Google Patentsopen access

Gel electrolyte system for solid state battery — GM Global Technology Operations LLC (US12412928B2)

ABSTRACT

Abstract

An electrochemical cell that cycles lithium ions is provided. The electrochemical cell includes a first electrode, a second electrode, and an electrolyte layer disposed between the first electrode and the second electrode. The first electrode includes a first plurality of solid-state electroactive material particles and a first polymeric gel electrolyte, where the first polymeric gel electrolyte includes a first additive. The second electrode includes a second plurality of solid-state electroactive material particles and a second polymeric gel electrolyte that is different from the first polymeric gel electrolyte, where the second polymeric gel electrolyte includes a second additive. The electrolyte layers include a third polymeric gel electrolyte that is different from both the first polymeric gel electrolyte and the second polymeric gel electrolyte.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit and priority of Chinese Patent Application No. 202110929032.X filed Aug. 13, 2021. The entire disclosure of the above application is incorporated herein by reference.

INTRODUCTION

This section provides background information related to the present disclosure which is not necessarily prior art.

Electrochemical energy storage devices, such as lithium-ion batteries, can be used in a variety of products, including automotive products such as start-stop systems (e.g., 12V start-stop systems), battery-assisted systems (“μBAS”), Hybrid Electric Vehicles (“HEVs”), and Electric Vehicles (“EVs”). Typical lithium-ion batteries include two electrodes and an electrolyte component and/or separator. One of the two electrodes can serve as a positive electrode or cathode, and the other electrode can serve as a negative electrode or anode. Lithium-ion batteries may also include various terminal and packaging materials. Rechargeable lithium-ion batteries operate by reversibly passing lithium ions back and forth between the negative electrode and the positive electrode. For example, lithium ions may 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/or electrolyte may be disposed between the negative and positive electrodes. The electrolyte is suitable for conducting lithium ions between the electrodes and, like the two electrodes, may be in a solid form, a liquid form, or a solid-liquid hybrid form. In the instances of solid-state batteries, which include a solid-state electrolyte layer disposed between the solid-state electrodes, the solid-state electrolyte physically separates the solid-state electrodes so that a distinct separator is not required.

Solid-state batteries have advantages over batteries that include a separator and a liquid electrolyte. These advantages can include a longer shelf life with lower self-discharge, simpler thermal management, a reduced need for packaging, and the ability to operate within a wider temperature window. For example, solid-state electrolytes are generally non-volatile and non-flammable, so as to allow cells to be cycled under harsher conditions without experiencing diminished potential or thermal runaway, which can potentially occur with the use of liquid electrolytes. However, solid-state batteries often experience comparatively low power capabilities. Low power capabilities may be a result of interfacial resistance within the solid-state electrodes and/or at the electrode, and solid-state electrolyte layer interfacial resistance caused by limited contact, or void spaces, between the solid-state active particles and/or the solid-state electrolyte particles. Accordingly, it would be desirable to develop high-performance solid-state battery designs, materials, and methods that improve power capabilities, as well as energy density.

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 solid-state batteries, for example to bipolar solid-state batteries, including a polymeric gel electrolyte system and exhibiting enhanced interfacial contact, and to methods for forming the same.

In various aspects, the present disclosure provides an electrochemical cell that cycles lithium ions. The electrochemical cell may include a first electrode, a second electrode, and an electrolyte layer disposed between the first electrode and the second electrode. The first electrode may include a first plurality of solid-state electroactive material particles and a first polymeric gel electrolyte. The second electrode may include a second plurality of solid-state electroactive material particles and a second polymeric gel electrolyte that is different from the first polymeric gel electrolyte. The electrolyte layer may include a third polymeric gel electrolyte that is different from both the first polymeric gel electrolyte and the second polymeric gel electrolyte.

In one aspect, the first polymeric gel electrolyte may include greater than 0 wt. % to less than or equal to about 10 wt. % of a first additive; and the second polymeric gel electrolyte may include greater than 0 wt. % to less than or equal to about 10 wt. % of a second additive.

In one aspect, the first additive may include a compound having an unsaturated carbon bond, a sulfur-containing compound, a halogen-containing compound, a methyl substituted glycolide derivative, a maleimide (MI), a compound containing an electron withdrawing group, and combinations thereof.

In one aspect, the unsaturated carbon bond containing compound may include vinylene carbonate (VC), vinyl ethylene carbonate (VEC), and combinations thereof.

In one aspect, the sulfur-containing compound may include ethylene sulfite (ES), propylene sulfite (PyS), and combinations thereof.

In one aspect, the halogen-containing compound may include fluoroethylene carbonate (FEC), chloro-ethylene carbonate (Cl-EC), and combinations thereof.

In one aspect, the second additive may include a boron-containing compound, a silicon-containing compound, a phosphorus-containing compound, a compound containing at least one of a phenyl group, a thiophene aniline group, a maleimide group, an aniline group, an anisole group, an adamantyl group, a furan group, and a thiophene group, and combinations thereof.

In one aspect, the boron-containing compound may include lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), tris(trimethylsilyl)borate (TMSB), and combinations thereof.

In one aspect, the silicon-containing compound may include tris(trimethylsilyl)phosphate (TMSP), tris(trimethylsilyl)borate (TMSB), and combinations thereof.

In one aspect, the phosphorus-containing compound may include triphenyl phosphine (TPP), ethyl diphenylphosphinite (EDP), triethyl phosphite (TEP), and combinations thereof.

In one aspect, the compound containing at least one of a phenyl group, a thiophene aniline group, a maleimide group, an aniline group, an anisole group, an adamantyl group, a furan group, and a thiophene group may include biphenyl (BP), o-terphenyl (OT), 2,2′-bis[4-(4 maleimidophenoxy)phenyl]propane (BMP), N,N-dimethyl-aniline (DMA), and combinations thereof.

In one aspect, the first polymeric gel electrolyte and the second polymeric gel electrolyte may each further include greater than or equal to about 0.1 wt. % to less than or equal to about 50 wt. % of a polymer host.

In one aspect, the first polymeric gel electrolyte and the second polymeric gel electrolyte may each include a polymer host independently selected from the group consisting of: poly(ethylene oxide) (PEO), poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP), poly(methyl methacrylate) (PMMA), carboxymethyl cellulose (CMC), polyacrylonitrile (PAN), polyvinylidene difluoride (PVDF), poly(vinyl alcohol) (PVA), polyvinylpyrrolidone (PVP), lithium polyacrylate (LiPAA), and combinations thereof.

In one aspect, the first polymeric gel electrolyte and the second polymeric gel electrolyte may each further include greater than or equal to about 5 wt. % to less than or equal to about 90 wt. % of a liquid electrolyte.

In one aspect, the third polymeric gel electrolyte may include greater than or equal to about 0.1 wt. % to less than or equal to about 50 wt. % of a polymer host, and greater than or equal to about 5 wt. % to less than or equal to about 90 wt. % of a liquid electrolyte.

In one aspect, the polymer host may be selected from the group consisting of: poly(acrylonitrile) (PAN), poly(ethylene oxide) (PEO), poly(ethylene glycol) (PEG), polyethylene carbonate (PEC), poly(trimethylene carbonate) (PTMC), poly(propylene carbonate) (PPC), polyvinylidene difluoride (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), and combinations thereof.

In one aspect, the electrolyte layer may be a free-standing membrane defined by the third polymeric gel electrolyte. The free-standing membrane may have a thickness greater than or equal to about 5 μm to less than or equal to about 1,000 μm.

In one aspect, the electrolyte layer may further include greater than 0 wt. % to less than or equal to about 80 wt. % of a plurality of solid-state electrolyte particles.

In one aspect, the electrochemical cell further may further include a first bipolar current collector disposed on or adjacent to an exposed surface of the first electrode and parallel with the electrolyte layer; a second bipolar current collector disposed on or adjacent to an exposed surface of the second electrode and parallel with the electrolyte layer; and one or more polymer blockers coupled to and extending between the first bipolar current collector and the second bipolar current collector.

In various aspects, the present disclosure provides an electrochemical cell that cycles lithium ions. The electrochemical cell may include a first electrode, a second electrode, and an electrolyte layer disposed between the first electrode and the second electrode. The first electrode may include a first plurality of solid-state electroactive material particles and a first polymeric gel electrolyte. The first polymeric gel electrolyte may include greater than 0 wt. % to less than or equal to about 10 wt. % of a first additive, greater than or equal to about 0.1 wt. % to less than or equal to about 15 wt. % of a first polymer host, and greater than or equal to about 5 wt. % to less than or equal to about 90 wt. % of a first liquid electrolyte. The second electrode may include a second plurality of solid-state electroactive material particles and a second polymeric gel electrolyte. The second polymeric gel electrolyte may include greater than 0 wt. % to less than or equal to about 10 wt. % of a second additive, greater than or equal to about 0.1 wt. % to less than or equal to about 15 wt. % of a second polymer host, and greater than or equal to about 5 wt. % to less than or equal to about 90 wt. % of a second liquid electrolyte. The electrolyte layer may include a third polymeric gel electrolyte. The third polymeric gel electrolyte may include greater than or equal to about 10 wt. % to less than or equal to about 50 wt. % of a third polymer host and greater than or equal to about 5 wt. % to less than or equal to about 90 wt. % of a third liquid electrolyte.

In one aspect, the first liquid electrolyte, the second liquid electrolyte, and the third liquid electrolyte are the same or different.

In one aspect, the first polymer host and the second polymer host may be independently selected from the group consisting of: poly(ethylene oxide) (PEO), poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP), poly(methyl methacrylate) (PMMA), carboxymethyl cellulose (CMC), polyacrylonitrile (PAN), polyvinylidene difluoride (PVDF), poly(vinyl alcohol) (PVA), polyvinylpyrrolidone (PVP), lithium polyacrylate (LiPAA), and combinations thereof.

In one aspect, the third polymer host may be selected from the group consisting of: poly(acrylonitrile) (PAN), poly(ethylene oxide) (PEO), poly(ethylene glycol) (PEG), polyethylene carbonate (PEC), poly(trimethylene carbonate) (PTMC), poly(propylene carbonate) (PPC), polyvinylidene difluoride (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), and combinations thereof.

In one aspect, the first additive may be selected from the group consisting of: vinylene carbonate (VC), vinyl ethylene carbonate (VEC), ethylene sulfite (ES), propylene sulfite (PyS), fluoroethylene carbonate (FEC), chloro-ethylene carbonate (Cl-EC), and combinations thereof.

In one aspect, the second additive may be selected from the group consisting of: bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), tris(trimethylsilyl)borate (TMSB), tris(trimethylsilyl)phosphate (TMSP), triphenyl phosphine (TPP), ethyl diphenylphosphinite (EDP), triethyl phosphite (TEP), biphenyl (BP), o-terphenyl (OT), 2,2′-bis[4-(4 maleimidophenoxy)phenyl]propane (BMP), N,N-dimethyl-aniline (DMA), and combinations thereof.

In various aspects, the present disclosure provides a method for forming an electrochemical cell that cycles lithium ions. The method may include preparing a first gel-assisted electrode, preparing a second gel-assisted electrode, and preparing an electrolyte layer comprising a third precursor liquid. Preparing the first gel-assisted electrode may include contacting a first precursor electrode and a first precursor liquid that includes a first solvent and a first additive, and removing the first solvent to form the first gel-assisted electrode. Preparing the second gel-assisted electrode may include contacting a second precursor electrode and a second precursor liquid that includes a second solvent and a second additive, and removing the second solvent to form the second gel-assisted electrode. The first precursor liquid may be different from the second and third precursor liquids. The second precursor liquid may be different from the first and third precursor liquids. The method may further include stacking the first gel-assisted electrode, the second gel-assisted electrode, and the electrolyte layer to form the electrochemical cell, where the electrolyte layer is disposed between the first gel-assisted electrode and the second gel-assisted electrode.

In one aspect, the first additive may be selected from the group consisting of: vinylene carbonate (VC), vinyl ethylene carbonate (VEC), ethylene sulfite (ES), propylene sulfite (PyS), fluoroethylene carbonate (FEC), chloro-ethylene carbonate (Cl-EC), and combinations thereof.

In one aspect, the second additive may be selected from the group consisting of: bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), tris(trimethylsilyl)borate (TMSB), tris(trimethylsilyl)phosphate (TMSP), triphenyl phosphine (TPP), ethyl diphenylphosphinite (EDP), triethyl phosphite (TEP), biphenyl (BP), o-terphenyl (OT), 2,2′-bis[4-(4 maleimidophenoxy)phenyl]propane (BMP), N,N-dimethyl-aniline (DMA), 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.

BRIEF DESCRIPTION OF THE 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 A is an illustration of an example solid-state battery in accordance with various aspects of the present disclosure;

FIG. 1 B is an example solid-state battery having a polymeric gel electrolyte system in accordance with various aspects of the present disclosure;

FIG. 2 is another example solid-state battery having a polymeric gel electrolyte system in accordance with various aspects of the present disclosure;

FIG. 3 is another example solid-state battery having a polymeric gel electrolyte system in accordance with various aspects of the present disclosure;

FIG. 4 is a flowchart illustrating an exemplary method for fabricating a battery including a polymeric gel electrolyte system in accordance with various aspects of the present disclosure;

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CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit and priority of Chinese Patent Application No. 202110929032.X filed Aug. 13, 2021. The entire disclosure of the above application is incorporated herein by reference.

INTRODUCTION

This section provides background information related to the present disclosure which is not necessarily prior art.

Electrochemical energy storage devices, such as lithium-ion batteries, can be used in a variety of products, including automotive products such as start-stop systems (e.g., 12V start-stop systems), battery-assisted systems (“μBAS”), Hybrid Electric Vehicles (“HEVs”), and Electric Vehicles (“EVs”). Typical lithium-ion batteries include two electrodes and an electrolyte component and/or separator. One of the two electrodes can serve as a positive electrode or cathode, and the other electrode can serve as a negative electrode or anode. Lithium-ion batteries may also include various terminal and packaging materials. Rechargeable lithium-ion batteries operate by reversibly passing lithium ions back and forth between the negative electrode and the positive electrode. For example, lithium ions may 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/or electrolyte may be disposed between the negative and positive electrodes. The electrolyte is suitable for conducting lithium ions between the electrodes and, like the two electrodes, may be in a solid form, a liquid form, or a solid-liquid hybrid form. In the instances of solid-state batteries, which include a solid-state electrolyte layer disposed between the solid-state electrodes, the solid-state electrolyte physically separates the solid-state electrodes so that a distinct separator is not required.

Solid-state batteries have advantages over batteries that include a separator and a liquid electrolyte. These advantages can include a longer shelf life with lower self-discharge, simpler thermal management, a reduced need for packaging, and the ability to operate within a wider temperature window. For example, solid-state electrolytes are generally non-volatile and non-flammable, so as to allow cells to be cycled under harsher conditions without experiencing diminished potential or thermal runaway, which can potentially occur with the use of liquid electrolytes. However, solid-state batteries often experience comparatively low power capabilities. Low power capabilities may be a result of interfacial resistance within the solid-state electrodes and/or at the electrode, and solid-state electrolyte layer interfacial resistance caused by limited contact, or void spaces, between the solid-state active particles and/or the solid-state electrolyte particles. Accordingly, it would be desirable to develop high-performance solid-state battery designs, materials, and methods that improve power capabilities, as well as energy density.

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 solid-state batteries, for example to bipolar solid-state batteries, including a polymeric gel electrolyte system and exhibiting enhanced interfacial contact, and to methods for forming the same.

In various aspects, the present disclosure provides an electrochemical cell that cycles lithium ions. The electrochemical cell may include a first electrode, a second electrode, and an electrolyte layer disposed between the first electrode and the second electrode. The first electrode may include a first plurality of solid-state electroactive material particles and a first polymeric gel electrolyte. The second electrode may include a second plurality of solid-state electroactive material particles and a second polymeric gel electrolyte that is different from the first polymeric gel electrolyte. The electrolyte layer may include a third polymeric gel electrolyte that is different from both the first polymeric gel electrolyte and the second polymeric gel electrolyte.

In one aspect, the first polymeric gel electrolyte may include greater than 0 wt. % to less than or equal to about 10 wt. % of a first additive; and the second polymeric gel electrolyte may include greater than 0 wt. % to less than or equal to about 10 wt. % of a second additive.

In one aspect, the first additive may include a compound having an unsaturated carbon bond, a sulfur-containing compound, a halogen-containing compound, a methyl substituted glycolide derivative, a maleimide (MI), a compound containing an electron withdrawing group, and combinations thereof.

In one aspect, the unsaturated carbon bond containing compound may include vinylene carbonate (VC), vinyl ethylene carbonate (VEC), and combinations thereof.

In one aspect, the sulfur-containing compound may include ethylene sulfite (ES), propylene sulfite (PyS), and combinations thereof.

In one aspect, the halogen-containing compound may include fluoroethylene carbonate (FEC), chloro-ethylene carbonate (Cl-EC), and combinations thereof.

In one aspect, the second additive may include a boron-containing compound, a silicon-containing compound, a phosphorus-containing compound, a compound containing at least one of a phenyl group, a thiophene aniline group, a maleimide group, an aniline group, an anisole group, an adamantyl group, a furan group, and a thiophene group, and combinations thereof.

In one aspect, the boron-containing compound may include lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), tris(trimethylsilyl)borate (TMSB), and combinations thereof.

In one aspect, the silicon-containing compound may include tris(trimethylsilyl)phosphate (TMSP), tris(trimethylsilyl)borate (TMSB), and combinations thereof.

In one aspect, the phosphorus-containing compound may include triphenyl phosphine (TPP), ethyl diphenylphosphinite (EDP), triethyl phosphite (TEP), and combinations thereof.

In one aspect, the compound containing at least one of a phenyl group, a thiophene aniline group, a maleimide group, an aniline group, an anisole group, an adamantyl group, a furan group, and a thiophene group may include biphenyl (BP), o-terphenyl (OT), 2,2′-bis[4-(4 maleimidophenoxy)phenyl]propane (BMP), N,N-dimethyl-aniline (DMA), and combinations thereof.

In one aspect, the first polymeric gel electrolyte and the second polymeric gel electrolyte may each further include greater than or equal to about 0.1 wt. % to less than or equal to about 50 wt. % of a polymer host.

In one aspect, the first polymeric gel electrolyte and the second polymeric gel electrolyte may each include a polymer host independently selected from the group consisting of: poly(ethylene oxide) (PEO), poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP), poly(methyl methacrylate) (PMMA), carboxymethyl cellulose (CMC), polyacrylonitrile (PAN), polyvinylidene difluoride (PVDF), poly(vinyl alcohol) (PVA), polyvinylpyrrolidone (PVP), lithium polyacrylate (LiPAA), and combinations thereof.

In one aspect, the first polymeric gel electrolyte and the second polymeric gel electrolyte may each further include greater than or equal to about 5 wt. % to less than or equal to about 90 wt. % of a liquid electrolyte.

In one aspect, the third polymeric gel electrolyte may include greater than or equal to about 0.1 wt. % to less than or equal to about 50 wt. % of a polymer host, and greater than or equal to about 5 wt. % to less than or equal to about 90 wt. % of a liquid electrolyte.

In one aspect, the polymer host may be selected from the group consisting of: poly(acrylonitrile) (PAN), poly(ethylene oxide) (PEO), poly(ethylene glycol) (PEG), polyethylene carbonate (PEC), poly(trimethylene carbonate) (PTMC), poly(propylene carbonate) (PPC), polyvinylidene difluoride (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), and combinations thereof.

In one aspect, the electrolyte layer may be a free-standing membrane defined by the third polymeric gel electrolyte. The free-standing membrane may have a thickness greater than or equal to about 5 μm to less than or equal to about 1,000 μm.

In one aspect, the electrolyte layer may further include greater than 0 wt. % to less than or equal to about 80 wt. % of a plurality of solid-state electrolyte particles.

In one aspect, the electrochemical cell further may further include a first bipolar current collector disposed on or adjacent to an exposed surface of the first electrode and parallel with the electrolyte layer; a second bipolar current collector disposed on or adjacent to an exposed surface of the second electrode and parallel with the electrolyte layer; and one or more polymer blockers coupled to and extending between the first bipolar current collector and the second bipolar current collector.

In various aspects, the present disclosure provides an electrochemical cell that cycles lithium ions. The electrochemical cell may include a first electrode, a second electrode, and an electrolyte layer disposed between the first electrode and the second electrode. The first electrode may include a first plurality of solid-state electroactive material particles and a first polymeric gel electrolyte. The first polymeric gel electrolyte may include greater than 0 wt. % to less than or equal to about 10 wt. % of a first additive, greater than or equal to about 0.1 wt. % to less than or equal to about 15 wt. % of a first polymer host, and greater than or equal to about 5 wt. % to less than or equal to about 90 wt. % of a first liquid electrolyte. The second electrode may include a second plurality of solid-state electroactive material particles and a second polymeric gel electrolyte. The second polymeric gel electrolyte may include greater than 0 wt. % to less than or equal to about 10 wt. % of a second additive, greater than or equal to about 0.1 wt. % to less than or equal to about 15 wt. % of a second polymer host, and greater than or equal to about 5 wt. % to less than or equal to about 90 wt. % of a second liquid electrolyte. The electrolyte layer may include a third polymeric gel electrolyte. The third polymeric gel electrolyte may include greater than or equal to about 10 wt. % to less than or equal to about 50 wt. % of a third polymer host and greater than or equal to about 5 wt. % to less than or equal to about 90 wt. % of a third liquid electrolyte.

In one aspect, the first liquid electrolyte, the second liquid electrolyte, and the third liquid electrolyte are the same or different.

In one aspect, the first polymer host and the second polymer host may be independently selected from the group consisting of: poly(ethylene oxide) (PEO), poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP), poly(methyl methacrylate) (PMMA), carboxymethyl cellulose (CMC), polyacrylonitrile (PAN), polyvinylidene difluoride (PVDF), poly(vinyl alcohol) (PVA), polyvinylpyrrolidone (PVP), lithium polyacrylate (LiPAA), and combinations thereof.

In one aspect, the third polymer host may be selected from the group consisting of: poly(acrylonitrile) (PAN), poly(ethylene oxide) (PEO), poly(ethylene glycol) (PEG), polyethylene carbonate (PEC), poly(trimethylene carbonate) (PTMC), poly(propylene carbonate) (PPC), polyvinylidene difluoride (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), and combinations thereof.

In one aspect, the first additive may be selected from the group consisting of: vinylene carbonate (VC), vinyl ethylene carbonate (VEC), ethylene sulfite (ES), propylene sulfite (PyS), fluoroethylene carbonate (FEC), chloro-ethylene carbonate (Cl-EC), and combinations thereof.

In one aspect, the second additive may be selected from the group consisting of: bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), tris(trimethylsilyl)borate (TMSB), tris(trimethylsilyl)phosphate (TMSP), triphenyl phosphine (TPP), ethyl diphenylphosphinite (EDP), triethyl phosphite (TEP), biphenyl (BP), o-terphenyl (OT), 2,2′-bis[4-(4 maleimidophenoxy)phenyl]propane (BMP), N,N-dimethyl-aniline (DMA), and combinations thereof.

In various aspects, the present disclosure provides a method for forming an electrochemical cell that cycles lithium ions. The method may include preparing a first gel-assisted electrode, preparing a second gel-assisted electrode, and preparing an electrolyte layer comprising a third precursor liquid. Preparing the first gel-assisted electrode may include contacting a first precursor electrode and a first precursor liquid that includes a first solvent and a first additive, and removing the first solvent to form the first gel-assisted electrode. Preparing the second gel-assisted electrode may include contacting a second precursor electrode and a second precursor liquid that includes a second solvent and a second additive, and removing the second solvent to form the second gel-assisted electrode. The first precursor liquid may be different from the second and third precursor liquids. The second precursor liquid may be different from the first and third precursor liquids. The method may further include stacking the first gel-assisted electrode, the second gel-assisted electrode, and the electrolyte layer to form the electrochemical cell, where the electrolyte layer is disposed between the first gel-assisted electrode and the second gel-assisted electrode.

In one aspect, the first additive may be selected from the group consisting of: vinylene carbonate (VC), vinyl ethylene carbonate (VEC), ethylene sulfite (ES), propylene sulfite (PyS), fluoroethylene carbonate (FEC), chloro-ethylene carbonate (Cl-EC), and combinations thereof.

In one aspect, the second additive may be selected from the group consisting of: bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), tris(trimethylsilyl)borate (TMSB), tris(trimethylsilyl)phosphate (TMSP), triphenyl phosphine (TPP), ethyl diphenylphosphinite (EDP), triethyl phosphite (TEP), biphenyl (BP), o-terphenyl (OT), 2,2′-bis[4-(4 maleimidophenoxy)phenyl]propane (BMP), N,N-dimethyl-aniline (DMA), 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.

BRIEF DESCRIPTION OF THE 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 A is an illustration of an example solid-state battery in accordance with various aspects of the present disclosure;

FIG. 1 B is an example solid-state battery having a polymeric gel electrolyte system in accordance with various aspects of the present disclosure;

FIG. 2 is another example solid-state battery having a polymeric gel electrolyte system in accordance with various aspects of the present disclosure;

FIG. 3 is another example solid-state battery having a polymeric gel electrolyte system in accordance with various aspects of the present disclosure;

FIG. 4 is a flowchart illustrating an exemplary method for fabricating a battery including a polymeric gel electrolyte system in accordance with various aspects of the present disclosure;

FIG. 5 A is a graphical illustration demonstrating cycle performance of an example battery cell prepared in accordance with various aspects of the present disclosure;

FIG. 5 B is a graphical illustration demonstrating discharge of an example battery cell prepared in accordance with various aspects of the present disclosure; and

FIG. 5 C is a graphical illustration demonstrating rate tests for an example battery cell prepared in accordance with various aspects of the present disclosure.

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 “a,” “an,” and “the” may be intended to include the plural forms as well, unless the context clearly indicates otherwise. The terms “comprises,” “comprising,” “including,” and “having,” 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 “comprising,” 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 “consisting of” or “consisting essentially of.” 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 “consisting of,” the alternative embodiment excludes any additional compositions, materials, components, elements, features, integers, operations, and/or process steps, while in the case of “consisting essentially of,” 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 “on,” “engaged to,” “connected to,” or “coupled to” 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 “directly on,” “directly engaged to,” “directly connected to,” or “directly coupled to” 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., “between” versus “directly between,” “adjacent” versus “directly adjacent,” etc.). As used herein, the term “and/or” 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 “first,” “second,” 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 “before,” “after,” “inner,” “outer,” “beneath,” “below,” “lower,” “above,” “upper,” and the like, may be used herein for ease of description to describe one element or feature&#39;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 “about” whether or not “about” actually appears before the numerical value. “About” 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 “about” is not otherwise understood in the art with this ordinary meaning, then “about” as used herein indicates at least variations that may arise from ordinary methods of measuring and using such parameters. For example, “about” 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.

The current technology pertains to solid-state batteries (SSBs), for example only, bipolar solid-state batteries, and methods of forming and using the same. Solid-state batteries may include at least one solid component, for example, at least one solid electrode, but may also include semi-solid or gel, liquid, or gas components, in certain variations. Solid-state batteries may have a bipolar stack design comprising a plurality of bipolar electrodes where a first mixture of solid-state electroactive material particles (and optional solid-state electrolyte particles) is disposed on a first side of a current collector, and a second mixture of solid-state electroactive material particles (and optional solid-state electrolyte particles) is disposed on a second side of a current collector that is parallel with the first side. The first mixture may include, as the solid-state electroactive material particles, positive electrode or cathode material particles. The second mixture may include, as solid-state electroactive material particles, negative electrode or anode material particles. The solid-state electrolyte particles in each instance may be the same or different.

Such solid-state batteries may be incorporated into energy storage devices, like rechargeable lithium-ion batteries, which may be used in automotive transportation applications (e.g., motorcycles, boats, tractors, buses, mobile homes, campers, and tanks). The present technology, however, may also be used in other electrochemical devices, including aerospace components, consumer goods, devices, buildings (e.g., houses, offices, sheds, and warehouses), office equipment and furniture, and industrial equipment machinery, agricultural or farm equipment, or heavy machinery, by way of non-limiting example. In various aspects, the present disclosure provides a rechargeable lithium-ion battery that exhibits high temperature tolerance, as well as improved safety and superior power capability and life performance.

An exemplary and schematic illustration of a solid-state electrochemical cell unit (also referred to as a “solid-state battery” and/or “battery”) 20 that cycles lithium ions is shown in FIGS. 1 A and 1 B . The battery 20 includes a negative electrode (i.e., anode) 22 , a positive electrode (i.e., cathode) 24 , and an electrolyte layer 26 that occupies a space defined between the two or more electrodes. The electrolyte layer 26 is a solid-state or semi-solid state separating layer that physically separates the negative electrode 22 from the positive electrode 24 . The electrolyte layer 26 may include a first plurality of solid-state electrolyte particles 30 . A second plurality of solid-state electrolyte particles 90 may be mixed with negative solid-state electroactive particles 50 in the negative electrode 22 , and a third plurality of solid-state electrolyte particles 92 may be mixed with positive solid-state electroactive particles 60 in the positive electrode 24 , so as to form a continuous electrolyte network, which may be a continuous lithium-ion conduction network.

A first bipolar current collector 32 may be positioned at or near the negative electrode 22 . A second bipolar current collector 34 may be positioned at or near the positive electrode 24 . The first and second bipolar current collectors 32 , 34 may be the same or different. For example, the first and second bipolar current collectors 32 , 34 may each have a thickness greater than or equal to about 2 μm to less than or equal to about 30 μm. The first and second bipolar current collectors 32 , 34 may each be metal foils including at least one of stainless steel, aluminum, nickel, iron, titanium, copper, tin, alloys thereof, or any other electrically conductive material known to those of skill in the art.

