JP2003051298A - Group battery equipped with pressure-equalized non- aqueous electrolyte secondary batteries - Google Patents
Group battery equipped with pressure-equalized non- aqueous electrolyte secondary batteriesInfo
- Publication number
- JP2003051298A JP2003051298A JP2001239704A JP2001239704A JP2003051298A JP 2003051298 A JP2003051298 A JP 2003051298A JP 2001239704 A JP2001239704 A JP 2001239704A JP 2001239704 A JP2001239704 A JP 2001239704A JP 2003051298 A JP2003051298 A JP 2003051298A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- case
- electrolyte secondary
- aqueous electrolyte
- group battery
- 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
- Sealing Battery Cases Or Jackets (AREA)
- Secondary Cells (AREA)
- Battery Mounting, Suspending (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、均圧装置を備えた
非水電解質二次電池からなる単電池を備えた群電池に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a group battery provided with a unit cell composed of a non-aqueous electrolyte secondary battery provided with a pressure equalizer.
【０００２】[0002]
【従来の技術】現在、携帯用無線電話、携帯用パソコ
ン、携帯用ビデオカメラ等の各種携帯可能な電子機器用
の電源として、高エネルギー密度で、しかも軽量な二次
電池が採用されている。そのような要求を満たす典型的
な二次電池としては、リチウム金属やリチウム合金等の
活物質、又はリチウムイオンをホスト物質（ここでホス
ト物質とは、リチウムイオンを吸蔵及び放出できる物質
をいう）である炭素に吸蔵させたリチウムインターカレ
ーション化合物を負極材料とし、ＬｉＣｌＯ４、ＬｉＰ
Ｆ６等のリチウム塩を溶解した非プロトン性の有機溶媒
を電解液とする非水電解質二次電池がある。2. Description of the Related Art Currently, a lightweight secondary battery having a high energy density is used as a power source for various portable electronic devices such as a portable radio telephone, a portable personal computer, a portable video camera and the like. As a typical secondary battery satisfying such requirements, an active material such as lithium metal or a lithium alloy, or a lithium ion host material (here, the host material means a material capable of inserting and extracting lithium ion) The lithium intercalation compound occluded in carbon is used as a negative electrode material, and LiClO 4 , LiP
There is a non-aqueous electrolyte secondary battery in which an aprotic organic solvent in which a lithium salt such as F 6 is dissolved is used as an electrolytic solution.
【０００３】一方、産業用や電気自動車用の大型電池と
しては、これまで、アルカリ系二次電池や鉛蓄電池が広
く用いられてきたが、これらの用途にも非水電解質二次
電池を利用することが考えられ、放電容量が２０Ａｈ以
上の大型非水電解質二次電池の開発もおこなわれてい
る。また、大型非水電解質二次電池を深海用に利用する
動きも強まっている。On the other hand, as a large battery for industrial use and electric vehicles, an alkaline secondary battery and a lead storage battery have been widely used so far, but a non-aqueous electrolyte secondary battery is also used for these purposes. Therefore, a large nonaqueous electrolyte secondary battery having a discharge capacity of 20 Ah or more is being developed. In addition, there is an increasing movement to use large non-aqueous electrolyte secondary batteries for deep sea applications.
【０００４】有機電解液二次電池を深海用に用いる技術
は特願昭６３−２９１７８８号公報に記載され、均圧装
置としてジャバラなどを用いることが開示されている。
また、特願平９−１７４０１号公報においては、均圧装
置を備えた有機電解液二次電池を複数個組み合せて群電
池とし、電池収納槽内に収納された複数の単電池と、電
池収納槽内の空間部に、絶縁油として流動パラフィン等
を充填する技術が開示されている。A technique for using the organic electrolyte secondary battery for deep sea is disclosed in Japanese Patent Application No. 63-291788, and it is disclosed that a bellows or the like is used as a pressure equalizing device.
Further, in Japanese Patent Application No. 9-17401, a plurality of organic electrolyte secondary batteries provided with a pressure equalizing device are combined to form a group battery, and a plurality of unit cells stored in a battery storage tank and a battery storage A technique of filling a liquid paraffin or the like as insulating oil into a space in a tank is disclosed.
【０００５】大型の非水電解質二次電池においては、電
池ケース内に収納する発電要素も大型になり、電池ケー
スに機械的強度が要求されることや、放電時の電池内部
の温度上昇を避けるために、電池ケース外部表面から放
熱する必要があるため、金属製電池ケースが使用されて
いる。特に大型非水電解質二次電池の場合には、電池外
部からの水分の侵入を防止するためにも、金属製電池ケ
ースを使用する必要がある。In a large non-aqueous electrolyte secondary battery, the power generating element housed in the battery case also becomes large, and mechanical strength is required for the battery case and the temperature rise inside the battery during discharging is avoided. Therefore, a metal battery case is used because it is necessary to radiate heat from the outer surface of the battery case. Particularly in the case of a large non-aqueous electrolyte secondary battery, it is necessary to use a metal battery case also in order to prevent water from entering from the outside of the battery.
【０００６】均圧装置を備え、金属ケースを用いた大型
非水電解質二次電池を複数個接続した群電池において
は、高圧下で侵入してくる水の悪影響から電池を保護す
るために、上記特願平９−１７４０１号公報に記載され
ているように、単電池間に絶縁油を満たしておく必要が
あった。In a group battery provided with a pressure equalizer and connected with a plurality of large non-aqueous electrolyte secondary batteries using a metal case, in order to protect the battery from the adverse effect of water invading under high pressure, As described in Japanese Patent Application No. 9-17401, it was necessary to fill the insulating oil between the unit cells.
【０００７】ところが、金属製ケースを用いた単電池を
複数個収納した群電池において、電池を移動したり、組
電池にセットする場合、あるいは故障した個々の電池を
交換する場合、電池が大きくて重いために、取り扱いが
困難であり、電池間のショート防止のためには、金属電
池ケース外部表面を絶縁しておく必要があった。However, in a group battery containing a plurality of single cells using a metal case, the batteries are large when they are moved or set in an assembled battery or when a defective individual battery is replaced. Since it is heavy, it is difficult to handle, and it is necessary to insulate the outer surface of the metal battery case in order to prevent a short circuit between the batteries.
【０００８】金属製電池ケース外部表面を良好に絶縁す
る方法としては、特開平９−９２２３７号公報に記載さ
れているように、円筒状金属電池ケースの表面にウレタ
ンゴム系弾性絶縁体層を設ける方法が開示されている。As a method for satisfactorily insulating the outer surface of the metal battery case, a urethane rubber elastic insulator layer is provided on the surface of the cylindrical metal battery case, as described in JP-A-9-92237. A method is disclosed.
【０００９】[0009]
【発明が解決しようとする課題】しかし、従来の電池の
ように、金属ケース表面に、薄いあるいはやわらかい絶
縁性フィルムを貼り付けたり、絶縁塗料を塗布した場合
には、大型電池どうしのぶつかりによって、絶縁膜が破
壊され、ショートが発生する可能性が高くなる。However, like a conventional battery, when a thin or soft insulating film is attached to the surface of a metal case or an insulating paint is applied to the surface of the metal case, the large batteries collide with each other, which causes a problem. There is a high possibility that the insulating film will be destroyed and a short circuit will occur.
【００１０】また、絶縁油は、水や海水と混ざらないと
いう機能とは別に、電池が放電時に発熱した場合、絶縁
油によって冷却されるが、電池表面に単に絶縁膜をとり
つける場合には、冷却効果に乏しかった。In addition to the function that the insulating oil does not mix with water or seawater, when the battery generates heat during discharge, it is cooled by the insulating oil, but when the insulating film is simply attached to the surface of the battery, the insulating oil is cooled. The effect was poor.
【００１１】本発明はこれらの問題点を解決するために
なされたもので、その目的は、金属製ケースと均圧装置
とを備えた非水電解質二次電池からなる単電池を、複数
個直列または／および並列に接続し、単電池間に絶縁油
を満たして群電池ケースに収納した群電池において、故
障した電池を交換する場合や電池を移動する場合、電池
どうしがぶつかった場合でも、金属ケース表面の絶縁層
が破れないようにするものである。同時に、電池が発熱
した場合に、絶縁油による冷却効果を高めるものであ
る。The present invention has been made to solve these problems, and its object is to provide a plurality of single cells, which are non-aqueous electrolyte secondary batteries having a metal case and a pressure equalizer, in series. In addition, and / or in parallel, when connecting the cells in parallel and filling the insulating oil between the cells and storing them in the group battery case, replace the defective battery, move the battery, or even if the batteries collide with each other, metal This is to prevent the insulating layer on the case surface from breaking. At the same time, when the battery heats up, the cooling effect of the insulating oil is enhanced.
【００１２】[0012]
【課題を解決するための手段】請求項１の発明は、金属
製ケースと均圧装置とを備えた非水電解質二次電池から
なる単電池を、複数個直列または／および並列に接続
し、単電池間に絶縁油を満たして群電池ケースに収納し
た群電池において、単電池ケース表面にロックウェル硬
度が９０以上の絶縁板を設けたことを特徴とする。According to a first aspect of the present invention, a plurality of unit cells each including a non-aqueous electrolyte secondary battery including a metal case and a pressure equalizer are connected in series or / and in parallel, In a group battery in which insulating oil is filled between the unit cells and housed in a group battery case, an insulating plate having a Rockwell hardness of 90 or more is provided on the surface of the unit cell case.
【００１３】請求項１の発明によれば、大型の単電池が
ぶつかった場合でも、金属製単電池ケース表面の絶縁が
良好に保たれ、電池どうしのショートを防止することが
できる。According to the first aspect of the present invention, even when a large unit cell collides, the surface of the metal unit cell case can be well insulated, and a short circuit between the cells can be prevented.
【００１４】請求項２の発明は、上記群電池において、
絶縁板がホリプロピレンであることを特徴とする。According to a second aspect of the present invention, in the above group battery,
It is characterized in that the insulating plate is polypropylene.
【００１５】請求項２の発明によれば、単電池間の絶縁
をより良好に保つことができる。According to the second aspect of the invention, the insulation between the unit cells can be better maintained.
【００１６】請求項３の発明は、上記群電池において、
絶縁板表面が電池の上下方向の溝を有することを特徴と
する。According to a third aspect of the present invention, in the above group battery,
The surface of the insulating plate has a groove in the vertical direction of the battery.
【００１７】請求項３の発明によれば、絶縁油の対流が
容易となり、電池を効果的に冷却することができる。According to the third aspect of the invention, the convection of the insulating oil is facilitated and the battery can be effectively cooled.
【００１８】請求項４の発明は、上記群電池において、
絶縁油が軽質流動パラフィンであることを特徴とする。According to a fourth aspect of the present invention, in the above group battery,
The insulating oil is light liquid paraffin.
【００１９】請求項４の発明によれば、電池をより効果
的に冷却することができる。According to the invention of claim 4, the battery can be cooled more effectively.
【００２０】[0020]
【発明の実施の形態】本発明の群電池は、金属製ケース
と均圧装置とを備えた非水電解質二次電池からなる単電
池を複数個接続し、単電池間に絶縁油を満たして、群電
池ケースに収納したものであり、主に深海用に使用する
ものである。そして、単電池ケース表面にロックウェル
硬度が９０以上の絶縁板を設けたことを特徴とする。BEST MODE FOR CARRYING OUT THE INVENTION The group battery of the present invention comprises a plurality of non-aqueous electrolyte secondary batteries each having a metal case and a pressure equalizer, which are connected to each other, and insulating oil is filled between the unit cells. It is stored in the battery pack case and is mainly used for deep water. An insulating plate having a Rockwell hardness of 90 or more is provided on the surface of the unit cell case.
【００２１】単電池ケース表面に、ロックウェル硬度が
９０以上の絶縁板を設けることにより、電池を移動した
り、組電池にセットする場合、あるいは故障した個々の
単電池を交換する場合、電池が大きくて重いために、取
り扱いが困難で、電池どうしがぶつかった場合でも、金
属製電池ケース外部表面を良好に絶縁することができ、
電池間のショートを防止することができる。By providing an insulating plate having a Rockwell hardness of 90 or more on the surface of the unit cell case, the battery can be moved when it is moved or set in an assembled battery, or when a defective individual unit cell is replaced. Because it is large and heavy, it is difficult to handle, and even if the batteries collide with each other, the outer surface of the metal battery case can be well insulated,
It is possible to prevent a short circuit between the batteries.
【００２２】各種プラスチックのロックウェル硬度の試
験方法はＪＩＳ−Ｋ ６９１１で定められており、本発
明ではロックウェル硬度が９０以上の絶縁板を使用す
る。ロックウェル硬度が９０以上の材料としては、ポリ
プロピレン（Ｒ＝９３）、塩化ビニル樹脂（Ｒ＝１１
５）、フェノール樹脂（Ｒ＝１１８）等があるが、これ
らの中では、取り扱い易さや金属製電池ケース表面への
取付け易さなどからポリプロピレンを使用することが好
ましい。The test method for the Rockwell hardness of various plastics is defined in JIS-K6911, and an insulating plate having a Rockwell hardness of 90 or more is used in the present invention. Materials having a Rockwell hardness of 90 or more include polypropylene (R = 93) and vinyl chloride resin (R = 11)
5), phenol resin (R = 118), and the like. Among them, polypropylene is preferably used because it is easy to handle and can be easily attached to the surface of a metal battery case.
【００２３】また、金属電池ケース表面に設ける絶縁板
の厚さは、最低０．３ｍｍ必要であり、これよりも薄い
と、大型電池どうしがぶつかった場合には、絶縁板が破
壊されて、良好な絶縁を保てなくなる。なお、絶縁を保
つという意味からは、絶縁板の厚さはいくら厚くてもよ
いが、絶縁板の厚さが増すと、群電池全体の体積当りや
重量当りのエネルギー密度が小さくなるため、絶縁が保
もたれる最小の厚さとすることが好ましい。In addition, the thickness of the insulating plate provided on the surface of the metal battery case must be at least 0.3 mm, and if it is thinner than this, when the large batteries collide with each other, the insulating plate is destroyed and is good. Can no longer maintain good insulation. The thickness of the insulating plate may be any thickness from the standpoint of maintaining insulation, but if the thickness of the insulating plate is increased, the energy density per volume or weight of the entire group battery will decrease, so It is preferable that the thickness be the minimum thickness that can hold.
【００２４】さらに、単電池を複数接続する方法として
は、直列、並列または直列と並列が混合していてもよ
く、群電池の電圧と容量によって選択することができ
る。Further, as a method of connecting a plurality of unit cells, series, parallel, or a mixture of series and parallel may be used, and the method can be selected according to the voltage and capacity of the group battery.
【００２５】図１は、均圧装置を備えた非水電解質二次
電池の単電池の外観を示したもので、図１において、１
は非水電解質二次電池、２は金属製電池ケース、３は正
極端子、４は負極端子、５は注液栓、６は均圧装置、７
は金属製電池ケース表面に設けた絶縁板（ハッチング部
分）である。FIG. 1 shows the appearance of a non-aqueous electrolyte secondary battery unit equipped with a pressure equalizer.
Is a non-aqueous electrolyte secondary battery, 2 is a metal battery case, 3 is a positive electrode terminal, 4 is a negative electrode terminal, 5 is a liquid injection stopper, 6 is a pressure equalizing device, 7
Is an insulating plate (hatched portion) provided on the surface of the metal battery case.
【００２６】この単電池においては、じゃばら型の均圧
装置６は電池の下部に設けられている。また、金属製電
池ケース２を使用し、その表面には絶縁板７が設けられ
ており、この絶縁板７としてはロックウェル硬度が９０
以上の材料を使用する。なお、絶縁板７は金属製電池ケ
ース２の表面の一部に設けてもよいが、電池表面の絶縁
を良好にするためには、金属製電池ケース２の表面の全
面を覆うように設けることが好ましい。In this unit cell, the bellows type pressure equalizer 6 is provided at the bottom of the battery. Further, a metal battery case 2 is used, and an insulating plate 7 is provided on the surface thereof. The insulating plate 7 has a Rockwell hardness of 90.
The above materials are used. The insulating plate 7 may be provided on a part of the surface of the metal battery case 2, but in order to improve the insulation of the battery surface, it is provided so as to cover the entire surface of the metal battery case 2. Is preferred.
【００２７】図２は、本発明になる群電池の断面構造を
示したもので、図２において、記号１および６は図１と
同じものを示し、８は群電池ケース、９は接続体、１０
は絶縁油、１１は外部との連絡孔である。FIG. 2 shows a sectional structure of the group battery according to the present invention. In FIG. 2, symbols 1 and 6 are the same as those in FIG. 1, 8 is a group battery case, 9 is a connection body, 10
Is an insulating oil, and 11 is a communication hole with the outside.
【００２８】この群電池は、群電池ケース８の中に複数
個（図２では４個）の単電池１が収納され、これらの単
電池１は接続体９によって、直列または／および並列に
接続されている。群電池ケース８の内部の空間は絶縁油
１０で満たされており、この絶縁油１０は、外部の例え
ば海水などと、連絡孔１１を通して連絡されている。群
電池ケース８の材料としては、ステンレス鋼をはじめと
する金属や、ガラス繊維強化プラスチックス（ＦＲＰ）
などを使用することができる。In this group battery, a plurality (four in FIG. 2) of unit cells 1 are housed in a group battery case 8, and these unit cells 1 are connected in series or / and in parallel by a connecting body 9. Has been done. The space inside the group battery case 8 is filled with insulating oil 10, and this insulating oil 10 is connected to the outside, for example, seawater, through a communication hole 11. Materials for the battery pack case 8 include metals such as stainless steel, and glass fiber reinforced plastics (FRP).
Etc. can be used.
【００２９】この群電池が深海で使用される場合、外部
からの圧力が絶縁油１０を介して単電池１に加わり、均
圧装置６が働いて、単電池１の内部は、外部の圧力と等
しくなり、単電池１が押しつぶされることはない。そし
て、絶縁油１０によって、単電池１は海水などと接触す
ることがなく、非水電解質二次電池への悪影響は防止さ
れる。When this group battery is used in the deep sea, a pressure from the outside is applied to the unit cell 1 through the insulating oil 10 and the pressure equalizing device 6 operates so that the inside of the unit cell 1 is exposed to the external pressure. It becomes equal and the unit cell 1 is not crushed. The insulating oil 10 prevents the unit cell 1 from coming into contact with seawater or the like, and prevents adverse effects on the non-aqueous electrolyte secondary battery.
【００３０】さらに、本発明は、単電池の金属製電池ケ
ースの表面に設けられた絶縁板が、電池の上下方向の溝
を有することを特徴とする。図３は溝を有する絶縁板を
設けた単電池の例を示したもので、図３において、記号
１〜７は図１と同じものを示し、１２は絶縁板に設けら
れた溝である。Furthermore, the present invention is characterized in that the insulating plate provided on the surface of the metal battery case of the unit cell has a groove in the vertical direction of the battery. FIG. 3 shows an example of a unit cell provided with an insulating plate having a groove. In FIG. 3, symbols 1 to 7 indicate the same as those in FIG. 1, and 12 is a groove provided in the insulating plate.
【００３１】電池の放電時には、電池内部の温度が上昇
し、電池ケース表面から放熱するが、この熱は絶縁油に
吸収され、この時絶縁油は対流によって上方へ移動す
る。この時、図３のように、絶縁板に電池の上下方向の
溝を設けることにより、絶縁油の対流が容易となり、電
池を効果的に冷却することができる。When the battery is discharged, the temperature inside the battery rises and heat is radiated from the surface of the battery case, but this heat is absorbed by the insulating oil, and at this time, the insulating oil moves upward by convection. At this time, as shown in FIG. 3, by providing a groove in the vertical direction of the battery on the insulating plate, convection of the insulating oil is facilitated, and the battery can be cooled effectively.
【００３２】なお、図３では、溝の方向はほぼ垂直であ
るが、必ずしも垂直である必要はなく、図４に示すよう
に、ある程度斜め方向であってもよいし、水平方向や水
平方向に近い溝が設けられていてもよい。In FIG. 3, the direction of the groove is almost vertical, but it is not always required to be vertical, and as shown in FIG. 4, it may be oblique to some extent, or may be horizontal or horizontal. Close grooves may be provided.
【００３３】本発明においては、絶縁油としては、密度
が小さく、水と混ざらない性質の油なら、種類は特に限
定されず、その例としては、流動パラフィン、デカリ
ン、シリコンオイル、フッ素オイルなどを使用すること
ができる。これらの絶縁油の中では、軽質流動パラフィ
ンが最適である。軽質流動パラフィンの物性は、２０℃
での比重が０．８２０〜０．８４５の範囲、屈折率（ｎ
２０／Ｄ）が１．４６〜０１．４７０の範囲、３７℃に
おける粘度が１０〜１５ｃｐｓの範囲にある。この軽質
流動パラフィンは非水電解質二次電池中の有機電解液を
溶解しないため、万が一有機電解液が漏れた場合でも絶
縁特性に変化がなく、また粘度が上記のような値である
ため流動性が良く、電池をより効果的に冷却することが
できる。In the present invention, the insulating oil is not particularly limited in kind as long as it has a low density and is immiscible with water, and examples thereof include liquid paraffin, decalin, silicone oil, and fluorine oil. Can be used. Of these insulating oils, light liquid paraffin is most suitable. The physical properties of light liquid paraffin are 20 ℃
With a specific gravity of 0.820 to 0.845 and a refractive index (n
20 / D) is in the range of 1.46 to 01.470, and the viscosity at 37 ° C. is in the range of 10 to 15 cps. This light liquid paraffin does not dissolve the organic electrolytic solution in the non-aqueous electrolyte secondary battery, so even if the organic electrolytic solution leaks, the insulation characteristics do not change, and the viscosity is the above value, so the fluidity is high. Good, and the battery can be cooled more effectively.
【００３４】本発明の非水電解質二次電池においては、
正極活物質、炭素材料、電解液等は、従来の電池におい
て用いられている材料ならすべて使用することができ
る。正極活物質としては、ＬｉＣｏＯ２、ＬｉＮｉ
Ｏ２、ＭｎＯ2、ＬｉＭｎ2Ｏ4等の組成式ＬｉxＭＯ2ま
たはＬｉyＭ2Ｏ4（ただし、Ｍは遷移金属、０≦ｘ≦
１、０≦ｙ≦２）で表される複合酸化物やトンネル状の
孔を有する酸化物、層状構造の金属カルコゲン化物等を
用いることができる。In the non-aqueous electrolyte secondary battery of the present invention,
As the positive electrode active material, the carbon material, the electrolytic solution and the like, all materials used in conventional batteries can be used. Examples of the positive electrode active material include LiCoO 2 and LiNi
O 2, MnO 2, a composition formula such as LiMn 2 O 4 Li x MO 2 or Li y M 2 O 4 (provided that, M is a transition metal, 0 ≦ x ≦
It is possible to use a complex oxide represented by 1, 0 ≦ y ≦ 2), an oxide having a tunnel-shaped hole, a metal chalcogenide having a layered structure, or the like.
【００３５】炭素材料としては、コークス、メソカーボ
ンマイクロビーズ（ＭＣＭＢ）、メソフェーズピッチ系
炭素繊維、熱分解気相成長炭素繊維等の易黒鉛化性炭素
の熱処理物、フェノール樹脂焼成体、ポリアクリロニト
リル系炭素繊維、擬等方性炭素、フルフリルアルコール
樹脂焼成体等の難黒鉛化性炭素の熱処理物、天然黒鉛、
人造黒鉛、黒鉛化ＭＣＭＢ、黒鉛化メソフェーズピッチ
系炭素繊維、黒鉛ウイスカー等の黒鉛質材料、またはこ
れらの混合物を使用することができる。Examples of the carbon material include coke, mesocarbon microbeads (MCMB), mesophase pitch carbon fiber, heat-treated graphitizable carbon such as pyrolytic vapor growth carbon fiber, phenol resin fired body, polyacrylonitrile system. Carbon fiber, pseudo-isotropic carbon, heat-treated non-graphitizable carbon such as fired furfuryl alcohol resin, natural graphite,
Artificial graphite, graphitized MCMB, graphitized mesophase pitch-based carbon fiber, graphite material such as graphite whiskers, or a mixture thereof can be used.
【００３６】電解液としては、その溶媒として、エチレ
ンカーボネート、ジメチルカーボネート、ジエチルカー
ボネート、エチルメチルカーボネート等の極性溶媒、も
しくはこれらの混合物を用いることができ、溶媒に含ま
せる塩としては、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＡｓ
Ｆ6、ＬｉＣｌＯ4、ＬｉＣＦ3ＳＯ3、ＬｉＣＦ3ＣＯ2等
のリチウム塩またはこれらの混合物を用いることができ
る。As the electrolyte, a polar solvent such as ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, or a mixture thereof can be used as the solvent, and LiPF 6 , as a salt contained in the solvent, LiBF 4 , LiAs
F 6, LiClO 4, LiCF 3 SO 3, LiCF 3 lithium salts such as CO 2 or may be a mixture thereof.
【００３７】また、本発明において、セパレータとして
は、ポリエチレンおよびポリプロピレン製微多孔膜、ま
たはこれらを複合した微多孔膜等のポリオレフィン系微
多孔膜など、従来の非水電解質二次電池に使用されたも
のを用いることができる。さらに、電池の形状として
は、角型、円筒型、長円筒型など、あらゆる形状の電池
を使用することができる。In the present invention, the separator used in the conventional non-aqueous electrolyte secondary battery is a microporous membrane made of polyethylene and polypropylene, or a polyolefin microporous membrane such as a composite microporous membrane. Any thing can be used. Further, as the shape of the battery, a battery of any shape such as a prismatic type, a cylindrical type, and an oblong type can be used.
【００３８】[0038]
【実施例】つぎに、本発明の実施例として、放電容量４
００Ａｈの非水電解質二次電池について述べる。ここで
試作した非水電解質二次電池の単電池の外観は図１に示
したのと同様である。電池の外形寸法は１３８×１３８
×３７４ｍｍであり、端子部の高さは３０ｍｍである。
電池ケースの材質はＳＵＳ３０４とし、ケースの厚さは
０．８ｍｍとした。EXAMPLE Next, as an example of the present invention, a discharge capacity of 4
A 00 Ah non-aqueous electrolyte secondary battery will be described. The appearance of the unit cell of the non-aqueous electrolyte secondary battery prototyped here is the same as that shown in FIG. External dimensions of the battery are 138 x 138
× 374 mm, and the height of the terminal portion is 30 mm.
The material of the battery case was SUS304, and the thickness of the case was 0.8 mm.
【００３９】正極板は、正極活物質としてのコバルト酸
リチウム８９ｗｔ％と導電助剤としてのアセチレンブラ
ック（ＡＢ）３ｗｔ％と結着剤としてのポリフッ化ビニ
リデン（ＰＶｄＦ）８ｗｔ％とからなる正極合剤を、厚
さ５０μｍのアルミニウム集電体の両面に塗布したもの
で、合剤層塗布部分の寸法は１２７×３４０ｍｍ、合剤
層の塗布重量は３．４ｇ／１００ｃｍ２、極板厚みは２
８０μｍ、リード幅は３０×７０ｍｍとした。The positive electrode plate is composed of 89 wt% lithium cobalt oxide as a positive electrode active material, 3 wt% acetylene black (AB) as a conductive additive, and 8 wt% polyvinylidene fluoride (PVdF) as a binder. Is applied to both sides of an aluminum current collector having a thickness of 50 μm, the dimensions of the mixture layer application portion are 127 × 340 mm, the application weight of the mixture layer is 3.4 g / 100 cm 2 , and the electrode plate thickness is 2
The width was 80 μm and the lead width was 30 × 70 mm.
【００４０】負極板は、負極活物質としての黒鉛９４ｗ
ｔ％と結着剤としてのポリフッ化ビニリデン（ＰＶｄ
Ｆ）６ｗｔ％とからなる負極合剤を、厚さ２５μｍの銅
箔集電体の両面に塗布したもので、合剤層塗布部分の寸
法は１３１×３４５ｍｍ、合剤塗布層の塗布重量は１．
８ｇ／１００ｃｍ２、極板厚みは２６０μｍ、リード幅
は３０×７０ｍｍとした。The negative electrode plate is made of graphite 94w as a negative electrode active material.
t% and polyvinylidene fluoride (PVd as a binder
F) A negative electrode mixture composed of 6 wt% was applied to both sides of a copper foil current collector having a thickness of 25 μm. The size of the mixture layer applied portion was 131 × 345 mm, and the application weight of the mixture applied layer was 1 ．
8 g / 100 cm 2 , the electrode plate thickness was 260 μm, and the lead width was 30 × 70 mm.
【００４１】セパレータは、厚さ３０μｍのポリエチレ
ン（ＰＥ）を二重にして用いた。電解液としては、エチ
レンカーボネート（ＥＣ）とジメチルカーボネート（Ｄ
ＭＣ）とジエチルカーボネート（ＤＥＣ）の体積比２：
２：１混合溶媒に、ＬｉＰＦ ６を１ｍｏｌ／ｌ溶解した
有機電解液を使用した。The separator is made of polyethylene having a thickness of 30 μm.
(PE) was used in duplicate. As the electrolyte,
Ren carbonate (EC) and dimethyl carbonate (D
Volume ratio of MC) to diethyl carbonate (DEC) 2:
2: 1 mixed solvent, LiPF 6Was dissolved in 1 mol / l
An organic electrolyte was used.
【００４２】発電要素の形状は積層型とし、負極板―セ
パレータ―正極板―セパレータの準に、正極板１８０
枚、負極板１８１枚を積層したものであり、正極板およ
び負極板は発電要素の上部で、それぞれリードをまと
め、端子と接続されている。このようにして、公称容量
４００Ａｈの非水電解質二次電池を作製した。The shape of the power generation element is a laminated type, and the positive electrode plate 180
One plate and one negative plate 181 are laminated, and the positive electrode plate and the negative electrode plate are connected to the terminals by assembling the leads at the upper part of the power generation element. In this way, a non-aqueous electrolyte secondary battery having a nominal capacity of 400 Ah was produced.
【００４３】［実施例１］上記非水電解質二次電池の電
池ケース表面に４種類の絶縁体を設けた電池を作製し
た。各電池５個を、４０Ａ定電流で４．０Ｖまで充電、
４０Ａ定電流で３．０Ｖまで放電という条件で、１０サ
イクルの予備充放電をおこなった後、図５に示したよう
に、一方の電池に他方の電池を３０ｃｍの高さから落下
させてぶつけ、その後の電池ケース表面の絶縁抵抗を、
絶縁抵抗計で測定し、絶縁抵抗が１０ＭΩ以上の電池を
良品とし、絶縁抵抗が１０ＭΩ未満の電池を不良品とし
た。Example 1 A battery was prepared in which four types of insulators were provided on the surface of the battery case of the above non-aqueous electrolyte secondary battery. Charge 5 batteries to 40V at 40A constant current,
After performing 10 cycles of preliminary charge and discharge under the condition that the battery was discharged at a constant current of 40 A to 3.0 V, as shown in FIG. 5, one battery was dropped onto the other battery from a height of 30 cm and bumped. The insulation resistance of the battery case surface after that,
A battery having an insulation resistance of 10 MΩ or more was measured as an acceptable product, and a battery having an insulation resistance of less than 10 MΩ was determined as a defective product.
【００４４】図５において、１３は横倒しにして水平に
置いた電池、１４は水平に置いた電池の電池ケース表
面、１５は落下させる電池、１６は落下させる電池の電
池ケースの一辺、１７は落下させる電池の電池ケースの
かどである。そして、電池１５を矢印の方向に落下させ
た場合に、電池ケースの一辺１６または電池ケースのか
ど１７が、水平に置いた電池１３の電池ケース表面１４
にぶつかるようにした。絶縁体の内容および試験結果を
表１に示した。In FIG. 5, 13 is a battery which is laid down horizontally, 14 is a battery case surface of a battery which is laid horizontally, 15 is a battery to be dropped, 16 is one side of the battery case of the battery to be dropped, and 17 is dropped. It is the battery case corner of the battery. Then, when the battery 15 is dropped in the direction of the arrow, the side 16 of the battery case or the corner 17 of the battery case causes the battery case surface 14 of the battery 13 placed horizontally.
I tried to hit it. The contents of the insulator and the test results are shown in Table 1.
【００４５】[0045]
【表１】 [Table 1]
【００４６】表１の結果から、電池ケース表面に厚さ
０．５０ｍｍのポリプロピレン板を設けた本発明の電池
Ａでは、すべて絶縁が良好であったのに対し、電池Ｂ、
ＣおよびＤでは不良電池が多数となった。From the results of Table 1, all of the batteries A of the present invention in which a polypropylene plate having a thickness of 0.50 mm was provided on the surface of the battery case had good insulation, whereas the batteries B,
In C and D, the number of defective batteries increased.
【００４７】［実施例２］つぎに、本発明の電池Ａにお
いて、ポリプロピレン板の厚みを変えて、実施例１と同
様の試験をおこなった。ポリプロピレン板の厚みおよび
試験結果を表２に示した。Example 2 Next, in the battery A of the present invention, the same test as in Example 1 was conducted by changing the thickness of the polypropylene plate. The thickness of the polypropylene plate and the test results are shown in Table 2.
【００４８】[0048]
【表２】 [Table 2]
【００４９】表２の結果から、ポリプロピレン板の厚み
を０．３ｍｍ以上とすれば、絶縁が良好に保たれること
が示された。なお、ポリプロピレン板に代えて、塩化ビ
ニル樹脂板やフェノール樹脂板を使用して、実施例２と
同様の試験をおこなったが、いずれもポリプロピレン板
の同様の結果が得られた。From the results in Table 2, it was shown that good insulation can be maintained when the thickness of the polypropylene plate is 0.3 mm or more. In addition, a vinyl chloride resin plate or a phenol resin plate was used instead of the polypropylene plate, and the same test as in Example 2 was performed, but the same results as for the polypropylene plate were obtained.
【００５０】［実施例３］実施例１で述べた、電池ケー
ス表面に厚さ０．５ｍｍのポリプロピレン板を設けた電
池Ａと、電池Ａのポリプロピレン板に、図３に示したよ
うに、幅５ｍｍ、深さ０．２ｍｍの溝を５ｍｍ間隔で設
けた電池Ｋを作製した。そして、電池Ａおよび電池Ｋの
底面には、厚さ０．５ｍｍのポリプロピレン板を貼り付
けた。[Embodiment 3] As described in Embodiment 1, a battery A having a polypropylene plate with a thickness of 0.5 mm provided on the surface of the battery case, and a polypropylene plate of the battery A have a width as shown in FIG. A battery K having grooves of 5 mm and a depth of 0.2 mm provided at intervals of 5 mm was produced. Then, a polypropylene plate having a thickness of 0.5 mm was attached to the bottom surfaces of the batteries A and K.
【００５１】そして、電池Ａおよび電池Ｋを、内径１４
２×１４２ｍｍ、高さ４００ｍｍの金属製ケース内に設
置し、金属製ケース内の空所を軽質流動パラフィンで満
たし、放電時の電池ケースの表面温度を比較した。各電
池５個を、４０Ａ定電流で４．０Ｖまで充電、４０Ａ定
電流で３．０Ｖまで放電という条件で、１０サイクルの
予備充放電をおこなった後、４０Ａ定電流で４．０Ｖま
で充電し、その後、環境温度を２５℃として１６時間放
置後、環境温度を２５℃に保ちながら、４０Ａ定電流で
３．０Ｖまで放電し、放電開始後８時間目の電池ケース
の表面温度を測定した。表面温度の平均値は、電池Ａで
は２９℃、電池Ｋでは２６℃となり、電池ケース表面の
絶縁板に溝を設けることにより、冷却効果が高くなるこ
とが示された。Then, the batteries A and K have an inner diameter of 14
It was installed in a metal case having a size of 2 × 142 mm and a height of 400 mm, the empty space in the metal case was filled with light liquid paraffin, and the surface temperature of the battery case during discharge was compared. Five batteries were charged at 40A constant current to 4.0V and discharged at 40A constant current to 3.0V. After 10 cycles of preliminary charge / discharge, 40A constant current was charged to 4.0V. Then, after leaving the environment temperature at 25 ° C. for 16 hours, it was discharged to 3.0 V at a constant current of 40 A while keeping the environment temperature at 25 ° C., and the surface temperature of the battery case was measured 8 hours after the start of discharge. The average surface temperature was 29 ° C. for the battery A and 26 ° C. for the battery K, and it was shown that the cooling effect is enhanced by providing the groove on the insulating plate on the surface of the battery case.
【００５２】[0052]
【発明の効果】本発明は、金属製ケースと均圧装置とを
備えた非水電解質二次電池からなる単電池を、複数個直
列または／および並列に接続し、単電池間に絶縁油を満
たして群電池ケースに収納した群電池において、単電池
ケース表面にロックウェル硬度が９０以上の絶縁板を設
けたもので、大型の単電池がぶつかった場合でも、金属
製単電池ケース表面の絶縁が良好に保たれ、電池どうし
のショートを防止することができる。Industrial Applicability According to the present invention, a plurality of single cells composed of a non-aqueous electrolyte secondary battery provided with a metal case and a pressure equalizer are connected in series or / and in parallel, and insulating oil is applied between the single cells. In a group battery that is filled and housed in the group battery case, an insulating plate with a Rockwell hardness of 90 or more is provided on the surface of the unit cell case, and even if a large unit cell collides, insulation of the metal unit cell case surface Is kept good and short circuit between batteries can be prevented.
【００５３】また、本発明は、単電池ケース表面に設け
た絶縁板に、電池の上下方向の溝を設けたもので、この
溝のために絶縁油の対流が容易となり、電池を効果的に
冷却することができる。Further, according to the present invention, the insulating plate provided on the surface of the unit cell case is provided with the groove in the vertical direction of the battery. This groove facilitates the convection of the insulating oil, thereby effectively making the battery effective. Can be cooled.
【図１】均圧装置を備えた非水電解質二次電池の単電池
の外観を示す図。FIG. 1 is a diagram showing an appearance of a single cell of a non-aqueous electrolyte secondary battery provided with a pressure equalizer.
【図２】本発明になる群電池の断面構造を示す図。FIG. 2 is a diagram showing a cross-sectional structure of a group battery according to the present invention.
【図３】絶縁板に、電池の上下方向にほぼ垂直の溝を設
けた単電池の例を示す図。FIG. 3 is a diagram showing an example of a unit cell in which a groove that is substantially vertical to the battery is provided in an insulating plate.
【図４】絶縁板に、電池の上下方向に斜めの溝を設けた
単電池の例を示す図。FIG. 4 is a diagram showing an example of a unit cell in which an insulating plate is provided with oblique grooves in the vertical direction of the cell.
【図５】電池の落下試験を示す図。FIG. 5 is a diagram showing a battery drop test.
１ 非水電解質二次電池 ２ 金属製電池ケース ６ 均圧装置 ７ 金属製電池ケース表面に設けた絶縁板 ８ 群電池ケース １０ 絶縁油 １２ 絶縁板に設けられた溝 1 Non-aqueous electrolyte secondary battery 2 Metal battery case 6 Pressure equalizer 7 Insulation plate provided on the metal battery case surface 8 group battery case 10 insulating oil 12 Grooves provided on the insulating plate
フロントページの続き Ｆターム(参考） 5H011 AA01 AA13 BB01 CC02 DD11 5H029 AJ11 AJ12 AK03 AK05 AL06 AL07 AL18 AM03 AM05 AM07 BJ06 BJ22 BJ23 BJ27 CJ06 DJ02 EJ11 EJ12 HJ00 5H040 AA18 AA28 AS01 AS04 AT06 AY03 JJ03 LL06 NN00 Continued front page F term (reference) 5H011 AA01 AA13 BB01 CC02 DD11 5H029 AJ11 AJ12 AK03 AK05 AL06 AL07 AL18 AM03 AM05 AM07 BJ06 BJ22 BJ23 BJ27 CJ06 DJ02 EJ11 EJ12 HJ00 5H040 AA18 AA28 AS01 AS04 AT06 AY03 JJ03 LL06 NN00
Claims (4)
電解質二次電池からなる単電池を、複数個直列または／
および並列に接続し、単電池間に絶縁油を満たして群電
池ケースに収納した群電池において、前記単電池ケース
表面にロックウェル硬度が９０以上の絶縁板を設けたこ
とを特徴とする群電池。1. A plurality of single cells comprising a non-aqueous electrolyte secondary battery provided with a metal case and a pressure equalizer in series or /
And a group battery connected in parallel and filled with insulating oil between the unit cells and housed in a group battery case, wherein an insulating plate having a Rockwell hardness of 90 or more is provided on the surface of the unit cell case. .
徴とする請求項１に記載の群電池。2. The group battery according to claim 1, wherein the insulating plate is polypropylene.
ることを特徴とする請求項１または２に記載の群電池。3. The group battery according to claim 1, wherein the surface of the insulating plate has a groove in the vertical direction of the battery.
を特徴とする請求項１、２または３に記載の群電池。4. The group battery according to claim 1, wherein the insulating oil is light liquid paraffin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001239704A JP2003051298A (en) | 2001-08-07 | 2001-08-07 | Group battery equipped with pressure-equalized non- aqueous electrolyte secondary batteries |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001239704A JP2003051298A (en) | 2001-08-07 | 2001-08-07 | Group battery equipped with pressure-equalized non- aqueous electrolyte secondary batteries |
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|---|---|
| JP2003051298A true JP2003051298A (en) | 2003-02-21 |
Family
ID=19070410
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| JP2001239704A Pending JP2003051298A (en) | 2001-08-07 | 2001-08-07 | Group battery equipped with pressure-equalized non- aqueous electrolyte secondary batteries |
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| JP2009266691A (en) * | 2008-04-25 | 2009-11-12 | Honda Motor Co Ltd | Method of manufacturing power storage device and metal battery case |
| US8053098B2 (en) | 2007-06-27 | 2011-11-08 | Toyota Jidosha Kabushiki Kaisha | Power storage unit that effectively controls pressure and vehicle |
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| JP2019154230A (en) * | 2013-03-15 | 2019-09-12 | ハダル， インコーポレイテッド | System and method for pressure energy system |
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2001
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8227101B2 (en) | 2007-06-20 | 2012-07-24 | Toyota Jidosha Kabushiki Kaisha | Power storage unit with coolant resistivity detector |
| US8053098B2 (en) | 2007-06-27 | 2011-11-08 | Toyota Jidosha Kabushiki Kaisha | Power storage unit that effectively controls pressure and vehicle |
| JP2009266691A (en) * | 2008-04-25 | 2009-11-12 | Honda Motor Co Ltd | Method of manufacturing power storage device and metal battery case |
| JP4692853B2 (en) * | 2008-04-25 | 2011-06-01 | 本田技研工業株式会社 | Power storage device and metal battery case manufacturing method |
| JP2012221881A (en) * | 2011-04-13 | 2012-11-12 | Ydk:Kk | Group battery unit for deep-sea, method and program of equalizing voltage value of cell |
| JP2019154230A (en) * | 2013-03-15 | 2019-09-12 | ハダル， インコーポレイテッド | System and method for pressure energy system |
| CN107681095A (en) * | 2016-08-02 | 2018-02-09 | 罗伯特·博世有限公司 | Lithium storage battery |
| CN107681095B (en) * | 2016-08-02 | 2023-09-26 | 罗伯特·博世有限公司 | Lithium accumulator |
| JP2022192002A (en) * | 2021-06-16 | 2022-12-28 | 樹錦 陳 | Flame-resistant explosion-protection battery pack for electric vehicle and manufacturing method of the same |
| JP7379556B2 (en) | 2021-06-16 | 2023-11-14 | 樹錦 陳 | Flameproof and explosion-proof battery pack for electric vehicles and its manufacturing method |
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