All-solid battery including a solid electrolyte and a layer of polymer material

Abstract

A process for producing all-solid, thin-layer batteries that do not lead to the appearance of phases at the interface between electrolyte layers to be assembled. Such a process for producing a battery may occur at low temperature without causing inter-diffusion phenomena at the interfaces with the electrodes.

1 - 27 . (canceled) 
     
     
         28 . An all-solid-state thin layer battery, fabricated by a process comprising:
 a) forming an anode material layer by depositing at least one anode material on a first conductive substrate, selected from a group formed by a metal sheet, or a metal strip, or a metallized insulating sheet, or a metallized insulating strip, or a metallized insulating film, said first conductive substrate, or conductive elements thereof, configured to serve as an anode current collector;   b) forming a cathode material layer by depositing at least one cathode material on a second conductive substrate, selected from a group formed by a metal sheet, or a metal strip, or a metallized insulating sheet, or a metallized insulating strip, or a metallized insulating film, said second conductive substrate, or conductive elements thereof, configured to serve as a cathode current collector;   c) forming an electrolyte material layer by depositing on at least one of the anode material layer and/or the cathode material layer, at least one solid electrolyte material;   d) depositing a layer of a cross-linked polymer material comprising ionic groups having a thickness of less than 10 μm:
 on the anode material layer coated with the electrolyte material layer and/or on the cathode material layer uncoated or coated with the electrolyte material layer; or 
 on the cathode material layer coated with the electrolyte material layer and/or on the anode material layer uncoated or coated with the electrolyte material layer; 
   e) stacking the anode material layer obtained in step a), c) or d) face to face in series with the cathode material layer obtained in b), c) or d) such that the stack includes at least one electrolyte material layer obtained in c) and at least one cross-linked polymer material layer obtained in d); and   f) performing a heat treatment and/or a mechanical compression of the stack obtained in e) to obtain the all-solid-state thin-layer battery.   
     
     
         29 . The all-solid-state thin layer battery of  claim 28 , wherein the at least one cross-linked polymer material is chosen from polymethyl methacrylates, polyamines, polyimides, or polysiloxanes. 
     
     
         30 . The all-solid-state thin layer battery of  claim 28 , wherein the ionic groups are chosen from the following cations: imidazolium, pyrazolium, tetrazolium, pyridinium, pyrrolidinium, ammonium, phosphonium or sulfonium; and/or from the following anions: bis(trifluoromethane)sulfonimide, bis(fluorosulfonyl)imide, or n-(nonafluorobutane-sulfonyl)-n-(trifluoromethanesulfonyl)-imide. 
     
     
         31 . The all-solid-state thin layer battery of  claim 28 , wherein the at least one anode material layer, and/or the at least one cathode material layer include electrically conductive materials, and/or nanoparticles of lithium ion conductive materials, or cross-linked solid polymer materials comprising ionic groups. 
     
     
         32 . The all-solid-state thin layer battery of  claim 28 , wherein the anode material layer is produced from a material chosen from:
 (i) tin oxynitrides;   (ii) lithiated iron phosphate;   (iii) mixed silicon and tin oxynitrides (formed as SiSn 0.87 O 1.2 N 1.72 ; as well as oxynitrides-carbides formed as Si a Sn b C c O y N z , with a>0, b>0, a+b≤2, 0<c<10, 0<y<24, 0<z<17; Si a Sn b C c O y N z X n  with X n  comprising at least one of the elements among F, Cl, Br, I, S, Se, Te, P, As, Sb, Bi, Ge, Pb and a>0, b>0, a+b>0, a+b≤2, 0<c<10, 0<y<24 and 0<z<17; and Si a Sn b O y N z X n  with X n  comprising at least one of the elements among F, Cl, Br, I, S, Se, Te, P, As, Sb, Bi, Ge, Pb and a>0, b>0, a+b≤2, 0<y≤4 and 0<z≤3;   (iv) nitrides of type Si x N y  (with x=3 and y=4), Sn x N y  (with x=3 and y=4), Zn x N y  (with x=3 and y=4), and Li 3-x M x N (with M=Co, Ni, Cu);   (v) oxides SnO 2 , Li 4 Ti 5 O 12 , SnB 0.6 P 0.4 O 2.9  and TiO 2 .   
     
     
         33 . The all-solid-state thin layer battery of  claim 28 , wherein the cathode material layer is produced from material chosen from:
 (i) oxides LiMn 2 O 4 , LiCoO 2 , LiNiO 2 , LiMn 1.5 Ni 0.5 O 4 , LiMn 1.5 Ni 0.5-x X x O 4  (in which X is selected from Al, Fe, Cr, Co, Rh, Nd, and other rare earth elements, and in which 0<x<0.1), and LiFeO 2 , LiMn 1/3 Ni 1/3 Co 1/3 O 4 ;   (ii) phosphates LiFePO 4 , LiMnPO 4 , LiCoPO 4 , LiNiPO 4 , Li 3 V 2 (PO 4 ) 3 , phosphates of formula LiMM′PO 4 , with M and M′ (M≠M′) selected from Fe, Mn, Ni, Co, V;   (iii) all lithiated forms of the following chalcogenides: V 2 O 5 , V 3 O 8 , TiS 2 , titanium oxysulfides (TiO y S z ), tungsten oxysulfides (WO y S z ), CuS, and CuS 2 .   
     
     
         34 . The all-solid-state thin layer battery of  claim 28 , further comprising at least one encapsulating layer on the multi-stack, the at least one encapsulating layer composed of a ceramic material, a vitreous material, or a vitroceramic material. 
     
     
         35 . The all-solid-state thin layer battery of  claim 28 , further comprising an anode terminal and a cathode terminal. 
     
     
         36 . A battery, fabricated by a process comprising:
 a) forming an anode material layer by depositing at least one anode material on a first conductive substrate, selected from a group formed by a metal sheet, or a metal strip, or a metallized insulating sheet, or a metallized insulating strip, or a metallized insulating film, said first conductive substrate, or conductive elements thereof, configured to serve as an anode current collector;   b) forming a cathode material layer by depositing at least one cathode material on a second conductive substrate, selected from a group formed by a metal sheet, or a metal strip, or a metallized insulating sheet, or a metallized insulating strip, or a metallized insulating film, said second conductive substrate, or conductive elements thereof, configured to serve as a cathode current collector;   c) forming an electrolyte material layer by depositing on at least one of the anode material layer and/or the cathode material layer, at least one solid electrolyte material;   d) depositing a layer of a cross-linked polymer material comprising ionic groups having a thickness of less than 10 μm:
 on the anode material layer coated with the electrolyte material layer and/or on the cathode material layer uncoated or coated with the electrolyte material layer; or 
 on the cathode material layer coated with the electrolyte material layer and/or on the anode material layer uncoated or coated with the electrolyte material layer; 
   e) stacking the anode material layer obtained in step a), c) or d) face to face in series with the cathode material layer obtained in b), c) or d) such that the stack includes at least one electrolyte material layer obtained in c) and at least one cross-linked polymer material layer obtained in d); and   f) performing a heat treatment and/or a mechanical compression of the stack obtained in e) to obtain the battery.   
     
     
         37 . The battery of  claim 36 , wherein the at least one cross-linked polymer material is chosen from polymethyl methacrylates, polyamines, polyimides, or polysiloxanes. 
     
     
         38 . The battery of  claim 36 , wherein the ionic groups are chosen from the following cations: imidazolium, pyrazolium, tetrazolium, pyridinium, pyrrolidinium, ammonium, phosphonium or sulfonium; and/or from the following anions: bis(trifluoromethane)sulfonimide, bis(fluorosulfonyl)imide, or n-(nonafluorobutane-sulfonyl)-n-(trifluoromethanesulfonyl)-imide. 
     
     
         39 . The battery of  claim 36 , wherein the at least one anode material layer, and/or the at least one cathode material layer include electrically conductive materials, and/or nanoparticles of lithium ion conductive materials, or cross-linked solid polymer materials comprising ionic groups. 
     
     
         40 . The battery of  claim 36 , wherein the anode material layer is produced from a material chosen from:
 (i) tin oxynitrides;   (ii) lithiated iron phosphate;   (iii) mixed silicon and tin oxynitrides (formed as SiSn 0.87 O 1.2 N 1.72 ; as well as oxynitrides-carbides formed as Si a Sn b C c O y N z , with a>0, b>0, a+b≤2, 0<c<10, 0<y<24, 0<z<17; Si a Sn b C c O y N z X n  with X n  comprising at least one of the elements among F, Cl, Br, I, S, Se, Te, P, As, Sb, Bi, Ge, Pb and a>0, b>0, a+b>0, a+b≤2, 0<c<10, 0<y<24 and 0<z<17; and Si a Sn b O y N z X n  with X n  comprising at least one of the elements among F, Cl, Br, I, S, Se, Te, P, As, Sb, Bi, Ge, Pb and a>0, b>0, a+b≤2, 0<y≤4 and 0<z≤3;   (iv) nitrides of type Si x N y  (with x=3 and y=4), Sn x N y  (with x=3 and y=4), Zn x N y  (with x=3 and y=4), and Li 3-x M x N (with M=Co, Ni, Cu);   (v) oxides SnO 2 , Li 4 Ti 5 O 12 , SnB 0.6 P 0.4 O 2.9  and TiO 2 .   
     
     
         41 . The battery of  claim 36 , wherein the cathode material layer is produced from material chosen from:
 (i) oxides LiMn 2 O 4 , LiCoO 2 , LiNiO 2 , LiMn 1.5 Ni 0.5 O 4 , LiMn 1.5 Ni 0.5-x X x O 4  (in which X is selected from Al, Fe, Cr, Co, Rh, Nd, and other rare earth elements, and in which 0<x<0.1), and LiFeO 2 , LiMn 1/3 Ni 1/3 CO 1/3 O 4 ;   (ii) phosphates LiFePO 4 , LiMnPO 4 , LiCoPO 4 , LiNiPO 4 , Li 3 V 2 (PO 4 ) 3 , phosphates of formula LiMM′PO 4 , with M and M′ (M≠M′) selected from Fe, Mn, Ni, Co, V;   (iii) all lithiated forms of the following chalcogenides: V 2 O 5 , V 3 O 8 , TiS 2 , titanium oxysulfides (TiO y S z ), tungsten oxysulfides (WO y S z ), CuS, and CuS 2 .   
     
     
         42 . The battery of  claim 36 , further comprising at least one encapsulating layer on the multi-stack, the at least one encapsulating layer composed of a ceramic material, a vitreous material, or a vitroceramic material. 
     
     
         43 . The battery of  claim 36 , further comprising an anode terminal and a cathode terminal. 
     
     
         44 . A thin-layer, three-dimensional battery, fabricated by a process comprising:
 a) forming an anode material layer by depositing at least one anode material on a first conductive substrate, selected from a group formed by a metal sheet, or a metal strip, or a metallized insulating sheet, or a metallized insulating strip, or a metallized insulating film, said first conductive substrate, or conductive elements thereof, configured to serve as an anode current collector;   b) forming a cathode material layer by depositing at least one cathode material on a second conductive substrate, selected from a group formed by a metal sheet, or a metal strip, or a metallized insulating sheet, or a metallized insulating strip, or a metallized insulating film, said second conductive substrate, or conductive elements thereof, configured to serve as a cathode current collector;   c) forming an electrolyte material layer by depositing on at least one of the anode material layer and/or the cathode material layer, at least one solid electrolyte material;   d) depositing a layer of a cross-linked polymer material comprising ionic groups having a thickness of less than 10 μm:
 on the anode material layer coated with the electrolyte material layer and/or on the cathode material layer uncoated or coated with the electrolyte material layer; or 
 on the cathode material layer coated with the electrolyte material layer and/or on the anode material layer uncoated or coated with the electrolyte material layer; 
   e) stacking the anode material layer obtained in step a), c) or d) face to face in series with the cathode material layer obtained in b), c) or d) such that the stack includes at least one electrolyte material layer obtained in c) and at least one cross-linked polymer material layer obtained in d); and   f) performing a heat treatment and/or a mechanical compression of the stack obtained in e) to obtain the thin-layer, three-dimensional battery.