JPH09306541A - Nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte batteryInfo
- Publication number
- JPH09306541A JPH09306541A JP8146680A JP14668096A JPH09306541A JP H09306541 A JPH09306541 A JP H09306541A JP 8146680 A JP8146680 A JP 8146680A JP 14668096 A JP14668096 A JP 14668096A JP H09306541 A JPH09306541 A JP H09306541A
- Authority
- JP
- Japan
- Prior art keywords
- aqueous electrolyte
- negative electrode
- silicate
- electrolyte secondary
- secondary battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、正極と、炭素材
料を用いた負極と、溶質に含フッ素リチウム塩を含む非
水電解液とを備えた非水電解質電池において、サイクル
特性、保存特性及び負荷特性が良好な非水電解質電池に
関するものである。TECHNICAL FIELD The present invention relates to a non-aqueous electrolyte battery comprising a positive electrode, a negative electrode using a carbon material, and a non-aqueous electrolyte solution containing a fluorine-containing lithium salt as a solute. The present invention relates to a non-aqueous electrolyte battery having good load characteristics.
【０００２】[0002]
【従来の技術】近年、高出力，高エネルギー密度の新型
電池として、電解液に非水電解液を用い、リチウムの酸
化，還元を利用して放電や充電を行なうようにした非水
電解質電池が利用されるようになった。2. Description of the Related Art In recent years, as a new battery with high output and high energy density, there has been a non-aqueous electrolyte battery which uses a non-aqueous electrolyte solution as an electrolyte solution and discharges and charges by utilizing oxidation and reduction of lithium. It came to be used.
【０００３】そして、このような非水電解質電池として
は、様々な種類のものが存在し、その一つとして、負極
にリチウムイオン等の吸蔵，放出が行なえる炭素材料を
用いると共に、非水電解液における溶質にＬｉＰＦ6 ，
ＬｉＢＦ4 等の含フッ素リチウム塩を用いたもの等が知
られている。There are various types of such non-aqueous electrolyte batteries, one of which is a carbon material capable of absorbing and desorbing lithium ions or the like for the negative electrode and the non-aqueous electrolyte battery. LiPF 6 as the solute in the liquid,
Those using a fluorine-containing lithium salt such as LiBF 4 are known.
【０００４】しかし、このように負極に炭素材料を用い
ると共に非水電解液に含フッ素リチウム塩を含む溶質を
用いた非水電解質電池においては、サイクル特性や充電
保存特性が悪く、また一般に高い電流で放電を行なった
場合に放電容量が低下し、負荷特性も悪いという問題も
あった。However, in such a non-aqueous electrolyte battery using a carbon material for the negative electrode and a solute containing a fluorine-containing lithium salt in the non-aqueous electrolyte, the cycle characteristics and the charge storage characteristics are poor, and generally a high current is used. There is also a problem that the discharge capacity is reduced when the discharge is carried out at 1, and the load characteristics are poor.
【０００５】[0005]
【発明が解決しようとする課題】この発明は、上記のよ
うに負極に炭素材料を用いると共に、非水電解液に含フ
ッ素リチウム塩を含む溶質を用いた非水電解質電池にお
ける上記のような様々な問題を解決することを課題とす
るものであり、上記のような非水電解質電池において、
サイクル特性や保存特性や負荷特性に優れた非水電解質
電池が得られるようにすることを課題とするものであ
る。DISCLOSURE OF THE INVENTION The present invention provides various kinds of non-aqueous electrolyte batteries using a carbon material for the negative electrode as described above and a solute containing a fluorine-containing lithium salt for the non-aqueous electrolyte. The problem is to solve various problems, in the non-aqueous electrolyte battery as described above,
It is an object to obtain a non-aqueous electrolyte battery having excellent cycle characteristics, storage characteristics and load characteristics.
【０００６】そして、本発明者等は、上記の非水電解質
電池において保存特性等が低下する原因について検討し
たところ、非水電解液に溶質として含有させた含フッ素
リチウム塩の分解によってフッ化水素ＨＦが発生し、こ
のＨＦがリチウムを吸蔵した状態にある炭素等と反応
し、これによって充放電反応に関与するリチウム等が消
費されて、上記の非水電解質電池における保存特性等が
悪くなると考え、この発明を完成するに至ったのであ
る。Then, the present inventors examined the cause of the deterioration of the storage characteristics and the like in the above non-aqueous electrolyte battery. As a result, hydrogen fluoride was decomposed by decomposition of the fluorine-containing lithium salt contained as a solute in the non-aqueous electrolyte. It is considered that HF is generated, and this HF reacts with carbon or the like in a state in which lithium is occluded, thereby consuming lithium or the like involved in the charge / discharge reaction and deteriorating the storage characteristics and the like in the nonaqueous electrolyte battery. The present invention has been completed.
【０００７】[0007]
【課題を解決するための手段】この発明においては、上
記のような課題を解決するため、正極と、炭素材料を用
いた負極と、溶質に含フッ素リチウム塩を含む非水電解
液とを備えた非水電解質電池において、上記の負極及び
／又は非水電解液に対してｘＭ１2 Ｏ・ｙＳｉＯ2 、ｘ
Ｍ２Ｏ・ｙＳｉＯ2 、ｘＭ３2 Ｏ3 ・ｙＳｉＯ2 （式
中、Ｍ１〜Ｍ３はＫ，Ｎａ，Ｍｇ，Ｃａ，Ｆｅ，Ａｌか
ら選択される金属元素であり、ｘは１〜２、ｙは１〜４
である。）の何れかの式で示される少なくとも一種類の
ケイ酸塩を含有させるようにしたのである。In order to solve the above problems, the present invention comprises a positive electrode, a negative electrode using a carbon material, and a nonaqueous electrolytic solution containing a fluorine-containing lithium salt as a solute. In the non-aqueous electrolyte battery, xM1 2 O · ySiO 2 , x with respect to the above negative electrode and / or the non-aqueous electrolyte solution.
M2O · ySiO 2 , xM3 2 O 3 · ySiO 2 (In the formula, M1 to M3 are metal elements selected from K, Na, Mg, Ca, Fe and Al, x is 1 to 2 and y is 1 to 1). Four
It is. ) At least one kind of silicate represented by any one of the formulas is included.