In certain variations, the first bipolar current collector 34 and/or the second bipolar current collector 34 may be a cladded foil, for example, where one side (e.g., the first side or the second side) of the current collector 32 , 34 includes one metal (e.g., first metal) and another side (e.g., the other side of the first side or the second side) of the current collector 232 includes another metal (e.g., second metal). The cladded foil may include, for example only, aluminum-copper (Al—Cu), nickel-copper (Ni—Cu), stainless steel-copper (SS—Cu), aluminum-nickel (Al—Ni), aluminum-stainless steel (Al—SS), and nickel-stainless steel (Ni—SS). In certain variations, the first bipolar current collector 232 A and/or second bipolar current collectors 232 B may be pre-coated, such as graphene or carbon-coated aluminum current collectors.

In each instance, the first bipolar current collector 32 and the second bipolar current collector 34 respectively collect and move free electrons to and from an external circuit 40 (as shown by the block arrows). For example, an interruptible external circuit 40 and a load device 42 may connect the negative electrode 22 (through the first bipolar current collector 32 ) and the positive electrode 24 (through the second bipolar current collector 34 ).

The battery 20 can generate an electric current (indicated by arrows in FIGS. 1 A and 1 B ) 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 when the negative electrode 22 has a lower potential than the positive electrode 24 . The chemical potential difference between the negative electrode 22 and the positive electrode 24 drives electrons produced by a reaction, for example, the oxidation of intercalated lithium, at the negative electrode 22 , through the external circuit 40 toward the positive electrode 24 . Lithium ions, which are also produced at the negative electrode 22 , are concurrently transferred through the electrolyte layer 26 toward the positive electrode 24 . The electrons flow through the external circuit 40 and the lithium ions migrate across the electrolyte layer 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 (in the direction of the arrows) until the lithium in the negative electrode 22 is depleted and the capacity of the battery 20 is diminished.

The battery 20 can be charged or reenergized at any time by connecting an external power source (e.g., charging device) to the battery 20 to reverse the electrochemical reactions that occur during battery discharge. The external power source that may be used to charge the battery 20 may vary depending on the size, construction, and particular end-use of the battery 20 . Some notable and exemplary external power sources include, but are not limited to, an AC-DC converter connected to an AC electrical power grid though a wall outlet and a motor vehicle alternator. The connection of the external power source to the battery 20 promotes a reaction, for example, non-spontaneous oxidation of intercalated lithium, at the positive electrode 24 so that electrons and lithium ions are produced. The electrons, which flow back toward the negative electrode 22 through the external circuit 40 , and the lithium ions, which move across the electrolyte layer 26 back toward 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, a complete discharging event followed by a complete charging event is considered to be a cycle, where lithium ions are cycled between the positive electrode 24 and the negative electrode 22 .

Although the illustrated example includes a single positive electrode 24 and a single negative electrode 22 , the skilled artisan will recognize that the current teachings apply to various other configurations, including those having one or more cathodes and one or more anodes, as well as various current collectors and current collector films with electroactive particle layers disposed on or adjacent to or embedded within one or more surfaces thereof. Likewise, it should be recognized that the battery 20 may include a variety of other components that, while not depicted here, are nonetheless known to those of skill in the art. For example, the battery 20 may include a casing, a gasket, terminal caps, 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 solid-state electrolyte 26 layer.

In many configurations, each of the negative electrode current collector 32 , the negative electrode 22 , the electrolyte layer 26 , the positive electrode 24 , and the positive electrode current collector 34 are prepared as relatively thin layers (for example, from several microns to a millimeter or less in thickness) and assembled in layers connected in series arrangement to provide a suitable electrical energy, battery voltage and power package, for example, to yield a Series-Connected Elementary Cell Core (“SECC”). In various other instances, the battery 20 may further include electrodes 22 , 24 connected in parallel to provide suitable electrical energy, battery voltage, and power for example, to yield a Parallel-Connected Elementary Cell Core (“PECC”).

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, voltage, energy, 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 . The battery 20 can generate an electric current to the load device 42 that can be operatively connected to the external circuit 40 . The load device 42 may be fully or partially powered by the electric current passing through the external circuit 40 when the battery 20 is discharging. 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, by way of non-limiting example. The load device 42 may also be an electricity-generating apparatus that charges the battery 20 for purposes of storing electrical energy.

With renewed reference to FIGS. 1 A and 1 B , the solid-state electrolyte layer 26 provides electrical separation—preventing physical contact—between the negative electrode 22 and the positive electrode 24 . The solid-state electrolyte layer 26 also provides a minimal resistance path for internal passage of ions. In various aspects, the solid-state electrolyte layer 26 may be defined by a first plurality of solid-state electrolyte particles 30 . For example, the solid-state electrolyte layer 26 may be in the form of a layer or a composite that comprises the first plurality of solid-state electrolyte particles 30 . The solid-state electrolyte particles 30 may have an average particle diameter greater than or equal to about 0.02 μm to less than or equal to about 20 μm, optionally greater than or equal to about 0.1 μm to less than or equal to about 10 μm, and in certain aspects, optionally greater than or equal to about 0.1 μm to less than or equal to about 1 μm. The solid-state electrolyte layer 26 may be in the form of a layer having a thickness greater than or equal to about 5 μm to less than or equal to about 200 μm, optionally greater than or equal to about 10 μm to less than or equal to about 100 μm, optionally about 40 μm, and in certain aspects, optionally about 30 μm. The solid-state electrolyte layer 26 may have an interparticle porosity 80 between the solid-state electrolyte particles 30 that is greater than 0 vol. % to less than or equal to about 50 vol. %, optionally greater than or equal to about 1 vol. % to less than or equal to about 40 vol. %, and in certain aspects, optionally greater than or equal to about 2 vol. % to less than or equal to about 20 vol. %.

The solid-state electrolyte particles 30 may comprise one or more sulfide-based particles, oxide-based particles, metal-doped or aliovalent-substituted oxide particles, inactive oxide particles, nitride-based particles, hydride-based particles, halide-based particles, and borate-based particles.

In certain variations, the oxide-based particles may comprise one or more garnet ceramics, LISICON-type oxides, NASICON-type oxides, and Perovskite type ceramics. For example, the garnet ceramics may be selected from the group consisting of: Li 7 La 3 Zr 2 O 12 , Li 6.2 Ga 0.3 La 2.95 Rb 0.05 Zr 2 O 12 , Li 6.85 La 2.9 Ca 0.1 Zr 1.75 Nb 0.25 O 12 , Li 6.25 Al 0.25 La 3 Zr 2 O 12 , Li 6.75 La 3 Zr 1.75 Nb 0.25 O 12 , and combinations thereof. The LISICON-type oxides may be selected from the group consisting of: Li 2+2x Zn 1−x GeO 4 (where 0&lt;x&lt;1), Li 14 Zn(GeO 4 ) 4 , Li 3+x (P 1−x Si x )O 4 (where 0&lt;x&lt;1), Li 3+x Ge x V 1−x O 4 (where 0&lt;x&lt;1), and combinations thereof. The NASICON-type oxides may be defined by LiMM′(PO 4 ) 3 , where M and M′ are independently selected from Al, Ge, Ti, Sn, Hf, Zr, and La. For example, in certain variations, the NASICON-type oxides may be selected from the group consisting of: Li 1+x Al x Ge 2−x (PO 4 ) 3 (LAGP) (where 0&lt;x&lt;2), Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 , Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , LiTi 2 (PO 4 ) 3 , LiGeTi(PO 4 ) 3 , LiGe 2 (PO 4 ) 3 , LiHf 2 (PO 4 ) 3 , and combinations thereof. The Perovskite-type ceramics may be selected from the group consisting of: Li 3.3 La 0.53 TiO 3 , LiSr 1.65 Zr 1.3 Ta 1.7 O 9 , Li 2x−y Sr 1−x Ta y Zr 1−y O 3 (where x=0.75y and 0.60&lt;y&lt;0.75), Li 3/8 Sr 7/16 Nb 3/4 Zr 1/4 O 3 , Li 3x La (2/3−8) TiO 3 (where 0&lt;x&lt;0.25), and combinations thereof.

In certain variations, the metal-doped or aliovalent-substituted oxide particles may include, for example only, aluminum (Al) or niobium (Nb) doped Li 7 La 3 Zr 2 O 12 , antimony (Sb) doped Li 7 La 3 Zr 2 O 12 , gallium (Ga) doped Li 7 La 3 Zr 2 O 12 , chromium (Cr) and/or vanadium (V) substituted LiSn 2 P 3 O 12 , aluminum (Al) substituted Li 1++y Al x Ti 2−x Si Y P 3−y O 12 (where 0&lt;x&lt;2 and 0&lt;y&lt;3), and combinations thereof.

In certain variations, the sulfide-based particles may include, for example only, a pseudobinary sulfide, a pseudoternary sulfide, and/or a pseudoquaternary sulfide. Example pseudobinary sulfide systems include Li 2 S—P 2 S 5 systems (such as, Li 3 PS 4 , Li 7 P 3 S 11 , and Li 9.6 P 3 S 12 ), Li 2 S—SnS 2 systems (such as, Li 4 SnS 4 ), Li 2 S—SiS 2 systems, Li 2 S—GeS 2 systems, Li 2 S—B 2 S 3 systems, Li 2 S—Ga 2 S 3 system, Li 2 S—P 2 S 3 systems, and Li 2 S—Al 2 S 3 systems. Example pseudoternary sulfide systems include Li 2 O—Li 2 S—P 2 S 5 systems, Li 2 S—P 2 S 5 —P 2 O 5 systems, Li 2 S—P 2 S 5 —GeS 2 systems (such as, Li 3.25 Ge 0.25 P 0.75 S 4 and Li 10 GeP 2 S 12 ), Li 2 S—P 2 S 5 —LiX systems (where X is one of F, Cl, Br, and I) (such as, Li 6 PS 5 Br, Li 6 PS 5 Cl, L 7 P 2 S 8 I, and Li 4 PS 4 I), Li 2 S—As 2 S 5 —SnS 2 systems (such as, Li 3.833 Sn 0.833 As 0.166 S 4 ), Li 2 S—P 2 S 5 —Al 2 S 3 systems, Li 2 S—LiX—SiS 2 systems (where X is one of F, Cl, Br, and I), 0.4LiI·0.6Li 4 SnS 4 , and Li 11 Si 2 PS 12 . Example pseudoquaternary sulfide systems include Li 2 O—Li 2 S—P 2 S 5 —P 2 O 5 systems, Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 , Li 7 P 2.9 Mn 0.1 S 10.7 I 0.3 , and Li 10.35 [Sn 0.27 Si 1.08 ]P 1.65 S 12 .

In certain variations, the inactive oxide particles may include, for example only, SiO 2 , Al 2 O 3 , TiO 2 , ZrO 2 , and combinations thereof the nitride-based particles may include, for example only, Li 3 N, Li 7 PN 4 , LiSi 2 N 3 , and combinations thereof; the hydride-based particles may include, for example only, LiBH 4 , LiBH 4 —LiX (where x=Cl, Br, or I), LiNH 2 , Li 2 NH, LiBH 4 —LiNH 2 , Li 3 AlH 6 , and combinations thereof; the halide-based particles may include, for example only, LiI, Li 3 InCl 6 , Li 2 CdC 14 , Li 2 MgCl 4 , LiCdI 4 , Li 2 ZnI 4 , Li 3 OCl, Li 3 YCl 6 , Li 3 YBr 6 , and combinations thereof and the borate-based particles may include, for example only, Li 2 B 4 O 7 , Li 2 O—B 2 O 3 —P 2 O 5 , and combinations thereof.

In various aspects, the first plurality of solid-state electrolyte particles 30 may include one or more electrolyte materials selected from the group consisting of: Li 2 S—P 2 S 5 system, Li 2 S—P 2 S 5 —MO x system (where 1&lt;x&lt;7), Li 2 S—P 2 S 5 —MS x system (where 1&lt;x&lt;7), Li 10 GeP 2 S 12 (LGPS), Li 6 PS 5 X (where X is Cl, Br, or I) (lithium argyrodite), Li 7 P 2 S 8 I, Li 10.35 Ge 1.35 P 1.65 S 12 , Li 3.25 Ge 0.25 P 0.75 S 4 (thio-LISICON), Li 10 SnP 2 S 12 , Li 10 SiP 2 S 12 , Li 9.54 Si 1.74 P 1.44 S 11.7 O 0.3 , (1−x)P 2 S 5 -xLi 2 S (where 0.5&lt;x&lt;0.7), Li 3.4 Si 0.4 P 0.6 S 4 , PLi 10 GeP 2 S 11.7 O 0.3 , 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 1.63 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 , Li 3.833 Sn 0.833 As 0.16 S 4 , Li 7 La 3 Zr 2 O 12 , Li 6.2 Ga 0.3 La 2.95 Rb 0.05 Zr 2 O 12 , Li 6.85 La 2.9 Ca 0.1 Zr 1.75 Nb 0.25 O 12 , Li 6.25 Al 0.25 La 3 Zr 2 O 12 , Li 6.75 La 3 Zr 1.75 Nb 0.25 O 12 , Li 6.75 La 3 Zr 1.75 Nb 0.25 O 12 , Li 2+2x Zn 1−x GeO 4 (where 0&lt;x&lt;1), Li 14 Zn(GeO 4 ) 4 , Li 3+x (P 1−x Si x )O 4 (where 0&lt;x&lt;1), Li 3+x Ge x V 1−x O 4 (where 0&lt;x&lt;1), LiMM′(PO 4 ) 3 (where M and M′ are independently selected from Al, Ge, Ti, Sn, Hf, Zr, and La), Li 3.3 La 0.53 TiO 3 , LiSr 1.65 Zr 1.3 Ta 1.7 O 9 , Li 2x−y Sr 1−x Ta y Zr 1−y O 3 (where x=0.75y and 0.60&lt;y&lt;0.75), Li 3/8 Sr 7/16 Nb 3/4 Zr 1/4 O 3 , Li 3x La (2/3−x) TiO 3 (where 0&lt;x&lt;0.25), aluminum (Al) or niobium (Nb) doped Li 7 La 3 Zr 2 O 12 , antimony (Sb) doped Li 7 La 3 Zr 2 O 12 , gallium (Ga) doped Li 7 La 3 Zr 2 O 12 , chromium (Cr) and/or vanadium (V) substituted LiSn 2 P 3 O 12 , aluminum (Al) substituted Li 1+x+y Al x Ti 2−x Si y P 3−y O 12 (where 0&lt;x&lt;2 and 0&lt;y&lt;3), LiI—Li 4 SnS 4 , Li 4 SnS 4 , Li 3 N, Li 7 PN 4 , LiSi 2 N 3 , LiBH 4 , LiBH 4 —LiX (where x=Cl, Br, or I), LiNH 2 , Li 2 NH, LiBH 4 —LiNH 2 , Li 3 AlH 6 , LiI, Li 3 InCl 6 , Li 2 CdC 14 , Li 2 MgCl 4 , LiCdI 4 , Li 2 ZnI 4 , Li 3 OCl, Li 2 B 4 O 7 , Li 2 O—B 2 O 3 —P 2 O 5 , and combinations thereof.

In certain variations, the first plurality of solid-state electrolyte particles 30 may include one or more electrolyte materials selected from the group consisting of: Li 2 S—P 2 S 5 system, Li 2 S—P 2 S 5 —MO x system (where 1&lt;x&lt;7), Li 2 S—P 2 S 5 —MS x system (where 1&lt;x&lt;7), Li 10 GeP 2 S 12 (LGPS), Li 6 PS 5 X (where X is Cl, Br, or I) (lithium argyrodite), Li 7 P 2 S 8 I, Li 10.35 Ge 1.35 P 1.65 S 12 , Li 3.25 Ge 0.25 P 0.75 S 4 (thio-LISICON), Li 10 SnP 2 S 12 , Li 10 SiP 2 S 12 , Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 , (1−x)P 2 S 5−x Li 2 S (where 0.5≤x≤0.7), Li 3.4 Si 0.4 P 0.6 S 4 , PLi 10 GeP 2 S 11.7 O 0.3 , 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 1.63 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 , Li 3.833 Sn 0.833 As 0.16 S 4 , and combinations thereof.

Although not illustrated, the skilled artisan will recognize that in certain instances, one or more binder particles may be mixed with the solid-state electrolyte particles 30 . For example, in certain aspects the solid-state electrolyte layer 26 may include greater than or equal to about 0 wt. % to less than or equal to about 10 wt. %, and in certain aspects, optionally greater than or equal to about 0.5 wt. % to less than or equal to about 10 wt. %, of the one or more binders. The one or more polymeric binders may include, for example only, polyvinylidene difluoride (PVDF), polytetrafluoroethylene (PTFE), ethylene propylene diene monomer (EPDM) rubber, nitrile butadiene rubber (NBR), styrene-butadiene rubber (SBR), and lithium polyacrylate (LiPAA).

The negative electrode 22 may be formed from a lithium host material that is capable of functioning as a negative terminal of a lithium-ion battery. The negative electrode 22 may be in the form of a layer having a thickness greater than or equal to about 5 μm to less than or equal to about 400 μm, and in certain aspects, optionally greater than or equal to about 10 μm to less than or equal to about 300 μm. In certain variations, the negative electrode 22 may be defined by a plurality of the negative solid-state electroactive particles 50 . The negative solid-state electroactive particles 50 may have an average particle diameter greater than or equal to about 0.01 μm to less than or equal to about 50 and in certain aspects, optionally greater than or equal to about 1 μm to less than or equal to about 20 μm.

In certain instances, as illustrated, the negative electrode 22 may be a composite comprising a mixture of the negative solid-state electroactive particles 50 and the second plurality of solid-state electrolyte particles 90 . For example, the negative electrode 22 may include greater than or equal to about 30 wt. % to less than or equal to about 98 wt. %, and in certain aspects, optionally greater than or equal to about 50 wt. % to less than or equal to about 95 wt. %, of the negative solid-state electroactive particles 50 and greater than or equal to about 0 wt. % to less than or equal to about 50 wt. %, and in certain aspects, optionally greater than or equal to about 5 wt. % to less than or equal to about 20 wt. %, of the second plurality of solid-state electrolyte particles 90 . The negative electrodes 22 may have an interparticle porosity 82 between the negative solid-state electroactive particles 50 and/or the solid-state electrolyte particles 90 that is greater than or equal to about 0 vol. % to less than or equal to about 50 vol. %, and in certain aspects, optionally greater than or equal to about 2 vol. % to less than or equal to about 20 vol. %.

The second plurality of solid-state electrolyte particles 90 may be the same as or different from the first plurality of solid-state electrolyte particles 30 . In certain variations, the negative solid-state electroactive particles 50 may comprise one or more carbonaceous negative electroactive materials, such as graphite, graphene, hard carbon, soft carbon, and carbon nanotubes (CNTs). In other variations, the negative solid-state electroactive particles 50 may be silicon-based comprising, for example, a silicon alloy and/or silicon-graphite mixture. In still other variations, the negative electrode 22 may include a lithium alloy or a lithium metal. In still further variations, the negative electrode 22 may comprise one or more negative electroactive materials, such as lithium titanium oxide (Li 4 Ti 5 O 12 ), metal oxides (e.g., TiO 2 and/or V 2 O 5 ), metal sulfides (e.g., FeS), transition metals (e.g., tin (Sn)), and other lithium-accepting materials. Thus, the negative solid-state electroactive particles 50 may be selected from the group including, for example only, lithium, graphite, graphene, hard carbon, soft carbon, carbon nanotubes, silicon, silicon-containing alloys, tin-containing alloys, and any combination thereof.

In certain variations, the negative electrode 22 further includes one or more conductive additives and/or binder materials. For example, the negative solid-state electroactive particles 50 (and/or second plurality of solid-state electrolyte particles 90 ) may be optionally intermingled with one or more electrically conductive materials (not shown) that provide an electron conduction path and/or at least one polymeric binder material (not shown) that improves the structural integrity of the negative electrode 22 .

For example, the negative solid-state electroactive particles 50 (and/or second plurality of solid-state electrolyte particles 90 ) may be optionally intermingled with binders, such as polyvinylidene difluoride (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), polytetrafluoroethylene (PTFE), sodium carboxymethyl cellulose (CMC), ethylene propyle

CLAIMS

Claims ( 19 )

What is claimed is:

1. An electrochemical cell that cycles lithium ions, the electrochemical cell comprising:

a first electrode comprising a first plurality of solid-state electroactive material particles and a first polymeric gel electrolyte, the first polymeric gel electrolyte comprising greater than 0 wt. % to less than or equal to about 10 wt. % of a first additive comprising a compound having an unsaturated carbon bond, a sulfur-containing compound, a halogen-containing compound, a methyl substituted glycolide derivative, a maleimide (MI), a compound containing an electron withdrawing group, and combinations thereof;

a second electrode comprising a second plurality of solid-state electroactive material particles and a second polymeric gel electrolyte that is different from the first polymeric gel electrolyte, the second polymeric gel electrolyte comprising greater than 0 wt. % to less than or equal to about 10 wt. % of a second additive that is different from the first additive; and

an electrolyte layer disposed between the first electrode and the second electrode, the electrolyte layer comprising a third polymeric gel electrolyte that is different from both the first polymeric gel electrolyte and the second polymeric gel electrolyte.

2. The electrochemical cell of claim 1 , wherein the unsaturated carbon bond containing compound comprises vinylene carbonate (VC), vinyl ethylene carbonate (VEC), and combinations thereof;

the sulfur-containing compound comprises ethylene sulfite(ES), propylene sulfite (PyS), and combinations thereof; and

the halogen-containing compound comprises fluoroethylene carbonate (FEC), chloro-ethylene carbonate (CI-EC), and combinations thereof.

3. The electrochemical cell of claim 1 , wherein the second additive comprises a boron-containing compound, a silicon-containing compound, a phosphorus-containing compound, a compound containing at least one of a phenyl group, a thiophene aniline group, a maleimide group, an aniline group, an anisole group, an adamantyl group, a furan group, and a thiophene group, and combinations thereof.

4. The electrochemical cell of claim 3 , wherein the boron-containing compound comprises lithium bis(oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiDFOB), tris(trimethylsilyl) borate (TMSB), and combinations thereof;

the silicon-containing compound comprises tris(trimethylsilyl)phosphate (TMSP), tris(trimethylsilyl) borate (TMSB), and combinations thereof;

the phosphorus-containing compound comprises triphenyl phosphine (TPP), ethyl diphenylphosphinite (EDP), triethyl phosphite (TEP), and combinations thereof; and

the compound containing at least one of a phenyl group, a thiophene aniline group, a maleimide group, an aniline group, an anisole group, an adamantyl group, a furan group, and a thiophene group comprises biphenyl (BP), o-terphenyl (OT), 2,2′-bis[4-(4 maleimidophenoxy)phenyl]propane (BMP), N,N-dimethyl-aniline (DMA), and combinations thereof.

5. The electrochemical cell of claim 1 , wherein the first polymeric gel electrolyte and the second polymeric gel electrolyte each further comprises greater than or equal to about 0.1 wt. % to less than or equal to about 50 wt. % of a polymer host.

6. The electrochemical cell of claim 5 , wherein the first polymeric gel electrolyte and the second polymeric gel electrolyte each comprise a polymer host independently selected from the group consisting of: poly(ethylene oxide) (PEO), poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP), poly(methyl methacrylate) (PMMA), carboxymethyl cellulose (CMC), polyacrylonitrile (PAN), polyvinylidene difluoride (PVDF), poly(vinyl alcohol) (PVA), polyvinylpyrrolidone (PVP), lithium polyacrylate (LiPAA), and combinations thereof.

7. The electrochemical cell of claim 1 , wherein the first polymeric gel electrolyte and the second polymeric gel electrolyte each further comprises greater than or equal to about 5 wt. % to less than or equal to about 90 wt. % of a liquid electrolyte.

8. The electrochemical cell of claim 1 , wherein the third polymeric gel electrolyte comprises greater than or equal to about 0.1 wt. % to less than or equal to about 50 wt. % of a polymer host, and greater than or equal to about 5 wt. % to less than or equal to about 90 wt. % of a liquid electrolyte.

9. The electrochemical cell of claim 8 , wherein the polymer host is selected from the group consisting of: poly(acrylonitrile) (PAN), poly(ethylene oxide) (PEO), poly(ethylene glycol) (PEG), polyethylene carbonate (PEC), poly(trimethylene carbonate) (PTMC), poly(propylene carbonate) (PPC), polyvinylidene difluoride (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), and combinations thereof.

10. The electrochemical cell of claim 8 , wherein the electrolyte layer is a free-standing membrane defined by the third polymeric gel electrolyte, wherein the free-standing membrane has a thickness greater than or equal to about 5 micrometers to less than or equal to about 1,000 micrometers.

11. The electrochemical cell of claim 8 , wherein the electrolyte layer further comprises greater than 0 wt. % to less than or equal to about 80 wt. % of a plurality of solid-state electrolyte particles.

12. The electrochemical cell of claim 1 , wherein the electrochemical cell further comprises:

a first bipolar current collector disposed on or adjacent to an exposed surface of the first electrode and parallel with the electrolyte layer;

a second bipolar current collector disposed on or adjacent to an exposed surface of the second electrode and parallel with the electrolyte layer; and

one or more polymer blockers coupled to and extending between the first bipolar current collector and the second bipolar current collector.

13. An electrochemical cell that cycles lithium ions, the electrochemical cell comprising:

a first electrode comprising a first plurality of solid-state electroactive material particles and a first polymeric gel electrolyte comprising greater than 0 wt. % to less than or equal to about 10 wt. % of a first additive, greater than or equal to about 0.1 wt. % to less than or equal to about 15 wt. % of a first polymer host, and greater than or equal to about 5 wt. % to less than or equal to about 90 wt. % of a first liquid electrolyte;

a second electrode comprising a second plurality of solid-state electroactive material particles and a second polymeric gel electrolyte comprising greater than 0 wt. % to less than or equal to about 10 wt. % of a second additive that is different from the first additive and is selected from the group consisting of: lithium bis(oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiDFOB), tris(trimethylsilyl) borate (TMSB), tris(trimethylsilyl)phosphate (TMSP), triphenyl phosphine (TPP), ethyl diphenylphosphinite (EDP), triethyl phosphite (TEP), biphenyl (BP), o-terphenyl (OT), 2,2′-bis[4-(4 maleimidophenoxy)phenyl]propane (BMP), N,N-dimethyl-aniline (DMA), and combinations thereof, greater than or equal to about 0.1 wt. % to less than or equal to about 15 wt. % of a second polymer host, and greater than or equal to about 5 wt. % to less than or equal to about 90 wt. % of a second liquid electrolyte; and

an electrolyte layer disposed between the first electrode and the second electrode, the electrolyte layer comprising a third polymeric gel electrolyte comprising greater than or equal to about 10 wt. % to less than or equal to about 50 wt. % of a third polymer host and greater than or equal to about 5 wt. % to less than or equal to about 90 wt. % of a third liquid electrolyte.

14. The electrochemical cell of claim 13 , wherein the first liquid electrolyte, the second liquid electrolyte, and the third liquid electrolyte are different.

15. The electrochemical cell of claim 13 , wherein the first polymer host and the second polymer host are independently selected from the group consisting of: poly(ethylene oxide) (PEO), poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP), poly(methyl methacrylate) (PMMA), carboxymethyl cellulose (CMC), polyacrylonitrile (PAN), polyvinylidene difluoride (PVDF), poly(vinyl alcohol) (PVA), polyvinylpyrrolidone (PVP), lithium polyacrylate (LiPAA), and combinations thereof; and

the third polymer host is selected from the group consisting of: poly(acrylonitrile) (PAN), poly(ethylene oxide) (PEO), poly(ethylene glycol) (PEG), polyethylene carbonate (PEC), poly(trimethylene carbonate) (PTMC), poly(propylene carbonate) (PPC), polyvinylidene difluoride (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), and combinations thereof.

16. The electrochemical cell of claim 13 , wherein the first additive is selected from the group consisting of: vinylene carbonate (VC), vinyl ethylene carbonate (VEC), ethylene sulfite(ES), propylene sulfite (PyS), fluoroethylene carbonate (FEC), chloro-ethylene carbonate (Cl-EC), and combinations thereof.

17. A method for forming an electrochemical cell that cycles lithium ions, the method comprising:

preparing a first gel-assisted electrode, wherein preparing the first gel-assisted electrode comprises contacting a first precursor electrode and a first precursor liquid comprising a first solvent and a first additive comprising a compound having an unsaturated carbon bond, a sulfur-containing compound, a halogen-containing compound, a methyl substituted glycolide derivative, a maleimide (MI), a compound containing an electron withdrawing group, and combinations thereof and removing the first solvent to form the first gel-assisted electrode;

preparing a second gel-assisted electrode, wherein preparing the second gel-assisted electrode comprises contacting a second precursor electrode and a second precursor liquid comprising a second solvent and a second additive that is different from the first additive, and removing the second solvent to form the second gel-assisted electrode;

preparing an electrolyte layer comprising a third precursor liquid, wherein the first precursor liquid is different from the second and third precursor liquids and the second precursor liquid is different from the first and third precursor liquids; and

stacking the first gel-assisted electrode, the second gel-assisted electrode, and the electrolyte layer to form the electrochemical cell, wherein the electrolyte layer is disposed between the first gel-assisted electrode and the second gel-assisted electrode.

18. The method of claim 17 , wherein

the second additive is selected from the group consisting of: lithium bis(oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiDFOB), tris(trimethylsilyl) borate (TMSB), tris(trimethylsilyl)phosphate (TMSP), triphenyl phosphine (TPP), ethyl diphenylphosphinite (EDP), triethyl phosphite (TEP), biphenyl (BP), o-terphenyl (OT), 2,2′-bis[4-(4 maleimidophenoxy)phenyl]propane (BMP), N,N-dimethyl-aniline (DMA), and combinations thereof.

19. The method of claim 17 , wherein the unsaturated carbon bond containing compound comprises vinylene carbonate (VC), vinyl ethylene carbonate (VEC), and combinations thereof;

the sulfur-containing compound comprises ethylene sulfite(ES), propylene sulfite (PyS), and combinations thereof; and

the halogen-containing compound comprises fluoroethylene carbonate (FEC), chloro-ethylene carbonate (Cl-EC), and combinations thereof.

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苏州大学

A kind of polarity gel electrolyte and its application in solid-state lithium-sulfur cell

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