JPH10255767A - Set battery for use in electric vehicle - Google Patents
Set battery for use in electric vehicleInfo
- Publication number
- JPH10255767A JPH10255767A JP9055796A JP5579697A JPH10255767A JP H10255767 A JPH10255767 A JP H10255767A JP 9055796 A JP9055796 A JP 9055796A JP 5579697 A JP5579697 A JP 5579697A JP H10255767 A JPH10255767 A JP H10255767A
- Authority
- JP
- Japan
- Prior art keywords
- active material
- negative electrode
- electric vehicle
- type
- 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.)
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Secondary Cells (AREA)
- Battery Mounting, Suspending (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は電気自動車用の組電
池に関し、特に、その瞬間最大出力特性と充放電容量の
両方の改善に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an assembled battery for an electric vehicle, and more particularly to an improvement in both an instantaneous maximum output characteristic and a charge / discharge capacity.
【０００２】[0002]
【従来の技術】複数の単電池を含む電気自動車用組電池
のように、家庭用２次電池に比べて遙かに大きなエネル
ギ密度を必要とする２次電池を開発するために、渦巻型
電極を備えた２次電池が注目されている。なぜならば、
薄くて柔軟な帯状の正極と負極とを帯状のセパレータを
介して重ね合わせて巻回することによって得られる渦巻
型電極においては、正極と負極の実効面積を非常に大き
くすることができ、これによって２次電池のエネルギ密
度を増大させることができるからである。なお、ここに
いう渦巻型電極とは、必ずしも円形の断面を有する円柱
状のものに限られず、たとえば矩形断面を有する、角柱
状に巻回されたもしくは円柱状に巻回された後加圧変型
させた渦巻型電極などをも含む。2. Description of the Related Art In order to develop a secondary battery requiring a much larger energy density than a home secondary battery, such as an assembled battery for an electric vehicle including a plurality of cells, a spiral electrode is required. Are attracting attention. because,
In a spiral electrode obtained by laminating and winding a thin and flexible strip-shaped positive electrode and a negative electrode via a strip-shaped separator, the effective area of the positive electrode and the negative electrode can be greatly increased, This is because the energy density of the secondary battery can be increased. In addition, the spiral electrode here is not necessarily limited to a columnar electrode having a circular cross section, and for example, has a rectangular cross section, is wound in a prismatic shape, or is deformed by pressure after being wound in a cylindrical shape. Also includes a spiral-shaped electrode and the like.
【０００３】図２は、渦巻型電極の一例として、円柱状
渦巻型電極の巻回状態を模式的な斜視図で示している。
渦巻型電極においては、正極１は帯状の金属箔の集電体
とその両面に被着された粉末状の正極活物質とを含み、
負極２は帯状の金属箔の集電体とその両面に被着された
粉末状の負極活物質とを含んでいる。これらの帯状正極
１と帯状正極２のそれぞれには、電流を取出すための正
極集電タブ１ａと負極集電タブ２ａが接合されている。FIG. 2 is a schematic perspective view showing a wound state of a cylindrical spiral electrode as an example of a spiral electrode.
In the spiral electrode, the positive electrode 1 includes a current collector of a strip-shaped metal foil and a powdery positive electrode active material attached to both surfaces thereof,
The negative electrode 2 includes a current collector of a band-shaped metal foil and a powdery negative electrode active material adhered to both surfaces thereof. Each of the strip-shaped positive electrode 1 and the strip-shaped positive electrode 2 is joined with a positive electrode current collecting tab 1a and a negative electrode current collecting tab 2a for extracting current.
【０００４】図２においては図面の煩雑化を避けるため
にただ１対の正極集電タブ１ａと負極集電タブ２ａが示
されているが、実際には帯状の正極１と負極２の長さ方
向に所定の間隔で複数の正極集電タブ１ａと複数の負極
タブ２ａが接合されている。これらの集電タブは、たと
えば電極活物質層上から集電体を貫通する鳩目止めによ
って取付けることができる。より好ましくは、集電タブ
が取付けられる領域において金属箔集電体が電極活物質
層から露出されており、集電タブがその集電体表面に直
接溶着されることによって取付けられる。この溶着に
は、スポット溶接，超音波溶接等の種々の溶接方法を用
いることができる。FIG. 2 shows only one pair of the positive electrode current collecting tab 1a and the negative electrode current collecting tab 2a to avoid complication of the drawing. A plurality of positive electrode current collecting tabs 1a and a plurality of negative electrode tabs 2a are joined at predetermined intervals in the direction. These current collecting tabs can be attached by, for example, eyelets penetrating the current collector from above the electrode active material layer. More preferably, the metal foil current collector is exposed from the electrode active material layer in a region where the current collecting tab is mounted, and the current collecting tab is mounted by directly welding to the current collector surface. Various welding methods such as spot welding and ultrasonic welding can be used for this welding.
【０００５】複数の正極集電タブ１ａが接合された帯状
正極１と複数の負極集電タブ２ａが接合された帯状負極
２は、図２に示されているように、セパレータ３を介し
て互いに積層されて巻回される。As shown in FIG. 2, a strip-shaped positive electrode 1 having a plurality of positive electrode current collecting tabs 1a joined thereto and a band-shaped negative electrode 2 having a plurality of negative electrode current collecting tabs 2a joined thereto are provided with a separator 3 interposed therebetween. Laminated and wound.
【０００６】図３は、図２に示されているような巻回に
よって得られた渦巻型電極とさらに電解液を含む単電池
（単セルともいう）の一例を示す概略的な斜視図であ
る。このような単電池において、たとえば電池缶１０は
約６４ｍｍφの外径と約４００ｍｍの長さを有してい
る。図２に示されているような正極集電タブ１ａと負極
集電タブ２ａは、それぞれ正極端子１１と負極端子１２
に電気的に接続されており、これらの正極端子１１と負
極端子１２はそれぞれ正極絶縁パッキング１３と負極絶
縁パッキング１４によって電池缶１０から電気的に分離
されている。FIG. 3 is a schematic perspective view showing an example of a unit cell (also referred to as a unit cell) containing a spiral electrode obtained by winding as shown in FIG. 2 and an electrolytic solution. . In such a unit cell, for example, the battery can 10 has an outer diameter of about 64 mmφ and a length of about 400 mm. A positive current collecting tab 1a and a negative current collecting tab 2a as shown in FIG.
The positive terminal 11 and the negative terminal 12 are electrically separated from the battery can 10 by a positive insulating packing 13 and a negative insulating packing 14, respectively.
【０００７】[0007]
【発明が解決しようとする課題】通常、電気自動車用組
電池は、図３に示されているような比較的大きな単電池
の複数個を直列接続して得られる。そのような組電池中
で直列接続された複数のセルにおいては、各セル間での
充放電の不均一性を防止するために、各セル間で同量の
電極活物質を含ませることにより容量の不均一性をでき
るだけ小さくすることが好ましいと考えられている（１
９９６年，電池討論会，第２４１頁参照）。Normally, an assembled battery for an electric vehicle is obtained by connecting a plurality of relatively large cells as shown in FIG. 3 in series. In a plurality of cells connected in series in such an assembled battery, in order to prevent non-uniform charge / discharge between the cells, the capacity is increased by including the same amount of electrode active material between the cells. It is considered preferable to minimize the non-uniformity of
996, Battery Symposium, page 241).
【０００８】しかし、組電池の容量を増大させるために
各セル中の粉末状の電極活物質量を増大させれば、活物
質が密に充填されてその中へ電解液が浸入しにくくな
る。すなわち、各セル中の電極活物質層の含液性が低下
し、電流負荷特性（瞬間最大出力特性）が低下する。他
方、電極活物質層の含液性を改善するために活物質の充
填密度を低下させれば、各セルの充放電容量が低下す
る。However, if the amount of the powdered electrode active material in each cell is increased in order to increase the capacity of the battery pack, the active material is densely packed and the electrolyte does not easily penetrate therein. That is, the liquid content of the electrode active material layer in each cell decreases, and the current load characteristics (instantaneous maximum output characteristics) decrease. On the other hand, if the packing density of the active material is reduced to improve the liquid content of the electrode active material layer, the charge / discharge capacity of each cell is reduced.
【０００９】ところで、電気自動車用組電池としては、
自動車の加速時には大きな瞬間最大出力を発揮すること
が望まれ、他方、１回の充電で長距離走行を可能にする
ために大きな充放電容量を有することも望まれる。しか
し、上述のように、各セル中の電極活物質層の充填密度
に関して、各セルの出力特性と容量とが相反する関係に
あるので、先行技術においては電気自動車用組電池の出
力特性と容量との双方を改善することは困難であった。By the way, as an assembled battery for an electric vehicle,
When accelerating the vehicle, it is desired to exhibit a large instantaneous maximum output. On the other hand, it is also desired to have a large charge / discharge capacity in order to enable long-distance traveling with one charge. However, as described above, with respect to the packing density of the electrode active material layer in each cell, the output characteristics and capacity of each cell are in a conflicting relationship. It was difficult to improve both.
【００１０】このような先行技術における課題に鑑み、
本発明は、瞬間最大出力特性と充放電容量の両方が改善
された電気自動車用組電池を提供することを目的として
いる。In view of such problems in the prior art,
An object of the present invention is to provide an assembled battery for an electric vehicle in which both the instantaneous maximum output characteristics and the charge / discharge capacity are improved.
【００１１】[0011]
【課題を解決するための手段】本発明による電気自動車
用組電池においては、種類Ａの複数の直列接続された単
電池と種類Ｂの複数の直列接続された単電池とが相互に
並列接続されており、これらの単電池の各々は炭素材料
を活物質として含む負極，リチウムイオンと電気化学反
応可能な材料を活物質として含む正極，および非水電解
液を含み、それらの正負極の対向容量比は実質的に１．
０に設定されており、種類Ａと種類Ｂの単電池間におけ
る負極単位面積当りの活物質量比が０．４５〜０．７５
の範囲内にあり、かつ両種類の単電池の負極単位面積当
りの活物質密度が５〜１３ｍｇ／ｃｍ2 の範囲内にある
ことを特徴としている。In the assembled battery for an electric vehicle according to the present invention, a plurality of series-connected cells of type A and a plurality of series-connected cells of type B are connected in parallel with each other. Each of these cells includes a negative electrode containing a carbon material as an active material, a positive electrode containing a material capable of electrochemically reacting with lithium ions as an active material, and a non-aqueous electrolyte, and the opposite capacity of the positive and negative electrodes. The ratio is substantially 1.
0, and the ratio of the amount of active material per unit area of the negative electrode between the type A and type B cells is 0.45 to 0.75.
And the active material density per unit area of the negative electrode of both types of unit cells is in the range of 5 to 13 mg / cm 2 .
【００１２】このような電気自動車用組電池は、より好
ましくは、種類Ａの単電池が６〜８ｍｇ／ｃｍ2 の範囲
内の負極活物質密度を有し、種類Ｂの単電池は１１〜１
３ｍｇ／ｃｍ2 の範囲内の負極活物質密度を有してい
る。[0012] In such an electric vehicle assembled battery, more preferably, the type A cells have a negative electrode active material density in the range of 6 to 8 mg / cm 2 , and the type B cells are 11 to 1
It has a negative electrode active material density within a range of 3 mg / cm 2 .
【００１３】電気自動車用組電池において、さらに好ま
しくは、負極活物質の炭素材料として黒鉛粉末が用いら
れ、この黒鉛粉末における黒鉛結晶のＣ軸方向の結晶子
の大きさの値Ｌｃは１５０Å以上であり、かつＣ軸方向
の原子面間隔の値ｄ002 は３．３８Å以下である。In the battery pack for an electric vehicle, graphite powder is more preferably used as a carbon material of the negative electrode active material, and the value Lc of the crystallite in the C-axis direction of the graphite crystal in the graphite powder is 150 ° or more. And the value d 002 of the atomic plane spacing in the C-axis direction is 3.38 ° or less.
【００１４】[0014]
【発明の実施の形態】図１は、本発明の実施の形態の一
例による電気自動車用組電池を示す模式的なブロック図
である。この組電池においては、互いに直列接続された
種類Ａの５個の単電池と互いに直列接続された種類Ｂの
５個の単電池とを含んでいる。そして、種類Ａの単電池
のシリーズと種類Ｂの単電池のシリーズとは互いに並列
接続されている。FIG. 1 is a schematic block diagram showing an assembled battery for an electric vehicle according to an embodiment of the present invention. This assembled battery includes five cells of type A connected in series to each other and five cells of type B connected in series to each other. The series of type A cells and the series of type B cells are connected to each other in parallel.
【００１５】これらの単電池ＡとＢが図３に示されてい
るような円柱状のセルで形成される場合、電池缶１０内
に図２に示されているような帯状正極１と帯状負極２が
巻回された渦巻型電極が挿入され、その後に電池缶１０
内に非水電解液が注入される。When these unit cells A and B are formed of cylindrical cells as shown in FIG. 3, a band-shaped positive electrode 1 and a band-shaped negative electrode as shown in FIG. 2 is wound, and the spirally wound electrode is inserted.
A non-aqueous electrolyte is injected into the inside.
【００１６】正極の粉末状活物質としては、マンガン，
コバルト，ニッケル，バナジウム，ニオブ，モリブデ
ン，および銅の少なくとも１つを含む金属酸化物の他
に、フッ化炭素，硫化鉄等の少なくとも１つを含むもの
を用いることができる。As the powdery active material of the positive electrode, manganese,
In addition to a metal oxide containing at least one of cobalt, nickel, vanadium, niobium, molybdenum, and copper, an oxide containing at least one of carbon fluoride, iron sulfide, and the like can be used.
【００１７】粉末状の負極活物質としては、通常は炭素
材料が用いられ、たとえば黒鉛粉末やコークス等が用い
られ得る。As the powdered negative electrode active material, a carbon material is usually used, and for example, graphite powder, coke or the like can be used.
【００１８】非水電解液の溶質としては、ＬｉＰＦ6 ，
ＬｉＢＦ4 ，ＬｉＣＦ3 ＳＯ3 ，ＬｉＡｓＦ6 ，ＬｉＮ
（ＣＦ3 ＳＯ2 ）2 ，ＬｉＯＳＯ2 （ＣＦ2 ）3 Ｃ
Ｆ3 ，ＬｉＣｌＯ4 等の少なくとも１つを含むものを用
いることができる。As the solute of the non-aqueous electrolyte, LiPF 6 ,
LiBF 4 , LiCF 3 SO 3 , LiAsF 6 , LiN
(CF 3 SO 2 ) 2 , LiOSO 2 (CF 2 ) 3 C
A material containing at least one of F 3 and LiClO 4 can be used.
【００１９】非水電解液の溶媒としては、エチレンカー
ボネイト、プロピレンカーボネイト、ブチレンカーボネ
イト、ビニレンカーボネイト、シクロペンタノン、スル
フォラン、３−メチルスルフォラン、２，４−ジメチル
スルフォラン、３−メチル−１，３−オキサゾリジン−
２−オン、γ−ブチルラクトン、ジメチルカーボネイ
ト、ジエチルカーボネイト、エチルメチルカーボネイ
ト、メチルプロピルカーボネイト、ブチルメチルカーボ
ネイト、エチルプロピルカーボネイト、ブチルエチルカ
ーボネイト、ジプロピルカーボネイト、１，２−ジメト
キシエタン、テトラヒドロフラン、２−メチルテトラヒ
ドロフラン、１，３−ジオキシソラン、酢酸メチル、酢
酸エチル等の少なくとも１つを含むものを用いることが
できる。As the solvent of the non-aqueous electrolyte, ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, cyclopentanone, sulfolane, 3-methylsulfolane, 2,4-dimethylsulfolane, 3-methyl-1, 3-oxazolidine-
2-one, γ-butyl lactone, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, butyl methyl carbonate, ethyl propyl carbonate, butyl ethyl carbonate, dipropyl carbonate, 1,2-dimethoxyethane, tetrahydrofuran, 2- A material containing at least one of methyltetrahydrofuran, 1,3-dioxysolan, methyl acetate, ethyl acetate, and the like can be used.
【００２０】以上のように形成され得る図１の組電池に
おいて、種類Ａの単電池における負極単位面積当りの活
物質量が種類Ｂの単電池に比べて０．４５〜０．７５の
範囲内に設定され、かつ両種類の単電池の負極単位面積
当りの活物質密度は５〜１３ｍｇ／ｃｍ2 の範囲内に設
定される。ただし、いずれの単電池においても正負極の
対向容量比は実質的に１．０に設定される。In the assembled battery of FIG. 1 which can be formed as described above, the amount of the active material per unit area of the negative electrode of the type A cell is in the range of 0.45 to 0.75 as compared with the type B cell. The active material density per unit area of the negative electrode of both types of unit cells is set in the range of 5 to 13 mg / cm 2 . However, in each of the cells, the opposed capacity ratio between the positive and negative electrodes is set to substantially 1.0.
【００２１】より好ましくは、種類Ａの単電池は６〜８
ｍｇ／ｃｍ2 の範囲内の負極活物質密度を有し、種類Ｂ
の単電池は１１〜１３ｍｇ／ｃｍ2 の範囲内の負極活物
質密度を有するように設定される。More preferably, the type A cell is 6 to 8
having a negative electrode active material density in the range of mg / cm 2 ,
Are set to have a negative electrode active material density in the range of 11 to 13 mg / cm 2 .
【００２２】さらに好ましくは、種類Ａと種類Ｂのいず
れかの単電池においても負極の活物質として黒鉛粉末が
用いられ、この黒鉛粉末において黒鉛結晶のＣ軸方向の
結晶子の大きさの値Ｌｃは１５０Å以上であり、かつＣ
軸方向の原子面間隔の値ｄ00 2 は３．３８Å以下のもの
を用いるのが良い。More preferably, a graphite powder is used as an active material of the negative electrode in any of the cells of the type A and the type B, and in this graphite powder, the value Lc of the crystallite size in the C-axis direction of the graphite crystal is obtained. Is not less than 150 ° and C
It is preferable to use a value d 00 2 of the atomic plane spacing in the axial direction of 3.38 ° or less.
【００２３】[0023]
【実施例】以下において、本発明のいくつかの実施例に
よる組電池を説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, assembled batteries according to some embodiments of the present invention will be described.
【００２４】［実施例１］ （種類Ａの単電池用渦巻型電極Ａｅの作製） 正極の作製：５μｍの平均粒径を有するＬｉＣｏＯ2 粉
末の正極活物質と人造黒鉛粉末の導電材とを９：１の重
量比で混合して正極合剤が調製された。この正極合剤
と、ポリフッ化ビニリデンをＮ−メチル−２−ピロリド
ン（ＮＭＰ）に５重量％溶かした結着剤溶液とが固形分
重量比９５：５で混練されてスラリーが調製された。こ
のスラリーは、２０μｍの厚さを有するアルミ箔の集電
体の両面にドクタブレード法によって塗布された。この
とき、正極用スラリーは負極との対向容量比（単位面積
当りの正極容量／単位面積当りの負極容量）が１．０に
なるように塗布される。集電体に塗布されたスラリー状
の正極活物質層は１５０℃で２時間真空乾燥され、粗電
極が作製された。この粗電極を圧延した後に両側縁をス
リットすることにより、０．１００ｍｍの厚さ，３１０
ｍｍの幅，および５９００ｍｍの長さを有する帯状の正
極が作製された。なお、この圧延の前後において、アル
ミ箔の集電体の厚さはほとんど変化しない。[Example 1] (Preparation of spiral electrode Ae for type A single cell) Preparation of positive electrode: A positive electrode active material of LiCoO 2 powder having an average particle size of 5 μm and a conductive material of artificial graphite powder were mixed in 9 pieces. The mixture was mixed at a weight ratio of 1: 1 to prepare a positive electrode mixture. This positive electrode mixture and a binder solution obtained by dissolving 5% by weight of polyvinylidene fluoride in N-methyl-2-pyrrolidone (NMP) were kneaded at a solid content weight ratio of 95: 5 to prepare a slurry. This slurry was applied to both surfaces of an aluminum foil current collector having a thickness of 20 μm by a doctor blade method. At this time, the slurry for the positive electrode is applied so that the facing capacity ratio with respect to the negative electrode (positive capacity per unit area / negative capacity per unit area) becomes 1.0. The slurry-like positive electrode active material layer applied to the current collector was vacuum-dried at 150 ° C. for 2 hours to produce a coarse electrode. After rolling the coarse electrode, slitting both side edges results in a thickness of 0.100 mm, 310 mm.
A strip-shaped positive electrode having a width of 5 mm and a length of 5900 mm was produced. Before and after the rolling, the thickness of the aluminum foil current collector hardly changes.
【００２５】負極の作製：スチレンブタジエンゴム（Ｓ
ＢＲ）のディスパージョンと黒鉛粉末を水に分散させ
て、さらに増粘剤であるカルボキシメチルセルロース
（ＣＭＣ）を添加して負極用スラリーが調製された。こ
のとき用いられた黒鉛粉末のＣ軸方向における結晶子の
大きさＬｃは１０００Åより大きく、Ｃ軸方向の平均原
子面間隔ｄ002は３．３５Åであり、そして平均粒径は
２０μｍであった。また、このスラリーが乾燥された後
の負極における重量組成比が（黒鉛粉末）：ＳＢＲ：Ｃ
ＭＣ＝１００重量部：５重量部：１重量部になるように
調製された。このようなスラリーが厚さ１８μｍの銅箔
の集電体の両面に塗布され、乾燥されて粗電極が作製さ
れた。このとき、銅箔の集電体の片面上には８ｍｇ／ｃ
ｍ2 の活物質量が被着された。この粗電極を圧延して両
側縁をスリットすることにより、０．１４０ｍｍの厚
さ，３２０ｍｍの幅，および６０００ｍｍの長さを有す
る帯状の負極が得られた。Preparation of negative electrode: Styrene butadiene rubber (S
The dispersion of (BR) and the graphite powder were dispersed in water, and carboxymethyl cellulose (CMC) as a thickener was further added to prepare a slurry for a negative electrode. The graphite powder used at this time had a crystallite size Lc in the C-axis direction of more than 1000 °, an average atomic plane distance d 002 in the C-axis direction of 3.35 °, and an average particle size of 20 μm. The weight composition ratio of the negative electrode after the slurry was dried was (graphite powder): SBR: C
MC: 100 parts by weight: 5 parts by weight: 1 part by weight. Such a slurry was applied to both surfaces of a copper foil current collector having a thickness of 18 μm and dried to prepare a coarse electrode. At this time, 8 mg / c was applied on one side of the copper foil current collector.
m 2 of active material was deposited. By rolling this coarse electrode and slitting both side edges, a strip-shaped negative electrode having a thickness of 0.140 mm, a width of 320 mm, and a length of 6000 mm was obtained.
【００２６】（種類Ｂの単電池用渦巻型電極Ｂｅの作
製） 正極の作製：種類Ａの電池用渦巻型電極Ａｅの場合と同
様に、種類Ｂの電池用渦巻型電極Ｂｅのための正極が作
製された。(Preparation of Type B Single-Cell Spiral Electrode Be) Preparation of Positive Electrode: As in the case of the type A battery spiral electrode Ae, a positive electrode for the type B battery spiral electrode Be is used. Made.
【００２７】負極の作製：渦巻型電極Ａｅと同様に渦巻
型電極Ｂｅ用の負極が作製されたが、渦巻型電極Ｂｅ用
の負極の活物質量は１１ｍｇ／ｃｍ2 に設定された。Preparation of Negative Electrode: A negative electrode for the spiral electrode Be was prepared in the same manner as the spiral electrode Ae, but the active material amount of the negative electrode for the spiral electrode Be was set to 11 mg / cm 2 .
【００２８】（電解液とセパレータ）非水電解液として
は、ＥＣ（エチレンカーボネイト）とＤＥＣ（ジエチル
カーボネイト）を２：３の体積比で含む混合溶媒にＬｉ
ＰＦ6 の溶質を１モル／リットルだけ溶かした溶液が用
いられた。また、セパレータとしては、ポリプロピレン
製の微多孔膜が用いられた。(Electrolyte and Separator) As a non-aqueous electrolyte, a mixed solvent containing EC (ethylene carbonate) and DEC (diethyl carbonate) in a volume ratio of 2: 3 is used.
Solution of solute of PF 6 by 1 mol / l was used. As the separator, a microporous film made of polypropylene was used.
【００２９】（単電池の組立）以上のようにして用意さ
れた帯状正極と帯状負極をセパレータを介して巻回する
ことにより渦巻型電極ＡｅとＢｅを作製し、円筒形の電
池缶内に挿入した後に電解液が注入されて図３に示され
ているようなリチウム２次電池が作製された。(Assembly of a single cell) The band-shaped positive electrode and the band-shaped negative electrode prepared as described above are wound around a separator to produce spiral electrodes Ae and Be, and inserted into a cylindrical battery can. After that, an electrolytic solution was injected to produce a lithium secondary battery as shown in FIG.
【００３０】（組電池の作製）図１に示されているよう
に、渦巻型電極Ａｅを含む種類Ａの単電池５個が直列接
続され、渦巻型電極Ｂｅを含む種類Ｂの単電池の５個が
直列接続された。そして、これらの単電池Ａのシリーズ
と単電池Ｂのシリーズが互いに並列接続されて組電池に
された。(Fabrication of assembled battery) As shown in FIG. 1, five type A cells including a spiral electrode Ae are connected in series, and a type B single cell including a spiral electrode Be is connected. Were connected in series. Then, the series of the cell A and the series of the cell B were connected in parallel to each other to form an assembled battery.
【００３１】（初期充放電試験）このように作製された
組電池において、２５℃の温度の下に０．１２５Ｃの電
流量で２０．５０Ｖまで充電した後に、１Ｃの電流量で
１３．７５Ｖまで放電させ、そのときに得られた容量が
初期放電容量として定められた。(Initial charge / discharge test) The battery thus prepared was charged to 20.50 V at a current of 0.125 C at a temperature of 25 ° C., and then increased to 13.75 V at a current of 1 C. The battery was discharged, and the capacity obtained at that time was defined as the initial discharge capacity.
【００３２】（最大出力の測定）得られた組電池におい
て、２５℃の温度の下に０．１２５Ｃの電流量で２０．
５Ｖまで充電した後に、０Ｃから３Ｃまでの各電流で１
０秒間ずつ放電し、そのときの電圧が測定された。得ら
れた電流−電圧曲線において最も大きな出力値が最大出
力値とされた。(Measurement of maximum output) In the obtained assembled battery, at a temperature of 25 ° C and a current amount of 0.125C, 20.
After charging to 5V, 1 at each current from 0C to 3C
The battery was discharged for 0 seconds, and the voltage at that time was measured. The largest output value in the obtained current-voltage curve was regarded as the maximum output value.
【００３３】［実施例２，３および比較例１〜３］負極
の活物質量が表１の電極ＡｅとＢｅ欄に示されているよ
うに設定された以外は実施例１の場合と同様に実施例
２，３および比較例１〜３による組電池が作製されて電
池特性の試験が行なわれた。なお、従来の典型的な組電
池は比較例１によるものである。Examples 2 and 3 and Comparative Examples 1 to 3 In the same manner as in Example 1 except that the amount of the active material of the negative electrode was set as shown in the column of electrodes Ae and Be in Table 1. Battery packs according to Examples 2 and 3 and Comparative Examples 1 to 3 were manufactured and tested for battery characteristics. Note that the conventional typical battery pack is based on Comparative Example 1.
【００３４】[0034]
【表１】 [Table 1]
【００３５】表１の結果から、負極の活物質量が少ない
電極Ａｅはその充填密度が小さいので電解液の含液性に
優れ、高い瞬間出力（電流負荷特性）を発揮することが
できると考えられる。他方、比較例３の組電池において
は、電極Ｂｅの活物質量が多すぎてその充填密度が大き
いので、十分な含液性を得ることができなくて活物質の
すべてが充放電に寄与し得ないために放電容量が低下し
たものと考えられる。From the results shown in Table 1, it is considered that the electrode Ae having a small amount of the active material of the negative electrode has a low packing density, so that the electrode Ae is excellent in the liquid content of the electrolyte and can exhibit a high instantaneous output (current load characteristic). Can be On the other hand, in the battery pack of Comparative Example 3, since the amount of the active material of the electrode Be was too large and the packing density thereof was large, sufficient liquid-containing property could not be obtained, and all of the active material contributed to charge and discharge. It is considered that the discharge capacity was lowered because it could not be obtained.
【００３６】［実施例４，５および比較例４，５］負極
の活物質量が表２の電極ＡｅとＢｅの欄に示されている
ように設定された以外は実施例１の場合と同様に、実施
例４，５および比較例４，５による組電池が作製されて
電池の特性試験が行なわれた。Examples 4 and 5 and Comparative Examples 4 and 5 The same as in Example 1 except that the amount of the active material of the negative electrode was set as shown in the column of electrodes Ae and Be in Table 2. Then, assembled batteries according to Examples 4 and 5 and Comparative Examples 4 and 5 were manufactured, and a battery characteristic test was performed.
【００３７】[0037]
【表２】 [Table 2]
【００３８】［実施例６〜８および比較例６〜８］負極
の活物質にコークスが用いられ、その活物質量が表３の
電極ＡｅとＢｅの欄に示されているように設定された以
外は実施例１の場合と同様に、実施例６〜８および比較
例６〜８による組電池が作製されて電池の特性試験が行
なわれた。Examples 6 to 8 and Comparative Examples 6 to 8 Coke was used as the active material of the negative electrode, and the amount of the active material was set as shown in the columns of the electrodes Ae and Be in Table 3. Except for the above, the assembled batteries according to Examples 6 to 8 and Comparative Examples 6 to 8 were manufactured in the same manner as in Example 1, and the battery characteristic test was performed.
【００３９】[0039]
【表３】 [Table 3]
【００４０】以上のような表１，表２，および表３の結
果から明らかなように、電池Ａ中の負極活物質量が５ｍ
ｇ／ｃｍ2 未満の場合には組電池の充放電容量が著しく
低下し、逆に電池Ｂ中の負極活物質量が１３ｍｇ／ｃｍ
2 を超えれば組電池の最大出力特性が低下することがわ
かる。また、組電池が十分な最大出力特性を有するため
には電池Ａ中の負極活物質量が８ｍｇ／ｃｍ2 以下であ
ることが好ましく、十分な容量を有するためには電池Ｂ
中の負極活物質量が１１ｍｇ／ｃｍ2 以上であるのが好
ましいことがわかる。このような関係から、組電池にお
いて、電池Ａの負極単位面積当りの活物質量は電池Ｂに
比べて０．４５〜０．７５の範囲内にあることが好まし
い。As is apparent from the results of Tables 1, 2 and 3, the amount of the negative electrode active material in Battery A was 5 m
When the amount is less than g / cm 2, the charge / discharge capacity of the assembled battery is significantly reduced, and conversely, the amount of the negative electrode active material in Battery B is 13 mg / cm 2.
It can be seen that if it exceeds 2 , the maximum output characteristics of the battery pack will decrease. Also, the amount of the negative electrode active material in the battery A is preferably 8 mg / cm 2 or less in order for the battery pack to have sufficient maximum output characteristics, and the battery B in order to have sufficient capacity.
It can be seen that the amount of the negative electrode active material in the inside is preferably 11 mg / cm 2 or more. From such a relationship, in the battery pack, the amount of the active material per unit area of the negative electrode of the battery A is preferably in the range of 0.45 to 0.75 as compared with the battery B.
【００４１】なお、負極集電体の銅箔の厚みは１８μｍ
であるので、表１〜３に示された面積当りの活物質量を
Ａｄ（ｍｇ／ｃｍ2 ）とすれば、三次元的充填密度Ｄｄ
（ｇ／ｃｃ）は次式で表わされる。The thickness of the copper foil of the negative electrode current collector was 18 μm.
Therefore, assuming that the amount of active material per area shown in Tables 1 to 3 is Ad (mg / cm 2 ), the three-dimensional packing density Dd
(G / cc) is represented by the following equation.
【００４２】Ｄｄ＝Ａｄ×１０-3／０．００６１ ここで、０．００６１の数値は、｛（負極の最終厚さ１
４０μｍ）−（銅箔の厚さ１８μｍ）｝／２＝０．００
６１ｃｍとして得られるものである。Dd = Ad × 10 −3 /0.0061 Here, the numerical value of 0.0061 is Δ (final thickness of negative electrode 1
40 μm) − (18 μm thick copper foil)｝ / 2 = 0.00
It is obtained as 61 cm.
【００４３】[0043]
【発明の効果】以上のように、本発明によれば、電極活
物質の充填密度の比較的小さな種類Ａの単電池と電極活
物質密度の比較的大きな種類Ｂの単電池を組合せた組電
池を作製することにより、瞬間最大出力特性と充放電容
量の両方が改善された電気自動車用組電池を提供するこ
とができる。As described above, according to the present invention, an assembled battery comprising a type A cell having a relatively low density of electrode active material and a type B cell having a relatively high electrode active material density is combined. By preparing a battery pack, it is possible to provide an assembled battery for an electric vehicle in which both the instantaneous maximum output characteristics and the charge / discharge capacity are improved.
【図１】本発明の実施の形態の一例による電気自動車用
組電池を示す模式的なブロック図である。FIG. 1 is a schematic block diagram showing an assembled battery for an electric vehicle according to an example of an embodiment of the present invention.
【図２】渦巻型電極の巻回状態を説明するための模式的
な斜視図である。FIG. 2 is a schematic perspective view for explaining a wound state of a spiral electrode.
【図３】自動車用組電池に用いられる円柱状の単電池の
外観の一例を示す概略的な斜視図である。FIG. 3 is a schematic perspective view showing an example of the external appearance of a columnar unit cell used for an automobile battery pack.
１ 帯状正極 １ａ 正極集電タブ ２ 帯状負極 ２ａ 負極集電タブ ３ セパレータ １０ 電池缶 １１ 正極端子 １２ 負極端子 １３ 正極絶縁パッキング １４ 負極絶縁パッキング DESCRIPTION OF SYMBOLS 1 Strip-shaped positive electrode 1a Positive electrode current collecting tab 2 Strip-shaped negative electrode 2a Negative electrode current collecting tab 3 Separator 10 Battery can 11 Positive terminal 12 Negative terminal 13 Positive insulating packing 14 Negative insulating packing
───────────────────────────────────────────────────── フロントページの続き (72)発明者 近野 義人 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 (72)発明者 米津 育郎 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 (72)発明者 能間 俊之 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 (72)発明者 西尾 晃治 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Yoshito Chino 2-5-5 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Inventor Ikuro Yonezu 2-chome Keihanhondori, Moriguchi-shi, Osaka No. 5 Sanyo Electric Co., Ltd. (72) Inventor Toshiyuki Noma 2-5-5 Sanyo Electric Co., Ltd., Moriguchi-shi, Osaka (72) Inventor Koji Nishio Keihan-Hondori, Moriguchi-shi, Osaka 2-5-5 Sanyo Electric Co., Ltd.
Claims (3)
電池と種類Ｂの複数の直列接続された単電池とが互いに
並列接続されており、 前記単電池の各々は、炭素材料を活物質として含む負
極，リチウムイオンと電気化学反応可能な材料を活物質
として含む正極，および非水電解液を含み、それらの正
負極の対向容量比は実質的に１．０に設定されており、 前記種類Ａと種類Ｂの単電池間における負極単位面積当
りの活物質量比が０．４５〜０．７５の範囲内にあり、
かつ前記両種類の単電池の負極単位面積当りの活物質密
度が５〜１３ｍｇ／ｃｍ2 の範囲内にあることを特徴と
する電気自動車用組電池。1. An assembled battery for an electric vehicle, wherein a plurality of type A series-connected cells and a plurality of type B series-connected cells are connected in parallel to each other. Each of the unit cells includes a negative electrode containing a carbon material as an active material, a positive electrode containing a material capable of electrochemically reacting with lithium ions as an active material, and a non-aqueous electrolyte. It is substantially set to 1.0, the active material amount ratio per unit area of the negative electrode between the type A and type B cells is in the range of 0.45 to 0.75,
An assembled battery for an electric vehicle, wherein the active material density per unit area of the negative electrode of the two types of unit cells is in the range of 5 to 13 mg / cm 2 .
2 の範囲内の負極活物質密度を有し、前記種類Ｂの単電
池は１１〜１３ｍｇ／ｃｍ2 の範囲内の負極活物質密度
を有することを特徴とする請求項１に記載の電気自動車
用組電池。2. The cell of the type A is 6 to 8 mg / cm.
2. The electric vehicle according to claim 1, wherein the cell of the type B has a negative electrode active material density in a range of 11 to 13 mg / cm 2 . Battery pack.
鉛粉末であり、この黒鉛粉末において黒鉛結晶のＣ軸方
向の結晶子の大きさの値Ｌｃは１５０Å以上であり、か
つＣ軸方向の原子面間隔の値ｄ002 は３．３８Å以下で
あることを特徴とする請求項１または２に記載の電気自
動車用組電池。3. The carbon material as an active material of the negative electrode is a graphite powder, and in this graphite powder, a value Lc of a crystallite in a C-axis direction of the graphite crystal is 150 ° or more, and 3. The battery pack for an electric vehicle according to claim 1, wherein the value d 002 of the atomic plane spacing is 3.38 ° or less. 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05579697A JP3363738B2 (en) | 1997-03-11 | 1997-03-11 | Battery pack for electric vehicles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05579697A JP3363738B2 (en) | 1997-03-11 | 1997-03-11 | Battery pack for electric vehicles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10255767A true JPH10255767A (en) | 1998-09-25 |
| JP3363738B2 JP3363738B2 (en) | 2003-01-08 |
Family
ID=13008883
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05579697A Expired - Fee Related JP3363738B2 (en) | 1997-03-11 | 1997-03-11 | Battery pack for electric vehicles |
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| Country | Link |
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| US10651458B2 (en) | 2004-01-16 | 2020-05-12 | Hitachi Chemical Company, Ltd. | Negative electrode for lithium secondary battery and lithium secondary battery |
| JP2005251513A (en) * | 2004-03-03 | 2005-09-15 | Sanyo Electric Co Ltd | Battery assembly using nonaqueous electrolyte secondary battery |
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| JP2010507215A (en) * | 2006-10-16 | 2010-03-04 | エルジー・ケム・リミテッド | High power secondary battery system with asymmetrically charged cells |
| JP2008218248A (en) * | 2007-03-06 | 2008-09-18 | Hitachi Powdered Metals Co Ltd | Lithium secondary battery |
| JP2009038037A (en) * | 2008-10-14 | 2009-02-19 | Hitachi Chem Co Ltd | Negative electrode for lithium secondary battery and lithium secondary battery |
| JP2009152208A (en) * | 2009-01-09 | 2009-07-09 | Sanyo Electric Co Ltd | Power supply unit for vehicle |
| JP2011040410A (en) * | 2010-10-20 | 2011-02-24 | Sony Corp | Nonaqueous electrolyte secondary battery |
| JP2013530510A (en) * | 2011-06-09 | 2013-07-25 | エルジー ケム． エルティーディ． | Electrode assembly and lithium secondary battery including the same |
| CN103959536A (en) * | 2011-06-09 | 2014-07-30 | 株式会社Lg化学 | Electrode assembly and lithium secondary battery comprising same |
| US9537178B2 (en) | 2011-06-09 | 2017-01-03 | Lg Chem, Ltd. | Electrode assembly and lithium secondary battery including the same |
| US9692027B2 (en) | 2011-06-09 | 2017-06-27 | Lg Chem, Ltd. | Electrode assembly and lithium secondary battery including the same |
| JP2012109280A (en) * | 2012-03-12 | 2012-06-07 | Hitachi Chem Co Ltd | Negative electrode for lithium secondary battery and lithium secondary battery |
| JP2015144142A (en) * | 2015-05-11 | 2015-08-06 | 日立化成株式会社 | Negative electrode for lithium secondary battery and lithium secondary battery |
| GB2591755A (en) * | 2020-02-05 | 2021-08-11 | Dar Yun Energy Science Tech Co Ltd | Power-supplying battery of electric vehicle |
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