JP2023533234A - 固体電解質材料を含む全固体電池を製造する方法 - Google Patents
固体電解質材料を含む全固体電池を製造する方法 Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
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- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 238000000429 assembly Methods 0.000 description 1
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- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
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- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical group [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VROAXDSNYPAOBJ-UHFFFAOYSA-N lithium;oxido(oxo)nickel Chemical group [Li+].[O-][Ni]=O VROAXDSNYPAOBJ-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/0468—Compression means for stacks of electrodes and separators
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/052—Li-accumulators
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/04—Processes of manufacture in general
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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Abstract
Description
実施例1
正極活物質としてLiNi0.8Co0.1Mn0.1O2、固体電解質としてLi2S-P2S5、バインダーとしてニトリルブタジエンラバー(NBR)、導電材として気相成長炭素繊維(Vapor Grown Carbon Fiber;VGCF)を75.5:22.1:1.5:1の比率(重量比)でアニソールに投入して正極活物質層形成用スラリー(固形分含量70wt%)を用意した。これをアルミニウム薄膜(厚さ約10μm)の一面に塗布して60℃で6時間乾燥して正極を用意した。
第1及び第2加圧は450MPaの圧力で行い、第3加圧は100MPaの圧力で行うことを除き、実施例1と同様の方法で電極組立体を製造した。
実施例と同様の方法で正極、負極及び固体電解質膜(60μm)を用意して順次に積層した。これを500MPaで5分間加圧して電極組立体を収得した。収得された前記電極組立体において、正極の気孔度は20vol%、固体電解質膜の気孔度は10vol%であった。加圧はCIP装置を用いて行った。
450MPaの圧力を印加することを除き、比較例1と同様の方法で電極組立体を収得した。
実施例1、実施例2、比較例1及び比較例2で収得された電極組立体を用いて全固体電池を製造した。これらを対象にして3回充放電を繰り返した後、開放回路電圧(OCV)を測定した。前記充放電は、4.25Vまで(0.01Cカットオフ)0.1CでCC(定電流)-CV(定電圧)モードで充電し、0.1Cで3Vまで放電した。前記開放回路電圧は日置製の電圧測定機を用いて測定した。実施例1、実施例2、比較例1及び比較例2の初回充放電の結果を下記の表1に示した。比較例1及び比較例2の場合は、充放電効率が低く(約43%水準)、電池性能が低下したことが分かった。一方、実施例1及び実施例2の場合は、約93%水準と高かった。また、実施例1及び比較例1の1回目~3回目の充放電プロファイルをそれぞれ図4(実施例1)及び図5(比較例1)に示した。これらから確認できるように、比較例1の電池の場合は、非可逆容量が高くて放電容量が充分に発現できず、実施例1に比べて電池性能が低かった。
Claims (10)
- S1)正極と第1固体電解質膜とを積層し加圧して正極部材を収得する第1加圧工程と、
S2)第2固体電解質膜を用意し、前記第2固体電解質膜を加圧する第2加圧工程と、
S3)前記正極部材、前記加圧された第2固体電解質膜、及び負極を順次に積層し加圧して電極組立体を収得する第3加圧工程と、
を含む、全固体電池の製造方法。 - 前記第1加圧工程が、15℃~30℃の温度条件及び300MPa~600MPaの圧力条件で行われる、請求項1に記載の全固体電池の製造方法。
- 前記正極部材における第1固体電解質膜の気孔度が45vol%~60vol%である、請求項1または2に記載の全固体電池の製造方法。
- 前記第2加圧工程が、15℃~30℃の温度条件及び300MPa~600MPaの圧力条件で行われる、請求項1から3のいずれか一項に記載の全固体電池の製造方法。
- 前記第3加圧工程が、第1加圧工程時及び第2加圧工程時に印加される圧力よりも低い圧力下で行われる、請求項1から4のいずれか一項に記載の全固体電池の製造方法。
- 前記第3加圧工程が、100MPa~300MPaの圧力条件で行われる、請求項5に記載の全固体電池の製造方法。
- 前記負極は、集電体及び前記集電体の表面に形成された電極活物質層を含み、前記電極活物質層は、リチウム金属を含む、請求項1から6のいずれか一項に記載の全固体電池の製造方法。
- 前記第1固体電解質膜及び第2固体電解質膜は、固体電解質材料を含み、前記固体電解質材料は、硫化物系固体電解質材料を含む、請求項1から7のいずれか一項に記載の全固体電池の製造方法。
- 前記第3加圧工程は、第1加圧工程時及び第2加圧工程時に印加される圧力よりも低い圧力下で行われ、
前記負極は、負極活物質としてリチウム金属を含み、
前記第1固体電解質膜及び第2固体電解質膜は固体電解質材料を含み、前記固体電解質材料は硫化物系固体電解質材料を含む、請求項1から8のいずれか一項に記載の全固体電池の製造方法。 - 前記第1加圧工程時に正極の周縁に保護部材を囲んで加圧して固体電解質膜の損傷を防止する、請求項1から9のいずれか一項に記載の全固体電池の製造方法。
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