N 2,4-dimethylthiolane 1,1-dioxide Chemical compound CC1CC(C)S(=O)(=O)C1 WKFQMDFSDQFAIC-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910018091 Li 2 S Inorganic materials 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- DISYGAAFCMVRKW-UHFFFAOYSA-N butyl ethyl carbonate Chemical compound CCCCOC(=O)OCC DISYGAAFCMVRKW-UHFFFAOYSA-N 0.000 description 1
- FWBMVXOCTXTBAD-UHFFFAOYSA-N butyl methyl carbonate Chemical compound CCCCOC(=O)OC FWBMVXOCTXTBAD-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000005402 stannate group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2045—Light-sensitive devices comprising a semiconductor electrode comprising elements of the fourth group of the Periodic System (C, Si, Ge, Sn, Pb) with or without impurities, e.g. doping materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Clocks (AREA)
- Electromechanical Clocks (AREA)
- Secondary Cells (AREA)
- Hybrid Cells (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、太陽電池と二次
電池とを組み合わせた太陽電池一体型二次電池及びこの
ような太陽電池一体型二次電池を使用した時計に係り、
特に、上記の太陽電池一体型二次電池の厚みを薄くし
て、腕時計等の時計における電源として好適に利用でき
るようにした太陽電池一体型二次電池及びこのような太
陽電池一体型二次電池を用いた時計に関するものであ
る。The present invention relates to a solar cell-integrated secondary battery in which a solar cell and a secondary battery are combined, and a timepiece using such a solar cell-integrated secondary battery.
In particular, a solar cell-integrated secondary battery and a solar cell-integrated secondary battery in which the thickness of the above-described solar cell-integrated secondary battery is reduced so that the solar cell-integrated secondary battery can be suitably used as a power source in a watch such as a wristwatch The present invention relates to a timepiece using a watch.
【０００２】[0002]
【従来の技術】近年、腕時計等において、その電源に太
陽電池を用いたものが使用されるようになったが、単に
太陽電池によって発電された電力だけで時計を動作させ
るようにした場合、暗い場所等においては時計が止まっ
てしまうため、特開昭６２−２０３５２５号公報に示さ
れるように、太陽電池と二次電池とを組み合わせ、太陽
電池によって発電された電力を二次電池に充電させ、暗
い場所等においてはこの二次電池による放電によって時
計を動作させるようにしたものが開発された。2. Description of the Related Art In recent years, wristwatches and the like have used a solar cell as a power source. However, when a watch is operated only by electric power generated by the solar cell, it becomes dark. Since the clock stops at a place or the like, as shown in JP-A-62-203525, a solar battery and a secondary battery are combined, and the power generated by the solar battery is charged into the secondary battery. In a dark place or the like, a watch has been developed in which the timepiece is operated by discharging the secondary battery.
【０００３】しかし、上記の公報に示されるものは、単
に太陽電池と二次電池とを組み合わせただけで、太陽電
池と二次電池とを別個に設けると共に、この二次電池に
おける充放電を制御する制御回路も別個に設けているた
め、このような太陽電池と二次電池とを組み合わせたも
のを腕時計等の時計の電源に使用した場合に、二次電池
におけるエネルギー密度が低くなり、十分な充放電容量
を得るためには、この時計の厚みが厚くなってしまう等
の問題があった。However, the above-mentioned publication discloses that a solar cell and a secondary battery are provided separately by simply combining a solar cell and a secondary battery, and the charge and discharge of the secondary battery are controlled. Control circuit is also provided separately, so that when a combination of such a solar cell and a secondary battery is used as a power source for a watch such as a wristwatch, the energy density of the secondary battery is reduced, and In order to obtain a charge / discharge capacity, there has been a problem that the thickness of the timepiece is increased.
【０００４】[0004]
【発明が解決しようとする課題】この発明は、太陽電池
と二次電池とを組み合わせて腕時計等の時計の電源に使
用する場合における上記のような問題を解決することを
課題とするものであり、太陽電池と二次電池とを組み合
わせて用いる場合に、二次電池の充放電容量を低下させ
ることなく、太陽電池と二次電池とを組み合わせたもの
の厚みを薄くすることができ、この太陽電池と二次電池
とを組み合わせたものを腕時計等の時計の電源に用いた
場合において、その時計の厚みを薄くさせることを課題
とするものである。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems when a solar cell and a secondary battery are combined and used as a power source for a timepiece such as a wristwatch. When using a combination of a solar cell and a secondary battery, the thickness of the combination of the solar cell and the secondary battery can be reduced without reducing the charge / discharge capacity of the secondary battery. It is an object of the present invention to reduce the thickness of a watch when a combination of the battery and a secondary battery is used as a power source of a watch such as a wristwatch.
【０００５】[0005]
【課題を解決するための手段】この発明の請求項１にお
ける太陽電池一体型二次電池においては、上記のような
課題を解決するため、太陽電池と二次電池とを組み合わ
せてなる太陽電池一体型二次電池において、導電面を有
する太陽電池の基板を上記の二次電池における正極又は
負極の外装体として用いるようにした。According to a first aspect of the present invention, there is provided a solar cell-integrated secondary battery in which a solar cell and a secondary battery are combined to solve the above-mentioned problems. In the body type secondary battery, a substrate of a solar cell having a conductive surface was used as an outer package of the positive electrode or the negative electrode in the above secondary battery.
【０００６】ここで、この請求項１における太陽電池一
体型二次電池においては、上記のように太陽電池におけ
る基板を二次電池における正極又は負極の外装体として
使用するため、二次電池における正極又は負極の外装体
を別個に設ける必要がなく、この太陽電池一体型二次電
池における全体の厚みを薄くすることができる。Here, in the solar cell-integrated secondary battery according to the first aspect, since the substrate in the solar cell is used as the positive electrode or the negative electrode in the secondary battery as described above, the positive electrode in the secondary battery is used. Alternatively, there is no need to separately provide an outer package of the negative electrode, and the overall thickness of the solar cell integrated secondary battery can be reduced.
【０００７】ここで、上記の太陽電池一体型二次電池に
おいて使用する太陽電池としては、一般に使用されてい
る公知のものを用いることができ、アモルファス、単結
晶、多結晶等のいずれの構造の太陽電池であってもよ
い。そして、この太陽電池を直列に適当な数だけ接続さ
せて、発電される電圧を二次電池の充電電圧に対応させ
るようにする。Here, as the solar cell used in the above-described solar cell integrated type secondary battery, a commonly used known solar cell can be used, and any structure such as amorphous, single crystal, and polycrystalline can be used. It may be a solar cell. Then, an appropriate number of the solar cells are connected in series, so that the generated voltage corresponds to the charging voltage of the secondary battery.
【０００８】また、この太陽電池における基板として
は、上記のように導電面を有するものであれば良く、例
えば、薄い金属板で構成されたものや、プラスチックフ
ィルムに金属膜を設けたもの等を使用することができ
る。The substrate of the solar cell may be any substrate having a conductive surface as described above. For example, a substrate composed of a thin metal plate or a plastic film provided with a metal film may be used. Can be used.
【０００９】一方、上記の太陽電池一体型二次電池に使
用する二次電池としても、一般に使用されている公知の
ものを用いることができるが、太陽電池における基板を
正極又は負極の外装体として使用すると共にその厚みを
薄くするため、一般に扁平なコイン型になったものが用
いられる。On the other hand, as the secondary battery used for the above-mentioned solar battery integrated type secondary battery, a commonly used known battery can be used. In order to use and reduce the thickness, a flat coin-shaped one is generally used.
【００１０】また、この発明の請求項２における太陽電
池一体型二次電池のように、その二次電池に固体電解質
を用いた固体電解質二次電池を使用すると、この二次電
池における厚みをさらに薄くすることができ、またその
活物質にリチウムを利用した固体電解質二次電池を用い
ると、この二次電池の厚みを薄くした場合においても十
分な充放電容量が得られるようになる。Further, when a solid electrolyte secondary battery using a solid electrolyte is used for the secondary battery as in the solar battery integrated secondary battery according to the second aspect of the present invention, the thickness of the secondary battery is further increased. When a solid electrolyte secondary battery using lithium as its active material is used, a sufficient charge / discharge capacity can be obtained even when the thickness of the secondary battery is reduced.
【００１１】ここで、このようにリチウムを活物質とし
て用いる固体電解質二次電池においては、その正極材料
として、例えば、リチウムイオンの吸蔵，放出が可能な
ＬｉＣｏＯ2 、ＬｉＮｉＯ2 、ＬｉＭｎ2 Ｏ4 、ＬｉＭ
ｎＯ2 、ＬｉＭ1XＭ2yＯZ （Ｍ1 ，Ｍ2 は遷移金属であ
り、ｘ，ｙ，ｚは任意の実数である。）で表されるリチ
ウム遷移金属化合物等が好適に使用される。Here, in the solid electrolyte secondary battery using lithium as an active material, as a cathode material, for example, LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , which can occlude and release lithium ions, can be used. LiM
nO 2, LiM 1X M 2y O Z (M 1, M 2 is a transition metal, x, y, z are an arbitrary real number.) lithium transition metal compounds represented by is suitably used.
【００１２】また、負極材料としては、例えば、リチウ
ムイオンの吸蔵放出が可能な黒鉛，コークス，高分子焼
成体等の炭素材料、金属リチウム、リチウムと他の金属
との合金、金属酸化物、金属硫化物等が使用される。Examples of the negative electrode material include carbon materials such as graphite, coke, and polymer fired bodies capable of inserting and extracting lithium ions, lithium metal, alloys of lithium and other metals, metal oxides, and metal oxides. Sulfides and the like are used.
【００１３】また、固体電解質としては、例えば、ポリ
エチレンオキシド、ポリプロピレンオキシド、ポリエチ
レンオキシド誘導体等の高分子材料中にＬｉＰＦ6 ，Ｌ
ｉＣｌＯ4 等のリチウム塩からなる溶質を含有させたも
のや、上記の溶質を有機溶媒に溶解させた非水電解液を
含浸させたゲル状のものや、Ｌｉ2 Ｓ等の無機固体電解
質を用いることができ、また溶質を溶解させる有機溶媒
としては、例えば、エチレンカーボネート、プロピレン
カーボネート、ブチレンカーボネート、ビニレンカーボ
ネート、シクロペンタノン、スルホラン、ジメチルスル
ホラン、３−メチル−１，３−オキサゾリジン−２−オ
ン、γ−ブチロラクトン、ジメチルカーボネート、ジエ
チルカーボネート、エチルメチルカーボネート、メチル
プロピルカーボネート、ブチルメチルカーボネート、エ
チルプロピルカーボネート、ブチルエチルカーボネー
ト、ジプロピルカーボネート、１，２−ジメトキシエタ
ン、テトラヒドロフラン、２−メチルテトラヒドロフラ
ン、１，３−ジオキソラン、酢酸メチル、酢酸エチル等
の溶媒を１種又は２種以上組み合わせて用いることがで
きる。As the solid electrolyte, for example, a polymer material such as polyethylene oxide, polypropylene oxide or polyethylene oxide derivative contains LiPF 6 , L
Use a solute containing a solute composed of a lithium salt such as iClO 4, a gel-like one impregnated with a non-aqueous electrolyte in which the above solute is dissolved in an organic solvent, or an inorganic solid electrolyte such as Li 2 S Examples of the organic solvent that can dissolve solutes include ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, cyclopentanone, sulfolane, dimethyl sulfolane, 3-methyl-1,3-oxazolidin-2-one. Γ-butyrolactone, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, butyl methyl carbonate, ethyl propyl carbonate, butyl ethyl carbonate, dipropyl carbonate, 1,2-dimethoxyethane, tetrahydrofura , 2-methyltetrahydrofuran, 1,3-dioxolan, methyl acetate, ethyl acetate and the like can be used alone or in combination of two or more.
【００１４】また、上記の二次電池における正極を太陽
電池の基板に接触させると、この正極と太陽電池の基板
とが反応するおそれがあるが、この発明の請求項３にお
ける太陽電池一体型二次電池のように、二次電池におけ
る負極を太陽電池の基板に接触させると、この負極と太
陽電池の基板とが反応するということがなく、安定して
使用できるようになる。When the positive electrode of the secondary battery is brought into contact with the solar cell substrate, the positive electrode may react with the solar cell substrate. When a negative electrode of a secondary battery is brought into contact with a substrate of a solar cell as in a secondary battery, the negative electrode and the substrate of the solar cell do not react with each other and can be used stably.
【００１５】また、この発明の請求項３における太陽電
池一体型二次電池のように、その二次電池における負極
の負極材料に金属酸化物を用いると、負極材料に炭素材
料や金属リチウム等を用いた場合よりも太陽電池の基板
との接触が改善され、集電体を用いなくても集電が適切
に行なわれるようになり、炭素材料や金属リチウム等を
用いた場合に比べて、二次電池におけるサイクル特性が
向上する。ここで、このような金属酸化物としては、チ
タン酸リチウム，ニオビウム酸リチウム，スズ酸リチウ
ム，鉄酸リチウム，珪酸リチウム等を使用することがで
きる。Further, when a metal oxide is used as the negative electrode material of the negative electrode of the secondary battery as in the solar cell integrated type secondary battery according to claim 3 of the present invention, a carbon material, metal lithium, or the like is used as the negative electrode material. The contact with the substrate of the solar cell is improved as compared with the case where the solar cell is used, and the current can be appropriately collected without using the current collector. The cycle characteristics of the secondary battery are improved. Here, as such a metal oxide, lithium titanate, lithium niobate, lithium stannate, lithium ferrate, lithium silicate and the like can be used.
【００１６】そして、上記のような太陽電池一体型二次
電池を腕時計等の時計の電源に使用すると、この太陽電
池一体型二次電池が上記のように薄く形成されるため、
この太陽電池一体型二次電池を用いた時計全体の厚みも
薄くすることができる。When the above-described solar cell-integrated secondary battery is used as a power source for a timepiece such as a wristwatch, the solar cell-integrated secondary battery is formed to be thin as described above.
The thickness of the entire timepiece using the solar cell-integrated secondary battery can also be reduced.
【００１７】また、上記の太陽電池の基板に二次電池と
共に、この二次電池における充放電を制御する制御回路
を一体に設けると、さらにこの時計全体の厚みを薄くす
ることができる。Further, when a control circuit for controlling charging and discharging of the secondary battery is provided integrally with the secondary battery on the substrate of the solar cell, the thickness of the entire timepiece can be further reduced.
【００１８】[0018]
【実施例】以下、この発明の実施例に係る太陽電池一体
型二次電池及びこの太陽電池一体型二次電池を使用した
時計について具体的に説明すると共に、比較例を挙げ、
この実施例に示す太陽電池一体型二次電池を用いた時計
においては、その厚みを薄くできることを明らかにす
る。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a solar cell integrated secondary battery according to an embodiment of the present invention and a timepiece using the solar cell integrated secondary battery will be specifically described, and a comparative example will be described.
It is clear that the timepiece using the solar cell-integrated secondary battery described in this embodiment can be reduced in thickness.
【００１９】（実施例１）この実施例においては、図１
に示すように、ＳＵＳ製で直径が２０ｍｍ、厚みが０．
２ｍｍになった基板１１に絶縁層１２を介して太陽電池
１０を設けるようにした。(Embodiment 1) In this embodiment, FIG.
As shown in the figure, the product is made of SUS and has a diameter of 20 mm and a thickness of 0.1 mm.
The solar cell 10 was provided on the substrate 11 having a thickness of 2 mm with the insulating layer 12 interposed therebetween.
【００２０】また、この太陽電池１０と一体化させる二
次電池２０を設けるにあたっては、下記のようにして作
製した正極と負極と固体電解質とを用いるようにした。In providing the secondary battery 20 to be integrated with the solar cell 10, a positive electrode, a negative electrode and a solid electrolyte prepared as described below were used.
【００２１】［正極の作製］正極を作製するにあたって
は、正極材料にＬｉＣｏＯ2 を使用し、このＬｉＣｏＯ
2 と、導電剤である人工黒鉛と、結着剤であるポリフッ
化ビニリデンとを８０：１０：１０の重量比で混合さ
せ、これにＮ−メチル−２−ピロリドン（ＮＭＰ）を加
えてスラリー化し、このスラリーを正極集電体であるア
ルミニウム箔の片面にドクターブレード法により塗布
し、これを１５０℃で２時間真空乾燥させて正極を作製
した。[Preparation of Positive Electrode] In preparing a positive electrode, LiCoO 2 was used as a positive electrode material.
2 , artificial graphite as a conductive agent, and polyvinylidene fluoride as a binder in a weight ratio of 80:10:10, and N-methyl-2-pyrrolidone (NMP) was added thereto to form a slurry. The slurry was applied to one surface of an aluminum foil as a positive electrode current collector by a doctor blade method, and dried in a vacuum at 150 ° C. for 2 hours to produce a positive electrode.
【００２２】［負極の作製］負極を作製するにあたって
は、負極材料に格子面（００２）における面間隔ｄ002
が３．３５Åで、ｃ軸方向の結晶子の大きさＬｃが１０
００Å以上の炭素粉末を用い、この炭素粉末と結着剤で
あるポリフッ化ビニリデンとを９０：１０の重量比で混
合させ、これにＮＭＰを加えてスラリー化し、このスラ
リーを負極集電体である銅箔の片面にドクターブレード
法により塗布し、これを１５０℃で２時間真空乾燥させ
て負極を作製した。[Preparation of Negative Electrode] In preparing the negative electrode, the negative electrode material was prepared by adding a spacing d002 between lattice planes (002).
Is 3.35 °, and the crystallite size Lc in the c-axis direction is 10
Using a carbon powder of 00 ° or more, this carbon powder and polyvinylidene fluoride as a binder are mixed at a weight ratio of 90:10, and NMP is added thereto to form a slurry, and this slurry is used as a negative electrode current collector. One side of the copper foil was applied by a doctor blade method, and this was vacuum-dried at 150 ° C. for 2 hours to produce a negative electrode.
【００２３】［固体電解質の作製］固体電解質を作製す
るにあたっては、分子量が２００００〜１０００００の
ポリエチレンオキシドを１１０℃で１０時間真空乾燥さ
せた後、これにヘキサフルオロリン酸リチウムＬｉＰＦ
6 をジメチルカーボネートに１ｍｏｌ／ｌの割合で溶解
させた溶液を含浸させ、その後、これを１１０℃で２時
間真空乾燥させてジメチルカーボネートを除去し、ポリ
エチレンオキシドとＬｉＰＦ6 とが９５：５の重量比に
なった固体電解質を作製した。[Preparation of Solid Electrolyte] In preparing a solid electrolyte, polyethylene oxide having a molecular weight of 20,000 to 100,000 was vacuum-dried at 110 ° C. for 10 hours, and then lithium hexafluorophosphate LiPF was added thereto.
6 was impregnated with a solution of 1 mol / l in dimethyl carbonate, and then vacuum-dried at 110 ° C. for 2 hours to remove dimethyl carbonate. The weight ratio of polyethylene oxide and LiPF 6 was 95: 5. A solid electrolyte having a ratio was prepared.
【００２４】そして、上記の太陽電池１０の基板１１に
おいて、絶縁層１２を介して太陽電池１０が設けられた
面と反対側の面に、上記のように作製した負極２１と固
体電解質２２と正極２３とを積層させると共に、この正
極２３上にアルミニウムからなる正極外装体２４を設
け、この正極外装体２４と上記の基板１１との間におい
て、上記のように積層された負極２１と固体電解質２２
と正極２３の周囲にポリエチレン樹脂からなる絶縁パッ
キン２５を配し、１５０℃でこの絶縁パッキン２５を正
極外装体２４と基板１１とに溶着させて太陽電池一体型
二次電池を作製し、この絶縁パッキン２５により正極外
装体２４と基板１１とを電気的に絶縁させると共に、二
次電池２０を封口させるようにした。Then, on the substrate 11 of the solar cell 10, the negative electrode 21, the solid electrolyte 22, and the positive electrode 22 formed as described above are provided on the surface opposite to the surface on which the solar cell 10 is provided via the insulating layer 12. 23, and a cathode case 24 made of aluminum is provided on the cathode 23. Between the cathode case 24 and the substrate 11, the anode 21 and the solid electrolyte 22 stacked as described above are provided.
And an insulating packing 25 made of polyethylene resin around the positive electrode 23, and the insulating packing 25 is welded to the positive electrode package 24 and the substrate 11 at 150 ° C. to produce a solar cell integrated secondary battery. The packing 25 electrically insulates the positive electrode package 24 from the substrate 11 and seals the secondary battery 20.
【００２５】そして、この実施例においては、上記のよ
うに作製した太陽電池一体型二次電池を用い、この太陽
電池一体型二次電池を設けた残りの空間に、上記の二次
電池２０における充放電を制御する制御回路３０や、時
計ムーブメント４０を設けるようにした。なお、この実
施例においては、制御回路３０が基板１１に接している
が、この制御回路３０は上記の基板１１と一体形成され
ていない。In this embodiment, a solar cell integrated secondary battery manufactured as described above is used, and the remaining space provided with the solar cell integrated secondary battery is A control circuit 30 for controlling charging and discharging and a clock movement 40 are provided. In this embodiment, the control circuit 30 is in contact with the substrate 11, but the control circuit 30 is not formed integrally with the substrate 11.
【００２６】このようにして太陽電池１０と二次電池２
０を一体形成し、それとは別に、制御回路３０とムーブ
メント４０とを設けた場合、その全体の厚みを３．０ｍ
ｍと薄くすることができた。As described above, the solar cell 10 and the secondary battery 2
When the control circuit 30 and the movement 40 are separately provided, the total thickness of the control circuit 30 and the movement 40 is 3.0 m.
m.
【００２７】（実施例２）この実施例においては、図２
に示すように、上記の実施例１の場合と同様にして太陽
電池一体型二次電池を作製する一方、上記の太陽電池１
０の基板１１において、二次電池２０が設けられた面と
同じ面に、この二次電池２０の充放電を制御する制御回
路３０を一体形成し、残りの空間に時計ムーブメント４
０を設けるようにした。(Embodiment 2) In this embodiment, FIG.
As shown in FIG. 7, a solar cell integrated type secondary battery is manufactured in the same manner as in the above-described Example 1, while the solar cell 1
The control circuit 30 for controlling the charging and discharging of the secondary battery 20 is integrally formed on the same surface of the substrate 11 as the surface on which the secondary battery 20 is provided, and the clock movement 4 is provided in the remaining space.
0 was provided.
【００２８】このようにして太陽電池１０と二次電池２
０及び制御回路３０を一体形成し、それとは別に時計ム
ーブメント４０とを設けた場合、その全体の厚みを２．
６ｍｍと更に薄くすることができた。Thus, the solar cell 10 and the secondary battery 2
0 and the control circuit 30 are integrally formed, and when a clock movement 40 is provided separately from the control circuit 30, the overall thickness is set to 2.
The thickness could be further reduced to 6 mm.
