JPH10188957A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JPH10188957A JPH10188957A JP8355330A JP35533096A JPH10188957A JP H10188957 A JPH10188957 A JP H10188957A JP 8355330 A JP8355330 A JP 8355330A JP 35533096 A JP35533096 A JP 35533096A JP H10188957 A JPH10188957 A JP H10188957A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- carbon material
- lithium secondary
- charge
- 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.)
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明が属する技術分野】本発明は、炭素材料を負極の
リチウムイオン吸蔵材とするリチウム二次電池に係わ
り、詳しくは充放電サイクル特性を改善することを目的
とした、負極の改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery using a carbon material as a lithium ion storage material for a negative electrode, and more particularly to an improvement of a negative electrode for the purpose of improving charge / discharge cycle characteristics.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】近年、
非水電解液を電解液として使用するリチウム二次電池
が、アルカリ水溶液を電解液として使用するアルカリ二
次電池と異なり、水の分解電圧を考慮する必要がないた
めに高電圧設計が可能であるなどの理由から、注目され
ている。2. Description of the Related Art In recent years,
Unlike a lithium secondary battery using a non-aqueous electrolyte as an electrolyte, unlike an alkaline secondary battery using an alkaline aqueous solution as an electrolyte, a high voltage design is possible because there is no need to consider the decomposition voltage of water. For such reasons, attention has been paid.
【０００３】従来、この種の二次電池の負極材料として
は、当初、金属リチウムが考えられていたが、金属リチ
ウムを使用した場合は、樹枝状の電析リチウムがセパレ
ータを貫通し、内部短絡が起こる虞れがあるため、最近
の実用電池では、リチウムイオンを電気化学的に吸蔵及
び放出することが可能な炭素材料が負極材料として使用
されている。Conventionally, metallic lithium was initially considered as a negative electrode material for this type of secondary battery. However, when metallic lithium is used, dendritic electrodeposited lithium penetrates through the separator, causing an internal short circuit. Therefore, in a recent practical battery, a carbon material capable of electrochemically storing and releasing lithium ions is used as a negative electrode material.
【０００４】炭素材料を使用した負極は、炭素材料と結
着剤とを混練して得た負極合剤を加圧成形したり、炭素
材料、結着剤及び増粘剤からなるスラリー乃至ペースト
を導電性の基体に塗布したり、することにより作製され
る。A negative electrode using a carbon material is prepared by kneading a carbon material and a binder to form a negative electrode mixture under pressure, or forming a slurry or paste comprising a carbon material, a binder and a thickener. It is produced by coating or applying to a conductive substrate.
【０００５】しかしながら、この種の負極を使用した場
合、結着剤や増粘剤が、負極が電解液を均一に保持する
のを妨げるので、充放電反応が均一に行われにくく、炭
素材料に局所的な劣化が起こり易い。このため、この種
の負極を使用したリチウム二次電池には、充放電サイク
ルに伴う電池容量の低下が著しい、すなわち充放電サイ
クル特性が良くない、という問題がある。However, when this type of negative electrode is used, the binder and the thickener prevent the negative electrode from holding the electrolytic solution uniformly, so that the charge / discharge reaction is difficult to be performed uniformly, and the carbon material is hardly used. Local degradation is likely to occur. For this reason, the lithium secondary battery using this kind of negative electrode has a problem that the battery capacity is significantly reduced due to charge / discharge cycles, that is, the charge / discharge cycle characteristics are not good.
【０００６】したがって、本発明は、充放電サイクル特
性に優れた、炭素材料を負極のリチウムイオン吸蔵材と
するリチウム二次電池を提供することを目的とする。Accordingly, an object of the present invention is to provide a lithium secondary battery using a carbon material as a lithium ion storage material for a negative electrode, which is excellent in charge / discharge cycle characteristics.
【０００７】[0007]
【課題を解決するための手段】本発明に係るリチウム二
次電池（以下、「本発明電池」と称する）は、正極と、
炭素材料をリチウムイオン吸蔵材とする負極と、電解液
とを備えるリチウム二次電池であって、前記炭素材料
に、電解液を孔内に保持することが可能な無機多孔質粒
子粉末が添加混合されている。A lithium secondary battery according to the present invention (hereinafter referred to as "battery of the present invention") comprises a positive electrode,
A lithium secondary battery including a negative electrode using a carbon material as a lithium ion storage material and an electrolyte, wherein inorganic carbon particles capable of holding the electrolyte in pores are added to the carbon material. Have been.
【０００８】無機多孔質粒子粉末の具体例としては、シ
リカゲル、アルミナ及びシリカアルミナの各粒子粉末が
挙げられる。無機多孔質粒子粉末は、一種単独を使用し
てもよく、必要に応じて二種以上を併用してもよい。Specific examples of the inorganic porous particle powder include silica gel, alumina and silica-alumina particle powder. One kind of the inorganic porous particle powder may be used alone, or two or more kinds thereof may be used in combination as needed.
【０００９】無機多孔質粒子粉末としては、Ａｒ（アル
ゴン）を被吸着体とするＢＥＴ法による比表面積が１０
０ｍ2 ／ｇ以上のものが電解液を保持する能力に優れて
おり、好ましい。The inorganic porous particle powder has a specific surface area of 10 according to the BET method using Ar (argon) as an object to be adsorbed.
Those having 0 m 2 / g or more are excellent in the ability to hold the electrolyte and are preferred.
【００１０】無機多孔質粒子粉末の好適な添加量は、炭
素材料１００重量部に対して、０．５〜１０重量部であ
る。同添加量が０．５重量部未満の場合は、負極の含液
性が充分に改善されず、充放電反応が充分に均一化され
ない。一方、同添加量が１０重量部を超えた場合は、炭
素材料の充填量が減少するため、充放電サイクル初期の
電池容量が小さくなるとともに、芯体（集電体）との密
着性が悪くなるため、充放電サイクル時に活物質が芯体
から剥離して、充放電サイクル特性が低下する。The preferable addition amount of the inorganic porous particle powder is 0.5 to 10 parts by weight based on 100 parts by weight of the carbon material. If the amount is less than 0.5 part by weight, the liquid content of the negative electrode is not sufficiently improved, and the charge / discharge reaction is not sufficiently uniform. On the other hand, when the addition amount exceeds 10 parts by weight, the filling amount of the carbon material decreases, so that the battery capacity at the beginning of the charge / discharge cycle decreases and the adhesion to the core (current collector) deteriorates. Therefore, the active material peels off from the core during the charge / discharge cycle, and the charge / discharge cycle characteristics are degraded.
【００１１】本発明の特徴は、炭素材料を負極のリチウ
ムイオン吸蔵材とするリチウム二次電池の充放電サイク
ル特性を改善するために、炭素材料に、電解液を孔内に
保持することが可能な無機多孔質粒子粉末を添加した点
にある。それゆえ、正極材料、電解液などの電池を構成
する他の材料については特に制限は無く、リチウム二次
電池用として従来使用され、或いは提案されている種々
の材料を使用することが可能である。The feature of the present invention is that an electrolyte can be held in a hole in a carbon material in order to improve the charge / discharge cycle characteristics of a lithium secondary battery using the carbon material as a lithium ion storage material for a negative electrode. In that the addition of a fine inorganic porous particle powder. Therefore, other materials constituting the battery such as the positive electrode material and the electrolyte are not particularly limited, and various materials conventionally used or proposed for lithium secondary batteries can be used. .
【００１２】正極材料としては、ＬｉＣｏＯ2 、ＬｉＮ
ｉＯ2 、ＬｉＭｎＯ2 、ＬｉＶＯ2、ＬｉＮｂＯ2 等の
金属酸化物が例示される。As the cathode material, LiCoO 2 , LiN
Metal oxides such as iO 2 , LiMnO 2 , LiVO 2 , and LiNbO 2 are exemplified.
【００１３】電解液としては、エチレンカーボネート、
プロピレンカーボネート、ブチレンカーボネート、ビニ
レンカーボネート等の環状炭酸エステル、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、メチルプロピルカーボネート、エチルプロピル
カーボネート、ブチルメチルカーボネート、ブチルエチ
ルカーボネート、ジプロピルカーボネート等の鎖状炭酸
エステル又は環状炭酸エステルと鎖状炭酸エステルとの
混合溶媒に、ＬｉＰＦ6 、ＬｉＢＦ4 、ＬｉＣＦ3 ＳＯ
3 、ＬｉＡｓＦ6 、ＬｉＮ（ＣＦ3 ＳＯ2 ）2 、ＬｉＯ
ＳＯ2 （ＣＦ2）3 ＣＦ3 等の電解質塩を溶かしたもの
が例示される。As the electrolyte, ethylene carbonate,
Propylene carbonate, butylene carbonate, cyclic carbonate such as vinylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, butyl methyl carbonate, butyl ethyl carbonate, chain carbonate such as dipropyl carbonate or LiPF 6 , LiBF 4 , LiCF 3 SO in a mixed solvent of a cyclic carbonate and a chain carbonate
3, LiAsF 6, LiN (CF 3 SO 2) 2, LiO
An example in which an electrolyte salt such as SO 2 (CF 2 ) 3 CF 3 is dissolved is exemplified.
【００１４】本発明電池の負極は、炭素材料と無機多孔
質粒子粉末と結着剤とを混練して得た負極合剤を加圧成
形したり、炭素材料、無機多孔質粒子粉末、結着剤及び
増粘剤からなるスラリー乃至ペーストを導電性の基体に
塗布したり、することにより作製される。結着剤の具体
例としては、スチレン−ブタジエン共重合体の外、メチ
ルアクリレート、メチルメタアクリレート（以下、アク
リレートとメタクリレートとを総称して（メタ）アクリ
レートと記す）、エチル（メタ）アクリレート、ブチル
（メタ）アクリレート、（メタ）アクリロニトリル、ヒ
ドロキシエチル（メタ）アクリレート等のエチレン性不
飽和カルボン酸エステル又はアルリル酸、メタクリル
酸、イタコン酸、フマル酸、マレイン酸等のエチレン性
不飽和カルボン酸の重合体又は共重合体；及びポリビニ
リデンフルオライド、ポリテトラフルオロエチレン等の
フッ素系樹脂が挙げられる。また、増粘剤の具体例とし
ては、カルボキシメチルセルロース、メチルセルロー
ス、ヒドロキシメチルセルロース、エチルセルロース、
ポリビニルアルコール、ポリアクリル酸、ポリアクリル
酸塩、酸化スターチ、リン酸化スターチ及びカゼインが
挙げられる。The negative electrode of the battery of the present invention can be formed by pressure-forming a negative electrode mixture obtained by kneading a carbon material, inorganic porous particle powder, and a binder, or forming a carbon material, inorganic porous particle powder, It is prepared by applying or applying a slurry or paste comprising an agent and a thickener to a conductive substrate. Specific examples of the binder include styrene-butadiene copolymer, methyl acrylate, methyl methacrylate (hereinafter, acrylate and methacrylate are collectively referred to as (meth) acrylate), ethyl (meth) acrylate, and butyl. (Meth) acrylate, (meth) acrylonitrile, ethylenically unsaturated carboxylic acid ester such as hydroxyethyl (meth) acrylate or the like, or heavy ethylenically unsaturated carboxylic acid such as allylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, etc. And a fluorine-based resin such as polyvinylidene fluoride and polytetrafluoroethylene. Specific examples of the thickener include carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, ethylcellulose,
Polyvinyl alcohol, polyacrylic acid, polyacrylates, oxidized starch, phosphorylated starch and casein.
【００１５】本発明電池は、電解液を孔内に保持可能な
無機多孔質粒子粉末が、負極の炭素材料に添加混合され
ているので、無添加の場合に比べて、負極に電解液が均
一いきわたる。このため、充放電反応が均一に行われる
ようになり、充放電サイクル時に炭素材料の部分的な劣
化が起こりにくくなる。In the battery of the present invention, since the inorganic porous particle powder capable of holding the electrolytic solution in the pores is added to and mixed with the carbon material of the negative electrode, the electrolytic solution is more uniform in the negative electrode than in the case of no addition. It goes all the way. For this reason, the charge / discharge reaction is performed uniformly, and partial deterioration of the carbon material during the charge / discharge cycle is less likely to occur.
【００１６】[0016]
【実施例】以下、本発明を実施例に基づいてさらに詳細
に説明するが、本発明は下記実施例に何ら限定されるも
のではなく、その要旨を変更しない範囲において適宜変
更して実施することが可能なものである。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples, and the present invention may be practiced by appropriately changing the gist of the invention. Is possible.
【００１７】（実施例１〜６） 〔正極の作製〕正極活物質としての平均粒径５μｍのＬ
ｉＣｏＯ2 粉末と、導電剤としての炭素粉末とを、重量
比９：１で混合し、この混合物９５重量部と、ポリフッ
化ビニリデン５重量部の５重量％Ｎ−メチル−２−ピロ
リドン（ＮＭＰ）溶液とを混練して正極合剤スラリーを
調製し、この正極合剤スラリーを正極集電体としてのア
ルミニウム箔の両面にドクターブレード法により塗布
し、１５０°Ｃで２時間真空乾燥して、アルミニウム箔
の各面に厚さ５０μｍの正極活物質層が形成された正極
を作製した。(Examples 1 to 6) [Preparation of positive electrode] L having an average particle size of 5 µm as a positive electrode active material
and ICoO 2 powder, a carbon powder as a conductive agent, the weight ratio of 9: 1 mixture, and the mixture 95 parts by weight, 5 wt% N-methyl-2-pyrrolidone polyvinylidene fluoride 5 parts by weight (NMP) The mixture was kneaded with a solution to prepare a positive electrode mixture slurry, and this positive electrode mixture slurry was applied to both sides of an aluminum foil as a positive electrode current collector by a doctor blade method, and vacuum-dried at 150 ° C. for 2 hours. A positive electrode having a 50 μm-thick positive electrode active material layer formed on each surface of the foil was produced.
【００１８】〔負極の作製〕平均粒径２０μｍの天然黒
鉛粉末〔ｃ軸方向の結晶子の大きさ（Ｌｃ）＞１０００
Å；格子面（００２）面の面間隔（ｄ002 ）＝３．３５
Å）〕と、結着剤としてのスチレン−ブタジエンゴム
（ＳＢＲ）ラテックス（固形分：４８重量％）とを水に
分散させ、この分散液に、Ａｒを被吸着体とするＢＥＴ
法による比表面積（以下の比表面積もこの測定法による
比表面積である）が１０、８０、１００、２００、５０
０又は１０００ｍ2 ／ｇで、平均粒径が５μｍのシリカ
ゲル（ＳｉＯ2 ）と、増粘剤としてのカルボキシメチル
セルロース（ＣＭＣ）とを混合して負極合剤スラリーを
調製した。この調製において、乾固後の負極に含まれる
天然黒鉛粉末とＳＢＲ（固形分）とシリカゲルとＣＭＣ
の重量比が１００：３：５：２になるようにした。次い
で、各負極合剤スラリーを負極集電体としての銅箔の両
面にドクターブレード法により塗布し、１１０°Ｃで２
時間真空乾燥して、銅箔の各面に厚さ５０μｍの炭素材
料層が形成された負極を作製した。[Preparation of Negative Electrode] Natural graphite powder having an average particle size of 20 μm [crystallite size (Lc) in c-axis direction> 1000]
Å; spacing (d 002 ) of lattice plane (002) plane = 3.35
Å)] and styrene-butadiene rubber (SBR) latex (solid content: 48% by weight) as a binder are dispersed in water, and BET using Ar as an object to be adsorbed is added to this dispersion.
Specific surface area (the following specific surface area is also the specific surface area according to this measurement method) is 10, 80, 100, 200, 50
A negative electrode mixture slurry was prepared by mixing silica gel (SiO 2 ) having a mean particle size of 5 μm with 0 or 1000 m 2 / g, and carboxymethyl cellulose (CMC) as a thickener. In this preparation, the natural graphite powder, SBR (solid content), silica gel and CMC contained in the dried negative electrode were used.
Was adjusted to be 100: 3: 5: 2. Next, each negative electrode mixture slurry was applied to both surfaces of a copper foil as a negative electrode current collector by a doctor blade method, and was applied at 110 ° C. for 2 hours.
After vacuum drying for a time, a negative electrode in which a carbon material layer having a thickness of 50 μm was formed on each surface of the copper foil was produced.
【００１９】〔電解液の調製〕エチレンカーボネートと
ジエチルカーボネートとの体積比２：３の混合溶媒に、
ＬｉＰＦ6 を１モル／リットル溶かして電解液を調製し
た。[Preparation of Electrolyte Solution] A mixed solvent of ethylene carbonate and diethyl carbonate at a volume ratio of 2: 3 was added to
LiPF 6 was dissolved at 1 mol / liter to prepare an electrolytic solution.
【００２０】〔リチウム二次電池の作製〕上記の正極、
各負極及び電解液を用いて、順にＡＡサイズのリチウム
二次電池Ａ１（比表面積１０ｍ2 ／ｇのシリカゲルを使
用），Ａ２（比表面積８０ｍ2 ／ｇのシリカゲルを使
用），Ａ３（比表面積１００ｍ2 ／ｇのシリカゲルを使
用），Ａ４（比表面積２００ｍ2 ／ｇのシリカゲルを使
用），Ａ５（比表面積５００ｍ2 ／ｇのシリカゲルを使
用），Ａ６（比表面積１０００ｍ2 ／ｇのシリカゲルを
使用）を作製した。セパレータとしてポリプロピレン製
の微多孔膜を使用した。[Preparation of Lithium Secondary Battery]
Using the respective negative electrodes and the electrolytic solution, AA size lithium secondary batteries A1 (using silica gel having a specific surface area of 10 m 2 / g), A2 (using silica gel having a specific surface area of 80 m 2 / g), A3 (using a specific surface area of 100 m 2 ) 2 / g of silica gel), A4 (using a silica gel with a specific surface area of 200 m 2 / g), A5 (using a silica gel with a specific surface area of 500 m 2 / g), A6 (using a silica gel with a specific surface area of 1000 m 2 / g) Was prepared. A microporous polypropylene membrane was used as a separator.
【００２１】（実施例７〜１２）負極の作製において、
シリカゲルに代えて、比表面積が１０、８０、１００、
２００、５００又は１０００ｍ2 ／ｇで、平均粒径が７
μｍのアルミナ（Ａｌ2Ｏ3 ）を使用したこと以外は実
施例１〜６と同様にして、リチウム二次電池Ａ７（比表
面積１０ｍ2 ／ｇのアルミナを使用），Ａ８（比表面積
８０ｍ2 ／ｇのアルミナを使用），Ａ９（比表面積１０
０ｍ2 ／ｇのアルミナを使用），Ａ１０（比表面積２０
０ｍ2 ／ｇのアルミナを使用），Ａ１１（比表面積５０
０ｍ2 ／ｇのアルミナを使用），Ａ１２（比表面積１０
００ｍ2 ／ｇのアルミナを使用）を作製した。(Examples 7 to 12) In the production of the negative electrode,
Instead of silica gel, the specific surface area is 10, 80, 100,
200, 500 or 1000 m 2 / g with an average particle size of 7
except for using μm of alumina (Al 2 O 3) in the same manner as in Example 1-6, (using alumina having a specific surface area of 10 m 2 / g) lithium secondary batteries A7, A8 (specific surface area 80 m 2 / g of alumina), A9 (specific surface area 10
0 m 2 / g of alumina), A10 (specific surface area 20
0 m 2 / g of alumina), A11 (specific surface area 50
0 m 2 / g alumina), A12 (specific surface area 10
00 m 2 / g alumina).
【００２２】（実施例１３〜１８）負極の作製におい
て、シリカゲルに代えて、比表面積が１０、８０、１０
０、２００、５００又は１０００ｍ2 ／ｇで、平均粒径
が５μｍのシリカアルミナ（ＳｉＯ2 とＡｌ2 Ｏ3 のモ
ル比９：１）を使用したこと以外は実施例１〜６と同様
にして、リチウム二次電池Ａ１３（比表面積１０ｍ2 ／
ｇのシリカアルミナを使用），Ａ１４（比表面積８０ｍ
2 ／ｇのシリカアルミナを使用），Ａ１５（比表面積１
００ｍ2 ／ｇのシリカアルミナを使用），Ａ１６（比表
面積２００ｍ2／ｇのシリカアルミナを使用），Ａ１７
（比表面積５００ｍ2 ／ｇのシリカアルミナを使用），
Ａ１８（比表面積１０００ｍ2 ／ｇのシリカアルミナを
使用）を作製した。(Examples 13 to 18) In the preparation of the negative electrode, the specific surface area was 10, 80, 10 instead of silica gel.
Except that 0, 200, 500 or 1000 m 2 / g and an average particle size of 5 μm silica alumina (9: 1 molar ratio of SiO 2 and Al 2 O 3 ) was used, the same as in Examples 1 to 6 , Lithium secondary battery A13 (specific surface area 10 m 2 /
g of silica alumina), A14 (specific surface area 80 m
2 / g silica alumina), A15 (specific surface area 1
00 m 2 / g silica alumina), A16 (using a specific surface area of 200 m 2 / g silica alumina), A17
(Using a silica alumina having a specific surface area of 500 m 2 / g),
A18 (using a silica alumina having a specific surface area of 1000 m 2 / g) was produced.
【００２３】（比較例１）負極の作製において、シリカ
ゲルを添加せずに、乾固後の負極に含まれる天然黒鉛粉
末とＳＢＲ（固形分）とＣＭＣの重量比が１００：３：
２になるようにしたこと以外は実施例１〜６と同様にし
て、リチウム二次電池Ｂ１（比較電池）を作製した。Comparative Example 1 In the preparation of the negative electrode, without adding silica gel, the weight ratio of natural graphite powder, SBR (solid content) and CMC contained in the dried negative electrode was 100: 3:
A lithium secondary battery B1 (comparative battery) was produced in the same manner as in Examples 1 to 6, except that the battery was changed to No. 2.
【００２４】（比較例２）天然黒鉛粉末（実施例１〜６
で使用したものと同じもの）と、ＳＢＲラテックス（実
施例１〜６で使用したものと同じもの）とを水に分散さ
せ、この分散液に、ポリテトラフルオロエチレン（ＰＴ
ＦＥ）を水に分散させたディスパージョン（固形分：６
０重量％）と、ＣＭＣとを混合して負極合剤スラリーを
調製した。この調製において、乾固後の負極に含まれる
天然黒鉛粉末とＳＢＲ（固形分）とＰＴＦＥとＣＭＣの
重量比が１００：３：２：２になるようにした。次い
で、この負極合剤スラリーを負極集電体としての銅箔の
両面にドクターブレード法により塗布し、１１０°Ｃで
２時間真空乾燥して、銅箔の各面に厚さ５０μｍの炭素
材料層が形成された負極を作製し、負極にこの負極を使
用したこと以外は実施例１〜６と同様にしてリチウム二
次電池Ｂ２（比較電池）を作製した。(Comparative Example 2) Natural graphite powder (Examples 1 to 6)
And the same SBR latex (same as that used in Examples 1 to 6) were dispersed in water, and polytetrafluoroethylene (PT
FE) dispersed in water (solid content: 6)
0% by weight) and CMC to prepare a negative electrode mixture slurry. In this preparation, the weight ratio of the natural graphite powder, SBR (solid content), PTFE, and CMC contained in the dried negative electrode was adjusted to 100: 3: 2: 2. Next, this negative electrode mixture slurry is applied to both surfaces of a copper foil as a negative electrode current collector by a doctor blade method, and dried in vacuum at 110 ° C. for 2 hours, and a carbon material layer having a thickness of 50 μm is formed on each surface of the copper foil. Was produced, and a lithium secondary battery B2 (comparative battery) was produced in the same manner as in Examples 1 to 6, except that the negative electrode was used as the negative electrode.
【００２５】〈各電池の充放電サイクル特性〉各電池に
ついて、２５°Ｃにて１Ｃで４．１Ｖまで充電した後、
２５°Ｃにて１Ｃで２．７５Ｖまで放電する工程を１サ
イクルとする充放電サイクルを１０００サイクル行い、
１サイクル目の放電容量に対する１０００サイクル目の
放電容量の比率（％）を求めて、各電池の充放電サイク
ル特性を調べた。結果を図１に示す。図１は、各電池の
充放電サイクル特性を、縦軸に１サイクル目の放電容量
に対する１０００サイクル目の放電容量の比率（％）
を、横軸に使用した無機多孔質粒子粉末の比表面積（ｍ
2 ／ｇ）をそれぞれとって、示したグラフである。<Charge / Discharge Cycle Characteristics of Each Battery> Each battery was charged to 4.1 V at 1 C at 25 ° C.
1000 cycles of a charge / discharge cycle in which a step of discharging to 2.75 V at 1 C at 25 ° C. is one cycle,
The ratio (%) of the discharge capacity at the 1000th cycle to the discharge capacity at the first cycle was determined, and the charge / discharge cycle characteristics of each battery were examined. The results are shown in FIG. FIG. 1 shows the charge / discharge cycle characteristics of each battery. The vertical axis represents the ratio (%) of the discharge capacity at the 1000th cycle to the discharge capacity at the first cycle.
Is the specific surface area of the inorganic porous particle powder used on the horizontal axis (m
2 / g).
【００２６】図１に示すように、本発明電池Ａ１〜Ａ１
８は、比較電池Ｂ１，Ｂ２に比べて、充放電サイクル特
性に優れている。この事実から、無機多孔質粒子粉末を
炭素材料に添加混合することにより、充放電サイクル特
性が改善されることが分かる。また、図１に示すよう
に、シリカゲル、アルミナ及びシリカアルミナのいずれ
を使用した場合も、比表面積が１００ｍ2 ／ｇ以上のも
のを使用したときに、充放電サイクル特性が顕著に改善
されている。この事実から、無機多孔質粒子粉末として
は、比表面積が１００ｍ2 ／ｇ以上のものを使用するこ
とが好ましいことが分かる。As shown in FIG. 1, the batteries A1 to A1 of the present invention
No. 8 is more excellent in charge / discharge cycle characteristics than the comparative batteries B1 and B2. From this fact, it is understood that the charge and discharge cycle characteristics are improved by adding and mixing the inorganic porous particle powder with the carbon material. In addition, as shown in FIG. 1, when using any one of silica gel, alumina and silica-alumina, when the specific surface area is 100 m 2 / g or more, the charge / discharge cycle characteristics are remarkably improved. . From this fact, it is understood that it is preferable to use a powder having a specific surface area of 100 m 2 / g or more as the inorganic porous particle powder.
【００２７】〈無機多孔質粒子粉末の添加量と充放電サ
イクル特性の関係〉負極の作製において、乾固後の負極
に含まれる天然黒鉛粉末とＳＢＲ（固形分）と比表面積
が５００ｍ2 ／ｇのシリカゲルとＣＭＣの重量比が１０
０：３：Ｘ：２（Ｘ＝０．１、０．５、２．５、７．
５、１０又は１５）になるようにしたこと以外は実施例
１〜６と同様にして、リチウム二次電池Ａ１９（Ｘ＝
０．１），Ａ２０（Ｘ＝０．５），Ａ２１（Ｘ＝２．
５），Ａ２２（Ｘ＝７．５），Ａ２３（Ｘ＝１０），Ａ
２４（Ｘ＝１５）を作製した。また、負極の作製におい
て、乾固後の負極に含まれる天然黒鉛粉末とＳＢＲ（固
形分）と比表面積が５００ｍ2 ／ｇのアルミナとＣＭＣ
の重量比が１００：３：Ｙ：２（Ｙ＝０．１、０．５、
２．５、７．５、１０又は１５）になるようにしたこと
以外は実施例７〜１２と同様にして、リチウム二次電池
Ａ２５（Ｙ＝０．１），Ａ２６（Ｙ＝０．５），Ａ２７
（Ｙ＝２．５），Ａ２８（Ｙ＝７．５），Ａ２９（Ｙ＝
１０），Ａ３０（Ｙ＝１５）を作製した。さらに、負極
の作製において、乾固後の負極に含まれる天然黒鉛粉末
とＳＢＲ（固形分）と比表面積が５００ｍ2 ／ｇのシリ
カアルミナとＣＭＣの重量比が１００：３：Ｚ：２（Ｚ
＝０．１、０．５、２．５、７．５、１０又は１５）に
なるようにしたこと以外は実施例１３〜１８と同様にし
て、リチウム二次電池Ａ３１（Ｚ＝０．１），Ａ３２
（Ｚ＝０．５），Ａ３３（Ｚ＝２．５），Ａ３４（Ｚ＝
７．５），Ａ３５（Ｚ＝１０），Ａ３６（Ｚ＝１５）を
作製した。次いで、先と同様の充放電サイクル試験を行
い、各電池の充放電サイクル特性を調べた。結果を図２
に示す。図２は、各電池の充放電サイクル特性を、縦軸
に１サイクル目の放電容量に対する１０００サイクル目
の放電容量の比率（％）を、横軸に天然黒鉛粉末１００
重量部に対する無機多孔質粒子粉末の添加量（重量部）
をそれぞれとって、示したグラフである。なお、図２に
は、本発明電池Ａ５（Ｘ＝５），Ａ１１（Ｙ＝５），Ａ
１７（Ｚ＝５）及び比較電池Ｂ１（Ｘ，Ｙ，Ｚ＝０）の
充放電サイクル特性も示してある。<Relationship between the amount of inorganic porous particle powder added and charge / discharge cycle characteristics> In the preparation of the negative electrode, the specific surface area of the natural graphite powder, SBR (solid content) and the specific surface area of the dried negative electrode was 500 m 2 / g. Weight ratio of silica gel to CMC is 10
0: 3: X: 2 (X = 0.1, 0.5, 2.5, 7.
5, 10 or 15), except that the lithium secondary battery A19 (X =
0.1), A20 (X = 0.5), A21 (X = 2.
5), A22 (X = 7.5), A23 (X = 10), A
24 (X = 15) were produced. In the preparation of the negative electrode, natural graphite powder, SBR (solid content), alumina having a specific surface area of 500 m 2 / g and CMC contained in the dried negative electrode were used.
Is 100: 3: Y: 2 (Y = 0.1, 0.5,
The lithium secondary batteries A25 (Y = 0.1) and A26 (Y = 0.5) in the same manner as in Examples 7 to 12 except that the values were changed to 2.5, 7.5, 10 or 15). ), A27
(Y = 2.5), A28 (Y = 7.5), A29 (Y =
10), A30 (Y = 15) were produced. Further, in the preparation of the negative electrode, the weight ratio of natural graphite powder, SBR (solid content), silica alumina having a specific surface area of 500 m 2 / g, and CMC contained in the negative electrode after drying was 100: 3: Z: 2 (Z
= 0.1, 0.5, 2.5, 7.5, 10 or 15) in the same manner as in Examples 13 to 18 except that the lithium secondary battery A31 (Z = 0.1 ), A32
(Z = 0.5), A33 (Z = 2.5), A34 (Z =
7.5), A35 (Z = 10) and A36 (Z = 15). Next, the same charge / discharge cycle test as described above was performed, and the charge / discharge cycle characteristics of each battery were examined. Figure 2 shows the results.
Shown in FIG. 2 shows the charge / discharge cycle characteristics of each battery, the vertical axis represents the ratio (%) of the discharge capacity at the 1000th cycle to the discharge capacity at the first cycle, and the horizontal axis represents 100% of natural graphite powder.
Addition amount of inorganic porous particle powder to parts by weight (parts by weight)
Is a graph showing each of the graphs. FIG. 2 shows the batteries A5 (X = 5), A11 (Y = 5), A
17 (Z = 5) and the charge / discharge cycle characteristics of the comparative battery B1 (X, Y, Z = 0) are also shown.
【００２８】図２に示すように、シリカゲル、アルミナ
及びシリカアルミナのいずれを使用した場合も、天然黒
鉛粉末１００重量部に対する無機多孔質粒子粉末の添加
量が０．５〜１０重量部のときに、充放電サイクル特性
が顕著に改善されている。この事実から、天然黒鉛粉末
１００重量部に対する無機多孔質粒子粉末の添加量は、
０．５〜１０重量部が好ましいことが分かる。As shown in FIG. 2, regardless of the use of silica gel, alumina or silica-alumina, when the amount of the inorganic porous particle powder is 0.5 to 10 parts by weight relative to 100 parts by weight of natural graphite powder. In addition, the charge / discharge cycle characteristics are remarkably improved. From this fact, the amount of the inorganic porous particle powder added to 100 parts by weight of the natural graphite powder is
It is understood that 0.5 to 10 parts by weight is preferable.
【００２９】上記の実施例では、本発明を円筒形のリチ
ウム二次電池に適用する場合を例に挙げて説明したが、
電池の形状は特に限定されず、本発明は扁平形、角形な
ど種々の形状のリチウム二次電池に適用し得るものであ
る。In the above embodiment, the case where the present invention is applied to a cylindrical lithium secondary battery has been described as an example.
The shape of the battery is not particularly limited, and the present invention can be applied to lithium secondary batteries having various shapes such as a flat shape and a square shape.
【００３０】また、上記の実施例では、無機多孔質粒子
粉末として、シリカゲル、アルミナ又はシリカアルミナ
を使用したが、電解液を孔内に保持することが可能なも
のであれば特に制限なく使用することが可能である。In the above embodiment, silica gel, alumina or silica-alumina was used as the inorganic porous particle powder, but any material can be used without any particular limitation as long as the electrolyte can be held in the pores. It is possible.
【００３１】[0031]
【発明の効果】充放電サイクル特性に優れたリチウム二
次電池が提供される。According to the present invention, a lithium secondary battery having excellent charge / discharge cycle characteristics is provided.
【図１】本発明電池及び比較電池の充放電サイクル特性
を示すグラフである。FIG. 1 is a graph showing charge / discharge cycle characteristics of a battery of the present invention and a comparative battery.
【図２】無機多孔質粒子粉末の添加量と充放電サイクル
特性の関係を示すグラフである。FIG. 2 is a graph showing the relationship between the amount of inorganic porous particle powder added and charge / discharge cycle characteristics.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 能間 俊之 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 (72)発明者 西尾 晃治 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Toshiyuki Noma 2-5-5 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Inventor Koji Nishio 2-chome Keihanhondori, Moriguchi-shi, Osaka No. 5-5 in Sanyo Electric Co., Ltd.
Claims (4)
とする負極と、電解液とを備えるリチウム二次電池にお
いて、前記炭素材料に、電解液を孔内に保持することが
可能な無機多孔質粒子粉末が添加混合されていることを
特徴とするリチウム二次電池。1. A lithium secondary battery comprising a positive electrode, a negative electrode using a carbon material as a lithium ion storage material, and an electrolytic solution, wherein the carbon material has an inorganic porous material capable of holding an electrolytic solution in pores. A lithium secondary battery characterized in that porous particles are added and mixed.
アルミナ及びシリカアルミナから選ばれた少なくとも１
種である請求項１記載のリチウム二次電池。2. The method according to claim 1, wherein the inorganic porous particle powder is silica gel,
At least one selected from alumina and silica alumina
The lithium secondary battery according to claim 1, which is a seed.
００ｍ2 ／ｇ以上である請求項１又は２記載のリチウム
二次電池。3. The inorganic porous particle powder has a specific surface area of 1
The lithium secondary battery according to claim 1, wherein the lithium secondary battery is at least 00 m 2 / g.
１００重量部に対して、０．５〜１０重量部添加混合さ
れている請求項１〜３のいずれかに記載のリチウム二次
電池。4. The lithium secondary battery according to claim 1, wherein 0.5 to 10 parts by weight of the inorganic porous particle powder is added to 100 parts by weight of the carbon material. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8355330A JPH10188957A (en) | 1996-12-20 | 1996-12-20 | Lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8355330A JPH10188957A (en) | 1996-12-20 | 1996-12-20 | Lithium secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10188957A true JPH10188957A (en) | 1998-07-21 |
Family
ID=18443310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8355330A Pending JPH10188957A (en) | 1996-12-20 | 1996-12-20 | Lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10188957A (en) |
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| EP1039567A1 (en) * | 1999-03-25 | 2000-09-27 | Sony Corporation | Non-aqueous electrolyte battery |
| JP2001176500A (en) * | 1999-12-08 | 2001-06-29 | Samsung Sdi Co Ltd | Negative electrode active material slurry composition for lithium secondary battery, and method of manufacturing negative electrode using the same |
| EP1148563A2 (en) * | 1997-03-13 | 2001-10-24 | Matsushita Electric Industrial Co., Ltd. | Lithium ion secondary battery |
| WO2004055925A1 (en) * | 2002-12-17 | 2004-07-01 | Mitsubishi Chemical Corporation | Nonaqueous electrolyte secondary battery-use cathode and nonaqueous electrolyte secondary battery |
| JP2004253379A (en) * | 2003-01-29 | 2004-09-09 | Jfe Chemical Corp | Negative electrode material and negative electrode for lithium-ion secondary battery, and lithium-ion secondary battery |
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| US7491467B2 (en) | 2002-12-17 | 2009-02-17 | Mitsubishi Chemical Corporation | Negative electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery using the same |
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| WO2013047016A1 (en) * | 2011-09-27 | 2013-04-04 | 三洋電機株式会社 | Negative electrode of non-aqueous electrolyte secondary cell and non-aqueous electrolyte secondary cell |
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1996
- 1996-12-20 JP JP8355330A patent/JPH10188957A/en active Pending
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|---|---|---|---|---|
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| EP1148563A2 (en) * | 1997-03-13 | 2001-10-24 | Matsushita Electric Industrial Co., Ltd. | Lithium ion secondary battery |
| EP1148563A3 (en) * | 1997-03-13 | 2001-11-07 | Matsushita Electric Industrial Co., Ltd. | Lithium ion secondary battery |
| US6517973B1 (en) | 1999-03-25 | 2003-02-11 | Sony Corporation | Non-aqueous electrolyte battery |
| EP1039567A1 (en) * | 1999-03-25 | 2000-09-27 | Sony Corporation | Non-aqueous electrolyte battery |
| JP2001176500A (en) * | 1999-12-08 | 2001-06-29 | Samsung Sdi Co Ltd | Negative electrode active material slurry composition for lithium secondary battery, and method of manufacturing negative electrode using the same |
| US7491467B2 (en) | 2002-12-17 | 2009-02-17 | Mitsubishi Chemical Corporation | Negative electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery using the same |
| WO2004055925A1 (en) * | 2002-12-17 | 2004-07-01 | Mitsubishi Chemical Corporation | Nonaqueous electrolyte secondary battery-use cathode and nonaqueous electrolyte secondary battery |
| JP2004253379A (en) * | 2003-01-29 | 2004-09-09 | Jfe Chemical Corp | Negative electrode material and negative electrode for lithium-ion secondary battery, and lithium-ion secondary battery |
| JP4507517B2 (en) * | 2003-06-30 | 2010-07-21 | 日本ゼオン株式会社 | Method for manufacturing electrode for electric double layer capacitor |
| JP2005026271A (en) * | 2003-06-30 | 2005-01-27 | Nippon Zeon Co Ltd | Method of manufacturing electrode for electric double layer capacitor |
| EP1555244A2 (en) * | 2004-01-16 | 2005-07-20 | Korea Institute Of Science And Technology | Carbon-porous media composite electrode and preparation method thereof |
| US7505250B2 (en) | 2004-01-16 | 2009-03-17 | Korea Institute Of Science And Technology | Carbon-porous media composite electrode and preparation method thereof |
| EP1555244A3 (en) * | 2004-01-16 | 2009-12-30 | Korea Institute Of Science And Technology | Carbon-porous media composite electrode and preparation method thereof |
| JP2010129363A (en) * | 2008-11-27 | 2010-06-10 | Jfe Chemical Corp | Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
| WO2013047016A1 (en) * | 2011-09-27 | 2013-04-04 | 三洋電機株式会社 | Negative electrode of non-aqueous electrolyte secondary cell and non-aqueous electrolyte secondary cell |
| JP2017174664A (en) * | 2016-03-24 | 2017-09-28 | トヨタ自動車株式会社 | Secondary battery |
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| US11424441B2 (en) | 2017-07-04 | 2022-08-23 | Lg Energy Solution, Ltd. | Electrode and lithium secondary battery comprising same |
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