JPH0479476B2 - - Google Patents
Info
- Publication number
- JPH0479476B2 JPH0479476B2 JP58197011A JP19701183A JPH0479476B2 JP H0479476 B2 JPH0479476 B2 JP H0479476B2 JP 58197011 A JP58197011 A JP 58197011A JP 19701183 A JP19701183 A JP 19701183A JP H0479476 B2 JPH0479476 B2 JP H0479476B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- aqueous electrolyte
- negative electrode
- solvent
- methoxyethanol
- 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 - Lifetime
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 20
- 229910052744 lithium Inorganic materials 0.000 claims description 20
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 16
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000011149 active material Substances 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 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
- 239000000203 mixture Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- NYPFJVOIAWPAAV-UHFFFAOYSA-N sulfanylideneniobium Chemical compound [Nb]=S NYPFJVOIAWPAAV-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-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)
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、チタン或いはニオブの硫化物、セレン
化物などを活物質とする正極と、少くとも一つの
溶媒と少くとも一つの溶質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) Field of Industrial Application The present invention relates to a negative electrode using lithium or an alloy containing lithium as an active material, and a negative electrode containing molybdenum trioxide, vanadium pentoxide, titanium or niobium sulfide, selenide, etc. The present invention relates to a non-aqueous electrolyte secondary battery comprising a positive electrode having as an active material, and a non-aqueous electrolyte comprising at least one solvent and at least one solute.
(ロ) 従来技術
この種電池は放電時にイオンとなつて溶出した
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下させるに至り充放電サ
イクル特性が悪いという問題があつた。(b) Prior art In this type of battery, the lithium eluted as ions during discharge is deposited as metallic lithium on the negative electrode surface during charging, but since the deposited lithium is in the form of fine particles with a large surface area, the activity is low. Therefore, there was a problem in that the non-aqueous electrolyte reacted with the solvent constituting the non-aqueous electrolyte, decomposing the solvent and deteriorating the non-aqueous electrolyte, resulting in poor charge-discharge cycle characteristics.
(ハ) 発明の目的
本発明は充放電サイクル特性に優れた非水電解
液二次電池を提供することを目的とする。(c) Object of the invention The object of the present invention is to provide a non-aqueous electrolyte secondary battery with excellent charge-discharge cycle characteristics.
(ニ) 発明の構成
本発明は上記目的を達成すべくなされたもので
ありその要旨とするところは、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、正極と、
少くとも一つの溶媒と少くとも一つの溶質とから
なる前記非水電解液に、２メトキシエタノール、
ジエチレングリコールモノメチルエーテルのうち
の少なくとも１種を添加し、且つその添加量を、
溶媒に対して0.5〜5.0モル％としたことを特徴と
する非水電解液二次電池にある。(d) Structure of the Invention The present invention has been made to achieve the above object, and its gist is to provide a negative electrode using lithium or an alloy containing lithium as an active material, a positive electrode,
2-methoxyethanol,
At least one type of diethylene glycol monomethyl ether is added, and the amount added is
A non-aqueous electrolyte secondary battery characterized in that the amount is 0.5 to 5.0 mol% relative to the solvent.
本発明電池によれば、非水電解液に添加した２
メトキシエタノール、ジエチレングリコールモノ
メチルエーテルのうちの少なくとも１種とリチウ
ムとが反応してリチウム表面に被膜が形成され、
この被膜を介してリチウムの溶出、電析が生じる
ことになり、活性な電析リチウムが直接非水電解
液と接しないため活性な電析リチウムと溶媒との
反応が抑制されるので充放電サイクル特性が改善
される。 According to the battery of the present invention, 2 added to the non-aqueous electrolyte
At least one of methoxyethanol and diethylene glycol monomethyl ether reacts with lithium to form a film on the lithium surface,
Lithium elution and electrodeposition occur through this film, and since the active electrodeposited lithium does not come into direct contact with the non-aqueous electrolyte, the reaction between the active electrodeposited lithium and the solvent is suppressed, so the charge/discharge cycle is reduced. Characteristics are improved.
(ホ) 実施例
以下本発明の実施例につき図面に基づき説明す
る。(E) Embodiments Examples of the present invention will be described below based on the drawings.
第１図は電池の半断面図を示し、１，２はステ
ンレス製の正負極缶であつてポリプロピレンより
なる絶縁パツキング３により隔離されている。４
はリチウム圧延板よりなる負極であつて負極缶２
の内底面に固着せる負極集電体５に圧着されてい
る。６は正極であつて二硫化チタン活物質に導電
剤としてのアセチレンブラツク及び結着剤として
のフツ素樹脂粉末を重量比で80：10：10の割合で
混合した合剤を正極固定用リング７内に成型して
なり、正極缶１の内底面に固着した正極集電体８
に圧接されている。９はポリプロピレン不織布よ
りなるセパレータであつて、このセパレータに次
述の電解液が含浸されている。 FIG. 1 shows a half-sectional view of the battery, with numerals 1 and 2 representing positive and negative electrode cans made of stainless steel, which are separated by an insulating packing 3 made of polypropylene. 4
is a negative electrode made of a lithium rolled plate, and the negative electrode can 2
The negative electrode current collector 5 is crimped to the inner bottom surface of the negative electrode current collector 5. 6 is a positive electrode, and a positive electrode fixing ring 7 is made of a mixture of a titanium disulfide active material, acetylene black as a conductive agent, and fluorine resin powder as a binder in a weight ratio of 80:10:10. A positive electrode current collector 8 is molded inside and fixed to the inner bottom surface of the positive electrode can 1.
is pressed against. 9 is a separator made of polypropylene nonwoven fabric, and this separator is impregnated with the following electrolytic solution.
即ち、電解液は溶媒としてのプロピレンカーボ
ネートに溶質としての過塩素酸リチウムを１モ
ル／溶解したものであり、この溶解液には２メ
トキシエタノール又はジエチレングリコールモノ
メチルエーテルが添加されている。 That is, the electrolytic solution is a solution of 1 mol/mol of lithium perchlorate as a solute in propylene carbonate as a solvent, and 2-methoxyethanol or diethylene glycol monomethyl ether is added to this solution.
第２図は２メトキシエタノールを添加した非水
電解液を用いて組立てた電池におけるサイクル数
と２メトキシエタノールの添加量割合との関係を
示す図であり、又第３図はジエチレングリコール
モノメチルエーテルを添加した非水電解液を用い
て組立てた電池におけるサイクル数とジエチレン
グリコールモノメチルエーテルの添加量割合との
関係を示す図である。 Figure 2 shows the relationship between the number of cycles and the ratio of the amount of 2-methoxyethanol added in a battery assembled using a non-aqueous electrolyte containing 2-methoxyethanol, and Figure 3 shows the relationship between the number of cycles and the ratio of the amount of 2-methoxyethanol added. FIG. 3 is a diagram showing the relationship between the number of cycles and the proportion of diethylene glycol monomethyl ether added in a battery assembled using the non-aqueous electrolyte.
尚、第２図及び第３図における条件は充電電流
２ｍＡ、充電終止電圧4.0Vとし、放電電流２ｍ
Ａで放電し放電時間が６時間の時点で電池電圧が
1.5V以下となつたものは電池寿命が尽きたもの
とした。 The conditions in Figures 2 and 3 are a charging current of 2 mA, a charging end voltage of 4.0 V, and a discharging current of 2 mA.
Discharge at A, and when the discharge time is 6 hours, the battery voltage will be
If the voltage was below 1.5V, it was assumed that the battery life had run out.
(ヘ) 発明の効果
第２図及び第３図から明白なるように２メトキ
シエタノールもしくはジエチレングリコールモノ
メチルエーテルを添加すれば充放電サイクル特性
が向上するのが伺え、特にその添加量として溶媒
に対して0.5〜5.0モル％の範囲で最も優れた特性
を示すことがわかる。(f) Effects of the invention As is clear from FIGS. 2 and 3, it can be seen that the addition of 2-methoxyethanol or diethylene glycol monomethyl ether improves the charge-discharge cycle characteristics, and in particular, the amount added is 0.5% relative to the solvent. It can be seen that the most excellent properties are exhibited in the range of ~5.0 mol%.
この理由を考察するに、２メトキシエタノール
もしくはジエチレングリコールモノメチルエーテ
ルとリチウムが反応してリチウム負極表面にリチ
ウムイオン選択透過性の被膜が形成されると考え
られ、この被膜を介してリチウムの溶出、電析が
生じることになり、活性な電析リチウムが直接非
水電解液と接しないため活性な電析リチウムと溶
媒との反応が抑制されるので充放電サイクル特性
が改善される。 Considering the reason for this, it is thought that 2-methoxyethanol or diethylene glycol monomethyl ether reacts with lithium to form a lithium ion selectively permeable film on the surface of the lithium negative electrode, and through this film, lithium is eluted and deposited. Since the active electrodeposited lithium does not come into direct contact with the non-aqueous electrolyte, the reaction between the active electrodeposited lithium and the solvent is suppressed, thereby improving the charge-discharge cycle characteristics.
上述した如く、非水電解液に、２メトキシエタ
ノール、ジエチレングリコールモノメチルエーテ
ルのうちの少なくとも１種を添加し、且つその添
加量を、溶媒に対して0.5〜5.0モル％としたこと
により充放電サイクル特性に優れた非水電解液二
次電池を得ることができるものであり、その工業
的価値は極めて大である。 As mentioned above, the charge/discharge cycle characteristics are improved by adding at least one of 2-methoxyethanol and diethylene glycol monomethyl ether to the non-aqueous electrolyte, and adding the amount in the range of 0.5 to 5.0 mol% relative to the solvent. It is possible to obtain a non-aqueous electrolyte secondary battery with excellent properties, and its industrial value is extremely large.
第１図は本発明電池の半断面図、第２図は２メ
トキシエタノールの添加量割合とサイクル数との
関係を示す図、第３図はジエチレングリコールモ
ノメチルエーテルの添加量割合とサイクル数との
関係を示す図である。
１……正極缶、２……負極缶、３……絶縁パツ
キング、４……負極、６……正極、９……セパレ
ータ。
Figure 1 is a half-sectional view of the battery of the present invention, Figure 2 is a diagram showing the relationship between the addition amount ratio of 2-methoxyethanol and the number of cycles, and Figure 3 is the relationship between the addition amount ratio of diethylene glycol monomethyl ether and the number of cycles. FIG. 1... Positive electrode can, 2... Negative electrode can, 3... Insulating packing, 4... Negative electrode, 6... Positive electrode, 9... Separator.
Claims (1)
する負極と、正極と、少なくとも一つの溶媒と少
なくとも一つの溶質とかとらなる非水電解液とを
備え、 前記非水電解液に、２メトキシエタノール、ジ
エチレングリコールモノメチルエーテルのうちの
少なくとも１種を添加し、 且つその添加量を、溶媒に対して0.5〜5.0モル
％とすることを特徴とする非水電解液二次電池。[Scope of Claims] 1. A negative electrode comprising lithium or an alloy containing lithium as an active material, a positive electrode, and a non-aqueous electrolyte comprising at least one solvent and at least one solute, the non-aqueous electrolyte comprising: , 2-methoxyethanol, and diethylene glycol monomethyl ether, and the amount thereof added is 0.5 to 5.0 mol % based on the solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58197011A JPS6089075A (en) | 1983-10-20 | 1983-10-20 | Nonaqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58197011A JPS6089075A (en) | 1983-10-20 | 1983-10-20 | Nonaqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6089075A JPS6089075A (en) | 1985-05-18 |
| JPH0479476B2 true JPH0479476B2 (en) | 1992-12-16 |
Family
ID=16367297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58197011A Granted JPS6089075A (en) | 1983-10-20 | 1983-10-20 | Nonaqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6089075A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5403544B2 (en) * | 2009-09-07 | 2014-01-29 | セイコーインスツル株式会社 | Electrolytic solution for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery using the same |
| JP5721193B2 (en) * | 2013-10-18 | 2015-05-20 | セイコーインスツル株式会社 | Electrolytic solution for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery using the same |
| JP7056734B2 (en) * | 2018-05-29 | 2022-04-19 | 株式会社村田製作所 | Lithium ion secondary battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59130073A (en) * | 1983-01-17 | 1984-07-26 | Nippon Telegr & Teleph Corp <Ntt> | Electrolyte for lithic battery |
-
1983
- 1983-10-20 JP JP58197011A patent/JPS6089075A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59130073A (en) * | 1983-01-17 | 1984-07-26 | Nippon Telegr & Teleph Corp <Ntt> | Electrolyte for lithic battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6089075A (en) | 1985-05-18 |
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