Patent Application
20170155169
The disclosure generally relates to ceramic ion-conducing structures. More particularly the disclosure generally relates to ceramic ion conducting structures for use in ion-conducting batteries.
Lithium ion batteries (LiBs) have the highest volumetric and gravimetric energy densities compared to all other rechargeable batteries making LiBs the prime candidate for a wide range of applications, from portable electronics to electric vehicles (EVs). Current LiBs are based mainly on positive electrodes such as LiCoO2 and LiFePO4, a Li+ conducting organic electrolyte (e.g., LiPF6 dissolved in ethylene carbonate-diethyl carbonate), and a graphitic Li anode. Unfortunately, there are several technological problems that exist with current state-of-the art LiBs: safety due to combustible organic based electrolytes and potential for Li dendrite shorting across the organic electrolytes; degradation due to the formation of reaction products at the anode and cathode electrolyte interfaces (solid electrolyte interphase—SEI); and power/energy density limitations by poor electrochemical stability of the organic electrolyte with respect to both Li-metal anodes and higher voltage cathodes. Other batteries based on sodium, magnesium, and other ion conducting electrolytes have similar issues. The present disclosure is pertinent to a need for new materials that can be used to improve batteries.
In an aspect, the present disclosure provides ceramic ion-conducing structures (e.g., ceramic ion-conducing materials having particular structural features and/or properties). The structures can be in the form of a single layer or multilayer structures. For example, a multilayer structure can comprise layers of ceramic ion-conducing structures, where the individual layers have the same or different porosity. The ceramic ion-conducing structures can be ion-conducting electrolyte materials (e.g., solid-state electrolyte materials). The ion-conducing ceramic structures can be formed by a method (e.g., a tape casting method) disclosed herein. For example, a ceramic ion-conducing structure is formed by a method disclosed herein.
A ceramic ion-conducting structure can be a layer. The ceramic ion-conducing structures can have a dense region (e.g., a dense layer) and one (e.g., a bilayer structure) or two (e.g., a triple layer structure) porous regions (e.g., porous layer(s)). The porosity of the dense region is less than that of the porous region(s). A cathode material and/or an anode material can be disposed on a porous region of a ceramic ion-conducing structure forming a discrete cathode-material containing region and/or a discrete anode-material containing region of the ceramic ion-conducing structure. It is desirable that a ceramic ion-conducing structure not allow dendrites to form (form dendrites) during cycling. Accordingly, in an example, the ceramic ion-conducing material (or a ceramic ion-conducting structure) does not have observable dendrites (e.g., lithium dendrites).
In an aspect the present disclosure provides methods of fabricating ceramic-ionic conducing structures. The methods are based on particular slurry formulation methods and/or particular sintering methods. The methods can be tape casting methods. A method of fabricating ceramic ionic-conducing structures can comprise forming a slurry. The slurry can be used in a tape casting method. The order of addition of components (starting materials) during formation of the slurry and/or milling time(s) can be critical.
In an aspect, the present disclosure provides uses of ceramic ion-conducing structures. For example, the ceramic ion conducing structures can be used as solid-state electrolyte materials in ion-conducing batteries (e.g., solid-state ion-conducing batteries). An ion-conducting battery can comprise ion-conducting solid state electrolyte comprising one or more ceramic ion conducing material of the present disclosure.
For a fuller understanding of the nature and objects of the disclosure, reference should be made to the following detailed description taken in conjunction with the accompanying figures.
Although claimed subject matter will be described in terms of certain embodiments, other embodiments, including embodiments that do not provide all of the benefits and features set forth herein, are also within the scope of this disclosure. Various structural, logical, process step, and electronic changes may be made without departing from the scope of the disclosure.
Ranges of values are disclosed herein. The ranges set out a lower limit value and an upper limit value. Unless otherwise stated, the ranges include all values to the magnitude of the smallest value (either lower limit value or upper limit value) and ranges between the values of the stated range.
The present disclosure provides ceramic ion-conducing structures and methods of fabricating ceramic ion-conducing structures from ceramic ion-conducting materials. Also provided are uses of ceramic ion-conducing structures.
All ranges disclosed herein are inclusive of their upper and lower limits, and include each value there between to the hundredth decimal place, and all ranges within those limits.
In an aspect, the present disclosure provides ceramic ion-conducing structures (e.g., ceramic ion-conducing materials having particular structural features and/or properties). The structures can be in the form of a single layer or multilayer structures. For example, a multilayer structure can comprise layers of ceramic ion-conducing structures, where the individual layers have the same or different porosity. The ceramic ion-conducing structures can be ion-conducting electrolyte materials (e.g., solid-state electrolyte materials). The ion-conducing ceramic structures can be formed by a method (e.g., a tape casting method) disclosed herein. For example, a ceramic ion-conducing structure is formed by a method disclosed herein.
A ceramic ion-conducting structure can be a layer. For example, a layer has a dimension (e.g., a thickness perpendicular to the longest dimension of the material) of 1 μm to 200 μm, including all 0.1 micron values and ranges therebetween.
The ceramic ion-conducing structures can have a dense region (e.g., a dense layer) and one (e.g., a bilayer structure) or two (e.g., a triple layer structure) porous regions (e.g., porous layer(s)). The porosity of the dense region is less than that of the porous region(s).
A cathode material and/or an anode material can be disposed on a porous region of a ceramic ion-conducing structure forming a discrete cathode-material containing region and/or a discrete anode-material containing region of the ceramic ion-conducing structure. For example, each of these regions of the ceramic ion-conducting structure has, independently, a dimension (e.g., a thickness perpendicular to the longest dimension of the material) of 1 μm to 200 μm, including all 0.1 micron values and ranges therebetween.
The dense regions and porous regions described herein can be discrete dense layers and discrete porous layers. Accordingly, the ceramic ion-conducing structures can have a dense layer and one or two porous layers.
