JP2000090982A - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary batteryInfo
- Publication number
- JP2000090982A JP2000090982A JP11074096A JP7409699A JP2000090982A JP 2000090982 A JP2000090982 A JP 2000090982A JP 11074096 A JP11074096 A JP 11074096A JP 7409699 A JP7409699 A JP 7409699A JP 2000090982 A JP2000090982 A JP 2000090982A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- active material
- electrode active
- electrolyte secondary
- secondary 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.)
- Granted
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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電気自動車など始
動時に高い電力を必要とする電動機械において、その電
源に利用できる非水電解質二次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte secondary battery that can be used as a power source in an electric machine such as an electric vehicle that requires a high power at the time of starting.
【０００２】[0002]
【従来の技術】従来より、シート状の集電体と、該集電
体上に一様な厚さで形成され、リチウムイオンを放出で
きる正極活物質より主としてなる正極活物質層とから構
成されている正極と、該正極から放出された該リチウム
イオンを吸蔵および放出できる負極活物質より構成され
ている負極と、該正極と該負極との間で該リチウムイオ
ンを移動させる電解質とを備えるリチウム二次電池があ
る。2. Description of the Related Art Conventionally, a current collector in the form of a sheet and a positive electrode active material layer formed of a uniform thickness on the current collector and mainly composed of a positive electrode active material capable of releasing lithium ions are constituted. A positive electrode, a negative electrode comprising a negative electrode active material capable of occluding and releasing the lithium ions released from the positive electrode, and an electrolyte for transferring the lithium ions between the positive electrode and the negative electrode. There is a secondary battery.
【０００３】このようなリチウム二次電池は３Ｖ以上の
高い電圧を発生することができるため、種々の電源に利
用されている。中でも、負極活物質にカーボン材料が用
いられているとともに、カーボネート系の有機物を溶媒
とする非水電解液が電解質に用いられている非水電解質
二次電池（リチウムイオン二次電池とも呼ばれている）
は、良好なサイクル特性と、高い安全性とを有するた
め、携帯電話やビデオカメラなどの携帯用電子機器の電
源に多く用いられている。Since such a lithium secondary battery can generate a high voltage of 3 V or more, it is used for various power supplies. Among them, a non-aqueous electrolyte secondary battery (also called a lithium ion secondary battery) in which a carbon material is used as a negative electrode active material and a non-aqueous electrolyte using a carbonate-based organic material as a solvent is used as an electrolyte. Yes)
Because of its excellent cycle characteristics and high safety, it is widely used as a power source for portable electronic devices such as mobile phones and video cameras.
【０００４】ところで、自動車などの動力機械では、そ
の始動時や馬力を上げるときに高い動力エネルギーを必
要とし、例えば、電気自動車は、その発進時や加速時に
特に高い電力を必要とする。このように始動時や馬力を
上げるときに高い電力を必要とする動力機械において
は、数秒ないし１０秒程度の時間だけでもその高い電力
を供給できる電源が求められている。[0004] By the way, power machines such as automobiles require high power energy when starting or raising horsepower. For example, electric vehicles require particularly high power when starting or accelerating. As described above, in a power machine that requires high power at the time of starting or raising horsepower, a power source that can supply the high power even for a time of only several seconds to about 10 seconds is required.
【０００５】この要求に対して、リチウムイオン二次電
池などの非水電解質二次電池が、良好なサイクル特性
と、高い安全性とを有するとして、その電源に利用する
ことが検討されている。しかしながら、このような非水
電解質二次電池では、電極における電池反応が活物質内
部へのリチウムイオンの拡散を伴うために大きな電池反
応速度を得ることが難しく、また、その電極間を移動す
るリチウムイオンの移動速度はそれほど大きくないなど
の理由により、大きな電流を出力し続けることが難し
い。[0005] In response to this demand, non-aqueous electrolyte secondary batteries such as lithium ion secondary batteries are considered to have good cycle characteristics and high safety, and are being studied for use as power sources. However, in such a non-aqueous electrolyte secondary battery, it is difficult to obtain a large battery reaction rate because the battery reaction at the electrode involves diffusion of lithium ions into the active material, and lithium moving between the electrodes is difficult. It is difficult to keep outputting a large current because the ion movement speed is not so high.
【０００６】従来の非水電解質二次電池では、以上のよ
うな理由により、高々１０秒の時間と言えども、３Ｖ以
上の電圧で高電流を出力させることが難しく、先の要求
で求められている高い電力を容易に出力できなかった。[0006] In the conventional non-aqueous electrolyte secondary battery, it is difficult to output a high current at a voltage of 3 V or more, even for a time of at most 10 seconds, for the above reasons. High power could not be easily output.
【０００７】[0007]
【発明が解決しようとする課題】本発明は上記実情に鑑
みてなされたものであり、少なくとも１０秒の間、３Ｖ
以上の電圧で高電流を出力させることが容易にできる非
水電解質二次電池を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and has a power supply of 3 V for at least 10 seconds.
An object of the present invention is to provide a non-aqueous electrolyte secondary battery capable of easily outputting a high current at the above voltage.
【０００８】[0008]
【課題を解決するための手段】シート状の集電体と、該
集電体上に形成され、リチウムイオンを放出できる正極
活物質より主としてなる正極活物質層とから構成されて
いる正極と、該正極から放出された該リチウムイオンを
吸蔵および放出できる負極活物質より構成されている負
極と、該正極と該負極との間で該リチウムイオンを移動
させる非水電解質とを備える非水電解質二次電池におい
ては、非水電解質に接している正極活物質層の表面で電
池反応が最も高密度に起こっている。A positive electrode comprising a sheet-like current collector and a positive electrode active material layer formed on the current collector and mainly composed of a positive electrode active material capable of releasing lithium ions, A non-aqueous electrolyte comprising a negative electrode composed of a negative electrode active material capable of occluding and releasing the lithium ions released from the positive electrode, and a non-aqueous electrolyte for moving the lithium ions between the positive electrode and the negative electrode In the secondary battery, the battery reaction occurs at the highest density on the surface of the positive electrode active material layer in contact with the nonaqueous electrolyte.
【０００９】従って、正極活物質層の表面積を大きくす
ることにより、単位時間当たりの電池反応の反応量を増
加させることができ、その結果として、電池が出力可能
な電流の大きさを大きくすることができる。その表面積
が小さすぎると、大きな電流を出力できなくなってしま
う。しかしながら、正極活物質層の表面積は無制限に大
きくできる訳でなく、限られた電池容積で占めることの
できる正極の体積は限られており、正極活物質層の表面
積を大きくするにはその層の厚みを小さくしなければな
らない。このときに正極活物質層の表面積を必要以上に
大きくすると、電池の構成における集電体、集電リー
ド、セパレータの割合がそれぞれ増え、その結果、電極
の活物質の割合が減少する。そのため、電池の重量が増
加して電池のエネルギー密度が低下するだけでなく、高
電流を流すことが難しくなってしまう。Therefore, by increasing the surface area of the positive electrode active material layer, the amount of battery reaction per unit time can be increased, and as a result, the amount of current that can be output by the battery can be increased. Can be. If the surface area is too small, a large current cannot be output. However, the surface area of the positive electrode active material layer cannot always be increased without limit, and the volume of the positive electrode that can be occupied by the limited battery volume is limited. The thickness must be reduced. At this time, if the surface area of the positive electrode active material layer is made unnecessarily large, the ratio of the current collector, the current collecting lead, and the separator in the battery configuration increases, and as a result, the ratio of the active material of the electrode decreases. Therefore, not only does the weight of the battery increase and the energy density of the battery decreases, but also it becomes difficult to flow a high current.
【００１０】そこで、本発明者は、同一の正極活物質層
の表面積において、高い電流を出力できる電極の構造に
ついて検討を行った。そして、放電容量の３０％を充電
した後に、放電を開始してから少なくとも１０秒後の該
電圧が３Ｖとなるように定電流で放電させたときの放電
率を最大放電率（Ｒmax；単位Ｃ）として、正極活物質
層の電池容量１Ａｈ当たりの最適な表面積を鋭意研究し
た。Therefore, the present inventors have studied the structure of an electrode capable of outputting a high current in the same surface area of the positive electrode active material layer. Then, after charging 30% of the discharge capacity, the discharge rate when discharging at a constant current so that the voltage becomes 3 V at least 10 seconds after the start of the discharge, is defined as the maximum discharge rate (R max ; unit). As C), the inventors studied diligently the optimum surface area of the positive electrode active material layer per 1 Ah of battery capacity.
【００１１】その結果、正極活物質層の電池容量１Ａｈ
当たりの表面積が２０Ｒmax未満であると、正極活物質
の量に対して導電材、結着剤およびリード材料の量の割
合が大きくなって、正極活物質層の単位面積あたりの最
大電流値が低下し、目的の最大電流値が得られなくなる
ことがわかった。一方、正極活物質層の電池容量１Ａｈ
当たりの表面積が７５Ｒmaxを超えると、電池の重量が
大きくなってエネルギー密度が低下し、少なくとも１０
秒の間、３Ｖ以上の電圧で高電流を出力させることがで
きなくなることがわかった。本発明は、このような知見
に基づいてなされたものである。As a result, the battery capacity of the positive electrode active material layer is 1 Ah.
If the surface area per unit is less than 20R max , the ratio of the amount of the conductive material, the binder, and the amount of the lead material to the amount of the positive electrode active material is increased, and the maximum current value per unit area of the positive electrode active material layer is reduced. It was found that the target current value could not be obtained. On the other hand, the battery capacity of the positive electrode active material layer is 1 Ah
When the surface area per unit exceeds 75R max , the weight of the battery increases, the energy density decreases, and at least 10
It has been found that it is impossible to output a high current at a voltage of 3 V or more for seconds. The present invention has been made based on such findings.
【００１２】すなわち、本発明の非水電解質二次電池
は、シート状の集電体と、該集電体上に形成され、リチ
ウムイオンを放出できる正極活物質より主としてなる正
極活物質層とから構成されている正極と、該正極から放
出された該リチウムイオンを吸蔵および放出できる負極
活物質より構成されている負極と、該正極と該負極との
間で該リチウムイオンを移動させる非水電解質とを備
え、該正極及び該負極の端子間に少なくとも３Ｖの電圧
を生じさせることのできる非水電解質二次電池におい
て、放電容量の３０％を充電した後に、放電を開始して
から少なくとも１０秒後の該電圧が３Ｖとなるように定
電流で放電させたときの放電率を最大放電率（Ｒmax；
単位Ｃ）とすると、前記正極活物質層の電池容量１Ａｈ
当たりの表面積が２０Ｒmax〜７５Ｒmax（単位ｃｍ2）
にあることを特徴とする。That is, the non-aqueous electrolyte secondary battery of the present invention comprises a sheet-shaped current collector and a positive electrode active material layer formed on the current collector and mainly composed of a positive electrode active material capable of releasing lithium ions. A positive electrode, a negative electrode comprising a negative electrode active material capable of occluding and releasing the lithium ions released from the positive electrode, and a non-aqueous electrolyte for moving the lithium ions between the positive electrode and the negative electrode In a non-aqueous electrolyte secondary battery capable of generating a voltage of at least 3 V between the terminals of the positive electrode and the negative electrode, after charging 30% of the discharge capacity, at least 10 seconds after starting discharge Thereafter, the discharge rate when discharging at a constant current so that the voltage becomes 3 V is defined as the maximum discharge rate (R max ;
Assuming unit C), the battery capacity of the positive electrode active material layer is 1 Ah
Surface area per the 20R max ~75R max (unit cm 2)
Is characterized in that:
【００１３】この本発明の非水電解質二次電池では、正
極活物質層の電池容量１Ａｈ当たりの表面積が、上述の
不具合が生じない２０Ｒmax〜７５Ｒmaxに限定されてい
るため、少なくとも１０秒の間、３Ｖ以上の電圧で高電
流を出力させることが容易にできる。[0013] In the non-aqueous electrolyte secondary battery of the present invention, the surface area per battery capacity 1Ah of the positive electrode active material layer, because it is limited to 20R max ~75R max in which the aforementioned problem does not occur, at least 10 seconds In the meantime, it is possible to easily output a high current at a voltage of 3 V or more.
【００１４】[0014]
【発明の実施の形態】本発明の非水電解質二次電池で
は、コイン型電池、ボタン型電池、円筒型電池及び角型
電池等の公知の電池構造をとることができる。正極には
公知の正極活物質を用いることができる。リチウムと遷
移金属との複合酸化物は、その電気抵抗が低く、リチウ
ムイオンの拡散性能に優れ、高い充放電効率と良好な充
放電サイクル特性とが得られるため、本正極活物質に好
ましい材料である。リチウムマンガン酸化物は、マンガ
ンの資源が豊富であることから低コスト化を図ることが
できる上でも特に好ましい。DESCRIPTION OF THE PREFERRED EMBODIMENTS The non-aqueous electrolyte secondary battery of the present invention can have a known battery structure such as a coin battery, a button battery, a cylindrical battery, and a square battery. Known positive electrode active materials can be used for the positive electrode. A composite oxide of lithium and a transition metal is a preferable material for the present positive electrode active material because its electric resistance is low, the diffusion performance of lithium ions is excellent, high charge / discharge efficiency and good charge / discharge cycle characteristics are obtained. is there. Lithium manganese oxide is particularly preferable in that it can reduce the cost because the manganese resources are abundant.
