JP2000173667A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JP2000173667A JP2000173667A JP10361911A JP36191198A JP2000173667A JP 2000173667 A JP2000173667 A JP 2000173667A JP 10361911 A JP10361911 A JP 10361911A JP 36191198 A JP36191198 A JP 36191198A JP 2000173667 A JP2000173667 A JP 2000173667A
- Authority
- JP
- Japan
- Prior art keywords
- electrode body
- thickness
- negative electrode
- positive electrode
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は薄型リチウム二次電
池の改良に関する。The present invention relates to an improvement in a thin lithium secondary battery.
【０００２】[0002]
【従来の技術】リチウム二次電池は、現存する二次電池
の中で最も高いエネルギー密度を達成可能であるため、
携帯用電子機器の小型軽量化に伴う二次電池高エネルギ
ー密度化の要望を満たすものとして最も期待されてお
り、薄型化が進められている。2. Description of the Related Art Since a lithium secondary battery can achieve the highest energy density among existing secondary batteries,
It is most expected to satisfy the demand for a higher energy density of a secondary battery accompanying the reduction in size and weight of portable electronic devices, and the reduction in thickness has been promoted.
【０００３】リチウム二次電池の負極体材料としては、
現在、リチウムイオンの吸蔵・放出可能な黒鉛等の炭素
材料が最も広く用いられている。一方、正極材料として
は、リチウムイオンを吸蔵・放出可能なリチウム含有遷
移金属酸化物が一般に使用されており、中でも電池とし
た際の起電力が大きく、高エネルギー密度化可能なコバ
ルト酸リチウムが最も広く用いられている。負極体であ
る炭素材料と、正極体であるリチウム含有遷移金属酸化
物は、単位体積当たりに吸蔵・放出するリチウムイオン
量がほぼ同等であるため、従来のリチウム二次電池にお
いては、負極体と正極体の厚みはほぼ同等であった。As a negative electrode material of a lithium secondary battery,
At present, carbon materials such as graphite capable of occluding and releasing lithium ions are most widely used. On the other hand, as a positive electrode material, a lithium-containing transition metal oxide capable of occluding and releasing lithium ions is generally used. Among them, lithium cobalt oxide, which has a large electromotive force and a high energy density in a battery, is most preferable. Widely used. In the conventional lithium secondary battery, the carbon material as the negative electrode body and the lithium-containing transition metal oxide as the positive electrode body have almost the same amount of lithium ions inserted and extracted per unit volume. The thickness of the positive electrode body was almost equal.
【０００４】[0004]
【発明が解決しようとする課題】リチウム二次電池の厚
みの大部分は正極体及び負極体により占められている。
したがって、リチウム二次電池薄型化のためには、電極
体の厚みを減少する事が最も効果的であるが、そのため
には電極体単位体積当たりのリチウムイオン吸蔵・放出
量を増加する必要がある。しかし従来正極体に用いるリ
チウム含有遷移金属酸化物は、結晶中に吸蔵し得るリチ
ウムイオンの量が理論的に一定であるため、リチウムイ
オン吸蔵量の大巾増加は困難であった。また負極体とし
て用いられる炭素材料も、結晶性の黒鉛系炭素材料にお
いてはリチウムイオン吸蔵量に理論的に限界があり、ア
モルファス化したピッチ系炭素材料においても電流密度
の高い領域ではリチウムイオン吸蔵量の増加が困難であ
った。即ち、上記従来のリチウムイオン二次電池におい
ては、薄型化に一定の限界があった。Most of the thickness of a lithium secondary battery is occupied by a positive electrode body and a negative electrode body.
Therefore, to reduce the thickness of the lithium secondary battery, it is most effective to reduce the thickness of the electrode body, but for that purpose, it is necessary to increase the amount of lithium ions absorbed and released per unit volume of the electrode body. . However, it has been difficult for lithium-containing transition metal oxides conventionally used for the positive electrode body to greatly increase the amount of lithium ions absorbed because the amount of lithium ions that can be absorbed in the crystal is theoretically constant. The carbon material used as the negative electrode body also has a theoretical limit on the amount of lithium ion occlusion in a crystalline graphite-based carbon material, and the amount of lithium ion occlusion in a region where the current density is high even in an amorphous pitch-based carbon material. Was difficult to increase. That is, in the above-described conventional lithium ion secondary battery, there is a certain limit to the reduction in thickness.
【０００５】しかしながら、種々検討の結果、負極体に
ついては、炭素材料に代え、体積膨張率が正極体よりも
大きな材料に変更することにより、リチウムイオン吸蔵
・放出量を大巾増加し、電極体の厚み減少が可能である
ことがわかった。こうした材料として例えば、スズ酸化
物（特開平０７−２６３０２８号公報）、ケイ素酸化物
（特開平０６−３２５７６５号公報）、リチウム遷移金
属複合窒化物（特開平０９−１０２３１１号公報）、ケ
イ素／炭素複合物（ＷＯ９８／２４１３５号）等が報告
されており、これらはいずれも正極の２倍以上のリチウ
ムイオン吸蔵・放出が可能である。However, as a result of various investigations, the negative electrode body was replaced with a material having a larger volume expansion coefficient than that of the positive electrode body instead of the carbon material, thereby greatly increasing the amount of lithium ion occlusion and release, and thus the electrode body. It was found that the thickness could be reduced. Examples of such materials include tin oxide (JP-A-07-263028), silicon oxide (JP-A-06-325765), lithium transition metal composite nitride (JP-A-09-102311), and silicon / carbon. Composites (WO98 / 24135) and the like have been reported, and all of them can occlude and release lithium ions more than twice as much as the positive electrode.
【０００６】[0006]
【課題を解決するための手段】本発明においては、リチ
ウム二次電池において、負極体の体積膨張率（リチウム
イオン吸蔵時とリチウムイオン放出時との体積比）が正
極体よりも大きく、かつ負極体の厚みを、放電時を基準
として正極体の厚みの半分以下とすることにより、リチ
ウム二次電池の薄型化が可能であることを見出した。According to the present invention, in a lithium secondary battery, the negative electrode body has a larger volume expansion coefficient (volume ratio between lithium ion occlusion and lithium ion release) than the positive electrode body, and It has been found that the thickness of the lithium secondary battery can be reduced by setting the thickness of the body to half or less of the thickness of the positive electrode body on the basis of discharge.
【０００７】[0007]
【発明の実施の形態】本発明は、正極体材料に比較して
体積膨張率の大きな材料を負極体とし、かつ放電時を基
準として正極体の半分以下の厚さとする。この負極体と
正極体をイオン伝導層を介して配置し、これを積層し又
は巻回して容器中に密閉して薄型のリチウム二次電池を
提供するものである。DETAILED DESCRIPTION OF THE INVENTION In the present invention, a material having a larger volume expansion coefficient than a material of a positive electrode body is used as a negative electrode body, and has a thickness not more than half the thickness of the positive electrode body on the basis of discharge. The negative electrode body and the positive electrode body are arranged via an ion conductive layer, and are laminated or wound and sealed in a container to provide a thin lithium secondary battery.
【０００８】本発明の正極体材料には、一般的なリチウ
ムイオン吸蔵・放出材料が使用でき、例えば遷移金属の
リチウム含有酸化物、好ましくはコバルト、ニッケル又
はマンガンを金属元素とする金属酸リチウムが使用でき
る。As the positive electrode material of the present invention, a general lithium ion occlusion / release material can be used. For example, a lithium-containing oxide of a transition metal, preferably lithium metal oxide containing cobalt, nickel or manganese as a metal element is used. Can be used.
【０００９】一方、負極体材料は、正極体に比較して体
積膨張率の高い材料が使用でき、例えば、スズ酸化物、
ケイ素酸化物、リチウム遷移金属複合窒化物、ケイ素／
炭素複合物等が使用できる。体積膨張率とは、リチウム
イオン充電時と放電時との体積比である。これらの負極
体材料は、正極体よりも大きな体積膨張率を示す。例え
ば、最も一般的な正極体であるコバルト酸リチウムの体
積膨張率が約１０３％であるのに対し、スズ酸化物、ケ
イ素酸化物、リチウム遷移金属複合窒化物、ケイ素／炭
素複合物等は約１４０〜２００％の体積膨張率を示す。On the other hand, as the negative electrode body material, a material having a higher volume expansion coefficient than the positive electrode body can be used.
Silicon oxide, lithium transition metal composite nitride, silicon /
Carbon composites and the like can be used. The volume expansion rate is a volume ratio between lithium ion charging and discharging. These negative electrode materials show a larger volume expansion coefficient than the positive electrode material. For example, while the volume expansion coefficient of lithium cobalt oxide, which is the most common cathode body, is about 103%, tin oxide, silicon oxide, lithium transition metal composite nitride, silicon / carbon composite, etc. It shows a volume expansion coefficient of 140 to 200%.
【００１０】リチウムイオン充放電に伴う体積膨張率が
大きな材料を用いることにより、負極体の単位体積当た
りのリチウムイオン吸蔵・放出量を増加して負極の薄型
化を行うことが可能となる。上記負極体材料は、いずれ
も正極体材料に比べて単位体積当たり２倍以上のリチウ
ムイオンを吸蔵・放出可能である。By using a material having a large volume expansion rate due to lithium ion charging / discharging, the amount of lithium ions absorbed and released per unit volume of the negative electrode body can be increased, and the negative electrode can be made thinner. Each of the above-mentioned negative electrode materials can occlude and release twice or more lithium ions per unit volume as compared with the positive electrode material.
【００１１】したがって、本発明のリチウム二次電池
は、従来正極体と同等であった負極体の厚みその半分以
下とすることにより電池を薄型化しながら、従来の電池
と同等の容量、即ち従来同等のリチウムイオンの吸蔵・
放出量を保ち得る。Therefore, the lithium secondary battery of the present invention has a capacity equal to that of the conventional battery, that is, a capacity equivalent to that of the conventional battery, while being reduced in thickness by making the thickness of the negative electrode body equal to or less than half the thickness of the conventional positive electrode body. Occlusion of lithium ions
Can maintain release.
【００１２】尚、負極体の厚みを正極体の半分以下とす
ることは、電池薄型化と同時に、良好なサイクル特性を
得る観点においても重要な意味を持つ。リチウムイオン
吸蔵・放出時の正極体及び負極体の体積膨張・収縮に起
因して電池全体の厚みが変化するが、電池全体厚みの変
化は、サイクル特性劣化の原因となり得る。例えば、リ
チウム二次電池は、一般に正極集電体、正極体、非水電
解液を含有するセパレータ若しくは高分子電解質、負極
体、負極集電体の積層体から成り、この積層体が複数枚
重ねられ若しくは巻き回されて外装缶等の容器中に密封
されるが、この積層体各層間の電気的接触は外装缶から
の圧力によって維持されている場合が多い。したがっ
て、電極体の膨張により電池の厚みが増した場合、上記
積層体には外装缶からの大きな圧力がかかり、正極体−
負極体間の短絡を招くおそれがある。一方、電極体の収
縮により電池の厚みが減少した場合は、上記積層体にか
かる圧力が減少し、積層体各層間の電気的接触が不十分
となるため、電池内部抵抗の増加によるサイクル特性の
劣化を招くおそれがある。よって、負極体の体積膨張率
が正極体に比べて大きな場合、負極体の厚みの正極体厚
みに対する比率が高いほど電池全体の厚み変化が増大
し、サイクル特性が劣化する。即ち、本発明において、
負極体の厚みを正極体の半分以下とすることは、電池を
薄型化すると同時に電池サイクル特性の劣化を抑制する
効果を持つ。It is important to make the thickness of the negative electrode body less than half the thickness of the positive electrode body from the viewpoint of obtaining good cycle characteristics while reducing the thickness of the battery. The thickness of the entire battery changes due to volume expansion and contraction of the positive electrode body and the negative electrode body at the time of lithium ion occlusion and release, and the change in the overall battery thickness may cause deterioration of cycle characteristics. For example, a lithium secondary battery generally includes a positive electrode current collector, a positive electrode body, a separator or a polymer electrolyte containing a non-aqueous electrolyte, a negative electrode body, and a negative electrode current collector. The laminate is wound or wound and sealed in a container such as an outer can, but the electrical contact between the layers of the laminate is often maintained by the pressure from the outer can. Therefore, when the thickness of the battery increases due to the expansion of the electrode body, a large pressure is applied to the laminate from the outer can, and the positive electrode
There is a possibility that a short circuit may occur between the negative electrode bodies. On the other hand, when the thickness of the battery decreases due to contraction of the electrode body, the pressure applied to the laminate decreases, and electrical contact between the layers of the laminate becomes insufficient. Deterioration may be caused. Therefore, when the volume expansion coefficient of the negative electrode body is larger than that of the positive electrode body, as the ratio of the thickness of the negative electrode body to the thickness of the positive electrode body increases, the change in the thickness of the entire battery increases, and the cycle characteristics deteriorate. That is, in the present invention,
Making the thickness of the negative electrode body less than half the thickness of the positive electrode body has the effect of reducing the thickness of the battery and at the same time suppressing the deterioration of the battery cycle characteristics.
【００１３】また、負極体は、電池容量を維持しながら
電池を薄型化するためには正極体よりも高い体積膨張率
を有することが必要であるが、一方サイクル特性の観点
からはできるだけ低い体積膨張率を有することが好まし
い。上述の負極体材料中、ケイ素／炭素複合物、特にこ
れを高温焼成したケイ素／炭素複合焼成物は、他の材料
と同等のリチウムイオンを吸蔵・放出可能でありなが
ら、体積膨張率が低いため最も好ましい材料である。ス
ズ酸化物、ケイ素酸化物、リチウム遷移金属複合窒化物
がいずれも２００％近い体積膨張率を示すのに対し、ケ
イ素／炭素複合焼成物の体積膨張率は約１４０％にとど
まる。Further, the negative electrode body needs to have a higher volume expansion coefficient than the positive electrode body in order to make the battery thinner while maintaining the battery capacity. On the other hand, from the viewpoint of cycle characteristics, the negative electrode body has a volume as low as possible. It preferably has an expansion coefficient. Among the above-mentioned negative electrode materials, the silicon / carbon composite, especially the fired silicon / carbon composite obtained by sintering the silicon / carbon composite at a high temperature, can absorb and release lithium ions equivalent to other materials, but has a low volume expansion coefficient. It is the most preferred material. Tin oxide, silicon oxide, and lithium transition metal composite nitride all exhibit a volume expansion coefficient of nearly 200%, while the silicon / carbon composite fired product has a volume expansion coefficient of only about 140%.
【００１４】また、ケイ素／炭素複合焼成物は、スズ酸
化物及びケイ素酸化物に比して約１．５倍の初回充放電
効率を示し、空気及び水と容易に反応するリチウム遷移
金属複合窒化物に比して電池製造工程における取り扱い
が容易である。即ち、ケイ素／炭素複合焼成物は、充放
電効率及び電池製造時の取り扱い容易の観点からも好ま
しい負極体材料であると言える。[0014] The fired silicon / carbon composite exhibits an initial charge / discharge efficiency of about 1.5 times that of tin oxide and silicon oxide, and easily reacts with air and water. It is easier to handle in a battery manufacturing process than a product. That is, it can be said that the silicon / carbon composite fired product is a preferable negative electrode material from the viewpoint of charge / discharge efficiency and easy handling during battery production.
【００１５】ケイ素／炭素複合焼成物は、ケイ素材料を
有機材料又は炭素材料の共存下で、非酸化雰囲気中にお
いて熱処理することにより得られる。ケイ素材料には、
ケイ素単体の使用が望ましいが、焼成によりケイ素に変
化し得るケイ素化合物を用いても良く、例えば、酸化ケ
イ素などの無機ケイ素化合物や、シリコーン樹脂、有機
ケイ素化合物等の材料を用いることができる。有機材料
は熱処理により炭化する材料であれば良く、特に限定さ
れないが、例えばウレタン樹脂、フェノール樹脂、ポリ
フッ化ビニリデン等が挙げられる。炭素材料には、黒
鉛、ピッチ等の易黒鉛化性炭素、ガラス状炭素等の難黒
鉛化性炭素のいずれも使用可能である。ケイ素／炭素複
合焼成物は、炭化が十分に進行し、二酸化ケイ素や炭化
ケイ素を実質的に含まないことが望ましく、そのために
は、熱処理を、窒素雰囲気等の非酸化性雰囲気下、４０
０〜１５００℃で行うことが好ましい。４００℃未満の
処理では炭化が不十分であり、１５００℃を超える熱処
理では炭化ケイ素が生成するからである。The fired silicon / carbon composite can be obtained by heat-treating a silicon material in the presence of an organic material or a carbon material in a non-oxidizing atmosphere. Silicon materials include:
Although it is preferable to use silicon alone, a silicon compound that can be converted into silicon by firing may be used. For example, materials such as an inorganic silicon compound such as silicon oxide, a silicone resin, and an organic silicon compound can be used. The organic material may be any material that can be carbonized by heat treatment, and is not particularly limited. Examples thereof include a urethane resin, a phenol resin, and polyvinylidene fluoride. As the carbon material, any of graphitizable carbon such as graphite and pitch, and non-graphitizable carbon such as glassy carbon can be used. It is desirable that the silicon / carbon composite fired product is sufficiently carbonized and substantially free of silicon dioxide and silicon carbide. For that purpose, heat treatment is performed under a non-oxidizing atmosphere such as a nitrogen atmosphere under a non-oxidizing atmosphere.
It is preferably performed at 0 to 1500 ° C. This is because carbonization is insufficient at a temperature lower than 400 ° C., and silicon carbide is generated at a temperature higher than 1500 ° C.
【００１６】ところで、上述の負極体及び正極体材料
は、いずれも粉体であるため、これらを一体成形して電
極体を形成する必要がある。電極体形成法は、大きく塗
膜法と燒結法とに分類される。塗膜法は、電極体材料、
バインダー及び導電材等の混合物を溶媒分散させたスラ
リーを調整し、これを集電体となる金属箔に塗布し、溶
媒揮発させて塗膜体に形成する方法である。燒結法は、
電極体材料を導電材等と共にペレット状に加圧成形後、
高温燒結させて燒結体に形成する方法である。燒結法に
は、塗膜法により形成した塗膜体を加圧成形し、高温燒
結させて燒結体とする方法もある。一般に、燒結法は、
塗膜法に比して同じ電気容量に対して約２０−４０％薄
い電極を形成可能である。本発明の負極体及び正極体の
形成には、塗膜法及び燒結法のいずれを用いても良く、
異種の方法の組み合わせでも良い。Since the above-mentioned negative electrode body and positive electrode body material are both powders, it is necessary to integrally form them to form an electrode body. Electrode body forming methods are broadly classified into a coating method and a sintering method. The coating method uses electrode material,
In this method, a slurry in which a mixture of a binder, a conductive material, and the like is dispersed in a solvent is prepared, the slurry is applied to a metal foil serving as a current collector, and the solvent is volatilized to form a coated body. The sintering method is
After pressure molding the electrode material together with the conductive material into a pellet,
This is a method of sintering at a high temperature to form a sintered body. As a sintering method, there is also a method in which a coated body formed by the coating method is pressure-formed and sintered at a high temperature to obtain a sintered body. Generally, the sintering method is
It is possible to form an electrode which is about 20-40% thinner for the same electric capacity as compared with the coating method. For the formation of the negative electrode body and the positive electrode body of the present invention, any of a coating method and a sintering method may be used,
A combination of different methods may be used.
【００１７】負極体及び正極体を燒結法で形成する場
合、正極体厚みは４０〜１０００μｍ、好ましくは２０
０〜４００μｍとすることが望ましく、負極体厚みは２
０〜５００μｍ、好ましくは５０〜１５０μｍとするこ
とが望ましい。電極体厚みの好適値上限は高電流密度に
おける容量の低下抑制の観点に基づくものであり、厚み
好適値下限は充放電に寄与しない構成部材の体積比率を
抑制する観点に基づくものである。When the negative electrode body and the positive electrode body are formed by a sintering method, the thickness of the positive electrode body is 40 to 1000 μm, preferably 20 to 1000 μm.
The thickness of the negative electrode body is desirably 2 to 400 μm.
It is desirable that the thickness be 0 to 500 μm, preferably 50 to 150 μm. The upper limit of the preferable thickness of the electrode body is based on the viewpoint of suppressing a decrease in capacity at a high current density, and the lower limit of the preferable thickness is based on the viewpoint of suppressing the volume ratio of a component that does not contribute to charging and discharging.
【００１８】一方、負極体及び正極体を塗膜法により形
成する場合、燒結法と同様の理由から、正極体厚みを４
０〜３００μｍとし、負極体厚みを２０〜１５０μｍと
することが望ましい。On the other hand, when the negative electrode body and the positive electrode body are formed by a coating method, the thickness of the positive electrode body is set to 4 for the same reason as in the sintering method.
It is desirable that the thickness be 0 to 300 μm and the thickness of the negative electrode body be 20 to 150 μm.
【００１９】尚、本発明のリチウム二次電池に使用する
電解質には、有機溶媒にリチウム化合物を溶解させた非
水電解液、又はリチウム化合物を固溶あるいはリチウム
化合物を溶解させた有機溶媒を保持させた高分子固体電
解質を用いることができる。上記有機溶媒やリチウム化
合物はこの種の電池に用いられるものであればいずれも
使用可能である。The electrolyte used in the lithium secondary battery of the present invention contains a nonaqueous electrolyte in which a lithium compound is dissolved in an organic solvent, or a solid solution of a lithium compound or an organic solvent in which a lithium compound is dissolved. The solid polymer electrolyte thus formed can be used. Any of the above organic solvents and lithium compounds can be used as long as they are used in this type of battery.
【００２０】[0020]
【実施例】実施例１ （正極体の作製）炭酸リチウム粉末と炭酸コバルト粉末
をモル比１：１となるよう混合し、大気雰囲気中８００
℃にて１時間仮焼成した。次いでこれを粉砕し、平均粒
径５μｍの球状ポリメチルメタクリレート粒子を混合し
て加圧成形し、大気雰囲気中８００℃で１０時間焼成し
直径１９ｍｍ、厚さ０．５ｍｍの正極体を得た。EXAMPLE 1 (Preparation of positive electrode body) Lithium carbonate powder and cobalt carbonate powder were mixed at a molar ratio of 1: 1 and 800
Calcination was performed for 1 hour at ℃. Next, this was pulverized, mixed with spherical polymethyl methacrylate particles having an average particle size of 5 μm, pressed, and fired at 800 ° C. for 10 hours in an air atmosphere to obtain a positive electrode body having a diameter of 19 mm and a thickness of 0.5 mm.
【００２１】（負極体の作製）純度９９．９％、平均粒
径１μｍの結晶質ケイ素粉末（高純度化学（株）製）８
０重量部とグラファイト／ピッチ混合物（グラファイト
９０重量部とピッチ１０重量部の混合物、商品名グラフ
ィトン、大阪化成（株）製）２０重量部とを窒素雰囲気
下１１００℃３時間焼成した後、粉砕して原料粉末を得
た。原料粉末９０重量部とポリフッ化ビニリデンのｎ−
メチル−２−ピロリドン溶液（１４重量％）７０重量部
とを混合してペースト状とし、その一部をポリエチレン
テレフタレート製シートに塗布後、１００ｇ／ｍ2の圧
力で圧着して乾燥させた。これを直径１９ｍｍの円板形
に切り出し、窒素雰囲気下８００℃で３時間焼成して厚
さ０．２ｍｍの負極体を得た。(Preparation of Negative Electrode Body) Crystalline silicon powder having a purity of 99.9% and an average particle diameter of 1 μm (manufactured by Kojundo Chemical Co., Ltd.) 8
0 parts by weight and 20 parts by weight of a graphite / pitch mixture (a mixture of 90 parts by weight of graphite and 10 parts by weight of pitch, trade name: Grafton, manufactured by Osaka Kasei Co., Ltd.) are fired at 1100 ° C. for 3 hours in a nitrogen atmosphere, and then pulverized. Thus, a raw material powder was obtained. 90 parts by weight of raw material powder and n-polyvinylidene fluoride
It was mixed with 70 parts by weight of a methyl-2-pyrrolidone solution (14% by weight) to form a paste. A part of the paste was applied to a polyethylene terephthalate sheet, and then pressed and dried under a pressure of 100 g / m 2 . This was cut into a disk shape having a diameter of 19 mm and fired at 800 ° C. for 3 hours in a nitrogen atmosphere to obtain a negative electrode body having a thickness of 0.2 mm.
【００２２】（コイン型電池の作製）得られた正極体、
負極体各２枚を、正極集電体であるアルミニウム箔、負
極集電体である銅箔及びセパレーターとともに電気的並
列接続となるよう積層し、ステンレス製外装缶に収納し
て厚さ１．８ｍｍのコイン型電池を作製した。尚、電解
液にはエチレンカーボネートとジメチルカーボネートの
混合溶媒（体積比１：１）に六フッ化リンリチウムを１
ｍｏｌ／ｌ溶解したものを用いた。(Preparation of coin type battery)
Two pieces of the negative electrode body are laminated together with an aluminum foil as a positive electrode current collector, a copper foil as a negative electrode current collector and a separator so as to be electrically connected in parallel, and housed in a stainless steel outer can to have a thickness of 1.8 mm. Was manufactured. The electrolyte was prepared by mixing lithium phosphate hexafluoride in a mixed solvent of ethylene carbonate and dimethyl carbonate (volume ratio 1: 1).
The solution dissolved in mol / l was used.
【００２３】（コイン型電池の評価）４．１Ｖ−２．５
ｖ間において繰り返し充放電を行い、充放電に伴う電池
厚みの変化量及び放電容量を測定した。電池厚みの変化
量とは、充放電時の厚み変化量の放電終了時厚みに対す
る比率であり、初め１０サイクルの平均値とした。電池
厚みの変化量は約５％であり、３０サイクル後の放電容
量は初回放電容量の約８５％であった。(Evaluation of coin-type battery) 4.1 V-2.5
The battery was repeatedly charged and discharged during v, and the change in battery thickness and the discharge capacity due to the charge and discharge were measured. The amount of change in the battery thickness is a ratio of the amount of change in the thickness during charge / discharge to the thickness at the end of discharge, and was initially an average value of 10 cycles. The change in battery thickness was about 5%, and the discharge capacity after 30 cycles was about 85% of the initial discharge capacity.
【００２４】実施例２ 正極体及び負極体の厚み、積層枚数を除いては、実施例
１と同様の方法によりコイン型電池を作製した。正極体
の厚みを０．３ｍｍ、負極体の厚みを０．１ｍｍとし、
正極体及び負極体各４枚を積層して厚さ３ｍｍのコイン
型電池を作製した。電池厚みの変化量は約７％であり、
３０サイクル後の放電容量は初回放電容量の約９０％で
あった。Example 2 A coin-type battery was manufactured in the same manner as in Example 1 except for the thickness of the positive electrode body and the negative electrode body and the number of laminated layers. The thickness of the positive electrode body is 0.3 mm, the thickness of the negative electrode body is 0.1 mm,
Four positive electrode bodies and four negative electrode bodies were laminated to prepare a coin-type battery having a thickness of 3 mm. The change in battery thickness is about 7%,
The discharge capacity after 30 cycles was about 90% of the initial discharge capacity.
【００２５】比較例 正極体及び負極体の厚み、積層枚数を除いては、実施例
１と同様の方法によりコイン型電池を作製した。正極体
の厚みを０．２ｍｍ、負極体の厚みを０．２ｍｍとし、
正極体及び負極体各４枚を積層して厚さ３ｍｍのコイン
型電池を作製した。電池厚みの変化量は約１４％であ
り、３０サイクル後の放電容量は初回放電容量の約７０
％であった。Comparative Example A coin-type battery was manufactured in the same manner as in Example 1 except for the thickness of the positive electrode body and the negative electrode body and the number of stacked layers. The thickness of the positive electrode body is 0.2 mm, the thickness of the negative electrode body is 0.2 mm,
Four positive electrode bodies and four negative electrode bodies were laminated to prepare a coin-type battery having a thickness of 3 mm. The change in battery thickness was about 14%, and the discharge capacity after 30 cycles was about 70% of the initial discharge capacity.
%Met.
【００２６】実施例１、２は、負極体の厚みを正極体の
厚みの半分以下として薄型電池を作製したものであり、
比較的良好なサイクル特性を示している。一方、比較例
は、負極体の厚みを正極体の厚み同等として薄型電池を
作製しており、実施例１及び２に対し、サイクル特性が
劣っている。比較例は電池厚みの変化量が実施例１及び
２の２倍以上であったことより、充放電に伴う電池の厚
み変化に起因する集電体−電極体間の接触抵抗の増加の
ためサイクル特性が劣化したものと考えられる。In Examples 1 and 2, a thin battery was manufactured by setting the thickness of the negative electrode body to half or less of the thickness of the positive electrode body.
It shows relatively good cycle characteristics. On the other hand, in the comparative example, a thin battery was manufactured with the thickness of the negative electrode body equal to the thickness of the positive electrode body, and the cycle characteristics were inferior to those of Examples 1 and 2. In the comparative example, the amount of change in the battery thickness was more than twice that in Examples 1 and 2, and the cycle was increased due to the increase in the contact resistance between the current collector and the electrode body due to the change in the thickness of the battery due to charging and discharging. It is considered that the characteristics were deteriorated.
【００２７】[0027]
【発明の効果】本発明は以上説明したように構成されて
いるため、電気容量を確保しながらリチウム二次電池の
薄型化を可能とする。As described above, the present invention is configured as described above, so that the thickness of the lithium secondary battery can be reduced while securing the electric capacity.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 一色 信之 和歌山県和歌山市湊1334番地 花王株式会 社研究所内 Ｆターム(参考） 5H003 AA02 AA04 BA01 BA03 BB01 BB04 BB05 BD00 BD02 5H014 AA02 AA06 BB01 BB06 CC01 EE08 EE10 HH00 HH06 5H029 AJ00 AJ03 AJ05 AK03 AL01 AL02 AL06 AL18 AM03 AM05 AM07 BJ02 BJ03 BJ12 BJ14 CJ01 CJ02 CJ22 DJ02 DJ04 DJ11 HJ00 HJ04 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Nobuyuki Isshiki 1334 Minato, Wakayama-shi, Wakayama Prefecture F-term in Kao Corporation Research Laboratories (Reference) 5H003 AA02 AA04 BA01 BA03 BB01 BB04 BB05 BD00 BD02 5H014 AA02 AA06 BB01 BB06 CC01 EE08 EE10 EE10 HH00 HH06 5H029 AJ00 AJ03 AJ05 AK03 AL01 AL02 AL06 AL18 AM03 AM05 AM07 BJ02 BJ03 BJ12 BJ14 CJ01 CJ02 CJ22 DJ02 DJ04 DJ11 HJ00 HJ04
Claims (4)
置し、これを積層し又は巻回して容器中に密封してなる
リチウム二次電池において、 前記負極体の体積膨張率（リチウムイオン吸蔵時とリチ
ウムイオン放出時との体積比）が前記正極体よりも大き
く、かつ該負極体の厚みを、放電時を基準として該正極
体の厚みの半分以下としたことを特徴とするリチウム二
次電池。1. A lithium secondary battery in which a negative electrode body and a positive electrode body are arranged via an ion conductive layer, and are laminated or wound and sealed in a container. The volume ratio between the time of occlusion of ions and the time of release of lithium ions) is greater than that of the positive electrode body, and the thickness of the negative electrode body is set to be equal to or less than half the thickness of the positive electrode body based on discharge. Rechargeable battery.
ケルから成る群より選択された１つの金属のリチウム含
有酸化物を含む一方、前記負極体が、ズズ酸化物、ケイ
素酸化物、リチウム遷移金属複合窒化物、ケイ素／炭素
複合物から成る群より選択された１つを含む請求項１記
載のリチウム二次電池。2. The positive electrode body includes a lithium-containing oxide of one metal selected from the group consisting of cobalt, manganese, and nickel, while the negative electrode body includes a tin oxide, a silicon oxide, and a lithium transition metal. 2. The lithium secondary battery according to claim 1, comprising one selected from the group consisting of a composite nitride and a silicon / carbon composite.
有機材料又は炭素材料の存在下において熱処理して得ら
れるケイ素／炭素複合焼成物を含む請求項２記載のリチ
ウム二次電池。3. The lithium secondary battery according to claim 2, wherein the negative electrode body includes a silicon / carbon composite fired product obtained by heat-treating silicon or a compound thereof in the presence of an organic material or a carbon material.
結体、または厚み２０〜１５０μｍの塗膜体である請求
項１記載のリチウム二次電池。4. The lithium secondary battery according to claim 1, wherein the negative electrode body is a sintered body having a thickness of 20 to 500 μm or a coated body having a thickness of 20 to 150 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36191198A JP3291260B2 (en) | 1998-12-03 | 1998-12-03 | Lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36191198A JP3291260B2 (en) | 1998-12-03 | 1998-12-03 | Lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000173667A true JP2000173667A (en) | 2000-06-23 |
| JP3291260B2 JP3291260B2 (en) | 2002-06-10 |
Family
ID=18475271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP36191198A Expired - Fee Related JP3291260B2 (en) | 1998-12-03 | 1998-12-03 | Lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3291260B2 (en) |
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| US11387443B1 (en) | 2021-11-22 | 2022-07-12 | Enevate Corporation | Silicon based lithium ion battery and improved cycle life of same |
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| JP3291260B2 (en) | 2002-06-10 |
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