JPH0421991B2 - - Google Patents
Info
- Publication number
- JPH0421991B2 JPH0421991B2 JP58004358A JP435883A JPH0421991B2 JP H0421991 B2 JPH0421991 B2 JP H0421991B2 JP 58004358 A JP58004358 A JP 58004358A JP 435883 A JP435883 A JP 435883A JP H0421991 B2 JPH0421991 B2 JP H0421991B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- negative electrode
- positive electrode
- aqueous electrolyte
- separator
- 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
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 7
- 239000011149 active material Substances 0.000 claims description 5
- -1 composed of lithium Chemical compound 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 239000004743 Polypropylene Substances 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
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000012530 fluid Substances 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
- 239000012046 mixed solvent 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
- 229920001155 polypropylene Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-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
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000005096 rolling process Methods 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
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B75/00—Other engines
- F02B75/02—Engines characterised by their cycles, e.g. six-stroke
- F02B2075/022—Engines characterised by their cycles, e.g. six-stroke having less than six strokes per cycle
- F02B2075/027—Engines characterised by their cycles, e.g. six-stroke having less than six strokes per cycle four
-
- G—PHYSICS
- G05—CONTROLLING; REGULATING
- G05B—CONTROL OR REGULATING SYSTEMS IN GENERAL; FUNCTIONAL ELEMENTS OF SUCH SYSTEMS; MONITORING OR TESTING ARRANGEMENTS FOR SUCH SYSTEMS OR ELEMENTS
- G05B2219/00—Program-control systems
- G05B2219/10—Plc systems
- G05B2219/11—Plc I-O input output
- G05B2219/1171—Detect only input variation, changing, transition state of variable
-
- G—PHYSICS
- G05—CONTROLLING; REGULATING
- G05B—CONTROL OR REGULATING SYSTEMS IN GENERAL; FUNCTIONAL ELEMENTS OF SUCH SYSTEMS; MONITORING OR TESTING ARRANGEMENTS FOR SUCH SYSTEMS OR ELEMENTS
- G05B2219/00—Program-control systems
- G05B2219/10—Plc systems
- G05B2219/14—Plc safety
- G05B2219/14143—Structure, low pass filter, debouncing input, output driver with ramp
-
- 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)
- Battery Electrode And Active Subsutance (AREA)
Description
(イ) 産業上の利用分野
本発明はリチウム又はリチウムを主体とする合
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、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。
(ロ) 従来技術
従来のこの種電池においてはサイクル特性に問
題があり、その主たる要因としては負極活物質で
あるリチウム又はリチウムを主体とする合金の性
能劣化、充放電サイクルに伴うセパレータ中の電
解液量不足にある。
即ち、負極となるリチウム又はリチウムを主体
とする合金板を所定寸法に圧延圧着する工程で表
面にLiOH、Li2O、Li2O3、Li3Nなどの不活性被
膜が生成する。この不活性被膜が充放電の繰返し
で一部電解液中に溶解し電解液を構成する有機溶
媒を分解したり、充電時に一部残存する被膜上に
リチウムが析出して所謂デンドライトを発生する
ことになる。
又、充放電の繰返しで負極表面は多孔度の大な
る海綿状のリチウムが生成して厚みが増し、正極
の膨張と相まつてセパレータを圧縮することにな
りセパレータ中の電解液が絞り出され電解液不足
となつて電池性能の低下を招く。
(ハ) 発明の目的
本発明は前述せる従来電池の問題点を解消し、
この種電池のサイクル特性向上を目的とする。
(ニ) 発明の構成
本発明は正極と、リチウム又はリチウムを主体
とする合金を活物質とし前記正極の容量と同等若
しくはそれ以上を予備的に充放電処理した負極
と、非水電解液とを備えた非水電解液二次電池に
ある。
(ホ) 実施例
以下本発明の実施例につき詳述する。
第１図は本発明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によつて隔離されて
いる。４は後述するように予じめ充放電処理した
リチウム板よりなる負極であつて、負極缶２の内
底面に固着された負極集電体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アセ
チレンブラツク導電剤及びフツ素樹脂結着剤を
80：10：10（重量比）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
あり、このセパレータにはプロピレンカーボネー
ト1.2ジメトキシエタンとの等体積混合溶媒に過
塩素酸リチウムを１モル／溶解した非水電解液
が含浸されている。
そして負極容量200ｍAH、正極容量120ｍAH
とし正極支配型の電池（容量120ｍAH）を作成
した。
而して、負極としては次の操作により予備的に
充放電処理を行なつたものを用いた。
即ち、厚み0.5mm、直径18.0mmのリチウム板、
或いはリチウムを主体とする合金としてのリチウ
ム−アルミニウム合金板（モル比85：15）を負極
缶の内底面に圧着し、そして対極（陽極）として
リチウム板、電解液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等体積混合溶媒に
１モル／の過塩素酸リチウムを溶解したものを
用い、下表の如く予備充放電量を異ならせた負極
を作成した。
(a) Industrial application field The present invention relates to a negative electrode whose active material is lithium or an alloy mainly composed of lithium, and a sulfide of molybdenum trioxide, vanadium pentoxide, titanium or niobium,
The present invention relates to a non-aqueous electrolyte secondary battery that includes a positive electrode using selenide or the like as an active material and a non-aqueous electrolyte. (b) Prior art Conventional batteries of this type have problems with cycle characteristics, the main causes of which are deterioration in the performance of lithium or lithium-based alloys, which are the negative electrode active materials, and electrolysis in the separator during charge/discharge cycles. The fluid level is insufficient. That is, in the process of rolling and compressing a lithium or lithium-based alloy plate to be a negative electrode into a predetermined size, an inert film of LiOH, Li 2 O, Li 2 O 3 , Li 3 N, etc. is formed on the surface. During repeated charging and discharging, some of this inert film dissolves in the electrolyte, decomposing the organic solvent that makes up the electrolyte, and lithium precipitates on the film that partially remains during charging, creating so-called dendrites. become. In addition, due to repeated charging and discharging, a highly porous and spongy lithium lithium is formed on the surface of the negative electrode, increasing its thickness, which together with the expansion of the positive electrode compresses the separator, squeezing out the electrolyte in the separator and causing electrolysis. This results in a lack of fluid, leading to a decline in battery performance. (c) Purpose of the invention The present invention solves the problems of the conventional batteries mentioned above,
The aim is to improve the cycle characteristics of this type of battery. (d) Structure of the Invention The present invention comprises a positive electrode, a negative electrode that uses lithium or a lithium-based alloy as an active material and has been preliminarily charged and discharged to a capacity equal to or greater than that of the positive electrode, and a non-aqueous electrolyte. It is a non-aqueous electrolyte secondary battery equipped with (e) Examples Examples of the present invention will be described in detail below. FIG. 1 shows a half cross-sectional view of the battery of the present invention, 1, 2
are positive and negative electrode cans made of stainless steel, and are separated by an insulating packing 3 made of polypropylene. Reference numeral 4 denotes a negative electrode made of a lithium plate that has been previously charged and discharged as will be described later, and is crimped to a negative electrode current collector 5 fixed to the inner bottom surface of the negative electrode can 2 . 6 is a positive electrode, which is made of a titanium disulfide active material, an acetylene black conductive agent and a fluororesin binder.
A mixture mixed at a ratio of 80:10:10 (weight ratio) is molded into a positive electrode fixing ring 7, which is pressed into contact with a positive electrode current collector 8 fixed to the inner bottom surface of the positive electrode can 1.
Reference numeral 9 denotes a separator made of polypropylene nonwoven fabric, and this separator is impregnated with a non-aqueous electrolyte in which 1 mol/mol of lithium perchlorate is dissolved in a mixed solvent of propylene carbonate and 1.2 dimethoxyethane in equal volumes. And negative electrode capacity 200mAH, positive electrode capacity 120mAH
A positive electrode-dominated battery (capacity 120 mAH) was created. The negative electrode used was one that had been preliminarily charged and discharged by the following procedure. That is, a lithium plate with a thickness of 0.5 mm and a diameter of 18.0 mm.
Alternatively, a lithium-aluminum alloy plate (molar ratio 85:15), which is an alloy mainly composed of lithium, is crimped onto the inner bottom surface of the negative electrode can, and a lithium plate is used as the counter electrode (anode), and propylene carbonate and 1.2 dimethoxyethane are used as the electrolyte. Negative electrodes were prepared using 1 mol/mole of lithium perchlorate dissolved in a mixed solvent of equal volume as shown in the table below with different amounts of preliminary charge and discharge.
【表】
尚、充放電電流はいづれも２ｍＡ定電流とし
た。
第２図は上表における各負極を用いた電池のサ
イクル特性を示し、実線はリチウム単独、破線は
リチウム−アルミニウム合金でありサイクル条件
は充電電流２ｍＡ、充電終止電圧4.0V、放電電
流２ｍＡ、放電終止電圧1.5Vとし放電量が90ｍ
AH以下となつた時点で電池終了とした。
(ヘ) 発明の効果
第２図より明白なるように、負極として予備的
に充放電処理したリチウム、或いはリチウムを主
体とする合金であるリチウム−アルミニウム合金
を用いた場合には無処理の場合に比してサイクル
特性が向上するのがわかる。この理由は充放電処
理によつて負極表面の不活性被膜が取除かれると
共に電池組立時に既に負極には充放電時に生成さ
れる海綿状のリチウムが形成されているため、電
池使用時における充放電の繰返しで生じる負極の
膨張が抑制される結果、セパレータに対する圧縮
力が抑制されセパレータから電解液を絞り出すと
いつた不都合もなく電解液不足を来たす懸念がな
いためである。
特に本発明の如く負極の予備充放電量を正極容
量と同等若しくはそれ以上とすることにより飛躍
的にサイクル特性が向上するが、これは負極のう
ち予備的に充放電処理した部分のみが電池の充放
電反応に関与するため新たな海綿状リチウムの生
成がなく負極の膨張がほとんど皆無となることに
よる。[Table] Note that the charging/discharging current was 2 mA constant current in all cases. Figure 2 shows the cycle characteristics of batteries using each of the negative electrodes in the above table, where the solid line is for lithium alone and the broken line is for lithium-aluminum alloy.The cycle conditions are charging current 2mA, charge end voltage 4.0V, discharge current 2mA, discharge The final voltage is 1.5V and the discharge amount is 90m.
The battery was terminated when it became below AH. (f) Effect of the invention As is clear from Figure 2, when lithium that has been preliminarily charged and discharged or a lithium-aluminum alloy, which is an alloy mainly composed of lithium, is used as the negative electrode, the result is lower than when no treatment is used. It can be seen that the cycle characteristics are improved. The reason for this is that the inert film on the surface of the negative electrode is removed during the charging and discharging process, and spongy lithium that is generated during charging and discharging has already been formed on the negative electrode when the battery is assembled. This is because the expansion of the negative electrode caused by repeated steps is suppressed, and as a result, the compressive force on the separator is suppressed, and there is no inconvenience caused by squeezing out the electrolyte from the separator, and there is no concern that the electrolyte will run out. In particular, as in the present invention, by making the amount of preliminary charge and discharge of the negative electrode equal to or greater than the capacity of the positive electrode, the cycle characteristics are dramatically improved. This is because no new spongy lithium is generated because it is involved in the charge/discharge reaction, and there is almost no expansion of the negative electrode.
第１図は本発明電池の半断面図、第２図はサイ
クル数と負極の予備充放電量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。
FIG. 1 is a half-sectional view of the battery of the present invention, and FIG. 2 is a diagram showing the relationship between the number of cycles and the amount of preliminary charge and discharge of the negative electrode. 1... Positive electrode can, 2... Negative electrode can, 3... Insulating packing, 4... Negative electrode, 6... Positive electrode, 9... Separator.
Claims (1)
合金を活物質とし、前記正極の容量と同等若しく
はそれ以上を予備的に充放電処理した負極と、非
水電解液とを備えた非水電解液二次電池。1 A non-aqueous electrolyte solution comprising a positive electrode, a negative electrode whose active material is lithium or an alloy mainly composed of lithium, and which has been preliminarily charged and discharged to a capacity equal to or greater than the capacity of the positive electrode, and a non-aqueous electrolyte solution. Next battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58004358A JPS59128780A (en) | 1983-01-14 | 1983-01-14 | Nonaqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58004358A JPS59128780A (en) | 1983-01-14 | 1983-01-14 | Nonaqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59128780A JPS59128780A (en) | 1984-07-24 |
| JPH0421991B2 true JPH0421991B2 (en) | 1992-04-14 |
Family
ID=11582161
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58004358A Granted JPS59128780A (en) | 1983-01-14 | 1983-01-14 | Nonaqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59128780A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01137563A (en) * | 1987-11-24 | 1989-05-30 | Japan Storage Battery Co Ltd | Manufacture of lithium secondary cell |
-
1983
- 1983-01-14 JP JP58004358A patent/JPS59128780A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59128780A (en) | 1984-07-24 |
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