JPS6119076A - Charge-discharge method of solid electrolyte secondary battery - Google Patents
Charge-discharge method of solid electrolyte secondary batteryInfo
- Publication number
- JPS6119076A JPS6119076A JP59140882A JP14088284A JPS6119076A JP S6119076 A JPS6119076 A JP S6119076A JP 59140882 A JP59140882 A JP 59140882A JP 14088284 A JP14088284 A JP 14088284A JP S6119076 A JPS6119076 A JP S6119076A
- Authority
- JP
- Japan
- Prior art keywords
- solid electrolyte
- charge
- secondary battery
- battery
- value
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
-
- 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、固体電解質二次電池の充・放電方式従来例の
構成とその問題点
一般に二次電池は、用いられる正極活物質、負極活物質
、電解質の可逆性、過電圧２分解電圧等の電気化学的性
質によシ決定されるその電池系固有の、その電圧値ある
いは電気量を越えるとくり２へ一／
返し充・放電特性が極端に低下する充・放電限界電圧あ
るいは電気量を有している。すなわち、従来の二次電池
の代表例であるニッケル・カドミウム電池とか鉛蓄電池
とかも、長年に経る検討を加え、それぞれの電池系に固
有の充・放電限界電圧あるいは電気量を見定め現在の充
・放電方式をとるに至っている。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to the structure of a conventional charging/discharging system for solid electrolyte secondary batteries and its problems. Exceeding the voltage value or amount of electricity unique to the battery system determined by the electrochemical properties such as electrolyte reversibility, overvoltage, and decomposition voltage will cause an extreme drop in charging and discharging characteristics. It has a charging/discharging limit voltage or quantity of electricity. In other words, we have studied the typical examples of conventional secondary batteries, such as nickel-cadmium batteries and lead-acid batteries, over many years, and have determined the charge/discharge limit voltage or amount of electricity unique to each battery system, and determined the current charge/discharge voltage. A discharge method has been adopted.
新しい正極活物質、負極活物質、電解質により構成され
る二次電池を実用に供するためには、この電池系固有の
充・放電限界電圧あるいは電気量を見定め、この電池系
固有の充・放電方式を与えることは必須の要件となる。In order to put a secondary battery composed of a new positive electrode active material, negative electrode active material, and electrolyte into practical use, the charging/discharging limit voltage or amount of electricity unique to this battery system must be determined, and the charging/discharging method unique to this battery system must be determined. It is an essential requirement to provide
一方、在来の液体電解質を用いるニッケル・カドミウム
電池等の二次電池とは異り、固体状の電解質を用いる固
体電解質二次電池は、原理的に液もれがなく小形・うす
形化がきわめて簡便にできることから、近年発展が著し
い省電力・省エネルギーが達成されるマイクロエレクト
ロニクス分野の小型電源として注目されるに至っている
。この固体電解質二次電池の中でも、Ｃｕ工ＴｉＳ２と
か３ベ−ノ
Ｃｕ、 Ｔｉ ＣｒｙＳ２＋１．ｓｙ等の層間化合物全
正極活物質とし、Ｃｕ■イオン導電性固体電解質を用い
る二次電池は、正極活物質の可逆性が優れ、固体電解質
のイオン伝導度は有機電解液電解質に匹適するくらい高
くかつ化学的に安定であることから優れた電池特性が期
待できる固体電解質二次電池として注目されるに至って
いる。On the other hand, unlike secondary batteries such as nickel-cadmium batteries that use conventional liquid electrolytes, solid electrolyte secondary batteries that use solid electrolytes do not leak in principle and can be made smaller and thinner. Because it is extremely easy to use, it has attracted attention as a compact power source for the microelectronics field, which has achieved remarkable power and energy savings in recent years. Among these solid electrolyte secondary batteries, Cu-TiS2, 3-vano Cu, TiCryS2+1. A secondary battery that uses an intercalation compound such as sy as an all-positive electrode active material and a Cu ion conductive solid electrolyte has excellent reversibility of the positive electrode active material, and the ionic conductivity of the solid electrolyte is high enough to be comparable to an organic electrolyte. Since it is also chemically stable, it has attracted attention as a solid electrolyte secondary battery that can be expected to have excellent battery characteristics.
該固体電解質二次電池の電池反応は：
放電 Ｃｕ ｘ＋ ６ Ｔ ｉＳ２
’ｔ Ｃｕｘ＋ ａ Ｔ Ｉ ＣｒｙＳ２＋１．６７
れておらず、したがって、該電池の良好なくり返し特性
を与える充・放電限界を定め難く、該固体電解質二次電
池を実用に供するために難点があった。The battery reaction of the solid electrolyte secondary battery is: Discharge Cu x+ 6 T iS2 't Cux+ a T I CryS2+1.67
Therefore, it is difficult to determine the charge/discharge limits that will give the battery good cycling characteristics, and this poses a problem in putting the solid electrolyte secondary battery into practical use.
発明の目的
本発明は、固体電解質二次電池について、良好なくり返
し充・放電特性を与える充・放電方式を提供することを
目的とする。OBJECTS OF THE INVENTION An object of the present invention is to provide a charging/discharging method that provides good repeated charging/discharging characteristics for a solid electrolyte secondary battery.
発明の構成
本発明を適用する固体電解質二次電池は、Ｃｕを主体と
する負極ｓ Ｃｕ ｘＴ Ｉ Ｓ２ ！ ＣｕｘＴ ｉ
Ｃｒ ｙＳ２ ＋ １ 、ｔｓ。Structure of the Invention A solid electrolyte secondary battery to which the present invention is applied has a negative electrode mainly composed of Cu. CuxT i
Cr yS2 + 1, ts.
（ｏ＜ｘ＜ｏ、２． ｏ、ｏｌ（ｙ（ｏ、２）の一群よ
シ選ばれる化合物を主体とする正極、ＲｂＣｕ ４ Ｉ
１ 、５ Ｃ１３，５＋Ｒｂｃｕ４ＲｂＣｕ４Ｉ”３
．７５等ｔ７） Ｃｕ” イ、ｔ ７ 導ｔ 性固体電
解質により構成される。そして該電池の使用に際しては
、上記正極化合物のＩの値が−０，１〜０．２１の間で
充・放電をくり返す。(o<x<o, 2. o, ol(y(o, 2), a positive electrode mainly composed of a compound selected from the group of
1,5 C13,5+Rbcu4RbCu4I"3
．． 75, etc. t7) Cu" i, t 7 Conductive solid electrolyte. When using the battery, charging and discharging are performed when the value of I of the positive electrode compound is between -0.1 and 0.21. Repeat.
実施例の説明
下記に示した構成の固体電解質二次電池を構成し、本発
明を適用する。Description of Examples A solid electrolyte secondary battery having the configuration shown below is constructed and the present invention is applied thereto.
６ページ
〔実施例１〕
電解質 ： ＲｂＣｕ４Ｉ、 、６Ｃ１，６を０．５
ｑｒ 。Page 6 [Example 1] Electrolyte: RbCu4I, , 6C1,6 at 0.5
qr.
負極合剤：Ｃｕ粉末８０重量％とＣｕ２Ｓ２ｏ重量％の
混合物４．７６重量部と前記
電解質１．２６重量部の混合物を
０．２ ｑｒ 。Negative electrode mixture: 0.2 qr of a mixture of 4.76 parts by weight of a mixture of 80% by weight of Cu powder and % by weight of Cu2S2o and 1.26 parts by weight of the electrolyte.
正極合剤：Ｃｕｏ、１ＴｉＳ２２重量部と前記電解質３
重量部の混合物をｏ、ｏｓ ｇｒ。Positive electrode mixture: Cuo, 1TiS22 parts by weight and the electrolyte 3
Parts by weight of the mixture were o, os gr.
上記の材料を２トン／ｃｄの圧力で三層に加圧成型して
直径７頗、厚さ約１１の電池を組み立てた。The above materials were pressure molded into three layers at a pressure of 2 tons/cd to assemble a battery with a diameter of 7 mm and a thickness of about 11 mm.
これらの電池を室温で、１００μへの定電流で、次表に
示す６種類の充・、放電サイクル試験ａ−ｆを行なった
。These batteries were subjected to six types of charge/discharge cycle tests a to f shown in the following table at room temperature and at a constant current of 100μ.
次表に示したＣｕｘＴｉＳ２ のＸ値は、次に示すＣ
ｕｏ、、Ｔ Ｉ Ｓ２１ ’；ｒ ｒ当りの充電あるい
は放電容量０（Ａｈ／ｃｙｒ）とＸの変化量であるΔＸ
との関係式よシ求めたΔＸ値を用いて求めたものである
。The X value of CuxTiS2 shown in the following table is
uo,, T I S21 '; r ΔX which is the amount of change in charge or discharge capacity 0 (Ah/cyr) per r and X
It was determined using the ΔX value determined from the relational expression.
２６．８
たとえば、試験電池を１００μＡで５時間放電した６２
、−７
ときのΔＸ値は、
と与えられ、放電前のＣｕｘＴｉＳ２ のＸ値を０．
１とすると、放電後のＣｕｘ Ｔ ｉＳ２ のＸ値は、
ｘ ＝ ０．１ ＋ ０．０９２ ＝ ０．１９２とな
る。26.8 For example, a test cell was discharged at 100 μA for 5 hours62
, -7, the ΔX value is given as follows, and the X value of CuxTiS2 before discharge is 0.
1, the X value of Cux T iS2 after discharge is
x = 0.1 + 0.092 = 0.192.
１００μＡで５時間充電した場合は、同様に算出して、
サイクル数と、各サイクル試験においてＸの値が７ベー
／
最大値をとる放電来電圧との関係を示しており、本発明
に従い、充・放電範囲が−ｏ、１（ｘ （ｏ、 ２１で
あるサイクル試験ａ、ｂ、ｃ、ｅ、では実用に耐える良
好なくり返し充・放電特性を与えることがわかる。When charging at 100 μA for 5 hours, the relationship between the number of cycles and the discharge voltage at which the value of X takes the maximum value in each cycle test is calculated in the same way. - It can be seen that the cycle tests a, b, c, and e, in which the discharge range is -o, 1(x (o, 21), give good repeated charge/discharge characteristics that can withstand practical use.
〔実施例２〕
電解質 ： ＲｂＣｕ ４Ｉ ＊ 、５Ｃ１３，５を０
．０５ ｇｒ ０負極合剤：Ｃｕ粉８０重量係とＣｕ２
Ｓ２０重量％の混合物４．７５重量部と前記電
解質１．２６ 重量部の混合物を０．２ｇ ｒ 。[Example 2] Electrolyte: RbCu 4I *, 5C13,5 0
．． 05 gr 0 negative electrode mixture: Cu powder 80 weight ratio and Cu2
0.2 g r of a mixture of 4.75 parts by weight of a mixture containing 20% by weight of S and 1.26 parts by weight of the electrolyte.
正極合剤：Ｃｕｏ、ｏ５ＴｉＣｒｏ、ｏ２６Ｓ２．０３
７６２重量部と前記電解質３重量部の混合物
を０．０６ｇｒ０
上記の材料を２トン／ｄ の圧力で三層に加圧成型して
直径７頗、厚さ約１ｍｌ＋の電池を組み立てた。Positive electrode mixture: Cuo, o5TiCro, o26S2.03
A mixture of 762 parts by weight of the electrolyte and 3 parts by weight of the above electrolyte was pressure-molded into three layers at a pressure of 2 tons/d2 to assemble a battery having a diameter of 7 mm and a thickness of about 1 ml+.
これらの電池を室温で、１ｏｏμＡの定電流で、次表に
示す６種類の充・放電サイクル試験ａ′〜ｆ′を行なっ
た。These batteries were subjected to six types of charge/discharge cycle tests a' to f' shown in the following table at room temperature and a constant current of 1 ooμA.
次表に示したＣｕｘＴｉＣｒｏ、。２６Ｓ２．。３□５
のＸ値は、次に示す’ ＣｕＯ，０５ＴｉＣｒ０．０２
５Ｓ２．０３５７１ｑｒ当りの充電あるいは放電容量Ｑ
（Ａｈ／ｑｒ）とＸの変化量であるΔＸとの関係式より
求めたΔχ値を用いて求めたものである。CuxTiCro, shown in the following table. 26S2. . 3□5
The X value of 'CuO,05TiCr0.02
Charging or discharging capacity Q per 5S2.03571qr
It is determined using the Δχ value determined from the relational expression between (Ah/qr) and ΔX, which is the amount of change in X.
たとえば、試験電池を１００μＡで５時間放電したとき
のΔＸ値は、
と与えられ、放電前のＣｕｘＴｉＣｒｏＤ２６Ｓ２．０
３□５のＸ値を０．０５とすると、放電後のＸ値は、ｘ
＝ ０．０５＋０．０９１−＝ ０．１４１ と
なる１００μＡで５時間充電した場合は、同様に算出し
て、
ｘ ＝ ０．０５−０．０９１ ＝ −０，０４１とな
る。For example, when the test battery is discharged at 100 μA for 5 hours, the ΔX value is given as: CuxTiCroD26S2.0 before discharge
If the X value of 3□5 is 0.05, the X value after discharge is x
= 0.05 + 0.091 - = 0.141 When charging for 5 hours at 100 μA, the calculation is made in the same manner as x = 0.05 - 0.091 = -0,041.
以下余白
９ ベーン
本発明に従い、充拳放電範囲が−０，１（ｘ ＜０．２
１であるサイクル試験ａ′、ｂ′、Ｃ′、ｅ′では実用
に耐える良好なくり返し充・放電特性を与えることがわ
かる。According to the present invention, the charging and discharging range is −0,1 (x <0.2
It can be seen that in the cycle tests a', b', C', and e', which are No. 1, good repeated charge/discharge characteristics that can withstand practical use are provided.
次に、本発明の充・放電方式についてその根拠を探るた
めに、実施例１で示した構成の固体電解質二次電池を１
ｏｏ／−１Ａの一定電流でＸが０までなるように充電し
た後、同じく１ｏＯμＡで放電を行ない、放電深さの異
なるすなわちＸ値の異なる電１０’＼
池の正極のＸ線回折を行なった。Next, in order to explore the basis for the charging/discharging method of the present invention, a solid electrolyte secondary battery having the configuration shown in Example 1 was constructed.
After charging with a constant current of oo/-1A so that .
Ｃｕ ｘＴ Ｉ Ｓ ２ の結晶形について分析した
ところ、Ｘの値が０．２１ を越える付近から、層状構
造を有した六方晶系のＴ ｚ Ｓ２構造に帰属される回
折ピークの他に、立方晶系の層状構造をもたないＣｕ７
．４４Ｔｉ１６Ｓ３２に帰属される回折ピークが出現し
始めることを見とめた。また、第３図は、この際の電池
電圧とＸ値の関係を示しているが、電池電圧は、Ｘが０
から０．２付近までは一様に減少し、すなわち、層状構
造をもつＣｕｘＴｉＳ２ 内でのＣｕの活量が一様に増
加するにつれてネルンスト式に従い電池電圧は一様に減
少する。Ｘが０．２付近を越えると電池電圧の減少はゆ
るやかになりほぼ平坦な電圧値を与え、先のＸ線回折の
結果と合わせて考えると正極には２つの結晶相が存在し
ていることがほぼ推定できる。An analysis of the crystal form of Cu x T I S 2 revealed that, in addition to the diffraction peaks attributed to the hexagonal T z S2 structure with a layered structure, from the vicinity where the value of X exceeds 0.21, a cubic crystal structure was observed. Cu7 does not have a layered structure
．． It was observed that a diffraction peak attributed to 44Ti16S32 began to appear. In addition, Fig. 3 shows the relationship between the battery voltage and the X value in this case.
In other words, as the activity of Cu in CuxTiS2 having a layered structure uniformly increases, the battery voltage uniformly decreases according to the Nernst equation. When X exceeds around 0.2, the battery voltage decreases slowly and gives an almost flat voltage value, which, when considered together with the previous X-ray diffraction results, indicates that two crystal phases exist in the positive electrode. can be roughly estimated.
以上のことから、充・放電くり返し試験においてＸが０
．２１以上では、くり返し特性が極端に悪くなる原因は
、正極活物質であるＣｕ ｘＴ ｉ Ｓ ２ あるい
はＣｕ ｘＴ Ｉ Ｃｒ ｙＳ ２ ＋ １．５ｙの層
状構造が、Ｘが０．２１１１ ベーン
を越えてくり返し充・放電することで徐々に破壊される
ことにあると本発明者らは考えている。なお、Ｘ値の下
限についても同様なことが考えられると本発明者らは考
えている。From the above, in the repeated charge/discharge test, X is 0.
．． 21 or more, the reason why the repeatability becomes extremely poor is that the layered structure of Cu xT i S 2 or Cu xT I Cr yS 2 + 1.5y, which is the positive electrode active material, repeats over the vane where X is 0.2111. The inventors believe that this is due to the fact that it is gradually destroyed by charging and discharging. Note that the present inventors believe that the same holds true for the lower limit of the X value.
発明の効果
本発明によれば、固体電解質二次電池に良好なくり返し
充・放電特性を発揮させることができる。Effects of the Invention According to the present invention, a solid electrolyte secondary battery can exhibit good repeated charge/discharge characteristics.
第１図および第２図は、本発明の一実施例の充・放電方
式における充・放電サイクル数と、各サイクルの放電末
電池電圧との関係を示す図、第３図は、電池の放電電圧
とＣｕ ｘＴ Ｉ Ｓ２ のＸ値との関係を示す図であ
る。
代理人の氏名 弁理士 中 尾 敏 男 ほか１名手続
補正書
昭和５９年１１ 月λλ日Figures 1 and 2 are diagrams showing the relationship between the number of charging/discharging cycles in the charging/discharging method of an embodiment of the present invention and the battery voltage at the end of discharge in each cycle, and Figure 3 is a diagram showing the relationship between the battery discharge voltage at the end of each cycle. It is a figure which shows the relationship between voltage and the X value of Cu xT I S2. Name of agent: Patent attorney Toshio Nakao and one other person Procedural amendment November 1980, λλ
Claims (1)
＿ｘＴｉＣｒ＿ｙＳ＿２＿＋＿１＿．＿５＿ｙ（０＜ｘ
＜０．２０、０．０１＜ｙ＜０．２）の一群より選ばれ
る化合物を主体とする正極と、Ｃｕ＾■イオン導電性固
体電解質で構成される固体電解質二次電池の充・放電を
、前記正極化合物のｘの値が−０．１〜０．２１の間で
くり返し行なうことを特徴とする固体電解質二次電池の
充・放電方式。Negative electrode mainly made of metallic copper, Cu_xTiS_2, CU
_xTiCr_yS_2_+_1_. _5_y(0<x
<0.20, 0.01<y<0.2) A positive electrode mainly composed of a compound selected from the group of A charging/discharging method for a solid electrolyte secondary battery, characterized in that the positive electrode compound is repeatedly charged and discharged while the value of x is between -0.1 and 0.21.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59140882A JPS6119076A (en) | 1984-07-06 | 1984-07-06 | Charge-discharge method of solid electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59140882A JPS6119076A (en) | 1984-07-06 | 1984-07-06 | Charge-discharge method of solid electrolyte secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6119076A true JPS6119076A (en) | 1986-01-27 |
Family
ID=15278960
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59140882A Pending JPS6119076A (en) | 1984-07-06 | 1984-07-06 | Charge-discharge method of solid electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6119076A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016048730A (en) * | 2014-08-27 | 2016-04-07 | 株式会社日本触媒 | Thermoelectric conversion material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5569964A (en) * | 1978-08-21 | 1980-05-27 | Haering Rudolph Roland | Cathode for molybdenum disulfide lithium battery |
| JPS57107568A (en) * | 1980-12-25 | 1982-07-05 | Matsushita Electric Ind Co Ltd | Reversible copper electrode |
-
1984
- 1984-07-06 JP JP59140882A patent/JPS6119076A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5569964A (en) * | 1978-08-21 | 1980-05-27 | Haering Rudolph Roland | Cathode for molybdenum disulfide lithium battery |
| JPS57107568A (en) * | 1980-12-25 | 1982-07-05 | Matsushita Electric Ind Co Ltd | Reversible copper electrode |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016048730A (en) * | 2014-08-27 | 2016-04-07 | 株式会社日本触媒 | Thermoelectric conversion material |
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