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Solid-state battery having an electrode comprising of an electronically … — GM Global Technology Operations LLC (US20210050596A1)

ABSTRACT

Abstract

A solid-state battery cell for a lithium ion battery is disclosed. The battery cell includes a first electrode; a second electrode; and an ionically conductive layer sandwiched between the first electrode and the second electrode. At least one of the first electrode and the second electrode includes an electronically conductive polymer (ECP). The at least one of the first electrode and the second electrode comprises about 20-98 weight percent (wt %) of an active material, about 0.1-30 wt % of the ECP, and about 5-70 wt % of an ionically conductive material that includes one or more of a solid-state electrolyte (SSE) material and a lithium salt.

Description

INTRODUCTION

The present disclosure relates to rechargeable solid-state batteries and, more particularly, a solid-state battery having an electrode comprising of an electronically conductive polymer.

Rechargeable batteries are known to be used in consumer electronic applications from small electronic devices, such as cell phones to larger electronic devices such as laptop computers. Modern rechargeable lithium ion batteries have the ability to hold a relatively high energy density as compared to older types of rechargeable batteries such as nickel metal hydride, nickel cadmium, or lead acid batteries. A benefit of rechargeable lithium ion batteries is that the batteries can be completely or partially charged and discharged over many cycles without retaining a charge memory. In addition, rechargeable lithium ion batteries can be used in larger applications, such as for electric and hybrid vehicles due to the batteries' high power density, long cycle life, and ability to be formed into a wide variety of shapes and sizes so as to efficiently fill available space in such vehicles.

Modern rechargeable lithium ion batteries typically utilize organic liquid electrolyte to carry or conduct lithium cations (Li + ) between a cathode active material and an anode active material. To further enhance battery performance, organic liquid electrolyte is replaced by solid-state electrolyte (SSE) in more modern batteries. Solid-state electrolytes could broaden the working temperature range and improve energy density of rechargeable lithium ion batteries. Rechargeable lithium ion batteries having solid-state electrolytes are known to be referred to as rechargeable solid-state lithium ion batteries.

For the majorities of known electrodes used in rechargeable solid-state lithium batteries, conductive carbon additives are utilized to obtain the desired electronic conduction pathways. However, it was found that the inclusion of carbon additives in the electrodes can stimulate the electrochemical decomposition of solid-state electrolyte, especially the sulfide-based solid-state electrolyte such as Li 10 GeP 2 S 12 (LGPS), and the decomposition products at the interface will lead to a large interfacial resistance and inferior kinetic performance.

Thus, while rechargeable solid-state lithium batteries achieve their intended purpose for use in electric and hybrid vehicles, there is a need for continuous improvement in the composition of the electrodes to obtain the desired electronic conduction pathways with minimal to no decomposition of the solid-state electrolyte (e.g. LGPS) at the interface.

SUMMARY

According to several aspects, a battery cell is provided. The battery cell includes a first electrode, a second electrode, and an ionically conductive layer sandwiched between the first electrode and the second electrode. At least one of the first electrode and the second electrode includes an electronically conductive polymer (ECP).

In an additional aspect of the present disclosure, the ECP includes π-conjugated polymeric chains.

In another aspect of the present disclosure, the ECP includes at least one of a polypyrrole (PPy), a polyaniline (PANI), a polythiophene (PT), a poly(3,4-ethylenedioxy thiophene) (PEDOT), a poly(3,4-propylenedioxy thiophene) (PProDOT) and PEDOT:poly(4-styrene sulfonate) (PEDOT:PSS), polyacetylene (PA), and poly(p-phenylenevinylene) (PPV).

In another aspect of the present disclosure, the ECP can also be further modified by functional group, such as poly(3-hexylthiophene).

In another aspect of the present disclosure, at least one of the first electrode and the second electrode, further includes a solid-state electrolyte material.

In another aspect of the present disclosure, the solid-state electrolyte (SSE) material includes at least one of a sulfide-based SSE including a Li 2 S—P 2 S 5 system and lithium argyrodite Li 6 PS 5 X, wherein X=Cl, Br, or I; an oxide-based SSE including Li 7 La 3 Zr 2 O 12 ; a polymer-based SSE including a polyethylene oxide (PEO) with LiTFSI, a nitride-based SSE including a LiSi 2 N 3 ; a hydride-based SSE including LiBH 4 —LiNH 2 ; a halide-based SSE including Li 3 OCl, a borate-based SSE including Li 2 O—B 2 O 3 —P 2 O 5 ; an inorganic SSE/polymer-based hybrid electrolyte including Li 7 La 3 Zr 2 O 12 /polyvinylidene fluoride (PVDF)/Li salt hybrid solid electrolyte; and a surface-modified SSE including Indium (In)-deposited Li 7 La 3 Zr 2 O 12 .

In another aspect of the present disclosure, the battery cell further includes a liquid electrolyte permeating the first electrode, the ionically conductive layer, and the second electrode.

In another aspect of the present disclosure, at least one of the first electrode and the second electrode includes from about 20 weight percent (wt %) to about 98 wt % of an active material, from about 0.1 wt % to about 30 wt % of the ECP, and from about 5 wt % to about 70 wt % of a solid-state electrolyte (SSE) material.

In another aspect of the present disclosure, at least one of the first electrode and the second electrode includes from about 20 weight percent (wt %) to about 98 wt % of an active material, from about 0.1 wt % to about 30 wt % of the ECP, and from about 5 wt % to about 70 wt % of a lithium salt.

