ELECTROLYTE COMPOSITION FOR BATTERIES
20230238570 · 2023-07-27
Assignee
Inventors
Cpc classification
H01M4/505
ELECTRICITY
H01M10/056
ELECTRICITY
H01M4/525
ELECTRICITY
International classification
H01M10/056
ELECTRICITY
Abstract
An electrolyte composition for a battery is provided. The electrolyte composition includes a lithium salt in a carbonate-based solution and lithium difluoro(oxalate)borate present in the electrolyte composition in an amount from 0.1 part by weight to 5 parts by weight based on 100 parts by weight of the electrolyte composition.
Claims
1. An electrolyte composition for a battery, the electrolyte composition comprising: a lithium salt in a carbonate-based solution; and lithium difluoro(oxalate)borate present in the electrolyte composition in an amount from 0.1 part by weight to 5 parts by weight based on 100 parts by weight of the electrolyte composition.
2. The electrolyte composition of claim 1, wherein the lithium difluoro(oxalate)borate is present in the electrolyte composition in an amount from 0.5 parts by weight to 1.5 parts by weight based on 100 parts by weight of the electrolyte composition.
3. The electrolyte composition of claim 1, wherein the lithium difluoro(oxalate)borate is present in the electrolyte composition in an amount of 1 part by weight based on 100 parts by weight of the electrolyte composition.
4. The electrolyte composition of claim 2, further comprising: fluoroethylene carbonate present in the electrolyte composition in an amount from 1 part by weight to 10 parts by weight based on 100 parts by weight of the electrolyte composition; and vinylene carbonate present in the electrolyte composition in an amount from 1 part by weight to 10 parts by weight based on 100 parts by weight of the electrolyte composition.
5. The electrolyte composition of claim 2, further comprising: fluoroethylene carbonate present in the electrolyte composition in an amount of 2 parts by weight based on 100 parts by weight of the electrolyte composition; and vinylene carbonate present in the electrolyte composition in an amount of 1 part by weight based on 100 parts by weight of the electrolyte composition.
6. The electrolyte composition of claim 1, wherein the lithium salt includes lithium hexafluorophosphate present in an amount of 1 mole per 1 liter of the carbonate-based solution.
7. The electrolyte composition of claim 1, wherein the lithium salt is selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(oxalato)borate, and lithium perchlorate; and wherein the lithium salt is present in an amount from 0.5 moles to 1.5 moles per 1 liter of the carbonate-based solution.
8. The electrolyte composition of claim 1, wherein the carbonate-based solution includes ethylene carbonate and dimethyl carbonate present in a ratio of 3 parts ethylene carbonate to 7 parts dimethyl carbonate.
9. The electrolyte composition of claim 1, wherein the carbonate-based solution includes two solvents selected from the group consisting of dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate; and wherein the two solvents are present in a mixing ratio of from 1:9 to 9:1.
10. The electrolyte composition of claim 1, wherein the lithium difluoro(oxalate)borate is present in the electrolyte composition in an amount from 0.5 parts by weight to 1.5 parts by weight based on 100 parts by weight of the electrolyte composition; wherein the lithium salt includes lithium hexafluorophosphate present in an amount from 0.5 moles to 2 moles per 1 liter of the carbonate-based solution; and wherein the carbonate-based solution includes ethylene carbonate and dimethyl carbonate present in a ratio ranging from 2 parts ethylene carbonate to 8 parts dimethyl carbonate to 5 parts ethylene carbonate to 5 parts dimethyl carbonate.
11. The electrolyte composition of claim 1, wherein the lithium difluoro(oxalate)borate is present in the electrolyte composition in an amount from 0.5 parts by weight to 1.5 parts by weight based on 100 parts by weight of the electrolyte composition; wherein the lithium salt includes lithium hexafluorophosphate present in an amount from 0.5 moles to 2 moles per 1 liter of the carbonate-based solution; and wherein the carbonate-based solution includes ethylene carbonate and dimethyl carbonate present in a ratio ranging from 2 parts ethylene carbonate to 8 parts dimethyl carbonate to 5 parts ethylene carbonate to 5 parts dimethyl carbonate; and wherein the electrolyte composition further comprises: fluoroethylene carbonate present in the electrolyte composition in an amount from 1 part by weight to 5 parts by weight based on 100 parts by weight of the electrolyte composition; and vinylene carbonate present in the electrolyte composition in an amount from 1 part by weight to 5 parts by weight based on 100 parts by weight of the electrolyte composition.
