JP2013073763A - Secondary battery - Google Patents

Secondary battery Download PDF

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JP2013073763A
JP2013073763A JP2011211592A JP2011211592A JP2013073763A JP 2013073763 A JP2013073763 A JP 2013073763A JP 2011211592 A JP2011211592 A JP 2011211592A JP 2011211592 A JP2011211592 A JP 2011211592A JP 2013073763 A JP2013073763 A JP 2013073763A
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active material
negative electrode
positive electrode
electrode
secondary battery
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JP5708934B2 (en
Inventor
Koichi Taniyama
晃一 谷山
Koji Kitada
耕嗣 北田
Hiroshi Tanada
浩 棚田
Hajime Tsunekawa
肇 恒川
Yoshio Tagawa
嘉夫 田川
Takuya Miyashita
拓也 宮下
Keigo Atobe
啓吾 跡部
Masahiko Hibino
真彦 日比野
Kana Tamaru
奏 田丸
Kaori Nagata
香織 永田
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Mitsubishi Motors Corp
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Mitsubishi Motors Corp
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Priority to JP2011211592A priority Critical patent/JP5708934B2/en
Priority to KR1020120095337A priority patent/KR20130033954A/en
Priority to CN201210320665.1A priority patent/CN103022408B/en
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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
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • 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

Abstract

PROBLEM TO BE SOLVED: To provide a secondary battery in which an electrolytic solution easily penetrates into an electrode body.SOLUTION: The secondary battery comprises: an electrode part formed by laminating, via a separator 51, a cathode member in which cathode layers containing a cathode active material are provided on both surfaces of a cathode collector 41, and an anode member in which anode layers containing an anode active material are provided on both surfaces of an anode collector 31; and an electrolytic solution. The cathode layers are provided with grooves 45, and the anode collector is provided with through holes 35.

Description

本発明は二次電池に関する。   The present invention relates to a secondary battery.

従来より、電気自動車には、二次電池としてリチウムイオン電池が用いられている。リチウムイオン電池は、電極板と非水電解液とが共に外装ケース内に収納されてなるものである。電極板は、正極集電箔の両面に正極活物質層が塗布され形成された正極部材と、負極集電箔の両面に負極活物質層が塗布され形成された負極部材とを有し、これらがセパレータを介して積層されて巻回されている。   Conventionally, lithium-ion batteries have been used as secondary batteries in electric vehicles. A lithium ion battery is one in which an electrode plate and a non-aqueous electrolyte are both housed in an outer case. The electrode plate has a positive electrode member formed by applying a positive electrode active material layer on both sides of the positive electrode current collector foil, and a negative electrode member formed by applying a negative electrode active material layer on both sides of the negative electrode current collector foil. Are laminated and wound via a separator.

このような二次電池では、電解液を外装ケース内に注入して電極体に電解液を浸していく（特許文献１参照）。   In such a secondary battery, an electrolytic solution is injected into the outer case and the electrolytic solution is immersed in the electrode body (see Patent Document 1).

特開２００９−４８９６４号公報（段落０００２等）JP 2009-48964 (paragraph 0002 etc.)

この場合に、電極板に電解液が十分に浸されていないと所望の充放電効率を得ることができないので、一般に電極液を外装ケースから注入していく場合には、電解液が電極体に浸透するまでに時間がかかることから製造時間がかかるという問題がある。このため、例えば圧力をかけて電極により電解液を浸透させやすくすることも考えられるが、十分に製造時間を短縮することはできない。   In this case, since the desired charge / discharge efficiency cannot be obtained unless the electrolyte is sufficiently immersed in the electrode plate, in general, when the electrode liquid is injected from the outer case, the electrolyte is applied to the electrode body. Since it takes time to penetrate, there is a problem that manufacturing time is required. For this reason, for example, it is conceivable that the electrolyte is easily infiltrated with the electrode by applying pressure, but the manufacturing time cannot be sufficiently shortened.

そこで、本発明の課題は、上記従来技術の問題点を解決することにあり、電解液が電極体に浸透しやすい二次電池を提供しようとするものである。   Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, and an object of the present invention is to provide a secondary battery in which an electrolytic solution easily penetrates into an electrode body.

本発明の二次電池は、正極集電体の両面に正極活物質を含む正極層が設けられた正極部材と、負極集電体の両面に負極活物質を含む負極層が設けられた負極部材とが、セパレータを介して積層されてなる電極部と、電解質液とを備えた二次電池であって、前記正極層には溝部が設けられており、かつ、前記負極集電体には、貫通孔が設けられていることを特徴とする。溝部及び貫通孔が設けられていることで、電解液が電極部の内部中央まで浸透しやすく、製造時間を短縮することが可能である。   The secondary battery of the present invention includes a positive electrode member in which a positive electrode layer containing a positive electrode active material is provided on both sides of a positive electrode current collector, and a negative electrode member in which a negative electrode layer containing a negative electrode active material is provided on both sides of the negative electrode current collector Is a secondary battery comprising an electrode part laminated via a separator and an electrolyte solution, the positive electrode layer is provided with a groove, and the negative electrode current collector has A through hole is provided. By providing the groove and the through hole, the electrolytic solution can easily penetrate to the inner center of the electrode portion, and the manufacturing time can be shortened.

本発明の好ましい実施形態としては、前記電極部は、正極部材と負極部材とセパレータとからなる電極板が巻回してなるものであることが挙げられる。   As preferable embodiment of this invention, the said electrode part is mentioned by winding the electrode plate which consists of a positive electrode member, a negative electrode member, and a separator.

応力を効率的に緩和するためには、前記溝部は、前記電極部の巻回してできた湾曲された部分に形成されていることが好ましい。このように設けることで、リチウムデンドライドの析出を抑制することが可能である。   In order to relieve stress efficiently, the groove is preferably formed in a curved portion formed by winding the electrode portion. By providing in this way, it is possible to suppress precipitation of lithium dendride.

前記溝部は、前記正極層のうち、内周側に位置する部分に形成されていることが好ましい。   The groove is preferably formed in a portion located on the inner peripheral side of the positive electrode layer.

前記溝部が、前記電極部の軸方向に沿って設けられていることが好ましい。このように設けられていることで、電極部の軸方向に対して電解液が浸透しやすく、これにより電極部の内部中央までより電解液が浸透しやすい。   It is preferable that the groove portion is provided along the axial direction of the electrode portion. By being provided in this way, the electrolytic solution easily penetrates in the axial direction of the electrode part, and thereby the electrolytic solution more easily penetrates to the inner center of the electrode part.

前記溝部が、前記電極部の前記軸方向における端部に露出していることが好ましい。溝部が端部に露出していることで、電解液が電極部に浸透しやすく、より電極部の中央まで電解液を浸透させることができる。   It is preferable that the groove portion is exposed at an end portion of the electrode portion in the axial direction. Since the groove part is exposed at the end part, the electrolytic solution easily penetrates into the electrode part, and the electrolytic solution can penetrate more into the center of the electrode part.

本発明の二次電池によれば、電解液の浸透が従来に比較して早く製造時間を短縮できると共に応力集中による端部での割れを防止したという優れた効果を奏し得る。   According to the secondary battery of the present invention, the permeation of the electrolytic solution can be shortened as compared with the prior art, and the excellent effect of preventing cracking at the end due to stress concentration can be obtained.

二次電池の構造を示す模式的断面図である。It is typical sectional drawing which shows the structure of a secondary battery. 二次電池の電極部の模式的上面図である。It is a typical top view of the electrode part of a secondary battery. 二次電池の電極部の端部を示す模式的上面図である。It is a typical top view which shows the edge part of the electrode part of a secondary battery. 図３におけるA-A線での模式的断面図である。FIG. 4 is a schematic cross-sectional view taken along line AA in FIG. 3. 負極電極箔の模式的斜視図である。It is a typical perspective view of negative electrode foil. 電解液の浸透を示す模式的断面図である。It is typical sectional drawing which shows the osmosis | permeation of electrolyte solution. 溝部の形状を説明するための電極部の模式的側面図である。It is a typical side view of the electrode part for demonstrating the shape of a groove part.

本発明の二次電池について、図１〜７を用いて説明する。   The secondary battery of this invention is demonstrated using FIGS.

図１に示すように、二次電池１は、電池ケース１１を有する。電池ケース１１内には、電極部（電極体）１２が絶縁板１３により電池ケース１１とは絶縁されて収容されている。電池ケース１１内は、電解液（例えばエチレンカーボネート）１４で満たされており、電池ケース１１は蓋部１５によって封止されている。   As shown in FIG. 1, the secondary battery 1 has a battery case 11. In the battery case 11, an electrode portion (electrode body) 12 is accommodated and insulated from the battery case 11 by an insulating plate 13. The inside of the battery case 11 is filled with an electrolytic solution (for example, ethylene carbonate) 14, and the battery case 11 is sealed with a lid portion 15.

電極部１２は、負極タブ１６と正極タブ１７とが設けられていて、それぞれ電極部１２の後述する負極部材及び正極部材に接続されている。負極タブ１６は、蓋部１５に設けられた負極端子１８に接続され、正極タブ１７は蓋部１５に設けられた正極端子１９に接続される。   The electrode part 12 is provided with a negative electrode tab 16 and a positive electrode tab 17, and is connected to a later-described negative electrode member and positive electrode member of the electrode part 12. The negative electrode tab 16 is connected to a negative electrode terminal 18 provided on the lid portion 15, and the positive electrode tab 17 is connected to a positive electrode terminal 19 provided on the lid portion 15.

かかる電極部１２について図２を用いて説明する。   The electrode unit 12 will be described with reference to FIG.

電極部１２は、一つの電極板２１が巻回されることで構成されている。具体的には、電極部１２は、上面視において、直線状の中央部２２と、中央部２２の外側にあり、略半円状となるように巻回された端部２３とから構成されている。   The electrode unit 12 is configured by winding one electrode plate 21. Specifically, the electrode part 12 is configured by a linear central part 22 and an end part 23 which is outside the central part 22 and wound so as to be substantially semicircular when viewed from above. Yes.

電極部１２の端部２３の拡大図である図３及びその一部断面図である図４に示すように、電極板２１は、セパレータ５１を介して負極板３０と正極板４０とからなるものである。負極板３０は、負極集電箔３１並びにその内周側の面に形成された第１負極活物質層３２及びその外周側の面に形成された第２負極活物質層３３からなる。また、正極板４０は、正極集電箔４１並びにその内周側の面に形成された第１正極活物質層４２及びその外周側の面に形成された第２正極活物質層４３からなる。負極板３０と正極板４０との間には、セパレータ５１が設けられている。即ち、電極板２１はセパレータ５１を介して負極板３０と正極板４０とからなり、負極板３０側が内側に配されるように電極板２１を巻回することで電極部１２が構成されている。   As shown in FIG. 3 which is an enlarged view of the end portion 23 of the electrode portion 12 and FIG. 4 which is a partial cross-sectional view thereof, the electrode plate 21 is composed of a negative electrode plate 30 and a positive electrode plate 40 with a separator 51 interposed therebetween. It is. The negative electrode plate 30 includes a negative electrode current collector foil 31, a first negative electrode active material layer 32 formed on an inner peripheral surface thereof, and a second negative electrode active material layer 33 formed on an outer peripheral surface thereof. The positive electrode plate 40 includes a positive electrode current collector foil 41, a first positive electrode active material layer 42 formed on an inner peripheral surface thereof, and a second positive electrode active material layer 43 formed on an outer peripheral surface thereof. A separator 51 is provided between the negative electrode plate 30 and the positive electrode plate 40. That is, the electrode plate 21 is composed of the negative electrode plate 30 and the positive electrode plate 40 with the separator 51 interposed therebetween, and the electrode unit 12 is configured by winding the electrode plate 21 so that the negative electrode plate 30 side is arranged inside. .

負極集電箔３１は、本実施形態では銅箔を用いている。負極集電箔３１には、図５に示すように複数の貫通孔３５が全面に亘って等間隔に設けられている。詳しくは後述するが、負極集電箔３１に貫通孔３５が設けられていることで、電極部１２への電解液の浸透性を向上させている。本実施形態では、貫通孔３５の形状は円形状であるが、これに限定されず、例えば略矩形状であってもよい。負極集電箔３１における貫通孔３５は、例えば銅を電気分解で溶かした後に析出させることで形成されている。   The negative electrode current collector foil 31 uses a copper foil in the present embodiment. As shown in FIG. 5, the negative electrode current collector foil 31 is provided with a plurality of through holes 35 at equal intervals over the entire surface. As will be described in detail later, the penetration of the electrolytic solution into the electrode portion 12 is improved by providing the negative electrode current collector foil 31 with the through hole 35. In the present embodiment, the shape of the through hole 35 is a circular shape, but is not limited thereto, and may be, for example, a substantially rectangular shape. The through hole 35 in the negative electrode current collector foil 31 is formed by, for example, precipitating after dissolving copper by electrolysis.

各活物質層は、それぞれ電極の活物質とバインダーとを含む。正極活物質としては、通常用いられる活物質、例えばリチウムを吸蔵および放出可能な金属酸化物、例えば層状構造型の金属酸化物、スピネル型の金属酸化物及び金属化合物、酸化酸塩型の金属酸化物などが挙げられる。層状構造型の金属酸化物としては、リチウムニッケル系複合酸化物、リチウムコバルト系複合酸化物、三元系複合酸化物（ＬｉＣｏ１／３Ｎｉ１／３Ｍｎ１／３Ｏ２）が挙げられる。リチウムニッケル系複合酸化物としては、好ましくはニッケル酸リチウム（ＬｉＮｉＯ２）が挙げられる。リチウムコバルト系複合酸化物としては、好ましくはコバルト酸リチウム（ＬｉＣｏＯ２）が挙げられる。スピネル型の金属酸化物としては、マンガン酸リチウム（ＬｉＭｎ２Ｏ４）等のリチウムマンガン系複合酸化物が挙げられる。酸化酸塩型の金属酸化物としては、リン酸鉄リチウム（ＬｉＦｅＰＯ４）、リン酸マンガンリチウム（ＬｉＭｎＰＯ４）、リン酸シリコンリチウム等が挙げられる。本実施形態では、正極の活物質として、コバルト酸リチウムを用いることができる。 Each active material layer includes an electrode active material and a binder, respectively. As the positive electrode active material, a commonly used active material, for example, a metal oxide capable of inserting and extracting lithium, for example, a layered structure type metal oxide, a spinel type metal oxide and metal compound, an oxide type metal oxide Such as things. Examples of the layered structure type metal oxide include lithium nickel composite oxide, lithium cobalt composite oxide, and ternary composite oxide (LiCo 1/3 Ni 1/3 Mn 1/3 O 2 ). The lithium-nickel-based composite oxide, and the like, preferably a lithium nickelate (LiNiO 2). Examples of the lithium cobalt composite oxide, and preferably lithium cobalt oxide (LiCoO 2). Examples of the spinel-type metal oxide include lithium manganese complex oxides such as lithium manganate (LiMn 2 O 4 ). Examples of the oxide metal oxide include lithium iron phosphate (LiFePO 4 ), lithium manganese phosphate (LiMnPO 4 ), and lithium silicon phosphate. In the present embodiment, lithium cobalt oxide can be used as the positive electrode active material.

負極活物質としては、通常用いられる活物質、例えば金属リチウム、リチウム合金、金属酸化物、金属硫化物、金属窒化物、および黒鉛等の炭素材料等を挙げることができる。金属酸化物としては、例えばスズ酸化物やケイ素酸化物などの不可逆性容量をもつものが挙げられる。炭素系材料としての黒鉛としては、人造黒鉛であっても天然黒鉛であっても良く、本実施形態では、負極の活物質としてはグラファイトを用いている。   Examples of the negative electrode active material include commonly used active materials such as metal lithium, lithium alloys, metal oxides, metal sulfides, metal nitrides, and carbon materials such as graphite. Examples of the metal oxide include those having irreversible capacity such as tin oxide and silicon oxide. The graphite as the carbon-based material may be artificial graphite or natural graphite. In this embodiment, graphite is used as the active material of the negative electrode.

バインダーとしては、通常用いられるバインダー、例えばポリフッ化ビニリデンを用いることができる。なお、活物質層にはアセチレンブラック等の導電性向上剤、電解質（例えば、リチウム塩（支持電解質）、イオン伝導性ポリマー等）が含まれていてもよい。また、イオン伝導性ポリマーが含まれる場合には、前記ポリマーを重合させるための重合開始剤が含まれてもよい。   As the binder, a commonly used binder such as polyvinylidene fluoride can be used. The active material layer may contain a conductivity improver such as acetylene black and an electrolyte (for example, a lithium salt (supporting electrolyte), an ion conductive polymer, etc.). When an ion conductive polymer is included, a polymerization initiator for polymerizing the polymer may be included.

そして、電極板２１は、端部２３において湾曲していることから、より内側に配された部分ほど、例えば充放電時に体積が増えることによる応力が大きくなることが考えられる。そこで、本実施形態では、第１正極活物質層４２に、電極板２１の長手方向に直交する方向に亘って形成された複数の溝部４５を設けている。各溝部４５は、電極部１２の上下端部に開口している。このように溝部４５を設けることで、端部２３における応力を逃がすことが可能である。   Since the electrode plate 21 is curved at the end portion 23, it is conceivable that the stress caused by the increase in volume at the time of charge / discharge, for example, increases as the portion is arranged on the inner side. Therefore, in the present embodiment, the first positive electrode active material layer 42 is provided with a plurality of groove portions 45 formed in a direction orthogonal to the longitudinal direction of the electrode plate 21. Each groove portion 45 is open at the upper and lower end portions of the electrode portion 12. By providing the groove 45 in this way, it is possible to release the stress at the end 23.

また、図６に示すように、溝部４５が設けられていることで、電極部１２の上面及び下面に開口する溝部４５からも電解液が浸透するのでより電解液が電極部１２の内部中央まで浸透しやすい。さらに、本実施形態では、負極集電箔３１としては貫通孔３５が設けられたものを用いている。このように貫通孔３５が設けられていることで、電極部１２内部に浸透した電解液１４が電極部１２の径方向により移動しやすく、電極部１２の内部中央まで浸透しやすい。従って電極部１２全体に電解液１４を簡易に均等に浸透させることが可能であり、二次電池の製造時間を短縮することが可能である。   Further, as shown in FIG. 6, since the groove portion 45 is provided, the electrolytic solution permeates from the groove portion 45 opened on the upper surface and the lower surface of the electrode portion 12, so that the electrolyte solution reaches the inner center of the electrode portion 12. Easy to penetrate. Further, in the present embodiment, the negative electrode current collector foil 31 is provided with a through hole 35. By providing the through-hole 35 in this way, the electrolyte solution 14 that has penetrated into the electrode portion 12 easily moves in the radial direction of the electrode portion 12 and easily penetrates to the inner center of the electrode portion 12. Therefore, the electrolytic solution 14 can be easily and evenly penetrated into the entire electrode portion 12, and the manufacturing time of the secondary battery can be shortened.

即ち、本実施形態では、負極集電箔３１に貫通孔３５が設けられていることで、電極部１２の径方向に対して電解液が浸透しやすく、かつ、溝部４５が設けられていることで、電解液が電極部１２の軸方向に対しても浸透しやすい。これにより、電極部１２の内部中央まで容易に電解液を浸透させることができる。   That is, in the present embodiment, the negative electrode current collector foil 31 is provided with the through hole 35 so that the electrolytic solution easily permeates in the radial direction of the electrode part 12 and the groove part 45 is provided. Thus, the electrolytic solution easily penetrates in the axial direction of the electrode portion 12. Thereby, electrolyte solution can be easily osmose | permeated to the inner center of the electrode part 12. FIG.

この場合に、正極活物質層のうち、より内周側に存在する第１正極活物質層４２に溝部４５を設けることが好ましい。電極部１２の端部２３においては、より内周側に位置する活物質層は隣接する活物質層と比較して体積が少ない。例えば、第２負極活物質層３３と第１正極活物質層４２と比較すると、体積が少ない。このため、電極部１２の端部２３においては、第２負極活物質層３３と第１正極活物質層４２とを比較すると、正極活物質よりも負極活物質が少ない。そうすると、リチウムイオンが第１正極活物質層４２から第２負極活物質層３３に移動した場合に、リチウムイオンの量が多すぎてリチウムデンドライドとして析出してしまい、電池性能を低下させてしまうことが考えられるため、これを防止する必要がある。   In this case, it is preferable to provide the groove part 45 in the 1st positive electrode active material layer 42 which exists in an inner peripheral side among positive electrode active material layers. In the end part 23 of the electrode part 12, the volume of the active material layer located on the inner peripheral side is smaller than that of the adjacent active material layer. For example, the volume is smaller than that of the second negative electrode active material layer 33 and the first positive electrode active material layer 42. For this reason, in the edge part 23 of the electrode part 12, when the 2nd negative electrode active material layer 33 and the 1st positive electrode active material layer 42 are compared, there are few negative electrode active materials than a positive electrode active material. As a result, when lithium ions move from the first positive electrode active material layer 42 to the second negative electrode active material layer 33, the amount of lithium ions is too large and precipitates as lithium dendride, thereby reducing battery performance. It is necessary to prevent this from happening.

そこで、本実施形態では、内周側に存在する第１正極活物質層４２にのみ溝部４５を設けて内周側の第１正極活物質層４２の体積を減少させていることで、充電時において第１正極活物質層４２から第２負極活物質層３３に移動するリチウムイオンの量を減少させることができるので、リチウムデンドライドの形成を防止し、効率的に電池を使用することができる。   Therefore, in the present embodiment, the groove 45 is provided only in the first positive electrode active material layer 42 existing on the inner peripheral side to reduce the volume of the first positive electrode active material layer 42 on the inner peripheral side. Since the amount of lithium ions moving from the first positive electrode active material layer 42 to the second negative electrode active material layer 33 can be reduced, the formation of lithium dendrites can be prevented and the battery can be used efficiently. .

なお、応力を低減させることのみを考慮すれば、溝部４５を例えば最も内側の第１負極活物質層３２や第２負極活物質層３３に設けることが考えられる。しかし、第１負極活物質層３２や第２負極活物質層３３に設けるとすれば、上述のように負極活物質が不足してリチウムデンドライドが析出しやすくなってしまい、電池性能を低下させてしまうことが考えられるので好ましくない。   In consideration of only reducing the stress, it is conceivable to provide the groove 45 in, for example, the innermost first negative electrode active material layer 32 or the second negative electrode active material layer 33. However, if the first negative electrode active material layer 32 and the second negative electrode active material layer 33 are provided, the negative electrode active material is insufficient as described above, so that lithium dendride is liable to precipitate, resulting in a decrease in battery performance. This is not preferable.

また、溝部４５を第２正極活物質層４３に設ける場合、応力を低減することができると同時に、電解液の浸透性が高くなるので好ましい。しかしながら、この場合には隣接する第１負極活物質層３２に対して第２正極活物質層４３における正極活物質の量が少なくなり、効率的に充放電を行うことができないおそれがある。従って、応力をある程度緩和しつつ、効率的に充放電を行うことができるように、第１正極活物質層４２に設けることが好ましい。   In addition, it is preferable to provide the groove 45 in the second positive electrode active material layer 43 because stress can be reduced and the permeability of the electrolytic solution is increased. However, in this case, the amount of the positive electrode active material in the second positive electrode active material layer 43 decreases with respect to the adjacent first negative electrode active material layer 32, and there is a possibility that charging and discharging cannot be performed efficiently. Therefore, it is preferable to provide the first positive electrode active material layer 42 so as to efficiently charge and discharge while relaxing the stress to some extent.

そして、このように第１正極活物質層４２に溝部４５を設けることで、リチウムデンドライドの析出を防止するために負極活物質層の体積を正極活物質層に比較して多くする必要もないために、正極活物質層を薄く設けることができる。その結果、本実施形態の電極板２１は、全体として巻数を多くすることができるので、正極活物質層の体積を減少させたとしても電池容量が低下することがなく、向上する。   In addition, by providing the groove portion 45 in the first positive electrode active material layer 42 in this way, it is not necessary to increase the volume of the negative electrode active material layer as compared with the positive electrode active material layer in order to prevent the precipitation of lithium dendride. Therefore, the positive electrode active material layer can be thinly provided. As a result, the electrode plate 21 of the present embodiment can increase the number of turns as a whole, so that even if the volume of the positive electrode active material layer is reduced, the battery capacity does not decrease and is improved.

このような溝部４５は、本実施形態では電極板２１の長手方向に対して直交する方向に延びるように設けられているが、これに限定されない。電極板２１の長手方向に対して直交する方向に沿うように設けられていればよい。例えば、図７（１）に示すように電極板２１の長手方向に対して傾斜するように設けられていてもよい。この場合であっても、上述のように溝部４５から電解液が浸透するように溝部４５の開口が電極部１２の上面及び下面に露出していることが好ましい。また、図７（２）に示すように溝部４５が電極部１２の軸方向だけでなく周方向にも延設されて互いに接続しあうように設けられていてもよい。   In the present embodiment, such a groove 45 is provided so as to extend in a direction orthogonal to the longitudinal direction of the electrode plate 21, but is not limited thereto. What is necessary is just to be provided so that the direction orthogonal to the longitudinal direction of the electrode plate 21 may be followed. For example, as shown in FIG. 7 (1), it may be provided so as to be inclined with respect to the longitudinal direction of the electrode plate 21. Even in this case, it is preferable that the opening of the groove portion 45 is exposed on the upper surface and the lower surface of the electrode portion 12 so that the electrolyte solution permeates from the groove portion 45 as described above. In addition, as shown in FIG. 7B, the groove 45 may be provided not only in the axial direction of the electrode part 12 but also in the circumferential direction so as to be connected to each other.

溝部４５の形状は、本実施形態では電極部１２の上面及び下面に開口し、かつ、負極側のセパレータ５１にのみ接する溝部であったが、これに限定されない。電極部１２の径方向における溝の深さはもっと深くなるように構成されていてもよい。例えば、溝部４５がセパレータ５１及び正極集電箔４１に接するように設けても良い。この場合には、製造時において未塗工の部分を設けて溝部４５としてもよい。   In this embodiment, the shape of the groove 45 is a groove that opens on the upper surface and the lower surface of the electrode portion 12 and is in contact with only the separator 51 on the negative electrode side, but is not limited thereto. The depth of the groove in the radial direction of the electrode portion 12 may be configured to be deeper. For example, the groove 45 may be provided so as to contact the separator 51 and the positive electrode current collector foil 41. In this case, it is good also as a groove part 45 by providing an uncoated part at the time of manufacture.

なお、この溝部４５は上述したように電解液の浸透性を向上させるものであるから、電極部１２の中央部２２にも形成されていてもよい。しかしながら、中央部２２においては内周側負極活物質層と外周側の正極活物質層との間における体積の違いは生じないので、あまり溝部４５を形成しすぎて正極活物質層の体積が減ると容積の減少が生じてしまうので、あまり多量に設けることは好ましくない。端部においてより多く設ける方が好ましい。   In addition, since this groove part 45 improves the permeability | transmittance of electrolyte solution as mentioned above, you may form also in the center part 22 of the electrode part 12. FIG. However, since the volume difference between the inner peripheral negative electrode active material layer and the outer peripheral positive electrode active material layer does not occur in the central portion 22, the groove portion 45 is formed too much to reduce the volume of the positive electrode active material layer. Therefore, it is not preferable to provide a large amount. It is preferable to provide more at the end.

本実施形態では、負極集電箔３１の全面に亘って貫通孔３５が設けられているが、これに限定されない。例えば、貫通孔３５の形成密度が、負極集電箔３１の短手方向の中央部が短手方向の端部よりも密となるようにしてもよい。この場合に、貫通孔３５を負極集電箔３１の短手方向の中央部にのみ形成してもよい。このように、貫通孔３５を負極集電箔３１の短手方向の中央部が短手方向の端部よりも密となるように形成することで、電解液１４の中央部への浸透性を高めることができる。また、負極集電箔３１の製造工程において、負極集電箔３１を平坦にするために縦横からテンションをかけて負極集電箔３１を引っ張るが、この際に集電箔の端部に貫通孔３５が多く形成されていると負極集電箔３１が破れてしまうおそれがあるので、貫通孔３５を負極集電箔３１の短手方向の中央部が短手方向の端部よりも密となるように形成することでこれを抑制することができる。   In the present embodiment, the through hole 35 is provided over the entire surface of the negative electrode current collector foil 31, but is not limited thereto. For example, the formation density of the through holes 35 may be such that the central portion in the short direction of the negative electrode current collector foil 31 is denser than the end portion in the short direction. In this case, the through hole 35 may be formed only in the central portion of the negative electrode current collector foil 31 in the short direction. Thus, by forming the through-hole 35 so that the central portion in the short direction of the negative electrode current collector foil 31 is denser than the end portion in the short direction, the permeability to the central portion of the electrolytic solution 14 can be increased. Can be increased. Further, in the manufacturing process of the negative electrode current collector foil 31, in order to make the negative electrode current collector foil 31 flat, the negative electrode current collector foil 31 is pulled by applying tension from the vertical and horizontal directions. Since the negative electrode current collector foil 31 may be torn if a large number of 35 is formed, the central portion of the through hole 35 in the short direction of the negative electrode current collector foil 31 is denser than the end portion in the short direction. This can be suppressed by forming as described above.

１ 二次電池
１１ 電池ケース
１２ 電極部
１３ 絶縁板
１４ 電解液
１５ 蓋部
１６ 負極タブ
１７ 正極タブ
１８ 負極端子
１９ 正極端子
２１ 電極板
２２ 中央部
２３ 端部
３１ 負極集電箔
３２ 第１負極活物質層
３３ 第２負極活物質層
３５ 貫通孔
４１ 正極集電箔
４２ 第１正極活物質層
４３ 第２正極活物質層
４５ 溝部
５１ セパレータ DESCRIPTION OF SYMBOLS 1 Secondary battery 11 Battery case 12 Electrode part 13 Insulation board 14 Electrolytic solution 15 Lid part 16 Negative electrode tab 17 Positive electrode tab 18 Negative electrode terminal 19 Positive electrode terminal 21 Electrode plate 22 Central part 23 End part 31 Negative electrode current collection foil 32 1st negative electrode active foil Material layer 33 Second negative electrode active material layer 35 Through hole 41 Positive electrode current collector foil 42 First positive electrode active material layer 43 Second positive electrode active material layer 45 Groove 51 Separator

Claims (6)

正極集電体の両面に正極活物質を含む正極層が設けられた正極部材と、負極集電体の両面に負極活物質を含む負極層が設けられた負極部材とが、セパレータを介して積層されてなる電極部と、電解質液とを備えた二次電池であって、
前記正極層には溝部が設けられており、かつ、前記負極集電体には、貫通孔が設けられていることを特徴とする二次電池。 A positive electrode member in which a positive electrode layer containing a positive electrode active material is provided on both sides of a positive electrode current collector and a negative electrode member in which a negative electrode layer containing a negative electrode active material is provided on both sides of the negative electrode current collector are stacked via a separator. A secondary battery comprising an electrode portion and an electrolyte solution,
A secondary battery, wherein the positive electrode layer is provided with a groove, and the negative electrode current collector is provided with a through hole. 前記電極部は、正極部材と負極部材とセパレータとからなる電極板が巻回してなるものであることを特徴とする請求項１記載の二次電池。   The secondary battery according to claim 1, wherein the electrode portion is formed by winding an electrode plate including a positive electrode member, a negative electrode member, and a separator. 前記溝部は、前記電極部の巻回してできた湾曲された部分に形成されていることを特徴とする請求項２記載の二次電池。   The secondary battery according to claim 2, wherein the groove portion is formed in a curved portion formed by winding the electrode portion. 前記溝部は、前記正極層のうち、内周側に位置する層のみに形成されていることを特徴とする請求項２又は３記載の二次電池。   4. The secondary battery according to claim 2, wherein the groove is formed only in a layer located on an inner peripheral side of the positive electrode layer. 5. 前記溝部が、前記電極部の軸方向に沿って設けられていることを特徴とする請求項１〜４のいずれか１項に記載の二次電池。   The secondary battery according to claim 1, wherein the groove portion is provided along an axial direction of the electrode portion. 前記溝部が、前記電極部の前記軸方向における端部に露出していることを特徴とする請求項１〜５のいずれか１項に記載の二次電池。   The secondary battery according to claim 1, wherein the groove portion is exposed at an end portion of the electrode portion in the axial direction.
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CN114613937A (en) * 2022-03-15 2022-06-10 东莞新能安科技有限公司 Electrochemical device and electronic device

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