JPH04104468A - Nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte batteryInfo
- Publication number
- JPH04104468A JPH04104468A JP2220360A JP22036090A JPH04104468A JP H04104468 A JPH04104468 A JP H04104468A JP 2220360 A JP2220360 A JP 2220360A JP 22036090 A JP22036090 A JP 22036090A JP H04104468 A JPH04104468 A JP H04104468A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- carbonate
- lithium
- positive electrode
- 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.)
- Granted
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 17
- -1 polypropylene Polymers 0.000 claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000011149 active material Substances 0.000 claims abstract description 10
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 8
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000002015 acyclic group Chemical group 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 4
- FWBMVXOCTXTBAD-UHFFFAOYSA-N butyl methyl carbonate Chemical compound CCCCOC(=O)OC FWBMVXOCTXTBAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 238000009831 deintercalation Methods 0.000 claims 1
- 238000009830 intercalation Methods 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004743 Polypropylene Substances 0.000 abstract description 2
- 239000011230 binding agent Substances 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 2
- 159000000002 lithium salts Chemical class 0.000 abstract description 2
- 229920001155 polypropylene Polymers 0.000 abstract description 2
- 239000002841 Lewis acid Substances 0.000 abstract 1
- 239000006230 acetylene black Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 150000007517 lewis acids Chemical class 0.000 abstract 1
- 229910001386 lithium phosphate Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 239000003960 organic solvent Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 244000175448 Citrus madurensis Species 0.000 description 1
- 235000017317 Fortunella Nutrition 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000003112 inhibitor Substances 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
- 239000012528 membrane Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
【発明の詳細な説明】
（イ） 産業上の利用分野
本発明は、正極と、リチウムを活物質とする負極と、溶
媒と溶質からなる非水系電解液とを備えた非水系電解液
電池において、特に電解液の改良に関するものである。[Detailed Description of the Invention] (a) Industrial Application Field The present invention relates to a non-aqueous electrolyte battery comprising a positive electrode, a negative electrode containing lithium as an active material, and a non-aqueous electrolyte comprising a solvent and a solute. , especially regarding the improvement of electrolytes.
（ロ） 従来の技術
リチウムを活物質とする負極を用いた非水系電解液電池
は、その高エネルギー密度や優れた保存特性などが注目
され、現在ら活発な研究開発が行われているが、この種
電池を実用化するｊ−で最も重要な課題となっているの
が、保存特性成るいはサイクル特性が良好な電解液の探
索である。(b) Conventional technology Non-aqueous electrolyte batteries using negative electrodes with lithium as the active material have attracted attention for their high energy density and excellent storage properties, and are currently undergoing active research and development. The most important issue in putting this type of battery into practical use is the search for an electrolyte with good storage and cycle characteristics.
特に、この種電池において、負極として活性なリチウム
を活物質とするため、また一方、正極では責な電位に保
たれるため、負極、正極それぞｈにおいて、電解液が分
解されやすい状況にある。In particular, in this type of battery, the negative electrode uses active lithium as the active material, while the positive electrode is kept at a negative potential, making it easy for the electrolyte to decompose at both the negative and positive electrodes. .
従って、電解液の選択において、こｆｔらの点を考慮し
た構成とすることが必要不可欠である。そのため、種々
の電解液を用いることが提案されているが、それらの大
部分は、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、Ｔ−フ゛チロラクトンなどの高沸点溶媒
に、］、］２−ジメトキシエタン１，３−ジオキソラン
、テトラヒドロフランなどの低粘度溶媒を混合した乙の
である。一方、溶質としては、過塩素酸リチウム、テト
ラフルオロホウ酸リチウム、ヘキサフルオロリン酸リチ
ウム、ヘキサフルオロヒ酸リチウム、トノフルオロメタ
ンスルホン酸リチウムなどを使用することが例示さｔし
ている。Therefore, it is essential to take these points into account when selecting an electrolytic solution. Therefore, it has been proposed to use various electrolytes, but most of them use high boiling point solvents such as propylene carbonate, ethylene carbonate, and T-butyrolactone as solvents, ], ]2-dimethoxyethane 1,3 - It is a mixture of low viscosity solvents such as dioxolane and tetrahydrofuran. On the other hand, examples of the solute include lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium hexafluoroarsenate, and lithium tonofluoromethanesulfonate.
（ハ） 発明が解決しようとする課題
しかしながら、上述したような電解液を用いても、必す
しも十分な電池特性が得られるわけではない。(c) Problems to be Solved by the Invention However, even if the electrolyte as described above is used, sufficient battery characteristics cannot necessarily be obtained.
そこで、本発明は前記間趙点に鑑みてなされたものであ
って、この種電池の高活性な正、負極と、電解液との反
応性を制御することにより、保合生、を性、更にニー次
電池を構成した場合にはサイクル特性に優れた非水系電
解液電池を提供するものである。Therefore, the present invention was made in view of the above-mentioned problems, and by controlling the reactivity between the highly active positive and negative electrodes of this type of battery and the electrolyte, it is possible to improve When configured as a secondary battery, it provides a non-aqueous electrolyte battery with excellent cycle characteristics.
（ニ） 課題を解決するための手段
本発明は、正極と、リチウムを活物質とする負極と、溶
媒と溶質からなる非水系電解液とを備えた非水系電解液
電池であって、前記溶媒が、非対象の非環状炭酸エステ
ルを含有していることを特徴とするものである。(d) Means for Solving the Problems The present invention provides a non-aqueous electrolyte battery comprising a positive electrode, a negative electrode containing lithium as an active material, and a non-aqueous electrolyte comprising a solvent and a solute. is characterized in that it contains an asymmetric acyclic carbonate.
そして、＋ｉｉｊ記非対象の非環状炭酸エステルとして
は、メチルエチル炭酸エステル、メチルプロピル炭酸エ
ステル、エチルプロピル炭酸エステル、メチルブチル炭
酸エステルからなる群より選択された少なくとも１種を
使用するのが好ましい。It is preferable to use at least one selected from the group consisting of methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, and methyl butyl carbonate as the non-target acyclic carbonate ester described in +iii.
また、前記正極としては、マンガン酸化物、或いはコバ
ルト酸化物、前記負極としては、リチウム金属、或いは
リチウムの吸蔵・放出可能な合金、酸化物、カーボンを
用いることができる。Further, as the positive electrode, manganese oxide or cobalt oxide can be used, and as the negative electrode, lithium metal, or an alloy, oxide, or carbon that can intercalate and deintercalate lithium can be used.
（ホ） 作用
前述した如く、この種電池では、電解液の分解反応が生
しやすく、これが種々の電池特性を劣化させる主因とな
っていると考えられる。しかしながら、溶媒に非対象の
非環状炭酸エステルを用いると、保存ＰＩ゛性に優れ、
サイクル特性も良好な電池が得られることを知得し、本
発明を完成するに十っな。即ち、電解液の溶媒に非対象
の非環状炭酸エステルを使用すると、それ自体化学的に
安定であるため、分解反応が起こりにくくなると考えら
ノする。(e) Effects As mentioned above, in this type of battery, decomposition reactions of the electrolyte tend to occur, and this is considered to be the main cause of deterioration of various battery characteristics. However, when an asymmetric acyclic carbonate is used as a solvent, it has excellent storage PI properties,
This knowledge was sufficient to complete the present invention by learning that a battery with good cycle characteristics can be obtained. That is, it is thought that if an asymmetric acyclic carbonate is used as a solvent for the electrolytic solution, the decomposition reaction will be less likely to occur because the carbonate itself is chemically stable.
