JPH0355028B2 - - Google Patents
Info
- Publication number
- JPH0355028B2 JPH0355028B2 JP60104238A JP10423885A JPH0355028B2 JP H0355028 B2 JPH0355028 B2 JP H0355028B2 JP 60104238 A JP60104238 A JP 60104238A JP 10423885 A JP10423885 A JP 10423885A JP H0355028 B2 JPH0355028 B2 JP H0355028B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- solid electrolyte
- positive electrode
- negative electrode
- 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
- 239000010949 copper Substances 0.000 claims description 29
- 239000007784 solid electrolyte Substances 0.000 claims description 25
- 150000002500 ions Chemical class 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 239000011651 chromium Substances 0.000 description 20
- 239000010410 layer Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 11
- 239000007774 positive electrode material Substances 0.000 description 10
- 229910019540 RbCu4I1.5Cl3.5 Inorganic materials 0.000 description 5
- 150000004770 chalcogenides Chemical class 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910017267 Mo 6 S 8 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000010955 niobium Chemical group 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000007787 solid Substances 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
-
- 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)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (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
本発明では、常温で高イオン導電性を有する固
体電解質を用いた、オールソリツド・ステイトの
固体電解質二次電池に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an all-solid-state solid electrolyte secondary battery using a solid electrolyte having high ionic conductivity at room temperature.
従来の技術
常温で高イオン導電性を有する固体電解質を用
いた電池は、電池のオールソリツド・ステイト化
が可能なことから、液もれが本質的になく、保存
中の自己放電のきわめて少ない高信頼性の電池と
なる。Conventional technology Batteries using solid electrolytes that have high ionic conductivity at room temperature can be made into an all-solid state, so they are highly reliable with essentially no leakage and extremely low self-discharge during storage. It becomes a sexual battery.
このような電池について、従来は一回の放電で
寿命が尽きてしまう一次電池がもつぱら提案され
ていた。しかし、電気回路素子の小形化が特徴で
あるマイクロエレクトロニクス分野の電源として
該電池を使用する場合、当然ながら電池も小形で
あることが要求される。電池は小形化すればする
ほど容量は小さくなるから、一回の放電で寿命が
尽きてしまう一次電池に代り、くり返し使用ので
きる二次電池が有用となつてくる。 As for such batteries, primary batteries, whose life spans end after one discharge, have conventionally been proposed. However, when the battery is used as a power source in the field of microelectronics, which is characterized by miniaturization of electric circuit elements, the battery is naturally required to be small. As batteries become smaller, their capacity decreases, so secondary batteries, which can be used repeatedly, are becoming more useful in place of primary batteries, which expire after a single discharge.
二次電池を構成する際必要となる要件は、正極
材料および負極材料が、電池の充・放電に際して
可逆的な電気化学反応を行う能力を有することで
ある。 A necessary requirement when constructing a secondary battery is that the positive electrode material and the negative electrode material have the ability to perform a reversible electrochemical reaction during charging and discharging of the battery.
特に、正極材料としては、液体電解質を用いた
電池では、金属カルコゲン化物が、負極としては
Li等のアルカリ金属を用いた場合有用であること
が古くから知られている。この金属カルコゲン化
物は、層状結晶構造を有しており、電池放電に際
しては負極から遊離したアルカリ金属イオンを層
間に吸蔵し、充電に際してはアルカリ金属イオン
を層間より放出することで可逆的に電池反応を行
うことができる特徴を有している。 In particular, metal chalcogenides are used as positive electrode materials in batteries using liquid electrolytes, and metal chalcogenides are used as negative electrode materials.
It has long been known that the use of alkali metals such as Li is useful. This metal chalcogenide has a layered crystal structure, and when the battery is discharged, the alkali metal ions released from the negative electrode are occluded between the layers, and when the battery is charged, the alkali metal ions are released from the interlayers, resulting in a reversible battery reaction. It has the feature of being able to do the following.
発明が解決しようとする問題点
以上のような金属カルコゲン化物を、銅を主体
とする負極と、Cu+導電性固体電解質とするオー
ルソリツド・ステイト二次電池の正極材料として
使えるであろうということは当該分野の技術者で
あれば容易に考えつくことであるが、金属カルコ
ゲン化物のうちどのようなものが、また、どの程
度までCu+イオンを自由にその層間に出し入れで
きるか全くわからなかつた。Problems to be Solved by the Invention It is possible to use the metal chalcogenide described above as a positive electrode material for an all-solid-state secondary battery that has a copper-based negative electrode and a Cu + conductive solid electrolyte. As a person skilled in the art would easily think, it was not known at all which types of metal chalcogenides and to what extent Cu + ions can be freely transferred between the layers.
問題点を解決するための手段
本発明は、Cuを主体とする負極と、Cu+イオン
導電性固体電解質と、正極材料として、Cu+イオ
ンを層間に自由に出し入れできる、NbS2の一部
をクロム、Cr、で置換した層状結晶構造を有し
た新規な化合物、Nb1-yCryS2+1.5y（ｙ：0.01−
0.10）とで構成される良好な充・放電サイクル特
性を発揮する固体電解質二次電池を提供する。Means for Solving the Problems The present invention consists of a negative electrode mainly composed of Cu, a Cu + ion conductive solid electrolyte, and a part of NbS 2 as a positive electrode material, which allows Cu + ions to be freely transferred between the layers. A new compound with a layered crystal structure substituted with chromium, Cr, Nb 1-y Cr y S 2+1.5y (y: 0.01-
0.10) and which exhibits good charge/discharge cycle characteristics.
作 用
本発明に従う新規な正極材料であるNb1-yCry
S2+1.5yは、NbS2のNb4+（イオン半径が0.63Å）を
Cr3+（イオン半径が0.55Å）で一部置換すること
で、Cu+イオンのＳ−Ｓ層間への出し入れに伴う
結晶のゆがみを軽減し、Cu+イオンのＳ−Ｓ層間
への吸蔵可能量すなわち、電池放電に際しては放
電容量を、結晶構造的にあるいは静電的に増加す
ることが出来る。そして、該正極材料を用いた固
体電解質二次電池は、高容量でしかも良好な充・
放電サイクル特性を与えることができる。Function Nb 1-y Cr y, which is a novel positive electrode material according to the present invention
S 2+1.5y is Nb 4+ of NbS 2 (ion radius is 0.63 Å)
By partially substituting Cr 3+ (ion radius: 0.55 Å), distortion of the crystal caused by the movement of Cu + ions into and out of the SS layer can be reduced, and Cu + ions can be stored between the SS layers. In other words, during battery discharge, the discharge capacity can be increased either crystallographically or electrostatically. A solid electrolyte secondary battery using this positive electrode material has high capacity and good charging/charging properties.
It can provide discharge cycle characteristics.
実施例
実施例 １
第１図の曲線ａは、Cu+イオン導電性固体電解
質としてRbCu4I1.5Cl3.5を用い、Cuを主体とする
負極と、Nb0.98Cr0.02S2.03正極とで構成される第
２図で示した断面構造を有した直径７mmの固体電
解質二次電池を、20℃、100μAの一定電流値で放
電した際の電池電圧の変化をｘ値、すなわち、放
電の進行と共に負極からのCu+イオンは正極の層
間に吸蔵され正極はCuxNb0.98Cr0.02S2.03と表され
るが、このｘ値を横軸に示したものである。この
曲線ａからわかるように、ｘの増加すなわち放電
の進行に伴い電池電圧は単調な減少を示し、この
減少はｘが0.30付近まで続き、0.30を越えると平
坦部が現れる。Examples Example 1 Curve a in Figure 1 uses RbCu 4 I 1.5 Cl 3.5 as the Cu + ion conductive solid electrolyte, and is composed of a negative electrode mainly composed of Cu and a Nb 0.98 Cr 0.02 S 2.03 positive electrode. When a solid electrolyte secondary battery with a diameter of 7 mm and having the cross-sectional structure shown in Figure 2 is discharged at 20°C with a constant current value of 100 μA, the change in battery voltage is the x value, that is, the change in battery voltage from the negative electrode as the discharge progresses. Cu + ions are occluded between the layers of the positive electrode, and the positive electrode is expressed as Cu x Nb 0.98 Cr 0.02 S 2.03 , and this x value is shown on the horizontal axis. As can be seen from this curve a, the battery voltage shows a monotonous decrease as x increases, that is, the discharge progresses, and this decrease continues until x is around 0.30, and a plateau appears when x exceeds 0.30.
曲線ｂは、正極材料としてｙ＝０、すなわち
Crの入つていないNbS2を用いた電池について電
池ａと同様の放電を行つた際の電池電圧を示して
いる。ｘが０〜0.30間の電池電圧の減少のし方
は、比較例として示したNbS2を正極とする電池
の曲線ｂより、本発明に従うNb0.98Cr0.02S2.03を
正極とする電池の曲線ａの方がゆるやかである。 Curve b shows that y=0 as the positive electrode material, i.e.
It shows the battery voltage when a battery using NbS 2 without Cr was discharged in the same way as battery a. The manner in which the battery voltage decreases when x is between 0 and 0.30 is as follows from curve b for a battery using NbS 2 as a positive electrode shown as a comparative example, and curve a for a battery using Nb 0.98 Cr 0.02 S 2.03 as a positive electrode according to the present invention. is more gradual.
すなわち、Nb1-yCryS2+1.5y（ｙ：0.01〜0.10）
は、ｘが0.30付近まで単一の層状結晶構造を保持
でき、ｘが0.30までCu+イオンをスムーズに出し
入れできる。 That is, Nb 1-y Cr y S 2+1.5y (y: 0.01 to 0.10)
can maintain a single layered crystal structure until x is around 0.30, and Cu + ions can be smoothly inserted and removed until x is around 0.30.
NbS2の場合は、電池電圧の平坦部は、ｘ＝
0.25付近から現われ始め、また電池電圧はａより
も低く、Cu+イオンの出し入れ易さはNb1-yCry
S2+1.5yに較べると劣る。 For NbS 2 , the plateau of the cell voltage is x=
It starts to appear around 0.25, the battery voltage is lower than a, and the ease with which Cu + ions can be taken in and out is Nb 1-y Cr y
It is inferior to S 2+1.5y .
第３図の曲線ａは、本発明に従う第１図に示し
た特性を示す電池と同様の電池を、ｘの値が０〜
0.25の間で、20℃、100μAで充・放電をくり返し
た際の、各サイクルの放電末の電池電圧と充・放
電サイクル数との関係を示したもので、100サイ
クルを越える良好なサイクル特性を与える。 Curve a in FIG. 3 shows a battery similar to the battery according to the invention and exhibiting the characteristics shown in FIG.
This graph shows the relationship between the battery voltage at the end of each cycle and the number of charge/discharge cycles when charging and discharging are repeated at 20℃ and 100μA between 0.25 and 20℃, and the number of charge/discharge cycles is good. give.
本発明に従う新規な正極材料であるNb1-yCry
S2+1.5yは、金属Nb粉末、金属Cr粉末を所定の割
合で混合したもの、あるいはNbとCrの合金粉末
を収納した石英ガラス容器に、イオウ蒸気を徐々
に送り込み900℃で加熱反応することで得ること
ができるし、あるいはより簡便な方法としては、
NbS2粉末とCr2S3粉末とを所定の割合で混合し、
約７mmφのペレツト状に約３トンの圧力で成形し
たものを、石英ガラス管に0.1Torrの圧力以下で
真空封入し、900℃で約72時間加熱反応すること
でも得ることができる。 Nb 1-y Cr y , a novel positive electrode material according to the present invention
S 2+1.5y is produced by gradually feeding sulfur vapor into a quartz glass container containing a mixture of metallic Nb powder and metallic Cr powder in a predetermined ratio, or containing an alloy powder of Nb and Cr, and reacting by heating at 900℃. Or, as a simpler method,
Mix NbS 2 powder and Cr 2 S 3 powder at a predetermined ratio,
It can also be obtained by molding pellets of about 7 mmφ under a pressure of about 3 tons, vacuum-sealing them in a quartz glass tube at a pressure of 0.1 Torr or less, and heating and reacting at 900° C. for about 72 hours.
実施例 ２
ｙ値が、原料仕込み量で0.01、0.02、0.05、
0.10、0.20、0.30であるNb1-yCryS2+1.5yを合成し
これらを正極材料とする図２に示した断面の構造
を有する直径７mmの固体電解質電池を構成した。Example 2 The y value is 0.01, 0.02, 0.05, depending on the amount of raw material charged.
Nb 1-y Cr y S 2+1.5y of 0.10, 0.20, and 0.30 was synthesized, and a solid electrolyte battery with a diameter of 7 mm and having a cross-sectional structure shown in FIG. 2 was constructed using these as positive electrode materials.
正極（粉末）：Nb1-yCryS2+1.5y＋RbCu4I1.5Cl3.5
（重量比２：３）…0.06gr
固体電解質（粉末）：RbCu4I1.5Cl3.5 …0.05gr
負極（粉末）：Cu＋Cu1.59Ｓ＋RbCu4I1.5Cl3.5
（重量比１：3.4：1.2）…0.075gr
上記正極粉末と固体電解質粉末と負極粉末とを
層状に三層に約３トンの圧力でプレスし電池ペレ
ツトとし、次に、正極および負極側に導電性カー
ボンフイルムより成る集電体と、電極リードと熱
圧着した後、電池全体をエポキシ樹脂で被膜する
ことで電池を作つた。第２図は、このようにして
作つた固体電解質二次電池の断面図を示してお
り、１は正極層、２は固体電解質層、３は負極
層、４は集電体、５は電極リード、６は樹脂パツ
ケージである。Positive electrode (powder): Nb 1-y Cr y S 2+1.5y +RbCu 4 I 1.5 Cl 3.5
(Weight ratio 2:3)...0.06gr Solid electrolyte (powder): RbCu 4 I 1.5 Cl 3.5 ...0.05gr Negative electrode (powder): Cu+Cu 1.59 S+RbCu 4 I 1.5 Cl 3.5
(Weight ratio 1:3.4:1.2)...0.075gr The above positive electrode powder, solid electrolyte powder, and negative electrode powder are pressed into three layers under a pressure of about 3 tons to form battery pellets, and then the positive electrode and negative electrode sides are conductive. A battery was fabricated by thermocompressing a current collector made of carbon film and an electrode lead, and then coating the entire battery with epoxy resin. Figure 2 shows a cross-sectional view of the solid electrolyte secondary battery made in this way, where 1 is a positive electrode layer, 2 is a solid electrolyte layer, 3 is a negative electrode layer, 4 is a current collector, and 5 is an electrode lead. , 6 is a resin package.
第４図は、このようにして作つた電池を、20
℃、100μAの定電流値でｘの値の範囲が０〜0.25
で充放電を行つた際の各サイクルの放電末期の電
池電圧と充・放電サイクル数との関係を示したも
ので、本発明に従い、Crをｙ値として0.01、
0.02、0.05、0.10含んだNb1-yCryS2+1.5yを正極と
した電池は、すぐれたサイクル特性を与えること
がわかる。 Figure 4 shows the battery made in this way.
℃, the value of x ranges from 0 to 0.25 at a constant current value of 100μA
It shows the relationship between the battery voltage at the end of discharge of each cycle and the number of charging/discharging cycles when charging and discharging is performed.According to the present invention, Cr is 0.01 as a y value,
It can be seen that batteries using Nb 1-y Cr y S 2+1.5y containing 0.02, 0.05, and 0.10 as the positive electrode have excellent cycle characteristics.
なお、本発明の実施例において、Cu+イオン導
電性固体電解質としてRbCu4I1.5Cl3.5を用いたが、
他のCu+イオン導電性固体電解質、例えば
RbCu4I1.25Cl3.75、Rb0.75K0.25Cu4I1.5Cl3.5、CuBr
にヘキサメチレンテトラミン等の第４級アンモニ
ウム塩を添加した固体電解質等を用いても本発明
と同様の効果が得られることは言うまでもない。
さらに、Cuを主体とする負極として、Cu＋
Cu1.59Ｓ＋Cu+イオン導電性固体電解質より成る
混合物の他に、Cu＋Cu+イオン導電性固体電解質
より成る混合物や、Cu5Mo6S8＋Cu+イオン導電
性固体電解質よりなる混合物等を用いても本発明
と同様の効果が得られることは言うまでもない。 In addition, in the examples of the present invention, RbCu 4 I 1.5 Cl 3.5 was used as the Cu + ion conductive solid electrolyte, but
Other Cu + ion conductive solid electrolytes, e.g.
RbCu 4 I 1.25 Cl 3.75 , Rb 0.75 K 0.25 Cu 4 I 1.5 Cl 3.5 , CuBr
It goes without saying that the same effects as the present invention can be obtained by using a solid electrolyte to which a quaternary ammonium salt such as hexamethylenetetramine is added.
Furthermore, as a negative electrode mainly composed of Cu,
In addition to the mixture of Cu 1.59 S + Cu + ion-conductive solid electrolyte, mixtures of Cu + Cu + ion-conductive solid electrolyte, Cu 5 Mo 6 S 8 + Cu + ion-conductive solid electrolyte, etc. can also be used. It goes without saying that the same effect as the invention can be obtained.
発明の効果
本発明に従い、正極材料としてNb1-yCry
S2+1.5yを有し、Cuを主体とする負極と、Cu+イオ
ン導電性固体電解質とで構成される固体電解質二
次電池は、分極の小さいすなわち放電時の電池電
圧の低下のゆるやかな、かつ優れた充・放電特性
を与える。Effects of the Invention According to the present invention, Nb 1-y Cr y is used as a positive electrode material.
A solid electrolyte secondary battery, which has S 2+1.5y and is composed of a Cu-based negative electrode and a Cu + ion conductive solid electrolyte, has low polarization, that is, a gradual drop in battery voltage during discharge. , and provides excellent charge/discharge characteristics.
第１図は、本発明の一実施例の固体電解質二次
電池の放電時の電圧の変化を示す図、第２図は同
電池の構造を示す断面図、第３図は同電池の充・
放電サイクル特性図、第４図は同電池の充・放電
サイクル特性図である。
ａ……本発明の一実施例の電池、ｂ……比較例
の電池、１……正極層、２……固体電解質層、３
……負極層。
Fig. 1 is a diagram showing voltage changes during discharging of a solid electrolyte secondary battery according to an embodiment of the present invention, Fig. 2 is a cross-sectional view showing the structure of the battery, and Fig. 3 is a diagram showing charging and
Discharge cycle characteristic diagram, FIG. 4 is a charge/discharge cycle characteristic diagram of the same battery. a...Battery of an example of the present invention, b...Battery of a comparative example, 1...Positive electrode layer, 2...Solid electrolyte layer, 3
...Negative electrode layer.
Claims (1)
体電解質と、Nb1-yCryS2+1.5yで表わされる硫化
物（ただし、ｙ：0.01〜0.10）を主体とする正極
より構成されることを特徴とする固体電解質二次
電池。1 Consisting of a negative electrode mainly composed of copper, a Cu + ion conductive solid electrolyte, and a positive electrode mainly composed of a sulfide represented by Nb 1-y Cr y S 2+1.5y (y: 0.01 to 0.10) A solid electrolyte secondary battery characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60104238A JPS61263053A (en) | 1985-05-16 | 1985-05-16 | Solid electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60104238A JPS61263053A (en) | 1985-05-16 | 1985-05-16 | Solid electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61263053A JPS61263053A (en) | 1986-11-21 |
| JPH0355028B2 true JPH0355028B2 (en) | 1991-08-22 |
Family
ID=14375377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60104238A Granted JPS61263053A (en) | 1985-05-16 | 1985-05-16 | Solid electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61263053A (en) |
-
1985
- 1985-05-16 JP JP60104238A patent/JPS61263053A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61263053A (en) | 1986-11-21 |
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