JPH0384869A - Manufacture of solid secondary cell - Google Patents
Manufacture of solid secondary cellInfo
- Publication number
- JPH0384869A JPH0384869A JP1220745A JP22074589A JPH0384869A JP H0384869 A JPH0384869 A JP H0384869A JP 1220745 A JP1220745 A JP 1220745A JP 22074589 A JP22074589 A JP 22074589A JP H0384869 A JPH0384869 A JP H0384869A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- electrolyte
- secondary battery
- electrode layer
- producing
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000007787 solid Substances 0.000 title claims description 11
- 239000003792 electrolyte Substances 0.000 claims abstract description 50
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 23
- 239000011230 binding agent Substances 0.000 claims abstract description 21
- 229920001651 Cyanoacrylate Polymers 0.000 claims abstract description 19
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920001971 elastomer Polymers 0.000 claims abstract description 14
- 239000005060 rubber Substances 0.000 claims abstract description 14
- 239000007772 electrode material Substances 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 230000010354 integration Effects 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 230000002093 peripheral effect Effects 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims 1
- 229910001431 copper ion Inorganic materials 0.000 claims 1
- 239000010416 ion conductor Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000007599 discharging Methods 0.000 description 14
- -1 W Os Inorganic materials 0.000 description 11
- 238000007600 charging Methods 0.000 description 11
- 239000010408 film Substances 0.000 description 9
- 230000007423 decrease Effects 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000007606 doctor blade method Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000007784 solid electrolyte Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910020042 NbS2 Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Secondary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は構成材料がすべて固体のいわゆる固体二次電池
の製造法に関すａ
従来の技術
各種の電源として使われる電池のうち構成材料がすべて
固体であるいわゆる固体電池は液漏れがなく、したがっ
て高信頼性が期待でき、小形軽量化も可能などの理由で
一次 二次電池ともに注目されてきｔも 現在のとこ
ろ各種機器のメモリーバックアップ用を中心に考えられ
ていも
この固体電池では電池内でイオンを動かすための固体電
解質としてＬｉ゛イオン導電性固体電解質、Ａｇ”イオ
ン導電性固体電解質、Ｈ０イオン導電性固体電解質、そ
れにＲｂＣｕ４Ｉ ＋、ｓＣｌｉ、ｓ、 ＣｕＩ−Ｃ
ｕｓ〇−Ｍ２Ｏ３などのＣｕ”イオン導電性固体電解質
などが取上げられてン）モ
また 正極用材料としてはＣｕｓ、＋Ｔ ｉ Ｓ２、Ａ
ｇ＊、＋Ｔ ｉ Ｓａ、Ｃｕｓ、＋Ｎ ｂ Ｓ２、Ａｇ
＠、＋ＮｂＳ２、Ｗ Ｏｓ、それにＣｕ ｙＭ Ｏｅ
Ｓ＠−ｚ、ＦｅｖＭｏｅＳｓ−ｔなどのシェブレル相化
合物が挙げられてい＆ −Ｘ 負極にはＣｕ、 Ａ
ｇ、 Ｌ ｉ ＋、５ＷＱｓそれに正極用と同様の
シェブレル相化合物が試みられていも
また電極材料と結着剤で電極シートを、電解質と結着剤
で電解質シートをそれぞれ作製し 両シートを一体化す
る方法が簡単で連続生産性上優れていも この際の結着
剤としては公知のゴム系樹脂やフッ素樹脂が強度や可撓
性の点で優れているとされていも
さらに放電特性や寿命などの点で有望である電解質とし
てＲｂＣｕ４Ｉ ＋、ｓＣｌｓ、ｓなどのＣｕ ＋イオ
ン導電性固体電解質、正極および負極用材料としてＣｕ
ｉ＋Ｍ Ｏａ Ｓ ＠−ｚなどのシェブレル相化合物
を用いた際に 大気中の水分による電極や電解質材料の
変質などの悪影響を受けやすい力曳 これに対しては電
極層と電解質層とを加熱下で加圧一体化して密着度を上
げることにより、充放電を繰返した際の内部抵抗の増加
を抑制できることが知られている。[Detailed Description of the Invention] Industrial Field of Application The present invention relates to a method for manufacturing so-called solid-state secondary batteries whose constituent materials are all solid. Certain so-called solid-state batteries do not leak, so they can be expected to be highly reliable, and they can be made smaller and lighter, so both primary and secondary batteries have been attracting attention.Currently, they are mainly considered for memory backup in various devices. However, in this solid state battery, the solid electrolytes for moving ions within the battery include a Li' ion conductive solid electrolyte, an Ag' ion conductive solid electrolyte, a H0 ion conductive solid electrolyte, and RbCu4I +, sCli, s, and CuI. -C
Cu" ion conductive solid electrolytes such as us〇-M2O3 have been taken up. In addition, as positive electrode materials, Cu, +T i S2, A
g*, +T i Sa, Cus, +N b S2, Ag
@, +NbS2, W Os, and Cu yM Oe
Chevrel phase compounds such as S@-z and FevMoeSs-t are mentioned.
g, L i +, 5WQs, and Chevrel phase compounds similar to those for positive electrodes have been tried; however, an electrode sheet is made from the electrode material and a binder, and an electrolyte sheet is made from an electrolyte and a binder, and both sheets are integrated. Although this method is simple and superior in terms of continuous productivity, well-known rubber resins and fluororesins are used as binders in this case, and although they are said to be superior in terms of strength and flexibility, Cu+ ion conductive solid electrolytes such as RbCu4I+, sCls, and s are promising electrolytes in terms of electrolytes, and Cu as positive and negative electrode materials.
When using Chevrel phase compounds such as i+M Oa S @-z, the electrode and electrolyte materials are susceptible to adverse effects such as deterioration due to moisture in the atmosphere. It is known that increasing the degree of adhesion through pressure integration can suppress an increase in internal resistance when charging and discharging are repeated.
発明が解決しようとする課題
このような構成の固体二次電池を製造し充放電を行なっ
たとこム その条件にもよるが比較的少ないサイクル数
で容量の低下が認められた すなわち充放電を繰返すと
内部抵抗が増加して性能の劣化が認められｔも その
原因について調べた結果この電池の場合も他の電解質に
溶液を用いる電池の場合の電池と同様に とくに電極層
が充放電の過程で若干でも膨張することが認められｔも
このような溶液を用いる電池の場合には溶液が膨張
の大きな原因であり外観からも明らかに観察できもこれ
に対して固体二次電池で（よ 当然溶液は存在しないの
でその度合は小さい力支 しかし膨張でもあると今度は
逆に液がないので電極層と電解質層との密着性が低下し
内部抵抗が増加して諸性能が劣化すも
以上の問題を更に詳しく分析した粘気 次の３つの課題
が明らかとなった
ゴム系結着剤は取扱いの点やシートの見かけの強度では
有利であも しかし 樹脂に可撓性があることからこの
ような変形から生ずる密着性の劣化にはそれほど有効で
ない（第１の課題）ことが解っｔら
電極層と電解質層とを一体化する際に 両者の密着性を
高るためには温度は高く圧力は大きいほうがよＩ、％
しかし きびしい条件で一体化すると、結着剤の軟化
により電解質層や電極層が変形するという問題（第２の
課題）が生ずる。Problem to be Solved by the Invention When a solid-state secondary battery with such a configuration was manufactured and charged and discharged, a decrease in capacity was observed after a relatively small number of cycles, depending on the conditions.In other words, charging and discharging were repeated. As a result, we investigated the cause of this and found that the internal resistance increased and the performance deteriorated.As a result, in this battery, as in other batteries that use a solution as the electrolyte, the electrode layer is particularly affected during the charging and discharging process. In the case of batteries that use such solutions, the solution is a major cause of expansion, and this can be clearly observed from the external appearance. However, if there is expansion, the adhesion between the electrode layer and electrolyte layer decreases because there is no liquid, increasing internal resistance and deteriorating various performances, but this is a problem. A more detailed analysis of the viscosity revealed the following three issues.Although rubber-based binders are advantageous in terms of handling and the apparent strength of the sheet, however, due to the flexibility of the resin, It turns out that it is not very effective against deterioration of adhesion caused by deformation (the first problem), so when integrating the electrode layer and electrolyte layer, high temperature and pressure are necessary to improve the adhesion between the two. The bigger the better I,%
However, if they are integrated under strict conditions, a problem arises in that the electrolyte layer and electrode layer are deformed due to softening of the binder (second problem).
加圧一体化後に防湿のために金属および樹脂からなる薄
板を電槽として用ｔ、％ その周囲を加熱融着する暇
温度に考慮を払わないと、電極層や電解質層中の結着
剤が軟化して密着度が低下するという問題（第３の課題
）が生じる。If a thin plate made of metal and resin is used as a battery case to prevent moisture after pressurized integration, the binder in the electrode layer and electrolyte layer may A problem (third problem) arises that the degree of adhesion decreases due to softening.
課題を解決するための手段
請求項１記載の発明は第１の課題を解決するたへ 電極
材料とゴム系結着剤を主とする電極層と、電解質とゴム
系結着剤を主とする電解質層とにシアノアクリレート単
量体溶液を含浸した眞 これら電極層および電解質層を
加熱下で加圧により一体化することを特徴とする
請求項３記載の発明は第２の課題を解決するた吹 電極
材料を主とする電極層と、電解質を主とする電解質層と
を一体化した後に 電池周辺部にゼリー状シアノアクリ
レートを塗布することを特徴とすも 好ましくはゼリー
状シアノアクリレートを塗布した後金属および樹脂から
なる薄板を電槽として用（＼ その周囲を加熱融着する
ことにより電池を構威すも
請求項６記載の発明は第３の課題を解決するた碌 電極
材料に結着剤を加えた電極層と、電解質に結着剤を加え
た電解質層とを加熱下で加圧一体化した抵 薄型のリチ
ウム電池などに利用されている金属および樹脂からなる
薄膜を電槽として用１、Ｎ、これをプレス機により電極
層と電解質層とを前記加圧一体化時の温度よりも高温で
加圧しなか板 好ましくは減圧下でその周囲を加熱融着
することにより電池を構成することを特徴とすも 金属
としてはアルミニウー／、、鏡 ニッケ／１４ ス
テンレススチー／ｋ チタンなど、樹脂はポリエチレ
ン、ポリプロピレンなどのポリオレフィン系のそれぞれ
薄板がよ鶏 さらに電池周辺部に接着剤を被覆した後に
前記手段を講じてもよ賎
作 用
請求項Ｉ記載の発明に用いるシアノアクリレート樹脂（
よ ゴム系樹脂よりも硬い樹脂であり、このような密着
性の低下とくに高温での低下の抑制には効果が大きいこ
とが解った これにより、両樹脂の相乗効果で取扱性と
良好な密着性の維持が可能になっ九
請求項３記載の発明で（よ 一体化した後に電池周辺部
にゼリー状シアノアクリレートを塗布するので樹脂が電
極層や電解質層にしみこむことなく、しかもシアノアク
リレート樹脂は強度が大きいので電極層と電解質層とが
強固に付着した状態を保つことができも したがって充
放電の過程で生じる若干の膨張も抑制し内部抵抗が増大
することなく優れた放電性能や自己放電性が得られ さ
らに比較的少ないサイクル数で容量が低下することがな
くなも またゼリー状シアノアクリレートを塗布した後
金属および樹脂からなる薄板を電槽として用し＼ その
周囲を加熱融着することにより大気中の湿気による電解
質などへの悪影響を除くことができも
請求項６記載の発明で（よ 電極層と電解質層の加圧一
体化時よりも高い温度のもとで加圧しつつその周囲を加
熱融着することにより電池を構威すも したがってこの
工程で電極層と電解質層の最終的な加圧一体化が行われ
る。これら、により電極層と電解質層との密着度の低下
の防止と防湿を可能にすも
実施例
（実施例１）
電極用材料として銅シェプレル（ＣｕｓＭｏａＳ・）を
１０００ｇ用す＼ これに電解質としてＲｂＣｕ ４
Ｉ ＋、ｓＣＩ ｓ、ｓを用いて、この粉末５００ｇを
角丸 市販の摺潰機を用いて２時間ｓｉ 混合すもこ
のようにして得られた混合粉末に 結着剤として市販の
スチレン−ブタジェン系の樹脂が８ｗｔ％になるように
そのトルエン溶液を加え充分撹拌してペーストを得も
これを用いて公知のドクターブレード法により厚さ０
．３５ｍｍの電極シート、を作製し乾燥すも ついでこ
れに市販のシアノアクリレート単量体をトルエンで１０
倍に希釈した溶液を含浸後乾燥する。Means for Solving the Problem The invention according to claim 1 is for solving the first problem.An electrode layer mainly composed of an electrode material and a rubber-based binder, and an electrolyte and a rubber-based binder are mainly used. In order to solve the second problem, the invention according to claim 3 is characterized in that the electrode layer and the electrolyte layer are integrated by applying pressure under heat. It is characterized by applying jelly-like cyanoacrylate to the peripheral area of the battery after integrating an electrode layer mainly made of blown electrode material and an electrolyte layer mainly consisting of electrolyte. Preferably, jelly-like cyanoacrylate is applied. A thin plate made of metal and resin is then used as a battery case (by heating and fusing the periphery, a battery is constructed. However, the invention set forth in claim 6 is capable of solving the third problem. A thin film made of metal and resin, which is used in thin and thin lithium batteries, can be used as a battery case by integrating an electrode layer containing a binder and an electrolyte layer containing an electrolyte and a binder under heat and pressure. 1.N, the electrode layer and the electrolyte layer are pressurized using a press machine at a temperature higher than the temperature at which the electrode layer and the electrolyte layer are integrated, and the battery is constructed by heating and fusing the periphery of the plate, preferably under reduced pressure. The metals are aluminum, mirrors, nickel, stainless steel, titanium, etc., and the resins are thin sheets of polyolefin, such as polyethylene and polypropylene.Furthermore, after coating the surrounding area of the battery with adhesive, Even if the above-mentioned means are taken, the cyanoacrylate resin (
It is a harder resin than rubber-based resins, and it has been found to be highly effective in suppressing the decline in adhesion, especially at high temperatures.As a result, the synergistic effect of both resins improves ease of handling and good adhesion. With the invention described in claim 3, it is possible to maintain the cyanoacrylate (jelly-like cyanoacrylate is applied to the periphery of the battery after integration, so the resin does not seep into the electrode layer or electrolyte layer, and the cyanoacrylate resin has high strength. Since the electrode layer and electrolyte layer are large, it is possible to maintain a strong adhesion between the electrode layer and the electrolyte layer. Therefore, the slight expansion that occurs during the charging and discharging process is suppressed, and the internal resistance does not increase, resulting in excellent discharge performance and self-discharge properties. In addition, after applying the jelly-like cyanoacrylate, a thin plate made of metal and resin is used as a battery case, and the surrounding area is heated and fused, so that the capacity does not decrease with a relatively small number of cycles. In the invention as claimed in claim 6, it is possible to eliminate the adverse effect of moisture on the electrolyte, etc. Although a battery is constructed by fusing, the electrode layer and the electrolyte layer are finally integrated under pressure in this process.This prevents a decrease in the degree of adhesion between the electrode layer and the electrolyte layer and prevents moisture. Example (Example 1) 1000 g of copper sheprel (CusMoaS) is used as an electrode material. In addition, RbCu 4 is used as an electrolyte.
Using I+, sCI s, s, 500 g of this powder was rounded with a commercially available grinder for 2 hours, and the resulting mixed powder was mixed with commercially available styrene-butadiene as a binder. Add the toluene solution so that the resin content of the system is 8wt% and stir thoroughly to obtain a paste. Using this, use the known doctor blade method to obtain a paste with a thickness of 0.
．． A 35 mm electrode sheet was prepared and dried. Next, a commercially available cyanoacrylate monomer was added to it with toluene for 10 minutes.
After impregnating with the diluted solution, dry it.
電解質としｒＲｂ Ｃｕ ａ Ｉ ＋、ｓＣｌ ３．ｓ
ヲ用Ｌ１． Ｍ着剤として市販のスチレン−ブタジェ
ンゴム系樹脂が１２ｗｔ％になるように そのトルエン
溶液を加え充分撹拌してペーストを得も やはりこれも
公知のドクターブレード法により厚さ０．１０ｍｍの電
解質シートを作成する。ついでこれに市販のシアノアク
リレート単量体をトルエンで５倍に希釈した溶液を含浸
後乾燥すも
電解質シートの両面に電極シートを配してこれを１８０
℃に加熱したプレス機で５００ｋｇ／１ｍ８の条件で加
圧し一体化すも カーボンブラッ微粉末を分散させた市
販のカーボンフィルムを多電体として当てた眞 さらに
その外側に厚さ０１ｍｍのＣｕ板を当ててＩ２０ｔ、
５００ｋｇ／（ｍ２の条件で加圧一体化しｔも こ
れに公知のボリチレンとアルミニウム箔製ラミネートで
封止し］電池を構成した 電池の有効面積は２０ｃｍ”
でも この電池をＡとすも
つぎ番ヘ 比較のために前記電極シフトへのシフノア
クリレート単量体溶液の含浸と乾燥は行わづ他はＡの電
池と同じ工程によって得られた電池４Ｂとして加えｔも
以上の２つの電池Ａ、 Ｂについてまず７０Ｃ，”？
。rRb Cu a I +, sCl as electrolyte 3. s
Woyo L1. Add a toluene solution of a commercially available styrene-butadiene rubber resin as an M adhesive so that the concentration is 12 wt%, and stir thoroughly to obtain a paste.An electrolyte sheet with a thickness of 0.10 mm is also created using the well-known doctor blade method. do. Next, this was impregnated with a solution of a commercially available cyanoacrylate monomer diluted 5 times with toluene, and then dried. Electrode sheets were placed on both sides of the electrolyte sheet, and the electrolyte sheet was heated at 180%
A commercially available carbon film with finely dispersed carbon black powder was applied as a multi-electric body, and a Cu plate with a thickness of 0.1 mm was placed on the outside. I20t,
500 kg/(integrated under pressure under m2 conditions and sealed with a well-known polyethylene and aluminum foil laminate) The effective area of the battery is 20 cm.
However, this battery is also referred to as battery A.For comparison, the electrode shift was impregnated with Schifnoacrylate monomer solution and dried, but otherwise it was added as battery 4B obtained by the same process as battery A. Regarding the two batteries A and B whose t is 70C,"?
.
の充放電での放電電圧と容量を比較しｆ；０．５Ａで０
．５８Ｖまでの充！ −０，５ｍＡで０．３までの放
電を行ったところＡ、 Ｂとも平均電圧！；０．４９
Ｖ、 放電容量は２６．２ｍＡｈを示しあそこでつぎ
にこの充放電の条件で各電池の寿４特性を調べた 電池
は いずれも１０セル用い六周囲温度を８０ｔとしｔも
その結果 放電容量が初期の６０％にまで劣化する
サイクル数戟 Ａでは８５０〜９００サイクルであった
のに対して、Ｂでは３００〜３４０サイクルであっｔラ
この結果から明らかなようにＡが長寿命であっｔう
（実施例２）
電解質としてＲｂ Ｃｕ ａ Ｉ ＋、ｓＣｌ ｓ、ｓ
ヲ用ｔ＝＼ この粉末５００ｇと、電極用材料として銅
シユブレル（Ｃｕ ＊Ｍ ０６８ ｓ）を１ｏｏｏｇ用
い混合すもこの混合粉末に 結着剤として市販のゴム系
樹脂が８ｗｔ％になるように そのトルエン溶液を加え
充分撹拌してペーストを得る。これを公知のドクターブ
レード法により厚さ０．３５ｍｍの電極シートを作威す
も
電解質とり、てＲｂｃｕ４Ｉ＋、ｓｃ ｌａ、ｓをＪｆ
Ｈｚ結着剤として、やはりゴム系樹脂が１０ｗｔ％にな
るように そのトルエン溶液を加え充分撹拌してペース
トを得も これを公知のドクターブレード法により厚さ
０．２５ｍｍの電解質シートを作成する。Compare the discharge voltage and capacity during charging and discharging of f; 0 at 0.5A.
．． Charge up to 58V! When discharging up to 0.3 at -0.5 mA, the average voltage for both A and B! ;0.49
V, the discharge capacity was 26.2mAh, and then we investigated the life characteristics of each battery under these charging and discharging conditions.The batteries were all 10 cells, and the ambient temperature was 80t.As a result, the discharge capacity was at the initial stage. It took 850 to 900 cycles for A to degrade to 60% of its lifespan, while it took 300 to 340 cycles for B. As is clear from these results, A has a longer lifespan ( Example 2) Rb Cu a I +, sCl s, s as electrolytes
500g of this powder was mixed with 100g of copper shubrel (Cu * M 068 s) as an electrode material, and a commercially available rubber resin was added as a binder to the mixed powder so that the amount was 8wt%. Add the toluene solution and stir thoroughly to obtain a paste. This was used to make an electrode sheet with a thickness of 0.35 mm using the known doctor blade method.
As a Hz binder, a toluene solution containing 10 wt % of the rubber resin was added and thoroughly stirred to obtain a paste, which was then used to prepare an electrolyte sheet with a thickness of 0.25 mm using the known doctor blade method.
ついで電解質シートを中心に その両面に電極シートを
配し これを１６０ｔ’に加熱したプレス機で５００ｋ
ｇ／ｃｍ”の条件で加圧しｆ、、 ツい］このように
して得られた電池素子の主に周辺部に市販のゼリー状シ
アノアクリレートを塗布した後電池素子の両面にゴム中
にカーボンブラック微粉末を分散させた市販のカーボン
フィルムを集電体として当てた樵 さらにその外側に厚
さ０．３ｍｎのＡｌ板と電池周辺部にポリエチレン樹脂
フィルムを当てて１２０ｔ、 ５００ｋｇ／ｃｍ”７
）条件１周辺部のポリエチレン樹脂フィルムを加熱溶着
して一体化した この電池をＡとすも
つぎに比較のために電池素子の主に周辺部にゼリー状シ
アノアクリレートの塗布は行わず他はＡと同じ工程によ
って得られた電池をＢとして加えた。Next, electrode sheets were placed on both sides of the electrolyte sheet, and this was pressed through a press heated to 160 tons for 500 kph.
After applying a commercially available jelly-like cyanoacrylate mainly to the periphery of the battery element thus obtained, carbon black was applied to both sides of the battery element in the rubber. A woodcutter applied a commercially available carbon film with fine powder dispersed thereon as a current collector.Furthermore, a 0.3mm thick Al plate was placed on the outside and a polyethylene resin film was placed around the battery to produce a 120t, 500kg/cm”7
) Condition 1 This battery is called A, in which the polyethylene resin film around the periphery is heat-welded and integrated.Next, for comparison, jelly-like cyanoacrylate is not applied mainly to the periphery of the battery element, and the others are A. A battery obtained by the same process as above was added as B.
以上の２つの電池についてまず通常の充放電での放電電
圧と容量を比較し？、、０．６０Ｖ定電圧夫電−２，０
ｍＡで０．２５Ｖまでの放電を行ったところＡでは平均
電圧は０．４８Ｖ、放電容量は２６．２ｍＡｈを示した
のに対して、Ｂではそれぞれ０．４６Ｖ、２１．６ｒｎ
Ａｈであり、いずれもＡが優れていｔも
そこでつぎにこの充放電の条件で各電池の自己放電特性
を調べ′Ｆ、、０．６０Ｖ定電圧充電後３５定電圧充電
後置５℃後容量を調べたところ維持率がＡでは９２％で
あったのにＢでは８８％であっｆ。First, compare the discharge voltage and capacity of the above two batteries during normal charging and discharging. ,,0.60V constant voltage power -2,0
When discharging to 0.25V at mA, the average voltage in A was 0.48V and the discharge capacity was 26.2mAh, whereas in B, it was 0.46V and 21.6rn, respectively.
Ah, A is excellent in all cases, and t is the same.Then, we next examined the self-discharge characteristics of each battery under these charging and discharging conditions.' When we investigated the retention rate, the retention rate was 92% for A, but 88% for B.
最後に２つの電池の寿命特性を調べｔラ 電池（よい
ずれも１０セル用いた 周囲温度を３０℃とした その
結果 放電容量が初期の６０％にまで劣化するサイクル
数力ｔＡでは９５０〜１０１０サイクルであったのに対
してＢでは７５０〜８１０サイクルであっｔラ この
結果から明らかなようにＡが長寿命であっ丸
（実施例３）
正および負電極用材料として銅シェブレル（ＣｕｚＭｏ
ｅｓ＊）を１０００ｇ用（＼ これに電解質としテＲｂ
Ｃｕ ａ Ｉ ＋、ｓＣ１１Ｇを用（＼コノ粉末５゜
Ｏｇに結着剤として市販のアクリル系樹脂が８ｗｔ％に
なるよう番ヘ そのアセトン溶液を加え充分撹拌して
ペーストを得る。これを公知のドクターブレード法によ
り厚さ０．３５ｍｍの電極シートを作成すも
電解質としてＲｂＣｕ４Ｉ＋、５Ｃ１３，８を用ｔＸ％
ヤはり結着剤として市販のアクリル系樹脂が１１ｗｔ％
になるように そのアセトン溶液を加え充分撹拌してペ
ーストを得も これを公知のドクターブレード法により
厚さ０．１２ｍｍの電解質シートを作威すも
正極用シート、電解質シート、負極用シートの順にそれ
ぞれシートを重ね まずこれを１５０°Ｃに加熱したプ
レス機で５００ｋｇ／ｃｍ”の条件で加圧し その後に
その両面にゴム中にカーボンブラック微粉末を分散させ
た市販のカーボンフィルムを集電体として当てた後、
さらにその外側に厚さ０．３ｒｒｚａ 径２６ｍｍの
Ｃｕ板を当てて１２０覧 ５００ｋｇ／ｃｍ”の条件で
加圧一体化しｔらこれを電池周辺部に咳る部分に厚さ０
．１０ｍｍのポリプロピレンフィルムを用いこれと一体
化した厚さ０．０８ｍｍのアルミニウム板２枚の間に挟
ム アルミニウム板の上から内側のポリプロピレンフィ
ルムを真空ポンプで減圧にしなか板１７０℃のもと２０
０ ｋｇ／ｃｍ”の条件で加熱融着して電池を構成しｆ
、 この電池をＡとすも なおＣｕ板とアルミニウム
板は導電性接着剤で接着固定した
つぎに比較のためにポリプロピレンフィルムを真空ポン
プで減圧にしながら１４０℃のもと２００ｋｇ／ｃｍ”
の条件で加熱融着し 他はＡと同じ工程による電池を構
成してＢとして加えｔもこの両電池の特性を比較し１．
まず通常の充放電での放電電圧と容量を調べ？、、
、０．５８Ｖ定充電・−０，２ｍＡで０．３Ｖまでの放
電を行ったとこムＡでは平均電圧は０．４８Ｖ、放電容
量は４．８ｍＡｈに対して、Ｂテ！−１，ソれぞれ０．
４７Ｖ、４．６ｍＡｈであり、ＡはややＢよりやや優れ
ていｆ。Finally, we investigated the life characteristics of the two batteries. (10 cells were used in each case. The ambient temperature was 30°C.) As a result, the number of cycles at which the discharge capacity deteriorates to 60% of the initial value is 950 to 1010 cycles. On the other hand, B had a cycle life of 750 to 810 cycles.As is clear from these results, A had a long life and was round (Example 3).
es*) for 1000g (＼ Use this as an electrolyte and
Cu a I +, sC11G was added to the acetone solution of the commercially available acrylic resin as a binder at 8 wt % to 5° Og of powder. Add the acetone solution and stir thoroughly to obtain a paste. An electrode sheet with a thickness of 0.35 mm was prepared by the doctor blade method using RbCu4I+, 5C13,8 as the electrolyte.
Commercially available acrylic resin as a binder is 11wt%
Add the acetone solution and stir thoroughly to obtain a paste. Then, use the well-known doctor blade method to make an electrolyte sheet with a thickness of 0.12 mm. The sheets are stacked one on top of the other, and first they are pressed at 500kg/cm'' using a press heated to 150°C, and then a commercially available carbon film made of fine carbon black powder dispersed in rubber is used as a current collector on both sides. After guessing,
Furthermore, a Cu plate with a thickness of 0.3 mm and a diameter of 26 mm was placed on the outside of the plate, and the pressure was applied to the area of 500 kg/cm.
．． A 10 mm polypropylene film was sandwiched between two 0.08 mm thick aluminum plates integrated with the polypropylene film. The inner polypropylene film from above the aluminum plate was depressurized with a vacuum pump, and the plate was heated to 170°C for 20 minutes.
0 kg/cm" to form a battery.
, This battery is called A. The Cu plate and aluminum plate were fixed with conductive adhesive. Next, for comparison, a polypropylene film was heated to 200 kg/cm at 140°C under reduced pressure with a vacuum pump.
A battery was constructed using the same process as A except for heating and fusing under the following conditions, and t was added as B to compare the characteristics of both batteries.1.
First, check the discharge voltage and capacity during normal charging and discharging? ,,
, 0.58V constant charge and discharge to 0.3V at -0.2mA In case A, the average voltage was 0.48V and the discharge capacity was 4.8mAh, whereas in case B! -1, sore 0.
47V, 4.6mAh, A is slightly better than B.
そこで、つぎに各電池の寿命特性を調べｔ−０゜６ｖ定
電圧充電−０，５ｍＡで０．３Ｖまでの放電の条件とし
電池は いずれも１０セル用いｔも周囲温度を４０℃
とし１． その結電 放電容量が初期の７５％にまで
劣化するサイクル数力＜、Ａでは１１００〜１２００サ
イクルであったのに対して、Ｂでは１０００−１１００
サイクルであり、Ａが長寿命であった
発明の効果
充放電の過程でとくに電極層が膨張して電極層と電解質
層との密着性が低下する現象を抑制することができるの
で、電池の充放電中での内部抵抗の増加を抑えることが
でき、優れた放電性能や長寿命化が可能になんTherefore, we next investigated the life characteristics of each battery and set the conditions of constant voltage charging at t-0°6V and discharging to 0.3V at -0.5mA.The batteries were all 10 cells and the ambient temperature was 40°C.
Toshi 1. The number of cycles at which the discharge capacity deteriorates to 75% of the initial value is 1100 to 1200 cycles in A, while it is 1000 to 1100 in B.
The effect of the invention is that A has a long life.It is possible to suppress the phenomenon in which the electrode layer expands during the charging and discharging process and the adhesion between the electrode layer and the electrolyte layer decreases, so that the charging and discharging of the battery can be suppressed. It is possible to suppress the increase in internal resistance during discharge, resulting in excellent discharge performance and long life.
Claims
解質とゴム系結着剤を主とする電解質層とに、シアノア
クリレート単量体溶液を含浸させた後、これら電極層お
よび電解質層を加熱下で加圧により一体化することを特
徴とする固体二次電池の製造法。
倍に希釈した溶液を含浸させ、電解質層にシアノアクリ
レート単量体の２〜５倍の希釈溶液を含浸させることを
特徴とする請求項１記載の固体二次電池の製造法。
電解質層とを一体化した後に、電池周辺部にゼリー状シ
アノアクリレートを塗布することを特徴とする固体二次
電池の製造法。
および樹脂からなる薄板を電槽として用い、その周囲を
加熱融着することにより電池を構成することを特徴とす
る請求項３記載の固体二次電池の製造法。
オン導電体であることを特徴とする請求項１または３記
載の固体二次電池の製造法。
着剤を主とする電解質層とを加熱下で加圧一体化した後
、金属および樹脂からなる薄板を電槽として用い、これ
を加圧一体化時よりも高い温度のもとで加圧しつつその
周囲を加熱融着することにより電池を構成することを特
徴とする固体二次電池の製造法。
電池を構成することを特徴とする請求項６記載の固体二
次電池の製造法。
に減圧下で加圧することにより電池を構成することをこ
とを特徴とする請求項６記載の固体二次電池の製造法。
池の製造法。
ススチール、チタンなど、樹脂がポリオレフィン系のそ
れぞれ薄膜である請求項６記載の固体二次電池の製造法
。
2. The method for producing a solid secondary battery according to claim 1, wherein the electrolyte layer is impregnated with a solution diluted to a volume of 2 to 5 times the amount of the cyanoacrylate monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1220745A JPH0384869A (en) | 1989-08-28 | 1989-08-28 | Manufacture of solid secondary cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1220745A JPH0384869A (en) | 1989-08-28 | 1989-08-28 | Manufacture of solid secondary cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0384869A true JPH0384869A (en) | 1991-04-10 |
Family
ID=16755871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1220745A Pending JPH0384869A (en) | 1989-08-28 | 1989-08-28 | Manufacture of solid secondary cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0384869A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0859417A3 (en) * | 1997-02-12 | 2003-05-02 | Mitsubishi Denki Kabushiki Kaisha | Adhesive for battery, battery using the same and method of fabricating a battery using the same |
| KR100388905B1 (en) * | 2000-09-22 | 2003-06-25 | 삼성에스디아이 주식회사 | Lithium secondary battery |
| JP2010205449A (en) * | 2009-02-27 | 2010-09-16 | Nippon Zeon Co Ltd | Electrolyte layer for all-solid secondary battery, laminate for all-solid secondary battery, and all-solid secondary battery |
-
1989
- 1989-08-28 JP JP1220745A patent/JPH0384869A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0859417A3 (en) * | 1997-02-12 | 2003-05-02 | Mitsubishi Denki Kabushiki Kaisha | Adhesive for battery, battery using the same and method of fabricating a battery using the same |
| KR100388905B1 (en) * | 2000-09-22 | 2003-06-25 | 삼성에스디아이 주식회사 | Lithium secondary battery |
| JP2010205449A (en) * | 2009-02-27 | 2010-09-16 | Nippon Zeon Co Ltd | Electrolyte layer for all-solid secondary battery, laminate for all-solid secondary battery, and all-solid secondary battery |
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