JP2975627B2 - Battery - Google Patents
BatteryInfo
- Publication number
- JP2975627B2 JP2975627B2 JP2074442A JP7444290A JP2975627B2 JP 2975627 B2 JP2975627 B2 JP 2975627B2 JP 2074442 A JP2074442 A JP 2074442A JP 7444290 A JP7444290 A JP 7444290A JP 2975627 B2 JP2975627 B2 JP 2975627B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- battery
- active material
- electrolyte
- negative electrode
- 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 - Fee Related
Links
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
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】 （イ）産業上の利用分野 本発明は、リチウム又はリチウムを含む合金を活物質
とする負極と、三酸化モリブデン、五酸化バナジウム、
チタン、或るいはニオブの酸化物、セレン化物、二酸化
マンガン、二酸化コバルト、或るいはそれらとリチウム
との化合物などを活物質とする正極と、少なくとも一つ
の溶媒とからなる非水電解液とを備えた非水電解液二次
電池に関するものである。DETAILED DESCRIPTION OF THE INVENTION (A) Industrial application field The present invention relates to a negative electrode using lithium or an alloy containing lithium as an active material, molybdenum trioxide, vanadium pentoxide,
A nonaqueous electrolyte comprising a positive electrode having titanium, or an oxide of niobium, selenide, manganese dioxide, cobalt dioxide, or a compound of lithium with them as an active material, and at least one solvent. The present invention relates to a non-aqueous electrolyte secondary battery provided.
（ロ）従来の技術 上記の電池は放電時にイオンとなって溶出したリチウ
ムが充電時に金属リチウムとして負極表面に電析するの
であるが、この電析リチウムは表面積の大なる微粒子状
であるため活性度が高く、そのため非水電解液を構成す
る溶媒と反応して溶媒を分解し非水電解液を劣化させる
に至り充放電サイクル特性が悪いという欠点があった。(B) Conventional technology In the above-mentioned battery, lithium eluted as ions during discharging is deposited on the negative electrode surface as metallic lithium during charging. However, since the deposited lithium is in the form of fine particles having a large surface area, it is active. Therefore, it has a drawback that it reacts with the solvent constituting the non-aqueous electrolyte to decompose the solvent and deteriorate the non-aqueous electrolyte, resulting in poor charge / discharge cycle characteristics.
又、充電時にリチウムがデンドライド状に析出し、こ
れが正極に達し、内部短絡が生じ、電池特性が劣化する
という問題点があった。In addition, there is a problem that lithium precipitates in a dendritic state during charging, reaches the positive electrode, causes an internal short circuit, and deteriorates battery characteristics.
これを解決する方法として電解液中にクラウンエーテ
ルを添加する技術（特公昭58−12992号公報）や、フェ
ノール誘導体を添加する技術（特公昭56−22112号公
報）が提案されているが、いずれも実用化には至ってい
ない。As a method for solving this, a technique of adding a crown ether to an electrolytic solution (Japanese Patent Publication No. 58-12992) and a technique of adding a phenol derivative (Japanese Patent Publication No. 56-22112) have been proposed. Has not yet been put to practical use.
（ハ）発明が解決しようとする課題 本発明が解決しようとする課題は電解液中に今まで使
われていなかった添加剤を用いて負極であるリチウムの
充電効率を向上させ、電池のサイクル特性を改善するこ
とである。(C) Problems to be Solved by the Invention Problems to be solved by the present invention are to improve the charge efficiency of lithium as a negative electrode by using an additive which has not been used in the electrolyte solution, and to improve the cycle characteristics of the battery. Is to improve.
（ニ）課題を解決するための手段 第１の発明は、リチウム、又はリチウムを含む合金を
活物質とする負極と、二酸化モリブデン、又は五酸化バ
ナジウム、又はニオブの酸化物、又はセレン化物、又は
二酸化マンガン、又は二酸化コバルト、或いはこれらの
物質とリチウムとの化合物を活物質とする正極と、電解
液とより成り、前記電解液中にチオ尿素 を添加してなる電池である。(D) Means for Solving the Problems The first invention is directed to a negative electrode containing lithium or an alloy containing lithium as an active material, and an oxide or selenide of molybdenum dioxide, vanadium pentoxide, or niobium, or A positive electrode having manganese dioxide or cobalt dioxide, or a compound of these substances and lithium as an active material, and an electrolytic solution, wherein thiourea is contained in the electrolytic solution; Is a battery obtained by adding
第２の発明はリチウム、又はリチウムを含む合金を活
物質とする負極と、二酸化モリブデン、又は五酸化バナ
ジウム、又はニオブの酸化物、又はセレン化物、又は二
酸化マンガン、又は二酸化コバルト、或いはこれらの物
質とリチウムとの化合物を活物質とする正極と、電解液
とより成り、前記電解液中に一般式 （R1、R2は水素またはアルキル基）で表わされる添加剤
を添加してなる電池である。A second invention provides a negative electrode using lithium or an alloy containing lithium as an active material, and an oxide or selenide of molybdenum dioxide, vanadium pentoxide, or niobium, or manganese dioxide, or cobalt dioxide, or a material thereof. A positive electrode comprising a compound of and lithium as an active material, and an electrolyte, wherein the electrolyte has a general formula (R 1 and R 2 are hydrogen or an alkyl group).
第３の発明は上記添加剤の添加量が0.01vol％以上で
あることを特徴とする電池である。A third invention is a battery characterized in that the amount of the additive is 0.01 vol% or more.
第４の発明は上記添加剤の添加量が0.01vol％以上20v
ol％以下であることを特徴とする電池である。In the fourth invention, the amount of the additive is 0.01 vol% or more and 20 v
ol% or less.
第５の発明は上記負極は、リチウム、リチウム合金、
リチウム−炭素化合物より選択される少なくとも１種類
の材料によって形成されることを特徴とする電池であ
る。In a fifth aspect, the negative electrode is lithium, a lithium alloy,
A battery formed of at least one material selected from lithium-carbon compounds.
（ホ）作用 上記構成の如く、チオ尿素、アニスアルデヒド等の添
加剤を電解液中に添加すると、リチウムイオンが容易に
溶媒和（イオンの周りに溶媒分子がくっつく状態）し、
このため充電時にリチウムが、リチウム金属、リチウム
合金またはリチウム−炭素化合物からなる負極上に析出
する際にこれらの添加剤も取り込まれ、電析状態が変化
し、デンドライトの生成が抑制され、充放電効率を向上
させる。(E) Action As described above, when additives such as thiourea and anisaldehyde are added to the electrolyte, lithium ions easily solvate (solvent molecules adhere around the ions),
Therefore, when lithium is deposited on a negative electrode made of a lithium metal, a lithium alloy or a lithium-carbon compound during charging, these additives are also taken in, and the state of electrodeposition changes, dendrite generation is suppressed, and charge / discharge is suppressed. Improve efficiency.
又、電析リチウムの電解液溶媒や、電解液溶質との反
応も緩和し、非導電性被膜の形成を抑制し、電池のサイ
クル特性が向上する。In addition, the reaction of the deposited lithium with the electrolyte solvent or the electrolyte solute is also moderated, the formation of a non-conductive film is suppressed, and the cycle characteristics of the battery are improved.
（ヘ）実施例 以下本発明を実施例について図面に基づき詳細に説明
する。(F) Example Hereinafter, the present invention will be described in detail with reference to examples with reference to the drawings.
第１図は電池の判断面図を示し、（１）（２）はステ
ンレス製の正、負極缶であって、ポリプロピレンよりな
る絶縁パッキング（３）により隔離されている。FIG. 1 shows a judgment view of a battery. (1) and (2) are stainless steel positive and negative electrode cans, which are separated by an insulating packing (3) made of polypropylene.
（４）はリチウム圧延板よりなる負極であって、前記
負極缶（２）の内底面に固着せる負極集電体（５）に圧
着されている。Reference numeral (4) denotes a negative electrode made of a rolled lithium plate, which is pressed to a negative electrode current collector (5) fixed to the inner bottom surface of the negative electrode can (2).
（６）は正極であって二酸化マンガンとリチウムとの
焼成体よりなる活物質に導電剤としてのアセチレンブラ
ック、及び結着剤としてのフッ素樹脂粉末を重量比で8
0:10:10の割合で混合した合剤を正極固定用リング
（７）内に成形してなり、正極缶（１）の内定面に固着
した正極集電体（８）に圧接されている。(6) is a positive electrode comprising an active material composed of a fired body of manganese dioxide and lithium, acetylene black as a conductive agent and fluororesin powder as a binder in a weight ratio of 8%.
The mixture mixed at a ratio of 0:10:10 is formed into a positive electrode fixing ring (7), and is pressed against a positive electrode current collector (8) fixed to a fixed surface of a positive electrode can (1). .
（９）はポリプロピレン不織布よりなるセパレータで
あって、このセパレータに後述の電解液が含浸されてい
る。(9) is a separator made of a polypropylene nonwoven fabric, and this separator is impregnated with an electrolytic solution described later.
［作製例１］ 電解液として、LiPF6が1mol/となるように溶解して
作製したブチレンカーボネートと、２メチル−テトラヒ
ドロフランとの等体積混合溶媒を用い、この溶媒にチオ
尿素を0vol％から20vol％まで添加した電解液を用いて
Ａ−１〜Ａ−９の電池を作製した。[Preparation Example 1] As an electrolytic solution, a mixed solvent of butylene carbonate prepared by dissolving LiPF 6 at a concentration of 1 mol / and 2 methyl-tetrahydrofuran was used. %, And the batteries A-1 to A-9 were produced using the electrolyte solution added up to%.
表−１にこれら電池についての添加剤の濃度と充放電
サイクル特性との関係を示す。この時の実験条件は、各
電池を、放電は2mAで電池電圧が2.0Vとなるまで行い、
充電は2mAで電池電圧が3.5Vとなるまで行い、初期の放
電容量の1/2に達した時点をサイクル寿命とするもので
ある。Table 1 shows the relationship between the additive concentration and the charge / discharge cycle characteristics for these batteries. The experimental conditions at this time were as follows: each battery was discharged until the battery voltage reached 2.0 V at 2 mA.
Charging is performed at 2 mA until the battery voltage reaches 3.5 V, and the point in time when half of the initial discharge capacity is reached is defined as the cycle life.
上記の表−１から電解液中に適度（0.01〜20vol％）
のチオ尿素を添加することは電池のサイクル寿命に好影
響を与えることが分かる。 From Table 1 above, appropriate in electrolyte (0.01-20 vol%)
It can be seen that the addition of thiourea has a favorable effect on the cycle life of the battery.
又、チオ尿素の添加量は、0.1〜20vol％が望ましく、
更に、1.0〜5.0vol％のときに最もサイクル寿命が長い
ことが明らかである。Also, the addition amount of thiourea is preferably 0.1 to 20 vol%,
Further, it is clear that the cycle life is the longest when 1.0 to 5.0 vol%.
［作製例２］ 電解液として、LiAsF6が1mol/となるように溶解し
て作製した４メチル−1,3ジオキソランと、ジメトキシ
エタンとの等体積混合溶媒を用い、この溶媒にパラ−ア
ニスアルデヒドを0vol％から20vol％まで添加した電解
液を用いてＢ−１〜Ｂ−９の電池を作製した。[Preparation Example 2] As an electrolytic solution, an equal volume mixed solvent of 4-methyl-1,3 dioxolane prepared by dissolving LiAsF 6 at 1 mol / and dimethoxyethane was used, and para-anisaldehyde was used as the solvent. B-1 to B-9 were prepared using an electrolytic solution containing 0 to 20 vol% of the compound (A).
表−２にこれら電池についての添加剤の濃度と充放電
サイクル特性との関係を示す。尚、ここでの充放電のプ
ロセスも前述の作製例１と同様に設定した。Table 2 shows the relationship between the additive concentration and the charge / discharge cycle characteristics for these batteries. The charge / discharge process was set in the same manner as in Production Example 1 described above.
上記の表−２から電解液中に適度（0.01〜20vol％）
のアニスアルデヒドを添加することは電池のサイクル寿
命に好影響を与えることが分かる。 From Table 2 above, moderate in electrolyte (0.01-20 vol%)
It can be seen that the addition of anisaldehyde has a positive effect on the cycle life of the battery.
又、アニスアルデヒドの添加量は、0.1〜20vol％が望
ましく、更に、1.0〜5.0vol％のときに最もサイクル寿
命が長いことが明らかである。Further, it is clear that the addition amount of anisaldehyde is desirably 0.1 to 20 vol%, and that the cycle life is the longest when it is 1.0 to 5.0 vol%.
ところで、作製例２においてパラ−アニスアルデヒド を例示したが、この他に、 等でも有効である。By the way, in Preparation Example 2, para-anisaldehyde was used. Was exemplified, but in addition to this, Is also effective.
更に、上記各作製例において、電解液溶媒としてプロ
ピレンカーボネート、エチレンカーボネート、２−メチ
ル−テトラヒドロフラン、４メチル−1,3−ジオキソラ
ン、ジメトキシエタンを例示し、又電解質としてLiCl
O4,LiAsF6,LiPF6を例示したが、これらに限定されるも
のではない。Further, in each of the above production examples, propylene carbonate, ethylene carbonate, 2-methyl-tetrahydrofuran, 4-methyl-1,3-dioxolan, and dimethoxyethane are exemplified as the electrolyte solvent, and LiCl is used as the electrolyte.
O 4 , LiAsF 6 , and LiPF 6 are exemplified, but are not limited thereto.
即ち、上記溶媒の他に、1,3−ジオキソラン,2メチル
−1,3−ジオキソラン、テトラヒドロフラン、スルフォ
ラン、３メチル−スルフォラン、ジメチルスルフォキシ
ド、ビニレンカーボネート、ジエトキシエタン、オルト
ギ酸メチル等の溶媒が使用可能である。又、上記電解質
の他に、 LiCF3SO3、LiBF4、LiSbF6、 LiAlCl4、Li3AlF6 等が使用可能である。That is, in addition to the above solvents, solvents such as 1,3-dioxolan, 2-methyl-1,3-dioxolan, tetrahydrofuran, sulfolane, 3methyl-sulfolane, dimethyl sulfoxide, vinylene carbonate, diethoxyethane, methyl orthoformate, and the like. Can be used. In addition to the above electrolyte, LiCF 3 SO 3 , LiBF 4 , LiSbF 6 , LiAlCl 4 , Li 3 AlF 6 and the like can be used.
又、更に、第１図には本発明の１実施例として、扁平
型電池を例示してあるが、角型電池や、円筒型電池にも
応用できることは言うまでもない。Further, FIG. 1 illustrates a flat battery as an embodiment of the present invention, but it goes without saying that the present invention can be applied to a square battery and a cylindrical battery.
（ト）発明の効果 本発明は以上の説明の如く、電解液に、チオ尿素、 或いは、アニスアルデヒド等の一般式 で表わされる添加剤を添加することにより、電池の充放
電サイクル特性が著しく向上する。(G) Effect of the Invention As described above, the present invention provides a method for preparing a thiourea, Or a general formula such as anisaldehyde By adding the additive represented by the formula, the charge / discharge cycle characteristics of the battery are significantly improved.
この理由はリチウムの電析時に、これら添加物が取り
込まれ、リチウム局の表面形態に影響を与え、充放電効
率が向上し、又、電解液溶媒や、よ溶質とリチウムとの
反応性を緩和するためであると考えられる。The reason for this is that these additives are taken in during the deposition of lithium, affecting the surface morphology of the lithium terminal, improving the charge and discharge efficiency, and reducing the reactivity between the electrolyte solvent and the solute and the lithium with the solute. It is thought to be.
以上のように本発明によれば、充放電サイクル寿命が
極めて長い電池を得ることが可能となり、工業的価値の
極めて高い電池が得られる。As described above, according to the present invention, it is possible to obtain a battery having an extremely long charge / discharge cycle life, and to obtain a battery having extremely high industrial value.
