JP2000090936A - Winding type secondary battery and collector therefor - Google Patents
Winding type secondary battery and collector thereforInfo
- Publication number
- JP2000090936A JP2000090936A JP10257722A JP25772298A JP2000090936A JP 2000090936 A JP2000090936 A JP 2000090936A JP 10257722 A JP10257722 A JP 10257722A JP 25772298 A JP25772298 A JP 25772298A JP 2000090936 A JP2000090936 A JP 2000090936A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- electrode body
- wound
- conductive layer
- metal
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Secondary Cells (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は巻回式二次電池に係り、
特にリチウム二次電池に好適な巻回式電極構造の改良に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wound type secondary battery,
In particular, the present invention relates to an improvement in a wound electrode structure suitable for a lithium secondary battery.
【０００２】[0002]
【従来の技術】リチウム二次電池は金属リチウムの析出
溶解反応を利用するもので、小型で電池容量が大きい理
由から、特に携帯型電子装置の電源用として期待されて
いる。このようなリチウム二次電池の電極体に巻回構造
を採用したものが知られている。2. Description of the Related Art A lithium secondary battery utilizes a deposition and dissolution reaction of metallic lithium, and is expected to be used particularly as a power source for portable electronic devices because of its small size and large battery capacity. It is known that such a lithium secondary battery employs a wound structure for an electrode body.
【０００３】図６は巻回式電池の巻回体の構成図であ
る。なお、図６においては、説明を容易に理解するため
に正極体と負極体とセパレータとを一体物として図面上
区別せずに示している。前記巻回体１０は大別して正極
体２０と負極体３０とセパレータ４０とよりなる。すな
わち、正極体２０と負極体３０とがセパレータ４０を介
して渦巻状に巻回され、巻き止めテープ５０で固定され
る。正極体２０に設けられた正極リード２１が電池缶の
正極端子に接続され、負極体３０に設けられた負極リー
ド３１が負極端子に接続される。この巻回体１０は金属
缶に装着され、その後、金属缶に電解液を注入しプレス
機等で金属缶を封口して巻回式二次電池が形成される。FIG. 6 is a structural view of a wound body of a wound type battery. In FIG. 6, for easy understanding of the description, the positive electrode body, the negative electrode body, and the separator are shown as one body without being distinguished in the drawing. The wound body 10 roughly includes a positive electrode body 20, a negative electrode body 30, and a separator 40. That is, the positive electrode body 20 and the negative electrode body 30 are spirally wound with the separator 40 interposed therebetween, and are fixed with the winding tape 50. The positive electrode lead 21 provided on the positive electrode body 20 is connected to the positive electrode terminal of the battery can, and the negative electrode lead 31 provided on the negative electrode body 30 is connected to the negative electrode terminal. The wound body 10 is mounted on a metal can, and thereafter, an electrolytic solution is injected into the metal can, and the metal can is sealed with a press or the like to form a wound secondary battery.
【０００４】図７は従来技術に係る正極体の構造図であ
る。上記正極体２０は単３サイズの場合で厚さ約２５０
μｍ、幅約３６mm、長さ約２６cmである。この正極体２
０は大略、集電体２２と正極合剤２３とから構成されて
いる。集電体２２は正極体２０のベースとなるアルミニ
ウムまたはアルミニウム合金である。そして正極合剤２
３は正極活物質と導電剤と結着材を溶媒で溶解したもの
である。正極活物質はLiCoO2、LiMnO4、LiNiO2、LiMn3O
6 等である。集電体２２の表裏両面に正極合剤２３を塗
布または圧着した領域が正極合剤領域２４である。また
集電領域２５は正極合剤２３を塗布されておらずアルミ
箔が露出した領域で、巻回体の前端部の領域である。こ
の集電領域２５に正極体リード２１が設けられている。FIG. 7 is a structural view of a cathode body according to the prior art. The positive electrode body 20 has a thickness of about 250 in the case of AA size.
μm, about 36 mm in width and about 26 cm in length. This positive electrode body 2
Numeral 0 generally includes a current collector 22 and a positive electrode mixture 23. The current collector 22 is aluminum or an aluminum alloy serving as a base of the positive electrode body 20. And positive electrode mixture 2
No. 3 is obtained by dissolving a positive electrode active material, a conductive agent and a binder in a solvent. The positive electrode active material is LiCoO2, LiMnO4, LiNiO2, LiMn3O
6 mag. A region where the positive electrode mixture 23 is applied or pressed on both the front and back surfaces of the current collector 22 is a positive electrode mixture region 24. The current collecting area 25 is an area where the positive electrode mixture 23 is not applied and the aluminum foil is exposed, and is an area at the front end of the wound body. The positive electrode lead 21 is provided in the current collecting region 25.
【０００５】次に、前述した負極体３０はリチウム箔ま
たはリチウム合金であり、単３サイズの場合で厚さ約１
５０μｍ、幅約３８mm、長さ約２８cmである。更に、セ
パレータ４０は多孔質ポリエチレンであり、単３サイズ
の場合で厚さ約２５μｍ、幅約４０mm、長さ約３０cmで
ある。図８は正極体と負極体とセパレータとの関係を示
す配置図である。Next, the above-mentioned negative electrode body 30 is made of a lithium foil or a lithium alloy, and has a thickness of about 1 in the case of AA size.
It is 50 μm, about 38 mm wide and about 28 cm long. Further, the separator 40 is made of porous polyethylene, and has a thickness of about 25 μm, a width of about 40 mm, and a length of about 30 cm in the case of AA size. FIG. 8 is an arrangement diagram showing a relationship among a positive electrode body, a negative electrode body, and a separator.
