JPH0348620B2 - - Google Patents
Info
- Publication number
- JPH0348620B2 JPH0348620B2 JP63021893A JP2189388A JPH0348620B2 JP H0348620 B2 JPH0348620 B2 JP H0348620B2 JP 63021893 A JP63021893 A JP 63021893A JP 2189388 A JP2189388 A JP 2189388A JP H0348620 B2 JPH0348620 B2 JP H0348620B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode active
- positive electrode
- active material
- lithium
- battery
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】
〔発明の技術分野〕
本発明は、小型にして放電容量の大きい一次お
よび二次電池に関し、さらに詳細にはリチウムを
負極活物質として用いる電池に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to primary and secondary batteries that are small in size and have a large discharge capacity, and more particularly to batteries that use lithium as a negative electrode active material.
従来からリチウムを負極活性質として用いる高
エネルギ密度電池に関する提案はなされており、
例えば正極活物質として、Br2およびI2等のよう
なハロゲン、CuF2、AgF2、AgF、NiF2、
CuCl2、AgCl2、NiCl2、CoF3、MuF3、SbF3、
CdF2、AsF3、HgF2、CuBr、CdCl2、PbCl2、
NiClおよびCoCl2等のような金属ハロゲン化物、
AgSCN、CuSCNおよびNi（SCN）2等のような金
属ロダン化物、MnO2、Cr2O3、V2O5、SnO2、
PbO2、TiO2、Bi2O2、CrO3、Fe3O4、NiO、
HgO、AgO、Cu2O、CuO、Ag2WO4等のような
金属酸化物、
NiSx、AgBS、CuBS、Pb2B2S5および
MnB4S4等のような層状化合物、フツ化黒鉛、さ
らにはベンゾキノン類、ジニトロベンゼン等のよ
うなオキシハライド等を用いた電池が提案されて
いる。そして具体的には、例えば正極活物質とし
て黒鉛およびフツ素のインターカレーシヨン化合
物、負極活物質としてリチウム金属をそれぞれ使
用した電池が知られており（米国特許第3514337
号明細書参照）。また、フツ化黒鉛を正極活物質
としたリチウム負極（松下電器社製）および二酸
化マンガンを正極活物質としたリチウム電池（三
洋電機社製）が既に市販されている。しかしなが
ら、これらの電池は充電不能で二次電池として使
用できないという欠点がある。また、正極活物質
としてチタン、タンタル、バナジウムの硫化物、
セレン化物、テルル化物を用いた電池（米国特許
第4009052号明細書参照）等が開示されている。
しかしながら、これらの電池はその電池特性から
必ずしも十分であるとは言えなかつた。
Proposals have been made for high energy density batteries that use lithium as the negative electrode active material.
For example, as positive electrode active materials, halogens such as Br 2 and I 2 , CuF 2 , AgF 2 , AgF, NiF 2 ,
CuCl2 , AgCl2 , NiCl2 , CoF3 , MuF3 , SbF3 ,
CdF 2 , AsF 3 , HgF 2 , CuBr, CdCl 2 , PbCl 2 ,
Metal halides, such as NiCl and CoCl2 etc.
Metal rhodanides such as AgSCN, CuSCN and Ni (SCN) 2 , MnO2 , Cr2O3 , V2O5 , SnO2 ,
PbO2 , TiO2 , Bi2O2 , CrO3 , Fe3O4 , NiO ,
Metal oxides like HgO, AgO, Cu2O , CuO , Ag2WO4 etc. , NiSx , AgBS, CuBS, Pb2B2S5 and
Batteries using layered compounds such as MnB 4 S 4 , graphite fluoride, and oxyhalides such as benzoquinones and dinitrobenzene have been proposed. Specifically, for example, batteries are known that use graphite and fluorine intercalation compounds as positive electrode active materials, and lithium metal as negative electrode active materials (U.S. Pat. No. 3,514,337).
(see specification). Furthermore, a lithium negative electrode (manufactured by Matsushita Electric Co., Ltd.) using graphite fluoride as a positive electrode active material and a lithium battery (manufactured by Sanyo Electric Co., Ltd.) using manganese dioxide as a positive electrode active material are already commercially available. However, these batteries have the disadvantage that they are not rechargeable and cannot be used as secondary batteries. In addition, sulfides of titanium, tantalum, and vanadium are used as positive electrode active materials.
Batteries using selenide and telluride (see US Pat. No. 4,009,052) and the like have been disclosed.
However, these batteries could not necessarily be said to be sufficient due to their battery characteristics.
本発明は、このような現状に鑑みてなされたも
のであり、その目的は小型であり、かつ放電容量
が大で高エネルギ密度のしかも充電可能な電池を
提供することである。
The present invention has been made in view of the current situation, and an object thereof is to provide a battery that is small in size, has a large discharge capacity, has a high energy density, and is rechargeable.
本発明を概説すれば、本発明の電池は、正極活
物質は、六員環に二つのケント基を有するピリミ
ジン誘導体であり、負極活物質はリチウムであ
り、電解質物質は正極活物質およびリチウムに対
して化学的に安定であり、かつリチウムイオンが
正極活物質と電気化学反応をするための移動を行
う物質であることを特徴とするものである。 To summarize the present invention, in the battery of the present invention, the positive electrode active material is a pyrimidine derivative having two Kent groups in a six-membered ring, the negative electrode active material is lithium, and the electrolyte material is a positive electrode active material and lithium. It is characterized by being a substance that is chemically stable, and in which lithium ions move to perform an electrochemical reaction with the positive electrode active material.
本発明によれば、小型で放電容量が大きく、さ
らに高エネルギ密度の、しかも充電可能な電池を
提供しえるという利点がある。 According to the present invention, there is an advantage that it is possible to provide a battery that is small in size, has a large discharge capacity, has a high energy density, and is rechargeable.
本発明を詳細に説明すると、本発明の電池の正
極活物質は六員環に二つのケトン基を有するピリ
ミジン誘導体であり、このケトン基部分で電気化
学的反応を行う。
To explain the present invention in detail, the positive electrode active material of the battery of the present invention is a pyrimidine derivative having two ketone groups in a six-membered ring, and an electrochemical reaction is carried out in this ketone group moiety.
このような六員環に二つのケトン基を有するピ
リミジン誘導体は、本発明において基本的に限定
されるものではなく、前記ケトン基部分で電気化
学的反応を行うものであれば、いかなるものでも
よい。たとえばチミン、カフエインなどを具体例
として挙げることができる。 Such a pyrimidine derivative having two ketone groups on a six-membered ring is not fundamentally limited in the present invention, and any pyrimidine derivative may be used as long as it undergoes an electrochemical reaction in the ketone group portion. . Specific examples include thymine and caffeine.
このような正極活物質の典型的な例としてチミ
ンの反応を下記に式(1)として示す。 As a typical example of such a positive electrode active material, the reaction of thymine is shown below as formula (1).
本発明における正極活物質として前記六員環に
二つのケトン基を有するピリミジン誘導体または
これと結合剤粉末との混合物をニツケル、ステン
レス等の支持体上に膜状に圧着成形するか、また
は前記六員環に二つのケトン基を有するピリミジ
ン誘導体に導電性を付与するための炭素粉末を混
合し、この混合物（正極合剤）を金属容器に入
れ、あるいは前記混合物を結合剤と混合してニツ
ケル、ステンレス等の支持体上に圧着成形する等
の手段により形成することができる。 As a positive electrode active material in the present invention, a pyrimidine derivative having two ketone groups on the six-membered ring or a mixture of the same and a binder powder is pressure-molded into a film on a support such as nickel or stainless steel, or A pyrimidine derivative having two ketone groups in its member ring is mixed with carbon powder to impart conductivity, and this mixture (positive electrode mixture) is placed in a metal container, or the mixture is mixed with a binder to produce nickel, It can be formed by means such as compression molding on a support such as stainless steel.
負極活物質であるリチウムは、一般のリチウム
電池のそれと同様にシート状として、またはその
シートをニツケルまたはステンレスの網に圧着し
て負極として形成することができる。 Lithium, which is the negative electrode active material, can be formed into a sheet like that of a general lithium battery, or the sheet can be pressed onto a nickel or stainless steel mesh to form the negative electrode.
電解質としては、例えばプロピレンカーボネー
ト、エチレンカーボネート、γ−ブチロラクト
ン、１，２−ジメトキシエタン等の非プロトン性
有機溶媒とLiClO4、LiAlcl4、LiBF4、LiCI、
LiPF6、LiAsF6等のリチウム塩との組み合わせ、
またはLi+を伝導体とする固体電解質あるいは溶
融塩等一般にリチウムを負極活物質として用いた
電池で使用される既知の電解質を用いることがで
きる。 Examples of electrolytes include aprotic organic solvents such as propylene carbonate, ethylene carbonate, γ-butyrolactone, and 1,2-dimethoxyethane, and LiClO 4 , LiAlcl 4 , LiBF 4 , LiCI,
Combination with lithium salts such as LiPF 6 and LiAsF 6 ,
Alternatively, known electrolytes that are generally used in batteries using lithium as a negative electrode active material, such as solid electrolytes or molten salts that use Li + as a conductor, can be used.