【図面の簡単な説明】 第１図は本発明電池の半断面図、第２図及び第３図は夫
々種々の添加剤の添加量と充放電サイクル特性との関係
を示す図である。 （１）……正極缶、 （２）……負極缶、 （３）……絶縁パッキング、 （４）……負極、 （６）……正極、 （９）……セパレータ。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a half sectional view of the battery of the present invention, and FIGS. 2 and 3 are diagrams each showing the relationship between the amount of various additives added and the charge / discharge cycle characteristics. (1) Positive electrode can, (2) Negative electrode can, (3) Insulating packing, (4) Negative electrode, (6) Positive electrode, (9) Separator.
フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) H01M 10/40 Continuation of front page (58) Field surveyed (Int.Cl. 6 , DB name) H01M 10/40
Claims (5)
質とする負極と、二酸化モリブデン、又は五酸化バナジ
ウム、又はニオブの酸化物、又はセレン化物、又は二酸
化マンガン、又は二酸化コバルト、或いはこれらの物質
とリチウムとの化合物を活物質とする正極と、電解液と
よりなり、前記電解液中にチオ尿素 を添加してなる電池。1. A negative electrode comprising lithium or an alloy containing lithium as an active material, and an oxide or selenide of molybdenum dioxide, vanadium pentoxide, or niobium, or manganese dioxide, or cobalt dioxide, or a material thereof. And a positive electrode having a compound of lithium and an active material as an active material, and thiourea in the electrolytic solution. The battery which added.
質とする負極と、二酸化モリブデン、又は五酸化バナジ
ウム、又はニオブの酸化物、又はセレン化物、又は二酸
化マンガン、又は二酸化コバルト、或いはこれらの物質
とリチウムとの化合物を活物質とする正極と、電解液と
よりなり、前記電解液中に一般式 （R1、R2は水素またはアルキル基）で表わされる添加剤
を添加してなる電池。2. A negative electrode comprising lithium or an alloy containing lithium as an active material, and an oxide or selenide of molybdenum dioxide, vanadium pentoxide, or niobium, manganese dioxide, or cobalt dioxide, or a material thereof. A positive electrode having a compound of lithium and an active material as an active material, and an electrolyte, wherein the electrolyte has a general formula A battery comprising an additive represented by the formula (R 1 and R 2 are hydrogen or an alkyl group).
あることを特徴とする請求項または記載の電池。3. The battery according to claim 1, wherein the amount of the additive is 0.01 vol% or more.
ol％以下であることを特徴とする請求項またはまた
は記載の電池。4. The method according to claim 1, wherein the amount of the additive is 0.01 vol% or more and 20 v
ol% or less.
チウム−炭素化合物より選択される少なくとも１種類の
材料によって形成されることを特徴とする請求項また
はまたはまたは記載の電池。5. The battery according to claim 1, wherein the negative electrode is formed of at least one material selected from lithium, a lithium alloy, and a lithium-carbon compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2074442A JP2975627B2 (en) | 1990-03-23 | 1990-03-23 | Battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2074442A JP2975627B2 (en) | 1990-03-23 | 1990-03-23 | Battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03285271A JPH03285271A (en) | 1991-12-16 |
| JP2975627B2 true JP2975627B2 (en) | 1999-11-10 |
Family
ID=13547354
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2074442A Expired - Fee Related JP2975627B2 (en) | 1990-03-23 | 1990-03-23 | Battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2975627B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1172878B1 (en) * | 2000-07-14 | 2011-06-22 | Mitsubishi Chemical Corporation | Non-aqueous electrolytic solution and secondary battery containing same |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4934919B2 (en) * | 2000-07-14 | 2012-05-23 | 三菱化学株式会社 | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery |
| CN109256587A (en) * | 2018-07-18 | 2019-01-22 | 青海泰丰先行锂能科技有限公司 | Lithium metal secondary battery electrolyte and the lithium metal secondary battery for using the electrolyte |
| CN114631216A (en) * | 2019-11-05 | 2022-06-14 | 国立大学法人九州大学 | Electrolyte solution |
-
1990
- 1990-03-23 JP JP2074442A patent/JP2975627B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1172878B1 (en) * | 2000-07-14 | 2011-06-22 | Mitsubishi Chemical Corporation | Non-aqueous electrolytic solution and secondary battery containing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03285271A (en) | 1991-12-16 |
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