WO2009141958A1 - 二次電池用電極群およびこれを用いた二次電池 - Google Patents
二次電池用電極群およびこれを用いた二次電池 Download PDFInfo
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- WO2009141958A1 WO2009141958A1 PCT/JP2009/001761 JP2009001761W WO2009141958A1 WO 2009141958 A1 WO2009141958 A1 WO 2009141958A1 JP 2009001761 W JP2009001761 W JP 2009001761W WO 2009141958 A1 WO2009141958 A1 WO 2009141958A1
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- electrode plate
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- 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
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
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- 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
- H01M10/04—Construction or manufacture in general
- H01M10/0431—Cells with wound or folded electrodes
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- 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
- H01M10/052—Li-accumulators
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- 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
- H01M10/058—Construction or manufacture
- H01M10/0583—Construction or manufacture of accumulators with folded construction elements except wound ones, i.e. folded positive or negative electrodes or separators, e.g. with "Z"-shaped electrodes or separators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- 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
Definitions
- Patent Document 1 As a method for suppressing the breakage of the electrode plate, in Patent Document 1, as shown in FIG. 16, a mixture layer 92 provided on one surface of a current collector 91 is mixed with a plurality of recesses 93 to form a unit 92U of the mixture layer. A method of forming the electrode plate 90 by dividing into two is described.
- a thin portion having a thin mixture layer is formed instead of the uncoated portion.
- (A) is sectional drawing which showed the structure of the electrode group in the 2nd Embodiment of this invention, (b) is the elements on larger scale, (c) is a positive electrode plate before forming an electrode group, a negative electrode It is sectional drawing which showed the structure of the board and the separator. It is sectional drawing which showed the structure of the positive electrode plate in the 2nd Embodiment of this invention, a negative electrode plate, and a separator. It is sectional drawing which showed the structure of the positive electrode plate in the 2nd Embodiment of this invention, a negative electrode plate, and a separator. It is sectional drawing which showed the structure of the positive electrode plate in the 2nd Embodiment of this invention, a negative electrode plate, and a separator. It is sectional drawing which showed the structure of the positive electrode plate in the 2nd Embodiment of this invention, a negative electrode plate, and a separator.
- the mixture layer is prevented from falling off due to cracking or peeling of the mixture layer that occurs when the electrode plates 14 and 24 are wound, and the electrode plate
- the bending stress applied to the electrode plate due to the difference between the inner and outer circumferences of the thickness can be reduced. Thereby, the fracture
- the surface of the negative electrode current collector 21 is formed so as to cover the negative electrode mixture layers 22a and 22b as shown in FIG. 6 with respect to the formation pattern of the uncoated portions 23a and 23b shown in FIG.
- the porous insulating layers 6a and 6b may be formed.
- the inside of the die coater manifold is depressurized to reduce the discharge amount of the negative electrode mixture paint, and then returned to the original pressure again. By discharging the paint, the thin portions of the negative electrode mixture layers 22a and 22b can be formed.
- the uncoated portion 13 a is provided only on one side of the positive electrode current collector 11, but it may be provided on both sides of the positive electrode current collector 11. Moreover, although the uncoated part 13a was provided only in the positive electrode plate 14, you may provide an uncoated part also in the negative electrode plate 24. FIG. Alternatively, an uncoated portion may be provided only on the negative electrode plate 24.
- the formation pattern of the uncoated portions 13a and 13b without the positive electrode mixture layer is not limited to the pattern shown in FIG. 9C, and for example, various formation patterns as shown in FIGS. 10 to 14 are applied. Can do.
- FIG. 10 shows an uncoated portion 13a, 13b without the positive electrode mixture layers 12a, 12b formed by shifting the phase between the front surface and the back surface of the positive electrode plate.
- FIG. 13 shows an example in which the pitch for forming the uncoated portions 13a and 13b without the positive electrode mixture layers 12a and 12b is changed between the front surface and the back surface of the positive electrode plate. It is formed larger than the peripheral pitch P11 (the width is the same).
- the electrode group tensile stress is applied to the positive electrode mixture layer 12a on the outer peripheral side of the positive electrode plate 14, and compressive stress is applied to the positive electrode mixture layer 12b on the inner peripheral side.
- the pitch of the uncoated portions 13 a and 13 b without the positive electrode mixture layers 12 a and 12 b is increased in order from the winding start side to the winding end side of the electrode group (P11 ⁇ P12). ⁇ P13..., P21 ⁇ P22 ⁇ P23...), And the outer peripheral pitch is made larger than the inner peripheral pitch (P21> P11, P22> P12, P23> P13). Is.
- the electrode group 4 is configured, bending stress is applied to the positive electrode plate 14 on the winding start side from the winding end side due to the difference in the radius of curvature, but the pitch of the uncoated portions 13a and 13b is wound from the winding start side. By increasing the width toward the end side, the stress difference caused by the difference in the radius of curvature between the winding start side and the winding end side of the positive electrode plate 14 can be effectively reduced.
- a positive electrode plate 14 using a composite lithium oxide as an active material and a negative electrode plate 24 using a material capable of holding lithium as an active material are spirally wound through a separator 31 to be flattened.
- the electrode group 4 is formed.
- the electrode group 4 is housed in the bottomed flat battery case 36 together with the insulating plate 37, and the negative electrode lead 33 led out from the upper part of the electrode group 4 is connected to a terminal 40 having a gasket 39 attached to the periphery.
- the sealing plate 38 is inserted into the opening of the battery case 36, and the sealing plate 38 and the battery case 36 are welded along the outer periphery of the opening of the battery case 36. Seal.
- a rectangular secondary battery 30 is obtained by pouring a predetermined amount of non-aqueous electrolyte into the battery case 36 from the plug opening 41 and then welding the plug 42 to the sealing plate 38. Can do.
- the positive electrode mixture paint is applied to both surfaces of the positive electrode current collector 11 made of an aluminum foil having a thickness of 15 ⁇ m.
- the coating parts 13a and 13b were provided with the same phase and the same pitch and applied, and after drying, the positive electrode plate 14 in which the thickness of the positive electrode mixture layers 12a and 12b on one side was 100 ⁇ m was produced.
- the positive electrode plate 14 was pressed to a total thickness of 165 ⁇ m, so that the thickness of the positive electrode mixture layers 12 a and 12 b on one side was 75 ⁇ m. Then, the positive electrode plate 14 was produced by slitting into a prescribed width of the square secondary battery.
- the negative electrode mixture paint was applied to both surfaces of the negative electrode current collector 21 having a thickness of 10 ⁇ m and a copper foil with a width of 5 mm in the longitudinal direction and having no negative electrode mixture layer.
- the processed parts 23a and 23b were provided with the same phase and the same pitch and applied, and after drying, a negative electrode plate 24 in which the thickness of the negative electrode mixture layers 22a and 22b on one side was 110 ⁇ m was prepared.
- Example 2 In the same manner as in Example 1, a positive electrode plate 14 without an uncoated portion without a positive electrode mixture layer as shown in FIG. 3 was produced.
- a rectangular secondary battery 30 as shown in FIG. 15 was produced in the same manner as in Example 1.
- Example 3 In the same manner as in Example 1, a positive electrode plate 14 having no uncoated portion without a positive electrode mixture layer as shown in FIG. 4 was produced.
- Example 4 In the same manner as in Example 1, a positive electrode plate 14 without an uncoated portion without a positive electrode mixture layer as shown in FIG. 5 was produced.
- a rectangular secondary battery 30 as shown in FIG. 15 was produced in the same manner as in Example 1.
- Example 2 a negative electrode plate 24 in which uncoated portions 23a and 23b were provided on both surfaces of the negative electrode current collector 21 as shown in FIG.
- variety of the uncoated parts 23a and 23b was 5 mm.
- porous insulating layers 6a and 6b made of the same material as in Example 5 were formed on the surfaces of the uncoated portions 23a and 23b.
- Table 1 is a table showing the configurations of Examples 1 to 6 and Comparative Example 1 described above.
- Comparative Example 1 the mixture layer dropped off or the electrode plate was broken after winding.
- the capacity retention rate after 500 cycles is low, and the frequency of occurrence of electrode plate breakage, buckling, lithium deposition, and mixture layer dropout is high.
- the exothermic temperature is high in any of the tests of dropping, round bar crushing, and heating at 150 ° C. These are considered to be caused by an internal short circuit due to the mixture dropping or breaking at the location where the mixture layer is present at the location where the radius of curvature is small.
- the battery in which the porous insulating layers 6a and 6b are applied to the surface of the electrode plate is subjected to physical impact from the outside, and the positive electrode plate 14 and the negative electrode plate 24 are brought into contact with each other. Even if it generates heat, it does not spread any further, so the safety in an internal short circuit is even better.
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Abstract
Description
図1(a)は、本発明の第1の実施形態における二次電池用電極群の構成を模式的に示した断面図、図1(b)は、扁平状に形成された電極群の長径方向の端部にある湾曲部近傍を拡大した部分断面図、図1(c)は、電極群を形成する前の正極板、負極板およびセパレータの構成を示した断面図である。
第1の実施形態では、扁平状の電極群の長径方向の端部にある湾曲部に、集電体上に合剤層が形成されていない未塗工部を設けることによって、電極群の構成時に加わる応力、若しくは充放電時の電極板の膨張収縮に伴う応力を緩和して、電極板の破断等を抑制する効果を奏するようにしたが、円筒状の電極群の場合でも、電極群の巻き始め側においては、曲率半径の小さい部位が生じるため、かかる部位に、合剤層が形成されていない未塗工部を設けることによって、同様の効果を奏することができる。
(a)正極板の作製
活物質としてコバルト酸リチウムを100重量部、導電材としてアセチレンブラックを活物質100重量部に対して2重量部、結着材としてポリフッ化ビニリデンを活物質100重量部に対して2重量部とを適量のN-メチル-2-ピロリドンと共に混練することで、正極合剤塗料を作製した。
活物質として人造黒鉛を100重量部、結着材としてスチレン-ブタジエン共重合体ゴム粒子分散体(固形分40重量%)を活物質100重量部に対して2.5重量部(結着材の固形分換算で1重量部)、増粘剤としてカルボキシメチルセルロースを活物質100重量部に対して1重量部、および適量の水とともに攪拌し、負極合剤塗料を作製した。
以上のようにして作製した正極板14と負極板24とを用いて、図15に示すような角形二次電池30を作製した。
実施例1と同様の方法で、図3に示したような正極合剤層のない未塗工部を設けていない正極板14を作製した。
実施例1と同様の方法で、図4に示したような正極合剤層のない未塗工部を設けていない正極板14を作製した。
実施例1と同様の方法で、図5に示したような正極合剤層のない未塗工部を設けていない正極板14を作製した。
実施例1と同様の方法で、図6に示したような正極合剤層のない未塗工部を設けていない正極板14を作製した。
実施例1と同様の方法で、図7に示したような正極合剤層のない未塗工部を設けていない正極板14を作製した。
実施例1と同様の方法で、未塗工部を設けていない正極板14および、負極板24を作製し、これを用いて、実施例1と同様の方法で、図15に示すような角形二次電池30を作製した。
上記各実施例と比較例でそれぞれ作製した100個の電極群4の中から40個を抜き出し、電極群4を解体して、電極板の破断や合剤層の脱落の有無を観察した。
上記各実施例と比較例でそれぞれ作製した60個の角形二次電池のうち30個を抜き出して、充放電を500サイクル繰り返したときの初期容量に対する容量維持率と、500サイクル繰り返した後に、電極群を解体して、電極板の破断や合剤層の脱落の有無を観察した。
上記各実施例と比較例でそれぞれ作製した60個の角形二次電池のうち30個を抜き出して、上限電圧4.2V、電流2Aの条件で2時間充電を行った後に、1.5mの高さからコンクリート面上に、角形二次電池30の6面に対して各10回落下試験を行い、室温25℃にて10個の発熱温度を測定し、10個の平均値を求めた。
上述の角形二次電池を、上限電圧4.2V、電流2Aの条件で2時間充電を行った後、電池を寝かせた状態で長さ方向に対し垂直方向に、直径10mmの丸棒で圧壊試験を実施し、室温25℃にて10個の発熱温度を測定し、10個の平均値を求めた。
上述の角形二次電池を、上限電圧4.2V、電流2Aの条件で2時間充電を行った後、電池を恒温層に挿入し、常温から5℃/分の条件で恒温層の温度を150℃まで昇温させて、そのときの電池発熱温度を測定し10個の平均値を求めた。
上記実施例1~6と同様の方法で、図2~図8に示したような正極板14および負極板24を作製し、図15に示すような角形二次電池30を作製し、これを実施例7~12とした。ただし、実施例7~12では、実施例1~6において形成した未塗工部の代わりに、合剤層の肉薄部を形成した。なお、肉薄部の厚みは9μmとした。なお、比較例2は、上記比較例1と同じ構成のものである。
上記実施例1~6と同様の方法で、図2、図10、図4、図11~13、図5、図14、図6、図7に示したような正極板14および負極板24を作製して、これを用いて図9に示すような円筒状の電極群を作製し、さらに、この電極群を用いて円筒形二次電池を作製し、これを実施例13~22とした。ただし、未塗工部の形成に関しては、図2、4、5、6、7に示した正極板14および負極板24を、逆の構成とした。また、正極合剤層を覆うともに、正極合剤層のない未塗工部上にも多孔性絶縁層を形成した正極板14を用いて円筒状の電極群を作製し、これを実施例23とした。また、実施例1と同様の方法で、未塗工部を設けていない正極板14、負極板24を用いて円筒状の電極群を作製し、これを比較例3とした。
円筒形二次電池を、上限電圧4.25Vで充電を行った後、分解することなく60℃の恒温槽内に入れ、電池温度が60℃に達するまでキープした。加圧子に鉄製の釘(直径3mm)を用いて電極群に突き刺した。加圧条件は1mm/秒、最大圧力を30kNとした。
6a,6b 多孔性絶縁層
11 正極集電体
12a,12b 正極合剤層
13a,13b 正極合剤層の未塗工部
14 正極板
21 負極集電体
22a,22b 負極合剤層
23a,23b 負極合剤層の未塗工部
24 負極板
30 角形二次電池
31 セパレータ
32 正極リード
33 負極リード
36 電池ケース
37 絶縁板
38 封口板
39 ガスケット
40 端子
41 封栓口
42 封栓
Claims (9)
- 正極集電体上に正極合剤層が形成された正極板、および負極集電体上に負極合剤層が形成された負極板が、セパレータを介して捲回された二次電池用電極群であって、
前記電極群は、扁平状に形成されており、
前記正極板および前記負極板の少なくとも一方の極板は、前記電極群の長径方向の端部にある湾曲部において、前記集電体上に前記合剤層が形成されていない未塗工部を有している、二次電池用電極群。 - 前記未塗工部は、前記集電体の両面のうち、少なくとも前記電極群の内周側の面に形成されている、請求項1に記載の二次電池用電極群。
- 前記未塗工部は、前記集電体の両面に形成されており、前記電極群の内周側の面に形成された未塗工部は、前記電極群の外周側の面に形成された未塗工部よりも幅が広く形成されている、請求項1に記載の二次電池用電極群。
- 前記未塗工部が形成された前記集電体の表面に、多孔性絶縁層が形成されている、請求項1に記載の二次電池用電極群。
- 前記未塗工部の代わりに、前記合剤層の厚みが薄い肉薄部が形成されている、請求項1に記載の二次電池用電極群。
- 前記未塗工部は、前記集電体の両面に形成されており、前記集電体の一方の面に形成された未塗工部と、前記集電体の他方の面に形成された未塗工部とは、位相をずらして形成されている、請求項1に記載の二次電池用電極群。
- 前記電極群は、扁平状の代わりに円筒状に形成されており、
前記未塗工部は、前記扁平状の電極群の長径方向の端部にある湾曲部の代わりに、前記円筒状の電極群の巻き始め側にある曲率半径の小さい部位において形成されている、請求項1に記載の二次電池用電極群。 - 前記電極群は、捲回された電極群の代わりに、前記正極板および負極板がセパレータを介してつづら折れ状に積層された電極群からなる、請求項1に記載の二次電池用電極群。
- 正極板、負極板、およびセパレータを備えた電極群が、電解液とともに電池ケース内に収納された二次電池であって、
前記電極群は、請求項1~8の何れかに記載された二次電池用電極群からなる、二次電池。
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CN200980118224XA CN102037584A (zh) | 2008-05-22 | 2009-04-16 | 二次电池用电极群与使用其的二次电池 |
US12/918,029 US20100310924A1 (en) | 2008-05-22 | 2009-04-16 | Electrode group for secondary battery and secondary battery using the same |
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US20150044555A1 (en) * | 2009-11-03 | 2015-02-12 | Samsung Sdi Co., Ltd. | Rechargeable battery |
CN110165282A (zh) * | 2018-02-14 | 2019-08-23 | 三星Sdi株式会社 | 电极组件和包括该电极组件的二次电池 |
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Also Published As
Publication number | Publication date |
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CN102037584A (zh) | 2011-04-27 |
JP2010080427A (ja) | 2010-04-08 |
KR20100112174A (ko) | 2010-10-18 |
US20100310924A1 (en) | 2010-12-09 |
JP4744617B2 (ja) | 2011-08-10 |
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