JPH04363862A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JPH04363862A JPH04363862A JP3136904A JP13690491A JPH04363862A JP H04363862 A JPH04363862 A JP H04363862A JP 3136904 A JP3136904 A JP 3136904A JP 13690491 A JP13690491 A JP 13690491A JP H04363862 A JPH04363862 A JP H04363862A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- vanadium
- secondary battery
- lithium secondary
- lithium
- 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.)
- Granted
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 16
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 claims abstract description 21
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 11
- 239000003792 electrolyte Substances 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 3
- 239000005486 organic electrolyte Substances 0.000 abstract 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 28
- -1 vanadium octoxide Chemical compound 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 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
- 239000002075 main ingredient Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、移動用直流電源やメモ
リーバックアップ用電源などに使用される充放電可能な
リチウム二次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rechargeable and dischargeable lithium secondary battery used as a mobile DC power source, a memory backup power source, and the like.
【０００２】0002
【従来の技術】従来より、充放電が可能なリチウム二次
電池として、正極に五酸化バナジウム、負極に金属リチ
ウムまたはリチウム合金、電解液にリチウム塩を溶解し
た有機溶媒を用いた電池系があって、これは３ボルトの
高い端子電圧をもっており、エネルギー密度もニッケル
・カドミウム電池の１．５〜２倍もあって、有望な電池
として知られている。[Prior Art] Conventionally, there have been battery systems that use vanadium pentoxide as a positive electrode, metallic lithium or a lithium alloy as a negative electrode, and an organic solvent in which a lithium salt is dissolved in an electrolyte as a rechargeable lithium secondary battery. This battery has a high terminal voltage of 3 volts and an energy density of 1.5 to 2 times that of a nickel-cadmium battery, making it a promising battery.
【０００３】0003
【発明が解決しようとする課題】従来の前記する五酸化
バナジウム系電池は、その正極が一般的には五酸化バナ
ジウムを９０％前後含有し、カーボンブラックと、結着
剤が夫々数％で構成されていて、五酸化バナジウムは、
１電子反応で（化１）式に示すようにＶ２ Ｏ５ １モ
ル当り、１ファラデー（２６．８アンペア・時）の電気
容量を有している。[Problems to be Solved by the Invention] In the conventional vanadium pentoxide-based batteries mentioned above, the positive electrode generally contains around 90% vanadium pentoxide, and is composed of carbon black and a binder each in several percentages. Vanadium pentoxide is
It is a one-electron reaction and has a capacitance of 1 faraday (26.8 ampere-hour) per 1 mole of V2O5 as shown in formula (1).
【０００４】0004
【化１】[Chemical formula 1]
【０００５】しかしながら、実際には前記の正極をもつ
電池を放電してみると、反応利用率は高くなく、とくに
高負荷電流で放電したときの放電容量は、７０％前後に
低下してしまうもので、この放電時の正極の反応効率が
低いということが問題であった。However, when a battery with the above-mentioned positive electrode is actually discharged, the reaction utilization rate is not high, and the discharge capacity drops to around 70% especially when discharged at a high load current. However, the problem was that the reaction efficiency of the positive electrode during discharge was low.
【０００６】[0006]
【課題を解決するための手段】本発明は、前記の課題を
解決するために、正極を構成する合剤として、五酸化バ
ナジウムまたは八酸化バナジウムまたはこれら両者の混
合物などのバナジウム酸化物を主体とし、これに炭化バ
ナジウムを添加したものを使用したものである。炭化バ
ナジウムの添加量は、広い範囲で有効であるが、正極合
剤の５〜２０重量％がとくに効果的である。[Means for Solving the Problems] In order to solve the above-mentioned problems, the present invention uses vanadium oxide, such as vanadium pentoxide, vanadium octoxide, or a mixture of both, as the main ingredient for the positive electrode. , to which vanadium carbide was added. The amount of vanadium carbide added is effective within a wide range, but 5 to 20% by weight of the positive electrode mixture is particularly effective.
【０００７】[0007]
【作用】本発明のリチウム二次電池では、五酸化バナジ
ウムや八酸化バナジウムなどのバナジウム酸化物を主体
とする正極に炭化バナジウムを混入したことにより、放
電時において正極の反応効率が大きく向上している。[Function] In the lithium secondary battery of the present invention, by mixing vanadium carbide into the positive electrode, which is mainly made of vanadium oxide such as vanadium pentoxide or vanadium octoxide, the reaction efficiency of the positive electrode is greatly improved during discharge. There is.
【０００８】これは、炭化バナジウムが半導体的な性質
を有しているために正極を主体となって構成しているバ
ナジウム酸化物の粉末粒子間の電気的接触を良好にする
と同時に、バナジウム酸化物粒子が電解液により、よく
濡れるようになるからである。さらに炭化バナジウムは
、その中にリチウムイオンが出入りし、電池反応活物質
として作用していると考えられる。Since vanadium carbide has semiconducting properties, it improves electrical contact between vanadium oxide powder particles that mainly constitute the positive electrode, and at the same time, vanadium oxide This is because the particles become well wetted by the electrolyte. Furthermore, vanadium carbide is thought to function as a battery reaction active material, with lithium ions moving in and out of the vanadium carbide.
【０００９】また、バナジウム酸化物例えば五酸化バナ
ジウムでは３．５ボルトの高電位を有するが、炭化バナ
ジウムは、このような高電位に対して安定であり、分解
したとしても、バナジウムと炭素に分解するのみであっ
て正極の主体であるバナジウム酸化物に対して悪影響を
及ぼすことは考えられないものである。In addition, vanadium oxide, such as vanadium pentoxide, has a high potential of 3.5 volts, but vanadium carbide is stable against such high potentials, and even if it decomposes, it will not decompose into vanadium and carbon. However, it is unlikely that it would have any adverse effect on vanadium oxide, which is the main component of the positive electrode.
【００１０】0010
【実施例】以下、本発明の一実施例を図面を参照しなが
ら説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described below with reference to the drawings.
【００１１】図１において、１は正極端子を兼ねたケー
スで、負極端子を兼ねた封口板２によって封口されてい
る。３は前記ケース１と封口板２とを絶縁しケース１を
密封するポリプロピレン製ガスケット、４はポリプロピ
レン製の微孔膜でできたセパレータで、正極５と負極６
との間に介在し、かつ電解液を含浸したものである。本
実施例における正極５は、炭化バナジウムの添加量の効
果を明らかにするために、五酸化バナジウムを一定量の
２０４ｍｇ（理論電気容量約３０ミリアンペア・時）と
し、これに炭化バナジウム粉末の添加量を夫々、０、１
、２、５、１０、２０、３０、４０重量％とし、導電材
であるカーボンブラックを５重量％、結着剤であるフッ
素樹脂を５重量％の重量比となるように混合して混練し
たものを直径１５ｍｍの大きさのペレットに成形したも
ので、これらを高温真空乾燥によって脱水処理して、正
極として電池を夫々構成したものである。前記の負極６
は、リチウムが５重量％のリチウム・アルミニウム合金
であり、厚さを０．３ｍｍ、直径を１５ｍｍとしたもの
である。そして集電用のネット７が内部に入っている。
なお、電解液は、プロピレンカーボネートと、１、２ジ
メトキシエタンを１：１で混合した溶媒に過塩素酸リチ
ウムを１モル／リットル溶解したものを用いた。電池の
大きさは、直径２０ｍｍ、厚さ２．５ｍｍとした。In FIG. 1, a case 1 also serves as a positive terminal, and is sealed by a sealing plate 2 that also serves as a negative terminal. 3 is a polypropylene gasket that insulates the case 1 and the sealing plate 2 and seals the case 1; 4 is a separator made of a polypropylene microporous membrane;
and is impregnated with an electrolyte. In order to clarify the effect of the amount of vanadium carbide added, the positive electrode 5 in this example was made using a constant amount of vanadium pentoxide of 204 mg (theoretical electric capacity of about 30 milliampere-hours), and an amount of vanadium carbide powder added thereto. are respectively 0 and 1
, 2, 5, 10, 20, 30, and 40% by weight, carbon black as a conductive material was mixed and kneaded at a weight ratio of 5% by weight, and fluororesin as a binder was 5% by weight. The pellets were molded into pellets with a diameter of 15 mm, and these were dehydrated by high-temperature vacuum drying to form batteries as positive electrodes. The negative electrode 6
is a lithium-aluminum alloy containing 5% by weight of lithium, and has a thickness of 0.3 mm and a diameter of 15 mm. A current collecting net 7 is included inside. The electrolytic solution used was one in which 1 mol/liter of lithium perchlorate was dissolved in a solvent containing a 1:1 mixture of propylene carbonate and 1,2-dimethoxyethane. The size of the battery was 20 mm in diameter and 2.5 mm in thickness.
【００１２】正極を主体となって構成する五酸化バナジ
ウムに炭化バナジウムの添加量が０から４０重量％まで
の前記８種類の電池を用い、定電流１ミリアンペアで１
０時間の充放電を２０回行ったのち、３．５ボルトの定
電圧、１００オームの保護抵抗で１０時間満充電後、３
ミリアンペアおよび、１０ミリアンペアの定電流で放電
し、２．５ボルトに至るまでの電気容量を測定し、充電
電気容量に対する放電利用率を測定した。その結果を図
２、図３に示す。Using the above-mentioned eight types of batteries in which the amount of vanadium carbide added to vanadium pentoxide, which mainly constitutes the positive electrode, is from 0 to 40% by weight, a constant current of 1 milliampere was used.
After charging and discharging for 0 hours 20 times, after fully charging for 10 hours with a constant voltage of 3.5 volts and a protective resistance of 100 ohms, 3
The battery was discharged at a constant current of 10 milliamperes and 10 milliamperes, and the electric capacity up to 2.5 volts was measured, and the discharge utilization rate with respect to the charging electric capacity was measured. The results are shown in FIGS. 2 and 3.
【００１３】図２、図３から明らかなように、炭化バナ
ジウムが五酸化バナジウムを主体とする正極に僅かでも
含有すると放電利用率は上昇する。As is clear from FIGS. 2 and 3, if even a small amount of vanadium carbide is contained in the positive electrode mainly composed of vanadium pentoxide, the discharge utilization rate increases.
【００１４】そして、とくに、１０ミリアンペア放電の
正極の放電利用率では約５重量％の炭化バナジウムの添
加量から添加効果が大となり、２０重量％でほぼ飽和状
態となる。実際の電池では、大きさが制限されているの
で、炭化バナジウムの添加量は、最小の体積、重量であ
ることが望ましい。したがって、炭化バナジウムの最適
添加量は５〜２０重量％である。[0014] Particularly, in terms of the discharge utilization rate of the positive electrode for 10 milliampere discharge, the effect of adding vanadium carbide becomes great starting from an amount of about 5% by weight, and becomes almost saturated at 20% by weight. Since the size of an actual battery is limited, it is desirable that the amount of vanadium carbide added be the minimum volume and weight. Therefore, the optimum amount of vanadium carbide added is 5 to 20% by weight.
【００１５】なお、炭化バナジウム添加の効果は、正極
を主となって構成するバナジウム酸化物が五酸化バナジ
ウム（Ｖ２ Ｏ５ ）の場合に限られるものでなく、勿
論アモルファス状の五酸化バナジウムであっても、八酸
化バナジウム（Ｖ３ Ｏ８ ）、または五酸化バナジウ
ムと八酸化バナジウムとの混合物であっても同様の効果
が得られた。[0015] The effect of adding vanadium carbide is not limited to the case where the vanadium oxide that mainly constitutes the positive electrode is vanadium pentoxide (V2O5). Similar effects were also obtained using vanadium octoxide (V3O8) or a mixture of vanadium pentoxide and vanadium octoxide.
【００１６】[0016]
【発明の効果】以上の実施例の説明から明らかなように
、本発明によれば炭化バナジウムの添加によって、バナ
ジウム酸化物を主体とする正極の放電利用率、とくに高
負荷放電特性を向上させるものであり、従来より充放電
サイクル寿命の優れたリチウム二次電池を実現するもの
である。[Effects of the Invention] As is clear from the description of the above embodiments, according to the present invention, the addition of vanadium carbide improves the discharge utilization rate, especially the high-load discharge characteristics, of a positive electrode mainly composed of vanadium oxide. This realizes a lithium secondary battery with a superior charge/discharge cycle life compared to conventional lithium secondary batteries.
【図１】本発明の一実施例におけるコイン形のリチウム
二次電池の断面図[Fig. 1] A cross-sectional view of a coin-shaped lithium secondary battery in an embodiment of the present invention.
【図２】炭化バナジウムの含有率による正極の３ミリア
ンペア放電利用率の変化を示した図[Figure 2] Diagram showing changes in the 3 milliampere discharge utilization rate of the positive electrode depending on the content of vanadium carbide
【図３】炭化バナジウムの含有率による正極の１０ミリ
アンペア放電利用率の変化を示した図[Figure 3] Diagram showing changes in the 10 mA discharge utilization rate of the positive electrode depending on the vanadium carbide content
１ ケース ２ 封口板 ４ セパレータ ５ 正極 ６ 負極 1 case 2 Sealing plate 4 Separator 5 Positive electrode 6 Negative electrode
Claims (2)
、リチウムを主体とする負極と、リチウム塩を溶解した
有機溶媒を主体とする電解液を有する再充電可能なリチ
ウム二次電池であって、前記正極は炭化バナジウムを含
有したリチウム二次電池。1. A rechargeable lithium secondary battery comprising a positive electrode mainly composed of vanadium oxide, a negative electrode mainly composed of lithium, and an electrolyte mainly composed of an organic solvent in which lithium salt is dissolved, The positive electrode is a lithium secondary battery containing vanadium carbide.
し、５〜２０重量％である請求項１記載のリチウム二次
電池。2. The lithium secondary battery according to claim 1, wherein the content of vanadium carbide is 5 to 20% by weight based on the positive electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3136904A JP2819201B2 (en) | 1991-06-10 | 1991-06-10 | Lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3136904A JP2819201B2 (en) | 1991-06-10 | 1991-06-10 | Lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04363862A true JPH04363862A (en) | 1992-12-16 |
| JP2819201B2 JP2819201B2 (en) | 1998-10-30 |
Family
ID=15186291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3136904A Expired - Fee Related JP2819201B2 (en) | 1991-06-10 | 1991-06-10 | Lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2819201B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008103094A (en) * | 2006-10-17 | 2008-05-01 | Samsung Sdi Co Ltd | Non-aqueous secondary battery |
| US8187750B2 (en) | 2006-09-19 | 2012-05-29 | Samsung Sdi Co., Ltd. | Negative active material including lithium vanadium oxide for non-aqueous rechargeable battery, and non-aqueous rechargeable battery including same |
-
1991
- 1991-06-10 JP JP3136904A patent/JP2819201B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8187750B2 (en) | 2006-09-19 | 2012-05-29 | Samsung Sdi Co., Ltd. | Negative active material including lithium vanadium oxide for non-aqueous rechargeable battery, and non-aqueous rechargeable battery including same |
| JP2008103094A (en) * | 2006-10-17 | 2008-05-01 | Samsung Sdi Co Ltd | Non-aqueous secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2819201B2 (en) | 1998-10-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |