JP2016174005A - Nonaqueous electrolyte secondary battery and method for manufacturing the same - Google Patents
Nonaqueous electrolyte secondary battery and method for manufacturing the same Download PDFInfo
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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
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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
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Abstract
Description
本発明は、非水電解質二次電池に関する。 The present invention relates to a non-aqueous electrolyte secondary battery.
近年、例えば電気自動車やハイブリッドカーなどにも非水電解質二次電池を用いる試みがなされている。このような用途においては、高出力であることに加えて、長寿命であることが強く要求される。 In recent years, attempts have been made to use nonaqueous electrolyte secondary batteries in, for example, electric vehicles and hybrid cars. In such applications, in addition to high output, a long life is strongly required.
例えば特許文献１には、非水電解質二次電池の非水電解質にリチウムビス（オキサレート）ボレート（ＬｉＢＯＢ）を添加することにより、非水電解質二次電池のサイクル寿命を改善できることが記載されている。 For example, Patent Document 1 describes that the cycle life of a nonaqueous electrolyte secondary battery can be improved by adding lithium bis (oxalate) borate (LiBOB) to the nonaqueous electrolyte of the nonaqueous electrolyte secondary battery. .
本発明者らは、鋭意研究した結果、非水電解質二次電池の非水電解質にＬｉＢＯＢを添加した場合、サイクル寿命は改善されるものの、外部からの衝撃による電池圧壊などの異常時に、電池内部が発熱しやすくなることを見出した。その結果、本発明を成すに至った。 As a result of intensive studies, the inventors have found that when LiBOB is added to the non-aqueous electrolyte of the non-aqueous electrolyte secondary battery, the cycle life is improved, but in the event of abnormalities such as battery collapse due to external impact, Has found that it tends to generate heat. As a result, the present invention has been achieved.
本発明の主な目的は、上記のような異常時においても電池内部の発熱が抑制された非水電解質二次電池を提供することにある。 A main object of the present invention is to provide a non-aqueous electrolyte secondary battery in which heat generation inside the battery is suppressed even in the case of an abnormality as described above.
本発明に係る非水電解質二次電池は、電極体と、非水電解質と、容器と、配線材とを備える。電極体は、正極と、負極と、セパレータとを有する。負極は、正極と対向している。セパレータは、正極と負極との間に配されている。非水電解質は、リチウムビス（オキサレート）ボレート（ＬｉＢＯＢ）を含む。容器は、電極体及び非水電解質を収納している。容器には、端子が設けられている。配線材は、端子と電極体とを接続している。配線材の横断面積が、１．５ｍｍ２以上である。 The nonaqueous electrolyte secondary battery according to the present invention includes an electrode body, a nonaqueous electrolyte, a container, and a wiring material. The electrode body has a positive electrode, a negative electrode, and a separator. The negative electrode is opposed to the positive electrode. The separator is disposed between the positive electrode and the negative electrode. The non-aqueous electrolyte includes lithium bis (oxalate) borate (LiBOB). The container contains an electrode body and a nonaqueous electrolyte. The container is provided with a terminal. The wiring material connects the terminal and the electrode body. The cross-sectional area of the wiring material is 1.5 mm 2 or more.
本発明によれば、外部からの衝撃による電池圧壊などの異常時においても電池内部が発熱しにくい非水電解質二次電池を提供することができる。 According to the present invention, it is possible to provide a non-aqueous electrolyte secondary battery in which the inside of a battery is unlikely to generate heat even when there is an abnormality such as battery collapse due to external impact.
以下、本発明を実施した好ましい形態の一例について説明する。但し、下記の実施形態は、単なる例示である。本発明は、下記の実施形態に何ら限定されない。 Hereinafter, an example of the preferable form which implemented this invention is demonstrated. However, the following embodiment is merely an example. The present invention is not limited to the following embodiments.
また、実施形態等において参照する各図面において、実質的に同一の機能を有する部材は同一の符号で参照することとする。また、実施形態等において参照する図面は、模式的に記載されたものである。図面に描画された物体の寸法の比率などは、現実の物体の寸法の比率などとは異なる場合がある。図面相互間においても、物体の寸法比率等が異なる場合がある。具体的な物体の寸法比率等は、以下の説明を参酌して判断されるべきである。 Moreover, in each drawing referred in embodiment etc., the member which has a substantially the same function shall be referred with the same code | symbol. The drawings referred to in the embodiments and the like are schematically described. A ratio of dimensions of an object drawn in a drawing may be different from a ratio of dimensions of an actual object. The dimensional ratio of the object may be different between the drawings. The specific dimensional ratio of the object should be determined in consideration of the following description.
図１に示される非水電解質二次電池１は、角形の非水電解質二次電池である。非水電解質二次電池１は、どのような用途にも使用可能であるが、例えば、電気自動車やハイブリッド自動車に好適に用いられる。非水電解質二次電池１の容量は、通常、５Ａｈ〜５０Ａｈである。 A nonaqueous electrolyte secondary battery 1 shown in FIG. 1 is a rectangular nonaqueous electrolyte secondary battery. The nonaqueous electrolyte secondary battery 1 can be used for any application, but is preferably used for, for example, an electric vehicle and a hybrid vehicle. The capacity of the nonaqueous electrolyte secondary battery 1 is usually 5 Ah to 50 Ah.
非水電解質二次電池１は、図１〜図４に示される容器１０と、図２〜図５に示される電極体２０とを有する。 The nonaqueous electrolyte secondary battery 1 has a container 10 shown in FIGS. 1 to 4 and an electrode body 20 shown in FIGS.
図５に示されるように、電極体２０は、正極２１と、負極２２と、セパレータ２３とを有する。正極２１と負極２２とは対向している。正極２１と負極２２との間には、セパレータ２３が配されている。正極２１と負極２２とセパレータ２３とは、巻回された後に、プレスされて扁平形状とされている。すなわち、電極体２０は、正極２１、負極２２及びセパレータ２３の扁平状の巻回体によって構成されている。 As shown in FIG. 5, the electrode body 20 includes a positive electrode 21, a negative electrode 22, and a separator 23. The positive electrode 21 and the negative electrode 22 are opposed to each other. A separator 23 is disposed between the positive electrode 21 and the negative electrode 22. The positive electrode 21, the negative electrode 22, and the separator 23 are rolled and then pressed into a flat shape. That is, the electrode body 20 is constituted by a flat wound body of the positive electrode 21, the negative electrode 22 and the separator 23.
正極２１は、正極集電体２１ａと、正極活物質層２１ｂとを有する。正極集電体２１ａは、例えば、アルミニウムやアルミニウム合金などにより構成することができる。正極集電体２１ａの厚みは、例えば、０．５ｍｍ〜１．５ｍｍ程度であることが好ましく、０．６ｍｍ〜１．０ｍｍ程度であることがより好ましい。正極活物質層２１ｂは、正極集電体２１ａの少なくとも一方の表面上に設けられている。正極活物質層２１ｂは、正極活物質を含む。好ましく用いられる正極活物質としては、例えば、コバルト、ニッケル及びマンガンのうちの少なくとも一種を含むリチウム酸化物等が挙げられる。コバルト、ニッケル及びマンガンのうちの少なくとも一種を含むリチウム酸化物の具体例としては、例えば、リチウム含有ニッケルコバルトマンガン複合酸化物（ＬｉＮｉｘＣｏｙＭｎｚＯ２、ｘ+ｙ+ｚ＝１、０≦ｘ≦１、０≦ｙ≦１、０≦ｚ≦１）、コバルト酸リチウム（ＬｉＣｏＯ２）、マンガン酸リチウム（ＬｉＭｎ２Ｏ４）、ニッケル酸リチウム（ＬｉＮｉＯ２）、またはこれらの酸化物に含まれる遷移金属の一部を他の元素で置換した化合物等のリチウム含有遷移金属複合酸化物等が挙げられる。なかでも、リチウム含有ニッケルコバルトマンガン複合酸化物（ＬｉＮｉｘＣｏｙＭｎｚＯ２、ｘ+ｙ+ｚ＝１、０≦ｘ≦１、０≦ｙ≦１、０≦ｚ≦１）、またはこれらの酸化物に含まれる遷移金属の一部を他の元素で置換した化合物等のリチウム含有遷移金属複合酸化物が正極活物質としてより好ましく用いられる。正極活物質層２１ｂは、正極活物質に加え、例えば導電材やバインダーなどの他の成分を適宜含んでいてもよい。 The positive electrode 21 includes a positive electrode current collector 21a and a positive electrode active material layer 21b. The positive electrode current collector 21a can be made of, for example, aluminum or an aluminum alloy. The thickness of the positive electrode current collector 21a is, for example, preferably about 0.5 mm to 1.5 mm, and more preferably about 0.6 mm to 1.0 mm. The positive electrode active material layer 21b is provided on at least one surface of the positive electrode current collector 21a. The positive electrode active material layer 21b contains a positive electrode active material. Examples of the positive electrode active material preferably used include lithium oxide containing at least one of cobalt, nickel and manganese. Cobalt, specific examples of the lithium oxide containing at least one of nickel and manganese, for example, lithium-containing nickel-cobalt-manganese composite oxide (LiNi x Co y Mn z O 2, x + y + z = 1,0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 ≦ z ≦ 1), lithium cobaltate (LiCoO 2 ), lithium manganate (LiMn 2 O 4 ), lithium nickelate (LiNiO 2 ), or oxides thereof Examples thereof include lithium-containing transition metal composite oxides such as compounds in which a part of the transition metal contained is substituted with another element. Among them, lithium-containing nickel cobalt manganese composite oxide (LiNi x Co y Mn z O 2 , x + y + z = 1, 0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 ≦ z ≦ 1), or these A lithium-containing transition metal composite oxide such as a compound in which a part of the transition metal contained in the oxide is substituted with another element is more preferably used as the positive electrode active material. The positive electrode active material layer 21b may appropriately include other components such as a conductive material and a binder in addition to the positive electrode active material.
負極２２は、負極集電体２２ａと、負極活物質層２２ｂとを有する。負極集電体２２ａは、例えば、銅や銅合金などにより構成することができる。負極集電体２２ａの厚みは、例えば、０．５ｍｍ〜１．５ｍｍ程度であることが好ましく、０．６ｍｍ〜１．０ｍｍ程度であることがより好ましい。負極活物質層２２ｂは、負極集電体２２ａの少なくとも一方の表面上に設けられている。負極集電体２２ａは、負極活物質を含む。負極活物質は、リチウムを可逆的に吸蔵・放出できるものであれば特に限定されない。好ましく用いられる負極活物質としては、例えば、炭素材料、リチウムと合金化する材料、酸化スズなどの金属酸化物などが挙げられる。炭素材料の具体例としては、例えば、天然黒鉛、人造黒鉛
、メソフェーズピッチ系炭素繊維（ＭＣＦ）、メソカーボンマイクロビーズ（ＭＣＭＢ）、コークス、ハードカーボン、フラーレン、カーボンナノチューブなどが挙げられる。リチウムと合金化する材料としては、例えば、ケイ素、ゲルマニウム、スズ及びアルミニウムからなる群から選ばれた１種以上の金属、またはケイ素、ゲルマニウム、スズ及びアルミニウムからなる群から選ばれた１種以上の金属を含む合金からなるものが挙げられる。なかでも、天然黒鉛、人造黒鉛、メソフェーズピッチ系炭素繊維（ＭＣＦ）が負極活物質として好ましく用いられる。負極活物質層２２ｂは、負極活物質に加え、例えば導電材やバインダーなどの他の成分を適宜含んでいてもよい。
The negative electrode 22 includes a negative electrode current collector 22a and a negative electrode active material layer 22b. The negative electrode current collector 22a can be made of, for example, copper or a copper alloy. The thickness of the negative electrode current collector 22a is preferably, for example, about 0.5 mm to 1.5 mm, and more preferably about 0.6 mm to 1.0 mm. The negative electrode active material layer 22b is provided on at least one surface of the negative electrode current collector 22a. The negative electrode current collector 22a includes a negative electrode active material. The negative electrode active material is not particularly limited as long as it can reversibly store and release lithium. Examples of the negative electrode active material preferably used include a carbon material, a material alloyed with lithium, and a metal oxide such as tin oxide. Specific examples of the carbon material include natural graphite, artificial graphite, mesophase pitch-based carbon fiber (MCF), mesocarbon microbeads (MCMB), coke, hard carbon, fullerene, and carbon nanotube. Examples of the material to be alloyed with lithium include one or more metals selected from the group consisting of silicon, germanium, tin, and aluminum, or one or more types selected from the group consisting of silicon, germanium, tin, and aluminum. The thing which consists of an alloy containing a metal is mentioned. Of these, natural graphite, artificial graphite, and mesophase pitch carbon fiber (MCF) are preferably used as the negative electrode active material. The negative electrode active material layer 22b may appropriately include other components such as a conductive material and a binder in addition to the negative electrode active material.
セパレータは、例えば、ポリエチレンやポリプロピレンなどの樹脂からなる多孔質シートなどにより構成することができる。 The separator can be constituted by, for example, a porous sheet made of a resin such as polyethylene or polypropylene.
電極体２０は、容器１０内に収納されている。容器１０内には、非水電解質も収納されている。非水電解質は、溶質として、リチウムビス（オキサレート）ボレート（ＬｉＢＯＢ）を含む。非水電解質におけるＬｉＢＯＢの含有量は０．０５ｍｏｌ／Ｌ〜０．２０ｍｏｌ／Ｌであることが好ましく、０．１０ｍｏｌ／Ｌ〜０．１８ ｍｏｌ／Ｌであることがより好ましい。なお、ＬｉＢＯＢの好ましい含有量の範囲は、組立後かつ初回充電前の非水電解質二次電池中の非水電解質を基準としたものである。このような基準を設けたのは、ＬｉＢＯＢを含む非水電解質二次電池を充電すると、その含有量が徐々に低下してしまうためである。 The electrode body 20 is accommodated in the container 10. A non-aqueous electrolyte is also stored in the container 10. The non-aqueous electrolyte contains lithium bis (oxalate) borate (LiBOB) as a solute. The content of LiBOB in the non-aqueous electrolyte is preferably 0.05 mol / L to 0.20 mol / L, and more preferably 0.10 mol / L to 0.18 mol / L. In addition, the range of preferable content of LiBOB is based on the non-aqueous electrolyte in the non-aqueous electrolyte secondary battery after assembly and before the first charge. The reason for setting such a standard is that when a non-aqueous electrolyte secondary battery containing LiBOB is charged, its content gradually decreases.
非水電解質は、溶質として、ＬｉＢＯＢに加え、例えば、ＬｉＸＦｙ（式中、Ｘは、Ｐ、Ａｓ、Ｓｂ、Ｂ、Ｂｉ、Ａｌ、ＧａまたはＩｎであり、ＸがＰ、ＡｓまたはＳｂのときｙは６であり、ＸがＢ、Ｂｉ、Ａｌ、Ｇａ、またはＩｎのときｙは４である）、リチウムペルフルオロアルキルスルホン酸イミドＬｉＮ（ＣｍＦ２ｍ＋１ＳＯ２）（ＣｎＦ２ｎ＋１ＳＯ２）（式中、ｍ及びｎはそれぞれ独立して１〜４の整数である）、リチウムペルフルオロアルキルスルホン酸メチドＬｉＣ（ＣｐＦ２ｐ＋１ＳＯ２）（ＣｑＦ２ｑ＋１ＳＯ２）（ＣｒＦ２ｒ＋１ＳＯ２）（式中、ｐ、ｑ及びｒはそれぞれ独立して１〜４の整数である）、ＬｉＣＦ３ＳＯ３、ＬｉＣｌＯ４、Ｌｉ２Ｂ１０Ｃｌ１０、及びＬｉ２Ｂ１２Ｃｌ１２などが挙げられる。溶質としては、これらの中でも、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＮ（ＣＦ３ＳＯ２）２、ＬｉＮ（Ｃ２Ｆ５ＳＯ２）２、ＬｉＮ（ＣＦ３ＳＯ２）（Ｃ４Ｆ９ＳＯ２）、ＬｉＣ（ＣＦ３ＳＯ２）３、ＬｉＣ（Ｃ２Ｆ５ＳＯ２）３などのうちの少なくとも一種を含んでいてもよい。非水電解質は、溶媒として、例えば、環状カーボネート、鎖状カーボネートまたは環状カーボネートと鎖状カーボネートとの混合溶媒などを含んでいてもよい。環状カーボネートの具体例としては、例えば、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、ビニレンカーボネートなどが挙げられる。鎖状カーボネートの具体例としては、例えば、ジメチルカーボネート、メチルエチルカーボネート、ジエチルカーボネートなどが挙げられる。 In addition to LiBOB, the nonaqueous electrolyte is, for example, LiXF y (wherein X is P, As, Sb, B, Bi, Al, Ga or In, and X is P, As or Sb) y is 6, X is B, Bi, the y when Al, Ga or in, a 4), lithium perfluoroalkyl sulfonic acid imide LiN (C m F 2m + 1 SO 2) (C n F 2n + 1 SO 2) (wherein, m and n are each independently an integer of 1 to 4), lithium perfluoroalkyl sulfonic acid methide LiC (C p F 2p + 1 SO 2) (C q F 2q + 1 SO 2) (C r F 2r + 1 SO 2 ) (wherein p, q and r are each independently an integer of 1 to 4), LiCF 3 SO 3 , LiClO 4, Li 2 B 10 Cl 10 and Li 2 B 12 Cl 12 etc. are mentioned. Among these, as solutes, LiPF 6 , LiBF 4 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) (C 4 F 9 SO 2 ), It may contain at least one of LiC (CF 3 SO 2 ) 3 , LiC (C 2 F 5 SO 2 ) 3 and the like. The nonaqueous electrolyte may contain, for example, a cyclic carbonate, a chain carbonate, or a mixed solvent of a cyclic carbonate and a chain carbonate as a solvent. Specific examples of the cyclic carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, and the like. Specific examples of the chain carbonate include dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate and the like.
容器１０は、容器本体１１と、封口板１２とを有する。容器本体１１は、一方側の端部が閉口された矩形管状に設けられている。容器本体１１は、開口を有する。この開口は、封口板１２により塞がれている。これにより、直方体状の内部空間が区画形成されている。この内部空間に電極体２０及び非水電解質が収容されている。 The container 10 includes a container body 11 and a sealing plate 12. The container body 11 is provided in a rectangular tubular shape whose one end is closed. The container body 11 has an opening. This opening is closed by the sealing plate 12. Thereby, a rectangular parallelepiped internal space is defined. The electrode body 20 and the nonaqueous electrolyte are accommodated in this internal space.
封口板１２には、正極端子１３と、負極端子１４とが取り付けられている。正極端子１３及び負極端子１４のそれぞれと、封口板１２とは図示しない絶縁材によって電気的に絶縁されている。 A positive electrode terminal 13 and a negative electrode terminal 14 are attached to the sealing plate 12. Each of the positive terminal 13 and the negative terminal 14 and the sealing plate 12 are electrically insulated by an insulating material (not shown).
図２及び図４に示されるように、正極端子１３は、正極配線材１５によって、正極２１の正極集電体２１ａと電気的に接続されている。正極配線材１５は、例えば、アルミニウ
ムやアルミニウム合金などにより構成することができる。図２及び図３に示されるように、負極端子１４は、負極配線材１６によって、負極２２の負極集電体２２ａと電気的に接続されている。負極配線材１６は、例えば、銅や銅合金などにより構成することができる。
As shown in FIGS. 2 and 4, the positive electrode terminal 13 is electrically connected to the positive electrode current collector 21 a of the positive electrode 21 by the positive electrode wiring member 15. The positive electrode wiring member 15 can be made of, for example, aluminum or an aluminum alloy. As shown in FIGS. 2 and 3, the negative electrode terminal 14 is electrically connected to the negative electrode current collector 22 a of the negative electrode 22 by the negative electrode wiring member 16. The negative electrode wiring member 16 can be made of, for example, copper or copper alloy.
正極配線材１５と、負極配線材１６とは、例えば、図６に示す配線材１７によって構成することができる。配線材１７は、少なくとも一つの第１の部分１７ａと、第２の部分１７ｂとを有する。第１の部分１７ａは、溶接などにより、正極集電体２１ａまたは負極集電体２２ａにより接合されることで、正極２１または負極２２に電気的に接続されている。本実施形態では、第１の部分１７ａが２つ設けられており、これら２つの第１の部分１７ａによって電極体２０が挟持されている。 The positive electrode wiring material 15 and the negative electrode wiring material 16 can be constituted by, for example, a wiring material 17 shown in FIG. The wiring member 17 has at least one first portion 17a and a second portion 17b. The first portion 17a is electrically connected to the positive electrode 21 or the negative electrode 22 by being joined by the positive electrode current collector 21a or the negative electrode current collector 22a by welding or the like. In the present embodiment, two first portions 17a are provided, and the electrode body 20 is sandwiched between the two first portions 17a.
第１の部分１７ａは、第２の部分１７ｂに電気的に接続されている。第２の部分１７ｂは、電極体２０よりも封口板１２側に配されている。この第２の部分１７ｂが、正極端子１３または負極端子１４に電気的に接続されている。具体的には、正極配線材１５を構成している配線材１７の第２の部分１７ｂが正極端子１３に電気的に接続されている。負極配線材１６を構成している配線材１７の第２の部分１７ｂが負極端子１４に電気的に接続されている。 The first portion 17a is electrically connected to the second portion 17b. The second portion 17 b is arranged closer to the sealing plate 12 than the electrode body 20. The second portion 17 b is electrically connected to the positive terminal 13 or the negative terminal 14. Specifically, the second portion 17 b of the wiring member 17 constituting the positive electrode wiring member 15 is electrically connected to the positive electrode terminal 13. A second portion 17 b of the wiring member 17 constituting the negative electrode wiring member 16 is electrically connected to the negative electrode terminal 14.
配線材の横断面積は、非水電解質二次電池の容量等に応じて適宜設定される。通常、配線材の横断面積は、配線材により大きな電力ロスが生じないような値に設定される。この観点からは、配線材の横断面積は十分に大きいことが好ましいと考えられる。しかしながら、配線材の横断面積を大きくしすぎると、配線材が大型化すると共に重くなる。よって、非水電解質二次電池が大型化すると共に重くなる。従って、配線材は、配線材により大きな電力ロスが生じない範囲において、極力細く、小型に設計される。 The cross-sectional area of the wiring material is appropriately set according to the capacity of the nonaqueous electrolyte secondary battery. Usually, the cross-sectional area of the wiring material is set to a value that does not cause a large power loss due to the wiring material. From this viewpoint, it is considered preferable that the cross-sectional area of the wiring material is sufficiently large. However, if the cross-sectional area of the wiring material is too large, the wiring material becomes large and heavy. Therefore, the nonaqueous electrolyte secondary battery becomes larger and heavier. Accordingly, the wiring material is designed to be as thin and small as possible within a range in which a large power loss is not caused by the wiring material.
例えば、本実施形態の非水電解質二次電池１のように、電池容量が５〜５０Ａｈであるような場合には、配線材の横断面積は、１．５〜１０ｍｍ２程度とするのが一般的である。 For example, when the battery capacity is 5 to 50 Ah as in the non-aqueous electrolyte secondary battery 1 of this embodiment, the cross-sectional area of the wiring material is generally about 1.5 to 10 mm 2. Is.
上述のように、非水電解質二次電池１においては、非水電解質がＬｉＢＯＢを含む。このため、改善されたサイクル寿命を実現することができる。しかしながら、本発明者らが鋭意研究した結果、非水電解質がＬｉＢＯＢを含む非水電解質二次電池は、外部からの衝撃による電池圧壊などの異常時に電池内部が発熱しやすいことが見出された。これは、上記のような異常時に電極体２０が加熱されることとなり、一定温度を超えるとＬｉＢＯＢに由来する反応生成物が新たな発熱反応が生じてしまうことが原因であると推察される。ここで、非水電解質二次電池１では、配線材１７の横断面積（詳細には、配線材１７の集電体２１ａ、２２ａと接続された部分と、端子１３，１４と接続された部分とを接続している接続部の最も細い部分の横断面積）が、１．５ｍｍ２以上である。このため、電極体２０の熱は、配線材１７及び容器１０を経由して発散しやすい。つまり上記のような異常時において、非水電解質二次電池１の電極体２０の温度上昇が抑制されるため、温度上昇に伴って生じる発熱反応を回避することができる。 As described above, in the nonaqueous electrolyte secondary battery 1, the nonaqueous electrolyte contains LiBOB. For this reason, an improved cycle life can be realized. However, as a result of intensive studies by the present inventors, it has been found that a non-aqueous electrolyte secondary battery in which the non-aqueous electrolyte contains LiBOB tends to generate heat inside the battery when there is an abnormality such as battery collapse due to an external impact. . It is assumed that this is because the electrode body 20 is heated at the time of the abnormality as described above, and a reaction product derived from LiBOB causes a new exothermic reaction when the temperature exceeds a certain temperature. Here, in the nonaqueous electrolyte secondary battery 1, the cross-sectional area of the wiring member 17 (specifically, the portion connected to the current collectors 21 a and 22 a of the wiring member 17, and the portion connected to the terminals 13 and 14) The cross-sectional area of the thinnest part of the connection part connecting the two ) is 1.5 mm 2 or more. For this reason, the heat of the electrode body 20 tends to diverge through the wiring member 17 and the container 10. That is, since the temperature rise of the electrode body 20 of the non-aqueous electrolyte secondary battery 1 is suppressed at the time of the abnormality as described above, an exothermic reaction caused by the temperature rise can be avoided.