【０００８】そして、この発明における非水電解質電池
のように、上記のケイ酸塩を負極や非水電解液中に含有
させると、このケイ酸塩が非水電解液の溶質に用いた含
フッ素リチウム塩の分解生成物であるＨＦと反応してＨ
Ｆが消費され、これによりリチウムを吸蔵した状態にあ
る炭素等がＨＦと反応するのが抑制され、この非水電解
質電池における保存特性やサイクル特性の劣化が抑制さ
れるようになる。When the silicate is contained in the negative electrode or the non-aqueous electrolyte as in the non-aqueous electrolyte battery of the present invention, the fluorinated silicate used as the solute of the non-aqueous electrolyte is used. H by reacting with HF which is a decomposition product of a lithium salt
F is consumed, and as a result, carbon or the like in the state of occluding lithium is suppressed from reacting with HF, and deterioration of storage characteristics and cycle characteristics in this non-aqueous electrolyte battery is suppressed.
【０００９】また、上記のようなケイ酸塩を非水電解液
中に含有させると、電極に対する非水電解液の浸透性が
向上して負荷特性も良くなり、高い電流で放電を行なっ
た場合における放電容量の低下も抑制されるものと考え
られる。When the silicate as described above is contained in the non-aqueous electrolytic solution, the permeability of the non-aqueous electrolytic solution into the electrode is improved and the load characteristics are improved. It is considered that the reduction of the discharge capacity at the time is suppressed.
【００１０】ここで、この非水電解質電池において、負
極に用いる炭素材料としては、公知の炭素材料を使用す
ることができるが、特に、炭素材料として、Ｃ6 Ｌｉま
でリチウムが吸蔵される充電特性に優れた黒鉛を用いた
場合に対して有効である。Here, in this non-aqueous electrolyte battery, a known carbon material can be used as the carbon material used for the negative electrode. In particular, as the carbon material, charging characteristics in which lithium is absorbed up to C 6 Li. This is effective when using excellent graphite.
【００１１】また、上記のケイ酸塩を非水電解液中に含
有させる場合、その量が少ないと、含フッ素リチウム塩
の分解生成物であるＨＦを十分に消費させることができ
ず、サイクル特性や充電保存特性を十分に向上させるこ
とができなくなる一方、このケイ酸塩の量が多くなりす
ぎると、この非水電解液におけるイオン伝導性が悪くな
ったり、この非水電解液が正極材料と反応したりして、
保存特性が劣化するため、好ましくは、上記のケイ酸塩
が非水電解液中に０．１〜１０重量％含有されるように
する。Further, when the above-mentioned silicate is contained in the non-aqueous electrolytic solution, if the amount thereof is small, HF which is a decomposition product of the fluorine-containing lithium salt cannot be sufficiently consumed and the cycle characteristics are deteriorated. While it becomes impossible to sufficiently improve the charge storage characteristics and the charge storage characteristics, if the amount of the silicate is too large, the ionic conductivity in the non-aqueous electrolytic solution becomes poor, or the non-aqueous electrolytic solution becomes a positive electrode material. Reacting,
Since the storage characteristics deteriorate, the silicate is preferably contained in the non-aqueous electrolyte in an amount of 0.1 to 10% by weight.
【００１２】また、上記のケイ酸塩を負極中に含有させ
る場合には、前記のＨＦとの反応を十分に抑制すると共
に、負極における特性が低下するのを抑制するため、前
記のケイ酸塩が負極材料である炭素材料に対して０．１
〜５重量％の範囲で含有されるようにすることが好まし
い。When the above-mentioned silicate is contained in the negative electrode, the reaction with the above-mentioned HF is sufficiently suppressed and the characteristics of the negative electrode are prevented from being deteriorated. Is 0.1 with respect to the carbon material that is the negative electrode material
It is preferable that the content is in the range of 5 wt%.
【００１３】ここで、この発明における非水電解質電池
において、非水電解液に含有させる含フッ素リチウム塩
の溶質としては、例えば、ＬｉＰＦ6 、ＬｉＢＦ4 、Ｌ
ｉＡｓＦ6 、ＬｉＣＦ3 ＳＯ3 、ＬｉＮ（ＣＦ3 ＳＯ
2 ）2 、ＬｉＳｂＦ6 、ＬｉＳｉＦ6 、ＬｉＡｌＦ4 、
ＬｉＣ（ＣＦ3 ＳＯ2 ）3 、ＬｉＮ（Ｃ2 Ｆ5 ＳＯ2 ）
2 等が存在し、またこのような含フッ素リチウム塩とそ
れ以外の溶質を合わせて用いた場合においても有効であ
る。Here, in the non-aqueous electrolyte battery according to the present invention, the solute of the fluorine-containing lithium salt contained in the non-aqueous electrolyte is, for example, LiPF 6 , LiBF 4 , L.
iAsF 6 , LiCF 3 SO 3 , LiN (CF 3 SO
2) 2, LiSbF 6, LiSiF 6, LiAlF 4,
LiC (CF 3 SO 2) 3 , LiN (C 2 F 5 SO 2)
2 and the like exist, and it is also effective when such a fluorine-containing lithium salt and a solute other than that are used together.
【００１４】また、この非水電解液における溶媒として
は、公知のものを使用することができ、例えば、プロピ
レンカーボネート、エチレンカーボネート、γ−ブチロ
ラクトン、ジメチルカーボネート、ジメチルスルホキシ
ド、アセトニトリル、ブチレンカーボネート、１，２−
ジメトキシエタン、ジエチルカーボネート等の有機溶媒
を１種又は２種以上組み合わせて使用することができ
る。As the solvent in this non-aqueous electrolytic solution, known solvents can be used, for example, propylene carbonate, ethylene carbonate, γ-butyrolactone, dimethyl carbonate, dimethyl sulfoxide, acetonitrile, butylene carbonate, 1, 2-
Organic solvents such as dimethoxyethane and diethyl carbonate can be used alone or in combination of two or more.
【００１５】また、この発明における非水電解質電池に
おける正極においても公知の正極材料を使用することが
でき、リチウムを活物質とする場合、リチウムを吸蔵，
放出することができる材料、例えば、マンガン，コバル
ト，ニッケル，鉄，バナジウム，ニオブの少なくとも１
種を含むリチウム遷移金属複合酸化物等を使用すること
ができ、より具体的には、ＬｉＣｏＯ2 、ＬｉＮｉＯ
2 、ＬｉＭｎＯ2 、ＬｉＦｅＯ2 等の材料を使用するこ
とができる。Also, a known positive electrode material can be used for the positive electrode in the non-aqueous electrolyte battery according to the present invention. When lithium is used as the active material, lithium is occluded,
A material capable of being released, eg at least one of manganese, cobalt, nickel, iron, vanadium, niobium
A lithium transition metal composite oxide containing a seed can be used, and more specifically, LiCoO 2 , LiNiO 2 , and the like.
Can be used 2, LiMnO 2, LiFeO 2 or the like materials.
【００１６】[0016]
【実施例】以下、この発明に係る非水電解質電池につい
て、実施例を挙げて具体的に説明すると共に、比較例を
挙げて、この実施例に係る非水電解質電池がサイクル特
性や保存特性や負荷特性の点で優れていることを明らか
にする。なお、この発明における非水電解質電池は下記
の実施例に示したものに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できる
ものである。EXAMPLES Hereinafter, the non-aqueous electrolyte battery according to the present invention will be specifically described with reference to Examples, and comparative examples will be given to show that the non-aqueous electrolyte battery according to this example has cycle characteristics and storage characteristics. It is clarified that it is superior in terms of load characteristics. The non-aqueous electrolyte battery according to the present invention is not limited to those shown in the following examples, but can be implemented by appropriately changing the scope of the invention without changing its gist.
【００１７】（実施例１）この実施例１においては、下
記のようにして作製した正極と負極とを用いると共に、
下記のようにして調製した非水電解液を用い、図１に示
すようなＡＡサイズの円筒型の非水電解質二次電池を作
製した。(Example 1) In Example 1, the positive electrode and the negative electrode produced as follows were used, and
Using the non-aqueous electrolyte solution prepared as described below, an AA size cylindrical non-aqueous electrolyte secondary battery as shown in FIG. 1 was produced.
【００１８】［正極の作製］正極を作製するにあたって
は、正極材料として、リチウムコバルト複合酸化物Ｌｉ
ＣｏＯ2 を使用し、このＬｉＣｏＯ2 粉末と、導電剤で
ある人造黒鉛粉末と、結着剤であるポリフッ化ビニリデ
ンを溶解させた５重量％Ｎ−メチルピロリドン溶液とを
加え、ＬｉＣｏＯ2 粉末９０重量部に対して、人造黒鉛
粉末が５重量部、ポリフッ化ビニリデンが５重量部の割
合になるようにし、これらを混練してスラリーを調製し
た。そして、このスラリーを正極集電体であるアルミニ
ウム箔の両面にドクターブレード法により塗布し、これ
を１５０℃で２時間真空乾燥させて正極を作製した。[Production of Positive Electrode] In producing the positive electrode, a lithium cobalt composite oxide Li is used as a positive electrode material.
Using CoO 2 , this LiCoO 2 powder, artificial graphite powder that is a conductive agent, and a 5 wt% N-methylpyrrolidone solution in which polyvinylidene fluoride that is a binder is dissolved are added, and 90 wt% of LiCoO 2 powder is added. 5 parts by weight of artificial graphite powder and 5 parts by weight of polyvinylidene fluoride were mixed with the parts, and these were kneaded to prepare a slurry. Then, this slurry was applied to both surfaces of an aluminum foil, which is a positive electrode current collector, by a doctor blade method, and this was vacuum dried at 150 ° C. for 2 hours to produce a positive electrode.
【００１９】［負極の作製］負極を作製するにあたって
は、負極材料に天然黒鉛を用い、この天然黒鉛粉末９５
重量部に対して、結着剤であるポリフッ化ビニリデンが
５重量部含まれるようにして、このポリフッ化ビニリデ
ンを溶解させた５重量％Ｎ−メチルピロリドン溶液を加
え、これらを混練してスラリーを調製した。そして、こ
のスラリーを負極集電体である銅箔の両面に塗布し、こ
れを１５０℃で２時間真空乾燥させて負極を作製した。[Manufacture of Negative Electrode] When manufacturing a negative electrode, natural graphite was used as a negative electrode material, and this natural graphite powder 95 was used.
With respect to 5 parts by weight of polyvinylidene fluoride as a binder, 5% by weight of a polyvinylidene fluoride-dissolved N-methylpyrrolidone solution was added, and these were kneaded to form a slurry. Prepared. And this slurry was apply | coated to both surfaces of the copper foil which is a negative electrode collector, this was vacuum-dried at 150 degreeC for 2 hours, and the negative electrode was produced.
【００２０】［非水電解液の調製］非水電解液を調製す
るにあたっては、溶媒にエチレンカーボネートとジエチ
ルカーボーネートとを１：１の体積比で混合させた混合
溶媒を用い、この混合溶媒に六フッ化リン酸リチウムＬ
ｉＰＦ6 を１ｍｏｌ／ｌの割合で溶解させ、更にこれに
ケイ酸塩としてＮａ2 Ｏ・ＳｉＯ2 を１重量％の割合に
なるように添加させて非水電解液を調製した。[Preparation of Non-Aqueous Electrolyte] In preparing the non-aqueous electrolyte, a mixed solvent prepared by mixing ethylene carbonate and diethyl carbonate in a volume ratio of 1: 1 was used as the solvent. Lithium hexafluorophosphate L
The iPF 6 was dissolved in a proportion of 1 mol / l, were further prepared thereto to a Na 2 O · SiO 2 was added to a proportion of 1% by weight silicate non-aqueous electrolyte solution.
