JPH0265056A - Nonaqueous secondary battery - Google Patents
Nonaqueous secondary batteryInfo
- Publication number
- JPH0265056A JPH0265056A JP63216168A JP21616888A JPH0265056A JP H0265056 A JPH0265056 A JP H0265056A JP 63216168 A JP63216168 A JP 63216168A JP 21616888 A JP21616888 A JP 21616888A JP H0265056 A JPH0265056 A JP H0265056A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- negative electrode
- battery
- microns
- 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.)
- Pending
Links
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 52
- 239000000956 alloy Substances 0.000 claims abstract description 52
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 39
- 229910008367 Li-Pb Inorganic materials 0.000 claims description 16
- 229910006738 Li—Pb Inorganic materials 0.000 claims description 16
- 239000010419 fine particle Substances 0.000 claims description 16
- 229910000733 Li alloy Inorganic materials 0.000 abstract description 9
- 239000001989 lithium alloy Substances 0.000 abstract description 9
- 238000000465 moulding Methods 0.000 abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052744 lithium Inorganic materials 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 description 12
- 230000003247 decreasing effect Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000003792 electrolyte Substances 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 3
- 239000002244 precipitate Substances 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- -1 Li-Ge Inorganic materials 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910008266 Li-Ag Inorganic materials 0.000 description 1
- 229910007975 Li-Ga Inorganic materials 0.000 description 1
- 229910008029 Li-In Inorganic materials 0.000 description 1
- 229910008445 Li—Ag Inorganic materials 0.000 description 1
- 229910006620 Li—Ga Inorganic materials 0.000 description 1
- 229910006670 Li—In Inorganic materials 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 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
- 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
- H01M4/40—Alloys based on alkali metals
-
- 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
-
- 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)
- Secondary Cells (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、非水電解液を使用した二次電池に係り、特に
Ｌｉ（リチウム）を含む合金で負極活物質を形成した高
エネルギー密度の非水系二次電池に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a secondary battery using a non-aqueous electrolyte, and particularly to a high-energy-density secondary battery in which a negative electrode active material is formed of an alloy containing Li (lithium). Regarding non-aqueous secondary batteries.
従来の非水系二次電池においては、Ｌｉを負極活物質と
し、非水電解液を用いており、このタイプの二次電池は
高密度電池として注目されている。Conventional nonaqueous secondary batteries use Li as a negative electrode active material and a nonaqueous electrolyte, and this type of secondary battery is attracting attention as a high-density battery.
このような電池は、一般に、負極活物質として金＠Ｌｉ
、正極活物質として各種の眉間化合物や導電性高分子な
ど、さらに電解液としてＬｉ塩を安定な有機溶媒に溶か
した溶液を用いる。しかし、負極として金属Ｌｉをその
まま用いた場合、充放電を繰り返すうちにＬｉがデンド
ライト状に析出し、電池の短絡を引き起こすことや、電
流効率が悪いことなどが挙げられる。そこで、これらを
避けるための方法が種々検討されている。その−っとし
て、金属Ｌｉを単体で用いる代わりに、Ｌｉを他の金属
、例えばＡ１などとの合金として用いることが有効であ
ることが知られている（特公昭４９−１２０４４号公報
参照）、Ｌｉ合金電極は、充電時Ｌｉが析出する際に、
金属Ｌｉとして析出するのではなく、母材の金属との合
金として析出する。そのため、Ｌｉ単体として析出する
よりも電気化学的に安定となり、デンドライト状の析出
が抑制され、電流効率が向上する。このような合金とし
ては、Ｌ １−Ｍｇ＋ Ｌ ｉ−Ａ Ｉ 、 Ｌ ｉ−
８ｉ 。Such batteries generally use gold@Li as the negative electrode active material.
As the positive electrode active material, various compounds and conductive polymers are used, and as the electrolyte, a solution of Li salt dissolved in a stable organic solvent is used. However, if metallic Li is used as it is as a negative electrode, Li will precipitate in the form of dendrites during repeated charging and discharging, causing short circuits in the battery and poor current efficiency. Therefore, various methods to avoid these problems are being studied. For this reason, it is known that instead of using metal Li alone, it is effective to use Li as an alloy with other metals, such as A1 (see Japanese Patent Publication No. 12044/1983). When Li alloy electrode precipitates during charging,
It does not precipitate as metallic Li, but as an alloy with the base metal. Therefore, it is electrochemically more stable than when precipitated as a single Li, suppresses dendrite-like precipitation, and improves current efficiency. Such alloys include L 1-Mg+ Li-A I, Li-
8i.
Ｌｉ−Ｇａ、Ｌｉ−Ｇｅ、Ｌｉ−Ｉｎ、Ｌｉ−Ａｇ。Li-Ga, Li-Ge, Li-In, Li-Ag.
Ｌ ｉ−Ｓ ｎ 、 Ｌ ｉ−３ｂ 、 Ｌ ｉ−Ｂ
ｉ 、 Ｌ ｉ−Ｐ ｂなどが挙げられる。しかし、こ
れらの合金電極を用いた場合の問題点は、充放電時にお
ける電極の膨潤、収縮による崩壊、および、それに伴う
電池の容量低下であった。こうした合金電極の劣化はい
ずれの合金でも起り得るが、Ｌ ｉ−Ｐ ｂなどの合金
は、比較的、充放電サイクル寿命が長いことが知られて
いる（特公昭５４−１４１８６９号公報参照）。また、
これらの合金にさらに第三成分の金属、例えばＭ ｇ
ｒ Ｃａ ＊ Ｇ ａ ＨＩ ｎ ｒ Ｓ ｘ ＋Ｇｅ
、Ｓｎなどを少量添加することにより、電極の充放電特
性が一層改善されることも知られている（特公昭６１−
６６３７０号公報参照）。しかし、これらの合金系にお
いても、二次電池の負極として要求される寿命に対し充
分とはいえない。L i-S n , L i-3b , L i-B
i, Li-Pb, and the like. However, the problem with using these alloy electrodes is that the electrodes collapse due to swelling and shrinkage during charging and discharging, and the battery capacity decreases as a result. Such deterioration of alloy electrodes can occur with any alloy, but alloys such as Li-Pb are known to have a relatively long charge-discharge cycle life (see Japanese Patent Publication No. 141869/1986). Also,
In addition to these alloys, a third component metal such as Mg
r Ca * G a HI n r S x +Ge
It is also known that the charging and discharging characteristics of the electrode can be further improved by adding a small amount of , Sn, etc.
(See Publication No. 66370). However, even in these alloy systems, it cannot be said that the life span required for a negative electrode of a secondary battery is sufficient.
二次電池の電極では、数百回の充放電サイクルの繰り返
しに対して安定であることが必要である。Electrodes for secondary batteries need to be stable over hundreds of charge/discharge cycles.
前述のような負極電極の崩壊は、電極の体積変化が起こ
る以上必然的なものであるが、崩壊をある程度抑制する
必要がある。Although the collapse of the negative electrode as described above is inevitable as the volume of the electrode changes, it is necessary to suppress the collapse to some extent.
従来の非水系二次電池にあっては、負極が充放電サイク
ルの繰り返しに対して安定を欠き、崩壊して短寿命であ
る問題点があった。Conventional non-aqueous secondary batteries have a problem in that the negative electrode lacks stability against repeated charge/discharge cycles, collapses, and has a short lifespan.
本発明の目的は、Ｌｉ系合金の崩壊を抑制し、負極の長
寿命化、ひいては、電池の長寿命化を図った非水系二次
電池を提供することにある。An object of the present invention is to provide a non-aqueous secondary battery that suppresses the disintegration of the Li-based alloy and extends the life of the negative electrode and, by extension, the life of the battery.
前記の目的を達成するため、本発明に係る非水系二次電
池は、正極とＬｉ合金の負極との組合せと、負極と正極
との間を絶縁するセパレータと、非水電解液とからなる
非水系二次電池において、Ｌｉ系合金よりなる粒径が７
０〜１５０ミクロンの粒子に、Ｌｉ系合金よりなる粒径
が１０〜７０ミクロンの微粒子を、微粒子に対する粒子
の体積比率が２０〜８０％の割合で混合し、その混合体
で負極を形成するように構成されており、負極はＬ ｉ
−Ｐ ｂ系合金で形成されるものとする。In order to achieve the above object, the non-aqueous secondary battery according to the present invention includes a non-aqueous secondary battery consisting of a combination of a positive electrode and a Li alloy negative electrode, a separator that insulates between the negative electrode and the positive electrode, and a non-aqueous electrolyte. In an aqueous secondary battery, the particle size of Li-based alloy is 7
Fine particles of Li-based alloy with a particle size of 10 to 70 microns are mixed with particles of 0 to 150 microns at a volume ratio of 20 to 80% of the particles to the fine particles, and the mixture forms a negative electrode. The negative electrode is L i
- It shall be made of a Pb-based alloy.
本発明によれば、非水系二次電池の負極を特定の粒径分
布をもつＬｉ系合金粉末の成形体で形成したことにより
、Ｌｉ合金の強度が向上し、放電でリチウムが抜けた状
態でも、負極は安定して成形時の形状を保持し続ける。According to the present invention, by forming the negative electrode of a non-aqueous secondary battery with a compact of Li-based alloy powder having a specific particle size distribution, the strength of the Li alloy is improved, even when lithium is removed during discharge. , the negative electrode stably maintains its shape during molding.
本発明の一実施例を第１図および第２図を参照しながら
説明する。An embodiment of the present invention will be described with reference to FIGS. 1 and 2.
第１図に示されるように、正極３とＬｉ系合金の負極１
との組合せと、負極１と正極３との間を絶縁するセパレ
ータ２と、非水電解液とからなる非水系二次電池におい
て、Ｌｉ系合金よりなる粒径が７０〜１５０ミクロンの
粒子と、Ｌｉ系合金よりなる粒径が１０〜７０ミクロン
の微粒子を、微粒子に対する粒子の体積比率が２０〜８
０％の割合で混合し、その混合体で負極１を形成する構
成であり、負極はＬ ｉ−Ｐ ｂ系合金で形成されるも
のとする。As shown in FIG. 1, a positive electrode 3 and a negative electrode 1 made of Li-based alloy
, a separator 2 that insulates between the negative electrode 1 and the positive electrode 3, and a non-aqueous electrolyte, in which particles having a particle size of 70 to 150 microns made of a Li-based alloy; Fine particles made of Li-based alloy with a particle size of 10 to 70 microns are used, and the volume ratio of particles to fine particles is 20 to 8.
The negative electrode 1 is formed from the mixture at a ratio of 0%, and the negative electrode is made of a Li-Pb alloy.
本発明の効果を確認するために、種々のＬｉ合金電極に
ついて、充放電サイクルを繰り返し、活性の低下したの
ちの電極を調べたが、いずれのＬｉ合金を用いた場合で
も、負極電極の化学的な変化は小さかった。活性の低下
は、電極が膨潤し集電体から浮き上がったために電気的
接触を失ったこと、または、電極が体積の膨潤、収縮を
繰り返すうちに崩壊して微粒子化し、電解液中に分散し
てしまったことの二つが主原因であることがわがった。In order to confirm the effects of the present invention, charge and discharge cycles were repeated for various Li alloy electrodes, and the electrodes were examined after their activity had decreased. However, no matter which Li alloy was used, the chemical The changes were small. The decrease in activity may be due to the electrode swelling and lifting from the current collector, resulting in a loss of electrical contact, or as the electrode repeatedly expands and contracts in volume, it collapses into fine particles and is dispersed in the electrolyte. I found out that the two things that happened were the main causes.
いずれの原因に対しても、合金粒子間の強固な密着性が
必要である。しかし、粒子間に適度な空隙がなければ電
解液が内部に浸透しないために、ごく表面の活性種しか
電極として鋤かないことになり、容量低下や短寿命を引
き起こす。また、Ｌｉ金属箔などを用いると、デンドラ
イトを生じて電池の短絡を起こしやすい。そこで１合金
の粒径を規定して、粒子間の密着性に優れ、かつ電極中
のＬｉの拡散が容易であるような最適粒径を検討した。For any of these reasons, strong adhesion between alloy particles is required. However, if there are no adequate gaps between the particles, the electrolyte will not penetrate into the particles, so only the active species on the very surface will act as electrodes, causing a decrease in capacity and a short lifespan. Furthermore, if Li metal foil or the like is used, dendrites are likely to occur and short circuits in the battery may occur. Therefore, we defined the grain size of one alloy and investigated the optimum grain size that would provide excellent adhesion between grains and facilitate the diffusion of Li in the electrode.
その結果、粒径が７０から１５０ミクロンの大きさの粒
子と、１０から７０ミクロンの大きさの微粒子との混合
体で成形され、かつ、後者（微粒子）に対する前者（粒
子）の体積比率が、２０から８０パーセントの範囲にあ
るものが好ましいことがわかった。粒径が１５０ミクロ
ンより大きい粒子を用いた場合は、成形性が悪く、強度
の点で著しく劣ることがわかった。１０ミクロンより小
さい微粒子を用いた場合は、微粒子であるために成形し
難いこと、また、できた成形体は非常に脆いため ８ｔ
ｏｎ／ａＪ以上の成形圧が必要であることがわかった。As a result, a mixture of particles with a particle size of 70 to 150 microns and fine particles with a size of 10 to 70 microns is formed, and the volume ratio of the former (particles) to the latter (fine particles) is as follows. A range of 20 to 80 percent has been found to be preferred. It was found that when particles having a particle size larger than 150 microns were used, the moldability was poor and the strength was significantly inferior. When using fine particles smaller than 10 microns, it is difficult to mold them because they are fine particles, and the molded product formed is very brittle.
It was found that a molding pressure of on/aJ or more is required.
また、粒径の大きいものと、小さいものとを、それぞれ
、単独に用いて成形した場合は、これらを混合して成形
した場合に比べて、成形性、強度とも劣ることがわかっ
た。It was also found that when particles with a large particle size and those with a small particle size are molded individually, both moldability and strength are inferior to when a mixture of these particles is molded.
モして粒径の大きいものが小さいものに対して２０体積
パーセントより少ない場合は、電池の寿命が著しく短い
ことがわかった。粒径の大きいものが小さいものに対し
て８０体積パーセントより多い場合は、成形性、強度の
両点で著しく劣ることがわかった。It was also found that when the amount of large particles is less than 20% by volume compared to the small particles, the life of the battery is significantly shortened. It was found that when the amount of large particles exceeds 80% by volume of the small particles, both moldability and strength are significantly inferior.
次に本実施例及び比較例について説明する。Next, the present example and comparative example will be explained.
実施例Ｉ
Ｌｉ、Ｐｂを原子比で４＝１の割合で秤量して鉄製るつ
ぼに入れ、Ａｒガス雰囲気下で８００℃で加熱して溶融
後、焼鈍してＬｉ−Ｐｂ合金を調整した。その合金を乳
鉢に入れて粉砕し、粒径が７０〜１５０ミクロンの粒子
と、１０〜７０ミクロンの微粒子との２種類に分け、後
者（微粒子）に対する前者（粒子）の体積比率を２０パ
ーセントとして混合した。この混合物をプレスにより２
ｔｏｎ／ ｃＡの圧力を加えて、厚さ０ 、４ ａｎ、
外径１５ｎｔｎφのディスク状に成形した。そしてこの
ディスク状合金を負極とし、ポリアニリンを正極とする
第１図に示されるようなコイン型の電池を組み立てた。Example I Li and Pb were weighed in an atomic ratio of 4=1, placed in an iron crucible, heated at 800°C in an Ar gas atmosphere to melt, and then annealed to prepare a Li-Pb alloy. The alloy is crushed in a mortar and divided into two types: particles with a diameter of 70 to 150 microns and fine particles with a diameter of 10 to 70 microns, and the volume ratio of the former (particles) to the latter (fine particles) is set at 20%. Mixed. Press this mixture into 2
Apply pressure of ton/cA, thickness 0, 4 an,
It was molded into a disk shape with an outer diameter of 15 ntnφ. A coin-shaped battery as shown in FIG. 1 was assembled using this disc-shaped alloy as a negative electrode and polyaniline as a positive electrode.
本電池はディスク状合金製の負極１と、ポリプロピレン
製不織布のセパレータ２と、ポリアニリンをディスク状
に成形した正極３と、セパレータ２に含浸したＬ ｘ
Ｐ Ｆ ｂのプロピレンカーボネート、エチレンカーボ
ネートおよび１，２−ジメトキシエタン溶液と、これら
を密閉する負極側ケース４、ガスケント５および正極側
ケース６とからなるように構成されている。前記の電池
に電流１ｍＡで４ｖまで充電し、同じく電流１ｍＡで１
゜５■まで放電する操作を繰り返した結果、電池の放電
容量は、第２図に示されるＡのように推移し、容量が３
ｍＡｈ以下に低下するまでに、１０００サイクルの充
放電が可能であった。This battery includes a negative electrode 1 made of a disc-shaped alloy, a separator 2 made of a nonwoven polypropylene fabric, a positive electrode 3 made of polyaniline shaped into a disc, and an L x impregnated into the separator 2.
It consists of a propylene carbonate, ethylene carbonate, and 1,2-dimethoxyethane solution of P F b, and a negative electrode case 4, a gasket 5, and a positive electrode case 6 that seal these solutions. Charge the above battery to 4V with a current of 1mA, and also charge it with a current of 1mA to 1V.
As a result of repeating the discharging operation to ゜5■, the discharge capacity of the battery changed as shown in Figure 2 A, and the capacity reached 3.
1000 cycles of charging and discharging were possible before the battery voltage decreased to mAh or less.
実施例２
実施例１と同様の方法で、７０〜１５０ミクロンの粒径
のＬｉ−Ｐｂ合金および、１０〜７０ミクロンの微粒径
のＬｉ−Ｐｂ合金を後者に対する前者の体積比率を８０
パーセントとして混合しディスク状に成形した。そして
このディスク状合金を負極とする実施例１と同様の構成
のコイン型電池を作製した。この電池に１ｍＡで４ｖま
で充電し、同じく電流１ｍＡで１．５Ｖまで放電する操
作を繰り返した結果、電池の放電容量は、第２図に示さ
れるＢのように推移し、容量が３ ｍＡｈ以下に低下す
るまでのサイクル数は、８００サイクルであった。Example 2 In the same manner as in Example 1, a Li-Pb alloy with a grain size of 70 to 150 microns and a Li-Pb alloy with a fine grain size of 10 to 70 microns were prepared at a volume ratio of 80 to the latter.
It was mixed as a percentage and formed into a disk shape. A coin-shaped battery having the same configuration as in Example 1 was fabricated using this disc-shaped alloy as a negative electrode. As a result of repeating the operation of charging this battery to 4V at 1mA and discharging it to 1.5V at the same current of 1mA, the discharge capacity of the battery changed as shown in B shown in Figure 2, and the capacity decreased to 3mAh or less. The number of cycles until the temperature decreased to 800 was 800 cycles.
実施例３
Ｌｉ、ＡＩを原子比で１：１の割合で秤量して鉄製るつ
ぼに入れ、Ａｒガス雰囲気下で８００°Ｃで加熱して溶
融後、焼鈍してＬｉ−Ａ１合金を調整した。その合金を
乳鉢に入れて粉砕し、粒径が７０〜１５０ミクロンの粒
子と、１０〜７０ミクロンの微粒子との２種類に分け、
後者に対する前者の体積比率を５０パーセントとして混
合し、ディスク状に成形した。そしてこのディスク状合
金を負極とする実施例１と同様の構成のコイン型電池を
作製した。この電池に１ｍＡで４ｖまで充電し、同じく
電流１ｍＡで１．５ｖまで放電する操作を繰り返した結
果、電池の放電容量は、第２図に示されるＣのように推
移し、容量が３ｍＡｈ以下に低下するまでのサイクル数
は、８０ｏサイクルの充放電が可能であった。Example 3 Li and AI were weighed in an atomic ratio of 1:1, placed in an iron crucible, heated at 800°C in an Ar gas atmosphere to melt, and then annealed to prepare a Li-A1 alloy. The alloy is placed in a mortar and crushed, divided into two types: particles with a particle size of 70 to 150 microns and fine particles of 10 to 70 microns,
The volume ratio of the former to the latter was 50%, and the mixture was molded into a disk shape. A coin-shaped battery having the same configuration as in Example 1 was fabricated using this disc-shaped alloy as a negative electrode. As a result of repeating the operation of charging this battery to 4V at 1mA and discharging it to 1.5V at the same current of 1mA, the discharge capacity of the battery changed as shown in Figure 2 C, and the capacity decreased to 3mAh or less. As for the number of cycles until the battery decreased, 80o cycles of charging and discharging were possible.
比較例１
実施例１と同様の方法で、２００〜１５０ミクロンの粒
径のＬｉ−Ｐｂ合金および、１０〜７０ミクロンの微粒
径のＬｉ−Ｐｂ合金を後者に対する前者の体積比率を５
０パーセントとして混合してディスク状に成形した。そ
してこのディスク状合金を負極とする実施例１と同様の
構成のコイン型電池を作製した。この電池に１ｍＡで４
ｖまで充電し、同じく電流１．＋＋＋Ａで１．５Ｖまで
放電する操作を繰り返した結果、電池の放電容量は、第
２図に示されるＤのように８００サイクルで急激に低下
した。解体した結果、負極合金が集電体から浮き上がっ
ていることがわかった。Comparative Example 1 A Li-Pb alloy with a grain size of 200 to 150 microns and a Li-Pb alloy with a fine grain size of 10 to 70 microns were prepared in the same manner as in Example 1, with the volume ratio of the former to the latter being 5.
It was mixed as 0% and formed into a disk shape. A coin-shaped battery having the same configuration as in Example 1 was fabricated using this disc-shaped alloy as a negative electrode. 4 at 1mA for this battery
Charge to v, and the same current is 1. As a result of repeating the operation of discharging to 1.5 V at +++A, the discharge capacity of the battery suddenly decreased after 800 cycles, as shown by D in FIG. 2. Upon disassembly, it was discovered that the negative electrode alloy was floating above the current collector.
比較例２
実施例１と同様の方法で、７０〜１５０ミクロンの粒径
のＬ］、−Ｐｂ合金および、１〜１０ミクロンの粒径の
Ｌｉ−Ｐｂ合金を後行に対する前者の体積比率を５０パ
ーセントとして混合してディスク状に成形した。そして
このディスク状合金を負極とする実施例１と同様の構成
のコイン型電池を作製した。この電池に１ｍＡで４ｖま
で充電し、同じく電流１ｍＡで１．５ｖまで放電する操
作を繰り返した結果、電池の放電容量は、第２図に示さ
れるＥのように推移し、容量が３ｍＡｈ以下に低下する
までのサイクル数は、２００サイクルにすぎなかった。Comparative Example 2 In the same manner as in Example 1, a -Pb alloy with a grain size of 70 to 150 microns and a Li-Pb alloy with a grain size of 1 to 10 microns were added to the rear by increasing the volume ratio of the former to 50. The mixture was mixed as a percentage and formed into a disk shape. A coin-shaped battery having the same configuration as in Example 1 was fabricated using this disc-shaped alloy as a negative electrode. As a result of repeating the operation of charging this battery to 4V at 1mA and discharging it to 1.5V at the same current of 1mA, the discharge capacity of the battery changed as shown in Fig. 2, and the capacity decreased to 3mAh or less. It took only 200 cycles to reach a decline.
解体して調べた結果、微粒子が電解液中に溶は出してい
た。When it was dismantled and examined, it was found that fine particles had dissolved into the electrolyte.
比較例３
実施例１と同様の方法で、７０〜１５０ミクロンの粒径
のＬｉ−Ｐｂ合金および、１０〜７０ミクロンの粒径の
Ｌ ｉ−Ｐ ｂ合金を後者に対する前者の体積比率を９
０パーセントとして混合してディスク状に成形した。そ
してこのディスク状合金を負極とする実施例１と同様の
構成のコイン型電池を作製した。この電池で、１ｍＡで
４Ｖまで充電し、同じく電流ＬｍＡで１．５ｖまで放電
する操作を繰り返したところ、電池の放電容量が３ ｍ
Ａｈ以下に低下するまでのサイクル数は、６０サイクル
にすぎなかった。Comparative Example 3 In the same manner as in Example 1, a Li-Pb alloy with a particle size of 70 to 150 microns and a Li-Pb alloy with a particle size of 10 to 70 microns were prepared at a volume ratio of 9 to the latter.
It was mixed as 0% and formed into a disk shape. A coin-shaped battery having the same configuration as in Example 1 was fabricated using this disc-shaped alloy as a negative electrode. When this battery was repeatedly charged to 4 V at 1 mA and discharged to 1.5 V at the same current LmA, the discharge capacity of the battery was 3 m.
The number of cycles until it decreased to below Ah was only 60 cycles.
比較例４
実施例１と同様の方法で、７０〜１５０ミクロンの粒径
のＬ ｉ−Ｐ ｂ合金および、１０〜７０ミクロンの粒
径のＬ ｉ−Ｐ ｂ合金を後者に対する前者の体積比率
を１０パーセントとして混合してディスク状に成形した
。そしてこのディスク状合金を負極とする実施例１と同
様の構成のコイン型電池を作製した。この電池で１ｍＡ
で４ｖまで充電し、同じく電流１ｍＡで１．５ｖまで放
電する操作を繰り返した結果、電池の放電容量が３ ｍ
Ａｈ以下に低下するまでのサイクル数は３０サイクルに
すぎなかった。Comparative Example 4 A Li-Pb alloy with a particle size of 70 to 150 microns and a Li-Pb alloy with a particle size of 10 to 70 microns were prepared in the same manner as in Example 1, and the volume ratio of the former to the latter was determined. The mixture was mixed at 10% and formed into a disk. A coin-shaped battery having the same configuration as in Example 1 was fabricated using this disc-shaped alloy as a negative electrode. 1mA with this battery
As a result of repeating the operation of charging to 4V with a current of 1mA and discharging to 1.5V with a current of 1mA, the discharge capacity of the battery was 3m.
The number of cycles until it decreased to below Ah was only 30 cycles.
比較例５
実施例１と同様の方法で、１０〜７０ミクロンの粒径の
Ｌ ｉ−Ｐ ｂ合金および、７０〜１５０ミクロンの粒
径のＬ ｉ−Ｐ ｂ合金を単独それぞれディスク状に成
形した。しかし、これらは成形体に反りや歪みが生じて
成形が難しく、また、割れが入って電極として使えない
ものもあった。成形圧を８ｔｏｎ／ａＪに上げて成形し
、これらの合金を負極とする実施例１と同様の構成のコ
イン型電池を作製した。これらの電池に１ｍＡで４ｖま
で充電し、同じく電流１ｍＡで１．５ｖまで放電する操
作を繰り返した結果、電池の放電容量が３ ｍＡｈ以下
に低下するまでのサイクル数は、１００サイクル、およ
び、３００サイクルにすぎなかった。Comparative Example 5 In the same manner as in Example 1, a Li-Pb alloy with a grain size of 10 to 70 microns and a Li-Pb alloy with a grain size of 70 to 150 microns were individually molded into a disk shape. . However, these molded products were difficult to mold because they were warped and distorted, and some of them were unusable as electrodes due to cracks. The molding pressure was increased to 8 ton/aJ to produce a coin-shaped battery having the same structure as Example 1 using these alloys as a negative electrode. As a result of repeating the operation of charging these batteries to 4V at 1mA and discharging them to 1.5V at the same current of 1mA, the number of cycles until the battery discharge capacity decreased to 3mAh or less was 100 cycles and 300 cycles. It was just a cycle.
本発明によれば、非水系二次電池の負極を合金粒子の粒
径が７０〜１００ミクロンの粒子に対して１０〜７０ミ
クロンの微粒子を体積比率で２０〜８０％混合した混合
体で形成することによって、充放電を繰り返した場合の
寿命の長い負極を容易に得ることができ、さらに、これ
を負極に用いることにより長寿命の非水系二次電池を得
ることができる。According to the present invention, the negative electrode of a nonaqueous secondary battery is formed of a mixture of alloy particles having a particle size of 70 to 100 microns and fine particles of 10 to 70 microns in a volume ratio of 20 to 80%. By doing so, a negative electrode with a long life when repeatedly charged and discharged can be easily obtained, and furthermore, by using this as the negative electrode, a non-aqueous secondary battery with a long life can be obtained.
第１図は本発明の実施例を示す断面図、第２図は本発明
の実施例１，２．３および比較例１，２を説明する放電
容量の充放電サイクル数に対する変化を示すグラフであ
る。
１・・・負極、２・・・セパレータ、
３・・・正極、４・・・負極ケース、
Ａ・・・実施例１の電池の放電容量変化、Ｂ・・・実施
例２の電池の放電容量変化、Ｃ・・・実施例３の電池の
放電容量変化。
Ｄ・・・比較例１の電池の放電容量変化、Ｅ ・比較例
２の電池の放電容量変化。Fig. 1 is a cross-sectional view showing an example of the present invention, and Fig. 2 is a graph showing changes in discharge capacity with respect to the number of charge/discharge cycles, explaining Examples 1, 2.3 and Comparative Examples 1, 2 of the present invention. be. DESCRIPTION OF SYMBOLS 1... Negative electrode, 2... Separator, 3... Positive electrode, 4... Negative electrode case, A... Discharge capacity change of the battery of Example 1, B... Discharge of the battery of Example 2 Capacity change, C: Change in discharge capacity of the battery of Example 3. D: Change in discharge capacity of the battery of Comparative Example 1, E. Change in discharge capacity of the battery of Comparative Example 2.
Claims (1)
記正極との間を絶縁するセパレータと、非水電解液とか
らなる非水系二次電池において、前記Ｌｉ系合金よりな
る粒径が７０〜１５０ミクロンの粒子と、前記Ｌｉ系合
金よりなる粒径が１０〜７０ミクロンの微粒子を、該微
粒子に対する前記粒子の体積比率が２０〜８０パーセン
トの割合で混合し、その混合体で前記負極を形成したこ
とを特徴とする非水系二次電池。 ２、負極はＬｉ−Ｐｂ系合金で形成されたことを特徴と
する請求項１記載の非水系二次電池。[Scope of Claims] 1. A non-aqueous secondary battery comprising a combination of a positive electrode and a negative electrode made of a Li-based alloy, a separator for insulating between the negative electrode and the positive electrode, and a non-aqueous electrolyte; Particles of a Li-based alloy with a particle size of 70 to 150 microns and fine particles of the Li-based alloy with a particle size of 10 to 70 microns are mixed at a volume ratio of 20 to 80% of the particles to the fine particles. , a nonaqueous secondary battery characterized in that the negative electrode is formed of a mixture thereof. 2. The non-aqueous secondary battery according to claim 1, wherein the negative electrode is made of a Li-Pb alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63216168A JPH0265056A (en) | 1988-08-30 | 1988-08-30 | Nonaqueous secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63216168A JPH0265056A (en) | 1988-08-30 | 1988-08-30 | Nonaqueous secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0265056A true JPH0265056A (en) | 1990-03-05 |
Family
ID=16684353
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63216168A Pending JPH0265056A (en) | 1988-08-30 | 1988-08-30 | Nonaqueous secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0265056A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0442410U (en) * | 1990-08-13 | 1992-04-10 | ||
| US6008563A (en) * | 1997-10-29 | 1999-12-28 | Mitsubishi Denki Kabushiki Kaisha | Reluctance motor and compressor-driving reluctance motor |
-
1988
- 1988-08-30 JP JP63216168A patent/JPH0265056A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0442410U (en) * | 1990-08-13 | 1992-04-10 | ||
| US6008563A (en) * | 1997-10-29 | 1999-12-28 | Mitsubishi Denki Kabushiki Kaisha | Reluctance motor and compressor-driving reluctance motor |
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