JPH0522348B2 - - Google Patents
Info
- Publication number
- JPH0522348B2 JPH0522348B2 JP57200671A JP20067182A JPH0522348B2 JP H0522348 B2 JPH0522348 B2 JP H0522348B2 JP 57200671 A JP57200671 A JP 57200671A JP 20067182 A JP20067182 A JP 20067182A JP H0522348 B2 JPH0522348 B2 JP H0522348B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- battery
- negative electrode
- solid
- discharge
- 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.)
- Expired - Lifetime
Links
- 239000007784 solid electrolyte Substances 0.000 claims description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910000838 Al alloy Inorganic materials 0.000 claims description 6
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims 2
- 229910052744 lithium Inorganic materials 0.000 description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 17
- 238000007599 discharging Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005411 Van der Waals force Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明は金属リチウムを主体とする負極を有す
る固体状の二次電池に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a solid secondary battery having a negative electrode mainly composed of metallic lithium.
従来例の構成とその問題点
固体電解質を用いることによつて特徴づけられ
る固体状の電池で、現在もつぱら提唱され、また
実際に実用化されている電池は、ほとんどが一次
電池である。固体電解質材料としては、リチウム
イオン導電性の物質あるいは銀イオン導電性の物
質を用いることが提唱されている。この中でもリ
チウムイオン導電性の固体電解質は、イオン導電
率が銀イオン導電性の固体電解質に較べると数桁
小さく電池とした際大電流が取り出せない欠点は
有しているものの、分解電圧は銀イオン導電性固
体電解質の0.6V程度に較べると1.8〜3.4Vと数倍
高く、電池電圧の高い、すなわち高エネルギー密
度の電池が得られることから、近年、電子機器の
低消費電流化が進むにつれて、高エネルギー密度
である特徴が増々注目され、もつぱらリチウムイ
オン導電性固体電解質が選ばれ、これを用いたリ
チウム固体電池が一次電池として実用化されるに
至つている。Structures of conventional examples and their problems Most of the solid-state batteries that are characterized by the use of solid electrolytes and that are currently being proposed and actually put into practical use are primary batteries. It has been proposed to use a lithium ion conductive substance or a silver ion conductive substance as the solid electrolyte material. Among these, the lithium ion conductive solid electrolyte has an ionic conductivity several orders of magnitude smaller than that of the silver ion conductive solid electrolyte, and although it has the disadvantage of not being able to draw a large current when used as a battery, the decomposition voltage of the silver ion Compared to the 0.6V of conductive solid electrolytes, it is several times higher at 1.8 to 3.4V, and can provide batteries with high battery voltage, that is, high energy density.In recent years, as electronic devices have become lower in current consumption, Lithium ion conductive solid electrolytes have attracted increasing attention due to their high energy density, and lithium solid-state batteries using them have been put into practical use as primary batteries.
一方、このようなリチウム固体電池の電子機器
への使われ方は、半導体メモリ素子の発達により
主電源が切れた場合においてもメモリ保持を損な
わないように、補助電源として、いわゆるメモリ
バツクアツプ用の電源として使われ方が主流とな
つてきている。補助電源として用いられるのに好
ましい電池特性としては、放電容量，放電電流が
いかに小さくても、小型で、すなわち半導体メモ
リ素子と同一プリント基板上に組み込め、さらに
は、半導体メモリ素子と一緒に樹脂モールドパツ
ケージされるくらいの小型さで、かつ、容量が尽
きた場合においても電池交換が不必要であるこ
と、すなわち、充電による再生が可能であること
が挙げられる。 On the other hand, due to the development of semiconductor memory elements, lithium solid-state batteries are being used in electronic devices as auxiliary power supplies, so-called memory backup batteries, so that memory retention will not be impaired even if the main power supply is cut off. Its use as a power source is becoming mainstream. Preferred battery characteristics for use as an auxiliary power source are that no matter how small the discharge capacity and discharge current are, it is small, that it can be incorporated on the same printed circuit board as the semiconductor memory element, and that it can be molded in resin together with the semiconductor memory element. It is small enough to be packaged, and even if the battery runs out, there is no need to replace the battery, that is, it can be regenerated by charging.
このような必要性に対して現在は、有機電解液
を用いるリチウム二次電池が提唱されているが、
液体を用いているため、電池構成物を液密に保持
しておく容器が必要であり、このため先に述べた
小型化をはかるのは至難であつた。 To meet this need, lithium secondary batteries using organic electrolytes are currently being proposed.
Since a liquid is used, a container is required to hold the battery components in a liquid-tight manner, which makes it extremely difficult to achieve the above-mentioned miniaturization.
そこで、このような小型化に対して、有機電解
液を用いる電池に対して決定的な優位さを持つ固
体電解質を用いた固体状二次電池の実用化が期待
される。すなわち固体状二次電池は、後に本発明
の実施様態で詳しく説明するが、電池構成物を特
に別途定められた形状の容器に納める必要はなく
樹脂等により発電要素を被覆するだけで良く、小
型化が容易にはかられるし、さらには、電池の構
成にあたつては、半導体プロセスで通常用いられ
ている真空蒸着法，スパツタリング法などの薄膜
化技術を用いての小型化も容易に可能であるとい
う優位さを持つている。 Therefore, for such miniaturization, it is expected that solid secondary batteries using solid electrolytes, which have a decisive advantage over batteries using organic electrolytes, will be put to practical use. In other words, solid-state secondary batteries, which will be explained in detail later in the embodiments of the present invention, do not require the battery components to be housed in a container with a specially determined shape; it is sufficient to simply cover the power generating element with resin, etc., and the battery is small and compact. In addition, the battery structure can be easily miniaturized using thin film techniques such as vacuum evaporation and sputtering, which are commonly used in semiconductor processes. It has the advantage of being
しかし、以上のような決定的とも言われる優位
さにもかかわらず、固体二次電池の実用化がいま
だなされていないのは、ひとつには電池の充放電
に際してリチウムイオンを可逆的に出し入れが可
能な適当な正極活物質がいまだ見い出されていな
いこと、またひとつには、充電に際してリチウム
負極側に、金属リチウムが霧状あるいは樹枝状に
析出するため、充放電がくり返し行われると、つ
いには正極と負極とが金属リチウムでつながれ内
部短絡を生じるという問題があるためであつた。 However, despite the so-called decisive advantages mentioned above, solid-state secondary batteries have not yet been put into practical use. One reason is that lithium ions can be reversibly put in and taken out when charging and discharging the battery. Another reason is that a suitable cathode active material has not yet been found. Another reason is that during charging, metallic lithium is deposited in the form of mist or dendrites on the lithium negative electrode side, so when charging and discharging are repeated, the positive electrode will eventually disappear. This was due to the problem that the negative electrode and the negative electrode were connected by metallic lithium, causing an internal short circuit.
発明の目的
本発明は、充・放電くり返し特性の優れ固体状
のリチウム二次電池を提供することを目的とす
る。OBJECTS OF THE INVENTION An object of the present invention is to provide a solid-state lithium secondary battery with excellent repeated charge/discharge characteristics.
発明の構成
本発明の電池は、正極活物質として二酸化チタ
ンを用い、金属リチウムを主体とする可逆性のリ
チウム負極、好適にはリチウム−アルミニウム合
金を主体とする負極、リチウムイオン導電性固体
電解質より構成され、電池構成要素がすべて固体
の二次電池である。Structure of the Invention The battery of the present invention uses titanium dioxide as a positive electrode active material, a reversible lithium negative electrode mainly composed of metallic lithium, preferably a negative electrode mainly composed of a lithium-aluminum alloy, and a lithium ion conductive solid electrolyte. It is a secondary battery with all battery components being solid.
本発明に正極活物質として用いる二酸化チタン
は酸化の程度によりその結晶構造は層状構造を有
し、互いにフアンデルワールス力で結合した反復
層から成り立つている。そして個々の層は、酸素
原子のシート間にサンドイツチされたチタン原子
を含む少なくとも１つのシートから成つている。
反復層間でリチウムイオンの出し入れが容易に起
こるため、すなわち、各層を結合するフアンデル
ワールス力の弱さのため急速なリチウムイオンの
拡散を容易にするので、電池の充・放電が可能と
なつている。また、負極は、可逆性のリチウム負
極，好適にはリチウム−アルミニウム合金負極で
あるので、充電反応による霧状あるいは樹枝状の
リチウム負極の成長が生じ難く充・放電をくり返
し行つても内部短絡が生じることはない。 Titanium dioxide used as a positive electrode active material in the present invention has a layered crystal structure depending on the degree of oxidation, and is composed of repeated layers bonded to each other by van der Waals forces. Each layer then consists of at least one sheet containing sandwiched titanium atoms between sheets of oxygen atoms.
