CA3236554A1 - System and method for 3d printing porous zinc structures - Google Patents
System and method for 3d printing porous zinc structures Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/10—Formation of a green body
- B22F10/18—Formation of a green body by mixing binder with metal in filament form, e.g. fused filament fabrication [FFF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- 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
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
- B33Y40/20—Post-treatment, e.g. curing, coating or polishing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/60—Treatment of workpieces or articles after build-up
- B22F10/64—Treatment of workpieces or articles after build-up by thermal means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/80—Data acquisition or data processing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/1103—Making porous workpieces or articles with particular physical characteristics
- B22F3/1115—Making porous workpieces or articles with particular physical characteristics comprising complex forms, e.g. honeycombs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/114—Making porous workpieces or articles the porous products being formed by impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- 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
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- 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
- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- 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
- B33Y50/00—Data acquisition or data processing for additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- 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
- B33Y80/00—Products made by additive manufacturing
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- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
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- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- 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
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- 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
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/244—Zinc electrodes
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- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/30—Low melting point metals, i.e. Zn, Pb, Sn, Cd, In, Ga
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—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
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- 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
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- 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
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- 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
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Abstract
Freeform fabrication of architected porous zinc via 3D printing. Ink including zinc powders, solvents and binders is created with printability. At least one 3D model is created with microarchitectures. Extrusion-based direct-writing is used to manufacture free-standing 3D zinc structures. Post-processing conditions generate final architected porous zinc products.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims priority of US patent application No.
17/453,396, filed on November 3, 2021 and titled "SYSTEM AND METHOD FOR 3D
PRINTING POROUS ZINC STRUCTURES", which is hereby incorporated by reference in its entirety.
STATEMENT AS TO RIGHTS TO APPLICATIONS MADE UNDER
FEDERALLY SPONSORED RESEARCH AND DEVELOPMENT
[0001] The present application claims priority of US patent application No.
17/453,396, filed on November 3, 2021 and titled "SYSTEM AND METHOD FOR 3D
PRINTING POROUS ZINC STRUCTURES", which is hereby incorporated by reference in its entirety.
STATEMENT AS TO RIGHTS TO APPLICATIONS MADE UNDER
FEDERALLY SPONSORED RESEARCH AND DEVELOPMENT
[0002] This invention was made with Government support under Contract No.
DE-AC52-07NA27344 awarded by the United States Department of Energy. The Government has certain rights in the invention.
BACKGROUND
Field of Endeavor 100031 The present disclosure relates to 3D printing and more particularly to systems and methods for 3D printing porous zinc structures.
State of Technology 100041 This section provides background information related to the present disclosure which is not necessarily prior art.
[0005] Zinc is an earth-abundant metal that has been used as a potential "beyond lithium" material for its high theoretical capacity, low redox potential, and good water compatibility. Therefore, it can be directly used as cheap anode for its high reversibility in aqueous zinc-based batteries. However, detrimental dendrites, corrosion, and hydrogen evolution are main issues causing the anode degradation during cycling.
Especially, the dead zinc from falling dendrites exacerbates localized uneven electric field and ions migration inducing even worse side reactions. Therefore, dendrite-free zinc anodes have become the prerequisite for the long-life batteries.
[0006]
Conventional Zn foils or plates always suffer from quick passivation without full utilization of excess active materials leading to a low energy density. Several 3D current collectors have been created to support Zn, such as carbons (i.e., graphene foam, carbon nanotube networks), and metals (i.e., nickel foam, porous copper, steel mesh).
However, these scaffolds add extra weight and have interfacial affinity problems with deposited zinc. Recently, 3D pure Zn anodes including wires, sponges, foams, nanosheets, and nanoporous monoliths and alloys have also been developed, whereas their randomly porous structures impedes the mass transfer of electrolyte and considerably increases the ion transfer distance.
[0007]
Additive manufacturing is a category of freeform fabrication techniques that build 3D structures by sequentially layering one material on top of another in a desired pattern. The direct ink writing is one of extrusion-based additive manufacturing methods that employ a computer-controlled translation stage to deposit customized "inks" through a print head into programmed designs. The patterns are generated by stacking 2D layers consisting of simple, one-dimensional filaments to complex, 3D structures. The inks are administered through micro-nozzles, and filament diameter is determined by nozzle size, print speed, and rates of ink flow and solidification. Here, we develop a new colloidal-based zinc ink to print self-supported 3D anodes with designed internal structure show greater degree of freedom to regulate the electron transfer kinetics, ion flux, and nucleation barrier and sites.
SUMMARY
[0008]
Features and advantages of the disclosed apparatus, systems, and methods will become apparent from the following description. Applicant is providing this description, which includes drawings and examples of specific embodiments, to give a broad representation of the apparatus, systems, and methods. Various changes and modifications within the spirit and scope of the application will become apparent to those skilled in the art from this description and by practice of the apparatus, systems, and methods. The scope of the apparatus, systems, and methods is not intended to be limited to the particular forms disclosed and the application covers all modifications, equivalents, and alternatives falling within the spirit and scope of the apparatus, systems, and methods as defined by the claims.
Applicant's apparatus, systems, and methods provide freeform fabrication of architected porous zinc via 3D printing. Ink including zinc powders, solvents and binders is created with printability. At least one 3D model is created with microarchitectures.
Extrusion-based direct-writing is used to manufacture free-standing 3D zinc structures.
Post-processing conditions generate final architected porous zinc products.
In one aspect the present disclosure relates to a method of forming 3D zinc structures. In one embodiment, an ink includes a copolymer binder, a zinc powder, and an organic volatile solvent system. The method may involve providing a zinc micro-powder and mixing the powder with an organic binder and solvents system to form a shear-reversible ink. In another embodiment, a method includes printing a 3D
structure using an ink, drying and annealing the printed structure. A 3D printing technique may be used to write the ink into versatile shapes and structures. The 3D printing may be performed to apply the ink to form a plurality of ink layers, one on top of another, to form a wet three dimensional part having a desired shape and desired dimensions. The ink may be used to form a wet part with minimal collapsing due to its instant shape retention by controllable solvents evaporation. The wet part may then be dried in the air to form a freestanding green part. The dried part may then be annealed to form a finished zinc part in controlled atmosphere, temperature, and time.
In another aspect the present disclosure relates to a system for forming a porous zinc. The system may include a controller and a deposition component controlled by the controller for depositing an ink. The controller may be further configured to implement a 3D printing technique to write the ink at the corresponding speed of solvents evaporation rate. The 3D printing technique may be used by the controller to form a plurality of ink layers one on top of another to forma wet three dimensional part. In yet another embodiment, a product includes a 3D printed structure having ligaments, where an average diameter of the ligaments is in a range of about 200 microns, and pores size of
DE-AC52-07NA27344 awarded by the United States Department of Energy. The Government has certain rights in the invention.
BACKGROUND
Field of Endeavor 100031 The present disclosure relates to 3D printing and more particularly to systems and methods for 3D printing porous zinc structures.
State of Technology 100041 This section provides background information related to the present disclosure which is not necessarily prior art.
[0005] Zinc is an earth-abundant metal that has been used as a potential "beyond lithium" material for its high theoretical capacity, low redox potential, and good water compatibility. Therefore, it can be directly used as cheap anode for its high reversibility in aqueous zinc-based batteries. However, detrimental dendrites, corrosion, and hydrogen evolution are main issues causing the anode degradation during cycling.
Especially, the dead zinc from falling dendrites exacerbates localized uneven electric field and ions migration inducing even worse side reactions. Therefore, dendrite-free zinc anodes have become the prerequisite for the long-life batteries.
[0006]
Conventional Zn foils or plates always suffer from quick passivation without full utilization of excess active materials leading to a low energy density. Several 3D current collectors have been created to support Zn, such as carbons (i.e., graphene foam, carbon nanotube networks), and metals (i.e., nickel foam, porous copper, steel mesh).
However, these scaffolds add extra weight and have interfacial affinity problems with deposited zinc. Recently, 3D pure Zn anodes including wires, sponges, foams, nanosheets, and nanoporous monoliths and alloys have also been developed, whereas their randomly porous structures impedes the mass transfer of electrolyte and considerably increases the ion transfer distance.
[0007]
Additive manufacturing is a category of freeform fabrication techniques that build 3D structures by sequentially layering one material on top of another in a desired pattern. The direct ink writing is one of extrusion-based additive manufacturing methods that employ a computer-controlled translation stage to deposit customized "inks" through a print head into programmed designs. The patterns are generated by stacking 2D layers consisting of simple, one-dimensional filaments to complex, 3D structures. The inks are administered through micro-nozzles, and filament diameter is determined by nozzle size, print speed, and rates of ink flow and solidification. Here, we develop a new colloidal-based zinc ink to print self-supported 3D anodes with designed internal structure show greater degree of freedom to regulate the electron transfer kinetics, ion flux, and nucleation barrier and sites.
SUMMARY
[0008]
Features and advantages of the disclosed apparatus, systems, and methods will become apparent from the following description. Applicant is providing this description, which includes drawings and examples of specific embodiments, to give a broad representation of the apparatus, systems, and methods. Various changes and modifications within the spirit and scope of the application will become apparent to those skilled in the art from this description and by practice of the apparatus, systems, and methods. The scope of the apparatus, systems, and methods is not intended to be limited to the particular forms disclosed and the application covers all modifications, equivalents, and alternatives falling within the spirit and scope of the apparatus, systems, and methods as defined by the claims.
Applicant's apparatus, systems, and methods provide freeform fabrication of architected porous zinc via 3D printing. Ink including zinc powders, solvents and binders is created with printability. At least one 3D model is created with microarchitectures.
Extrusion-based direct-writing is used to manufacture free-standing 3D zinc structures.
Post-processing conditions generate final architected porous zinc products.
In one aspect the present disclosure relates to a method of forming 3D zinc structures. In one embodiment, an ink includes a copolymer binder, a zinc powder, and an organic volatile solvent system. The method may involve providing a zinc micro-powder and mixing the powder with an organic binder and solvents system to form a shear-reversible ink. In another embodiment, a method includes printing a 3D
structure using an ink, drying and annealing the printed structure. A 3D printing technique may be used to write the ink into versatile shapes and structures. The 3D printing may be performed to apply the ink to form a plurality of ink layers, one on top of another, to form a wet three dimensional part having a desired shape and desired dimensions. The ink may be used to form a wet part with minimal collapsing due to its instant shape retention by controllable solvents evaporation. The wet part may then be dried in the air to form a freestanding green part. The dried part may then be annealed to form a finished zinc part in controlled atmosphere, temperature, and time.
In another aspect the present disclosure relates to a system for forming a porous zinc. The system may include a controller and a deposition component controlled by the controller for depositing an ink. The controller may be further configured to implement a 3D printing technique to write the ink at the corresponding speed of solvents evaporation rate. The 3D printing technique may be used by the controller to form a plurality of ink layers one on top of another to forma wet three dimensional part. In yet another embodiment, a product includes a 3D printed structure having ligaments, where an average diameter of the ligaments is in a range of about 200 microns, and pores size of
3 about 500 microns. A surface treated substrate may be used for delaminating the wet part after drying. A subsystem may be included for annealing the dried part to form a finished part.
[00012]
These printed zinc structures have large surface area and tailored porosity to facilitate the electrons and ions transport and even electric field and ion distribution as potential electrodes for high performance zinc-ion supercapacitors or batteries. Further areas of applicability will become apparent from the description provided herein. It should be understood that the description and specific examples are intended for purposes of illustration only and are not intended to limit the Scope of the present disclosure.
[00013]
Embodiments of this presentation comprise a method of 3D printing a porous zinc structure, comprising the steps of: creating a 3D model of the porous zinc structure, providing zinc ink, 3D printing said zinc ink into a porous zinc lattice structure using said 3D model, and post processing said porous zinc lattice structure to produce the porous zinc structure.
[00014]
According to embodiments of this presentation, the step of creating a 3D
model of a porous zinc structure comprises creating a 3D model of a porous zinc structure wherein said porous zinc structure has microarchitectures.
[00015]
According to embodiments of this presentation, the step of providing zinc ink comprises providing zinc powders, providing solvents, and providing binders to produce said zinc ink.
[00016]
According to embodiments of this presentation, the step of 3D printing said zinc ink into a porous zinc lattice structure using said 3D model comprises extrusion-based direct-writing 3D printing said zinc ink into a porous zinc lattice structure using said 3D
model.
[00017]
According to embodiments of this presentation, the step of 3D printing said zinc ink into a porous zinc lattice structure using said 3D model comprises 3D
printing said zinc ink into a large area porous zinc lattice structure.
[00018]
According to embodiments of this presentation, the step of 3D printing said zinc ink into a porous zinc lattice structure using said 3D model comprises extrusion-based
[00012]
These printed zinc structures have large surface area and tailored porosity to facilitate the electrons and ions transport and even electric field and ion distribution as potential electrodes for high performance zinc-ion supercapacitors or batteries. Further areas of applicability will become apparent from the description provided herein. It should be understood that the description and specific examples are intended for purposes of illustration only and are not intended to limit the Scope of the present disclosure.
[00013]
Embodiments of this presentation comprise a method of 3D printing a porous zinc structure, comprising the steps of: creating a 3D model of the porous zinc structure, providing zinc ink, 3D printing said zinc ink into a porous zinc lattice structure using said 3D model, and post processing said porous zinc lattice structure to produce the porous zinc structure.
[00014]
According to embodiments of this presentation, the step of creating a 3D
model of a porous zinc structure comprises creating a 3D model of a porous zinc structure wherein said porous zinc structure has microarchitectures.
[00015]
According to embodiments of this presentation, the step of providing zinc ink comprises providing zinc powders, providing solvents, and providing binders to produce said zinc ink.
[00016]
According to embodiments of this presentation, the step of 3D printing said zinc ink into a porous zinc lattice structure using said 3D model comprises extrusion-based direct-writing 3D printing said zinc ink into a porous zinc lattice structure using said 3D
model.
[00017]
According to embodiments of this presentation, the step of 3D printing said zinc ink into a porous zinc lattice structure using said 3D model comprises 3D
printing said zinc ink into a large area porous zinc lattice structure.
[00018]
According to embodiments of this presentation, the step of 3D printing said zinc ink into a porous zinc lattice structure using said 3D model comprises extrusion-based
4 direct-writing 3D printing said zinc ink into a free-standing 3D porous zinc lattice structure using said 3D model.
[000191 According to embodiments of this presentation, the step of post processing said porous zinc lattice structure comprises heat treatment of said porous zinc lattice structure.
According to embodiments of this presentation, the step of creating a 3D
model comprises creating a 3D model of an anode for a zinc battery, wherein said step of 3D printing said zinc ink into a porous zinc lattice structure using said 3D
model comprises 3D printing said zinc ink into a porous zinc lattice structure of an anode for a zinc battery using said 3D model of an anode for a zinc battery, and wherein said step of post processing said porous zinc lattice structure to produce the porous zinc structure comprises post processing said porous zinc lattice structure of an anode for a zinc battery to produce an anode for a zinc battery_ According to embodiments of this presentation, the step of creating a 3D
model comprises creating a 3D model of a current collector for a supercapacitor, wherein said step of 3D printing said zinc ink into a porous zinc lattice structure using said 3D
model comprises 3D printing said zinc ink into a porous zinc lattice structure of a current collector for a supercapacitor, and wherein said step of post processing said porous zinc lattice structure to produce the porous zinc structure comprises post processing said porous zinc lattice structure of a current collector for a supercapacitor to produce the porous zinc structure.
[000221 Another embodiment of this presentation comprises a method of 3D
printing a porous zinc anode, comprising the steps of creating a 3D model of the porous zinc anode, providing zinc ink, 3D printing said zinc ink into a porous zinc lattice anode using said 3D model, and post processing said porous zinc lattice anode to produce the porous zinc anode.
[00023]
According to einbodiments of this presentation, the step of creating a 3D
model of a porous zinc anode comprises creating a 3D model of a porous zinc anode wherein said porous zinc anode has microarchitectures.
[00024]
According to embodiments of this presentation, the step of providing zinc ink comprises providing zinc powders, providing solvents, and providing binders to produce said zinc ink.
[00025]
According to embodiments of this presentation, the step of 3D printing said zinc ink into a porous zinc lattice anode using said 3D model comprises extrusion-based direct-writing 3D printing said zinc ink into a porous zinc lattice anode using said 3D
model.
[00026]
According to embodiments of this presentation, the step of 3D printing said zinc ink into a porous zinc lattice anode using said 3D model comprises 3D
printing said zinc ink into a large area porous zinc lattice anode.
[00027]
According to embodiments of this presentation, the step of 3D printing said zinc ink into a porous zinc lattice anode using said 3D model comprises extrusion-based direct-writing 3D printing said zinc ink into a free-standing 3D porous zinc lattice anode using said 3D model.
[00028]
According to embodiments of this presentation, the step of post processing said porous zinc lattice anode comprises heat treatment of said porous zinc lattice anode.
[00029]
Another embodiment of this presentation comprises an apparatus for making a porous zinc structure, comprising: means for producing zinc ink, means for creating a 3D model of a porous zinc structure, means for 3D printing said zinc ink into a porous zinc lattice structure using said 3D model, and means for post processing said porous zinc lattice structure to produce the porous zinc structure.
[00030] According to embodiments of this presentation, the means for producing zinc ink comprises means for providing zinc powders, providing solvents, and providing binders to produce said zinc ink.
[00031] According to embodiments of this presentation, the means for creating a 3D
model of a porous zinc structure comprises means creating a 3D model of a porous zinc structure anode for a zinc battery, wherein the means for 3D printing said zinc ink into a porous zinc lattice structure using said 3D model comprises means for 3D
printing said zinc ink into a porous zinc lattice structure of an anode for a zinc battery using said 3D
model of an anode for a zinc battery, and wherein the means for post processing said porous zinc lattice structure to produce the porous zinc structure comprises means for post processing said porous zinc lattice structure to produce the porous zinc structure of an anode for a zinc battery to produce an anode for a zinc battery.
[00032] According to embodiments of this presentation, the means for creating a 3D
model of a porous zinc structure comprises means creating a 3D model of a porous zinc structure current collector for a supercapacitor, wherein the means for 3D
printing said zinc ink into a porous zinc lattice structure using said 3D model comprises means for 3D
printing said zinc ink into a porous zinc lattice structure of a supercapacitor using said 3D
model of a current collector for a supercapacitor, and wherein the means for post processing said porous zinc lattice structure to produce the porous zinc structure comprises means for post processing said porous zinc lattice structure to produce the porous zinc structure of a current collector for a supercapacitor.
[00033] Other embodiments of this presentation comprise a freeform fabrication of archnected porous zinc via 3D printing, where ink includim zinc powders, solvents and binders is created with printability; at least one 3D model is created with microarchitectures; extrusion-based direct-writing is used to manufacture free-standing 3D
zinc structures; and post-processing conditions generate final architected porous zinc products.
[000341 Other aspects and advantages of the present invention will become apparent from the following detailed description, which, when taken in conjunction with the drawings, illustrate by way of example the principles of the invention.
1000351 The system for forming a porous zinc of the present disclosure has use in a wide range of technologies, such as catalysis, desalination, energy storage, and filtration.
The system for forming a porous zinc of the present disclosure has use in energy storage and particularly for Li-ion batteries.
[000361 The apparatus, systems, and methods are susceptible to modifications and alternative forms. Specific embodiments are shown by way of example. It is to be understood that the apparatus, systems, and methods are not limited to the particular forms disclosed. The apparatus, systems, and methods cover all modifications, equivalents, and alternatives falling within the spirit and scope of the application as defined by the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
1000371 The present disclosure relates to 3D printing and more particularly to systems and methods for 3D printing porous zinc structures.
[000381 The accompanying drawings, which are incorporated into and constitute a part of the specification, illustrate specific embodiments of the apparatus, systems, and methods and, together with the general description given above, and the detailed description of the specific embodiments, serves to explain the principles of the apparatus, systems, and methods.
1000391 FIG. 1 is a flowchart that illustrates one embodiment of the inventor's apparatus, systems, and methods for producing hierarchical zinc structures.
1000401 FIG. 2 is a flow diagram that illustrates the steps of zinc-based colloidal inks preparation.
[000411 FIG. 3 illustrates one embodiment of the 3D model of the inventor's microlattice anode.
[00042]
FIG. 4 is an illustrative flow diagram that depicts the steps of the inventor's direct ink writing apparatus, systems, and methods for producing zinc microlattice.
[00043]
FIG. 5 shows a series of optical images illustrating various shapes and structures of 3D-printed zinc.
[00044]
FIG. 6 is a series of optical images and scanning electron microscope images illustrate the structure and morphology of a hierarchically porous zinc lattice after post-processing.
[00045]
FIG. 7 is a flowchart that illustrates another embodiment of the inventor's apparatus, systems, and methods for producing hierarchical zinc structures.
DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS
[00046]
Referring to the drawings, to the following detailed description, and to incorporated materials, detailed information about the apparatus, systems, and methods is provided including the description of specific embodiments. The detailed description serves to explain the principles of the apparatus, systems, and methods. The apparatus, systems, and methods are susceptible to modifications and alternative forms.
The application is not limited to the particular forms disclosed. The application covers all modifications, equivalents, and alternatives falling within the spirit and scope of the apparatus, systems, and methods as defined by the claims.
[00047]
Unless otherwise specifically defined herein, all terms are to be given their broadest possible interpretation including meanings implied from the specification as well as meanings understood by those skilled in the art and/or as defined in dictionaries, treatises, etc. It must also be noted that, as used in the specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless otherwise specified. As also used herein, the term "about" denotes an interval of accuracy that ensures the technical effect of the feature in question. In various approaches, the term "about" when combined with a value, refers to plus and minus 10 % of the reference value.
For example, a thickness of about 10 rim refers to a thickness of 10 nm 1 urn, a temperature of about 50 C refers to a temperature of 50 C 5 C ,etc. The nanoscale is defined as between I
nanometer and about 500 nanometers. For the purposes of this description, macropores are defined as having an average diameter of greater than 1 millimeter (mm).
Mesopores are defined as having an average diameter of less than 1 mm and greater than about 10 microns (urn). Micropores are defined as having an average diameter less than about 10 urn and greater than about 100 nanometers (urn). Nanopores are defined as having an average diameter less than 1 urn and greater than 0 nanometers. These ranges are approximate and may overlap, e.g., a large nanopore may also be defined as a small micropore.
A list of acronyms used in the description is provided below.
3D Three-dimensional "C Celsius cm centimeter DIW Direct ink writing um micron mg milligram mm millimeter nm nanometer SEM Scanning electron microscope [00048]
The present invention uses an additive manufacturing operation, in one example a DIW additive manufacturing process, to fabricate hierarchical porous zinc with deterministically controlled, application specific, 3D architectures.
Arbitrary macroscopic architectures and sample shapes can be printed according to the application requirements.
Moreover, the structure of distinct levels of porosity can be tuned independently which enables application specific multiscale architectures of virtually any geometric 3D shape_ The following description discloses several preferred embodiments of hierarchically porous zinc foams and/or related additive manufacturing systems, methods, and products formed by the same.
Referring now to FIG. 1, a flow chart illustrates one embodiment of the inventor's apparatus, systems, and methods for producing 3D zinc structures.
The flow charter is designated generally by the reference numeral 100. As illustrated in the flow charter 100, the system includes a number of steps. The steps in FIG. 1 are identified and described below.
[00050]
Step I - ZINC INKS DEVELOPMENT (Reference numeral 102) - In step 1, a zinc powder based extrudable ink is developed.
[00051]
Step 2 - 3D MODEL DESIGN (Reference numeral 103) - In step 2, the 3D
geometrical models are designed using computer aided design (CAD) software or other systems for creating a digital model.
[00052]
Step 3 - EXTRUSION-BASED FABRICATION OF 3D ZINC (Reference numeral 104) - In step 3, the direct ink writing is employed to extrude developed inks into designed structures following the model from Step 2.
[00053]
Step 4 - POST-PROCESSING OF 3D ZINC STRUCTURES (Reference numeral 105) - In step 4, the as-printed green bodies are processed by drying and annealing to obtain the final products.
[00054]
FIG. 7 is a flowchart that illustrates another embodiment of the inventor's apparatus, systems, and methods for producing hierarchical zinc structures.
[00055]
FIG. 2 provides an illustrative flow diagram of the inks development (Reference numeral 200). In an exemplary approach, solid-state copolymer beads 202 with entangled polymeric chains 204 are dissolved into organic solvents 210. The resultant polymer solvation 206 is obtained due to the chains release in solvents. Then, zinc micro-powders 208 are added and thoroughly mixed with the polymer solution 212 to form a uniform colloidal ink.
[00056]
Referring now to FIG. 3, one embodiment of the model of the inventor's microlattice is illustrated. The model is designated generally by the reference numeral 300.
The model 300 shown in Fig. 3 illustrates a model for the construction of a square lattice 302 made of the colloidal ink. The model 300 is one embodiment of the model described in the flow charter of FIG. 1 under the heading -Step 2." The model 300 is designed using computer aided design (CAD) software or other systems for creating a digital model. The model 300 consists of orthogonally stacked parallel filaments array 304 with total of 8 layers. The filament diameter (d) is generally of 200 um, and center-to-center spacing (L) can be varied from 300-800 um.
[00057] FIG. 4 provides an illustrative flow diagram of the direct ink writing system 400 to make the inventor's zinc microlattice made of colloidal inks. In this example, the DIW operation using the x-y-z motion stage and high precision dispenser forms an extrusion-based, room temperature manufacturing process. The colloidal ink in this example is housed in a 10 ml syringe barrel attached by a Luer-Lok to a smooth-flow tapered nozzle. An air-powered electronically controlled fluid dispenser provides the appropriate pressure to extrude the ink through the nozzle. The target pattern in this example is printed using a mechanical bearing positioning gantry, whose motion is controlled by writing the appropriate G-code commands from the 3D model. The extrusion process may be controlled by controlling the extrusion pressure and printing speed during the writing operation. The organic solvents may evaporate instantaneously 402 after filament deposition leading to a quick fluid-to-solid transition of the ink.
The 3D lattice structure is printed in a layer-by-layer scheme onto the alumina plate with hydrophobic coatings. After deposition, the as-printed structure may undergo a slow solvent removal process 408 in the air, and the dissolved copolymers may recover to solid-state and the chains may "glue" zinc particle together to form a green body 404. Finally, the green body will be annealed 410 at higher temperature using optimized heating profile to form the zinc particles fusion and surface morphology improvement 406. This process enables the varying structures to be printed with virtually any 3D shape.
1000581 FIG. 5 (500) shows four optical images of real 3D-printed zinc structures of large area lattice 502, high aspect-ratio honeycomb 504, tri-angle lattice 506, and circular lattice 508.
[00059] Fig. 6 (600) shows optical and SEM images of the zinc lattice structure and morphology after annealing.
[00060] Referring now to FIG. 7, a flow chart illustrates additional embodiments of the inventor's apparatus, systems, and methods for producing 3D zinc structures. The flow charter is designated generally by the reference numeral 700. As illustrated in theifl ow charter 700, the system includes a number of steps. The steps in FIG. 7 are identified and described below.
[00061]
Step 1 ¨ ZINC INKS DEVELOPMENT (Reference numeral 702) ¨ In step 1, a zinc powder based extrudable ink is developed. This step of providing zinc ink includes providing zinc powders, providing solvents, and providing binders to produce said zinc ink.
Step 2 ¨ 3D MODEL DESIGN (Reference numeral 703) ¨ In step 2, the 3D
geometrical models are designed using computer aided design (CAD) software or other systems for creating a digital model. In one embodiment this step of creating a 3D model of a porous zinc structure includes creating a 3D model of a porous zinc anode. In another embodiment this step of creating a 3D model of a porous zinc structure includes creating a 3D model of a porous zinc current collector for a super capacitor. In yet another embodiment this step of creating a 3D model of a porous zinc structure includes creating a 3D model of a porous zinc current collector for a hybrid super capacitor.
[00063]
Step 3 ¨ EXTRUSION-BASED FABRICATION OF 3D ZINC (Reference numeral 704) ¨ In step 3, the direct ink writing is employed to extrude developed inks into designed structures following the model from Step 2. In one embodiment this step of direct ink writing of a porous zinc structure includes direct ink writing a porous zinc anode. In another embodiment this step of direct ink writing a 3D porous zinc structure includes direct ink writing of a porous zinc current collector for a super capacitor.
In yet another embodiment this step of direct ink writing a 3D porous zinc structure includes direct ink writing of a porous zinc current collector for a hybrid super capacitor.
[00064]
Step 4 ¨ POST-PROCESSING OF 3D ZINC STRUCTURES (Reference numeral 705) ¨ In step 4, the as-printed green bodies are processed by drying and annealing to obtain the final products. In one embodiment this step of post processing of a porous zinc structure includes post processing a porous zinc anode. In another embodiment this step of post processing of a porous zinc structure includes post processing a porous zinc super capacitor. I-n yet another embodiment this step of post processing of a porous zinc structure includes post processing a porous zinc hybrid super capacitor.
[00065] Various embodiment described herein may be used for aqueous batteries, for example zinc-manganese oxide batteries. Some embodiments may be used for other enemy storage systems, for example zinc-air batteries, flow batteries and zinc-ion hybrid supercapacitors.
1000661 The inventive concepts disclosed herein have been presented by way of example to illustrate the myriad features thereof in a plurality of illustrative scenarios, embodiments, and/or implementations. It should be appreciated that the concepts generally disclosed are to be considered as modular, and may be implemented in any combination, permutation, or synthesis thereof. In addition, any modification, alteration, or equivalent of the presently disclosed features, functions, and concepts that would be appreciated by a person having ordinary skill in the art upon reading the instant descriptions should also be considered within the scope of this disclosure_ 1000671 While various embodiments have been described above, it should be understood that they have been presented by way of example only, and not limitation. Thus, the breadth and scope of an embodiment of the present invention should not be limited by any of the above-described exemplary embodiments, but should be defined only in accordance with the following claims and their equivalents.
1000681 Therefore, it will be appreciated that the scope of the present application fully encompasses other embodiments which may become obvious to those skilled in the art. In the claims, reference to an element in the singular is not intended to mean one and only one" unless explicitly so stated, but rather "one or more." All structural and functional equivalents to the elements of the above-described preferred embodiment that are known to those of ordinary skill in the art are expressly incorporated herein by reference and are intended to be encompassed by the present claims. Moreover, it is not necessary for a device to address each and every problem sought to be solved by the present apparatus, systems, and methods, for it to be encompassed by the present claims.
Furthermore, no element or component in the present disclosure is intended to be dedicated to the public regardless of whether the element or component is explicitly recited in the claims. No claim element herein is to be construed under the provisions of 35 U.S.C. 112, sixth paragraph, unless the element is expressly recited using the phrase "means for."
While the apparatus, systems, and methods may be susceptible to various modifications and alternative forms, specific embodiments have been shown by way of example in the drawings and have been described in detail herein. However, it should be understood that the application is not intended to be limited to the particular forms disclosed. Rather, the application is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the application as defined by the following appended claims.
[000191 According to embodiments of this presentation, the step of post processing said porous zinc lattice structure comprises heat treatment of said porous zinc lattice structure.
According to embodiments of this presentation, the step of creating a 3D
model comprises creating a 3D model of an anode for a zinc battery, wherein said step of 3D printing said zinc ink into a porous zinc lattice structure using said 3D
model comprises 3D printing said zinc ink into a porous zinc lattice structure of an anode for a zinc battery using said 3D model of an anode for a zinc battery, and wherein said step of post processing said porous zinc lattice structure to produce the porous zinc structure comprises post processing said porous zinc lattice structure of an anode for a zinc battery to produce an anode for a zinc battery_ According to embodiments of this presentation, the step of creating a 3D
model comprises creating a 3D model of a current collector for a supercapacitor, wherein said step of 3D printing said zinc ink into a porous zinc lattice structure using said 3D
model comprises 3D printing said zinc ink into a porous zinc lattice structure of a current collector for a supercapacitor, and wherein said step of post processing said porous zinc lattice structure to produce the porous zinc structure comprises post processing said porous zinc lattice structure of a current collector for a supercapacitor to produce the porous zinc structure.
[000221 Another embodiment of this presentation comprises a method of 3D
printing a porous zinc anode, comprising the steps of creating a 3D model of the porous zinc anode, providing zinc ink, 3D printing said zinc ink into a porous zinc lattice anode using said 3D model, and post processing said porous zinc lattice anode to produce the porous zinc anode.
[00023]
According to einbodiments of this presentation, the step of creating a 3D
model of a porous zinc anode comprises creating a 3D model of a porous zinc anode wherein said porous zinc anode has microarchitectures.
[00024]
According to embodiments of this presentation, the step of providing zinc ink comprises providing zinc powders, providing solvents, and providing binders to produce said zinc ink.
[00025]
According to embodiments of this presentation, the step of 3D printing said zinc ink into a porous zinc lattice anode using said 3D model comprises extrusion-based direct-writing 3D printing said zinc ink into a porous zinc lattice anode using said 3D
model.
[00026]
According to embodiments of this presentation, the step of 3D printing said zinc ink into a porous zinc lattice anode using said 3D model comprises 3D
printing said zinc ink into a large area porous zinc lattice anode.
[00027]
According to embodiments of this presentation, the step of 3D printing said zinc ink into a porous zinc lattice anode using said 3D model comprises extrusion-based direct-writing 3D printing said zinc ink into a free-standing 3D porous zinc lattice anode using said 3D model.
[00028]
According to embodiments of this presentation, the step of post processing said porous zinc lattice anode comprises heat treatment of said porous zinc lattice anode.
[00029]
Another embodiment of this presentation comprises an apparatus for making a porous zinc structure, comprising: means for producing zinc ink, means for creating a 3D model of a porous zinc structure, means for 3D printing said zinc ink into a porous zinc lattice structure using said 3D model, and means for post processing said porous zinc lattice structure to produce the porous zinc structure.
[00030] According to embodiments of this presentation, the means for producing zinc ink comprises means for providing zinc powders, providing solvents, and providing binders to produce said zinc ink.
[00031] According to embodiments of this presentation, the means for creating a 3D
model of a porous zinc structure comprises means creating a 3D model of a porous zinc structure anode for a zinc battery, wherein the means for 3D printing said zinc ink into a porous zinc lattice structure using said 3D model comprises means for 3D
printing said zinc ink into a porous zinc lattice structure of an anode for a zinc battery using said 3D
model of an anode for a zinc battery, and wherein the means for post processing said porous zinc lattice structure to produce the porous zinc structure comprises means for post processing said porous zinc lattice structure to produce the porous zinc structure of an anode for a zinc battery to produce an anode for a zinc battery.
[00032] According to embodiments of this presentation, the means for creating a 3D
model of a porous zinc structure comprises means creating a 3D model of a porous zinc structure current collector for a supercapacitor, wherein the means for 3D
printing said zinc ink into a porous zinc lattice structure using said 3D model comprises means for 3D
printing said zinc ink into a porous zinc lattice structure of a supercapacitor using said 3D
model of a current collector for a supercapacitor, and wherein the means for post processing said porous zinc lattice structure to produce the porous zinc structure comprises means for post processing said porous zinc lattice structure to produce the porous zinc structure of a current collector for a supercapacitor.
[00033] Other embodiments of this presentation comprise a freeform fabrication of archnected porous zinc via 3D printing, where ink includim zinc powders, solvents and binders is created with printability; at least one 3D model is created with microarchitectures; extrusion-based direct-writing is used to manufacture free-standing 3D
zinc structures; and post-processing conditions generate final architected porous zinc products.
[000341 Other aspects and advantages of the present invention will become apparent from the following detailed description, which, when taken in conjunction with the drawings, illustrate by way of example the principles of the invention.
1000351 The system for forming a porous zinc of the present disclosure has use in a wide range of technologies, such as catalysis, desalination, energy storage, and filtration.
The system for forming a porous zinc of the present disclosure has use in energy storage and particularly for Li-ion batteries.
[000361 The apparatus, systems, and methods are susceptible to modifications and alternative forms. Specific embodiments are shown by way of example. It is to be understood that the apparatus, systems, and methods are not limited to the particular forms disclosed. The apparatus, systems, and methods cover all modifications, equivalents, and alternatives falling within the spirit and scope of the application as defined by the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
1000371 The present disclosure relates to 3D printing and more particularly to systems and methods for 3D printing porous zinc structures.
[000381 The accompanying drawings, which are incorporated into and constitute a part of the specification, illustrate specific embodiments of the apparatus, systems, and methods and, together with the general description given above, and the detailed description of the specific embodiments, serves to explain the principles of the apparatus, systems, and methods.
1000391 FIG. 1 is a flowchart that illustrates one embodiment of the inventor's apparatus, systems, and methods for producing hierarchical zinc structures.
1000401 FIG. 2 is a flow diagram that illustrates the steps of zinc-based colloidal inks preparation.
[000411 FIG. 3 illustrates one embodiment of the 3D model of the inventor's microlattice anode.
[00042]
FIG. 4 is an illustrative flow diagram that depicts the steps of the inventor's direct ink writing apparatus, systems, and methods for producing zinc microlattice.
[00043]
FIG. 5 shows a series of optical images illustrating various shapes and structures of 3D-printed zinc.
[00044]
FIG. 6 is a series of optical images and scanning electron microscope images illustrate the structure and morphology of a hierarchically porous zinc lattice after post-processing.
[00045]
FIG. 7 is a flowchart that illustrates another embodiment of the inventor's apparatus, systems, and methods for producing hierarchical zinc structures.
DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS
[00046]
Referring to the drawings, to the following detailed description, and to incorporated materials, detailed information about the apparatus, systems, and methods is provided including the description of specific embodiments. The detailed description serves to explain the principles of the apparatus, systems, and methods. The apparatus, systems, and methods are susceptible to modifications and alternative forms.
The application is not limited to the particular forms disclosed. The application covers all modifications, equivalents, and alternatives falling within the spirit and scope of the apparatus, systems, and methods as defined by the claims.
[00047]
Unless otherwise specifically defined herein, all terms are to be given their broadest possible interpretation including meanings implied from the specification as well as meanings understood by those skilled in the art and/or as defined in dictionaries, treatises, etc. It must also be noted that, as used in the specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless otherwise specified. As also used herein, the term "about" denotes an interval of accuracy that ensures the technical effect of the feature in question. In various approaches, the term "about" when combined with a value, refers to plus and minus 10 % of the reference value.
For example, a thickness of about 10 rim refers to a thickness of 10 nm 1 urn, a temperature of about 50 C refers to a temperature of 50 C 5 C ,etc. The nanoscale is defined as between I
nanometer and about 500 nanometers. For the purposes of this description, macropores are defined as having an average diameter of greater than 1 millimeter (mm).
Mesopores are defined as having an average diameter of less than 1 mm and greater than about 10 microns (urn). Micropores are defined as having an average diameter less than about 10 urn and greater than about 100 nanometers (urn). Nanopores are defined as having an average diameter less than 1 urn and greater than 0 nanometers. These ranges are approximate and may overlap, e.g., a large nanopore may also be defined as a small micropore.
A list of acronyms used in the description is provided below.
3D Three-dimensional "C Celsius cm centimeter DIW Direct ink writing um micron mg milligram mm millimeter nm nanometer SEM Scanning electron microscope [00048]
The present invention uses an additive manufacturing operation, in one example a DIW additive manufacturing process, to fabricate hierarchical porous zinc with deterministically controlled, application specific, 3D architectures.
Arbitrary macroscopic architectures and sample shapes can be printed according to the application requirements.
Moreover, the structure of distinct levels of porosity can be tuned independently which enables application specific multiscale architectures of virtually any geometric 3D shape_ The following description discloses several preferred embodiments of hierarchically porous zinc foams and/or related additive manufacturing systems, methods, and products formed by the same.
Referring now to FIG. 1, a flow chart illustrates one embodiment of the inventor's apparatus, systems, and methods for producing 3D zinc structures.
The flow charter is designated generally by the reference numeral 100. As illustrated in the flow charter 100, the system includes a number of steps. The steps in FIG. 1 are identified and described below.
[00050]
Step I - ZINC INKS DEVELOPMENT (Reference numeral 102) - In step 1, a zinc powder based extrudable ink is developed.
[00051]
Step 2 - 3D MODEL DESIGN (Reference numeral 103) - In step 2, the 3D
geometrical models are designed using computer aided design (CAD) software or other systems for creating a digital model.
[00052]
Step 3 - EXTRUSION-BASED FABRICATION OF 3D ZINC (Reference numeral 104) - In step 3, the direct ink writing is employed to extrude developed inks into designed structures following the model from Step 2.
[00053]
Step 4 - POST-PROCESSING OF 3D ZINC STRUCTURES (Reference numeral 105) - In step 4, the as-printed green bodies are processed by drying and annealing to obtain the final products.
[00054]
FIG. 7 is a flowchart that illustrates another embodiment of the inventor's apparatus, systems, and methods for producing hierarchical zinc structures.
[00055]
FIG. 2 provides an illustrative flow diagram of the inks development (Reference numeral 200). In an exemplary approach, solid-state copolymer beads 202 with entangled polymeric chains 204 are dissolved into organic solvents 210. The resultant polymer solvation 206 is obtained due to the chains release in solvents. Then, zinc micro-powders 208 are added and thoroughly mixed with the polymer solution 212 to form a uniform colloidal ink.
[00056]
Referring now to FIG. 3, one embodiment of the model of the inventor's microlattice is illustrated. The model is designated generally by the reference numeral 300.
The model 300 shown in Fig. 3 illustrates a model for the construction of a square lattice 302 made of the colloidal ink. The model 300 is one embodiment of the model described in the flow charter of FIG. 1 under the heading -Step 2." The model 300 is designed using computer aided design (CAD) software or other systems for creating a digital model. The model 300 consists of orthogonally stacked parallel filaments array 304 with total of 8 layers. The filament diameter (d) is generally of 200 um, and center-to-center spacing (L) can be varied from 300-800 um.
[00057] FIG. 4 provides an illustrative flow diagram of the direct ink writing system 400 to make the inventor's zinc microlattice made of colloidal inks. In this example, the DIW operation using the x-y-z motion stage and high precision dispenser forms an extrusion-based, room temperature manufacturing process. The colloidal ink in this example is housed in a 10 ml syringe barrel attached by a Luer-Lok to a smooth-flow tapered nozzle. An air-powered electronically controlled fluid dispenser provides the appropriate pressure to extrude the ink through the nozzle. The target pattern in this example is printed using a mechanical bearing positioning gantry, whose motion is controlled by writing the appropriate G-code commands from the 3D model. The extrusion process may be controlled by controlling the extrusion pressure and printing speed during the writing operation. The organic solvents may evaporate instantaneously 402 after filament deposition leading to a quick fluid-to-solid transition of the ink.
The 3D lattice structure is printed in a layer-by-layer scheme onto the alumina plate with hydrophobic coatings. After deposition, the as-printed structure may undergo a slow solvent removal process 408 in the air, and the dissolved copolymers may recover to solid-state and the chains may "glue" zinc particle together to form a green body 404. Finally, the green body will be annealed 410 at higher temperature using optimized heating profile to form the zinc particles fusion and surface morphology improvement 406. This process enables the varying structures to be printed with virtually any 3D shape.
1000581 FIG. 5 (500) shows four optical images of real 3D-printed zinc structures of large area lattice 502, high aspect-ratio honeycomb 504, tri-angle lattice 506, and circular lattice 508.
[00059] Fig. 6 (600) shows optical and SEM images of the zinc lattice structure and morphology after annealing.
[00060] Referring now to FIG. 7, a flow chart illustrates additional embodiments of the inventor's apparatus, systems, and methods for producing 3D zinc structures. The flow charter is designated generally by the reference numeral 700. As illustrated in theifl ow charter 700, the system includes a number of steps. The steps in FIG. 7 are identified and described below.
[00061]
Step 1 ¨ ZINC INKS DEVELOPMENT (Reference numeral 702) ¨ In step 1, a zinc powder based extrudable ink is developed. This step of providing zinc ink includes providing zinc powders, providing solvents, and providing binders to produce said zinc ink.
Step 2 ¨ 3D MODEL DESIGN (Reference numeral 703) ¨ In step 2, the 3D
geometrical models are designed using computer aided design (CAD) software or other systems for creating a digital model. In one embodiment this step of creating a 3D model of a porous zinc structure includes creating a 3D model of a porous zinc anode. In another embodiment this step of creating a 3D model of a porous zinc structure includes creating a 3D model of a porous zinc current collector for a super capacitor. In yet another embodiment this step of creating a 3D model of a porous zinc structure includes creating a 3D model of a porous zinc current collector for a hybrid super capacitor.
[00063]
Step 3 ¨ EXTRUSION-BASED FABRICATION OF 3D ZINC (Reference numeral 704) ¨ In step 3, the direct ink writing is employed to extrude developed inks into designed structures following the model from Step 2. In one embodiment this step of direct ink writing of a porous zinc structure includes direct ink writing a porous zinc anode. In another embodiment this step of direct ink writing a 3D porous zinc structure includes direct ink writing of a porous zinc current collector for a super capacitor.
In yet another embodiment this step of direct ink writing a 3D porous zinc structure includes direct ink writing of a porous zinc current collector for a hybrid super capacitor.
[00064]
Step 4 ¨ POST-PROCESSING OF 3D ZINC STRUCTURES (Reference numeral 705) ¨ In step 4, the as-printed green bodies are processed by drying and annealing to obtain the final products. In one embodiment this step of post processing of a porous zinc structure includes post processing a porous zinc anode. In another embodiment this step of post processing of a porous zinc structure includes post processing a porous zinc super capacitor. I-n yet another embodiment this step of post processing of a porous zinc structure includes post processing a porous zinc hybrid super capacitor.
[00065] Various embodiment described herein may be used for aqueous batteries, for example zinc-manganese oxide batteries. Some embodiments may be used for other enemy storage systems, for example zinc-air batteries, flow batteries and zinc-ion hybrid supercapacitors.
1000661 The inventive concepts disclosed herein have been presented by way of example to illustrate the myriad features thereof in a plurality of illustrative scenarios, embodiments, and/or implementations. It should be appreciated that the concepts generally disclosed are to be considered as modular, and may be implemented in any combination, permutation, or synthesis thereof. In addition, any modification, alteration, or equivalent of the presently disclosed features, functions, and concepts that would be appreciated by a person having ordinary skill in the art upon reading the instant descriptions should also be considered within the scope of this disclosure_ 1000671 While various embodiments have been described above, it should be understood that they have been presented by way of example only, and not limitation. Thus, the breadth and scope of an embodiment of the present invention should not be limited by any of the above-described exemplary embodiments, but should be defined only in accordance with the following claims and their equivalents.
1000681 Therefore, it will be appreciated that the scope of the present application fully encompasses other embodiments which may become obvious to those skilled in the art. In the claims, reference to an element in the singular is not intended to mean one and only one" unless explicitly so stated, but rather "one or more." All structural and functional equivalents to the elements of the above-described preferred embodiment that are known to those of ordinary skill in the art are expressly incorporated herein by reference and are intended to be encompassed by the present claims. Moreover, it is not necessary for a device to address each and every problem sought to be solved by the present apparatus, systems, and methods, for it to be encompassed by the present claims.
Furthermore, no element or component in the present disclosure is intended to be dedicated to the public regardless of whether the element or component is explicitly recited in the claims. No claim element herein is to be construed under the provisions of 35 U.S.C. 112, sixth paragraph, unless the element is expressly recited using the phrase "means for."
While the apparatus, systems, and methods may be susceptible to various modifications and alternative forms, specific embodiments have been shown by way of example in the drawings and have been described in detail herein. However, it should be understood that the application is not intended to be limited to the particular forms disclosed. Rather, the application is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the application as defined by the following appended claims.
Claims
THE CLAIMS ARE:
Clairn 1. A method of 3D printina a porous zinc structure, comprisina the steps of:
creating a 3D model of the porous zinc structure, providing zinc ink, 3D printing said zinc ink into a porous zinc lattice stnicture using said 3D
model, and post processina said porous zinc lattice stnicture to produce the porous zinc structure.
Clairn 2. The method of 3D printing a porous zinc structure of clairn 1 wherein said step of creating a 3D model of a porous zinc stnicture comprises creating a 31) model of a porous zinc structure wherein said porous zinc structure has microarchitectures.
Claini 3. The niethod of 3D printing a porous zinc structure of claim 1 wherein said step of providing zinc ink comprises providing zinc powders, providing solvents, and providing binders to produce said zinc ink.
Claim 4. Thc method of 3D printing a porous zinc structure of clairn 1 wherein said step of 3D printing said zinc ink into a porous zinc lattice structure usina said 3D rnodel cornprises extmsion-hased direct-writing 3D printing said zinc ink into a porous zinc lattice structure using said 3D rnodcl.
Claim 5. Thc method of 3D printing a porous zinc structure of claim 1 wherein said step of 3D printing said zinc ink into a porous zinc lattice structure using said 3D model comprises 3D
printina said zinc ink into a lame area porous zinc lattice structure.
Clairn 6. The method of 3D printing a porous zinc structure of claim 1 wherein said step of 3D printing said zinc ink into a porous zinc lattice stnicture using said 3D model comprises extrusion-based direct-writing 3D printing said zinc ink into a free-standing 31) porous zinc lattice structure using said 3D model.
Claim 7. The method of 3D printing porous zinc structure of claim I wherein said step of post processing said porous zinc lattice structure comprises heat trcatnicnt of said porous zinc lattice structure.
Claim 8. Thc method of 3D printing porous zinc structure of claim I
wherein said step of creating. a 3D model comprises creating a 3D rnodel of an anode for a zinc battery, wherein said stcp of 3D printing said zinc ink into a porous zinc lattice structure using said 3D model cornprises 3D printing said zinc ink into a porous zinc lattice structure of an anode for a zinc battery using said 3D model of an anode for a zinc battery, and wherein said stop of post processing said porous zinc latticc structurc to produce the porous zinc structure cornprises post processing said porous zinc lattice structure of an anode for a zinc battery to produce an anode for a zinc battery.
Clairn 9. The rnethod of 3D printing porous zinc structure of clairn 1 wherein said step of creating a 3D model cornprises creating a 3D model of a current collcctor for a supercapacitor, wherein said step of 3D printing said zinc ink into a porous zinc lattice structure using said 3D model comprises 3D printing said zinc ink into a porous zinc lattice structure of a current collector for a supercapacitor, and wherein said step of post processing said porous zinc lattice structure to produce the porous zinc structure comprises post processing said porous zinc lattice structure of a current collector for a supercapacitor to producc the porous zinc structurc.
Claini 10. A mothod of 3D printing a porous zinc anode, cornprising the stops of:
creating a 3D rnodel of the porous zinc anode, providing zinc ink, 3D printing said zinc ink into a porous zinc lattice anode using said 3D
model, and post processing said porous zinc lattice anode to produce the porous zinc anode.
Claim 11. The method of 3D printing a porous zinc anode of claim 10 wherein said step of creating a 3D model of a porous zinc anode cornprises creating a 3D rnodel of a porous zinc anode wherein said porous zinc anode has microarchitectures.
Claim 12. Thc mcthod of 3D printing a porous zinc anodc of claim 10 whcrcin said stcp of providing zinc ink comprises providing zinc powders, providing solvents, and providing binders to produce said zinc ink.
Clairn 13. The rnethod of 3D printing a porous zinc anode of claim 10 wherein said step of 3D printing said zinc ink into a porous zinc lattice anode using said 3D
model comprises extrusion-based direct-writing 3D printing said zinc ink into a porous zinc lattice anode using said 3D model.
Claim 14. The method of 3D printing a porous zinc anode of claim 10 wherein said step of 3D printing said zinc ink into a porous zinc lattice anode using said 3D
model comprises 3D
printing said zinc ink into a large area porous zinc lattice anode.
Clairn 15. The method of 3D printing a porous zinc anode of claim 10 wherein said step of 3D printing said zinc ink into a porous zinc lattice anode using said 3D
model comprises extrusion-based direct-writing 3D printing said zinc ink into a frcc-standing 3D porous zinc lanice anode using said 3D rnodel.
Claim 16. The method of 3D printing porous zinc anodes of claim 10 wherein said step of post processing said porous zinc lattice anode comprises heat treatment of said porous zinc lattice a node_ Claim 17. An apparatus for making a porous zinc structure, comprising:
means for producing zinc ink, means for creating a 3D model of a porous zinc structure, means for 3D printing said zinc ink into a porous zinc lattice structure using said 3D
model, and means for post processing said porous zinc lattice structure to produce the porous zinc structure.
Claim 18_ The apparatus for inaking a porous zinc structure of claim 17 wherein said rneans for producing zinc ink cornprises rneans for providing zinc powders, providing solvents, and providing binders to produce said zinc ink.
Claim 19. Thc apparatus for rnaking a porous zinc structure of claim 17 wherein said means for creating a 3D model of a porous zinc structure comprises means creating a 3D model of a porous zinc structure anode for a zinc battery, wherein said means for 3D printing said zinc ink into a porous zinc lattice structure using said 3D model comprises means for 3D printing said zinc ink into a porous zinc lattice structure of an anode for a zinc battery using said 3D model of an anode for a zinc battery, and wherein said means for post processing said porous zinc lattice structure to produce thc porous zinc structure comprises means for post processing said porous zinc lattice structure to produce the porous zinc structure of an anode for a zinc battety to produce an anode for a zinc battery.
Claim 20. The apparatus for tnaking a porous zinc structure of claim 17 wherein said means for creating a 3D model of a porous zinc structure comprises means creating a 3D model of a porous zinc structure current collector for a supercapacitor, wherein said means for 3D printing said zinc ink into a porous zinc lattice structure using said 3D model comprises means for 3D printing said zinc ink into a porous zinc lattice structure of a supercapacitor using said 3D model of a current collector for a supercapacitor, and wherein said means for post processing said porous zinc lattice structure to produce the porous zinc structure comprises means for post processing said porous zinc lattice structure to produce the porous zinc structure of a current collector for a supercapacitor.
Clairn 1. A method of 3D printina a porous zinc structure, comprisina the steps of:
creating a 3D model of the porous zinc structure, providing zinc ink, 3D printing said zinc ink into a porous zinc lattice stnicture using said 3D
model, and post processina said porous zinc lattice stnicture to produce the porous zinc structure.
Clairn 2. The method of 3D printing a porous zinc structure of clairn 1 wherein said step of creating a 3D model of a porous zinc stnicture comprises creating a 31) model of a porous zinc structure wherein said porous zinc structure has microarchitectures.
Claini 3. The niethod of 3D printing a porous zinc structure of claim 1 wherein said step of providing zinc ink comprises providing zinc powders, providing solvents, and providing binders to produce said zinc ink.
Claim 4. Thc method of 3D printing a porous zinc structure of clairn 1 wherein said step of 3D printing said zinc ink into a porous zinc lattice structure usina said 3D rnodel cornprises extmsion-hased direct-writing 3D printing said zinc ink into a porous zinc lattice structure using said 3D rnodcl.
Claim 5. Thc method of 3D printing a porous zinc structure of claim 1 wherein said step of 3D printing said zinc ink into a porous zinc lattice structure using said 3D model comprises 3D
printina said zinc ink into a lame area porous zinc lattice structure.
Clairn 6. The method of 3D printing a porous zinc structure of claim 1 wherein said step of 3D printing said zinc ink into a porous zinc lattice stnicture using said 3D model comprises extrusion-based direct-writing 3D printing said zinc ink into a free-standing 31) porous zinc lattice structure using said 3D model.
Claim 7. The method of 3D printing porous zinc structure of claim I wherein said step of post processing said porous zinc lattice structure comprises heat trcatnicnt of said porous zinc lattice structure.
Claim 8. Thc method of 3D printing porous zinc structure of claim I
wherein said step of creating. a 3D model comprises creating a 3D rnodel of an anode for a zinc battery, wherein said stcp of 3D printing said zinc ink into a porous zinc lattice structure using said 3D model cornprises 3D printing said zinc ink into a porous zinc lattice structure of an anode for a zinc battery using said 3D model of an anode for a zinc battery, and wherein said stop of post processing said porous zinc latticc structurc to produce the porous zinc structure cornprises post processing said porous zinc lattice structure of an anode for a zinc battery to produce an anode for a zinc battery.
Clairn 9. The rnethod of 3D printing porous zinc structure of clairn 1 wherein said step of creating a 3D model cornprises creating a 3D model of a current collcctor for a supercapacitor, wherein said step of 3D printing said zinc ink into a porous zinc lattice structure using said 3D model comprises 3D printing said zinc ink into a porous zinc lattice structure of a current collector for a supercapacitor, and wherein said step of post processing said porous zinc lattice structure to produce the porous zinc structure comprises post processing said porous zinc lattice structure of a current collector for a supercapacitor to producc the porous zinc structurc.
Claini 10. A mothod of 3D printing a porous zinc anode, cornprising the stops of:
creating a 3D rnodel of the porous zinc anode, providing zinc ink, 3D printing said zinc ink into a porous zinc lattice anode using said 3D
model, and post processing said porous zinc lattice anode to produce the porous zinc anode.
Claim 11. The method of 3D printing a porous zinc anode of claim 10 wherein said step of creating a 3D model of a porous zinc anode cornprises creating a 3D rnodel of a porous zinc anode wherein said porous zinc anode has microarchitectures.
Claim 12. Thc mcthod of 3D printing a porous zinc anodc of claim 10 whcrcin said stcp of providing zinc ink comprises providing zinc powders, providing solvents, and providing binders to produce said zinc ink.
Clairn 13. The rnethod of 3D printing a porous zinc anode of claim 10 wherein said step of 3D printing said zinc ink into a porous zinc lattice anode using said 3D
model comprises extrusion-based direct-writing 3D printing said zinc ink into a porous zinc lattice anode using said 3D model.
Claim 14. The method of 3D printing a porous zinc anode of claim 10 wherein said step of 3D printing said zinc ink into a porous zinc lattice anode using said 3D
model comprises 3D
printing said zinc ink into a large area porous zinc lattice anode.
Clairn 15. The method of 3D printing a porous zinc anode of claim 10 wherein said step of 3D printing said zinc ink into a porous zinc lattice anode using said 3D
model comprises extrusion-based direct-writing 3D printing said zinc ink into a frcc-standing 3D porous zinc lanice anode using said 3D rnodel.
Claim 16. The method of 3D printing porous zinc anodes of claim 10 wherein said step of post processing said porous zinc lattice anode comprises heat treatment of said porous zinc lattice a node_ Claim 17. An apparatus for making a porous zinc structure, comprising:
means for producing zinc ink, means for creating a 3D model of a porous zinc structure, means for 3D printing said zinc ink into a porous zinc lattice structure using said 3D
model, and means for post processing said porous zinc lattice structure to produce the porous zinc structure.
Claim 18_ The apparatus for inaking a porous zinc structure of claim 17 wherein said rneans for producing zinc ink cornprises rneans for providing zinc powders, providing solvents, and providing binders to produce said zinc ink.
Claim 19. Thc apparatus for rnaking a porous zinc structure of claim 17 wherein said means for creating a 3D model of a porous zinc structure comprises means creating a 3D model of a porous zinc structure anode for a zinc battery, wherein said means for 3D printing said zinc ink into a porous zinc lattice structure using said 3D model comprises means for 3D printing said zinc ink into a porous zinc lattice structure of an anode for a zinc battery using said 3D model of an anode for a zinc battery, and wherein said means for post processing said porous zinc lattice structure to produce thc porous zinc structure comprises means for post processing said porous zinc lattice structure to produce the porous zinc structure of an anode for a zinc battety to produce an anode for a zinc battery.
Claim 20. The apparatus for tnaking a porous zinc structure of claim 17 wherein said means for creating a 3D model of a porous zinc structure comprises means creating a 3D model of a porous zinc structure current collector for a supercapacitor, wherein said means for 3D printing said zinc ink into a porous zinc lattice structure using said 3D model comprises means for 3D printing said zinc ink into a porous zinc lattice structure of a supercapacitor using said 3D model of a current collector for a supercapacitor, and wherein said means for post processing said porous zinc lattice structure to produce the porous zinc structure comprises means for post processing said porous zinc lattice structure to produce the porous zinc structure of a current collector for a supercapacitor.
Applications Claiming Priority (3)
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|---|---|---|---|
| US17/453,396 | 2021-11-03 | ||
| US17/453,396 US20230132546A1 (en) | 2021-11-03 | 2021-11-03 | System and method for 3d printing porous zinc structures |
| PCT/US2022/048756 WO2023081246A1 (en) | 2021-11-03 | 2022-11-02 | System and method for 3d printing porous zinc structures |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA3236554A1 true CA3236554A1 (en) | 2023-05-11 |
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| CA3236554A Pending CA3236554A1 (en) | 2021-11-03 | 2022-11-02 | System and method for 3d printing porous zinc structures |
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| CA (1) | CA3236554A1 (en) |
| WO (1) | WO2023081246A1 (en) |
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| CN119695302B (en) * | 2024-11-22 | 2026-04-21 | 同济大学 | Cement-based zinc battery with low interface impedance and preparation method and application thereof |
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| EP0484605A1 (en) * | 1990-11-08 | 1992-05-13 | SORAPEC Société de Recherches et d'Applications Electrochimiques | Porous zinc-electrode |
| AU2015258978B2 (en) * | 2014-05-15 | 2018-08-02 | Northwestern University | Ink compositions for three-dimensional printing and methods of forming objects using the ink compositions |
| CN109844043A (en) * | 2016-09-30 | 2019-06-04 | 南洋理工大学 | Printing ink composition, the method and conductive equipment for forming conducting element |
| US11577316B2 (en) * | 2017-02-24 | 2023-02-14 | Hewlett-Packard Development Company, L.P. | Three-dimensional printing |
| US11198178B2 (en) * | 2017-08-16 | 2021-12-14 | Polyvalor, Limited Partnership | Metal 3D printing method and metallic 3D printed materials |
| US11173545B2 (en) * | 2017-10-23 | 2021-11-16 | Lawrence Livermore National Security, Llc | Hierarchical porous metals with deterministic 3D morphology and shape via de-alloying of 3D printed alloys |
| US11897193B2 (en) * | 2017-10-24 | 2024-02-13 | Hewlett-Packard Development Company, L.P. | Build material slurry |
| EP3752308A4 (en) * | 2018-02-15 | 2021-11-17 | University of Maryland, College Park | ORDERLY, POROUS SOLID ELECTROLYTE STRUCTURES, ELECTROCHEMICAL DEVICES THEREFORE, METHOD FOR MANUFACTURING THEREOF |
| WO2019177614A1 (en) * | 2018-03-15 | 2019-09-19 | Hewlett-Packard Development Company, L.P. | Composition |
| EP4049296A1 (en) * | 2019-10-22 | 2022-08-31 | Auburn University | 3d printing of additive-free mxene ink for fabrication of micro-supercapacitors with ultra high energy density |
| CN113426995B (en) * | 2021-06-07 | 2023-07-04 | 西湖大学 | Combustible 3D direct writing ink and preparation method and application thereof |
| CN113420504B (en) * | 2021-06-22 | 2022-11-04 | 清华大学 | A machine learning-based design method for degradable metal bone implants |
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| US20230132546A1 (en) | 2023-05-04 |
| WO2023081246A1 (en) | 2023-05-11 |
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