12. A battery comprising: an anode; a cathode; and an electrolyte composition including: a lithium salt in a carbonate-based solution; and lithium difluoro(oxalate)borate present in the electrolyte composition in an amount from 0.1 part by weight to 5 parts by weight based on 100 parts by weight of the electrolyte composition.
13. The battery of claim 12, wherein the anode is a silicon-based anode.
14. The battery of claim 13, wherein the silicon-based anode includes a material selected from the group consisting of silicon, silicon monoxide, Si/C and LixSiO, and a silicon blend with graphite.
15. The battery of claim 12, wherein the cathode is a nickel-based cathode.
16. The battery of claim 15, wherein the nickel-based cathode is a mixture including: a material selected from the group consisting of a nickel-cobalt-manganese-aluminum mixture, a nickel-manganese-cobalt mixture, and a nickel-cobalt-aluminum mixture; and a material selected from the group consisting of olivine LiMn.sub.xFe.sub.1-xPO.sub.4, lithium-iron-phosphate, and lithium manganese (III,IV) oxide.
17. The battery of claim 12, wherein the lithium difluoro(oxalate)borate is present in the electrolyte composition in an amount from 0.5 parts by weight to 1.5 parts by weight based on 100 parts by weight of the electrolyte composition; wherein the lithium salt includes lithium hexafluorophosphate present in an amount from 0.5 moles to 2 moles per 1 liter of the carbonate-based solution; and wherein the carbonate-based solution includes ethylene carbonate and dimethyl carbonate present in a ratio ranging from 2 parts ethylene carbonate to 8 parts dimethyl carbonate to 5 parts ethylene carbonate to 5 parts dimethyl carbonate.
18. The battery of claim 12, wherein the lithium difluoro(oxalate)borate is present in the electrolyte composition in an amount from 0.5 parts by weight to 1.5 parts by weight based on 100 parts by weight of the electrolyte composition; wherein the lithium salt includes lithium hexafluorophosphate present in an amount from 0.5 moles to 2 moles per 1 liter of the carbonate-based solution; and wherein the carbonate-based solution includes ethylene carbonate and dimethyl carbonate present in a ratio ranging from 2 parts ethylene carbonate to 8 parts dimethyl carbonate to 5 parts ethylene carbonate to 5 parts dimethyl carbonate; and wherein the electrolyte composition further includes: fluoroethylene carbonate present in the electrolyte composition in an amount from 1 part by weight to 5 parts by weight based on 100 parts by weight of the electrolyte composition; and vinylene carbonate present in the electrolyte composition in an amount from 1 part by weight to 5 parts by weight based on 100 parts by weight of the electrolyte composition.
19. A device comprising: an output component; and a battery configured for providing electrical energy to the device, the battery including: an anode; a cathode; and an electrolyte composition including: a lithium salt in a carbonate-based solution; and lithium difluoro(oxalate)borate present in the electrolyte composition in an amount from 0.1 part by weight to 5 parts by weight based on 100 parts by weight of the electrolyte composition.
20. The device of claim 19, wherein the lithium difluoro(oxalate)borate is present in the electrolyte composition in an amount from 0.5 parts by weight to 1.5 parts by weight based on 100 parts by weight of the electrolyte composition; wherein the lithium salt includes lithium hexafluorophosphate present in an amount from 0.5 moles to 2 moles per 1 liter of the carbonate-based solution; and wherein the carbonate-based solution includes ethylene carbonate and dimethyl carbonate present in a ratio ranging from 2 parts ethylene carbonate to 8 parts dimethyl carbonate to 5 parts ethylene carbonate to 5 parts dimethyl carbonate.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
[0037] During operation of a battery, chemical reactions taking place between the anode and the electrolyte composition cause a solid electrolyte interphase (SEI) layer to be formed upon an anode. Similarly, chemical reactions taking place between the cathode and the electrolyte composition cause a cathode electrolyte interphase (CEI) layer to be formed upon a cathode. The SEI layer and the CEI layer form as films upon the anode and cathode, respectively.
[0038] Increased stability in the SEI layer and the CEI layer may provide excellent useful life or increased electrode capacity retention in the anode and cathode, respectively.
