JPH01186754A - Nonaqueous electrolytic liquid secondary battery - Google Patents
Nonaqueous electrolytic liquid secondary batteryInfo
- Publication number
- JPH01186754A JPH01186754A JP63006351A JP635188A JPH01186754A JP H01186754 A JPH01186754 A JP H01186754A JP 63006351 A JP63006351 A JP 63006351A JP 635188 A JP635188 A JP 635188A JP H01186754 A JPH01186754 A JP H01186754A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- negative electrode
- battery
- secondary battery
- treatment
- 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
- 239000007788 liquid Substances 0.000 title description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 34
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 10
- 150000004292 cyclic ethers Chemical class 0.000 claims description 9
- -1 lithium hexafluoroarsenate Chemical compound 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 4
- 239000012528 membrane Substances 0.000 abstract 2
- VKJKOXNPYVUXNC-UHFFFAOYSA-K trilithium;trioxido(oxo)-$l^{5}-arsane Chemical compound [Li+].[Li+].[Li+].[O-][As]([O-])([O-])=O VKJKOXNPYVUXNC-UHFFFAOYSA-K 0.000 abstract 2
- 230000008021 deposition Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 150000003346 selenoethers Chemical class 0.000 description 2
- LBKMJZAKWQTTHC-UHFFFAOYSA-N 4-methyldioxolane Chemical compound CC1COOC1 LBKMJZAKWQTTHC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- LTRVAZKHJRYLRJ-UHFFFAOYSA-N lithium;butan-1-olate Chemical compound [Li+].CCCC[O-] LTRVAZKHJRYLRJ-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
-
- 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 本発明は非水電解液二次電池に関するものである。[Detailed description of the invention] (b) Industrial application fields The present invention relates to a non-aqueous electrolyte secondary battery.
（ロ）従来技術
非水電解液電池は高エネルギー密度を有し、且自己放電
が少ないという利点を有するため注目されている。(b) Prior Art Non-aqueous electrolyte batteries have attracted attention because they have the advantage of having high energy density and low self-discharge.
そしてリチウムを負極とし、二酸化マンガンやフッ化炭
素などを正極活物質とした一次電池系は既に実用化され
ており、又、三酸化モ９１デン、五酸化バナジウム、二
酸化マンガン、チタン或いはニオブの硫化物、セレン化
物などを正極活物質とする二次電池系も検討されている
。Primary battery systems that use lithium as the negative electrode and manganese dioxide or carbon fluoride as the positive electrode active material have already been put into practical use. Secondary battery systems using selenide, selenide, and the like as positive electrode active materials are also being considered.
（ハ）発明が解決しようとする課題
非水電解液二次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きな微
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ｔこ至り充放電サイクル特性に問題゛があった
。(c) Problems to be Solved by the Invention In non-aqueous electrolyte secondary batteries, lithium eluted as ions during discharge is deposited as metallic lithium on the negative electrode surface during charging, but this electrodeposited lithium has a surface area of Because they are in the form of large fine particles, they have high activity, and as a result, they react with the solvent that makes up the non-aqueous electrolyte, decomposing the solvent and degrading the non-aqueous electrolyte, resulting in problems with charge-discharge cycle characteristics. .
に）課題を解決するための手段
六フッ化砒酸リチウム（ＬｉＡｓＦ６）を溶解した環状
エーテルで処理したリチウムを負極として用いる。B) Means for Solving the Problems Lithium treated with a cyclic ether in which lithium hexafluoroarsenate (LiAsF6) is dissolved is used as a negative electrode.
又、処理に関しては上記処理液中にリチウムを浸漬する
のみで良いが、浸漬し通電処理する方がさらに好ましい
。Regarding the treatment, it is sufficient to simply immerse lithium in the above-mentioned treatment liquid, but it is more preferable to immerse the lithium and conduct an electric current treatment.
尚、環状エーテルの代表的なものとしてはテトラヒドロ
フラン（ＴＨＦ）、２メチル−テトラヒドロフラン（２
Ｍｅ−ＴＨＦ ）、４メチル−ジオキソラン（４Ｍｅ−
ＤＯＸＬ）が挙げられるがこれら化限定されない。Typical cyclic ethers include tetrahydrofuran (THF), 2methyl-tetrahydrofuran (2
Me-THF), 4methyl-dioxolane (4Me-
DOXL), but are not limited to these.
（ホ）作 用
六フッ化砒酸リチウムを溶解した環状エーテルでリチウ
ムを処理するとリチウム表面に保護被膜が形成される。(e) Effect When lithium is treated with a cyclic ether in which lithium hexafluoroarsenate is dissolved, a protective film is formed on the lithium surface.
このように処理したリチウムを負極に用いると、電池の
放電及び充電時、この保護被膜を介してリチウムの溶出
及び電析が生じることになり、活性な電析リチウムが直
接非水電解液と接触しないため溶媒との反応が抑制され
充放電・サイクル特性の改善が図れる。If lithium treated in this way is used in the negative electrode, lithium will be eluted and deposited through this protective film during battery discharging and charging, and the active deposited lithium will come into direct contact with the non-aqueous electrolyte. This suppresses reaction with the solvent and improves charge/discharge/cycle characteristics.
尚、保護被膜の形態について考察すると、例えば環状エ
ーテルとしてテトラヒドロフラン（ＴＨＥ）を例にとる
と、先ずＴＨＦとＬｉとが反応しＴＨＦが開環を起こし
てブトキシリチウム（Ｃ４Ｈ９０Ｌｉ）が生成し、つい
でこのＣ４Ｈ９０ＬｉとＬ ｉ’Ａ ｓ Ｆ ａとが反
応しこの反応生成物が保護被膜となるものと考えられる
。When considering the form of the protective film, for example, if we take tetrahydrofuran (THE) as a cyclic ether, first THF and Li react, THF undergoes ring opening to produce butoxylithium (C4H90Li), and then this It is thought that C4H90Li and Li'A s Fa react and this reaction product becomes a protective film.
（ハ）実施例
実施例１
負極の作成：第１表に示す如（ＬｉＡｓＦ６を１モル／
ｌ溶解した各種環状エーテルよりなる処理液（ａ）〜（
ψ中にリチウム板を浸漬し、０．５ｍＡ／ｄの電流密度
でリチウム板の理論容量の２〜３％を放電させた後、６
０°Ｃで１週間放置する。この処理により表面に被膜が
形成されたリチウム板が得られこれを負極とする。(c) Examples Example 1 Preparation of negative electrode: As shown in Table 1 (1 mol/1 mole of LiAsF6
l Treatment liquids (a) to (a) consisting of various dissolved cyclic ethers
After immersing the lithium plate in ψ and discharging 2 to 3% of the theoretical capacity of the lithium plate at a current density of 0.5 mA/d,
Leave at 0°C for 1 week. This treatment yields a lithium plate with a coating formed on its surface, which is used as a negative electrode.
第１図は電池の半断面図を示し、（１）は上記せる処理
済みのリチウム圧延板よりなる負極であって負極缶（２
）の内底面に固着せる負極集電体（３）に圧着されてい
る。（４）は正極であって二硫化チタン活物質に尋電剤
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
樹脂粉末を重爪比で８０：１０：１０の割合で混合した
合剤を成型したものであり、正極缶（５）の内底面に固
着した正極集電体（６）に圧接されている。（７）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
セパレータにはプロピレンカーボネートと１，２ジメト
キシエタンとの等容積混合溶媒にホウフッ化リチウムを
１モル／ｌ溶解した電解液が含浸されている。（８）は
絶縁バッキング、電池寸法は直径２４Ｗ１厚み３．０厘
である。FIG. 1 shows a half-sectional view of the battery, in which (1) is the negative electrode made of the above-mentioned treated lithium rolled plate, and the negative electrode can (2
) is crimped to a negative electrode current collector (3) which is fixed to the inner bottom surface of the electrode. (4) is a positive electrode, in which a mixture of titanium disulfide active material, acetylene black as a dielectric agent, and fluororesin powder as a binder are mixed in a ratio of 80:10:10 is molded. It is pressed into contact with a positive electrode current collector (6) fixed to the inner bottom surface of the positive electrode can (5). (7) is a separator made of polypropylene nonwoven fabric, and this separator is impregnated with an electrolytic solution in which 1 mol/l of lithium fluoroborate is dissolved in an equal volume mixed solvent of propylene carbonate and 1,2 dimethoxyethane. (8) is an insulating backing, and the battery dimensions are 24W in diameter and 3.0L in thickness.
このように作成した本発明電池を処理液に対応させて（
Ａ）〜（Ｃ）とする。The battery of the present invention created in this way was made compatible with the treatment liquid (
A) to (C).
比較例
第１表に示す処理液（ψ〜（０中にリチウム板を浸漬し
、０．５ｍＡ／ｃｄ電流密度でリチウム板の理論容量の
２〜３％を放電させた後、６０℃で１週間放置したリチ
ウムを負極として用いることを除いて他は実施例１と同
様の比較電池を作成した。Comparative Example A lithium plate was immersed in the treatment solution (ψ~(0) shown in Table 1, and after discharging 2 to 3% of the theoretical capacity of the lithium plate at a current density of 0.5 mA/cd, A comparative battery was prepared in the same manner as in Example 1 except that lithium that had been left for a week was used as the negative electrode.
この比較電池を処理液番こ対応させて（Ｄ）〜（Ｆ）と
する。尚、予じめ何ら処理をしないリチウム板を負極と
して用いた比較電池を（Ｇ）とする。These comparative batteries are shown as (D) to (F) corresponding to the treatment solution number. Note that a comparative battery (G) uses a lithium plate that has not been subjected to any treatment in advance as a negative electrode.
実施例２
第１表］こ示す如き処理液（ａ）〜（Ｃ）中にリチウム
板を浸漬して室温で２ケ月放置する。この処理により表
面に被膜が形成されたリチウム板を負極に用いることを
除いて他は実施例１と同様の本発明電池を作成した。こ
れらの電池を（Ａ）〜（Ｃ）とする。Example 2 Table 1] A lithium plate was immersed in treatment solutions (a) to (C) as shown below and left at room temperature for two months. A battery of the present invention was prepared in the same manner as in Example 1 except that a lithium plate whose surface was coated by this treatment was used as a negative electrode. These batteries are designated as (A) to (C).
第 １ 表
第２図はこれら電池のサイクル特性図を示し、サイクル
条件は充電電流２ｍＡで充電終止電圧６゜Ｏｖ、放電電
流２ｍＡで放電終止電圧１．Ｏｖとした。Table 1 and Figure 2 show the cycle characteristics of these batteries, and the cycle conditions are a charge current of 2 mA and a charge end voltage of 6°Ov, and a discharge current of 2 mA and a discharge end voltage of 1.0V. It was Ov.
第２図から明らかなように、本発明電池（Ａ）〜（Ｃ）
及び（Ａ′）〜（Ｃ′）は比較電池（Ｄ）〜（Ｇ）に比
してサイクル特性が改善されているのがわかる。この理
由は本発明のよう番こ六フッ化砒酸リチウムを溶解した
環状エーテルで処理したリチウム負極表面には、活性な
電析リチウムと溶媒との反応を阻止する保護被膜が形成
されているのに対し、比較電池ではこのような保護被膜
が形成されていないことに起因すると考えられる。As is clear from FIG. 2, batteries (A) to (C) of the present invention
It can be seen that the cycle characteristics of the batteries (A') to (C') are improved compared to the comparative batteries (D) to (G). The reason for this is that in the present invention, a protective film is formed on the surface of the lithium negative electrode treated with a cyclic ether in which lithium hexafluoroarsenate is dissolved, which prevents the reaction between the active electrodeposited lithium and the solvent. On the other hand, this is thought to be due to the fact that such a protective film was not formed in the comparative battery.
又、通電処理した本発明電池（Ａ）〜（Ｃ）の方が単に
処理液中に浸漬したのみの本発明電池（Ａ’）〜（Ｃ′
）に比してサイクル特性が優れるのは、通電処理によっ
てリチウム板の表面に予じめ存在していたＬｉＯＨ，Ｌ
ｉ２ＣＯａなどの電池性能に悪影響を与える物質を除去
しうろこと及び被膜が均一に形成されることに起因する
と考えられる。Moreover, the batteries (A) to (C) of the present invention that were subjected to current treatment were better than the batteries (A') to (C') of the present invention that were simply immersed in the treatment solution.
) The reason why the cycle characteristics are superior to that of
This is thought to be due to the fact that the scales and coating are uniformly formed by removing substances such as i2COa that adversely affect battery performance.
更に処理時間を短縮化しうるという利点もある。Furthermore, there is an advantage that processing time can be shortened.
尚、本発明においては実施例で開示した環状エーテル以
外の環状エーテルも用いることができるのは明らかであ
る。It is clear that cyclic ethers other than those disclosed in the Examples can also be used in the present invention.
（ト）発明の効果
上述した如く、リチウム負極を用いる非水電解液電池に
おいて、リチウムとして六フッ化砒酸リチウムを溶解し
た環状エーテルで処理したものを用いることにより、こ
の種電池のサイクル特性を改善す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。(g) Effects of the invention As mentioned above, in a non-aqueous electrolyte battery using a lithium negative electrode, the cycle characteristics of this type of battery are improved by using lithium treated with a cyclic ether in which lithium hexafluoroarsenate is dissolved. Therefore, its industrial value is extremely large.
第１図は本発明電池の半断面図、第２図は本発明電池と
比較電池のサイクル特性図である。FIG. 1 is a half-sectional view of the battery of the present invention, and FIG. 2 is a cycle characteristic diagram of the battery of the present invention and a comparative battery.
Claims (2)
処理したリチウムを負極として用いたことを特徴とする
非水電解液二次電池。(1) A non-aqueous electrolyte secondary battery characterized in that lithium treated with a cyclic ether in which lithium hexafluoroarsenate is dissolved is used as a negative electrode.
請求の範囲第（１）項記載の非水電解液二次電池。(2) The non-aqueous electrolyte secondary battery according to claim (1), wherein the treatment is an energization treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63006351A JPH01186754A (en) | 1988-01-14 | 1988-01-14 | Nonaqueous electrolytic liquid secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63006351A JPH01186754A (en) | 1988-01-14 | 1988-01-14 | Nonaqueous electrolytic liquid secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01186754A true JPH01186754A (en) | 1989-07-26 |
Family
ID=11635947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63006351A Pending JPH01186754A (en) | 1988-01-14 | 1988-01-14 | Nonaqueous electrolytic liquid secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01186754A (en) |
-
1988
- 1988-01-14 JP JP63006351A patent/JPH01186754A/en active Pending
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