JPH0433249A - Nonaqueous solvent secondary battery - Google Patents
Nonaqueous solvent secondary batteryInfo
- Publication number
- JPH0433249A JPH0433249A JP2137095A JP13709590A JPH0433249A JP H0433249 A JPH0433249 A JP H0433249A JP 2137095 A JP2137095 A JP 2137095A JP 13709590 A JP13709590 A JP 13709590A JP H0433249 A JPH0433249 A JP H0433249A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- metal core
- secondary battery
- battery
- conducting layer
- 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
- 239000002904 solvent Substances 0.000 title abstract 2
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- 239000000203 mixture Substances 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 5
- 239000011029 spinel Substances 0.000 claims abstract description 5
- 239000003125 aqueous solvent Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000006230 acetylene black Substances 0.000 abstract description 6
- 239000011230 binding agent Substances 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 abstract description 5
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 abstract description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 4
- 239000010935 stainless steel Substances 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 239000004020 conductor Substances 0.000 abstract description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 abstract description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 230000007423 decrease Effects 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- 201000009030 Carcinoma Diseases 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910014549 LiMn204 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QWVMUSBBWGTKML-UHFFFAOYSA-N [Li].[Mo](=S)=S Chemical compound [Li].[Mo](=S)=S QWVMUSBBWGTKML-UHFFFAOYSA-N 0.000 description 1
- FBDMJGHBCPNRGF-UHFFFAOYSA-M [OH-].[Li+].[O-2].[Mn+2] Chemical compound [OH-].[Li+].[O-2].[Mn+2] FBDMJGHBCPNRGF-UHFFFAOYSA-M 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- OKTJSMMVPCPJKN-YPZZEJLDSA-N carbon-10 atom Chemical compound [10C] OKTJSMMVPCPJKN-YPZZEJLDSA-N 0.000 description 1
- 150000001786 chalcogen compounds Chemical class 0.000 description 1
- 229910000313 chalcogen oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- CUUCCOKRHKXKFR-UHFFFAOYSA-N lithium titanium(4+) disulfide Chemical compound [Li+].[S--].[S--].[Ti+4] CUUCCOKRHKXKFR-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding 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
Abstract
Description
【発明の詳細な説明】
［発明の目的］
（産業上の利用分野）
本発明は非水溶媒二次電池に関し、特に正極の構造を改
良した非水溶媒二次電池に係わるものである。[Detailed Description of the Invention] [Object of the Invention] (Industrial Application Field) The present invention relates to a non-aqueous solvent secondary battery, and particularly to a non-aqueous solvent secondary battery with an improved structure of the positive electrode.
（従来の技術）
近年、カルコゲン化合物を正極合剤の活物質とし、リチ
ウム等のアルカリ金属を負極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。その中でも最近、カルコゲン酸化物を生活物質と
して、この酸化物と、リチウム或いはその酸化物との混
合物よりなる活物質を含む正極合剤からなる正極と、リ
チウムからなる負極を用いた非水溶媒二次電池が開発さ
れている。このような電池としては、例えば二硫化チタ
ン−リチウム電池、二硫化モリブデン−リチウム電池、
二酸化マンガン−リチウム電池等が知られている。これ
ら非水溶媒二次電池の正極は、ニッケル、ステンレス鋼
製の網、エキスバンドメタル等の金属芯体に活物質、結
着剤を含むシート状の正極合剤を圧着一体化した構造に
なっている。(Prior Art) In recent years, non-aqueous solvent secondary batteries that use a chalcogen compound as the active material of the positive electrode mixture and an alkali metal such as lithium as the negative electrode have attracted attention as having high energy. Among these, recently, non-aqueous solvent dielectrics using chalcogen oxide as a living substance, a positive electrode consisting of a positive electrode mixture containing an active material consisting of this oxide and a mixture of lithium or its oxide, and a negative electrode consisting of lithium have been developed. The next battery is being developed. Examples of such batteries include titanium disulfide-lithium batteries, molybdenum disulfide-lithium batteries,
Manganese dioxide-lithium batteries and the like are known. The positive electrodes of these non-aqueous solvent secondary batteries have a structure in which a sheet-like positive electrode mixture containing an active material and a binder is bonded to a metal core made of nickel, stainless steel mesh, expanded metal, etc. ing.
（発明が解決しようとする課題）
しかしながら、上述した非水溶媒二次電池の正極は、製
造プロセスが簡単であり電池の製造コストも安価である
にもかかわらず、実用化されていない。これは前述した
正極を用いて電池を製造すると、電池の充放電サイクル
寿命が短くなり、しかも個々の放電特性が不均質となる
ことによるものである。(Problems to be Solved by the Invention) However, the positive electrode of the non-aqueous solvent secondary battery described above has not been put into practical use, although the manufacturing process is simple and the manufacturing cost of the battery is low. This is because when a battery is manufactured using the above-mentioned positive electrode, the charge/discharge cycle life of the battery becomes short and the individual discharge characteristics become non-uniform.
即ち、前記非水溶媒二次電池の正極において、前記金属
芯体と正極合剤との圧着界面に導電性不良箇所があると
、電池反応が行われる際に該圧着界面の電流分布が不均
一となり、電流密度の粗密化が生じる。電流密度の粗密
化は、電解液の分解電圧より高い電圧で反応を行う部分
を前記圧着界面に生じさせる。このため、前記導電性不
良箇所が存在したまま電池反応が行われると、前述した
電解液の分解電圧より高い電圧で反応がなされる部分に
おいて、前記正極合剤中の電解液と、金属芯体が反応し
、電解液の分解が生じて、水素ガス、炭酸ガス等のガス
が発生する。このガスは、電池の充放電の繰り返しの度
に、前記金属芯体と正極合剤の界面に少しづつ蓄積され
、該正極合剤を金属芯体から徐々に剥離せしめる。従っ
て、前記金属芯体と正極合剤との界面での接触面積は、
充放電の繰り返しに伴い徐々に減少し、金属芯体と正極
合剤との間の電子伝導性が著しく低下する。その結果、
電池の充放電の繰り返しに伴って前記正極合剤が十分な
機能を有するにもかかわらず、充放電サイクル寿命が低
下し、電池性能の不均一化を生じさせるという問題があ
った。That is, in the positive electrode of the non-aqueous solvent secondary battery, if there is a poor conductivity at the crimped interface between the metal core and the positive electrode mixture, the current distribution at the crimped interface will be uneven when a battery reaction occurs. As a result, the current density becomes coarser and denser. The coarsening of the current density creates a portion at the pressure bonding interface where a reaction occurs at a voltage higher than the decomposition voltage of the electrolytic solution. Therefore, if a battery reaction is performed while the conductive defective portion is present, the electrolyte in the positive electrode mixture and the metal core may reacts, decomposition of the electrolyte occurs, and gases such as hydrogen gas and carbon dioxide gas are generated. This gas accumulates little by little at the interface between the metal core and the positive electrode mixture each time the battery is repeatedly charged and discharged, causing the positive electrode mixture to gradually peel off from the metal core. Therefore, the contact area at the interface between the metal core and the positive electrode mixture is:
It gradually decreases with repeated charging and discharging, and the electronic conductivity between the metal core and the positive electrode mixture decreases significantly. the result,
Despite the fact that the positive electrode mixture has a sufficient function as the battery is repeatedly charged and discharged, there is a problem in that the charge/discharge cycle life decreases and the battery performance becomes non-uniform.
本発明は上記従来の課題を解決するためになされたもの
で、正極合剤を所定の導電層を介して金属芯体に被覆す
ることによって、該正極合剤を電気的に良好に被覆した
正極を備え、充放電時に前記各部材の界面でのガス発生
を抑制した非水溶媒二次電池を提供しようとするもので
ある。The present invention has been made in order to solve the above-mentioned conventional problems, and by coating a metal core with a positive electrode mixture through a predetermined conductive layer, the present invention provides a positive electrode that is electrically well coated with the positive electrode mixture. It is an object of the present invention to provide a non-aqueous solvent secondary battery which is equipped with the following and suppresses gas generation at the interfaces of the respective members during charging and discharging.
［発明の構成］
（Ｒ題を解決するための手段）
本発明は金属芯体と、この芯体表面に形成され、かつカ
ー謎屡含む導電性樹脂からなる導電層と、この導電層上
に被覆形成したスピネル型ＬｉＭｎ２０４を主体とする
正極合剤とから構成された正極を具備したことを特徴と
する非水溶媒二次電池である。[Structure of the Invention] (Means for Solving Problem R) The present invention comprises a metal core, a conductive layer formed on the surface of the core and made of a conductive resin containing a carcinoma, and a conductive layer formed on the conductive layer. This is a non-aqueous solvent secondary battery characterized by comprising a positive electrode composed of a positive electrode mixture mainly composed of spinel-type LiMn204 coated thereon.
上記金属芯体としては、例えばニッケル、鉄、ニッケル
メッキを施した鉄、ステンレス鋼などの金属からなる金
網、エキスバンドメタル、パンチトメタル、金属箔等を
挙げることができる。Examples of the metal core include a wire mesh made of metal such as nickel, iron, nickel-plated iron, and stainless steel, expanded metal, punched metal, and metal foil.
上記アセチレンブラック、カーボンブラックからなる導
電層の厚さは、３〜１００７ｍの範囲とすることが望ま
しい。この理由は、導電層の厚さを３＃未満にすると、
電池の使用時における変形に伴い正極が変形し、金属芯
体が部分的に露出して導電層としての機能が損なわれ、
充分な導電性が得られなくなる恐れがある。一方導電層
の厚さが１００−を越えると、金属芯体に該導電層を形
成する工程に手間がかかり、電池の生産性が低下する恐
れがあるからである。The thickness of the conductive layer made of acetylene black or carbon black is preferably in the range of 3 to 1007 m. The reason for this is that when the thickness of the conductive layer is less than 3#,
As the battery deforms during use, the positive electrode deforms, and the metal core is partially exposed, impairing its function as a conductive layer.
There is a possibility that sufficient conductivity may not be obtained. On the other hand, if the thickness of the conductive layer exceeds 100 mm, the process of forming the conductive layer on the metal core takes time and effort, and there is a risk that the productivity of the battery will decrease.
上記アセチレンブラック、カーボンブラック等のカーボ
ンを含む導電性樹脂からなる導電層は、例えばポリオレ
フィン系樹脂溶液にアセチレンブラックの粉末を分散さ
せ、この分散溶液を金属芯体に塗布、乾燥することによ
り形成される。ここに用いるポリオレフィン系樹脂とし
ては、例えばポリエチレン、ポリプロピレン、ポリアク
リル酸等を挙げることができる。かかる導電性樹脂を構
成するポリオレフィン系樹脂とカーボン粉との配合割合
は、３〜３５重量％重量％水リオレフィン系樹脂溶液に
対し、前記カーボンの量粉末が１０〜５０重量％であり
、１０重量％未満にすると、該導電性樹脂の導電性が低
下し、内部抵抗の増加を生じて電池が作動しなくなる恐
れがあり、かといってそのカーボン粉末が５０重量％を
越えると、該導電性樹脂の結着力の低下を生じると共に
該導電性樹脂からなる導電層を金属芯体に均一に被覆す
ることが困難となるからである。The conductive layer made of a conductive resin containing carbon such as acetylene black or carbon black is formed by, for example, dispersing acetylene black powder in a polyolefin resin solution, applying this dispersion solution to a metal core, and drying it. Ru. Examples of the polyolefin resin used here include polyethylene, polypropylene, polyacrylic acid, and the like. The blending ratio of the polyolefin resin and carbon powder constituting the conductive resin is 3 to 35% by weight, 10 to 50% by weight of the carbon powder, and 10 to 50% by weight of the lyolefin resin solution. If the amount is less than 50% by weight, the conductivity of the conductive resin will decrease, causing an increase in internal resistance and the battery may become inoperable.On the other hand, if the amount of carbon powder exceeds 50% by weight, the conductivity This is because the binding force of the resin decreases and it becomes difficult to uniformly coat the metal core with a conductive layer made of the conductive resin.
また、導電性樹脂からなる導電層の厚さは、特に金属芯
体への導電層の被覆工程の簡便化と電池性能の安定化の
観点から、８０〜１００趨の範囲にすることがより望ま
しい。In addition, the thickness of the conductive layer made of conductive resin is preferably in the range of 80 to 100 mm, especially from the viewpoint of simplifying the process of coating the metal core with the conductive layer and stabilizing battery performance. .
上記スピネル型ＬｉＭｎ２Ｏ４は、例えばマンガン酸化
物とリチウム塩を混合し、加熱処理することにより生成
される。The spinel type LiMn2O4 is produced, for example, by mixing manganese oxide and lithium salt and heat-treating the mixture.
（作 用）
本発明によれば、金属芯体と、この芯体表面に形成され
、かつカーボンからなる導電層とこの導電層上に被覆形
成されたスピネル型ＬｉＭｎ２Ｏ４からなる正極合剤と
から構成された正極を用いることによって金属芯体と正
極合剤との界面での導電性を前記導電層により向上でき
、導電性不良箇所の発生を防止できる。このため、前記
金属芯体と電解液との反応によるガスを発生させること
がなく、前記界面の電流密度を均一化できる。(Function) According to the present invention, the electrode is composed of a metal core, a conductive layer formed on the surface of the core and made of carbon, and a positive electrode mixture made of spinel-type LiMn2O4 coated on the conductive layer. By using such a positive electrode, the conductivity at the interface between the metal core and the positive electrode mixture can be improved by the conductive layer, and occurrence of poor conductivity can be prevented. Therefore, gas is not generated due to the reaction between the metal core and the electrolytic solution, and the current density at the interface can be made uniform.
その結果、金属芯体に正極合剤を電気的に良好に接続で
きるため、安定した放電特性を有すると共に充放電サイ
クル寿命、重負荷特性等が改善された非水溶媒二次電池
を得ることができる。As a result, the positive electrode mixture can be electrically connected well to the metal core, making it possible to obtain a non-aqueous solvent secondary battery with stable discharge characteristics and improved charge/discharge cycle life, heavy load characteristics, etc. can.
一方、前記正極合剤を金属芯体にカーボンを含む導電性
樹脂からなる導電層を介して被覆することによって、該
導電性樹脂中のカーボンにより前記界面の導電性を向上
でき、かつ前記導電性樹脂の結着力により該金属芯体と
正極合剤の被覆性を良好にでき被覆不良箇所、剥離部の
発生を抑制できる。その結果、前記界面の電流密度を均
一化できると共に、被覆不良箇所、剥離箇所が生じるの
を防止できるため、前記界面での電流密度の粗密化を防
止でき、該電流密度の粗密化に伴うガス発生を抑制でき
る。On the other hand, by coating a metal core with the positive electrode mixture through a conductive layer made of a conductive resin containing carbon, the carbon in the conductive resin can improve the conductivity of the interface, and Due to the binding force of the resin, the coverage between the metal core and the positive electrode mixture can be improved, and the occurrence of poor coverage and peeling can be suppressed. As a result, the current density at the interface can be made uniform, and the occurrence of coating defects and peeling can be prevented, so it is possible to prevent the current density from becoming coarser and denser at the interface, and the gas caused by the coarser current density can be prevented. The occurrence can be suppressed.
従って、正極合剤の金属芯体からの剥離、脱落の防止及
び金属芯体への正極合剤の電気的に良好な接続により、
安定した放電特性を有すると共に充放電サイクル寿命、
重負荷特性等が改善された非水溶媒二次電池を得ること
ができる。Therefore, by preventing the positive electrode mixture from peeling or falling off from the metal core, and by ensuring good electrical connection of the positive electrode mixture to the metal core,
It has stable discharge characteristics and a long charge/discharge cycle life.
A non-aqueous solvent secondary battery with improved heavy load characteristics etc. can be obtained.
