JPS6259412B2 - - Google Patents
Info
- Publication number
- JPS6259412B2 JPS6259412B2 JP55052189A JP5218980A JPS6259412B2 JP S6259412 B2 JPS6259412 B2 JP S6259412B2 JP 55052189 A JP55052189 A JP 55052189A JP 5218980 A JP5218980 A JP 5218980A JP S6259412 B2 JPS6259412 B2 JP S6259412B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- active material
- electrode active
- negative electrode
- pentoxide
- 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
Links
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 14
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 13
- 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 13
- 238000009830 intercalation Methods 0.000 claims description 10
- 230000002687 intercalation Effects 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 10
- 239000005486 organic electrolyte Substances 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 239000007774 positive electrode material Substances 0.000 claims description 9
- 239000007773 negative electrode material Substances 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- 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)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
産業上の利用分野
本発明は有機電解液二次電池に関するものであ
る。
従来技術とその問題点
有機電解液を用いた二次電池は、高エネルギー
密度を得るために負極活物質にリチウムを、正極
活物質にできるだけ高い酸化力を有するNiF2、
AgClなどを用いたものが知られているが、いず
れもサイクル寿命が悪く、実用に耐えるものでは
なかつた。この原因は正極活物質の安定性にもよ
るが、負極活物質のリチウムが充放電サイクルの
経過とともに変形して容量が低下したり、樹枝状
に析出して内部短絡ブリツジを形成することによ
るところが大であつた。
発明の目的
本発明は上記欠点を解消するもので、有機電解
液を用いた二次電池が、アルカリ電解液のような
クリープ現象による漏液を生じないことと、水の
電気分解反応による充放電効率の低下を生じない
こととに着目し、サイクル寿命のすぐれた有機電
解液二次電池を得ることを目的とする。
発明の構成
本発明の有機電解液二次電池は、リチウム塩を
溶解した有機溶媒を電解液とし、充電状態で正極
活物質に五酸化バナジウムを、負極活物質にリチ
ウム・五酸化ニオブの層間化合物を用い、放電に
よつて前記層間化合物から正極活物質へ単位結晶
格子当り１個のリチウムイオンが移動し、リチウ
ム・五酸化バナジウムの層間化合物が形成される
ように負極容量を制限したものである。
実施例
以下実施例により説明する。第１図は本発明の
有機電解液二次電池の半截断面図である。第１図
において、１は正極活物質で、五酸化バナジウム
（V2O5）に黒鉛を添加してテフロンバインダーに
て円板状に成形したものである。２は負極活物質
で、五酸化ニオブ（Nb2O5）に黒鉛を添加してテ
フロンバインダーにて円板状に成形したものであ
る。３は円板状に打ち抜いた金属リチウムで、負
極活物質２の表面に直接接触させている。４はプ
ロピレンカーボネイトと１・２−ジメトキシエタ
ンとの１：１混合液に１モル／の過塩素酸リチ
ウムを溶解させてなる電解液が含浸されたガラス
繊維マツトよりなるセパレータ、５，６はそれぞ
れ正極および負極端子を兼ねるステンレス製の容
器と蓋で、各々の周縁部分はポリプロピレン製の
ガスケツト７を介してかしめられている。こうし
て組み立てられた電池の寸法は直径が20mm、高さ
が２mmで、組み立て直後には五酸化バナジウムと
リチウムとの電位差である約3.5Vの開路電圧を
示すが、常温にて１週間放置すれば次式の反応で
リチウム・五酸化ニオブの層間化合物が形成さ
れ、約1.7Vの開路電圧を示すようになる。
Nb2O5＋Li→Nb2O5・Li
上記の如き構成からなる電池の起電反応は次式
で表わされる。
INDUSTRIAL APPLICATION FIELD The present invention relates to an organic electrolyte secondary battery. Conventional technology and its problems Secondary batteries using organic electrolytes use lithium as the negative electrode active material and NiF 2 , which has as high oxidizing power as possible, as the positive electrode active material to obtain high energy density.