The ceramic ion-conducing structures conduct ions (e.g., lithium ions, sodium ions, or magnesium ions), for example, between the anode and cathode. The ceramic ion-conducing structures can be an ion-conducting solid-state electrolyte material for a battery or battery cell and can have a dense region (e.g., a dense layer) that is supported by one or more porous regions (e.g., porous layer(s)) (the porous region(s)/layer(s). The dense region of a ceramic ion-conducing structure is, for example, free of pin-hole defects.
The ceramic ion-conducing structures can have a dense region (e.g., a dense layer) and two porous regions (e.g., porous layers), where the porous regions are disposed on opposite sides of the dense region and cathode material is disposed on one of the porous regions and the anode material on the other porous region. If cathode material is disposed on the porous region, a conventional battery anode (e.g., a solid-state battery anode) can be formed on the opposite side of the dense region by known methods. If anode material is disposed in the porous region, a conventional battery cathode (e.g., a solid-state battery cathode) can be formed on the opposite side of the dense region.
The ceramic ion-conducing structure (e.g., a multilayer ceramic ion-conducting structure) can have a dense region. The dense region can be free of the cathode material and anode material. For example, this region has a dimension (e.g., a thickness perpendicular to the longest dimension of the material) of 1 μm to 100 including all 0.1 micron values and ranges therebetween. In another example, this region has a dimension of 5 μm to 40 μm. The dense region has less than 5% porosity. In various examples, the dense region has less than 4% porosity, 3% porosity, 2% porosity, or 1% porosity. Porosity can be determined by methods known in the art. For example, porosity can be determined by electron microscopy methods.
A porous region (e.g., porous layer) of the ceramic ion-conducing structure has a porous structure. The porous structure can have microstructural features (e.g., microporosity such as, for example, micropores less than 2 nm in size (e.g., longest dimension of a pore aperture)) and/or nanostructural features (e.g., nanoporosity). For example, each porous region, independently, has a porosity of 40% to 90%, including all 0.1% values and ranges therebetween. In another example, each porous region, independently, has a porosity of 40% to 70%. Where two porous regions are present the porosity of the two layers may be the same or different. The porosity of the individual regions can be selected to, for example, accommodate processing steps (e.g., higher porosity is easier to fill with electrode material (e.g., charge storage material) (e.g., cathode)) in subsequent screen-printing or infiltration step, and achieve a desired electrode material capacity, i.e., how much of the conducting material (e.g., Li, Na, Mg) is stored in the electrode materials. The porous region (e.g., layer) provide structural support to the dense layer so that the thickness of the dense layer can be reduced, thus reducing its resistance. The porous layer also extends ion conduction of the dense phase (solid electrolyte) into the electrode layer to reduce electrode resistance both in terms of ion conduction through electrode and interfacial resistance due to charge transfer reaction at electrode/electrolyte interface, the later improved by having more electrode/electrolyte interfacial area. For example, pore size can range from 100 nm to 200 microns, including all 0.1 micron values and ranges therebetween. The pores can have any morphology. Any pore morphology can be obtained based on selection of an appropriate pore-forming material. For example, PMMA is spherical, while the graphite is flakes. Other pore-forming materials with different morphologies can be used, such as spheres, rods, flakes, or irregular shapes such as, for example, a coral-like structure and string-like particles.
The ceramic ion-conducing structures (e.g., ceramic ion-conducting layer(s)) can have a random or an ordered porous structure. For example, a porous ceramic ion-conducing layer comprises pores that connect opposing sides of the layer. For example, a porous ceramic ion-conducing structure comprising multiple layers comprises a porous layer and a dense layer and the porous layer has pores extending from an outer (exposed) surface of the porous layer to the interface between the porous layer and dense layer. The ordered porous structure can be columnar structure (e.g., a columnar structure having a tortuosity of 1). The ordered structure can comprise patterns (e.g., grids) of non-planar structures in a layer or layers of a ceramic ion-conducing structure. The ordered structure can be formed by, for example, templating or 3-D printing methods.
Dendrites can form when lithium is cycled to the anode side. If dendrites of lithium form, they must not be able to protrude through the dense layer and contact the other electrode. It is desirable that a ceramic ion-conducing structure is hard enough and dense layer dense enough to prevent dendrites from propagating across the structure. It is desirable that a ceramic ion-conducing structure not allow dendrites to form (form dendrites) during cycling. Accordingly, in an example, the ceramic ion-conducing material (or a ceramic ion-conducting structure) does not have observable dendrites (e.g., lithium dendrites). Dendrites can be observed by methods known in the art. For example, the presence or absence of dendrites is determined by electron microscopy methods.
The ceramic ion-conducting structures can be in the form of a layer or layers (e.g., a layer or layers formed by tape casting). It is desirable that cells comprising one or more of the layers be stacked compactly and without flexing to the point of breaking. This is dependent on material and cell length, width and thickness dimensions. It is desirable that individual layers be flat. For example, a layer has a maximum P-V Error of 325 μm, where P-V Error=Peak height−Valley height. In various examples, a layer has a maximum P-V Error of 350 μm, 375 μm, 400 μm, 425 μm, 450 μm, 475 μm, or 500 μm.
The ceramic ion-conducing structure can comprise a ceramic ion-conducting material (e.g., a solid-state, ion-conducting electrolyte material). The ceramic ion-conducing structure can comprise a solid-state electrolyte (SSE), lithium-containing material. For example, the solid-state electrolyte, lithium-containing material is a lithium-garnet SSE material.
The ceramic ion-conducing material can be a Li-garnet material comprising cation-doped Li5La3M′2O12, cation-doped Li6La2BaTa2O12, cation-doped Li7La3Zr2O12, and cation-doped Li6BaY2M′2O12. The cation dopants are calcium, barium, yttrium, zinc, or combinations thereof and M′ is Nb, Zr, Ta, or combinations thereof.
For example, the Li-garnet material comprises Li5La3Nb2O12, Li5La3Ta2O12, Li7La3Zr2O12, Li6La2SrNb2O12, Li6La2BaNb2O12, Li6La2SrTa2O12, Li6La2BaTa2O12, Li7Y3Zr2O12, Li6.4Y3Zr1.4Ta0.6O12, Li6.5La2.5Ba0.5TaZrO12, Li6BaY2M12O12, Li7Y3Zr2O12, Li6.75La2.75Ca0.25Zr1.5Nb0.5O12, Li6.75BaLa2Nb1.75Zn0.25O12, or Li6.75BaLa2Ta1.75Zn0.25O12. For example, the Li-garnet material is Li7La2.75Ca0.25Zr1.75Nb0.25O12
The ceramic ion-conducing structure can comprise a sodium-containing, solid-state electrolyte material. For example, the ceramic ion-conducing material can be Na3Zr2Si2PO12 (NASICON) or beta-alumina.
The ceramic ion-conducing structure can comprise a solid-state electrolyte, magnesium-containing material. For example, the magnesium ion-conducting electrolyte material is MgZr4P6O24.
Standard x-ray diffraction analysis techniques may be performed to identify the crystal structure and phase purity of the ceramic ion-conducting structures.
In an aspect the present disclosure provides methods of fabricating ceramic-ionic conducing structures. The methods are based on particular slurry formulation methods and/or particular sintering methods. The methods can be tape casting methods.
A method of fabricating ceramic ionic-conducing structures can comprise forming a slurry. The slurry can be used in a tape casting method. The order of addition of components (starting materials) during formation of the slurry and/or milling time(s) can be critical.
For example, a slurry for dense ceramic ionic-conducing structures (e.g., a dense layer) can be formed by i) adding solvent(s) (e.g., isopropanol and toluene) to a dispersant (e.g., fish oils such as, for example, blown fish oils (e.g., ‘Blown Menhaden fish oil, Z-3’ from Tape Casting Warehouse, Inc.)) and mixing until the dispersant is dissolved in the solvent(s), ii) optionally, adding a sintering facilitating material (e.g., Al2O3) (which can increase conductivity) (e.g., at 0.1 to 0.2 mole per mole of ceramic material), and iii) adding the ceramic material. The sintering facilitating material, if present, and ceramic material can be added in any order. This mixture is milled (first milling) for 1 to 47 hours, including all 0.1 hour values and range therebetween. In various examples, the mixture is milled for at least 1 hour, at least 10 hours, or at least 24 hours. After the first milling step, plasticizer(s) (optionally, plasticizer(s) dissolved in a solvent) (e.g., BBP) is/are added to the mixture of dispersant, solvent(s), sintering facilitating material, if present, and ceramic material). After addition of plasticizer(s), binder(s) (optionally, binder(s) dissolved in a solvent) (e.g., PVB) is/are added. Optionally, solvent(s) is/are added after addition of the binder(s). This mixture is milled (second milling) for 12 to 48 hours, including all 0.1 hour values and range therebetween. Additional mixing (e.g., by agitation) can be carried out after addition (e.g., to provide a homogenous solution or uniform suspension) of any of the starting materials. For example, steps described in this example are carried out in the stated order and/or without any additional steps.
For example, a slurry for porous ceramic ionic-conducing structures (e.g., a porous layer) can be formed by i) adding one or more solvents to a dispersant (e.g., fish oils such as, for example, blown fish oils (e.g., ‘Blown Menhaden fish oil, Z-3’ from Tape Casting Warehouse, Inc.)) and mixing until the dispersant is dissolved in the solvent, ii) optionally, adding a sintering facilitating material (such as Al2O3) (which can increase conductivity), iii) optionally, adding a pore-forming material (e.g., PMMA or graphite), and iv.) adding the ceramic material. The sintering facilitating material, if present and ceramic material can be added in any order. This mixture is milled for 1 to 47 hours, including all 0.1 hour values and range therebetween. For example, the mixture is milled for at least 1 hour or at least 10 hours. After milling, plasticizer(s) (optionally, plasticizer(s) dissolved in a solvent) (e.g., BBP) is/are added to the mixture of dispersant, solvent(s), sintering facilitating material, if present, and ceramic material). After addition of plasticizer(s), binder(s) (optionally, binder(s) dissolved in a solvent) (e.g., PVB) is/are added. Optionally, solvent(s) is/are added after addition of the binder(s). The resulting mixture is milled (second milling) for 12 to 48 hours, including all integer hour values and range therebetween. Optionally, a pore-forming material (e.g., PMMA or graphite) is added. If pore-forming material(s) is/are added at this point, the resulting mixture is milled (third milling) for 10 minutes to 6 hours, including all integer minute values and ranges therebetween). At least one pore-forming material is added. After all the starting materials are added and milled, the mixture of starting materials is degassed. For example, the mixture is degassed 1 hour after the starting materials are added and milled. Additional mixing (e.g., by agitation) can be carried out after addition (e.g., to provide a homogenous solution or uniform suspension) of any of the starting materials. For example, steps described in this example are carried out in the stated order and/or without any additional steps.
A slurry can be filtered (e.g., before casting such as, for example, tape casting) to remove agglomerates that may interfere with casting. For example, the slurry is filtered with a mesh with 180 um spacing.
A variety of pore-forming materials (e.g., porogens) can be used. A pore-forming material can be any material that will vaporize or burn below 1000° C. Examples of pore-forming materials include, but are not limited to, carbon-containing materials (e.g., graphite (or graphitic materials), carbon fibers, carbon black, and the like), natural fibers (e.g., cellulose), starches, and polymer materials (e.g., PMMA, polyethylene, polystyrene, and the like). By selection of a pore-forming material (based on, for example, size and/or decomposition properties) a desired porosity (e.g., pore size and/or pore shape) can be obtained.
The mixing can carried out by known solid-state mixing techniques. The mixture of starting materials (e.g., dispersant, solvent(s), sintering facilitating material, ceramic material, plasticizer(s), binder(s), or combination thereof) can be ball milled.
The mixture may be milled with media such as stabilized-zirconia or alumina or another media known to one of ordinary skill in the art to achieve the prerequisite particle size distribution. To achieve the prerequisite particle size distribution, the calcined mixture may be milled using a technique such as vibratory milling, attrition milling, jet milling, ball milling, or another technique known to one of ordinary skill in the art, using media such as stabilized-zirconia, alumina, or another media known to one of ordinary skill in the art.
A method of fabricating ceramic-ionic conducing structures comprises forming a layer of a slurry. The layer can be formed by a tape casting method.
A method of fabricating ceramic-ionic conducing structures comprises forming a layer of a slurry. The layer can be formed on a tape using a tape casting methods.
A method of fabricating ceramic-ionic conducing structures comprises sintering a layer of a slurry. The sintering can be carried out in discrete steps (e.g., presintering (burn out) and sintering steps) or in single continuous step. The sintering can be carried out using equipment known in the art. It is desirable that the sintering be carried out and result in layers of ceramic-ionic conducing material that are flat (do not exhibit curling) and maintain all (or substantially all) of volatile compounds in the ceramic-ionic conducing material.
For example, sintering is carried out at 800° C. to 1200° C., including all integer ° C. values and ranges therebetween. In an example, sintering is carried out at 1000° C. to 1000° C. The sintering can be carried out for 1 minute to 24 hours, including all integer minute values and ranges therebetween. One having skill in the art will appreciate that smaller particles may be sintered at lower temperatures and/or shorter sintering times and larger particles may be sintered at higher temperatures and/or longer sintering times.
During sintering (both heating and cooling), various heating or cooling rates can be used. For example, heating rates of 1 to 5° C./min, including all integer C/min values, can be used to heat the layer of slurry to the desired sintering temperature. For example, cooling rates of 1 to 15° C./min, including all integer C/min values and ranges therebetween, can be used to cool the sample after the desired sintering (time and temperature). For example, cooling rates of 1 to 10° C./min or 5° C./min can be used. Without intending to be bound by any particular theory, it is considered that use of heating or cooling rates that are too high can result in warping of the layer (e.g., layer on a tape).
Sintering (including, for example, presintering and sintering steps) is carried out in a low humidity (less than 1% or less than or equal to 1% absolute humidity) or no observable humidity environment. Humidity can be determined by methods known in the art. Without intending to be bound by any particular theory, it is considered that sintering under low humidity (less than 1% or less than or equal to 1% absolute humidity) or no observable humidity environment will provide an ion-conducing ceramic material having a desired phase (e.g., garnet phase) and/or structure.
Presintering is carried out in an atmosphere comprising oxygen. Sintering is carried out under a flow of a gas or mixture of gasses. The flow of gas can be an inert gas flow (e.g., argon gas). It is desirable that an inert gas flow be sufficient to remove CO2 and/or H2O (which can be formed during the sintering process) such than no observable carbonate materials are formed. The gas flow can comprise oxygen.
A method of fabricating ceramic ionic-conducing structures can comprise forming slurry, a layer of a slurry, and/or sintering a layer of slurry. These steps (or a combination thereof) can be carried out in a tape casting method.
The steps of the method described herein are sufficient to carry out the methods of making the ceramic ion-conducing ceramic structures of the present invention. Thus, in an example, the method consists essentially of a combination of the steps of the methods disclosed herein. In another example, the method consists of such steps. In various examples, the method comprises, consists essentially of, or consists of a combination of the steps of the methods disclosed herein in the order disclosed. Any particular chemical composition or combination of compounds can comprise or consist or consist essentially of the recite composition or compounds.
In an aspect, the present disclosure provides uses of ceramic ion-conducing structures. For example, the ceramic ion conducing structures can be used as solid-state electrolyte materials in ion-conducing batteries (e.g., solid-state ion-conducing batteries).
An ion-conducting battery can comprise ion-conducting solid state electrolyte comprising one or more ceramic ion conducing material of the present disclosure. For example, the batteries are lithium-ion, solid-state electrolyte batteries, sodium-ion, solid-state electrolyte batteries, or magnesium-ion solid-state electrolyte batteries. Lithium-ion (Li+) batteries are used, for example, in portable electronics and electric cars, sodium-ion (Na+) batteries are used, for example, for electric grid storage to enable intermittent renewable energy deployment such as solar and wind, and magnesium-ion (Mg2+) batteries are expected to have higher performance than Li+ and Na+ because Mg2+ carries twice the charge for each ion.
Solid-state batteries have advantages over previous batteries. For example, the solid electrolyte is non-flammable providing enhanced safety, and also provides greater stability to allow high voltage electrodes for greater energy density. The battery design (
Solid state batteries comprise a cathode material, an anode material, and solid state electrolyte comprising one or more the ceramic ion-conducing materials. The ceramic ion conducing materials can have a dense region (e.g. a layer) and one or two porous regions (layers). The porous region(s) can be disposed on one side of the dense region or disposed on opposite sides of the dense region. The dense region and porous region(s) are fabricated from the same ceramic ion-conducing materials. The batteries conduct ions such as, for example, lithium ions, sodium ions, or magnesium ions.
The solid state battery can comprise a lithium-containing cathode material and/or a lithium-containing anode material, and a lithium-containing, ion-conducting, solid-state electrolyte material (e.g., a lithium containing ceramic ion-conducting structure). The solid state battery can comprise a sodium-containing cathode material and/or a sodium-containing anode material, and a sodium-containing, ion-conducting, solid-state electrolyte material (e.g., a sodium containing ceramic ion-conducting structure). The solid state battery can comprise a magnesium-containing cathode material and/or a magnesium-containing anode material, and a magnesium-containing, ion-conducting, solid-state electrolyte material (e.g., a magnesium containing ceramic ion-conducting structure).
The solid-state, ion-conducting electrolyte material is configured such that ions (e.g., lithium ions, sodium ions, or magnesium ions) diffuse into and out of the porous region(s) (e.g., porous layer(s)) of the solid-state, ion-conducting electrolyte material (e.g., ceramic ion-conducting structure) during charging and/or discharging of the battery. A solid-state, ion-conducting battery can comprise a solid-state, ion-conducting electrolyte material (e.g., a ceramic ion-conducting structure) comprising one or two porous regions (e.g., porous layer(s)) configured such that ions (e.g., lithium ions, sodium ions, or magnesium ions) diffuse into and out of the porous region(s) of solid-state, ion-conducting electrolyte material during charging and/or discharging of the battery.
The cathode comprises cathode material in electrical contact with the porous region of the ion-conducting, solid-state electrolyte material (e.g., ceramic ion-conducing structure). For example, the cathode material is an ion-conducting material that stores ions by mechanisms such as intercalation or reacts with the ion to form a secondary phase (e.g., an air or sulfide electrode). Examples of suitable cathode materials are known in the art.
The cathode material, if present, is disposed on at least a portion of a surface (e.g., a pore surface of one of the pores) of a porous region of the ion-conducting, solid-state electrolyte material (e.g., ceramic ion-conducing structure). The cathode material, when present, at least partially fills one or more pores (e.g., a majority of the pores) of a porous region or one of the porous regions of the ion-conducting, solid-state electrolyte material (e.g., ceramic ion-conducing structure). The cathode material can be infiltrated into at least a portion of the pores of the porous region of the ion-conducting, solid-state electrolyte material.
The cathode material can be disposed on at least a portion of the pore surface of the cathode side of the porous region of the ion-conducting, solid-state electrolyte material (e.g., ceramic ion-conducing structure), where the cathode side of the porous region of ion-conducting, solid-state electrolyte material is opposed to an anode side of the porous region of ion-conducting, solid-state electrolyte material (e.g., ceramic ion-conducing structure) on which the anode material is disposed.
The cathode material can be a lithium ion-conducting material. For example, the lithium ion-conducting cathode material is, lithium nickel manganese cobalt oxides (NMC, LiNixMnyCozO2, where x+y+z=1), such as LiCoO2, LiNi1/3Co1/3Mn0.3O2, LiNi0.5Co0.2Mn0.302, lithium manganese oxides (LMOs), such as LiMn2O4, LiNi0.5Mn1.5O4, lithium iron phosphates (LFPs) such as LiFePO4, LiMnPO4, and LiCoPO4, and Li2MMn3O8, where M is selected from Fe, Co, and combinations thereof. The ion-conducting cathode material can be a high energy ion-conducting cathode material such as Li2MMn3O8, wherein M is selected from Fe, Co, and combinations thereof.
The cathode material can be a sodium ion-conducting material. For example, the sodium ion-conducting cathode material is Na2V2O5, P2-Na2/3Fe1/2Mn1/2O2, Na3V2(PO4)3, NaMn1/3Co1/3Ni1/3PO4 and composite materials (e.g., composites with carbon black) thereof such as Na2/3Fe1/2Mn1/2O2@graphene composite.
The cathode material can be a magnesium ion-conducting material. For example, the magnesium ion-conducting cathode material is doped manganese oxide (e.g., MgxMnO2.yH2O).
The cathode material can be an organic sulfide or polysulfide. Examples of organic sulfides include carbynepolysulfide and copolymerized sulfur.
The cathode material can be an air electrode. Examples of materials suitable for air electrodes include those used in solid-state lithium ion batteries with air cathodes such as large surface area carbon particles (e.g., Super P which is a conductive carbon black) and catalyst particles (e.g., alpha-MnO2 nanorods) bound in a mesh (e.g., a polymer binder such as PVDF binder).
It may be desirable to use an electronically conductive material as part of the ion-conducting cathode material. For example, the ion-conducting cathode material also comprises an electrically conducting carbon material (e.g., graphene or carbon black), and the ion-conducting cathode material, optionally, further comprises an organic or gel ion-conducting electrolyte. The electronically conductive material may separate from the ion-conducting cathode material. For example, electronically conductive material (e.g., graphene) is disposed on at least a portion of a surface (e.g., a pore surface) of the porous region of the ceramic ion-conducting, SSE electrolyte structure and the ion-conducting cathode material is disposed on at least a portion of the electrically conductive material (e.g., graphene).
The anode comprises anode material in electrical contact with the porous region of the ion-conducting, solid-state electrolyte material (e.g., ceramic ion-conducing structure). For example, the anode material is the metallic form of the ion conducted in the solid state electrolyte (e.g., metallic lithium for a lithium-ion battery) or a compound that intercalates the conducting ion (e.g., lithium carbide, Li6C, for a lithium-ion battery). Examples of suitable anode materials are known in the art.
The anode material, if present, is disposed on at least a portion of a surface (e.g., a pore surface of one of the pores) of the porous region of the ion-conducting, solid-state electrolyte material (e.g., ceramic ion-conducing structure). The anode material, when present, at least partially fills one or more pores (e.g., a majority of the pores) of the porous region of ion-conducting, solid-state electrolyte material. The anode material can be infiltrated into at least a portion of the pores of the porous region of the ion-conducting, solid-state electrolyte material.
The anode material can be disposed on at least a portion of the pore surface of an anode-side porous region of the ion-conducting, solid-state electrolyte material (e.g., ceramic ion-conducing structure), where the anode side of the ion-conducting, solid-state electrolyte material is opposed to a cathode side of the porous, ion-conducting, solid-state electrolyte (e.g., ceramic ion-conducing structure) on which the cathode material is disposed.
The anode material can be a lithium-containing material. For example, the anode material is lithium metal, or an ion-conducting lithium-containing anode material such as lithium titanates (LTOs) such as Li4Ti5O12.
The anode material can be a sodium-containing material. For example, the anode material is sodium metal, or an ion-conducting sodium-containing anode material such as Na2C8H4O4 and Na0.66Li0.22Ti0.78O2.
The anode material can be a magnesium-containing material. For example, the anode material is magnesium metal.
The anode material can be a conducting material such as graphite, hard carbon, porous hollow carbon spheres and tubes, and tin and its alloys, tin/carbon, tin/cobalt alloy, or silicon/carbon.
The ion-conducting solid state batteries (e.g., lithium-ion solid state electrolyte batteries, sodium-ion solid state electrolyte batteries, or magnesium-ion solid state electrolyte batteries) can comprise current collector(s). The batteries can have a cathode-side (first) current collector disposed on the cathode-side of the porous, solid-state electrolyte material and an anode-side (second) current collector disposed on the anode-side of the porous, solid-state electrolyte material. The current collectors can be each independently fabricated of a metal (e.g., aluminum, copper, or titanium) or metal alloy (aluminum alloy, copper alloy, or titanium alloy).
The ion-conducting solid-state batteries (e.g., lithium-ion solid state electrolyte batteries, sodium-ion solid state electrolyte batteries, or magnesium-ion solid state electrolyte batteries) may comprise various additional structural components (such as bipolar plates, external packaging, and electrical contacts/leads to connect wires. The battery can further comprise bipolar plates. The battery can further comprise bipolar plates and external packaging, and electrical contacts/leads to connect wires. Repeat battery cell units can be separated by a bipolar plate.
The cathode material (if present), the anode material (if present), the SSE material, the cathode-side (first) current collector (if present), and the anode-side (second) current collector (if present) may form a cell. In this case, the solid-state, ion-conducting battery comprises a plurality of cells separated by one or more bipolar plates. The number of cells in the battery is determined by the performance requirements (e.g., voltage output) of the battery and is limited only by fabrication constraints. For example, the solid-state, ion-conducting battery comprises 1 to 500 cells, including all integer number of cells and ranges therebetween.
For example, an ion-conducting, solid-state battery or battery cell has one planar cathode and/or anode—electrolyte interface or no planar cathode and/or anode—electrolyte interfaces. For example, the battery or battery cell does not exhibit solid electrolyte interphase (SEI).
The following Statements provides examples of ceramic ion-conducting structures, methods of making a ceramic ion-conducting structures, and solid-state, ion-conducting batteries of the present disclosure.
Statement 1. A ceramic ion-conducting structure comprising a dense region (e.g., at least one dense layer) having a porosity of less than 5% and/or at least one porous region (e.g., porous layer) having a porosity of 40% to 90%.
Statement 2. A ceramic ion-conducting structure according to Statement 1, where the porous region has a random or ordered porous structure.
Statement 3. A ceramic ion-conducting structure according to any one of the preceding Statements, where the structure does not have observable dendrites (e.g., lithium dendrites in the case of structure having a lithium electrode material disposed on at least a portion of a surface of the structure).
Statement 4. A ceramic ion-conducting structure according to any one of the preceding Statements, where the structure is formed by a tape cast layer.
Statement 5. A method of making a ceramic ion-conducting structure comprising:
i) adding solvent(s) (e.g., isopropanol and toluene) to a dispersant (e.g., fish oil) and mixing until the dispersant is dissolved in the solvent(s),
ii) optionally, adding a sintering facilitating material (e.g., Al2O3) (e.g., at 0.1 to 0.2 mole per mole of ceramic material),
iii) adding a ceramic material,
iv) milling the resulting mixture from iii) for 1 to 47 hours,
v) adding plasticizer(s) (e.g., BBP) to the milled mixture from iv),
vi) adding binder(s) (e.g., PVP) to the mixture from v), Optionally, solvent(s) is/are added after addition of the binder(s),
vii) milling the mixture from vi) for 12 to 48 hours,
or
i) adding solvent(s) (e.g., isopropanol and toluene) to a dispersant (e.g., fish oil) and mixing until the dispersant is dissolved in the solvent(s),
ii) optionally, adding a sintering facilitating material (e.g., Al2O3) (e.g., at 0.1 to 0.2 mole per mole of ceramic material),
iii) optionally, adding a first pore-forming material (e.g., PMMA or graphite),
iv) adding a ceramic material,
v) milling the resulting mixture from iv) for 1 to 47 hours,
vi) adding plasticizer(s) (e.g., BBP) to the milled mixture from v),
vii) adding binder(s) (e.g., PVP) to the mixture from vi), Optionally, solvent(s) is/are added after addition of the binder(s),
viii) optionally, adding solvent(s) (e.g., isopropanol and toluene) to the mixture from vii),
ix) milling the mixture from vii) for 12 to 48 hours,
x) optionally, adding a second pore-forming material (e.g., PMMA or graphite),
xi) if a second pore-forming material is added, milling the mixture from ix), for 10 minutes to 6 hours, and
xii) degassing the mixture from viii) or milled mixture from x).
Statement 6. A method of making a ceramic ion-conducting ceramic structure according to Statement 5, further comprising: forming a layer of slurry on a substrate (e.g., a tape).
Statement 7. A method of making a ceramic ion-conducting ceramic structure according to any one of Statements 5 or 6 further comprising,
sintering a layer of slurry of claim 5 or the layer of slurry on a substrate of claim 6 at a temperature of 800° C. to 1200° C. for 1 minute to 24 hours.
Statement 8. A method of making a ceramic ion-conducting structure according to Statement 7, where the sintering is carried out in a low humidity (less than 1% or less than or equal to 1% absolute humidity) or no observable humidity environment.
Statement 9. A method of making a ceramic ion-conducting structure according to Statement 8, where the sintering is carried out under a flow of inert gas (e.g., argon gas).
Statement 10. A solid-state, ion-conducting battery comprising:
The following examples are presented to illustrate the present disclosure. They are not intended to limiting in any manner.
The following is an example describing structures (e.g., multilayer structures) comprising ionically conductive ceramics, which enables the production of various high performance solid state battery chemistries. These structures can have porous outer layers, which can contain electrochemically active electrode materials, that are separated by a dense center layer. This configuration can be used, for example, for high performance electrochemical energy storage systems, creating space for high loading of active materials, electronic separation between active materials, and ionic conduction throughout.
A multilayer ceramic can be a triple layer structure, bilayer structure, or ordered structure. For example,
Various battery chemistries benefit from such a multilayered structure. This structure allows for the use of an alkaline metal anode, which represents the best energy density and lowest voltage anode in each chemistry. This invention is useful in such chemistries as:
The fabrication of this product relies on a set of processing strategies that allow the creation of a well sintered ceramic body with the desired structure, phase and electrical properties. This example focuses specifically on the fabrication of the ionically conductive ceramic structure. To produce a high performance cell, it is desirable that the structure meets the requirements listed in Table 1, regardless of specific chemistry. The processes described herein used to create the structures shown in
Beyond these requirements, control over exact microstructure is important. The porosity of the anode and cathode (or more generally, “electrode”) layers must be well interconnected to create a low tortuosity. Optimal pore size is chemistry dependent. Because sulfur fills pores easily and is not conductive to lithium ions, Li—S chemistries benefit from small pores (on the order of 1-10 μm diameter). On the other hand, lithium ion chemistries with an oxide cathode are hard to fill with micron-plus sized commercially available cathode such as LiCoO2. These lithium ion chemistries benefit from larger pores (10-30 μm diameter). Ordered porosity with controlled aspect ratios allow the highest possible surface area with low tortuosity. Thickness of electrodes must be determined by design to allow high capacity and high rate capability.
This disclosure should not be limited by the materials synthesis method, dimensions of the structure, the size or dimension of the pores, the exact recipe of the tapes, or the source of the porogens. Discoveries that led to the successful fabrication of the structure include, for example, the atmospheric protection and the importance of particle size reduction.
Fabrication Procedure and Development. This section discusses the overall procedure including materials synthesis, milling, tapecasting, pre-sintering, sintering, and the nuanced procedures required to achieve the desired structure. The research that led to the development of these procedures will also be discussed.
The ionically conductive material can have, among other materials, various members of the lithium garnet family. There are many members of the garnet family which would satisfy the requirements of a viable device (e.g., low electronic conductivity). This work has been demonstrated with Li6.75La2.75Ca0.25Zr1.5Nb0.5O12 (LLCZN, nominal composition), a variant of the Li7La3Zr2O12 (LLZ) composition. The lithium garnet material is produced via solid state reaction by mixing CaCO3, La2O3, ZrO2, and Nb2O5 in stoichiometric quantities. LiOH, LiNO3 or Li2CO3 is added with 10% excess to account for volatility during sintering. The raw materials are mixed with isopropanol and 5 mm diameter yttria-stabilized zirconia (YSZ) balls to form a slurry for milling. After 24 hours of milling, the mixture is screened through a 38 μm mesh and separated from the milling media. The slurry is then dried for several hours in a 100° C. oven, lightly ground in a mortar and pestle to re-powderize. The powder is placed in a covered Al2O3 crucible and calcined at 900° C. for 10 hours. After calcining, the ceramic powder is milled in isopropanol for 3 days with 5 mm YSZ balls, then 18 days with 2 mm YSZ balls.
This synthesis procedure produces highly conductive, cubic phase lithium garnet as can be seen in the X-ray diffraction pattern in
From this LLCZN powder, complex microstructured ceramics can be scalably produced via tapecasting, followed by organic burnout, then high temperature sintering. While this is a widely employed technique in industry, every material requires unique formulations and compositions of tapecasting slurry to produce tapes that have the right properties and successfully produce the desired sintered structure. The slurries must cast nicely to produce tapes of consistent thickness and without defects. Tapes must be flexible and maintain this flexibility for a long shelf life. Tapes must be able to be laminated to one another well enough that delamination does not occur during sintering.
The slurry recipes in Tables 2 and 3 represent significant development work to produce tapes that meet these requirements. However, these are not the only functional recipes that were achieved and can be tailored to the desired structure, with increased or decreased porosity and changes of tape thickness among other possible variations. Furthermore, a significant component of successful tapecasting is the procedure used to create the slurry. These compositions could result in inferior tapes if the addition order and notes in Tables 2 and 3 are not followed.
Polymer-ceramic composite tapes are cast for the separator layer and the electrode layers separately. Slurries for tape casting are prepared by mixing the garnet and Al2O3 nanopowder in isopropanol, toluene and a small amount of fish oil for 24 hours. After the addition of polyvinyl butyral (PVB) and benzyl butyl phthalate (BBP), the solution is milled for another 24 hours. Slurries used to create the electrode layers of the triple layer contain 10 or 15 μm diameter crosslinked polymethyl methacrylate (PMMA) spheres and/or 7-11 um graphite particles to create porosity. An example slurry recipe for the electrolyte layer tape is given in Table 2, sorted by order of addition to the slurry and normalized to grams of garnet. Similarly, Table 3 shows a slurry recipe for a porous layer tape. These are not the only possible recipes to achieve viable apes, but are two examples of what has been used in our procedure. In addition to many variations on these recipes, we have also created tapes using all-PMMA pore porogen, all-graphite porogen, and other porogens such as starch and cellulose.
Control of porosity is achieved via selection of porogen. Only interconnected pores with an electronic path to the current collector will be electrochemically active. Furthermore, only pores with sufficiently sized connections are able to be filled with electrode material. The image shown in
It may be important that for each addition day, the materials added are mixed for 24 hours for proper homogeneity. On the day of tapecasting, the slurries are degassed to prevent bubbles from disrupting the process of tape drying and ceramic powder packing. Degassing is accomplished by stirring the slurry while pulling low (˜500 mmHg) vacuum. The slurries for the electrolyte and electrode layers are degassed for 1 and 3 hours, respectively. After degassing, tapecasting is performed by pouring the slurry into a reservoir. A sheet of silicone coated mylar is pulled under the reservoir at 10 cm/minute. The film thickness is limited by a doctor blade set to the desired height. Common heights for electrolyte layer tapes and electrode layer tapes are 178 μm and 465 μm, respectively. Smaller or larger blade heights can be used to produce thinner or thicker tapes. The tape is pulled onto a 49° C. heated bed for drying. Tapes are allowed to dry for around 1 hour before removing from the heated bed.
After tapecasting, the tapes are laminated together to form a triple layer. A section of porous-layer tape and a section electrolyte layer tape are pressed at 3 tons at 71° C. for 30 minutes. After pressing, the now bilayer tape is pressed with another section of porous-layer tape for 30 minutes to create a porous-dense-porous triple layer. Alternatively, all three-layers can be laminated at the same time. Cells are punched or cut from this triple layer depending on the desired size.
To produce the final sintered ceramic, punches from this triple layer tape are heated in a furnace to burn out the organics and sinter the ceramic particles into a single body. The tape punchout must sit on a bed of the mother powder. The tape punchout is either covered by more of the mother powder or by a powder nonreactive with garnet such as MgO. A porous Al2O3 block is placed on top of this powder to provide a small amount of compression to keep the cells flat while still providing gas flow. Various furnace profiles for the burnout and sintering stages have been shown to work.
An essential breakthrough that led to this product fabrication procedure was the discovery of humidity related reactions in the furnace. It was found that LLZ and LLCZN tapes could not consistently be taken through the burnout stage, between room temperature and about 650° C., without losing the garnet phase. After ruling out reactions during tapecasting, we discovered that the indoor humidity was causing reactions with the garnet in the furnace. Previous research has shown that lithium garnet is not stable in water. However, there has been no report of the stability of the material in humid conditions at an elevated temperature, such as the environment in a furnace on a humid day. This is not usually a concern because at high temperatures, the relative humidity of the atmosphere is very low. The absolute humidity, though, can be high. An additional concern was that organics in the tape are converted to water and CO2 during binder burnout stage, increasing the humidity and providing another possible reactant.
It can be seen in
It can be seen in
During the burnout (or “presintering”) phase, the PVB and BBP are oxidized and are carried away by the flowing furnace gas. It is important to provide sufficient oxygen for these reactions to happen. It is also important to burn slowly enough to not disturb the packing of the LLCZN ceramic particles. This is also the stage where the PMMA breaks down and volatilizes. The burnout profiles most commonly used are listed below:
After the burnout stage, the furnace does not need to be cooled to room temperature. The furnace can continue to heat to the full sintering temperature, usually at a rate of 3° C./minute. Due to the small particle size, high surface area, and sharp angles of the particles, all sintering temperatures used in this procedure are significantly lower than literature for the same materials. The two most commonly used sintering profiles in our process are a high temperature, short time profile and a lower temperature, longer time. Each of these temperatures can be reached with traditional, low cost nichrome heating elements:
Lithium garnet is notoriously difficult to sinter into a dense body. Most examples of dense sintering in literature include the use of hot-pressing, a procedure not suited for device fabrication. Significant work went into developing a procedure that would allow densification of the garnet during sintering. The most important development in this pursuit is the milling procedure that produces the powder shown in
The atmosphere in the furnace during the burnout and the sintering stage must be controlled. Oxygen or dry air is used during the burnout stage to allow for oxidation of organics. After the burnout stage, the gas for the sintering stage is run to completely flush the furnace. During the sintering hold, the gas flow is shut off and the sintering gas is held to slow lithium loss. The gas is flowed again during cooling. The sintering stage has been demonstrated in oxygen and argon, though we have demonstrated that the most important factors are avoidance of CO2 and humidity. Because graphite does not fully burn out below about 850° C., tapes including graphite must use an oxidizing atmosphere in the sintering stage if all graphite is to be fully removed.
Many alkaline conducting ceramics contain volatile elements that can be lost at a high rate at these elevated temperatures, hindering sinterability, resulting in reduced phase purity and/or device performance. In order to reduce lithium loss, factors affecting the rate of lithium loss were investigated. After binder burnout, the garnet is heated to temperatures between 800-1200° C. for sintering, depending on composition, particle size, and desired sintering time. At high temperature, loss of lithium in the form of volatile side phases can cause loss of garnet phase. The use of controlled gas environments during sintering can prevent the formation of some lithium-containing side phases by removing the reactants commonly found in air such as N2 and CO2.
The results of this study also indicate that CO2 is especially damaging to the garnet and should be avoided. For this reason, binder burnout is performed in O2 to cause more rapid combustion, reducing the amount of time the CO2 combustion product is in close proximity to the garnet.
After sintering, the desired structure is complete and is stored in an argon-filled glovebox to protect the surface of the garnet from carbonate formation.
The following is an example of a ceramic ion-conducting structure with ordered structures. For increased surface area, grids can be printed. An SEM of a 10 layer print on top of a dense tape after sintering is shown in
The following is an example of electrical data obtained using ceramic ion-conducting structures of the present disclosure.
Cycling data. The pores of a triple layer garnet structure were filled with lithium metal which was cycled from one porous layer to the other and back at high rate. In
This is the expected resistance as calculated from the conductivity of the material and the thickness of the dense layer. This is shown in
The following describes SEM analysis of an example of an electrical cell comprising a ceramic ion-conducting structure of the present disclosure.
SEM of lithium in garnet pores. An SEM analysis of the disassembled cycled cell was performed (see
The following describes analysis of the flatness of ceramic ion-conducting structures of the present disclosure.
Flatness of fabricated structures. Flatness of the sintered structures is important to allow compact stacking and prevent breakage. To measure flatness, grid scans were taken using the Keyence LK-H082 Ultra High-Speed/High-Accuracy Laser Displacement Sensor attachment of UMERC's new nScrypt 3D printer, which is capable of measuring sample topology with resolution better than 20 um in the x and y directions and about 7 um in the z direction.
The first scan, shown as a colormap in
It can be seen in
P-V Error=Peak height−Valley height (Eqn. 1)
In order to obtain an accurate measure, the z height of the sample holder must be absolutely zeroed and leveled. In order to achieve this, we can subtract the trilayer data from the grid scan of the background and fit a curve to it. This curve is used to subtract the background from the trilayer data points. The fitting of the background data can be seen in
We fabricated flatter cells by applying more consistent pressure to the tops of the cells during sintering. For the first cell, shown on the left of
Although the present disclosure has been described with respect to one or more particular embodiments and/or examples, it will be understood that other embodiments and/or examples of the present disclosure may be made without departing from the scope of the present disclosure.
This application claims priority to U.S. Provisional Application No. 62/260,817, filed on Nov. 30, 2015, the disclosure of which is hereby incorporated by reference.
This invention was made with government support under contract no. DEAR0000384 awarded by the United States Department of Energy. The government has certain rights in the invention.
| Number | Date | Country | |
|---|---|---|---|
| 62260817 | Nov 2015 | US |
