JPS63146355A - Nonaqueous electrolytic secondary cell - Google Patents
Nonaqueous electrolytic secondary cellInfo
- Publication number
- JPS63146355A JPS63146355A JP61291822A JP29182286A JPS63146355A JP S63146355 A JPS63146355 A JP S63146355A JP 61291822 A JP61291822 A JP 61291822A JP 29182286 A JP29182286 A JP 29182286A JP S63146355 A JPS63146355 A JP S63146355A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- charge
- grain size
- metal material
- discharge
- 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
- 239000007769 metal material Substances 0.000 claims abstract description 41
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 16
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 33
- 238000007599 discharging Methods 0.000 description 10
- 229910000925 Cd alloy Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910000743 fusible alloy Inorganic materials 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- -1 Iai Chemical class 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910000978 Pb alloy Inorganic materials 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000005324 grain boundary diffusion Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/0459—Electrochemical doping, intercalation, occlusion or alloying
- H01M4/0461—Electrochemical alloying
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、非水電解質二次電池の改良に関する。[Detailed description of the invention] Industrial applications The present invention relates to improvements in non-aqueous electrolyte secondary batteries.
従来の技術
現在まで、Ｉａｉ 、 Ｎａ等のアルカリ金属を負極活
物質として用い、ｒ−ブチロラクトン、テトラヒドロフ
ラン、プロピレンカーボネート、ジメトキシエタン等の
溶媒中に、溶質として、Ｌｉｅ１０４゜ＬｉＢＦ４．
ＬｉＣ／等を溶解した、いわゆる非水電解質を用いる二
次電池の開発が進められてきた。Prior Art Until now, alkali metals such as Iai, Na, etc. have been used as negative electrode active materials, and Lie104°LiBF4.
Development of a secondary battery using a so-called non-aqueous electrolyte in which LiC/etc. is dissolved has been progressing.
しかし、この種の二次電池はまだ実用化されていない。However, this type of secondary battery has not yet been put into practical use.
その理由は、充放電回数の寿命が短く、また、充放電に
際しての充放電効率が低いためであり、この性能劣化の
原因は、主に正極及び負極活物質の充放電における化学
的又は物理的可逆性の低下である。The reason for this is that the life of the number of charge/discharge cycles is short and the efficiency of charge/discharge during charging/discharging is low. This is a decrease in reversibility.
負極のこのような欠点を克服するため、従来よシ次式の
ごとく、充電時にＬｉ＋等のアルカリ金属イオンを吸厳
し、放電時に放出する材料Ｍを負極に用いることが提案
されている。In order to overcome these drawbacks of the negative electrode, it has been proposed to use a material M in the negative electrode, which strictly absorbs alkali metal ions such as Li+ during charging and releases them during discharge, as shown in the following formula.
この負極材料として、ム！や、可融合金（成分Ｂｉ、
Ｃｄ、 Ｉｎ、 Ｐｂ、 Ｓｎ、 Ｚｎ等）が知られて
いる（特開昭８０−４９５８６号公報）。As this negative electrode material, Mu! or fusible metal (component Bi,
Cd, In, Pb, Sn, Zn, etc.) are known (Japanese Unexamined Patent Publication No. 80-49586).
発明が解決しようとする問題点
しかし、このような金属材料を負極材料に用いても、大
幅な充放電寿命の向上が見られず、また、同じ金属材料
を用いても充放電寿命が異なるという問題点があった。Problems to be Solved by the Invention However, even if such metal materials are used as negative electrode materials, there is no significant improvement in charge/discharge life, and even if the same metal material is used, charge/discharge life differs. There was a problem.
やれは下記の理由による。This is done for the following reasons.
（１）式の性質を有する金属材料を負極材料に用いた場
合、金属材料は充電時にＬ１＋等のアルｌカリ金属イオ
ンを吸蔵し金属間化合物を形成する。この金属間化合物
の結晶構造は、元の金属材料の結晶構造と大きく異なる
ため、充電時における金属材料の膨張が著しい。逆に、
放電時にはアルカリ金属イオンがこの金属材料より放出
されるため、金属材料は元の結晶構造へ戻り収縮する。When a metal material having the properties of formula (1) is used as a negative electrode material, the metal material absorbs alkali metal ions such as L1+ and forms an intermetallic compound during charging. Since the crystal structure of this intermetallic compound is significantly different from the crystal structure of the original metal material, the metal material expands significantly during charging. vice versa,
During discharge, alkali metal ions are released from the metal material, so the metal material returns to its original crystal structure and contracts.
したがって、金属材料は充放電にともない、膨張、収縮
をくり返すことになる。Therefore, the metal material repeatedly expands and contracts as it is charged and discharged.
また、一般に、（１）式の性質を有する金属材料では、
充電時にＬｉ＋等のアルカリ金属イオンを吸蔵した場合
、硬く、また、もろくなる。In addition, generally, in a metal material having the property of formula (1),
If it absorbs alkali metal ions such as Li+ during charging, it becomes hard and brittle.
以上のような性質を金属材料は有しているため、充放電
にともない、金属材料は表面よシ微細化し、はなはなだ
しい場合には、金属材料の一部もしくは全部が粉末化し
脱落する。このため充放電寿命が低下することになる。Because metal materials have the above-mentioned properties, as they are charged and discharged, the surface of the metal material becomes finer, and in extreme cases, part or all of the metal material turns into powder and falls off. As a result, the charge/discharge life is reduced.
この金属材料の充放電による表面の微細化及び粉末化は
金属材料の結晶粒度が小さいほど著しい。The smaller the crystal grain size of the metal material, the more remarkable the surface refinement and powderization due to charging and discharging of the metal material.
また、同じ金属材料を用いても充放電寿命が異なる原因
は、同稲金属材料間の結晶粒度の差、及び、同−金属材
料内での結晶粒度の不均一分布である。上記のように、
金属材料の充放電寿命は金属材料の結晶粒度と関係があ
り、金属材料間での結晶粒度の差、及び、同−金属材料
内での結晶粒度の不均一分布が、充放電寿命のばらつき
に帰因する。Further, even when the same metal material is used, the difference in charge/discharge life is caused by differences in crystal grain size between the same metal materials and non-uniform distribution of crystal grain size within the same metal material. As described above,
The charge-discharge life of metal materials is related to the crystal grain size of the metal material, and differences in crystal grain size between metal materials and uneven distribution of crystal grain size within the same metal material cause variations in charge-discharge life. Attribute.
本発明はこのような従来の欠点を除去し、充放電をくシ
返しても、微細化、粉末化の小さい金属材料を作製する
ことによシ、充放電寿命のすぐれた信頼性の高い非水電
解質二次電池を提供することを目的とする。The present invention eliminates these conventional drawbacks and creates a highly reliable non-metallic material with an excellent charging/discharging life by producing a metal material that is less likely to become fine or powdered even after repeated charging and discharging cycles. The purpose is to provide a water electrolyte secondary battery.
問題点を解決するための手段
本発明の非水電解質二次電池は、上記負極の金属材料の
平均結晶粒度を１μゴ以上としたことを特徴とする。Means for Solving the Problems The nonaqueous electrolyte secondary battery of the present invention is characterized in that the metal material of the negative electrode has an average crystal grain size of 1 μg or more.
作用 この技術的手段による作用は次のようになる。action The effect of this technical means is as follows.
金属材料を用いて充電、すなわち、アルカリ金属イオン
を吸蔵させる場合、アルカリ金属イオンはまず粒界拡散
を行なった後、金属結晶粒内へ拡散７し、金属間化合物
を形成する。したがって、結晶粒度の小さい結晶粒はど
、粒界に囲まれる割合、すなわち、結晶粒の外周の長さ
と結晶粒度との比が高くなるため、優先的にアルカリ金
属イオンは結晶粒内へ容易に拡散する。When a metal material is used to charge, that is, to occlude alkali metal ions, the alkali metal ions first undergo grain boundary diffusion and then diffuse 7 into metal crystal grains to form an intermetallic compound. Therefore, since grains with small grain sizes are surrounded by grain boundaries, that is, the ratio of the outer circumference of the grain to the grain size, the alkali metal ions preferentially enter the grain easily. Spread.
一方、結晶粒度が大きい結晶粒の場合には、粒界に囲ま
れる割合が小さいため、アルカリ金属イオンは結晶粒内
深くまで拡散することができず、結晶粒の表面近くにと
どまっている。したがって、結晶粒度の大きい結晶粒は
どアルカリ金属イオンを多く容易に取り込むことができ
ず、結晶粒の膨張の割合が小さい。また、放電時にアル
カリ金属イオンを放出する場合には、粒度の小さい結晶
粒と比較すると収縮の割合は小さい。この結果、結晶粒
度の大きい結晶粒を有する金属材料は充放電で膨張、収
縮をくり返しても、結晶構造の破壊の度合が小さいので
安定である。On the other hand, in the case of a crystal grain having a large crystal grain size, since the ratio of being surrounded by grain boundaries is small, alkali metal ions cannot diffuse deep into the crystal grain and remain near the surface of the crystal grain. Therefore, crystal grains with a large crystal grain size cannot easily take in many alkali metal ions, and the rate of expansion of the crystal grains is small. Further, when alkali metal ions are released during discharge, the rate of shrinkage is small compared to crystal grains having a small particle size. As a result, a metal material having crystal grains with a large crystal grain size is stable even if it is repeatedly expanded and contracted by charging and discharging because the degree of destruction of the crystal structure is small.
上記の作用は、負極金属材料の平均結晶粒度が１μＲ以
上で得られる。平均結晶粒度がこれより小さいと、アル
カリ金属イオンが結晶粒深くまで拡散するため、充放電
時における金属材料の微細化、粉末化が起きる。The above effect can be obtained when the average crystal grain size of the negative electrode metal material is 1 μR or more. If the average crystal grain size is smaller than this, alkali metal ions will diffuse deep into the crystal grains, causing the metal material to become fine and powdered during charging and discharging.
以下本発明の実施例を示す。Examples of the present invention will be shown below.
実施例１ 負極に用いる金属材料として、ｐｂ７０重量％。Example 1 PB is 70% by weight as a metal material used for the negative electrode.
Ｃ（１３０重量％の可融合金を用いた。結゛晶粒度の調
整は、この合金の作製時の冷却速度の調整、及び、圧延
後の熱処理により行ない、平均結晶粒度はバインの切裁
法により調べた。また、充放電試験はすべて扁平型電池
で行なった。C (130% by weight fusible alloy was used. The crystal grain size was adjusted by adjusting the cooling rate during production of this alloy and by heat treatment after rolling. The average crystal grain size was determined by cutting the binder. All charging and discharging tests were conducted using flat batteries.
第３図は、本実施例に用いた扁平型電池の断面図である
。FIG. 3 is a cross-sectional view of the flat battery used in this example.
扁平型電池の作成は次のように行なった。厚さ１６０μ
ｍの鉛・カドミウム合金を直径１７ｍのディスクに打ち
抜き、負極集電体１をスポット溶接した封口板２に１ｔ
の圧力で圧着した。次に、この鉛・カドミウム合金上に
金属リチウム箔を２０１１ｇ圧着し、鉛・カドミウム合
金内にリチウムを吸蔵させ、鉛・カドミウム・リチウム
合金３を形成させ負極とした。The flat battery was produced as follows. Thickness 160μ
A 17 m diameter lead/cadmium alloy is punched out into a disc with a diameter of 17 m, and a 1 t.
It was crimped with the same pressure. Next, 2011 g of metal lithium foil was pressure-bonded onto this lead-cadmium alloy, lithium was occluded in the lead-cadmium alloy, and a lead-cadmium-lithium alloy 3 was formed to form a negative electrode.
正極には、Ｖ２Ｏ５，カーボンブラック、四弗化エチレ
ン樹脂を混合したものを用い、正極集電体４をスボクト
溶接した電池ケース６内へ直径１７．５ｍ＋に成型した
。For the positive electrode, a mixture of V2O5, carbon black, and tetrafluoroethylene resin was used, and the positive electrode current collector 4 was molded into a battery case 6 with a diameter of 17.5 m+ by welding.
セパレータ６には、ポリプロピレン不織布を用い、電解
液には、プロピレンカーボネートとジメトキシエタンを
等体積で混合したものに、ＬｉＣｌＯ４を１Ｍ／ｌ
の割合で溶解したものを用いた。A polypropylene non-woven fabric is used for the separator 6, and the electrolyte is a mixture of equal volumes of propylene carbonate and dimethoxyethane, and 1M/l of LiClO4.
A solution dissolved at the following ratio was used.
このように作成した扁平型電池を用いて、２ｍムの定電
流、充電上限電圧３．５Ｖ、放電容量！＋１１Ａｈの条
件で充放電試験を行なった。Using the flat battery created in this way, a constant current of 2mm, an upper limit charge voltage of 3.5V, and a discharge capacity! A charge/discharge test was conducted under the condition of +11 Ah.
第１図は、負極に用いた金属材料の鉛・カドミウム合金
の平均結晶粒度に対して、充放電寿命（放電終止電圧が
１．ｏＶに達するまでの充放電回数）をプロットしたも
のである。これより、平均結晶粒度が１μゴ以上であれ
ば充放電寿命は良好であることがわかる。FIG. 1 is a plot of the charge/discharge life (the number of charge/discharge cycles until the end-of-discharge voltage reaches 1.oV) versus the average grain size of the lead/cadmium alloy used as the metal material for the negative electrode. From this, it can be seen that if the average crystal grain size is 1 μg or more, the charge/discharge life is good.
実施例２
実施例１と同様の電池を作成し、２ｍムの定電施、充電
上限電圧３．５ Ｖ 、放電下限電圧２．０Ｖの条件で
充放電を行なった。第２図は、本発明の実施例である、
平均結晶粒度が１０μ扉である金属材料を負極に用いた
電池ムと、比較例として平均結晶粒度が０．５μゴの金
属材料を負極に用いた電池Ｂの各サイクルでの放電容量
をプロットした図である。これより、比較例の電池Ｂは
充放電をくり返した場合、放電容量が安定していないの
に対し、本発明の電池ムは、充放電をくり返しても放電
容量が安定しており、信頼性にすぐれることがわかる。Example 2 A battery similar to Example 1 was prepared, and charged and discharged under the conditions of a constant current of 2 mm, an upper limit charge voltage of 3.5 V, and a lower limit discharge voltage of 2.0 V. FIG. 2 is an embodiment of the present invention.
The discharge capacity at each cycle was plotted for Battery B using a metal material with an average crystal grain size of 10μ as the negative electrode and as a comparative example, Battery B using a metal material with an average grain size of 0.5μ as the negative electrode. It is a diagram. From this, the battery B of the comparative example has an unstable discharge capacity even after repeated charging and discharging, whereas the battery B of the present invention has a stable discharge capacity even after repeated charging and discharging, and is highly reliable. You can see that it is excellent.
なお、本発明では、鉛７０重量％、カドミウム３０重量
％の可融合金を用いたが、以上の効果は他の組成の可融
合金やム１等の金属等でも同様に得られる。これは、負
極金属材料へのＬ１＋等のアルカリ金属の拡散係数がほ
ぼ等しいことによると考えられる。In the present invention, a fusible alloy containing 70% by weight of lead and 30% by weight of cadmium is used, but the above effects can be similarly obtained with fusible alloys of other compositions and metals such as Mu1. This is considered to be because the diffusion coefficients of alkali metals such as L1+ into the negative electrode metal material are approximately equal.
発明の効果
以上の様に本発明は、負極に用いる金属材料の平均結晶
粒度を１μゴ以上にしているため、充放電によってアル
カリ金属イオンを吸蔵・放出させても微細化、粉末化し
にくい負極が得られる。したがって、本発明の金属材料
を負極に用いれば、充放電寿命のすぐれた、信頼性の高
い非水電解質二次電池を得ることができる。As described above, in the present invention, the average crystal grain size of the metal material used for the negative electrode is 1μ or more, so that the negative electrode is difficult to become fine and powder even when alkali metal ions are occluded and released by charging and discharging. can get. Therefore, if the metal material of the present invention is used for the negative electrode, a highly reliable nonaqueous electrolyte secondary battery with an excellent charge/discharge life can be obtained.
第１図は本発明の実施例の扁平を電池における負極の金
属材料の平均結晶粒度に対する充放電寿命をプロットし
た図、第２図は本発明の実施例の扁平型電池ムと比較例
Ｂの各充放電サイクルに対する放電容量をプロットした
図、第３図は本発明で用いた扁平型電池の断面図である
。
１・・・・・・負極集電体、２・・・・・・封口板、３
・・・・・・鉛・カドミウム・リチウム合金、４・・・
・・・正極集電体、６・・・・・・電池ケース、６・・
・・・・セパレータ。Figure 1 is a diagram plotting the charge/discharge life of a battery according to an embodiment of the present invention against the average crystal grain size of the metal material of the negative electrode in the battery, and Figure 2 is a diagram of a flat battery according to an embodiment of the present invention and a battery of comparative example B. FIG. 3, which is a diagram plotting the discharge capacity for each charge/discharge cycle, is a cross-sectional view of the flat battery used in the present invention. 1... Negative electrode current collector, 2... Sealing plate, 3
...Lead-cadmium-lithium alloy, 4...
...Positive electrode current collector, 6...Battery case, 6...
...Separator.
Claims (1)
電時にアルカリ金属イオンを吸蔵し、放電時にアルカリ
金属イオンを放出する金属材料を用いた負極を構成要素
とする電池であって、前記金属材料の平均結晶粒度が１
μｍ＾３以上であることを特徴とした非水電解質二次電
池。A battery comprising a positive electrode, a nonaqueous electrolyte conductive to alkali metal ions, and a negative electrode using a metal material that occludes alkali metal ions during charging and releases alkali metal ions during discharge, the battery comprising: The average grain size of the material is 1
A non-aqueous electrolyte secondary battery characterized by having a particle diameter of μm^3 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61291822A JPH0746606B2 (en) | 1986-12-08 | 1986-12-08 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61291822A JPH0746606B2 (en) | 1986-12-08 | 1986-12-08 | Non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63146355A true JPS63146355A (en) | 1988-06-18 |
| JPH0746606B2 JPH0746606B2 (en) | 1995-05-17 |
Family
ID=17773861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61291822A Expired - Fee Related JPH0746606B2 (en) | 1986-12-08 | 1986-12-08 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0746606B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11242954A (en) * | 1997-01-28 | 1999-09-07 | Canon Inc | Electrode structural body, secondary battery, and their manufacture |
| JP2009004250A (en) * | 2007-06-22 | 2009-01-08 | Panasonic Corp | Negative electrode active material and all solid polymer battery |
| US8318342B2 (en) | 2007-06-22 | 2012-11-27 | Panasonic Corporation | All solid-state polymer battery |
-
1986
- 1986-12-08 JP JP61291822A patent/JPH0746606B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11242954A (en) * | 1997-01-28 | 1999-09-07 | Canon Inc | Electrode structural body, secondary battery, and their manufacture |
| JP2009004250A (en) * | 2007-06-22 | 2009-01-08 | Panasonic Corp | Negative electrode active material and all solid polymer battery |
| US8318342B2 (en) | 2007-06-22 | 2012-11-27 | Panasonic Corporation | All solid-state polymer battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0746606B2 (en) | 1995-05-17 |
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| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |