JP5644715B2 - battery - Google Patents
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- JP5644715B2 JP5644715B2 JP2011177688A JP2011177688A JP5644715B2 JP 5644715 B2 JP5644715 B2 JP 5644715B2 JP 2011177688 A JP2011177688 A JP 2011177688A JP 2011177688 A JP2011177688 A JP 2011177688A JP 5644715 B2 JP5644715 B2 JP 5644715B2
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- 239000007784 solid electrolyte Substances 0.000 claims description 48
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 39
- 229910052717 sulfur Inorganic materials 0.000 claims description 39
- 239000011593 sulfur Substances 0.000 claims description 39
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 38
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 38
- 229910052794 bromium Inorganic materials 0.000 claims description 38
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 38
- 238000001514 detection method Methods 0.000 claims description 37
- 239000003792 electrolyte Substances 0.000 description 37
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 18
- 229910001416 lithium ion Inorganic materials 0.000 description 18
- 238000000034 method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 229910018091 Li 2 S Inorganic materials 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 239000007773 negative electrode material Substances 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000005001 laminate film Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000006091 Macor Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002203 sulfidic glass Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002482 conductive additive Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Secondary Cells (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Description
本発明は電池に関する。 The present invention relates to a battery.
リチウムイオン二次電池は、他の二次電池よりもエネルギー密度が高く、高電圧での動作が可能という特徴を有している。そのため、リチウムイオン二次電池は小型軽量化を図りやすい二次電池として携帯電話等の情報機器に使用されている。また、近年は電気自動車やハイブリッド自動車用等の大型機器の動力用としても、リチウムイオン二次電池の需要が高まっている。 A lithium ion secondary battery has the characteristics that it has higher energy density than other secondary batteries and can operate at a high voltage. Therefore, lithium ion secondary batteries are used in information devices such as mobile phones as secondary batteries that are easy to reduce in size and weight. In recent years, the demand for lithium ion secondary batteries has also increased for powering large equipment such as electric vehicles and hybrid vehicles.
リチウムイオン二次電池には、正極層及び負極層と、これらの間に配置される電解質層とが備えられている。当該電解質層に用いられる電解質としては、例えば非水系の液体状や固体状の物質が知られている。液体状の電解質（以下において、「電解液」という。）は、正極層や負極層の内部へと浸透しやすい。そのため、電解液が用いられる場合には、正極層や負極層に含有されている活物質と電解質との界面が形成され易いので、電池の性能を向上させやすい。ところが、広く用いられている電解液は可燃性であるため、安全性を確保するためのシステムを搭載する必要がある。一方、不燃性である固体状の電解質（以下において、「固体電解質」という。）を用いると、上記システムを簡素化できる。それゆえ、不燃性である固体電解質を含有する層（以下において、「固体電解質層」という。）が備えられる形態のリチウムイオン二次電池（以下において、「固体電池」という。）が提案されている。 A lithium ion secondary battery includes a positive electrode layer and a negative electrode layer, and an electrolyte layer disposed therebetween. As an electrolyte used for the electrolyte layer, for example, a non-aqueous liquid or solid substance is known. A liquid electrolyte (hereinafter referred to as “electrolytic solution”) easily penetrates into the positive electrode layer and the negative electrode layer. Therefore, when the electrolytic solution is used, the interface between the active material contained in the positive electrode layer or the negative electrode layer and the electrolyte is easily formed, so that the battery performance is easily improved. However, since the widely used electrolyte is flammable, it is necessary to mount a system for ensuring safety. On the other hand, when a solid electrolyte that is nonflammable (hereinafter referred to as “solid electrolyte”) is used, the above system can be simplified. Therefore, a lithium ion secondary battery (hereinafter referred to as “solid battery”) in a form provided with a layer containing a solid electrolyte that is nonflammable (hereinafter referred to as “solid electrolyte layer”) has been proposed. Yes.
このようなリチウムイオン二次電池は、用途に応じた電圧を得るため、複数の素電池を接続して構成することがある。このとき、一部の素電池で過充電になったとしても、どの素電池が過充電になっているのかを検知することが困難であった。そのため、過充電により電池に異常が生じた場合、該電池に備えられた一部の素電池にしか問題がない場合であったとしても、該電池を一度解体してから各素電池の電圧や劣化等を検査しなければならなかった。そこで、特許文献１のように、素電池の過充電を検知可能な電池に関する技術がこれまでに提案されている。 Such a lithium ion secondary battery may be configured by connecting a plurality of unit cells in order to obtain a voltage according to the application. At this time, even if some of the unit cells are overcharged, it is difficult to detect which unit cell is overcharged. Therefore, when an abnormality occurs in a battery due to overcharging, even if there is a problem only with some of the unit cells provided in the battery, the voltage of each unit cell is We had to inspect for deterioration. Therefore, as in Patent Document 1, a technique related to a battery capable of detecting overcharge of a unit cell has been proposed so far.
特許文献１に開示されている技術によれば、素電池の過充電を検知可能であると考えられる。しかしながら、特許文献１に開示されている技術では、素電池の電圧や温度の検知によって過充電を検知しているため、各素電池に電圧検出線や温度検出線を設けなければならなかった。そのため、特許文献１に開示されている技術では、電池の製造費用が増大するなどの問題があった。 According to the technique disclosed in Patent Document 1, it is considered that overcharge of a unit cell can be detected. However, in the technique disclosed in Patent Document 1, since overcharge is detected by detecting the voltage and temperature of the unit cell, each unit cell has to be provided with a voltage detection line and a temperature detection line. For this reason, the technique disclosed in Patent Document 1 has a problem that the manufacturing cost of the battery increases.
そこで本発明は、簡便に過充電を検知可能な電池を提供することを課題とする。 Then, this invention makes it a subject to provide the battery which can detect an overcharge simply.
上記課題を解決するために、本発明は以下の構成をとる。すなわち、
本発明は、ヨウ素、硫黄又は臭素を含む電解質を備えた素電池と、該電解質からヨウ素、硫黄又は臭素が発せられたことを視覚的に検知可能な検知手段と、を備えた電池である。
In order to solve the above problems, the present invention has the following configuration. That is,
The present invention is a battery including a unit cell including an electrolyte containing iodine, sulfur, or bromine, and a detection unit that can visually detect that iodine, sulfur, or bromine is emitted from the electrolyte.