【００２９】（比較例１）この比較例においては、図３
に示すように、実施例１と同じ太陽電池１０の基板１１
において、絶縁層１２を介して太陽電池１０が設けられ
た面と反対側の面に時計ムーブメント４０を一体に設
け、この時計ムーブメント４０を介して二次電池２０と
この二次電池２０の充放電を制御する制御回路３０とを
設けるようにした。Comparative Example 1 In this comparative example, FIG.
As shown in FIG.
, A clock movement 40 is integrally provided on the surface opposite to the surface on which the solar cell 10 is provided via the insulating layer 12, and the secondary battery 20 and the charging / discharging of the secondary battery 20 are provided via the clock movement 40. And a control circuit 30 for controlling the control.
【００３０】ここで、この比較例において、上記のよう
に二次電池２０を設けるにあたっては、上記の実施例１
の場合とは異なって負極外装体２６を設ける必要があ
り、この負極外装体２６と正極外装体２４との間に、負
極２１と固体電解質２２と正極２３とを積層させるよう
にしたため、この二次電池２０の厚みが、上記の各実施
例の場合に比べて厚くなった。Here, in this comparative example, when providing the secondary battery 20 as described above, the above-described first embodiment was used.
Unlike the case of the above, it is necessary to provide the negative electrode package 26, and the negative electrode 21, the solid electrolyte 22, and the positive electrode 23 are laminated between the negative electrode package 26 and the positive electrode package 24. The thickness of the secondary battery 20 was larger than that of each of the above embodiments.
【００３１】また、上記のようにして太陽電池１０と時
計ムーブメント４０と二次電池２０と制御回路３０とを
設けた場合、その全体の厚みが５．０ｍｍと、上記の各
実施例の場合に比べて厚くなった。When the solar cell 10, the clock movement 40, the secondary battery 20, and the control circuit 30 are provided as described above, the overall thickness is 5.0 mm, It was thicker than that.
【００３２】（実施例３）この実施例３においても、図
４に示すように、上記の実施例１と同様に、ＳＵＳ製の
基板１１に絶縁層１２を介して太陽電池１０を設けるよ
うにした。(Embodiment 3) In this embodiment 3, as shown in FIG. 4, the solar cell 10 is provided on an SUS substrate 11 with an insulating layer 12 interposed therebetween, as in the above-described embodiment 1. did.
【００３３】また、この太陽電池１０と一体化させる二
次電池２０を設けるにあたっては、下記のようにして作
製した正極と負極と固体電解質とを用いるようにした。In providing the secondary battery 20 to be integrated with the solar cell 10, a positive electrode, a negative electrode and a solid electrolyte prepared as described below were used.
【００３４】［正極の作製］正極を作製するにあたって
は、正極材料にＬｉＣｏＯ2 を使用し、このＬｉＣｏＯ
2 と、導電剤である炭素と、結着剤であるポリテトラフ
ルオロエチレンとを８０：１０：１０の重量比で混合さ
せて正極合剤を調製し、この正極合剤を直径が１４ｍ
ｍ、厚みが４００μｍの円板状に加圧成形し、正極集電
体を用いないようにして正極を作製した。[Preparation of Positive Electrode] In preparing the positive electrode, LiCoO 2 was used as a positive electrode material.
2 , a conductive agent, carbon, and a binder, polytetrafluoroethylene, were mixed at a weight ratio of 80:10:10 to prepare a positive electrode mixture.
A positive electrode was produced by pressing into a disk having a thickness of 400 μm and a thickness of 400 μm without using a positive electrode current collector.
【００３５】［負極の作製］負極を作製するにあたって
は、負極材料に黒鉛を用い、この黒鉛粉末と結着剤であ
るポリテトラフルオロエチレンとを９０：１０の重量比
で混合させて負極合剤を調製し、この負極合剤を直径が
１４ｍｍ、厚みが４００μｍの円板状に加圧成形し、負
極集電体を用いないようにして負極を作製した。[Preparation of Negative Electrode] In preparing the negative electrode, graphite was used as a negative electrode material, and this graphite powder and polytetrafluoroethylene as a binder were mixed at a weight ratio of 90:10 to prepare a negative electrode mixture. This negative electrode mixture was pressure-formed into a disk having a diameter of 14 mm and a thickness of 400 μm, and a negative electrode was produced without using a negative electrode current collector.
【００３６】［固体電解質の作製］固体電解質を作製す
るにあたっては、加熱溶融させたポリエチレンオキシド
１ｋｇに対してヘキサフルオロリン酸リチウムＬｉＰＦ
6 を１ｍｏｌの割合で添加し、これを硬化させて直径が
１４ｍｍ、厚みが１００μｍになった円板状の固体電解
質を作製した。[Preparation of Solid Electrolyte] In preparing a solid electrolyte, lithium hexafluorophosphate LiPF was added to 1 kg of polyethylene oxide heated and melted.
6 was added at a rate of 1 mol, and this was cured to produce a disk-shaped solid electrolyte having a diameter of 14 mm and a thickness of 100 μm.
【００３７】そして、上記の太陽電池１０の基板１１に
おいて、絶縁層１２を介して太陽電池１０が設けられた
面と反対側の面に、上記のように作製した負極２１と固
体電解質２２と正極２３とを積層させると共に、この正
極２３上に直径が２０ｍｍ、厚みが１００μｍの円板状
になったＳＵＳ製の正極外装体２４を設け、この正極外
装体２４と上記の基板１１との間において、上記のよう
に積層された負極２１と固体電解質２２と正極２３の周
囲にポリエチレン樹脂からなる絶縁パッキン２５を配
し、この絶縁パッキン２５により正極外装体２４と基板
１１とを電気的に絶縁させると共に、この絶縁パッキン
２５を正極外装体２４と基板１１とに溶着させて二次電
池２０を封口し、太陽電池一体型二次電池を作製した。On the substrate 11 of the solar cell 10, the negative electrode 21, the solid electrolyte 22, and the positive electrode 22 formed as described above are provided on the surface opposite to the surface on which the solar cell 10 is provided via the insulating layer 12. 23, and a disc-shaped positive-electrode casing 24 made of SUS having a diameter of 20 mm and a thickness of 100 μm is provided on the positive electrode 23, and between the positive-electrode casing 24 and the substrate 11. An insulating packing 25 made of polyethylene resin is disposed around the negative electrode 21, the solid electrolyte 22, and the positive electrode 23 stacked as described above, and the insulating packing 25 electrically insulates the positive electrode package 24 and the substrate 11. At the same time, the insulating packing 25 was welded to the positive electrode case 24 and the substrate 11 to seal the secondary battery 20, thereby producing a solar cell integrated secondary battery.
【００３８】そして、この実施例においては、上記のよ
うに作製した太陽電池一体型二次電池において、二次電
池２０が設けられていない太陽電池１０の部分に接する
ようにして、この二次電池２０における充放電を制御す
る制御回路３０を設けるようにした。In this embodiment, in the solar cell integrated type secondary battery manufactured as described above, the secondary battery 20 is provided in contact with the portion of the solar cell 10 where the secondary battery 20 is not provided. 20 is provided with a control circuit 30 for controlling charging and discharging.
【００３９】（比較例２）この比較例においては、図５
に示すように、上記の実施例３において、太陽電池１０
の基板１１と接するようにして二次電池２０を設けるに
あたり、太陽電池１０の基板１１と負極２１との間に、
直径が２０ｍｍ、厚みが１００μｍの円板状になったＳ
ＵＳ製の負極外装体２６を設けるようにし、それ以外
は、上記の実施例３の場合と同様にして、太陽電池一体
型二次電池を作製した。Comparative Example 2 In this comparative example, FIG.
As shown in FIG.
In providing the secondary battery 20 so as to be in contact with the substrate 11 of the solar cell 10, between the substrate 11 of the solar cell 10 and the negative electrode 21,
S in the shape of a disk with a diameter of 20 mm and a thickness of 100 μm
A solar cell integrated secondary battery was produced in the same manner as in Example 3 except that a US-made negative electrode case 26 was provided.
【００４０】そして、上記の実施例３と比較例２の太陽
電池一体型二次電池における二次電池２０のエネルギー
密度を比較すると、実施例３の二次電池２０において
は、負極外装体２６が設けられていない分だけ、比較例
２の二次電池２０に比べてエネルギー密度が高くなって
おり、比較例２の二次電池２０においてはそのエネルギ
ー密度が１００Ｗｈ／ｌであったのに対して、実施例３
の二次電池２０においてはそのエネルギー密度が１５０
Ｗｈ／ｌとなっており、エネルギー密度が約１．５倍向
上していた。When the energy densities of the secondary batteries 20 in the solar cell integrated secondary batteries of the above-mentioned Example 3 and Comparative Example 2 are compared, in the secondary battery 20 of Example 3, the negative The energy density is higher than that of the secondary battery 20 of Comparative Example 2 by the amount not provided, whereas the energy density of the secondary battery 20 of Comparative Example 2 was 100 Wh / l. Example 3
Secondary battery 20 has an energy density of 150
Wh / l, and the energy density was improved about 1.5 times.
【００４１】（実施例４〜９）これらの実施例において
は、上記の実施例３における太陽電池一体型二次電池の
作製において、二次電池２０に使用する負極材料だけを
下記の表１に示すように変更し、それ以外は、上記の実
施例３の場合と同様にして各太陽電池一体型二次電池を
作製した。(Examples 4 to 9) In these examples, only the negative electrode materials used for the secondary battery 20 in the fabrication of the solar cell integrated type secondary battery in the above-mentioned Example 3 are shown in Table 1 below. The solar cell integrated secondary batteries were fabricated in the same manner as in Example 3 except for the following changes.
【００４２】そして、上記の実施例３及びこれらの実施
例４〜９の各太陽電池一体型二次電池において、各二次
電池２０を太陽電池１０によってそれぞれ充電終止電圧
２．５Ｖまで充電させた後、放電終止電圧１Ｖまで放電
させ、このような充放電を繰り返して行ない、放電容量
が初期放電容量の半分になるまでのサイクル数を求め
て、その結果を下記の表１に合わせて示した。Then, in each of the solar cell integrated type secondary batteries of Example 3 and Examples 4 to 9 above, each secondary battery 20 was charged by the solar cell 10 to a charge end voltage of 2.5 V. Thereafter, the battery was discharged to a discharge end voltage of 1 V, and such charge / discharge was repeated. The number of cycles until the discharge capacity became half of the initial discharge capacity was obtained. The results are shown in Table 1 below. .
【００４３】[0043]
【表１】 [Table 1]
【００４４】この結果から明らかなように、太陽電池一
体型二次電池における二次電池２０において、その負極
２１に負極集電体を使用しない場合、その負極材料とし
て、チタン酸リチウム，ニオビウム酸リチウム，スズ酸
リチウム，鉄酸リチウム，珪酸リチウムからなる金属酸
化物を用いると、負極材料に黒鉛等の炭素材料や金属リ
チウムを用いた場合に比べて、二次電池２０におけるサ
イクル特性が向上していた。As is apparent from these results, in the secondary battery 20 of the solar cell integrated type secondary battery, when the negative electrode current collector is not used for the negative electrode 21, lithium titanate and lithium niobate are used as the negative electrode material. When a metal oxide comprising lithium, lithium stannate, lithium ferrate, and lithium silicate is used, the cycle characteristics of the secondary battery 20 are improved as compared with the case where a carbon material such as graphite or metal lithium is used as the negative electrode material. Was.
【００４５】[0045]
【発明の効果】以上詳述したように、この発明の請求項
１における太陽電池一体型二次電池においては、太陽電
池における基板を二次電池における正極又は負極の外装
体として使用するようにしたため、二次電池における正
極又は負極の外装体を別個に設ける必要がなく、この太
陽電池一体型二次電池における全体の厚みを薄くするこ
とができた。As described in detail above, in the solar cell integrated secondary battery according to the first aspect of the present invention, the substrate in the solar cell is used as the outer package of the positive electrode or the negative electrode in the secondary battery. In addition, it is not necessary to separately provide the outer package of the positive electrode or the negative electrode in the secondary battery, and the overall thickness of the solar cell integrated secondary battery can be reduced.
【００４６】また、この発明の請求項２における太陽電
池一体型二次電池のように、その二次電池として固体電
解質二次電池を使用すると、この二次電池における厚み
をさらに薄くすることができ、またその活物質にリチウ
ムを利用した固体電解質二次電池を用いると、この二次
電池の厚みを薄くした場合においても、十分な充放電容
量が得られるようになった。Further, when a solid electrolyte secondary battery is used as the secondary battery as in the solar cell integrated secondary battery according to the second aspect of the present invention, the thickness of the secondary battery can be further reduced. When a solid electrolyte secondary battery using lithium as its active material is used, a sufficient charge / discharge capacity can be obtained even when the thickness of the secondary battery is reduced.
【００４７】さらに、この発明の請求項３における太陽
電池一体型二次電池のように、二次電池における負極を
太陽電池の基板に接触させると、この負極と太陽電池の
基板とが反応するということがなく、安定して使用でき
るようになり、またこの二次電池における負極の負極材
料として金属酸化物を用いると、負極材料に炭素材料や
金属リチウム等を用いた場合に比べて、二次電池におけ
るサイクル特性が向上した。Further, when the negative electrode of the secondary battery is brought into contact with the solar cell substrate as in the solar cell integrated secondary battery according to the third aspect of the present invention, the negative electrode reacts with the solar cell substrate. The use of a metal oxide as the negative electrode material of the negative electrode in this secondary battery makes the secondary battery more secondary than the case where a carbon material or metal lithium is used as the negative electrode material. The cycle characteristics of the battery were improved.
【００４８】そして、上記のような太陽電池一体型二次
電池を腕時計等の時計の電源に使用すると、この太陽電
池一体型二次電池を用いた時計全体の厚みも薄くするこ
とができるようになり、また二次電池における負極を太
陽電池の基板に接触させると共に、その負極の負極材料
として金属酸化物を用いると、長期にわたって時計の電
源として好適に使用できるようになった。When the above-described solar cell-integrated secondary battery is used as a power source for a timepiece such as a wristwatch, the thickness of the entire timepiece using the solar cell-integrated secondary battery can be reduced. In addition, when a negative electrode of a secondary battery is brought into contact with a substrate of a solar cell and a metal oxide is used as a negative electrode material of the negative electrode, the negative electrode can be suitably used as a power source of a watch for a long time.
【００４９】また、上記の太陽電池の基板に二次電池と
共に、この二次電池の充放電を制御する制御回路を一体
に設けると、さらにこの時計全体の厚みを薄くすること
ができた。When a control circuit for controlling the charging and discharging of the secondary battery is provided integrally with the secondary battery on the substrate of the solar battery, the thickness of the entire timepiece can be further reduced.
【図１】この発明の実施例１において、太陽電池に二次
電池と制御回路と時計ムーブメントとを組み合わせて設
けた状態を示した概略説明図である。FIG. 1 is a schematic explanatory view showing a state in which a solar cell is provided with a combination of a secondary battery, a control circuit, and a timepiece movement in Embodiment 1 of the present invention.
【図２】この発明の実施例２において、太陽電池に二次
電池と制御回路と時計ムーブメントとを組み合わせて設
けた状態を示した概略説明図である。FIG. 2 is a schematic explanatory view showing a state in which a secondary battery, a control circuit, and a timepiece movement are provided in combination in a solar battery in Embodiment 2 of the present invention.
【図３】比較例１において、太陽電池に二次電池と制御
回路と時計ムーブメントとを組み合わせて設けた状態を
示した概略説明図である。FIG. 3 is a schematic explanatory view showing a state where a secondary battery, a control circuit, and a timepiece movement are provided in combination in a solar battery in Comparative Example 1.
【図４】この発明の実施例３において、太陽電池と二次
電池と制御回路とを組み合わせて設けた状態を示した概
略説明図である。FIG. 4 is a schematic explanatory view showing a state in which a solar cell, a secondary cell, and a control circuit are provided in combination in Embodiment 3 of the present invention.
【図５】比較例２において、太陽電池と二次電池と制御
回路とを組み合わせて設けた状態を示した概略説明図で
ある。FIG. 5 is a schematic explanatory view showing a state in which a solar cell, a secondary battery, and a control circuit are provided in combination in Comparative Example 2.
【符号の説明】 １０ 太陽電池 １１ 太陽電池の基板 ２０ 二次電池 ２１ 負極 ２２ 固体電解質 ２３ 正極 ２４ 正極外装体 ３０ 制御回路 ４０ 時計ムーブメント[Description of Signs] 10 Solar cell 11 Solar cell substrate 20 Secondary battery 21 Negative electrode 22 Solid electrolyte 23 Positive electrode 24 Positive electrode casing 30 Control circuit 40 Clock movement
───────────────────────────────────────────────────── フロントページの続き (72)発明者 能間 俊之 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 (72)発明者 西尾 晃治 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Toshiyuki Noma 2-5-5 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Inventor Koji Nishio 2-chome, Keihanhondori, Moriguchi-shi, Osaka No. 5-5 in Sanyo Electric Co., Ltd.
Claims (5)
る太陽電池一体型二次電池において、導電面を有する太
陽電池の基板を上記の二次電池における正極又は負極の
外装体として用いたことを特徴とする太陽電池一体型二
次電池。1. A solar cell integrated secondary battery comprising a combination of a solar cell and a secondary battery, wherein a solar cell substrate having a conductive surface is used as an outer package of a positive electrode or a negative electrode in the secondary battery. A solar cell integrated type secondary battery characterized by the above-mentioned.
