JP4889935B2 - Aluminum hard foil electrode material and lithium ion secondary battery using the same - Google Patents
Aluminum hard foil electrode material and lithium ion secondary battery using the same Download PDFInfo
- Publication number
- JP4889935B2 JP4889935B2 JP2004294607A JP2004294607A JP4889935B2 JP 4889935 B2 JP4889935 B2 JP 4889935B2 JP 2004294607 A JP2004294607 A JP 2004294607A JP 2004294607 A JP2004294607 A JP 2004294607A JP 4889935 B2 JP4889935 B2 JP 4889935B2
- Authority
- JP
- Japan
- Prior art keywords
- foil
- aluminum
- electrode material
- aluminum hard
- hard foil
- 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 - Fee Related
Links
- 239000011888 foil Substances 0.000 title claims description 124
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 91
- 229910052782 aluminium Inorganic materials 0.000 title claims description 91
- 239000007772 electrode material Substances 0.000 title claims description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 19
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 19
- 238000005096 rolling process Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000007774 positive electrode material Substances 0.000 claims description 14
- 239000000956 alloy Substances 0.000 claims description 11
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 8
- 239000011149 active material Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 description 21
- 238000004519 manufacturing process Methods 0.000 description 16
- 238000000576 coating method Methods 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 238000003825 pressing Methods 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 229910018084 Al-Fe Inorganic materials 0.000 description 1
- 229910018131 Al-Mn Inorganic materials 0.000 description 1
- 229910018192 Al—Fe Inorganic materials 0.000 description 1
- 229910018461 Al—Mn Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 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
- 239000003792 electrolyte Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
Images
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
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Description
この発明は、アルミニウム硬箔、例えばリチウムイオン二次電池の正極材として用いられ、歪みの少ないアルミニウム硬箔の製造方法に関し、さらにこの方法により製造されたアルミニウム硬箔、この硬箔に電極活物質を塗布したアルミニウム硬箔電極材、それを用いたリチウムイオン二次電池に関する。 The present invention relates to a method for producing an aluminum hard foil, for example, a positive electrode material for a lithium ion secondary battery, and a less distorted aluminum hard foil. The present invention relates to an aluminum hard foil electrode material to which is applied, and a lithium ion secondary battery using the same.
なお、この明細書において、「アルミニウム」の語はアルミニウムおよびその合金を含む意味で用いる。 In this specification, the term “aluminum” is used to include aluminum and its alloys.
上記のようなリチウムイオン二次電池の正極材は、ＬｉＣｏＯ2等の活物質とカーボン等の導電材とＰＶＤ等の結着材とをペースト状に混練したのち、これを１０〜２０μｍ程度のアルミニウム硬箔の両面に１００〜２００μｍ程度の厚みにコーティングし、次いで乾燥、プレス、スリット、裁断の各工程を順次的に実施することにより製作される。 The positive electrode material of the lithium ion secondary battery as described above is obtained by kneading an active material such as LiCoO 2 , a conductive material such as carbon, and a binder material such as PVD into a paste, and then mixing the paste with aluminum of about 10 to 20 μm It is manufactured by coating the both sides of the hard foil to a thickness of about 100 to 200 μm, and then sequentially carrying out the steps of drying, pressing, slitting and cutting.
このような製造工程において、電極用基材となるアルミニウム硬箔の箔圧延時に歪みが発生することがある。例えば図１に示すように、アルミニウム硬箔（Ｓ）の圧延の幅方向（Ｄ１）において、圧延方向（Ｄ２）にプレッシャーラインと称される、幅０．２〜１．５mm程度の線状の歪み（Ｐ）が５〜２０mm間隔で発生することがある。このような歪み（
Ｐ）が存在していると、ペーストのコーティング工程において塗工むらが発生し、活物質の厚みのばらつきや塗膜端縁の直線性不良が発生するという問題がある。さらに、乾燥工程において乾燥むらが生じたり、プレス工程において均一なプレスを行い得ず、最悪の場合には電池ケースへの収容が困難になるというような問題もある。また、上記の乾燥工程において、アルミニウム硬箔は軟化して強度が低下し、次のプレス工程で軟化した箔が延ばされることとなるが、アルミニウム箔は延性がありコーティング材は延性が非常に小さいため、アルミニウム箔に凹凸が存在しているとコーティング材と箔との密着性が低下し、甚しい場合にはコーティング材の剥離を生じるという問題もある。
In such a manufacturing process, distortion may occur during foil rolling of the aluminum hard foil serving as the electrode substrate. For example, as shown in FIG. 1, in the rolling width direction (D1) of the aluminum hard foil (S), a linear shape having a width of about 0.2 to 1.5 mm, called a pressure line in the rolling direction (D2). Distortion (P) may occur at intervals of 5 to 20 mm. Such distortion (
If P) is present, coating unevenness occurs in the paste coating step, resulting in problems such as variations in the thickness of the active material and poor linearity of the coating film edge. Further, there is a problem that uneven drying occurs in the drying process, and uniform pressing cannot be performed in the pressing process, and in the worst case, it becomes difficult to accommodate the battery case. In the above drying process, the hard aluminum foil is softened and the strength is reduced, and the softened foil is extended in the next pressing process. However, the aluminum foil is ductile and the coating material has very low ductility. For this reason, if the aluminum foil is uneven, the adhesion between the coating material and the foil is lowered, and if it is severe, there is a problem that the coating material is peeled off.
このようなことから、塗工むらや活物質の剥離等のないリチウムイオン二次電池の正極材を得るためには、可及的に歪のないアルミニウム硬箔の提供が望まれる。しかもまた、今後電池容量を向上するためには、活物質の均一塗布とその物質の密度の増大を図る必要があり、そのためにも歪みのないより平坦なアルミニウム硬質箔の提供が望まれている。 For this reason, in order to obtain a positive electrode material for a lithium ion secondary battery that does not have uneven coating or peeling of the active material, it is desired to provide an aluminum hard foil that is as distorted as possible. Moreover, in order to improve the battery capacity in the future, it is necessary to uniformly apply the active material and increase the density of the material. For this reason, it is desired to provide a flat aluminum hard foil without distortion. .
一般に、アルミニウム箔の歪みの矯正方法としては箔圧延後に焼鈍する方法がある。また、アルミニウム箔や板の歪みの矯正方法としては、板圧延終了後または箔圧延終了後に張力付与する方法がある（例えば特許文献１、２）。
しかしながら、硬箔を焼鈍すると軟化するため、リチウムイオン二次電池の正極材として必要な強度を維持することができないという問題点がある。 However, since it hardens when the hard foil is annealed, there is a problem that the strength required as the positive electrode material of the lithium ion secondary battery cannot be maintained.
また、箔圧延後に張力を付与する方法では、通常の巻き取り張力４〜５ｋｇ／ｍｍ2に対し、７ｋｇ／ｍｍ2以上の張力を付与すると歪みを緩和することができる。しかし、張力付与では完全に歪みを除去することはできず、過剰な張力を付与すると箔が破断したり形状不良を引き起こすおそれもある。 In the method for imparting tension after foil rolling with respect to the normal winding tension 4~5kg / mm 2, it is possible to relax the strain Granting 7 kg / mm 2 or more tension. However, the strain cannot be completely removed by applying a tension, and if an excessive tension is applied, the foil may break or cause a shape defect.
この発明は、このような技術的背景に鑑みてなされたものであって、強度を低下させることなく歪みの少ない平坦なアルミニウム硬箔を製造することを目的とする。 The present invention has been made in view of such a technical background, and an object of the present invention is to manufacture a flat aluminum hard foil with less distortion without reducing the strength.
前記目的を達成するために、本発明のアルミニウム硬箔の製造方法は、下記（１）〜（５）に記載の構成を有する。
（１） 箔圧延後のアルミニウム箔に、４０〜１５０℃で１時間以上保持する低温熱処理を施すことを特徴とするアルミニウム硬箔の製造方法。
（２） 低温熱処理を４５〜１２０℃で行う前項１に記載のアルミニウム硬箔の製造方法。
（３） 低温熱処理は、箔をコイルに巻いた状態でバッチ処理する前項１または２に記載のアルミニウム硬箔の製造方法。
（４） アルミニウム箔はＪＩＳ １０００系合金、３０００系合金、８０００系合金のいずれかからなる前項１〜３のいずれか１項に記載のアルミニウム硬箔の製造方法。
（５） アルミニウム箔の箔厚は４〜５０μｍである前項１〜４のいずれか１項に記載のアルミニウム硬箔の製造方法。
In order to achieve the above object, the method for producing an aluminum hard foil of the present invention has the configurations described in the following (1) to (5).
(1) A method for producing an aluminum hard foil, comprising subjecting the aluminum foil after foil rolling to low-temperature heat treatment that is maintained at 40 to 150 ° C. for 1 hour or more.
(2) The manufacturing method of the aluminum hard foil of the preceding clause 1 which performs low-temperature heat processing at 45-120 degreeC.
(3) Low temperature heat processing is a manufacturing method of the aluminum hard foil of the preceding clause 1 or 2 which batch-processes in the state which wound foil around the coil.
(4) Aluminum foil is a manufacturing method of the aluminum hard foil of any one of the preceding clauses 1-3 which consists of either JIS1000 type | system | group alloy, 3000 type | system | group alloy, and 8000 type | system | group alloy.
(5) The manufacturing method of the aluminum hard foil of any one of the preceding clauses 1-4 whose foil thickness of aluminum foil is 4-50 micrometers.
本発明のアルミニウム硬箔は下記（６）に記載の構成を有する。
（６） 前項１〜５のいずれか１項の方法により製造されたことを特徴とするアルミニウム硬箔。
The aluminum hard foil of this invention has the structure as described in following (6).
(6) An aluminum hard foil produced by the method according to any one of items 1 to 5 above.
本発明のアルミニウム硬箔電極材は下記（７）（８）に記載の構成を有する。
（７） 前項６に記載のアルミニウム硬箔を電極用基材とし、この電極用基材上に電極活物質を含む電極材料を塗布してなることを特徴とするアルミニウム硬箔電極材。
（８） 電極活物質を含む電極材料が、リチウムイオン二次電池の正極材料である前項７に記載のアルミニウム硬箔電極材。
The aluminum hard foil electrode material of this invention has the structure as described in following (7) (8).
(7) An aluminum hard foil electrode material, wherein the hard aluminum foil according to item 6 is used as an electrode base material, and an electrode material containing an electrode active material is applied onto the electrode base material.
(8) The aluminum hard foil electrode material according to item 7, wherein the electrode material containing an electrode active material is a positive electrode material of a lithium ion secondary battery.
本発明のリチウムイオン二次電池は下記（９）に記載の構成を有する。
（９） 電極用基材または電極材として、前項６に記載のアルミニウム硬箔、または前項７または８に記載のアルミニウム硬箔電極材を用いてなることを特徴とするリチウムイオン二次電池。
The lithium ion secondary battery of this invention has the structure as described in following (9).
(9) A lithium ion secondary battery comprising the aluminum hard foil according to item 6 or the aluminum hard foil electrode material according to item 7 or 8 as the electrode substrate or electrode material.
（１）の発明にかかるアルミニウム箔の製造方法によれば、箔圧延によって得た強度を低下させることなく歪みを解消し、平坦なアルミニウム硬箔を製造できる。 According to the manufacturing method of the aluminum foil concerning invention of (1), distortion is eliminated and the flat aluminum hard foil can be manufactured, without reducing the intensity | strength obtained by foil rolling.
（２）の発明にかかるアルミニウム箔の製造方法によれば、特に歪み解消効果が大きい。
い。
According to the manufacturing method of the aluminum foil concerning invention of (2), especially the distortion elimination effect is large.
Yes.
（３）の発明にかかるアルミニウム箔の製造方法によれば、効率良く低温熱処理を行える。 According to the manufacturing method of the aluminum foil concerning invention of (3), low temperature heat processing can be performed efficiently.
（４）の発明にかかるアルミニウム箔の製造方法によれば、リチウムイオン二次電池の正極材の電極用基材に適したアルミニウム硬箔を製造できる。 According to the manufacturing method of the aluminum foil concerning invention of (4), the aluminum hard foil suitable for the base material for electrodes of the positive electrode material of a lithium ion secondary battery can be manufactured.
（５）の発明にかかるアルミニウム箔の製造方法によれば、そのアルミニウム箔の厚さにおいて箔圧延による歪みが生じやすくかつ張力付与による歪み解消が困難なものであるため、本発明の適用意義が大きい。 According to the method for producing an aluminum foil according to the invention of (5), the thickness of the aluminum foil is likely to be distorted by foil rolling and difficult to eliminate the strain by applying tension. large.
（６）の発明にかかるアルミニウム硬箔は、箔圧延によって得た強度を維持しつつ歪みが解消された平坦なアルミニウム硬箔である。 The aluminum hard foil according to the invention of (6) is a flat aluminum hard foil in which distortion is eliminated while maintaining the strength obtained by foil rolling.
（７）の発明にかかるアルミニウム硬箔電極は、電極用基材の歪みが解消されて平坦であるため、電極活物質を含む電極材料の塗工性および密着性が良好である。 Since the aluminum hard foil electrode according to the invention of (7) is flat with the distortion of the electrode base material eliminated, the coating property and adhesion of the electrode material containing the electrode active material are good.
（８）の発明にかかるアルミニウム硬箔電極は、リチウムイオン二次電池用正極材となし得る。 The aluminum hard foil electrode according to the invention of (8) can be formed as a positive electrode material for a lithium ion secondary battery.
（９）の発明にかかるリチウムイオン二次電池は、電極材において電極用基材への電極材料の均一塗布が達成されるため、高い電池容量が得られるとともに、充放電に対しても高い容量安定性が得られる。
In the lithium ion secondary battery according to the invention of (9), since uniform application of the electrode material to the electrode base material is achieved in the electrode material, a high battery capacity is obtained and a high capacity for charge and discharge is also obtained. Stability is obtained.
本発明のアルミニウム硬箔の製造方法は、箔圧延後のアルミニウム箔に低温熱処理を施すことによって箔を軟化させることなく歪みを解消し、平坦なアルミニウム硬箔を製造するものである。 The manufacturing method of the aluminum hard foil of the present invention eliminates the distortion without softening the foil by subjecting the aluminum foil after the foil rolling to a low temperature heat treatment, and manufactures a flat aluminum hard foil.
低温熱処理条件は、４０〜１５０℃で１時間以上保持することにより行う。処理温度が４０℃未満では長時間をかけても歪み解消効果に乏しく、１５０℃を超えると箔が軟化し、箔圧延によって得た強度が低下するためである。好ましい処理温度は４５〜１２０℃であり、特に好ましい処理温度は５０〜８０℃である。処理時間は１時間未満では歪み解消効果に乏しいため、１時間以上とする。本発明は低温熱処理であるから長時間保持しても材料強度が低下するおそれはなく、処理時間の上限に制限はない。ただし、２４時間を超える長時間処理を施しても歪み解消効果が飽和してそれ以上の効果が得られない。このため、処理時間は処理効率の点で２４時間以下が好ましい。歪みは処理温度が高いほど短時間で緩和されるため、処理温度に応じて適宜処理時間を設定すれば良い。処理時間は、４５〜１２０℃の処理では１〜４０時間が好ましく、５０〜８０℃の処理では２〜２４時間が好ましい。 The low temperature heat treatment condition is performed by holding at 40 to 150 ° C. for 1 hour or longer. This is because if the treatment temperature is less than 40 ° C., the effect of eliminating the distortion is poor even if it takes a long time, and if it exceeds 150 ° C., the foil is softened and the strength obtained by foil rolling is reduced. A preferable processing temperature is 45 to 120 ° C, and a particularly preferable processing temperature is 50 to 80 ° C. If the treatment time is less than 1 hour, the effect of eliminating distortion is poor, so it is 1 hour or more. Since the present invention is a low-temperature heat treatment, there is no risk that the material strength will decrease even if it is held for a long time, and there is no upper limit on the treatment time. However, even if the treatment is performed for a long time exceeding 24 hours, the distortion eliminating effect is saturated and no further effect can be obtained. Therefore, the processing time is preferably 24 hours or less from the viewpoint of processing efficiency. Since the strain is alleviated in a shorter time as the processing temperature is higher, the processing time may be appropriately set according to the processing temperature. The treatment time is preferably 1 to 40 hours for the treatment at 45 to 120 ° C, and preferably 2 to 24 hours for the treatment at 50 to 80 ° C.
前記低温熱処理は張力を付与する必要がないため、箔をコイルに巻いた状態でバッチ処理することができ、簡単な装置と処理で歪み解消処理を行うことができる。また、同時に多くのアルミニウム硬箔の熱処理を行うことができ、生産効率が良い。ただし、本発明は、箔を巻き取りながら連続的に低温熱処理することを排除するものではない。連続処理の場合は、通常の３９〜４９Ｎ／ｍｍ2（４〜５ｋｇ／ｍｍ2）程度の巻き取り張力はもとより、箔の破断や形状不良が生じない範囲で張力を付与することができる。 Since the low-temperature heat treatment does not require application of tension, batch processing can be performed while the foil is wound around a coil, and distortion can be eliminated with a simple apparatus and processing. Moreover, many aluminum hard foils can be heat-treated at the same time, and the production efficiency is good. However, the present invention does not exclude continuous low temperature heat treatment while winding the foil. In the case of continuous treatment, not only the usual winding tension of 39 to 49 N / mm 2 (4 to 5 kg / mm 2 ), but also tension can be applied within a range in which the foil is not broken or defective in shape.
アルミニウム箔の材質は特に限定されることはなく、例えばＪＩＳ Ａ１０８５、Ａ１０８０、Ａ１Ｎ３０、Ａ１１００、Ａ１２００等の１０００系合金（純アルミニウム系）、Ａ３００３，Ａ３００４等の３０００系合金（Ａｌ−Ｍｎ系）、Ａ８０７９、Ａ８０２１等の８０００系合金（Ａｌ−Ｆｅ系）等の各種のものを用いれば良い。これらのアルミニウム箔はリチウムイオン二次電池の正極用基材として用いられる材料合金である。 The material of the aluminum foil is not particularly limited. For example, 1000 series alloys (pure aluminum series) such as JIS A1085, A1080, A1N30, A1100, A1200, 3000 series alloys (Al-Mn series) such as A3003, A3004, Various materials such as 8000 series alloys (Al-Fe series) such as A8079 and A8021 may be used. These aluminum foils are material alloys used as a positive electrode base material for lithium ion secondary batteries.
本発明の方法は対象する硬箔の厚さを限定するものではないが、厚さが４〜５０μｍの箔への適用を推奨できる。この範囲の厚さの箔は図１に示した圧延方向の歪み（Ｐ）が生じやすく、かつ張力付与による歪み解消が困難であるため、本発明の適用意義が大きいためである。また、前記範囲の箔厚のアルミニウム箔はリチウムイオン二次電池の電極材の電極用基材として好適に用いることができる。特に好ましい箔厚は１０〜３０μｍである。 Although the method of the present invention does not limit the thickness of the target hard foil, application to a foil having a thickness of 4 to 50 μm can be recommended. This is because the foil having a thickness in this range is likely to cause a distortion (P) in the rolling direction shown in FIG. 1 and it is difficult to eliminate the distortion by applying a tension. Moreover, the aluminum foil of the foil thickness of the said range can be used suitably as an electrode base material of the electrode material of a lithium ion secondary battery. A particularly preferred foil thickness is 10 to 30 μm.
上述した低温熱処理に供するアルミニウム箔は、常法に従い熱間圧延、冷間圧延、箔圧延の順次的実施によって製造すれば良い。また、低温熱処理は、アルミニウム箔が箔圧延時の加工硬化によって得た強度を保持している状態で行えば良く、箔圧延直後に連続して行うことも、箔圧延後に時間を隔てて行うこともできる。 The aluminum foil to be subjected to the low-temperature heat treatment described above may be manufactured by sequentially performing hot rolling, cold rolling, and foil rolling according to a conventional method. The low-temperature heat treatment may be performed in a state in which the aluminum foil retains the strength obtained by work hardening at the time of foil rolling, and may be performed continuously immediately after foil rolling or at intervals after foil rolling. You can also.
こうして、歪みを矯正したアルミニウム硬箔は、例えばリチウムイオン二次電池の電極材の正極用基材や負極用基材として用いられる。例えば、電極活物質と導電材と結着材とをペースト状に混練して電極材料とし、この電極材料を前記アルミニウム硬箔の片面または両面に１００〜２００μｍ程度の厚みにコーティングし、次いで乾燥、プレス、スリット、裁断の各工程を順次的に実施して電極材が作製される。アルミニウム硬箔は、低温熱処理が施されて歪みが解消されているから、コーティング工程における塗工むらの発生や活物質の厚みのばらつきを防止でき、さらに、乾燥工程における乾燥むらやプレス工程におけるプレスの不均一、コーテング材と箔との密着性の低下等の不都合を引き起こすことはなくなり、ひいては電池容量の向上および充放電に対する容量安定性の向上に寄与する。 Thus, the aluminum hard foil whose distortion has been corrected is used as, for example, a positive electrode substrate or a negative electrode substrate of an electrode material of a lithium ion secondary battery. For example, an electrode active material, a conductive material, and a binder are kneaded into a paste to form an electrode material. This electrode material is coated on one or both sides of the aluminum hard foil to a thickness of about 100 to 200 μm, and then dried. The electrode material is produced by sequentially performing the steps of pressing, slitting and cutting. Since the aluminum hard foil has been subjected to low-temperature heat treatment to eliminate distortion, it can prevent uneven coating in the coating process and variations in the thickness of the active material. Furthermore, uneven drying in the drying process and pressing in the pressing process can be prevented. This causes no inconveniences such as non-uniformity of the coating material and lowering of the adhesion between the coating material and the foil, thereby contributing to improvement of battery capacity and capacity stability against charge / discharge.
本発明は、以下の実施例に限定されない。 The present invention is not limited to the following examples.
ＪＩＳ Ａ１０８５、Ａ３００３およびＡ８０２１を用い、定法により厚さ１５μｍのアルミニウム硬箔を製作した。箔圧延によって得られたアルミニウム硬箔はＨ１８材に相当するものであり、圧延方向の線状の微少歪み（Ｐ）（図１参照）が発生したものである。また、この歪み（Ｐ）は目視によって観察しうるものであった。
このアルミニウム箔に対し、表１（Ａ１０８５）、表２（Ａ３００３）および表（Ａ８０２１）に示す温度および時間の熱処理を施した。熱処理は、いずれもコイルの状態でバッチ処理するものとした。
Using JIS A1085, A3003 and A8021, an aluminum hard foil having a thickness of 15 μm was manufactured by a conventional method. The aluminum hard foil obtained by foil rolling corresponds to the H18 material, and a linear slight strain (P) in the rolling direction (see FIG. 1) is generated. Moreover, this distortion (P) was observable visually.
This aluminum foil was subjected to heat treatment at the temperatures and times shown in Table 1 (A1085), Table 2 (A3003), and Table (A8021). All heat treatments were batch-treated in a coil state.
得られた箔アルミニウム硬箔について、目視により歪みの解消状態を観察するとともに、耐力、引張強度、伸びの機械的性質を測定した。これらの結果を表１〜３に併せて示す。 About the obtained foil aluminum hard foil, while observing the cancellation | release state of distortion visually, the mechanical property of yield strength, tensile strength, and elongation was measured. These results are also shown in Tables 1-3.
表１〜３に示すように、所定条件で低温熱処理することによって、熱処理をしない比較例１，１１、２１と比較して、機械的性質を低下させることなく、歪みを解消あるいは緩和することができた。一方、１５０℃を超える温度で熱処理した比較例２，１２、２２では、歪みが解消されたものの機械的性質が低下した。 As shown in Tables 1 to 3, by performing low-temperature heat treatment under predetermined conditions, distortion can be eliminated or alleviated without deteriorating mechanical properties as compared with Comparative Examples 1, 11, and 21 without heat treatment. did it. On the other hand, in Comparative Examples 2, 12, and 22 that were heat-treated at a temperature exceeding 150 ° C., the mechanical properties were lowered although the distortion was eliminated.
さらに、各アルミニウム硬箔を電極用基材とするリチウムイオン二次電池の正極材（電極材）を製作した。 Furthermore, the positive electrode material (electrode material) of the lithium ion secondary battery which uses each aluminum hard foil as a base material for electrodes was manufactured.
まず、ＬｉＣｏＯ2等の活物質とカーボン等の導電材とＰＶＤ等の結着材とをペースト状に混練して正極材料（電極材料）を作った。そして、この正極材料を上記アルミニウム硬箔の両面に１００μｍの厚みにコーティングし、次いで２００℃×３０分乾燥した。乾燥後において、複数の正極用材料の乾燥状態を調べたところ、各実施例のアルミニウム硬箔を用いたものについては完全にかつ均一に乾燥していたが、比較例１，１１、２１のアルミニウム硬箔を用いたものについては乾燥むらが認められた。 First, an active material such as LiCoO 2 , a conductive material such as carbon, and a binder such as PVD were kneaded into a paste to produce a positive electrode material (electrode material). The positive electrode material was coated on both sides of the aluminum hard foil to a thickness of 100 μm, and then dried at 200 ° C. for 30 minutes. After drying, when the drying state of the plurality of positive electrode materials was examined, those using the aluminum hard foil of each example were completely and uniformly dried, but the aluminum of Comparative Examples 1, 11, and 21 Uneven drying was observed in the case of using the hard foil.
次に、プレス、スリット、裁断の各工程を実施してリチウムイオン二次電池の正極材を得た。そして、アルミニウム硬箔とコーティング材との密着状態を調べたところ、各実施例のアルミニウム硬箔を用いたものについては剥離もほとんどなく良好な密着状態が得られていた。これに対し、比較例１，１１、２１のアルミニウム硬箔を用いたものについては、わずかな剥離が認められた。 Next, pressing, slitting, and cutting steps were performed to obtain a positive electrode material for a lithium ion secondary battery. And when the adhesion state of aluminum hard foil and a coating material was investigated, there was almost no peeling about what used the aluminum hard foil of each Example, and the favorable adhesion state was obtained. On the other hand, about the thing using the aluminum hard foil of Comparative Examples 1, 11, and 21, slight peeling was recognized.
次に、本発明のアルミニウム硬箔を用いた正極材と、リチウム箔の負極と、炭酸プロピピレン（ＰＣ）と炭酸ジメチル（ＤＭＣ）を体積比で１：２の割合で混合した非水系電解液にＬｉＰＦ6を１モル／リットルの濃度で溶解したものを電解液として用い、アルミニウムラミネート袋を外装袋とした非水系二次電池（以下、ラミ袋電池と記載）を組み立てた。 Next, a positive electrode material using the aluminum hard foil of the present invention, a negative electrode of a lithium foil, and a non-aqueous electrolyte mixed with propylene carbonate (PC) and dimethyl carbonate (DMC) in a volume ratio of 1: 2. A solution obtained by dissolving LiPF 6 at a concentration of 1 mol / liter was used as an electrolyte, and a non-aqueous secondary battery (hereinafter referred to as a lami bag battery) using an aluminum laminated bag as an outer bag was assembled.
得られたラミ袋電池に対し、充放電サイクル試験を実施した。試験の条件として、充放電レート１Ｃ（クーロン）、電圧範囲３．１〜４．３Ｖに設定し、３０サイクル充放電を繰り返したところ、容量変化は見られず、良好なサイクル特性が確認された。 A charge / discharge cycle test was performed on the resulting laminated bag battery. As test conditions, a charge / discharge rate of 1 C (coulomb) and a voltage range of 3.1 to 4.3 V were set, and when 30 cycles of charge and discharge were repeated, no change in capacity was observed, and good cycle characteristics were confirmed. .
Ｓ…アルミニウム硬箔
Ｐ…歪み
Ｄ１…アルミニウム硬箔の幅方向
Ｄ２…アルミニウム硬箔の圧延方向
S ... Aluminum hard foil P ... Strain D1 ... Width direction of aluminum hard foil D2 ... Rolling direction of aluminum hard foil
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004294607A JP4889935B2 (en) | 2003-10-09 | 2004-10-07 | Aluminum hard foil electrode material and lithium ion secondary battery using the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003350401 | 2003-10-09 | ||
| JP2003350401 | 2003-10-09 | ||
| JP2004294607A JP4889935B2 (en) | 2003-10-09 | 2004-10-07 | Aluminum hard foil electrode material and lithium ion secondary battery using the same |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008241287A Division JP4971276B2 (en) | 2003-10-09 | 2008-09-19 | Aluminum hard foil electrode material and manufacturing method thereof |
| JP2008241288A Division JP4971277B2 (en) | 2003-10-09 | 2008-09-19 | Aluminum hard foil electrode material and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005133207A JP2005133207A (en) | 2005-05-26 |
| JP4889935B2 true JP4889935B2 (en) | 2012-03-07 |
Family
ID=34656041
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004294607A Expired - Fee Related JP4889935B2 (en) | 2003-10-09 | 2004-10-07 | Aluminum hard foil electrode material and lithium ion secondary battery using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4889935B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4906062B2 (en) * | 2006-03-20 | 2012-03-28 | 東洋アルミニウム株式会社 | Packaging material, manufacturing method thereof and press-through pack |
| JP4559513B2 (en) | 2008-09-09 | 2010-10-06 | 株式会社神戸製鋼所 | Laminate and composite molded body |
| JP5463803B2 (en) * | 2009-08-31 | 2014-04-09 | 日産自動車株式会社 | Thin film electrode and laminated battery |
| JP5591583B2 (en) * | 2010-05-14 | 2014-09-17 | 株式会社Ｕａｃｊ | Aluminum alloy foil for lithium-ion battery electrode current collector |
| JP5567719B2 (en) * | 2012-07-26 | 2014-08-06 | 三菱アルミニウム株式会社 | Method for producing aluminum alloy foil for positive electrode current collector of lithium ion secondary battery, aluminum alloy foil for lithium ion secondary battery positive electrode current collector and lithium ion secondary battery |
| JP6431314B2 (en) * | 2014-08-13 | 2018-11-28 | 三菱アルミニウム株式会社 | Method for producing aluminum alloy foil |
| CN114976037A (en) * | 2022-06-23 | 2022-08-30 | 华星先进科学技术应用研究(天津)有限公司 | Aluminum-based negative electrode plate for lithium ion battery and lithium ion secondary battery |
-
2004
- 2004-10-07 JP JP2004294607A patent/JP4889935B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005133207A (en) | 2005-05-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11108052B2 (en) | Rolled copper foil for negative electrode current collector of secondary battery, negative electrode of secondary battery and secondary battery using the rolled copper, and method for manufacturing rolled copper foil for negative electrode current collector of secondary battery | |
| JP6475404B2 (en) | Aluminum alloy foil for electrode current collector and method for producing the same | |
| JP5947593B2 (en) | Method for producing aluminum foil for positive electrode current collector of lithium ion secondary battery | |
| CN111477833B (en) | Lithium ion battery pole piece and laser cutting and manufacturing method thereof | |
| EP2818566B1 (en) | Aluminum alloy foil for electrode charge collector, and method for producing same | |
| JP4870359B2 (en) | Degreasing method of aluminum foil | |
| JPWO2013161726A1 (en) | Aluminum alloy foil for electrode current collector, method for producing the same, and lithium ion secondary battery | |
| JP2011023129A (en) | Method of manufacturing positive electrode plate for nonaqueous secondary battery, and manufacturing device therefor | |
| JP4889935B2 (en) | Aluminum hard foil electrode material and lithium ion secondary battery using the same | |
| KR20250002575A (en) | Composite current collector and its manufacturing method, electrode electrode piece and secondary battery | |
| CN104956533A (en) | Material for fuel cell separator and manufacturing method thereof | |
| JP2018519632A (en) | Electrolytic copper foil for lithium secondary battery and lithium secondary battery including the same | |
| JP4971277B2 (en) | Aluminum hard foil electrode material and manufacturing method thereof | |
| JP2014114480A (en) | Electrode collector aluminum alloy foil and method for manufacturing the same | |
| JP2010236055A (en) | Aluminum alloy foil for lithium ion secondary battery and method for producing the same | |
| JP2014143008A (en) | Anode collector copper foil for lithium ion secondary battery, manufacturing method of anode for lithium ion secondary battery and evaluation method of anode collector copper foil for lithium ion secondary battery | |
| JP5406229B2 (en) | Degreasing method of aluminum hard foil, aluminum hard foil, aluminum hard foil electrode material, and lithium ion secondary battery using the same | |
| CN118737776B (en) | Porous silicon-based cathode electron source and preparation method and equipment thereof | |
| JPH1143749A (en) | Method for producing aluminum foil for lithium battery with low distortion | |
| JP5490761B2 (en) | Rolled copper foil for secondary battery negative electrode current collector, negative electrode material for lithium ion secondary battery and lithium ion secondary battery using the same | |
| WO2025145656A1 (en) | High-specific-surface-area current collector and manufacturing method therefor, electrode sheet and battery | |
| CN110323449A (en) | Lithium ion battery current collector rolled copper foil and lithium ion battery | |
| JP2018076590A (en) | Aluminum alloy foil for electrode collector body and manufacturing method therefor | |
| JPWO2018043117A1 (en) | Aluminum alloy hard thin foil for secondary battery positive electrode current collector, secondary battery positive current collector and method for producing aluminum alloy hard thin foil | |
| JP2014060092A (en) | Method for manufacturing negative electrode collector copper foil, negative electrode collector copper foil, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070531 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20080709 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080722 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080919 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20081021 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20111028 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20111214 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 4889935 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20141222 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20141222 Year of fee payment: 3 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: R3D02 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |