JPH0458150B2 - - Google Patents
Info
- Publication number
- JPH0458150B2 JPH0458150B2 JP59043581A JP4358184A JPH0458150B2 JP H0458150 B2 JPH0458150 B2 JP H0458150B2 JP 59043581 A JP59043581 A JP 59043581A JP 4358184 A JP4358184 A JP 4358184A JP H0458150 B2 JPH0458150 B2 JP H0458150B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- solid electrolyte
- battery
- negative electrode
- thin layer
- 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
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
-
- 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
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
Description
【発明の詳細な説明】
(イ) 産業上の利用分野
本発明はリチウムを負極活性物質とする固体電
解質電池の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (a) Industrial Application Field The present invention relates to a method for manufacturing a solid electrolyte battery using lithium as a negative electrode active material.
(ロ) 従来技術
この種電池は固体状の電解質を用いるため漏液
の心配がなく、且自己放電も小さいという利点を
有するが固体電解質の導電率は液状電解質に比し
て数段低く高率放電特性に問題があつた。(b) Prior art Since this type of battery uses a solid electrolyte, there is no need to worry about liquid leakage, and it has the advantage of having low self-discharge. However, the conductivity of the solid electrolyte is several orders of magnitude lower than that of the liquid electrolyte, making it highly efficient. There was a problem with the discharge characteristics.
現在、一般的に用いられている固体電解質とし
ては例えば特公昭56−9785号公報に開示されてい
るようにヨウ化リチウム−アルミナ系がある。こ
の系の固体電解質は室温で導電率が10-5S／cmと
比較的高い値を有するもののヨウ化リチウムは完
全に安定ではないため分解してヨウ素を遊離し、
導電率の低下や電池缶材料の腐蝕を招くという不
都合がある。この現象は特に高温での保存、放電
において著しい。 As solid electrolytes commonly used at present, there is a lithium iodide-alumina system as disclosed in Japanese Patent Publication No. 56-9785, for example. Although this type of solid electrolyte has a relatively high conductivity of 10 -5 S/cm at room temperature, lithium iodide is not completely stable and decomposes to liberate iodine.
This has the disadvantage of causing a decrease in electrical conductivity and corrosion of the battery can material. This phenomenon is particularly noticeable during storage and discharge at high temperatures.
一方、特開昭55−104078号公報に開示されてい
る窒化リチウムは室温での導電率が10-3S／cmと
高く最近特に注目されている。ところで特開昭55
−104078号公報による固体電解質としての窒化リ
チウムを作成する際して負極リチウムの表面に窒
素ガスを反応させて窒化リチウム層を形成する方
法が開示されている。 On the other hand, lithium nitride disclosed in Japanese Patent Application Laid-Open No. 55-104078 has recently attracted particular attention as it has a high electrical conductivity of 10 -3 S/cm at room temperature. By the way, JP-A-1975
Japanese Patent No. 104078 discloses a method of forming a lithium nitride layer by reacting nitrogen gas on the surface of a lithium negative electrode when producing lithium nitride as a solid electrolyte.
しかしながら、本発明者等の実験による上記作
成法では問題があることがわかつた。 However, it has been found through experiments by the present inventors that there is a problem with the above production method.
即ち、第２図に示す如く負極リチウム１′を真
空下で加熱して表面をミラー状にしたのち窒素ガ
スと反応させるのであるが、真空中に存在する不
純物によつて不純物被膜（例えば酸化物被膜）
３′が表面に形成されている。そのため窒素ガス
（N2）を接触させた場合、被膜３′が存在してい
る部分では窒化リチウムが生成されず活性な部分
のみ局部的に窒化リチウム４′が生成し厚み（垂
直）方向に進行する。それ故、この状態で正極と
組合わせると不純物被膜３′が容易に破壊して正
負極が短絡し電池形態をなさなかつた。つまり負
極リチウムの一部表面のみに窒化リチウム層を形
成することは負極リチウムの表面に不純物被膜が
存在する場合には不可能と云える。 That is, as shown in FIG. 2, the negative electrode lithium 1' is heated under vacuum to make its surface mirror-like and then reacted with nitrogen gas. coating)
3' is formed on the surface. Therefore, when nitrogen gas (N 2 ) is brought into contact, lithium nitride 4' is not generated in the area where the coating 3' exists, but lithium nitride 4' is generated locally only in the active area and progresses in the thickness (vertical) direction. do. Therefore, when combined with a positive electrode in this state, the impurity coating 3' would be easily destroyed, the positive and negative electrodes would be short-circuited, and the battery would not form. In other words, it can be said that it is impossible to form a lithium nitride layer only on a part of the surface of the negative electrode lithium when an impurity film exists on the surface of the negative electrode lithium.
又、窒化リチウム固体電解質を作成する方法と
して窒化リチウムの粉末を加圧成型するという方
法があるが、この場合には成型時にひび割れを生
じるため薄層の固体電解質を作成するのは困難で
ある。 In addition, there is a method to create a lithium nitride solid electrolyte by press-molding lithium nitride powder, but in this case, it is difficult to create a thin layer of solid electrolyte because cracks occur during molding.
(ハ) 発明の目的
本発明の目的とするところは、上記従来電池の
問題点を解消することにあり、薄層で且均一な窒
化リチウム固体電解質を作成すると共に固体電解
質と負極リチウムとの接触抵抗を減じて、高率放
電可能な薄型の固体電解質電池の製造方法を提供
するものである。(c) Purpose of the Invention The purpose of the present invention is to solve the above-mentioned problems of conventional batteries, and to create a thin and uniform lithium nitride solid electrolyte, and to improve the contact between the solid electrolyte and the negative electrode lithium. The present invention provides a method for manufacturing a thin solid electrolyte battery capable of high rate discharge with reduced resistance.
(ニ) 発明の構成
本発明の固体電解質電池の製造方法は、負極リ
チウムの一側面に、薄層リチウムを圧着する第１
工程と、前記薄層リチウムに窒素ガスを反応させ
て、窒化リチウム層を形成する第２工程と、前記
窒化リチウム層に、正極を圧着する第３工程とを
有することを特徴とするものである。(d) Structure of the Invention The method for manufacturing a solid electrolyte battery of the present invention comprises a first step of press-bonding a thin layer of lithium onto one side of the negative electrode lithium.
A second step of reacting the thin layer of lithium with nitrogen gas to form a lithium nitride layer, and a third step of press-bonding a positive electrode to the lithium nitride layer. .
(ホ) 実施例 以下本発明の実施例について詳述する。(e) Examples Examples of the present invention will be described in detail below.
負極はリチウムを1.0mmの厚みに圧延した圧延
板を10.0mmφに打抜いたものを使用した。 The negative electrode used was a rolled plate made of lithium rolled to a thickness of 1.0 mm and punched out to a diameter of 10.0 mm.
固体電解質の作成に際しては、第１図に示す如
く前記負極リチウム１の一側面に、0.1mm厚みの
薄層リチウム２を圧着し、ついで負極リチウム１
の他側面をマスキングした状態で密閉容器（図示
せず）に入れ、この密閉容器内に窒素ガス（N2）
を導入し、室温から150℃の間で薄層リチウム２
と窒素ガスN2とを接触させて窒化リチウム４を
形成する。尚３は薄層リチウム２の表面に存在す
る不純物の被膜である。 When creating the solid electrolyte, as shown in FIG.
Place it in a sealed container (not shown) with the other side masked, and inject nitrogen gas (N 2 ) into the sealed container.
A thin layer of lithium 2 was introduced between room temperature and 150℃.
and nitrogen gas N 2 to form lithium nitride 4. Note that 3 is a film of impurities present on the surface of the thin layer lithium 2.
この場合、窒化リチウムは第２図の場合と同様
に薄層リチウム２の表面の活性部分のみに局部的
に生成し厚み（垂直）方向に進行するが、その進
行は薄層リチウム２と負極リチウム１とがそれぞ
れ個別のものを圧着したものであるため両者の接
合部までで、それ以後は薄層リチウム２の水平方
向に主に進行して薄層リチウム２がほぼ均一に窒
化リチウム４に変化すると共に一部は更に垂直方
向に進行して負極リチウム１の表面にも若干窒化
リチウム４が生成して負極リチウムと窒化リチウ
ム固体電解質との接触抵抗が減じられる。 In this case, as in the case of Fig. 2, lithium nitride is locally generated only on the active part of the surface of the thin layer lithium 2 and progresses in the thickness (vertical) direction, but the progress is between the thin layer lithium 2 and the anode lithium. Since 1 and 1 are individually crimped together, the process ends at the joint between the two, and after that, it mainly progresses in the horizontal direction of the thin layer lithium 2, and the thin layer lithium 2 almost uniformly changes to lithium nitride 4. At the same time, some of the lithium nitride 4 further propagates in the vertical direction to generate some lithium nitride 4 on the surface of the negative electrode lithium 1, thereby reducing the contact resistance between the negative electrode lithium and the lithium nitride solid electrolyte.
正極合剤としてはヨウ化鉛粉末に20重量％の鉛
粉末を添加混合したものを用いた。 As the positive electrode mixture, a mixture of lead iodide powder and 20% by weight of lead powder was used.
電池の組立に際しては、前記正極合剤300mgを
10.0mmφに加圧成型した正極を前記窒化リチウム
層に圧着して本発明電池Ａとする。 When assembling the battery, add 300mg of the above positive electrode mixture.
A positive electrode press-molded to a diameter of 10.0 mm is pressed onto the lithium nitride layer to obtain a battery A of the present invention.
尚、比較のために窒化リチウム層粉末を３ト
ン／cm2で加圧し、厚み0.3mm、径10.0mmφに成型
したるものを固体電解質とし、この固体電解質を
正負極間に圧着して比較電池Ｂを作成した。 For comparison, lithium nitride layer powder was pressurized at 3 tons/cm 2 and molded to a thickness of 0.3 mm and a diameter of 10.0 mm as a solid electrolyte, and this solid electrolyte was pressed between the positive and negative electrodes to make a comparative battery. B was created.
第３図及び第４図はこれら電池の特性比較図を
示し、第１図は電流一電圧特性、第２図は60℃、
270KΩ負荷における放電特性である。 Figures 3 and 4 show comparison diagrams of the characteristics of these batteries. Figure 1 shows the current-voltage characteristics, Figure 2 shows the 60℃,
This is the discharge characteristic under a 270KΩ load.
(ヘ) 発明の効果
第３図及び第４図より明白なるように本発明電
池Ａは比較電池Ｂに比して優れた特性を示してい
る。(F) Effects of the Invention As is clear from FIGS. 3 and 4, the battery A of the present invention exhibits superior characteristics compared to the comparative battery B.
この理由を考察するに、比較電池における固体
電解質は窒化リチウム粉末を出発物質とし、これ
を加圧成型したものであるため薄層化が困難であ
り、電気抵抗の大なる固体電解質しか得られない
と共に固体電解質と負極リチウムとの界面におけ
る接触抵抗も大なるものである。 Considering the reason for this, the solid electrolyte in the comparison battery uses lithium nitride powder as a starting material and is pressure-molded, so it is difficult to make it thin, and only solid electrolytes with high electrical resistance can be obtained. At the same time, the contact resistance at the interface between the solid electrolyte and the negative electrode lithium is also large.
これに対して本発明電池では負極リチウムとは
区別して薄層リチウムを準備し、これらを予じめ
圧着したのち、薄層リチウムに窒素ガスを反応さ
せて窒化リチウム層を形成するものであり、薄層
リチウム自体は特開昭55−104078号公報に開示さ
れている場合と同様に表面の活性部分のみ局部的
に窒化リチウムが生成し厚み（垂直）方向に進行
するが、この進行が負極リチウムと薄層リチウム
の接合部に達するとそれ以後は薄層リチウムの水
平方向に主に進行することになり、薄層で且均一
な窒化リチウム固体電解質を得ることができると
共に負極リチウムの表面にも若干窒化リチウムが
生成して負極リチウムと窒化リチウム層固体電解
質との接触抵抗が減じられることによつて電池特
性が向上すると考えられる。 On the other hand, in the battery of the present invention, a thin layer of lithium is prepared separately from the negative electrode lithium, and after these are pressure bonded in advance, a lithium nitride layer is formed by reacting the thin layer of lithium with nitrogen gas, In the thin layer lithium itself, as in the case disclosed in JP-A-55-104078, lithium nitride is generated locally only in the active part of the surface and progresses in the thickness (vertical) direction, but this progress is caused by the formation of negative electrode lithium. After reaching the junction between the thin layer lithium and the thin layer lithium, the process proceeds mainly in the horizontal direction of the thin layer lithium, making it possible to obtain a thin and uniform lithium nitride solid electrolyte as well as the surface of the negative electrode lithium. It is thought that the battery characteristics are improved by generating some lithium nitride and reducing the contact resistance between the negative electrode lithium and the lithium nitride layer solid electrolyte.
依つて本発明によれば、高率放電可能な薄型の
固体電解質電池を得ることができその工業的価値
は極めて大である。 Therefore, according to the present invention, a thin solid electrolyte battery capable of high rate discharge can be obtained, and its industrial value is extremely large.
第１図は本発明電池における窒化リチウム固体
電解質の作成経過を模式的に示す図、第２図は従
来電池における窒化リチウム固体電解質の作成経
過を模式的に示す図、第３図及び第４図は本発明
電池と比較電池との特性比較図を示し、第３図は
電流−電圧特性、第４図は放電特性である。
１……負極リチウム、２……薄層リチウム、３
……不純物被膜、４……窒化リチウム層、Ａ……
本発明電池、Ｂ……比較電池。
Fig. 1 is a diagram schematically showing the preparation process of the lithium nitride solid electrolyte in the battery of the present invention, Fig. 2 is a diagram schematically showing the preparation process of the lithium nitride solid electrolyte in the conventional battery, Figs. 3 and 4 3 shows a comparison diagram of the characteristics of the battery of the present invention and a comparison battery, FIG. 3 shows the current-voltage characteristics, and FIG. 4 shows the discharge characteristics. 1... Negative electrode lithium, 2... Thin layer lithium, 3
...Impurity film, 4...Lithium nitride layer, A...
Inventive battery, B...comparative battery.
Claims (1)
着する第１工程と、 前記薄層リチウムに窒素ガスを反応させて、窒
化リチウム層を形成する第２工程と、 前記窒化リチウム層に、正極を圧着する第３工
程とを有する固体電解質電池の製造方法。[Claims] 1. A first step of press-bonding a thin layer of lithium to one side of the negative electrode lithium; a second step of reacting the thin layer of lithium with nitrogen gas to form a lithium nitride layer; and the nitriding step. A method for manufacturing a solid electrolyte battery, comprising a third step of press-bonding a positive electrode to a lithium layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59043581A JPS60189169A (en) | 1984-03-06 | 1984-03-06 | Solid electrolyte battery manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59043581A JPS60189169A (en) | 1984-03-06 | 1984-03-06 | Solid electrolyte battery manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60189169A JPS60189169A (en) | 1985-09-26 |
| JPH0458150B2 true JPH0458150B2 (en) | 1992-09-16 |
Family
ID=12667729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59043581A Granted JPS60189169A (en) | 1984-03-06 | 1984-03-06 | Solid electrolyte battery manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60189169A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61263060A (en) * | 1985-05-17 | 1986-11-21 | Matsushita Electric Ind Co Ltd | Thin film solid electrolyte battery |
| DE102013017594A1 (en) * | 2013-09-27 | 2015-04-02 | Forschungszentrum Jülich GmbH | Production method for electrochemical cells of a solid-state battery |
| JP6254412B2 (en) * | 2013-10-07 | 2017-12-27 | 古河機械金属株式会社 | Method for producing lithium nitride |
| US11367889B2 (en) * | 2017-08-03 | 2022-06-21 | Palo Alto Research Center Incorporated | Electrochemical stack with solid electrolyte and method for making same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58198865A (en) * | 1982-05-17 | 1983-11-18 | Toshiba Corp | Manufacturing method of lithium nitride solid electrolyte cell |
-
1984
- 1984-03-06 JP JP59043581A patent/JPS60189169A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60189169A (en) | 1985-09-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |