JPH0831454A - Coin-shaped nonaqueous electrolyte secondary battery - Google Patents
Coin-shaped nonaqueous electrolyte secondary batteryInfo
- Publication number
- JPH0831454A JPH0831454A JP6161117A JP16111794A JPH0831454A JP H0831454 A JPH0831454 A JP H0831454A JP 6161117 A JP6161117 A JP 6161117A JP 16111794 A JP16111794 A JP 16111794A JP H0831454 A JPH0831454 A JP H0831454A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- lithium
- pellet
- secondary battery
- coin
- 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
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 52
- 239000008188 pellet Substances 0.000 claims abstract description 45
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 238000007599 discharging Methods 0.000 abstract description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 20
- -1 polyethylene Polymers 0.000 description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910013553 LiNO Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はコイン形非水電解液二次
電池に関し、特に炭素材からなる負極ペレットを備える
コイン形リチウム二次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coin type non-aqueous electrolyte secondary battery, and more particularly to a coin type lithium secondary battery having a negative electrode pellet made of a carbon material.
【０００２】[0002]
【従来の技術】近年、電子機器のポータブル化に伴い、
その駆動用電源として、小型で軽量、かつ、エネルギー
密度が高いリチウム二次電池の開発が要望されている。
また、省資源、環境保護の面から、従来、一次電池が主
に使用されているメモリーバックアップ等の用途におい
ても、二次電池化が進んでおり、コイン形のリチウム二
次電池が商品化されている。2. Description of the Related Art In recent years, along with portable electronic devices,
As a driving power source, there is a demand for the development of a lithium secondary battery that is small, lightweight, and has a high energy density.
Further, from the viewpoint of resource saving and environmental protection, secondary batteries are being used in applications such as memory backup where primary batteries have been mainly used, and coin-type lithium secondary batteries have been commercialized. ing.
【０００３】従来、リチウム二次電池としては、負極活
物質としてリチウム又はリチウム合金を用い、正極活物
質としてＬｉＭｎ2 Ｏ4 、ＬｉＭｎ2 Ｏ3 とＭｎＯ2 と
の複合体などのリチウム複合酸化物、モリブデン、バナ
ジウム、チタン、ニオブなどの酸化物、硫化部、セレン
化物などを用い、電解質としてプロピレンカーボネー
ト、ジオキソラン、ジメトキシエタンなどの非水電解液
を用いるものが提案されている。Conventionally, as a lithium secondary battery, lithium or a lithium alloy is used as a negative electrode active material, and a lithium composite oxide such as LiMn 2 O 4 , a complex of LiMn 2 O 3 and MnO 2 is used as a positive electrode active material, It has been proposed to use oxides such as molybdenum, vanadium, titanium, and niobium, sulfides, selenides, and the like, and use a nonaqueous electrolytic solution such as propylene carbonate, dioxolane, and dimethoxyethane as an electrolyte.
【０００４】しかし、これらの電池では、負極に金属リ
チウムを用いる場合には、充電時にリチウムがデンドラ
イト状に析出するために、内部短絡が発生したり、容量
減少を生じたりする問題があり、また、充電で析出した
リチウムは非常に活性であるため、安全性の確保に問題
がある。さらに、負極にリチウム合金を用いる場合に
は、デンドライトの発生は防止できるが、合金の放電深
度が深くなると合金が劣化し、深い放電深度におけるサ
イクル特性に問題がある。However, in these batteries, when metallic lithium is used for the negative electrode, lithium is deposited in a dendrite form during charging, so that there is a problem that an internal short circuit occurs or the capacity decreases. Since lithium deposited by charging is very active, there is a problem in ensuring safety. Further, when a lithium alloy is used for the negative electrode, the generation of dendrite can be prevented, but the alloy deteriorates as the depth of discharge of the alloy deepens, and there is a problem in the cycle characteristics at a deep depth of discharge.
【０００５】このような問題を解決するために、近年、
負極に炭素質物を用いるコイン形非水電解液二次電池が
高電圧で充放電サイクル特性に優れ、安全性も高いこと
から開発され商品化されている。In order to solve such a problem, in recent years,
A coin type non-aqueous electrolyte secondary battery using a carbonaceous material for the negative electrode has been developed and commercialized because of its high voltage and excellent charge / discharge cycle characteristics and high safety.
【０００６】しかし、前記の負極に炭素質物を用いるコ
イン形非水電解液二次電池は、予め負極炭素質物にリチ
ウムを吸蔵させる必要がある。この吸蔵方法としては、
従来、図４（ａ）に示すように負極缶（６）の内面に集
電体（５）を介して金属リチウム（４）を圧着し、その
上に負極ペレット（２）を載置して電池を組み立てて放
置し、電気化学的にリチウムを負極炭素質物に吸蔵させ
る方法が用いられている。However, in the coin type non-aqueous electrolyte secondary battery using the carbonaceous material for the negative electrode, it is necessary to occlude lithium in the negative electrode carbonaceous material in advance. For this storage method,
Conventionally, as shown in FIG. 4 (a), metallic lithium (4) is pressure-bonded to the inner surface of a negative electrode can (6) via a current collector (5), and the negative electrode pellet (2) is placed thereon. A method is used in which a battery is assembled, left standing, and electrochemically occludes lithium in a negative electrode carbonaceous material.
【０００７】ところで、このような電池では、電池組立
後の放置により金属リチウムが炭素質物に吸蔵され、図
４（ｂ）に示すような構造になるが、炭素質物はリチウ
ムを吸蔵しても体積増加が少ないため、金属リチウムが
吸蔵された分だけ電池内容の厚さが減少する。その際、
電池内容の総高が低下することにより、負極ペレットと
負極缶の電気的接触が不十分となり、特に金属リチウム
の厚さが厚い場合には接触不良を生じ易く、その結果、
内部抵抗の増大、ならびに充放電サイクル特性、貯蔵特
性及び耐衝撃性の低下を招くこととなる。By the way, in such a battery, metallic lithium is occluded in the carbonaceous material by leaving it after the battery is assembled, and the structure shown in FIG. 4 (b) is obtained. Since the increase is small, the thickness of the battery content is reduced by the amount of absorbed lithium metal. that time,
Due to the decrease in the total height of the battery contents, the electrical contact between the negative electrode pellet and the negative electrode can becomes insufficient, and particularly when the thickness of the metallic lithium is large, poor contact is likely to occur, and as a result,
This leads to an increase in internal resistance and a decrease in charge / discharge cycle characteristics, storage characteristics and impact resistance.
【０００８】[0008]
【発明が解決しようとする課題】本発明の目的は、この
ような課題を解決して、重負荷特性、充放電サイクル特
性、貯蔵特性及び耐衝撃性に優れたコイン形非水電解液
二次電池を提供することである。SUMMARY OF THE INVENTION An object of the present invention is to solve these problems and to provide a coin-type non-aqueous electrolyte secondary electrolyte excellent in heavy load characteristics, charge / discharge cycle characteristics, storage characteristics and impact resistance. It is to provide a battery.
【０００９】[0009]
【課題を解決するための手段】本発明は、正極、リチウ
ムを吸蔵・放出可能な炭素質物を含む負極ペレット、当
該負極ペレットにリチウムを供給するための金属リチウ
ム、集電体を内面に備える負極缶、セパレータ及び非水
電解液を備えるコイン形非水電解液二次電池において、
前記負極ペレットの前記負極缶に対する側に凹部を備
え、当該凹部中に前記金属リチウムを配置することを特
徴とするコイン形非水電解液二次電池に関し、また前記
負極ペレットの凹部に加えて、前記負極ペレットと集電
体を内面に備える前記負極の間に金属リチウムを配置す
る電池に関する。The present invention is directed to a positive electrode, a negative electrode pellet containing a carbonaceous material capable of occluding and releasing lithium, metallic lithium for supplying lithium to the negative electrode pellet, and a negative electrode having a current collector on its inner surface. In a coin-shaped non-aqueous electrolyte secondary battery comprising a can, a separator and a non-aqueous electrolyte,
Provided with a recess on the side of the negative electrode pellet to the negative electrode can, the coin-shaped non-aqueous electrolyte secondary battery, characterized in that the lithium metal is placed in the recess, in addition to the recess of the negative electrode pellet, The present invention relates to a battery in which metallic lithium is arranged between the negative electrode pellet and the negative electrode having a current collector on its inner surface.
【００１０】本発明に用いる炭素質物としては、有機高
分子化合物やコークス、ピッチ等を焼成したもの；又は
人造グラファイトや天然グラファイト等の炭素質物が挙
げられる。Examples of the carbonaceous material used in the present invention include those obtained by firing an organic polymer compound, coke, pitch, etc .; or carbonaceous materials such as artificial graphite and natural graphite.
【００１１】本発明に用いる負極は、例えば次のような
方法によって作製されるピッチ系炭素材料を、５００〜
３，０００℃の温度及び常圧もしくは減圧下の条件下に
焼成する。このピッチ系炭素材料としては、炭素繊維、
球状炭素等を用いることができる。For the negative electrode used in the present invention, for example, a pitch-based carbon material produced by the following method is used.
Baking is performed at a temperature of 3,000 ° C. and under normal pressure or reduced pressure. As the pitch-based carbon material, carbon fiber,
Spherical carbon or the like can be used.
【００１２】負極ペレットは、例えば以下のようにして
成形することができる。まず、炭素質物の粉末とゴム系
高分子、ポリエチレン等の結着剤を、９９：１〜８５：
１５、好ましくは９７：３〜９０：１０の重量比でミキ
サー等を用いて混合する。次いで、混合物を凸部を設け
た金型に入れて加圧プレス機を用いて、３〜７ton/cm2
の圧力下に、凹部を有するペレット状に成形するもので
ある。また、別の方法として、加圧プレス機を用いて３
〜７ton/cm2 の圧力下に、まず円柱状ペレットを成形
し、ついでこの円柱状のペレットの一方の平面にかきと
り方法などにより凹部を設ける方法も挙げられる。The negative electrode pellet can be molded, for example, as follows. First, a carbonaceous material powder and a binder such as a rubber-based polymer and polyethylene are added at 99: 1 to 85:
The mixture is mixed in a weight ratio of 15, preferably 97: 3 to 90:10 using a mixer or the like. Then, the mixture is put into a mold provided with a convex portion and a pressure press is used to obtain 3 to 7 ton / cm 2
It is molded into pellets having concave portions under the pressure of. As another method, use a pressure press machine to
It is also possible to first form a cylindrical pellet under a pressure of ˜7 ton / cm 2 , and then to form a concave portion on one flat surface of this cylindrical pellet by scraping or the like.
【００１３】このようにして得られる負極ペレットの一
例を図３に示す。凹部の形状は特に限定されるものでは
ないが、通常、円柱状、直方体状、楕円柱状等の形状が
挙げられ、好ましくは円柱状である。また、ペレットの
厚さに対する凹部の深さの比も特に限定されるものでは
ないが、通常２〜２０、好ましくは３〜１５である。こ
の比が２未満ではペレットとして十分な強度が得られ
ず、２０を越えたのでは金属リチウムを配置するための
十分な体積が得られないからである。An example of the negative electrode pellet thus obtained is shown in FIG. The shape of the concave portion is not particularly limited, but usually, a shape such as a columnar shape, a rectangular parallelepiped shape, an elliptical columnar shape, etc. can be mentioned, and preferably a cylindrical shape. Further, the ratio of the depth of the recesses to the thickness of the pellets is not particularly limited, but is usually 2 to 20, preferably 3 to 15. This is because if the ratio is less than 2, sufficient strength as pellets cannot be obtained, and if it exceeds 20, a sufficient volume for arranging metallic lithium cannot be obtained.
【００１４】本願発明の請求項１に示す実施態様を図１
（ａ）に示す。この実施態様では、負極ペレット２の凹
部２Ａ中に金属リチウム４を配置しているため、電池組
立後の放置によって金属リチウムが完全に炭素質物に吸
蔵されても、図１（ｂ）に示すような構造になり、電池
内容の厚さは変化せず、電池内容の総高も変化しないた
め、負極ペレットと負極缶の電気的接触を良好な状態に
保つことができ、重負荷特性、充放電サイクル特性、貯
蔵特性及び耐衝撃性の向上を図ることができる。An embodiment shown in claim 1 of the present invention is shown in FIG.
(A). In this embodiment, since the metallic lithium 4 is arranged in the recess 2A of the negative electrode pellet 2, even if the metallic lithium is completely occluded in the carbonaceous material by being left after the battery is assembled, as shown in FIG. 1 (b). With this structure, the thickness of the battery contents does not change, and the total height of the battery contents does not change, so the electrical contact between the negative electrode pellet and the negative electrode can can be maintained in a good state, heavy load characteristics, charge / discharge It is possible to improve cycle characteristics, storage characteristics and impact resistance.
【００１５】本願発明の請求項２に示す実施態様を図２
（ａ）に示す。負極ペレット（２）の凹部（２Ａ）に加
えて、該負極ペレット（２）と負極缶（６）の間にも金
属リチウム（４）を配置した場合には、凹部に金属リチ
ウムを配置してあるために、負極ペレットと負極缶の間
に配置する金属リチウムの厚さを薄くすることができ
る。電池組立後に金属リチウムが炭素質物に吸蔵され
て、図２（ｂ）に示すような構造になる際に電池内容の
厚さの変化が小さくなるため、負極ペレットと負極缶の
電気的接触を良好な状態に保ちつつ、負極ペレットの凹
部の体積を小さくすることが可能となる。その結果、負
極量の低下を押さえることができ、図１に示す実施態様
の場合と同様に、重負荷特性、充放電サイクル特性、貯
蔵特性及び耐衝撃性の向上を図ることができる。The embodiment shown in claim 2 of the present invention is shown in FIG.
(A). When metallic lithium (4) is arranged between the negative electrode pellet (2) and the negative electrode can (6) in addition to the concave portion (2A) of the negative electrode pellet (2), metallic lithium is arranged in the concave portion. Therefore, the thickness of the metallic lithium arranged between the negative electrode pellet and the negative electrode can can be reduced. After the battery is assembled, metallic lithium is occluded in the carbonaceous material, and when the structure shown in FIG. 2 (b) is obtained, the change in the thickness of the battery content is small, so that the electrical contact between the negative electrode pellet and the negative electrode can is good. It is possible to reduce the volume of the concave portion of the negative electrode pellet while maintaining such a state. As a result, it is possible to suppress the decrease in the amount of the negative electrode, and it is possible to improve the heavy load characteristics, the charge / discharge cycle characteristics, the storage characteristics, and the impact resistance as in the case of the embodiment shown in FIG.
【００１６】本発明に用いる正極としては、例えば硝酸
リチウム（ＬｉＮＯ3 ）と二酸化マンガン（ＭｎＯ2 ）
を３００〜４００℃で熱処理して得られるＬｉx ＭｎＯ
2 、４５０〜８００℃で熱処理して得られるＬｉＭｎ2
Ｏ4 、水酸化リチウム（ＬｉＯＨ）と二酸化マンガンを
３００〜４００℃で熱処理して得られるＬｉ2 ＭｎＯ3
とＭｎＯ2 の複合体、五酸化バナジウムなどを活物質と
し、これに人造黒鉛、アセチレンブラックなどの導電性
材料及びポリテトラフルオロエチレン、ポリエチレン、
ゴム系高分子などの結着剤を配合し、ペレット状に成形
したものを用いることができる。Examples of the positive electrode used in the present invention include lithium nitrate (LiNO 3 ) and manganese dioxide (MnO 2 ).
Of Li x MnO obtained by heat treatment of 300 to 400 ° C.
2 , LiMn 2 obtained by heat treatment at 450 to 800 ° C.
Li 2, MnO 3 obtained by heat treatment of O 4 , lithium hydroxide (LiOH) and manganese dioxide at 300 to 400 ° C.
And MnO 2 composite, vanadium pentoxide, etc. as the active material, and conductive materials such as artificial graphite, acetylene black and polytetrafluoroethylene, polyethylene,
It is possible to use a pellet formed by mixing a binder such as a rubber-based polymer.
【００１７】セパレータには、例えばポリエチレン、ポ
リプロピレンなどのポリオレフィン系樹脂の不織布や、
これらの多孔膜などを用いることができる。For the separator, for example, a non-woven fabric of polyolefin resin such as polyethylene or polypropylene,
These porous films and the like can be used.
【００１８】電解液としては、例えばエチレンカーボネ
ート、プロピレンカーボネート、ジメチルカーボネー
ト、ジエチルカーボネート、エチルメチルカーボネート
などから選ばれる一種以上の非水溶媒に、六フッ化リン
酸リチウム（ＬｉＰＦ6 ）、過塩素酸リチウム（ＬｉＣ
ｌＯ4 ）、ホウフッ化リチウム（ＬｉＢＦ4 ）などの電
解質を０．２〜１．５mol/l の濃度で溶解させたものを
用いることができる。As the electrolytic solution, for example, one or more non-aqueous solvent selected from ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, etc., lithium hexafluorophosphate (LiPF 6 ) and perchloric acid are used. Lithium (LiC
lO 4), an electrolyte, such as lithium borofluoride (LiBF 4) can be used which is dissolved at a concentration of 0.2~1.5mol / l.
【００１９】[0019]
【実施例】つぎに、実施例及び比較例を挙げて、本発明
を添付図面にしたがって、より具体的に説明する。EXAMPLES Next, the present invention will be explained more concretely with reference to the accompanying drawings by showing examples and comparative examples.
【００２０】実施例１ （１）正極の作製 硝酸リチウム（ＬｉＮＯ3 ）と二酸化マンガン（ＭｎＯ
2 ）とを、１：３のモル比で混合し、２８０℃で５時間
予備焼成した後に３２０℃で１０時間焼成して、Ｌｉ
0.3 ＭｎＯ2 を合成し、活物質とした。ついで、これに
導電性材料として人造黒鉛、結着剤としてポリテトラフ
ルオロエチレン樹脂を、活物質：導電性材料、結着剤を
９０：１０：５の重量比で混合し、これを加圧プレス機
を用いて２．５ton/cm2 の圧力でプレス成形して、直径
１９．２mm、厚さ０．９mm及び重量０．７３ｇの正極ペ
レット（１）を作製した。Example 1 (1) Preparation of Positive Electrode Lithium nitrate (LiNO 3 ) and manganese dioxide (MnO)
2 ) and 1) are mixed in a molar ratio of 1: 3, pre-baked at 280 ° C for 5 hours, and then baked at 320 ° C for 10 hours to prepare Li
0.3 MnO 2 was synthesized and used as an active material. Next, artificial graphite as a conductive material and polytetrafluoroethylene resin as a binder were mixed with the active material: conductive material and the binder at a weight ratio of 90: 10: 5, and the mixture was pressed. A positive electrode pellet (1) having a diameter of 19.2 mm, a thickness of 0.9 mm and a weight of 0.73 g was produced by press molding using a machine at a pressure of 2.5 ton / cm 2 .
【００２１】（２）負極の作製 ピッチ系炭素繊維を粉砕した後、２，８００℃で焼成し
て得られた炭素質物を活物質とし、これに結着剤として
ＳＢＲラテックスを固形分で重量比、９５：５の割合に
なるように混合後、乾燥した。ついで、この混合物を加
圧プレス機を用いて２．５ton/cm2 の圧力でプレス成形
して、直径１９．７mm、厚さ１．２mm、凹部径１６mm、
凹部高さ０．２mm及び重量０．３９ｇの、図３に示すよ
うな凹部を備えた負極ペレット（２）を作製した。(2) Preparation of Negative Electrode Carbonaceous material obtained by crushing pitch-based carbon fiber and then firing at 2,800 ° C. was used as an active material, and SBR latex as a binder was added to this as a solid content by weight ratio. , 95: 5, and then dried. Then, this mixture was press-molded using a pressure press machine at a pressure of 2.5 ton / cm 2 , and the diameter was 19.7 mm, the thickness was 1.2 mm, and the recess diameter was 16 mm.
A negative electrode pellet (2) having a recess height of 0.2 mm and a weight of 0.39 g and having recesses as shown in FIG. 3 was produced.
【００２２】（３）電池の組立 ポリプロピレン製の絶縁パッキング（８）を勘合したＳ
ＵＳ３０４からなる負極缶（６）の内面にＳＵＳ３０４
製の負極集電体（５）をスポット溶接し、その上に厚さ
０．３mmのリチウムフォイルを外径１５．８mmに打ち抜
いたもの（４）を圧着した。その上に、上記負極ペレッ
ト（２）、セパレータ（３）を順に重ねた。エチレンカ
ーボネート及びジエチルカーボネートを容積比で１：１
に混合し、過塩素酸リチウム（ＬｉＣｌＯ4 ）を１モル
/l溶解させた非水電解液をセパレータ（３）に注入した
後、このセパレータ（３）の上に正極ペレット（１）を
置き、さらにその上に前記非水電解液を注入後、内面に
集電体としてコロイダルカーボンを塗布したＳＵＳ４３
０からなる正極缶（７）を嵌合した。つぎに、正極缶
（７）の周縁部をかしめて封口し、外径２４．５mm、高
さ３．０mmのコイン形リチウム二次電池を作製した。つ
いで、このようにして組み立てた電池を室温下に７日間
放置することによって、金属リチウムを負極炭素質物に
吸蔵させ、図１（ｂ）に示す構造の電池（Ａ）を得た。(3) Battery assembly S fitted with polypropylene insulation packing (8)
SUS304 is formed on the inner surface of the negative electrode can (6) made of US304.
A negative electrode current collector (5) made of was manufactured by spot welding, and a lithium foil having a thickness of 0.3 mm punched out to an outer diameter of 15.8 mm (4) was crimped thereon. The negative electrode pellet (2) and the separator (3) were sequentially stacked on it. Volumetric ratio of ethylene carbonate and diethyl carbonate 1: 1
And 1 mole of lithium perchlorate (LiClO 4 )
/ l After injecting the dissolved non-aqueous electrolyte into the separator (3), the positive electrode pellet (1) is placed on the separator (3), and the non-aqueous electrolyte is further injected onto the positive electrode pellet (1). SUS43 coated with colloidal carbon as a current collector
A positive electrode can (7) consisting of 0 was fitted. Next, the periphery of the positive electrode can (7) was caulked and sealed to prepare a coin-type lithium secondary battery having an outer diameter of 24.5 mm and a height of 3.0 mm. Then, the battery thus assembled was allowed to stand at room temperature for 7 days to occlude metallic lithium in the negative electrode carbonaceous material to obtain a battery (A) having a structure shown in FIG. 1 (b).
【００２３】（４）放電試験 上記のように組み立てた電池を、２５０μA 及び２mAの
定電流で２Ｖまで放電した。得られた放電容量を表１
に、放電特性を図５（ａ）及び（ｂ）にそれぞれ示す。(4) Discharge test The battery assembled as described above was discharged to 2 V at a constant current of 250 μA and 2 mA. The obtained discharge capacity is shown in Table 1.
The discharge characteristics are shown in FIGS. 5 (a) and 5 (b), respectively.
【００２４】（５）充放電サイクル試験 上記のように組み立てた電池を、１mAの定電流で３．５
〜２Ｖの電圧範囲で充放電を繰り返した。１サイクル目
の放電容量に対する２５及び５０サイクル目の放電容量
維持率を表２にそれぞれ示す。(5) Charge / Discharge Cycle Test The battery assembled as described above was subjected to 3.5 mA at a constant current of 1 mA.
Charging and discharging were repeated in a voltage range of ˜2V. Table 2 shows the discharge capacity retention ratios at the 25th and 50th cycles with respect to the discharge capacity at the first cycle.
【００２５】（６）貯蔵試験 上記のように組み立てた電池を６０℃で２０日間貯蔵し
た後、２０℃の温度で２５０μA の定電流で２Ｖまで放
電した。貯蔵前の放電容量に対する貯蔵後の放電容量維
持率を表３に示す。(6) Storage Test The battery assembled as described above was stored at 60 ° C. for 20 days and then discharged to 2 V at a constant current of 250 μA at a temperature of 20 ° C. Table 3 shows the discharge capacity retention rate after storage with respect to the discharge capacity before storage.
【００２６】（７）落下試験 同じく上記のように組み立てた電池を、高さ７５cmから
厚さ３cmのラワン板上にランダムに１０回落下させた
後、２５０μA の定電流で２Ｖまで放電した。落下前の
放電容量に対する落下後の放電容量維持率を表４に示
す。(7) Drop Test The battery assembled as described above was dropped 10 times randomly on a Lauan plate having a height of 75 cm to a thickness of 3 cm, and then discharged to 2 V with a constant current of 250 μA. Table 4 shows the discharge capacity retention ratio after the drop with respect to the discharge capacity before the drop.
【００２７】実施例２ 負極ペレットとして直径１９．７mm、厚さ１．２mm、凹
部径１６mm、凹部高さ０．１mm及び重量０．４１ｇにプ
レス成形したものを用い、金属リチウムとして厚さ０．
１５mmのリチウムフォイルを外径１９mmに打ち抜いたも
のを負極缶内面に圧着し、さらにその上に厚さ０．１mm
のリチウムフォイルを外径１５．８mmに打ち抜いたもの
を圧着して用いた以外は実施例１と同様にして図２
（ａ）に示すような電池を作製した。次いで、このよう
にして組み立てた電池を室温下に７日間放置することに
よって、金属リチウムを負極炭素質物に吸蔵させ、図２
（ｂ）に示す構造の電池（Ｂ）を得た。電池（Ｂ）の放
電容量を表１に、放電特性を図５（ａ）及び（ｂ）に、
その他の各特性を表２〜４に示す。Example 2 A negative electrode pellet was press-molded to have a diameter of 19.7 mm, a thickness of 1.2 mm, a recess diameter of 16 mm, a recess height of 0.1 mm and a weight of 0.41 g.
A 15 mm lithium foil punched out to an outer diameter of 19 mm was crimped onto the inner surface of the negative electrode can, and then 0.1 mm thick.
2 was carried out in the same manner as in Example 1 except that a lithium foil punched with an outer diameter of 15.8 mm was used by pressure bonding.
A battery as shown in (a) was produced. Then, the battery thus assembled was allowed to stand at room temperature for 7 days to allow metallic lithium to be occluded in the negative electrode carbonaceous material.
A battery (B) having a structure shown in (b) was obtained. The discharge capacity of the battery (B) is shown in Table 1, the discharge characteristics are shown in FIGS. 5 (a) and 5 (b),
Other properties are shown in Tables 2-4.
【００２８】比較例１ 負極ペレットとして凹部を設けず直径１９．７mm、厚さ
１．２mm、及び重量０．４３ｇにプレス成形したものを
用い、金属リチウムに厚さ０．２３mmのリチウムフォイ
ルを外径１９mmに打ち抜いたものを用いた以外は実施例
１と同様にして図４（ａ）に示すような電池を作製し
た。次いで、このようにして組み立てた電池を室温下に
７日間放置することによって、金属リチウムを負極炭素
質物に吸蔵させ、図４（ｂ）に示す構造の電池（Ｃ）を
得た。電池（Ｃ）の放電容量を表１に、放電特性を図５
（ａ）及び（ｂ）に、その他の各特性を表２〜４に示
す。Comparative Example 1 A negative electrode pellet was used which was press-molded to have a diameter of 19.7 mm, a thickness of 1.2 mm and a weight of 0.43 g without forming a recess, and a lithium foil having a thickness of 0.23 mm was removed from metallic lithium. A battery as shown in FIG. 4 (a) was produced in the same manner as in Example 1 except that a punched out piece having a diameter of 19 mm was used. Next, the battery thus assembled was allowed to stand at room temperature for 7 days to occlude metallic lithium in the negative electrode carbonaceous material to obtain a battery (C) having a structure shown in FIG. 4 (b). The discharge capacity of the battery (C) is shown in Table 1, and the discharge characteristics are shown in FIG.
(A) and (b) show other respective characteristics in Tables 2-4.
【００２９】[0029]
【表１】 [Table 1]
【００３０】[0030]
【表２】 [Table 2]
【００３１】[0031]
【表３】 [Table 3]
【００３２】[0032]
【表４】 [Table 4]
【００３３】以上の結果から本発明の実施例に用いた電
池は、比較例で用いたものに比べて、低電流放電での放
電容量の差は小さいが、高電流での放電容量は大きく、
負荷特性が向上し、また、充放電サイクル特性、貯蔵特
性も向上している。さらに、落下試験による特性劣化も
なく耐衝撃性も向上していることが明らかである。From the above results, the batteries used in the examples of the present invention have a small difference in discharge capacity at low current discharge as compared with those used in comparative examples, but have large discharge capacities at high currents.
The load characteristics are improved, and the charge / discharge cycle characteristics and storage characteristics are also improved. Furthermore, it is clear that the characteristics are not deteriorated by the drop test and the impact resistance is improved.
【００３４】[0034]
【発明の効果】本発明により、重負荷特性、充放電サイ
クル特性、貯蔵特性、耐衝撃性に優れたコイン形非水電
解液二次電池を提供することができる。According to the present invention, it is possible to provide a coin type non-aqueous electrolyte secondary battery excellent in heavy load characteristics, charge / discharge cycle characteristics, storage characteristics and impact resistance.
【図１】本発明のコイン形非水電解液二次電池の縦断面
図である。FIG. 1 is a vertical cross-sectional view of a coin type non-aqueous electrolyte secondary battery of the present invention.
【図２】本発明のコイン形非水電解液二次電池の縦断面
図である。FIG. 2 is a vertical cross-sectional view of a coin type non-aqueous electrolyte secondary battery of the present invention.
【図３】本発明に用いる凹部を備える負極ペレットを示
す図である。FIG. 3 is a view showing a negative electrode pellet having a recess used in the present invention.
【図４】比較例の非水電解液二次電池の縦断面図であ
る。FIG. 4 is a vertical cross-sectional view of a non-aqueous electrolyte secondary battery of a comparative example.
【図５】実施例及び比較例の放電特性図である。FIG. 5 is a discharge characteristic diagram of Examples and Comparative Examples.
１ 正極ペレット ２ 負極ペレット ２Ａ 負極ペレット凹部 ３ セパレータ ４ 金属リチウム ５ 集電体 ６ 負極缶 ７ 正極缶 ８ 絶縁パッキング DESCRIPTION OF SYMBOLS 1 Positive electrode pellet 2 Negative electrode pellet 2A Negative electrode pellet recess 3 Separator 4 Metal lithium 5 Current collector 6 Negative electrode can 7 Positive electrode can 8 Insulating packing
Claims (2)
質物を含む負極ペレット、当該負極ペレットにリチウム
を供給するための金属リチウム、集電体を内面に備える
負極缶、セパレータ及び非水電解液を備えるコイン形非
水電解液二次電池において、前記負極ペレットの前記負
極缶に対する側に凹部を備え、当該凹部中に前記金属リ
チウムを配置することを特徴とするコイン形非水電解液
二次電池。1. A positive electrode, a negative electrode pellet containing a carbonaceous material capable of inserting and extracting lithium, metallic lithium for supplying lithium to the negative electrode pellet, a negative electrode can having a current collector on its inner surface, a separator and a non-aqueous electrolyte. In a coin-type non-aqueous electrolyte secondary battery comprising: a coin-type non-aqueous electrolyte secondary battery, characterized in that a recess is provided on the side of the negative electrode pellet with respect to the negative electrode can, and the metallic lithium is placed in the recess. battery.
負極ペレットと集電体を内面に備える前記負極缶の間に
金属リチウムを配置する請求項１記載のコイン形非水電
解液二次電池。2. The coin-shaped non-aqueous electrolyte secondary battery according to claim 1, wherein metallic lithium is disposed between the negative electrode can and the negative electrode can having the current collector on its inner surface, in addition to the concave portion of the negative electrode pellet. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6161117A JPH0831454A (en) | 1994-07-13 | 1994-07-13 | Coin-shaped nonaqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6161117A JPH0831454A (en) | 1994-07-13 | 1994-07-13 | Coin-shaped nonaqueous electrolyte secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0831454A true JPH0831454A (en) | 1996-02-02 |
Family
ID=15728933
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6161117A Pending JPH0831454A (en) | 1994-07-13 | 1994-07-13 | Coin-shaped nonaqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0831454A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7462571B2 (en) | 2004-07-28 | 2008-12-09 | Tokyo Electron Limited | Film formation method and apparatus for semiconductor process for forming a silicon nitride film |
| US12155029B2 (en) | 2019-01-21 | 2024-11-26 | Lg Energy Solution, Ltd. | Material, negative electrode comprising same and methods for manufacturing same |
-
1994
- 1994-07-13 JP JP6161117A patent/JPH0831454A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7462571B2 (en) | 2004-07-28 | 2008-12-09 | Tokyo Electron Limited | Film formation method and apparatus for semiconductor process for forming a silicon nitride film |
| US12155029B2 (en) | 2019-01-21 | 2024-11-26 | Lg Energy Solution, Ltd. | Material, negative electrode comprising same and methods for manufacturing same |
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