# US 11,444,347 B2 · Three-dimensional rechargeable battery with solid-state electrolyte > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,444,347 B2 - Document ID: US11444347B2 - Status: Granted - Kind: B2 - Application number: 16/651,777 - Filed: 2018-02-28 - Published: 2020-08-13 - Granted: 2022-09-13 - Earliest claimed: 2017-10-09 - Assignees: Lawrence Livermore National Security, LLC - Applicants: Lawrence Livermore National Security, LLC - Inventors: Sourabh K. Saha; Robert M. Panas - Web page: https://patentgrep.com/patent/US11444347B2 ## CPC - H01M 4/134: Electrodes based on metals, Si or alloys - H01M 12/08: composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type - H01M 4/382: {Lithium (H01M4/405 takes precedence)} - H01M 4/86: Inert electrodes with catalytic activity, e.g. for fuel cells - H01M 4/88: Processes of manufacture - H01M 10/052: Li-accumulators - H01M 10/0565: Polymeric materials, e.g. gel-type or solid-type - H01M 10/0569: characterised by the solvents - B33Y 80/00: Products made by additive manufacturing - H01M 2004/027: {Negative electrodes} - H01M 2004/8689: {Positive electrodes} - H01M 2300/0071: Oxides - H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY - B33Y: ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING ## Abstract A scaffold of an electrolyte is fabricated in polymer material using 3D printing techniques. A thin layer of solid electrolyte is deposited on the scaffold followed by burning off the polymer. This leaves behind a 3D foam-like solid electrolyte with two distinct non-overlapping volumes. Lithium followed by a conductive layer (for anode) is then deposited through one volume on the first surface whereas a porous or non-porous conductive layer is deposited on the opposite surface through the second volume. The non-porous conductive layer on the second surface is made porous by a selective timed etch. ## Claims ### Claim 1 A three-dimensional battery comprising: a non-planar thin solid electrolyte layer that separates two non-overlapping volumes, wherein a first non-overlapping volume is in the form of a network of pores, and wherein the diameter of pores in the first non-overlapping volume is smaller than 5 micrometers; a layer of electrically conductive anode material located in the first non-overlapping volume and in contact with the solid electrolyte layer, wherein at least one part of the anode material is capable of undergoing electrochemical oxidation; a porous electrically conductive thin cathode film located in a second non-overlapping volume and conformally covering the solid electrolyte layer; and a passage in the second non-overlapping volume for flowing an oxidizing gas, wherein the oxidizing gas contacts the porous cathode film. ### Claim 2 (depends on 1) The battery of claim 1, wherein the thickness of the solid electrolyte layer lies between 5 nm and 500 nm. ### Claim 3 (depends on 1) The battery of claim 1, wherein the solid electrolyte layer is ceramic. ### Claim 4 (depends on 1) The battery of claim 1, wherein the diameter of pores in the first non-overlapping volume is smaller than 1 micrometer. ### Claim 5 (depends on 1) The battery of claim 1, wherein the thickness of the solid electrolyte layer is uniform. ### Claim 6 (depends on 1) The battery of claim 1, wherein a spacing between pores in the first non-overlapping volume lies between 10 nanometers and 10 micrometers. ### Claim 7 (depends on 1) The battery of claim 1, wherein a spacing of the pores in the first non-overlapping volume is non-uniform and is scaled by the shortest distance of the pores from any external edge of the battery. ### Claim 8 (depends on 1) The battery of claim 1, wherein the anode material substantially fills the first non-overlapping volume. ### Claim 9 (depends on 1) The battery of claim 1, wherein the porous cathode film is in the form of a mixture of multiple materials such as i) catalyst material, ii) carbon nanoparticles, and iii) carbon nanotubes. ### Claim 10 (depends on 1) The battery of claim 1, wherein the anode material is lithium metal. ### Claim 11 (depends on 1) The battery of claim 1, wherein the anode material is a mixture of various metals. ### Claim 12 (depends on 1) The battery of claim 1, wherein the anode material is a mixture of various metals and silicon. ### Claim 13 (depends on 1) The battery of claim 1, wherein the solid electrolyte layer is an oxide of aluminum or silicon. ### Claim 14 (depends on 1) The battery of claim 1, wherein the oxidizing gas is pure oxygen. ### Claim 15 A method of fabricating a three-dimensional battery comprising the steps of: providing a foam structure which is the geometric inverse of a network of pores, wherein the diameter of inverse pores is smaller than 5 micrometers; encasing the foam structure with a non-planar thin solid electrolyte layer; removing the material of the foam structure, wherein removing the material leaves the electrolyte layer intact as a shell around a network of pores; filling the network of pores in the interior of the electrolyte shell with an electrically conductive anode material, wherein at least one part of the anode material is capable of undergoing electrochemical oxidation; encasing the exterior of the electrolyte shell with a porous electrically conductive thin cathode film which is in contact with the electrolyte shell, wherein the resulting cathode structure is gas permeable; and attaching separate electrodes to the anode material and to a cathode material. ### Claim 16 (depends on 15) The method of claim 15, wherein the network of pores is substantially filled with the anode material. ### Claim 17 (depends on 15) The method of claim 15, wherein the foam structure is fabricated by two-photon lithography. ### Claim 18 (depends on 15) The method of claim 15, wherein the solid electrolyte layer is formed by atomic-layer deposition over the foam structure. ### Claim 19 (depends on 15) The method of claim 15, wherein the material of the foam structure is removed by thermal burnout. ### Claim 20 (depends on 15) The method of claim 15, wherein the material of the foam structure is removed by chemical etching. ### Claim 21 (depends on 15) The method of claim 15, wherein the anode material is transported into the network of pores via a liquid wicking operation. ### Claim 22 (depends on 15) The method of claim 15, wherein the anode material is transported into the network of pores via a gaseous deposition operation. ### Claim 23 (depends on 15) The method of claim 15, wherein the cathode film is formed by electrophoretic deposition of a mixture of nanoparticle. ### Claim 24 A method of making a micro-battery, comprising the steps of: 3D print a scaffold of an electrolyte using a polymer material, deposit a thin layer of solid electrolyte on the scaffold, burn off the polymer material, provide remaining 3D foam-like solid electrolyte with two distinct non-overlapping volumes, provide first a lithium layer followed by depositing a conductive layer (anode) is deposited on a first volume (surface), provide second a conductive layer deposited on a second volume (surface), and etch the second volume (surface to make it porous).