JPH0370343B2 - - Google Patents
Info
- Publication number
- JPH0370343B2 JPH0370343B2 JP57200669A JP20066982A JPH0370343B2 JP H0370343 B2 JPH0370343 B2 JP H0370343B2 JP 57200669 A JP57200669 A JP 57200669A JP 20066982 A JP20066982 A JP 20066982A JP H0370343 B2 JPH0370343 B2 JP H0370343B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- battery
- negative electrode
- solid
- ion conductive
- 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
- 229910052744 lithium Inorganic materials 0.000 claims description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 21
- 239000007784 solid electrolyte Substances 0.000 claims description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims description 14
- 239000007787 solid Substances 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
- 230000002441 reversible effect Effects 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 5
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 4
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims 2
- 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
- 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
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 description 2
- 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
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 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
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering 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
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical group [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 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
- 238000010248 power generation Methods 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
- 238000007736 thin film deposition technique Methods 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 lower 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 is lower than that of the silver ion conductive solid electrolyte. Compared to the 0.6V of ion-conductive solid electrolytes, it is several times higher at 1.8 to 3.4V, making it possible to obtain batteries with high battery voltage, that is, high energy density. Lithium ion conductive solid electrolytes have been chosen, and lithium solid-state batteries using them have been put into practical use as primary batteries, as their high energy density has attracted increasing attention.
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の使われ方が主
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諸に樹脂モール
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 now being used in electronic devices as auxiliary power supplies, so-called memory backup batteries, so that memory retention will not be lost even if the main power supply is cut off. Its use as a power source has become 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 is, it can be incorporated on the same printed circuit board as the semiconductor memory element, and
Furthermore, it is small enough to be packaged in a resin mold together with a semiconductor memory element, and there is no need to replace the battery even when the capacity is exhausted, that is, it can be regenerated by charging. Can be mentioned.
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
実施態様で詳しく説明するが、電池構成物を時に
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
型化が容易にはかれるし、さらには、電池の構成
に当たつては、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を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 battery components to be housed in a container with a separately determined shape.
All that is needed is to cover the power generation element with a resin or the like, which makes it easy to downsize the battery.Furthermore, when constructing the battery, thin film deposition methods such as vacuum evaporation and sputtering, which are commonly used in semiconductor processes, can be used. It has the advantage of being easily miniaturized using technology.
しかし、以上のような決定的とも言われる優位
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
な適当な正極活性物がいまだ見い出されていない
こと、またひとつは、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 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.Also, 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 and negative electrodes eventually become separated. This was due to the problem of internal short circuits caused by the metal lithium connecting the two.
発明の目的
本発明は、充・放電くり返し特性の優れた固体
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、正極活物質として五酸化ニオ
ブ（Nd2O5）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 niobium pentoxide (Nd 2 O 5 ) 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, It is a secondary battery composed of a lithium ion conductive solid electrolyte, and all battery components are solid.
本発明に正極活物質として用いる五酸化ニオブ
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ニオブ原
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に生じ難く、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。 Niobium pentoxide 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 niobium 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 or dendritic lithium negative electrode due to the charging reaction is less likely to occur, and even after repeated charging and discharging, the internal No short circuits will occur.
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、活物質の五酸化ニオブ
（Nb2O5）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、Nb2O5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。なお、
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, which consists of a mixture of 90 to 70 parts by weight of niobium pentoxide (Nb 2 O 5 ) as an active material and 10 to 30 parts by weight of a lithium ion conductive solid electrolyte, and Nb 2 O 5 is approximately Weigh the above mixture so that it is 3 mmol, and apply it under a pressure of 300 MPa to a diameter of 18 mm and a thickness of
It is molded into a disc shape of approximately 0.4 mm. In addition,
Although it is not necessary to particularly mix a conductive material into the positive electrode mixture, a conductive material such as carbon may be added in the case of large current discharge applications.
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・C 4 H 9 I was used. Here, a value of 4 to 6 is suitably selected as the n value. Electrolyte layer 2 is made by applying the above electrolyte powder to a diameter of 300MPa.
It is molded into a disc shape of approximately 18 mm and 0.4 mm thick.
３は可逆性リチウム負極で、LixAlで表される
リチウム−アルミニウム合金よりなる直径18mm、
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0.1mm
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等を用いてもよい。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 represented by Li x Al, with a diameter of 18 mm.
It is disc-shaped with a thickness of 0.5 mm. Although 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 0.1mm
It is a disk. 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 cell
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、本実施例の電池と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 battery of this example and the current 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。また、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;
There is no inferiority at all compared to the discharge voltage of conventional solid-state primary batteries. Furthermore, as is clear from FIG. 3, regarding 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・C4H9Ia（ａ＝５〜７）で表されるポ
リ沃化１−ブチルピリジニウムを塗布し、乾燥雰
囲気において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
を用いて電池を構成した。Example 2 Instead of the lithium ion conductive solid electrolyte layer 2 of Example 1, a layer having the chemical formula C 5 H 5 N・C 4 H 9 I a (a=5 to 7) was formed on the surface of the reversible lithium negative electrode. LiI was formed by applying 1-butylpyridinium polyiodide and holding it at 60℃ for 24 hours in a dry atmosphere.
A battery was constructed using a lithium ion conductive solid electrolyte layer mainly composed of .
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層を形成した電池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考えられる。 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 an electrolyte layer 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. This is thought to be because the bond between the negative electrode and the solid electrolyte layer is better than that of the battery.
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, in addition to the 1-butylpyridinium polyiodide, similar effects can be obtained by using other 1-alkylpyridinium polyiodides having different alkyl groups.
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)
極と、五酸化ニオブを主体とする正極、及びリチ
ウムイオン導電性固体電解質より構成した固体状
二次電池。 ２ 可逆性リチウム負極が、リチウム−アルミニ
ウム合金である特許請求の範囲第１項記載の固体
状二次電池。 ３ 前記電解質層が、リチウム負極とポリ沃化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
性固体電解質層である特許請求の範囲第１項記載
の固体状二次電池。[Scope of Claims] 1. A solid secondary battery comprising a reversible lithium negative electrode mainly composed of metallic lithium, a positive electrode mainly composed of niobium pentoxide, and a lithium ion conductive solid electrolyte. 2. The solid state secondary battery according to claim 1, wherein the reversible lithium negative electrode is a lithium-aluminum alloy. 3 The electrolyte layer includes a lithium negative electrode and polyiodide 1
- The solid state secondary battery according to claim 1, which is a lithium ion conductive solid electrolyte layer mainly composed of lithium iodide formed by contacting with alkylpyridinium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57200669A JPS5990359A (en) | 1982-11-15 | 1982-11-15 | solid state secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57200669A JPS5990359A (en) | 1982-11-15 | 1982-11-15 | solid state secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5990359A JPS5990359A (en) | 1984-05-24 |
| JPH0370343B2 true JPH0370343B2 (en) | 1991-11-07 |
Family
ID=16428260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57200669A Granted JPS5990359A (en) | 1982-11-15 | 1982-11-15 | solid state secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5990359A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6391496B1 (en) | 1999-03-25 | 2002-05-21 | Sanyo Electric Co., Ltd. | Lithium secondary battery with orthorhombic molybdenum and niobium oxide electrodes |
-
1982
- 1982-11-15 JP JP57200669A patent/JPS5990359A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5990359A (en) | 1984-05-24 |
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