# US 11,444,310 B2 · Dimensional constraints for three-dimensional batteries > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,444,310 B2 - Document ID: US11444310B2 - Status: Granted - Kind: B2 - Application number: 17/335,725 - Filed: 2021-06-01 - Published: 2022-05-19 - Granted: 2022-09-13 - Earliest claimed: 2016-05-13 - Assignees: Enovix Operations Inc. - Applicants: Enovix Corporation - Inventors: Robert S. Busacca; Ashok Lahiri; Murali Ramasubramanian; Bruno A. Valdes; Gardner Cameron Dales; Christopher J. Spindt; Geoffrey Matthew Ho; Harrold J. Rust, III; James D. Wilcox; John F. Varni; Kim Han Lee; Nirav S. Shah; Richard J. Contreras; Lynn Van Erden; Vladimir Dioumaev - Web page: https://patentgrep.com/patent/US11444310B2 ## CPC - H01M 10/02: Details (of electrodes H01M4/00; of non-active parts H01M50/00) - H01M 4/02: Electrodes composed of, or comprising, active material - H01M 10/052: Li-accumulators - H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries - H01M 10/054: Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium - H01M 10/058: Construction or manufacture - H01M 10/0585: of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators - H01M 10/44: Methods for charging or discharging (circuits for charging H02J7/00) - H01M 2004/021: {Physical characteristics, e.g. porosity, surface area} - Y02E 60/10: Energy storage using batteries - Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product - H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY - Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS ## Abstract A secondary battery is provided for cycling between a charged and a discharged state, the secondary battery including a battery enclosure, an electrode assembly, carrier ions, a non-aqueous liquid electrolyte within the battery enclosure, and a set of electrode constraints. The set of electrode constraints includes a primary constraint system having first and second primary growth constraints and at least one primary connecting member, the first and second primary growth constraints separated from each other in the longitudinal direction, wherein the primary constraint array restrains growth of the electrode assembly in the longitudinal direction such that any increase in the Feret diameter of the electrode assembly in the longitudinal direction over 20 consecutive cycles of the secondary battery is less than 20%. The set of electrode constraints further includes a secondary constraint system having first and second secondary growth constraints connected by at least one secondary connecting member, wherein the secondary constraint system at least partially restrains growth of the electrode assembly in a second direction upon cycling of the secondary battery. ## Claims ### Claim 1 A method of manufacturing a structure comprising an electrode assembly, carrier ions, and a constraint system, the method comprising forming the electrode assembly, the electrode assembly having mutually perpendicular longitudinal, transverse, and vertical axes, a first longitudinal end surface and a second longitudinal end surface separated from each other in the longitudinal direction, and a lateral surface surrounding an electrode assembly longitudinal axis AEA and connecting the first and second longitudinal end surfaces, the lateral surface having opposing first and second regions on opposite sides of the longitudinal axis and separated in a first direction that is orthogonal to the longitudinal axis, the electrode assembly having a maximum width WEA measured in the longitudinal direction, a maximum length LEA bounded by the lateral surface and measured in the transverse direction, and a maximum height HEA bounded by the lateral surface and measured in the vertical direction, the ratio of each of LEA and WEA to HEA being at least 2:1, respectively, the electrode assembly comprising a population of electrode structures, a population of counter-electrode structures, and an electrically insulating separator material electrically separating members of the electrode and counter-electrode populations, with members of the electrode and counter-electrode structure populations being arranged in an alternating sequence in the longitudinal direction, constraining the electrode assembly with the constraint system, the constraint system comprising first and second primary growth constraints separated from each other in the longitudinal direction, the first and second primary growth constraints being placed in tension with one another via connection through first and second primary connecting members, the first and second primary connecting members being separated from each other in the vertical direction, and connecting one or more of (i) member(s) of the population of electrode structures, or (ii) member(s) of population of counter-electrode structures to the first and second primary connecting members. ### Claim 2 (depends on 1) The method according to claim 1, comprising connecting both member(s) of the population of electrode structures and member(s) of population of counter-electrode structures to the first and second primary connecting members. ### Claim 3 (depends on 1) The method according to claim 1, comprising connecting member(s) of the population of electrode structures to the first and second primary connecting members. ### Claim 4 (depends on 1) The method according to claim 1, comprising forming an electrode assembly in which members of the population of electrode structures comprise an electrode current collector, and comprising connecting the first and second primary connecting members to the electrode current collectors of the members of the population of electrode structures. ### Claim 5 (depends on 1) The method according to claim 1, comprising forming an electrode assembly in which members of the population of counter-electrode structures comprise a counter-electrode current collector, and comprising connecting the first and second primary connecting members to the counter-electrode current collectors of the members of the population of counter-electrode structures. ### Claim 6 (depends on 1) The method according to claim 1, wherein the constraint system comprises first and second secondary growth constraints separated in a second direction and being placed in tension with one another via connection through first and second secondary connecting members. ### Claim 7 (depends on 6) The method according to claim 6, wherein the first and second secondary growth constraints correspond to the first and second primary connecting members, and the first and second secondary connecting members correspond to any of (i) the first and second primary growth constraints, (ii) the member(s) of the population of electrode structures, or (ii) the member(s) of population of counter-electrode structures to the first and second primary connecting members. ### Claim 8 (depends on 1) The method according to claim 1, wherein at least a portion of the constraint system comprises any of stainless steel, aluminum, titanium, beryllium copper, copper, nickel, alumina, zirconia, yttria-stabilized zirconia, Schott D263 tempered glass, polyetheretherketone (PEEK), PEEK with carbon, polyphenylene sulfide (PPS) with carbon, polyetheretherketone (PEEK) with 30% glass, polyimide, E Glass Std Fabric/Epoxy, 0 deg, E Glass UD/Epoxy, 0 deg, Kevlar Std Fabric/Epoxy, 0 deg, Kevlar UD/Epoxy, 0 deg, Carbon Std Fabric/Epoxy, 0 deg, Carbon UD/Epoxy, 0 deg, Toyobo Zylon® HM Fiber/Epoxy, Kevlar 49 Aramid Fiber, S Glass Fibers, Carbon Fibers, Vectran UM LCP Fibers, Dyneema, and Zylon, or combinations thereof. ### Claim 9 (depends on 1) The method of claim 1, wherein the electrode assembly comprises at least 10 electrode structures and at least 10 counter-electrode structures. ### Claim 10 (depends on 1) The method of claim 1, wherein the electrode assembly comprises at least 50 electrode structures and at least 50 counter-electrode structures. ### Claim 11 (depends on 1) The method of claim 1, wherein at least a portion of the constraint system comprises a sheet of material having a thickness in the range of about 10 to about 100 micrometers. ### Claim 12 (depends on 1) The method of claim 1, wherein at least a portion of the constraint system comprises a sheet of material having a thickness in the range of about 30 to about 75 micrometers. ### Claim 13 (depends on 1) The method of claim 1, comprising constraining the electrode assembly such that the first and second primary growth constraints exert a pressure on the first and second longitudinal end surfaces that exceeds the pressure maintained on the electrode assembly in each of two directions that are mutually perpendicular and perpendicular to the stacking direction. ### Claim 14 (depends on 1) The method of claim 1, comprising constraining the electrode assembly such that the first and second primary growth constraints exert a pressure on the first and second longitudinal end surfaces that exceeds the pressure maintained on the electrode assembly in each of two directions that are mutually perpendicular and perpendicular to the stacking direction by a factor of at least 2. ### Claim 15 (depends on 1) The method of claim 1, comprising constraining the electrode assembly such that the first and second primary growth constraints exert a pressure on the first and second longitudinal end surfaces that exceeds the pressure maintained on the electrode assembly in each of two directions that are mutually perpendicular and perpendicular to the stacking direction by a factor of at least 3. ### Claim 16 (depends on 1) The method of claim 1, wherein the structure is a secondary battery further comprising a battery enclosure. ### Claim 17 (depends on 16) The method of claim 16, comprising hermetically sealing the electrode assembly and constraint system within the battery enclosure. ### Claim 18 (depends on 16) The method of claim 16, comprising filling the battery enclosure with non-aqueous liquid electrolyte. ### Claim 19 (depends on 1) The method of claim 1, wherein the carrier ions are selected from the group consisting of lithium, potassium, sodium, calcium, and magnesium. ### Claim 20 (depends on 19) The method of claim 19, wherein the carrier ions comprise lithium ions. ### Claim 21 (depends on 1) The method of claim 1, comprising forming an electrode assembly wherein each member of the population of electrode structures comprises a layer of an electrode active material and each member of the population of counter-electrode structures comprises a layer of a counter-electrode active material, and wherein the electrode active material has the capacity to accept more than one mole of carrier ion per mole of electrode active material when the structure is provided as a part of a secondary battery that is charged from a discharged state to a charged state. ### Claim 22 (depends on 1) The method of claim 1, comprising forming an electrode assembly wherein each member of the population of electrode structures comprises a layer of an electrode active material and each member of the population of counter-electrode structures comprises a layer of a counter-electrode active material, and wherein the electrode active material comprises an anodically active material selected from the group consisting of metals, alloys, oxides and compounds capable of forming an alloy with lithium. ### Claim 23 (depends on 22) The method of claim 22, wherein the electrode active material comprises an anodically active material selected from the group consisting of aluminum, tin, silicon, an oxide thereof, a nitride thereof, a fluoride thereof, or other alloy thereof. ### Claim 24 (depends on 22) The method of claim 22, wherein the electrode active material comprises one or more of graphite, silicon, and an oxide thereof. ### Claim 25 (depends on 22) The method of claim 22, wherein the electrode active material comprises graphite. ### Claim 26 (depends on 22) The method of claim 22, wherein the electrode active material comprise silicon. ### Claim 27 (depends on 1) The method of claim 1, wherein members of the population of electrode structures comprising electrode current collectors, and members of the population of counter-electrode structures comprising counter-electrode current collectors, and wherein the first and second primary connecting members are affixed to (i) the electrode current collectors of the members of the population of electrode structures, and/or (ii) the counter-electrode current collectors of the members of the population of counter-electrode structures, by any one or more of adhering, gluing, welding, bonding, soldering, sintering, press contacting, brazing, thermal spraying joining, clamping, wire bonding, ribbon bonding, ultrasonic bonding, ultrasonic welding, resistance welding, laser beam welding, electron beam welding, induction welding, cold welding, plasma spraying, flame spraying, and arc spraying. ### Claim 28 (depends on 27) The method of claim 27, wherein the electrode current collectors and/or counter-electrode current collectors are under tension. ### Claim 29 (depends on 1) The method of claim 1, wherein the first and second primary connecting members each comprise a thickness that is less than 20% of a height of members of the electrode or counter-electrode structure population. ### Claim 30 (depends on 1) The method of claim 1, wherein the surface area of the first and second longitudinal end surfaces is less than 15% of the surface area of the electrode assembly. ### Claim 31 (depends on 1) The method of claim 1, wherein a surface area of a projection of the electrode assembly in a plane orthogonal to the longitudinal direction, is smaller than the surface areas of projections of the electrode assembly onto other orthogonal planes. ### Claim 32 (depends on 1) The method of claim 1, wherein the electrically insulating separator material comprises a microporous separator material comprising a particulate material and a binder, and has a void fraction of at least 20 vol. %. ### Claim 33 (depends on 1) The method of claim 1, comprising connecting the first and second primary connecting members to top and bottom ends of (i) member(s) of the population of electrode structures, or (ii) member(s) of population of counter-electrode structures to the first and second primary connecting members. ### Claim 34 (depends on 21) The method of claim 21, wherein the counter-electrode active material comprises a cathodically active material comprising a cathode material selected from transition metal oxides, transition metal sulfides, transition metal nitrides, lithium-transition metal oxides, lithium-transition metal sulfides, and lithium-transition metal nitrides. ### Claim 35 (depends on 34) The method of claim 34, wherein the transition metal elements of these transition metal oxides, transition metal sulfides, and transition metal nitrides can include metal elements having a d-shell or f-shell. ### Claim 36 (depends on 35) The method of claim 35, wherein the transition metal element are selected from the group consisting of Sc, Y, lanthanoids, actinoids, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pb, Pt, Cu, Ag, and Au. ### Claim 37 (depends on 34) The method of claim 34, wherein the cathodically active material is selected from the group consisting of LiCoO2, LiNi0.5Mn1.5O4, Li(NixCoyAl2)O2, LiFePO4, Li2MnO4, V2O5, molybdenum oxysulfides, phosphates, silicates, vanadates and combinations thereof. ### Claim 38 (depends on 4) The method of claim 4, wherein the electrode current collector comprises a metal selected from the group consisting of aluminum, carbon, chromium, gold, nickel, NiP, palladium, platinum, rhodium, ruthenium, an alloy of silicon and gold, an alloy of silicon and nickel, titanium, or a combination thereof. ### Claim 39 (depends on 5) The method of claim 5, wherein the counter-electrode current collector comprises a metal selected from the group consisting of aluminum, carbon, chromium, gold, nickel, NiP, palladium, platinum, rhodium, ruthenium, an alloy of silicon and gold, an alloy of silicon and nickel, titanium, or a combination thereof. ### Claim 40 (depends on 1) The method of claim 1, wherein the constraint system comprises a material having an ultimate tensile strength of at least 10,000 psi (>70 MPa). ### Claim 41 (depends on 1) A structure manufactured according to the method of claim 1, the structure comprising the electrode assembly, carrier ions, and constraint system. ### Claim 42 A method of manufacturing a secondary battery comprising a battery enclosure, an electrode assembly, carrier ions, and a constraint system, the method comprising forming the electrode assembly, the electrode assembly having mutually perpendicular longitudinal, transverse, and vertical axes, a first longitudinal end surface and a second longitudinal end surface separated from each other in the longitudinal direction, and a lateral surface surrounding an electrode assembly longitudinal axis AEA and connecting the first and second longitudinal end surfaces, the lateral surface having opposing first and second regions on opposite sides of the longitudinal axis and separated in a first direction that is orthogonal to the longitudinal axis, the electrode assembly having a maximum width WEA measured in the longitudinal direction, a maximum length LEA bounded by the lateral surface and measured in the transverse direction, and a maximum height HEA bounded by the lateral surface and measured in the vertical direction, the ratio of each of LEA and WEA to HEA being at least 2:1, respectively, the electrode assembly comprising a population of electrode structures, a population of counter-electrode structures, and an electrically insulating separator material electrically separating members of the electrode and counter-electrode populations, with members of the electrode and counter-electrode structure populations being arranged in an alternating sequence in the longitudinal direction, and constraining the electrode assembly with the constraint system, the constraint system comprising first and second primary growth constraints separated from each other in the longitudinal direction, the first and second primary growth constraints being placed in tension with one another via connection through first and second primary connecting members, the first and second primary connecting members being separated from each other in the vertical direction, and connecting one or more of (i) member(s) of the population of electrode structures, or (ii) member(s) of population of counter-electrode structures to the first and second primary connecting members. ### Claim 43 (depends on 42) The method of claim 42, comprising filling the battery enclosure with non-aqueous liquid electrolyte. ### Claim 44 (depends on 42) The method according to claim 42, comprising connecting both member(s) of the population of electrode structures and member(s) of population of counter-electrode structures to the first and second primary connecting members. ### Claim 45 (depends on 42) The method according to claim 42, comprising connecting member(s) of the population of electrode structures to the first and second primary connecting members. ### Claim 46 (depends on 42) The method according to claim 42, comprising forming an electrode assembly in which members of the population of electrode structures comprise an electrode current collector, and comprising connecting the first and second primary connecting members to the electrode current collectors of the members of the population of electrode structures. ### Claim 47 (depends on 42) The method according to claim 42, comprising forming an electrode assembly in which members of the population of counter-electrode structures comprise a counter-electrode current collector, and comprising connecting the first and second primary connecting members to the counter-electrode current collectors of the members of the population of counter-electrode structures. ### Claim 48 (depends on 42) The method according to claim 42, wherein the constraint system comprises first and second secondary growth constraints separated in a second direction and being placed in tension with one another via connection through first and second secondary connecting members. ### Claim 49 (depends on 48) The method according to claim 48, wherein the first and second secondary growth constraints correspond to the first and second primary connecting members, and the first and second secondary connecting members correspond to any of (i) the first and second primary growth constraints, (ii) the member(s) of the population of electrode structures, or (ii) the member(s) of population of counter-electrode structures to the first and second primary connecting members. ### Claim 50 (depends on 42) The method according to claim 42, wherein at least a portion of the constraint system comprises any of stainless steel, aluminum, titanium, beryllium copper, copper, nickel, alumina, zirconia, yttria-stabilized zirconia, Schott D263 tempered glass, polyetheretherketone (PEEK), PEEK with carbon, polyphenylene sulfide (PPS) with carbon, polyetheretherketone (PEEK) with 30% glass, polyimide, E Glass Std Fabric/Epoxy, 0 deg, E Glass UD/Epoxy, 0 deg, Kevlar Std Fabric/Epoxy, 0 deg, Kevlar UD/Epoxy, 0 deg, Carbon Std Fabric/Epoxy, 0 deg, Carbon UD/Epoxy, 0 deg, Toyobo Zylon® HM Fiber/Epoxy, Kevlar 49 Aramid Fiber, S Glass Fibers, Carbon Fibers, Vectran UM LCP Fibers, Dyneema, and Zylon, or combinations thereof. ### Claim 51 (depends on 42) The method of claim 42, wherein the electrode assembly comprises at least 10 electrode structures and at least 10 counter-electrode structures. ### Claim 52 (depends on 42) The method of claim 42, wherein the electrode assembly comprises at least 50 electrode structures and at least 50 counter-electrode structures. ### Claim 53 (depends on 42) The method of claim 42, wherein at least a portion of the constraint system comprises a sheet of material having a thickness in the range of about 10 to about 100 micrometers. ### Claim 54 (depends on 42) The method of claim 42, wherein at least a portion of the constraint system comprises a sheet of material having a thickness in the range of about 30 to about 75 micrometers. ### Claim 55 (depends on 42) The method of claim 42, comprising constraining the electrode assembly such that the first and second primary growth constraints exert a pressure on the first and second longitudinal end surfaces that exceeds the pressure maintained on the electrode assembly in each of two directions that are mutually perpendicular and perpendicular to the stacking direction. ### Claim 56 (depends on 42) The method of claim 42, comprising constraining the electrode assembly such that the first and second primary growth constraints exert a pressure on the first and second longitudinal end surfaces that exceeds the pressure maintained on the electrode assembly in each of two directions that are mutually perpendicular and perpendicular to the stacking direction by a factor of at least 2. ### Claim 57 (depends on 42) The method of claim 42, comprising constraining the electrode assembly such that the first and second primary growth constraints exert a pressure on the first and second longitudinal end surfaces that exceeds the pressure maintained on the electrode assembly in each of two directions that are mutually perpendicular and perpendicular to the stacking direction by a factor of at least 3. ### Claim 58 (depends on 42) The method of claim 42, wherein the carrier ions are selected from the group consisting of lithium, potassium, sodium, calcium, and magnesium. ### Claim 59 (depends on 58) The method of claim 58, wherein the carrier ions comprise lithium ions. ### Claim 60 (depends on 42) The method of claim 42, comprising forming an electrode assembly wherein each member of the population of electrode structures comprises a layer of an electrode active material and each member of the population of counter-electrode structures comprises a layer of a counter-electrode active material, and wherein the electrode active material comprises an anodically active material selected from the group consisting of metals, alloys, oxides and compounds capable of forming an alloy with lithium. ### Claim 61 (depends on 60) The method of claim 60, wherein the electrode active material comprises an anodically active material selected from the group consisting of aluminum, tin, silicon, an oxide thereof, a nitride thereof, a fluoride thereof, or other alloy thereof. ### Claim 62 (depends on 46) The method of claim 46, wherein the electrode current collectors are under tension. ### Claim 63 (depends on 42) The method of claim 42, wherein the first and second primary connecting members each comprise a thickness that is less than 20% of a height of members of the electrode or counter-electrode structure population. ### Claim 64 (depends on 42) The method of claim 42, wherein the surface area of the first and second longitudinal end surfaces is less than 15% of the surface area of the electrode assembly. ### Claim 65 (depends on 42) The method of claim 42, wherein the constraint system comprises a material having an ultimate tensile strength of at least 10,000 psi (>70 MPa). ### Claim 66 (depends on 42) A secondary battery manufactured according to the method of claim 42, the secondary battery comprising the battery enclosure, electrode assembly, carrier ions, and constraint system. ### Claim 67 (depends on 66) The secondary battery of claim 66, further comprising a non-aqueous liquid electrolyte within the battery enclosure.