Products using materials such as AgCl are known, but all of them had poor cycle life and were not practical. The cause of this depends on the stability of the positive electrode active material, but the lithium in the negative electrode active material may deform as the charge/discharge cycle progresses, resulting in a decrease in capacity, or it may precipitate into dendritic forms, forming internal short bridges. It was big and warm. Purpose of the Invention The present invention solves the above-mentioned drawbacks, and aims to provide a secondary battery using an organic electrolyte that does not leak due to the creep phenomenon unlike alkaline electrolytes, and that charges and discharges due to the electrolysis reaction of water. The purpose of this invention is to obtain an organic electrolyte secondary battery with excellent cycle life, with a focus on not causing a decrease in efficiency. Structure of the Invention The organic electrolyte secondary battery of the present invention uses an organic solvent in which a lithium salt is dissolved as an electrolyte, and in a charged state, vanadium pentoxide is used as a positive electrode active material, and an interlayer compound of lithium and niobium pentoxide is used as a negative electrode active material. The negative electrode capacity is limited so that one lithium ion per unit crystal lattice moves from the intercalation compound to the positive electrode active material by discharge, forming an intercalation compound of lithium and vanadium pentoxide. . Examples The following examples will be explained below. FIG. 1 is a half-cut sectional view of the organic electrolyte secondary battery of the present invention. In FIG. 1, 1 is a positive electrode active material, which is made by adding graphite to vanadium pentoxide (V 2 O 5 ) and molding it into a disk shape using a Teflon binder. 2 is a negative electrode active material, which is made by adding graphite to niobium pentoxide (Nb 2 O 5 ) and molding it into a disk shape using a Teflon binder. 3 is a metal lithium punched into a disk shape, which is brought into direct contact with the surface of the negative electrode active material 2. 4 is a separator made of glass fiber mat impregnated with an electrolytic solution prepared by dissolving 1 mole of lithium perchlorate in a 1:1 mixture of propylene carbonate and 1,2-dimethoxyethane, and 5 and 6 are each a separator made of glass fiber mat. The container and lid are made of stainless steel and serve as positive and negative electrode terminals, and the peripheral edges of each are caulked with a gasket 7 made of polypropylene interposed therebetween. The dimensions of the battery assembled in this way are 20 mm in diameter and 2 mm in height, and it exhibits an open circuit voltage of approximately 3.5 V, which is the potential difference between vanadium pentoxide and lithium, immediately after assembly, but if left at room temperature for a week. An intercalation compound of lithium and niobium pentoxide is formed by the following reaction, and it exhibits an open circuit voltage of approximately 1.7V. Nb 2 O 5 +Li→Nb 2 O 5 ·Li The electromotive reaction of the battery configured as above is expressed by the following equation.
【表】
充電
(Liの層間 (電解液中)
化合物)
すなわち放電時には負極側のリチウム・五酸化
ニオブの層間化合物の結晶格子から正極側の五酸
化バナジウムの結晶格子へ単位結晶格子当り１個
のリチウムイオンが移動してリチウム・五酸化バ
ナジウムの層間化合物が形成され、充電時には正
極側のリチウム・五酸化バナジウムの層間化合物
の結晶格子から負極側の五酸化ニオブの結晶格子
へリチウムイオンが移動してリチウム・五酸化ニ
オブの層間化合物が形成される反応である。この
反応は形状保存反応と言われ、活物質自体の溶解
や析出を伴わず、活物質の元の形状が保存され
る。従つて従来の二次電池の寿命原因である樹枝
状金属の析出や活物質の脱落も原理的に起こり得
ず、極めて長寿命の電池を得ることができる。
また本発明においては、充電状態のリチウム・
五酸化ニオブの層間化合物を電池内で五酸化ニオ
ブとリチウムとを自動的に反応させて形成してい
るので、工業的にも極めて有利である。
五酸化バナジウムは従来から一次電池の正極活
物質として用いられることが検討されているが、
単位結晶格子当り２〜３個のリチウムイオンの移
動を伴うのが普通であり、この場合は充電しても
回復しない。ところが研究の結果、放電量を一定
限度内に抑えれば充電により回復させることがで
きることが判明した。実用的にはこのように放電
量を一定限度内に抑えることは難しく、過放電に
なることが予測されるので、本発明においては、
五酸化バナジウムを過放電させないように負極容
量を少なくしたものである。すなわち重量比で五
酸化バナジウム１に対し、リチウムを0.038以
下、五酸化ニオブを1.46以上にしてリチウム・五
酸化ニオブの層間化合物が形成されるようにすれ
ば、五酸化バナジウムの単位結晶格子当り１個の
リチウムイオンの移動に抑えることができ、充電
により容量を回復させることができる。
第２図は本発明の有機電解液二次電池を1mA
の充電電流および放電電流で充放電させた時の充
放電電圧特性図である。第２図から充放電は約
1.5Vの電圧で行われ、その容量は約20mAhであ
ることがわかる。この本発明電池は、同一寸法の
リチウムを負極とした一次電池が約3V，60mAh
程度であるのに比較すれば、容量は３分の１にな
るものの、繰返し充放電を行うことができきると
いう特徴を有するものである。
発明の効果
実施例において詳述した如く、本発明の有機電
解液二次電池は、ニツケル−カドミウム二次電池
のようなアルカリ電解液を用いた二次電池に比べ
て漏液を生じることが少なく、長期間にわたる使
用に耐えうるものである。[Table] Charging
(Li interlayer (in electrolyte)
Compound)
In other words, during discharge, one lithium ion per unit crystal lattice moves from the crystal lattice of the intercalation compound of lithium and niobium pentoxide on the negative electrode side to the crystal lattice of vanadium pentoxide on the positive electrode side, and the intercalation compound of lithium and vanadium pentoxide moves. During charging, lithium ions move from the crystal lattice of the lithium/vanadium pentoxide intercalation compound on the positive electrode side to the niobium pentoxide crystal lattice on the negative electrode side, forming a lithium/niobium pentoxide intercalation compound. be. This reaction is called a shape preservation reaction, and the original shape of the active material is preserved without dissolving or precipitating the active material itself. Therefore, the precipitation of dendritic metals and the falling off of active materials, which are causes of the lifespan of conventional secondary batteries, cannot occur in principle, making it possible to obtain a battery with an extremely long lifespan. In addition, in the present invention, lithium in a charged state
Since the interlayer compound of niobium pentoxide is formed by automatically reacting niobium pentoxide and lithium within the battery, it is extremely advantageous from an industrial perspective. Vanadium pentoxide has been considered for use as a positive electrode active material in primary batteries, but
It is normal that 2 to 3 lithium ions move per unit crystal lattice, and in this case, it does not recover even after charging. However, research has revealed that it is possible to recover by charging if the amount of discharge is kept within a certain limit. In practice, it is difficult to suppress the amount of discharge within a certain limit in this way, and over-discharge is expected, so in the present invention,
The negative electrode capacity is reduced to prevent vanadium pentoxide from being over-discharged. In other words, if the weight ratio of lithium is 0.038 or less and niobium pentoxide is 1.46 or more to 1 vanadium pentoxide to form an interlayer compound of lithium and niobium pentoxide, 1 per unit crystal lattice of vanadium pentoxide can be formed. It is possible to limit the movement of lithium ions to just a few lithium ions, and the capacity can be restored by charging. Figure 2 shows the organic electrolyte secondary battery of the present invention at 1 mA.
FIG. 3 is a charging/discharging voltage characteristic diagram when charging and discharging at charging current and discharging current of . From Figure 2, charging and discharging is approximately
It can be seen that it is done at a voltage of 1.5V and its capacity is about 20mAh. This invention battery has a primary battery of the same size with lithium as an anode of approximately 3V and 60mAh.
Although the capacity is only one-third of that of conventional batteries, it has the characteristic of being able to be repeatedly charged and discharged. Effects of the Invention As detailed in the Examples, the organic electrolyte secondary battery of the present invention causes less leakage than a secondary battery using an alkaline electrolyte such as a nickel-cadmium secondary battery. , can withstand long-term use.
第１図は本発明の有機電解液二次電池の半截断
面図、第２図は本発明電池の充放電電圧特性の一
例である。
１…正極活物質、２…負極活物質
FIG. 1 is a half-sectional view of an organic electrolyte secondary battery of the present invention, and FIG. 2 is an example of the charging/discharging voltage characteristics of the battery of the present invention. 1... Positive electrode active material, 2... Negative electrode active material
Claims (1)
し、充電状態で正極活物質に五酸化バナジウム
を、負極活物質に五酸化ニオブと金属リチウムと
を電気的に接触させることによつて形成したリチ
ウム・五酸化ニオブの層間化合物を用い、放電に
よつてリチウム・五酸化ニオブの層間化合物から
正極活物質へ単位結晶格子当り１個のリチウムが
移動し、リチウム・五酸化バナジウムの層間化合
物が形成されるように負極容量を制限したことを
特徴とする有機電解液二次電池。1. Lithium salt formed by using an organic solvent in which a lithium salt is dissolved as an electrolyte and electrically contacting vanadium pentoxide as a positive electrode active material and niobium pentoxide and metallic lithium as a negative electrode active material in a charged state. Using an intercalation compound of niobium pentoxide, one lithium per unit crystal lattice is transferred from the intercalation compound of lithium and niobium pentoxide to the positive electrode active material by discharge, and an intercalation compound of lithium and vanadium pentoxide is formed. An organic electrolyte secondary battery characterized by having a limited negative electrode capacity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5218980A JPS56147368A (en) | 1980-04-18 | 1980-04-18 | Organic electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5218980A JPS56147368A (en) | 1980-04-18 | 1980-04-18 | Organic electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56147368A JPS56147368A (en) | 1981-11-16 |
| JPS6259412B2 true JPS6259412B2 (en) | 1987-12-10 |
Family
ID=12907847
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5218980A Granted JPS56147368A (en) | 1980-04-18 | 1980-04-18 | Organic electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56147368A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003077544A (en) * | 2001-09-06 | 2003-03-14 | Yuasa Corp | Secondary battery |
| JP2015138611A (en) * | 2014-01-21 | 2015-07-30 | トヨタ自動車株式会社 | Method for manufacturing positive electrode for secondary battery |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6199279A (en) * | 1984-10-19 | 1986-05-17 | Doudensei Muki Kagoubutsu Gijutsu Kenkyu Kumiai | Solid electrolyte secondary battery |
| US5015547A (en) * | 1988-07-08 | 1991-05-14 | Matsushita Electric Industrial Co., Ltd. | Lithium secondary cell |
| JP2763561B2 (en) * | 1988-12-27 | 1998-06-11 | 松下電器産業株式会社 | Organic electrolyte secondary battery |
| JP3019326B2 (en) * | 1989-06-30 | 2000-03-13 | 松下電器産業株式会社 | Lithium secondary battery |
| US10923717B2 (en) | 2016-11-03 | 2021-02-16 | Lg Chem, Ltd. | Lithium ion secondary battery |
-
1980
- 1980-04-18 JP JP5218980A patent/JPS56147368A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003077544A (en) * | 2001-09-06 | 2003-03-14 | Yuasa Corp | Secondary battery |
| JP4496688B2 (en) * | 2001-09-06 | 2010-07-07 | 株式会社ジーエス・ユアサコーポレーション | Secondary battery |
| JP2015138611A (en) * | 2014-01-21 | 2015-07-30 | トヨタ自動車株式会社 | Method for manufacturing positive electrode for secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56147368A (en) | 1981-11-16 |
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