電池において、上記の二次電池が固体電解質二次電池で
あることを特徴とする太陽電池一体型二次電池。2. The solar cell integrated secondary battery according to claim 1, wherein the secondary battery is a solid electrolyte secondary battery.
型二次電池において、上記の二次電池における負極を太
陽電池の基板に接触させると共に、この負極における負
極材料に金属酸化物を用いたことを特徴とする時計。3. The solar cell integrated secondary battery according to claim 1, wherein the negative electrode of the secondary battery is brought into contact with a substrate of the solar cell, and a metal oxide is used as a negative electrode material of the negative electrode. A watch characterized by the presence.
陽電池一体型二次電池を電源に用いたことを特徴とする
時計。4. A timepiece using the solar cell integrated type secondary battery according to claim 1 as a power supply.
の太陽電池における導電面を有する基板に、上記の二次
電池における充放電を制御する制御回路を一体に形成し
たことを特徴とする時計。5. The timepiece according to claim 4, wherein a control circuit for controlling charging and discharging of the secondary battery is formed integrally with a substrate having a conductive surface of the solar cell. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9236690A JPH1174002A (en) | 1997-06-30 | 1997-09-02 | Secondary battery integrated with solar cell and watch |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17360497 | 1997-06-30 | ||
| JP9-173604 | 1997-06-30 | ||
| JP9236690A JPH1174002A (en) | 1997-06-30 | 1997-09-02 | Secondary battery integrated with solar cell and watch |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1174002A true JPH1174002A (en) | 1999-03-16 |
Family
ID=26495519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9236690A Pending JPH1174002A (en) | 1997-06-30 | 1997-09-02 | Secondary battery integrated with solar cell and watch |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1174002A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007080779A (en) * | 2005-09-16 | 2007-03-29 | Mitsubishi Electric Corp | Battery integrally formed substrate |
| KR100782016B1 (en) | 2005-12-26 | 2007-12-06 | 주식회사 나래나노텍 | Lithium-Polymer Battery having Solar Cell |
| KR100934956B1 (en) * | 2007-09-13 | 2010-01-06 | 한국과학기술연구원 | Photovoltaic Driven Secondary Battery System |
| JP2011008967A (en) * | 2009-06-23 | 2011-01-13 | Idemitsu Kosan Co Ltd | Solar battery compound lithium battery module |
| US7976975B2 (en) | 2006-09-05 | 2011-07-12 | Seiko Epson Corporation | Battery device and electronic apparatus |
| JP2016151530A (en) * | 2015-02-18 | 2016-08-22 | セイコーインスツル株式会社 | Solar drive unit, solar movement, and timekeeper |
| CN106104962A (en) * | 2014-03-14 | 2016-11-09 | 株式会社村田制作所 | Charging circuit and use the module of this kind of charging circuit |
-
1997
- 1997-09-02 JP JP9236690A patent/JPH1174002A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007080779A (en) * | 2005-09-16 | 2007-03-29 | Mitsubishi Electric Corp | Battery integrally formed substrate |
| KR100782016B1 (en) | 2005-12-26 | 2007-12-06 | 주식회사 나래나노텍 | Lithium-Polymer Battery having Solar Cell |
| US7976975B2 (en) | 2006-09-05 | 2011-07-12 | Seiko Epson Corporation | Battery device and electronic apparatus |
| KR100934956B1 (en) * | 2007-09-13 | 2010-01-06 | 한국과학기술연구원 | Photovoltaic Driven Secondary Battery System |
| JP2011008967A (en) * | 2009-06-23 | 2011-01-13 | Idemitsu Kosan Co Ltd | Solar battery compound lithium battery module |
| CN106104962A (en) * | 2014-03-14 | 2016-11-09 | 株式会社村田制作所 | Charging circuit and use the module of this kind of charging circuit |
| EP3118966A4 (en) * | 2014-03-14 | 2017-11-22 | Murata Manufacturing Co., Ltd. | Charging circuit and module using same |
| US10461571B2 (en) | 2014-03-14 | 2019-10-29 | Murata Manufacturing Co., Ltd. | Charging circuit and module using the same |
| JP2016151530A (en) * | 2015-02-18 | 2016-08-22 | セイコーインスツル株式会社 | Solar drive unit, solar movement, and timekeeper |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Placke et al. | Lithium ion, lithium metal, and alternative rechargeable battery technologies: the odyssey for high energy density | |
| JP2003100353A (en) | Hybrid power source element and its manufacturing method | |
| JPH10312826A (en) | Nonaqueous electrolyte battery and charging method therefor | |
| JP2007095380A (en) | Battery | |
| US5789110A (en) | Cathode-active material blends comprising Lix Mn2 O4 (0<x≦2) | |
| JP5002918B2 (en) | Secondary battery | |
| JP2006302756A (en) | Battery | |
| JP4412885B2 (en) | Lithium secondary battery | |
| JPH1174002A (en) | Secondary battery integrated with solar cell and watch | |
| JPH1083838A (en) | Whole solid lithium battery | |
| JP3378756B2 (en) | Lithium battery | |
| JPH11339856A (en) | Manufacture of sheet-type lithium-ion secondary battery | |
| JP2000133274A (en) | Polymer lithium secondary battery | |
| JP2006228602A (en) | Battery | |
| JP2600214B2 (en) | Non-aqueous electrolyte secondary battery | |
| JP2000149994A (en) | Polymer electrolyte lithium secondary battery | |
| JP3172444B2 (en) | Negative electrode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery provided with the same | |
| JP2020027742A (en) | Manufacturing method for all-solid-state battery | |
| JP2001052750A (en) | Polymer lithium secondary battery | |
| JP2001085061A (en) | Electrochemical device | |
| JP2003115326A (en) | Nonaqueous electrolyte secondary battery | |
| JPH11111337A (en) | Polymer electrolyte secondary battery | |
| JPH11354155A (en) | Nonaqueous electrolyte secondary battery | |
| JP2006318759A (en) | Battery | |
| JP2001085060A (en) | Electrochemical device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040309 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20040706 |