【００２１】［電池の作製］そして、この実施例１の非
水電解質二次電池を作製するにあたっては、図１に示す
ように、上記のようにして作製した正極１と負極２との
間にそれぞれセパレータ３としてリチウムイオン透過性
のポリプロピレン性の微多孔膜を介在させ、これらをス
パイラル状に巻いて電池缶４内に収容させた後、この電
池缶４内に上記の非水電解液を注液して封口し、正極１
を正極リード５を介して正極外部端子６に接続させると
共に負極２を負極リード７を介して電池缶４に接続さ
せ、正極外部端子６と電池缶４とを絶縁パッキン８によ
り電気的に分離させた。[Production of Battery] Then, in producing the non-aqueous electrolyte secondary battery of Example 1, as shown in FIG. 1, between the positive electrode 1 and the negative electrode 2 produced as described above. A lithium ion-permeable polypropylene microporous film is interposed as each separator 3 and these are spirally wound to be housed in a battery can 4, and then the nonaqueous electrolyte solution is poured into the battery can 4. Liquid and seal, positive electrode 1
Is connected to the positive electrode external terminal 6 via the positive electrode lead 5, the negative electrode 2 is connected to the battery can 4 via the negative electrode lead 7, and the positive electrode external terminal 6 and the battery can 4 are electrically separated by the insulating packing 8. It was
【００２２】（実施例２〜６）これらの実施例において
は、上記の実施例１における非水電解液の調製におい
て、非水電解液中に加えるケイ酸塩の種類を変更させ、
実施例２ではＮａ2 Ｏ・ＳｉＯ2 を、実施例３ではＮａ
2 Ｏ・２ＳｉＯ2 を、実施例４ではＮａ2 Ｏ・４ＳｉＯ
2 を、実施例５ではＣａＯ・ＳｉＯ2 を、実施例６では
ＣａＯ・ＭｇＯ・２ＳｉＯ2 をそれぞれ非水電解液中に
１重量％含有されるようにし、それ以外については上記
実施例１の場合と同様にして各非水電解質二次電池を作
製した。(Examples 2 to 6) In these examples, in the preparation of the nonaqueous electrolytic solution in the above Example 1, the kind of silicate added to the nonaqueous electrolytic solution was changed,
In Example 2, Na 2 O.SiO 2 was used, and in Example 3, Na 2 O.SiO 2 was used.
2 O · 2SiO 2 was used in Example 4 as Na 2 O · 4SiO
2, Example 5, CaO · SiO 2, Example and 6 in CaO · MgO · 2SiO 2 to be contained 1% by weight in the nonaqueous electrolytic solution each, in the above Example 1 for others Each non-aqueous electrolyte secondary battery was produced in the same manner as in.
【００２３】（比較例１）この比較例においては、上記
の実施例１の非水電解質二次電池における非水電解液の
調製において、非水電解液中に何れのケイ酸塩も添加し
ないようにし、それ以外については上記実施例１の場合
と同様にして非水電解質二次電池を作製した。(Comparative Example 1) In this comparative example, in the preparation of the non-aqueous electrolyte solution in the non-aqueous electrolyte secondary battery of Example 1 described above, no silicate was added to the non-aqueous electrolyte solution. A non-aqueous electrolyte secondary battery was manufactured in the same manner as in Example 1 except for the above.
【００２４】次に、上記のようにして作製した実施例１
〜６及び比較例１の各非水電解質二次電池について保存
特性及びサイクル特性を調べ、その結果を下記の表１に
示した。ここで、保存特性については、各非水電解質二
次電池を充電電流２００ｍＡで充電終止電圧４．２Ｖま
で充電させた後、放電電流２００ｍＡで放電終止電圧
２．７５Ｖまで放電させて、保存前における放電容量を
測定する一方、上記のように充電させた各非水電解質二
次電池を温度６０℃で１０日間保存した後、これらの各
非水電解質二次電池を取り出して室温に戻し、上記のよ
うに放電電流２００ｍＡで放電終止電圧２．７５Ｖまで
放電させて保存後における放電容量を測定し、各非水電
解質二次電池における保存前の放電容量に対する保存後
の放電容量の容量残存率（％）を求めた。また、サイク
ル特性については、各非水電解質二次電池を充電電流２
００ｍＡで充電終止電圧４．２Ｖまで充電させ、放電電
流２００ｍＡで放電終止電圧２．７５Ｖまで放電させ、
このような充放電を１サイクルとして５００サイクル繰
り返し、１サイクルあたりにおける放電容量の劣化率
（％）を求めた。Next, the first embodiment manufactured as described above was used.
6 to 6 and the non-aqueous electrolyte secondary batteries of Comparative Example 1 were examined for storage characteristics and cycle characteristics, and the results are shown in Table 1 below. Here, regarding storage characteristics, each non-aqueous electrolyte secondary battery was charged at a charging current of 200 mA to a charge end voltage of 4.2 V, and then discharged at a discharge current of 200 mA to a discharge end voltage of 2.75 V, before storage. While measuring the discharge capacity, each of the non-aqueous electrolyte secondary batteries charged as described above was stored at a temperature of 60 ° C. for 10 days, and then each of these non-aqueous electrolyte secondary batteries was taken out and returned to room temperature. The discharge capacity after storage was measured by discharging to a discharge end voltage of 2.75 V at a discharge current of 200 mA, and the residual capacity ratio of the discharge capacity after storage to the discharge capacity before storage in each non-aqueous electrolyte secondary battery (% ) Was asked. Regarding the cycle characteristics, charge current 2 for each non-aqueous electrolyte secondary battery.
It is charged to a charge end voltage of 4.2 V at 00 mA, and discharged to a discharge end voltage of 2.75 V at a discharge current of 200 mA,
Such charging / discharging was set as one cycle, repeated 500 times, and the deterioration rate (%) of the discharge capacity per one cycle was obtained.
【００２５】[0025]
【表１】 [Table 1]
【００２６】この結果、溶質にＬｉＰＦ6 を用いた非水
電解液中に上記のような各種のケイ酸塩を含有させた実
施例１〜６の各非水電解質二次電池においては、ケイ酸
塩を添加しなかった比較例１の非水電解質二次電池に比
べて、１サイクルあたりにおける放電容量の劣化率が低
くなっていると共に、保存後における容量残存率も高く
なっており、保存特性及びサイクル特性が比較例１の非
水電解質二次電池に比べて向上していた。As a result, in each of the non-aqueous electrolyte secondary batteries of Examples 1 to 6 in which the above-mentioned various silicates were contained in the non-aqueous electrolyte solution using LiPF 6 as the solute, silicic acid was used. Compared to the non-aqueous electrolyte secondary battery of Comparative Example 1 in which no salt was added, the deterioration rate of the discharge capacity per cycle was low, and the residual capacity rate after storage was also high. And the cycle characteristics were improved as compared with the non-aqueous electrolyte secondary battery of Comparative Example 1.
【００２７】（実施例７〜１１）これらの実施例におい
ては、上記の実施例１の非水電解質二次電池における非
水電解液の調製において、非水電解液中に加えるケイ酸
塩Ｎａ2 Ｏ・ＳｉＯ2 の量を、下記の表２に示すように
０．０５重量％、０．１重量％、５重量％、１０重量
％、２０重量％に変更させ、それ以外については、上記
実施例１の場合と同様にして非水電解質二次電池を作製
した。(Examples 7 to 11) In these Examples, the silicate Na 2 added to the non-aqueous electrolyte in the preparation of the non-aqueous electrolyte in the non-aqueous electrolyte secondary battery of Example 1 above. As shown in Table 2 below, the amount of O.SiO 2 was changed to 0.05% by weight, 0.1% by weight, 5% by weight, 10% by weight, and 20% by weight. A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1.
【００２８】そして、これらの実施例７〜１１における
各非水電解質電池においても、上記の場合と同様にし
て、保存後における容量残存率（％）と１サイクルあた
りの劣化率（％）とを求め、その結果を上記の実施例１
のものと合わせて下記の表２に示した。Also in each of the non-aqueous electrolyte batteries in Examples 7 to 11, the capacity remaining rate (%) after storage and the deterioration rate (%) per cycle were determined in the same manner as above. Obtained, and the result is obtained in Example 1 above.
The results are shown in Table 2 below.
【００２９】[0029]
【表２】 [Table 2]
【００３０】この結果、非水電解液中に添加させるケイ
酸塩Ｎａ2 Ｏ・ＳｉＯ2 の添加量を０．１〜１０重量％
の範囲にした実施例１及び実施例８〜１０の各非水電解
質二次電池においては、１サイクルあたりにおける劣化
率が低く、容量残存率も高くなっており、保存特性及び
サイクル特性が十分に向上されていた。[0030] As a result, the amount of silicate Na 2 O · SiO 2 which is added in the nonaqueous electrolytic solution of 0.1 to 10 wt%
In each of the non-aqueous electrolyte secondary batteries of Example 1 and Examples 8 to 10 in which the range was set, the deterioration rate per cycle was low, the capacity remaining rate was high, and the storage characteristics and cycle characteristics were sufficient. Had been improved.
【００３１】一方、上記のケイ酸塩Ｎａ2 Ｏ・ＳｉＯ2
の添加量が０．０５重量％になった実施例７の非水電解
質二次電池においては、上記のケイ酸塩による効果が十
分に得られず、また添加量が２０重量％になった実施例
１１の非水電解質二次電池においては、非水電解液にお
ける伝導度が低下したり、正極材料がこの非水電解液と
反応したりして、何れも１サイクルあたりの劣化率が高
く、容量残存率も低くなっており、保存特性及びサイク
ル特性が十分に向上されていなかった。On the other hand, the above-mentioned silicate Na 2 O.SiO 2
In the non-aqueous electrolyte secondary battery of Example 7 in which the added amount of 0.05% by weight was obtained, the above effect of the silicate was not sufficiently obtained, and the addition amount was 20% by weight. In the non-aqueous electrolyte secondary battery of Example 11, the conductivity in the non-aqueous electrolytic solution was lowered, or the positive electrode material reacted with this non-aqueous electrolytic solution, and thus the deterioration rate per cycle was high, The capacity remaining rate was also low, and the storage characteristics and cycle characteristics were not sufficiently improved.
【００３２】（実施例１２〜１６）これらの実施例にお
いては、上記の実施例１の非水電解質二次電池における
非水電解液の調製において、非水電解液中にケイ酸塩を
加えないようにする一方、負極の作製において、負極材
料である天然黒鉛粉末に対して、ケイ酸塩Ｎａ2 Ｏ・Ｓ
ｉＯ2 を、下記の表３に示すように０．０５重量％、
０．１重量％、１重量％、５重量％、１０重量％含有さ
せるようにし、それ以外については、上記実施例１の場
合と同様にして各非水電解質二次電池を作製した。(Examples 12 to 16) In these Examples, no silicate was added to the non-aqueous electrolyte in the preparation of the non-aqueous electrolyte in the non-aqueous electrolyte secondary battery of Example 1 described above. On the other hand, in the production of the negative electrode, the silicate Na 2 O · S is added to the natural graphite powder, which is the negative electrode material.
0.05% by weight of iO 2 as shown in Table 3 below,
0.1% by weight, 1% by weight, 5% by weight, 10% by weight, and other than that, each non-aqueous electrolyte secondary battery was manufactured in the same manner as in Example 1 above.
【００３３】そして、これらの実施例１２〜１６におけ
る各非水電解質電池についても、上記の場合と同様にし
て、保存後における容量残存率（％）と１サイクルあた
りの劣化率（％）とを求め、その結果を表３に合わせて
示した。Also for each of the nonaqueous electrolyte batteries in Examples 12 to 16, the capacity remaining rate (%) after storage and the deterioration rate (%) per cycle were stored in the same manner as above. The results are shown in Table 3 together.
【００３４】[0034]
【表３】 [Table 3]
【００３５】この結果、負極中にケイ酸塩Ｎａ2 Ｏ・Ｓ
ｉＯ2 を添加させる場合、負極材料である黒鉛粉末に対
して上記のケイ酸塩を０．１〜５重量％の範囲で添加さ
せた実施例１３〜１５の非水電解質二次電池において
は、１サイクルあたりの劣化率が低くなると共に容量残
存率が高くなっており、保存特性及びサイクル特性が十
分に向上されていた。As a result, the silicate Na 2 O.S
In the case of adding iO 2 , in the non-aqueous electrolyte secondary batteries of Examples 13 to 15, in which the above-mentioned silicate is added in the range of 0.1 to 5% by weight with respect to the graphite powder as the negative electrode material, The deterioration rate per cycle was low and the capacity remaining rate was high, and storage characteristics and cycle characteristics were sufficiently improved.
【００３６】一方、黒鉛粉末に対して上記のケイ酸塩Ｎ
ａ2 Ｏ・ＳｉＯ2 の添加量が０．０５重量％になった実
施例１２の非水電解質二次電池においては、上記のケイ
酸塩による効果が十分に得られず、１サイクルあたりの
劣化率が高く、容量残存率も低くなっており、また添加
量が１０重量％になった実施例１６の非水電解質二次電
池においても、１サイクルあたりの劣化率が高く、容量
残存率も低くなっており、保存特性及びサイクル特性が
十分に向上されていなかった。On the other hand, the above-mentioned silicate N is added to the graphite powder.
In the non-aqueous electrolyte secondary battery of Example 12 in which the added amount of a 2 O · SiO 2 was 0.05% by weight, the above effect of the silicate could not be sufficiently obtained, and deterioration per cycle In the non-aqueous electrolyte secondary battery of Example 16 in which the addition rate was 10% by weight, the deterioration rate per cycle was high and the remaining capacity rate was low. The storage characteristics and cycle characteristics were not sufficiently improved.
【００３７】（実施例１７〜２０）これらの実施例にお
いては、上記の実施例１の非水電解質二次電池における
非水電解液の調製において、非水電解液中に加える溶質
の種類だけを下記の表４に示すように変更させ、溶質と
して、実施例１７ではＬｉＢＦ4 を、実施例１８ではＬ
ｉＡｓＦ6 を、実施例１９ではＬｉＣＦ3 ＳＯ3 を、実
施例２０ではＬｉＮ（ＣＦ3 ＳＯ2 ）2 を用い、上記の
エチレンカーボネートとジエチルカーボネートとの混合
溶媒にこれらの溶質をそれぞれ１ｍｏｌ／ｌの割合で溶
解させるようにし、これにケイ酸塩としてＮａ2 Ｏ・Ｓ
ｉＯ2 を１重量％添加させて非水電解液を調製し、それ
以外については、上記実施例１の場合と同様にして非水
電解質二次電池を作製した。(Examples 17 to 20) In these Examples, only the kind of solute to be added to the non-aqueous electrolytic solution in the preparation of the non-aqueous electrolytic solution in the non-aqueous electrolyte secondary battery of Example 1 was used. The solute was changed as shown in Table 4 below, and as a solute, LiBF 4 was used in Example 17 and L was used in Example 18.
iAsF 6 , LiCF 3 SO 3 in Example 19 and LiN (CF 3 SO 2 ) 2 in Example 20 were used, and these solutes were mixed in an amount of 1 mol / l in a mixed solvent of ethylene carbonate and diethyl carbonate. It is made to dissolve in a ratio, and Na 2 O ・ S is added to this as a silicate.
A non-aqueous electrolyte was prepared by adding 1% by weight of iO 2 , and otherwise the non-aqueous electrolyte secondary battery was manufactured in the same manner as in Example 1.
【００３８】（比較例２）この比較例においては、上記
の実施例１の非水電解質二次電池における非水電解液の
調製において、その溶質として含フッ素リチウム塩では
ない過塩素酸リチウムＬｉＣｌＯ4 を用い、このＬｉＣ
ｌＯ4 を上記の混合溶媒に１ｍｏｌ／ｌの割合で溶解さ
せるようにし、これにケイ酸塩としてＮａ2 Ｏ・ＳｉＯ
2 を１重量％添加させて非水電解液を調製し、それ以外
については、上記実施例１の場合と同様にして非水電解
質二次電池を作製した。Comparative Example 2 In this Comparative Example, lithium perchlorate LiClO 4 which is not a fluorine-containing lithium salt is used as the solute in the preparation of the non-aqueous electrolyte solution in the non-aqueous electrolyte secondary battery of Example 1 described above. Using LiC
lO 4 was dissolved in the above mixed solvent at a ratio of 1 mol / l, and Na 2 O.SiO was used as a silicate.
1% by weight of 2 was added to prepare a non-aqueous electrolyte solution, and other than that, a non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1 above.
【００３９】次に、上記のようにして作製した実施例１
７〜２０及び比較例２の各非水電解質二次電池について
も、前記の場合と同様にして容量残存率（％）と１サイ
クルあたりの劣化率（％）とを求め、その結果を表４に
合わせて示した。Next, Example 1 produced as described above.
For each of the non-aqueous electrolyte secondary batteries of Nos. 7 to 20 and Comparative Example 2, the capacity remaining rate (%) and the deterioration rate per cycle (%) were determined in the same manner as in the above case, and the results are shown in Table 4. It is also shown.
【００４０】[0040]
【表４】 [Table 4]
【００４１】この結果、非水電解液における溶質に異な
った含フッ素リチウム塩を用いた実施例１７〜２０の各
非水電解質二次電池においても、上記の実施例１の非水
電解質二次電池の場合と同様に、非水電解液中にケイ酸
塩Ｎａ2 Ｏ・ＳｉＯ2 を含有させることにより、１サイ
クルあたりの劣化率が低くなっていると共に、容量残存
率も高くなっており、保存特性及びサイクル特性が十分
に向上されていた。As a result, also in the non-aqueous electrolyte secondary batteries of Examples 17 to 20 using different fluorine-containing lithium salts as solutes in the non-aqueous electrolyte solution, the non-aqueous electrolyte secondary battery of Example 1 was also used. As in the case of No. 3, by containing the silicate Na 2 O · SiO 2 in the non-aqueous electrolyte, the deterioration rate per cycle is low and the capacity remaining rate is high, The characteristics and cycle characteristics were sufficiently improved.
【００４２】これに対して、非水電解液における溶質に
含フッ素リチウム塩でないＬｉＣｌＯ4 を用いた比較例
２の非水電解質二次電池においては、この非水電解液中
に同様のケイ酸塩を添加させたとしても、１サイクルあ
たり劣化率が高く、また容量残存率も低くなっており、
ケイ酸塩を添加させた効果が得られなかった。On the other hand, in the non-aqueous electrolyte secondary battery of Comparative Example 2 using LiClO 4 which is not a fluorine-containing lithium salt as the solute in the non-aqueous electrolyte, the same silicate is contained in this non-aqueous electrolyte. , The deterioration rate per cycle is high and the capacity remaining rate is low.
The effect of adding silicate was not obtained.
【００４３】次に、上記の実施例１の非水電解質二次電
池における負極の作製において、その負極材料として、
上記の天然黒鉛に代わりにコークスを用い、それ以外に
ついては、上記実施例１と同様にして非水電解質二次電
池を作製した。Next, in the production of the negative electrode in the non-aqueous electrolyte secondary battery of the above Example 1, as the negative electrode material,
A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that coke was used instead of the above-mentioned natural graphite.
【００４４】そして、このように負極材料にコークスを
用いた非水電解質二次電池についても、前記の場合と同
様にして１サイクルあたりにおける放電容量の劣化率
（％）を調べると共に保存後における容量残存率（％）
を測定した。As for the non-aqueous electrolyte secondary battery using coke as the negative electrode material, the deterioration rate (%) of the discharge capacity per cycle was examined in the same manner as in the above case, and the capacity after storage was evaluated. Survival rate(%)
Was measured.
【００４５】この結果、負極材料にコークスを用いた非
水電解質二次電池においては、１サイクルあたりの劣化
率が０．０３〜０．０４％であり、また保存後における
容量残存率は８０％となっており、非水電解液中にケイ
酸塩Ｎａ2 Ｏ・ＳｉＯ2 を添加したにもかかわらず、サ
イクル特性や保存特性がほとんど向上されていなかっ
た。As a result, in the non-aqueous electrolyte secondary battery using coke as the negative electrode material, the deterioration rate per cycle was 0.03 to 0.04%, and the capacity remaining rate after storage was 80%. Therefore, even though the silicate Na 2 O.SiO 2 was added to the non-aqueous electrolyte, the cycle characteristics and the storage characteristics were hardly improved.
【００４６】これは、負極材料の種類により劣化機構が
異なるためであると考えられ、負極材料に黒鉛を用いた
場合に有効に作用するということがわかった。It is considered that this is because the deterioration mechanism differs depending on the type of negative electrode material, and it was found that when graphite is used as the negative electrode material, it works effectively.
【００４７】（比較例３）この比較例においては、上記
の実施例１の非水電解質二次電池における非水電解液の
作製において、非水電解液中にケイ酸塩ではないＬｉ2
ＣＯ3 を１重量％添加させるようにし、それ以外につい
ては、上記実施例１と同様にして非水電解質二次電池を
作製した。(Comparative Example 3) In this comparative example, in the preparation of the non-aqueous electrolyte solution in the non-aqueous electrolyte secondary battery of Example 1 above, Li 2 which is not a silicate in the non-aqueous electrolyte solution is used.
A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that 1% by weight of CO 3 was added.
【００４８】次に、上記の実施例１〜１１及び比較例４
の非水電解質二次電池について、充電電流２００ｍＡで
充電終止電圧４．２Ｖまで充電させ、放電電流５００ｍ
Ａで放電終止電圧２．７５Ｖまで放電させた場合におけ
る低率放電容量と、放電電流２０００ｍＡで放電終止電
圧２．７５Ｖまで放電させた場合における高率放電容量
を求めると共に、負荷特性として、低率放電容量に対す
る高率放電容量の比率（高率放電容量／低率放電容量）
×１００（％）を求め、その結果を下記の表５に示し
た。Next, the above Examples 1 to 11 and Comparative Example 4
The non-aqueous electrolyte secondary battery of No. 2 was charged at a charging current of 200 mA to an end-of-charge voltage of 4.2 V, and a discharging current of 500 m
A low rate discharge capacity when discharged to a discharge end voltage of 2.75 V at A and a high rate discharge capacity when discharged to a discharge end voltage of 2.75 V at a discharge current of 2000 mA are obtained, and as a load characteristic, a low rate Ratio of high rate discharge capacity to discharge capacity (high rate discharge capacity / low rate discharge capacity)
× 100 (%) was determined and the results are shown in Table 5 below.
【００４９】また、上記実施例１の非水電解質二次電池
と比較例３の非水電解質二次電池について、それぞれ放
電電流の電流値を変化させて放電を行ない、放電電流と
放電容量との関係を求め、その結果を図２に示した。Further, the non-aqueous electrolyte secondary battery of Example 1 and the non-aqueous electrolyte secondary battery of Comparative Example 3 were each discharged by changing the current value of the discharge current to obtain the discharge current and the discharge capacity. The relationship was determined and the result is shown in FIG.
【００５０】[0050]
【表５】 [Table 5]
【００５１】これらの結果、上記の実施例１〜１１のよ
うに非水電解液中にケイ酸塩を添加させた各非水電解質
二次電池においては、非水電解液中にケイ酸塩以外のＬ
ｉ2ＣＯ3 を添加した比較例４の非水電解質二次電池に
比べて低率放電容量に対する高率放電容量の比率が高く
なって負荷特性が向上されており、高い放電電流であっ
ても十分な放電容量が得られようになっていた。As a result, in each of the non-aqueous electrolyte secondary batteries in which the silicate was added to the non-aqueous electrolyte as in Examples 1 to 11 described above, the non-aqueous electrolyte did not contain silicates. L
Compared with the non-aqueous electrolyte secondary battery of Comparative Example 4 to which i 2 CO 3 was added, the ratio of the high rate discharge capacity to the low rate discharge capacity was increased and the load characteristics were improved, and even with a high discharge current. A sufficient discharge capacity could be obtained.
【００５２】[0052]
【発明の効果】以上詳述したように、この発明において
は、非水電解液の溶質に含フッ素リチウム塩を用いた非
水電解質電池において、負極や非水電解液中に前記のよ
うなケイ酸塩を含有させたため、保存特性やサイクル特
性の劣化が抑制されると共に、負荷特性も向上されて、
保存特性やサイクル特性に優れると共に、高い電流で放
電を行なった場合にも十分な放電容量をもつ非水電解質
電池が得られるようになった。As described in detail above, according to the present invention, in the non-aqueous electrolyte battery using the fluorine-containing lithium salt as the solute of the non-aqueous electrolyte, the above-mentioned silica is used in the negative electrode and the non-aqueous electrolyte. Since it contains an acid salt, deterioration of storage characteristics and cycle characteristics is suppressed, and load characteristics are also improved.
It has become possible to obtain a non-aqueous electrolyte battery which has excellent storage characteristics and cycle characteristics, and has sufficient discharge capacity even when discharged at a high current.
【図１】各実施例及び各比較例における非水電解質二次
電池の内部構造を示した断面説明図である。FIG. 1 is a cross-sectional explanatory view showing an internal structure of a non-aqueous electrolyte secondary battery in each of Examples and Comparative Examples.
【図２】実施例１と比較例４の各非水電解質二次電池に
おける放電電流と放電容量との関係を示した図である。FIG. 2 is a diagram showing a relationship between discharge current and discharge capacity in each nonaqueous electrolyte secondary battery of Example 1 and Comparative Example 4.
１ 正極 ２ 負極 1 Positive electrode 2 Negative electrode
───────────────────────────────────────────────────── 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 (3)
に含フッ素リチウム塩を含む非水電解液とを備えた非水
電解質電池において、上記の負極及び／又は非水電解液
に対してｘＭ１2 Ｏ・ｙＳｉＯ2 、ｘＭ２Ｏ・ｙＳｉＯ
2 、ｘＭ３2Ｏ3 ・ｙＳｉＯ2 （式中、Ｍ１〜Ｍ３は
Ｋ，Ｎａ，Ｍｇ，Ｃａ，Ｆｅ，Ａｌから選択される金属
元素であり、ｘは１〜２、ｙは１〜４である。）の何れ
かの式で示される少なくとも一種類のケイ酸塩を含有さ
せたことを特徴とする非水電解質電池。1. A non-aqueous electrolyte battery comprising a positive electrode, a negative electrode using a carbon material, and a non-aqueous electrolyte containing a fluorine-containing lithium salt as a solute, wherein the negative electrode and / or the non-aqueous electrolyte is XM1 2 O · ySiO 2 , xM2O · ySiO
2 , xM3 2 O 3 · ySiO 2 (wherein, M1 to M3 are metal elements selected from K, Na, Mg, Ca, Fe and Al, x is 1 to 2 and y is 1 to 4) A non-aqueous electrolyte battery containing at least one kind of silicate represented by any of the formulas.
いて、非水電解液に対して前記のケイ酸塩を０．１〜１
０重量％含有させたことを特徴とする非水電解質電池。2. The non-aqueous electrolyte battery according to claim 1, wherein 0.1 to 1 of the silicate is added to the non-aqueous electrolytic solution.
A non-aqueous electrolyte battery containing 0% by weight.
池において、負極における炭素材料に黒鉛を用いたこと
を特徴とする非水電解質電池。3. The non-aqueous electrolyte battery according to claim 1, wherein graphite is used as a carbon material in the negative electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14668096A JP3223111B2 (en) | 1996-05-15 | 1996-05-15 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14668096A JP3223111B2 (en) | 1996-05-15 | 1996-05-15 | Non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09306541A true JPH09306541A (en) | 1997-11-28 |
| JP3223111B2 JP3223111B2 (en) | 2001-10-29 |
Family
ID=15413172
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14668096A Expired - Fee Related JP3223111B2 (en) | 1996-05-15 | 1996-05-15 | Non-aqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3223111B2 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11204145A (en) * | 1998-01-20 | 1999-07-30 | Yuasa Corp | Lithium secondary battery |
| JPH11250933A (en) * | 1998-03-02 | 1999-09-17 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2000012081A (en) * | 1998-06-23 | 2000-01-14 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte lithium secondary battery |
| JP2000090987A (en) * | 1998-09-09 | 2000-03-31 | Matsushita Electric Ind Co Ltd | Method for measuring discharging capacity of non- aqueous electrolyte secondary 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 |
| JP2018063912A (en) * | 2016-10-14 | 2018-04-19 | Ａｔｔａｃｃａｔｏ合同会社 | Skeleton-forming agent, electrode arranged by use thereof, and manufacturing method of electrode |
| JP2018101638A (en) * | 2018-03-12 | 2018-06-28 | Ａｔｔａｃｃａｔｏ合同会社 | Skeleton-forming agent, electrode arranged by use thereof, and manufacturing method of electrode |
| JP2019003959A (en) * | 2018-10-10 | 2019-01-10 | Ａｔｔａｃｃａｔｏ合同会社 | Positive electrode for nonaqueous electrolyte secondary battery and battery using the same |
| JP2019212638A (en) * | 2018-03-12 | 2019-12-12 | Ａｔｔａｃｃａｔｏ合同会社 | Skeleton-forming agent, electrode arranged by use thereof, and manufacturing method of electrode |
| WO2020189452A1 (en) * | 2019-03-19 | 2020-09-24 | パナソニックＩｐマネジメント株式会社 | Negative electrode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery |
| JP2021193693A (en) * | 2019-09-06 | 2021-12-23 | Ａｔｔａｃｃａｔｏ合同会社 | Skeleton-forming agent, electrode arranged by use thereof, and manufacturing method of electrode |
-
1996
- 1996-05-15 JP JP14668096A patent/JP3223111B2/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11204145A (en) * | 1998-01-20 | 1999-07-30 | Yuasa Corp | Lithium secondary battery |
| JPH11250933A (en) * | 1998-03-02 | 1999-09-17 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2000012081A (en) * | 1998-06-23 | 2000-01-14 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte lithium secondary battery |
| JP2000090987A (en) * | 1998-09-09 | 2000-03-31 | Matsushita Electric Ind Co Ltd | Method for measuring discharging capacity of non- aqueous electrolyte secondary 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 |
| JP2018063912A (en) * | 2016-10-14 | 2018-04-19 | Ａｔｔａｃｃａｔｏ合同会社 | Skeleton-forming agent, electrode arranged by use thereof, and manufacturing method of electrode |
| JP2018101638A (en) * | 2018-03-12 | 2018-06-28 | Ａｔｔａｃｃａｔｏ合同会社 | Skeleton-forming agent, electrode arranged by use thereof, and manufacturing method of electrode |
| JP2019212638A (en) * | 2018-03-12 | 2019-12-12 | Ａｔｔａｃｃａｔｏ合同会社 | Skeleton-forming agent, electrode arranged by use thereof, and manufacturing method of electrode |
| JP2019003959A (en) * | 2018-10-10 | 2019-01-10 | Ａｔｔａｃｃａｔｏ合同会社 | Positive electrode for nonaqueous electrolyte secondary battery and battery using the same |
| WO2020189452A1 (en) * | 2019-03-19 | 2020-09-24 | パナソニックＩｐマネジメント株式会社 | Negative electrode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery |
| JP2021193693A (en) * | 2019-09-06 | 2021-12-23 | Ａｔｔａｃｃａｔｏ合同会社 | Skeleton-forming agent, electrode arranged by use thereof, and manufacturing method of electrode |
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| Publication number | Publication date |
|---|---|
| JP3223111B2 (en) | 2001-10-29 |
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