[0039] Lithium hexafluorophosphate (LiPF.sub.6) based electrolyte compositions in use within a battery may develop reactive species, such as hydrofluoric acid (HF). HF may interfere with interfacial structures of electrodes and cause degradation of the electrode surface that may contribute to capacity reduction over multiple operation cycles of the battery.
[0040] A cathode may be nickel based and may include manganese. Over multiple operation cycles of the battery, nickel and manganese may suffer from dissolution or may leach out of the cathode, thereby contributing to capacity reduction of the battery.
[0041] An electrolyte composition disclosed herein provides excellent cycle life for a battery. The battery may include a silicon-based anode and a nickel-based or nickel-rich cathode. In one embodiment, the electrolyte composition may include 1 molar or 1M LiPF.sub.6 in an ethylene carbonate (EC)/dimethyl carbonate (DMC) (3:7) solution. In one embodiment, the electrolyte composition may include excellent cycle performance and capacity retention by further including lithium difluoro(oxalate)borate (LiDFOB) at 1.0% by weight. In another embodiment, the electrolyte may include excellent cycle performance and capacity retention by further including LiDFOB at 1.0% by weight, and by further including fluoroethylene carbonate (FEC) at 2.0% by weight and vinylene carbonate (VC) at 1.0% by weight.
[0042] The carbonate-based solution may include ethylene carbonate and dimethyl carbonate present in a ratio of 3 parts ethylene carbonate to 7 parts dimethyl carbonate.
[0043] The electrolyte composition may include fluoroethylene carbonate present in the electrolyte composition in an amount from 1 part by weight to 10 parts by weight based on 100 parts by weight of the electrolyte composition. The electrolyte composition may include vinylene carbonate present in the electrolyte composition in an amount from 1 part by weight to 10 parts by weight based on 100 parts by weight of the electrolyte composition.
[0044] The electrolyte composition may include fluoroethylene carbonate present in the electrolyte composition in an amount of 2 parts by weight based on 100 parts by weight of the electrolyte composition. The electrolyte composition may include vinylene carbonate present in the electrolyte composition in an amount of 1 part by weight based on 100 parts by weight of the electrolyte composition.
[0045] An electrolyte composition for a battery is provided. The electrolyte composition includes a lithium salt in a carbonate-based solution. The electrolyte solution further includes lithium difluoro(oxalate)borate present in the electrolyte composition in an amount from 0.1 part by weight to 5 parts by weight based on 100 parts by weight of the electrolyte composition. The lithium difluoro(oxalate)borate may be present in the electrolyte composition in an amount of 1 part by weight based on 100 parts by weight of the electrolyte composition. The lithium difluoro(oxalate)borate may be present in the electrolyte composition in an amount of 1 part by weight based on 100 parts by weight of the electrolyte composition.
[0046] A number of alternatives to the electrolyte composition are provided. Throughout the disclosure, the solvent EC/DMC in a 3:7 solution may be substituted with various carbonate-based solvents. These carbonate-based solvents may include, without being limited to, two of the following: DMC, diethyl carbonate (DEC), EC, and propylene carbonate (PC). The electrolyte may include a mixture of two of the above carbonate solvents in various mixing ratios in a range from 1:9 to 9:1. The electrolyte compositions can include various types of lithium salt. Throughout the disclosure, 1M LiPF.sub.6 may be substituted with various lithium salts. At least one lithium salt can include, without being limited to, LiPF.sub.6, lithium tetrafluoroborate (LiBF.sub.4), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(oxalato)borate (LiBOB), and lithium perchlorate (LiClO.sub.4). The concentration of the lithium salt in the electrolyte can vary from 0.5M to 1.5M. In one embodiment, the disclosed electrolyte composition may include, without being limited to, 1M LiPF.sub.6 in EC/DMC 3:7 with a LiDFOB additive and/or 1M LiBF.sub.4 in EC/DEC 3:7 with a LiDFOB additive.
[0047] The lithium salt may include lithium hexafluorophosphate present in an amount of 1 mole per 1 liter of the carbonate-based solution.
[0048] The lithium salt may be selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(oxalato)borate, and lithium perchlorate. The lithium salt may be present in an amount from 0.5 moles to 1.5 moles per 1 liter of the carbonate-based solution.
[0049] The carbonate-based solution may include two solvents selected from the group consisting of dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate. The two solvents may be present in a mixing ratio of from 1:9 to 9:1.
[0050] The lithium difluoro(oxalate)borate may be present in the electrolyte composition in an amount from 0.5 parts by weight to 1.5 parts by weight based on 100 parts by weight of the electrolyte composition. The lithium salt may include lithium hexafluorophosphate present in an amount from 0.5 moles to 2 moles per 1 liter of the carbonate-based solution. The carbonate-based solution may include ethylene carbonate and dimethyl carbonate present in a ratio ranging from 2 parts ethylene carbonate to 8 parts dimethyl carbonate to 5 parts ethylene carbonate to 5 parts dimethyl carbonate.
[0051] The lithium difluoro(oxalate)borate may be present in the electrolyte composition in an amount from 0.5 parts by weight to 1.5 parts by weight based on 100 parts by weight of the electrolyte composition. The lithium salt may include lithium hexafluorophosphate present in an amount from 0.5 moles to 2 moles per 1 liter of the carbonate-based solution. The carbonate-based solution may include ethylene carbonate and dimethyl carbonate present in a ratio ranging from 2 parts ethylene carbonate to 8 parts dimethyl carbonate to 5 parts ethylene carbonate to 5 parts dimethyl carbonate. The electrolyte composition may further include fluoroethylene carbonate present in the electrolyte composition in an amount from 1 part by weight to 5 parts by weight based on 100 parts by weight of the electrolyte composition. The electrolyte composition may further include vinylene carbonate present in the electrolyte composition in an amount from 1 part by weight to 5 parts by weight based on 100 parts by weight of the electrolyte composition.
[0052] The disclosed electrolyte composition may be utilized with a variety of battery configurations. In one exemplary battery configuration, the anode of the battery may include a silicon-based anode, for example, including silicon (Si) and/or silicon monoxide (SiO) and/or modified Si/SiO (i.e., carbon coated Si/SiO) or a Si-carbon compound (Si/C). In another exemplary battery configuration, the cathode of the battery may include a nickel-based anode or nickel-rich cathode, for example, including relatively high levels of nickel (Ni). In another exemplary battery configuration, the anode of the battery may include a silicon-based anode, and the cathode of the battery may include a nickel-based anode or nickel-rich cathode. In another exemplary battery configuration, the anode of the battery may include Si, SiO, LixSiO, Si/C or a blend of these materials with graphite. In another exemplary battery configuration, the cathode of the battery may include a nickel-cobalt-manganese-aluminum mixture (NCMA), a nickel-manganese-cobalt mixture (NMC), a nickel-cobalt-aluminum mixture (NCA), olivine LiMn.sub.xFe.sub.1-xPO.sub.4 (LMFP), a lithium, iron, phosphate mixture (LFP), lithium manganese (III,IV) oxide (LiMn.sub.2O.sub.4 or LMO), or a blend of these materials.
[0053] The inclusion of LiDFOB in the disclosed electrolyte composition includes a plurality of benefits. Presence of LiDFOB in the disclosed concentration range promotes formation of a stable interphase upon the anode and the cathode. LiDFOB may sacrificially decompose and form stable electrode/electrolyte interphases (containing inorganic boron, fluorine, and carbonate compounds.)
[0054] Presence of LiDFOB in the disclosed concentration range promotes scavenging of HF within the electrolyte composition or reduces presence of HF in the electrolyte composition. LiDFOB may sequester phosphorus pentafluoride PF.sub.5 (from lithium hexafluorophosphate (LiPF.sub.6) salt), which may reduce an amount of HF formation. HF may consume Li ions to form lithium fluoride (LiF) which may be deposited on a surface of the electrodes.
[0055] Presence of LiDFOB in the disclosed concentration range mitigates dissolution or migration of nickel and manganese in the cathode.
[0056] The disclosed electrolyte composition may be utilized in a wide variety of batteries, including but not limited to lithium-ion, lithium-metal, lithium sulfur/oxygen batteries.
[0057] A battery is provided. The battery includes an anode, a cathode, and an electrolyte composition. The electrolyte composition includes a lithium salt in a carbonate-based solution. The electrolyte solution further includes lithium difluoro(oxalate)borate present in the electrolyte composition in an amount from 0.1 part by weight to 5 parts by weight based on 100 parts by weight of the electrolyte composition.
[0058] The anode may be a silicon-based anode.
[0059] The silicon-based anode may include a material selected from the group consisting of silicon, silicon monoxide, Si/C and LixSiO, and a silicon blend with graphite.
[0060] The cathode may be a nickel-based cathode.
[0061] The nickel-based cathode may be a mixture including a material selected from the group consisting of a nickel-cobalt-manganese-aluminum mixture, a nickel-manganese-cobalt mixture, and a nickel-cobalt-aluminum mixture. The mixture may further include a material selected from the group consisting of olivine LiMn.sub.xFe.sub.1-xPO.sub.4, lithium-iron-phosphate, and lithium manganese (III,IV) oxide.
[0062] The lithium difluoro(oxalate)borate may be present in the electrolyte composition in an amount from 0.5 parts by weight to 1.5 parts by weight based on 100 parts by weight of the electrolyte composition. The lithium salt may include lithium hexafluorophosphate present in an amount from 0.5 moles to 2 moles per 1 liter of the carbonate-based solution. The carbonate-based solution may include ethylene carbonate and dimethyl carbonate present in a ratio ranging from 2 parts ethylene carbonate to 8 parts dimethyl carbonate to 5 parts ethylene carbonate to 5 parts dimethyl carbonate.
[0063] The lithium difluoro(oxalate)borate may be present in the electrolyte composition in an amount from 0.5 parts by weight to 1.5 parts by weight based on 100 parts by weight of the electrolyte composition. The lithium salt may include lithium hexafluorophosphate present in an amount from 0.5 moles to 2 moles per 1 liter of the carbonate-based solution. The carbonate-based solution may include ethylene carbonate and dimethyl carbonate present in a ratio ranging from 2 parts ethylene carbonate to 8 parts dimethyl carbonate to 5 parts ethylene carbonate to 5 parts dimethyl carbonate. The electrolyte composition may further include fluoroethylene carbonate present in the electrolyte composition in an amount from 1 part by weight to 5 parts by weight based on 100 parts by weight of the electrolyte composition. The electrolyte composition may further include vinylene carbonate present in the electrolyte composition in an amount from 1 part by weight to 5 parts by weight based on 100 parts by weight of the electrolyte composition.
[0064] A device is provided. The device includes an output component and a battery configured for providing electrical energy to the device. The battery includes an anode, a cathode, and an electrolyte composition. The electrolyte composition includes a lithium salt in a carbonate-based solution. The electrolyte composition further includes lithium difluoro(oxalate)borate present in the electrolyte composition in an amount from 0.1 part by weight to 5 parts by weight based on 100 parts by weight of the electrolyte composition. The device may be a vehicle.
[0065] The lithium difluoro(oxalate)borate may be present in the electrolyte composition in an amount from 0.5 parts by weight to 1.5 parts by weight based on 100 parts by weight of the electrolyte composition. The lithium salt may include lithium hexafluorophosphate present in an amount from 0.5 moles to 2 moles per 1 liter of the carbonate-based solution. The carbonate-based solution may include ethylene carbonate and dimethyl carbonate present in a ratio ranging from 2 parts ethylene carbonate to 8 parts dimethyl carbonate to 5 parts ethylene carbonate to 5 parts dimethyl carbonate.
[0066] Referring now to the drawings, wherein like reference numbers refer to like features throughout the several views,
[0067] The anode 110 may be constructed of a silicon-based substance. The cathode 120 may be constructed of a nickel-based substance. In one embodiment, the cathode 120 may be constructed of a nickel manganese cobalt (NMC) substance.
[0068] The electrolyte composition 140 may include EC/DEC/EMC in a 1:1:1 composition. The electrolyte composition 140 the electrolyte composition may include 1 molar or 1M LiPF.sub.6 in an ethylene carbonate (EC)/dimethyl carbonate (DMC) (3:7) solution. In one embodiment, the electrolyte composition may include excellent cycle performance and capacity retention by further including lithium difluoro(oxalate)borate (LiDFOB) at 1.0% by weight. In another embodiment, the electrolyte may include excellent cycle performance and capacity retention by further including LiDFOB at 1.0% by weight, and by further including fluoroethylene carbonate (FEC) at 2.0% by weight and vinylene carbonate (VC) at 1.0% by weight.
[0069] The battery cell 100 may be utilized in a wide range of applications and powertrains.
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[0079] While the best modes for carrying out the disclosure have been described in detail, those familiar with the art to which this disclosure relates will recognize various alternative designs and embodiments for practicing the disclosure within the scope of the appended claims.