（実施例）
以下、本発明を円筒型リチウム二次電池に適用した例に
ついて第１図及び第２図（ａ） 、（ｂ）を参照して詳
細に説明する。(Example) Hereinafter, an example in which the present invention is applied to a cylindrical lithium secondary battery will be described in detail with reference to FIG. 1 and FIGS. 2(a) and 2(b).
実施例
図中の１は、底部に絶縁紙２が配置された負極端子を兼
ねる有底円筒型の金属製容器である。Reference numeral 1 in the drawings indicates a bottomed cylindrical metal container that also serves as a negative electrode terminal and has an insulating paper 2 disposed at the bottom.
前記容器１内には、円筒型の発電要素３が収納されてい
る。この発電要素３は、金属リチウムからなる負極４と
、多孔性ポリプロピレン薄膜にプロピレンカーボネート
を含浸したセパレータ５と、後述する正極６とを、この
順序で積層して帯状物とし、この帯状物を渦巻き状に捲
回することにより構成されている。A cylindrical power generation element 3 is housed within the container 1. This power generation element 3 consists of a negative electrode 4 made of metallic lithium, a separator 5 made of a porous polypropylene thin film impregnated with propylene carbonate, and a positive electrode 6 to be described later, which are laminated in this order to form a strip. It is constructed by winding it into a shape.
前記正極６は、第２図（ａ） 、（ｂ）に示す構造にな
っており、次のような方法により製造される。The positive electrode 6 has the structure shown in FIGS. 2(a) and 2(b), and is manufactured by the following method.
まず導電層９は、ポリアクリル酸水溶液（ポリアクリル
酸濃度３〜３５重量％）をメタノールで希釈した溶液１
００重量部と、アセチレングラツク１０重量部を混練し
た後、厚さ１０１のステンレス鋼からなる金属芯体８に
塗布、乾燥して作成する。正極合剤ｌＯは、電解二酸化
マンガンと炭酸リチウムを所定比で混合したものを８０
０℃で１４時間焼成することにより得られたスピネル型
Ｌ ｉ Ｍｎ２０４８２重量部と導電材としてアセチレ
ンブラック１５重量部とを混合する。つづいて結着剤溶
液は、エチレン単位ＢＯ〜７０モル％、プロピレン単位
４０〜３０モル％及びジシクロペンタジェン単位５モル
％以下からなり、分子量１０３〜１０７の三元共重合体
のエラストマー３重量部を、含有水分量を０．１重量％
に調整したトルエン溶液に溶解して結着剤溶液とする。First, the conductive layer 9 is prepared using a solution 1 prepared by diluting a polyacrylic acid aqueous solution (polyacrylic acid concentration 3 to 35% by weight) with methanol.
00 parts by weight and 10 parts by weight of acetylene glue, the mixture is coated on a metal core 8 made of stainless steel with a thickness of 101 mm, and dried. The positive electrode mixture 1O is a mixture of electrolytic manganese dioxide and lithium carbonate at a predetermined ratio.
20482 parts by weight of spinel type Li Mn obtained by firing at 0° C. for 14 hours and 15 parts by weight of acetylene black as a conductive material are mixed. Subsequently, the binder solution is made of a 3-weight terpolymer elastomer containing BO to 70 mol% of ethylene units, 40 to 30 mol% of propylene units, and 5 mol% or less of dicyclopentadiene units, and having a molecular weight of 103 to 107. part, and the water content is 0.1% by weight.
A binder solution is prepared by dissolving it in a toluene solution adjusted to .
この結着剤溶液１００重量部を前記ＬｉＭｎ２ｏ４とア
セチレンブラックの混合物９７重量部に混練する。次い
で、この混線物を前記導電層９上に塗布、乾燥して正極
合剤ｌＯを作成する。このようにして正極６を製造した
。さらに、正極６の金属芯体８と接続された正極り一ド
７を正極端子１２へ接続する。同様に負極４と接続して
いる負極り一ド１３を金属製容器１に接続し、封口板１
１で封口し金属製容器１の開口部を内方へ折曲して密封
口して、第１図の本発明実施例の円筒型リチウム二次電
池はなっている。100 parts by weight of this binder solution is kneaded with 97 parts by weight of the mixture of LiMn2o4 and acetylene black. Next, this mixed material is applied onto the conductive layer 9 and dried to prepare a positive electrode mixture IO. In this way, the positive electrode 6 was manufactured. Furthermore, the positive electrode wire 7 connected to the metal core 8 of the positive electrode 6 is connected to the positive electrode terminal 12 . Similarly, the negative electrode gate 13 connected to the negative electrode 4 is connected to the metal container 1, and the sealing plate 1 is connected to the metal container 1.
The cylindrical lithium secondary battery of the embodiment of the present invention shown in FIG. 1 is completed by sealing the metal container 1 with the metal container 1 and bending the opening inward to seal it.
（比較例）
金属芯体に正極合剤を導電層を介さずに直接被覆して構
成した正極を用いた以外、実施例と同様な構造の円筒型
リチウム二次電池を組み立てた。(Comparative Example) A cylindrical lithium secondary battery having the same structure as the example was assembled, except that a positive electrode formed by directly coating a metal core with a positive electrode mixture without intervening a conductive layer was used.
しかして、本実施例及び比較例のリチウム二次電池につ
いて、２０℃の室温で１５０ｍＡの電流により７時間充
電を行い、この後２．ＯＶの放電電圧を示すまで放電を
行う工程を１サイクルとして、放電容量の特性評価を行
った。その結果、第３図に示す特性図を得た。なお図中
のＡは５本実施例の二次電池の特性線、Ｂは比較例の二
次電池の特性線を示す。この第３図から明らがなように
本実施例の二次電池Ａは、サイクル数の増加に伴う放電
容量の低下は緩やかで優れた放電特性を有することがわ
かる。これに対し、比較例の二次電池Ｂにおいては、サ
イクル数の増加に伴う放電容量の低下が著しくなること
がわかる。特にサイクル数が１００回付近になると放電
容量が極端に低下する。The lithium secondary batteries of this example and comparative example were charged at a room temperature of 20° C. with a current of 150 mA for 7 hours, and then 2. Characteristic evaluation of the discharge capacity was performed using the process of discharging until the discharge voltage of OV was shown as one cycle. As a result, a characteristic diagram shown in FIG. 3 was obtained. Note that A in the figure shows the characteristic line of the secondary battery of the fifth example, and B shows the characteristic line of the secondary battery of the comparative example. As is clear from FIG. 3, it can be seen that the secondary battery A of this example has excellent discharge characteristics, with a gradual decrease in discharge capacity as the number of cycles increases. On the other hand, it can be seen that in secondary battery B of Comparative Example, the discharge capacity decreases significantly as the number of cycles increases. In particular, when the number of cycles approaches 100, the discharge capacity decreases extremely.
また、本実施例及び比較例の二次電池について、７５０
ｍＡの負荷による重負荷放電を行った。その結果、第４
図に示す放電接続時間と電池端子電圧との関係の特性図
を得た。なお、図中のＡは本実施例の二次電池の特性線
、Ｂは比較例の二次電池の特性線を示す。この第４図か
ら明らかなように本実施例の二次電池は、比較例の二次
電池に比べて放電端子電圧が急激に減少するまでの放電
接続時間が長くなり、重負荷における放電特性が大幅に
改善されていることがわかる。特に、比較例の二次電池
は放電時間が２５分間を越えると急激に電圧が低下する
のに対して、実施例の二次電池は４５分間を越えても急
激な電圧低下が生じず、安定した電池特性を示している
。In addition, for the secondary batteries of this example and comparative example, 750
Heavy load discharge was performed with a load of mA. As a result, the fourth
A characteristic diagram of the relationship between discharge connection time and battery terminal voltage shown in the figure was obtained. Note that A in the figure shows the characteristic line of the secondary battery of the present example, and B shows the characteristic line of the secondary battery of the comparative example. As is clear from FIG. 4, the secondary battery of this example has a longer discharge connection time until the discharge terminal voltage rapidly decreases than the secondary battery of the comparative example, and has poor discharge characteristics under heavy loads. It can be seen that it has been significantly improved. In particular, the secondary battery of the comparative example has a rapid voltage drop when the discharge time exceeds 25 minutes, whereas the secondary battery of the example does not have a sudden voltage drop even after 45 minutes and remains stable. This shows the battery characteristics.
更に、本実施例及び比較例の二次電池を各々１００個に
ついて、前述した放電容量の特性評価試験を５０サイク
ル行ない、その時点での電池容量分布を調べた。その結
果を下記第１表に示す。なお、下記第１表のＸは本実施
例及び比較例の二次電池１００個の電池容量の平均値で
あり、δは前記各容量値から得られた標準偏差を示す。Further, the above-described discharge capacity characteristic evaluation test was performed for 50 cycles on 100 secondary batteries of the present example and the comparative example, and the battery capacity distribution at that time was examined. The results are shown in Table 1 below. Note that X in Table 1 below is the average value of the battery capacity of 100 secondary batteries of the present example and comparative example, and δ represents the standard deviation obtained from each of the above-mentioned capacity values.
第１表
上記第１表から明らかなように、本実施例の二次電池は
比較例の二次電池に比べて、電池容量にバラツキが少な
く個々の電池の性能が向上され、かつ均一化されており
、電池性能の安定化がなされていることがわかる。Table 1 As is clear from Table 1 above, the secondary battery of this example has less variation in battery capacity than the secondary battery of the comparative example, and the performance of each individual battery is improved and uniform. It can be seen that the battery performance has been stabilized.
［発明の効果］
以上詳述した如く、本発明によれば正極合剤を所定の導
電層を介して金属芯体に被覆することによって、該正極
合剤を金属芯体に対して電気的に良好に被覆した正極を
備え、充放電時に前記各部材の界面でのガス発生を抑制
でき、ひいては電池容量の安定化を達成した充放電サイ
クル寿命、重負荷放電特性を向上した非水溶媒二次電池
を提供できる。[Effects of the Invention] As detailed above, according to the present invention, by coating the metal core with the positive electrode mixture through a predetermined conductive layer, the positive electrode mixture is electrically connected to the metal core. A non-aqueous solvent secondary battery equipped with a well-coated cathode that suppresses gas generation at the interface of each member during charging and discharging, which in turn stabilizes battery capacity and improves charge-discharge cycle life and heavy-load discharge characteristics. We can provide batteries.
第１図は本発明の実施例を示す非水溶媒二次電池の断面
図、第２図（ａ）は本発明の電池に用いられる正極を示
す正面図、（ｂ）は同図（ａ）のＡ−Ａ線断面図、第３
図は本発明の実施例Ａ及び比較例Ｂの充放電サイクル数
と放電容量との関係を示す特性図、第４図は本実施例Ａ
及び比較例Ｂの放電接続時間と電池端子電圧との関係を
示す特性図である。
１・・・容器、 ３・・・発電要素、４・・・
負極、 ５・・・セパレータ、６・・・正極
、 ８・・・金属芯体、９・・・導電層、
ＩＯ・・・正極合剤。
＄１図FIG. 1 is a cross-sectional view of a non-aqueous solvent secondary battery showing an example of the present invention, FIG. 2(a) is a front view showing a positive electrode used in the battery of the present invention, and FIG. A-A cross-sectional view of , 3rd
The figure is a characteristic diagram showing the relationship between the number of charge/discharge cycles and the discharge capacity of Example A of the present invention and Comparative Example B, and Figure 4 is a characteristic diagram showing the relationship between the number of charge/discharge cycles and discharge capacity of Example A of the present invention.
and FIG. 9 is a characteristic diagram showing the relationship between discharge connection time and battery terminal voltage of Comparative Example B. 1... Container, 3... Power generation element, 4...
Negative electrode, 5... Separator, 6... Positive electrode, 8... Metal core, 9... Conductive layer,
IO...Positive electrode mixture. $1 figure
Claims (1)
含む導電層と、該導電層上に被覆形成したスピネル型Ｌ
ｉＭｎ＿２Ｏ＿４を主体とする正極合剤とから構成され
た正極を具備したことを特徴とする非水溶媒二次電池。A metal core, a conductive layer formed on the surface of the core and containing carbon, and a spinel type L coated on the conductive layer.
1. A non-aqueous solvent secondary battery comprising a positive electrode composed of a positive electrode mixture mainly composed of iMn_2O_4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2137095A JPH0433249A (en) | 1990-05-29 | 1990-05-29 | Nonaqueous solvent secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2137095A JPH0433249A (en) | 1990-05-29 | 1990-05-29 | Nonaqueous solvent secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0433249A true JPH0433249A (en) | 1992-02-04 |
Family
ID=15190755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2137095A Pending JPH0433249A (en) | 1990-05-29 | 1990-05-29 | Nonaqueous solvent secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0433249A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100297402B1 (en) * | 1993-12-09 | 2001-12-01 | 카이저, 크루거 | Rechargeable battery |
| JP2005353377A (en) * | 2004-06-09 | 2005-12-22 | Nissan Motor Co Ltd | Polymer battery, manufacturing method therefor, battery pack and vehicle installing these |
| CN100463257C (en) * | 2005-01-28 | 2009-02-18 | 三星Sdi株式会社 | Anode active material, method of preparing the same, and anode and lithium battery employing the same |
-
1990
- 1990-05-29 JP JP2137095A patent/JPH0433249A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100297402B1 (en) * | 1993-12-09 | 2001-12-01 | 카이저, 크루거 | Rechargeable battery |
| JP2005353377A (en) * | 2004-06-09 | 2005-12-22 | Nissan Motor Co Ltd | Polymer battery, manufacturing method therefor, battery pack and vehicle installing these |
| CN100463257C (en) * | 2005-01-28 | 2009-02-18 | 三星Sdi株式会社 | Anode active material, method of preparing the same, and anode and lithium battery employing the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3111791B2 (en) | Non-aqueous electrolyte secondary battery | |
| EP3663265A2 (en) | Positive electrode active material for lithium secondary battery and lithium secondary battery including the same | |
| JP3291750B2 (en) | Non-aqueous electrolyte secondary battery and method of manufacturing the same | |
| US20200083531A1 (en) | Positive electrode active material for lithium secondary battery and lithium secondary battery including the same | |
| JPH10112318A (en) | Nonaqueous electrolyte secondary battery | |
| JP2000011991A (en) | Organic electrolyte secondary battery | |
| JP2001110453A (en) | Nonaqueous electrolytic solution secondary battery | |
| JPH0676860A (en) | Secondary battery and manufacture thereof | |
| JP2000357505A (en) | Nonaqueous electrolyte secondary battery | |
| CN217507387U (en) | Battery core and battery | |
| JPH07105970A (en) | Non-aqueous secondary battery and its manufacture | |
| JPH11126600A (en) | Lithium ion secondary battery | |
| JPH0433249A (en) | Nonaqueous solvent secondary battery | |
| JPH07130389A (en) | Nonaqueous electrolyte secondary battery | |
| JP4069988B2 (en) | Lithium ion secondary battery | |
| US5788720A (en) | Method for manufacturing positive electrode plates for an alkaline storage battery | |
| JP2003331823A (en) | Nonaqueous electrolyte secondary battery and method of manufacturing the battery | |
| JP3432922B2 (en) | Solid electrolyte secondary battery | |
| JPH0367462A (en) | Nonaqueous solvent secondary battery | |
| JPH09129264A (en) | Manufacture of nonaqueous electrolyte secondary battery | |
| JP2005071712A (en) | Manufacturing method of positive electrode | |
| JPH0982364A (en) | Nonaqueous electrolyte secondary battery | |
| CN110024203A (en) | Electrode assembly and rechargeable battery including the electrode assembly | |
| JPH07130394A (en) | Nonaqueous electrolyte secondary battery | |
| JP3489381B2 (en) | Non-aqueous electrolyte secondary battery |