In another aspect of the present disclosure, the lithium salt includes a lithium cation and at least one of a hexafluoroarsenate; a hexafluorophosphate; a tris(pentafluoroethyl)-trifluorophosphate (FAP); a perchorate; a tetrafluoroborate; a trifluoromethanesulfonate (Triflate); a bis(fluorosulfonyl)amide (FSI); a cyclo-difluoromethane-1,1-bis(sulfonyl)imide (DMSI); cyclo-difluoromethane-1,1-bis(sulfonyl)imide (HPSI); a bis(trifluoromethanesulfonyl)imide (TFSI); a bis(perfluoroethanesulfonyl)imide (SETT); a bis(oxalate)borate (BOB); a difluoro(oxalato)borate (DFOB); a bis(fluoromalonato)borate (BFMB); a tetracyanoborate (Bison); a dicyanotriazolate (DCTA), a dicyano-trifluoromethyl-imidazole (TDI); a dicyano-pentafluoroethyl)-imidazole (PDI); and other anion.

According to several aspects, an electrode is provided. The electrode includes an electrode layer having from about 20 weight % (wt %) to about 98 wt % of an electrode active material; from about 5 wt % to about 70 wt % of an ionically conductive material; and from about 0.1 wt % to about 30 wt % of an electronically conductive polymer.

In an additional aspect of the present disclosure, the electronically conductive polymer includes at least one of a polypyrrole (PPy), a Polyaniline (PANI), a polythiophene (PT), a poly(3,4-ethylenedioxy thiophene) (PEDOT), a poly(3,4-propylenedioxy thiophene) (PProDOT) and PEDOT:poly(4-styrene sulfonate) (PEDOT:PSS), polyacetylene (PA), and poly(p-phenylenevinylene) (PPV).

In another aspect of the present disclosure, the electronically conductive polymer can also be further modified by functional group, such as poly(3-hexylthiophene).

In another aspect of the present disclosure, the ionically conductive material includes a solid-state electrolyte (SSE) material comprising at least one of a sulfide-based SSE, an oxide-based SSE, a polymer-based SSE, a nitride-based SSE, a hydride-based SSE, a halide-based SSE, a borate-based SSE, an inorganic/polymer-based Hybrid electrolyte, and a surface-modified SE.

In another aspect of the present disclosure, the ionically conductive material includes a lithium salt having a lithium cation and at least one of a hexafluoroarsenate; a hexafluorophosphate; a tris(pentafluoroethyl)-trifluorophosphate (FAP); a perchorate; a tetrafluoroborate; a trifluoromethanesulfonate (Triflate); a bis(fluorosulfonyl)amide (FSI); a cyclo-difluoromethane-1,1-bis(sulfonyl)imide (DMSI); cyclo-difluoromethane-1,1-bis(sulfonyl)imide (HPSI); a bis(trifluoromethanesulfonyl)imide (TFSI); a bis(perfluoroethanesulfonyl)imide (SETT); a bis(oxalate)borate (BOB); a difluoro(oxalato)borate (DFOB); a bis(fluoromalonato)borate (BFMB); a tetracyanoborate (Bison); a dicyanotriazolate (DCTA), a dicyano-trifluoromethyl-imidazole (TDI); a dicyano-pentafluoroethyl)-imidazole (PDI)); and other anion.

In another aspect of the present disclosure, the electrode active material includes a cathode active material including at least one of: a lithium manganese oxide (LiMn 2 O 4 ); a lithium iron phosphate (LiFePO 4 ); a LiNi 0.5 Mn 15 O 4 ; a rock salt layered oxide including LiCoO 2 , LiNi x Mn y Co 1−x−y O 2 , LiNi x Mn 1−x O 2 , Li 1+x MO 2 ; a spinel such including LiMn 2 O 4 ; a polyanion cathode including LiV 2 (PO 4 ) 3 ; a coated or doped cathode material including LiNbO 3 coated LiNi 0.5 Mn 1.5 O 4

In another aspect of the present disclosure, the electrode includes of an anode active material including at least one of a carbonaceous material; a silicon; a silicon-graphite mixture; a lithium titanate (Li 4 Ti 5 O 12 ); a transition-metal; a metal oxide or metal sulfide including at least one of TiO 2 , FeS, SnO 2 ; and a lithium-Indium (Li—In).

In another aspect of the present disclosure, the electrode further includes from greater than 0 wt % to about 15 wt % of an electronically conductive additive. The electronically conductive additive includes at least one of a carbon black, a graphite, a graphene, a graphene oxide, a Super P, an acetylene black, a carbon nanofiber, and a carbon nanotube.

In another aspect of the present disclosure, the electrode further includes from greater than 0 wt % to about 15 wt % of a binder, wherein the binder includes at least one of a poly(tetrafluoroethylene) (PTFE), a sodium carboxymethyl cellulose (CMC), a styrene-butadiene rubber (SBR), a poly(vinylidene fluoride) (PVDF), a nitrile butadiene rubber (NBR), a styrene ethylene butylene styrene copolymer (SEBS), and a styrene butadiene styrene copolymer (SBS).

According to several aspects, a battery having an electrode. The electrode includes from about 20 weight % (wt %) to about 98 wt % of an electrode active material; from about 5 wt % to about 70 wt % of an ionically conductive material; and from about 0.1 wt % to about 30 wt % of an electronically conductive polymer (ECP). The ionically conductive material includes at least one of a solid-state electrolyte material and a lithium salt. The ECP includes at least one of a polypyrrole (PPy), a polyaniline (PANI), a polythiophene (PT), a poly(3,4-ethylenedioxy thiophene) (PEDOT), a poly(3,4-propylenedioxy thiophene) (PProDOT) and PEDOT:poly(4-styrene sulfonate) (PEDOT:PSS), polyacetylene (PA), and poly(p-phenylenevinylene) (PPV).

Further areas of applicability will become apparent from the description provided herein. It should be understood that the description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure in any way.

FIG. 1 is a diagrammatic representation of a rechargeable solid-state lithium ion battery cell having an electrode comprising of an electronically conductive polymer, according to an exemplary embodiment;

FIG. 2 is a diagrammatic representation of an exemplary electrode comprising of an electronically conductive polymer, according to an exemplary embodiment; and

FIG. 3 is a diagrammatic representation of a detailed portion of the electrode of FIG. 2 , according to an exemplary embodiment.

DETAILED DESCRIPTION

The following description is merely exemplary in nature and is not intended to limit the present disclosure, application, or uses. The illustrated embodiments are disclosed with reference to the drawings, wherein like numerals indicate corresponding parts throughout the several drawings. The figures are not necessarily to scale and some features may be exaggerated or minimized to show details of particular features. The specific structural and functional details disclosed are not intended to be interpreted as limiting, but as a representative basis for teaching one skilled in the art as to how to practice the disclosed concepts.

FIG. 1 shows an exemplary embodiment of a diagrammatic representation of a rechargeable solid-state lithium ion battery cell, generally indicated by reference number 100 (solid-state battery cell 100 ), having at least one electrode comprising of an electronically conductive polymer. The solid- state battery cell 100 includes a negative electrode 102 , a positive electrode 104 , and an ionically conductive layer 106 having a first ionically conductive material 108 a disposed between the negative electrode 102 and the positive electrode 104 . The negative electrode 102 is also referred to as an anode 102 and the <figure-callout id="104" label="positive electrode" filenames="US20210050

INTRODUCTION

The present disclosure relates to rechargeable solid-state batteries and, more particularly, a solid-state battery having an electrode comprising of an electronically conductive polymer.

Rechargeable batteries are known to be used in consumer electronic applications from small electronic devices, such as cell phones to larger electronic devices such as laptop computers. Modern rechargeable lithium ion batteries have the ability to hold a relatively high energy density as compared to older types of rechargeable batteries such as nickel metal hydride, nickel cadmium, or lead acid batteries. A benefit of rechargeable lithium ion batteries is that the batteries can be completely or partially charged and discharged over many cycles without retaining a charge memory. In addition, rechargeable lithium ion batteries can be used in larger applications, such as for electric and hybrid vehicles due to the batteries&#39; high power density, long cycle life, and ability to be formed into a wide variety of shapes and sizes so as to efficiently fill available space in such vehicles.

Modern rechargeable lithium ion batteries typically utilize organic liquid electrolyte to carry or conduct lithium cations (Li + ) between a cathode active material and an anode active material. To further enhance battery performance, organic liquid electrolyte is replaced by solid-state electrolyte (SSE) in more modern batteries. Solid-state electrolytes could broaden the working temperature range and improve energy density of rechargeable lithium ion batteries. Rechargeable lithium ion batteries having solid-state electrolytes are known to be referred to as rechargeable solid-state lithium ion batteries.

For the majorities of known electrodes used in rechargeable solid-state lithium batteries, conductive carbon additives are utilized to obtain the desired electronic conduction pathways. However, it was found that the inclusion of carbon additives in the electrodes can stimulate the electrochemical decomposition of solid-state electrolyte, especially the sulfide-based solid-state electrolyte such as Li 10 GeP 2 S 12 (LGPS), and the decomposition products at the interface will lead to a large interfacial resistance and inferior kinetic performance.

Thus, while rechargeable solid-state lithium batteries achieve their intended purpose for use in electric and hybrid vehicles, there is a need for continuous improvement in the composition of the electrodes to obtain the desired electronic conduction pathways with minimal to no decomposition of the solid-state electrolyte (e.g. LGPS) at the interface.

SUMMARY

According to several aspects, a battery cell is provided. The battery cell includes a first electrode, a second electrode, and an ionically conductive layer sandwiched between the first electrode and the second electrode. At least one of the first electrode and the second electrode includes an electronically conductive polymer (ECP).

In an additional aspect of the present disclosure, the ECP includes π-conjugated polymeric chains.

In another aspect of the present disclosure, the ECP includes at least one of a polypyrrole (PPy), a polyaniline (PANI), a polythiophene (PT), a poly(3,4-ethylenedioxy thiophene) (PEDOT), a poly(3,4-propylenedioxy thiophene) (PProDOT) and PEDOT:poly(4-styrene sulfonate) (PEDOT:PSS), polyacetylene (PA), and poly(p-phenylenevinylene) (PPV).

In another aspect of the present disclosure, the ECP can also be further modified by functional group, such as poly(3-hexylthiophene).

In another aspect of the present disclosure, at least one of the first electrode and the second electrode, further includes a solid-state electrolyte material.

In another aspect of the present disclosure, the solid-state electrolyte (SSE) material includes at least one of a sulfide-based SSE including a Li 2 S—P 2 S 5 system and lithium argyrodite Li 6 PS 5 X, wherein X=Cl, Br, or I; an oxide-based SSE including Li 7 La 3 Zr 2 O 12 ; a polymer-based SSE including a polyethylene oxide (PEO) with LiTFSI, a nitride-based SSE including a LiSi 2 N 3 ; a hydride-based SSE including LiBH 4 —LiNH 2 ; a halide-based SSE including Li 3 OCl, a borate-based SSE including Li 2 O—B 2 O 3 —P 2 O 5 ; an inorganic SSE/polymer-based hybrid electrolyte including Li 7 La 3 Zr 2 O 12 /polyvinylidene fluoride (PVDF)/Li salt hybrid solid electrolyte; and a surface-modified SSE including Indium (In)-deposited Li 7 La 3 Zr 2 O 12 .

In another aspect of the present disclosure, the battery cell further includes a liquid electrolyte permeating the first electrode, the ionically conductive layer, and the second electrode.

In another aspect of the present disclosure, at least one of the first electrode and the second electrode includes from about 20 weight percent (wt %) to about 98 wt % of an active material, from about 0.1 wt % to about 30 wt % of the ECP, and from about 5 wt % to about 70 wt % of a solid-state electrolyte (SSE) material.

In another aspect of the present disclosure, at least one of the first electrode and the second electrode includes from about 20 weight percent (wt %) to about 98 wt % of an active material, from about 0.1 wt % to about 30 wt % of the ECP, and from about 5 wt % to about 70 wt % of a lithium salt.

In another aspect of the present disclosure, the lithium salt includes a lithium cation and at least one of a hexafluoroarsenate; a hexafluorophosphate; a tris(pentafluoroethyl)-trifluorophosphate (FAP); a perchorate; a tetrafluoroborate; a trifluoromethanesulfonate (Triflate); a bis(fluorosulfonyl)amide (FSI); a cyclo-difluoromethane-1,1-bis(sulfonyl)imide (DMSI); cyclo-difluoromethane-1,1-bis(sulfonyl)imide (HPSI); a bis(trifluoromethanesulfonyl)imide (TFSI); a bis(perfluoroethanesulfonyl)imide (SETT); a bis(oxalate)borate (BOB); a difluoro(oxalato)borate (DFOB); a bis(fluoromalonato)borate (BFMB); a tetracyanoborate (Bison); a dicyanotriazolate (DCTA), a dicyano-trifluoromethyl-imidazole (TDI); a dicyano-pentafluoroethyl)-imidazole (PDI); and other anion.

According to several aspects, an electrode is provided. The electrode includes an electrode layer having from about 20 weight % (wt %) to about 98 wt % of an electrode active material; from about 5 wt % to about 70 wt % of an ionically conductive material; and from about 0.1 wt % to about 30 wt % of an electronically conductive polymer.

In an additional aspect of the present disclosure, the electronically conductive polymer includes at least one of a polypyrrole (PPy), a Polyaniline (PANI), a polythiophene (PT), a poly(3,4-ethylenedioxy thiophene) (PEDOT), a poly(3,4-propylenedioxy thiophene) (PProDOT) and PEDOT:poly(4-styrene sulfonate) (PEDOT:PSS), polyacetylene (PA), and poly(p-phenylenevinylene) (PPV).

In another aspect of the present disclosure, the electronically conductive polymer can also be further modified by functional group, such as poly(3-hexylthiophene).

In another aspect of the present disclosure, the ionically conductive material includes a solid-state electrolyte (SSE) material comprising at least one of a sulfide-based SSE, an oxide-based SSE, a polymer-based SSE, a nitride-based SSE, a hydride-based SSE, a halide-based SSE, a borate-based SSE, an inorganic/polymer-based Hybrid electrolyte, and a surface-modified SE.

In another aspect of the present disclosure, the ionically conductive material includes a lithium salt having a lithium cation and at least one of a hexafluoroarsenate; a hexafluorophosphate; a tris(pentafluoroethyl)-trifluorophosphate (FAP); a perchorate; a tetrafluoroborate; a trifluoromethanesulfonate (Triflate); a bis(fluorosulfonyl)amide (FSI); a cyclo-difluoromethane-1,1-bis(sulfonyl)imide (DMSI); cyclo-difluoromethane-1,1-bis(sulfonyl)imide (HPSI); a bis(trifluoromethanesulfonyl)imide (TFSI); a bis(perfluoroethanesulfonyl)imide (SETT); a bis(oxalate)borate (BOB); a difluoro(oxalato)borate (DFOB); a bis(fluoromalonato)borate (BFMB); a tetracyanoborate (Bison); a dicyanotriazolate (DCTA), a dicyano-trifluoromethyl-imidazole (TDI); a dicyano-pentafluoroethyl)-imidazole (PDI)); and other anion.

In another aspect of the present disclosure, the electrode active material includes a cathode active material including at least one of: a lithium manganese oxide (LiMn 2 O 4 ); a lithium iron phosphate (LiFePO 4 ); a LiNi 0.5 Mn 15 O 4 ; a rock salt layered oxide including LiCoO 2 , LiNi x Mn y Co 1−x−y O 2 , LiNi x Mn 1−x O 2 , Li 1+x MO 2 ; a spinel such including LiMn 2 O 4 ; a polyanion cathode including LiV 2 (PO 4 ) 3 ; a coated or doped cathode material including LiNbO 3 coated LiNi 0.5 Mn 1.5 O 4

In another aspect of the present disclosure, the electrode includes of an anode active material including at least one of a carbonaceous material; a silicon; a silicon-graphite mixture; a lithium titanate (Li 4 Ti 5 O 12 ); a transition-metal; a metal oxide or metal sulfide including at least one of TiO 2 , FeS, SnO 2 ; and a lithium-Indium (Li—In).

In another aspect of the present disclosure, the electrode further includes from greater than 0 wt % to about 15 wt % of an electronically conductive additive. The electronically conductive additive includes at least one of a carbon black, a graphite, a graphene, a graphene oxide, a Super P, an acetylene black, a carbon nanofiber, and a carbon nanotube.

In another aspect of the present disclosure, the electrode further includes from greater than 0 wt % to about 15 wt % of a binder, wherein the binder includes at least one of a poly(tetrafluoroethylene) (PTFE), a sodium carboxymethyl cellulose (CMC), a styrene-butadiene rubber (SBR), a poly(vinylidene fluoride) (PVDF), a nitrile butadiene rubber (NBR), a styrene ethylene butylene styrene copolymer (SEBS), and a styrene butadiene styrene copolymer (SBS).

According to several aspects, a battery having an electrode. The electrode includes from about 20 weight % (wt %) to about 98 wt % of an electrode active material; from about 5 wt % to about 70 wt % of an ionically conductive material; and from about 0.1 wt % to about 30 wt % of an electronically conductive polymer (ECP). The ionically conductive material includes at least one of a solid-state electrolyte material and a lithium salt. The ECP includes at least one of a polypyrrole (PPy), a polyaniline (PANI), a polythiophene (PT), a poly(3,4-ethylenedioxy thiophene) (PEDOT), a poly(3,4-propylenedioxy thiophene) (PProDOT) and PEDOT:poly(4-styrene sulfonate) (PEDOT:PSS), polyacetylene (PA), and poly(p-phenylenevinylene) (PPV).

Further areas of applicability will become apparent from the description provided herein. It should be understood that the description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure in any way.

FIG. 1 is a diagrammatic representation of a rechargeable solid-state lithium ion battery cell having an electrode comprising of an electronically conductive polymer, according to an exemplary embodiment;

FIG. 2 is a diagrammatic representation of an exemplary electrode comprising of an electronically conductive polymer, according to an exemplary embodiment; and

FIG. 3 is a diagrammatic representation of a detailed portion of the electrode of FIG. 2 , according to an exemplary embodiment.

DETAILED DESCRIPTION

The following description is merely exemplary in nature and is not intended to limit the present disclosure, application, or uses. The illustrated embodiments are disclosed with reference to the drawings, wherein like numerals indicate corresponding parts throughout the several drawings. The figures are not necessarily to scale and some features may be exaggerated or minimized to show details of particular features. The specific structural and functional details disclosed are not intended to be interpreted as limiting, but as a representative basis for teaching one skilled in the art as to how to practice the disclosed concepts.

FIG. 1 shows an exemplary embodiment of a diagrammatic representation of a rechargeable solid-state lithium ion battery cell, generally indicated by reference number 100 (solid-state battery cell 100 ), having at least one electrode comprising of an electronically conductive polymer. The solid- state battery cell 100 includes a negative electrode 102 , a positive electrode 104 , and an ionically conductive layer 106 having a first ionically conductive material 108 a disposed between the negative electrode 102 and the positive electrode 104 . The negative electrode 102 is also referred to as an anode 102 and the positive electrode 104 is also referred to as a cathode 104 . A plurality of the solid- state battery cells 100 may be folded or stacked to form a rechargeable solid-state lithium battery, and achieve a desired battery voltage, power and energy.

The negative electrode 102 includes an anode layer 110 and a negative current collector 112 . The anode layer 110 is preferably formed of a second ionically conductive material 108 b , an anode active material 113 , and a first electronically conductive polymer 114 a in intimate contact with the second ionically conductive material 108 b and anode active material 113 . The second ionically conductive material 108 b may be the same as that of the first ionically conductive material 108 a in the ionically conductive layer 106 . Alternatively, the second ionically conductive material 108 b may be different from that of the first ionically conductive material 108 a in the ionically conductive layer 106 .

The positive electrode 104 includes a cathode layer 116 and a positive current collector 118 . The cathode layer 116 is preferably formed of a third ionically conductive material 108 c , a cathode active material 117 , a second electronically conductive polymer 114 b in intimate contact with the third ionically conductive material 108 c and cathode active material 117 . The third ionically conductive material 108 c may be the same as that of the first ionically conductive material 108 a in the ionically conductive layer 106 or the second ionically conductive material 108 b in the anode layer 110 . Alternatively, the third ionically conductive material 108 c may be different from that of the first ionically conductive material 108 a in the ionically conductive layer 106 and that of the second ionically conductive material 108 b in the anode layer 110 .

Preferably the first, second, and third ionically

conductive materials

108 a , 108 b , 108 c possess a high ionically conductivity and low electronic conductivity, and exhibit a good chemical stability. Preferred ionically

conductive material

108 a , 108 b , 108 c includes one or more solid-state electrolyte materials selected from the following group of solid-state electrolytes (SSE):

Sulfide-based SSE, such as: Li 2 S—P 2 S 5 , Li 2 S—P 2 S 5 -MS x , LGPS (Li 10 GeP 2 S 12 ), thio-LISICON (Li 3.25 Ge 0.25 P 0.75 S 4 ), Li 3.4 Si 0.4 P 0.6 S 4 , Li 10 GeP 2 S 11.7 O 0.3 , lithium argyrodite Li 6 PS 5 X (X=Cl, Br, or I), Li 9.54 Si 1.74 P 1.44 S 11.7 O 10.3 , Li 9.6 P 3 S 12 , Li 7 P 3 S 11 , Li 9 P 3 S 9 O 3 , Li 10.35 Ge 1.35 P 1.65 S 12 , Li 10.35 Si 1.35 P 1.65 S 12 , Li 9.81 Sn 0.81 P 2.19 S 12 , Li 10 (Si 0.5 Ge 0.5 )P 2 S 12 , Li 10 (Ge 0.5 Sn 0.5 )P 2 S 12 , Li 10 (Si 0.5 Sn 0.5 )P 2 S 12 ; Oxide-based SSE, such as: perovskite type (Li 3x La 2/3−x TiO 3 ), NASICON type (LiTi 2 (PO 4 ) 3 ), Li 1+x Al x Ti 2−x (PO 4 ) 3 (LATP), Li 1+x Al x Ge 2−x (PO 4 ) 3 (LAGP), Li 1+x Y x Zr 2−x (PO 4 ) 3 (LYZP), LISICON type (Li 14 Zn(GeO 4 ) 4 ), Garnet type (Li 6.5 La 3 Zr 1.75 Te 0.25 O 12 ); Polymer-based SSE, such as: the polymer host together with a lithium salt act as a solid solvent. polymer: PEO, PPO, PEG, PMMA, PAN, PVDF, PVDF-HFP, PVC; Nitride-based SSE, such as: Li 3 N, Li 7 PN 4 , LiSi 2 N 3 ; Hydride-based SSE, such as: LiBH 4 , LiBH 4 —LiX (X=Cl, Br or I), LiNH 2 , Li 2 NH, LiBH 4 —LiNH 2 , Li 3 AlH 6 ; Halide-based, such as: LiI, Li 2 CdCl 4 , Li 2 MgCl 4 , Li 2 Cdl 4 , Li 2 Znl 4 , Li 3 OCl Borate-based SSE, such as: Li 2 B 4 O 7 , Li 2 O—B 2 O 3 —P 2 O 5 ; Inorganic SSE/polymer-based hybrid electrolyte such as Li 7 La 3 Zr 2 O 12 /polyvinylidene fluoride (PVDF)/Li salt hybrid solid electrolyte; and Surface-modified/doped SSE such as Indium (In)-deposited Li 7 La 3 Zr 2 O 12

The solid- state battery cell 100 includes a first separator interlayer 120 a disposed between the negative electrode 102 and the ionically conductive layer 106 such that first separator interlayer 120 a is in direct intimate contact with both the negative electrode 102 and the ionically conductive layer 106 . A second separator interlayer 120 b is disposed between the positive electrode 104 and the solid- state electrolyte layer 106 such that the second separator interlayer 120 b is in direct intimate contact with both the positive electrode 104 and the solid- state electrolyte layer 106 .

The first and second separator interlayers

120 a , 120 b may be formed of one or more lithium ions (Li + ) ionically conductive materials including, but are not limited to, one or more of a polymer-based material, an inorganic material, a polymer-inorganic hybrid, and a metal and/or metal oxide material. The polymer-based material includes one or more of a poly(ethylene glycol) methyl-ether acrylate mixed with Al 2 O 3 and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), polyethylene oxide (PEO) with LiTFSI, poly(vinylidene fluoride) copolymer with hexafluoropropylene (PVDF-HFP)-based gel electrolyte. The inorganic material includes 70% Li 2 S-29% P 2 S 5 -1% P 2 O 5 . The polymer-inorganic hybrid material includes a mixture of PEO, LiTFSI, and 75% Li 2 S-24% P 2 S 5 -1% P 2 O 5 (LPOS) in mol %. The metal and metal oxide material include one or more of Nb, Al, Si and Al 2 O 3 .

While a first separator interlayer 120 a and a second separator interlayer 120 b are shown, an alternative embodiment of the solid state battery 100 may include only a single separator interlayer, which may be disposed between the negative electrode 102 and the ionically conductive layer 106 or disposed between the positive electrode 104 and the ionically conductive layer 106 . Yet another alternative embodiment of the solid- state battery 100 may include no separator interlayers.

The solid- state battery cell 100 may include a liquid electrolyte permeating the anode layer 110 , the ionically conductive layer 106 , and the cathode layer 116 to aid in the facilitation of the transfer of lithium ions between the anode 102 and cathode 104 . The liquid electrolyte 120 includes, but not limited to, ionic liquids such as Li (triethylene glycol dimethyl ether) bis(trifluoromethanesulfonyl)imide (Li(G3)TFSI)); carbonate-based electrolytes (such as LiPF 6 -EC/DEC with additives), and concentrated electrolytes (such as LiTFSI in acetonitrile).

FIG. 2 is a diagrammatic representation of an exemplary solid-state lithium ion battery electrode 200 (electrode 200 ) having an electrode layer 201 comprising of an electrode active material 202 , an ionically conductive material 204 , and an electronically conductive polymer 206 . The electrode 200 includes a current collector 208 in coextensive contact with the electrode layer 201 . The electrode 200 may be that of the negative electrode 102 or that of the positive electrode 104 of the battery cell 100 of FIG. 1 depending on the composition of the electrode active material 202 in the electrode layer 201 .

In one embodiment the electrode layer 201 comprising an electrode active material 202 , a solid-state electrolyte material as the ionically conductive material 204 , and an electronically conductive polymer 206 . The weight percent (wt %) of the electrode active material 202 is in a range from about 20 wt % to about 98 wt %; the wt % of the solid electrolyte material is in a range of from about 5 weight wt % to about 70 wt %; and the wt % of the electronically conductive polymer 206 is in a range from about 0.1 wt % to about 30 wt %.

In another embodiment the electrode 200 comprises an electrode active material 202 , a lithium salt as the ionically conductive material 204 , and an electronically conductive polymer 206 . The weight percent (wt %) of the active material is in a range of from about 20 wt % to about 98 wt %; the wt % of the lithium salt is in a range of from about 5 wt % to about 70 wt %; and the wt % of the electronically conductive polymer is in a range from about 0.1 wt % to about 30 wt %. The lithium salt includes a lithium cation and at least one of a hexafluoroarsenate; hexafluorophosphate; tris(pentafluoroethyl)-trifluorophosphate (FAP); perchorate; tetrafluoroborate, trifluoromethanesulfonate (Triflate); bis(fluorosulfonyl)amide (FSI); cyclo-difluoromethane-1,1-bis(sulfonyl)imide (DMSI); cyclo-difluoromethane-1,1-bis(sulfonyl)imide (HPSI), bis(trifluoromethanesulfonyl)imide (TFSI); bis(perfluoroethanesulfonyl)imide (SETT); bis(oxalate)borate (BOB); difluoro(oxalato)borate (DFOB); bis(fluoromalonato)borate (BFMB); tetracyanoborate (Bison); dicyanotriazolate (DCTA), dicyano-trifluoromethyl-imidazole (TDI); and dicyano-pentafluoroethyl)-imidazole (PDI); and other anion.

FIG. 3 is a detailed portion of the electrode 200 of FIG. 2 showing the interaction between the electrode active material 202 , ionically conductive material 204 , and electronically conductive polymer 206 . Lithium ions (Li + ) are shown moving between the electrode active material 202 and the ionically conductive material 204 . Electrons (e−) are shown moving between the electrode active material 202 and the electronically conductive polymer 206 . The electronically conductive polymer 206 provides a 3D electronically conductive network for electron transfer within the solid- state battery cell 100 . Electronically conductive polymers are attractive organic materials due to their high electrical conductivity (up to 10 3 S/cm), easy processing, good affinity to many other materials, and controllable thickness and morphology. Representative electronically conductive polymers based on π-conjugated structures includes: polypyrrole (PPy), polyaniline (PANI), polythiophene (PT), poly(3,4-ethylenedioxy thiophene) (PEDOT), poly(3,4-propylenedioxy thiophene) (PProDOT) and PEDOT:poly(4-styrene sulfonate) (PEDOT:PSS), polyacetylene (PA), and poly(p-phenylenevinylene) (PPV). The electronically conductive polymer may be modified by other functional group, such as poly(3-hexylthiophene.

Electronically conductive additives 210 such as carbon black, graphite, graphene, graphene oxide, Super P, acetylene black, carbon nanofibers, and carbon nanotubes may also be added to further enhance the electronical conductivity of electrode 200 . The wt % of electronically conductive additive 210 is in a range of from greater than 0 to about 15 wt %. Binders 212 such as poly(tetrafluoroethylene) (PTFE), sodium carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR), poly(vinylidene fluoride) (PVDF), nitrile butadiene rubber (NBR), styrene ethylene butylene styrene copolymer (SEBS), and styrene butadiene styrene copolymer (SBS) may also be added into electrode 200 to further enhance the mechanical integrity of electrode. The wt % of binder is in a range of from greater than 0 to about 15 wt %.

Referring back to FIG. 2 , in one exemplary embodiment, the electrode 200 is that of the negative electrode 102 of the solid- state battery cell 100 of FIG. 1 . In this exemplary embodiment, the electrode layer 201 is an anode layer 110 having an anode active material 113 , the ionically conductive material 204 is at least one of a solid- state electrolyte material 108 b or a lithium salt, and the electronically conductive polymer 206 is a first electronically conductive polymer 114 a , and the current collector 208 is a negative current collector 112 . The anode layer 110 includes a thickness of between about 1 micrometer and about 1000 micrometers. The negative current collector 112 includes a thickness of between about 4 micrometers and about 100 micrometers. The negative current collector 113 is preferably a thin-film copper or nickel foil that coextensively contacts the anode active material 113 , the solid- state electrolyte material 108 b , and the electronically conductive polymer 114 a in the negative electrode 102 .

The anode active material 113 comprises a lithium host material that is capable of storing lithium at a lower electrochemical potential relative to the cathode active material 117 . The anode active material 113 may include a carbonaceous material such as graphite, hard carbon, and soft carbon; silicon; silicon-graphite mixture; lithium titanate (Li 4 Ti 5 O 12 ); a transition-metal such as Sn; a metal oxide or metal sulfide such as TiO 2 , FeS, SnO 2 ; and other lithium-accepting anode materials such as lithium-Indium (Li—In).

In another exemplary embodiment, the electrode 200 is that of the positive electrode 104 of the solid- state battery cell 100 of FIG. 1 . In this embodiment, the electrode layer 201 is a cathode layer 116 having a cathode active material 117 , the ionically conductive material 204 is at least one of a solid- state electrolyte material 108 c or a lithium salt, the electronically conductive polymer 206 is a second electronically conductive polymer 114 b , and the current collector 208 is a positive current collector 118 . The cathode layer 116 includes a thickness of between about 1 micrometer and about 1000 micrometers. The

CLAIMS

Claims ( 20 )

What is claimed is:

1 . A battery cell, comprising:

a first electrode; a second electrode; and an ionically conductive layer sandwiched between the first electrode and the second electrode; wherein at least one of the first electrode and the second electrode, comprises an electronically conductive polymer (ECP).

2 . The battery cell of claim 1 , wherein the ECP comprises a π-conjugated polymeric chain.

3 . The battery cell of claim 2 , wherein the ECP comprises at least one of a polypyrrole (PPy), a polyaniline (PANI), a polythiophene (PT), a poly(3,4-ethylenedioxy thiophene) (PEDOT), a poly(3,4-propylenedioxy thiophene) (PProDOT), PEDOT:poly(4-styrene sulfonate) (PEDOT:PSS), polyacetylene (PA), a poly(p-phenylenevinylene) (PPV), and a poly(3-hexylthiophene)

4 . The battery cell of claim 1 , further comprising a separator interlayer in direct intimate contact with the ionically conductive layer and one of the first electrode and the second electrode.

5 . The battery cell of claim 1 , wherein the at least one of the first electrode and the second electrode, further comprises a solid-state electrolyte material.

6 . The battery cell of claim 5 , wherein the solid-state electrolyte (SSE) material comprises at least one of a sulfide-based SSE including a Li 2 S—P 2 S 5 system and lithium argyrodite Li 6 PS 5 X, wherein X=Cl, Br, or I; an oxide-based SSE including Li 7 La 3 Zr 2 O 12 ; a polymer-based SSE including a polyethylene oxide (PEO) with LiTFSI, a nitride-based SSE including a LiSi 2 N 3 ; a hydride-based SSE including LiBH 4 —LiNH 2 ; a halide-based SSE including Li 3 OCl, a borate-based SSE including Li 2 O—B 2 O 3 —P 2 O 5 ; an inorganic SSE/polymer-based hybrid electrolyte including Li 7 La 3 Zr 2 O 12 /polyvinylidene fluoride (PVDF)/Li salt hybrid solid electrolyte; and a surface-modified SSE including Indium (In)-deposited Li 7 La 3 Zr 2 O 12 .

7 . The battery cell of claim 6 , further comprising a liquid electrolyte permeating the first anode, the ionically conductive layer, and the second anode.

8 . The battery cell of claim 1 , wherein the at least one of the first electrode and the second electrode comprises from about 20 weight percent (wt %) to about 98 wt % of an active material, from about 0.1 wt % to about 30 wt % of the ECP, and from about 5 wt % to about 70 wt % of a solid-state electrolyte (SSE) material.

9 . The battery cell of claim 1 , wherein the at least one of the first electrode and the second electrode comprises from about 20 weight percent (wt %) to about 98 wt % of an active material, from about 0.1 wt % to about 30 wt % of the ECP, and from about 5 wt % to about 70 wt % of a lithium salt.

10 . The battery cell of claim 9 , wherein the lithium salt comprises a lithium cation and at least one of a hexafluoroarsenate; a hexafluorophosphate; a tris(pentafluoroethyl)-trifluorophosphate (FAP); a perchorate; a tetrafluoroborate; a trifluoromethanesulfonate (Triflate); a bis(fluorosulfonyl)amide (FSI); a cyclo-difluoromethane-1,1-bis(sulfonyl)imide (DMSI); cyclo-difluoromethane-1,1-bis(sulfonyl)imide (HPSI); a bis(trifluoromethanesulfonyl)imide (TFSI); a bis(perfluoroethanesulfonyl)imide (BETI), a bis(oxalate)borate (BOB); a difluoro(oxalato)borate (DFOB); a bis(fluoromalonato)borate (BFMB); a tetracyanoborate (Bison); a dicyanotriazolate (DCTA), a dicyano-trifluoromethyl-imidazole (TDI); and a dicyano-pentafluoroethyl)-imidazole (PDI).

11 . An electrode comprising:

an electrode layer having: from about 20 weight % (wt %) to about 98 wt % of an electrode active material; from about 5 wt % to about 70 wt % of an ionically conductive material; and from about 0.1 wt % to about 30 wt % of an electronically conductive polymer.

12 . The electrode of claim 11 , wherein the electronically conductive polymer comprises at least one of a polypyrrole (PPy), a polyaniline (PANI), a polythiophene (PT), a poly(3,4-ethylenedioxy thiophene) (PEDOT), a poly(3,4-propylenedioxy thiophene) (PProDOT) and a PEDOT:poly(4-styrene sulfonate) (PEDOT:PSS), a polyacetylene (PA), a poly(p-phenylenevinylene) (PPV), and a poly(3-hexylthiophene).

13 . The electrode of claim 12 , wherein the electrode active material comprises a lithium transition-metal oxide.

14 . The electrode of claim 12 , wherein the ionically conductive material comprises a

solid-state electrolyte (SSE) material comprising at least one of a Sulfide-based SSE, an Oxide-based SSE, a Polymer-based SSE, a Nitride-based SSE, a Hydride-based SSE, a Halide-based SSE, a Borate-based SSE, an Inorganic SSE, a Polymer-based Hybrid electrolyte, and a Surface-Modified SE.

15 . The electrode of claim 12 , wherein the ionically conductive material comprises a lithium salt having a lithium cation and at least one of a hexafluoroarsenate; a hexafluorophosphate; a tris(pentafluoroethyl)-trifluorophosphate (FAP); a perchorate; a tetrafluoroborate; a trifluoromethanesulfonate (Triflate); a bis(fluorosulfonyl)amide (FSI); a cyclo-difluoromethane-1,1-bis(sulfonyl)imide (DMSI); cyclo-difluoromethane-1,1-bis(sulfonyl)imide (HPSI); a bis(trifluoromethanesulfonyl)imide (TFSI); a bis(perfluoroethanesulfonyl)imide (SETT); a bis(oxalate)borate (BOB), a difluoro(oxalato)borate (DFOB); a bis(fluoromalonato)borate (BFMB); a tetracyanoborate (Bison); a dicyanotriazolate (DCTA); a dicyano-trifluoromethyl-imidazole (TDI); a dicyano-pentafluoroethyl)-imidazole (PDI).

16 . The electrode of claim 12 , wherein the electrode active material comprises a cathode active material including at least one of:

a lithium manganese oxide (LiMn 2 O 4 ); a lithium iron phosphate (LiFePO 4 ); a LiNi 0.5 Mn 1.5 O 4 ; a LiNbO3 coated LiNi 0.5 Mn 1.5 O 4 ; a rock salt layered oxide including LiCoO 2 , LiNi x Mn y Co 1−x−y O 2 , LiNi x Mn 1−x O 2 , Li 1+x MO 2 ; a spinel such including LiMn 2 O 4 ; and a polyanion cathode including LiV 2 (PO 4 ) 3 .

17 . The electrode of claim 12 , wherein the electrode comprises of an anode active material including at least one of a carbonaceous material; a silicon; a silicon-graphite mixture; a lithium titanate (Li 4 Ti 5 O 12 ); a transition-metal; a metal oxide or sulfide including at least one of TiO 2 , FeS, SnO 2 ; and a lithium-Indium (Li—In).

18 . The electrode of claim 12 , further comprising:

from greater than 0 wt % to about 15 wt % of an electronically conductive additive, wherein the electronically conductive additive includes at least one of a carbon black, a graphite, a graphene, a graphene oxide, a Super P, an acetylene black, a carbon nanofiber, and a carbon nanotube.

19 . The electrode of claim 12 , further comprising:

from greater than 0 wt % to about 15 wt % of a binder, wherein the binder includes at least one of a poly(tetrafluoroethylene) (PTFE), a sodium carboxymethyl cellulose (CMC), a styrene-butadiene rubber (SBR), a poly(vinylidene fluoride) (PVDF), a nitrile butadiene rubber (NBR), a styrene ethylene butylene styrene copolymer (SEBS), and a styrene butadiene styrene copolymer (SBS).

20 . A battery comprising an electrode, wherein the electrode includes:

from about 20 weight % (wt %) to about 98 wt % of an electrode active material; from about 5 wt % to about 70 wt % of an ionically conductive material; and from about 0.1 wt % to about 30 wt % of an electronically conductive polymer (ECP); wherein the ionically conductive material includes at least one of a solid-state electrolyte material and a lithium salt; and wherein the ECP comprises at least one of a polypyrrole (PPy), a polyaniline (PANI), a polythiophene (PT), a poly(3,4-ethylenedioxy thiophene) (PEDOT), a poly(3,4-propylenedioxy thiophene) (PProDOT) and PEDOT:poly(4-styrene sulfonate) (PEDOT:PSS), polyacetylene (PA), and poly(p-phenylenevinylene) (PPV).

US16/817,012

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Solid-state battery having an electrode comprising of an electronically conductive polymer

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2024-09-06

远景动力技术(鄂尔多斯市)有限公司

All-solid-state battery pole piece and preparation method thereof and all-solid-state battery

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2021-02-23

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2024-04-19

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