JPH05190205A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JPH05190205A JPH05190205A JP4001924A JP192492A JPH05190205A JP H05190205 A JPH05190205 A JP H05190205A JP 4001924 A JP4001924 A JP 4001924A JP 192492 A JP192492 A JP 192492A JP H05190205 A JPH05190205 A JP H05190205A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- secondary battery
- electrode
- lithium secondary
- active material
- 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
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
-
- 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)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、リチウムなどのアルカ
リ金属を負極活物質とするリチウム二次電池に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery using an alkali metal such as lithium as a negative electrode active material.
【０００２】[0002]
【従来の技術】電解液として有機電解液を用い、リチウ
ムなどのアルカリ金属を負極活物質とするリチウム二次
電池は、水溶液系の二次電池に比べてエネルギー密度が
高く、かつ低温特性が優れていることから注目を集めて
いる。2. Description of the Related Art A lithium secondary battery using an organic electrolyte as an electrolyte and an alkali metal such as lithium as a negative electrode active material has a higher energy density and excellent low temperature characteristics than an aqueous secondary battery. It's getting a lot of attention.
【０００３】しかしながら、充電によって生ずる活性な
リチウムが電解液の有機溶媒と反応することや、析出し
たリチウムがデンドライト状に成長し、析出リチウムと
溶媒との反応により絶縁層が形成されるために電子伝導
性のないリチウムが生成すること（Ｒ．Ｓｅｌｉｍ ａ
ｎｄ Ｂｒｏ，Ｊ．Ｅｌｅｃｔｒｏｃｈｅｍ．Ｓｏｃ，
１２１，１４５７（１９７４）など）により、リチウム
極の充放電効率が悪いという問題点がある。また、デン
ドライト状に成長したリチウムにより電池の内部短絡が
発生することなどの問題点もあり、実用的に十分なリチ
ウム二次電池は得られていない。However, the active lithium generated by charging reacts with the organic solvent of the electrolytic solution, and the deposited lithium grows in the form of dendrites, and the reaction between the deposited lithium and the solvent forms an insulating layer. Generation of non-conductive lithium (R. Selim a
nd Bro, J.D. Electrochem. Soc,
121, 1457 (1974)), there is a problem that the charge and discharge efficiency of the lithium electrode is poor. In addition, there is a problem that an internal short circuit of the battery occurs due to lithium grown in a dendrite shape, and a practically sufficient lithium secondary battery has not been obtained.
【０００４】従来、このようなリチウム二次電池におけ
るリチウム極の問題点を解決するために、リチウム極に
種々の合金、例えばＬｉ−Ａｌ合金（特開昭６３−１１
４０６２号、６３−２８５８７８号公報など）を用いる
ことや、電解液に種々の添加物、例えば有機Ｌｉ化合物
（特開平１−２８６２６２号公報）、ノニオン系界面活
性剤（特開平２−１２７７６号公報）、燐酸トリエチル
（特開平１−１０２８６２号公報）などを添加すること
が提案されている。Conventionally, in order to solve the problem of the lithium electrode in such a lithium secondary battery, various alloys such as Li-Al alloys have been added to the lithium electrode (Japanese Patent Laid-Open No. 63-11).
No. 4062, 63-285878, etc.), various additives to the electrolytic solution, such as an organic Li compound (JP-A-1-286262), and a nonionic surfactant (JP-A-2-12776). ), Triethyl phosphate (JP-A-1-102862) and the like have been proposed.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、前記提
案のリチウム二次電池においても、充電時にリチウム負
極上にデンドライト状のリチウムが析出し、セパレータ
を貫通して正極側に達し内部短絡が発生する課題や、充
電時に析出した活性なリチウムが電解液と反応すること
や、反応によって生じた絶縁性被膜のために析出したリ
チウムが電気的に孤立し、次の放電に用いられず充放電
効率が低下するという課題を有している。However, also in the above-mentioned proposed lithium secondary battery, dendrite-like lithium is deposited on the lithium negative electrode during charging, penetrates the separator and reaches the positive electrode side, and an internal short circuit occurs. Also, the active lithium deposited during charging reacts with the electrolytic solution, and the lithium deposited due to the insulating film formed by the reaction is electrically isolated and is not used for the next discharge, resulting in reduced charge / discharge efficiency. There is a problem of doing.
【０００６】本発明は上記従来の課題を解決するもの
で、充電時のリチウム極のデンドライト発生を抑制し、
リチウム極の充放電効率の良いリチウム二次電池を提供
することを目的とする。The present invention solves the above-mentioned conventional problems by suppressing the generation of dendrites at the lithium electrode during charging,
An object of the present invention is to provide a lithium secondary battery having a high charge / discharge efficiency of a lithium electrode.
【０００７】[0007]
【課題を解決するための手段】この目的を達成するため
に、本発明のリチウム二次電池は、リチウム金属または
リチウム合金を活物質とする負極と、有機電解液とセパ
レータを介して、金属酸化物、金属硫化物などを活物質
とする正極とからなるリチウム二次電池において、エチ
レンカーボネイト、プロピレンカーボネイト、ジメトキ
シエタンなどの有機溶媒に亜燐酸ジエステルを混合して
電解質の溶媒として用いたものである。In order to achieve this object, a lithium secondary battery of the present invention comprises a negative electrode using a lithium metal or a lithium alloy as an active material, an organic electrolytic solution and a separator, and a metal oxide. In a lithium secondary battery composed of a positive electrode containing a metal sulfide as an active material, a mixture of an organic solvent such as ethylene carbonate, propylene carbonate, or dimethoxyethane with a diester of phosphite is used as a solvent for the electrolyte. ..
【０００８】[0008]
【作用】亜燐酸ジエステルをエチレンカーボネイト、プ
ロピレンカーボネイトなどの有機溶媒と混合して電解液
の溶媒として用いることにより、カーボネイト系などの
従来の有機溶媒だけの場合とは異なったリチウムと電解
液の界面が形成され、リチウム極のデンドライト発生を
抑制し、析出リチウムと有機溶媒との反応を阻害するこ
とによりリチウム極の充放電効率を改善するものと考え
られる。リチウム二次電池を得ることができる。[Function] By mixing the phosphite diester with an organic solvent such as ethylene carbonate or propylene carbonate and using it as a solvent for the electrolytic solution, an interface between lithium and the electrolytic solution which is different from the case where only a conventional organic solvent such as a carbonate type is used. It is considered that the formation of the lithium electrode suppresses the generation of dendrites in the lithium electrode and inhibits the reaction between the deposited lithium and the organic solvent, thereby improving the charge / discharge efficiency of the lithium electrode. A lithium secondary battery can be obtained.
【０００９】[0009]
【実施例】以下本発明の実施例について、図を参照しな
がら説明する。Embodiments of the present invention will be described below with reference to the drawings.
【００１０】（実施例１）図１は、本発明の実施例に用
いた直径２０ｍｍ、高さ１．６ｍｍのコイン形電池の断
面図である。図中、１はステンレス製ケース、２はステ
ンレス製封口板、３は金属リチウムを活物質とする負極
で、封口板２の内面に圧着されている。４はポリプロピ
レン製セパレータである。５は二酸化マンガンを活物質
とする正極で、二酸化マンガンと、導電材のカーボンブ
ラックと、結着剤のフッ素樹脂を重量比８０：１０：１
０の配合比で混合し、直径１４．５ｍｍ、高さ０．８ｍ
ｍのペレット状に成型したものである。６はポリプロピ
レン製ガスケットである。電解液はエチレンカーボネイ
ト（ＥＣ）と、ジメトキシエタン（ＤＭＥ）と、亜燐酸
ジエステルの一種である亜燐酸ジエチルを体積比６０：
３９：１の配合比で混合した混合溶媒に、電解質として
過塩素酸リチウム（ＬｉＣｌＯ4 ）を１モル／ｌの濃度
に溶解したものである。(Embodiment 1) FIG. 1 is a sectional view of a coin type battery used in an embodiment of the present invention and having a diameter of 20 mm and a height of 1.6 mm. In the figure, 1 is a case made of stainless steel, 2 is a sealing plate made of stainless steel, 3 is a negative electrode whose active material is metallic lithium, and is pressure-bonded to the inner surface of the sealing plate 2. 4 is a polypropylene separator. Reference numeral 5 is a positive electrode using manganese dioxide as an active material. Manganese dioxide, carbon black as a conductive material, and fluororesin as a binder are in a weight ratio of 80: 10: 1.
Mixing at a compounding ratio of 0, diameter 14.5 mm, height 0.8 m
m pellets. 6 is a polypropylene gasket. The electrolytic solution contained ethylene carbonate (EC), dimethoxyethane (DME), and diethyl phosphite, which is a kind of phosphorous acid diester, in a volume ratio of 60:
Lithium perchlorate (LiClO 4 ) as an electrolyte was dissolved at a concentration of 1 mol / l in a mixed solvent mixed at a compounding ratio of 39: 1.
【００１１】（実施例２）電解液として、混合溶媒をエ
チレンカーボネイト（ＥＣ）と、ジメトキシエタン（Ｄ
ＭＥ）と、亜燐酸ジエチルを体積比６０：３０：１０の
配合比で混合したものを用いたこと以外は実施例１と同
一の構成とした。Example 2 As an electrolytic solution, a mixed solvent of ethylene carbonate (EC) and dimethoxyethane (D) was used.
ME) and diethyl phosphite were mixed at a volume ratio of 60:30:10, and the same constitution as in Example 1 was used.
【００１２】（実施例３）電解液として、混合溶媒をエ
チレンカーボネイト（ＥＣ）と、ジメトキシエタン（Ｄ
ＭＥ）と、亜燐酸ジエチルを体積比６０：２０：２０の
配合比で混合したものを用いたこと以外は実施例１と同
一の構成とした。Example 3 As an electrolytic solution, a mixed solvent of ethylene carbonate (EC) and dimethoxyethane (D) was used.
ME) and diethyl phosphite were mixed at a volume ratio of 60:20:20, and the same configuration as in Example 1 was used.
【００１３】（従来例）電解液として、混合溶媒をエチ
レンカーボネイト（ＥＣ）と、ジメトキシエタン（ＤＭ
Ｅ）を体積比６０：４０の配合比で混合したものを用い
たこと以外は実施例１と同一の構成とした。(Conventional example) As an electrolytic solution, a mixed solvent of ethylene carbonate (EC) and dimethoxyethane (DM)
The same configuration as in Example 1 was used, except that E) was mixed at a mixing ratio of 60:40 by volume.
【００１４】図２は、上記実施例１〜３と従来例の電池
を２０°Ｃ、０．５ｍＡの定電流で充放電サイクルを行
った際の放電容量（カット電圧２．０Ｖ）と充放電サイ
クルの関係を示したものである。図２から明らかなよう
に、亜燐酸ジエチルを混合した本発明の実施例はいずれ
も、充放電サイクルによる放電容量の劣化が従来例より
も改良されていること、即ち、リチウム極の充放電効率
が向上していることが分かる。FIG. 2 shows the discharge capacity (cut voltage 2.0 V) and charge / discharge when the batteries of Examples 1 to 3 and the conventional example were subjected to a charge / discharge cycle at a constant current of 20 ° C. and 0.5 mA. It shows the relationship of cycles. As is clear from FIG. 2, in all the examples of the present invention in which diethyl phosphite was mixed, the deterioration of the discharge capacity due to the charge / discharge cycle was improved as compared with the conventional example, that is, the charge / discharge efficiency of the lithium electrode. It can be seen that has improved.
【００１５】亜燐酸ジエチルを混合することによって、
リチウム極の充放電効率が向上する理由はまだ不明であ
るが、リチウム極が電解液と接する界面の状態、あるい
はリチウムと電解液が反応して形成されるリチウムの表
面被膜の状態が従来例の場合と異なっているためと考え
られる。By mixing with diethyl phosphite,
Although the reason why the charge and discharge efficiency of the lithium electrode is improved is still unknown, the state of the interface where the lithium electrode contacts the electrolytic solution or the state of the surface coating film of lithium formed by the reaction between the lithium electrode and the electrolytic solution is not known. This is probably because it is different from the case.
【００１６】また、図２から明らかなように、亜燐酸ジ
エチルを混合することによるリチウム極の充放電効率を
向上させる効果は、１〜２０体積％の範囲が好ましく、
５〜１５体積％の範囲がより好ましいことが分かる。As is apparent from FIG. 2, the effect of improving the charge / discharge efficiency of the lithium electrode by mixing diethyl phosphite is preferably in the range of 1 to 20% by volume,
It can be seen that the range of 5 to 15% by volume is more preferable.
【００１７】なお、本実施例では亜燐酸ジエステルとし
て亜燐酸ジエチルを用いたが、亜燐酸ジメチル、亜燐酸
ジブチル、亜燐酸ジイソプロピル、亜燐酸ジフェニルな
どを用いてもよい。また、混合溶媒としても本実施例の
エチレンカーボネイト、ジメトキシエタン以外のプロピ
レンカーボネイト、２−メチルテトラハイドロフラン、
ジエチレンカーボネイト、γ−ブチロラクトン、１，３
−ジオキソランなどを用いてもよい。また同様に電解質
も本実施例の過塩素酸リチウム（ＬｉＣｌＯ4 ）以外の
６フッ化リン酸リチウム（ＬｉＰＦ6 ），トリフロロメ
タンスルホン酸リチウム（ＬｉＣＦ3 ＳＯ3 ）などを用
いてもよい。さらに、Ｌｉ−Ａｌなどの合金を負極活物
質とし、ＬｉＣｏＯ2 やＭｏＳ2 などを正極活物質とし
て用いることも可能である。Although diethyl phosphite is used as the phosphite diester in this embodiment, dimethyl phosphite, dibutyl phosphite, diisopropyl phosphite, diphenyl phosphite, etc. may be used. Further, as a mixed solvent, ethylene carbonate of the present example, propylene carbonate other than dimethoxyethane, 2-methyltetrahydrofuran,
Diethylene carbonate, γ-butyrolactone, 1,3
-Dioxolane or the like may be used. Similarly, as the electrolyte, lithium hexafluorophosphate (LiPF 6 ) other than lithium perchlorate (LiClO 4 ) of the present embodiment, lithium trifluoromethanesulfonate (LiCF 3 SO 3 ) or the like may be used. Further, an alloy such as Li-Al can be used as the negative electrode active material, and LiCoO 2 , MoS 2 or the like can be used as the positive electrode active material.
【００１８】[0018]
【発明の効果】このように本発明は、リチウム金属また
はリチウム合金からなる負極と有機電解液とセパレータ
を介して、金属酸化物または金属硫化物を活物質とする
正極とからなるリチウム二次電池において、上記有機電
解液に亜燐酸ジエステルを含有させることにより、リチ
ウム極の充放電効率を向上させ、充放電サイクル特性の
優れたリチウム二次電池を得ることができるものであ
る。As described above, the present invention provides a lithium secondary battery comprising a negative electrode made of lithium metal or a lithium alloy, an organic electrolyte and a positive electrode having a metal oxide or a metal sulfide as an active material via a separator. In the above, by adding phosphite diester to the above-mentioned organic electrolytic solution, the charge / discharge efficiency of the lithium electrode can be improved and a lithium secondary battery having excellent charge / discharge cycle characteristics can be obtained.
【図１】本発明リチウム二次電池の一実施例の断面図FIG. 1 is a sectional view of an embodiment of a lithium secondary battery of the present invention.
【図２】本発明の実施例と従来例によるリチウム二次電
池の充放電サイクル特性図FIG. 2 is a charge / discharge cycle characteristic diagram of lithium secondary batteries according to an example of the present invention and a conventional example.
１ ケース ２ 封口板 ３ 負極 ４ セパレータ ５ 正極 ６ ガスケット 1 Case 2 Sealing Plate 3 Negative Electrode 4 Separator 5 Positive Electrode 6 Gasket
Claims (2)
質とする負極と、有機電解液とセパレータを介して、金
属酸化物、金属硫化物などを活物質とする正極とからな
るリチウム二次電池において、上記電解液は亜燐酸ジエ
ステルを含有していることを特徴とするリチウム二次電
池。1. A lithium secondary battery comprising a negative electrode using lithium metal or a lithium alloy as an active material, and a positive electrode using a metal oxide, a metal sulfide or the like as an active material via an organic electrolytic solution and a separator, The lithium secondary battery, wherein the electrolytic solution contains a phosphorous acid diester.
含有率は１〜２０体積％であることを特徴とする請求項
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 the phosphite diester in the electrolytic solution is 1 to 20% by volume.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4001924A JPH05190205A (en) | 1992-01-09 | 1992-01-09 | Lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4001924A JPH05190205A (en) | 1992-01-09 | 1992-01-09 | Lithium secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05190205A true JPH05190205A (en) | 1993-07-30 |
Family
ID=11515150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4001924A Pending JPH05190205A (en) | 1992-01-09 | 1992-01-09 | Lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05190205A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0917224A1 (en) * | 1997-11-05 | 1999-05-19 | Wilson Greatbatch Ltd. | Phosphonate additives for non-aqueous electrolyte in alkali metal electrochemical cells |
| US6200701B1 (en) | 1999-01-25 | 2001-03-13 | Wilson Greatbatch Ltd. | Phosphonate additives for nonaqueous electrolyte in rechargeable cells |
| US6495285B2 (en) | 1999-01-25 | 2002-12-17 | Wilson Greatbatch Ltd. | Phosphonate additives for nonaqueous electrolyte in rechargeable electrochemical cells |
| US6537698B2 (en) | 2001-03-21 | 2003-03-25 | Wilson Greatbatch Ltd. | Electrochemical cell having an electrode with a phosphonate additive in the electrode active mixture |
| JP2008041635A (en) * | 2006-07-13 | 2008-02-21 | Sony Corp | Nonaqueous electrolyte composition, and nonaqueous electrolyte secondary battery |
-
1992
- 1992-01-09 JP JP4001924A patent/JPH05190205A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0917224A1 (en) * | 1997-11-05 | 1999-05-19 | Wilson Greatbatch Ltd. | Phosphonate additives for non-aqueous electrolyte in alkali metal electrochemical cells |
| US6096447A (en) * | 1997-11-05 | 2000-08-01 | Wilson Greatbatch Ltd. | Phosphonate additives for nonaqueous electrolyte in alkali metal electrochemical cells |
| US6200701B1 (en) | 1999-01-25 | 2001-03-13 | Wilson Greatbatch Ltd. | Phosphonate additives for nonaqueous electrolyte in rechargeable cells |
| US6495285B2 (en) | 1999-01-25 | 2002-12-17 | Wilson Greatbatch Ltd. | Phosphonate additives for nonaqueous electrolyte in rechargeable electrochemical cells |
| US6537698B2 (en) | 2001-03-21 | 2003-03-25 | Wilson Greatbatch Ltd. | Electrochemical cell having an electrode with a phosphonate additive in the electrode active mixture |
| JP2008041635A (en) * | 2006-07-13 | 2008-02-21 | Sony Corp | Nonaqueous electrolyte composition, and nonaqueous electrolyte secondary battery |
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