JPH0630247B2 - Method for manufacturing non-aqueous solvent secondary battery - Google Patents
Method for manufacturing non-aqueous solvent secondary batteryInfo
- Publication number
- JPH0630247B2 JPH0630247B2 JP61126647A JP12664786A JPH0630247B2 JP H0630247 B2 JPH0630247 B2 JP H0630247B2 JP 61126647 A JP61126647 A JP 61126647A JP 12664786 A JP12664786 A JP 12664786A JP H0630247 B2 JPH0630247 B2 JP H0630247B2
- Authority
- JP
- Japan
- Prior art keywords
- aqueous solvent
- secondary battery
- lithium
- solvent secondary
- negative electrode
- 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.)
- Expired - Lifetime
Links
- 239000003125 aqueous solvent Substances 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000000034 method Methods 0.000 title description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 20
- 239000011368 organic material Substances 0.000 claims description 8
- -1 transition metal chalcogen compound Chemical class 0.000 claims description 8
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910015044 LiB Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- 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)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は負極の製造方法を改良した非水溶媒二次電池の
製造方法に関する。The present invention relates to a method for manufacturing a non-aqueous solvent secondary battery, which is an improved method for manufacturing a negative electrode.
［従来の技術］ 近年、リチウムを負極活物質として用いる非水溶媒二次
電池は高いエネルギーを有するものとして注目されてい
る。かかる非水溶媒二次電池としては、従来より正極活
物質としてリチウムと層間化合物を形成するＴｉＳ２、
Ｖ２Ｏ５等の遷移金属カルコゲン化合物を用いたものが
製品化されている。[Prior Art] In recent years, non-aqueous solvent secondary batteries using lithium as a negative electrode active material have been attracting attention as having high energy. As such a non-aqueous solvent secondary battery, TiS 2 , which forms an intercalation compound with lithium as a positive electrode active material,
Those using a transition metal chalcogen compound such as V 2 O 5 have been commercialized.
［発明が解決しようとする問題点］ しかしながら、上述した非水溶媒二次電池では負極にリ
チウム金属を用いているため、放電時にイオンとなって
溶出したリチウムが充電時に金属リチウムとして負極に
電析する際、デンドライトが形成され、その高活性さに
より非水溶媒電解液の分解を誘発し、充放電サイクルを
低下させる。また、デンドライトが更に成長し、セパレ
ータを通過して正極に達すると、正極、負極を短絡さ
せ、著しい容量低下を招く問題があった。[Problems to be Solved by the Invention] However, in the above-mentioned non-aqueous solvent secondary battery, since lithium metal is used for the negative electrode, lithium that has been eluted as ions during discharge is deposited on the negative electrode as metallic lithium during charging. In doing so, dendrites are formed, and their high activity induces the decomposition of the non-aqueous solvent electrolyte, which reduces the charge / discharge cycle. Further, when the dendrite further grows and passes through the separator and reaches the positive electrode, there is a problem that the positive electrode and the negative electrode are short-circuited, resulting in a remarkable decrease in capacity.
本発明は、上記従来の問題点を解決するためになされた
もので、容量劣化を著しく抑制できると共に特に重負荷
における充放電サイクル寿命を向上した非水溶媒二次電
池の製造方法を提供しようとするものである。The present invention has been made to solve the above-mentioned conventional problems, and it is an object of the present invention to provide a method for manufacturing a non-aqueous solvent secondary battery that can significantly suppress capacity deterioration and that has improved charge / discharge cycle life particularly under heavy load. To do.
［問題点を解決するための手段］ 本発明は、遷移金属カルコゲン化合物を主構成材とする
正極と、前記正極にセパレータを介して対向配置され、
リチウムを含浸した有機物焼成体からなる負極とを具備
した非水溶媒二次電池の製造方法において、有機物焼成
体をカソード、金属リチウムをアノードとし、これらを
リチウムを含む電解液中に浸漬して逐次電流密度を上げ
ながら電解処理を行うことによりリチウムが前記セパレ
ータ側ほど濃度が高くなるように含浸された負極を作製
する工程を具備したことを特徴とする非水溶媒二次電池
の製造方法である。[Means for Solving Problems] In the present invention, a positive electrode containing a transition metal chalcogen compound as a main constituent material and a positive electrode that are opposed to the positive electrode via a separator,
In a method for producing a non-aqueous solvent secondary battery comprising a negative electrode made of an organic fired body impregnated with lithium, the organic fired body is used as a cathode and metallic lithium is used as an anode, and these are successively immersed in an electrolyte solution containing lithium. A method for producing a non-aqueous solvent secondary battery, comprising a step of producing a negative electrode in which lithium is impregnated so that the concentration becomes higher toward the separator side by performing electrolytic treatment while increasing current density. .
上記遷移金属カルコゲン化合物としては、例えばバナジ
ウム酸化物、モリブデン酸化物あるいはバナジウム酸化
物とタングステン酸化物との固溶体等を挙げることがで
きる。Examples of the transition metal chalcogen compound include vanadium oxide, molybdenum oxide, and solid solutions of vanadium oxide and tungsten oxide.
上記有機物焼成体は、例えばエポキシ樹脂、フェノール
樹脂、アクリル樹脂、ハロゲン化ビニル樹脂、ポリイミ
ド、ポリアミド等の合成樹脂を非酸化性雰囲気下で所定
温度にて炭素化することにより得られるものである。な
お、本発明の方法により製造された非水溶媒二次電池は
上記遷移金属カルコゲン化合物にカーボンブラック、ア
セチレンブラック等の導電剤粉末及びポリテトラフルオ
ロエチレン等の結着剤粉末を混合し、所望の形状に成形
し、これをニッケル、ステンレス等の導電材からなる網
体、エキスパンドに圧着して正極とし、この正極に前記
有機物焼成体をセパレータを介して対向配置し、更に非
水溶媒電解液と組合わせることによって構成される。電
解液としては、ＬｉＣｌＯ４、ＬｉＰＦ６、ＬｉＢ
Ｆ４、ＬｉＣｌ、ＬｉＡＳＦ６等のリチウム塩、その他
一般にＬｉ系電池において使用される既知の電解質と、
プロピレンカーボネート、１，２−ジメトキシエタン、
γ−ブチロラクトン、ジオキソラン、エチレンカーボネ
ート、２−メチルテトラヒドロフラン等の非プロトン性
有機溶媒との混合物が使用される。The organic material fired body is obtained by carbonizing a synthetic resin such as an epoxy resin, a phenol resin, an acrylic resin, a vinyl halide resin, a polyimide or a polyamide at a predetermined temperature in a non-oxidizing atmosphere. Incidentally, the non-aqueous solvent secondary battery produced by the method of the present invention, the transition metal chalcogen compound is mixed with a conductive agent powder such as carbon black and acetylene black and a binder powder such as polytetrafluoroethylene, the desired mixture. Shaped into a shape, nickel, a net made of a conductive material such as stainless steel, and pressure-bonded to the expand to a positive electrode, the organic material fired body is placed opposite to this positive electrode via a separator, and further a non-aqueous solvent electrolyte Composed by combining. As the electrolytic solution, LiClO 4 , LiPF 6 , LiB
Lithium salts such as F 4 , LiCl, and LiA S F 6 , and other known electrolytes generally used in Li-based batteries,
Propylene carbonate, 1,2-dimethoxyethane,
Mixtures with aprotic organic solvents such as γ-butyrolactone, dioxolane, ethylene carbonate, 2-methyltetrahydrofuran are used.
［作用］ 本発明によれば、合成樹脂を炭素化した有機物焼成体を
カソード、金属リチウムをアノードとし、これらをリチ
ウムを含む電解液中に浸漬して逐次電流密度を上げなが
ら電解処理を行うことによりリチウムがセパレータ側ほ
ど濃度が高くなるように含浸された負極を作製すると、
前記有機物焼成体の表面に残留させることなく、その空
隙全てにリチウムを効率良く含浸させることができる。
従って、前記負極を組込んだ二次電池は、デンドライト
の形成を防止することができるため、放電容量を向上で
き、かつ内部短絡が生じるのを防止することができる。
このため、重負荷における充放電サイクル寿命を向上す
ることができる。[Operation] According to the present invention, an organic fired body obtained by carbonizing a synthetic resin is used as a cathode and metallic lithium is used as an anode, and these are immersed in an electrolytic solution containing lithium to perform electrolytic treatment while successively increasing the current density. When a negative electrode in which lithium is impregnated so that the concentration becomes higher on the separator side is produced,
It is possible to efficiently impregnate all the voids with lithium without leaving the surface on the surface of the organic material fired body.
Therefore, since the secondary battery incorporating the negative electrode can prevent the formation of dendrites, the discharge capacity can be improved and the internal short circuit can be prevented.
Therefore, the charge / discharge cycle life under heavy load can be improved.
［発明の実施例］ 以下、本発明の製造方法をボタン型非水溶媒二次電池に
適用した例について第１図を参照して詳細に説明する。[Examples of the Invention] Hereinafter, an example in which the manufacturing method of the present invention is applied to a button type non-aqueous solvent secondary battery will be described in detail with reference to FIG.
実施例 第１図中の１は、ステンレス製正極容器であり、この容
器１底面にはステンレス網よりなる正極集電体２がスポ
ット溶接されている。この正極集電体２には、Ｖ２Ｏ５
＋５モル％ＷＯ３からなる固溶体を主成分とする正極活
物質とアセチレンブラックとポリテトロフルオロエチレ
ンとが重量比で７０：２５：５の正極合剤３が圧着され
ている。この正極合剤３上には、多孔質ポリプロピレン
製薄膜からなるセパレータ４及び後述する方法に作製さ
れたリチウムを該セパレータ４側ほど濃度を高くした有
機物焼成体からなる負極５が載置されている。そして、
前記容器１の開口部にパッキング６を介してステンレス
製負極容器７を設けることにより、前記各容器１、７内
に前記正極合剤３、セパレータ４及び負極５を密閉して
いる。前記容器１、７内には、プロピレンカーボネート
にＬｉＣｌＯ４を１モル／ｌの濃度で溶解した電解液が
収容されている。Example 1 in FIG. 1 is a positive electrode container made of stainless steel, and a positive electrode current collector 2 made of stainless steel net is spot-welded to the bottom surface of the container 1. The positive electrode current collector 2 contains V 2 O 5
A positive electrode mixture 3 in which the positive electrode active material containing a solid solution of +5 mol% WO 3 as a main component, acetylene black, and polytetrofluoroethylene in a weight ratio of 70: 25: 5 is pressure-bonded. On this positive electrode mixture 3, a separator 4 made of a thin film made of porous polypropylene and a negative electrode 5 made of an organic material fired body in which the concentration of lithium produced by the method described later is increased toward the separator 4 side are placed. . And
By providing a stainless steel negative electrode container 7 in the opening of the container 1 via a packing 6, the positive electrode mixture 3, the separator 4 and the negative electrode 5 are sealed in the respective containers 1 and 7. An electrolytic solution in which LiClO 4 is dissolved in propylene carbonate at a concentration of 1 mol / l is contained in the containers 1 and 7.
前記負極５は、次のような方法により製造した。The negative electrode 5 was manufactured by the following method.
まず、フェノール樹脂をＮ２雰囲気中、１１００℃で数
時間炭素化して有機物焼成体とし、この焼成体を加圧成
形して直径９mm、厚さ０．５mmの成形体とした後、この
成形体をカソード、金属リチウムをアノードとし、これ
らを互いに対向してプロピレンカーボネートにＬｉＣｌ
Ｏ４を１モル／ｌの濃度で溶解した電解溶液に浸漬し
た。つづいて、前記カソード、アノード間に電流密度を
０．５ｍＡ／cm2→１．０ｍＡ／cm2→２．０ｍＡ／cm2
の順で各々８時間通電してアノードと対向する有機物焼
成体の表面ほどリチウム濃度の高い有機物焼成体を作製
した。なお、かかる電解においてアノードと対向する有
機物焼成体の表面が前記セパレータ側に配置される。First, a phenol resin is carbonized in an N 2 atmosphere at 1100 ° C. for several hours to form an organic fired body, and the fired body is pressure-molded into a molded body having a diameter of 9 mm and a thickness of 0.5 mm. As a cathode and metallic lithium as an anode.
It was immersed in an electrolytic solution in which O 4 was dissolved at a concentration of 1 mol / l. Subsequently, the current density between the cathode and the anode is 0.5 mA / cm 2 → 1.0 mA / cm 2 → 2.0 mA / cm 2
In this order, the electricity was applied for 8 hours each to produce an organic material fired body having a higher lithium concentration on the surface of the organic material fired body facing the anode. In this electrolysis, the surface of the fired organic material facing the anode is arranged on the separator side.
比較例 負極として、金属リチウムシートを用いた以外、実施例
と同様な構造のボタン型非水溶媒二次電池を組立てた。Comparative Example A button type non-aqueous solvent secondary battery having the same structure as that of the example was assembled except that a metal lithium sheet was used as the negative electrode.
しかして、本実施例及び比較例のボタン型非水溶媒二次
電池について１０ｋΩの定負荷で３Ｖから２Ｖまだ放電
を行ない、再び３Ｖまで充電する工程を１サイクルと
し、各サイクル毎の容量変化を調べる充放電サイクル特
性評価試験を行なったところ、第２図に示す特性図を得
た。なお、第２図において、横軸はサイクル数を示し、
縦軸は各サイクルにおける初期容量に対する放電容量劣
化率（％）を示す。図中のＡは、本実施例の電池におけ
る特性線を、Ｂは比較例の同特性線を夫々示す。この第
２図より明らかなように、本発明の方法で製造された非
水溶媒二次電池は従来の方法で製造された同電池（比較
例）に比べて放電容量劣化率を低減でき、重負荷におけ
る充放電サイクル寿命を著しく向上できることがわか
る。Then, the button type non-aqueous solvent secondary batteries of the present example and the comparative example are discharged from 3 V to 2 V under a constant load of 10 kΩ and charged to 3 V again as one cycle, and the capacity change in each cycle is changed. A charge / discharge cycle characteristic evaluation test was conducted to obtain the characteristic diagram shown in FIG. In addition, in FIG. 2, the horizontal axis represents the number of cycles,
The vertical axis represents the discharge capacity deterioration rate (%) with respect to the initial capacity in each cycle. In the figure, A shows the characteristic line of the battery of this example, and B shows the same characteristic line of the comparative example. As is clear from FIG. 2, the non-aqueous solvent secondary battery manufactured by the method of the present invention can reduce the discharge capacity deterioration rate as compared with the same battery manufactured by the conventional method (Comparative Example). It can be seen that the charge / discharge cycle life under load can be significantly improved.
なお、上記実施例ではボタン型構造の二次電池に適用し
た場合について説明したが、これに限定されない。例え
ば円筒形、扁平形、角形等の非水溶媒二次電池にも同様
に適用できる。In addition, although the case where the present invention is applied to the secondary battery having the button type structure has been described in the above embodiment, the present invention is not limited to this. For example, it can be similarly applied to a non-aqueous solvent secondary battery having a cylindrical shape, a flat shape, a prismatic shape, or the like.
［発明の効果］ 以上詳述した如く、本発明によれば容量劣化を著しく抑
制できると共に特に重負荷における充放電サイクル寿命
を向上した非水溶媒二次電池の製造方法を提供できる。[Effects of the Invention] As described in detail above, according to the present invention, it is possible to provide a method for manufacturing a non-aqueous solvent secondary battery that can significantly suppress capacity deterioration and, particularly, has improved charge / discharge cycle life under heavy load.
第１図は本発明の一実施例を示すボタン型非水溶媒二次
電池の断面図、第２図は本実施例及び比較例の非水溶媒
二次電池における充放電サイクル数と放電容量劣化率と
の関係を示す特性図である。 １……正極容器、３……正極合剤、４……セパレータ、
５……負極、７……負極容器。FIG. 1 is a cross-sectional view of a button type non-aqueous solvent secondary battery showing one embodiment of the present invention, and FIG. 2 is a charge / discharge cycle number and discharge capacity deterioration in the non-aqueous solvent secondary batteries of this embodiment and a comparative example. It is a characteristic view which shows the relationship with a rate. 1 ... Positive electrode container, 3 ... Positive electrode mixture, 4 ... Separator,
5 ... Negative electrode, 7 ... Negative electrode container.
Claims (1)
る正極と、前記正極にセパレータを介して対向配置さ
れ、リチウムを含浸した有機物焼成体からなる負極とを
具備した非水溶媒二次電池の製造方法において、有機物
焼成体をカソード、金属リチウムをアノードとし、これ
らをリチウムを含む電解液中に浸漬して逐次電流密度を
上げながら電解処理を行うことによりリチウムが前記セ
パレータ側ほど濃度が高くなるように含浸された負極を
作製する工程を具備したことを特徴とする非水溶媒二次
電池の製造方法。1. A non-aqueous solvent secondary battery comprising a positive electrode containing a transition metal chalcogen compound as a main constituent, and a negative electrode made of a fired organic material impregnated with lithium and facing each other with a separator interposed therebetween. In the manufacturing method, the organic sintered material is used as a cathode, metallic lithium is used as an anode, and these are immersed in an electrolytic solution containing lithium to perform electrolytic treatment while successively increasing the current density, so that the concentration of lithium becomes higher on the separator side. A method for producing a non-aqueous solvent secondary battery, comprising the step of producing a negative electrode impregnated as described above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61126647A JPH0630247B2 (en) | 1986-05-31 | 1986-05-31 | Method for manufacturing non-aqueous solvent secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61126647A JPH0630247B2 (en) | 1986-05-31 | 1986-05-31 | Method for manufacturing non-aqueous solvent secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62283571A JPS62283571A (en) | 1987-12-09 |
| JPH0630247B2 true JPH0630247B2 (en) | 1994-04-20 |
Family
ID=14940379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61126647A Expired - Lifetime JPH0630247B2 (en) | 1986-05-31 | 1986-05-31 | Method for manufacturing non-aqueous solvent secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0630247B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19922948B4 (en) * | 1998-05-15 | 2005-08-18 | Nec Corp. | Electric double layer capacitor with short circuit function |
| USRE43573E1 (en) | 1997-02-24 | 2012-08-14 | Genesis Microchip (Delaware) Inc. | Method and system for displaying an analog image by a digital display device |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4308915B2 (en) * | 1997-02-12 | 2009-08-05 | スカイラブ テクノロジーズ グループ，インコーポレイテッド | Polyimide battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0789483B2 (en) * | 1984-05-07 | 1995-09-27 | 三洋化成工業株式会社 | Secondary battery |
-
1986
- 1986-05-31 JP JP61126647A patent/JPH0630247B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE43573E1 (en) | 1997-02-24 | 2012-08-14 | Genesis Microchip (Delaware) Inc. | Method and system for displaying an analog image by a digital display device |
| DE19922948B4 (en) * | 1998-05-15 | 2005-08-18 | Nec Corp. | Electric double layer capacitor with short circuit function |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62283571A (en) | 1987-12-09 |
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