非水電解質二次電池１がより発熱しにくくする観点からは、配線材１７の横断面積が１．５ｍｍ２以上であることが好ましく、３．０ｍｍ２以上であることがより好ましい。但し、配線材１７の横断面積が大きすぎると、非水電解質二次電池１が大型化しすぎたり、非水電解質二次電池１の重量が増大しすぎたりする場合がある。従って、配線材１７の横断面積は、１０ｍｍ２以下であることが好ましく、７ｍｍ２以下であることがより好ましい。同様に、配線材１７の厚みは、０．５ｍｍ以上であることが好ましく、０．６ｍｍ以上であることがより好ましい。配線材１７の厚みは、１．５ｍｍ以下であることが好まし
く、１．０ｍｍ以下であることがより好ましい。
From the viewpoint of making the nonaqueous electrolyte secondary battery 1 more difficult to generate heat, the cross-sectional area of the wiring member 17 is preferably 1.5 mm 2 or more, and more preferably 3.0 mm 2 or more. However, if the cross-sectional area of the wiring member 17 is too large, the nonaqueous electrolyte secondary battery 1 may become too large or the weight of the nonaqueous electrolyte secondary battery 1 may increase excessively. Therefore, the cross-sectional area of the wiring member 17 is preferably 10 mm 2 or less, and more preferably 7 mm 2 or less. Similarly, the thickness of the wiring member 17 is preferably 0.5 mm or more, and more preferably 0.6 mm or more. The thickness of the wiring member 17 is preferably 1.5 mm or less, and more preferably 1.0 mm or less.
また、非水電解質二次電池１がより発熱しにくくする観点からは、配線材１７の熱伝導率が、１５０Ｗ／ｍ・Ｋ以上であることが好ましく、２００Ｗ／ｍ・Ｋ以上であることが好ましい。 Further, from the viewpoint of making the nonaqueous electrolyte secondary battery 1 more difficult to generate heat, the thermal conductivity of the wiring member 17 is preferably 150 W / m · K or more, and preferably 200 W / m · K or more. preferable.
なお、上記構成によれば非水電解質二次電池が低温環境下に曝された場合、電池内部の温度も低下しやすくなるため、出力特性が低下してしまう。低温環境下においても出力特性の低下を抑制するために、非水電解質はジフルオロリン酸リチウムを含むことが好ましい。非水電解質におけるジフルオロリン酸リチウムの含有量は０．０１ｍｏｌ／Ｌ〜０．２０ｍｏｌ／Ｌであることが好ましく、０．０３ｍｏｌ／Ｌ〜０．１０ｍｏｌ／Ｌであることがより好ましい。ジフルオロリン酸リチウムの好ましい含有量の範囲は、組立後かつ初回充電前の非水電解質二次電池中の非水電解質を基準としたものである。このような基準を設けたのは、ジフルオロリン酸リチウムを含む非水電解質二次電池を充電すると、その含有量が徐々に低下してしまうためである。 In addition, according to the said structure, when a nonaqueous electrolyte secondary battery is exposed to a low temperature environment, since the temperature inside a battery will also fall easily, output characteristics will fall. In order to suppress a decrease in output characteristics even in a low temperature environment, the nonaqueous electrolyte preferably contains lithium difluorophosphate. The content of lithium difluorophosphate in the non-aqueous electrolyte is preferably 0.01 mol / L to 0.20 mol / L, and more preferably 0.03 mol / L to 0.10 mol / L. A preferable range of the content of lithium difluorophosphate is based on the nonaqueous electrolyte in the nonaqueous electrolyte secondary battery after assembly and before the first charge. The reason for setting such a standard is that when a non-aqueous electrolyte secondary battery containing lithium difluorophosphate is charged, its content gradually decreases.
ＬｉＢＯＢは、非水電解質二次電池を組み立てた直後において、電解液中に存在していればよい。例えば、組み立て後に充放電を行った後においては、ＬｉＢＯＢは、ＬｉＢＯＢの変成体として存在している場合もある。また、ＬｉＢＯＢまたはＬｉＢＯＢの変成体の少なくとも一部が負極活物質層上に存在している場合もある。そのような場合も、本発明の技術的範囲に含まれる。 LiBOB only needs to be present in the electrolyte immediately after the non-aqueous electrolyte secondary battery is assembled. For example, after charging / discharging after assembly, LiBOB may exist as a modified LiBOB. In some cases, at least a part of LiBOB or a modified LiBOB exists on the negative electrode active material layer. Such a case is also included in the technical scope of the present invention.
１…非水電解質二次電池
１０…容器
１１…容器本体
１２…封口板
１３…正極端子
１４…負極端子
１５…正極配線材
１６…負極配線材
１７…配線材
１７ａ…第１の部分
１７ｂ…第２の部分
２０…電極体
２１…正極
２１ａ…正極集電体
２１ｂ…正極活物質層
２２…負極
２２ａ…負極集電体
２２ｂ…負極活物質層
２３…セパレータ
DESCRIPTION OF SYMBOLS 1 ... Nonaqueous electrolyte secondary battery 10 ... Container 11 ... Container main body 12 ... Sealing board 13 ... Positive electrode terminal 14 ... Negative electrode terminal 15 ... Positive electrode wiring material 16 ... Negative electrode wiring material 17 ... Wiring material 17a ... 1st part 17b ... 1st part 2 part 20 ... electrode body 21 ... positive electrode 21a ... positive electrode current collector 21b ... positive electrode active material layer 22 ... negative electrode 22a ... negative electrode current collector 22b ... negative electrode active material layer 23 ... separator
Claims (4)
リチウムビス（オキサレート）ボレート（ＬｉＢＯＢ）を含む非水電解質と、
開口を有する角形の容器本体と、正極端子及び負極端子が取り付けられており前記開口を封口する封口板とを含み、前記電極体及び前記非水電解質を収納する容器と、
前記正極端子又は前記負極端子と、前記電極体とを接続している配線材と、
を備え、
前記配線材の横断面積が、３．０ｍｍ２〜１０ｍｍ２であり、
前記配線材の熱伝導率が１５０Ｗ／ｍ・Ｋ以上であり、
前記配線材の厚みが、０．５ｍｍ以上であり、
容量が５〜４０Ａｈであり、
前記正極は、正極集電体と、前記正極の端部に前記正極集電体の両面に正極活物質層が形成されていない部分が設けられるように前記正極集電体の両面に形成された前記正極活物質層を含み、
前記負極は、負極集電体と、前記負極の端部に前記負極集電体の両面に負極活物質層が形成されていない部分が設けられるように前記負極集電体の両面に形成された前記負極活物質層を含み、
前記正極の端部に設けられた前記正極集電体において前記正極集電体の両面に前記正極活物質層が形成されていない部分が、前記巻回体である電極体の巻回軸が延びる方向における一方の端部側に配置されると共に、前記容器本体において前記封口板に対して垂直に配置され且つ前記封口板の長手方向における一方の端部側に配置される側壁部側に配置され、
前記負極の端部に設けられた前記負極集電体において前記負極集電体の両面に前記負極活物質層が形成されていない部分が、前記巻回体である電極体の巻回軸が延びる方向における他方の端部側に配置されると共に、前記容器本体において前記封口板に対して垂直に配置され且つ前記封口板の長手方向における他方の端部側に配置される側壁部側に配置され、
前記配線材は、前記正極集電体において前記正極活物質層が形成されていない部分、又は、前記負極集電体において前記負極活物質層が形成されていない部分に接続され、
前記配線材は、前記電極体と前記封口板の間で前記正極端子又は前記負極端子に接続されている非水電解質二次電池。 A flat wound body having a positive electrode, a negative electrode facing the positive electrode, and a separator disposed between the positive electrode and the negative electrode, and in which the positive electrode, the negative electrode, and the separator are wound. An electrode body,
A non-aqueous electrolyte comprising lithium bis (oxalate) borate (LiBOB);
A rectangular container body having an opening, a positive electrode terminal and a sealing plate to which the negative electrode terminal is attached and sealing the opening, and a container for storing the electrode body and the nonaqueous electrolyte;
A wiring material connecting the positive electrode terminal or the negative electrode terminal and the electrode body;
With
Cross-sectional area of the wiring member is a 3.0 mm 2 to 10 mm 2,
The wiring material has a thermal conductivity of 150 W / m · K or more,
The wiring material has a thickness of 0.5 mm or more,
The capacity is 5-40Ah,
The positive electrode was formed on both sides of the positive electrode current collector so that a positive electrode current collector and a portion where the positive electrode active material layer was not formed on both sides of the positive electrode current collector were provided at the end of the positive electrode Including the positive electrode active material layer,
The negative electrode was formed on both sides of the negative electrode current collector so that a negative electrode current collector and a portion where the negative electrode active material layer was not formed on both sides of the negative electrode current collector were provided at the end of the negative electrode Including the negative electrode active material layer,
In the positive electrode current collector provided at the end of the positive electrode, portions where the positive electrode active material layer is not formed on both surfaces of the positive electrode current collector extend the winding axis of the electrode body that is the wound body. Disposed on one end side in the direction, and disposed on the side of the side wall that is disposed perpendicular to the sealing plate in the container body and disposed on the one end side in the longitudinal direction of the sealing plate. ,
In the negative electrode current collector provided at the end of the negative electrode, the portion where the negative electrode active material layer is not formed on both surfaces of the negative electrode current collector extends the winding axis of the electrode body that is the wound body Disposed on the other end side in the direction, and disposed on the side of the side wall that is disposed perpendicular to the sealing plate in the container body and disposed on the other end side in the longitudinal direction of the sealing plate. ,
The wiring member is connected to a portion where the positive electrode active material layer is not formed in the positive electrode current collector, or a portion where the negative electrode active material layer is not formed in the negative electrode current collector,
The said wiring material is a nonaqueous electrolyte secondary battery connected to the said positive electrode terminal or the said negative electrode terminal between the said electrode body and the said sealing board.
非水電解質と、
開口を有する角形の容器本体と、正極端子及び負極端子が取り付けられており前記開口を封口する封口板とを含み、前記電極体及び前記非水電解質を収納する容器と、
前記正極端子又は前記負極端子と、前記電極体とを接続している配線材と、
を備え、
前記配線材の横断面積が、３．０ｍｍ２〜１０ｍｍ２であり、
前記配線材の熱伝導率が１５０Ｗ／ｍ・Ｋ以上であり、
前記配線材の厚みが、０．５ｍｍ以上であり、
容量が５〜４０Ａｈであり、
前記正極は、正極集電体と、前記正極の端部に前記正極集電体の両面に正極活物質層が形成されていない部分が設けられるように前記正極集電体の両面に形成された前記正極活物質層を含み、
前記負極は、負極集電体と、前記負極の端部に前記負極集電体の両面に負極活物質層が形成されていない部分が設けられるように前記負極集電体の両面に形成された前記負極活物質層を含み、
前記正極の端部に設けられた前記正極集電体において前記正極集電体の両面に前記正極活物質層が形成されていない部分が、前記巻回体である電極体の巻回軸が延びる方向における一方の端部側に配置されると共に、前記容器本体において前記封口板に対して垂直に配置され且つ前記封口板の長手方向における一方の端部側に配置される側壁部側に配置され、
前記負極の端部に設けられた前記負極集電体において前記負極集電体の両面に前記負極活物質層が形成されていない部分が、前記巻回体である電極体の巻回軸が延びる方向における他方の端部側に配置されると共に、前記容器本体において前記封口板に対して垂直に配置され且つ前記封口板の長手方向における他方の端部側に配置される側壁部側に配置され、
前記配線材は、前記正極集電体において前記正極活物質層が形成されていない部分、又は、前記負極集電体において前記負極活物質層が形成されていない部分に接続され、
前記配線材は、前記電極体と前記封口板の間で前記正極端子又は前記負極端子に接続されている非水電解質二次電池の製造方法であって、
リチウムビス（オキサレート）ボレート（ＬｉＢＯＢ）を含む前記非水電解質を前記容器内に収納する工程を有する非水電解質二次電池の製造方法。 A flat wound body having a positive electrode, a negative electrode facing the positive electrode, and a separator disposed between the positive electrode and the negative electrode, and in which the positive electrode, the negative electrode, and the separator are wound. An electrode body,
A non-aqueous electrolyte,
A rectangular container body having an opening, a positive electrode terminal and a sealing plate to which the negative electrode terminal is attached and sealing the opening, and a container for storing the electrode body and the nonaqueous electrolyte;
A wiring material connecting the positive electrode terminal or the negative electrode terminal and the electrode body;
With
Cross-sectional area of the wiring member is a 3.0 mm 2 to 10 mm 2,
The wiring material has a thermal conductivity of 150 W / m · K or more,
The wiring material has a thickness of 0.5 mm or more,
The capacity is 5-40Ah,
The positive electrode was formed on both sides of the positive electrode current collector so that a positive electrode current collector and a portion where the positive electrode active material layer was not formed on both sides of the positive electrode current collector were provided at the end of the positive electrode Including the positive electrode active material layer,
The negative electrode was formed on both sides of the negative electrode current collector so that a negative electrode current collector and a portion where the negative electrode active material layer was not formed on both sides of the negative electrode current collector were provided at the end of the negative electrode Including the negative electrode active material layer,
In the positive electrode current collector provided at the end of the positive electrode, portions where the positive electrode active material layer is not formed on both surfaces of the positive electrode current collector extend the winding axis of the electrode body that is the wound body. Disposed on one end side in the direction, and disposed on the side of the side wall that is disposed perpendicular to the sealing plate in the container body and disposed on the one end side in the longitudinal direction of the sealing plate. ,
In the negative electrode current collector provided at the end of the negative electrode, the portion where the negative electrode active material layer is not formed on both surfaces of the negative electrode current collector extends the winding axis of the electrode body that is the wound body Disposed on the other end side in the direction, and disposed on the side of the side wall that is disposed perpendicular to the sealing plate in the container body and disposed on the other end side in the longitudinal direction of the sealing plate. ,
The wiring member is connected to a portion where the positive electrode active material layer is not formed in the positive electrode current collector, or a portion where the negative electrode active material layer is not formed in the negative electrode current collector,
The wiring material is a method for producing a non-aqueous electrolyte secondary battery connected to the positive terminal or the negative terminal between the electrode body and the sealing plate,
A method for producing a nonaqueous electrolyte secondary battery, comprising the step of housing the nonaqueous electrolyte containing lithium bis (oxalate) borate (LiBOB) in the container.
前記負極は、前記電極体の巻回軸が延びる方向における一方の端部に前記負極集電体の両面に前記負極活物質層が形成されていない部分を有し、前記電極体の巻回軸が延びる方向における他方の端部においては前記負極集電体の両面に前記負極活物質層が形成されている請求項２又は３に記載の非水電解質二次電池の製造方法。
The wiring material is connected to the negative terminal and the negative electrode,
The negative electrode has a portion in which the negative electrode active material layer is not formed on both surfaces of the negative electrode current collector at one end in a direction in which the winding axis of the electrode body extends, and the winding axis of the electrode body The method for producing a nonaqueous electrolyte secondary battery according to claim 2 or 3, wherein the negative electrode active material layer is formed on both surfaces of the negative electrode current collector at the other end in the direction in which the negative electrode extends.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016111537A JP6128266B2 (en) | 2016-06-03 | 2016-06-03 | Non-aqueous electrolyte secondary battery and manufacturing method thereof |
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| JP2020107439A (en) * | 2018-12-26 | 2020-07-09 | トヨタ自動車株式会社 | Secondary battery cooling structure |
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