JPH07296812A - Negative electrode and li secondary battery - Google Patents
Negative electrode and li secondary batteryInfo
- Publication number
- JPH07296812A JPH07296812A JP6113807A JP11380794A JPH07296812A JP H07296812 A JPH07296812 A JP H07296812A JP 6113807 A JP6113807 A JP 6113807A JP 11380794 A JP11380794 A JP 11380794A JP H07296812 A JPH07296812 A JP H07296812A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- lithium
- secondary battery
- amorphous
- amorphous lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- 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]
【産業上の利用分野】本発明は、デンドライトが成長し
にくくてサイクル寿命に優れ、急速充電できて高出力が
得られるＬｉ二次電池及びその負極に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery and a negative electrode thereof, which are difficult to grow dendrites, have excellent cycle life, and can be rapidly charged to obtain high output.
【０００２】[0002]
【従来の技術】従来、負極に金属リチウムを用いてなる
非水電解液型のＬｉ二次電池が知られていた。かかる電
池は、エネルギー密度や起電力に優れる利点を有するも
のの、充電時に負極表面に金属リチウムが樹枝状に析出
したデンドライトが成長しやすく、そのデンドライトで
正負極間が短絡したり、負極よりデンドライトが脱落し
て不活性化し負極の効率低下や劣化を招き、電池のサイ
クル寿命を低下させて実用性に乏しい問題点があった。2. Description of the Related Art Conventionally, a non-aqueous electrolyte type Li secondary battery using metallic lithium as a negative electrode has been known. Although such a battery has an advantage of excellent energy density and electromotive force, a dendrite in which metal lithium is dendriticly deposited on the negative electrode surface during charging is easily grown, and the dendrite short-circuits between the positive and negative electrodes, or the dendrite is more negative than the negative electrode. There is a problem in that it falls off and becomes inactive, resulting in a decrease in efficiency and deterioration of the negative electrode, a decrease in the cycle life of the battery, and poor practicality.
【０００３】前記に鑑みて、Ａｌ、Ｂｉ、Ｐｂ、Ｓｎ、
Ｉｎ等とＬｉとのリチウム合金を負極に用いる方式も提
案されている。しかしながら、金属リチウムからなる負
極に比べて電池の作動電圧が低下し、エネルギー密度も
小さくなる問題点があった。In view of the above, Al, Bi, Pb, Sn,
A method using a lithium alloy of In or the like and Li for the negative electrode has also been proposed. However, the operating voltage of the battery is lower than that of the negative electrode made of metallic lithium, and the energy density is also low.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、デンドライ
トが成長しにくくてエネルギー密度や起電力に優れる負
極を得て、サイクル寿命に優れ、大電流による急速充電
ができて高出力を得ることができるＬｉ二次電池を得る
ことを課題とする。DISCLOSURE OF THE INVENTION According to the present invention, it is possible to obtain a negative electrode which is difficult for dendrite to grow and is excellent in energy density and electromotive force, and which has excellent cycle life and can be rapidly charged by a large current to obtain a high output. An object is to obtain a Li secondary battery that can be used.
【０００５】[0005]
【課題を解決するための手段】本発明は、アモルファス
リチウム又は／及びアモルファスリチウム合金からなる
層を少なくとも表面に有することを特徴とするＬｉ二次
電池用の負極、及びかかる負極を有することを特徴とす
るＬｉ二次電池を提供するものである。DISCLOSURE OF THE INVENTION The present invention is characterized by having a layer of amorphous lithium or / and an amorphous lithium alloy on at least the surface thereof, and a negative electrode for a Li secondary battery, and having such a negative electrode. The Li secondary battery is provided.
【０００６】[0006]
【実施態様の例示】負極は、アモルファスリチウム又は
／及びアモルファスリチウム合金のテープや粉末成形
物、あるいはスラリー塗布方式、溶着ないし蒸着方式等
により導電性支持基材の表面に当該アモルファスリチウ
ム等の層を付設したものなどとして形成される。また導
電性支持基材としては、銅、ニッケル、ステンレス、ア
ルミニウム、銀等の金属からなるシートやネット、カー
ボンファイバやその織布の如き複合物等からなる炭素質
基材などが用いられる。リチウム合金としては、リチウ
ム以外の成分の含有量が原子比に基づいて４０％以下、
特に２０％以下のものが用いられる。Ｌｉ二次電池は、
電解質含有の多孔質絶縁膜を介して正極と負極を配置し
たものなどとして形成される。[Exemplary Embodiment] A negative electrode is formed by forming a layer of amorphous lithium or the like on the surface of a conductive supporting substrate by a tape or powder molding of amorphous lithium or / and an amorphous lithium alloy, or a slurry coating method, a welding or vapor deposition method, or the like. It is formed as an attached one. Further, as the conductive supporting base material, a sheet or net made of a metal such as copper, nickel, stainless steel, aluminum or silver, a carbonaceous base material made of a composite material such as carbon fiber or its woven cloth, and the like are used. As a lithium alloy, the content of components other than lithium is 40% or less based on the atomic ratio,
In particular, 20% or less is used. Li secondary battery,
It is formed as a structure in which a positive electrode and a negative electrode are arranged via a porous insulating film containing an electrolyte.
【０００７】[0007]
【作用】アモルファスリチウム又は／及びアモルファス
リチウム合金を負極の活物質とすることにより、充電時
に負極の表面にデンドライト成長の特異点となる結晶粒
界等の活性ポイントが形成されにくくてＬｉイオンの析
出が均一化され、かつアモルファス構造に基づく高い原
子空孔密度により析出したリチウムが負極内部に効率よ
く拡散して負極表面の特定箇所に活性ポイントが集中す
ることも防止され、これによりデンドライトの発生が抑
制される。その結果、エネルギー密度や起電力に優れる
負極を得ることができ、この負極を用いて充電効率、作
動電圧、放電容量、サイクル寿命、出力に優れるＬｉ二
次電池を形成することができる。[Function] By using amorphous lithium and / or amorphous lithium alloy as the negative electrode active material, it is difficult to form active points such as crystal grain boundaries that are peculiar points of dendrite growth on the surface of the negative electrode during charging, and Li ions are deposited. Is also homogenized, and lithium deposited due to the high atomic vacancy density based on the amorphous structure is efficiently diffused inside the negative electrode, and active points are prevented from concentrating on a specific portion of the negative electrode surface, which causes dendrite generation. Suppressed. As a result, a negative electrode having excellent energy density and electromotive force can be obtained, and by using this negative electrode, a Li secondary battery having excellent charging efficiency, operating voltage, discharge capacity, cycle life, and output can be formed.
【０００８】[0008]
【実施例】本発明の負極は、アモルファスリチウム又は
／及びアモルファスリチウム合金からなる層を少なくと
も表面に有するものであり、Ｌｉ二次電池の形成に用い
るものである。従って本発明の負極は、例えば当該アモ
ルファスリチウム等のテープや粉末成形物、あるいは導
電性支持基材の表面に当該アモルファスリチウム等の層
を付設したものなどの適宜な形態物として形成すること
ができる。その例を図１、図２に示した。EXAMPLES The negative electrode of the present invention has a layer made of amorphous lithium and / or an amorphous lithium alloy on at least the surface thereof, and is used for forming a Li secondary battery. Therefore, the negative electrode of the present invention can be formed in a suitable form such as a tape or powder molded product of the amorphous lithium or the like, or a layer of the amorphous lithium or the like attached to the surface of the conductive support substrate. . Examples thereof are shown in FIGS. 1 and 2.
【０００９】図１に例示の負極１は、アモルファスリチ
ウム又は／及びアモルファスリチウム合金からなる粉末
を粉末成形したものからなる。図２に例示の負極２は、
導電性支持基材２２の表面に当該アモルファスリチウム
等からなる負極活性層２１を付設したものからなる。な
お当該アモルファスリチウム等からなる層は、導電性支
持基材の両面に設けられていてもよいし、片面又は両面
に部分的に設けられていてもよい。The negative electrode 1 illustrated in FIG. 1 is formed by powder molding a powder of amorphous lithium or / and an amorphous lithium alloy. The negative electrode 2 illustrated in FIG.
The conductive support substrate 22 is provided with the negative electrode active layer 21 made of amorphous lithium or the like on the surface thereof. The layer made of amorphous lithium or the like may be provided on both sides of the conductive support substrate, or may be partially provided on one side or both sides.
【００１０】アモルファスリチウム、アモルファスリチ
ウム合金の形成は、例えば融液冷却方式、液体急冷方
式、アトマイズ方式、真空蒸着方式、スパッタリング方
式、プラズマＣＶＤ方式、光ＣＶＤ方式、熱ＣＶＤ方式
などの適宜な方式で形成することができる。Amorphous lithium and amorphous lithium alloys can be formed by an appropriate method such as a melt cooling method, a liquid quenching method, an atomizing method, a vacuum deposition method, a sputtering method, a plasma CVD method, a photo CVD method, a thermal CVD method. Can be formed.
【００１１】アモルファスを形成するためのリチウム合
金としては、Ｌiと、例えばＡl、Ｐb、Ｓn、Ｉn、Ｂi、
Ａｇ、Ｂａ、Ｃａ、Ｈg、Ｐd、Ｐt、Ｓr、Ｔｅなどの金
属との２元又は３元以上の合金に、必要に応じてＳi、
Ｃd、Ｚn、Ｌa等を添加したものなどがあげられ、公知
物のいずれも用いうる。As a lithium alloy for forming an amorphous material, Li and, for example, Al, Pb, Sn, In, Bi,
Binary or ternary or more alloys with metals such as Ag, Ba, Ca, Hg, Pd, Pt, Sr and Te, and Si, if necessary,
Examples thereof include those to which Cd, Zn, La, etc. have been added, and any known material can be used.
【００１２】ちなみに、前記リチウム合金の具体例とし
ては、例えばＡｌ、Ｂｉ、Ｓｎ又はＩｎ等とＬｉとの金
属間化合物などからなるＬｉ合金、ＬiとＰbの合金にＬ
a等を添加して機械的特性を改善したもの、あるいはＡ
ｇ、Ａｌ、Ｍｇ、Ｚｎ又はＣａの少なくとも１種からな
るＸ成分を含むＬｉ−Ｘ−Ｔｅ系合金などがあげられ
る。By the way, as a specific example of the lithium alloy, for example, a Li alloy composed of an intermetallic compound of Al, Bi, Sn, In or the like and Li, or an alloy of Li and Pb is L.
A with improved mechanical properties by adding a, or A
Examples thereof include a Li-X-Te-based alloy containing an X component composed of at least one of g, Al, Mg, Zn, and Ca.
【００１３】リチウム合金におけるリチウム以外の成分
の含有量は、原子比に基づいて４０％以下、就中５〜３
０％、特に１０〜２０％が好ましい。その含有量が４０
％を超えると負極活物質としてのエネルギー密度の低下
が著しい場合があり、２０％を超えると起電力が低下す
る場合がある。また５％未満では合金化による特性の改
善効果に乏しい場合がある。The content of components other than lithium in the lithium alloy is 40% or less based on the atomic ratio, especially 5 to 3
0%, especially 10 to 20% is preferable. Its content is 40
If it exceeds 20%, the energy density of the negative electrode active material may significantly decrease, and if it exceeds 20%, the electromotive force may decrease. If it is less than 5%, the effect of improving the properties due to alloying may be poor.
【００１４】充放電のサイクル寿命、高起電力性、高放
電容量性、高エネルギー密度性などの点より特に好まし
く用いうるリチウム合金は、Ｌｉ−Ａｇ−Ｔｅ系合金か
らなるＬｉ：Ａｇ：Ｔｅの原子比が８０〜１５０：１〜
２０：０．００１〜３０のものなどであり、Ｌｉを８０
原子％以上含有するものである。A lithium alloy which can be particularly preferably used from the viewpoints of charge / discharge cycle life, high electromotive force, high discharge capacity, high energy density, etc. is Li: Ag: Te composed of Li-Ag-Te alloy. Atomic ratio 80-150: 1-
20: 0.001 to 30 and the like, 80% Li
It contains at least atomic%.
【００１５】本発明において負極は任意な形態とするこ
とができ、その形成は例えば、１種又は２種以上のアモ
ルファスリチウム又は／及びアモルファスリチウム合金
の粉末を必要に応じポリフッ化ビニリデンやエチレン・
プロピレン・ジエン共重合体の如き適宜な結着剤を用い
て粉末成形する方法、又は結着剤と分散媒等を用いて調
製したスラリーを注形する方法や導電性支持基材に塗布
する方法、あるいは上記したアモルファス形成方式で導
電性支持基材の表面に当該アモルファスリチウム等から
なる層を溶着ないし蒸着層等として設ける方法などの適
宜な方法で行うことができる。In the present invention, the negative electrode may be in any form, and for example, one or two or more kinds of amorphous lithium or / and amorphous lithium alloy powder may be used for the formation of polyvinylidene fluoride or ethylene.
A method of powder molding using an appropriate binder such as propylene / diene copolymer, a method of casting a slurry prepared using a binder and a dispersion medium, or a method of applying it to a conductive supporting substrate. Alternatively, it can be carried out by an appropriate method such as a method of forming a layer made of the amorphous lithium or the like on the surface of the conductive support base material as a welding or vapor deposition layer by the above-mentioned amorphous forming method.
【００１６】前記において当該アモルファスリチウム等
の粉末としては、形成目的の負極形態等に応じて適宜な
粒径のものを用いてよい。負極特性等の点より好ましく
用いうる粉末は、平均粒径に基づき１〜１００μm以
下、就中５〜８０μm、特に１０〜５０μmのものであ
る。なお結着剤の使用量は強度等に応じて適宜に決定し
てよく、一般には形成負極の機械的強度や電極特性等の
点より当該アモルファスリチウム等の粉末の０．１〜３
０重量％、就中１〜２０重量％、特に２〜１５重量％が
好ましい。In the above, as the powder of the amorphous lithium or the like, those having an appropriate particle size may be used according to the form of the negative electrode to be formed. The powder which can be preferably used from the viewpoint of negative electrode characteristics and the like is one having a particle size of 1 to 100 μm or less, especially 5 to 80 μm, especially 10 to 50 μm based on the average particle size. The amount of the binder used may be appropriately determined depending on the strength and the like. Generally, from the viewpoint of mechanical strength of the formed negative electrode, electrode characteristics, etc., 0.1 to 3 of the powder of amorphous lithium or the like is used.
0% by weight, especially 1 to 20% by weight, especially 2 to 15% by weight is preferable.
【００１７】導電性支持基材についても、形成目的の負
極形態等に応じて適宜なものを用いてよい。その例とし
ては、銅、ニッケル、ステンレス、アルミニウム、銀等
の金属からなるシートやネット、カーボンファイバやそ
の織布の如き複合物等からなる炭素質基材などがあげら
れる。シート状の負極形成を目的とする場合、その導電
性支持基材としては一般に、１〜５００μm、就中５〜
３００μm、特に１０〜１００μmの厚さのものが用いら
れる。その場合、導電性支持基材上に設ける当該アモル
ファスリチウム等からなる層の厚さは任意で、電極の使
用目的等に応じて適宜に決定してよく、一般には５〜８
００μm、就中１０〜５００μm、特に２０〜３００μm
とされる。As the conductive supporting substrate, any suitable one may be used depending on the form of the negative electrode to be formed. Examples thereof include a sheet or net made of a metal such as copper, nickel, stainless steel, aluminum or silver, and a carbonaceous substrate made of a composite such as carbon fiber or its woven cloth. When the purpose is to form a sheet-shaped negative electrode, the conductive supporting base material is generally 1 to 500 μm, especially 5 to 5 μm.
A thickness of 300 μm, particularly 10 to 100 μm, is used. In that case, the thickness of the layer made of amorphous lithium or the like provided on the conductive supporting substrate is arbitrary and may be appropriately determined depending on the purpose of use of the electrode, etc., and generally 5 to 8
00μm, especially 10-500μm, especially 20-300μm
It is said that
【００１８】本発明の負極は、Ｌｉ二次電池を形成する
ためのものであるが、そのＬｉ二次電池の形成について
は、かかる負極を用いる点を除いて特に限定はなく、電
解質と正極を用いて従来に準じて行うことができる。従
ってＬi二次電池の形態なども使用目的等に応じて適宜
に決定することができ、例えばコイン型やボタン型、あ
るいは捲回体型などのように、電解質含有の多孔質絶縁
膜を介して正極と負極を配置した形態等の適宜な形態と
することができる。The negative electrode of the present invention is for forming a Li secondary battery, but there is no particular limitation on the formation of the Li secondary battery except that such a negative electrode is used. It can be performed according to conventional methods. Therefore, the form of the Li secondary battery can be appropriately determined according to the purpose of use and the like. For example, like a coin type, a button type, or a wound type, a positive electrode is provided through a porous insulating film containing an electrolyte. A suitable form such as a form in which the negative electrode and the negative electrode are arranged can be adopted.
【００１９】ちなみに、図３にコイン型のものを例示し
た。３は負極缶、４，８は集電用のニッケル板、５は負
極、６は電解質層（多孔質絶縁膜からなるセパレー
タ）、７は正極、９は正極缶、１０は絶縁封止材であ
る。なお前記した捲回体型のものは、テープ状ないしシ
ート状の正・負極を多孔質絶縁膜からなるセパレータを
介し捲回して正・負極部を形成する缶体に収容したもの
である。前記したシート状等の正・負極の厚さは任意で
あるが、数〜数百μm程度の厚さのものとすることもで
きる。Incidentally, a coin type is illustrated in FIG. 3 is a negative electrode can, 4 and 8 are nickel plates for collecting current, 5 is a negative electrode, 6 is an electrolyte layer (a separator made of a porous insulating film), 7 is a positive electrode, 9 is a positive electrode can, and 10 is an insulating sealing material. is there. The above-mentioned wound body type is one in which a tape-shaped or sheet-shaped positive / negative electrode is housed in a can body which is wound around a separator made of a porous insulating film to form a positive / negative electrode portion. The thickness of the positive and negative electrodes such as the above-mentioned sheet is arbitrary, but it may be about several to several hundreds of μm.
【００２０】電解質としては、Ｌｉイオンの移動を可能
とした適宜なものを用いることができる。その例として
は、塩類電解性ポリマーにリチウム塩を混合してなるも
のの如きポリマー電解質、無機Ｌｉ固体電解質、ないし
それを樹脂中に分散させてなるものの如き固体電解質、
エステルやエーテル等の有機溶媒にリチウム塩を溶解さ
せてなる非水電解液系のものなどがあげられる。As the electrolyte, it is possible to use an appropriate electrolyte capable of moving Li ions. Examples thereof include polymer electrolytes such as those obtained by mixing a lithium salt with a salt-electrolytic polymer, inorganic Li solid electrolytes, or solid electrolytes such as those obtained by dispersing it in a resin,
Examples include non-aqueous electrolyte-based electrolytes prepared by dissolving a lithium salt in an organic solvent such as ester or ether.
【００２１】前記の塩類電解性ポリマーの代表例として
は、ポリエチレンオキシド、ポリホスファゼン、ポリア
ジリジン、ポリエチレンスルフィド、それらの誘導体や
混合物、複合体などがあげられる。なお固体電解質の場
合には、それが正・負極間のセパレータを兼ねうる利点
を有している。Typical examples of the above salt-electrolytic polymers include polyethylene oxide, polyphosphazene, polyaziridine, polyethylene sulfide, their derivatives, mixtures and complexes. The solid electrolyte has the advantage that it can also serve as a separator between the positive and negative electrodes.
【００２２】また前記有機溶媒の代表例としては、プロ
ピレンカーボネート、エチレンカーボネート、ジメチル
カーボネート、ジエチルカーボネート、テトラヒドロフ
ラン、２−メチルテトラヒドロフラン、ジメトキシエタ
ン、ジメチルスルホキシド、スルホラン、γ−ブチロラ
クトン、１，２−ジメトキシエタン、ジエチルエーテ
ル、１，３−ジオキソラン、蟻酸メチル、酢酸メチル、
Ｎ，Ｎ−ジメチルホルムアミド、アセトニトリル、それ
らの混合物などがあげられる。Typical examples of the organic solvent include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, tetrahydrofuran, 2-methyltetrahydrofuran, dimethoxyethane, dimethylsulfoxide, sulfolane, γ-butyrolactone and 1,2-dimethoxyethane. , Diethyl ether, 1,3-dioxolane, methyl formate, methyl acetate,
Examples thereof include N, N-dimethylformamide, acetonitrile, a mixture thereof and the like.
【００２３】リチウム塩の代表例としては、ＬiＩ、Ｌi
ＣＦ3ＳＯ3、Ｌi（ＣＦ2ＳＯ2）2、ＬiＢＦ4、ＬiＣlＯ
4、ＬiＡlＣl4、ＬiＰＦ4、ＬiＰＦ6、ＬiＡsＦ3、Ｌi
ＡsＦ6などがあげられる。電解液におけるリチウム塩濃
度は０．１〜３モル／リットルが一般的であるが、これ
に限定されない。なお前記した非水電解液等の形成に際
しては、寿命や放電容量、起電力等の電池特性の向上な
どを目的として、必要に応じて２−メチルフラン、チオ
フェン、ピロール、クラウンエーテル、Ｌｉ錯イオン形
成剤（大環状化合物等）などの有機添加物を添加するこ
ともできる。Typical examples of the lithium salt are LiI and Li.
CF 3 SO 3 , Li (CF 2 SO 2 ) 2 , LiBF 4 , LiClO
4 , LiAlCl 4 , LiPF 4 , LiPF 6 , LiAsF 3 , Li
AsF 6 and the like. The concentration of lithium salt in the electrolytic solution is generally 0.1 to 3 mol / liter, but is not limited to this. In the formation of the above-mentioned non-aqueous electrolyte solution, 2-methylfuran, thiophene, pyrrole, crown ether, Li complex ions are added as necessary for the purpose of improving battery characteristics such as life, discharge capacity and electromotive force. It is also possible to add organic additives such as forming agents (such as macrocyclic compounds).
【００２４】正極については、カーボンや金属系のも
の、共役系ポリマー等の有機導電性物質系のものなどの
適宜なものを用いることができる。前記金属系正極の例
としては、Ｌｉを含有する、Ｔｉ、Ｍｏ、Ｃｕ、Ｎｂ、
Ｖ、Ｍｎ、Ｃｒ、Ｎｉ、Ｃｏ、Ｐ等の金属の複合酸化
物、硫化物、セレン化物などがあげられ、その代表的具
体例としては、ＭｎＯ2、ＬｉＣｏＯ2、ＬiwＣo1-x-yＭ
xＰyＯ2+z（ただし、Ｍは１種又は２種以上の遷移金
属、ｗは０＜ｗ≦２、ｘは０≦ｘ＜１、ｙは０＜ｙ＜
１、ｚは−１≦ｚ≦４である。）、あるいはＬiないし
Ｌi・Ｃoのリン酸塩及び／又はＣoないしＬi・Ｃoの酸
化物を成分として１モルのＬiあたり０．１モル以上の
Ｃoと０．２モル以上のＰを含有するものなどを活物質
とするものがあげられる。As the positive electrode, an appropriate one such as carbon or metal based one, organic conductive material based one such as conjugated polymer or the like can be used. Examples of the metal-based positive electrode include Li, Ti, Mo, Cu, Nb,
Examples thereof include complex oxides of metals such as V, Mn, Cr, Ni, Co and P, sulfides and selenides, and typical examples thereof include MnO 2 , LiCoO 2 , Li w Co 1-xy M.
x P y O 2 + z (where M is one or more transition metals, w is 0 <w ≦ 2, x is 0 ≦ x <1, y is 0 <y <
1 and z are −1 ≦ z ≦ 4. ), Or a phosphate containing Li to Li · Co and / or an oxide of Co to Li · Co and containing 0.1 mol or more of Co and 0.2 mol or more of P per 1 mol of Li. The active material is, for example.
【００２５】なおシート状等の正極の形成は、例えば活
物質を必要に応じてアセチレンブラックやケッチェンブ
ラック等の導電材料及びポリテトラフルオロエチレンや
ポリエチレン等の結着剤と共にキャスティング方式や圧
縮成形方式、ロール成形方式、ドクターブレード方式、
各種の蒸着方式や圧延方式、熱間押出方式などの、上記
した負極形成方式に準じた適宜な方式で成形する方法な
どにより行うことができる。従って正極は、導電性支持
基材に正極材を半田付けやろう付け、超音波溶接、スポ
ット溶接、バインダ樹脂による塗布付着等の適宜な方式
で接着してなる補強形態物とすることもできる。The positive electrode in the form of a sheet is formed, for example, by a casting method or a compression molding method in which an active material is used together with a conductive material such as acetylene black or Ketjen black and a binder such as polytetrafluoroethylene or polyethylene as required. , Roll forming method, doctor blade method,
It can be performed by a method such as various vapor deposition methods, rolling methods, hot extrusion methods and the like, which are formed by an appropriate method according to the above-mentioned negative electrode forming method. Therefore, the positive electrode may be a reinforced form in which the positive electrode material is adhered to the conductive supporting base material by an appropriate method such as soldering, brazing, ultrasonic welding, spot welding, or coating with a binder resin.
【００２６】一方、上記した正・負極間に介在させる多
孔質絶縁膜（セパレータ）としては、例えばポリプロピ
レン等からなる多孔性ポリマーフィルムやガラスフィル
ター、不織布などの適宜な多孔性素材を用いることがで
きる。電解質含有の多孔質絶縁膜の形成は、多孔質絶縁
膜に電解質ないし電解液を含浸させたり、充填する方
式、あるいは電池缶内に電解液等を充填する方式などの
適宜な方式で行うことができる。On the other hand, as the porous insulating film (separator) interposed between the positive electrode and the negative electrode, an appropriate porous material such as a porous polymer film made of polypropylene or the like, a glass filter, a nonwoven fabric or the like can be used. . The electrolyte-containing porous insulating film may be formed by an appropriate method such as a method of impregnating or filling the porous insulating film with an electrolyte or an electrolytic solution, or a method of filling the battery can with the electrolytic solution or the like. it can.
【００２７】Ｌｉ二次電池に対する充電は、一定電流を
連続して通電する方式のほか、適宜なパルス電源を用い
てパルス電流を供給する方式などによっても行うことが
できる。パルス電流による充電方式では、通電・停止が
繰り返されるため電解質の濃度変化が抑制されてデンド
ライトがより成長しにくい利点がある。The Li secondary battery can be charged by a method of continuously supplying a constant current, or a method of supplying a pulse current by using an appropriate pulse power source. The charging method using a pulse current has the advantage that dendrites are less likely to grow because the concentration change of the electrolyte is suppressed because energization / stopping is repeated.
【００２８】実施例１ 高純度アルゴン雰囲気（露点度−６０℃）下、純リチウ
ムをステンレス製加熱容器中にて約３００℃で融解し、
アルゴンガスで内部より加圧してその融液を高速回転下
の一対の銅製双ロールに噴出させて急冷凝固させて得た
アモルファスＬｉテープを、４０mm幅にカットし、それ
をエキスパンドニッケルの両面に片面厚２０〜１００μ
mとなるように加圧密着させ、長さ２７０mmにカットし
て負極シートを得た。Example 1 Pure lithium was melted at about 300 ° C. in a stainless steel heating container under a high-purity argon atmosphere (dew point -60 ° C.),
Amorphous Li tape obtained by pressurizing it from the inside with argon gas and ejecting the melt onto a pair of copper twin rolls under high speed rotation and rapidly solidifying it was cut into a width of 40 mm, which was then applied to both sides of expanded nickel on one side. Thickness 20-100μ
It was pressed and adhered so as to have a length of m and cut into a length of 270 mm to obtain a negative electrode sheet.
【００２９】一方、ＬｉＣｏＯ2４６部（重量部、以下
同じ）、アセチレンブラック４部、ポリフッ化ビニリデ
ン１部及びＮ−メチルピロリドン４９部を混合してなる
ペーストを厚さ２０μm、幅４２mmのアルミニウム箔上
にドクターブレード方式にて片面厚１００μmで両面に
塗布し、２００℃で１分間仮乾燥後それを圧延し長さ２
５０mmにカットして真空下、１２０℃で３時間本乾燥し
正極シートを得た。On the other hand, an aluminum foil having a thickness of 20 μm and a width of 42 mm was formed by mixing 46 parts of LiCoO 2 (weight part, the same applies hereinafter), 4 parts of acetylene black, 1 part of polyvinylidene fluoride and 49 parts of N-methylpyrrolidone. Apply a doctor blade method on both sides with a thickness of 100μm on both sides, and temporarily dry at 200 ° C for 1 minute and then roll it to a length of 2
It was cut into 50 mm and dried under vacuum at 120 ° C. for 3 hours to obtain a positive electrode sheet.
【００３０】次に、前記の負極シートと正極シートをア
ルゴン雰囲気下、ステンレス又はニッケルメッキ鉄から
なる正・負極缶内に、空孔率４０〜４５％、厚さ２５μ
mのポリプロピレン不織布からなるセパレータを介して
配置し、それに電解液を充填してＡＡサイズＬｉ二次電
池を形成した。なお前記の電解液は、含水率が２０ppm
以下のプロピレンカーボネートと１，２−ジメトキシエ
タンの混合液（体積比：１／１）にＬiＣlＯ4を１モル
／リットル濃度で添加した溶液からなる。Next, the negative electrode sheet and the positive electrode sheet were placed in a positive and negative electrode can made of stainless steel or nickel-plated iron under an argon atmosphere and the porosity was 40 to 45% and the thickness was 25 μm.
It was arranged via a separator made of m polypropylene non-woven fabric and filled with an electrolytic solution to form an AA size Li secondary battery. The above electrolyte solution has a water content of 20 ppm.
It consists of a solution prepared by adding LiClO 4 at a concentration of 1 mol / liter to the following mixed solution of propylene carbonate and 1,2-dimethoxyethane (volume ratio: 1/1).
【００３１】実施例２ Ｌｉ、Ａｇ、Ｔｅを原子比率でＬｉ：Ａｇ：Ｔｅ＝９
０：１０：０．５に配合し、アルゴン雰囲気中で５００
℃にて溶解させて合金化して得たＬｉ-Ａｇ-Ｔｅ合金
を、純リチウムに代えて用いたほかは、実施例１に準じ
て負極シートを得、それを用いてＬｉ二次電池を得た。Example 2 Li: Ag: Te = 9 in atomic ratio Li: Ag: Te = 9
Formulated at 0: 10: 0.5 and 500 in an argon atmosphere.
A negative electrode sheet was obtained in the same manner as in Example 1 except that the Li-Ag-Te alloy obtained by melting and alloying at 0 ° C was used instead of pure lithium, and a Li secondary battery was obtained using the negative electrode sheet. It was
【００３２】実施例３ 高純度アルゴン雰囲気（露点度−６０℃）下、実施例２
に準じて得たＬｉ-Ａｇ-Ｔｅ合金をステンレス製加熱容
器中にて約３００℃で融解し、その融液出口でアルゴン
ガスを吹き付けて霧状とし、それを急冷凝固させて得た
アモルファスリチウム合金粉末７９部を、黒鉛粉末（導
電剤）２０部及びフッ素樹脂粉末（結着剤）１部と混合
し、それを厚さ１０μm、幅４０mmの銅箔の両面に片面
厚２０〜１００μmとなるように加圧密着させ、長さ２
７０mmにカットして負極シートを得、それを用いて実施
例１に準じＬｉ二次電池を得た。Example 3 Example 2 under a high-purity argon atmosphere (dew point -60 ° C.)
Amorphous lithium obtained by melting the Li-Ag-Te alloy obtained in accordance with 1) in a stainless steel heating container at about 300 ° C, spraying argon gas at the melt outlet to form a mist, and rapidly solidifying it. 79 parts of alloy powder is mixed with 20 parts of graphite powder (conductive agent) and 1 part of fluororesin powder (binder), and the thickness of each side is 20 to 100 μm on both sides of a copper foil having a thickness of 10 μm and a width of 40 mm. And press it tightly, length 2
It was cut into 70 mm to obtain a negative electrode sheet, and by using it, a Li secondary battery was obtained according to Example 1.
【００３３】比較例 アモルファスリチウム負極シートに代えて、金属リチウ
ムの圧延テープからなる厚さ１００μmの負極シートを
用いたほかは実施例１に準じてＡＡサイズＬｉ二次電池
を得た。Comparative Example An AA size Li secondary battery was obtained in the same manner as in Example 1 except that a negative electrode sheet made of rolled metal lithium and having a thickness of 100 μm was used in place of the amorphous lithium negative electrode sheet.
【００３４】評価試験 実施例又は比較例で得たＡＡサイズＬｉ二次電池につい
て電流密度１mA／cm2で、上限（充電）電圧４．２Ｖ、
下限（放電）２．７Ｖの条件で充放電を繰り返し、初期
の電池容量（放電容量）の６０％以下の容量となった時
点を寿命の終点としてそのサイクル寿命を調べた。Evaluation Test Regarding the AA size Li secondary batteries obtained in Examples or Comparative Examples, the current density was 1 mA / cm 2 , the upper limit (charging) voltage was 4.2 V,
The charging / discharging was repeated under the condition of the lower limit (discharging) of 2.7 V, and the cycle life was examined with the time point when the capacity reached 60% or less of the initial battery capacity (discharge capacity) as the end point of the life.
【００３５】前記の結果を表に示した。なお表には、負
極の１０サイクル目のエネルギー密度も示した。 The above results are shown in the table. The table also shows the energy density of the negative electrode at the 10th cycle.
【００３６】[0036]
【発明の効果】本発明によれば、金属リチウムに匹敵す
るエネルギー密度や起電力等の特性を示す上に、デンド
ライトが成長しにくい負極を得ることができ、作動電圧
や放電容量等に優れる高エネルギー密度、高出力の、か
つサイクル寿命の長さに優れ、しかも大電流による急速
充電が可能な種々の形態のＬｉ二次電池を得ることがで
きる。EFFECTS OF THE INVENTION According to the present invention, it is possible to obtain a negative electrode in which dendrites are hard to grow while exhibiting characteristics such as energy density and electromotive force comparable to those of metallic lithium, and which is excellent in operating voltage and discharge capacity. It is possible to obtain various types of Li secondary batteries having excellent energy density, high output, long cycle life, and capable of rapid charging with a large current.
【図１】負極例の断面図。FIG. 1 is a cross-sectional view of an example of a negative electrode.
【図２】他の負極例の断面図。FIG. 2 is a sectional view of another example of a negative electrode.
【図３】電池例の説明図。FIG. 3 is an explanatory diagram of a battery example.
１，２，５：負極 ２１：アモルファス系の負極活性層 ２２：導電性支持基材 ３：負極缶 ６：電解質層（多孔質絶縁膜からなるセパレータ） ７：正極 1, 2, 5: Negative electrode 21: Amorphous negative electrode active layer 22: Conductive support base material 3: Negative electrode can 6: Electrolyte layer (separator made of porous insulating film) 7: Positive electrode
Claims (3)
ファスリチウム合金からなる層を少なくとも表面に有す
ることを特徴とするＬｉ二次電池用の負極。1. A negative electrode for a Li secondary battery, which has a layer made of amorphous lithium and / or an amorphous lithium alloy on at least the surface thereof.
ム又は／及びアモルファスリチウム合金からなる層を有
する請求項１に記載の負極。2. The negative electrode according to claim 1, which has a layer made of amorphous lithium and / or an amorphous lithium alloy on the conductive support substrate.
とを特徴とするＬｉ二次電池。3. A Li secondary battery comprising the negative electrode according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6113807A JPH07296812A (en) | 1994-04-28 | 1994-04-28 | Negative electrode and li secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6113807A JPH07296812A (en) | 1994-04-28 | 1994-04-28 | Negative electrode and li secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07296812A true JPH07296812A (en) | 1995-11-10 |
Family
ID=14621565
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6113807A Pending JPH07296812A (en) | 1994-04-28 | 1994-04-28 | Negative electrode and li secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07296812A (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6203944B1 (en) | 1998-03-26 | 2001-03-20 | 3M Innovative Properties Company | Electrode for a lithium battery |
| US6255017B1 (en) | 1998-07-10 | 2001-07-03 | 3M Innovative Properties Co. | Electrode material and compositions including same |
| WO2001078167A1 (en) * | 2000-04-05 | 2001-10-18 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous electrolyte secondary cell |
| WO2002003485A1 (en) * | 2000-06-30 | 2002-01-10 | Nec Corporation | Lithium secondary cell and method for manufacture thereof |
| JP2002212705A (en) * | 2001-01-22 | 2002-07-31 | Sumitomo Electric Ind Ltd | Method and system for thin film deposition |
| US6428933B1 (en) | 1999-04-01 | 2002-08-06 | 3M Innovative Properties Company | Lithium ion batteries with improved resistance to sustained self-heating |
| KR20020095448A (en) * | 2001-06-14 | 2002-12-26 | 닛뽕덴끼 가부시끼가이샤 | Lithium secondary battery with an improved negative electrode structure and method of forming the same |
| EP1282179A2 (en) * | 2001-07-31 | 2003-02-05 | Nec Corporation | Negative electrode for rechargeable battery |
| US6664004B2 (en) | 2000-01-13 | 2003-12-16 | 3M Innovative Properties Company | Electrode compositions having improved cycling behavior |
| US6699336B2 (en) | 2000-01-13 | 2004-03-02 | 3M Innovative Properties Company | Amorphous electrode compositions |
| US6964829B2 (en) | 2000-11-06 | 2005-11-15 | Nec Corporation | Lithium secondary cell and method for manufacturing same |
| JP2011026707A (en) * | 2010-09-13 | 2011-02-10 | Sumitomo Electric Ind Ltd | Thin film manufacturing method and thin film manufacturing apparatus |
| JP2011070939A (en) * | 2009-09-25 | 2011-04-07 | Toyota Central R&D Labs Inc | All-solid type lithium secondary battery |
| WO2019123951A1 (en) * | 2017-12-22 | 2019-06-27 | 昭和電工株式会社 | Lithium-ion secondary cell |
| CN113493887A (en) * | 2021-06-25 | 2021-10-12 | 天津中能锂业有限公司 | Method for non-crystallizing surface of metal lithium strip, product and application thereof |
| CN114883530A (en) * | 2021-02-05 | 2022-08-09 | 恒大新能源技术(深圳)有限公司 | Lithium metal negative electrode, preparation method thereof and lithium secondary battery |
-
1994
- 1994-04-28 JP JP6113807A patent/JPH07296812A/en active Pending
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6436578B2 (en) | 1998-03-26 | 2002-08-20 | 3M Innovative Properties Company | Electrode compositions with high coulombic efficiencies |
| US6203944B1 (en) | 1998-03-26 | 2001-03-20 | 3M Innovative Properties Company | Electrode for a lithium battery |
| US6255017B1 (en) | 1998-07-10 | 2001-07-03 | 3M Innovative Properties Co. | Electrode material and compositions including same |
| US6428933B1 (en) | 1999-04-01 | 2002-08-06 | 3M Innovative Properties Company | Lithium ion batteries with improved resistance to sustained self-heating |
| US6664004B2 (en) | 2000-01-13 | 2003-12-16 | 3M Innovative Properties Company | Electrode compositions having improved cycling behavior |
| US6699336B2 (en) | 2000-01-13 | 2004-03-02 | 3M Innovative Properties Company | Amorphous electrode compositions |
| WO2001078167A1 (en) * | 2000-04-05 | 2001-10-18 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous electrolyte secondary cell |
| WO2002003485A1 (en) * | 2000-06-30 | 2002-01-10 | Nec Corporation | Lithium secondary cell and method for manufacture thereof |
| US6818353B2 (en) | 2000-06-30 | 2004-11-16 | Nec Corporation | Lithium secondary battery and manufacturing method thereof |
| US6964829B2 (en) | 2000-11-06 | 2005-11-15 | Nec Corporation | Lithium secondary cell and method for manufacturing same |
| JP2002212705A (en) * | 2001-01-22 | 2002-07-31 | Sumitomo Electric Ind Ltd | Method and system for thin film deposition |
| KR20020095448A (en) * | 2001-06-14 | 2002-12-26 | 닛뽕덴끼 가부시끼가이샤 | Lithium secondary battery with an improved negative electrode structure and method of forming the same |
| EP1282179A2 (en) * | 2001-07-31 | 2003-02-05 | Nec Corporation | Negative electrode for rechargeable battery |
| EP1282179A3 (en) * | 2001-07-31 | 2005-06-29 | Nec Corporation | Negative electrode for rechargeable battery |
| JP2011070939A (en) * | 2009-09-25 | 2011-04-07 | Toyota Central R&D Labs Inc | All-solid type lithium secondary battery |
| JP2011026707A (en) * | 2010-09-13 | 2011-02-10 | Sumitomo Electric Ind Ltd | Thin film manufacturing method and thin film manufacturing apparatus |
| WO2019123951A1 (en) * | 2017-12-22 | 2019-06-27 | 昭和電工株式会社 | Lithium-ion secondary cell |
| CN114883530A (en) * | 2021-02-05 | 2022-08-09 | 恒大新能源技术(深圳)有限公司 | Lithium metal negative electrode, preparation method thereof and lithium secondary battery |
| CN113493887A (en) * | 2021-06-25 | 2021-10-12 | 天津中能锂业有限公司 | Method for non-crystallizing surface of metal lithium strip, product and application thereof |
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