また、電池構成上必要ならば多孔質のポリプロ
ピレン等よりなる隔膜を使用してもよい。 Further, if necessary for the battery configuration, a diaphragm made of porous polypropylene or the like may be used.
次に本発明を実施例により説明するが、本発明
はこれらにより何ら限定されるものではない。 Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto in any way.
なお、実施例において電池作製および測定はア
ルゴンガス雰囲気下で行つた。 In addition, in the examples, battery fabrication and measurements were performed under an argon gas atmosphere.
実施例 １
第１図は本発明の一具体例であるボタン型電池
の特性測定用電池セルの断面概略図であり、１は
Niメツキを施した黄銅製容器、２はリチウム負
極、３は多孔質ポリプロピレン製隔膜、４はカー
ボン繊維よりなるフエルト、５は正極合剤、６
ａ，６ｂはテフロン製容器、７はNiリード線を
示す。容器１の直径26mmの凹室内に正極合剤５を
挿入し、その上に電解液含浸用のフエルト４を載
せ、隔膜３を介してリチウム負極を載置し、容器
６ａ，６ｂで締めつけた。リチウム負極２は直径
20mmの円板で、カーボン繊維よりなるフエルト
４、隔膜３も円板形である。Example 1 FIG. 1 is a schematic cross-sectional view of a battery cell for measuring the characteristics of a button-type battery, which is a specific example of the present invention.
Ni-plated brass container, 2 is a lithium negative electrode, 3 is a porous polypropylene diaphragm, 4 is a felt made of carbon fiber, 5 is a positive electrode mixture, 6
a and 6b are Teflon containers, and 7 is a Ni lead wire. A positive electrode mixture 5 was inserted into a concave chamber with a diameter of 26 mm in a container 1, a felt 4 for impregnating an electrolytic solution was placed thereon, a lithium negative electrode was placed with a diaphragm 3 in between, and the containers 6a and 6b were tightened. Lithium negative electrode 2 has a diameter
The felt 4 made of carbon fiber and the diaphragm 3 are also disk-shaped.
電解液としては蒸溜脱水プロピレンカーボネー
トに溶解したLiClO4の１モル／溶液を用い、
隔膜３、フエルト４および正極合剤５に含浸させ
て使用した。正極合剤５として、カフエイン0.1
ｇと0.1ｇのアセチレンブラツクを混合したもの
を使用した。 As the electrolyte, 1 mol/solution of LiClO 4 dissolved in distilled and dehydrated propylene carbonate was used.
It was used by impregnating the diaphragm 3, felt 4, and positive electrode mixture 5. Caffeine 0.1 as positive electrode mixture 5
A mixture of 0.1 g and 0.1 g of acetylene black was used.
このようにして作製した電池の開路電圧は
3.03Vであつた。１ｍＡの定電流放電を行つたと
ころ、放電時間と電圧の関係は第２図のようにな
り、1V終止電圧の放電容量は120Ah／Kgであり、
エネルギ密度は135Wh／Kgであつた。1V終止電
圧まで式(2)の如く放電反応が起こるとすると、利
用率は44％となる。 The open circuit voltage of the battery made in this way is
It was 3.03V. When a constant current discharge of 1mA is performed, the relationship between discharge time and voltage is as shown in Figure 2, and the discharge capacity at a final voltage of 1V is 120Ah/Kg.
The energy density was 135Wh/Kg. Assuming that the discharge reaction occurs as shown in equation (2) up to the final voltage of 1V, the utilization rate will be 44%.
実施例 ２
正極合剤として0.1ｇ（式(1)）と0.1ｇのアセチ
レンブラツクを実施例１と同じ電解液と混合して
用いた以外は実施例１と同様にして第１図に示し
た電池を作製した。 Example 2 The same procedure as in Example 1 was carried out as shown in Figure 1 except that 0.1 g (formula (1)) and 0.1 g of acetylene black were used as the positive electrode mixture mixed with the same electrolyte as in Example 1. A battery was created.
この電池の開路電圧は3.05Vであつた。１ｍＡ
の定電流放電を行つたところ放電時間と電圧の関
係は第３図ａのようになり、1V終止電圧での放
電容量は85Ah／Kgであり、エネルギ密度は
108Wh／Kgであつた。放電後、６時間、１ｍＡ
定電流放電を行つたところ、放電時間と電圧の関
係は第３図ｂに示すようになつた。1V終止電圧
の放電容量は440Ah／Kgとなり、エネルギ密度は
574Wh／Kgであつた。さらに放電後、40時間、
１ｍＡの定電流充電した後１ｍＡで定電流放電を
行つたところ放電時間と電圧の関係は第３図ｃの
ようになつた。1Vの終止電圧の放電容量は
300Ah／Kgであり、エネルギ密度は415Wh／Kgで
あつた。 The open circuit voltage of this battery was 3.05V. 1mA
When constant current discharge was performed, the relationship between discharge time and voltage was as shown in Figure 3a, and the discharge capacity at a final voltage of 1V was 85Ah/Kg, and the energy density was
It was 108Wh/Kg. 1mA for 6 hours after discharge
When constant current discharge was performed, the relationship between discharge time and voltage was as shown in FIG. 3b. The discharge capacity at 1V final voltage is 440Ah/Kg, and the energy density is
It was 574Wh/Kg. After further discharge, 40 hours,
When the battery was charged at a constant current of 1 mA and then discharged at a constant current of 1 mA, the relationship between the discharge time and the voltage was as shown in Figure 3c. The discharge capacity for a final voltage of 1V is
The energy density was 300Ah/Kg, and the energy density was 415Wh/Kg.
以上説明したように本発明によるリチウム電池
によれば、リチウム電池の正極活物質として、六
員環に二つのケトン基を有するピリミジン誘導体
を使用することにより、小型でかつ高エネルギ密
度の充放電可能な電池を形成できるという利点を
生じる。
As explained above, according to the lithium battery according to the present invention, by using a pyrimidine derivative having two ketone groups in a six-membered ring as the positive electrode active material of the lithium battery, charging and discharging is possible with a small size and high energy density. This gives rise to the advantage that it is possible to form a battery with a high quality.
第１図は本発明による一具体例であるボタン型
電池の特性測定用電池セルの断面概略図、第２図
および第３図は本発明の実施例における電池の放
電時間と電圧の関係を示した図である。
１……容器、２……リチウム負極、３……隔
膜、４……フエルト、５……正極合剤、６ａ，６
ｂ……テフロン製容器、７……Niリード線。
FIG. 1 is a schematic cross-sectional view of a battery cell for measuring the characteristics of a button-type battery, which is a specific example of the present invention, and FIGS. 2 and 3 show the relationship between battery discharge time and voltage in an embodiment of the present invention. This is a diagram. 1... Container, 2... Lithium negative electrode, 3... Diaphragm, 4... Felt, 5... Positive electrode mixture, 6a, 6
b...Teflon container, 7...Ni lead wire.
Claims (1)
するピリミジン誘導体であり、負極活物質はリチ
ウムであり、電解質物質は正極活物質およびリチ
ウムに対して化学的に安定であり、かつリチウム
イオンが正極活物質と電気化学反応をするための
移動を行う物質であることを特徴とする電池。1 The positive electrode active material is a pyrimidine derivative having two ketone groups on a six-membered ring, the negative electrode active material is lithium, and the electrolyte material is chemically stable with respect to the positive electrode active material and lithium, and is lithium ion A battery characterized in that is a substance that moves to perform an electrochemical reaction with a positive electrode active material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63021893A JPS63225475A (en) | 1988-02-03 | 1988-02-03 | Battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63021893A JPS63225475A (en) | 1988-02-03 | 1988-02-03 | Battery |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP576880A Division JPS56103870A (en) | 1980-01-23 | 1980-01-23 | Battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63225475A JPS63225475A (en) | 1988-09-20 |
| JPH0348620B2 true JPH0348620B2 (en) | 1991-07-25 |
Family
ID=12067783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63021893A Granted JPS63225475A (en) | 1988-02-03 | 1988-02-03 | Battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63225475A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4576662B2 (en) * | 2000-04-25 | 2010-11-10 | 三菱化学株式会社 | Positive electrode material for lithium secondary battery, positive electrode for lithium secondary battery, and lithium secondary battery |
-
1988
- 1988-02-03 JP JP63021893A patent/JPS63225475A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63225475A (en) | 1988-09-20 |
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