WO2023278839A2 - Batterie à électrolyte solide sans anode, logeable, à dilatation de volume - Google Patents
Batterie à électrolyte solide sans anode, logeable, à dilatation de volume Download PDFInfo
- Publication number
- WO2023278839A2 WO2023278839A2 PCT/US2022/035944 US2022035944W WO2023278839A2 WO 2023278839 A2 WO2023278839 A2 WO 2023278839A2 US 2022035944 W US2022035944 W US 2022035944W WO 2023278839 A2 WO2023278839 A2 WO 2023278839A2
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- WO
- WIPO (PCT)
- Prior art keywords
- anode
- battery cell
- buffer layer
- lithium ion
- current collector
- Prior art date
Links
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 103
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 102
- 239000003792 electrolyte Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011889 copper foil Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 2
- 230000008961 swelling Effects 0.000 abstract description 26
- 229910052744 lithium Inorganic materials 0.000 description 18
- 238000007747 plating Methods 0.000 description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000007784 solid electrolyte Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000003273 ketjen black Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910013188 LiBOB Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000016507 interphase Effects 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- HEWZVZIVELJPQZ-UHFFFAOYSA-N 2,2-dimethoxypropane Chemical compound COC(C)(C)OC HEWZVZIVELJPQZ-UHFFFAOYSA-N 0.000 description 1
- AWCKLOPZHLHTAD-UHFFFAOYSA-N 4-[4-(4-carbamimidoyl-2-methoxyphenoxy)butoxy]-3-methoxybenzenecarboximidamide Chemical compound COC1=CC(C(N)=N)=CC=C1OCCCCOC1=CC=C(C(N)=N)C=C1OC AWCKLOPZHLHTAD-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N DMBan Natural products CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- 239000002227 LISICON Substances 0.000 description 1
- 239000005279 LLTO - Lithium Lanthanum Titanium Oxide Substances 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical compound [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 description 1
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- -1 lithium ions Chemical class 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- Anode-free solid-state battery cells with a high energy density and/or high power density tend to swell when charged.
- ions such as lithium ions
- the anode current collector effectively functions as both the anode and the current collector.
- ions may plate at the battery’s anode current collector and occupy a substantial amount of volume. The plating of these ions at the anode current collector may cause the battery cell to swell. This swelling can cause significant problems.
- the swelling can cause pressure to be exerted within the battery cell, potentially degrading components with the battery cell.
- This swelling may degrade the anode current collector over time, causing it to fracture, crack, or break apart; thus degrading the performance of the battery cell.
- the battery cell may include a cathode current collector layer.
- the battery cell may include a cathode that is layered with the cathode current collector layer.
- the battery cell may include a solid-state electrolyte layer.
- the battery cell may include a lithium ion buffer layer.
- the solid-state electrolyte layer can be located between the cathode and the lithium ion buffer layer.
- the lithium ion buffer layer can be porous.
- the lithium ion buffer layer can be in direct contact with the solid-state electrolyte layer. Lithium ions can be stored within the lithium ion buffer layer when the anode-free solid-state battery cell is charged.
- An anode current collector may be in direct contact with the lithium ion buffer layer.
- Embodiments of such an anode-free solid-state battery cell may include one or more of the following features:
- the lithium ion buffer layer can be electrically conductive and sufficiently flexible for the anode-free solid-state battery cell to be rolled into a jelly-roll style battery cell.
- the anode current collector may be a copper foil layer.
- a cylindrical battery cell housing may be present.
- the cathode current collector layer, the cathode, the solid-state electrolyte layer, the lithium ion buffer layer, and the anode current collector can be rolled together to form a jell-roll style anode-free solid-state battery cell and inserted within the cylindrical battery cell housing.
- the lithium ion buffer layer may be less than 20 pm thick.
- the lithium ion buffer layer may be graphite.
- the anode-free solid-state battery cell can have a power density of at least 1000 Watt-hours per liter.
- the anode-free solid-state battery cell can have an energy density of at least 400 Watt-hours per kilogram.
- the porosity of the lithium ion buffer layer may be greater than 70%.
- FIG. 1 illustrates an embodiment of a battery cell that includes a buffer layer to structure store lithium ions.
- FIG. 2 illustrates an embodiment of a charge and discharge cycle showing lithium plating when a buffer layer structures the lithium plating.
- FIG. 3 illustrates an embodiment of a charge and discharge cycle for a cross-section of a solid-state battery having a buffer layer to store lithium ions.
- FIG. 4 illustrates an embodiment of a method for creating a battery cell that exhibits a decreased amount of swelling.
- the amount of swelling that occurs during charge cycles may be decreased.
- components within the battery cell may degrade at a slower rate over charge and discharge cycles.
- a copper foil is used as both the anode and anode current collector in an anode-free solid-state battery (SSB)
- the copper foil may be prone to cracking due to one or more cycles during which the battery cell has swelled.
- the amount of swelling may be exacerbated since within the jelly-roll, the battery cell layers may repeat multiple times.
- “Anode-free” refers to a battery cell having no dedicated anode host to receive ions attracted to the anode current collector. More specifically, the hosts include any materials that can accommodate and host lithium-ions, such as graphite, silicon, lithium titanium oxide, and lithium-metal.
- lithium metal in the case of a lithium ion battery nucleates (or plates) directly on the anode current collector, which is typically copper or stainless steel, during charging. During discharge, lithium metal strips from the anode current collector as lithium ions and migrates to the cathode of the battery cell. This nucleation of lithium metal on the anode current collector can cause swelling.
- a porous buffer layer may be created between the anode current collector and the solid-state electrolyte.
- the buffer layer can have properties including being: electrically conductive, chemically inert, ionically conductive (even if the voids within the buffer layer is a vacuum), flexible, thin, and sufficiently porous to admit lithium ions.
- the buffer layer accommodates lithium ion nucleation by functioning as a scaffolding that provides “storage” for lithium ions when the battery cell is charged. Rather than the majority of lithium ions plating directly onto the anode current collector and causing swelling between the anode current collector and solid-state electrolyte, lithium ions may be stored within the porous structure of the buffer layer.
- the buffer layer may be sufficiently porous that voids are present to accommodate lithium ions migrating toward the anode current collector during charging. By the ions filling these pre-existing voids, swelling is largely avoided. When the ions fill these pre-existing voids, no chemical bond between the lithium metal and the buffer layer is formed. During discharge, when lithium ions migrate toward the cathode through the solid-state electrolyte, the voids within the buffer material become empty again. Therefore, the volume of the buffer material, and the battery cell as a whole, may exhibit less swelling due to charge and discharge cycles when the buffer layer is present.
- the buffer layer can be ionically conductive (even if voids within the buffer layer are not filled with electrolyte) due to in-situ formation of Li-ion conductive by-product during a first charge cycle; the ionic conductivity gets much higher after formation processor through the first charge and discharge cycle.
- the by-product can be a solid-electrolyte interphase (SEI), which consists of lithium-compounds and is ionically conductive.
- SEI solid-electrolyte interphase
- FIG. 1 illustrates an embodiment of a battery cell 100 that includes a buffer layer to structure store lithium ions.
- Battery cell 100 may be a solid-state battery cell.
- battery cell 100 may be an anode-free battery cell, meaning that the anode current collector functions as both the current collector and anode.
- Battery cell 100 may include: cathode current collector 101; cathode layer 102; solid-state electrolyte layer 103; buffer layer 104; and anode current collector 105.
- Such a battery cell may be designed to have a power density of at least 1000 Watt-hours per liter and/or an energy density of at least 400 Watt-hours per kilogram.
- Battery cell 100 may be created by layers 101-105 being layered together then rolled into a “jelly-roll” style battery cell. Once rolled, a cylindrical housing may be used to house the rolled layers of battery cell 100. Since battery cell 100 may be rolled, layers 101-105 may need to be flexible such that damage to layers 101-105 does not result from the layers being rolled. Further, reducing swelling in a jelly-roll style battery cell may be particularly beneficial since the battery cell’s layers are rolled together: any swelling that occurs can compound since the layers of the battery cell repeat multiple times within the jelly -roll.
- Cathode current collector 101 and anode current collector 105 may be materials that are conductive and will exhibit electrochemical stability.
- Cathode current collector 101 may be a metallic layer that is conductive and is non-reactive with cathode layer 102 and is stable at the operating potential of cathode layer 102.
- cathode current collector 101 may be composed of aluminum.
- a thin foil of aluminum may be used.
- anode current collector 105 may be a metallic layer that is conductive, non-reactive with buffer layer 104, and stable at the operating potential at which anode current collector 105 will function (as the anode of battery cell).