後に詳述するように、ヨウ素、硫黄又は臭素を含む電解質を備えた素電池が過充電になると該電解質からヨウ素、硫黄又は臭素が揮発する。本発明において「検知手段」とは、上記のように電解質からヨウ素、硫黄又は臭素が揮発したことを視覚的に認識可能な方法によって検知できる手段を意味する。 As described in detail later, when a unit cell including an electrolyte containing iodine, sulfur, or bromine is overcharged, iodine, sulfur, or bromine volatilizes from the electrolyte. In the present invention, the “detecting means” means means capable of detecting the volatilization of iodine, sulfur or bromine from the electrolyte as described above by a visually recognizable method.
上記本発明の電池において、検知手段が白色部材であることが好ましい。 In the battery of the present invention, the detection means is preferably a white member.
本発明において「白色部材」とは、表面の少なくとも一部が白色の部材を意味する。また、本発明において「白色」とは、表面色の一種であって、対象物体の表面において可視光線（３６０ｎｍ以上８６０ｎｍ以下の波長域の光）が５０％以上乱反射されることによって知覚できる色を意味する。白色部材における可視光線の反射率（視覚的に認識される白さ）は、ヨウ素、硫黄又は臭素が白色部材に付着したことを認識できる程度であればよい。 In the present invention, the “white member” means a member whose surface is at least partially white. Further, in the present invention, “white” is a kind of surface color, and is a color that can be perceived by 50% or more of irregular reflection of visible light (light in a wavelength range of 360 nm to 860 nm) on the surface of the target object. means. The visible light reflectance (whiteness visually recognized) in the white member may be such that iodine, sulfur, or bromine can be recognized as attached to the white member.
また、上記本発明の電池において、素電池が検知手段とともに容器に収容されている、又は、素電池が容器に収容されるとともに該容器の内面に検知手段が備えられていることが好ましい。 In the battery of the present invention, it is preferable that the unit cell is accommodated in the container together with the detection unit, or the unit cell is accommodated in the container and the detection unit is provided on the inner surface of the container.
ここに「容器の内面に検知手段が備えられている」とは、少なくとも容器の内面の一部、すなわち少なくとも容器の素電池が配置されている側の面の一部に検知手段が備えられていること意味する。容器全体が検知手段で構成されていてもよい。 Here, “the detection means is provided on the inner surface of the container” means that the detection means is provided on at least a part of the inner surface of the container, that is, at least a part of the surface of the container where the unit cells are disposed. Means that The entire container may be constituted by the detection means.
本発明の電池では、電解質にヨウ素、硫黄又は臭素を含む素電池を備えており、該素電池が過充電となったとき、後述するように電解質からヨウ素、硫黄又は臭素が揮発する。また、本発明の電池では、電解質からヨウ素、硫黄又は臭素が発せられたことを視覚的に検知可能な検知手段を備えている。よって、本発明の電池によれば、電解質からヨウ素、硫黄又は臭素が発せられたことを検知手段で検知することによって、素電池が過充電になっていることを視覚的に検知できる。したがって、本発明によれば、簡便に過充電を検知可能な電池を提供することができる。 The battery of the present invention includes a unit cell containing iodine, sulfur or bromine in the electrolyte. When the unit cell is overcharged, iodine, sulfur or bromine volatilizes from the electrolyte as will be described later. Further, the battery of the present invention is provided with a detecting means that can visually detect that iodine, sulfur or bromine is emitted from the electrolyte. Therefore, according to the battery of the present invention, it is possible to visually detect that the unit cell is overcharged by detecting that the iodine, sulfur or bromine is emitted from the electrolyte by the detection means. Therefore, according to the present invention, a battery capable of easily detecting overcharge can be provided.
また、本発明の電池において、検知手段を白色部材とすることによって、電解質からヨウ素、硫黄又は臭素が発せられたことを視覚的に検知することが、より容易になる。よって、より簡便に過充電を検知可能な電池を提供することができる。 In the battery of the present invention, it is easier to visually detect that iodine, sulfur or bromine is emitted from the electrolyte by using a white member as the detection means. Therefore, the battery which can detect overcharge more simply can be provided.
さらに、本発明の電池において、素電池が検知手段とともに容器に収容されている、又は、素電池が容器に収容されるとともに該容器の内面に検知手段が備えられている形態とすることによって、電解質から発せられたヨウ素、硫黄又は臭素を検知手段によって検知することがより容易になる。よって、より簡便に過充電を検知可能な電池を提供することができる。 Furthermore, in the battery of the present invention, the unit cell is accommodated in the container together with the detection means, or the unit cell is accommodated in the container and the inner surface of the container is provided with the detection means. It becomes easier to detect iodine, sulfur or bromine emitted from the electrolyte by the detection means. Therefore, the battery which can detect overcharge more simply can be provided.
本発明の上記した作用及び利得は、次に説明する発明を実施するための形態から明らかにされる。以下、本発明を図面に示す実施形態に基づき説明する。ただし、以下に示す形態は本発明の例示であり、本発明はこれら実施形態に限定されるものではない。なお、各図面は、図示と理解のしやすさの便宜上、簡略化しており、適宜縮尺等は変更している。また、以下の本発明の説明では、本発明の電池が固体電解質層を用いたリチウムイオン二次電池（固体電池）である場合について主に説明する。 The above-described operation and gain of the present invention will be clarified from embodiments for carrying out the invention described below. Hereinafter, the present invention will be described based on embodiments shown in the drawings. However, the form shown below is an illustration of this invention and this invention is not limited to these embodiment. Each drawing is simplified for convenience of illustration and understanding, and the scale and the like are changed as appropriate. In the following description of the present invention, the case where the battery of the present invention is a lithium ion secondary battery (solid battery) using a solid electrolyte layer will be mainly described.
図１は、本発明の電池１０を説明する断面図である。図１に示したように、電池１０は、素電池１及び検知手段２と、これらを収容する容器３と、を備えている。 FIG. 1 is a cross-sectional view illustrating a battery 10 of the present invention. As shown in FIG. 1, the battery 10 includes a unit cell 1 and detection means 2, and a container 3 that accommodates them.
素電池１は、ヨウ素、硫黄又は臭素を含む電解質を備えている。当該ヨウ素、硫黄、又は臭素は、イオン状態で電解質に含まれている。素電池１が過充電となると、素電池１の電圧が高くなることによってイオン状態で電解質に含まれていたヨウ素、硫黄、又は臭素は酸化されて分子状態となり、揮発し易くなる。このようにして揮発したヨウ素、硫黄、又は臭素は、後述する検知手段２によって視覚的に検知可能なため、電池１０によれば、素電池１の過充電を簡便に検知できる。 The unit cell 1 includes an electrolyte containing iodine, sulfur, or bromine. The iodine, sulfur, or bromine is contained in the electrolyte in an ionic state. When the unit cell 1 is overcharged, the voltage of the unit cell 1 increases, so that iodine, sulfur, or bromine contained in the electrolyte in an ionic state is oxidized into a molecular state, and is easily volatilized. Since iodine, sulfur, or bromine volatilized in this way can be visually detected by the detection means 2 described later, according to the battery 10, overcharge of the unit cell 1 can be easily detected.
図２は、素電池１の一例を説明する断面図である。素電池１は、ヨウ素、硫黄又は臭素を含む電解質を備えている以外は、公知の固体電池に備えられる素電池と同様の構成とすることができる。図２に例示した素電池１は、正極層１ｂと、負極層１ｄと、正極層１ｂ及び負極層１ｄに挟持された固体電解質層１ｃと、正極層１ｂに接続された正極集電体１ａと、負極層１ｄ接続された負極集電体１ｅとを備えている。正極層１ｂは正極集電体１ａを介して正極端子１ｆに接続されており、負極層１ｄは負極集電体１ｅを介して負極端子１ｇに接続されている。また、図１には表れていないが、素電池１は、正極端子１ｆ及び負極端子１ｇがそれぞれの一端を容器３の外側に露出するようにして、容器３に収容されている。 FIG. 2 is a cross-sectional view illustrating an example of the unit cell 1. The unit cell 1 can have the same configuration as that of a unit cell provided in a known solid battery except that it includes an electrolyte containing iodine, sulfur, or bromine. The unit cell 1 illustrated in FIG. 2 includes a positive electrode layer 1b, a negative electrode layer 1d, a solid electrolyte layer 1c sandwiched between the positive electrode layer 1b and the negative electrode layer 1d, and a positive electrode current collector 1a connected to the positive electrode layer 1b. And a negative electrode current collector 1e connected to the negative electrode layer 1d. The positive electrode layer 1b is connected to the positive electrode terminal 1f via the positive electrode current collector 1a, and the negative electrode layer 1d is connected to the negative electrode terminal 1g via the negative electrode current collector 1e. Although not shown in FIG. 1, the unit cell 1 is accommodated in the container 3 such that the positive electrode terminal 1 f and the negative electrode terminal 1 g are exposed to the outside of the container 3.
このような素電池１は、例えば以下の工程を経て製造することができる。素電池１を製造する際には、まず、正極層１ｂ及び負極層１ｄの間に固体電解質層１ｃを配置する。正極層１ｂは、例えば、少なくとも正極活物質及び固体電解質を溶媒に分散して作製した正極合剤を、正極集電体１ａの表面に塗布する過程を経て作製することができる。負極層１ｄは、例えば、負極活物質及び固体電解質を溶媒に分散して作製した負極合剤を、負極集電体１ｅの表面に塗布する過程を経て作製することができる。また、固体電解質層１ｃは、例えば、固体電解質を溶媒に分散して作製した電解質層用組成物を、正極層１ｂの表面に塗布する過程を経て作製することができる。このようにして固体電解質層１ｃを作製したら、固体電解質層１ｃが正極層１ｂ及び負極層１ｄで挟まれるようにして素電池１を作製する。例えば、正極層１ｂの表面に形成した固体電解質層１ｃの上に、負極集電体１ｅの表面に形成した負極層１ｄを積層し、積層方向の両端側から圧縮力を付与する過程を経て、素電池１を作製することができる。次に、素電池１を作製したら、端部が容器３の外側に配置された正極端子１ｆと正極集電体１ａとが接続されるとともに、端部が容器３の外側に配置された負極端子１ｆと負極集電体１ｇとが接続されるようにしながら、素電池１を容器３内に収容する。 Such a unit cell 1 can be manufactured through the following processes, for example. When manufacturing the unit cell 1, first, the solid electrolyte layer 1c is disposed between the positive electrode layer 1b and the negative electrode layer 1d. The positive electrode layer 1b can be prepared, for example, through a process in which a positive electrode mixture prepared by dispersing at least a positive electrode active material and a solid electrolyte in a solvent is applied to the surface of the positive electrode current collector 1a. The negative electrode layer 1d can be prepared, for example, through a process in which a negative electrode mixture prepared by dispersing a negative electrode active material and a solid electrolyte in a solvent is applied to the surface of the negative electrode current collector 1e. The solid electrolyte layer 1c can be produced, for example, through a process in which a composition for an electrolyte layer produced by dispersing a solid electrolyte in a solvent is applied to the surface of the positive electrode layer 1b. After producing the solid electrolyte layer 1c in this way, the unit cell 1 is produced such that the solid electrolyte layer 1c is sandwiched between the positive electrode layer 1b and the negative electrode layer 1d. For example, the negative electrode layer 1d formed on the surface of the negative electrode current collector 1e is laminated on the solid electrolyte layer 1c formed on the surface of the positive electrode layer 1b, and a process of applying compressive force from both ends in the lamination direction is performed. The unit cell 1 can be manufactured. Next, when the unit cell 1 is manufactured, the positive electrode terminal 1f whose end is arranged outside the container 3 and the positive electrode current collector 1a are connected, and the negative electrode terminal whose end is arranged outside the container 3 The unit cell 1 is accommodated in the container 3 while connecting the 1f and the negative electrode current collector 1g.
固体電解質層１ｃは、公知のリチウムイオン二次電池に備えられる固体電解質層と同様の形態とすることができる。すなわち、固体電解質層１ｃに含有させる固体電解質としては、例えば、Ｌｉ３ＰＯ４等の酸化物系固体電解質のほか、Ｌｉ３ＰＳ４や、モル比でＬｉ２Ｓ：Ｐ２Ｓ５＝５０：５０〜１００：０となるようにＬｉ２Ｓ及びＰ２Ｓ５を混合して作製した硫化物系固体電解質（例えば、モル比で、Ｌｉ２Ｓ：Ｐ２Ｓ５＝７５：２５となるようにＬｉ２Ｓ及びＰ２Ｓ５を混合して作製した硫化物固体電解質）等を例示することができる。また、固体電解質層の作製時には、後述する正極層１ｂの作製時に使用可能な溶媒等を適宜用いることができる。 The solid electrolyte layer 1c can have the same form as the solid electrolyte layer provided in a known lithium ion secondary battery. That is, as a solid electrolyte to be contained in the solid electrolyte layer 1c, for example, Li 3 PS 4 in addition to an oxide-based solid electrolyte such as Li 3 PO 4 or Li 2 S: P 2 S 5 = 50: A sulfide-based solid electrolyte prepared by mixing Li 2 S and P 2 S 5 so as to be 50 to 100: 0 (for example, the molar ratio is Li 2 S: P 2 S 5 = 75: 25) Examples thereof include sulfide solid electrolytes prepared by mixing Li 2 S and P 2 S 5 with the same. Moreover, the solvent etc. which can be used at the time of preparation of the positive electrode layer 1b mentioned later can be used suitably at the time of preparation of a solid electrolyte layer.
素電池１において、正極層１ｂに含有させる正極活物質としては、リチウムイオン二次電池の正極層に含有させることが可能な公知の正極活物質を適宜用いることができる。そのような正極活物質としては、コバルト酸リチウム（ＬｉＣｏＯ２）やニッケル酸リチウム（ＬｉＮｉＯ２）等の層状、オリビン構造、又はスピネル構造の化合物を例示することができる。また、正極層１ｂは、ヨウ素、硫黄又は臭素を含む電解質を備えている。そのような電解質としては、例えば、Ｌｉ３ＰＳ４や、モル比でＬｉ２Ｓ：Ｐ２Ｓ５＝５０：５０〜１００：０となるようにＬｉ２Ｓ及びＰ２Ｓ５を混合して作製した硫化物系固体電解質（例えば、モル比で、Ｌｉ２Ｓ：Ｐ２Ｓ５＝７５：２５となるようにＬｉ２Ｓ及びＰ２Ｓ５を混合して作製した硫化物固体電解質）等を例示することができる。このほか、正極層１ｂには、正極活物質と固体電解質とを結着させるバインダーや導電性を向上させる導電助剤が含有されていても良い。正極層１ｂに含有させることが可能なバインダーとしては、ブチレンゴム等を例示することができる。正極層１ｂに含有させることが可能な導電助剤としては、カーボンブラック等の炭素材料や、金属材料を例示することができる。また、正極層１ｂの作製時には、リチウムイオン二次電池の正極層作製時に用いるスラリーを調整する際に使用可能な公知の溶媒を適宜用いることができる。そのような溶媒としては、ヘプタン等を例示することができる。 In the unit cell 1, a known positive electrode active material that can be contained in the positive electrode layer of the lithium ion secondary battery can be appropriately used as the positive electrode active material contained in the positive electrode layer 1b. As such a positive electrode active material, a layered compound such as lithium cobaltate (LiCoO 2 ) or lithium nickelate (LiNiO 2 ), an olivine structure, or a spinel structure compound can be exemplified. Further, the positive electrode layer 1b includes an electrolyte containing iodine, sulfur, or bromine. As such an electrolyte, for example, Li 3 PS 4 or Li 2 S and P 2 S 5 are mixed so that the molar ratio is Li 2 S: P 2 S 5 = 50: 50 to 100: 0. The produced sulfide solid electrolyte (for example, the sulfide solid electrolyte produced by mixing Li 2 S and P 2 S 5 so that the molar ratio is Li 2 S: P 2 S 5 = 75: 25), etc. Can be illustrated. In addition, the positive electrode layer 1b may contain a binder that binds the positive electrode active material and the solid electrolyte and a conductive auxiliary agent that improves conductivity. Examples of the binder that can be contained in the positive electrode layer 1b include butylene rubber. Examples of the conductive aid that can be contained in the positive electrode layer 1b include carbon materials such as carbon black and metal materials. Moreover, the known solvent which can be used when preparing the slurry used at the time of positive electrode layer preparation of a lithium ion secondary battery can be used suitably at the time of preparation of the positive electrode layer 1b. As such a solvent, heptane and the like can be exemplified.
負極層１ｄに含有させる負極活物質としては、リチウムイオン二次電池の負極層に含有させることが可能な公知の負極活物質を適宜用いることができる。そのような負極活物質としては、グラファイト等を例示することができる。また、負極層１ｄには、リチウムイオン二次電池の負極層に含有させることが可能な公知の固体電解質を適宜含有させることができる。そのような固体電解質としては、固体電解質層１ｃに含有させることが可能な上記固体電解質等を例示することができる。このほか、負極層１ｄには、負極活物質と固体電解質とを結着させるバインダーや導電性を向上させる導電助剤が含有されていても良い。負極層１ｄに含有させることが可能なバインダーや導電助剤としては、正極層１ｂに含有させることが可能な上記バインダーや導電助剤等を例示することができる。また、負極層１ｄの作製時には、正極層１ｂの作製時に使用可能な上記溶媒等を適宜用いることができる。 As the negative electrode active material contained in the negative electrode layer 1d, a known negative electrode active material that can be contained in the negative electrode layer of the lithium ion secondary battery can be appropriately used. Examples of such a negative electrode active material include graphite. The negative electrode layer 1d can appropriately contain a known solid electrolyte that can be contained in the negative electrode layer of the lithium ion secondary battery. Examples of such a solid electrolyte include the solid electrolyte that can be contained in the solid electrolyte layer 1c. In addition, the negative electrode layer 1d may contain a binder that binds the negative electrode active material and the solid electrolyte and a conductive additive that improves conductivity. Examples of the binder and conductive additive that can be contained in the negative electrode layer 1d include the binder and conductive aid that can be contained in the positive electrode layer 1b. Moreover, the said solvent etc. which can be used at the time of preparation of the positive electrode layer 1b can be used suitably at the time of preparation of the negative electrode layer 1d.
正極集電体１ａ及び負極集電体１ｅ、並びに、正極端子１ｆ及び負極端子１ｇは、リチウムイオン二次電池の正極集電体及び負極集電体、並びに、正極端子及び負極端子として使用可能な公知の導電性材料によって構成することができる。そのような導電性材料としては、Ｃｕ、Ｎｉ、Ａｌ、Ｖ、Ａｕ、Ｐｔ、Ｍｇ、Ｆｅ、Ｔｉ、Ｃｏ、Ｃｒ、Ｚｎ、Ｇｅ、Ｉｎからなる群から選択される一又は二以上の元素を含む金属材料を例示することができる。 The positive electrode current collector 1a and the negative electrode current collector 1e, and the positive electrode terminal 1f and the negative electrode terminal 1g can be used as a positive electrode current collector and a negative electrode current collector, and a positive electrode terminal and a negative electrode terminal of a lithium ion secondary battery. It can be composed of a known conductive material. Examples of such a conductive material include one or more elements selected from the group consisting of Cu, Ni, Al, V, Au, Pt, Mg, Fe, Ti, Co, Cr, Zn, Ge, and In. Examples of the metal material to be included can be given.
次に、検知手段２について説明する。検知可能２は、素電池１に備えられた電解質からヨウ素、硫黄又は臭素が上述したようにして揮発したことを視覚的に検知可能な手段である。検知可能２は、素電池１に備えられた電解質から揮発したヨウ素、硫黄、又は臭素を検知し得る形態であればよく、形状及び配置位置等は特に限定されない。 Next, the detection means 2 will be described. Detectable 2 is a means that can visually detect that iodine, sulfur or bromine has volatilized from the electrolyte provided in the unit cell 1 as described above. Detectable 2 may be in any form that can detect iodine, sulfur, or bromine volatilized from the electrolyte provided in the unit cell 1, and the shape and arrangement position are not particularly limited.
検知手段２は、例えば、表面の少なくとも一部が白色である部材（以下、「白色部材」という。）とすることができる。本発明において「白色」とは、表面色の一種であって、対象物体の表面において可視光線（３６０ｎｍ以上８６０ｎｍ以下の波長域の光）が５０％以上乱反射されることによって知覚できる色を意味する。このような白色部材によって検知手段２を構成すれば、ヨウ素、硫黄、又は臭素が白色部材に付着したときに該付着部が変色したことを容易に認識できるため、素電池１に備えられた電解質からヨウ素、硫黄、又は臭素が揮発したことを視覚的に容易に検知できる。白色部材における可視光線の反射率（視覚的に認識される白さ）は、上述したようにして電解質から揮発したヨウ素、硫黄又は臭素が白色部材に付着した際に、ヨウ素、硫黄又は臭素が白色部材に付着したことを視覚的に認識できる程度であればよい。このような白色部材の具体例としては、例えば、マコール（登録商標）を挙げることができる。マコール（登録商標）は加工性に優れるため、本発明に好適に用いることができる。 The detection means 2 can be, for example, a member whose surface is at least partly white (hereinafter referred to as “white member”). In the present invention, “white” is a kind of surface color, and means a color that can be perceived when 50% or more of visible light (light in a wavelength region of 360 nm to 860 nm) is irregularly reflected on the surface of the target object. . If the detecting means 2 is constituted by such a white member, it is possible to easily recognize that the attached portion has changed color when iodine, sulfur, or bromine adheres to the white member, and therefore the electrolyte provided in the unit cell 1 It can be easily detected visually that iodine, sulfur, or bromine has volatilized. The reflectance of visible light (whiteness visually recognized) in the white member is determined by the whiteness of iodine, sulfur or bromine when iodine, sulfur or bromine volatilized from the electrolyte adheres to the white member as described above. What is necessary is just to be able to visually recognize that it adheres to the member. A specific example of such a white member is, for example, Macor (registered trademark). Macor (registered trademark) is excellent in processability and can be suitably used in the present invention.
容器３は、電池１０の作動時の環境に耐え得る材料によって構成されていれば、その形態は特に限定されない。容器３は、例えば、アルミニウムやステンレス鋼等の金属製とすることができる。 If the container 3 is comprised with the material which can endure the environment at the time of the action | operation of the battery 10, the form will not be specifically limited. The container 3 can be made of metal such as aluminum or stainless steel.
本発明に関するこれまでの説明では、素電池を収容した容器内に検知手段が備えられた電池を例示したが、本発明の電池は当該形態に限定されない。本発明において検知手段は電解質から揮発したヨウ素、硫黄、又は臭素が付着し得る位置に備えられていればよい。したがって、検知手段は、素電池を収容した容器の内面に備えられていてもよく、素電池を収容した容器全体が検知手段で構成されていてもよい。また、検知手段は素電池とともにラミネートフィルムに封入されていてもよい。このようなラミネートフィルムとしては、リチウムイオン二次電池に使用される公知のものを特に限定することなく用いることができる。すなわち、リチウムイオン二次電池の使用時の環境に耐えることができ、気体や液体を透過させない性質を有し、且つ、密封することができるフィルムを、特に限定されることなく用いることができる。そのようなフィルムの構成材料としては、ポリエチレン、ポリフッ化ビニルやポリ塩化ビニリデン等の樹脂フィルムのほか、これらの表面にアルミニウム等の金属を蒸着させた金属蒸着フィルム等を例示することができる。 In the description so far regarding the present invention, the battery in which the detection means is provided in the container containing the unit cell has been exemplified, but the battery of the present invention is not limited to this form. In the present invention, the detection means may be provided at a position where iodine, sulfur, or bromine volatilized from the electrolyte can adhere. Therefore, the detection means may be provided on the inner surface of the container containing the unit cells, or the entire container containing the unit cells may be constituted by the detection means. Moreover, the detection means may be enclosed in the laminate film together with the unit cell. As such a laminate film, a known film used for a lithium ion secondary battery can be used without any particular limitation. That is, a film that can withstand the environment during use of the lithium ion secondary battery, has a property of not allowing gas or liquid to permeate, and can be sealed can be used without particular limitation. Examples of the constituent material of such a film include resin films such as polyethylene, polyvinyl fluoride, and polyvinylidene chloride, and metal deposited films obtained by depositing a metal such as aluminum on these surfaces.
なお、検知手段は、ヨウ素、硫黄、又は臭素が付着したときにその状態を電池の外側から観察できる形態で備えられていることが好ましい。素電池が過充電となったことを、電池を分解しなくても検知可能となるからである。ヨウ素、硫黄、又は臭素が検知手段に付着した状態を電池の外側から観察できる形態とは、例えば、検知手段を収容した上記容器やラミネートフィルムに透明な部分を設けた形態を挙げることができる。ただし、本発明は当該形態に限定されず、ヨウ素、硫黄、又は臭素が検知手段に付着した状態を電池の外側から観察できない形態であってもよい。この場合、電池の使用時には素電池が過充電となっていることを検知し難くなるが、電池のリサイクル時等において、容器やラミネートフィルムを外した際に素電池が過充電となっていたか否かを判別可能となるため、劣化していない若しくは劣化の少ない素電池を選別することが容易になる。 In addition, it is preferable that the detection means is provided in a form in which the state can be observed from the outside of the battery when iodine, sulfur, or bromine adheres. This is because it is possible to detect that the unit battery is overcharged without disassembling the battery. The form in which the state where iodine, sulfur, or bromine adheres to the detection means can be observed from the outside of the battery includes, for example, a form in which a transparent portion is provided on the container or laminate film containing the detection means. However, this invention is not limited to the said form, The form which cannot observe the state which the iodine, sulfur, or bromine adhered to the detection means from the outer side of a battery may be sufficient. In this case, it is difficult to detect that the unit cell is overcharged when the battery is used, but whether the unit cell was overcharged when the container or laminate film was removed during battery recycling, etc. Therefore, it becomes easy to select a unit cell that is not deteriorated or has little deterioration.
また、本発明に関するこれまでの説明では、検知手段として白色部材を例示したが、本発明の電池は当該形態に限定されない。本発明において検知手段はヨウ素、硫黄、又は臭素が付着したことを視覚的に認識できる色であれば特に限定されない。 Moreover, in the above description regarding this invention, although the white member was illustrated as a detection means, the battery of this invention is not limited to the said form. In the present invention, the detection means is not particularly limited as long as it can visually recognize that iodine, sulfur, or bromine has adhered.
また、本発明に関するこれまでの説明では、正極層がヨウ素、硫黄又は臭素を含む電解質を備えた電池を例示したが、本発明の電池は当該形態に限定されない。ヨウ素、硫黄又は臭素を含む電解質は、当該電解質を備えた素電池が過充電となったときに当該電解質に含まれるヨウ素、硫黄又は臭素が揮発し得る場所に備えられていればよい。すなわち、ヨウ素、硫黄又は臭素を含む電解質が正極層には備えられておらず、固体電解質層に備えられていてもよい。また、正極層と固体電解質層の両方に、ヨウ素、硫黄又は臭素を含む電解質が備えられていてもよい。ただし、素電池が過充電となったときに該素電池に備えられた電解質に含まれるヨウ素、硫黄又は臭素がより揮発し易くなるという観点からは、ヨウ素、硫黄又は臭素を含む電解質が正極層に備えられていることが好ましい。 Moreover, although the positive electrode layer illustrated the battery provided with the electrolyte containing an iodine, sulfur, or bromine in the past description regarding this invention, the battery of this invention is not limited to the said form. The electrolyte containing iodine, sulfur or bromine may be provided in a place where iodine, sulfur or bromine contained in the electrolyte can be volatilized when the unit cell including the electrolyte is overcharged. That is, the electrolyte containing iodine, sulfur or bromine is not provided in the positive electrode layer, but may be provided in the solid electrolyte layer. Moreover, the electrolyte containing iodine, sulfur, or bromine may be provided in both the positive electrode layer and the solid electrolyte layer. However, from the viewpoint that iodine, sulfur or bromine contained in the electrolyte provided in the unit cell becomes more volatile when the unit cell is overcharged, the electrolyte containing iodine, sulfur or bromine is a positive electrode layer. Is preferably provided.
また、本発明に関するこれまでの説明では、１つの素電池が備えられる電池を例示したが、本発明の電池は当該形態に限定されない。本発明の電池において、備えられる素電池の数は特に限定されない。本発明の電池に複数の素電池が備えられる場合、各素電池に対応させて検知手段を設けることが好ましい。各素電池に対応させて検知手段を設けることによって、どの素電池が過充電となったかを容易に検知することができる。したがって、複数の素電池を備える場合において、過充電となった素電池のみを交換することが容易となり、電池の再生が容易になる。なお、「各素電池に対応させて検知手段を設ける」とは、例えば、素電池と検知手段とが１つの容器に収容された構成単位を複数備えた電池とすることや、少なくとも内面に検知手段を備えた容器に素電池が収容された構成単位を複数備えた電池とすることが考えられる。 Moreover, although the battery description provided with one unit cell was illustrated in the description so far regarding this invention, the battery of this invention is not limited to the said form. In the battery of the present invention, the number of unit cells provided is not particularly limited. When a plurality of unit cells are provided in the battery of the present invention, it is preferable to provide detection means corresponding to each unit cell. By providing detection means corresponding to each unit cell, it is possible to easily detect which unit cell is overcharged. Therefore, in the case where a plurality of unit cells are provided, it is easy to replace only the overcharged unit cell, and the battery can be easily regenerated. Note that “providing detection means corresponding to each unit cell” means, for example, that a unit cell and a detection unit include a plurality of structural units housed in one container, or at least an inner surface is detected. A battery including a plurality of structural units in which unit cells are housed in a container provided with means is conceivable.
また、本発明に関するこれまでの説明では、巻回されていない素電池を備えた電池を例示したが、本発明の電池は当該形態に限定されない。本発明の電池には、正極層と負極層との間に固体電解質層が配設されるように、正極層と固体電解質層と負極層とを積層した後、これを巻回する過程を経て作製した素電池が備えられていても良い。 Moreover, in the above description regarding this invention, although the battery provided with the unit cell which is not wound was illustrated, the battery of this invention is not limited to the said form. In the battery of the present invention, the positive electrode layer, the solid electrolyte layer, and the negative electrode layer are laminated so that the solid electrolyte layer is disposed between the positive electrode layer and the negative electrode layer, and then wound. The produced unit cell may be provided.
また、本発明に関するこれまでの説明では、リチウムイオン二次電池に本発明が適用される場合を例示したが、本発明は当該形態に限定されない。本発明の電池は、正極層と負極層との間を、リチウムイオン以外のイオンが移動する形態とすることも可能である。そのようなイオンとしては、ナトリウムイオン、カリウムイオン、マグネシウムイオン、カルシウムイオン等を例示することができる。リチウムイオン以外のイオンが移動する形態とする場合、正極活物質、固体電解質、及び、負極活物質は、移動するイオンに応じて適宜選択すれば良い。 Moreover, although the case where this invention is applied to a lithium ion secondary battery was illustrated in the past description regarding this invention, this invention is not limited to the said form. The battery of the present invention can also be configured such that ions other than lithium ions move between the positive electrode layer and the negative electrode layer. Examples of such ions include sodium ions, potassium ions, magnesium ions, calcium ions and the like. In the case where ions other than lithium ions move, the positive electrode active material, the solid electrolyte, and the negative electrode active material may be appropriately selected according to the moving ions.
また、本発明に関するこれまでの説明では、固体電解質層を有する固体電池に本発明が適用される場合を例示したが、本発明は当該形態に限定されない。本発明の電池は、電解液を用いた電解質層を有する電池であっても良い。 Moreover, although the case where this invention is applied to the solid battery which has a solid electrolyte layer was illustrated in the past description regarding this invention, this invention is not limited to the said form. The battery of the present invention may be a battery having an electrolyte layer using an electrolytic solution.
以下、実施例により本発明をさらに詳しく説明する。ただし本発明は実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples.
＜固体電解質の合成＞
Ｌｉ２Ｓ（日本化学工業社製）を０．４２１ｇと、Ｐ２Ｓ５（シグマ アルドリッチ ジャパン社製）を０．６７９ｇと、ＬｉＩ（シグマ アルドリッチ ジャパン社製）を１．３４ｇ秤量し、メノウ乳鉢で５分間混合した。その後、ヘプタンを４ｇ加え、遊星型ボールミルを用いて４０時間メカニカルミリングすることで固体電解質を得た。
<Synthesis of solid electrolyte>
Weigh 0.421 g of Li 2 S (manufactured by Nippon Chemical Industry Co., Ltd.), 0.679 g of P 2 S 5 (manufactured by Sigma Aldrich Japan), and 1.34 g of LiI (manufactured by Sigma Aldrich Japan), and agate mortar. For 5 minutes. Thereafter, 4 g of heptane was added, and a solid electrolyte was obtained by mechanical milling for 40 hours using a planetary ball mill.
＜正極合剤の作製＞
昭和電工社製のＶＧＣＦ（登録商標）を０．５１ｍｇと、上記固体電解質を５．０３ｍｇ秤量し、これらを乳鉢で１０分間混合した後、正極活物質としてＬｉＮｉ１／３Ｃｏ１／３Ｍｎ１／３Ｏ２（日亜化学社製）を１２．０３ｍｇ加えてさらに混合したものを正極合剤とした。
<Preparation of positive electrode mixture>
0.51 mg of VGCF (registered trademark) manufactured by Showa Denko KK and 5.03 mg of the above solid electrolyte were weighed and mixed in a mortar for 10 minutes, and then LiNi 1/3 Co 1/3 Mn 1 as a positive electrode active material A mixture of 12.03 mg of / 3 O 2 (manufactured by Nichia Corporation) and further mixed was used as the positive electrode mixture.
＜負極合剤の作製＞
負極活物質としてグラファイト（三菱化学社製）を９．０６ｍｇと、上記固体電解質を８．２４ｍｇ秤量し、これらを混合したものを負極合剤とした。
<Preparation of negative electrode mixture>
As a negative electrode active material, 9.06 mg of graphite (manufactured by Mitsubishi Chemical Corporation) and 8.24 mg of the solid electrolyte were weighed, and a mixture thereof was used as a negative electrode mixture.
＜試験用電池の作製＞
図３は、実施例で作製した試験用電池を説明する断面図である。図３を参照しつつ試験用電池の作製方法について説明する。まず、上記固体電解質を１８ｍｇ秤量して、マコール（登録商標）製の絶縁リング１２の中空部に投入し、一対のピストン２０、２０で押圧して固体電解質層１１ｃを作製した。このとき固体電解質に加えた圧力は１ｔｏｎ／ｃｍ２であった。また、絶縁リング１２の中空部の軸心（ピストン２０、２０でプレスされる方向）に垂直な方向の断面積は１ｃｍ２であった。次に、固体電解質層１１ｃの一方の面側に上記正極合剤を１７．５７ｍｇのせてピストン２０、２０で押圧し、固体電解質層１１ｃの一方の面側に正極層１１ｂを形成した。このときピストン２０、２０によって加えた圧力は１ｔｏｎ／ｃｍ２であった。次に、固体電解質層１１ｃの他方の面側に上記負極合剤を１７．３ｍｇのせてピストン２０、２０で押圧し、固体電解質層１１ｃの他方の面側に負極層１１ｄを形成した。このときピストン２０、２０によって加えた圧力は４ｔｏｎ／ｃｍ２であった。このようにして形成された、正極層１１ｂ、固体電解質層１１ｃ、及び負極層１１ｄを有する積層体の正極層１１ｂに正極集電体（不図示）を接続し、負極層１１ｄに負極集電体（不図示）を接続して、試験用電池を作製した。
<Production of test battery>
FIG. 3 is a cross-sectional view illustrating the test battery produced in the example. A method for producing a test battery will be described with reference to FIG. First, 18 mg of the solid electrolyte was weighed and put into a hollow portion of an insulating ring 12 made of Macor (registered trademark), and pressed by a pair of pistons 20 and 20 to produce a solid electrolyte layer 11c. At this time, the pressure applied to the solid electrolyte was 1 ton / cm 2 . Further, the cross-sectional area in the direction perpendicular to the axial center of the hollow portion of the insulating ring 12 (the direction pressed by the pistons 20 and 20) was 1 cm 2 . Next, 17.57 mg of the positive electrode mixture was placed on one surface side of the solid electrolyte layer 11c and pressed by the pistons 20 and 20, thereby forming the positive electrode layer 11b on one surface side of the solid electrolyte layer 11c. At this time, the pressure applied by the pistons 20 and 20 was 1 ton / cm 2 . Next, 17.3 mg of the negative electrode mixture was placed on the other surface side of the solid electrolyte layer 11c and pressed by the pistons 20 and 20, thereby forming the negative electrode layer 11d on the other surface side of the solid electrolyte layer 11c. At this time, the pressure applied by the pistons 20 and 20 was 4 ton / cm 2 . A positive electrode current collector (not shown) is connected to the positive electrode layer 11b of the laminate including the positive electrode layer 11b, the solid electrolyte layer 11c, and the negative electrode layer 11d, and the negative electrode current collector is connected to the negative electrode layer 11d. (Not shown) was connected to produce a test battery.
＜評価＞
上記のようにして作製した試験用電池を以下に説明する方法で評価した。
（実験例１）
上記のようにして作製した試験用電池について、０．３ｍＡで４．２Ｖまで定電流充電した後、２．５Ｖまで０．３ｍＡで放電を行った。その後、４．１Ｖまで充電して電圧を調整し、Ｓｏｌａｒｔｒｏｎ社製の電気化学測定システムでインピーダンス解析を行い、反応抵抗を求めた。その後、電池を４．５５Ｖまで充電し、６０℃の恒温槽で３０日間放置した。その後、電池を２５℃に戻し、上記と同様にして反応抵抗を測定した。また、試験用電池を作製した直後（初期）及び放置後の絶縁リング１２の色を、１２５色のＲＧＢカラーチャートを用いて評価した。その結果を表１に示した。また、放置後の絶縁リング１２についてＳＥＭ−ＥＤＸを用いて元素分析を行った。その結果を図４に示した。
<Evaluation>
The test battery produced as described above was evaluated by the method described below.
(Experimental example 1)
About the test battery produced as mentioned above, after carrying out constant current charge to 4.2V at 0.3 mA, it discharged at 0.3 mA to 2.5V. Thereafter, the voltage was adjusted by charging to 4.1 V, and impedance analysis was performed with an electrochemical measurement system manufactured by Solartron to determine the reaction resistance. Thereafter, the battery was charged to 4.55 V and left in a constant temperature bath at 60 ° C. for 30 days. Thereafter, the battery was returned to 25 ° C., and the reaction resistance was measured in the same manner as described above. In addition, the color of the insulating ring 12 immediately after (initial) and after leaving the test battery was evaluated using an RGB color chart of 125 colors. The results are shown in Table 1. In addition, element analysis was performed on the insulating ring 12 after being left using SEM-EDX. The results are shown in FIG.
（実験例２）
放置前の充電電圧を４．１Ｖとした以外は実験例１と同様にして反応抵抗を測定し、１２５色のＲＧＢカラーチャートを用いて評価した。その結果を表１に示した。
(Experimental example 2)
The reaction resistance was measured in the same manner as in Experimental Example 1 except that the charging voltage before standing was 4.1 V, and evaluated using an RGB color chart of 125 colors. The results are shown in Table 1.
（実験例３）
放置前の充電電圧を３．７２Ｖとした以外は実験例１と同様にして反応抵抗を測定し、１２５色のＲＧＢカラーチャートを用いて評価した。その結果を表１に示した。
(Experimental example 3)
The reaction resistance was measured in the same manner as in Experimental Example 1 except that the charging voltage before standing was 3.72 V, and evaluated using an RGB color chart of 125 colors. The results are shown in Table 1.
図３からは、電池が過充電となった実験例１では硫黄及びヨウ素が絶縁リング１２に付着していたことがわかる。また、表１に示した結果より、過充電となった場合は絶縁リング１２が変色したことがわかる。これらのことから、本発明の電池によれば、過充電となったことを白色部材（絶縁リング）の色の変化によって簡便に検知できることがわかる。 From FIG. 3, it can be seen that in Experimental Example 1 in which the battery was overcharged, sulfur and iodine were attached to the insulating ring 12. Further, from the results shown in Table 1, it can be seen that the insulation ring 12 is discolored when overcharge occurs. From these facts, it can be seen that according to the battery of the present invention, overcharge can be easily detected by a change in the color of the white member (insulating ring).
１ 素極体
１ａ 正極集電体
１ｂ、１１ｂ 正極層
１ｃ、１１ｃ 固体電解質層
１ｄ、１１ｄ 負極層
１ｅ 負極集電体
２、１２ 白色部材
３ 容器
１０ 電池
２０ ピストン
DESCRIPTION OF SYMBOLS 1 Elementary electrode body 1a Positive electrode collector 1b, 11b Positive electrode layer 1c, 11c Solid electrolyte layer 1d, 11d Negative electrode layer 1e Negative electrode collector 2, 12 White member 3 Container 10 Battery 20 Piston
Claims (2)
前記素電池が前記検知手段とともに容器に収容されている、又は、前記素電池が容器に収容されるとともに該容器の内面に前記検知手段が備えられている、
二次電池。 A unit cell comprising a solid electrolyte containing iodine, sulfur or bromine, and a detection means capable of visually detecting that the iodine, sulfur or bromine is emitted from the solid electrolyte ,
The unit cell is accommodated in a container together with the detection means, or the unit cell is accommodated in a container and the detection means is provided on the inner surface of the container.
Secondary battery.
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