JPH0458469A - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary batteryInfo
- Publication number
- JPH0458469A JPH0458469A JP2167627A JP16762790A JPH0458469A JP H0458469 A JPH0458469 A JP H0458469A JP 2167627 A JP2167627 A JP 2167627A JP 16762790 A JP16762790 A JP 16762790A JP H0458469 A JPH0458469 A JP H0458469A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- active material
- electrode active
- battery
- lithium ions
- 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 description 9
- 239000007774 positive electrode material Substances 0.000 claims abstract description 48
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 17
- 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
- 239000003792 electrolyte Substances 0.000 claims description 4
- 239000001989 lithium alloy Substances 0.000 claims description 4
- 239000007773 negative electrode material Substances 0.000 claims description 4
- 101100069231 Caenorhabditis elegans gkow-1 gene Proteins 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 24
- 239000013078 crystal Substances 0.000 abstract description 18
- 229910015685 LixMnOy Inorganic materials 0.000 abstract description 5
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 abstract description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 abstract description 4
- 238000003795 desorption Methods 0.000 abstract description 2
- 229910020050 NbSe3 Inorganic materials 0.000 abstract 1
- 229910003092 TiS2 Inorganic materials 0.000 abstract 1
- 230000008595 infiltration Effects 0.000 abstract 1
- 238000001764 infiltration Methods 0.000 abstract 1
- 229910052961 molybdenite Inorganic materials 0.000 abstract 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 25
- 230000007423 decrease Effects 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229910017326 LixMn Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 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
- 239000006182 cathode active material Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010304 firing Methods 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
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 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
- 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
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (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を負極活物質とす
る非水電解液二次電池に係り、特に正極の改良に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a non-aqueous electrolyte secondary battery using lithium or a lithium alloy as a negative electrode active material, and particularly relates to improvement of a positive electrode.
（ロ）従来の技術
この種の二次電池の正極活ＯＩｗとじては、二酸化マン
ガン（ＭｎＯ７）、三酸化モリブデ／（〜１００、）、
五酸化バナジウム（ｖ−０５）、チタン或いはニオブの
硫化物等が（Ｔｉｅ、等）が提案され、一部実用化され
ているものもある。これらの正極活物質は、放電、充電
時に、その結晶構造中に、リチウムイオンが侵入、脱離
し、放電、充電反応が進行する。しかし、これらの活物
質を正極に用いて電池を組み立て、放電、充電をくり返
−た場合、放電、充電のサイクルの進行に伴い巳だいに
放電容量が低下−でゆくという間趙点がある。(b) Prior art The positive electrode active OIw of this type of secondary battery includes manganese dioxide (MnO7), molybdenum trioxide/(~100,),
Vanadium pentoxide (v-05), titanium, niobium sulfide, etc. have been proposed (Tie, etc.), and some have been put into practical use. When these cathode active materials are discharged or charged, lithium ions enter and leave their crystal structures, and the discharge and charge reactions proceed. However, when a battery is assembled using these active materials as a positive electrode, and then discharged and charged repeatedly, there is a problem in that the discharge capacity gradually decreases as the discharge and charge cycles progress. .
この理由を、主として正極活物質の代表例である二酸化
マンガンを例にとり説明する。リチウムやリチウム合金
を負極活物質とし、正極活物質をＭ ｎ Ｏ２とじて、
電池を構成し放電反応を行なうと、Ｍ ｎ Ｏ、の結晶
構造中にリチウムが挿入される。このとき結晶格子が広
がり、二酸化マンガン粒子の膨張が起こる。放電終了後
、充電を行うと、正極活物質より挿入されたリチウムイ
オンの脱離がおこるが、侵入したリチウムイオンの一部
はＭ ｎ Ｏ＋の結晶構造内にとり込まれ充電によって
とり出すことができない。また、放電で広がった結晶格
子も、ある程度は収縮するが、放電前と同じ大きさには
戻らない。二回目以降の放電では、結晶格子の広がりは
１回目に比べて小さく、またこの広がりは充電によって
収縮する。The reason for this will be explained mainly by taking as an example manganese dioxide, which is a typical example of a positive electrode active material. Using lithium or lithium alloy as the negative electrode active material and M n O2 as the positive electrode active material,
When a battery is constructed and a discharge reaction is performed, lithium is inserted into the crystal structure of M n O. At this time, the crystal lattice expands and the manganese dioxide particles expand. When charging is performed after discharging, the lithium ions inserted from the positive electrode active material are desorbed, but some of the lithium ions that have entered are incorporated into the crystal structure of M n O + and cannot be taken out by charging. . Also, the crystal lattice expanded by the discharge shrinks to some extent, but does not return to the same size as before the discharge. In the second and subsequent discharges, the spread of the crystal lattice is smaller than in the first time, and this spread is contracted by charging.
即ち、第一回目の放電時にのみ、特異的な結晶格子の広
がりが起こり、この広がりは通常の充放電では元にもど
らない。上述のような第一回目の放電時に結晶構造が広
がる現象は、Ｍ ｎ Ｏ、だけに限らず、Ｍ ｏ Ｏｓ
、Ｖ２Ｏ６、Ｍ ｏ Ｓ 、、ＴｉＳ７、ＮｂＳｅ、、
ＬｉｘＭｎＯｙ等の結晶構造中へ放電時にリチウムイオ
ンが侵入するタイプの正極活物質に共通して見られる現
象である。これは、結晶構造中にある程度のリチウムイ
オンが侵入巳で結晶格子が広がることによって、それ以
後のリチウムイオンの侵入および脱離が容易になること
と、それと同時に、最初に侵入し、結晶格子の広がりを
生じせしめたリチウムイオンは、結晶中で安定な位置に
とり込まれてしまうと考えられる。この最初の放電時の
結晶格子の広がりは、電池特性上、様々な問題点をひき
起こす。即ち、■正極活物質粒子が膨張することにより
、正極中の導電材と正極活物質の接合性が悪くなり、正
極活物質の利用率が低下する、■・正極が集電体より剥
離する、■膨張した正極に電解液が吸収され、正極−負
極間の電解液が減少する、等の弊害を生じ、正極の充放
電サイクル特性を低下させる原因の１つとなっている。That is, only during the first discharge, a specific broadening of the crystal lattice occurs, and this broadening does not return to its original state during normal charging and discharging. The above-mentioned phenomenon in which the crystal structure spreads during the first discharge is not limited to M n O, but also M o Os.
, V2O6, M o S , , TiS7, NbSe, ,
This is a phenomenon commonly observed in positive electrode active materials of the type in which lithium ions invade into the crystal structure during discharge, such as LixMnOy. This is because the crystal lattice expands when a certain amount of lithium ions penetrate into the crystal structure, making it easier for subsequent lithium ions to enter and leave the crystal structure. It is thought that the lithium ions that caused the spread were incorporated into stable positions within the crystal. This expansion of the crystal lattice during the first discharge causes various problems in terms of battery characteristics. That is, (1) the expansion of the positive electrode active material particles deteriorates the bonding properties between the conductive material in the positive electrode and the positive electrode active material, resulting in a decrease in the utilization rate of the positive electrode active material; (2) the positive electrode peels off from the current collector; (2) The electrolyte is absorbed by the expanded positive electrode, causing problems such as a decrease in the amount of electrolyte between the positive and negative electrodes, which is one of the causes of deterioration of the charge-discharge cycle characteristics of the positive electrode.
また、負極活物質であるリチウムが、正極中に挿入され
た後残留するため過剰のリチウムが必要となり、電池体
積あたりの容量が低下するとともに、−度ある程度の深
度まで放電されたリチウムは充放電特性が劣化する欠点
がある。In addition, since lithium, which is the active material of the negative electrode, remains after being inserted into the positive electrode, excess lithium is required, which reduces the capacity per battery volume, and the lithium that has been discharged to a certain depth is not charged or discharged. The disadvantage is that the characteristics deteriorate.
（ハ）発明が解決しようとする課題
本発明は斯る問題点に鑑みてなされたものであって、非
水電解液二次電池の充放電サイクルの進行に伴う正極容
量の低下を抑制し、この種電池のサイクル特性の向上を
計るものである。(c) Problems to be Solved by the Invention The present invention has been made in view of the above problems, and aims to suppress the decrease in positive electrode capacity as the charge/discharge cycle of a non-aqueous electrolyte secondary battery progresses. The aim is to improve the cycle characteristics of this type of battery.
（ニ）課題を解決するための手段
本発明は、リチウムあるいはリチウム合金を負極活物質
とする負極と、リチウムイオンが侵入、脱離可能な正極
活物質からなる正極とを備えた非水電解液二次電池であ
って、前記正極活物質が電池外で予備的に放電及び充電
されたものであ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 comprising a negative electrode made of lithium or a lithium alloy as a negative electrode active material, and a positive electrode made of a positive electrode active material into which lithium ions can enter and escape. The secondary battery is characterized in that the positive electrode active material is preliminarily discharged and charged outside the battery.
ここで、前記正極活物質としては、Ｍ ｎ Ｏｔ、λ１
ｏＯ８、Ｘ′、Ｏ６、Ｍ ｏ Ｓ ＋、ＴｉＳ、、Ｎｂ
５ｅ１、Ｌ ｉ ｘ Ｍ ｎ ＯΣ・のうちから選択さ
れた少なくとも１種を含むものが好ましい。Here, as the positive electrode active material, M n Ot, λ1
oO8, X', O6, M o S +, TiS,, Nb
5e1, L i x M n OΣ· is preferable.
また、前記正極活物質の予備的放電量としては、正極容
量の１０％〜１００％とするのが好適である。Further, the preliminary discharge amount of the positive electrode active material is preferably 10% to 100% of the positive electrode capacity.
（ホ）作 用
本発明の如く、正極活物質が電池内に組込れる迄に、電
池外で予備的に放電及び充電されたものを用いることに
より、電池内における正極の膨張、収縮を抑制すること
が可能となる。即ち、放電により正極活物質の結晶格子
内に一部リチウムイオンがとり込まれ、一部残留するリ
チウムイオンも存在するので、結晶格子が大きくなり、
これ以降のリチウムイオンの脱離及び侵入が容易となる
。(E) Function As in the present invention, expansion and contraction of the positive electrode inside the battery is suppressed by using a positive electrode active material that has been preliminarily discharged and charged outside the battery before it is incorporated into the battery. It becomes possible to do so. In other words, some lithium ions are incorporated into the crystal lattice of the positive electrode active material due to discharge, and some lithium ions remain, so the crystal lattice becomes larger.
Subsequent desorption and intrusion of lithium ions becomes easy.
そして、リチウムイオンが侵入、脱離可能な前記正極活
物質としては、Ｎ４ ｎ Ｏｔ、Ｍ ｏ Ｏ＋、■。Examples of the positive electrode active material into which lithium ions can enter and leave are N4 n Ot, M o O+, and ■.
０６、Ｎ１ｏＳ＋、ＴｉＳ、、Ｎｂ５ｅｒ、ＬｉｘＭｎ
Ｏｙのうちから、選択された少なくとも１種を用５）る
のが好ましい。06, N1oS+, TiS, , Nb5er, LixMn
It is preferable to use at least one selected from 5) Oy.
また、前記正極活物質の予備的放を量としては、正極容
量の１０９ｏ〜１００％とするのが、好適である。Further, the amount of preliminary release of the positive electrode active material is preferably 109 to 100% of the positive electrode capacity.
（へ）実施例
以下、本発明の実施例と比較例との対比について詳述す
る。(f) Examples Hereinafter, comparisons between examples of the present invention and comparative examples will be explained in detail.
〔実施例１］
正極活物質としての化学二酸化マンガン（ＭｎＯ７）、
導電材としてのアセチレンブラックと、結着材としての
ＰＴＦＥとを、それぞｉｒ重量比で８０：１０： １
０に混合し、これに水を加えてペースト状にした。この
ペーストをステンレス集電板の両面に配置し、ローラー
で所定厚みに圧延し、正極とする。この正極を２５０℃
で真空熱処理した後、電解液としてのＩＭＬｉＣＪ２０
．−ＰＣ／Ｄ〜ｉＥ（Ｍｌ、）と負極リチウムからなる
電解槽内で、電位が負極に対し２．ＯＶになるまで前記
正極を放電する。この放電量は、はぼ正極容量の１００
％に相当する。この放電に引き続いて、今度は電圧が
４． 、 ＯＶになるまで充電する。[Example 1] Chemical manganese dioxide (MnO7) as a positive electrode active material,
Acetylene black as a conductive material and PTFE as a binder were mixed in an IR weight ratio of 80:10:1.
0 and added water to make a paste. This paste is placed on both sides of a stainless steel current collector plate and rolled to a predetermined thickness using a roller to form a positive electrode. This positive electrode was heated to 250°C.
After vacuum heat treatment in
．． -PC/D~iE (Ml, ) and a negative electrode lithium in an electrolytic cell with a potential of 2. The positive electrode is discharged until it reaches OV. This discharge amount is approximately 100% of the positive electrode capacity.
%. Following this discharge, the voltage now increases to 4. , Charge until it reaches OV.
充電後、正極を再びローラーで所定厚みに圧延し、電池
組立てに用いる。尚、正極を真空熱処理した後の工程は
、すべて、Ａ ｒ雰囲気中で行うものである。After charging, the positive electrode is again rolled to a predetermined thickness using a roller and used for battery assembly. Note that all steps after the vacuum heat treatment of the positive electrode are performed in an Ar atmosphere.
第１図は、この正極を用いて組み立てた本発明に係る円
筒電池の縦断面図である。FIG. 1 is a longitudinal sectional view of a cylindrical battery according to the present invention assembled using this positive electrode.
第１図中、正％１を、ポリプロピレン製セパレータ２を
介して、リチウム負極３とともに渦巻状に巻きとり、こ
ノｔを負極針４に挿入し、負極リード５をスポット溶接
により負極缶底部に溶接する。正極リード６は、正極キ
ャンプ７にスポット溶接され、絶縁バッキング８を介在
して、正極キャップ７により、負極針４が密閉されてい
る。In Fig. 1, the positive %1 is wound up in a spiral shape together with the lithium negative electrode 3 through a polypropylene separator 2, this tip is inserted into the negative electrode needle 4, and the negative electrode lead 5 is spot welded to the bottom of the negative electrode can. Weld. The positive electrode lead 6 is spot-welded to the positive electrode camp 7, and the negative electrode needle 4 is sealed by the positive electrode cap 7 with an insulating backing 8 interposed therebetween.
電解液には、プロピレンカーボネートと１．２ジメトキ
シエタンの混合溶媒に、過塩素酸リチウムを１モル／！
で溶解したものを用いている。The electrolyte contains 1 mol/! of lithium perchlorate in a mixed solvent of propylene carbonate and 1.2 dimethoxyethane.
I am using the solution dissolved in
このようにして組み立てた電池を、本発明電池Ａ１とす
る。The battery assembled in this manner is referred to as the battery A1 of the present invention.
実施例２コ
正極活物質としてＭ ｎ Ｏ、を用いることを除いては
、前記実施例１と同様にして本発明電池Ａ。Example 2 A battery A of the present invention was prepared in the same manner as in Example 1 except that MnO was used as the positive electrode active material.
を組み立てた。assembled.
［実施例３］
正極活物質として＼“２０５を用いることを除いては、
前記実施例１と同様にして本発明電池Ａ、を組み立てた
。[Example 3] Except for using \"205 as the positive electrode active material,
The battery A of the present invention was assembled in the same manner as in Example 1 above.
［実施例４コ
正極活物質としてＭ ｏ Ｓ 、を用いることを除いて
は、前記実施例１と同様にして本発明電池Ａ４を組み立
てた。[Example 4] A battery A4 of the present invention was assembled in the same manner as in Example 1 except that M o S was used as the positive electrode active material.
［実施例５］
正極活物質としてＴ ＋ Ｓ ｔを用いることを除いて
は、前記実施例１と同様にして本発明電池Ａ５を組み立
てた。[Example 5] A battery A5 of the present invention was assembled in the same manner as in Example 1 except that T + S t was used as the positive electrode active material.
［実施例６］
正極活物質としてＮ ｂ Ｓ ｅ ｓを用いることを除
いては、前記実施例１と同様にして本発明電池Ａ、を組
み立てた。[Example 6] A battery A of the present invention was assembled in the same manner as in Example 1 except that N b S e s was used as the positive electrode active material.
［実施例７］
正極活物質としてＬｉＯＨとＭ ｎ Ｏ２をＬ１対〜１
ｎの原子比が３対７になるように混合し、空気中で３７
５℃で２０時間焼成して作製したＬ１含有二酸化マンガ
ン（ＬｉｘＭｎＯｙ）を正極活物質として用いることを
除いては、前記実施例１と同様にして本発明電池Ａ７を
組み立てた。[Example 7] LiOH and MnO2 as positive electrode active materials in L1 to 1 ratio
Mix so that the atomic ratio of n is 3:7, and 37
A battery A7 of the present invention was assembled in the same manner as in Example 1, except that L1-containing manganese dioxide (LixMnOy) prepared by firing at 5° C. for 20 hours was used as the positive electrode active material.
［実施例８］
正極活物質としてＭ ｎ Ｏ、を用い、電解槽内での正
極の予備的放電量を、前記実施例１の予備的放電量に対
して５０％とし、これに続く充電は同様に４．ＯＶ迄と
することを除いては、前記実施例１と同様にして本発明
電池Ａ、を組み立てた。[Example 8] Using MnO as the positive electrode active material, the preliminary discharge amount of the positive electrode in the electrolytic cell was set to 50% of the preliminary discharge amount of Example 1, and the subsequent charging was Similarly 4. A battery A of the present invention was assembled in the same manner as in Example 1, except that the battery was up to OV.
［実施例９コ
正極活物質としてＭ ｎ Ｏｒを用い、電解槽内での正
極の予備的放電量を、実施例１の予備的放電量に対して
１０％とし、これに続く充電は同様に４ 、 ＯＶ迄と
することを除いては、前記実施例１と同様にして本発明
電池Ａ、を組み立てた。[Example 9] M n Or was used as the positive electrode active material, the preliminary discharge amount of the positive electrode in the electrolytic cell was set to 10% of the preliminary discharge amount of Example 1, and subsequent charging was carried out in the same manner. 4. Battery A of the present invention was assembled in the same manner as in Example 1 except that the battery was used up to OV.
［比較例１］
正極活物質としてＭ ｎ Ｏ、を用い、真空熱処理した
後の正極に予備的放電および充電を全く行なわずそのま
ま電池組立に使用することを除いては、前記実施例１と
同様にして比較電池Ｂ、を組み立てた。[Comparative Example 1] Same as Example 1, except that M n O was used as the positive electrode active material and the positive electrode after vacuum heat treatment was used for battery assembly without any preliminary discharging or charging. Comparative battery B was assembled.
「比較例２コ
正極活物質としてＭ ｏ Ｏｉを用ることを除いては、
前記比較例１と同様にして比較電池Ｂ２を組み立てた。"Comparative Example 2: Except for using MoOi as the positive electrode active material,
Comparative battery B2 was assembled in the same manner as in Comparative Example 1 above.
［比較例３］
正極活物質として■、０５を用ることを除いては、前記
比較例１と同様にして比較電池Ｂ、を組み立てた。[Comparative Example 3] Comparative battery B was assembled in the same manner as in Comparative Example 1, except that ■, 05 was used as the positive electrode active material.
Ｕ比較例４］
正極活物質としてＭ ｏ Ｓ ！を用ることを除いては
、前記比較例１と同様にして比較電池Ｂ、を組み立てた
。U Comparative Example 4] M o S as a positive electrode active material! Comparative battery B was assembled in the same manner as in Comparative Example 1, except that the battery B was used.
Ｅ比較例５］
正極活物質としてＴｉＳ、を用ることを除いては、前記
比較例１と同様にして比較電池Ｂ、を組み立てた。E Comparative Example 5] Comparative battery B was assembled in the same manner as Comparative Example 1, except that TiS was used as the positive electrode active material.
［比較例６″Ｊ
正極活物質と巳てＮ ｂ Ｓ ｅ ｈを用ることを除い
ては、前記比較例１と同様にして比較電池Ｂ６を組み立
てた。[Comparative Example 6″J Comparative battery B6 was assembled in the same manner as in Comparative Example 1 except that N b S eh was used instead of the positive electrode active material.
［比較例７］
正極活物質とＬで、ＬｉＯＨとＳｉ ｎ Ｏ、をＬｉ肘
λ１ｎの原子比が３対７になるように混合し、空気中で
３７５℃で２０時間焼成して作製したＬ１含有二酸化マ
ンガン（ＬｉｘＭｎＯｙ）を正極活物質として用いるこ
とを除いては、前記比較例１と同様にして比較電池Ｂ７
を組み立てた。[Comparative Example 7] L1 was prepared by mixing the positive electrode active material and L with LiOH and Si O such that the atomic ratio of Li elbow λ1n was 3:7, and baking the mixture in air at 375°C for 20 hours. Comparative battery B7 was prepared in the same manner as in Comparative Example 1 except that manganese dioxide (LixMnOy) containing manganese dioxide (LixMnOy) was used as the positive electrode active material.
assembled.
［比較例８］
正極活物質としてＭｎ Ｏ！を用い、電解槽内での正極
の予備的放電量を、前記実施例１の予備的放電量に対し
て５％とし、これに続く充電は同様に４．ＯＶ迄とする
ことを除いては、前記実施例１と同様にして比較電池Ｂ
、を組み立てた。[Comparative Example 8] MnO! as a positive electrode active material! The preliminary discharge amount of the positive electrode in the electrolytic cell was set to 5% of the preliminary discharge amount in Example 1, and the subsequent charging was carried out in the same manner as in 4. Comparative battery B
, was assembled.
こｉｔら電池Ａ１〜Ａ、及びＢ、〜Ｂ、を用い、電池の
サイクル特性を比較した。この結果を、第２図乃至第８
図に示す。第２図乃至第８図は、電池のサイクル特性図
である。The cycle characteristics of the batteries were compared using batteries A1 to A, and B, to B. This result is shown in Figures 2 to 8.
As shown in the figure. 2 to 8 are cycle characteristic diagrams of the battery.
そして第２図は、正極活物質にＭ ｎ Ｏｘを用いた場
合の本発明電池Ａ１、Ａ８、Ａ、と、比較電池Ｂ７、Ｂ
８のサイクル特性図である。FIG. 2 shows inventive batteries A1, A8, A when M n Ox is used as the positive electrode active material, and comparative batteries B7, B.
8 is a cycle characteristic diagram of No. 8.
また、正極活物質として、Ｍ ｏ Ｏｓ、Ｖ、Ｏ，、λ
Ｉｏ Ｓｔ、ＴｉＳ、、Ｎ ｂ Ｓ ｅ ｈ、Ｌ ｉ
ｘ Ｍ ｎ Ｏｙを用いた本発明電池と比較電池のサイ
クル特性の比較をそれぞれ第３図乃至第８図に示す。In addition, as a positive electrode active material, M o Os, V, O,, λ
Io St, TiS,, N b S e h, L i
A comparison of the cycle characteristics of a battery of the present invention using x M n Oy and a comparative battery is shown in FIGS. 3 to 8, respectively.
第２図より、Ｍ ｎ Ｏ、を正極活物質とした場合、電
池外での予備的放電量が１０％以上のときに、予備的放
電量を０〜５％とした場合に比べて、サイクル寿命が著
しく向上していることがわかる。From Figure 2, when MnO is used as the positive electrode active material, when the amount of preliminary discharge outside the battery is 10% or more, the cycle rate is lower than when the amount of preliminary discharge is 0 to 5%. It can be seen that the lifespan has been significantly improved.
また、第３図乃至第８図に示されるように、ＭｎＯ２以
外の正極活物質を用いた場合でも、電池外で予備的放電
を行うことにより、それぞれサイクル特性が向上してい
ることがわかる。Moreover, as shown in FIGS. 3 to 8, it can be seen that even when positive electrode active materials other than MnO2 are used, the cycle characteristics are improved by performing preliminary discharge outside the battery.
（ト）発明の効果
本発明の非水電解液二次電池は、正極活物質が電池外で
予備的に放電及び充電されたものであるから、サイクル
特性進行に伴う正極の膨張、収縮を抑制することが可能
となり、正極の容量低下が抑えられ、この種電池のサイ
クル特性の向上が計れるものであり、その工業的価値は
極めて大きい(G) Effects of the Invention In the non-aqueous electrolyte secondary battery of the present invention, since the positive electrode active material is preliminarily discharged and charged outside the battery, expansion and contraction of the positive electrode as cycle characteristics progress is suppressed. This makes it possible to suppress the decrease in the capacity of the positive electrode and improve the cycle characteristics of this type of battery, so its industrial value is extremely large.
電池のサイクル特性図である。
１・・・正極、２・・・セパレータ、３・・負極、４山
負極缶、５・・・負極リード、６・正極リード、７・・
・正極キャップ、８・・絶縁バッキング、
Ａ３、Ａ、、Ａ、、Ａ４、Ａ５、Ａ６、Ａ７、Ａ、。
Ａ、・・・本発明電池、
Ｂ２、Ｂ８、Ｂ１、Ｂ４、Ｂ５、Ｂ６、Ｂ９、Ｂ、・・
・比Ｖ電池。It is a cycle characteristic diagram of a battery. 1... Positive electrode, 2... Separator, 3... Negative electrode, 4-pole negative electrode can, 5... Negative electrode lead, 6... Positive electrode lead, 7...
- Positive electrode cap, 8... Insulating backing, A3, A,, A,, A4, A5, A6, A7, A,. A,...Battery of the present invention, B2, B8, B1, B4, B5, B6, B9, B,...
- Specific V battery.
Claims (3)
る負極と、リチウムイオンが侵入、脱離可能な正極活物
質からなる正極とを備えた電池であって、 前記正極活物質が電池外で予備的に放電及び充電された
ものであることを特徴とする非水電解液二次電池。(1) A battery comprising a negative electrode made of lithium or a lithium alloy as a negative electrode active material, and a positive electrode made of a positive electrode active material into which lithium ions can enter and escape, wherein the positive electrode active material is used as a preliminary material outside the battery. A non-aqueous electrolyte secondary battery characterized by being discharged and charged.
＿２Ｏ＿５、ＭｏＳ＿２、ＴｉＳ＿２、ＮｂＳｅ＿３、
Ｌｉ＿ｘＭｎＯ＿ｙのうちから選択された少なくとも１
種を含むことを特徴とする請求項１記載の非水電解液二
次電池。(2) The positive electrode active material is MnO_2, MoO_3, V
_2O_5, MoS_2, TiS_2, NbSe_3,
At least one selected from Li_xMnO_y
The non-aqueous electrolyte secondary battery according to claim 1, characterized in that the non-aqueous electrolyte secondary battery contains a seed.
０％〜１００％であることを特徴とする請求項（１）記
載の非水電解液二次電池。(3) The preliminary discharge amount of the positive electrode active material is 1 of the positive electrode capacity.
The nonaqueous electrolyte secondary battery according to claim 1, wherein the electrolyte content is 0% to 100%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2167627A JP2865387B2 (en) | 1990-06-26 | 1990-06-26 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2167627A JP2865387B2 (en) | 1990-06-26 | 1990-06-26 | Non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0458469A true JPH0458469A (en) | 1992-02-25 |
| JP2865387B2 JP2865387B2 (en) | 1999-03-08 |
Family
ID=15853295
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2167627A Expired - Lifetime JP2865387B2 (en) | 1990-06-26 | 1990-06-26 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2865387B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5466655A (en) * | 1993-06-21 | 1995-11-14 | Mitsubishi Paper Mills Limited | Heat-sensitive recording material |
| JP2002507313A (en) * | 1997-06-27 | 2002-03-05 | エルジー・ケミカル・リミテッド | Lithium ion secondary battery and method of manufacturing the same |
| JP2008098131A (en) * | 2006-09-13 | 2008-04-24 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery and its manufacturing method |
| WO2011030686A1 (en) * | 2009-09-09 | 2011-03-17 | 日本電気株式会社 | Secondary battery |
-
1990
- 1990-06-26 JP JP2167627A patent/JP2865387B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5466655A (en) * | 1993-06-21 | 1995-11-14 | Mitsubishi Paper Mills Limited | Heat-sensitive recording material |
| JP2002507313A (en) * | 1997-06-27 | 2002-03-05 | エルジー・ケミカル・リミテッド | Lithium ion secondary battery and method of manufacturing the same |
| JP2008098131A (en) * | 2006-09-13 | 2008-04-24 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery and its manufacturing method |
| WO2011030686A1 (en) * | 2009-09-09 | 2011-03-17 | 日本電気株式会社 | Secondary battery |
| JP5716667B2 (en) * | 2009-09-09 | 2015-05-13 | 日本電気株式会社 | Secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2865387B2 (en) | 1999-03-08 |
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