ABSTRACT
Abstract
A composite electrode for use in an all-solid-state electrochemical cell that cycles lithium ions is provided. The composite electrode comprises a solid-state electroactive material that undergoes volumetric expansion and contraction during cycling of the electrochemical cell and a solid-state electrolyte. The solid-state electroactive material is in the form of a plurality of particles and each particle has a plurality of internal pores formed therewithin. Each particle has an average porosity ranging from about 10% to about 75%, and the composite electrode has an interparticle porosity between the solid-state electroactive material and solid-state electrolyte particles ranging from about 5% to about 40%. The intraparticle pores and the interparticle porosity accommodate the volumetric expansion and contraction of the solid-state electroactive material so to minimize outward expansion of the electroactive particles, micro-cracking of the solid-state electrolyte, and delamination within the electrochemical cell.
Description
INTRODUCTION
This section provides background information related to the present disclosure which is not necessarily prior art.
The present disclosure relates to high-energy-density all-solid-state batteries including composite electrodes comprising solid-state electroactive materials that undergo volumetric expansion and contraction during cycling of the respective battery. More specifically, the solid-state electroactive materials are porous so to accommodate the volumetric expansion and contraction of the solid-state electroactive material inwardly and minimize outward expansion of the solid-state electroactive material and micro-cracking within the batteries.
High-energy density, electrochemical cells, such as lithium-ion batteries, can be used in a variety of consumer products and vehicles, including as Hybrid Electric Vehicles (âHEVsâ) and Electric Vehicles (âEVsâ). Typical lithium-ion and lithium-sulfur batteries include two electrodes, an electrolyte material, and a separator. One electrode serves as a positive electrode or cathode and another serves as a negative electrode or anode. Conventional rechargeable lithium-ion batteries operate by reversibly passing lithium ions back and forth between the negative electrode and the positive electrode. Lithium ions move from the positive electrode to the negative electrode during charging of the battery, and in the opposite direction when discharging the battery. A separator and an electrolyte may be disposed between the negative and positive electrodes. The electrolyte is suitable for conducting lithium ions and, like the two electrodes, may be in solid and/or liquid form.
All-solid-state batteries, including solid-state electrolytes suitable for conducting lithium ions between solid-state positive and negative electrodes while also physically separating the positive and negative electrodes, offer several advantages compared to conventional liquid-state batteries. For example, all-solid-state batteries are made with solid-state electrolytes which are generally non-volatile and non-flammable so to allow the all-solid-state batteries to be cycled under harsher conditions than liquid-state batteries with diminished potential for thermal runaway. All-solid-state batteries may thus also have further advantages, such as operation without thermal management systems, long shelf life with zero self-discharge, and a reduced need for packaging. However, all-solid-state batteries may have comparatively low energy density levels (e.g., about 230 Wh/kg for a graphite/NMC622 solid-state battery) because of void spaces between solid-state electroactive material particles not being filled by, for example, a liquid electrolyte, or an inflexibility in accommodating various stresses and strains within the battery.
As such, it may be desirable to incorporate high-capacity electrode materials such as silicon and/or sulfur to account for the comparatively low energy densities associated with all-solid-state batteries. However, the high-capacity electrode materials may present other challenges. For example, large volume changes, including volume expansion and contraction, of high-capacity electrode materials comprising silicon during lithiation and/or delithiation can potentially result in physical damage to the solid-state components that tend to be inflexible, including wrinkling, fracture, cracking, and delamination of the stacked layers forming the all-solid-state batteries. Accordingly, it would be desirable to develop high-performance electrode materials for robust, high-energy-density all-solid-state batteries.
SUMMARY
This section provides a general summary of the disclosure, and is not a comprehensive disclosure of its full scope or all of its features.
The present disclosure relates to low expansion electrodes for solid-state lithium ion batteries.
In various aspects, the present disclosure provides a composite electrode for use in an all-solid-state electrochemical cell that cycles lithium ions. The composite electrode includes a solid-state electroactive material and a solid-state electrolyte. The solid-state electroactive material includes a plurality of particles that undergoes volumetric expansion and contraction during cycling of the electrochemical cell. Each particle of the plurality of particles has a plurality of internal pores formed therein. The composite electrode has an average interparticle porosity between respective particles of the plurality of particles of the solid-state electroactive material and the solid-state electrolyte ranging from greater than or equal to about 0% to less than or equal to about 40%. The plurality of internal pores of the solid-state electroactive material accommodate the volumetric expansion and contraction of the solid-state electroactive material inwardly so to minimize outward expansion of the plurality of particles and together with the interparticle porosity minimizes micro-cracking of the composite electrode.
In one aspect, the solid-state electroactive material includes silicon and each particle of the plurality of particles has an average porosity that ranges from greater than or equal to about 10% to less than or equal to about 75%.
In one aspect, the solid-state electroactive material includes one or more of the following: (i) silicon oxide (SiO 2 ), where each solid-state electroactive material particle has an average porosity ranging from greater than or equal to about 10% to less than or equal to about 60%; (ii) sulfur (S), where each solid-state electroactive material particle has an average porosity ranging from greater than or equal to about 10% to less than or equal to about 45%; and ferrous disulfide (FeS 2 ), where each solid-state electroactive material has an average porosity ranging from greater than or equal to about 10% to less than or equal to about 60%.
In one aspect, each particle of the plurality of particles has a honeycomb-like structure.
In one aspect, each particle of the plurality of particles has a round structure.
In one aspect, the solid-state electrolyte is from the group consisting of: Li 10 MP 2 S 12 (where M is selected from silicon (Si), tin (Sn), and germanium (Ge)), (Li 2 S) x (MS 2 ) y (P 2 S 5 ) 100âxây (where M is selected from silicon (Si), tin (Sn), and germanium (Ge) and where 40â¤xâ¤85, 0â¤yâ¤40, and 100âxây>0), polyethylene oxide (PEO), polyacrylonitrile (PAN), lithium lanthanum titanate (Li 0.67âx La 3x TiO 3 ) (LLTO), lithium lanthanum zirconium oxide (Li 7 La 3 Zr 2 O 12 ) (LLZO), lithium aluminum titanium phosphate (Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 ) (LATP), oxide glass, and combinations thereof.
In one aspect, if the solid-state electrolyte includes Li 10 MP 2 S 12 , the solid-state electrolyte further includes one or more dopants selected from the group consisting of lithium chloride (LiCl), lithium iodide (LiI), and combinations thereof.
In one aspect, if the solid-state electrolyte includes polyethylene oxide (PEO), the solid-state electrolyte further includes one or more salts selected from the group consisting of lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI) and combinations thereof.
In one aspect, if the solid-state electrolyte includes polyacrylonitrile (PAN), the solid-state electrolyte further includes one or more salts selected from the group consisting of lithium perchlorate (LiCO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI) and combinations thereof.
In one aspect, the composite electrode includes greater than or equal to about 30 wt. % to less than or equal to about 90 wt. % of the solid-state electroactive material, and greater than or equal to about 10 wt. % to less than or equal to about 70 wt. % of the solid-state electrolyte.
In one aspect, the composite electrode further includes at least one of: a conductive additive selected from the group consisting of: graphite, carbon-based materials, powdered nickel, conductive metal particles, conductive polymers, and combinations thereof; a binder selected from the group consisting of: polyvinylidene difluoride (PVdF), ethylene propylene diene monomer (EPDM) rubber, carboxymethoxyl cellulose (CMC), nitrile butadiene rubber (NBR), lithium polyacrylate (LiPAA), sodium polyacrylate (NaPAA), sodium alginate, lithium alginate, and combinations thereof; and a reinforcing filler selected from the group consisting of: silica-based glass fibers, alumina fibers, boron nitride fibers, thermoplastic polymer fibers, and combinations thereof.
In one aspect, the composite electrode includes greater than or equal to about 0 wt. % to less than or equal to about 25 wt. % of the conductive additive; greater than or equal to about 0 wt. % to less than or equal to about 20 wt. % of the binder; and greater than or equal to about 0 wt. % to less than or equal to about 40 wt. % of reinforcing filler.
In various other aspects, the present disclosure provides an all-solid-state electrochemical cell that cycles lithium ions. The all-solid-state electrochemical cell includes a first solid-state electrode, a second solid-state electrode opposing the first solid-state electrode, and a separator disposed between the first solid-state electrode and the second solid-state electrode. The first solid-state electrode includes a solid-state electroactive material and a solid-state electrolyte. The solid-state electroactive material is in the form of a plurality of particles that undergoes volumetric expansion and contraction during cycling of the electrochemical cell. Each particle of the plurality of particles includes a plurality of intraparticle pores. Each particle of the plurality of particles may have an average porosity ranging from greater than or equal to about 10% to less than or equal to about 75%. The intraparticle pores of the solid-state electroactive material accommodate the volumetric expansion and contraction of the solid-state electroactive material inwardly so to minimize outward expansion of the plurality of particles in the first solid-state electrode. The first solid-state electrode has an average interparticle porosity between respective particles of the plurality of particles of the solid-state electroactive material and the solid-state electrolyte ranging from greater than or equal to about 0% to less than or equal to about 40%. The interparticle porosity together with the internal pores of the solid-state electroactive material minimizes micro-cracking and delamination within the all-solid-state electrochemical cell.
In one aspect, the solid-state electroactive material may be a first solid-state electroactive material that is selected from the group consisting of: silicon (Si), silicon dioxide (SiO 2 ), tin (Sn), ferrous disulfide (FeS 2 ), ferrous sulfide (Fe 1âx S, where 0â¤xâ¤0.2), one or more carbon lithium hosts, and combinations thereof; and the second solid-state electrode may include a second solid-state electroactive material that is selected from the group consisting of: nickel manganese cobalt oxide (NMC), lithium manganese nickel metal oxide (LMNO), lithium manganese oxide (LiMn 2 O 2 ) (LMO), lithium iron phosphate (LiFePO 4 ) (LFP), and combinations thereof.
In one aspect, the solid-state electroactive material may be a first solid-state electroactive material that is selected from the group consisting of: sulfur (S), ferrous sulfide (FeS 2 ), ferrous fluoride (FeF 2 ), and combinations thereof; and the second solid-state electrode may include a second solid-state electroactive material that includes lithium metal.
In one aspect, the solid-state electroactive material is a first solid-state electroactive material and the solid-state electrolyte is a first solid-state electrolyte, and the second electrode comprises a second solid-state electroactive material and a second solid-state electrolyte.
In one aspect, the separator is formed by one of the first and second solid-state electrolytes.
In one aspect, the plurality of particles is a plurality of first particles and the second solid-state electroactive material is in the form of a plurality of second particles and each particle of the plurality of second particles has an average porosity ranging from greater than or equal to about 10% to less than or equal to about 75%.
In one aspect, the first solid-state electroactive material is selected from the group consisting of: sulfur (S), ferrous sulfide (FeS 2 ), ferrous fluoride (FeF 2 ), and combinations thereof, and the second solid-state electroactive material is selected from the group consisting of silicon, silicon dioxide (SiO 2 ), tin (Sn), ferrous disulfide (FeS 2 ), ferrous sulfide (Fe 1âx S, where 0â¤xâ¤0.2), one or more carbon lithium hosts, and combinations thereof.
In one aspect, the first solid-state electroactive material is sulfur and each first particle has a porosity ranging from greater than or equal to about 10 wt. % to less than or equal to about 45 wt. %.
In one aspect, the separator is formed from a solid-state electrolyte selected from the group consisting of: Li 10 MP 2 S 12 (where M is selected from silicon (Si), tin (Sn), and germanium (Ge)), (Li 2 S) x (MS 2 ) y (P 2 S 5 ) 100âxây (where M is selected from silicon (Si), tin (Sn), and germanium (Ge) and where 40â¤xâ¤90, 0â¤yâ¤40, and 100âxây>0), polyethylene oxide (PEO), polyacrylonitrile (PAN), lithium lanthanum titanate (Li 0.67âx La 3x TiO 3 ) (LLTO), lithium lanthanum zirconium oxide (Li 7 La 3 Zr 2 O 12 ) (LLZO), lithium aluminum titanium phosphate (Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 ) (LATP), oxide glass, and combinations thereof.
In one aspect, if the solid-state electrolyte includes Li 10 MP 2 S 12 , the solid-state electrolyte further includes one or more dopants selected from the group consisting of lithium chloride (LiCl), lithium iodide (LiI), and combinations thereof.
In one aspect, if the solid-state electrolyte includes polyethylene oxide (PEO), the solid-state electrolyte further includes one or more salts selected from the group consisting of lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI) and combinations thereof.
In one aspect, if the solid-state electrolyte includes polyacrylonitrile (PAN), the solid-state electrolyte further includes one or more salts selected from the group consisting of lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI) and combinations thereof.
Further areas of applicability will become apparent from the description provided herein. The description and specific examples in this summary are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure.
DRAWINGS
The drawings described herein are for illustrative purposes only of selected embodiments and not all possible implementations, and are not intended to limit the scope of the present disclosure.
FIG. 1 is a schematic of an example of an all-solid-state electrochemical battery cell;</d
INTRODUCTION
This section provides background information related to the present disclosure which is not necessarily prior art.
The present disclosure relates to high-energy-density all-solid-state batteries including composite electrodes comprising solid-state electroactive materials that undergo volumetric expansion and contraction during cycling of the respective battery. More specifically, the solid-state electroactive materials are porous so to accommodate the volumetric expansion and contraction of the solid-state electroactive material inwardly and minimize outward expansion of the solid-state electroactive material and micro-cracking within the batteries.
High-energy density, electrochemical cells, such as lithium-ion batteries, can be used in a variety of consumer products and vehicles, including as Hybrid Electric Vehicles (âHEVsâ) and Electric Vehicles (âEVsâ). Typical lithium-ion and lithium-sulfur batteries include two electrodes, an electrolyte material, and a separator. One electrode serves as a positive electrode or cathode and another serves as a negative electrode or anode. Conventional rechargeable lithium-ion batteries operate by reversibly passing lithium ions back and forth between the negative electrode and the positive electrode. Lithium ions move from the positive electrode to the negative electrode during charging of the battery, and in the opposite direction when discharging the battery. A separator and an electrolyte may be disposed between the negative and positive electrodes. The electrolyte is suitable for conducting lithium ions and, like the two electrodes, may be in solid and/or liquid form.
All-solid-state batteries, including solid-state electrolytes suitable for conducting lithium ions between solid-state positive and negative electrodes while also physically separating the positive and negative electrodes, offer several advantages compared to conventional liquid-state batteries. For example, all-solid-state batteries are made with solid-state electrolytes which are generally non-volatile and non-flammable so to allow the all-solid-state batteries to be cycled under harsher conditions than liquid-state batteries with diminished potential for thermal runaway. All-solid-state batteries may thus also have further advantages, such as operation without thermal management systems, long shelf life with zero self-discharge, and a reduced need for packaging. However, all-solid-state batteries may have comparatively low energy density levels (e.g., about 230 Wh/kg for a graphite/NMC622 solid-state battery) because of void spaces between solid-state electroactive material particles not being filled by, for example, a liquid electrolyte, or an inflexibility in accommodating various stresses and strains within the battery.
As such, it may be desirable to incorporate high-capacity electrode materials such as silicon and/or sulfur to account for the comparatively low energy densities associated with all-solid-state batteries. However, the high-capacity electrode materials may present other challenges. For example, large volume changes, including volume expansion and contraction, of high-capacity electrode materials comprising silicon during lithiation and/or delithiation can potentially result in physical damage to the solid-state components that tend to be inflexible, including wrinkling, fracture, cracking, and delamination of the stacked layers forming the all-solid-state batteries. Accordingly, it would be desirable to develop high-performance electrode materials for robust, high-energy-density all-solid-state batteries.
SUMMARY
This section provides a general summary of the disclosure, and is not a comprehensive disclosure of its full scope or all of its features.
The present disclosure relates to low expansion electrodes for solid-state lithium ion batteries.
In various aspects, the present disclosure provides a composite electrode for use in an all-solid-state electrochemical cell that cycles lithium ions. The composite electrode includes a solid-state electroactive material and a solid-state electrolyte. The solid-state electroactive material includes a plurality of particles that undergoes volumetric expansion and contraction during cycling of the electrochemical cell. Each particle of the plurality of particles has a plurality of internal pores formed therein. The composite electrode has an average interparticle porosity between respective particles of the plurality of particles of the solid-state electroactive material and the solid-state electrolyte ranging from greater than or equal to about 0% to less than or equal to about 40%. The plurality of internal pores of the solid-state electroactive material accommodate the volumetric expansion and contraction of the solid-state electroactive material inwardly so to minimize outward expansion of the plurality of particles and together with the interparticle porosity minimizes micro-cracking of the composite electrode.
In one aspect, the solid-state electroactive material includes silicon and each particle of the plurality of particles has an average porosity that ranges from greater than or equal to about 10% to less than or equal to about 75%.
In one aspect, the solid-state electroactive material includes one or more of the following: (i) silicon oxide (SiO 2 ), where each solid-state electroactive material particle has an average porosity ranging from greater than or equal to about 10% to less than or equal to about 60%; (ii) sulfur (S), where each solid-state electroactive material particle has an average porosity ranging from greater than or equal to about 10% to less than or equal to about 45%; and ferrous disulfide (FeS 2 ), where each solid-state electroactive material has an average porosity ranging from greater than or equal to about 10% to less than or equal to about 60%.
In one aspect, each particle of the plurality of particles has a honeycomb-like structure.
In one aspect, each particle of the plurality of particles has a round structure.
In one aspect, the solid-state electrolyte is from the group consisting of: Li 10 MP 2 S 12 (where M is selected from silicon (Si), tin (Sn), and germanium (Ge)), (Li 2 S) x (MS 2 ) y (P 2 S 5 ) 100âxây (where M is selected from silicon (Si), tin (Sn), and germanium (Ge) and where 40â¤xâ¤85, 0â¤yâ¤40, and 100âxây>0), polyethylene oxide (PEO), polyacrylonitrile (PAN), lithium lanthanum titanate (Li 0.67âx La 3x TiO 3 ) (LLTO), lithium lanthanum zirconium oxide (Li 7 La 3 Zr 2 O 12 ) (LLZO), lithium aluminum titanium phosphate (Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 ) (LATP), oxide glass, and combinations thereof.
In one aspect, if the solid-state electrolyte includes Li 10 MP 2 S 12 , the solid-state electrolyte further includes one or more dopants selected from the group consisting of lithium chloride (LiCl), lithium iodide (LiI), and combinations thereof.
In one aspect, if the solid-state electrolyte includes polyethylene oxide (PEO), the solid-state electrolyte further includes one or more salts selected from the group consisting of lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI) and combinations thereof.
In one aspect, if the solid-state electrolyte includes polyacrylonitrile (PAN), the solid-state electrolyte further includes one or more salts selected from the group consisting of lithium perchlorate (LiCO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI) and combinations thereof.
In one aspect, the composite electrode includes greater than or equal to about 30 wt. % to less than or equal to about 90 wt. % of the solid-state electroactive material, and greater than or equal to about 10 wt. % to less than or equal to about 70 wt. % of the solid-state electrolyte.
In one aspect, the composite electrode further includes at least one of: a conductive additive selected from the group consisting of: graphite, carbon-based materials, powdered nickel, conductive metal particles, conductive polymers, and combinations thereof; a binder selected from the group consisting of: polyvinylidene difluoride (PVdF), ethylene propylene diene monomer (EPDM) rubber, carboxymethoxyl cellulose (CMC), nitrile butadiene rubber (NBR), lithium polyacrylate (LiPAA), sodium polyacrylate (NaPAA), sodium alginate, lithium alginate, and combinations thereof; and a reinforcing filler selected from the group consisting of: silica-based glass fibers, alumina fibers, boron nitride fibers, thermoplastic polymer fibers, and combinations thereof.
In one aspect, the composite electrode includes greater than or equal to about 0 wt. % to less than or equal to about 25 wt. % of the conductive additive; greater than or equal to about 0 wt. % to less than or equal to about 20 wt. % of the binder; and greater than or equal to about 0 wt. % to less than or equal to about 40 wt. % of reinforcing filler.
In various other aspects, the present disclosure provides an all-solid-state electrochemical cell that cycles lithium ions. The all-solid-state electrochemical cell includes a first solid-state electrode, a second solid-state electrode opposing the first solid-state electrode, and a separator disposed between the first solid-state electrode and the second solid-state electrode. The first solid-state electrode includes a solid-state electroactive material and a solid-state electrolyte. The solid-state electroactive material is in the form of a plurality of particles that undergoes volumetric expansion and contraction during cycling of the electrochemical cell. Each particle of the plurality of particles includes a plurality of intraparticle pores. Each particle of the plurality of particles may have an average porosity ranging from greater than or equal to about 10% to less than or equal to about 75%. The intraparticle pores of the solid-state electroactive material accommodate the volumetric expansion and contraction of the solid-state electroactive material inwardly so to minimize outward expansion of the plurality of particles in the first solid-state electrode. The first solid-state electrode has an average interparticle porosity between respective particles of the plurality of particles of the solid-state electroactive material and the solid-state electrolyte ranging from greater than or equal to about 0% to less than or equal to about 40%. The interparticle porosity together with the internal pores of the solid-state electroactive material minimizes micro-cracking and delamination within the all-solid-state electrochemical cell.
In one aspect, the solid-state electroactive material may be a first solid-state electroactive material that is selected from the group consisting of: silicon (Si), silicon dioxide (SiO 2 ), tin (Sn), ferrous disulfide (FeS 2 ), ferrous sulfide (Fe 1âx S, where 0â¤xâ¤0.2), one or more carbon lithium hosts, and combinations thereof; and the second solid-state electrode may include a second solid-state electroactive material that is selected from the group consisting of: nickel manganese cobalt oxide (NMC), lithium manganese nickel metal oxide (LMNO), lithium manganese oxide (LiMn 2 O 2 ) (LMO), lithium iron phosphate (LiFePO 4 ) (LFP), and combinations thereof.
In one aspect, the solid-state electroactive material may be a first solid-state electroactive material that is selected from the group consisting of: sulfur (S), ferrous sulfide (FeS 2 ), ferrous fluoride (FeF 2 ), and combinations thereof; and the second solid-state electrode may include a second solid-state electroactive material that includes lithium metal.
In one aspect, the solid-state electroactive material is a first solid-state electroactive material and the solid-state electrolyte is a first solid-state electrolyte, and the second electrode comprises a second solid-state electroactive material and a second solid-state electrolyte.
In one aspect, the separator is formed by one of the first and second solid-state electrolytes.
In one aspect, the plurality of particles is a plurality of first particles and the second solid-state electroactive material is in the form of a plurality of second particles and each particle of the plurality of second particles has an average porosity ranging from greater than or equal to about 10% to less than or equal to about 75%.
In one aspect, the first solid-state electroactive material is selected from the group consisting of: sulfur (S), ferrous sulfide (FeS 2 ), ferrous fluoride (FeF 2 ), and combinations thereof, and the second solid-state electroactive material is selected from the group consisting of silicon, silicon dioxide (SiO 2 ), tin (Sn), ferrous disulfide (FeS 2 ), ferrous sulfide (Fe 1âx S, where 0â¤xâ¤0.2), one or more carbon lithium hosts, and combinations thereof.
In one aspect, the first solid-state electroactive material is sulfur and each first particle has a porosity ranging from greater than or equal to about 10 wt. % to less than or equal to about 45 wt. %.
In one aspect, the separator is formed from a solid-state electrolyte selected from the group consisting of: Li 10 MP 2 S 12 (where M is selected from silicon (Si), tin (Sn), and germanium (Ge)), (Li 2 S) x (MS 2 ) y (P 2 S 5 ) 100âxây (where M is selected from silicon (Si), tin (Sn), and germanium (Ge) and where 40â¤xâ¤90, 0â¤yâ¤40, and 100âxây>0), polyethylene oxide (PEO), polyacrylonitrile (PAN), lithium lanthanum titanate (Li 0.67âx La 3x TiO 3 ) (LLTO), lithium lanthanum zirconium oxide (Li 7 La 3 Zr 2 O 12 ) (LLZO), lithium aluminum titanium phosphate (Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 ) (LATP), oxide glass, and combinations thereof.
In one aspect, if the solid-state electrolyte includes Li 10 MP 2 S 12 , the solid-state electrolyte further includes one or more dopants selected from the group consisting of lithium chloride (LiCl), lithium iodide (LiI), and combinations thereof.
In one aspect, if the solid-state electrolyte includes polyethylene oxide (PEO), the solid-state electrolyte further includes one or more salts selected from the group consisting of lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI) and combinations thereof.
In one aspect, if the solid-state electrolyte includes polyacrylonitrile (PAN), the solid-state electrolyte further includes one or more salts selected from the group consisting of lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI) and combinations thereof.
Further areas of applicability will become apparent from the description provided herein. The description and specific examples in this summary are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure.
DRAWINGS
The drawings described herein are for illustrative purposes only of selected embodiments and not all possible implementations, and are not intended to limit the scope of the present disclosure.
FIG. 1 is a schematic of an example of an all-solid-state electrochemical battery cell;
FIG. 2A is an illustration of a high-energy density electroactive particle comprising an electroactive material that undergoes volumetric expansion and contraction during lithiation and delithiation and that has a plurality of pores formed therewithin, prior to the volumetric expansion of the electroactive material;
FIG. 2B is an illustration of a high-energy density electroactive particle comprising an electroactive material that undergoes volumetric expansion and contraction during lithiation and delithiation and that has a plurality of pores formed therewithin, following the volumetric expansion of the electroactive material; and
FIG. 3 is an illustration of a composite electrode including the high-energy density electroactive particles shown in FIGS. 2A and 2B and a solid-state electrolyte.
Corresponding reference numerals indicate corresponding parts throughout the several views of the drawings.
DETAILED DESCRIPTION
Example embodiments are provided so that this disclosure will be thorough, and will fully convey the scope to those who are skilled in the art. Numerous specific details are set forth such as examples of specific compositions, components, devices, and methods, to provide a thorough understanding of embodiments of the present disclosure. It will be apparent to those skilled in the art that specific details need not be employed, that example embodiments may be embodied in many different forms and that neither should be construed to limit the scope of the disclosure. In some example embodiments, well-known processes, well-known device structures, and well-known technologies are not described in detail.
The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting. As used herein, the singular forms âa,â âan,â and âtheâ may be intended to include the plural forms as well, unless the context clearly indicates otherwise. The terms âcomprises,â âcomprising,â âincluding,â and âhaving,â are inclusive and therefore specify the presence of stated features, elements, compositions, steps, integers, operations, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. Although the open-ended term âcomprising,â is to be understood as a non-restrictive term used to describe and claim various embodiments set forth herein, in certain aspects, the term may alternatively be understood to instead be a more limiting and restrictive term, such as âconsisting ofâ or âconsisting essentially of.â Thus, for any given embodiment reciting compositions, materials, components, elements, features, integers, operations, and/or process steps, the present disclosure also specifically includes embodiments consisting of, or consisting essentially of, such recited compositions, materials, components, elements, features, integers, operations, and/or process steps. In the case of âconsisting of,â the alternative embodiment excludes any additional compositions, materials, components, elements, features, integers, operations, and/or process steps, while in the case of âconsisting essentially of,â any additional compositions, materials, components, elements, features, integers, operations, and/or process steps that materially affect the basic and novel characteristics are excluded from such an embodiment, but any compositions, materials, components, elements, features, integers, operations, and/or process steps that do not materially affect the basic and novel characteristics can be included in the embodiment.
Any method steps, processes, and operations described herein are not to be construed as necessarily requiring their performance in the particular order discussed or illustrated, unless specifically identified as an order of performance. It is also to be understood that additional or alternative steps may be employed, unless otherwise indicated.
When a component, element, or layer is referred to as being âon,â âengaged to,â âconnected to,â or âcoupled toâ another element or layer, it may be directly on, engaged, connected or coupled to the other component, element, or layer, or intervening elements or layers may be present. In contrast, when an element is referred to as being âdirectly on,â âdirectly engaged to,â âdirectly connected to,â or âdirectly coupled toâ another element or layer, there may be no intervening elements or layers present. Other words used to describe the relationship between elements should be interpreted in a like fashion (e.g., âbetweenâ versus âdirectly between,â âadjacentâ versus âdirectly adjacent,â etc.). As used herein, the term âand/orâ includes any and all combinations of one or more of the associated listed items.
Although the terms first, second, third, etc. may be used herein to describe various steps, elements, components, regions, layers and/or sections, these steps, elements, components, regions, layers and/or sections should not be limited by these terms, unless otherwise indicated. These terms may be only used to distinguish one step, element, component, region, layer or section from another step, element, component, region, layer or section. Terms such as âfirst,â âsecond,â and other numerical terms when used herein do not imply a sequence or order unless clearly indicated by the context. Thus, a first step, element, component, region, layer or section discussed below could be termed a second step, element, component, region, layer or section without departing from the teachings of the example embodiments.
Spatially or temporally relative terms, such as âbefore,â âafter,â âinner,â âouter,â âbeneath,â âbelow,â âlower,â âabove,â âupper,â and the like, may be used herein for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the figures. Spatially or temporally relative terms may be intended to encompass different orientations of the device or system in use or operation in addition to the orientation depicted in the figures.
Throughout this disclosure, the numerical values represent approximate measures or limits to ranges to encompass minor deviations from the given values and embodiments having about the value mentioned as well as those having exactly the value mentioned. Other than in the working examples provided at the end of the detailed description, all numerical values of parameters (e.g., of quantities or conditions) in this specification, including the appended claims, are to be understood as being modified in all instances by the term âaboutâ whether or not âaboutâ actually appears before the numerical value. âAboutâ indicates that the stated numerical value allows some slight imprecision (with some approach to exactness in the value; approximately or reasonably close to the value; nearly). If the imprecision provided by âaboutâ is not otherwise understood in the art with this ordinary meaning, then âaboutâ as used herein indicates at least variations that may arise from ordinary methods of measuring and using such parameters. For example, âaboutâ may comprise a variation of less than or equal to 5%, optionally less than or equal to 4%, optionally less than or equal to 3%, optionally less than or equal to 2%, optionally less than or equal to 1%, optionally less than or equal to 0.5%, and in certain aspects, optionally less than or equal to 0.1%.
In addition, disclosure of ranges includes disclosure of all values and further divided ranges within the entire range, including endpoints and sub-ranges given for the ranges.
Example embodiments will now be described more fully with reference to the accompanying drawings.
An exemplary and schematic illustration of an all-solid-state electrochemical cell (also referred to as the battery) that cycles lithium ions is shown in FIG. 1 . The battery 20 includes a negative electrode 22 , a positive electrode 24 , and a separator 26 disposed between the electrodes
22 , 24 and that may be formed by a solid- state electrolyte 30 . The solid- state electrolyte 30 may also be present in the negative electrode 22 and the positive electrode 24 . A negative electrode current collector 32 may be positioned at or near the negative electrode 22 , and a positive electrode current collector 34 may be positioned at or near the positive electrode 24 . The negative electrode current collector 32 and the positive electrode current collector 34 respectively collect and move free electrons to and from an external circuit 40 . An interruptible external circuit 40 and load device 42 connect the negative electrode 22 (through the negative electrode current collector 32 ) and the positive electrode 24 (through the positive electrode current collector 34 ).
In solid-state batteries, the separator 26 can be defined by or formed from the solid- state electrolyte 30 and can operate as both an electrical insulator and a separator. The separator 26 is defined between the negative electrode 22 and the positive electrode 24 , so as to provide electrical separation and prevent physical contact between the negative and positive electrodes
22 , 24 and the occurrence of a short circuit that may result from such physical contact. The separator 26 , in addition to providing a physical barrier between the negative and positive electrodes
22 , 24 , also provides a minimal resistance path for internal passage of lithium ions (and, in certain instances, related anions) during cycling of the lithium ions to facilitate functioning of the battery 20 .
The battery 20 can generate an electric current during discharge by way of reversible electrochemical reactions that occur when the external circuit 40 is closed (to connect the negative electrode 22 and the positive electrode 24 ) and the negative electrode 22 contains a relatively greater quantity of lithium. The chemical potential difference between the positive electrode 24 and the negative electrode 22 drives electrons produced at the negative electrode 22 through the external circuit 40 towards the positive electrode 24 . Lithium ions, which are also produced at the negative electrode 22 , are concurrently transferred through the separator 26 towards the positive electrode 24 . The electrons flow through the external circuit 40 and the lithium ions migrate across the separator 26 to the positive electrode 24 , where they may be plated, reacted, or intercalated. The electric current passing through the external circuit 40 can be harnessed and directed through the load device 42 until the lithium in the negative electrode 22 is depleted and the capacity of the battery 20 is diminished. In lithium-ion batteries, lithium intercalates and/or alloys in the electroactive materials. In lithium-sulfur batteries, instead of intercalating or alloying, the lithium dissolves from the negative electrode and migrates to the positive electrode where it reacts/plates during discharge, while during charging, lithium plates on the negative electrode 22 .
The battery 20 can be charged or re-energized at any time by connecting an external power source to the battery 20 to reverse the electrochemical reactions that occur during battery discharge. The connection of the external power source to the battery 20 compels the production of electrons and release of lithium ions from the positive electrode 24 . The electrons, which flow back towards the negative electrode 22 , reunite at the negative electrode 22 and replenish it with lithium for consumption during the next battery discharge cycle. As such, each discharge and charge event is considered to be a cycle, where lithium ions are cycled between the negative and positive electrodes
22 , 24 .
The external power source that may be used to charge the battery 20 may vary depending on size, construction, and particular end-use of the battery 20 . Some notable and exemplary external power sources include an AC wall outlet and a motor vehicle alternator. In many lithium-ion battery configurations, each of the negative current collector 32 , the negative electrode 22 , the separator 26 , the positive electrode 24 , and the positive current collector 34 are prepared as relatively thin layers (e.g., from several microns to a millimeter or less in thickness) and assembled in layers connected in electrical parallel arrangement to provide a suitable electrical energy and power package.
Further, in certain aspects, the battery 20 can include a variety of other components that, while not depicted here, are nonetheless known to those of skill in the art. For instance, the battery 20 may include a casing, gasket, terminal caps, tabs, battery terminals, and any other conventional components or materials that may be situated within the battery 20 , including between or around the negative electrode 22 , the positive electrode 24 , and/or the separator 25 . As noted above, the size and shape of the battery 20 may vary depending on the particular applications for which it is designed. Battery-powered vehicles and hand-held consumer electronic devices are two examples where the battery 20 would most likely be designed to different size, capacity, and power-output specifications. The battery 20 may also be connected in series or parallel with other similar lithium-ion cells or batteries to produce a greater voltage output, energy, and power if it is required by the load device 42 .
Accordingly, the battery 20 can generate electric current to a load device 42 that can be operatively connected to the external circuit 40 . While the load device 42 may be any number of known electrically-powered devices, a few specific examples of power-consuming load devices include an electric motor for a hybrid vehicle or an all-electric vehicle, a laptop computer, a tablet computer, a cellular phone, and cordless power tools or appliances. The load device 42 may also be a power-generating apparatus that charges the battery 20 for purposes of storing energy. In certain other variations, the electrochemical cell may be a supercapacitor, such as a lithium-ion based supercapacitor.
With renewed reference to FIG. 1 , in various instances, the solid- state electrolyte separator 26 may be defined by or formed from a ceramic material, glass material, polymeric material, or any combination thereof. For example, in various variations, the separator 26 may be in the form of a layer comprising one or more of a polymeric electrolyte, a ceramic electrolyte, or a glass electrolyte. Such materials may be in particle form. In certain variations, the electrolyte separator 26 may be a composite that comprises the polymer electrolyte, the ceramic electrolyte, the glass electrolyte, or combinations thereof. The electrolyte separator 26 may have a thickness ranging from greater than or equal to about 1 μm to less than or equal to about 1 mm, and in certain aspects, optionally from greater than or equal to about 5 μm to less than or equal to about 100 μm. The electrolyte separator 26 may be formed by a casting method, hot pressing, cold pressing, physical deposition, or a combination of these methods. An interparticle porosity 80 between the solid- state electrolyte particles 30 forming the electrolyte separator 26 may be influenced by the forming method. In certain instances, the separator 26 may have an interparticle porosity 80 ranging from greater than or equal to about 0 vol. % to less than or equal to about 40 vol. %, optionally from greater than or equal to about 5 vol. % to less than or equal to about 40 vol. %, optionally from greater than or equal to about 5 vol. % to less than or equal to about 30 vol. %, and in certain aspects, optionally from greater than or equal to about 5 vol. % to less than or equal to about 20 vol. %.
In certain aspects, the ceramic material includes, for example, an oxide-based ceramic or sulfide or oxy-sulfide glass or glass-ceramic. In certain aspects, the sulfide and oxy-sulfide glasses may be formed by combining one or more glass formers and one or more glass modifiers, and in certain instances, an optional dopant. For a sulfide glass, both the glass former and the glass modifier include sulfur. An oxy-sulfide glass can include one of (i) an oxide forming system (e.g., an oxide-containing glass former and an oxide-containing glass modifier) with a sulfide co-former and (ii) a sulfide forming system (e.g., a sulfide-containing glass former and a sulfide-containing glass modifier) with an oxide co-former. The respective glass formers and the glass modifiers can react to form a sulfide or oxy-sulfide glass that enables the formation of mobile alkali metal cations.
The glass formers may include one or more glass-forming sulfides or oxides. In certain instances, the glass-forming sulfide may be selected from the group consisting of: phosphorous pentasulfide (P 2 S 5 ), tin disulfide (SnS 2 ), germanium disulfide (GeS 2 ), boron sulfide (B 2 S 3 ), silicon disulfide (SiS 2 ), arsenic trisulfide (As 2 S 3 ), and combinations thereof. The glass-forming oxides may be selected from the group consisting of: silicon dioxide (SiO 2 ), germanium dioxide (GeO 2 ), phosphorus pentoxide (P 2 O 5 ), boron trioxide (B 2 O 3 ), and combinations thereof. The glass modifiers may also include one or more sulfides or oxides. In certain instances, the sulfide-containing glass modifier may be selected from the group consisting of: lithium sulfide (Li 2 S), sodium sulfide (Na 2 S), and combinations thereof. The oxide-containing glass modifier may be selected from the group consisting of: lithium oxide (Li 2 O), sodium oxide (Na 2 O), and combinations thereof. To support advantageous electrolytic activity, at least one of the glass former and the glass modifier may contain sulfur. The optional dopant may be included to improve glass formability and/or stability. The optional dopant may be selected from the group consisting of: lithium chloride (LiCl), lithium iodide (LiI), lithium metasilicate (Li 2 SiO 3 ), lithium phosphate (Li 3 PO 4 ), lithium orthosilicate (Li 4 SiO 4 ), and combinations thereof.
In various variations, non-limiting examples of ceramic oxides include: phosphates (e.g., lithium aluminum titanium phosphate (Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 ) (LATP)), perovskites (e.g., lithium lanthanum titanate (Li 0.67âx La 3x TiO 3 ) (LLTO)), and garnets (e.g., lithium lanthanum zirconium oxide (Li 7 La 3 Zr 2 O 12 ) (LLZO)). A non-limiting example of a sulfide glass is lithium phosphorous sulfide (70Li 2 Sâ30P 2 S 5 ) (LPS). A non-limiting example of a sulfide glass-ceramic is lithium phosphorus sulfide (70Li 2 Sâ30P 2 S 5 ) (c-LPS) which has been devitrified to form the ionically conductive Li 7 P 3 S 11 crystalline phase. Polymeric materials may include solid-state polymeric electrolytes such as polyethylene oxide (PEO), by way of non-limiting example. Other inorganic materials may include anti-perovskites, complex hydrides, oxide glasses, oxysulfide glasses, and LiPON, by way of non-limiting examples. Other organic materials may include poly(methyl methacrylate) ((C 5 O 2 H 8 ) n ) (PMMA), polyacrylonitrile ((C 3 H 3 N) n ) (PAN), polyvinylidene fluoride ((C 2 H 2 F 2 ) n ) (PVDF), and gel electrolytes (i.e., polymers plasticized with solvent) by way of non-limiting example.
The electrolyte separator 26 may further include one or more binders (not shown) and/or one or more reinforcing additives or fillers (not shown). For example, the separator 26 may include one or more binders selected from the group consisting of: polyvinylidene difluoride (PVdF), ethylene propylene diene monomer (EPDM) rubber, carboxymethoxyl cellulose (CMC), nitrile butadiene rubber (NBR), lithium polyacrylate (LiPAA), sodium polyacrylate (NaPAA), sodium alginate, lithium alginate, and combinations thereof. In certain aspects, the electrolyte separator 26 may include greater than or equal to about 0 wt. % to less than or equal to about 20 wt. % of the one or more binders. The electrolyte separator 26 may include one or more reinforcing fillers selected from the group consisting of: silica-based glass fibers, alumina fibers, boron nitride fibers, thermoplastic polymer fibers, and combinations thereof. For example, the electrolyte separator 26 may include greater than or equal to about 0 wt. % to less than or equal to about 40 wt. % of the one or more reinforcing fillers.
The positive electrode 24 may be in a solid-state and include a lithium-based electroactive material that can undergo lithium intercalation and deintercalation, alloying and dealloying, or plating or stripping, while functioning as the positive terminal of the battery 20 . The positive electrode 24 may be a composite electrode including particles of a positive electroactive material 50 admixed and formed with particles of a solid- state electrolyte 90 . In certain aspects, the positive electrode 24 may include greater than or equal to about 30 wt. % to less than or equal to about 90 wt. %, and in certain aspects, optionally greater than or equal to about 40 wt. % to less than or equal to about 80 wt. % of the solid- state electroactive material 50 . The positive electrode 24 may include greater than or equal to about 10 wt. % to less than or equal to about 70 wt. %, and in certain aspects, optionally greater than or equal to about 20 wt. % to less than or equal to about 60 wt. % of the solid- state electrolyte 90 .
The solid- state electrolyte 90 combined with the positive electroactive material 50 that forms the <figure-callout id="24" label="positive electrode" filenames="US11239459-20220201-D00000.png,US11239459-20220201-D00001.png"
CLAIMS
Claims ( 20 )
What is claimed is:
1. A composite electrode for use in an all-solid-state electrochemical cell that cycles lithium ions, the composite electrode comprising:
a solid-state electroactive material in the form of a plurality of solid-state electroactive material particles that undergoes volumetric expansion and contraction during cycling of the electrochemical cell,
wherein each solid-state electroactive material particle of the plurality of solid-state electroactive particles comprises a plurality of internal pores formed therein; and
a solid-state electrolyte in the form of a plurality of solid-state electrolyte particles that are intermingled with and contacting the solid-state electroactive material,
wherein the composite electrode has an interparticle porosity between the solid-state electroactive material particles and the solid-state electrolyte particles ranging from greater than 0% to less than or equal to about 40%,
wherein the plurality of internal pores of the solid-state electroactive material particles accommodate the volumetric expansion and contraction of the solid-state electroactive material inwardly so to minimize outward expansion of the solid-state electroactive material particles, and
wherein the internal pores of the solid-state electroactive material particles together with the interparticle porosity minimizes micro-cracking of the composite electrode.
2. The composite electrode of claim 1 , wherein the solid-state electroactive material comprises silicon and each solid-state electroactive material particle has an average porosity ranging from greater than or equal to about 10% to less than or equal to about 75%.
3. The composite electrode of claim 1 , wherein the solid-state electroactive material comprises one or more of the following:
(i) silicon oxide (SiO 2 ), wherein each solid-state electroactive material particle has an average porosity ranging from greater than or equal to about 10% to less than or equal to about 60%;
(ii) sulfur (S), wherein each solid-state electroactive material particle has an average porosity ranging from greater than or equal to about 10% to less than or equal to about 45%; and
(iii) ferrous disulfide (FeS 2 ), wherein each solid-state electroactive material has an average porosity ranging from greater than or equal to about 10% to less than or equal to about 60%.
4. The composite electrode of claim 1 , wherein each solid-state electroactive material particle has a honeycomb-like structure.
5. The composite electrode of claim 1 , wherein each solid-state electroactive material particle has a round structure.
6. The composite electrode of claim 1 , wherein the solid-state electrolyte is selected from the group consisting of: Li 10 MP 2 S 12 (where M is selected from silicon (Si), tin (Sn), and germanium (Ge)), (Li 2 S) x (MS 2 ) y (P 2 S 5 ) 100âxây (where M is selected from silicon (Si), tin (Sn), and germanium (Ge) and where 40â¤xâ¤85, 0â¤yâ¤40, and 100âxây>0), polyethylene oxide (PEO), polyacrylonitrile (PAN), lithium lanthanum titanate (Li 0.67âx La 3x TiO 3 ) (LLTO), lithium lanthanum zirconium oxide (Li 7 La 3 Zr 2 O 12 ) (LLZO), lithium aluminum titanium phosphate (Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 ) (LATP), oxide glass, and combinations thereof.
7. The composite electrode of claim 6 , wherein the solid-state electrolyte further comprises one or more dopants selected from the group consisting of lithium chloride (LiCl), lithium iodide (LiI), and combinations thereof, or
one or more salts selected from the group consisting of lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI) and combinations thereof.
8. The composite electrode of claim 1 , wherein the composite electrode comprises:
greater than or equal to about 30 wt. % to less than or equal to about 90 wt. % of the solid-state electroactive material, and
greater than or equal to about 10 wt. % to less than or equal to about 70 wt. % of the solid-state electrolyte.
9. The composite electrode of claim 8 , wherein the composite electrode further comprises at least one of:
a conductive additive selected from the group consisting of: graphite, carbon-based materials, powdered nickel, conductive metal particles, conductive polymers, and combinations thereof,
a binder selected from the group consisting of: polyvinylidene difluoride (PVdF), ethylene propylene diene monomer (EPDM) rubber, carboxymethoxyl cellulose (CMC), nitrile butadiene rubber (NBR), lithium polyacrylate (LiPAA), sodium polyacrylate (NaPAA), sodium alginate, lithium alginate, and combinations thereof; and
a reinforcing filler selected from the group consisting of: silica-based glass fibers, alumina fibers, boron nitride fibers, thermoplastic polymer fibers, and combinations thereof.
10. The composite electrode of claim 9 , wherein the composite electrode comprises:
greater than or equal to about 0 wt. % to less than or equal to about 25 wt. % of the conductive additive;
greater than or equal to about 0 wt. % to less than or equal to about 20 wt. % of the binder; and
greater than or equal to about 0 wt. % to less than or equal to about 40 wt. % reinforcing filler.
11. An all-solid-state electrochemical cell that cycles lithium ions comprising:
a first solid-state electrode comprising:
a solid-state electroactive material in the form of a plurality of particles that undergoes volumetric expansion and contraction during cycling of the electrochemical cell,
wherein each particle of the plurality of particles comprises a plurality of intraparticle pores and has an average porosity ranging from greater than or equal to about 10% to less than or equal to about 75%, and
wherein the intraparticle pores of the solid-state electroactive material accommodate the volumetric expansion and contraction of the solid-state electroactive material inwardly so to minimize outward expansion of the plurality of particles in the first solid-state electrode; and
a solid-state electrolyte in the form of a plurality of solid-state electrolyte particles that are intermingled with and contacting the solid-state electroactive material,
wherein the first solid-state electrode has an average interparticle porosity between the solid-state electroactive material particles and the solid-state electrolyte particles ranging from greater than or equal to about 0% to less than or equal to about 40%, and
wherein the interparticle porosity together with the intraparticle pores minimize micro-cracking and delamination within the all-solid-state electrochemical cell; and
a second solid-state electrode opposing the first solid-state electrode; and
a separator disposed between the first solid-state electrode and the second solid-state electrode.
12. The all-solid-state electrochemical cell of claim 11 , wherein the solid-state electroactive material is a first solid-state electroactive material selected from the group consisting of silicon (Si), silicon dioxide (SiO 2 ), tin (Sn), ferrous disulfide (FeS 2 ), ferrous sulfide (Fe 1âx S, where 0â¤xâ¤0.2), one or more carbon lithium hosts, and combinations thereof; and
wherein the second solid-state electrode comprises a second solid-state electroactive material selected from the group consisting of nickel manganese cobalt oxide (NMC), lithium manganese nickel metal oxide (LMNO), lithium manganese oxide (LiMn 2 O 2 ) (LMO), lithium iron phosphate LiFePO 4 (LFP), and combinations thereof.
13. The all-solid-state electrochemical cell of claim 11 , wherein the solid-state electroactive material is a first solid-state electroactive material selected from the group consisting of: sulfur (S), ferrous sulfide (FeS 2 ), ferrous fluoride (FeF 2 ), and combinations thereof; and
wherein the second solid-state electrode comprises a second solid-state electroactive material that comprises lithium metal.
14. The all-solid-state electrochemical cell of claim 11 , wherein the solid-state electroactive material is a first solid-state electroactive material and the solid-state electrolyte is a first solid-state electrolyte, and
wherein the second electrode comprises a second solid-state electroactive material and a second solid-state electrolyte.
15. The all-solid-state electrochemical cell of claim 14 , wherein the separator is formed by one of the first and second solid-state electrolytes.
16. The all-solid-state electrochemical cell of claim 14 , wherein the plurality of solid-state electroactive material particles is a plurality of first solid-state electroactive material particles, and the second solid-state electroactive material is in the form of a plurality of second solid-state-electroactive material particles and each solid-state electroactive material particle of the plurality of second solid-state electroactive material particles has an average porosity ranging from greater than or equal to about 10% to less than or equal to about 75%.
17. The all-solid-state electrochemical cell of claim 16 , wherein the first solid-state electroactive material is selected from the group consisting of: sulfur (S), ferrous sulfide (FeS 2 ), ferrous fluoride (FeF 2 ), and combinations thereof, and the second solid-state electroactive material is selected from the group consisting of silicon, silicon dioxide (SiO 2 ), tin (Sn), ferrous disulfide (FeS 2 ), ferrous sulfide (Fe 1âx S, where 0â¤xâ¤0.2), one or more carbon lithium hosts, and combinations thereof.
18. The all-solid-state electrochemical cell of claim 17 , wherein the first solid-state electroactive material is sulfur and each first particle has an average porosity ranging from greater than or equal to about 10 wt. % to less than or equal to about 45 wt. %.
19. The all-solid-state electrochemical cell of claim 11 , wherein the separator is formed from a solid-state electrolyte selected from the group consisting of: from the group consisting of: Li 10 MP 2 S 12 (where M is selected from silicon (Si), tin (Sn), and germanium (Ge)), (Li 2 S) x (MS 2 ) y (P 2 S 5 ) 100âxây (where M is selected from silicon (Si), tin (Sn), and germanium (Ge) and where 40â¤xâ¤85, 0â¤yâ¤40, and 100âxây>0), polyethylene oxide (PEO), polyacrylonitrile (PAN), lithium lanthanum titanate (Li 0.67âx LA 3x TiO 3 ) (LLTO), lithium lanthanum zirconium oxide (Li 7 La 3 Zr 2 O 12 ) (LLZO), lithium aluminum titanium phosphate (Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 ) (LATP), oxide glass, and combinations thereof.
20. The all solid-state electrochemical cell of claim 19 , wherein the solid-state electrolyte further comprises one or more dopants selected from the group consisting of lithium chloride (LiCl), lithium iodide (LiI), and combinations thereof, or
one or more salts selected from the group consisting of lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI) and combinations thereof.
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