【０００６】紙面垂直方向に下面からセパレータ４０、
負極体３０、セパレータ４０、正極体２０の順に配置さ
れている。これら負極体３０と正極体２０とをセパレー
タ４０を介して、正極体リード２１を上向きに配置し、
負極体リード３１を下向きに配置する。この状態で負極
体３０、セパレータ４０と正極体２０とを巻回すると図
６に示した巻回体１０ができる。[0006] The separator 40,
The negative electrode body 30, the separator 40, and the positive electrode body 20 are arranged in this order. The negative electrode body 30 and the positive electrode body 20 are disposed with the positive electrode body lead 21 facing upward via the separator 40,
The negative electrode lead 31 is arranged downward. When the negative electrode body 30, the separator 40, and the positive electrode body 20 are wound in this state, the wound body 10 shown in FIG. 6 is formed.
【０００７】[0007]
【発明が解決しようとする課題】上記のようにリチウム
を吸蔵する正極体を使ったリチウム二次電池は、充電時
に正極合剤中の正極活物質からリチウムが抜け出して負
極体に析出する。この析出したリチウムによって負極体
の体積が膨張する。また放電時には負極に析出したリチ
ウムが溶解し正極体の正極活物質に吸蔵される。しかし
析出したリチウムの一部は電解液と反応し、死リチウム
になり正極活物質に吸蔵されない。換言すると、この死
リチウムが負極体上に不可逆性の被膜として残る。この
ため充放電を繰り返す度に、この不可逆性の被膜が徐々
に増え続けて、さらに体積膨張を続ける。この体積膨張
は引張応力として巻回体に作用する。結果として、この
引張応力が巻回体を構成する正負極体からなる電極体の
集電体を破断する。As described above, in a lithium secondary battery using a positive electrode body that stores lithium, lithium escapes from the positive electrode active material in the positive electrode mixture during charging and deposits on the negative electrode body. The volume of the negative electrode body expands due to the deposited lithium. At the time of discharge, lithium precipitated on the negative electrode is dissolved and occluded in the positive electrode active material of the positive electrode body. However, part of the deposited lithium reacts with the electrolytic solution to become dead lithium and is not absorbed by the positive electrode active material. In other words, the dead lithium remains as an irreversible film on the negative electrode body. Therefore, each time charge and discharge are repeated, the irreversible film gradually increases and further expands in volume. This volume expansion acts on the wound body as tensile stress. As a result, this tensile stress breaks the current collector of the electrode body composed of the positive and negative electrode bodies constituting the wound body.
【０００８】つまり、巻回体で発生した引張応力が電極
体の集電体の破断強度を越えることにより渦巻状集電体
を横断する破断を生じる。この結果として、リード２
１、リード３１に連なる集電領域から切り離された領域
の電池エネルギーつまり電流を集電することができな
い。結果として電池の容量が大幅に減少する。本発明の
目的は各電極の集電体の破断による電池容量の減少を防
止し、電池を長期間安定に動作させることができる新し
い巻回式二次電池を提供するものである。That is, when the tensile stress generated in the wound body exceeds the breaking strength of the current collector of the electrode body, breakage occurs across the spiral current collector. As a result, lead 2
1. It is impossible to collect the battery energy, that is, the current, in a region separated from the current collecting region connected to the lead 31. As a result, the capacity of the battery is greatly reduced. SUMMARY OF THE INVENTION It is an object of the present invention to provide a new wound secondary battery that can prevent a decrease in battery capacity due to breakage of a current collector of each electrode and can operate a battery stably for a long period of time.
【０００９】[0009]
【課題を解決するための手段】請求項１に記載の発明
は、正極体と負極体とがセパレータを介して巻回されて
なる二次電池であって、前記正極体は金属基体と、前記
金属基体の片面または両面に形成された導電層とからな
る集電体の表面に正極合剤を塗布した構成を有すること
を特徴としている。従って充放電時に生じる体積膨張に
よる集電体の破断を防止でき、電池を長期間安定に動作
することができる。The invention according to claim 1 is a secondary battery in which a positive electrode body and a negative electrode body are wound with a separator interposed therebetween, wherein the positive electrode body comprises a metal base, It is characterized in that it has a configuration in which a positive electrode mixture is applied to the surface of a current collector comprising a conductive layer formed on one or both surfaces of a metal substrate. Therefore, it is possible to prevent the current collector from being broken due to volume expansion occurring at the time of charging and discharging, and to operate the battery stably for a long period of time.
【００１０】請求項２の発明は、前記金属基体はメッシ
ュ状のステンレス材からなり、前記導電層はアルミニウ
ムまたはアルミニウム合金材からなることを特徴として
いる。従って、伸長可能な金属基体は伸び率を向上する
ことができ、導電層は導電率を向上することができる。
請求項３の発明は、前記集電体の伸び率および強度は前
記正極合材の伸び率および強度より大きいことを特徴と
している。結果として体積膨張によって正極合剤が破断
されても集電体は破断されないため電池の容量を取り出
せることができる。[0010] The invention according to claim 2 is characterized in that the metal base is made of a mesh-like stainless material, and the conductive layer is made of aluminum or an aluminum alloy material. Therefore, the stretchable metal base can improve the elongation, and the conductive layer can improve the conductivity.
The invention of claim 3 is characterized in that the elongation and the strength of the current collector are larger than the elongation and the strength of the positive electrode mixture. As a result, even if the positive electrode mixture is broken by volume expansion, the current collector is not broken, so that the capacity of the battery can be taken out.
【００１１】請求項４の発明は、前記金属基体の伸び率
および強度は前記導電層の伸び率および強度より大き
く、前記導電層の導電率は前記金属基体の導電率より高
いことを特徴としている。従って、体積膨張によって正
極合剤、導電層が破断されても金属基体は破断されない
ため電池の容量を取り出すことができる。また電池の容
量つまり電流は導電用層の破断された部分のみ金属基体
をバイパスして導電層から取り出されるので電気抵抗を
増大することはない。従って、電池の容量を低下するこ
ともない。[0011] The invention of claim 4 is characterized in that the elongation and strength of the metal base are greater than the elongation and strength of the conductive layer, and the conductivity of the conductive layer is higher than the conductivity of the metal base. . Therefore, even if the positive electrode mixture and the conductive layer are broken by volume expansion, the metal substrate is not broken, so that the capacity of the battery can be taken out. Further, the capacity of the battery, that is, the current, is extracted from the conductive layer by bypassing the metal base only in the broken portion of the conductive layer, so that the electric resistance does not increase. Therefore, the capacity of the battery is not reduced.
【００１２】請求項５の発明は、正極体と負極体とがセ
パレータを介して巻回されてなる二次電池であって、前
記負極体はメッシュ状のステンレス材の基体の片面また
は両面に、リチウムまたはリチウム合金を設けているこ
とを特徴としている。従って、伸長可能な金属基体は伸
び率を向上することがでる。請求項６の発明は、金属缶
に巻回して封入された正極体と負極体の少なくとも一方
が伸長可能なメッシュ状の金属と、その上に積層された
他の金属層との２層構成の金属基体を有して成ることを
特徴としてる。結果として体積膨張によって正極体の正
極合剤、導電層または負極体のリチウムが破断されても
金属基体は破断されないため電池の容量を取り出せるこ
とができる。The invention according to claim 5 is a secondary battery in which a positive electrode body and a negative electrode body are wound with a separator interposed therebetween, wherein the negative electrode body is provided on one or both sides of a mesh-shaped stainless steel substrate. A feature is that lithium or a lithium alloy is provided. Therefore, the extensible metal base can improve the elongation rate. The invention according to claim 6 has a two-layer structure of a mesh-like metal in which at least one of a positive electrode body and a negative electrode body wound and sealed in a metal can is extensible, and another metal layer laminated thereon. It is characterized by having a metal substrate. As a result, even if the positive electrode mixture of the positive electrode body, the conductive layer or the lithium of the negative electrode body is broken by volume expansion, the metal base is not broken, so that the capacity of the battery can be taken out.
【００１３】[0013]
【発明の実施の形態】本発明の実施例を図面に基づいて
説明する。尚、従来例と同じ部分には同一符号を記して
説明を省略している。 ＜第１の実施例＞図１は第１の実施例に係る正極体の側
断面図である。図１は説明を理解し易いように正極体２
０の正極合剤領域２４の側断面を示した図である。Embodiments of the present invention will be described with reference to the drawings. The same parts as those in the conventional example are denoted by the same reference numerals, and description thereof is omitted. <First Embodiment> FIG. 1 is a side sectional view of a positive electrode body according to a first embodiment. FIG. 1 shows a cathode body 2 for easy understanding of the description.
FIG. 3 is a diagram showing a side cross section of a positive electrode mixture region 24 of No. 0;
【００１４】正極体２０は大略、集電体２２と正極合剤
２３とから構成されている。そして、この集電体２２は
メッシュ状の開口部２６を有する基材部としての伸長可
能な金属基体２２０と導電層２２１とから構成されてい
る。図２は第１の実施例に係る金属基体の平面図であ
る。この金属基体２２０は例えば、ＳＵＳ４３０の名で
呼ばれるステンレス材で、単３サイズの場合で厚さ約４
０μｍ、幅約３６mm、長さ約２６cmである。金属基体２
２０はメッシュ状に複数の開口部２６が設けられてい
る。この開口部２６は表裏貫通の孔である。一例とし
て、ひし形開口部２６の形状は短軸Ｐ１が約１．６mm、
横ピッチＰ２が約１．２mm、 長軸Ｐ３が約３．３mm、
縦ピッチＰ４が約２．０mmである。この金属基体２２０
の強度は約０．９０Kgf であり、引っ張速度１mm/ 分に
て破断するまでの伸びは約６１．９mmである。この開口
部２６を金属基体２２０に設けることによって伸び率が
増し、引張応力に耐えて破断されにくくなる。なお、開
口部２６の形状は上記ひし形に限らず他の任意形状であ
っても良い。 ＜電池の製作方法＞電池の製作方法について説明する。
まず、図１に示す正極体２０の製作方法を説明する。上
述したメッシュ状金属基体２２０の両面に導電層２２１
としてのアルミニウムをスパッタ製法等で厚さ約各１５
μｍに積層して集電体２２を製作する。ここでメッシュ
状金属基体２２０の導電率は約６０μオーム・cmであ
り、導電層２２１用としてのアルミニウムの導電率は約
２．８μオーム・cmである。また上述した寸法で形成し
た導電層２２１の巻回始終端間抵抗は０．０５オームで
ある。The cathode body 20 generally comprises a current collector 22 and a cathode mixture 23. The current collector 22 includes an extensible metal base 220 serving as a base having a mesh-shaped opening 26 and a conductive layer 221. FIG. 2 is a plan view of the metal base according to the first embodiment. The metal substrate 220 is, for example, a stainless steel material called SUS430, and has a thickness of about 4 in the case of AA size.
0 μm, width about 36 mm, length about 26 cm. Metal substrate 2
20 is provided with a plurality of openings 26 in a mesh shape. The opening 26 is a through-hole. As an example, the shape of the diamond-shaped opening 26 has a short axis P1 of about 1.6 mm,
The horizontal pitch P2 is about 1.2 mm, the major axis P3 is about 3.3 mm,
The vertical pitch P4 is about 2.0 mm. This metal substrate 220
Has a strength of about 0.90 kgf and an elongation before breaking at a pulling rate of 1 mm / min of about 61.9 mm. By providing the opening 26 in the metal base 220, the elongation rate is increased, and the material is resistant to tensile stress and hardly broken. The shape of the opening 26 is not limited to the above-mentioned rhombus, but may be any other shape. <Method of Manufacturing Battery> A method of manufacturing a battery will be described.
First, a method for manufacturing the positive electrode body 20 shown in FIG. 1 will be described. The conductive layers 221 are provided on both surfaces of the mesh-shaped metal base 220 described above.
About 15mm thick by sputtering method etc.
A current collector 22 is manufactured by laminating the current collector 22 to a thickness of μm. Here, the conductivity of the mesh-shaped metal base 220 is about 60 μΩ · cm, and the conductivity of aluminum for the conductive layer 221 is about 2.8 μΩ · cm. The resistance between the start and end of winding of the conductive layer 221 formed with the above-described dimensions is 0.05 ohm.
【００１５】この集電体２２の開口部２６に正極合剤２
３を充填し、更にこの集電体２２の両面に正極合剤２３
を厚さ約９０μｍ塗布し正極体２０を製作する。正極合
剤２３は正極活物質と導電剤と結着剤とを溶媒で溶解し
たものである。正極活物質はLiCoO2であり、導電剤はグ
ラファイトとアセチレンブラックの混合物であり、結着
剤はポリフッカビニリデンである。そして正極合剤２３
はこれらの正極活物質：導電剤：結着剤を９１：６：３
の割合に混合し、そして溶媒としてのＮ−メチルピロリ
ドンで溶解したペースト状のものを乾燥、圧延したもの
である。The positive electrode mixture 2 is placed in the opening 26 of the current collector 22.
3 and a positive electrode mixture 23 on both surfaces of the current collector 22.
Is applied to a thickness of about 90 μm to manufacture the positive electrode body 20. The positive electrode mixture 23 is obtained by dissolving a positive electrode active material, a conductive agent, and a binder with a solvent. The positive electrode active material is LiCoO2, the conductive agent is a mixture of graphite and acetylene black, and the binder is polyfukkavinylidene. And the positive electrode mixture 23
Represents 91: 6: 3 of these positive electrode active material: conductive agent: binder
And dried and rolled from a paste which was dissolved in N-methylpyrrolidone as a solvent.
【００１６】この集電体２２の強度は約０．７２Kgf で
あり、引っ張速度１mm/ 分にて破断するまでの伸びは約
３８．０mmである。また正極合剤２３の強度は固形化し
た状態で約０．５Kgf であり、引っ張速度１mm/ 分にて
破断するまでの１分間の伸びは約０．３mmである。本実
施例では正極活物質としてLiCoO2を用いたが、LiMn2o4
，LiNi(1-x)MxO2（ 0≦x ＜0.5 ，M はTi，V ，Cr，M
n，Fe，Co，Cu，Zn，Al，B の金属元素のうち一種類以
上），LiMn3O6 ，LiV2O5等の正極活物質を用いた場合も
同様の効果が得られる。The current collector 22 has a strength of about 0.72 kgf and an elongation before breaking at a pulling rate of 1 mm / min of about 38.0 mm. The strength of the positive electrode mixture 23 is about 0.5 kgf in a solidified state, and the elongation per minute before breaking at a pulling rate of 1 mm / min is about 0.3 mm. In this example, LiCoO2 was used as the positive electrode active material, but LiMn2o4
, LiNi (1-x) MxO2 (0 ≦ x <0.5, M is Ti, V, Cr, M
Similar effects can be obtained when a positive electrode active material such as n, Fe, Co, Cu, Zn, Al, or B is used, or LiMn3O6, LiV2O5, or the like.
【００１７】また本実施例では導電層２２１としてアル
ミニウムを用いたが、金属基体２２０よりも高い導電率
を有し、且つ電解液に酸化されないアルミニウム合金、
金、白金を用いても良い。また金属基体２２０としてＳ
ＵＳ４３０のステンレス材を用いたがＳＵＳ４３０以外
のステンレス材、アルミニウム合金、銅および銅合金等
を用いた場合も同様の効果がある。In this embodiment, aluminum is used for the conductive layer 221. However, an aluminum alloy having higher conductivity than the metal base 220 and not being oxidized by the electrolytic solution is used.
Gold or platinum may be used. Further, as the metal base 220, S
Although a stainless steel material of US430 is used, the same effect can be obtained when a stainless steel material other than SUS430, aluminum alloy, copper, copper alloy, or the like is used.
【００１８】次に、負極体３０はリチウム箔またはリチ
ウム合金であり、単３サイズの場合で厚さ約１５０μ
ｍ、幅約３８mm、長さ約２８cmである。更に、セパレー
タ４０は厚さ約２５μｍの多孔質ポリエチレンである。
前記セパレータ４０を介して正極体２０と負極体３０と
を巻回する。結果として従来と同型の巻回体ができる。Next, the negative electrode body 30 is made of a lithium foil or a lithium alloy, and has a thickness of about 150 μm in the case of AA size.
m, width about 38 mm, length about 28 cm. Further, the separator 40 is a porous polyethylene having a thickness of about 25 μm.
The positive electrode body 20 and the negative electrode body 30 are wound with the separator 40 interposed therebetween. As a result, a wound body of the same type as the conventional one is obtained.
【００１９】金属缶の内径に対して巻回体の内径は約
０．９mm程小さめであり、その間に若干の膨張吸収用と
しての間隙を設けてある。この巻回体を電池缶に封入し
両電極リードを金属缶の両端子と接続する。その後、電
解液を注入し、プレス機等で金属缶を封口すると巻回式
二次電池ができる。上記電解液はLiPF6 （６フッ化リン
酸リチウム）を１mol/リットル濃度で溶解した容積比
１：１のＥＣ（エチレンカーボネート）とＤＥＣ（ジエ
チルカーボネート）の混合液である。The inner diameter of the wound body is smaller than the inner diameter of the metal can by about 0.9 mm, and a gap is provided between them for absorbing some expansion. The wound body is sealed in a battery can, and both electrode leads are connected to both terminals of the metal can. Thereafter, an electrolytic solution is injected, and the metal can is sealed with a press or the like, whereby a wound type secondary battery is completed. The electrolyte is a mixture of EC (ethylene carbonate) and DEC (diethyl carbonate) in a volume ratio of 1: 1 in which LiPF6 (lithium hexafluorophosphate) is dissolved at a concentration of 1 mol / liter.
【００２０】上記の様に、正極体２０は開口部２６を持
つ金属基体２２０と、この金属基体２２０の両面に形成
された導電層２２１とからなる集電体２２の表面に正極
合剤２３を塗布した構成である。更に集電体２２の伸び
率および強度は正極合剤２３の伸び率および強度より大
きいものである。次に金属基体２２０の伸び率および強
度は導電層２２１の伸び率および強度より大きくして、
且つ導電層２２１の導電率は金属基体２２０の導電率よ
り高くしている。As described above, the positive electrode body 20 has the positive electrode mixture 23 on the surface of the current collector 22 including the metal base 220 having the opening 26 and the conductive layers 221 formed on both surfaces of the metal base 220. It is a configuration in which it is applied. Further, the elongation and strength of the current collector 22 are larger than the elongation and strength of the positive electrode mixture 23. Next, the elongation and the strength of the metal base 220 are set to be larger than the elongation and the strength of the conductive layer 221.
The conductivity of the conductive layer 221 is higher than the conductivity of the metal base 220.
【００２１】このような構成にすることによって、充放
電に伴う体積膨張が発生した場合は最初に正極合剤２３
が破断されることになるが集電体２２の金属基体２２０
が伸長可能であるので導電層２２１の破断には至らな
い。このため電池の容量を取り出せることができる。ま
た体積が更に膨張して正極合剤２３と導電層２２１が破
断された場合でも集電体２２の金属基体２２０自身の伸
長によって破断力を吸収すると共に、破断された導電層
部分の導通機能を補うので電池の容量を取り出すのに支
障を生じない。また電池の容量つまり電流は導電層２２
１の破断された部分のみ金属基体２２０をバイパスする
ために電池の容量を低下することもない。具体的には次
のようになる。With this configuration, when volume expansion occurs due to charging and discharging, first, the positive electrode mixture 23
Is broken, but the metal substrate 220 of the current collector 22 is broken.
Is stretchable, the conductive layer 221 is not broken. Therefore, the capacity of the battery can be taken out. Further, even when the volume further expands and the positive electrode mixture 23 and the conductive layer 221 are broken, the breaking force is absorbed by the extension of the metal base 220 of the current collector 22 itself, and the conduction function of the broken conductive layer portion is improved. Since it supplements, there is no problem in taking out the capacity of the battery. The capacity of the battery, that is, the current is
Since only one broken portion bypasses the metal base 220, the capacity of the battery is not reduced. Specifically, it is as follows.
【００２２】図３は正極体の正極合剤と導電層に亀裂を
生じた断面図である。体積膨張によって、正極合剤２３
と導電層２２１とに亀裂を生じ破断されている。しかし
金属基体２２０は伸び率が導電層２２１よりも大きいた
めに破断されていない。この状態になっても電池内の電
流ｉは下記のように流れる。導電層２２１の破断されて
いない部分では金属基体２２０よりも電気抵抗の小さい
導電層２２１を流れ、破断されている部分だけ金属基体
２２０をバイパスして流れる。そして再度破断されてい
ない部分では電気抵抗の小さい導電層２２１を流れる。
その後、正極体２０の集電領域２５に設けられたリード
端子から出力される。従って、金属基体２２０の大きな
伸び率が体積膨張による集電体２２の破断を防止し、導
電層２２１の高い導電率が電流の流れを容易する。FIG. 3 is a cross-sectional view in which a crack has occurred in the positive electrode mixture and the conductive layer of the positive electrode body. Due to the volume expansion, the positive electrode mixture 23
And the conductive layer 221 are cracked and broken. However, the metal base 220 is not broken because the elongation is larger than that of the conductive layer 221. Even in this state, the current i in the battery flows as follows. The unbroken portion of the conductive layer 221 flows through the conductive layer 221 having lower electric resistance than the metal base 220, and only the broken portion flows bypassing the metal base 220. Then, the portion not broken again flows through the conductive layer 221 having a small electric resistance.
Thereafter, the signal is output from a lead terminal provided in the current collecting region 25 of the positive electrode body 20. Therefore, the large elongation of the metal base 220 prevents the current collector 22 from breaking due to volume expansion, and the high conductivity of the conductive layer 221 facilitates the flow of current.
【００２３】結果として、集電領域２５から切り離され
た領域のエネルギーをも集電することができる。 ＜第２の実施例＞第１の実施例では正極側の金属基体に
伸長可能な金属基体を用いた構成について説明したが、
正極側と負極側の両方に伸長可能な金属基体を用いたの
がこの第２の実施例である。As a result, the energy in the area separated from the current collecting area 25 can also be collected. <Second Embodiment> In the first embodiment, the configuration using an extensible metal base as the metal base on the positive electrode side has been described.
In the second embodiment, an extensible metal substrate is used on both the positive electrode side and the negative electrode side.
【００２４】図４は金属基体にリチウム箔を設けた負極
体の断面図である。負極体３０の金属基体２２０として
も前述の正極体２０の金属基体２２０と同様に伸長可能
な金属基体２２０を用いる。ＳＵＳ４３０の名からなる
メッシュ状の金属基体２２０の両面に厚さ約７０μｍの
リチウム箔を貼合わせ又は圧着したものである。但し、
金属基体２２０であるＳＵＳ４３０とリチウム箔との合
金化を防止するためステンレスとリチウム箔との間に下
地として銅、ニッケル等の金属を設けている。FIG. 4 is a sectional view of a negative electrode body provided with a lithium foil on a metal base. As the metal base 220 of the negative electrode body 30, an extensible metal base 220 is used similarly to the metal base 220 of the positive electrode body 20 described above. It is formed by laminating or crimping a lithium foil having a thickness of about 70 μm on both sides of a mesh-shaped metal substrate 220 made of SUS430. However,
A metal such as copper or nickel is provided as a base between stainless steel and the lithium foil in order to prevent alloying of the metal base 220 SUS430 and the lithium foil.
【００２５】負極体３０の集電材２２の強度は約０．９
８Kgf であり、引っ張速度１mm/ 分にて破断するまでの
伸びは約６２．５mmである。リチウム箔の強度は約０．
１８Kgf であり、引っ張速度１mm/ 分にて破断するまで
の伸びは約７．５mmである。従って金属基体２２０の伸
び率、強度はリチウム箔またはリチウム合金の伸び率、
強度より大きい。この負極体３０を使用した点が第１の
実施例と異なる。この点以外は第１の実施例と同じであ
る。 ＜第３の実施例＞第３の実施例では負極側の集電体２２
のみに伸長可能な金属基体２２０を用い、正極側の集電
体２２は伸長可能な金属基体２２０を使用していない。The strength of the current collector 22 of the negative electrode body 30 is about 0.9.
It is 8 kgf and the elongation before breaking at a pulling speed of 1 mm / min is about 62.5 mm. The strength of the lithium foil is about 0.5.
It is 18 kgf and the elongation before breaking at a pulling speed of 1 mm / min is about 7.5 mm. Therefore, the elongation rate and strength of the metal base 220 are the same as those of the lithium foil or lithium alloy.
Greater than strength. The point that this negative electrode body 30 is used is different from the first embodiment. The other points are the same as those of the first embodiment. <Third Embodiment> In the third embodiment, the current collector 22 on the negative electrode side is used.
Only the extensible metal base 220 is used, and the current collector 22 on the positive electrode side does not use the extensible metal base 220.
【００２６】この場合、図５の断面図に示すように、正
極体２０はアルミニウムの両面に厚さ約１２０μｍの正
極合剤２３を塗布したものである。この正極体２０の強
度は約４．２０Kgf であり、引っ張速度１mm/ 分にて破
断するまでの伸びは約０．８mmである。この正極体２０
を使用した点が第２の実施例と異なる。しかしこの点以
外は第２の実施例と同じである。 ＜比較例１＞第２の実施例と異なる点は、金属基体２２
０の両面に導電層２２１を設けることなく正極合剤２３
を塗布した正極体２０を用いた点である。この正極体２
０の強度は０．６８Kgf であり、引っ張速度１mm/ 分に
て破断するまでの伸びは３６mmである。この点以外は第
２の実施例と同じである。 ＜比較例２＞負極体３０は厚さ約１０μｍの銅箔の両面
にリチウム箔を張り付けられている。この負極体３０の
強度は約４．８５Kgf であり、引っ張速度１mm/ 分にて
破断するまでの伸びは約０．６mmである。In this case, as shown in the cross-sectional view of FIG. 5, the positive electrode body 20 is formed by coating a positive electrode mixture 23 having a thickness of about 120 μm on both surfaces of aluminum. The strength of the positive electrode body 20 is about 4.20 kgf, and the elongation before breaking at a pulling rate of 1 mm / min is about 0.8 mm. This positive electrode body 20
Is different from the second embodiment. However, the other points are the same as the second embodiment. <Comparative Example 1> The difference from the second embodiment is that
0 without providing the conductive layer 221 on both surfaces thereof.
This is the point that the positive electrode body 20 coated with is used. This positive electrode body 2
The strength at 0 is 0.68 kgf and the elongation to break at a pulling speed of 1 mm / min is 36 mm. The other points are the same as the second embodiment. <Comparative Example 2> The negative electrode body 30 has a copper foil having a thickness of about 10 μm and lithium foils attached to both surfaces thereof. The strength of the negative electrode body 30 is about 4.85 kgf, and the elongation before breaking at a pulling rate of 1 mm / min is about 0.6 mm.
【００２７】そして正極体２０は厚さ約２０μｍのアル
ミニウムの両面に正極合剤２３を塗布されている。この
正極体２０の強度は４．２０Kgf であり、引っ張速度１
mm/分にて破断するまでの伸びは０．８mmである。これ
らの負極体３０と正極体２０とを使用した点が第２の実
施例と異なる。この点以外は第２の実施例と同じであ
る。換言すると負極体３０、正極体２０共に伸長可能な
金属基体２２０を使用しない従来技術の電池と同じであ
る。 ＜充放電試験＞第１、２、３の実施例の電池及び比較例
１、２の電池を各５セル製作し充放電時の容量変化を試
験した。The positive electrode body 20 has a positive electrode mixture 23 applied to both surfaces of aluminum having a thickness of about 20 μm. The strength of the positive electrode body 20 was 4.20 kgf, and the
The elongation to break at mm / min is 0.8 mm. The difference from the second embodiment is that these negative electrode bodies 30 and positive electrode bodies 20 are used. The other points are the same as the second embodiment. In other words, it is the same as the battery of the related art which does not use the extensible metal base 220 for both the negative electrode body 30 and the positive electrode body 20. <Charge / Discharge Test> Five cells of each of the batteries of the first, second, and third embodiments and the batteries of Comparative Examples 1 and 2 were manufactured, and a change in capacity during charge / discharge was tested.
【００２８】上記４種類の電池の充放電試験条件につい
ては、 (1) 充電：４．２Ｖカットオフ、充電電流密度０．３
mA/ 平方cm (2) 休止：１分間 (3) 放電：３．０Ｖカットオフ、充電電流密度１mA/
平方cm (4) 休止：１分間 上記(1) から(4) を繰り返し行った。The charge / discharge test conditions for the above four types of batteries are as follows: (1) Charge: 4.2 V cutoff, charge current density 0.3
mA / square cm (2) Rest: 1 minute (3) Discharge: 3.0 V cut-off, charge current density 1 mA /
Square cm (4) Rest: 1 minute The above (1) to (4) were repeated.
【００２９】表１は第１、２、３の実施例の電池及び比
較例１、２の電池との充電放電試験結果である。Table 1 shows the results of charge / discharge tests of the batteries of the first, second and third embodiments and the batteries of Comparative Examples 1 and 2.
【００３０】[0030]
【表１】 [Table 1]
【００３１】充放電を交互に５０サイクル行い、１サイ
クル前の電池容量と比較して３０％以上の減衰を電極破
断と判断し、３０％までの減衰は良品として判断した。
結果として、第１の実施例のように正極体のみに金属基
体２２０と導電層２２１とを使用した場合は評価数５セ
ルの電池の内４セルが良品として判断された。The charging and discharging were alternately performed for 50 cycles, and an attenuation of 30% or more compared with the battery capacity one cycle before was judged as electrode breakage, and an attenuation of up to 30% was judged as a non-defective product.
As a result, when the metal substrate 220 and the conductive layer 221 were used only for the positive electrode body as in the first embodiment, 4 cells out of the batteries having the evaluation number of 5 cells were judged as non-defective.
【００３２】更に、第２の実施例のように正負極体共に
金属基体２２０を使用した場合は評価数５セルの電池の
内５セルが良品として判断された。次に、第３の実施例
のように負極体にのみ金属基体２２０を使用した場合は
評価数５セルの電池の内４セルが良品として判断され
た。更に、比較例１のように正負極体に金属基体２２０
を使用した場合は評価数５セルの電池の内５セルが良品
として判断された。ただし導電層２２１を使用しないた
めに電池抵抗が大きくなり所定の電池容量を取り出せな
かった。従って比較例１の電池は製品として不適格とし
て判断された。Further, when the metal substrate 220 was used for both the positive and negative electrodes as in the second embodiment, 5 of the batteries having the evaluation number of 5 were judged to be good. Next, when the metal substrate 220 was used only for the negative electrode body as in the third embodiment, 4 cells out of the batteries having the evaluation number of 5 cells were judged as non-defective. Further, as in Comparative Example 1, the metal base 220
When 5 was used, 5 cells out of the batteries having the evaluation number of 5 cells were judged as non-defective. However, since the conductive layer 221 was not used, the battery resistance increased, and a predetermined battery capacity could not be obtained. Therefore, the battery of Comparative Example 1 was determined to be unsuitable as a product.
【００３３】更に、比較例２のように正負極体に金属基
体２２０を使用しない場合は評価数５セルの電池の内３
セルが不良品として判断された。Further, when the metal base 220 was not used for the positive and negative electrodes as in Comparative Example 2, three out of five cells with the evaluation number of 5 were evaluated.
The cell was determined to be defective.
【００３４】[0034]
【発明の効果】以上説明したとおり、本発明のような巻
回型電池は、電極の破断による電池容量の減少を防止
し、充放電のサイクル寿命の長い電池が得られる。結果
として、電池を長期間安定に動作することができる。As described above, in the wound type battery according to the present invention, a decrease in battery capacity due to electrode breakage is prevented, and a battery having a long charge and discharge cycle life can be obtained. As a result, the battery can operate stably for a long period of time.
【図１】 第１の実施例に係る正極体の側断面図、FIG. 1 is a side sectional view of a positive electrode body according to a first embodiment,
【図２】 第１の実施例に係る金属基体の平面図、FIG. 2 is a plan view of a metal base according to the first embodiment,
【図３】 正極体の集電体に亀裂を生じた断面図、FIG. 3 is a cross-sectional view showing a crack in a current collector of a positive electrode body;
【図４】 金属基体にリチウムを設けた負極体の断面
図、FIG. 4 is a cross-sectional view of a negative electrode body provided with lithium on a metal base,
【図５】 アルミニウムに正極合剤を塗布した正極体の
断面図、FIG. 5 is a cross-sectional view of a positive electrode body obtained by applying a positive electrode mixture to aluminum.
【図６】 巻回型電池の巻回体の構成図、FIG. 6 is a configuration diagram of a wound body of the wound battery,
【図７】 従来技術に係る正極体の構造図、FIG. 7 is a structural diagram of a positive electrode body according to the related art;
【図８】 正極体と負極体とセパレータとの関係を示す
配置図である。FIG. 8 is an arrangement diagram showing a relationship among a positive electrode body, a negative electrode body, and a separator.
１０ 巻回体 ２０ 正極体 ２１ 正極リード ２２ 集電体 ２３ 正極合剤 ２４ 正極合剤領域 ２５ 集電領域 ２６ 開口部 ３０ 負極体 ３１ 負極リード ４０ セパレータ ５０ 巻き止めテープ DESCRIPTION OF SYMBOLS 10 Winding body 20 Positive electrode body 21 Positive electrode lead 22 Current collector 23 Positive electrode mixture 24 Positive electrode mixture area 25 Current collecting area 26 Opening 30 Negative electrode body 31 Negative electrode lead 40 Separator 50 Winding tape
───────────────────────────────────────────────────── フロントページの続き (72)発明者 堤 正巳 神奈川県川崎市中原区上小田中４丁目１番 １号 富士通株式会社内 (72)発明者 堀内 博志 神奈川県川崎市中原区上小田中４丁目１番 １号 富士通株式会社内 (72)発明者 宮下 勉 神奈川県川崎市中原区上小田中４丁目１番 １号 富士通株式会社内 Ｆターム(参考） 5H017 AA03 AS01 AS10 BB00 BB19 CC01 CC05 DD05 EE01 EE04 EE05 HH01 HH03 5H028 AA01 BB05 BB06 BB07 CC08 CC11 CC20 EE01 5H029 AJ03 AJ05 AJ11 AK03 AL12 AM01 AM02 AM06 BJ02 BJ14 CJ02 CJ03 CJ06 CJ07 CJ08 CJ24 DJ05 DJ06 EJ01 EJ04 EJ12 HJ01 HJ04 HJ05 HJ20 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Masami Tsutsumi 4-1-1 Kamikadanaka, Nakahara-ku, Kawasaki-shi, Kanagawa Prefecture Inside Fujitsu Limited (72) Inventor Hiroshi Horiuchi 4-1-1 Kamiodanaka, Nakahara-ku, Kawasaki-shi, Kanagawa Prefecture No. 1 Fujitsu Co., Ltd. (72) Inventor Tsutomu Miyashita 4-1-1, Kamiodanaka, Nakahara-ku, Kawasaki City, Kanagawa Prefecture F-term in Fujitsu Co., Ltd. 5H017 AA03 AS01 AS10 BB00 BB19 CC01 CC05 DD05 EE01 EE04 EE05 HH01 HH03 5H028 AA01 BB05 BB06 BB07 CC08 CC11 CC20 EE01 5H029 AJ03 AJ05 AJ11 AK03 AL12 AM01 AM02 AM06 BJ02 BJ14 CJ02 CJ03 CJ06 CJ07 CJ08 CJ24 DJ05 DJ06 EJ01 EJ04 EJ12 HJ01 HJ04 HJ04
Claims (6)
巻回されてなる二次電池であって、 前記正極体は金属基体と、 前記金属基体の片面または両面に形成された導電層とか
らなる集電体の表面に正極合剤を塗布した構成を有する
ことを特徴とする巻回式二次電池。1. A secondary battery in which a positive electrode body and a negative electrode body are wound with a separator interposed therebetween, wherein the positive electrode body comprises: a metal base; and a conductive layer formed on one or both surfaces of the metal base. A wound secondary battery having a configuration in which a positive electrode mixture is applied to the surface of a current collector made of
材からなり、 前記導電層はアルミニウムまたはアルミニウム合金材か
らなることを特徴とする請求項１記載の巻回式二次電
池。2. The wound secondary battery according to claim 1, wherein the metal substrate is made of a mesh-shaped stainless material, and the conductive layer is made of aluminum or an aluminum alloy material.
極合材の伸び率および強度より大きいことを特徴とする
請求項１記載の巻回式二次電池。3. The wound secondary battery according to claim 1, wherein the elongation and the strength of the current collector are larger than the elongation and the strength of the positive electrode mixture.
導電層の伸び率および強度より大きく、前記導電層の導
電率は前記金属基体の導電率より高いことを特徴とする
請求項１または２記載の集電体。4. The metal substrate according to claim 1, wherein the elongation and the strength of the metal substrate are larger than the elongation and the strength of the conductive layer, and the conductivity of the conductive layer is higher than the conductivity of the metal substrate. Current collector as described.
巻回されてなる二次電池であって、 前記負極体はメッシュ状のステンレス材の基体の片面ま
たは両面に、リチウムまたはリチウム合金を設けている
ことを特徴とする巻回式二次電池。5. A secondary battery in which a positive electrode body and a negative electrode body are wound with a separator interposed therebetween, wherein the negative electrode body is made of a mesh-shaped stainless steel base material on one or both sides of a lithium or lithium alloy. A wound type secondary battery, which is provided.
極体の少なくとも一方が伸長可能なメッシュ状の金属
と、その上に積層された他の金属層との２層構成の金属
基体を有して成ることを特徴とする巻回式リチウム二次
電池。6. A metal substrate having a two-layer structure including a mesh-shaped metal in which at least one of a positive electrode body and a negative electrode body is wound and enclosed in a metal can and another metal layer laminated thereon. A wound type lithium secondary battery comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10257722A JP2000090936A (en) | 1998-09-11 | 1998-09-11 | Winding type secondary battery and collector therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10257722A JP2000090936A (en) | 1998-09-11 | 1998-09-11 | Winding type secondary battery and collector therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000090936A true JP2000090936A (en) | 2000-03-31 |
Family
ID=17310204
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10257722A Pending JP2000090936A (en) | 1998-09-11 | 1998-09-11 | Winding type secondary battery and collector therefor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000090936A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006253095A (en) * | 2005-03-14 | 2006-09-21 | Mitsui Mining & Smelting Co Ltd | Manufacturing method of nonaqueous electrolyte secondary battery |
| WO2018119956A1 (en) * | 2016-12-29 | 2018-07-05 | 深圳深科先进投资管理有限公司 | Porous aluminum-foil anode and method for preparing same, and lithium secondary battery |
| WO2018119957A1 (en) * | 2016-12-29 | 2018-07-05 | 深圳先进技术研究院 | Porous tinfoil anode and method for preparing same, and sodium-ion secondary battery |
| KR20190039206A (en) * | 2016-09-16 | 2019-04-10 | 가부시키가이샤 무라타 세이사쿠쇼 | Negative electrode for lithium ion secondary battery, lithium ion secondary battery, battery pack, electric vehicle, electric power storage system, power tool and electronic device |
| CN113555561A (en) * | 2020-04-24 | 2021-10-26 | 北京小米移动软件有限公司 | Current collector, electrode, battery, current collector manufacturing method and electrode manufacturing method |
-
1998
- 1998-09-11 JP JP10257722A patent/JP2000090936A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006253095A (en) * | 2005-03-14 | 2006-09-21 | Mitsui Mining & Smelting Co Ltd | Manufacturing method of nonaqueous electrolyte secondary battery |
| KR20190039206A (en) * | 2016-09-16 | 2019-04-10 | 가부시키가이샤 무라타 세이사쿠쇼 | Negative electrode for lithium ion secondary battery, lithium ion secondary battery, battery pack, electric vehicle, electric power storage system, power tool and electronic device |
| KR102171213B1 (en) | 2016-09-16 | 2020-10-28 | 가부시키가이샤 무라타 세이사쿠쇼 | Negative electrode for lithium ion secondary batteries, lithium ion secondary batteries, battery packs, electric vehicles, power storage systems, power tools and electronic devices |
| WO2018119956A1 (en) * | 2016-12-29 | 2018-07-05 | 深圳深科先进投资管理有限公司 | Porous aluminum-foil anode and method for preparing same, and lithium secondary battery |
| WO2018119957A1 (en) * | 2016-12-29 | 2018-07-05 | 深圳先进技术研究院 | Porous tinfoil anode and method for preparing same, and sodium-ion secondary battery |
| CN113555561A (en) * | 2020-04-24 | 2021-10-26 | 北京小米移动软件有限公司 | Current collector, electrode, battery, current collector manufacturing method and electrode manufacturing method |
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