ここで、ｉｉｉ記非対象の非環状炭酸エステルとしては
、メチルエチル炭酸エステル、メチルプロピル炭酸エス
テル、エチルプロピル炭酸エステル、メチルブチル炭酸
エステルからなる群より選択さＩした少なくとも１種を
使用するのが好ましい。Here, it is preferable to use at least one selected from the group consisting of methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, and methyl butyl carbonate as the non-target acyclic carbonate ester in iii. .
そして、この種電池の溶質としては、トリフルオロメタ
ンスルホン酸リチウム、ヘキサフルオロフン酸すチウ１
１、テトラフルオロホウ酸リチウム、ヘキサフルオロヒ
酸リチウム、−キサフルオロアンチモン酸リチウム、過
塩素酸リチウムなどが使用可能である。The solutes for this type of battery include lithium trifluoromethanesulfonate and lithium hexafluorofurate.
1. Lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium -xafluoroantimonate, lithium perchlorate, etc. can be used.
（へ） 実施例
以下に、本発明の実施例と比較例との対比に言及し、詳
述する。(f) Examples Hereinafter, comparisons between examples of the present invention and comparative examples will be mentioned and explained in detail.
◎実験１
ここでは、非水系電解液二次電池を構成した場合につい
て述ｔ＼る。◎Experiment 1 Here, we will discuss the case of constructing a non-aqueous electrolyte secondary battery.
（実施例１）
第１図は、本発明の一実施例としての扁平形弁水系電解
液二次電池の半断面図である。〕はリチウム・アルミニ
ウム合金より成る負極であり、負極缶２の内底面に固着
せる負極集電体３に圧着さｉｚている。４は正極であっ
て充電可能な活物質であるマンガン酸化物８５重量％に
、導電剤としてアセチレンブラ／り１０重量％及び結着
剤としてフッ素樹脂５重量％の割合で加え、十分混合し
た後、成型したものである。そして、こメ′シを正極缶
５の内底面に固着せる正極集電体６に圧着した。(Example 1) FIG. 1 is a half-sectional view of a flat valve water-based electrolyte secondary battery as an example of the present invention. ] is a negative electrode made of a lithium-aluminum alloy, and is crimped to a negative electrode current collector 3 fixed to the inner bottom surface of the negative electrode can 2. 4 is a positive electrode and is a chargeable active material, 85% by weight of manganese oxide, 10% by weight of acetylene brane/resin as a conductive agent and 5% by weight of fluororesin as a binder, and after thorough mixing. , molded. Then, the paste was crimped onto the positive electrode current collector 6 which was fixed to the inner bottom surface of the positive electrode can 5.
７はポリプロピレン製多孔性膜よりなるセパレータであ
って、本発明の要旨とするメチルエチル炭酸エステル（
非対象の非環状炭酸エステル）とエチレンカーボネート
との混合物（５０：５０体積％）に、リチウム塩として
のへキサフルオロリン酸リチウム（フッ素系ルイス酸リ
チウム）を１モル、′１の割合で溶解した電解液が含浸
されている。尚、この電解液には、計材の腐食防止剤と
しての硝酸リチウムか：５００ｐｐｍ添加さノ′シてい
る。８は絶縁バッキングであり、この電池寸法は直径２
４ ｍ ｍ、高さ３ｍｍである。そして、このようにし
て構成した電池を、本発明電池Ａとしく比較例】）
有機溶媒として、プロピレンカーボネートと二手しンカ
ーボネートとの：昆合物（５０：５０ｆ本積？ｈ）を用
いた以外は、前記実施例１と同様の電池を作製した。そ
して、この電池を比較電池Ｗとした。7 is a separator made of a porous membrane made of polypropylene, which contains methyl ethyl carbonate (
Dissolve 1 mol of lithium hexafluorophosphate (fluorine-based lithium Lewis oxide) as a lithium salt in a mixture (50:50 volume %) of ethylene carbonate (non-target acyclic carbonate ester) and ethylene carbonate at a ratio of 1 mole. It is impregnated with electrolyte solution. Incidentally, 500 ppm of lithium nitrate was added to this electrolytic solution as a corrosion inhibitor for measuring materials. 8 is an insulating backing, and this battery has a diameter of 2
4 mm and height 3 mm. The battery constructed in this way was designated as the battery A of the present invention, and a comparative example]) A mixture of propylene carbonate and two-chain carbonate (50:50f/h) was used as the organic solvent. Except for this, a battery similar to that of Example 1 was produced. This battery was designated as Comparative Battery W.
これらの電池、へ、Ｗを用い、保存前後の放電特性を調
へた。この時の条件は、各電池Ａ、Ｗを充電状態で６０
℃で２０日間保存した後、放電電流２ ｍ ノ＼て放電
するというものである。この結果を、第２図に示す。Using these batteries, the discharge characteristics before and after storage were investigated. The conditions at this time are that each battery A and W is charged at 60
After being stored at ℃ for 20 days, it was discharged at a discharge current of 2 m. The results are shown in FIG.
これより、本発明電池Ａは、比較電池Ｗに比へて、保存
特性において優れたものであることが理解される。From this, it is understood that the battery A of the present invention is superior to the comparative battery W in terms of storage characteristics.
次に、これらの電池Ａ、Ｖｌｌを用い、保存後のサイク
ル特性を比較した。この時の充放電条件は、充放電電流
を１．５ｍＡ、充放電時間を３時間とし、放電時間内に
電池電圧が１．５■に達した電池をサイクル寿命とする
ものである。この結果を、第３図に示す。Next, using these batteries A and Vll, the cycle characteristics after storage were compared. The charging and discharging conditions at this time were such that the charging and discharging current was 1.5 mA, the charging and discharging time was 3 hours, and the cycle life of the battery was determined when the battery voltage reached 1.5 cm within the discharge time. The results are shown in FIG.
これより、本発明電池Ａと比較電池Ｗとを対比すると、
保存ｎＸＪのサイクル特性は同程度（図示せす）である
が、保存後のサイクル特性にどいて本発明電池Ａは、比
較電池〜へｌに比・＼て、優れていることが分かる。From this, comparing the present invention battery A and the comparison battery W,
Although the cycle characteristics of the stored nXJ are comparable (as shown in the figure), it can be seen that the battery A of the present invention is superior to the comparative batteries 1 in terms of the cycle characteristics after storage.
（実施例２）
正極として充放電可能なコバルト酸化物を用い、有機溶
媒としてメチルプロピル炭酸エステル（非対象の非環状
炭酸エステル）とＴ−ブチロラクトンとの混合物（３０
＋７０体偵％）金柑いた以外は、前記実施例１と同様の
電池を作製した。(Example 2) A chargeable and dischargeable cobalt oxide was used as the positive electrode, and a mixture of methylpropyl carbonate (asymmetric acyclic carbonate) and T-butyrolactone (30%
+70%) A battery was prepared in the same manner as in Example 1 except that kumquats were used.
そして、この電池を本発明電池■３とした。This battery was designated as Invention Battery #3.
（比較例２）
有機溶媒にＴ−ブチロラクトンを用いた以外は、前記実
施例２と同様の電池を作製した。そして、この電池を比
較電池Ｘとした。(Comparative Example 2) A battery similar to that of Example 2 was produced except that T-butyrolactone was used as the organic solvent. This battery was designated as Comparative Battery X.
これらの電池Ｂ、Ｘを用い、前記実施例１と同一・条件
にて、電池保存前後の放電特性を調べた。Using these batteries B and X, the discharge characteristics before and after battery storage were examined under the same conditions as in Example 1.
この結果を、第４図に示す。The results are shown in FIG.
これよｉ）、本発明電池Ｂと比較電池Ｘとを対比すると
、保存前の放電特性は同程度（図示せず）であるが、保
存後の放電特性において、本発明電池Ｂは、比較電池Ｘ
に比べて、優れており、保存特性が良好であることが理
解される。From this i), when comparing battery B of the present invention and comparative battery X
It is understood that the storage properties are superior to those of the previous one.
次に、各電池Ｂ、Ｘの保存に伴う内部抵抗の変化を調べ
た。この結果を、第５図に示す。Next, changes in internal resistance of each battery B and X during storage were investigated. The results are shown in FIG.
これより、本発明電池Ｂは、比較電池Ｘに比べて、内部
抵抗の一ヒ昇か小さく、保存後の放電特性におても優れ
たものであることが分かる。From this, it can be seen that the battery B of the present invention has a slightly higher internal resistance than the comparative battery X, and has excellent discharge characteristics after storage.
（実施例３）
工１極にリチウムのｌＩ＆蔵・放出可能なカーボンを用
い、有機溶媒としてメチルエチル炭酸エステル（非環状
炭酸エステル）とスルホランとの混合物（３０ニア０体
積％）を用いた以外は、前記実施例２と同様の電池を作
製した。そして、この電池を本発明電池Ｃとした。(Example 3) Except for using lithium lI and carbon that can be stored and released as the first electrode and using a mixture of methyl ethyl carbonate (acyclic carbonate) and sulfolane (30% by volume) as the organic solvent. A battery similar to that of Example 2 was prepared. This battery was designated as Invention Battery C.
（比較例３）
有機溶媒にスルホランを用いた以外は、前記実施例３と
同様の電池を作製した。そして、この電池を比較電池Ｙ
とした。(Comparative Example 3) A battery similar to that of Example 3 was produced except that sulfolane was used as the organic solvent. Then, compare this battery with battery Y
And so.
こｌ′Ｌらの電池Ｃ，Ｙを用い、がｊ記実施例１と同一
条件にて、電池保存前後の放電特性を調べた。Using the batteries C and Y of L'L et al., the discharge characteristics before and after storage of the batteries were investigated under the same conditions as in Example 1.
この結果を、第６図に示す。The results are shown in FIG.
これより、本発明電池Ｃと比較電池Ｙとを対比すると、
保存前の放電特性は同程度（図示せす）であるが、保存
後の放電特性において、本発明電池Ｃは、比較電池Ｙに
比べて、優ノ′シており、保存特性が良好であることが
理解さノする。From this, comparing the present invention battery C and the comparison battery Y,
Although the discharge characteristics before storage are the same (as shown in the figure), the battery C of the present invention is superior to the comparative battery Y in the discharge characteristics after storage, and has good storage characteristics. I understand that.
◎実験 ２
次にここでは、非水系電解液−次電池をＦｌに成した場
合について述べる。◎Experiment 2 Next, the case where a non-aqueous electrolyte secondary battery is made into Fl will be described.
（実施例・１）
負極としてリチウム金属を用い、正極には１，３５０〜
４３０℃の温度範囲で熱処理した二酸化マンガンを活物
質として用い、有機溶媒としてメチルエチル炭酸エステ
ル（非対象の非環状炭酸エステル）と１，２−ジメトキ
シエタンとの混合物（３０ニア０体積％）を用いた以外
は、前記実施例］と同様の電池を作製した。そして、こ
の電池を、本発明電池りとした。(Example 1) Lithium metal was used as the negative electrode, and 1,350 ~
Manganese dioxide heat-treated in a temperature range of 430°C was used as an active material, and a mixture of methyl ethyl carbonate (asymmetric acyclic carbonate) and 1,2-dimethoxyethane (30% by volume) was used as an organic solvent. A battery similar to that in the above Example was produced except that the following examples were used. This battery was then designated as the battery of the present invention.
（比較例４）
有機溶媒としてプロピレンカーボネートと１゜２−ジメ
トキシエタンとの混合物（３０ニア０体偵％）を用いた
以外は、前記実施例、１と同様の電池を作製した。そし
て、この電池を、比較電池Ｚとした。(Comparative Example 4) A battery was prepared in the same manner as in Example 1, except that a mixture of propylene carbonate and 1°2-dimethoxyethane (30% by weight) was used as the organic solvent. This battery was designated as Comparative Battery Z.
これらの電池り、Ｚを用い、前記実施例１と同一条件に
て、電池保存前後の放電特性を調べた。Using these batteries, the discharge characteristics before and after battery storage were investigated under the same conditions as in Example 1.
この結果を、第７図に示す。The results are shown in FIG.
こｉ″しより、本発明電池りと比較電池Ｚとを対比する
と、保存前の放電特性は同程度（図示せす）であるが、
保存後の放電特性において、本発明電池りは、比較電池
Ｚに比べて、優れており、保存特性が良好であることが
理解さメする。Therefore, when comparing the battery of the present invention and comparative battery Z, the discharge characteristics before storage are the same (as shown in the figure), but
It can be seen that the battery of the present invention is superior to Comparative Battery Z in terms of discharge characteristics after storage, and has good storage characteristics.
（ト）発明の効果
上述した如く、本発明は、正極と、リチウムを活物質と
する負極と、溶媒と溶質からなる非水系電解液とを備え
た非水系電解液電池において、前記溶媒が非対象の非環
状炭酸エステルを含有しているものであるから、この種
電池の保存特性、二次、１池を構成した場合にはサイク
ル特性を向−ヒさせるものであり、その−Ｌ業的価値は
極めて太きし）(G) Effects of the Invention As described above, the present invention provides a non-aqueous electrolyte battery comprising a positive electrode, a negative electrode containing lithium as an active material, and a non-aqueous electrolyte consisting of a solvent and a solute. Since it contains the target acyclic carbonate ester, it improves the storage characteristics of this type of battery and the cycle characteristics when a secondary battery is constructed. The value is extremely high)
第１図は本発明電池の半断面図、第２図は保存前後の電
池の放電特性図、第３図は保存後の電池のサイクル特性
図、第・１図は保存後の電池の放電特性図、第５図は保
存による電池内部抵抗の変化を示す図、第６図及び第７
図は保存後の電池の放電特性図である。
１ ・負極、２ 負極缶、３ ・負極集電体、１
体、７
・正極、５
セパレータ、
Ｂ、Ｃ１■）・・
Ｘ、Ｙ、Ｚ・・
正極計、６ ・正極集電
８ 絶縁バッキング、
・本発明電池、
・比較電池。Figure 1 is a half-sectional view of the battery of the present invention, Figure 2 is a diagram of the discharge characteristics of the battery before and after storage, Figure 3 is a diagram of the cycle characteristics of the battery after storage, and Figure 1 is the discharge characteristics of the battery after storage. Figure 5 is a diagram showing changes in battery internal resistance due to storage, Figures 6 and 7 are diagrams showing changes in battery internal resistance due to storage.
The figure shows the discharge characteristics of the battery after storage. 1 - Negative electrode, 2 Negative electrode can, 3 - Negative electrode current collector, 1 body, 7 - Positive electrode, 5 Separator, B, C1■)... X, Y, Z... Positive electrode meter, 6 - Positive electrode current collector 8 Insulating backing・Battery of the present invention, ・Comparative battery.
Claims (4)
溶質からなる非水系電解液とを備える電池であって、 前記溶媒が、非対象の非環状炭酸エステルを含有してい
ることを特徴とする非水系電解液電池。(1) A battery comprising a positive electrode, a negative electrode using lithium as an active material, and a non-aqueous electrolyte consisting of a solvent and a solute, wherein the solvent contains an acyclic carbonate ester. Characteristics of non-aqueous electrolyte batteries.
ル炭酸エステル、メチルプロピル炭酸エステル、エチル
プロピル炭酸エステル、メチルブチル炭酸エステルから
なる群より選択された少なくとも１種であることを特徴
とする請求項１記載の非水系電解液電池。(2) The non-target acyclic carbonate is at least one selected from the group consisting of methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, and methyl butyl carbonate. 1. The nonaqueous electrolyte battery according to 1.
化物であることを特徴とする請求項１記載の非水系電解
液電池。(3) The non-aqueous electrolyte battery according to claim 1, wherein the positive electrode is a manganese oxide or a cobalt oxide.
蔵・放出可能な合金、酸化物、カーボンであることを特
徴とする請求項１記載の非水系電解液電池。(4) The non-aqueous electrolyte battery according to claim 1, wherein the negative electrode is made of lithium metal, an alloy capable of intercalating and deintercalating lithium, an oxide, or carbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02220360A JP3123749B2 (en) | 1990-08-21 | 1990-08-21 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02220360A JP3123749B2 (en) | 1990-08-21 | 1990-08-21 | Non-aqueous electrolyte secondary battery |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000075581A Division JP2000277145A (en) | 2000-01-01 | 2000-03-17 | Nonaqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04104468A true JPH04104468A (en) | 1992-04-06 |
| JP3123749B2 JP3123749B2 (en) | 2001-01-15 |
Family
ID=16749920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02220360A Expired - Lifetime JP3123749B2 (en) | 1990-08-21 | 1990-08-21 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3123749B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0594965A1 (en) * | 1992-10-29 | 1994-05-04 | Fuji Photo Film Co., Ltd. | Nonaqueous secondary battery |
| EP0622862A1 (en) * | 1993-04-28 | 1994-11-02 | Sony Corporation | Secondary battery having non-aqueous electrolyte |
| JPH0714607A (en) * | 1993-04-28 | 1995-01-17 | Sony Corp | Nonaqueous electrolyte secondary battery |
| US5633099A (en) * | 1992-11-18 | 1997-05-27 | Mitsui Petrochemical Industries, Ltd. | Carbonate compounds, non-aqueous electrolytic solutions and batteries comprising non-aqueous electrolytic solutions |
| JP2007305381A (en) * | 2006-05-10 | 2007-11-22 | Mitsubishi Chemicals Corp | Non-aqueous electrolyte and non-aqueous electrolyte secondary battery using the same |
| EP2339684A2 (en) | 2005-06-10 | 2011-06-29 | Mitsubishi Chemical Corporation | Nonaqueous electrolytic solution, nonaqueous electrolyte secondary cell, and carbonate compounds |
-
1990
- 1990-08-21 JP JP02220360A patent/JP3123749B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0594965A1 (en) * | 1992-10-29 | 1994-05-04 | Fuji Photo Film Co., Ltd. | Nonaqueous secondary battery |
| US5633099A (en) * | 1992-11-18 | 1997-05-27 | Mitsui Petrochemical Industries, Ltd. | Carbonate compounds, non-aqueous electrolytic solutions and batteries comprising non-aqueous electrolytic solutions |
| EP0622862A1 (en) * | 1993-04-28 | 1994-11-02 | Sony Corporation | Secondary battery having non-aqueous electrolyte |
| JPH0714607A (en) * | 1993-04-28 | 1995-01-17 | Sony Corp | Nonaqueous electrolyte secondary battery |
| US5561005A (en) * | 1993-04-28 | 1996-10-01 | Sony Corporation | Secondary battery having non-aqueous electrolyte |
| EP2339684A2 (en) | 2005-06-10 | 2011-06-29 | Mitsubishi Chemical Corporation | Nonaqueous electrolytic solution, nonaqueous electrolyte secondary cell, and carbonate compounds |
| EP2485314A1 (en) | 2005-06-10 | 2012-08-08 | Mitsubishi Chemical Corporation | Nonaqueous electrolytic solution and nonaqueous electrolyte secondary cell |
| JP2007305381A (en) * | 2006-05-10 | 2007-11-22 | Mitsubishi Chemicals Corp | Non-aqueous electrolyte and non-aqueous electrolyte secondary battery using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3123749B2 (en) | 2001-01-15 |
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