Because lithium ions can easily move in and out between repeated layers, the weak van der Waals force that binds each layer facilitates rapid lithium ion diffusion, making it possible to charge and discharge the battery. There is. In addition, since the negative electrode is a reversible lithium negative electrode, preferably a lithium-aluminum alloy negative electrode, the growth of a mist-like or dendritic lithium negative electrode due to the charging reaction is difficult, and internal short circuits do not occur even after repeated charging and discharging. It never happens.
また、リチウムイオン導電性固体電解質として
は、nLiI・C5H5Ｎ・C4H9Ｉ，Li3Ｎ，mLiI・
nLi2Ｓ・P2O5など各種のものを用いることがで
きる。 In addition, as lithium ion conductive solid electrolytes, nLiI・C 5 H 5 N・C 4 H 9 I, Li 3 N, mLiI・
Various materials such as nLi 2 S.P 2 O 5 can be used.
実施例の説明 実施例 １ 第１図は固体電解質二次電池の構成例を示す。Description of examples Example 1 FIG. 1 shows an example of the structure of a solid electrolyte secondary battery.
１は正極合剤で、活物質の二酸化チタン
（TiO2）の90〜70重量部とリチウムイオン導電性
固体電解質の10〜30重量部との混合物からなり、
TiO2が約３ミリモルとなるように前記の混合物
を秤量し、300MPaの圧力で直径18mm、厚さ0.4mm
程度の円板状に成形したものである。なな、正極
合剤中に特に導電材の混合は必要としないが、大
電流放電用途の場合、カーボンなどの導電材を加
えてもよい。 1 is a positive electrode mixture consisting of a mixture of 90 to 70 parts by weight of titanium dioxide (TiO 2 ) as an active material and 10 to 30 parts by weight of a lithium ion conductive solid electrolyte;
The above mixture was weighed so that TiO 2 was about 3 mmol, and heated to a pressure of 300 MPa to a diameter of 18 mm and a thickness of 0.4 mm.
It is molded into a disk shape of about 100 yen. Although it is not necessary to specifically mix a conductive material in the positive electrode mixture, a conductive material such as carbon may be added in the case of a large current discharge application.
２はリチウムイオン導電性固体電解質層であ
る。この例では電解質として、nLiI・C5H5Ｎ・
C4H9Ｉで表されるものを用いた。ここにｎ値と
しては４〜６が好適に選ばれる。電解質層２は、
上記の電解質粉末を300MPaの圧力で直径18mm，
厚さ0.4mm程度の円板状に成形したものである。 2 is a lithium ion conductive solid electrolyte layer. In this example, the electrolyte is nLiI・C 5 H 5 N・
A compound represented by C 4 H 9 I was used. Here, a value of 4 to 6 is suitably selected as the n value. The electrolyte layer 2 is
The above electrolyte powder was heated to a diameter of 18 mm at a pressure of 300 MPa.
It is molded into a disc shape with a thickness of about 0.4 mm.
３は可逆性リチウム負極で、LixAlで表される
リチウム−アルミニウム合金板よりなる直径18
mm，厚さ0.5mmの円板状のものである。ｘの値と
しては0.08〜0.9まで目的に応じて変えられるが、
本実施例ではｘ＝0.8のものを用いている。４は
正極集電体であり、Cr含量が30重量％以上のFe
−Crフエライト系ステンレス鋼よりなる厚さ0.1
mmの円板である。もちろん、正極集電体材料とし
て、炭素，Au，Pd，Pt等を用いても良い。５は
負極集電体である。隣接するセルの負極集電体５
と正極集電体４は、グラフアイト導電ペイントに
より電気的に結合されて３セルが直列に接続され
ている。６，７は電極端子リードである。８は樹
脂被膜であり、エポキシ系の熱硬化性樹脂を被覆
して得たものである。もちろん光硬化性の樹脂等
を用いても良い。 3 is a reversible lithium negative electrode, made of a lithium-aluminum alloy plate represented by Li x Al, with a diameter of 18
It is disc-shaped with a thickness of 0.5 mm. The value of x can be changed from 0.08 to 0.9 depending on the purpose,
In this embodiment, x=0.8 is used. 4 is a positive electrode current collector, which is Fe with a Cr content of 30% by weight or more.
-Made of Cr ferrite stainless steel, thickness 0.1
It is a disk of mm. Of course, carbon, Au, Pd, Pt, etc. may be used as the positive electrode current collector material. 5 is a negative electrode current collector. Negative electrode current collector 5 of adjacent cells
and the positive electrode current collector 4 are electrically coupled by graphite conductive paint, and three cells are connected in series. 6 and 7 are electrode terminal leads. 8 is a resin coating, which is obtained by coating with an epoxy thermosetting resin. Of course, a photocurable resin or the like may also be used.
第２図は、本実施例の電池を20℃で、電流
30μAで放電した際の放電容量と端子電圧の関係
を示している。第３図は、30μAで3Vまで放電
し、同じ電流で6Vまで充電する充放電のくり返
しに伴う放電容量の変化を示したものである。第
３図中Ａは、負極をリチウム−アルミニウム合金
としたもの、Ｂはリチウム金属を用いた同様の構
成を有する電池についての充・放電特性を示して
いる。 Figure 2 shows the current of the battery of this example at 20°C.
It shows the relationship between discharge capacity and terminal voltage when discharging at 30μA. Figure 3 shows the change in discharge capacity due to repeated charging and discharging, in which the battery is discharged to 3V at 30μA and charged to 6V with the same current. In FIG. 3, A shows the charge/discharge characteristics of a battery using a lithium-aluminum alloy as the negative electrode, and B shows the charge/discharge characteristics of a battery having a similar structure using lithium metal.
第２図から明らかなように本発明に従う固体二
次電池の放電時の端子電圧はきわめて平坦で、従
来の固体一次電池の放電電圧に較べても遜色は全
くない。第３図から明らかなように、充放電特性
は、負極にリチウム−アルミニウム合金を用いた
ものは負極をリチウムとした電池に較べ、放電容
量が大きい。このことは、充電時におけるリチウ
ムの霧状あるいは樹枝状の析出による内部短絡に
よる自己放電が発生し難いことを示している。 As is clear from FIG. 2, the terminal voltage during discharge of the solid state secondary battery according to the present invention is extremely flat, and is not inferior at all to the discharge voltage of a conventional solid state primary battery. As is clear from FIG. 3, regarding the charge and discharge characteristics, the battery using a lithium-aluminum alloy for the negative electrode has a larger discharge capacity than the battery using lithium for the negative electrode. This indicates that self-discharge due to internal short circuit due to mist or dendrite precipitation of lithium during charging is unlikely to occur.
実施例 ２
実施例１のリチウムイオン導電性固体電解質層
２の代わりに可逆性リチウム負極の表面に化学式
C5H5Ｎ・C4H9・Ia（ａ＝５〜７）で表されるポリ
沃化ブチルピリジニウムを塗布し、乾燥雰囲気中
において60℃で24時間保持して形成したLiIを主
体とするリチウムイオン導電性固体電解質層を用
いた電池を構成した。Example 2 In place of the lithium ion conductive solid electrolyte layer 2 of Example 1, a chemical formula was formed on the surface of the reversible lithium negative electrode.
Mainly LiI formed by coating polybutylpyridinium iodide represented by C 5 H 5 N・C 4 H 9・I a (a = 5 to 7) and holding it at 60°C for 24 hours in a dry atmosphere. A battery using a lithium ion conductive solid electrolyte layer was constructed.
第４図はこの電池Ｃの放電電流密度と端子電圧
の関係を示している。Ａは、実施例１に示した電
池の特性を示している。ポリ沃化ブチルピリジニ
ウムを負極に塗布して電解質を構成した電池Ｃ
は、そうでない電池Ａに較べ電池内部抵抗が小さ
くなり、より大きな電流を取り出すことができ
る。この理由については明らかでないが、負極表
面上で負極のリチウムと沃素との化学反応で固体
電解質層を形成することによつて、単に固体電解
質層と負極とが圧力により接合されている実施例
１の電池Ａに較べ負極と固体電解質層との接合が
良好に得られるためであると本発明者らは考えて
いる。 FIG. 4 shows the relationship between the discharge current density and the terminal voltage of this battery C. A shows the characteristics of the battery shown in Example 1. Battery C in which the electrolyte was formed by coating the negative electrode with polybutylpyridinium iodide
Compared to battery A, which does not have this type of battery, the internal resistance of the battery is smaller, and a larger current can be extracted. Although the reason for this is not clear, Example 1 in which the solid electrolyte layer and the negative electrode are simply joined by pressure by forming a solid electrolyte layer on the surface of the negative electrode through a chemical reaction between lithium and iodine of the negative electrode. The present inventors believe that this is because the bonding between the negative electrode and the solid electrolyte layer is better than that in Battery A.
なお、ポリ沃化１−ブチルピリジニウムの他に
アルキル基の異なる他のポリ沃化１−アルキルピ
リジニウムを用いても同様な効果が得られること
は言うまでもない。 It goes without saying that similar effects can be obtained by using other 1-alkylpyridinium polyiodides having different alkyl groups in addition to 1-butylpyridinium polyiodide.
発明の効果
以上のように、本発明によれば、充放電のくり
返し特性に優れ、メモリーバツクアツプ用電源な
どとして好適な固体状二次電池を得ることができ
る。Effects of the Invention As described above, according to the present invention, it is possible to obtain a solid-state secondary battery that has excellent repeated charging and discharging characteristics and is suitable as a power source for memory backup.
第１図は本発明による電池の構成例を示す縦断
面図、第２図は放電時の端子電圧と放電容量の関
係を示す図、第３図は充放電回数と放電容量の関
係を示す図、第４図は放電電流密度と端子電圧の
関係を示す。
１……正極、２……固体電解質、３……負極。
FIG. 1 is a longitudinal cross-sectional view showing an example of the configuration of a battery according to the present invention, FIG. 2 is a diagram showing the relationship between the terminal voltage during discharge and the discharge capacity, and FIG. 3 is a diagram showing the relationship between the number of charging and discharging times and the discharge capacity. , FIG. 4 shows the relationship between discharge current density and terminal voltage. 1...Positive electrode, 2...Solid electrolyte, 3...Negative electrode.
Claims (1)
と、二酸化チタンを主体とする正極と、負極とポ
リ沃化１−アルキルピリジニウムとの接触により
形成される沃化リチウムを主体とするリチウムイ
オン導電性固体電解質より構成される固体状二次
電池。1 Consists of a negative electrode made of a lithium-aluminum alloy, a positive electrode mainly made of titanium dioxide, and a lithium ion conductive solid electrolyte mainly made of lithium iodide formed by contacting the negative electrode with 1-alkylpyridinium polyiodide. solid state secondary battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57200671A JPS5990360A (en) | 1982-11-15 | 1982-11-15 | Solid secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57200671A JPS5990360A (en) | 1982-11-15 | 1982-11-15 | Solid secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5990360A JPS5990360A (en) | 1984-05-24 |
| JPH0522348B2 true JPH0522348B2 (en) | 1993-03-29 |
Family
ID=16428294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57200671A Granted JPS5990360A (en) | 1982-11-15 | 1982-11-15 | Solid secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5990360A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5540742A (en) * | 1989-05-01 | 1996-07-30 | Brother Kogyo Kabushiki Kaisha | Method of fabricating thin film cells and printed circuit boards containing thin film cells using a screen printing process |
| US5217828A (en) * | 1989-05-01 | 1993-06-08 | Brother Kogyo Kabushiki Kaisha | Flexible thin film cell including packaging material |
| JP2014229502A (en) * | 2013-05-23 | 2014-12-08 | パナソニック株式会社 | Manufacturing method of all-solid state lamination battery |
| JP6466065B2 (en) * | 2014-02-03 | 2019-02-06 | 古河機械金属株式会社 | Positive electrode material, positive electrode, and lithium ion battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5661771A (en) * | 1979-10-23 | 1981-05-27 | Nec Corp | Battery |
| JPS5688265A (en) * | 1979-12-19 | 1981-07-17 | Citizen Watch Co Ltd | Solid-electrolyte battery |
-
1982
- 1982-11-15 JP JP57200671A patent/JPS5990360A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5661771A (en) * | 1979-10-23 | 1981-05-27 | Nec Corp | Battery |
| JPS5688265A (en) * | 1979-12-19 | 1981-07-17 | Citizen Watch Co Ltd | Solid-electrolyte battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5990360A (en) | 1984-05-24 |
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