- anode current collector 105 may be composed of copper. Typically, a thin foil of copper may be used.
- Cathode layer 102 can be in direct contact with cathode current collector 101.
- Cathode layer 102 may be various types of cathode material.
- cathode layer 102 may be Lithium Nickel Cobalt Aluminum Oxide (“NCA”, LiNiCoA102).
- NCA Lithium Nickel Cobalt Aluminum Oxide
- Other Nickel-based cathodes may also be possible, such as NCM622, NCM811, and OLO.
- Solid-state electrolyte layer 103 may in direct contact with cathode layer 102.
- Solid- state electrolyte layer 103 may be various forms of organic or inorganic solid-state electrolyte. Possible electrolytes that can be used include: LPS, LSPSC, LGPS, LBSO, LATSPO, LISICON, LICGC, LAGP, LLZO, LZO, LAGTP, LiBETI, LiBOB, LiTf, LiTF, LLTO, LLZP, LTASP, LTZP.
- a semi-solid electrolyte may be substituted for solid-state electrolyte layer 103.
- a semi-solid electrolyte can involve a liquid electrolyte being gelated by mixing a polymer with the electrolyte with a different polymerization degree.
- LiBOB bis(oxalato)borate
- LiB[C204]2 Li Bisoxalateborate
- LIODFB Lithium difluoro(oxalato)borate
- Lithium sulfate Li2S04, LiBF4, L1CF3O3S (Li trifluoromethanesulfonate)
- LiFSI Lithium bis(fluorosulfonyl)imide
- LiTFSI Lithium bis(trifluoromethanesulfonyl)imide
- lithium salts can be dissolved in an organic solution, such as Ethylene carbonate (EC), Dimethyl carbonate (DMC), Ethyl methyl carbonate (EMC), diethyl carbonate (DEC), 1,2-DME (Dimethoxy ethane), 2,2- DMP (Dimethoxypropane), 1,1-DMP, 2,2-DMB (Dimethoxybutane), 2,3-DMB, with 0.5-10M concentration with mixture of various hydrofluoric ether (HFE), which can stay as gel state with a mixture of some cross-linking polymers.
- Ethylene carbonate EC
- DMC Dimethyl carbonate
- EMC Ethyl methyl carbonate
- DEC diethyl carbonate
- 1,2-DME Dimethoxy ethane
- 2,2- DMP Dimethoxypropane
- 1,1-DMP 1,1-DMP
- 2,2-DMB Dimethoxybutane
- 2,3-DMB with 0.5-10M concentration with mixture of various hydro
- Buffer layer 104 Between solid-state electrolyte layer 103 and anode current collector 105 can be lithium ion buffer layer 104 (“buffer layer 104”).
- Buffer layer 104 may be: electrically conductive, non reactive with lithium and lithium ions, flexible, and have a high porosity. Buffer layer 104 may be between 100 nm and 30 pm thick. In some embodiments, the preferable thickness of buffer layer 104 may be 5 pm. Specifically, the thickness of buffer layer 104 may be selected to not substantially increase the volume or weight of battery cell 100. Specifically, the thicker buffer layer 104 is, the lower the energy and power density of battery cell 100 may be. Therefore, a thickness of buffer layer 104 may be selected to achieve a balance between energy/power density and ability to avoid swelling.
- Buffer layer 104 can be a carbon scaffold with a minimum capability of intercalation.
- the buffer layer bulk is electrically conductive, but ionically non-conductive.
- the surface of buffer layer 104 can be ionically conductive, on which either a solid-state electrolyte or gelated electrolyte is thinly covered, such as on the order of nanometers to a few micrometers.
- Lithium ions transport on the surface of the buffer layer through to anode current collector 105, then plate, thus filling up voids in buffer layer 104.
- This process allows for the voids to be utilized as a accommodator of the volume expansion, but still secures Lithium ion transport between the cathode and anode during the charge/discharge processes.
- a lithium- ion conductive by-product namely solid electrolyte interphase (SEI)
- SEI solid electrolyte interphase
- the amount of expected lithium plating may be determined. For example, 4mAh/cm 2 capacity corresponds to 20 pm lithium plating. Thus, if a cathode has a capacity of 4mAh/cm 2 , the expected amount of lithium expected to plate on an anode current collector is 20 pm. To create a buffer layer to accommodate 20 pm of lithium plating, Equation 1 can be used.
- V B P * T B Eq. 1
- Equation 1 VB represents the volume of the buffer layer, P represents the porosity, and TB the thickness. Therefore, a 25 pm thickness buffer layer having a porosity of 80% would allow for 20 pm of lithium plating to be stored by the buffer layer with little or no swelling.
- Buffer layer 104 may have a high porosity, such as between 5% and 90%. In some embodiments, the porosity may be greater than 70%. Porosity can be controlled by: density of carbon material used; slurry solid concentration; calendaring pressure; feature size distribution of carbon material used; slurry composition (carbon and binder ratio), etc.
- the voids within buffer layer 104 may help accommodate lithium ions that migrate to anode current collector 105 during charging. That is, the lithium ions fill in the voids within the buffer layer 104 when battery cell 100 is charging and is charged. Preferably, 50%-95% of lithium ions that migrate toward anode current collector 105 during charging will remain within buffer layer 104. The remaining 5%- 50% or less than 5%-50% will either plate between buffer layer 104 and anode current collector 105 or will reside or plate between solid-state electrolyte layer 103 and buffer layer 104.
- Buffer layer 104 may be sufficiently flexible such that when battery cell 100 is rolled into a jelly-roll, no or only limited damage occurs to buffer layer 104. Specifically, a strong electrical and physical interface between the material (e.g., copper) of anode current collector 105 and buffer layer 104 is required to remain present.
- material e.g., copper
- Materials that have a sufficient amount of porosity, electrical conductivity, flexibility, and ability to interface with copper can include one or more of the following: graphite, graphene, carbon black (CB), acetylene black (AB), and ketjen black (KB). These materials can be bound by binders, such as: SBR-CMC, LiPAA, PvDF.
- the carbon may be in the form of fibers (i.e., carbon fibers) or in flake form. Other forms of carbon or other materials may be used as buffer layer 104 if such materials.
- buffer layer 104 may be deposited onto anode current collector 105.
- buffer layer 104 may be a mix of grapheme, CB, AB, and KB to create voids large enough to accommodate lithium plating. Further, lithium diffusion on the surface of the graphene can help improve c-rate performance.
- FIG. 2 illustrates an embodiment 200 of a charge and discharge cycle showing lithium ion storage when a buffer layer is present against the anode current collector.
- FIG. 2 illustrates an embodiment 200 of a charge and discharge cycle showing lithium ion storage when a buffer layer is present against the anode current collector.
- battery cell 100 is illustrated.
- anode current collector 105 and a highly-magnified representation of buffer layer 104 is illustrated.
- buffer layer 104 is present with few, if any, lithium ions residing in the voids formed by the particles of buffer layer 104.
- buffer layer 104 is approximately 200 nm thick, as indicated by thickness 211.
- lithium ions 201 fill in the voids formed by the particles of buffer layer 104. Therefore, lithium ions still plate directly only anode current collector 105, but the volume of the lithium ions are present mostly within the voids formed by the particles of buffer layer 104. In the illustrated embodiment, a small amount of swelling has occurred due to the plating of lithium ions.
- Thickness 221 is approximately 3%-10% greater than thickness 211 because the amount of lithium ions exceeds the amount of space within the voids of buffer layer 104.
- buffer layer 104 may be made thicker to fully accommodate or nearly fully accommodate the lithium ions when the battery cell is fully charged.
- the lithium ions migrate away from anode current collector 105 toward the cathode.
- the swelling caused by the lithium ions plating subsides and the thickness of buffer layer 104 returns to approximately thickness 211.
- the amount of swelling when buffer layer 104 is present may be significantly less than if buffer layer 104 was not present and lithium ions were permitted to plate on anode current collector 105 without a porous buffer being present.
- FIG. 3 illustrates an embodiment 300 of charge and discharge cycles for a cross-section of a solid-state battery having a buffer layer to store lithium ions.
- buffer layer 104 is present with few, if any, lithium ions residing in the voids formed by the particles of buffer layer 104.
- Thickness 302 represents a baseline thickness that does not include any swelling caused by the plating of lithium ions.
- thickness 301 represents a baseline thickness for the battery cell when swelling is not present.
- lithium ions fill in the voids formed by the particles of the buffer layer, thus creating layer 330 that includes buffer layer 104 and lithium plating.
- Thickness 303 may be slightly greater than thickness 302 due to the lithium plating causing some amount of swelling.
- Thickness 303 may be approximately 3%-10% greater than thickness 302 because the amount of lithium ions exceeds the amount of space within the voids of buffer layer 104.
- thickness 302 may be slightly greater than thickness 301 because the amount of lithium ions exceeds the amount of space within the voids of buffer layer 104.
- buffer layer 104 may be made thicker to fully accommodate or nearly fully accommodate the lithium ions when the battery cell is fully charged.
- the lithium ions migrate away from anode current collector 105 to cathode layer 102 through solid-state electrolyte layer 103. Once all or most of the lithium ions have migrated, discharged state 310 may again be present. The swelling caused by the lithium ions plating subsides and the thickness of buffer layer 104 returns to approximately thickness 302. Similarly, the thickness of the battery cell may return to thickness 301. The amount of swelling when buffer layer 104 is present may be significantly less than if buffer layer 104 was not present and lithium ions were permitted to plate on anode current collector 105 without a porous buffer being present.
- FIG. 4 illustrates an embodiment of a method 400 for decreasing swelling of a battery cell when charged.
- an anode current collector layer may be created.
- This anode current collector layer may be a copper foil or some other form of conductive, flexible layer; such as Ni, Fe, Ni+Fe, carbon fiber sheet, etc.
- the SSB may be an “anode-free” SSB, therefore the anode current collector may function as both the anode and the anode current collector.
- a buffer layer may be created on the anode current collector. For instance, carbon particles may be deposited onto the anode current collector foil. The layer of carbon may be between 100 nm and 30 pm thick.
- a solid-state electrolyte layer may be placed or deposited onto the buffer layer.
- a cathode and cathode current collector may be placed or deposited onto the solid-state electrolyte layer.
- a first group of layers that includes the anode current collector and buffer layer may be created.
- a second group of layers that includes the cathode current collector, cathode, and solid electrolyte layer may be created. The two groups of layers may then be layered together.
- the solid electrolyte layers is included the in the first group of layers rather than the second or instead may be layered between the two groups when the battery cell is assembled.
- a cylindrical jelly-roll style solid-state battery may be created by rolling the layers together.
- the resulting cylindrical jelly-roll may be inserted into a cylindrical housing, such as a cylindrical canister, for storage. Electrical leads to the current collectors may be connected to terminals of the battery cell.
- the battery cell may be charged.
- the charging results in lithium ions migrating from the cathode toward the anode current collector.
- the ions are stored within the voids of the buffer layer that is immediately adjacent to the anode current collect. Since voids of a layer that is already present are being filled by the ions, the battery may swell significantly less than if the buffer layer was not present.
- the battery may be discharged.
- the discharge may cause ions to move through the solid-state electrolyte to the cathode. Therefore, the voids within the buffer layer may again be empty.
- Blocks 425 through 435 may repeat a large number of times. For instance, such as battery cell may be incorporated as part of a battery module of an electric vehicle.
- a battery cell created account to blocks 405-420 may be charged with 7559 Ah.
- the battery cell may discharge 6229 Ah, for an initial Coulombic efficiency of 82.4%.
- This battery may experience a radial volume expansion of about 86%.
- configurations may be described as a process which is depicted as a flow diagram or block diagram. Although each may describe the operations as a sequential process, many of the operations can be performed in parallel or concurrently. In addition, the order of the operations may be rearranged. A process may have additional steps not included in the figure.
Abstract
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EP22751502.0A EP4352800A2 (fr) | 2021-07-02 | 2022-07-01 | Batterie à électrolyte solide sans anode, logeable, à dilatation de volume |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US17/366,410 US11515539B2 (en) | 2019-05-16 | 2021-07-02 | Volume-expansion accommodable anode-free solid-state battery |
US17/366,410 | 2021-07-02 |
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WO2023278839A2 true WO2023278839A2 (fr) | 2023-01-05 |
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US11069897B2 (en) * | 2019-05-16 | 2021-07-20 | TeraWatt Technology Inc. | Volume-expansion accommodable anode-free solid-state battery |
US20240106010A1 (en) * | 2021-03-04 | 2024-03-28 | Heiq Materials Ag | Artificial Solid-Electrolyte Interphase Layer Material and Uses Thereof |
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