JPH1021913A - Battery chargeable and dischargeable reversibly for plural times - Google Patents
Battery chargeable and dischargeable reversibly for plural timesInfo
- Publication number
- JPH1021913A JPH1021913A JP8176214A JP17621496A JPH1021913A JP H1021913 A JPH1021913 A JP H1021913A JP 8176214 A JP8176214 A JP 8176214A JP 17621496 A JP17621496 A JP 17621496A JP H1021913 A JPH1021913 A JP H1021913A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- lithium
- negative electrode
- carbon
- oxide
- 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.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は可逆的に複数回の充
放電が可能な電池に係り、特に非水電解液を用いた二次
電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a battery that can be reversibly charged and discharged a plurality of times, and more particularly to a secondary battery using a non-aqueous electrolyte.
【０００２】[0002]
【従来の技術】近年、二次電池はパソコンや携帯電話な
どの電源として、あるいは電気自動車や電力貯蔵用の電
源として、なくてはならない重要な構成要素の一つとな
っている。2. Description of the Related Art In recent years, secondary batteries have become one of the essential components that are indispensable as power sources for personal computers and mobile phones, or as power sources for electric vehicles and power storage.
【０００３】携帯型コンピュータ（ペンコンピュータと
呼ばれるものも含む）や携帯情報端末(Personal Digita
l Assistant、あるいはPersonal Intelligent Communic
ator、あるいはハンドヘルド・コミュニケータ）といっ
た移動体通信（モービル・コンピューティング）が必要
とされる要求として、小型化，軽量化が挙げられる。し
かし、液晶表示パネルのバックライトや描画制御によっ
て消費される電力が高いことや、二次電池の容量が現状
ではまだ不十分であることなどの点から、システムのコ
ンパクト化が難しい状況にある。A portable computer (including a pen computer) and a personal digital assistant (Personal Digita)
l Assistant or Personal Intelligent Communic
A demand for mobile communication (mobile computing) such as an ator or a hand-held communicator includes miniaturization and weight reduction. However, it is difficult to make the system compact because the power consumed by the backlight and the drawing control of the liquid crystal display panel is high, and the capacity of the secondary battery is still insufficient at present.
【０００４】さらに、地球環境問題の高まりとともに排
ガスや騒音を出さない電気自動車が関心を集めている。
しかし、車体に対して電池の占める体積が極めて大きい
ことや、電池の総重量が著しく重いなどから、車内のス
ペースが狭い，車体の安定性が悪い，加速性が悪いなど
の問題点が生じている。これらもまた、二次電池のエネ
ルギー密度が低いことが原因となっている。[0004] Further, with the increase of global environmental problems, electric vehicles that do not emit exhaust gas and noise have attracted attention.
However, since the battery occupies an extremely large volume with respect to the vehicle body and the total weight of the battery is extremely heavy, there are problems such as a small space inside the vehicle, poor stability of the vehicle body, and poor acceleration. I have. These are also caused by the low energy density of the secondary battery.
【０００５】二次電池を用いたシステムの小型化を実現
させるには、二次電池のエネルギー密度を現在よりもさ
らに増加させる必要がある。非水電解液を用いた二次電
池用負極材料としては、リチウム金属やナトリウム金
属、これらを用いた合金が代表的であるが、充放電の間
にリチウム金属やナトリウム金属が樹枝状に析出し、内
部短絡を起こしたり、発火したりする欠点を有する。こ
れに対し、リチウム金属やナトリウム金属が樹枝状に析
出しないことから安全性の面で有利である、リチウムを
可逆的に挿入放出できる炭素を主体とする材料が実用化
されている。この材料の欠点は、真密度が低いために体
積当りのエネルギー密度が低いことにある。高エネルギ
ー密度化を図るためには、炭素材料の持っている体積当
りのエネルギー密度を向上させる必要がある。例えば、
リチウム二次電池用負極においてカーボン層の表面にリ
チウム合金からなる多孔性の層を形成する(特開平7−32
6342号），リチウム系金属層とカーボン層との積層構造
を有する粒状物を用いる（特開平7−326345 号），黒鉛
とリチウム含有金属酸化物からなる混合体を用いる（特
開平8−7886号）などがある。[0005] In order to reduce the size of a system using a secondary battery, it is necessary to further increase the energy density of the secondary battery compared to the present. As a negative electrode material for a secondary battery using a non-aqueous electrolyte, lithium metal, sodium metal, and alloys using these are typical.However, lithium metal or sodium metal precipitates in a dendritic manner during charge and discharge. It has the disadvantage of causing an internal short circuit or firing. On the other hand, a material mainly composed of carbon capable of reversibly inserting and releasing lithium has been put into practical use, which is advantageous in terms of safety since lithium metal and sodium metal do not precipitate in a dendritic manner. The disadvantage of this material is that the energy density per volume is low due to the low true density. In order to increase the energy density, it is necessary to increase the energy density per volume of the carbon material. For example,
In a negative electrode for a lithium secondary battery, a porous layer made of a lithium alloy is formed on the surface of a carbon layer (Japanese Patent Laid-Open No. 7-32).
No. 6342), a granular material having a laminated structure of a lithium-based metal layer and a carbon layer is used (JP-A-7-326345), and a mixture of graphite and a lithium-containing metal oxide is used (JP-A-8-7886). )and so on.
【０００６】[0006]
【発明が解決しようとする課題】非水電解液を用いた二
次電池のエネルギー密度を現在よりもさらに増加させる
ためには、二次電池用負極材料の体積エネルギー密度の
向上が必要である。カーボン層の表面に体積当りのエネ
ルギー密度の高いリチウム合金からなる層を形成するこ
とにより、エネルギー密度の向上が期待できる。しか
し、リチウム合金は樹枝状析出物を形成しやすいため、
安全性の面での問題が残る。リチウム系金属層とカーボ
ン層との積層構造を有する粒状物を用いる場合にも同様
である。また、黒鉛とリチウム含有金属酸化物からなる
混合体を用いる場合にも体積当りのエネルギー密度の高
いリチウム含有金属酸化物が存在することにより、エネ
ルギー密度は増加する。しかし、黒鉛とリチウム含有金
属酸化物とでは充電作動電位、すなわちリチウム挿入電
位が異なるため、黒鉛とリチウム含有金属酸化物が均一
に混合されていないと、リチウムが局所的に金属として
析出し、短絡や発火等の事故を起こしやすい。In order to further increase the energy density of a secondary battery using a non-aqueous electrolyte, it is necessary to improve the volume energy density of a negative electrode material for a secondary battery. By forming a layer made of a lithium alloy having a high energy density per volume on the surface of the carbon layer, an improvement in energy density can be expected. However, lithium alloys tend to form dendritic precipitates,
There remain security issues. The same applies to the case where a granular material having a laminated structure of a lithium-based metal layer and a carbon layer is used. Also, when a mixture of graphite and a lithium-containing metal oxide is used, the energy density increases due to the presence of the lithium-containing metal oxide having a high energy density per volume. However, since the charging operation potential, that is, the lithium insertion potential, differs between graphite and the lithium-containing metal oxide, if the graphite and the lithium-containing metal oxide are not uniformly mixed, lithium locally precipitates as a metal and short-circuits. Accidents such as fire and fire.
【０００７】このように、二次電池用負極材料の体積エ
ネルギー密度の向上を図るのに有効な方法はあまり見出
されていない。As described above, few effective methods have been found for improving the volume energy density of the negative electrode material for a secondary battery.
【０００８】本発明は体積当りのエネルギー密度が従来
のものより向上し、かつ短絡や発火のない安全性の高い
二次電池用負極材料を提供することを目的とする。[0008] It is an object of the present invention to provide a highly safe negative electrode material for a secondary battery which has a higher energy density per volume than conventional ones and is free from short-circuiting and ignition.
【０００９】[0009]
【課題を解決するための手段】本発明の電池および負極
は、負極活物質として、リチウムを挿入，放出するカー
ボンを主体とする材料の周りにＬｉ，Ｇｅ，Ｓｎ，Ｐ
ｂ，Ｓｂ，Ｂｉ，Ｂ，Ａｌ，Ｓｉ，Ｉｎから選ばれた少
なくとも１種を含む酸化物を被覆したものを使用するこ
とを特徴とする。リチウムを挿入，放出するカーボンを
主体とする材料としては、天然黒鉛（燐状黒鉛，燐片状
黒鉛，土状黒鉛など），人造黒鉛，石油系ピッチコーク
ス，石炭ピッチコークス，中空状炭素分子（フラーレ
ン），中空状炭素繊維（ナノチューブ），非晶質カーボ
ン等がある。これらのカーボンに銀，錫，銅，亜鉛，鉛
等の金属を担持あるいはめっきしたものを使用しても良
い。これらのカーボンの表面にＬｉ，Ｇｅ，Ｓｎ，Ｐ
ｂ，Ｓｂ，Ｂｉ，Ｂ，Ａｌ，Ｓｉ，Ｉｎから選ばれた少
なくとも１種以上を含む酸化物を被覆する。被覆する方
法としては、酸化物のターゲットを用いてカーボン表面
にスパッタ等で酸化物層を被覆させるドライプロセスに
よる方法，金属を電解めっき、あるいは無電解めっきし
た後、酸化雰囲気で熱処理して表面に酸化物皮膜を被覆
させる方法，カーボンの表面に微粒子の酸化物を混合さ
せながら機械的に融合させることによりカーボン表面に
酸化物層を形成させる方法などがある。被覆の形状とし
ては、膜状にカーボン表面を被覆しても、粒状にカーボ
ン表面に複数個の粒子が付着してもよい。被覆する量を
カーボンに対する酸化物の重量比で表すと、好ましくは
８０／２０から２０／８０の範囲であり、さらに好まし
くは６０／４０から４０／６０の範囲であり、最も好ま
しくは４５／５５から５５／４５の範囲である。この範
囲とは、カーボンの放電容量特性と酸化物の放電容量特
性とがほぼ同等となる領域を選択するのが良い。例え
ば、カーボンに放電容量が２００ｍＡｈ／ｇのものを使
用し、酸化物に放電容量が８００ｍＡｈ／ｇのものを使
用した場合には、カーボンに対する酸化物の重量比を２
０／８０とする。これによりカーボンの放電容量特性と
酸化物の放電容量特性とがほぼ同等となる。カーボンと
酸化物の容量をほぼ同等の容量にすることにより、一方
の材料だけが極端に使用されるということがないので、
デンドライトが生成しにくく、短絡や発火等の危険のな
い複合型の負極材料が得られる。両者の混合によって重
量当たりのエネルギー密度および体積当たりのエネルギ
ー密度が大きく低下することのないように、また、一方
の材料だけが極端に使われることによって起こる電流集
中がないように、両者の放電容量が同等となる領域で使
用する。また、カーボン表面に被覆することによって酸
化物を混合させているため、通常の混合方法に比べて均
一に酸化物が分散していることから、デンドライトが生
成しにくい。本発明は両者の材料の長所の相乗効果によ
って高エネルギー密度化とサイクルの長寿命化を達成で
きるものであり、カーボン単独でも、酸化物単独でも得
られない。A battery and a negative electrode according to the present invention comprise, as a negative electrode active material, Li, Ge, Sn, P
It is characterized by using a material coated with an oxide containing at least one selected from b, Sb, Bi, B, Al, Si and In. Materials mainly composed of carbon that inserts and releases lithium include natural graphite (phosphorous graphite, flaky graphite, earthy graphite, etc.), artificial graphite, petroleum pitch coke, coal pitch coke, hollow carbon molecules ( Fullerene), hollow carbon fiber (nanotube), amorphous carbon and the like. A material obtained by carrying or plating a metal such as silver, tin, copper, zinc, or lead on these carbons may be used. Li, Ge, Sn, P
An oxide containing at least one selected from b, Sb, Bi, B, Al, Si, and In is coated. As a method of coating, a method using a dry process of coating an oxide layer on a carbon surface by sputtering or the like using an oxide target, or electroplating or electroless plating of a metal, followed by heat treatment in an oxidizing atmosphere to form a coating on the surface. There are a method of coating an oxide film, and a method of forming an oxide layer on the carbon surface by mixing and mechanically fusing the oxides of fine particles on the carbon surface. Regarding the shape of the coating, the carbon surface may be coated in a film form, or a plurality of particles may be attached to the carbon surface in a granular form. The amount to be coated, expressed as a weight ratio of oxide to carbon, is preferably in the range of 80/20 to 20/80, more preferably in the range of 60/40 to 40/60, and most preferably 45/55. To 55/45. As this range, it is preferable to select a region in which the discharge capacity characteristics of carbon and the oxide are approximately equal. For example, when a discharge capacity of 200 mAh / g is used for carbon and a discharge capacity of 800 mAh / g is used for oxide, the weight ratio of oxide to carbon is 2%.
0/80. As a result, the discharge capacity characteristics of carbon and the discharge capacity characteristics of the oxide become substantially equal. By making the capacities of carbon and oxide almost equal, only one material will not be used extremely,
It is possible to obtain a composite negative electrode material in which dendrite is less likely to be generated and there is no danger such as short circuit or ignition. The discharge capacities of both materials should be such that the energy density per unit weight and the energy density per unit volume do not significantly decrease due to the mixture of the two, and there is no current concentration caused by the extreme use of only one of the materials. Use in the area where is equal. In addition, since the oxide is mixed by coating on the carbon surface, the oxide is more uniformly dispersed as compared with the ordinary mixing method, so that it is difficult to generate dendrites. According to the present invention, a high energy density and a long cycle life can be achieved by the synergistic effect of the advantages of both materials, and neither carbon alone nor oxide alone can be obtained.
【００１０】さらに本発明では該酸化物が非晶質である
ことを特徴とする。酸化物の負極としての充電反応は、
酸素のマトリックス中に存在するＬｉ，Ｇｅ，Ｓｎ，Ｐ
ｂ，Ｓｂ，Ｂｉ，Ｂ，Ａｌ，Ｓｉ，Ｉｎ等の元素と無秩
序に固溶あるいは合金化する形でリチウムが挿入する。
そのため、リチウムの挿入した後の酸化物は非晶質化す
る。従って、用いる酸化物は非晶質でも良い。この非晶
質酸化物の充電電位はカーボンの充電電位に比べて低い
ため、カーボンの外周に被覆することにより、カーボン
中に取り込まれなかったリチウムをデンドライト析出さ
せることなく非晶質の酸化物層内に取り込むことができ
る。Further, the present invention is characterized in that the oxide is amorphous. The charge reaction of the oxide as a negative electrode is
Li, Ge, Sn, P present in the oxygen matrix
Lithium is inserted in such a manner as to be randomly dissolved and alloyed with elements such as b, Sb, Bi, B, Al, Si, and In.
Therefore, the oxide after the insertion of lithium becomes amorphous. Therefore, the oxide used may be amorphous. Since the charge potential of this amorphous oxide is lower than the charge potential of carbon, the amorphous oxide layer is formed by coating the outer periphery of carbon without dendrite depositing lithium not taken into carbon. Can be taken in.
【００１１】電解液としては、例えばプロピレンカーボ
ネート，プロピレンカーボネート誘導体，エチレンカー
ボネート，ブチレンカーボネート，ビニレンカーボネー
ト，ガンマーブチルラクトン，ジメチルカーボネート，
ジエチルカーボネート，メチルエチルカーボネート、
１，２−ジメトキシエタン，２−メチルテトラヒドロフ
ラン，ジメチルスルフォキシド、１，３−ジオキソラ
ン，ホルムアミド，ジメチルホルムアミド，ジオキソラ
ン，アセトニトリル，ニトロメタン，ギサンメチル，酢
酸メチル，プロピオン酸メチル，プロピオン酸エチル，
リン酸トリエステル，トリメトキシメタン，ジオキソラ
ン誘導体，ジエチルエーテル、１，３−プロパンサルト
ン，スルホラン，３−メチル−２−オキサゾリジノン，
テトラヒドロフラン，テトラヒドロフラン誘導体，ジオ
キソラン、１，２−ジエトキシエタン、また、これらの
ハロゲン化物などからなる群より選ばれた少なくとも一
つ以上の非水溶媒とリチウム塩、例えばＬｉＣｌＯ4，
ＬｉＢＦ4，ＬｉＰＦ6， ＬｉＣＦ3ＳＯ3，ＬｉＣ
Ｆ3ＣＯ2，ＬｉＡｓＦ6，ＬｉＳｂＦ6，ＬｉＢ10Ｃ
ｌ10，ＬｉＡｌＣｌ4 ，ＬｉＣｌ，ＬｉＢｒ，ＬｉＩ，
低級脂肪族カルボン酸リチウム，クロロボランリチウ
ム，四フェニルホウ酸リチウムなどからなる群より選ば
れた少なくとも一つ以上の塩との混合溶液を用いること
により、本発明の負極活物質は良好な特性を示す。Examples of the electrolyte include propylene carbonate, propylene carbonate derivatives, ethylene carbonate, butylene carbonate, vinylene carbonate, gamma-butyl lactone, dimethyl carbonate,
Diethyl carbonate, methyl ethyl carbonate,
1,2-dimethoxyethane, 2-methyltetrahydrofuran, dimethylsulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, gisanmethyl, methyl acetate, methyl propionate, ethyl propionate,
Phosphate triester, trimethoxymethane, dioxolane derivative, diethyl ether, 1,3-propanesultone, sulfolane, 3-methyl-2-oxazolidinone,
At least one non-aqueous solvent selected from the group consisting of tetrahydrofuran, tetrahydrofuran derivative, dioxolan, 1,2-diethoxyethane, and halides thereof, and a lithium salt such as LiClO 4 ,
LiBF 4 , LiPF 6 , LiCF 3 SO 3 , LiC
F 3 CO 2, LiAsF 6, LiSbF 6, LiB 10 C
l 10 , LiAlCl 4 , LiCl, LiBr, LiI,
By using a mixed solution with at least one salt selected from the group consisting of lithium lower aliphatic carboxylate, lithium chloroborane, lithium tetraphenylborate, and the like, the negative electrode active material of the present invention exhibits good characteristics. .
【００１２】正極活物質としてはリチウムを挿入，放出
できるものであれば良いが、好ましくはリチウム含有遷
移金属酸化物である。例えば、ＬｉxＭｎ2Ｏ4,ＬｉxＣ
ｏＯ2，ＬｉxＮｉＯ2，ＬｉxＭｎＯ2，ＬｉxＭａＮｉ
(１−ａ)Ｏ2（ＭはＣｏ，Ｖ，Ｍｎ，Ｆｅ，Ｂ，Ｍｇ，
Ａｌ，Ｃｕ，Ｃｒのうち選ばれた１つ以上の元素、ａ＝
０.０１−０.９５）である。Any positive electrode active material may be used as long as it can insert and release lithium, and is preferably a lithium-containing transition metal oxide. For example, Li x Mn 2 O 4 , Li x C
oO 2 , Li x NiO 2 , Li x MnO 2 , Li x MaNi
(1-a) O 2 (M is Co, V, Mn, Fe, B, Mg,
One or more elements selected from Al, Cu and Cr, a =
0.01-0.95).
【００１３】本発明の可逆的に充放電が可能な電池の用
途は、特に限定されないが、例えばノートパソコン，ペ
ン入力パソコン，ポケットパソコン，ノート型ワープ
ロ，ポケットワープロ，電子ブックプレーヤー，携帯電
話，コードレスフォン子機，ページャー，ハンディータ
ーミナル，携帯コピー，電子手帳，電卓，液晶テレビ，
電気シェーバー，電動工具，電子翻訳機，自動車電話，
トランシーバー，音声入力機器，メモリーカード，バッ
クアップ電源，テープレコーダー，ラジオ，ヘッドホン
ステレオ，携帯プリンター，ハンディークリーナー，ポ
ータブルＣＤ，ビデオムービー，ナビゲーションシステ
ムなどの機器用の電源や、冷蔵庫，エアコン，テレビ，
ステレオ，温水器，オーブン電子レンジ，食器洗い器，
洗濯機，乾燥器，ゲーム機器，照明機器，玩具，ロード
コンディショナー，医療機器，自動車，電気自動車，ゴ
ルフカート，電動カート，電力貯蔵システムなどの電源
として使用することができる。また、民生用の他、軍需
用，宇宙用としても用いることができる。The use of the reversibly chargeable / dischargeable battery of the present invention is not particularly limited. Phone handset, pager, handy terminal, portable copy, electronic organizer, calculator, LCD TV,
Electric shaver, power tool, electronic translator, car phone,
Power supplies for equipment such as transceivers, voice input devices, memory cards, backup power supplies, tape recorders, radios, headphone stereos, portable printers, handy cleaners, portable CDs, video movies, navigation systems, refrigerators, air conditioners, televisions,
Stereo, water heater, microwave oven, dishwasher,
It can be used as a power source for washing machines, dryers, game devices, lighting devices, toys, road conditioners, medical devices, automobiles, electric vehicles, golf carts, electric carts, power storage systems, and the like. It can be used not only for civilian purposes but also for military use and space.
【００１４】本発明の電池を使用することにより、体積
当たりのエネルギー密度を向上できる。これにより、シ
ステムのコンパクト化が図れる。また、デンドライトシ
ョートが起こりにくく、長寿命で安全性の高い電池が得
られる。By using the battery of the present invention, the energy density per volume can be improved. As a result, the system can be made compact. In addition, a dendrite short circuit hardly occurs, and a long-life and highly safe battery can be obtained.
【００１５】[0015]
【発明の実施の形態】以下具体例をあげ、本発明をさら
に詳しく説明するが、発明の主旨を越えない限り、本発
明は実施例に限定されるものではない。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the examples unless it exceeds the gist of the invention.
【００１６】（実施例１）負極材料として人造黒鉛と，
これに被覆する被覆材料として（１)ＳｎＳｉＯ3（２）
Ａｌ2Ｏ3（３）ＳｎＯ（４）ＳｎＯ2（５）ＰｂＯ
（６）Ｓｂ2Ｏ3（７）ＬｉＢｉＯ2（８）ＧｅＯ2（９）
Ｂ2Ｏ3（１０）Ｉｎ2Ｏ3とをそれぞれ重量比で１：１と
なるように秤量した。これを遊星ボールミルを用いて回
転数２５０rpm,Ａｒ雰囲気中で１５時間回転させ、被覆
材料を黒鉛表面に被覆させた。この粉末を９３重量％，
結着剤としてポリフッ化ビニリデンを７重量％調製した
合剤を用い、らいかい機で３０分混煉後、厚さ３０ミク
ロンの銅箔の両面に塗布した。正極にはＬｉＣｏＯ2 粉
末を使用し、これを８７重量％，導電剤としてアセチレ
ンブラックを６重量％，結着剤としてポリフッ化ビニリ
デンを７重量％調製した合剤を用い、らいかい機で３０
分混煉後、厚さ２０ミクロンのアルミ箔の両面に塗布し
た。正負両極はプレス機で圧延成型し、端子をスポット
溶接した後１５０℃で５時間真空乾燥した。微多孔性ポ
リプロピレン製セパレータを介して正極と負極を積層
し、これを渦巻状に捲回し、アルミ製の電池缶に挿入し
た。負極端子は電池缶に、正極端子は電池蓋に溶接し
た。電解液には１mol のＬｉＰＦ6 を１リットルのエチ
レンカーボネートとジエチルカーボネートの混合溶液に
溶解したものを使用し、電池缶内に注液した。電池蓋を
かしめて１４００ｍＡｈ容量の円筒型電池を作製した。
電池は２８０ｍＡで４.２Ｖまで充電後、２８０ｍＡで
２.７Ｖまで放電する定電流充放電を行い、サイクル寿
命と体積エネルギー密度を評価した。結果を表１に示
す。(Example 1) Artificial graphite as a negative electrode material,
(1) SnSiO 3 (2)
Al 2 O 3 (3) SnO (4) SnO 2 (5) PbO
(6) Sb 2 O 3 (7) LiBiO 2 (8) GeO 2 (9)
B 2 O 3 (10) In 2 O 3 was weighed so that the weight ratio was 1: 1. This was rotated for 15 hours in an Ar atmosphere at a rotation speed of 250 rpm using a planetary ball mill to coat the graphite material with the coating material. 93% by weight of this powder,
Using a mixture prepared by preparing 7% by weight of polyvinylidene fluoride as a binder, the mixture was kneaded with a triturator for 30 minutes, and then applied to both surfaces of a copper foil having a thickness of 30 microns. LiCoO 2 powder was used for the positive electrode, a mixture prepared by preparing 87% by weight of this powder, 6% by weight of acetylene black as a conductive agent, and 7% by weight of polyvinylidene fluoride as a binder.
After mixing and mixing, it was applied to both sides of an aluminum foil having a thickness of 20 microns. The positive and negative electrodes were roll-formed by a press, and the terminals were spot-welded and then vacuum-dried at 150 ° C. for 5 hours. A positive electrode and a negative electrode were laminated with a microporous polypropylene separator interposed therebetween, spirally wound, and inserted into an aluminum battery can. The negative electrode terminal was welded to the battery can, and the positive electrode terminal was welded to the battery lid. As the electrolytic solution, a solution prepared by dissolving 1 mol of LiPF 6 in 1 liter of a mixed solution of ethylene carbonate and diethyl carbonate was used, and the solution was injected into the battery can. The battery cover was swaged to produce a cylindrical battery having a capacity of 1400 mAh.
After charging the battery to 4.2 V at 280 mA, the battery was charged and discharged at a constant current of 280 mA to 2.7 V, and the cycle life and volume energy density were evaluated. Table 1 shows the results.
【００１７】[0017]
【表１】 [Table 1]
【００１８】（比較例１）負極材料として人造黒鉛を９
３重量％，結着剤としてポリフッ化ビニリデンを７重量
％調製した合剤を用い、厚さ３０ミクロンの銅箔の両面
に塗布した。実施例１と同様にして電池を作製した。サ
イクル寿命と体積エネルギー密度の結果を表１に示す。
実施例１と比較して体積エネルギー密度が低い。(Comparative Example 1) 9 artificial graphite was used as a negative electrode material.
A mixture prepared by preparing 3% by weight and 7% by weight of polyvinylidene fluoride as a binder was applied to both surfaces of a copper foil having a thickness of 30 microns. A battery was manufactured in the same manner as in Example 1. Table 1 shows the results of the cycle life and the volume energy density.
The volume energy density is lower than that of Example 1.
【００１９】（比較例２）負極材料として人造黒鉛を４
７重量％，ＳｎＯを４６重量％，結着剤としてポリフッ
化ビニリデンを７重量％調製した合剤を用い、らいかい
機で３０分混煉後、厚さ３０ミクロンの銅箔の両面に塗
布した。実施例１と同様にして電池を作製した。サイク
ル寿命と体積エネルギー密度の結果を表１に示す。実施
例１と比較して寿命が短く、解体後、負極表面にリチウ
ムのデンドライ析出物を観察した。 （比較例３）負極材料として人造黒鉛とＳｎＯを重量比
で８５：１５となるように秤量した。これを遊星ボール
ミルを用いて実施例１と同じ条件でＳｎＯを黒鉛表面に
被覆させた。この粉末を９３重量％，１０重量％、結着
剤としてポリフッ化ビニリデンを７重量％調製した合剤
を用い、らいかい機で３０分混煉後、厚さ３０ミクロン
の銅箔の両面に塗布した。実施例１と同様にして電池を
作製した。サイクル寿命と体積エネルギー密度の結果を
表１に示す。実施例１と比較して寿命が短く、解体後、
負極表面にリチウムのデンドライ析出物を観察した。ま
た、実施例１と比較して体積エネルギー密度も低い。(Comparative Example 2) Artificial graphite was used as a negative electrode material.
Using a mixture prepared by preparing 7% by weight, 46% by weight of SnO, and 7% by weight of polyvinylidene fluoride as a binder, the mixture was kneaded for 30 minutes with a rake machine, and applied to both sides of a copper foil having a thickness of 30 microns. . A battery was manufactured in the same manner as in Example 1. Table 1 shows the results of the cycle life and the volume energy density. The life was shorter than that of Example 1, and after disassembly, dendritic deposits of lithium were observed on the negative electrode surface. (Comparative Example 3) As the negative electrode material, artificial graphite and SnO were weighed at a weight ratio of 85:15. This was coated on the graphite surface with SnO using a planetary ball mill under the same conditions as in Example 1. Using a mixture prepared by mixing 93% by weight and 10% by weight of this powder and 7% by weight of polyvinylidene fluoride as a binder, kneading the mixture for 30 minutes with a rake machine, and then applying the mixture to both sides of a 30 micron thick copper foil. did. A battery was manufactured in the same manner as in Example 1. Table 1 shows the results of the cycle life and the volume energy density. The life is shorter than that of Example 1, and after disassembly,
Dendritic deposits of lithium were observed on the negative electrode surface. Further, the volume energy density is lower than that of Example 1.
【００２０】（実施例２）負極材料としてＡｇを担持し
た非晶質カーボンと，これに被覆する被覆材料として
（１）ＳｎＳｉＯ3（２）Ａｌ2Ｏ3（３）ＳｎＯ（４）
ＳｎＯ2（５）ＰｂＯ（６）Ｓｂ2Ｏ3（７）ＬｉＢｉＯ2
（８）ＧｅＯ2（９）Ｂ2Ｏ3（１０）Ｉｎ2Ｏ3とをそれ
ぞれ重量比で１：１となるように秤量した。実施例１と
同様にして合金表面に被覆させ、これを用いて電池を作
製した。サイクル寿命と体積エネルギー密度の結果を表
２に示す。Example 2 Amorphous carbon carrying Ag as a negative electrode material and (1) SnSiO 3 (2) Al 2 O 3 (3) SnO (4) as a coating material for coating the same
SnO 2 (5) PbO (6) Sb 2 O 3 (7) LiBiO 2
(8) GeO 2 (9) B 2 O 3 (10) In 2 O 3 were weighed so as to have a weight ratio of 1: 1. The surface of the alloy was coated in the same manner as in Example 1, and a battery was produced using the alloy. Table 2 shows the results of the cycle life and the volume energy density.
【００２１】[0021]
【表２】 [Table 2]
【００２２】[0022]
【発明の効果】本発明によれば、体積エネルギー密度が
向上できるので、電池のコンパクト化が図れる。According to the present invention, since the volume energy density can be improved, the battery can be made compact.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山内 修子 茨城県日立市大みか町七丁目１番１号 株 式会社日立製作所日立研究所内 (72)発明者 堂園 利徳 茨城県日立市大みか町七丁目１番１号 株 式会社日立製作所日立研究所内 (72)発明者 村中 廉 茨城県日立市大みか町七丁目１番１号 株 式会社日立製作所日立研究所内 (72)発明者 吉川 正則 茨城県日立市大みか町七丁目１番１号 株 式会社日立製作所日立研究所内 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Shuko Yamauchi 7-1-1, Omika-cho, Hitachi City, Ibaraki Prefecture Inside Hitachi Research Laboratory, Hitachi, Ltd. (72) Inventor Toshinori Dozono 7-1, Omika-cho, Hitachi City, Ibaraki Prefecture No. 1 Hitachi, Ltd., Hitachi Research Laboratories (72) Inventor Ren Muranaka 7-1-1, Omika-cho, Hitachi City, Ibaraki Prefecture Inside Hitachi, Ltd. Hitachi Research Laboratory (72) Inventor Masanori Yoshikawa Hitachi, Ibaraki Prefecture 7-1-1, Omikacho Inside Hitachi Research Laboratory, Hitachi, Ltd.
Claims (3)
からなる可逆的に複数回の充放電が可能な電池に関し、
該負極における負極活物質に、リチウムを挿入，放出す
るカーボンを主体とする材料の周りにＬｉ，Ｇｅ，Ｓ
ｎ，Ｐｂ，Ｓｂ，Ｂｉ，Ｂ，Ａｌ，Ｓｉ，Ｉｎから選ば
れた少なくとも１種を含む酸化物を被覆したものを使用
することを特徴とする負極およびそれを用いた電池。1. A battery comprising a negative electrode, a positive electrode, and a non-aqueous electrolyte containing a lithium salt, which can be charged and discharged a plurality of times reversibly.
In the negative electrode active material of the negative electrode, around a material mainly composed of carbon that inserts and releases lithium, Li, Ge, S
A negative electrode and a battery using the negative electrode, which are coated with an oxide containing at least one selected from n, Pb, Sb, Bi, B, Al, Si, and In.
請求項１に記載の負極およびそれを用いた電池。2. The negative electrode according to claim 1, wherein the oxide is amorphous, and a battery using the negative electrode.
電池を用いた電池使用システム。3. A battery-using system using the negative electrode or the battery according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8176214A JPH1021913A (en) | 1996-07-05 | 1996-07-05 | Battery chargeable and dischargeable reversibly for plural times |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8176214A JPH1021913A (en) | 1996-07-05 | 1996-07-05 | Battery chargeable and dischargeable reversibly for plural times |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1021913A true JPH1021913A (en) | 1998-01-23 |
Family
ID=16009623
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8176214A Pending JPH1021913A (en) | 1996-07-05 | 1996-07-05 | Battery chargeable and dischargeable reversibly for plural times |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1021913A (en) |
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| KR100378013B1 (en) * | 1999-09-28 | 2003-03-29 | 삼성에스디아이 주식회사 | A anode material for lithium secondary battery, an electrode for lithium secondary battery, a lithium secondary battery and the method of preparing anode material for lithium secondary battery |
| KR100432669B1 (en) * | 2001-12-17 | 2004-05-22 | 삼성에스디아이 주식회사 | Negative active material for rechargeable lithium batteries and preparing for same |
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| JP2004220911A (en) * | 2003-01-15 | 2004-08-05 | Mitsubishi Materials Corp | Negative electrode material for lithium polymer battery, negative electrode using the same, lithium ion battery and lithium polymer battery using negative electrode |
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| CN100373664C (en) * | 2006-04-07 | 2008-03-05 | 北京科技大学 | Preparation method for high-capacity Sn-Ni alloy compound as lithium ion battery negative electrode material |
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| JP2011076822A (en) * | 2009-09-30 | 2011-04-14 | Hitachi Vehicle Energy Ltd | Lithium ion secondary battery |
| WO2012067102A1 (en) * | 2010-11-16 | 2012-05-24 | 日立マクセルエナジー株式会社 | Non-aqueous secondary battery |
| CN105070891A (en) * | 2015-09-06 | 2015-11-18 | 福建师范大学 | Preparation of Ge/GeO2-mesoporous carbon composite electrode material for lithium ion battery and application of Ge/GeO2-mesoporous carbon composite electrode material |
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-
1996
- 1996-07-05 JP JP8176214A patent/JPH1021913A/en active Pending
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| CN105070891A (en) * | 2015-09-06 | 2015-11-18 | 福建师范大学 | Preparation of Ge/GeO2-mesoporous carbon composite electrode material for lithium ion battery and application of Ge/GeO2-mesoporous carbon composite electrode material |
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