JPH01186563A - Nonaqueous electrolyte cell - Google Patents
Nonaqueous electrolyte cellInfo
- Publication number
- JPH01186563A JPH01186563A JP433288A JP433288A JPH01186563A JP H01186563 A JPH01186563 A JP H01186563A JP 433288 A JP433288 A JP 433288A JP 433288 A JP433288 A JP 433288A JP H01186563 A JPH01186563 A JP H01186563A
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- battery
- lithium
- mixed
- solute
- 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
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 11
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 239000012046 mixed solvent Substances 0.000 claims abstract description 15
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims abstract description 12
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 229910000733 Li alloy Inorganic materials 0.000 claims description 4
- 239000001989 lithium alloy Substances 0.000 claims description 4
- 238000009413 insulation Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 6
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 5
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- -1 r-butyrolactone Chemical compound 0.000 description 2
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
イ、産業上の利用分野
本発明はリチウム或いはリチウム合金からなる負極と、
金属の酸化物、硫化物、ノ１０ゲン化物などを活物質と
する正極と、溶媒と溶質とからなる非水電解液とを備え
た非水電解液電池に関するものである。DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention provides a negative electrode made of lithium or a lithium alloy;
The present invention relates to a non-aqueous electrolyte battery that includes a positive electrode that uses a metal oxide, sulfide, oxide, or the like as an active material, and a non-aqueous electrolyte that includes a solvent and a solute.
口、従来の技術
この種電池に用いられる非水電解液を構成する溶媒及び
溶質としては例えば特公昭４５−４００４１号公報或い
は特公昭５７−５２８６６号公報などく開示されている
ように種々のものが知られている。具体的には溶媒とし
てプロピレンカーボネート、ｒ−ブチロラクトン、ジメ
トキシエタン、テトラハイドロ７ラン、ジオキソランな
ど、又溶質として過塩素酸リチウム、ホウ７ツ化リチウ
ム、塩化リチウム、トリフルオロメタンスルホン酸リチ
ウムなどである。BACKGROUND OF THE INVENTION As the solvent and solute constituting the non-aqueous electrolyte used in this type of battery, various solvents and solutes are disclosed, for example, in Japanese Patent Publication No. 45-40041 and Japanese Patent Publication No. 57-52866. It has been known. Specifically, the solvents include propylene carbonate, r-butyrolactone, dimethoxyethane, tetrahydro7rane, dioxolane, etc., and the solutes include lithium perchlorate, lithium boro7trate, lithium chloride, lithium trifluoromethanesulfonate, and the like.
ハ６発明が解決しようとする課題
近年に至って、この種電池の適用分野の拡大に伴い電池
特性の改善が望まれており、その一つとして低温数！特
性の向上が要望されている。C.6 Problems to be Solved by the Invention In recent years, as the field of application of this type of battery has expanded, improvements in battery characteristics have been desired, and one of these is the improvement of low-temperature numbers! There is a demand for improved characteristics.
この種電池を放電すると放電に伴いリチウム負極表面の
リチウムイオン濃度が大きくなる。低温下においては溶
媒に対する溶質の溶解度が小さいため溶質がリチウム負
極表面上に析出し、リチウム負極の有効反応面積が減じ
られることになる。When this type of battery is discharged, the lithium ion concentration on the surface of the lithium negative electrode increases as the battery discharges. At low temperatures, the solubility of the solute in the solvent is low, so the solute precipitates on the surface of the lithium negative electrode, reducing the effective reaction area of the lithium negative electrode.
本発明は上記課題を解決することを目的とする。The present invention aims to solve the above problems.
二０課題を解決するための手段
本発明はリチウム或いはリチウム合金からなる負極と、
正極と、溶媒と溶質とからなる非水電解液とを備えた非
水電解液電池において、溶媒として少くともスルホラン
と１．３ジオキソランとを含む混合溶媒を用いることを
要旨とするものである。20 Means for Solving the Problems The present invention provides a negative electrode made of lithium or a lithium alloy,
The gist of the present invention is to use a mixed solvent containing at least sulfolane and 1.3 dioxolane as a solvent in a non-aqueous electrolyte battery comprising a positive electrode and a non-aqueous electrolyte consisting of a solvent and a solute.
ホ０作 用
低温放電特性の向上を計るには溶解度の大きい溶媒を用
いることが考えられる。一般に高粘度の溶媒は溶解度が
大きいことが知られている。しかしながら溶解速度が遅
いため高粘度溶媒単独では溶質の析出が生じるため低粘
度溶媒と組合せることが考えられる。In order to improve the low-temperature discharge characteristics, it is possible to use a solvent with high solubility. It is generally known that high viscosity solvents have high solubility. However, since the dissolution rate is slow and a high viscosity solvent alone causes precipitation of the solute, it may be considered to combine it with a low viscosity solvent.
そこで、種々の溶媒の組合せが考えられるが、本発明者
等は高粘度溶媒としてスルホランを用い、種々の低粘度
溶媒を組合せて鋭意検討し九ところ、低粘度溶媒として
１．３ジオキンランを用いた場合に、全く予想もしない
優れた特性を示すことがわかっ九。Therefore, various combinations of solvents can be considered, but the present inventors used sulfolane as a high viscosity solvent and conducted extensive studies on combinations of various low viscosity solvents, and finally decided to use 1.3 dioquinrane as a low viscosity solvent. In some cases, it has been found to exhibit excellent properties that were completely unexpected.
へ、実施例 以下本発明の実施例について詳述する。To, Example Examples of the present invention will be described in detail below.
溶媒としてスルホランと１．６ジオキソランとを１：１
の体積比で混合した混合溶媒を用い、この混合溶媒に溶
質として過塩素酸リチウムを１−ｗ／１溶解したものを
電解液とする。1:1 sulfolane and 1.6 dioxolane as solvents
Using a mixed solvent mixed at a volume ratio of , an electrolyte solution is prepared by dissolving 1-w/1 lithium perchlorate as a solute in this mixed solvent.
正極は３５０〜４′５０℃の温度範囲で熱処理した二酸
化マンガンを活物質としこの二酸化マンガンと、導電剤
としてのカーボン粉末及び結着剤としてのフッ素樹脂粉
末とを８５ ： １０ ： ５’の重量比で混合した混
合物を加圧成形し２５０〜５５０℃で熱処理したものを
用い、又負極はリチウム圧延板を所定寸夫に打抜いたも
のを用いて径２０．０鰭、厚み２、３−１電池容量１５
０ ｍＡＨの本発明電池を得た。この電池を人とする。The positive electrode uses manganese dioxide heat-treated at a temperature range of 350 to 4'50°C as an active material, and this manganese dioxide, carbon powder as a conductive agent, and fluororesin powder as a binder are mixed in a ratio of 85:10:5' by weight. A mixture mixed at the same ratio was pressure-molded and heat-treated at 250 to 550°C, and the negative electrode was a lithium rolled plate punched out to the specified dimensions, with a diameter of 20.0 fins and a thickness of 2 to 3 mm. 1 battery capacity 15
A battery of the present invention of 0 mAH was obtained. Let's say this battery is a person.
比較例１
溶媒としてスルホランとジメトキシエタン（低粘度）と
ｔ−１： １の体積比で混合した混合溶媒を用い、この
混合溶媒に溶質として過塩素酸リチウムを１モル／ｌ溶
解したものを電解液とする。Comparative Example 1 A mixed solvent consisting of sulfolane and dimethoxyethane (low viscosity) mixed at a volume ratio of t-1:1 was used as a solvent, and 1 mol/l of lithium perchlorate was dissolved as a solute in this mixed solvent and electrolyzed. Make it into a liquid.
以下は本発明電池と同様の比較電池を得た。この電池を
Ｂとする。A comparative battery similar to the battery of the present invention was obtained below. This battery is called B.
比較例２
溶媒としてスルホランとテトラハイドロフラン（低粘度
）とを１：１の体積比で混合した混合溶媒を用い、この
混合溶媒に溶質として過塩素酸リチウムを１モル／ｌ溶
解したも゛のを電解液とする。Comparative Example 2 A mixed solvent in which sulfolane and tetrahydrofuran (low viscosity) were mixed at a volume ratio of 1:1 was used as a solvent, and 1 mol/l of lithium perchlorate was dissolved as a solute in this mixed solvent. is used as the electrolyte.
以下は本発明電池と同様の比較電池を得た。この電池を
Ｃとする。A comparative battery similar to the battery of the present invention was obtained below. This battery is called C.
比較例５
溶媒としてプロピレンカーボネート（高粘度）とジメト
キシエタンとを１：１の体積比で混合した混合溶媒を用
い、この混合溶媒に溶質として過塩素酸リチウムを１モ
／ｌ、／Ｉ！溶解したものを電解液とする。Comparative Example 5 A mixed solvent in which propylene carbonate (high viscosity) and dimethoxyethane were mixed at a volume ratio of 1:1 was used as a solvent, and lithium perchlorate was added as a solute to this mixed solvent at 1 mo/l, /I! The dissolved material is used as an electrolyte.
以下は本発明電池と同様の比較電池を得九。この電池を
Ｃとする。The following is a comparison battery similar to the battery of the present invention. This battery is called C.
第１図はこれらの電池を温度−２０℃において３にΩの
定抵抗で放電した時の放電特性図である。FIG. 1 is a discharge characteristic diagram when these batteries were discharged at a temperature of -20 DEG C. with a constant resistance of 3 to .OMEGA.
第１図より本発明電池人は比較電池に比して優れた放電
特性を有することがわかる。From FIG. 1, it can be seen that the battery of the present invention has superior discharge characteristics compared to the comparative battery.
又、第２図は本発明電池人におけるスルホランと１，３
ジオキソランとの混合溶媒の混合体積比と電池放電容量
との関係を示す図であり、第２図より混合体積比として
は１：４〜４：１の範囲が好ましいことがわかる。In addition, Figure 2 shows the relationship between sulfolane and 1,3 in the battery of the present invention.
FIG. 2 is a diagram showing the relationship between the mixed volume ratio of the mixed solvent with dioxolane and the battery discharge capacity, and it can be seen from FIG. 2 that the mixed volume ratio is preferably in the range of 1:4 to 4:1.
尚、下表は各電池を放電した後、分解してリチウム負極
表面を肉眼観察した結果を示す。The table below shows the results of disassembling each battery and visually observing the surface of the lithium negative electrode after discharging each battery.
表
ト０発明の効果
上述した如く、リチウム或いはリチウム合金からなる負
極と、正極と、溶媒と溶質とからなる非水電解液とを備
える非水電解液電池において、溶媒として少くともスル
ホランと１．６ジオキソランとを含む混合溶媒を用いる
ことにより、低温放電特性を向上しうるものであり、こ
の種電池の利用分野拡大に資するところ極めて大である
。Table 0 Effects of the Invention As described above, in a non-aqueous electrolyte battery comprising a negative electrode made of lithium or a lithium alloy, a positive electrode, and a non-aqueous electrolyte made of a solvent and a solute, at least 1. By using a mixed solvent containing 6-dioxolane, the low-temperature discharge characteristics can be improved, which greatly contributes to expanding the field of use of this type of battery.
第１図は電池の低温放電特性図、第２図はスルホランと
１、３ジオキソランとの混合溶媒の混合体積比と電池放
電容量との関係を示す図である。
（至）・・・本発明電池、 ■００・・・比較電池。FIG. 1 is a diagram showing the low-temperature discharge characteristics of the battery, and FIG. 2 is a diagram showing the relationship between the mixed volume ratio of a mixed solvent of sulfolane and 1,3-dioxolane and the battery discharge capacity. (To)...Battery of the present invention, ■00...Comparison battery.
Claims (2)
極と、溶媒と溶質とからなる非水電解液とを備えるもの
であって、前記溶媒が少くともスルホランと１、３ジオ
キソランとを含む混合溶媒であることを特徴とする非水
電解液電池。(1) A device comprising a negative electrode made of lithium or a lithium alloy, a positive electrode, and a non-aqueous electrolyte made of a solvent and a solute, where the solvent is a mixed solvent containing at least sulfolane and 1,3-dioxolane. A non-aqueous electrolyte battery characterized by:
が１：４〜４：１の範囲であることを特徴とする特許請
求の範囲第（１）項記載の非水電解液電池。(2) The non-aqueous electrolyte battery according to claim (1), wherein the mixing volume ratio of sulfolane and 1,3-dioxolane is in the range of 1:4 to 4:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP433288A JPH01186563A (en) | 1988-01-12 | 1988-01-12 | Nonaqueous electrolyte cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP433288A JPH01186563A (en) | 1988-01-12 | 1988-01-12 | Nonaqueous electrolyte cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01186563A true JPH01186563A (en) | 1989-07-26 |
Family
ID=11581496
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP433288A Pending JPH01186563A (en) | 1988-01-12 | 1988-01-12 | Nonaqueous electrolyte cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01186563A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5142933A (en) * | 1974-09-27 | 1976-04-12 | Union Carbide Corp | Suruhoran mataha sonoarukiruchikanjudotaiofukumudenkaishitsuojusuruhisuiseidenchi |
| JPS6086770A (en) * | 1983-09-19 | 1985-05-16 | デユラセル・インターナシヨナル・インコーポレーテツド | Nonaqueous chemical battery |
-
1988
- 1988-01-12 JP JP433288A patent/JPH01186563A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5142933A (en) * | 1974-09-27 | 1976-04-12 | Union Carbide Corp | Suruhoran mataha sonoarukiruchikanjudotaiofukumudenkaishitsuojusuruhisuiseidenchi |
| JPS6086770A (en) * | 1983-09-19 | 1985-05-16 | デユラセル・インターナシヨナル・インコーポレーテツド | Nonaqueous chemical battery |
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