JP2000208167A - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary batteryInfo
- Publication number
- JP2000208167A JP2000208167A JP11010882A JP1088299A JP2000208167A JP 2000208167 A JP2000208167 A JP 2000208167A JP 11010882 A JP11010882 A JP 11010882A JP 1088299 A JP1088299 A JP 1088299A JP 2000208167 A JP2000208167 A JP 2000208167A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- active material
- lithium
- electrode active
- negative electrode
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、高容量で、高い安
全性、信頼性を有する非水電解質二次電池に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte secondary battery having high capacity, high safety and reliability.
【０００２】[0002]
【従来の技術】リチウムイオン二次電池は、電子機器の
駆動用電源やメモリ保持電源、例えば、携帯電話、コー
ドレス機器の電源、メモリーバックアップ用電源等の各
種の日常用途に需要が拡大している。また、電気自動車
等の比較的大きな電力が必要な用途の電力貯蔵用や人工
衛星用のバッテリー等の安全性、信頼性を特に必要とす
る大型の電源用としての特性の向上に関する研究開発が
盛んになされている。2. Description of the Related Art Demand for lithium ion secondary batteries is expanding for various daily uses such as a power supply for driving electronic equipment and a power supply for holding a memory, for example, a power supply for mobile phones, cordless equipment, and a power supply for memory backup. . In addition, research and development on improving the characteristics of large power sources that require particularly high safety and reliability, such as power storage for applications that require relatively large power such as electric vehicles and batteries for artificial satellites, etc., have been actively conducted. Has been made.
【０００３】リチウムイオン二次電池は、可燃性の有機
溶媒を電解液に用いているために、温度の異常上昇、過
放電、過充電、短絡等による発火、発煙の危険性があ
り、安全性の向上のために種々の手段が工夫されてきた
が、大型の電源用としてはより高度の安全性、信頼性の
確保が求められる。[0003] Since a lithium ion secondary battery uses a flammable organic solvent as an electrolyte, there is a risk of abnormal temperature rise, over-discharge, over-charge, ignition or smoke due to short-circuit, etc. Various means have been devised to improve the quality, but higher security and reliability are required for large power supplies.
【０００４】[0004]
【発明が解決しようとする課題】リチウムイオン二次電
池の高容量化を図る方法の一つに、正極活物質の充電深
度を最大限深く設定する方法がある。この場合、通常
は、ＬｉＣｏＯ2 等の正極活物質が相転移を起こしてサ
イクル寿命特性が劣化する寸前まで充電されている。し
かし、この手法の問題点は、充電深度が深いために、満
充電時の正極活物質の熱安定性が低下し、電池内部の短
絡時等に電池が発熱・発火を起こす危険性が比較的高い
ことである。One of the methods for increasing the capacity of a lithium ion secondary battery is to set the charge depth of the positive electrode active material as deeply as possible. In this case, usually, the positive electrode active material such as LiCoO 2 is charged up to the stage just before the cycle life characteristic is deteriorated due to the phase transition. However, the problem with this method is that since the charge depth is deep, the thermal stability of the positive electrode active material at the time of full charge decreases, and there is a relative danger that the battery will generate heat or fire when a short circuit occurs inside the battery. It is expensive.
【０００５】リチウムイオン二次電池の安全性は、正極
活物質の充電深度に大きく関与しており、充電深度が深
いほど電池内部の短絡時や圧壊時の発煙・発火の危険性
は増す。これに関し、本発明者らは、ＬｉＣｏＯ2 で
は、充電深度が１３０ｍＡｈ／ｇを超えた辺りから、熱
的に不安定になることを見出した。[0005] The safety of a lithium ion secondary battery greatly depends on the charge depth of the positive electrode active material. As the charge depth becomes deeper, the danger of smoking or ignition at the time of short-circuiting or crushing inside the battery increases. In this regard, the present inventors have found that LiCoO 2 becomes thermally unstable when the charge depth exceeds about 130 mAh / g.
【０００６】しかし、ＬｉＣｏＯ2 の場合、正極活物質
の充電深度を１３０ｍＡｈ／ｇ以下に設定するだけで
は、電池の安全性は向上するが、同時に容量の大幅な減
少につながってしまうため、実性能を満足する容量を有
する電池を開発するためには、高容量化技術との組み合
わせが必須となる。However, in the case of LiCoO 2 , if the charging depth of the positive electrode active material is simply set to 130 mAh / g or less, the safety of the battery is improved, but at the same time, the capacity is significantly reduced. In order to develop a battery having a capacity satisfying the above, a combination with a technology for increasing the capacity is essential.
【０００７】[0007]
【課題を解決するための手段】本発明は、リチウム含有
複合酸化物である正極活物質とリチウムイオンを吸蔵・
放出する負極活物質と、非水電解質とを備えてなる二次
電池において、公称電圧より下げた所定の電圧以下で用
いるようになされており、かつ、公称電圧まで充電した
際の電池の放電容量をＡとし、公称電圧より下げた所定
の電圧まで充電した際の電池の放電容量をＢとし、ま
た、負極活物質の最大可逆放電量をＣとしたとき、下記
の式のＤに相当する充電容量分のリチウム量をプリチャ
ージした負極活物質を用いることを特徴とする高容量
で、安全性に優れた非水電解質二次電池である。 式 Ａ−Ｂ≦Ｄ≦Ｃ−ＡSUMMARY OF THE INVENTION The present invention relates to a positive electrode active material, which is a lithium-containing composite oxide, and a device for storing lithium ions.
In a secondary battery including a negative electrode active material to be released and a non-aqueous electrolyte, the secondary battery is used at a predetermined voltage lower than a nominal voltage, and discharge capacity of the battery when charged to the nominal voltage Is A, the discharge capacity of the battery when charged to a predetermined voltage lower than the nominal voltage is B, and the maximum reversible discharge amount of the negative electrode active material is C, the charge corresponding to D in the following equation: A non-aqueous electrolyte secondary battery having a high capacity and excellent safety, characterized by using a negative electrode active material precharged with a lithium amount corresponding to a capacity. Formula AB ≦ D ≦ CA
【０００８】さらに、本発明は、リチウム含有複合酸化
物がコバルト酸リチウムであり、正極利用率が１３０ｍ
Ａｈ／ｇ以下となる電圧以下で用いるようになされてお
り、かつ、正極利用率が１４０ｍＡｈ／ｇ〜１５０ｍＡ
ｈ／ｇとなる電圧まで充電した際の電池の放電容量をＡ
とし、正極利用率が１３０ｍＡｈ／ｇ以下となる電圧ま
で充電した際の電池の放電容量をＢとし、また、負極活
物質の最大可逆放電量をＣとしたとき、下記の式のＤに
相当する充電容量分のリチウム量をプリチャージした負
極活物質を用いることを特徴とする非水電解質二次電池
である。 式 Ａ−Ｂ≦Ｄ≦Ｃ−ＡFurther, according to the present invention, the lithium-containing composite oxide is lithium cobalt oxide, and the utilization rate of the positive electrode is 130 m
Ah / g or less, and the positive electrode utilization rate is 140 mAh / g to 150 mA.
The discharge capacity of the battery when charged to a voltage of h / g
When the discharge capacity of the battery when charged to a voltage at which the positive electrode utilization rate is 130 mAh / g or less is B, and the maximum reversible discharge amount of the negative electrode active material is C, this corresponds to D in the following equation. A non-aqueous electrolyte secondary battery using a negative electrode active material precharged with a lithium amount corresponding to a charge capacity. Formula AB ≦ D ≦ CA
【０００９】本発明は、公称電圧より下げた所定の電圧
以下で用いるようになされており、これにより電池の安
全性を高めたものであり、さらに、このような状態で用
いても、従来に比べて放電容量の低下を起こすことなく
構成されたものである。The present invention is intended to be used at a predetermined voltage lower than the nominal voltage, thereby improving the safety of the battery. In comparison, the discharge capacity is not reduced.
【００１０】負極活物質にプリチャージするリチウム量
Ｄの値を、公称電圧まで充電した際の電池の放電容量
Ａ、公称電圧より下げた所定の電圧まで充電した際の電
池の放電容量Ｂとの差Ａ−Ｂと同等以上とするのは、放
電容量の低下を補うために必要な条件であり、また、負
極活物質にプリチャージするリチウム量Ｄの値を、負極
の最大可逆放電量Ｃとして、公称電圧まで充電した際の
電池の放電容量Ａとの差Ｃ−Ａと同等以下とするのは、
リチウムを過度に補足すると充放電によりリチウムの樹
枝状電析を生じる問題があり、これを防止するために必
要な条件である。The value of the amount of lithium D to be precharged to the negative electrode active material is defined as the discharge capacity A of the battery when charged to a nominal voltage and the discharge capacity B of the battery when charged to a predetermined voltage lower than the nominal voltage. The difference AB is equal to or more than the condition required to compensate for the decrease in the discharge capacity, and the value of the lithium amount D to be precharged to the negative electrode active material is defined as the maximum reversible discharge amount C of the negative electrode. , The difference between the discharge capacity A of the battery when charged to the nominal voltage and the difference CA is equal to or less than
If lithium is excessively supplemented, there is a problem that lithium dendritic deposition occurs due to charge and discharge, which is a necessary condition to prevent this.
【００１１】リチウムイオン二次電池の公称電圧は、サ
イクル寿命特性が劣化する直前の電圧として決められる
電圧であって、例えば、リチウム含有複合酸化物がコバ
ルト酸リチウムである場合には、正極利用率が１４０ｍ
Ａｈ／ｇ〜１５０ｍＡｈ／ｇとなる電圧（これは通常
４．１〜４．２Ｖに相当）であり、これにより放電容量
Ａが決まる。そして、できるだけ容量を大きくするため
には、できるだけ大きな電圧を基準にするのが好まし
い。公称電圧より下げた所定の電圧は、低ければそれだ
け安全性が向上することになるが、例えばリチウム含有
酸化物がコバルト酸リチウムである場合には、正極利用
率が１３０ｍＡｈ／ｇ以下となる電圧（これは通常４．
０５Ｖ以下の電圧に相当）が好ましく、容量をできるだ
け大きくするために、より好ましくは１３０ｍＡｈ／ｇ
となる電圧（これは通常４．０５Ｖの電圧に相当）とす
るのが良い。The nominal voltage of a lithium ion secondary battery is a voltage determined as a voltage immediately before the cycle life characteristic deteriorates. For example, when the lithium-containing composite oxide is lithium cobalt oxide, the positive electrode utilization factor Is 140m
The voltage is Ah / g to 150 mAh / g (this usually corresponds to 4.1 to 4.2 V), and this determines the discharge capacity A. In order to increase the capacity as much as possible, it is preferable to use as large a voltage as possible. The lower the predetermined voltage lower than the nominal voltage, the higher the safety is. However, for example, when the lithium-containing oxide is lithium cobalt oxide, the voltage at which the positive electrode utilization rate is 130 mAh / g or less ( This is usually 4.
05V or less), and more preferably 130 mAh / g to maximize the capacity.
(This usually corresponds to a voltage of 4.05 V).
【００１２】負極活物質の最大可逆放電量Ｃは、材料に
より異なるが、金属リチウムの悪影響を与える析出を生
じない範囲で可逆的に充放電を行える量として定まる。The maximum reversible discharge amount C of the negative electrode active material depends on the material, but is determined as an amount capable of reversibly charging / discharging within a range that does not cause precipitation that adversely affects the lithium metal.
【００１３】正極活物質の充電深度は、正極材料の種類
に応じて、それを用いた非水電解質二次電池の安全性を
考慮して適宜定める。例えば、ＬｉＣＯ2 の場合、釘刺
し試験結果によれば、１４０ｍＡｈ／ｇ（約４．１Ｖ充
電）では発煙を起こすが、１３０ｍＡｈ／ｇ（約４．０
５Ｖ充電）では発煙を起こさないように、それぞれの正
極材料によって安全性を確保するための所定の充電深度
レベルがあり、本発明の非水電解質二次電池は、正極材
料の種類に応じて、充電深度を安全性確保のための所定
の充電深度レベルとしたものである。The depth of charge of the positive electrode active material is appropriately determined according to the type of the positive electrode material in consideration of the safety of the nonaqueous electrolyte secondary battery using the same. For example, in the case of LiCO 2 , according to the nail penetration test result, smoke is generated at 140 mAh / g (about 4.1 V charge), but 130 mAh / g (about 4.0 V).
(5 V charge), there is a predetermined charging depth level for ensuring safety by each positive electrode material so as not to cause smoke. The non-aqueous electrolyte secondary battery of the present invention has the following characteristics depending on the type of the positive electrode material. The charging depth is a predetermined charging depth level for ensuring safety.
【００１４】[0014]
【発明の実施の形態】本発明では、正、負の電極板をシ
ート状にし、これらの電極をセパレータを介してロール
状に巻回した渦巻状構造を採用することができる。この
ようなシート状極板を製造する方法としては、ペースト
状の電極合剤をリバースロール式、ドクターブレード方
式等により銅、アルミニウム等の金属箔等の集電体シー
ト上に塗工する。電極合剤を塗布したシート状極板は、
熱風乾燥や真空乾燥した後ロールプレス機により均一に
加圧圧縮し、電極多孔度を約２５〜５０％の範囲に均一
に調整する。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, a spiral structure in which positive and negative electrode plates are formed into a sheet and these electrodes are wound in a roll via a separator can be employed. As a method for producing such a sheet-like electrode plate, a paste-like electrode mixture is applied on a current collector sheet such as a metal foil such as copper or aluminum by a reverse roll method, a doctor blade method, or the like. The sheet-shaped electrode plate coated with the electrode mixture
After hot-air drying or vacuum drying, it is uniformly pressed and compressed by a roll press machine to uniformly adjust the electrode porosity to a range of about 25 to 50%.
【００１５】加圧圧縮の際の圧力は、通常は、２００〜
１０００ｋｇ／ｃｍ2 が好ましい。これらの方法で製造
したシート状極板は、円筒形、長円筒形、角型等の電池
１個分の長さに裁断し、正極シート、セパレータ、負極
シートを順次積層した極板群を芯材を中心にしてロール
状に巻回して電池の容器に収納して使用する。The pressure at the time of pressurization and compression is usually 200 to
1000 kg / cm 2 is preferred. The sheet-shaped electrode plate manufactured by these methods is cut into a length of one battery such as a cylinder, a long cylinder, a square, and the like, and a positive electrode sheet, a separator, and a negative electrode sheet are laminated in this order. The material is wound around a roll and stored in a battery container for use.
【００１６】非水電解質電池のリチウムイオンを吸蔵・
放出する負極活物質としては、通常、炭素材料（例え
ば、黒鉛，石油コークス，クレゾール樹脂焼成炭素，フ
ラン樹脂焼成炭素，ポリアクリロニトリル繊維焼成炭
素，気相成長炭素，メソフェーズピッチ焼成炭素等）、
ＬｉＦｅ2 Ｏ2 、ＬｉＷＯ2 等のＬｉ含有複合酸化物、
Ｌｉ7 ＭｎＮ4 、Ｌｉ3 ＦｅＮ2 、Ｌｉ3 ＡｌＮ2 等の
Ｌｉ含有複合窒化物、ＡｌＳｂ、Ｍｇ2 Ｇｅ、Ｍｇ2 Ｓ
ｎ等の金属間化合物カルコゲン材料、Ｌｉx ＳｉＯ
y （０≦ｘ，０＜ｙ＜２）で示されるケイ素の低級酸化
物やケイ酸塩等の種々の材料を使用でき、本発明におい
ては、その種類は、特に限定されない。Occludes lithium ions in non-aqueous electrolyte batteries
As the anode active material to be released, a carbon material (eg,
For example, graphite, petroleum coke, cresol resin calcined carbon,
Run resin fired carbon, polyacrylonitrile fiber fired carbon
Element, vapor grown carbon, mesophase pitch calcined carbon, etc.),
LiFeTwoOTwo, LiWOTwoLi-containing composite oxides such as
Li7MnNFour, LiThreeFeNTwo, LiThreeAlNTwoEtc.
Li-containing composite nitride, AlSb, MgTwoGe, MgTwoS
n and other intermetallic compound chalcogen materials, LixSiO
yLower oxidation of silicon represented by (0 ≦ x, 0 <y <2)
Various materials such as materials and silicates can be used.
Thus, the type is not particularly limited.
【００１７】リチウム含有複合酸化物である正極活物質
の種類は、特に限定されず、例えば、ＬｉＣｏＯ2 、Ｌ
ｉＮｉＯ2 、ＬｉＭｎＯ2 、ＬｉＭｎ2 Ｏ4 、ＬｉＣｒ
3 Ｏ 8 、ＬｉＴｉ2 Ｏ４、ＬｉＦｅＯ2 等各種の材料を
使用できる。正極活物質は、例えば、導電助剤のカーボ
ン粉末と結着剤のポリフッ化ビニリデンとを混合して溶
剤のＮ−メチルピロリドンに溶解してペースト状にして
正極集電体に塗布する。A positive electrode active material which is a lithium-containing composite oxide
Is not particularly limited. For example, LiCoOTwo, L
iNiOTwo, LiMnOTwo, LiMnTwoOFour, LiCr
ThreeO 8, LiTiTwoO4, LiFeOTwoAnd various materials
Can be used. The positive electrode active material is, for example, a carbohydrate conductive agent.
Powder and polyvinylidene fluoride as a binder
Dissolve in N-methylpyrrolidone to make a paste
Apply to positive electrode current collector.
【００１８】電解質としては、例えばプロピレンカーボ
ネート、エチレンカーボネート、ジメチルカーボネー
ト、ジエチルカーボネート、γーブチロラクトン、１，
２−ジメトキシエタン、テトラヒドロキシフラン等の非
プロトン有機溶媒の少なくとも１種以上と、これらの溶
媒に溶ける種々のリチウム塩、例えば、ＬｉＣｌＯ4 、
ＬｉＢＦ6 、ＬｉＰＦ6 、ＬｉＣＦ3 ＳＯ3 、ＬｉＣＦ
3 ＣＯ2 、ＬｉＡｓＦ6等を使用できる。好ましい非水
電解液の具体例としては、例えば、１ＭのＬｉＰＦ6 ／
エチレンカーボネート＋ジメチルカ−ボネート＋ジエチ
ルカーボネート（２：２：１）を用いる。Examples of the electrolyte include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone,
At least one or more aprotic organic solvents such as 2-dimethoxyethane and tetrahydroxyfuran and various lithium salts soluble in these solvents, for example, LiClO 4 ,
LiBF 6 , LiPF 6 , LiCF 3 SO 3 , LiCF
3 CO 2 , LiAsF 6 or the like can be used. Specific examples of preferable non-aqueous electrolyte include, for example, 1M LiPF 6 /
Ethylene carbonate + dimethyl carbonate + diethyl carbonate (2: 2: 1) is used.
【００１９】セパレータとしては、厚み１０〜５０μｍ
の微多孔性フイルム（材質：ポリエチレン、ポリプロピ
レン）、リチウムイオン導電性固体電解質シート等のシ
ート状のものの他に、正極または負極シートの表面に直
接形成してなる絶縁層があげられる。絶縁層の厚みは、
１〜５０μｍが好ましく、材質は、リチウムイオン導電
性樹脂、リチウムイオン伝導性無機材料（セラミック
ス、ガラス）等が使用できる。The separator has a thickness of 10 to 50 μm.
In addition to the above-mentioned microporous films (materials: polyethylene and polypropylene), lithium ion conductive solid electrolyte sheets, and other sheet-like materials, an insulating layer directly formed on the surface of a positive electrode or negative electrode sheet can be used. The thickness of the insulating layer is
The thickness is preferably 1 to 50 μm, and as the material, a lithium ion conductive resin, a lithium ion conductive inorganic material (ceramics, glass) or the like can be used.
【００２０】負極へのＬｉのプリチャージ方法自体は、
予備吸蔵や予備挿入と称される公知の方法を使用でき
る。例えば、黒鉛材料からなる負極とリチウム金属電極
とをリチウム金属塩を含む非水電解液中に浸漬し、両極
を外部短絡して黒鉛材料に上記式のＤに相当する容量分
のＬｉを吸蔵させる。The method of precharging Li to the negative electrode itself is as follows.
A known method called pre-storing or pre-inserting can be used. For example, a negative electrode made of a graphite material and a lithium metal electrode are immersed in a non-aqueous electrolyte containing a lithium metal salt, and both electrodes are externally short-circuited to cause the graphite material to occlude Li by an amount corresponding to D in the above formula. .
【００２１】また、例えば、厚み３０μｍ程度のリチウ
ム金属、Ｌｉ−Ａｌ、Ｌｉ−Ｓｎ等のＬｉ合金、Ｌｉ合
金の混合物、Ｌｉ合金の酸化物からなる箔や微粉末を負
極表面に貼り付けたり、塗布分散させてもよい。また、
これらのリチウムをエージングして負極に拡散処理して
もよい。この場合、式Ａ−Ｂ≦Ｄ≦Ｃ−Ａを満たすリチ
ウム量とリチウム箔の厚み、微粉末の量は、１ｃｃ＝２
０６０ｍＡｈに相当、１ｍｇ＝３．８６ｍＡｈに相当す
る関係を基準として定めればよい。Further, for example, a foil or fine powder of lithium metal having a thickness of about 30 μm, a Li alloy such as Li—Al, Li—Sn, a mixture of Li alloys, and an oxide of a Li alloy is attached to the surface of the negative electrode, It may be applied and dispersed. Also,
The lithium may be aged and diffused to the negative electrode. In this case, the amount of lithium, the thickness of the lithium foil, and the amount of fine powder satisfying the formula AB ≦ D ≦ CA are 1 cc = 2.
The relationship may be determined based on the relationship corresponding to 060 mAh and 1 mg = 3.86 mAh.
【００２２】[0022]
【実施例】実施例１ 正極活物質として平均粒径１０μｍのＬｉＣｏＯ2 を９
０重量部、導電剤としてアセチレンブラックを５重量部
の割合でそれぞれ混合し、さらに結着剤としてポリフッ
化ビニリデンを５重量部の割合で加え、溶媒としてＮメ
チル−２−ピロリドンを添加し、混練して、スラリー状
の正極合剤塗布液を作製した。次いで、この正極合剤塗
布液を厚さ２０μｍのアルミニウム箔の表裏両面に、同
じ塗布重量（単位面積当たり）となるよう、片面ずつ塗
布した。EXAMPLES Example 1 9 LiCoO 2 having an average particle size of 10 μm was used as a positive electrode active material.
0 parts by weight, acetylene black as a conductive agent was mixed at a ratio of 5 parts by weight, polyvinylidene fluoride was added at a ratio of 5 parts by weight as a binder, and N-methyl-2-pyrrolidone was added as a solvent and kneaded. Thus, a slurry-like positive electrode mixture coating solution was prepared. Next, this positive electrode mixture coating solution was applied to both sides of an aluminum foil having a thickness of 20 μm so as to have the same application weight (per unit area), one by one.
【００２３】負極は、平均粒径２０μｍ、結晶性Ｌｃ＝
５００Ａ程度の人造黒鉛を９０重量部、結着剤としてポ
リフッ化ビニリデンを１０重量部の割合で加え、溶媒と
してＮメチル−２−ピロリドンを添加し、混練して、ス
ラリー状の負極合剤塗布液を厚さ１２μｍの銅箔の表裏
両面に、同じ塗布重量（単位面積当り）となるよう、片
面ずつ塗布したものを用いた。The negative electrode has an average particle size of 20 μm and a crystalline Lc =
90 parts by weight of artificial graphite of about 500 A, 10 parts by weight of polyvinylidene fluoride as a binder, N-methyl-2-pyrrolidone as a solvent, kneading, and a slurry-like negative electrode mixture coating solution Was applied to both sides of a copper foil having a thickness of 12 μm so as to have the same application weight (per unit area).
【００２４】これらの正極シートおよび負極シートを熱
風乾燥し、ロールプレスにより圧縮加工した。多孔度
は、正負極ともに３０％であった。このときの電極合剤
密度は、負極１．５ｇ／ｃｍ3 、正極３．２ｇ／ｃｍ3
となった。次いで、正、負極シートを厚み２５μｍのポ
リエチレン製微多孔膜セパレータを介して、正、負極シ
ートとも表面を外側に、裏面を内側になるようにしてロ
ール状に巻回し、長円筒形とした。These positive and negative electrode sheets were dried with hot air and compressed by a roll press. The porosity was 30% for both the positive and negative electrodes. Electrode mixture density at this time, negative 1.5 g / cm 3, a positive electrode 3.2 g / cm 3
It became. Next, the positive and negative electrode sheets were wound in a roll shape through a 25-μm-thick polyethylene microporous membrane separator so that both the positive and negative electrode sheets had their front surfaces facing out and their back surfaces facing inward to form a long cylindrical shape.
【００２５】この巻き終わったエレメントを電池ケース
外で、容積比で４：６のエチレンカーボネートとメチル
エチルカーボネート（ＥＣ＋ＤＭＣ）の混合溶液に六フ
ッ化リン酸リチウム（ＬｉＰＦ6 ）を１モル／リットル
溶解した電解液中に浸し、負極と金属リチウムを短絡し
て下記の表１に示す条件でプリチャージを行った。The wound element was dissolved outside the battery case in a mixed solution of ethylene carbonate and methyl ethyl carbonate (EC + DMC) in a volume ratio of 4: 6 by dissolving lithium hexafluorophosphate (LiPF 6 ) at 1 mol / liter. The negative electrode and metallic lithium were short-circuited and precharged under the conditions shown in Table 1 below.
【００２６】[0026]
【表１】 Ｒ１は、プリチャージなしの比較例である。充電方法
は、定電流充電とし、カットオフ電圧は、間欠充電の電
池番号１は、０．６５Ｖとし、それ以外は０．０Ｖとし
た。Ｄの値に相当する充電電気量は計算値である。電池
番号２、３、４は、充電電流を変えて対比したものであ
る。[Table 1] R1 is a comparative example without precharge. The charging method was constant-current charging, and the cutoff voltage was 0.65 V for battery number 1 for intermittent charging, and 0.0 V for the rest. The amount of charged electricity corresponding to the value of D is a calculated value. Battery numbers 2, 3, and 4 are obtained by changing the charging current.
【００２７】本実施例の電池の場合、公称電圧（４．１
Ｖ）まで充電した際の放電容量Ａは、６７８ｍＡｈであ
り、正極活物質の充電深度を所定レベル以下（４．０５
Ｖ）とした際の放電容量Ｂは、６２７ｍＡｈであり、ま
た、負極活物質の最大可逆放電量Ｃは、７９５ｍＡｈで
あり、下記の式のＤに相当する量のリチウムは、電池番
号１で７０ｍＡｈ、電池番号２で６５ｍＡｈ、電池番号
３で６５ｍＡｈ、電池番号４で６５ｍＡｈであり、式Ａ
−Ｂ≦Ｄ≦Ｃ−Ａを満たしている。In the case of the battery of this embodiment, the nominal voltage (4.1
V), the discharge capacity A is 678 mAh, and the charge depth of the positive electrode active material is set to a predetermined level or less (4.05).
V), the discharge capacity B is 627 mAh, the maximum reversible discharge amount C of the negative electrode active material is 795 mAh, and the amount of lithium corresponding to D in the following formula is 70 mAh in the battery number 1. The battery number 2 is 65 mAh, the battery number 3 is 65 mAh, and the battery number 4 is 65 mAh.
−B ≦ D ≦ CA is satisfied.
【００２８】次に電池番号１の電池とＲ１の電池につい
て、上記充電放電条件の内の充電電圧を４．１Ｖから
４．０５Ｖに変更して、これらを比較した。この結果、
Ｒ１の放電容量６２７ｍＡｈに対し、電池番号１では６
７７ｍＡｈとなった。また、電池番号１の電池について
釘刺し試験を行った結果、４．１Ｖ充電のものでは発煙
を生じたが、４．０５Ｖ充電のものでは発煙を生じなか
った。Next, the charging voltage of the battery No. 1 and the battery R1 was changed from 4.1 V to 4.05 V under the above charging and discharging conditions, and these were compared. As a result,
In contrast to the discharge capacity of R1 of 627 mAh,
77 mAh. Further, as a result of a nail penetration test performed on the battery of battery number 1, smoke was generated when the battery was charged at 4.1 V, but was not generated when the battery was charged at 4.05 V.
【００２９】プリチャージした電池番号１〜４のエレメ
ントを厚み１．２ｍｍのアルミニウム製容器に収容し、
電解液としては、容積比で４：６のエチレンカーボネー
トとメチルエチルカーボネート（ＥＣ＋ＭＥＣ）の混合
溶媒に六フッ化リン酸リチウム（ＬｉＰＦ6 ）を１モル
／リットル溶解したものを用い、容量１００Ａｈの電池
（厚み５０ｍｍ，幅１３０ｍｍ，高さ２１０ｍｍ）を作
製した。The precharged elements of battery numbers 1 to 4 are accommodated in a 1.2 mm thick aluminum container,
As the electrolytic solution, a solution of lithium hexafluorophosphate (LiPF 6 ) dissolved in a mixed solvent of ethylene carbonate and methyl ethyl carbonate (EC + MEC) at a volume ratio of 4: 6 at 1 mol / liter and a capacity of 100 Ah was used. (Thickness: 50 mm, width: 130 mm, height: 210 mm).
【００３０】この電池について、充電条件：１００ｍＡ
（０．１７ＣｍＡ）、４．１ＶＣＣ（定電流充電）、２
５℃とし、放電条件：６００ｍＡ（１ＣｍＡ）、終止電
圧２．７５Ｖ、２５℃として充放電した結果を図１に示
す。図１の記号は、下記のとおり、それぞれ表１の電池
番号に対応する。○＝Ｒ１、△＝Ｎｏ．１、□＝Ｎｏ．
２、▽＝Ｎｏ．３、×＝Ｎｏ．４。図１に示されるとお
り、プリチャージにより放電容量の増大が得られること
が明らかである。For this battery, the charging condition was 100 mA.
(0.17 CmA), 4.1 VCC (constant current charging), 2
FIG. 1 shows the results of charging and discharging at 5 ° C., discharge conditions: 600 mA (1 CmA), a final voltage of 2.75 V, and 25 ° C. The symbols in FIG. 1 correspond to the battery numbers in Table 1, respectively, as described below. ＝= R1, △ = No. 1, □ = No.
2, ▽ = No. 3, × = No. 4. As shown in FIG. 1, it is clear that the precharge can increase the discharge capacity.
【００３１】実施例２ 実施例１の負極活物質の人造黒鉛に代えて平均粒径４μ
ｍのアモルファスＳｉＯy を２０重量部と平均粒径４μ
ｍの人造黒鉛８０重量部とを混合し、これによって得ら
れる混合物に金属リチウム箔を張り付けた以外は、実施
例１と同様に電池を作製した。電池番号１、２は、金属
リチウムを貼り付けていない比較例であり、電池番号３
は、混合電極に、厚さ３０μｍの金属リチウム箔小片
０．０２６ｇをロールプレスにより貼り付けて電極とし
た実施例である。Example 2 An average particle size of 4 μm was used in place of artificial graphite as the negative electrode active material of Example 1.
20 parts by weight of amorphous SiO y having an average particle size of 4 μm.
m of artificial graphite of 80 parts by weight, and a lithium battery was adhered to the resulting mixture to produce a battery in the same manner as in Example 1. Battery Nos. 1 and 2 are comparative examples in which metallic lithium was not attached, and battery No. 3
Is an example in which 0.026 g of a small 30 μm-thick lithium metal foil was attached to a mixed electrode by a roll press to form an electrode.
【００３２】この電池を用いて、充電条件：ＣＣＣＶ、
３００ｍＡ（１ＣＡ）、４．１Ｖ、定電流定電圧充電、
２５℃の条件で充電した電池の初期充放電量は、下記の
とおりであった。Using this battery, charging conditions: CCCV,
300 mA (1 CA), 4.1 V, constant current, constant voltage charging,
The initial charge / discharge amount of the battery charged at 25 ° C. was as follows.
【００３３】 電池番号１：充電量３０４ｍＡｈ、放電量２９３ｍＡｈ 電池番号２：充電量３０７ｍＡｈ、放電量２９３ｍＡｈ 電池番号３：充電量４３８ｍＡｈ、放電量４２９ｍＡｈ 次に、電池番号３の電池を４．０５Ｖまで充電した以外
は上記と同様に充電した。この結果、その容量は、上記
条件で充電した電池番号１、２のいずれの電池よりも大
きかった。また、電池番号３の電池について釘刺し試験
を行った結果、４．１Ｖ充電のものでは発煙を生じた
が、４．０５Ｖ充電のものでは発煙を生じなかった。Battery No. 1: Charge amount 304 mAh, Discharge amount 293 mAh Battery No. 2: Charge amount 307 mAh, Discharge amount 293 mAh Battery No. 3: Charge amount 438 mAh, Discharge amount 429 mAh Next, battery No. 3 is charged to 4.05 V. The battery was charged in the same manner as described above except that the charging was performed. As a result, the capacity was larger than any of the batteries Nos. 1 and 2 charged under the above conditions. Further, as a result of a nail penetration test performed on the battery of battery number 3, smoke was generated when the battery was charged at 4.1 V, but was not generated when the battery was charged at 4.05 V.
【００３４】実施例２の場合、公称電圧（４．１）まで
充電した際の放電容量Ａは、３００ｍＡｈであり、正極
活物質の充電深度を所定レベル以下（４．０５Ｖ）とし
た際の放電容量Ｂは、２６２ｍＡｈであり、また、負極
活物質の最大可逆放電量Ｃは、４１０ｍＡｈであり、下
記の式のＤに相当する量のリチウムは、１００ｍＡｈで
あり、式Ａ−Ｂ≦Ｄ≦Ｃ−Ａを満たしている。In the case of Example 2, the discharge capacity A when charged to the nominal voltage (4.1) is 300 mAh, and the discharge when the charge depth of the positive electrode active material is set to a predetermined level or less (4.05 V). The capacity B is 262 mAh, the maximum reversible discharge amount C of the negative electrode active material is 410 mAh, the amount of lithium corresponding to D in the following formula is 100 mAh, and the formula AB ≦ D ≦ C -A is satisfied.
【００３５】[0035]
【発明の効果】本発明により、高容量でかつ安全性の高
い非水電解質二次電池を提供することができた。According to the present invention, a non-aqueous electrolyte secondary battery having high capacity and high safety can be provided.
【図１】実施例１のプリチャージ条件と放電容量の関係
を示すグラフ。FIG. 1 is a graph showing the relationship between precharge conditions and discharge capacity in Example 1.
Claims (2)
質とリチウムイオンを吸蔵・放出する負極活物質と、非
水電解質とを備えてなる二次電池において、公称電圧よ
り下げた所定の電圧以下で用いるようになされており、
かつ、公称電圧まで充電した際の電池の放電容量をＡと
し、公称電圧より下げた所定の電圧まで充電した際の電
池の放電容量をＢとし、また、負極活物質の最大可逆放
電量をＣとしたとき、下記の式のＤに相当する充電容量
分のリチウム量をプリチャージした負極活物質を用いる
ことを特徴とする高容量で、安全性に優れた非水電解質
二次電池。 式 Ａ−Ｂ≦Ｄ≦Ｃ−Ａ1. A secondary battery comprising a positive electrode active material that is a lithium-containing composite oxide, a negative electrode active material that occludes and releases lithium ions, and a non-aqueous electrolyte, has a predetermined voltage lower than a nominal voltage. It is made to be used in
Further, the discharge capacity of the battery when charged to the nominal voltage is A, the discharge capacity of the battery when charged to a predetermined voltage lower than the nominal voltage is B, and the maximum reversible discharge amount of the negative electrode active material is C. A non-aqueous electrolyte secondary battery with high capacity and excellent safety, characterized by using a negative electrode active material precharged with a lithium amount corresponding to a charge capacity corresponding to D in the following formula. Formula AB ≦ D ≦ CA
チウムであり、正極利用率が１３０ｍＡｈ／ｇ以下とな
る電圧以下で用いるようになされており、かつ、正極利
用率が１４０ｍＡｈ／ｇ〜１５０ｍＡｈ／ｇとなる電圧
まで充電した際の電池の放電容量をＡとし、正極利用率
が１３０ｍＡｈ／ｇ以下となる電圧まで充電した際の電
池の放電容量をＢとし、また、負極活物質の最大可逆放
電量をＣとしたとき、下記の式のＤに相当する充電容量
分のリチウム量をプリチャージした負極活物質を用いる
ことを特徴とする請求項１記載の非水電解質二次電池。 式 Ａ−Ｂ≦Ｄ≦Ｃ−Ａ2. The lithium-containing composite oxide is lithium cobalt oxide, which is used at a voltage of not more than 130 mAh / g and has a positive electrode utilization of 140 mAh / g to 150 mAh / g. A, the discharge capacity of the battery when charged to a voltage at which the positive electrode utilization rate is 130 mAh / g or less, and B, the maximum reversible discharge amount of the negative electrode active material. 2. The non-aqueous electrolyte secondary battery according to claim 1, wherein a negative electrode active material is used in which the amount of lithium corresponding to the charge capacity corresponding to D in the following formula is precharged. Formula AB ≦ D ≦ CA
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01088299A JP3575308B2 (en) | 1999-01-19 | 1999-01-19 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01088299A JP3575308B2 (en) | 1999-01-19 | 1999-01-19 | Non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000208167A true JP2000208167A (en) | 2000-07-28 |
| JP3575308B2 JP3575308B2 (en) | 2004-10-13 |
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ID=11762701
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP01088299A Expired - Fee Related JP3575308B2 (en) | 1999-01-19 | 1999-01-19 | Non-aqueous electrolyte secondary battery |
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| Country | Link |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003115326A (en) * | 2001-10-03 | 2003-04-18 | Japan Storage Battery Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2003346904A (en) * | 2002-05-29 | 2003-12-05 | Japan Storage Battery Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2004227931A (en) * | 2003-01-23 | 2004-08-12 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte rechargeable battery |
| JP2017069002A (en) * | 2015-09-29 | 2017-04-06 | 株式会社Ｇｓユアサ | Power storage device |
| KR20200135576A (en) * | 2011-10-05 | 2020-12-02 | 원드 매터리얼 인코포레이티드 | Silicon nanostructure active materials for lithium ion batteries and processes, compositions, components, and devices related thereto |
-
1999
- 1999-01-19 JP JP01088299A patent/JP3575308B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003115326A (en) * | 2001-10-03 | 2003-04-18 | Japan Storage Battery Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2003346904A (en) * | 2002-05-29 | 2003-12-05 | Japan Storage Battery Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2004227931A (en) * | 2003-01-23 | 2004-08-12 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte rechargeable battery |
| KR20200135576A (en) * | 2011-10-05 | 2020-12-02 | 원드 매터리얼 인코포레이티드 | Silicon nanostructure active materials for lithium ion batteries and processes, compositions, components, and devices related thereto |
| KR102323287B1 (en) * | 2011-10-05 | 2021-11-05 | 원드 매터리얼 인코포레이티드 | Silicon nanostructure active materials for lithium ion batteries and processes, compositions, components, and devices related thereto |
| JP2017069002A (en) * | 2015-09-29 | 2017-04-06 | 株式会社Ｇｓユアサ | Power storage device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3575308B2 (en) | 2004-10-13 |
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