Electrode for all solid-state secondary battery and method for producing same
An electrode for all-solid-state secondary batteries, which is capable of improving the high-temperature cycle characteristics of an all-solid-state secondary battery, includes a collector, a conductive adhesive layer and an electrode mixture layer. The electrode mixture layer contains a binder, an inorganic solid electrolyte that contains sulfur atoms, and an electrode active material. The conductive adhesive layer contains conductive particles and a binder for adhesive layers, the binder being composed of a diene polymer. The diene polymer contains 10-75% by mass of a diene monomer unit, and has an iodine number of 5-350 mg/100 mg. The sulfur atoms contained in the inorganic solid electrolyte and carbon-carbon double bonds of the diene polymer are crosslinked with each other.
1. An electrode for an all solid-state secondary battery comprising a current collector, a conductive adhesive agent layer and an electrode material mixture layer, wherein
said electrode material mixture layer includes a binder, an inorganic solid electrolyte having sulfur atom, and an electrode active material,
said conductive adhesive agent layer includes a conductive particle, and an adhesive agent binder comprising a diene based polymer,
said diene based polymer has 10 to 75 wt % of diene based monomer units and an iodine value is 5 to 350 mg/100 mg; and
the sulfur atom included in said inorganic solid electrolyte and a carbon-carbon double bond of said diene based polymer are crosslinked.
2. The electrode for the all solid-state secondary battery as set forth in claim 1 , wherein said diene based polymer is one or two or more selected from the group consisting of styrene-butadiene copolymer, styrene-isoprene copolymer, isobutylene-isoprene copolymer, ethylene-propylene-diene copolymer, acrylonitrile-butadiene copolymer and hydrogenates thereof.
3. The electrode for the all solid-state secondary battery as set forth in claim 1 wherein, said inorganic solid electrolyte is sulfide glass and/or sulfide glass ceramics comprising Li 2 S and P 2 S 5 , or ceramics comprising Li 2 S, P 2 S 5 , and GeS 2 .
4. The electrode for the all solid-state secondary battery as set forth in claim 1 , wherein said conductive adhesive agent layer includes a vulcanization accelerator which accelerates a crosslinking reaction between the sulfur atom included in said inorganic solid electrolyte and carbon carbon double bond of said diene based polymer.
5. An all solid-state secondary battery comprising a positive electrode, a solid electrolyte layer and a negative electrode, wherein
at least one of the positive electrode and the negative electrode is the electrode for the all solid-state secondary battery as set forth in claim 1 .
6. A production method of the electrode for the all solid-state secondary battery as set forth in claim 1 comprising,
a step of forming a conductive adhesive agent layer including the conductive particle and the adhesive agent layer binder comprising the diene based polymer having carbon-carbon double bond,
a step of coating an electrode slurry including the binder, the inorganic solid electrolyte having sulfur atom, and the electrode active material on said conductive adhesive agent layer,
a step of drying said electrode slurry which has been coated, and
said step of drying includes a step of drying at 25 to 90° C., and a step of drying at 100 to 200° C.
7. The electrode for the all solid-state secondary battery as set forth in claim 2 wherein, said inorganic solid electrolyte is sulfide glass and/or sulfide glass ceramics comprising Li 2 S and P 2 S 5 , or ceramics comprising Li 2 S, P 2 S 5 , and GeS 2 .
8. The electrode for the all solid-state secondary battery as set forth in claim 2 , wherein said conductive adhesive agent layer includes a vulcanization accelerator which accelerates a crosslinking reaction between the sulfur atom included in said inorganic solid electrolyte and carbon carbon double bond of said diene based polymer.
9. The electrode for the all solid-state secondary battery as set forth in claim 3 , wherein said conductive adhesive agent layer includes a vulcanization accelerator which accelerates a crosslinking reaction between the sulfur atom included in said inorganic solid electrolyte and carbon carbon double bond of said diene based polymer.
10. An all solid-state secondary battery comprising a positive electrode, a solid electrolyte layer and a negative electrode, wherein
at least one of the positive electrode and the negative electrode is the electrode for the all solid-state secondary battery as set forth in claim 2 .
11. An all solid-state secondary battery comprising a positive electrode, a solid electrolyte layer and a negative electrode, wherein
at least one of the positive electrode and the negative electrode is the electrode for the all solid-state secondary battery as set forth in claim 3 .
12. An all solid-state secondary battery comprising a positive electrode, a solid electrolyte layer and a negative electrode, wherein
at least one of the positive electrode and the negative electrode is the electrode for the all solid-state secondary battery as set forth in claim 4 .
13. A production method of the electrode for the all solid-state secondary battery as set forth in claim 2 comprising,
a step of forming a conductive adhesive agent layer including the conductive particle and the adhesive agent layer binder comprising the diene based polymer having carbon-carbon double bond,
a step of coating an electrode slurry including the binder, the inorganic solid electrolyte having sulfur atom, and the electrode active material on said conductive adhesive agent layer,
a step of drying said electrode slurry which has been coated, and
said step of drying includes a step of drying at 25 to 90° C., and a step of drying at 100 to 200° C.
14. A production method of the electrode for the all solid-state secondary battery as set forth in claim 3 comprising,
a step of forming a conductive adhesive agent layer including the conductive particle and the adhesive agent layer binder comprising the diene based polymer having carbon-carbon double bond,
a step of coating an electrode slurry including the binder, the inorganic solid electrolyte having sulfur atom, and the electrode active material on said conductive adhesive agent layer,
a step of drying said electrode slurry which has been coated, and
said step of drying includes a step of drying at 25 to 90° C., and a step of drying at 100 to 200° C.
15. A production method of the electrode for the all solid-state secondary battery as set forth in claim 4 comprising,
a step of forming a conductive adhesive agent layer including the conductive particle and the adhesive agent layer binder comprising the diene based polymer having carbon-carbon double bond,
a step of coating an electrode slurry including the binder, the inorganic solid electrolyte having sulfur atom, and the electrode active material on said conductive adhesive agent layer,
a step of drying said electrode slurry which has been coated, and
said step of drying includes a step of drying at 25 to 90° C., and a step of drying at 100 to 200° C.