【００１５】また、負極には公知の負極活物質を用いる
ことができるが、負極活物質は主として炭素からなるこ
とが好ましい。中でも結晶性の高い天然黒鉛や人造黒鉛
などからなるものを用いることが好ましい。このような
結晶性の高い炭素材を用いることにより、負極のリチウ
ムイオンの受け渡し効率を向上させることができる。負
極も、正極と同様に、シート状の集電体と、この集電体
上に一様な厚さで形成され、主として負極活物質より構
成されている負極活物質層とからなることが好ましい。Although a known negative electrode active material can be used for the negative electrode, it is preferable that the negative electrode active material is mainly composed of carbon. Above all, it is preferable to use one made of natural graphite or artificial graphite having high crystallinity. By using such a highly crystalline carbon material, the lithium ion transfer efficiency of the negative electrode can be improved. Like the positive electrode, the negative electrode also preferably includes a sheet-shaped current collector and a negative electrode active material layer formed on the current collector with a uniform thickness and mainly composed of the negative electrode active material. .
【００１６】非水電解質にも公知のものを用いることが
できるが、特に、エチレンカーボネート、プロピレンカ
ーボネートなどの高誘電率の主溶媒と、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
ートなどの低粘性の副溶媒との混合有機溶媒に、支持電
解質としてＬｉＰＦ6 やＬｉＢＦ4、ＬｉＡｓＦ6、Ｌｉ
Ｎ（ＳＯ2ＣＦ3）3、ＬｉＣ（ＳＯ2ＣＦ3）2などのリチ
ウム塩を溶解させたものを用いることが好ましい。ま
た、副溶媒として、ジメトキシエタン、テトラヒドロフ
ラン及びブチルラクトンなどを用いてもよい。Known non-aqueous electrolytes can be used. In particular, a high-dielectric main solvent such as ethylene carbonate and propylene carbonate and a low-viscosity auxiliary such as dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate are used. LiPF 6 , LiBF 4 , LiAsF 6 , or LiPF 6 as a supporting electrolyte in a mixed organic solvent with a solvent
It is preferable to use a material in which a lithium salt such as N (SO 2 CF 3 ) 3 or LiC (SO 2 CF 3 ) 2 is dissolved. Further, dimethoxyethane, tetrahydrofuran, butyl lactone, or the like may be used as a secondary solvent.
【００１７】本発明の非水電解質二次電池においては、
最大放電率が１２Ｃ以上であることが好ましい。このよ
うな非水電解質二次電池は、自動車など高い動力エネル
ギーが必要とされる動力機械に用いることができる。ま
た、１０Ｃで連続的に放電させたときの容量としては、
０．２Ｃの低電流を流した時の容量の５０％以上を確保
することが好ましい。In the non-aqueous electrolyte secondary battery of the present invention,
It is preferable that the maximum discharge rate is 12C or more. Such a non-aqueous electrolyte secondary battery can be used for power machines that require high power energy, such as automobiles. In addition, the capacity when continuously discharged at 10 C is as follows:
It is preferable to secure 50% or more of the capacity when a low current of 0.2 C flows.
【００１８】電気自動車などの動力機械では、１０Ｃ以
上で連続して作動させることが多い。容量性能をこのよ
うにさらに限定することにより、少なくとも３分の間
は、高電圧で高電流を出力することができ、高いエネル
ギーを供給できるようになる。本発明の非水電解質二次
電池では、前記正極活物質層の形態を次のように数値的
に限定することが好ましい。Power machines such as electric vehicles are often operated continuously at 10 C or higher. By further limiting the capacity performance in this way, a high voltage and a high current can be output for at least 3 minutes, and a high energy can be supplied. In the nonaqueous electrolyte secondary battery of the present invention, it is preferable that the form of the positive electrode active material layer be numerically limited as follows.
【００１９】正極活物質層は、４０〜７０μｍの層の厚
さを有することが好ましい。その厚さが４０μｍ未満で
あると、１０Ｃでの放電において、０．２Ｃの低電流を
流した時の容量の５０％以上の容量を確保することが難
しくなり、７０μｍを超えると、最大電流を１２Ｃ以上
にすることが難しくなる。正極活物質は、１〜１９μｍ
の２次粒子径を有することが好ましい。１μｍ未満の２
次粒子径を合成することは技術的に難しく、また、仮に
その正極活物質を容易に合成できたとしても、粒子どう
しの接合点数、および粒子と集電体との接合点数が多く
なり、バインダで電極形状を保持することが困難となっ
て、集電体上に正極活物質層を形成することが難しくな
る。また、その二次粒子径が１９μｍを超えると、正極
活物質層でのリチウムイオンの拡散経路が長くなってし
まう。それゆえ、最大電流を１２Ｃ以上にすることが難
しくなるとともに、その放電後に５０％以上の容量を確
保することが難しくなる。The positive electrode active material layer preferably has a layer thickness of 40 to 70 μm. If the thickness is less than 40 μm, it becomes difficult to secure a capacity of 50% or more of the capacity when a low current of 0.2 C flows in a discharge at 10 C. If the thickness exceeds 70 μm, the maximum current is reduced. It becomes difficult to make it 12C or more. The positive electrode active material is 1 to 19 μm
It is preferable to have a secondary particle diameter of 2 less than 1 μm
It is technically difficult to synthesize the secondary particle diameter, and even if the cathode active material can be easily synthesized, the number of junctions between particles and the number of junctions between particles and the current collector increase, and the binder becomes larger. Therefore, it becomes difficult to maintain the electrode shape, and it becomes difficult to form the positive electrode active material layer on the current collector. If the secondary particle diameter exceeds 19 μm, the diffusion path of lithium ions in the positive electrode active material layer becomes long. Therefore, it is difficult to make the maximum current 12 C or more, and it is also difficult to secure 50% or more capacity after the discharge.
【００２０】正極活物質層は、２８〜３８％の空隙率を
有することが好ましい。正極活物質層で拡散するリチウ
ムイオンは、その空隙に侵入している非水電解液を移動
することができ、非水電解液中での移動のしやすさは正
極活物質内でのものより大きい。その空隙率が、２８％
未満であると、リチウムイオンを正極活物質層において
十分な拡散速度で拡散させることが難しくなる。その結
果、１０Ｃでの放電において、０．２Ｃの低電流を流し
た時の容量の５０％以上の容量を確保することが難しく
なる。一方、その空隙率が３８％を超えると、正極活物
質層の電気抵抗が大きくなって高電流を出力することが
難しくなり、１０Ｃでの放電において、０．２Ｃの低電
流を流した時の容量の５０％以上の容量を確保すること
が難しくなる。The positive electrode active material layer preferably has a porosity of 28 to 38%. Lithium ions diffusing in the positive electrode active material layer can move the non-aqueous electrolyte that has penetrated into the void, and the mobility in the non-aqueous electrolyte is easier than that in the positive electrode active material. large. The porosity is 28%
If it is less than 3, it becomes difficult to diffuse lithium ions in the positive electrode active material layer at a sufficient diffusion rate. As a result, in discharging at 10 C, it becomes difficult to secure a capacity of 50% or more of the capacity when a low current of 0.2 C flows. On the other hand, if the porosity exceeds 38%, the electric resistance of the positive electrode active material layer becomes large, and it becomes difficult to output a high current. In the discharge at 10C, when a low current of 0.2C flows. It becomes difficult to secure a capacity of 50% or more of the capacity.
【００２１】正極活物質層は、２０Ω・ｃｍ以下のシー
ト抵抗を有することが好ましい。そのシート抵抗が２０
Ω・ｃｍを超えると、正極活物質層での抵抗により１０
Ｃでの放電において５０％以上の容量を確保することが
難しくなる。正極活物質層は、その表面積に対して８〜
１６ｍｇ／ｃｍ2の重量密度を有することが好ましい。
その重量密度が、８ｍｇ／ｃｍ2未満であると、その電
池反応を十分な反応量で行わせることが難しくなり、高
電流を出力することが難しくなる。一方、その重量密度
が、１６ｍｇ／ｃｍ2を超えると、最大電流を１２Ｃ以
上にすることが難しくなるとともに、１０Ｃでの放電に
おいて、０．２Ｃの低電流を流した時の容量の５０％以
上の容量を確保することが難しくなる。The positive electrode active material layer preferably has a sheet resistance of 20 Ω · cm or less. The sheet resistance is 20
If the resistance exceeds Ω · cm, the resistance of the positive electrode active material layer may cause
It becomes difficult to secure a capacity of 50% or more in the discharge at C. The positive electrode active material layer has a surface area of 8 to
It preferably has a weight density of 16 mg / cm 2 .
If the weight density is less than 8 mg / cm 2 , it is difficult to perform the battery reaction with a sufficient reaction amount, and it is difficult to output a high current. On the other hand, when the weight density exceeds 16 mg / cm 2 , it is difficult to increase the maximum current to 12 C or more, and at the discharge at 10 C, 50% or more of the capacity when a low current of 0.2 C flows. It is difficult to secure sufficient capacity.
【００２２】正極活物質と負極活物質との重量比（正極
活物質の重量／負極活物質の重量）が１．８〜２．９に
あることが好ましい。それらの重量比をこの範囲内にと
ることにより、これらのいずれかの活物質に無駄が生じ
ることなく、高電圧及び高電流を出力させることがで
き、高い放電容量を得ることができる。すなわち、正極
活物質と負極活物質とをバランスよく用いることによ
り、電池のエネルギー密度及び出力密度を向上させるこ
とができる。It is preferable that the weight ratio of the positive electrode active material to the negative electrode active material (weight of the positive electrode active material / weight of the negative electrode active material) is 1.8 to 2.9. By setting the weight ratio within this range, a high voltage and a high current can be output without wasting any of these active materials, and a high discharge capacity can be obtained. That is, by using the positive electrode active material and the negative electrode active material in a well-balanced manner, the energy density and the output density of the battery can be improved.
【００２３】さらに、正極および負極の活物質内でリチ
ウムイオンの拡散速度は、充電時には正極で速く、負極
では遅くなり、逆に放電時には正極では遅く、負極では
速くなる。そのため、正極活物質と負極活物質との重量
比をこの範囲に限定することにより、正極および負極で
の拡散速度のバランスが取れ、より高い電流を流すこと
が可能となる。Furthermore, the diffusion rate of lithium ions in the active materials of the positive electrode and the negative electrode is high at the positive electrode during charging, slow at the negative electrode, and conversely slow at the positive electrode and high at the negative electrode during discharging. Therefore, by limiting the weight ratio between the positive electrode active material and the negative electrode active material to this range, the diffusion speeds at the positive electrode and the negative electrode can be balanced, and a higher current can flow.
【００２４】ところで、正極活物質にリチウムマンガン
酸化物を用いた非水電解質二次電池では、充放電サイク
ルが多数繰り返されると、Ｌｉが頻繁に電極に出入りす
ることで、電極活物質の結晶構造が変化することがあ
る。こうした電極活物質の結晶構造の変化に伴って、電
極の導電性が低下したり、Ｍｎが電解液へ溶出したりす
ることがある。こうしたことは、高温下で電池が使用さ
れたときに起こりやすく、電池のサイクル特性や保存特
性を低下させる原因となる。特に、電極活物質の比表面
積が大きい電池や、電極活物質層の厚さが小さい電池で
は、電解液との反応面積が大きくなるため、Ｍｎの電解
液への溶出量が多くなり、この問題がより顕著に現れ
る。By the way, in a nonaqueous electrolyte secondary battery using lithium manganese oxide as a positive electrode active material, when a charge and discharge cycle is repeated many times, Li frequently enters and leaves the electrode, and the crystal structure of the electrode active material is increased. May change. With such a change in the crystal structure of the electrode active material, the conductivity of the electrode may decrease, or Mn may elute into the electrolyte. Such a phenomenon is likely to occur when the battery is used at a high temperature, and causes deterioration in the cycle characteristics and storage characteristics of the battery. In particular, in a battery having a large specific surface area of the electrode active material or a battery having a small thickness of the electrode active material layer, since the reaction area with the electrolytic solution is large, the amount of Mn eluted into the electrolytic solution is large, and this problem occurs. Appear more conspicuously.
【００２５】本発明者らは、前述のように正極活物質層
の厚さを４０〜７０μｍに限定したとき、適切な比表面
積を有する正極活物質を用いることで、負荷特性と高温
でのサイクル特性とを向上させることができることを見
出した。すなわち、前記正極活物質は、０．３〜１．２
ｍ2 ／ｇの比表面積を有することが好ましい。正極活物
質の比表面積が０．３ｍ2 ／ｇ未満であると、優れた負
荷特性を得ることが難しくなる。一方、正極活物質の比
表面積が１．２ｍ2 ／ｇを超えると、優れた高温サイク
ル特性を得ることが難しくなる。When the thickness of the positive electrode active material layer is limited to 40 to 70 μm as described above, the present inventors use a positive electrode active material having an appropriate specific surface area to provide load characteristics and high-temperature cycling. It has been found that the characteristics can be improved. That is, the positive electrode active material is 0.3 to 1.2.
It preferably has a specific surface area of m 2 / g. When the specific surface area of the positive electrode active material is less than 0.3 m 2 / g, it is difficult to obtain excellent load characteristics. On the other hand, when the specific surface area of the positive electrode active material exceeds 1.2 m 2 / g, it becomes difficult to obtain excellent high-temperature cycle characteristics.
【００２６】また、正極活物質にスピネル構造を有する
リチウムマンガン酸化物を用いる場合、そのリチウムマ
ンガン酸化物にさらにリチウムやＭｎ以外の陽イオンと
なりうる元素を添加した正極活物質を用いることによ
り、電池の高温でのサイクル特性を向上させることがで
きることを見出した。さらには、そのリチウムマンガン
酸化物のＭｎを、Ｍｎ以外の陽イオン元素で置換するこ
とにより、電池の高温でのサイクル特性をさらに確実に
向上させることができることを見出した。In the case where a lithium manganese oxide having a spinel structure is used as the positive electrode active material, the lithium manganese oxide is further used with a positive electrode active material other than lithium or Mn to be a cation. It has been found that the high temperature cycle characteristics can be improved. Furthermore, it has been found that by substituting Mn of the lithium manganese oxide with a cation element other than Mn, the cycle characteristics at high temperature of the battery can be more reliably improved.
【００２７】すなわち、前記正極活物質は、ＬｉＭｎY
ＭｅZＯ(4±σ)（ＭｅはＭｎ以外の陽イオンになりうる
元素）の組成式で表され、かつ（１＋Ｚ）／Ｙ＞１．０
５／１．９５を満たすことが好ましい。ここでＭｅは、
ＬｉＭｎ2Ｏ4のスピネル構造を構成するＭｎに置換され
たものであることがさらに好ましい。上記のように正極
活物質の比表面積及び組成を限定することにより、電解
液との反応によるＭｎの腐食及び溶出の抑制、並びに３
価のＭｎとＯの結合間で起こるヤンテラー歪みの分断を
行うことができる。その結果、高温下でのサイクル特性
及び保存特性が向上すると考えられる。That is, the positive electrode active material is LiMn Y
Me Z O (4 ± σ) (Me is an element that can be a cation other than Mn) represented by a composition formula, and (1 + Z) / Y> 1.0
It is preferable to satisfy 5 / 1.95. Where Me is
More preferably, LiMn 2 O 4 is substituted with Mn constituting the spinel structure. By limiting the specific surface area and composition of the positive electrode active material as described above, corrosion and elution of Mn due to reaction with the electrolytic solution can be suppressed, and
It is possible to divide the Janteller distortion occurring between the bonds of the valence Mn and O. As a result, it is considered that the cycle characteristics and storage characteristics at high temperatures are improved.
【００２８】また、上記のように正極活物質の組成を限
定する場合、前記Ｍｅは、Ｌｉと、IIＡからIIIＢ属の
元素との少なくとも一種であることが好ましく、さらに
は前記Ｍｅは、Ｌｉ、Ａｌ、Ｎｉ及びＣｏの少なくとも
１種であることが好ましい。このように正極活物質の組
成をさらに限定することにより、電解液との反応による
Ｍｎの腐食及び溶出の抑制、並びに３価のＭｎとＯの結
合間で起こるヤンテラー歪みの分断をさらに効果的に行
うことができる。その結果、高温下でのサイクル特性及
び保存特性がより一層向上する。When the composition of the positive electrode active material is limited as described above, it is preferable that Me is at least one of Li and an element belonging to Group IIA to IIIB, and more preferably, Me is Li, It is preferably at least one of Al, Ni and Co. By further limiting the composition of the positive electrode active material in this way, the suppression of corrosion and elution of Mn due to the reaction with the electrolytic solution, and the separation of Yanterer strain occurring between the bond of trivalent Mn and O are more effectively achieved. It can be carried out. As a result, cycle characteristics and storage characteristics at high temperatures are further improved.
【００２９】[0029]
【実施例】以下、実施例により本発明を具体的に説明す
る。 （実施例１）本実施例の非水電解質二次電池Ａは、図１
にその構造を概略的に示すように、シート状の集電体１
０ａと、集電体１０ａ上に形成され、リチウムイオンを
放出できる正極活物質より主としてなる正極活物質層１
０ｂとから構成されている正極１０と、正極１０から放
出されたリチウムイオンを吸蔵および放出できる負極活
物質より構成されている負極２０と、正極１０と負極２
０との間でリチウムイオンを移動させる非水電解液３０
とを備える円筒型電池である。The present invention will be described below in detail with reference to examples. (Embodiment 1) The non-aqueous electrolyte secondary battery A of this embodiment is shown in FIG.
As schematically shown in FIG.
0a and a positive electrode active material layer 1 mainly formed of a positive electrode active material formed on the current collector 10a and capable of releasing lithium ions.
0b, a negative electrode 20 composed of a negative electrode active material capable of occluding and releasing lithium ions released from the positive electrode 10, a positive electrode 10 and a negative electrode 2
Non-aqueous electrolyte 30 for transferring lithium ions between zero
And a cylindrical battery comprising:
【００３０】正極１０は、アルミニウムよりなる厚さ１
５μｍのシート状の正極集電体１０ａと、主としてリチ
ウムマンガン酸化物（Ｌｉ1.05Ｍｎ1.95Ｏ4）よりなる
正極活物質層１０ｂとから構成されており、この正極活
物質層１０ｂは、正極集電体１０ａの両側の表面上に４
５μｍの厚さで一様に形成されている。また、その空隙
率は３２．４％であり、シート抵抗は２０Ω・ｃｍであ
る。このシート抵抗は４端子法で測定されたものであ
る。さらに、その重量密度は、その表面積に対して１
１．５ｍｇ／ｃｍ2である。この正極１０は次のように
して成形したものである。The cathode 10 has a thickness of 1 made of aluminum.
It is composed of a 5 μm sheet-shaped positive electrode current collector 10a and a positive electrode active material layer 10b mainly composed of lithium manganese oxide (Li 1.05 Mn 1.95 O 4 ). 4 on both sides of body 10a
It is formed uniformly with a thickness of 5 μm. The porosity is 32.4%, and the sheet resistance is 20 Ω · cm. This sheet resistance is measured by a four-terminal method. Furthermore, its weight density is 1 to its surface area.
1.5 mg / cm 2 . This positive electrode 10 is formed as follows.
【００３１】先ず、正極活物質として、二次粒子径が
６．５μｍにあるＬｉ1.05Ｍｎ1.95Ｏ 4粉末を用意し
た。この二次粒子径はレーザー回折法により測定した値
である。また、導電材としてグラファイト粉末（ロンザ
社製ＫＳ−１５）を用意した。結着剤としてポリビニリ
デンフロライド（ＰＶＤＦ）を用意した。分散溶媒とし
てＮ−メチル−２ピロリドン（ＮＭＰ）を用意した。First, as the positive electrode active material, the secondary particle diameter is
Li at 6.5 μm1.05Mn1.95O FourPrepare the powder
Was. This secondary particle size is the value measured by the laser diffraction method.
It is. In addition, graphite powder (Lonza) is used as the conductive material.
KS-15) was prepared. Polyvinyl as binder
Denfluoride (PVDF) was prepared. As a dispersion solvent
To prepare N-methyl-2-pyrrolidone (NMP).
【００３２】これらＬｉ1.05Ｍｎ1.95Ｏ4粉末及び炭素
粉末をＰＶＤＦとともにＮＭＰに加え、よく混ぜ合わせ
てスラリー様の正極用合剤を得た。ここでは、Ｌｉ1.05
Ｍｎ 1.95Ｏ4粉末、炭素粉末及びＰＶＤＦを８７：１
０：３の重量比で配合した。この正極用合剤を、正極集
電体１０ａの両側の表面上にコンマコータ法により塗布
した後、高温槽で十分に乾燥させ、正極活物質層１０ｂ
を形成した。この正極活物質層１０ｂをプレス処理して
所定の密度にし、正極１０を得た。These Li1.05Mn1.95OFourPowder and carbon
Add powder to NMP with PVDF and mix well
Thus, a slurry-like mixture for a positive electrode was obtained. Here, Li1.05
Mn 1.95OFour87: 1 powder, carbon powder and PVDF
It was blended at a weight ratio of 0: 3. This positive electrode mixture is mixed with the positive electrode
Coating on both surfaces of electric body 10a by comma coater method
After that, it is sufficiently dried in a high-temperature bath, and
Was formed. This positive electrode active material layer 10b is pressed
The positive electrode 10 was obtained at a predetermined density.
【００３３】負極２０は、負極活物質にカーボン材料が
用いられているもので、銅箔よりなる負極集電体２０ａ
（厚さ１０μｍ）と、主としてカーボン材料よりなる負
極活物質層２０ｂとから構成されている。負極活物質層
２０ｂは、負極集電体２０ａの両側の表面上に３４μｍ
の厚さで一様に形成されている。この負極２０は次のよ
うにして成形したものである。The negative electrode 20 uses a carbon material as a negative electrode active material, and includes a negative electrode current collector 20a made of copper foil.
(Thickness: 10 μm) and a negative electrode active material layer 20b mainly made of a carbon material. The negative electrode active material layer 20b has a thickness of 34 μm on both surfaces of the negative electrode current collector 20a.
Is formed uniformly. This negative electrode 20 is formed as follows.
【００３４】先ず、メソフェーズカーボンマイクロビー
ズ（ＭＣＭＢ）粉末を用意し、このＭＣＭＢをＰＶＤＦ
とともにＮＭＰに加え、よく混ぜ合わせてスラリー様の
負極用合剤を得た。ここでは、正極活物質と負極活物質
との重量比（Ｌｉ1.05Ｍｎ1. 95Ｏ4粉末の重量／ＭＣＭ
Ｂ粉末の重量）が２．４となるように、４．１ｍｇ／ｃ
ｍ2のＭＣＭＢ粉末を用いた。また、ＭＣＭＢ粉末とＰ
ＶＤＦとを９５：５の重量比で配合した。この負極用合
剤を負極集電体２０ａの両側の表面上にコンマコータ法
により塗布した後、高温槽で十分に乾燥させて負極活物
質層２０ｂを形成し、負極２０を得た。First, mesophase carbon microbead (MCMB) powder is prepared, and this MCMB is PVDF.
Together with NMP and mixed well to obtain a slurry-like negative electrode mixture. Here, the weight ratio of the cathode active material and the anode active material (Li 1.05 Mn 1. 95 O 4 powder weight / MCM
4.1 mg / c so that the weight of B powder is 2.4.
m 2 of MCMB powder was used. Also, MCMB powder and P
VDF and 95: 5 by weight. The negative electrode mixture was applied on both surfaces of the negative electrode current collector 20a by a comma coater method, and then sufficiently dried in a high-temperature bath to form the negative electrode active material layer 20b, whereby the negative electrode 20 was obtained.
【００３５】以上で得られた正極１０及び負極２０をさ
らに１０Ｐａの減圧下において１２０℃で８時間加熱し
て、それらの電極中の水分をほぼ完全に除去した後、そ
れらの電極を間にポリエチレンよりなるセパレータ４０
（東燃タピルス社製）を挟んで巻回し、円柱状の巻回電
極体を形成した。また、非水電解液３０には、エチレン
カーボネート及びジエチルカーボネートを体積比３０：
７０で混合した溶媒に、支持塩としてＬｉＰＦ6 を１ｍ
ｏｌ／ｌ溶解させたものを用いた。The positive electrode 10 and the negative electrode 20 obtained above were further heated at 120 ° C. for 8 hours under a reduced pressure of 10 Pa to almost completely remove water from the electrodes. Separator 40 consisting of
(Made by Tonen Tapils) to form a cylindrical wound electrode body. The nonaqueous electrolyte 30 contains ethylene carbonate and diethyl carbonate in a volume ratio of 30:
1 m of LiPF 6 as a supporting salt was added to the solvent mixed at 70.
ol / l was used.
【００３６】先に得た巻回電極体を電池缶５０ａに挿入
した後、非水電解液３０を電池缶５０ａに注ぎ入れ、巻
回電極体を非水電解液３０に浸し、最後に正極端子５２
を備えた蓋部５０ｂを取り付けて図１に示される非水電
解質二次電池Ａを完成した。この非水電解質二次電池Ａ
は、１０．９Ａｈの放電容量をもち、正極１０及び負極
２０の端子間に３．０〜４．２Ｖの電圧を生じさせるこ
とができる。After the previously obtained wound electrode body is inserted into the battery can 50a, the non-aqueous electrolyte 30 is poured into the battery can 50a, the wound electrode body is immersed in the non-aqueous electrolyte 30, and finally the positive electrode terminal 52
A non-aqueous electrolyte secondary battery A shown in FIG. This non-aqueous electrolyte secondary battery A
Has a discharge capacity of 10.9 Ah and can generate a voltage of 3.0 to 4.2 V between the terminals of the positive electrode 10 and the negative electrode 20.
【００３７】この非水電解質二次電池Ａの正極活物質層
の表面積は、１０２００ｃｍ2であり、１Ａｈ当たりの
面積に換算すると９３５ｃｍ2／Ａｈとなる。また、こ
の電池では、放電容量の３０％を充電した後に、放電を
開始してから１０秒後の該電圧が３Ｖとなるように定電
流で放電させたとき、その最大電流値は２６４Ａであ
り、この値は最大放電率の値に換算すると２４Ｃに相当
する。従って、正極活物質層の表面積の値は、図２に示
されるその１Ａｈ当たりの表面積（ｃｍ2／Ａｈ）およ
び最大放電率Ｒmax（Ｃ）の関係を表す直線グラフの傾
きから、３０．３Ｒmaxと表すことができる。The surface area of the positive electrode active material layer of the non-aqueous electrolyte secondary battery A is 10200 cm 2 , which is 935 cm 2 / Ah in terms of area per 1 Ah. Further, when the battery was charged at 30% of the discharge capacity and then discharged at a constant current such that the voltage became 3 V 10 seconds after the discharge was started, the maximum current value was 264A. This value corresponds to 24C when converted to the value of the maximum discharge rate. Therefore, the value of the surface area of the positive electrode active material layer was determined to be 30.3 R from the slope of the linear graph showing the relationship between the surface area per 1 Ah (cm 2 / Ah) and the maximum discharge rate R max (C) shown in FIG. It can be expressed as max .
【００３８】なお、本実施例では、最大電流値を次のよ
うにして測定した。先ず、放電深度（ＤＯＤ）が７０％
となるようにして、放電容量の３０％を充電した。続い
て、１／３Ｃ、１Ｃ、３Ｃ、６Ｃ、１２Ｃ及び２４Ｃの
各放電率でそれぞれ放電を行った。放電を開始してから
１０秒後に、各放電における電圧をそれぞれ測定した。
放電率と１０秒後の電圧とが直線関係にあることを利用
し、これらの測定値から、放電を開始してから１０秒後
に電圧が３Ｖとなる電流値、すなわち最大電流値を求め
た。In this example, the maximum current value was measured as follows. First, the depth of discharge (DOD) is 70%
Thus, 30% of the discharge capacity was charged. Subsequently, discharge was performed at a discharge rate of 1 / 3C, 1C, 3C, 6C, 12C, and 24C, respectively. Ten seconds after the start of the discharge, the voltage at each discharge was measured.
Utilizing the fact that the discharge rate and the voltage after 10 seconds have a linear relationship, a current value at which the voltage becomes 3 V 10 seconds after the start of discharge, that is, a maximum current value was determined from these measured values.
【００３９】また、充電をＣＣ−ＣＶ、４．２Ｖの電
圧、並びに１Ｃの充電率で２．５時間行った後、０．２
Ｃおよび１０Ｃの放電率で３Ｖまで放電をおこなった。
その結果、１０Ｃで放電させたときの容量は、０．２Ｃ
の低電流を流した時の容量の９０％であった。また、こ
のときの出力密度の値は１６００Ｗ／ｋｇであった。 （実施例２）本実施例の非水電解質二次電池Ｂは、次の
形態及び特性を有する他は実施例１と同じ電池である。After charging was performed for 2.5 hours at a CC-CV voltage of 4.2 V and a charging rate of 1 C, charging was performed for 0.2 hours.
Discharge was performed up to 3V at a discharge rate of C and 10C.
As a result, the capacity when discharged at 10 C is 0.2 C
Was 90% of the capacity when a low current was passed. The value of the output density at this time was 1600 W / kg. (Example 2) A non-aqueous electrolyte secondary battery B of this example is the same as Example 1 except that it has the following form and characteristics.
【００４０】この非水電解質二次電池Ｂの正極活物質層
の表面積は、６７００ｃｍ2にあり、１Ａｈ当たりの面
積に換算すると８３８ｃｍ2である。この電池の最大電
流値は、実施例１と同様にして測定した結果、２６８Ａ
であることがわかった。この値は最大放電率の値に換算
すると３３Ｃに相当する。従って、正極活物質層の表面
積の値は、図２に示されるその１Ａｈ当たりの表面積
（ｃｍ2／Ａｈ）および最大放電率Ｒmax（Ｃ）の関係を
表す直線グラフの傾きから、２５Ｒmaxと表すことがで
きる。The surface area of the positive electrode active material layer of the non-aqueous electrolyte secondary battery B is in 6700Cm 2, a 838cm 2 in terms of area per 1 Ah. The maximum current value of this battery was measured in the same manner as in Example 1.
It turned out to be. This value corresponds to 33C when converted to the value of the maximum discharge rate. Therefore, the value of the surface area of the positive electrode active material layer is 25R max from the slope of the linear graph showing the relationship between the surface area per 1 Ah (cm 2 / Ah) and the maximum discharge rate R max (C) shown in FIG. Can be represented.
【００４１】また、正極活物質層のシート抵抗は０．６
Ω・ｃｍである。出力密度の値は２２００Ｗ／ｋｇであ
る。また、１０Ｃで放電させたときの容量は、０．２Ｃ
の低電流を流した時の容量の９２％であった。 （実施例３）本実施例の非水電解質二次電池Ｃは、次の
形態及び特性を有する他は実施例１と同じ電池である。The sheet resistance of the positive electrode active material layer was 0.6.
Ω · cm. The value of the power density is 2200 W / kg. The capacity when discharged at 10 C is 0.2 C
Was 92% of the capacity when a low current was passed. (Embodiment 3) A non-aqueous electrolyte secondary battery C of this embodiment is the same as Embodiment 1 except that it has the following form and characteristics.
【００４２】この非水電解質二次電池Ｃの正極活物質層
の表面積は、４００〜６８０ｃｍ2にあり、１Ａｈ当た
りの面積に換算すると４３２〜７３０ｃｍ2である。こ
の電池の最大電流値は、実施例１と同様にして測定した
結果、８〜１２．４Ａであることがわかった。この値は
最大放電率の値に換算すると８．６〜１３．４Ｃに相当
する。従って、正極活物質層の表面積の値は、図２に示
されるその１Ａｈ当たりの表面積（ｃｍ2／Ａｈ）およ
び最大放電率Ｒmax（Ｃ）の関係を表す直線グラフの傾
きから、６２．５Ｒmaxと表すことができる。The surface area of the positive electrode active material layer of the non-aqueous electrolyte secondary battery C is in 400～680Cm 2, a 432～730Cm 2 in terms of area per 1 Ah. The maximum current value of this battery was measured in the same manner as in Example 1, and was found to be 8 to 12.4 A. This value corresponds to 8.6 to 13.4 C when converted to the value of the maximum discharge rate. Accordingly, the value of the surface area of the positive electrode active material layer is calculated from the slope of 62.5 R from the slope of the linear graph showing the relationship between the surface area per 1 Ah (cm 2 / Ah) and the maximum discharge rate R max (C) shown in FIG. It can be expressed as max .
【００４３】なお、この正極活物質層は、正極集電体の
両側の表面上に３５〜７５μｍの厚さで一様に形成され
ており、そのシート抵抗は１０Ω・ｃｍである。出力密
度の値は６０８〜９６０Ｗ／ｋｇである。また、１０Ｃ
で放電させたときの容量は、０．２Ｃの低電流を流した
時の容量の７〜８３％であった。 （比較例１）本比較例の非水電解質二次電池Ｄは、次の
正極の形態及び特性を有する他は実施例１と同じ電池で
ある。The positive electrode active material layer is uniformly formed on both surfaces of the positive electrode current collector with a thickness of 35 to 75 μm, and has a sheet resistance of 10 Ω · cm. The value of the power density is 608-960 W / kg. Also, 10C
Was 7 to 83% of the capacity when a low current of 0.2 C was passed. (Comparative Example 1) A nonaqueous electrolyte secondary battery D of this comparative example is the same as Example 1 except that it has the following positive electrode form and characteristics.
【００４４】この非水電解質二次電池Ｄの正極活物質層
の表面積は、４８６〜８４２ｃｍ2にあり、１Ａｈ当た
りの面積に換算すると５２５〜９１０ｃｍ2である。こ
の電池の最大電流値は、実施例１と同様にして測定した
結果、７．２〜１０．６Ａであることがわかった。この
値は最大放電率の値に換算すると７．８〜１１．５Ｃに
相当する。従って、正極活物質層の表面積の値は、図２
に示されるその１Ａｈ当たりの表面積（ｃｍ2／Ａｈ）
および最大放電率Ｒmax（Ｃ）の関係を表す直線グラフ
の傾きから、７７Ｒmaxと表すことができる。The surface area of the positive electrode active material layer of the non-aqueous electrolyte secondary battery D is in 486～842Cm 2, a 525～910Cm 2 in terms of area per 1 Ah. The maximum current value of this battery was measured in the same manner as in Example 1, and was found to be 7.2 to 10.6 A. This value corresponds to 7.8 to 11.5 C when converted to the value of the maximum discharge rate. Accordingly, the value of the surface area of the positive electrode active material layer is as shown in FIG.
Surface area per 1 Ah (cm 2 / Ah)
And from the slope of the maximum discharge rate line graph showing the relationship R max (C), it can be expressed as 77R max.
【００４５】なお、この正極活物質層は、正極集電体の
両側の表面上に４５〜１２５μｍの厚さで一様に形成さ
れており、そのシート抵抗は２０Ω・ｃｍである。 ［各非水電解質二次電池の電池特性の評価］図２より、
上記の実施例の各非水電解質二次電池では、比較例１の
非水電解質二次電池Ｄと正極活物質層を同じ表面積とし
て比較したときに、いずれも高い最大放電率が得られる
ことがわかる。従って、上記の各実施例の非水電解質二
次電池では、少なくとも１０秒の間、３Ｖ以上の電圧で
高電流を出力させることが容易にできる。 ［正極活物質層の厚さの電池特性への影響］正極活物質
層の厚さが異なる電極を用い、１８６５０サイズの電池
を作製した。この電池の容量は約１Ａｈである。各電池
の正極活物質層の厚さには、図３でプロットされている
５種類の値をそれぞれとった。The positive electrode active material layer is uniformly formed on both surfaces of the positive electrode current collector with a thickness of 45 to 125 μm, and has a sheet resistance of 20 Ω · cm. [Evaluation of Battery Characteristics of Each Nonaqueous Electrolyte Secondary Battery] From FIG.
In each of the nonaqueous electrolyte secondary batteries of the above examples, when the nonaqueous electrolyte secondary battery D of Comparative Example 1 and the positive electrode active material layer were compared with the same surface area, a high maximum discharge rate could be obtained. Understand. Therefore, in the nonaqueous electrolyte secondary battery of each of the above embodiments, it is possible to easily output a high current at a voltage of 3 V or more for at least 10 seconds. [Effect of Thickness of Positive Electrode Active Material Layer on Battery Characteristics] A battery of 18650 size was manufactured using electrodes having different thicknesses of the positive electrode active material layer. The capacity of this battery is about 1 Ah. Five values plotted in FIG. 3 were taken as the thickness of the positive electrode active material layer of each battery.
【００４６】これらの電池を用い、実施例１で最大電流
値を測定した方法と同じようにして各電池の最大電流値
を求めた。また、充電をＣＣ−ＣＶ、４．２Ｖの電圧、
並びに１Ｃの充電率で２．５時間行った後、０．２Ｃお
よび１０Ｃの放電率で３Ｖまで放電をおこなった。図３
に、各電池の正極活物質層の厚さと、最大放電率、およ
び１０Ｃでの容量との関係を示した。なお、１０Ｃでの
放電容量の値を０．２Ｃでの放電容量に対する比で示し
た。Using these batteries, the maximum current value of each battery was determined in the same manner as in the method of measuring the maximum current value in Example 1. In addition, charging is performed by CC-CV, a voltage of 4.2 V,
After 2.5 hours at a charge rate of 1 C, the battery was discharged to 3 V at a discharge rate of 0.2 C and 10 C. FIG.
2 shows the relationship between the thickness of the positive electrode active material layer of each battery, the maximum discharge rate, and the capacity at 10C. In addition, the value of the discharge capacity at 10C was shown as a ratio to the discharge capacity at 0.2C.
【００４７】図３より、正極活物質層の厚さが４０〜７
０μｍにある電池においては、最大放電率が１２Ｃ以上
となり、かつ、１０Ｃで放電させたときの容量が、０．
２Ｃの低電流を流した時の容量の５０％以上であること
がわかる。 ［正極活物質の二次粒子径の電池特性への影響］正極活
物質層に用いられている正極活物質の二次粒子径が異な
る他は、実施例１の非水電解質二次電池と同じ電池を作
製した。各電池の正極活物質の二次粒子径には、図４で
プロットされている４種類の値をそれぞれとった。FIG. 3 shows that the thickness of the positive electrode active material layer is 40 to 7
In the battery at 0 μm, the maximum discharge rate is 12 C or more, and the capacity when discharged at 10 C is 0.
It can be seen that the capacity is 50% or more of the capacity when a low current of 2C flows. [Effect of Secondary Particle Diameter of Positive Electrode Active Material on Battery Characteristics] Same as the nonaqueous electrolyte secondary battery of Example 1 except that the secondary particle diameter of the positive electrode active material used in the positive electrode active material layer is different. A battery was manufactured. Four types of values plotted in FIG. 4 were taken as the secondary particle diameter of the positive electrode active material of each battery.
【００４８】これらの電池を用い、実施例１で最大電流
値を測定した方法と同じようにして各電池の最大電流値
を測定し、最大放電率を求めた。図４にその結果を示
す。この図より、正極活物質層に用いられている正極活
物質の二次粒子径が１〜１９μｍにある電池において
は、１２Ｃ以上の最大放電率が得られることがわかる。 ［正極活物質層の空隙率の電池特性への影響］正極活物
質層の空隙率が異なる他は、実施例１の非水電解質二次
電池と同じ電池を作製した。各電池の正極活物質層の空
隙率には、図５でプロットされている４種類の値をそれ
ぞれとった。Using these batteries, the maximum current value of each battery was measured in the same manner as the method of measuring the maximum current value in Example 1, and the maximum discharge rate was obtained. FIG. 4 shows the result. From this figure, it is understood that the maximum discharge rate of 12 C or more is obtained in a battery in which the secondary particle diameter of the positive electrode active material used in the positive electrode active material layer is 1 to 19 μm. [Effect of Porosity of Positive Electrode Active Material Layer on Battery Characteristics] The same battery as the nonaqueous electrolyte secondary battery of Example 1 was produced except that the porosity of the positive electrode active material layer was different. As the porosity of the positive electrode active material layer of each battery, four values plotted in FIG. 5 were respectively taken.
【００４９】充電をＣＣ−ＣＶ、４．２Ｖの電圧、並び
に１Ｃの充電率で２．５時間行った後、０．２Ｃおよび
１０Ｃの放電率で３Ｖまで放電をおこなった。図５に、
各電池の正極活物質層の空隙率と、１０Ｃでの放電容量
比との関係を示した。図５より、正極活物質層の空隙率
が２８〜３８％にある電池においては、１０Ｃで放電さ
せたときの容量が、０．２Ｃの低電流を流した時の容量
の５０％以上であることがわかる。 ［正極活物質層のシート抵抗による電池特性への影響］
正極活物質層のシート抵抗が異なる他は、実施例１の非
水電解質二次電池と同じ電池を作製した。各電池の正極
活物質層のシート抵抗には、図６でプロットされている
５種類の値をそれぞれとった。After charging was performed for 2.5 hours at a CC-CV voltage of 4.2 V and a charging rate of 1 C, the battery was discharged to 3 V at a discharging rate of 0.2 C and 10 C. In FIG.
The relationship between the porosity of the positive electrode active material layer of each battery and the discharge capacity ratio at 10 C is shown. From FIG. 5, in the battery in which the porosity of the positive electrode active material layer is 28 to 38%, the capacity when discharged at 10 C is 50% or more of the capacity when a low current of 0.2 C flows. You can see that. [Effect of battery resistance due to sheet resistance of positive electrode active material layer]
The same battery as the nonaqueous electrolyte secondary battery of Example 1 was produced except that the sheet resistance of the positive electrode active material layer was different. As the sheet resistance of the positive electrode active material layer of each battery, five values plotted in FIG. 6 were respectively taken.
【００５０】これらの電池を用い、実施例１で最大電流
値を測定した方法と同じようにして各電池の最大電流値
を測定し、最大放電率を求めた。図６にその結果を示
す。この図より、正極活物質層のシート抵抗が２０Ω・
ｃｍ以下にある電池で、１２Ｃ以上の最大放電率が得ら
れることがわかる。 ［正極活物質と負極活物質との重量比の電池特性への影
響］正極活物質と負極活物質との重量比（Ｌｉ1.05Ｍｎ
1.95Ｏ4粉末の重量／ＭＣＭＢ粉末の重量）が異なる他
は、実施例１の非水電解質二次電池と同じ電池を６種類
作製した。各電池の正極活物質と負極活物質との重量比
には、図７でプロットされている６種類の値をそれぞれ
とった。Using these batteries, the maximum current value of each battery was measured in the same manner as in the method of measuring the maximum current value in Example 1, and the maximum discharge rate was obtained. FIG. 6 shows the result. According to this figure, the sheet resistance of the positive electrode active material layer is 20 Ω ·
It is understood that a battery having a maximum discharge rate of 12 C or more can be obtained with a battery having a size of 12 cm or less. [Effect of Weight Ratio of Positive Electrode Active Material and Negative Electrode Active Material on Battery Characteristics] Weight ratio of positive electrode active material and negative electrode active material (Li 1.05 Mn
Except for the difference of 1.95 O 4 powder weight / MCMB powder weight), six types of the same batteries as the non-aqueous electrolyte secondary battery of Example 1 were produced. The weight ratio between the positive electrode active material and the negative electrode active material of each battery was set to the six values plotted in FIG.
【００５１】これらの電池を用い、実施例１で最大電流
値を測定した方法と同じようにして各電池の最大電流値
を測定し、最大放電率を求めた。図７にその結果を示
す。この図より、正極活物質と負極活物質との重量比が
１．８〜２．９にある電池で、１２Ｃ以上の最大放電率
が得られることがわかる。なお、このときの充電容量は
１８０〜３３０ｍＡｈ／ｇであった。 （実施例４−１）本実施例では、本発明の非水電解質二
次電池の負荷特性と高温でのサイクル特性とをさらに向
上させるために、前記正極活物質を構成するリチウムマ
ンガン酸化物について、以下のようにマンガンをリチウ
ムで置換することを検討した。Using these batteries, the maximum current value of each battery was measured in the same manner as the method of measuring the maximum current value in Example 1, and the maximum discharge rate was obtained. FIG. 7 shows the result. This figure shows that a battery having a weight ratio of the positive electrode active material to the negative electrode active material of 1.8 to 2.9 can obtain a maximum discharge rate of 12 C or more. The charging capacity at this time was 180 to 330 mAh / g. (Example 4-1) In this example, in order to further improve the load characteristics and the high-temperature cycle characteristics of the nonaqueous electrolyte secondary battery of the present invention, a lithium manganese oxide constituting the positive electrode active material was used. The inventors considered replacing manganese with lithium as described below.
【００５２】先ず、Ｌｉの原料としてＬｉＯＨ・Ｈ2 Ｏ
を用意し、Ｍｎの原料として酢酸Ｍｎを用意した。さら
に、ＬｉとＭｎとを架橋するためにクエン酸を用意し
た。これら各材料を、Ｌｉ及びＭｎのモル比で見た仕込
の組成比（Ｌｉ／Ｍｎ）が１．１／１．９となるように
秤量して純水中に溶解させることにより、Ｌｉ及びＭｎ
を含む水溶液を得た。なお、この水溶液の調製では、Ｌ
ｉの濃度が０．８０ｍｏｌ／Ｌとなり、Ｍｎの濃度が
１．３８ｍｏｌ／Ｌとなり、またクエン酸の濃度が１．
１９ｍｏｌ／Ｌとなるようにした。First, LiOH.H 2 O is used as a raw material for Li.
Was prepared, and Mn acetate was prepared as a raw material of Mn. Further, citric acid was prepared for crosslinking Li and Mn. Li and Mn are weighed and dissolved in pure water so that the composition ratio (Li / Mn) of the charged raw materials in terms of the molar ratio of Li and Mn is 1.1 / 1.9.
Was obtained. In the preparation of this aqueous solution, L
The concentration of i was 0.80 mol / L, the concentration of Mn was 1.38 mol / L, and the concentration of citric acid was 1.
It was adjusted to 19 mol / L.
【００５３】こうして得られた水溶液を５００Ｐａ程度
の減圧下において、１２０℃で加熱して水及び酢酸を蒸
発させ、ＬｉとＭｎとがクエン酸により架橋された乾燥
物を得た。次いで、この乾燥物を４００℃で４時間予備
焼成を行った後、８００〜９５０℃の焼成温度で焼成を
行って、リチウムマンガン酸化物を合成した。その結
果、比表面積が０．３〜１．２ｍ2 ／ｇの範囲にあっ
て、かつ２次粒子径が５〜１５μｍの範囲にある正極活
物質が得られた。この正極活物質について、ＩＣＰ分析
により組成を調べた結果、リチウムとマンガンの含有比
率（Ｌｉ／Ｍｎ）が１．１／１．９であることが分かっ
た。この含有比率は、出発原料の組成と良く一致してい
る。これらの正極活物質の電池特性を比較するために、
次のように正極を作製した。The aqueous solution thus obtained was heated at 120 ° C. under a reduced pressure of about 500 Pa to evaporate water and acetic acid to obtain a dried product in which Li and Mn were crosslinked with citric acid. Next, this dried product was pre-baked at 400 ° C. for 4 hours, and then fired at a firing temperature of 800 to 950 ° C. to synthesize lithium manganese oxide. As a result, a positive electrode active material having a specific surface area of 0.3 to 1.2 m 2 / g and a secondary particle diameter of 5 to 15 μm was obtained. As a result of examining the composition of this positive electrode active material by ICP analysis, it was found that the content ratio of lithium and manganese (Li / Mn) was 1.1 / 1.9. This content ratio is in good agreement with the composition of the starting material. To compare the battery characteristics of these positive electrode active materials,
A positive electrode was produced as follows.
【００５４】先ず、正極活物質と、導電剤であるグラフ
ァイト粉と、結着剤であるＰＶＤＦとを８６：１０：４
の重量比で混合した後、適量のＮＭＰを加えて混練し、
スラリー状の正極合剤を得た。次いで、正極集電体とし
てＡｌ箔上を用意し、この正極集電体上に正極合剤を一
様な厚さで塗布して、正極活物質層を形成した。この正
極活物質層をロールプレスによって圧縮を行い、正極を
完成した。なお、この正極の作製では、正極活物質層の
密度が２．８５ｇ／ｃｍ3 なるように正極合剤の塗布量
を調整した。First, a positive electrode active material, graphite powder as a conductive agent, and PVDF as a binder were mixed at 86: 10: 4.
After mixing at a weight ratio of, an appropriate amount of NMP is added and kneaded,
A slurry-like positive electrode mixture was obtained. Next, an Al foil was prepared as a positive electrode current collector, and a positive electrode mixture was applied on the positive electrode current collector in a uniform thickness to form a positive electrode active material layer. This positive electrode active material layer was compressed by a roll press to complete a positive electrode. In the production of the positive electrode, the amount of the positive electrode mixture applied was adjusted such that the density of the positive electrode active material layer was 2.85 g / cm 3 .
【００５５】この正極の作製方法により、正極活物質層
の厚さが５５μｍ、６５μｍ及び７５μｍの正極をそれ
ぞれ３種類作製した。一方、負極については、次のよう
にして作製した。先ず、負極活物質である天然黒鉛と、
結着剤であるＰＶＤＦとを９２．５：７．５の重量比で
混合した後、適量のＮＭＰを加えて混練し、スラリー状
の負極合剤を得た。次いで、負極集電体としてＣｕ箔を
用意し、この負極集電体上に負極合剤を塗布して、負極
活物質層を形成した。この負極活物質層をロールプレス
によって圧縮を行い、電極を完成した。なお、この負極
の作製では、正極活物質と負極活物質との電極表面に対
する単位面積当たりの重量比が、２４：１０となるよう
に負極合剤の塗布量を調整した。According to this method of producing a positive electrode, three types of positive electrodes having a positive electrode active material layer thickness of 55 μm, 65 μm and 75 μm were produced. On the other hand, the negative electrode was manufactured as follows. First, natural graphite which is a negative electrode active material,
After mixing with PVDF as a binder at a weight ratio of 92.5: 7.5, an appropriate amount of NMP was added and kneaded to obtain a slurry-like negative electrode mixture. Next, a Cu foil was prepared as a negative electrode current collector, and a negative electrode mixture was applied on the negative electrode current collector to form a negative electrode active material layer. This negative electrode active material layer was compressed by a roll press to complete an electrode. In the preparation of the negative electrode, the application amount of the negative electrode mixture was adjusted such that the weight ratio of the positive electrode active material and the negative electrode active material per unit area to the electrode surface was 24:10.
【００５６】セパレータには、２５μｍのポリエチレン
製の微孔フィルムを用意した。また、非水電解液には、
エチレンカーボネートとジメトキシエタンとを同じ体積
比率で混合して得た有機溶媒に、ＬｉＰＦ6 を１Ｍ溶解
して調製したものを用意した。以上の正極、負極及びセ
パレータを、正極と負極の間にセパレータが挟まれるよ
うに互いに重ね合わせて巻回して巻回電極体を形成し
た。この巻回電極体を電池缶（サイズ；φ１８ｍｍ、高
さ６５ｍｍ）に挿入した後、非水電解液を電池缶に注ぎ
入れ、巻回電極体を非水電解液に浸し、最後に正極端子
を備えた蓋部を取り付けて、図１に示したようなスパイ
ラル状の円筒型非水電解質二次電池Ａを完成した。As the separator, a 25 μm polyethylene microporous film was prepared. In addition, non-aqueous electrolytes include
One prepared by dissolving 1 M of LiPF 6 in an organic solvent obtained by mixing ethylene carbonate and dimethoxyethane at the same volume ratio was prepared. The above-mentioned positive electrode, negative electrode and separator were wound on top of each other so that the separator was sandwiched between the positive electrode and the negative electrode to form a wound electrode body. After inserting this wound electrode body into a battery can (size: φ18 mm, height 65 mm), a non-aqueous electrolyte is poured into the battery can, and the wound electrode body is immersed in the non-aqueous electrolyte. By attaching the provided lid, a spiral cylindrical non-aqueous electrolyte secondary battery A as shown in FIG. 1 was completed.
【００５７】こうして正極の正極活物質層の厚さが異な
る３種類の非水電解質二次電池を作製した。なお、これ
ら非水電解質二次電池の各正極の表面積は、電極の膜厚
によりそれぞれ７５６ｃｍ2、６７５ｃｍ2 、５４０ｃ
ｍ2 となった。これらの非水電解質二次電池の負荷特性
を、次の条件で充放電試験を行って評価した。この充放
電試験では、ＣＣ−ＣＶ、４．２Ｖの電圧でかつ１Ｃの
充電率で充電を２．５時間行った後、０．５Ｃ及び１０
Ｃの各放電率で定電流でそれぞれ３Ｖまで放電を行っ
た。Thus, three types of nonaqueous electrolyte secondary batteries having different thicknesses of the positive electrode active material layer of the positive electrode were manufactured. The surface area of each positive electrode of these nonaqueous electrolyte secondary batteries was 756 cm 2 , 675 cm 2 , 540 c
It became m 2. The load characteristics of these nonaqueous electrolyte secondary batteries were evaluated by performing a charge / discharge test under the following conditions. In this charge / discharge test, after charging was performed for 2.5 hours at a CC-CV, a voltage of 4.2 V and a charging rate of 1 C, 0.5 C and 10 C
The discharge was performed at a constant current to 3 V at each discharge rate of C.
【００５８】上記で作製された各電池について、上記各
条件で充放電を行ったときの放電容量をそれぞれ測定し
た。その測定結果を表１に示す。なお、表１には、１０
Ｃの放電率で放電を行ったときの放電容量（以下、１０
Ｃ放電容量と称する）と、０．５Ｃの放電率で放電を行
ったときの放電容量（以下、０．５Ｃ放電容量と称す
る）との放電容量比（１０Ｃ放電容量／０．５Ｃ放電容
量）を示した。With respect to each of the batteries produced as described above, the discharge capacity when charging and discharging were performed under the above-described conditions was measured. Table 1 shows the measurement results. In Table 1, 10
Discharge capacity when discharging at a discharge rate of C (hereinafter, 10
C discharge capacity) and the discharge capacity when discharging at a discharge rate of 0.5 C (hereinafter referred to as 0.5 C discharge capacity) (10 C discharge capacity / 0.5 C discharge capacity). showed that.
【００５９】表１より、正極の正極活物質層の厚さが７
５μｍの電池（Ｎｏ．１〜Ｎｏ．３）では、正極活物質
の比表面積が１．２ｍ2 ／ｇ以下になると、１０Ｃ放電
容量が、０．５Ｃ放電容量の６０％程度より低くなって
しまうことがわかる。特に、正極活物質の比表面積が
０．８ｍ2 ／ｇより小さくなると、１０Ｃ放電容量が、
０．５Ｃ放電容量の５０％以下に低下してしまうことが
わかる。As shown in Table 1, the thickness of the positive electrode active material layer of the positive electrode was 7
In a 5 μm battery (No. 1 to No. 3), when the specific surface area of the positive electrode active material becomes 1.2 m 2 / g or less, the 10 C discharge capacity becomes lower than about 60% of the 0.5 C discharge capacity. You can see that. In particular, when the specific surface area of the positive electrode active material becomes smaller than 0.8 m 2 / g, the 10 C discharge capacity becomes
It can be seen that the discharge capacity is reduced to 50% or less of the 0.5 C discharge capacity.
【００６０】それに対し、正極活物質層の厚さが６５μ
ｍの電池（Ｎｏ．４）では、正極活物質の比表面積が
０．３ｍ2 ／ｇ以上にあれば、１０Ｃ放電容量が０．５
Ｃ放電容量の８０％よりも大きいことがわかる。特に、
正極活物質層の厚さが５５μｍの電池（Ｎｏ．５〜Ｎ
ｏ．９）では、正極活物質の比表面積が０．３ｍ2 ／ｇ
以上にあれば、１０Ｃ放電容量が０．５Ｃ放電容量の９
０％以上にあることがわかる。On the other hand, the thickness of the positive electrode active material layer was 65 μm.
m battery (No. 4), if the specific surface area of the positive electrode active material is 0.3 m 2 / g or more, the 10 C discharge capacity is 0.5
It turns out that it is larger than 80% of C discharge capacity. In particular,
Batteries having a positive electrode active material layer thickness of 55 μm (Nos.
o. In 9), the specific surface area of the positive electrode active material is 0.3 m 2 / g.
If it is above, 10C discharge capacity is 9 of 0.5C discharge capacity.
It turns out that it is 0% or more.
【００６１】これらの結果から、正極活物質層の厚さを
４０〜７０μｍにする場合、比表面積が０．３ｍ2 ／ｇ
以上の正極活物質を用いれば、高負荷での放電容量が大
きくなり、負荷特性に優れる非水電解質二次電池が得ら
れることがわかる。一方、正極の正極活物質層の厚さが
５５μｍの電池（Ｎｏ．５〜Ｎｏ．９）について、それ
らの電池の高温でのサイクル特性を、次の条件でそれぞ
れ充放電試験を行って評価した。From these results, when the thickness of the positive electrode active material layer is 40 to 70 μm, the specific surface area is 0.3 m 2 / g.
It can be seen that the use of the above positive electrode active material increases the discharge capacity under a high load, and provides a nonaqueous electrolyte secondary battery having excellent load characteristics. On the other hand, for batteries (No. 5 to No. 9) in which the thickness of the positive electrode active material layer of the positive electrode was 55 μm, the high-temperature cycle characteristics of the batteries were evaluated by performing charge / discharge tests under the following conditions. .
【００６２】この充放電試験では、６０℃の恒温槽内
で、正極面積当たり１．１ｍＡ／ｃｍ 2 の定電流で４．
２Ｖまで充電を行った後、正極面積当たり１．１ｍＡ／
ｃｍ2の定電流で３Ｖまで放電を行った。この充放電を
１００サイクル行った。この充放電試験において、初期
サイクル（１回目）での放電容量（Ｃ1）と、１００サ
イクルでの放電容量（Ｃ100）とをそれぞれ測定した。
その測定結果を表１に併せて示す。なお、表１には、
｛Ｃ100／（Ｃ1×９９）｝×１００／１００サイクル
（％／サイクル）の値（劣化率）を示した。In this charge / discharge test, the inside of a 60 ° C.
1.1 mA / cm per positive electrode area TwoAt a constant current of 4.
After charging to 2 V, 1.1 mA /
cmTwoAt a constant current of 3 V. This charge and discharge
100 cycles were performed. In this charge / discharge test,
Discharge capacity (C) in the first cycle1) And 100
Discharge capacity at cycle (C100) Was measured.
Table 1 also shows the measurement results. In Table 1,
｛C100/ (C1× 99) Δ × 100/100 cycles
(% / Cycle) (deterioration rate).
【００６３】[0063]
【表１】 表１より、Ｎｏ．５〜Ｎｏ．９の各電池の劣化率を比較
すると、正極活物質の比表面積が低くなるにしたがって
劣化率が低下し、サイクル特性が向上していることがわ
かる。特に、正極活物質の比表面積が１．２ｍ2 ／ｇ以
下の電池（Ｎｏ．５〜Ｎｏ．８）では、比表面積が１．
４ｍ2 ／ｇの電池（Ｎｏ．９）よりも優れたサイクル特
性が得られることがわかる。[Table 1] From Table 1, No. 5-No. Comparing the deterioration rates of the batteries of No. 9 shows that the deterioration rate decreases as the specific surface area of the positive electrode active material decreases, and the cycle characteristics improve. In particular, in the batteries (No. 5 to No. 8) in which the specific surface area of the positive electrode active material is 1.2 m 2 / g or less, the specific surface area is 1.
It can be seen that cycle characteristics superior to the 4 m 2 / g battery (No. 9) were obtained.
【００６４】従って、正極活物質層の厚さを４０〜７０
μｍにする場合、正極活物質の比表面積を０．３〜１．
２ｍ2 ／ｇに限定することにより、非水電解質二次電池
の負荷特性及び高温でのサイクル特性を向上させること
が容易に可能なことがわかる。 （実施例４−２）実施例４−１の非水電解質二次電池で
は、ＬｉＭｎ2Ｏ4のスピネル構造において、ＬｉがＭｎ
の１６ｄ位置の一部に置換された構造を有していると考
えられる。そこで、そのリチウムの置換量と電池特性の
関係を評価するため、次のようにＬｉとＭｎの組成比が
異なるリチウムマンガン酸化物をそれぞれ合成して正極
活物質を調製した。Therefore, the thickness of the positive electrode active material layer is set to 40 to 70
When the thickness is set to μm, the specific surface area of the positive electrode active material is set to 0.3 to 1.
It can be seen that by limiting to 2 m 2 / g, it is possible to easily improve the load characteristics and the high-temperature cycle characteristics of the nonaqueous electrolyte secondary battery. (Example 4-2) In the nonaqueous electrolyte secondary battery of Example 4-1, in the spinel structure of LiMn 2 O 4 , Li was Mn.
Is considered to have a structure substituted at a part of the 16d position. Therefore, in order to evaluate the relationship between the lithium replacement amount and the battery characteristics, lithium manganese oxides having different composition ratios of Li and Mn were synthesized as follows to prepare a positive electrode active material.
【００６５】本実施例では、Ｌｉ及びＭｎのモル比で見
た各原料の仕込み組成比（Ｌｉ／Ｍｎ）が１．０５／
１．９５と、１．１５／１．８５となるように２種類の
前記水溶液をそれぞれ調製した他は、実施例４と同様に
して２種類の正極活物質を調製した。これらの正極活物
質の組成をＩＣＰ分析により組成を調べた結果、Ｌｉの
Ｍｎに対する組成比（Ｌｉ／Ｍｎ）が１．０５／１．８
５と、１．１５／１．８５とであることがわかり、原料
の仕込み組成と一致していることが分かった。また、そ
れらの正極活物質は、双方とも０．４ｍ2 ／ｇの比表面
積を有し、かつ１０μｍの２次粒子径を有することもわ
かった。In this example, the charged composition ratio (Li / Mn) of each raw material was 1.05 /
Two kinds of positive electrode active materials were prepared in the same manner as in Example 4, except that two kinds of the aqueous solutions were respectively prepared so as to be 1.95 and 1.15 / 1.85. As a result of examining the composition of these positive electrode active materials by ICP analysis, the composition ratio of Li to Mn (Li / Mn) was 1.05 / 1.8.
5 and 1.15 / 1.85, which was consistent with the charge composition of the raw materials. It was also found that both of these positive electrode active materials had a specific surface area of 0.4 m 2 / g and a secondary particle diameter of 10 μm.
【００６６】これら２種類の正極活物質を用い、実施例
４と同様にして、正極活物質層の厚さが５５μｍである
スパイラル状の円筒型非水電解質二次電池を２種類作製
した。これらの非水電解質二次電池について、実施例４
と同様に、６０℃の恒温槽内で充放電試験を行い、初期
サイクル（１回目）での放電容量（Ｃ1）と、１００サ
イクルでの放電容量（Ｃ100）とをそれぞれ測定した。
その測定結果を表１に併せて示す。Using these two types of positive electrode active materials, two types of spiral cylindrical nonaqueous electrolyte secondary batteries having a thickness of the positive electrode active material layer of 55 μm were produced in the same manner as in Example 4. Example 4 of these nonaqueous electrolyte secondary batteries
Similar to perform a charge and discharge test in a thermostat at 60 ° C., the discharge capacity in the initial cycle (1) and (C 1), discharge capacity at 100 cycles (C 100) and was measured.
Table 1 also shows the measurement results.
【００６７】表１において、Ｎｏ．６、Ｎｏ．１０及び
Ｎｏ．１１の各電池の劣化率を比較すると、同じ比表面
積の正極活物質を用いた電池においては、ＬｉのＭｎに
対する組成比（Ｌｉ／Ｍｎ）が増加するにしたがって劣
化率が低下し、高温でのサイクル特性が向上しているこ
とがわかる。特に、その組成比（Ｌｉ／Ｍｎ）が１．０
５／１．９５を超えた電池（Ｎｏ．６及びＮｏ．１１）
では、組成比（Ｌｉ／Ｍｎ）が１．０５／１．９５の電
池（Ｎｏ．１０）に比べて劣化率が低くなることがわか
る。In Table 1, no. 6, no. 10 and No. Comparing the deterioration rates of the batteries of No. 11, in the battery using the positive electrode active material having the same specific surface area, the deterioration rate decreases as the composition ratio of Li to Mn (Li / Mn) increases, It can be seen that the cycle characteristics have been improved. In particular, the composition ratio (Li / Mn) is 1.0
Batteries exceeding 5 / 1.95 (No. 6 and No. 11)
In this case, it can be seen that the deterioration ratio is lower than that of the battery (No. 10) having a composition ratio (Li / Mn) of 1.05 / 1.95.
【００６８】ＬｉのＭｎに対する組成比（Ｌｉ／Ｍｎ）
が１．０５／１．９５を超える非水電解質二次電池は、
その正極活物質の組成式をＬｉＭｎYＭｅZＯ(4±σ)で
表すと、ＭｅはＬｉであり、かつ（１＋Ｚ）／Ｙ＞１．
０５／１．９５を満たすものである。こうした条件を満
たす非水電解質二次電池では、極めて優れたサイクル特
性が得られることがわかる。 （実施例５）本発明の非水電解質二次電池の高温でのサ
イクル特性をさらに向上させるために、前記正極活物質
を構成するリチウムマンガン酸化物について、以下のよ
うにマンガンをリチウム以外の陽イオンになりうる元素
（以下、陽イオン元素と称する）で置換することを検討
した。Composition ratio of Li to Mn (Li / Mn)
Is greater than 1.05 / 1.95,
When the composition formula of the positive electrode active material is represented by LiMn Y Me Z O (4 ± σ ) , Me is Li and (1 + Z) / Y> 1.
It satisfies 05 / 1.95. It can be seen that in the nonaqueous electrolyte secondary battery satisfying these conditions, extremely excellent cycle characteristics can be obtained. Example 5 In order to further improve the high-temperature cycle characteristics of the nonaqueous electrolyte secondary battery of the present invention, the lithium manganese oxide constituting the positive electrode active material was changed to a positive electrode other than lithium as follows. Substitution with an element that can become an ion (hereinafter, referred to as a cation element) was studied.
【００６９】本実施例では、リチウムマンガン酸化物の
組成式をＬｉＭｎYＭｅZＯ(4±σ)で表すと、Ｍｅをリ
チウム及び陽イオン元素とし、かつＺ＝１（Ｌｉ）＋
０．５（陽イオン元素）とした。正極活物質の調製で
は、陽イオン元素としてＡｌ、Ｃｕ、Ｎｉ及びＣｏを用
い、各原料のＬｉ、Ｍｎ及び陽イオン元素で見た仕込み
組成比（Ｌｉ：Ｍｎ：陽イオン元素）が１．１：１．８
５：０．０５となるように前記水溶液をそれぞれ調製し
た他は、実施例４と同様にして、使用した陽イオン元素
が異なる４種類の正極活物質を調製した。これらの正極
活物質の組成をＩＣＰ分析により組成を調べた結果、い
ずれもＬｉとＭｎと陽イオン元素との組成比（Ｌｉ：Ｍ
ｎ：陽イオン元素）が１．１：０．０５：１．８５であ
ることがわかり、原料の仕込み組成と一致していること
が分かった。すなわち、Ｍｅは、Ｌｉと陽イオンとであ
って、その組成比Ｚは、Ｌｉの０．１と陽イオン元素の
０．０５を足し合わせたものである。In this embodiment, when the composition formula of the lithium manganese oxide is represented by LiMn Y Me Z O (4 ± σ ) , Me is lithium and a cation element, and Z = 1 (Li) +
0.5 (cationic element). In the preparation of the positive electrode active material, Al, Cu, Ni and Co were used as cation elements, and the charged composition ratio (Li: Mn: cation element) of Li, Mn and the cation element of each raw material was 1.1. : 1.8
Four kinds of positive electrode active materials having different cation elements were prepared in the same manner as in Example 4, except that the aqueous solutions were prepared so that the ratio became 5: 0.05. As a result of examining the composition of these positive electrode active materials by ICP analysis, the composition ratio of Li, Mn, and the cation element (Li: M
(n: cation element) was found to be 1.1: 0.05: 1.85, which was consistent with the charged composition of the raw materials. That is, Me is Li and a cation, and the composition ratio Z is the sum of 0.1 of Li and 0.05 of the cation element.
【００７０】また、これらの正極活物質は、いずれも
０．４ｍ2 ／ｇの比表面積を有し、かつ１０μｍの２次
粒子径を有することもわかった。これらの正極活物質を
用い、実施例４と同様にして、正極活物質層の厚さが５
５μｍであるスパイラル状の円筒型非水電解質二次電池
を４種類作製した。これらの非水電解質二次電池につい
て、実施例４と同様に、６０℃の恒温槽内で充放電試験
を行い、初期サイクル（１回目）での放電容量（Ｃ1）
と、１００サイクルでの放電容量（Ｃ100）とをそれぞ
れ測定した。その測定結果を表２に示す。It was also found that each of these positive electrode active materials had a specific surface area of 0.4 m 2 / g and a secondary particle diameter of 10 μm. Using these cathode active materials, the thickness of the cathode active material layer was 5 in the same manner as in Example 4.
Four types of 5 μm spiral cylindrical non-aqueous electrolyte secondary batteries were produced. For these non-aqueous electrolyte secondary batteries, a charge / discharge test was performed in a thermostat at 60 ° C. in the same manner as in Example 4, and the discharge capacity (C 1 ) in the initial cycle (first time) was measured.
And the discharge capacity (C 100 ) at 100 cycles were measured. Table 2 shows the measurement results.
【００７１】[0071]
【表２】 表２より、Ｎｏ．１２〜Ｎｏ．１５の各電池では、４０
％未満の低い劣化率が得られていることがわかる。従っ
て、陽イオンを添加することにより劣化率が低下し、高
温でのサイクル特性が向上していることがわかる。この
ように高温での特性が向上したのは、正極活物質の調製
においてＡｌ、Ｃｕ、Ｎｉ及びＣｏを添加したことによ
り、ＭｎとＯとの結合が強いリチウムマンガン酸化物が
合成されたことが考えられる。Ａｌ、Ｃｕ、Ｎｉ及びＣ
ｏは、いずれもIIＡからIIIＢ属の元素である。[Table 2] From Table 2, No. 12-No. For each of the 15 batteries, 40
It can be seen that a low deterioration rate of less than 10% is obtained. Therefore, it can be seen that the rate of deterioration is reduced by adding a cation, and the cycle characteristics at high temperatures are improved. The reason why the characteristics at high temperatures have been improved is that the addition of Al, Cu, Ni and Co in the preparation of the positive electrode active material resulted in the synthesis of a lithium manganese oxide having a strong bond between Mn and O. Conceivable. Al, Cu, Ni and C
o is an element belonging to any of IIA to IIIB.
【００７２】また、Ｎｏ．１２〜Ｎｏ．１５の各電池の
劣化率を比較すると、Ｎｏ．１３〜Ｎｏ．１５の各電池
では、３０％程度又はそれより低い劣化率が得られるこ
とがわかる。この結果より、Ｌｉ、Ａｌ、Ｎｉ、Ｃｏを
添加した正極活物質を用いることにより、さらに低い劣
化率が得られ、高温でのサイクル特性が特に向上するこ
とがわかる。In addition, No. 12-No. Comparing the deterioration rate of each battery of No. 15, 13-No. It can be seen that in each of the 15 batteries, a deterioration rate of about 30% or lower can be obtained. From these results, it can be seen that the use of the positive electrode active material to which Li, Al, Ni, and Co are added achieves a further lower deterioration rate and particularly improves the cycle characteristics at high temperatures.
【図１】 実施例１の非水電解質二次電池を概略的に示
す要部断面図である。FIG. 1 is a cross-sectional view schematically illustrating a main part of a nonaqueous electrolyte secondary battery according to a first embodiment.
【図２】 実施例１〜３及び比較例１の各非水電解質二
次電池において、正極活物質層の１Ａｈ当たりの表面積
と最大放電率Ｒmaxとの関係をそれぞれ示すグラフであ
る。FIG. 2 is a graph showing a relationship between a surface area per 1 Ah of a positive electrode active material layer and a maximum discharge rate R max in each of the nonaqueous electrolyte secondary batteries of Examples 1 to 3 and Comparative Example 1.
【図３】 本実施例の非水電解質二次電池において、正
極活物質層の厚さと、最大電流値、および１０Ｃでの容
量との関係を示すグラフである。FIG. 3 is a graph showing the relationship between the thickness of a positive electrode active material layer, the maximum current value, and the capacity at 10 C in the nonaqueous electrolyte secondary battery of the present example.
【図４】 本実施例の非水電解質二次電池において、正
極活物質の二次粒子径と最大放電率との関係を示すグラ
フである。FIG. 4 is a graph showing the relationship between the secondary particle diameter of the positive electrode active material and the maximum discharge rate in the nonaqueous electrolyte secondary battery of this example.
【図５】 本実施例の非水電解質二次電池において、正
極活物質層の空隙率と、１０Ｃでの放電容量比との関係
を示すグラフである。FIG. 5 is a graph showing the relationship between the porosity of the positive electrode active material layer and the discharge capacity ratio at 10 C in the nonaqueous electrolyte secondary battery of this example.
【図６】 本実施例の非水電解質二次電池において、正
極活物質層のシート抵抗と最大放電率との関係を示すグ
ラフである。FIG. 6 is a graph showing the relationship between the sheet resistance of the positive electrode active material layer and the maximum discharge rate in the non-aqueous electrolyte secondary battery of this example.
【図７】 本実施例の非水電解質二次電池において、正
極活物質と負極活物質との重量比と最大放電率との関係
を示すグラフである。FIG. 7 is a graph showing the relationship between the weight ratio of the positive electrode active material and the negative electrode active material and the maximum discharge rate in the non-aqueous electrolyte secondary battery of this example.
１０：正極 １０ａ：集電体 １０ｂ：正極活物質層 ２０：負極 ３０：非水電解液 10: positive electrode 10a: current collector 10b: positive electrode active material layer 20: negative electrode 30: non-aqueous electrolyte
フロントページの続き (72)発明者 大木島 俊 愛知県刈谷市昭和町１丁目１番地 株式会 社デンソー内 (72)発明者 小島 久尚 愛知県刈谷市昭和町１丁目１番地 株式会 社デンソー内Continued on the front page (72) Inventor Shun Okishima 1-1-1, Showa-cho, Kariya-shi, Aichi Prefecture Inside Denso Corporation (72) Inventor Hisao Kojima 1-1-1, Showa-cho, Kariya City, Aichi Prefecture Inside Denso Corporation
Claims (12)
され、リチウムイオンを放出できる正極活物質より主と
してなる正極活物質層とから構成されている正極と、該
正極から放出された該リチウムイオンを吸蔵および放出
できる負極活物質より構成されている負極と、該正極と
該負極との間で該リチウムイオンを移動させる非水電解
質とを備え、該正極及び該負極の端子間に少なくとも３
Ｖの電圧を生じさせることのできる非水電解質二次電池
において、 放電容量の３０％を充電した後に、放電を開始してから
少なくとも１０秒後の該電圧が３Ｖとなるように定電流
で放電させたときの放電率を最大放電率（Ｒma x；単位
Ｃ）とすると、前記正極活物質層の電池容量１Ａｈ当た
りの表面積が２０Ｒmax〜７５Ｒmax（単位ｃｍ2）にあ
ることを特徴とする非水電解質二次電池。1. A positive electrode comprising a sheet-shaped current collector, a positive electrode active material layer formed on the current collector and mainly composed of a positive electrode active material capable of releasing lithium ions, and a positive electrode formed from the positive electrode. A negative electrode composed of a negative electrode active material capable of inserting and extracting the lithium ions, and a non-aqueous electrolyte for moving the lithium ions between the positive electrode and the negative electrode; and terminals of the positive electrode and the negative electrode. At least 3 in between
In a non-aqueous electrolyte secondary battery capable of generating a voltage of V, after charging 30% of the discharge capacity, the battery is discharged at a constant current such that the voltage becomes 3 V at least 10 seconds after the start of discharge. maximum discharge rate discharge rate obtained while; when (R ma x units C), and characterized in that the surface area per battery capacity 1Ah of the positive electrode active material layer is in the 20R max ~75R max (unit cm 2) Non-aqueous electrolyte secondary battery.
項１に記載の非水電解質二次電池。2. The non-aqueous electrolyte secondary battery according to claim 1, wherein the maximum discharge rate is 12 C or more.
厚さを有する請求項１に記載の非水電解質二次電池。3. The non-aqueous electrolyte secondary battery according to claim 1, wherein the positive electrode active material layer has a thickness of 40 to 70 μm.
粒子径を有する請求項１に記載の非水電解質二次電池。4. The non-aqueous electrolyte secondary battery according to claim 1, wherein the positive electrode active material has a secondary particle size of 1 to 19 μm.
隙率を有する請求項１に記載の非水電解質二次電池。5. The non-aqueous electrolyte secondary battery according to claim 1, wherein the positive electrode active material layer has a porosity of 28 to 38%.
のシート抵抗を有する請求項１に記載の非水電解質二次
電池。6. The non-aqueous electrolyte secondary battery according to claim 1, wherein the positive electrode active material layer has a sheet resistance of 20 Ω · cm or less.
て８〜１６ｍｇ／ｃｍ2の重量密度を有する請求項１に
記載の非水電解質二次電池。7. The non-aqueous electrolyte secondary battery according to claim 1, wherein the positive electrode active material layer has a weight density of 8 to 16 mg / cm 2 with respect to the surface area.
量比が１．８〜２．９にある請求項１に記載の非水電解
質二次電池。8. The non-aqueous electrolyte secondary battery according to claim 1, wherein a weight ratio between the positive electrode active material and the negative electrode active material is in a range from 1.8 to 2.9.
／ｇの比表面積を有する請求項３に記載の非水電解質二
次電池。9. The positive electrode active material is 0.3 to 1.2 m 2.
The non-aqueous electrolyte secondary battery according to claim 3, which has a specific surface area of / g.
(4±σ)（ＭｅはＭｎ以外の陽イオンになりうる元素）
の組成式で表され、かつ（１＋Ｚ）／Ｙ＞１．０５／
１．９５を満たす請求項１〜８のいずれかに記載の非水
電解質二次電池。Wherein said positive active material, LiMn Y Me Z O
(4 ± σ ) (Me is an element other than Mn that can be a cation)
And (1 + Z) / Y> 1.05 /
The nonaqueous electrolyte secondary battery according to claim 1, which satisfies 1.95.
属の元素との少なくとも一種である請求項１０に記載の
非水電解質二次電池。11. The method according to claim 11, wherein Me is Li and IIA to IIIB.
The nonaqueous electrolyte secondary battery according to claim 10, wherein the nonaqueous electrolyte secondary battery is at least one element selected from the group consisting of a genus element.
ｏの少なくとも１種である請求項１１に記載の非水電解
質二次電池。12. The method according to claim 1, wherein the Me is Li, Al, Ni and C.
The non-aqueous electrolyte secondary battery according to claim 11, which is at least one of o.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07409699A JP4662089B2 (en) | 1998-07-14 | 1999-03-18 | Nonaqueous electrolyte secondary battery |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10-198256 | 1998-07-14 | ||
| JP19825698 | 1998-07-14 | ||
| JP07409699A JP4662089B2 (en) | 1998-07-14 | 1999-03-18 | Nonaqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000090982A true JP2000090982A (en) | 2000-03-31 |
| JP4662089B2 JP4662089B2 (en) | 2011-03-30 |
Family
ID=26415230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07409699A Expired - Lifetime JP4662089B2 (en) | 1998-07-14 | 1999-03-18 | Nonaqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4662089B2 (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001023614A (en) * | 1999-07-09 | 2001-01-26 | Sony Corp | Positive electrode and secondary battery using it |
| JP2001110456A (en) * | 1999-10-14 | 2001-04-20 | Ngk Insulators Ltd | Lithium secondary battery and manufacturing method for wound-type electrode body |
| WO2001078168A1 (en) * | 2000-04-11 | 2001-10-18 | Japan Energy Corporation | Positive electrode material for lithium secondary cell and lithium secondary cell using the same |
| JP2002203556A (en) * | 2000-12-28 | 2002-07-19 | Sony Corp | Non-aqueous electrolyte secondary battery |
| JP2003115326A (en) * | 2001-10-03 | 2003-04-18 | Japan Storage Battery Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2005243448A (en) * | 2004-02-26 | 2005-09-08 | Japan Storage Battery Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2007042525A (en) * | 2005-08-05 | 2007-02-15 | Hitachi Vehicle Energy Ltd | Lithium ion battery |
| JP2009123715A (en) * | 2007-06-28 | 2009-06-04 | Hitachi Maxell Ltd | Lithium ion secondary battery |
| JP2010073420A (en) * | 2008-09-17 | 2010-04-02 | Nissan Motor Co Ltd | Non-aqueous electrolyte secondary battery |
| WO2011036759A1 (en) * | 2009-09-25 | 2011-03-31 | トヨタ自動車株式会社 | Lithium secondary battery and process for producing same |
| JP2011070932A (en) * | 2009-09-25 | 2011-04-07 | Toyota Motor Corp | Lithium secondary battery |
| WO2012049777A1 (en) * | 2010-10-15 | 2012-04-19 | トヨタ自動車株式会社 | Secondary battery |
| US8298707B2 (en) | 2000-12-28 | 2012-10-30 | Sony Corporation | Positive active material and nonaqueous electrolyte secondary battery |
| JP2013251281A (en) * | 2013-09-19 | 2013-12-12 | Toyota Motor Corp | Lithium secondary battery, and method for manufacturing the same |
| WO2014084680A1 (en) * | 2012-11-29 | 2014-06-05 | 주식회사 엘지화학 | Apparatus and method for estimating output of secondary battery comprising blended positive electrode material |
| JP2015215947A (en) * | 2014-05-07 | 2015-12-03 | 株式会社カネカ | Electrode for nonaqueous electrolyte secondary batteries and nonaqueous electrolyte secondary battery |
| JPWO2014142066A1 (en) * | 2013-03-15 | 2017-02-16 | 株式会社東芝 | Battery electrode material and battery substrate, storage battery, dye-sensitized solar cell, capacitor, Li ion secondary battery using the same |
| JP2019057426A (en) * | 2017-09-21 | 2019-04-11 | オートモーティブエナジーサプライ株式会社 | Lithium ion secondary battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0817471A (en) * | 1994-06-28 | 1996-01-19 | Haibaru:Kk | Non-aqueous electrolytic secondary battery |
| JPH0869790A (en) * | 1994-08-31 | 1996-03-12 | Sony Corp | Nonaqueous electrolyte secondary battery |
| JPH09147859A (en) * | 1995-11-27 | 1997-06-06 | Nec Corp | Positive electrode active material for organic electrolyte secondary battery, its preparation and organic electrolyte secondary battery |
| JPH09330701A (en) * | 1996-06-06 | 1997-12-22 | Sony Corp | Nonaqueous electrolyte secondary battery |
| JPH1092429A (en) * | 1996-09-13 | 1998-04-10 | Toshiba Corp | Manufacture of non-aqueous solvent secondary battery and non-aqueous solvent secondary battery |
-
1999
- 1999-03-18 JP JP07409699A patent/JP4662089B2/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0817471A (en) * | 1994-06-28 | 1996-01-19 | Haibaru:Kk | Non-aqueous electrolytic secondary battery |
| JPH0869790A (en) * | 1994-08-31 | 1996-03-12 | Sony Corp | Nonaqueous electrolyte secondary battery |
| JPH09147859A (en) * | 1995-11-27 | 1997-06-06 | Nec Corp | Positive electrode active material for organic electrolyte secondary battery, its preparation and organic electrolyte secondary battery |
| JPH09330701A (en) * | 1996-06-06 | 1997-12-22 | Sony Corp | Nonaqueous electrolyte secondary battery |
| JPH1092429A (en) * | 1996-09-13 | 1998-04-10 | Toshiba Corp | Manufacture of non-aqueous solvent secondary battery and non-aqueous solvent secondary battery |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001023614A (en) * | 1999-07-09 | 2001-01-26 | Sony Corp | Positive electrode and secondary battery using it |
| JP2001110456A (en) * | 1999-10-14 | 2001-04-20 | Ngk Insulators Ltd | Lithium secondary battery and manufacturing method for wound-type electrode body |
| WO2001078168A1 (en) * | 2000-04-11 | 2001-10-18 | Japan Energy Corporation | Positive electrode material for lithium secondary cell and lithium secondary cell using the same |
| JP2002203556A (en) * | 2000-12-28 | 2002-07-19 | Sony Corp | Non-aqueous electrolyte secondary battery |
| US8298707B2 (en) | 2000-12-28 | 2012-10-30 | Sony Corporation | Positive active material and nonaqueous electrolyte secondary battery |
| JP2003115326A (en) * | 2001-10-03 | 2003-04-18 | Japan Storage Battery Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2005243448A (en) * | 2004-02-26 | 2005-09-08 | Japan Storage Battery Co Ltd | Nonaqueous electrolyte secondary battery |
| JP4688604B2 (en) * | 2005-08-05 | 2011-05-25 | 日立ビークルエナジー株式会社 | Lithium ion battery |
| JP2007042525A (en) * | 2005-08-05 | 2007-02-15 | Hitachi Vehicle Energy Ltd | Lithium ion battery |
| JP2009123715A (en) * | 2007-06-28 | 2009-06-04 | Hitachi Maxell Ltd | Lithium ion secondary battery |
| JP2010073420A (en) * | 2008-09-17 | 2010-04-02 | Nissan Motor Co Ltd | Non-aqueous electrolyte secondary battery |
| JP2011070932A (en) * | 2009-09-25 | 2011-04-07 | Toyota Motor Corp | Lithium secondary battery |
| CN102484290A (en) * | 2009-09-25 | 2012-05-30 | 丰田自动车株式会社 | Lithium secondary battery and process for producing same |
| WO2011036759A1 (en) * | 2009-09-25 | 2011-03-31 | トヨタ自動車株式会社 | Lithium secondary battery and process for producing same |
| JP5229598B2 (en) * | 2009-09-25 | 2013-07-03 | トヨタ自動車株式会社 | Lithium secondary battery and manufacturing method thereof |
| WO2012049777A1 (en) * | 2010-10-15 | 2012-04-19 | トヨタ自動車株式会社 | Secondary battery |
| JPWO2012049777A1 (en) * | 2010-10-15 | 2014-02-24 | トヨタ自動車株式会社 | Secondary battery |
| WO2014084680A1 (en) * | 2012-11-29 | 2014-06-05 | 주식회사 엘지화학 | Apparatus and method for estimating output of secondary battery comprising blended positive electrode material |
| US9389278B2 (en) | 2012-11-29 | 2016-07-12 | Lg Chem, Ltd. | Apparatus and method for estimating power of secondary blended comprising blended cathode material |
| JPWO2014142066A1 (en) * | 2013-03-15 | 2017-02-16 | 株式会社東芝 | Battery electrode material and battery substrate, storage battery, dye-sensitized solar cell, capacitor, Li ion secondary battery using the same |
| JP2013251281A (en) * | 2013-09-19 | 2013-12-12 | Toyota Motor Corp | Lithium secondary battery, and method for manufacturing the same |
| JP2015215947A (en) * | 2014-05-07 | 2015-12-03 | 株式会社カネカ | Electrode for nonaqueous electrolyte secondary batteries and nonaqueous electrolyte secondary battery |
| JP2019057426A (en) * | 2017-09-21 | 2019-04-11 | オートモーティブエナジーサプライ株式会社 | Lithium ion secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4662089B2 (en) | 2011-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4662089B2 (en) | Nonaqueous electrolyte secondary battery | |
| JP5360871B2 (en) | Non-aqueous electrolyte lithium ion secondary battery | |
| EP2597706B1 (en) | Lithium ion secondary battery | |
| JP2001325988A (en) | Charging method of non-aqueous electrolyte secondary battery | |
| JP2009252489A (en) | Method for manufacturing lithium secondary battery | |
| EP2631972A1 (en) | Method for producing composition for forming positive electrode material mixture layer and method for producing lithium ion secondary battery | |
| JP2010129471A (en) | Cathode active material and nonaqueous electrolyte battery | |
| CN108137346B (en) | Precursors for lithium transition metal oxide cathode materials for rechargeable batteries | |
| JP5151329B2 (en) | Positive electrode body and lithium secondary battery using the same | |
| JP6986077B2 (en) | Lithium-ion secondary battery and its manufacturing method | |
| JP3579280B2 (en) | Negative electrode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery provided with this negative electrode | |
| JPH11121012A (en) | Nonaqueous electrolytic battery | |
| JP2006216305A (en) | Secondary battery | |
| JP2007080583A (en) | Electrode for secondary battery, and secondary battery | |
| JP2006004739A (en) | Lithium secondary battery and positive electrode equipped with the battery, and its manufacturing method | |
| JP2001052699A (en) | Lithium secondary battery | |
| JP3501113B2 (en) | Non-aqueous secondary battery and method of manufacturing the same | |
| JP5168535B2 (en) | Lithium secondary battery and manufacturing method thereof | |
| JP2006066298A (en) | Lithium secondary battery | |
| JP4534291B2 (en) | Lithium secondary battery | |
| JP4780361B2 (en) | Lithium secondary battery | |
| JP2018113220A (en) | Method for manufacturing lithium ion secondary battery | |
| JP2001297750A (en) | Power-generating element for lithium secondary battery and lithium secondary battery using same | |
| JP2003168427A (en) | Nonaqueous electrolyte battery | |
| JP3124749B2 (en) | Lithium ion secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050613 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20080310 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080318 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080515 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20091215 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100205 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20101209 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20101222 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140114 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |