JP2001338692A - Lithium ion secondary cell - Google Patents
Lithium ion secondary cellInfo
- Publication number
- JP2001338692A JP2001338692A JP2000156929A JP2000156929A JP2001338692A JP 2001338692 A JP2001338692 A JP 2001338692A JP 2000156929 A JP2000156929 A JP 2000156929A JP 2000156929 A JP2000156929 A JP 2000156929A JP 2001338692 A JP2001338692 A JP 2001338692A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- ion secondary
- lithium ion
- positive electrode
- weight
- 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
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
【０００１】[0001]
【発明の属する技術分野】この発明は、リチウムイオン
二次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium ion secondary battery.
【０００２】[0002]
【従来の技術】リチウムイオン二次電池は、正極部と負
極部との間にセパレータが介装された電極体が非水電解
液と共に密閉容器内に配置されている。この正極部は、
一般式ＬｉＣｏＯ２で表されるコバルト酸リチウムを正
極活物質とし、負極部を構成する負極合剤は、リチウム
を吸蔵・放出可能な炭素材料、ポリマー、酸化物等を主
成分とする。非水電解液はリチウム塩を含んでいる。2. Description of the Related Art In a lithium ion secondary battery, an electrode body in which a separator is interposed between a positive electrode portion and a negative electrode portion is disposed in a closed container together with a non-aqueous electrolyte. This positive electrode part
Lithium cobalt oxide represented by the general formula LiCoO 2 is used as a positive electrode active material, and a negative electrode mixture constituting a negative electrode portion mainly contains a carbon material, a polymer, an oxide, and the like capable of inserting and extracting lithium. The non-aqueous electrolyte contains a lithium salt.
【０００３】このようなリチウムイオン二次電池の正極
部は、一般に、正極活物質としてＬｉＣｏＯ２で表され
るコバルト酸リチウムと導電剤とに加え、これら全体を
結合するバインダとで構成される。そして、この電池の
充電時には、リチウムイオンは正極部のＬｉＣｏＯ２か
ら脱ドープして非水電解液へ抜けだし、セパレータを介
して負極部へ移動する。逆に放電時には、このリチウム
イオンは、負極部から正極部へ移動する。The positive electrode portion of such a lithium ion secondary battery is generally composed of lithium cobalt oxide represented by LiCoO 2 as a positive electrode active material, a conductive agent, and a binder for binding the whole. When the battery is charged, lithium ions are dedoped from LiCoO 2 in the positive electrode portion, escape to the non-aqueous electrolyte, and move to the negative electrode portion via the separator. Conversely, during discharge, the lithium ions move from the negative electrode to the positive electrode.
【０００４】[0004]
【発明が解決しようとする課題】ところが、正極部が前
記のように構成されている場合、正極部に存在するバイ
ンダがＬｉＣｏＯ２と非水電解液との接触を阻害して両
者間の反応阻害が生じ、二次電池の放電容量が低下して
しまい、充分な高負荷特性が得られないという問題があ
った。However, when the positive electrode portion is configured as described above, the binder present in the positive electrode portion hinders the contact between LiCoO 2 and the non-aqueous electrolyte to inhibit the reaction between the two. This causes a problem that the discharge capacity of the secondary battery is reduced and sufficient high load characteristics cannot be obtained.
【０００５】[0005]
【課題を解決するための手段】そこで、本発明のリチウ
ムイオン二次電池は、一般式ＬｉＣｏＯ２で表されるコ
バルト酸リチウムを正極活物質とする正極部と、リチウ
ムを吸蔵・放出可能な炭素材料、ポリマー、酸化物等を
主成分とする負極合剤からなる負極部と、前記正極部と
前記負極部との間に介装されたセパレータとからなる電
極体が、リチウム塩を含んだ非水電解液と共に密閉容器
内に配置されたリチウムイオン二次電池において、前記
正極部に、一般式Ｌｉ２ＣＯ３で表される炭酸リチウム
を０．１乃至０．６重量％の範囲で添加してなる。ま
た、前記正極部のＬｉ２ＣＯ３の添加割合としては、
０．１乃至０．５重量％の範囲であることが好ましい。
このような構成のリチウムイオン二次電池にあっては、
前述した反応阻害が緩和され、高負荷特性が向上する。Accordingly, a lithium ion secondary battery according to the present invention comprises a positive electrode portion using lithium cobalt oxide represented by the general formula LiCoO 2 as a positive electrode active material, and a carbon material capable of occluding and releasing lithium. An electrode body composed of a negative electrode part composed of a negative electrode mixture containing a material, a polymer, an oxide or the like as a main component and a separator interposed between the positive electrode part and the negative electrode part is a non-electrode body containing a lithium salt. In a lithium ion secondary battery arranged in a closed container together with an aqueous electrolyte, lithium carbonate represented by the general formula Li 2 CO 3 is added to the positive electrode in a range of 0.1 to 0.6% by weight. It becomes. Further, as the addition ratio of Li 2 CO 3 in the positive electrode portion,
It is preferably in the range of 0.1 to 0.5% by weight.
In the lithium ion secondary battery having such a configuration,
The above-described reaction inhibition is reduced, and the high load characteristics are improved.
【０００６】[0006]
【発明の実施の形態】以下、本発明のリチウムイオン二
次電池を作成する手順の一実施例について説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, one embodiment of a procedure for producing a lithium ion secondary battery of the present invention will be described.
【０００７】本発明のリチウムイオン二次電池の正極に
ついては、まず、ＬｉＣｏＯ２（平均粒径約１２μｍ）
およびＬｉ２ＣＯ３（平均粒径約２〜３μｍ）９０重量
部と、アセチレンブラック５重量部と、バインダとし
て、四フッ化エチレンディスパージョン（固形分）３重
量部と、カルボキシメチルセルロース２重量部とに水を
加え、混ぜ合わせてペースト状にする。ここでは、Ｌｉ
２ＣＯ３の添加量が０．１〜０．６重量％、好ましくは
０．１〜０．５重量％の範囲内にあることとする。この
ペーストを厚さ約２０μｍのアルミ箔上に塗布して１０
０℃で乾燥し、その後、アルミ箔のもう一方の面にも同
様にペーストを塗布して乾燥する。そして得られた積層
体を厚さ１８０μｍにロール圧延する。これを幅約３４
ｍｍ、長さ約５５０ｍｍに裁断して、正極シート電極１
とする。For the positive electrode of the lithium ion secondary battery of the present invention, first, LiCoO 2 (average particle size: about 12 μm)
And 90 parts by weight of Li 2 CO 3 (average particle size of about 2 to 3 μm), 5 parts by weight of acetylene black, 3 parts by weight of ethylene tetrafluoride dispersion (solid content), and 2 parts by weight of carboxymethyl cellulose as a binder. Add water and mix to make a paste. Here, Li
The addition amount of 2 CO 3 is in the range of 0.1 to 0.6% by weight, preferably 0.1 to 0.5% by weight. This paste is applied on an aluminum foil having a thickness of about 20 μm and
After drying at 0 ° C., the paste is applied to the other side of the aluminum foil in the same manner and dried. Then, the obtained laminate is roll-rolled to a thickness of 180 μm. This is about 34 width
mm, and cut into a length of about 550 mm.
And
【０００８】一方、負極については、リチウムを吸蔵・
放出可能な材料として、天然黒鉛（平均粒径約１５μ
ｍ）９５重量部と、ＳＢＲラテックス３重量部と、カル
ボキシメチルセルロース２重量部とに水を加え、混ぜ合
わせてペースト状にする。このペーストを厚さ１４μｍ
の銅箔上に塗布して１００℃で乾燥し、その後、銅箔の
もう一方の面にも同様にペーストを塗布して乾燥する。
そして得られた積層体を厚さ１６０μｍにロール圧延す
る。これを幅約３８ｍｍ、長さ約５８０ｍｍに裁断し
て、負極シート電極２とする。On the other hand, for the negative electrode, lithium is inserted and stored.
Natural graphite (average particle size about 15μ)
m) Water is added to 95 parts by weight, 3 parts by weight of SBR latex, and 2 parts by weight of carboxymethylcellulose and mixed to form a paste. This paste is 14μm thick
And dried at 100 ° C., and then paste and dry the other side of the copper foil in the same manner.
Then, the obtained laminate is roll-rolled to a thickness of 160 μm. This is cut into a width of about 38 mm and a length of about 580 mm to obtain a negative electrode sheet electrode 2.
【０００９】正極シート電極１の端部にはアルミニウム
製のリードを、負極シート電極２の端部にはニッケル製
のリードをそれぞれ溶接する。An aluminum lead is welded to an end of the positive electrode sheet electrode 1 and a nickel lead is welded to an end of the negative electrode electrode 2.
【００１０】次に、正極シート電極１および負極シート
電極２を、それぞれのリードが長手方向の反対側に位置
するように配置し、それぞれのリードの耳が同じ方向に
出るように幅約３６ｍｍ、厚さ約２５μｍのポリエチレ
ン微多孔膜からなるセパレータ３を電極間に挟む。そし
て、図１に示すように、幅約２６ｍｍの巻き芯４を用
い、正極シート電極１と、負極シート電極２と、セパレ
ータ３とを重ねた積層体を巻回して電極体を作成する。Next, the positive electrode sheet electrode 1 and the negative electrode electrode 2 are arranged so that the respective leads are located on opposite sides in the longitudinal direction, and the width of the lead is about 36 mm so that the ears of the respective leads extend in the same direction. A separator 3 made of a microporous polyethylene membrane having a thickness of about 25 μm is sandwiched between the electrodes. Then, as shown in FIG. 1, using a winding core 4 having a width of about 26 mm, a stacked body in which the positive electrode sheet electrode 1, the negative electrode sheet electrode 2, and the separator 3 are stacked is wound to form an electrode body.
【００１１】得られた電極体を、図２に示すように、厚
さ約１０ｍｍ、幅約３５ｍｍ、高さ約５２ｍｍの角形の
ケース５内に収納し、ニッケル製のリード６をケース５
の開口部付近に溶接する。一方、アルミニウム製のリー
ドは、開口部を封止するための蓋７に設けた正極端子８
に溶接する。その後、ケース５と蓋７とをレーザシーム
溶接してケース５の開口部を封止した。The obtained electrode body is housed in a rectangular case 5 having a thickness of about 10 mm, a width of about 35 mm and a height of about 52 mm, as shown in FIG.
Weld near the opening. On the other hand, an aluminum lead has a positive electrode terminal 8 provided on a lid 7 for sealing the opening.
Weld to. Thereafter, the case 5 and the lid 7 were subjected to laser seam welding to seal the opening of the case 5.
【００１２】次に、蓋７に設けた注液口９から、電解液
をケース５の容量の７０％に達するまで注入し、１００
ｍＡで２時間充電する。その後、残りの電解液を注入す
る。そして注液口９を圧着した後、溶接してシールす
る。最後に、１００ｍＡ、４．２Ｖの定電圧充電を４時
間おこなう。用いた電解液は、ＥＣ、ＤＥＣ、ＤＭＣ及
びＥＭＣを各々２０、２０、２０、４０の割合で混合し
た溶媒に、溶質として１ＭのＬｉＰＦ６を含む。Next, an electrolyte is injected from a liquid inlet 9 provided in the lid 7 until the volume of the electrolyte reaches 70% of the volume of the case 5.
Charge for 2 hours at mA. After that, the remaining electrolyte is injected. Then, after the liquid injection port 9 is pressed, it is sealed by welding. Finally, constant voltage charging of 100 mA and 4.2 V is performed for 4 hours. The electrolyte used contained 1M LiPF 6 as a solute in a solvent in which EC, DEC, DMC and EMC were mixed at a ratio of 20, 20, 20, and 40, respectively.
【００１３】上記手順にしたがって作成したリチウムイ
オン二次電池の放電特性を図３のグラフに示した。この
グラフでは、縦軸を電池の放電容量比（％）、横軸をＬ
ｉ２ＣＯ３の添加量（重量％）とした。ここでいう放電
容量比とは、｛（３．６Ａの放電容量／０．２４Ａの放
電容量）×１００｝の式により得られる値である。The discharge characteristics of the lithium ion secondary battery prepared according to the above procedure are shown in the graph of FIG. In this graph, the vertical axis represents the discharge capacity ratio (%) of the battery, and the horizontal axis represents L.
The amount (% by weight) of i 2 CO 3 was determined. Here, the discharge capacity ratio is a value obtained by the formula of {(discharge capacity of 3.6 A / discharge capacity of 0.24 A) × 100}.
【００１４】このグラフから、電池の正極に添加するＬ
ｉ２ＣＯ３の添加量が０．１重量％のときに放電容量比
が７０％を超え、添加量が０．５〜０．６重量％のとき
にピークに達することが分かる。このことから、本発明
では電池の正極にＬｉ２ＣＯ ３を０．１〜０．６重量％
の範囲で添加することとした。From this graph, it can be seen that L added to the positive electrode of the battery
i2CO3Capacity ratio when 0.1% by weight is added
Is more than 70% and the added amount is 0.5 to 0.6% by weight
It can be seen that the peak is reached. From this, the present invention
Then Li for the positive electrode of the battery2CO 30.1 to 0.6% by weight
It was decided to add within the range.
【００１５】ところで、角形電池の場合、Ｌｉ２ＣＯ３
の添加量（重量％）と電極体の膨らみ（ｍｍ）との関係
を示す図４のグラフからも分かるように、Ｌｉ２ＣＯ３
の濃度が０．５重量％を超えてしまうと電極体が膨らん
で電池の外装ケースが変形してしまうので、添加量を
０．１〜０．５重量％の範囲に設定する。一方、円筒形
電池であれば、電極体の膨らみを考慮する必要がないの
で、Ｌｉ２ＣＯ３の添加量は０．１〜０．６重量％の範
囲に設定すればよい。By the way, in the case of a prismatic battery, Li 2 CO 3
As can be seen from the graph of FIG. 4 showing the relationship between the addition amount (% by weight) and the swelling (mm) of the electrode body, Li 2 CO 3
If the concentration exceeds 0.5% by weight, the electrode body swells and the outer case of the battery is deformed. Therefore, the addition amount is set in the range of 0.1 to 0.5% by weight. On the other hand, in the case of a cylindrical battery, since it is not necessary to consider the swelling of the electrode body, the amount of Li 2 CO 3 added may be set in the range of 0.1 to 0.6 wt%.
【００１６】本発明では、電池の正極にＬｉ２ＣＯ３を
０．１〜０．６重量％の範囲で添加することにより好適
な放電特性を得ることができるが、その理由としては次
のようなことが考えられる。In the present invention, favorable discharge characteristics can be obtained by adding Li 2 CO 3 to the positive electrode of the battery in the range of 0.1 to 0.6% by weight, for the following reasons. It is possible.
【００１７】電池の正極側では、ＬｉＣｏＯ２がリチウ
ムイオンをドープ・脱ドープする役割を果たすが、Ｌｉ
ＣｏＯ２の周りはバインダで被覆されており、ＬｉＣｏ
Ｏ２と電解液との接触が阻害されている。ところが、Ｌ
ｉ２ＣＯ３を正極に添加しておくと、充電時にこのＬｉ
２ＣＯ３が分解して収縮するとともに、ＣＯ２ガスおよ
びＯ２ガスが発生する。すると、発生したガスによって
バインダがＬｉＣｏＯ ２から引き離されるとともに、Ｌ
ｉ２ＣＯ３の収縮によりＬｉＣｏＯ２の周りにピンホー
ルが生成されるので、電解液がＬｉＣｏＯ２の周りに浸
透することができ、ＬｉＣｏＯ２と電解液との接触状態
が改善されて反応阻害が緩和される。したがって、リチ
ウムイオンのドープ・脱ドープがスムーズに行われ、放
電容量が向上することとなる。On the positive electrode side of the battery, LiCoO2But
It plays the role of doping and undoping ions
CoO2Is coated with a binder, and LiCo
O2And the contact with the electrolyte is inhibited. However, L
i2CO3If Li is added to the positive electrode, this Li
2CO3Decomposes and contracts, and CO2Gas and
And O2Gas is generated. Then, depending on the generated gas
The binder is LiCoO 2And L
i2CO3LiCoO due to shrinkage2Pinho around
Is produced, so that the electrolyte is LiCoO2Soak around
Can be transparent, LiCoO2State of contact between electrolyte and electrolyte
Is improved and reaction inhibition is reduced. Therefore, Lichi
The doping and undoping of um ions is performed smoothly,
The electric capacity is improved.
【００１８】[0018]
【発明の効果】以上説明したように、本発明によれば、
電池の正極に炭酸リチウムを０．１〜０．６重量％の範
囲で添加することによって、ＬｉＣｏＯ２と非水電解液
との反応阻害を緩和することができ、電池の放電容量を
向上させて充分な高負荷特性を得ることができる。As described above, according to the present invention,
By adding lithium carbonate in the range of 0.1 to 0.6% by weight to the positive electrode of the battery, the inhibition of the reaction between LiCoO 2 and the non-aqueous electrolyte can be reduced, and the discharge capacity of the battery can be improved. Sufficient high load characteristics can be obtained.
【図１】本発明の一実施例にかかるリチウムイオン二次
電池を作成する工程の一を示す図である。FIG. 1 is a view showing one step of manufacturing a lithium ion secondary battery according to one embodiment of the present invention.
【図２】本発明のリチウムイオン二次電池の一実施例を
示す図である。FIG. 2 is a view showing one embodiment of a lithium ion secondary battery of the present invention.
【図３】本発明の一実施例にかかるリチウムイオン二次
電池の放電容量比とＬｉ２Ｏ３の添加量との関係を示す
グラフである。FIG. 3 is a graph showing a relationship between a discharge capacity ratio and an added amount of Li 2 O 3 of a lithium ion secondary battery according to one example of the present invention.
【図４】本発明の一実施例にかかるリチウムイオン二次
電池の電極体の膨らみ量とＬｉ ２ＣＯ３の添加量との関
係を示すグラフである。FIG. 4 shows a lithium ion secondary battery according to one embodiment of the present invention.
Swelling amount and Li of battery electrode body 2CO3Relationship with the amount of
It is a graph which shows a relationship.
１ 正極シート電極 ２ 負極シート電極 ３ セパレータ 1 positive electrode sheet electrode 2 negative electrode sheet electrode 3 separator
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 5H029 AJ02 AJ03 AK03 AL02 AL06 AL07 AL16 AM01 AM07 BJ02 BJ14 DJ08 EJ03 HJ01 5H050 AA02 AA08 BA17 CA08 CB02 CB07 CB08 CB20 DA09 EA01 HA01 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 5H029 AJ02 AJ03 AK03 AL02 AL06 AL07 AL16 AM01 AM07 BJ02 BJ14 DJ08 EJ03 HJ01 5H050 AA02 AA08 BA17 CA08 CB02 CB07 CB08 CB20 DA09 EA01 HA01
Claims (1)
酸リチウムを正極活物質とする正極部と、リチウムを吸
蔵・放出可能な材料を主成分とする負極合剤からなる負
極部と、前記正極部と前記負極部との間に介装されたセ
パレータとからなる電極体が、リチウム塩を含んだ非水
電解液と共に密閉容器内に配置されたリチウムイオン二
次電池において、 前記正極部に、一般式Ｌｉ２ＣＯ３で表される炭酸リチ
ウムを０．１乃至０．６重量％の範囲で添加してなるこ
とを特徴とするリチウムイオン二次電池。1. A positive electrode part comprising lithium cobalt oxide represented by the general formula LiCoO 2 as a positive electrode active material, a negative electrode part comprising a negative electrode mixture containing a material capable of occluding and releasing lithium as a main component, and An electrode body comprising a separator interposed between the portion and the negative electrode portion, in a lithium ion secondary battery placed in a closed container with a non-aqueous electrolyte containing a lithium salt, in the positive electrode portion, A lithium ion secondary battery comprising lithium carbonate represented by the general formula Li 2 CO 3 in an amount of 0.1 to 0.6% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000156929A JP2001338692A (en) | 2000-05-26 | 2000-05-26 | Lithium ion secondary cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000156929A JP2001338692A (en) | 2000-05-26 | 2000-05-26 | Lithium ion secondary cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001338692A true JP2001338692A (en) | 2001-12-07 |
Family
ID=18661636
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000156929A Pending JP2001338692A (en) | 2000-05-26 | 2000-05-26 | Lithium ion secondary cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001338692A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9350049B2 (en) | 2013-11-28 | 2016-05-24 | Gs Yuasa International Ltd. | Electric storage device and electric storage apparatus |
| CN111509190A (en) * | 2019-01-30 | 2020-08-07 | 丰田自动车株式会社 | Positive electrode active material and nonaqueous electrolyte secondary battery provided with same |
-
2000
- 2000-05-26 JP JP2000156929A patent/JP2001338692A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9350049B2 (en) | 2013-11-28 | 2016-05-24 | Gs Yuasa International Ltd. | Electric storage device and electric storage apparatus |
| CN111509190A (en) * | 2019-01-30 | 2020-08-07 | 丰田自动车株式会社 | Positive electrode active material and nonaqueous electrolyte secondary battery provided with same |
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