Integrated all-solid-state secondary battery
In order to improve the safety of a rechargeable battery, methods for manufacturing the rechargeable battery using a solid-state electrolyte are being studied. However, a process of manufacturing the all-solid state rechargeable battery by separately preparing and laminating an electrode and a solid-state electrolyte is not only complicated, but also may cause side reactions due to residual moisture between the electrode and the solid-state electrolyte. In addition, additional processes are required to reduce the interface resistance between the electrode and the solid-state electrolyte. In order to solve these disadvantages, the present invention is to manufacture an integral all-solid state rechargeable battery by applying a mixed slurry of a conductive ceramic material and a polymer mixed with a solvent onto an electrode, evaporating the solvent, absorbing a liquid electrolyte, and then covering the electrode with a counter electrode. The manufacturing method of the integral all-solid state rechargeable battery has an effect of simplifying the manufacturing steps, suppressing side reactions, and reducing the interface resistance between the electrode and the solid-state electrolyte.
1 . A method for manufacturing an integral solid state rechargeable battery, comprising:
applying a mixed slurry containing 85 wt % to 99 wt % of a conductive ceramic material, 1 wt % to 15 wt % of a polymer when the sum of the conductive ceramic material and the polymer is set to 100 wt %, and a solvent onto an electrode;
drying the mixed slurry to remove the solvent to obtain a composite film containing the conductive ceramic material and the polymer;
absorbing 1 to 5 parts by weight of a liquid electrolyte with respect to 100 parts by weight of the composite film containing the conductive ceramic material and the polymer in the composite film to produce a solid state electrolyte, wherein the liquid electrolyte is prepared by dissolving a lithium salt or a sodium salt in a non-aqueous organic solvent; and
covering the electrode with another electrode after absorbing the liquid electrolyte.
2 . A method for manufacturing an integral solid state rechargeable battery, comprising:
applying a first mixed slurry containing 85 wt % to 99 wt % of a conductive ceramic material, 1 wt % to 15 wt % of a polymer, and a solvent onto an electrode;
drying the first mixed slurry to remove the solvent to obtain a first composite film containing the conductive ceramic material and the polymer;
applying a second mixed slurry, different from the first mixed slurry, containing 60 wt % to 99 wt % of a conductive ceramic material, 1 wt % to 40 wt % of a polymer, and a solvent onto the first composite film;
drying the second mixed slurry to remove the solvent to obtain a multilayered composite film consisting of the first composite film and a second composite film containing the conductive ceramic material and the polymer; and
absorbing 1 to 5 parts by weight of a liquid electrolyte with respect to 100 parts by weight of the multilayered composite film containing the conductive ceramic material and the polymer in the multilayered composite film to produce a solid state electrolyte, wherein the liquid electrolyte is prepared by dissolving a lithium salt or a sodium salt in a non-aqueous organic solvent; and
covering the electrode with another electrode after absorbing the liquid electrolyte.
3 . A method for manufacturing an integral solid state rechargeable battery, comprising:
preparing a positive electrode unit in which a positive electrode and a first solid electrolyte are integrated;
simultaneously or sequentially preparing a negative electrode unit in which a negative electrode and a second solid electrolyte are integrated; and
attaching the positive electrode unit and the negative electrode unit,
wherein the positive electrode unit is prepared through steps comprising:
applying a first mixed slurry containing 85 wt % to 99 wt % of a conductive ceramic material, 1 wt % to 15 wt % of a polymer, and a solvent onto the positive electrode;
drying the first mixed slurry to remove the solvent to obtain a first composite film containing the conductive ceramic material and the polymer; and
absorbing 1 to 5 parts by weight of a liquid electrolyte with respect to 100 parts by weight of the first composite film containing the conductive ceramic material and the polymer in the first composite film to produce a solid state electrolyte, wherein the liquid electrolyte is prepared by dissolving a lithium salt or a sodium salt in a non-aqueous organic solvent,
wherein the negative electrode unit is prepared through steps comprising:
applying a second mixed slurry containing 85 wt % to 99 wt % of a conductive ceramic material, 1 wt % to 15 wt % of a polymer, and a solvent onto the negative electrode;
drying the second mixed slurry to remove the solvent to obtain a second composite film containing the conductive ceramic material and the polymer; and
absorbing 1 to 5 parts by weight of a liquid electrolyte with respect to 100 parts by weight of the second composite film containing the conductive ceramic material and the polymer in the second composite film to produce another solid state electrolyte, wherein the liquid electrolyte is prepared by dissolving a lithium salt or a sodium salt in a non-aqueous organic solvent,
wherein the attaching step of the positive electrode unit and the negative electrode unit is performed after the absorbing step of the preparation of the positive electrode unit and the absorbing step of the preparation of the negative electrode unit.
4 . The method for manufacturing the integral solid state rechargeable battery according to claim 2 , wherein the multilayered composite film further includes another composite film in addition to the first composite film and the second composite film.
5 . The method for manufacturing the integral solid state rechargeable battery according to claim 3 , wherein one or both of the positive electrode unit and the negative electrode unit further includes another composite film in addition to the first composite film and the second composite film.
6 . The method for manufacturing the integral solid state rechargeable battery according to claim 1 , wherein the solvent used in the mixed slurry containing the conductive ceramic material, the polymer, and the solvent is N-methyl-2-pyrrolidone (NMP)-based one or derivative thereof, acetone-based one or derivative thereof, alcohol-based one or derivative thereof, methanol-based one or derivative thereof, dimethylacetamide (DMAc)-based one or derivative thereof, tetrahydrofuran (THF)-based one or derivative thereof, dimethylformamide (DMF)-based one or derivative thereof, distilled water, or a mixture thereof.
7 . The method for manufacturing the integral solid state rechargeable battery according to claim 1 , wherein the non-aqueous organic solvent is carbonate-based one, ester-based one, ether-based one, ketone-based one, alcohol-based one, aprotic solvent, or a combination thereof.
8 . The method for manufacturing the integral solid state rechargeable battery according to claim 1 , wherein the conductive ceramic material is lithium oxide-based one, lithium sulfide-based one, lithium phosphate-based one, amorphous ionic conductive material, NASICON, sodium sulfide-based one, or sodium oxide-based one.
9 . The method for manufacturing the integral solid state rechargeable battery according to claim 8 , wherein the lithium oxide-based conductive ceramic material is Li-β-Al 2 O 3 , Li—TiO 2 , Li—BaTiO 3 , Li—SiO 2 , (La,Li)TiO 3 (LLTO) ((La, Li)=La or Li), Li 5 La 3 Ta 2 O 12 , Li 6 La 2 CaTa 2 O 12 , Li 4 SiO 4 Li 3 BO 2.5 N 0.5 , Li 9 SiAlO 8 , Li 5 La 2 ANb 2 O 12 (A=Ca or Sr), Li 2 Nd 3 TeSbO 12 , Li 7 La 3 Zr 2 O 12 (LLZO), Li 5 La 3 Ta 2 O 12 , or Li 9 SiAlO 8 .
10 . The method for manufacturing the integral solid state rechargeable battery according to claim 8 , wherein the lithium sulfide-based conductive ceramic material is Li 10 GeP 2 S 12 , Li 7 P 2 S 11 , Li 3.25 Ge 0.25 P 0.75 S 4 (LGPS), Li 2 S—Si 2 S 5 , Li 2 S—Ga 2 S 3 —GeS 2 , Li 2 S—Sb 2 S 3 —GeS 2 , Li 2 S—P 2 S 5 , Li 2 S—P 2 S 5 —Li 4 SiO 4 , or Li 3.25 —Ge 0.25 —P 0.75 S 4 (Thio- LISICON).
11 . The method for manufacturing the integral solid state rechargeable battery according to claim 8 , wherein the lithium phosphate-based conductive ceramic material is LAGP (Li 1+x Al x Ge 2−x (PO 4 ) 3 ) (0<x<2), LTAP (Li 1+x Ti 2−x Al x (PO 4 ) 3 ) (0<x<2), Li 1+x Ti 2−x Al x Si y (PO 4 ) 3−y (0<x<2, 0<y<3), LiAl x Zr 2−x (PO 4 ) 3 (0<x<2), or LiTi x Zr 2−x (PO 4 ) 3 (0<x<2).
12 . The method for manufacturing the integral solid state rechargeable battery according to claim 8 , wherein the amorphous ionic conductive material is phosphorous-based glass, oxide-based glass, or oxide-sulfide based glass.
13 . The method for manufacturing the integral solid state rechargeable battery according to claim 8 , wherein the sodium oxide-based conductive ceramic material is Na3Zr2Si2PO12.
14 . The method for manufacturing the integral solid state rechargeable battery according to claim 1 , wherein the polymer is polyvinylidene fluoride (PVdF)-based one or copolymer thereof, poly [(vinylidene fluoride-co-trifluoroethylene]-based one or copolymer thereof, polyethylene glycol (PEO)-based one or copolymer thereof, polyacrylonitrile (PAN)-based one or copolymer thereof, poly(methylmethacrylate) (PMMA)-based one or copolymer thereof, polyvinyl chloride-based one or copolymer thereof, polyvinylpyrrolidone (PVP)-based one or copolymer thereof, polyimide (PI)-based one or copolymer thereof, polyethylene (PE)-based one or copolymer thereof, polyurethane (PU)-based one or copolymer thereof, polypropylene (PP)-based one or copolymer thereof, poly (propylene oxide) (PPO)-based one or copolymer thereof, poly (ethyleneimine) (PEI)-based one or copolymer thereof, poly (ethylene sulfide) (PES)-based one or copolymer thereof, poly (vinyl acetate) (PVAc)-based one or copolymer thereof, poly (ethylene succinate) (PESc)-based one or copolymer thereof, polyester-based one or copolymer thereof, polyamine-based one or copolymer thereof, polysulfide-based one or copolymer thereof, siloxane-based one or copolymer thereof, styrene-butadiene rubber (SBR)-based one or copolymer thereof, carboxymethylcellulose (CMC)-based one or copolymer thereof, a derivative thereof, or a combination thereof.
15 . The method for manufacturing the integral solid state rechargeable battery according to claim 1 ,
wherein the drying step of the mixed slurry is performed after the applying step, and the absorbing step is performed after the drying step.