Patent Application
20190372111
The present disclosure relates to electrochemically active materials, and more particularly to fluoride ion battery systems that include electrode materials with tailored structures and compositions to improve battery performance. More specifically, this disclosure relates to a fluoride shuttle battery and nanostructures of copper based cathode materials in the fluoride shuttle battery.
Metal nanoparticles are highly desirable for use in a number of applications including as catalysts, and as electrode materials for batteries. However, the use of metal nanoparticles may be limited by the system operating conditions or other factors.
F (fluoride) shuttle batteries are a novel and underexplored alternative next generation energy storage. Its energy density is much larger than lithium ion batteries, around four times in volumetric and two times at gravimetric densities. F-shuttle batteries offer lower cost and/or improved safety characteristics compared to lithium and lithium-ion batteries. Fluoride-ion batteries are electrochemical cells that operate via fluoride-mediated electrode reactions. For example, F− anions are shuttled between the cathode and the anode electrodes. During discharge, MeFx is reduced to Me (metal) or low valence MeFx and releases F− ions at the cathode side. Meanwhile, F− ions combine with metal to form MeFx and release electrons at the anode side. F-shuttle batteries can be manufactured as primary or secondary batteries.
Transition metal fluorides are usually used as cathode materials, and alkaline earth or rare-earth metals are used as anode materials.
There are two types of F-shuttle batteries, i.e., all-solid-state type and liquid type. Currently most of the research being conducted is focused on all-solid-state F-shuttle batteries, which may be rechargeable at elevated temperatures to some extent. However, slow reaction kinetics impose significant challenges to all-solid-state F-shuttle batteries. Fluoride-ion systems have been demonstrated in the solid state, for example, in U.S. Pat. No. 7,722,993 to Potanin, which describes an embodiment of a secondary electrochemical cell where fluoride ions are reversibly exchanged between anode and cathode electrodes during charge-discharge cycles, with these electrodes in contact with a solid-state fluoride-conducting electrolyte. Potanin describes solid state electrolytes containing fluorides of La, Ce or the compound fluorides based on them, together with alloying additives, such as fluoride/fluorides of alkaline-earth metals (CaF2, SrF2, BaF2) and/or fluorides of alkaline metals (LiF, KF, NaF) and/or alkaline metal chlorides (LiCl, KCl, NaCl), as well as a wide range of other compound fluorides. However, such electrochemical cells only operate usefully above room temperature (e.g. 150° C.) due to the limited conductivity of the solid-state electrolyte.
Reaction kinetics are good in the liquid type F-shuttle batteries. However, this type of F-shuttle battery still faces many challenges, such as the lack of good electrolytes and reversible cathode/anode materials at room temperature.
Recently, a F-shuttle battery assembled with heavy metals was reported to be reversible in an ionic liquid-based electrolyte at room temperature, where Bi was used as a cathode and Pb was used as an anode (K Okazaki, et al., Charge-Discharge Behavior Of Bismuth In A Liquid Electrolyte For Rechargeable Batteries Based On A Fluoride Shuttle, Acs Energy Letters, 2017, 2 1460-1464). However, the battery had a low voltage (˜0.2V) and a low capacity (maximum 0.15 mAh). Furthermore, Pb, which is known to be toxic and not environmental friendly, is used as anode in such a battery. Other attempts have also been made to provide fluoride ion-based electrochemical systems capable of using liquid electrolytes. For example, US 2011/0143219 A1 by Weiss et al. and U.S. Pat. No. 9,166,249 by Darolles et al. disclose fluoride-ion battery configurations that include a solvent-borne fluoride salt that is at least partially present in a dissolved state in the electrolyte. However, for many applications the chemical reactivity of the electrode materials with the liquid electrolyte is significant, and these liquid electrolyte systems do not provide sufficiently reliable high discharge and/or high capacity operation.
The following presents a simplified summary of one or more aspects of the present disclosure in order to provide a basic understanding of such aspects. This summary is not an extensive overview of all contemplated aspects and is intended to neither identify key or critical elements of all aspects nor delineate the scope of any or all aspects. Its purpose is to present some concepts of one or more aspects in a simplified form as a prelude to the more detailed description that is presented later.
In some embodiments, the present disclosure is directed to a fluoride shuttle battery which comprises a cathode, an anode, and an electrolyte between the cathode and the anode, wherein the cathode includes a cathode material, which comprises a metal nanostructure core and a shell layer surrounding the core.
These and other aspects of the invention will become more fully understood upon a review of the detailed description, which follows.
The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.
The detailed description set forth below in connection with the appended drawings is intended as a description of various configurations and is not intended to represent the only configurations in which the concepts described herein may be practiced. The detailed description includes specific details for the purpose of providing a thorough understanding of various concepts. However, it will be apparent to those skilled in the art that these concepts may be practiced without these specific details. In some instances, well known components are shown in block diagram form in order to avoid obscuring such concepts.
In general, the present disclosure is related to electrochemically active materials, and fluoride-ion battery systems that include electrode materials with tailored structures and compositions to improve battery performance. In some aspects, the present disclosure is related to core-shell nanoparticles, devices incorporating the core-shell nanoparticles, as well as methods of making and using the core-shell nanoparticles and devices including the core-shell nanoparticles.
As used herein, the core is not limited to particles, e.g., spherical particles, and also encompasses structures including, but not limited to, nanoparticles, nanotubes, nanowires, frames, flakes, nanoporous, sheets, thin films, and foams. In an embodiment, the size of the core material is determined either by electron conductivity or F− ion mobility. In an illustrative example, 20 nm may be the distance limit of F− ion penetration in the core material. If the path of either electron or F− is greater than 20 nm, resistance to this will prevent it. Accordingly, a spherical core particle having a diameter of less than or equal to 20 nm may be applied as the spherical particle has less than or equal to 20 nm pathway in all directions. Therefore, all or nearly all of the core material can be utilized, thereby reducing the weight and volume of the cathode. However, the core is not limited to spherical particles. Other core structures may be used that have a dimension that is greater than 20 nm, if it has, for example, a pathway of 20 nm or less in one direction. So while the spherical particle has less than or equal to 20 nm pathway in all directions, a flake (like a piece of paper, for example) may have very large distances in the x and y direction, but if diffusion/electron transport only occurs in the Z direction of 20 nm or less, since that is path of least resistance, it will dominate.
Primary and secondary electrochemical cells, such as batteries, utilizing fluoride ion charge carriers, active electrode materials, and suitable liquid electrolytes can provide an alternative to conventional state of the art lithium batteries and lithium ion batteries. Such fluoride-ion battery (FIB) systems can operate usefully at room temperature while utilizing fluoride anions carried in a liquid electrolyte as at least some of the charge carriers in an electrochemical cell. The FIB system has an anode and cathode physically separated from each other, but in common contact with a fluoride ion conducting electrolyte. The anode is typically a low potential element or compound, and can be a metal, metal fluoride, or intercalating composition. Similarly, the cathode can be element or composition, and can be a metal, metal fluoride, or intercalating composition that has a higher potential than the anode. Fluoride ions (F−) in the fluoride conducting electrolyte go from the cathode to the anode during discharge and from the anode to the cathode during the charge of the battery (
Transition metal fluorides are preferably used as cathode materials and alkaline earth or rare-earth metals are preferably used as anode materials. Examples of suitable anode and cathode metals are depicted in
During charge, the reverse reactions occur. For example, a FIB cell reaction based on fluoride anion transfer between Ca and Cu, both metals capable of forming metal fluorides, might be:
Discharge:
Ca+CuF2→CaF2+Cu
Charge:
CaF2+Cu→Ca+CuF2
Two major challenges exist to enable stable, reliable long-term cycling of FIB electrodes. Firstly, reversibility of the electrochemical reactions above is observed when the metal or metal fluoride active materials are nano-sized (i.e. at least one of the particle size dimensions is less than 1 μm). However, particles with such small dimensions have high surface energies and are often reactive with the electrolyte components (e.g. F−) to give undesirable side-reactions including “self-discharge” (i.e. a chemical reaction such as M+nF− →MFn that does not general electrical current). What is needed is formation of a coating, shell, layer or the like to encapsulate the active material particles while still permitting passage of F− ions when desired (i.e. during electrochemical charge or discharge) The encapsulating material can also protect the active materials from such side-reactions, enabling long-term cycling stability of these electrode materials.
Secondly, such electrochemical reactions are conversion processes, with the structure of the metal or metal fluoride being broken down during the electrochemical process and reformed as the metal fluoride or metal, respectively, during the process. This conversion process results in a significant volume change between charged and discharged states of the active material, as indicated by the examples given in Table 1 below:
Such significant volume changes limit usefulness of conformal protective coatings encapsulating an FIB electrode material particle, since one particular state of charge will not necessarily be conformal with the particle in a different state of charge, due to the volume changes. What is needed are compositions and processes that protect the electrode active material from side reactions with the electrolyte, allow ion conduction through an encapsulant, and have sufficient void space within the encapsulant and/or encapsulant expansion/contraction properties to accommodate the volume changes of the active material during charge and discharge without permitting direct contact between the active material and the electrolyte. In some embodiments, sufficient void space may be no void space. Such compositions and their preparation are outlined below.
As used herein, the term “about” is defined to being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment, the term “about” is defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.
In some embodiments as shown in
The metals or metal alloys used to form the core include, but are not limited to, iron nanoparticles, cobalt nanoparticles, nickel nanoparticles, copper nanoparticles, lead nanoparticles, and alkaline earth metal nanoparticles. In a preferred embodiment, the metal nanoparticles are selected from the group consisting of cobalt nanoparticles and copper nanoparticles. In another preferred embodiment, the metal nanoparticles are copper nanoparticles. The metals used to form the core may be synthesized by mixing a metal precursor solution with a reducing agent to form metal nanoparticles.
In some embodiments, the metal nanoparticles used to form the core may be synthesized in the presence of a stabilizer that prevents or otherwise inhibits oxidation of the metal nanoparticles during synthesis, and is readily removable from the metal nanoparticles prior to formation of the metal halide or metal oxyhalide shell thereon. For example, bulky polymers such as polyvinylpyrrolidone (molecular weight of 55,000 g/mol) used during metal nanoparticle synthesis inhibit oxidation of metal nanoparticles. However, such stabilizers are not readily removable from the metal nanoparticles following synthesis. Without being limited to any particular theory, residual stabilizer can form an additional layer between the core formed by the metal nanoparticles and the metal halide or oxyhalide shell that detracts from the performance of the core-shell nanoparticle in the desired system. For example, it is desirable to maintain the conductivity of core-shell nanoparticles used as electrode material in an F-Shuttle battery. However, core-shell materials including an additional layer of residual stabilizer between the core and the shell will likely result in an increased space between electrode materials; the additional layer of residual stabilizer and/or the resulting increased space may decrease the conductivity of the core-shell material. Without wishing to be bound to any particular theory, the additional layer of stabilizer may impede contact between the core and the shell to conduct fluoride ion, while the absence of the stabilizer may increase the likelihood of conducting fluoride ion from the core to the shell.
Therefore, a stabilizer may be used in the synthesis of the metal nanoparticles used to form the core that is readily removable therefrom to minimize the amount of stabilizer on the surface of the core prior to formation of the metal halide or metal oxyhalide shell directly thereon. In a non-limiting example, the one or more stabilizers that may be used in the synthesis of the metal nanoparticles includes a molecular weight (either individually or a weight average) of less than 1000 g/mol, optionally less than 500 g/mol, optionally less than 375 g/mol, and optionally less than 350 g/mol. Illustrative examples include hexadecyltrimethylammonium bromide (CTAB) with a molecular weight of 364 g/mol, citric acid with a molecular weight of 192 g/mol, and mixtures thereof.
In some embodiments, the shell of the core-shell nanoparticles may be formed by mixing isolated metal nanoparticles used to form the core with, for example, a metal salt solution and a halide salt solution that react to form the metal halide shell on the core. The shell is deposited directly on the metal core and may entirely surround the core as shown in
In some embodiments, the metal salt solution comprises two metal salts. In some such embodiments, one of the two metal salts is a barium salt. In some embodiments, the metal salt solution comprises a barium salt and a lanthanum salt. In some embodiments, the metal salt solution comprises barium nitrate and lanthanum nitrate. In some embodiments, the metal salt solution comprises barium nitrate and lanthanum nitrate in a ratio of about 1:10.
In other embodiments, the core (or electrode active material) may be separated from the shell (or encapsulant) by a void space. Compositions and processes according to such embodiments may protect the electrode active material from side reactions with the electrolyte, allow ion conduction through an encapsulant, and have sufficient void space within the encapsulant and/or encapsulant expansion/contraction properties to accommodate the volume changes of the active material during charge and discharge, without permitting direct contact between the active material and the electrolyte.
The terms core and electrode active material are used interchangeably herein. Similarly, the terms shell and encapsulant are used interchangeably herein.
In other embodiments, the present disclosure is directed to an electrode comprising the core-shell nanoparticles disclosed herein. All aspects and embodiments described with respect to the core-shell nanoparticles and methods of making thereof apply with equal force to the electrode. In a non-limiting example, the electrode is part of an F-shuttle battery system.
In some embodiments, the present disclosure is directed to an electrochemically active structure, comprising: a core comprising an active material, and a fluoride-containing shell at least partially surrounding the active material, wherein the fluoride-containing shell comprises a first metal and a second metal, and the first metal is barium. All aspects described with respect to the aforementioned embodiments apply to the present embodiment with equal force, and vice versa.
In some aspects, the active material comprises copper nanoparticles.
In some aspects, the fluoride-containing shell is directly attached to the core.
In some aspects, the second metal is lanthanum.
In some aspects, the barium and the lanthanum are present in a ratio of x to 1-x.
In some aspects, x is about 0.03 to about 0.15.
In some aspects, x is about 0.03.
In some embodiments, the present disclosure is directed to a method of making coated metal nanoparticles, the method comprising: a) providing a water/metal nanoparticle mixture; b) exposing the water/metal nanoparticle mixture to an inert atmosphere; and c) forming a fluoride-containing shell around a metal nanoparticle core, wherein the fluoride-containing shell comprises a first metal and a second metal, and the first metal is barium. All aspects described with respect to the aforementioned embodiments apply to the present embodiment with equal force, and vice versa.
In some aspects, the metal nanoparticles comprise copper nanoparticles.
In some aspects, the fluoride-containing shell is directly attached to the core.
In some aspects, the second metal is lanthanum.
In some aspects, the barium and the lanthanum are present in a ratio of x to 1-x.
In some aspects, x is about 0.03 to about 0.15.
In some aspects, the forming the fluoride-containing shell comprises adding a first metal salt, a second metal salt, and a fluoride-containing salt to the water/metal nanoparticle mixture to create a fluoride-containing shell around the metal nanoparticle core, wherein the first metal is a barium salt.
In some aspects, the second metal is a lanthanum salt.
In some aspects, the first metal salt is barium nitrate and the second metal salt is lanthanum nitrate.
In some aspects, the barium nitrate and the lanthanum nitrate are used in a molar ratio of about 1:10.
In some embodiments, the present disclosure is directed to an electrode comprising: a core comprising copper nanoparticles, and a fluoride containing shell at least partially surrounding the copper nanoparticles, wherein the fluoride-containing shell comprises barium and lanthanum in a ratio of x to 1-x. All aspects described with respect to the aforementioned embodiments apply to the present embodiment with equal force, and vice versa.
In some aspects, x is about 0.03 to about 0.15.
In some aspects, the present disclosure is directed to a fluoride shuttle battery comprising the electrode and a liquid electrolyte. Non-limiting examples of liquid electrolytes are described in U.S. patent application Ser. No. 15/228,876.
An “inert atmosphere” refers to a gaseous mixture that contains little or no oxygen and comprises inert or non-reactive gases or gases that have a high threshold before they react. An inert atmosphere may be, but is not limited to, molecular nitrogen or an inert gas, such as argon, or mixtures thereof.
A “reducing agent” is a substance that causes the reduction of another substance, while it itself is oxidized. Reduction refers to a gain of electron(s) by a chemical species, and oxidation refers to a loss of electron(s) by a chemical species.
A “metal salt” is an ionic complex wherein the cation(s) is(are) a positively charged metal ion(s) and the anion(s) is(are) a negatively charged ion(s). “Cation” refers to a positively charged ion, and “anion” refers to a negatively charged ion. In a “metal salt” according to the present disclosure, the anion may be any negatively charged chemical species. Metals in metal salts according to the present disclosure may include but are not limited to alkali metal salts, alkaline earth metal salts, transition metal salts, aluminum salts, or post-transition metal salts, and hydrates thereof.
“Alkali metal salts” are metal salts in which the metal ions are alkali metal ions, or metals in Group I of the periodic table of the elements, such as lithium, sodium, potassium, rubidium, cesium, or francium.
“Alkaline earth metal salts” are metal salts in which the metal ions are alkaline earth metal ions, or metals in Group II of the periodic table of the elements, such as beryllium, magnesium, calcium, strontium, barium, or radium.
“Transition metal salts” are metal salts in which the metal ions are transition metal ions, or metals in the d-block of the periodic table of the elements, including the lanthanide and actinide series. Transition metal salts include, but are not limited to, salts of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, actinium, thorium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium, and lawrencium.
“Post-transition metal salts” are metal salts in which the metal ions are post-transition metal ions, such as gallium, indium, tin, thallium, lead, bismuth, or polonium.
A “halide salt” is an ionic complex in which the anion(s) is(are) halide ion(s), including but not limited to fluoride ion(s), chloride ion(s), bromide ion(s), and iodide ion(s). A “fluoride salt” is an ionic complex in which the anion(s) is(are) fluoride ion(s). According to the present disclosure, the cation of the halide salt or the fluoride salt may be any positively charged chemical species.
A “metal fluoride” is an ionic complex in which the cation is one or more metal ion(s) and the anion(s) is(are) fluoride ion(s). According to some aspects of the present disclosure, the metal salt(s) and the fluoride salt react to create a metal fluoride shell around the metal nanoparticle core. Similarly, a “metal halide” is an ionic complex in which the cation is one or more metal ion(s) and the anion(s) is(are) halide ion(s).
A “fluoride-containing” salt is an ionic complex in which the anion(s) contain fluoride ion but are not limited to being solely fluoride. Instead, “fluoride-containing” salts include ionic complexes where the anion(s) contain fluoride itself in complex with other ions or atoms. “Fluoride-containing” salts suitable for use in aspects of the present disclosure include those known to persons of ordinary skill in the art, including, but not limited to, fluoride salts, non-metal fluoroanions such as tetrafluoroborate salts and hexafluorophosphate salts, and oxyfluoride salts. In some aspects of the present disclosure, the fluoride-containing salts may include quaternary ammonium fluorides and fluorinated organic compounds. According to some aspects of the present disclosure, the metal salt and the fluoride-containing salt react to create a fluoride-containing shell around the metal nanoparticle core.
The term “electrode” refers to an electrical conductor where ions and electrons are exchanged with an electrolyte and an outer circuit. “Positive electrode” and “cathode” are used synonymously in the present description and refer to the electrode having the higher electrode potential in an electrochemical cell (i.e. higher than (xi) the negative electrode). “Negative electrode” and “anode” are used synonymously in the present description and refer to the electrode having the lower electrode potential in an electrochemical cell (i.e. lower than the positive electrode). Cathodic reduction refers to a gain of electron(s) of a chemical species, and anodic oxidation refers to the loss of electron(s) of a chemical species. Positive and negative electrodes of the present invention may be provided in a range of useful configurations and form factors as known in the art of electrochemistry and battery science, including thin electrode designs, such as thin film electrode configurations. Electrodes are manufactured as known in the art, including as disclosed in, for example, U.S. Pat. No. 4,052,539, and Oxtoby et al., Principles of Modem Chemistry (1999), pp. 401-443.
The term “electrochemical cell” refers to devices and/or device components that convert chemical energy into electrical energy or vice versa. Electrochemical cells have two or more electrodes (e.g., positive and negative electrodes) and an electrolyte, wherein electrode reactions occurring at the electrode surfaces result in charge transfer processes. Electrochemical cells include, but are not limited to, primary batteries, secondary batteries, and electrolysis systems. General cell and/or battery construction is known in the art (see, e.g., Oxtoby et al., Principles of Modem Chemistry (1999), pp. 401-443).
“Electrolyte” refers to an ionic conductor which can be in the solid state, the liquid state (most common), or more rarely a gas (e.g., plasma).
The present disclosure is directed generally to an electrochemically active structure comprising a core and a shell at least partially surrounding the core, wherein the core comprises an electrochemically active material and the shell comprises a shell material. The present disclosure is also directed to a method of making the electrochemically active structure as described herein as well as electrochemical cells comprising the electrochemically active structure as described herein.
The electrochemically active structure as described herein comprises a core, wherein the core comprises an electrochemically active material. As used herein, the term “electrochemically active material” refers to a material capable of acting as an electrode in a primary or secondary electrochemical cell, for example, in an ion battery system. According to some aspects, the electrochemically active material may comprise a material capable of acting as a cathode in a liquid type fluoride (F) shuttle battery.
According to some aspects, the electrochemically active material according to the present disclosure may be a lightweight material which provides high capacity and high energy densities. Examples of electrochemically active materials useful according to the present disclosure include, but are not limited to, metals such as copper (Cu), iron (Fe), lead (Pb), bismuth (Bi), cobalt (Co), tin (Sn), lanthanum (La), cerium (Ce), calcium (Ca), magnesium (Mg), lithium (Li), alloys thereof, oxides, fluorides thereof, and combinations thereof. According to some aspects, the electrochemically active material comprises copper, copper (II) fluoride (CuF2), or a combination thereof.
According to some aspects, the electrochemically active material according to the present disclosure may be a lightweight material which provides high capacity and high energy densities. Examples of electrochemically active materials useful according to the present disclosure include, but are not limited to, metals such as copper (Cu), iron (Fe), lead (Pb), bismuth (Bi), cobalt (Co), tin (Sn), lanthanum (La), cerium (Ce), calcium (Ca), magnesium (Mg), lithium (Li), alloys thereof, oxides, fluorides thereof, and combinations thereof. According to some aspects, the electrochemically active material comprises copper, copper (II) fluoride (CuF2), or a combination thereof.
According to some aspects, the core may have a selected shape. For example, the core may comprise a nanoparticle (e.g., a spherical nanoparticle), nanotube, nanowire, frame, flake, nanoporous sheet, thin film, foam, or a combination thereof. According to some aspects, the size of the core may be determined either by electron conductivity or F− ion mobility. In an illustrative example, 20 nm may be the distance limit of F− ion penetration in the core material. If the path of either an electron or F− ion is greater than this distance limit (in this example, 20 nm), electron conductivity and/or F− ion mobility will be reduced or prevented. As such, according to some aspects, the core may comprise at least one dimension that is less than or equal to about the distance limit. For example, the core may comprise a spherical nanoparticle having a diameter of less than or equal to about the distance limit, as such a spherical nanoparticle will provide a pathway for an electron or F− ion that is less than or equal to about the distance limit in all directions. It should be understood that the core may have one or more dimensions that are greater than about the distance limit so long as it has a pathway of about the distance limit or less in at least one direction. For example, the core may comprise a flake having dimensions in the X and Y directions of greater than about the distance limit and a dimension in the Z direction of less than or equal to about the distance limit. According to some aspects, the distance limit may be about 20 nm, optionally about 30 nm, optionally about 40 nm, and optionally about 50 nm. According to some aspects, the distance limit may be between about 20 and 80 nm, optionally between about 30 and 70 nm, and optionally between about 40 and 60 nm. According to some aspects, the distance limit corresponds at least in part to certain aspects of the electrochemically active structure, for example, its shell. In particular, a shell having a relatively low ionic resistance will provide for a longer distance limit as F− ions are more easily able to traverse the shell to the core.
Examples of cores useful according to the present disclosure include, but are not limited to, a nanoparticle with a diameter of less than or equal to about the distance limit, a nanowire with at least one dimension of less than or equal to about the distance limit, a nanotube having a wall thickness of less than or equal to about the distance limit, a flake (e.g., a triangle, rectangle, square, circle, or oval) having a thickness of less than or equal to about the distance limit, a film having a thickness of less than or equal to about the distance limit, a foam having a pore wall thickness of less than or equal to about the distance limit, a sheet having a thickness of less than or equal to about the distance limit, a frame having a thickness of less than or equal to about the distance limit, a mesh having a wire thickness of less than or equal to about the distance limit, and combinations thereof.
According to some aspects, the core can include at least one dimension that is less than or equal to about 40 nm, optionally less than or equal to about 35 nm, optionally less than or equal to about 30 nm, optionally less than or equal to about 25 nm, optionally less than or equal to about 20 nm, optionally less than or equal to about 15 nm, and optionally less than or equal to about 10 nm. In some embodiments, the core can include at least one dimension from about 1-25 nm, optionally from about 1-20 nm, optionally from about 1-15 nm, optionally from about 1-10 nm, optionally from about 1-10 nm, and optionally from about 1-5 nm.
The electrochemically active structure further comprises a shell that at least partially surrounds the core. For example, the shell may surround the core such that at least about 50% of the core's surface area is covered by the shell, optionally at least about 60%, optionally at least about 70%, optionally at least about 80%, optionally at least about 90%, optionally at least about 95%, and optionally at least about 100%. According to some aspects, the molecular coverage of the shell on the core may be between about 1 and 100 nm−2, optionally between about 6 and 60 nm−2.
In some embodiments, the shell at least partially surrounding the core includes a thickness, wherein the ratio of thickness between the thickness of the metal nanostructure core and the thickness of the shell layer is from about 10:1 to about 1:1, optionally from about 9:1 to about 2:1, optionally from about 8:1 to about 3:1, optionally from about 7:1 to about 4:1, and optionally from about 6:1 to about 5:1.
According to some aspects, the shell at least partially surrounding the core has a thickness from about 1 nm to about 10 nm, optionally from about 2 nm to about 9 nm, optionally from about 3 nm to about 8 nm, optionally from about 4 nm to about 7 nm, optionally from about 5 nm to about 6 nm, and optionally about 5 nm.
According to some aspects, the shell at least partially surrounding the core has a thickness about 1 nm to 1 micron, optionally no more than 500 nm, optionally no more than 200 nm, optional no more than 100 nm, optionally no more than 50 nm, no more than 10 nm, optionally about no more than 9 nm, optionally about no more than 8 nm, optionally about no more than 7 nm, optionally about no more than 6 nm, optionally about no more than 5 nm, optionally about no more than 4 nm, optionally about no more than 3 nm, optionally about no more than 2 nm, and optionally about no more than 1 nm. Further wherein all ranges can optionally be described as about 1-500 nm, 1-200 nm, 1-100 nm, 1-50 nm, 1-10 nm, 1-5 nm, and 1-2 nm.
According to some aspects, a metal nanostructure core capable of forming a metal fluoride having a theoretical capacity in a liquid electrolyte is provided, the metal nanostructure core including at least one lesser dimension, and a shell at least partially surrounding the core, the shell including a thickness, wherein the thickness of the shell and the lesser dimension of the nanostructure core are provided in a ratio wherein the capacity of the material in the liquid electrolyte is from about 5% to 90%, optionally about 10% to 75%, optionally about 15% to 60%, optionally about 20% to 50%, optionally about 25% to 45%, and optionally about 30% to 40%, of the theoretical capacity of the metal fluoride.
According to some aspects, the metal nanostructure core has a thickness of no more than 30 nm, optionally no more than 25 nm, optionally no more than 20 nm, optionally no more than 20 nm, optionally no more than 15 nm, optionally no more than 10 nm, optionally no more than 8 nm, optionally no more than 6 nm, and optionally no more than 5 nm.
According to some aspects, the shell may comprise a shell material that is compatible with a liquid type F-shuttle battery. For example, the shell material may be selected such that dissolution of the core material into the liquid electrolyte of the liquid type F-shuttle battery during charge and/or discharge may be reduced or eliminated. The shell material may be selected to further provide adequate charge time. As used herein, the term “charge time” refers to the length of time required for a discharged liquid type F-shuttle battery electrode to fully charge, that is, the length of time required for F− in the fluoride conducting electrolyte to travel from the anode to the cathode during the charge of the battery. According to some aspects, the charge time may be between about 1 and 20 minutes, optionally been about 1 and 10 minutes, and optionally between about 3 and 5 minutes.
According to some aspects, the shell material may be selected in order to acceptably utilize the electrochemically active material comprised by the core during charge and/or discharge. It should be understood that utilization refers to the portion of the electrochemically active material that accepts F− ions during charging and/or the portion of the electrochemically active material that is reduced during discharging. According to some aspects, by selecting a shell material having a relatively low ionic resistance as described herein, at least about 50% of the electrochemically active material may be utilized during charge and/or discharge, optionally at least about 60%, optionally at least about 70%, optionally at least about 80%, optionally at least about 90%, and optionally at least about 100%.
According to some aspects, the shell material may comprise a “soft shell” material. As used herein, “soft” refers to a material as described herein, and in particular, a material that includes at least one material capable of self-assembly as described herein. Examples of soft shell materials include, but are not limited to, surfactants, certain polymers, a non-surfactant molecule having one or more specific functional groups, and combinations thereof. According to some aspects, the shell material may comprise an organic material, and in particular, an organic material that includes at least one material capable of self-assembly as described herein. Examples of organic shell materials include, but are not limited to, organic soft shell materials such as organic surfactants, organic or organic molecule-containing polymers, non-surfactant organic molecules having one or more specific functional groups, and combinations thereof.
According to some aspects, the specific functional groups as described herein may be selected from the group consisting of —COOH, —NH2, —COH, —OH, —SH, —PO3H, —SO3H, —CN, —NC, —R2P, —COO−, —COO—OOCR, ene-diol, —C≡N, —N≡N+(BF4−), -Sac, —SR, —SSR, —CSSH, —S2O3—Na+, —SeH, —SeSeR, —R2P═O, —PO32−/—P(O)(OH)2, —PO42−, —N≡C, —HC═CH2, —C≡CH, —SiH3, —SiCl3, —OCH2CH3, formula (I), formula (II), formula (III), and combinations thereof, wherein formula (I) is:
formula (II) is:
and formula (III) is:
wherein R′ and R″ are each independently an organic chain, particularly an organic chain capable of being partially or fully fluorinated, or an aromatic group, either alone or in combination with another R′ or R″, particularly an aromatic group substituted with one or more fluorophilic groups. Example organic chains useful for R′ and R″ include, but are not limited to, —(CF2)nCF3, (CH2CF2)nCF3, and (CF2CH2O)nCF3. Examples of functional groups according to formula (III) having at least one aromatic group are shown below as formula (IV):
and as formula (V):
It should be understood that each R′ and R″ may be the same as another R′ or R″, or may be different. According to some aspects, each R′ may show acceptable fluorination characteristics and/or each R″ may show acceptable stabilization characteristics. It should further be understood that the carbon atom having the unshared valence electrons in the carbene shown in formula (III) may be configured for attachment to one or more molecules comprised by the core, as described herein. Example materials comprising a functional group having formula (III) include those described in Smith et al., “N-Heterocyclic Carbenes in Materials Chemistry.” Chem. Rev., 2019, 119, 4986-5056, which is incorporated herein by reference in its entirety.
According to some aspects, the surfactant may comprise a surfactant useful for preparing the core as described herein, such as a surfactant having one or more functional groups selected from the group consisting of a polar head (e.g., a polar head comprising one or more of the specific functional groups as described herein), a carbon-containing tail (e.g., alkanes, alkynes, alkenes, and aromatic rings), a fluorocarbon-containing tail (e.g., aliphatic chains such as (CF2)n, (CHF)n, (CH2CF2)n, and (CH2OCH2CF2)n, and/or aromatic groups such as (C6-xFx-)n), and combinations thereof. Examples of surfactants useful according to the present disclosure may include, but are not limited to, oleylamine, oleic acid, tris(trimethylsilyl)silane, 3,3,4,4,5,5,6,6,7,7,8,8,9, 9,10,10,10-heptadecafluorodecanethiol, 2-(trifluoromethoxy)-benzenethiol, P-[12-(2,3,4, 5,6-pentafluorophenoxy)dodecyl]-Phosphonic acid, P-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10, 10-heptadecafluorodecyl)-Phosphonic acid, pentafluorobenzylphosphonic acid, perfluorododecanoic acid and combinations thereof. According to some aspects, the surfactant may comprise one or more surfactants useful in the production of the core.
According to some aspects, the certain polymers may comprise polymers capable of being formed via in-situ polymerization, particularly polymers capable of being formed via in-situ polymerization from their monomers or from shorter oligomeric species. Additionally or alternatively, the certain polymers may be capable of self-healing through hydrogen bonding. For example, the certain polymers may be capable of hydrogen bonding so as to autonomously and repeatedly “self-heal” imperfections in the shell, such as cracks and/or gaps that may result at least in part from volume expansion and/or contraction of the core during charge and discharge, as will be discussed in more detail below in regard to
According to some aspects, the shell may comprise one or more monolayers. According to some aspects, the shell may comprise one, two, three, or more monolayers. According to some aspects, each of the monolayers may be the same or different.
According to some aspects of the present disclosure, the shell material may comprise inorganic materials, such as metal salts. Examples of the metal salts used to form the shell include alkali metal salts, alkaline earth metal salts, and transition metal salts. In certain embodiments, the metal salt used to form the shell includes lanthanum salts, cerium salts, and magnesium salts. In certain embodiments, the metal salt used to form the shell is selected from the group consisting of lanthanum salts and cerium salts. In certain embodiments, the metal salt is a lanthanum salt. In a preferred embodiment, the lanthanum salt is lanthanum nitrate. In some embodiments, the halide salt is sodium fluoride. In a non-limiting example, the shell comprises a metal fluoride or metal oxyfluoride containing material (i.e. CeF3, CeOF, LaOF, LaF3). In some embodiments, the shell of the core-shell nanoparticles may be formed by mixing isolated metal nanoparticles used to form the core with, for example, a metal salt solution and a halide salt solution that react to form the metal halide shell on the core.
In some embodiments, the metal salt solution comprises two metal salts. In some such embodiments, one of the two metal salts is a barium salt. In some embodiments, the metal salt solution comprises a barium salt and a lanthanum salt. In some embodiments, the metal salt solution comprises barium nitrate and lanthanum nitrate. In some embodiments, the metal salt solution comprises barium nitrate and lanthanum nitrate in a ratio of about 1:10.
I. Cu Nanoparticles Encapsulated in LaF3 and Barium-Doped LaF3 Shells
A method of making Cu nanoparticles encapsulated in LaF3 or Barium-Doped LaF3 shells has been disclosed in U.S. patent application Ser. No. 16/013,739 (published as U.S. Pat. Appl. Pub. No. 2018/0301764), which is incorporated herein by reference in its entirety.
Core-shell nanoparticles with shells of the formula Cu@La0.97Ba0.03F2.97 are shown schematically in
Cu or CuF2 is useful as a cathode material for liquid type F-shuttle batteries. These materials are relatively inexpensive and are light weight, which provides a high capacity and a high energy density. Theoretical capacity of CuF2 is 528 mAh/g. However, pure Cu or CuF2 is easily dissolved into liquid electrolytes during charge and discharge. To solve this issue, a Cu core is coated with LaF3 or Ba doped LaF3 shell structures, which effectively prevents Cu from dissolution during charge/discharge cycling. For Cu@LaF3, for example, the LaF3 shell effectively prevents Cu from dissolution during charge/discharge. As a result, Cu can be converted to CuF2 during charge, and CuF2 can be reduced to Cu during discharge. With a Ba-doped shell (e.g., La0.97Ba0.03F2.97), the ionic conductivity of the shell can be improved 100 times compared to that of a LaF3 shell, i.e., the shell has low resistance. F− ions more easily pass through the shell so that more Cu can be fluorinated to CuF2 during charge. Capacity is doubled compared to the undoped LaF3 shell. (See
Due to poor electrical and ionic conductivities of many metal fluorides, it is necessary to design the structures of the metal fluorides to fully utilize the active materials and achieve their specific capacities and energy densities.
In one embodiment, for better utilization of the Cu/CuF2 electrode materials to achieve an energy density close to its theoretical capacity (i.e. 843.5 mAh/g for Cu and 528 mAh/g for CuF2), structural designs tailored to satisfy the requirement of no more than 20 nm thickness of Cu nanomaterials along at least one direction or one axis of the Cu nanostructure are preferred. Among these structures, Cu may be the active material having a LaF3 or BaxLa1-xF3-x coating/coverage in the range of ˜5-20 nm.
Examples of such Cu nanostructures include: nanoparticles, nanotubes, nanowires, nanoframes, nanoflakes, nano porous, sheets, thin films and the like. According to some aspects, such Cu nanostructures can comprise Cu thin films with a thickness no more than 20 nm. In some embodiments, such Cu nanostructures can comprise Cu Nanofoams With A Porous Wall Having A Thickness No More Than 20 nm. In some embodiments, such Cu nanostructures can comprise Cu mesh with a wire having a thickness no more than 20 nm.
(i) Cu Nanoparticles (“NP”).
A structural design of Cu core nanoparticles is illustrated in
NH4OH (0.5 mL, 14.5 M) was added to a stirring solution of CuCl2.2H2O (0.24 g, 1.4 mmol) and cetrimonium bromide (CTAB, 0.68 g, 1.87 mmol) in water (93 mL, DI) in an argon atmosphere at 23° C. Hydrazine hydrate (50-60%, 3 mL, 17.66 M) was added to a solution of CTAB (0.68 g, 1.87 mmol) and citric acid monohydrate (0.036 g, 0.18 mmol) in water (57 mL, DI). The hydrazine solution was immediately transferred to a 60 mL syringe and added over 5 minutes via a syringe pump to the Cu precursor solution. Once the addition of the hydrazine solution was complete the argon line was removed and the reaction was stirred open to air. Once exposed to air a solution of citric acid monohydrate (0.21 g, 1.0 mmol) in water (5 mL) was injected all at once. The mixture was then stirred for 1 hour, open to air. The Cu NP were isolated via centrifuge (12,000 rpm for 5 min.), the supernatant was discarded and the Cu NP were washed with EtOH (10 mL) twice. The product exhibited small, broad Cu peaks by XRD. See
The Cu NP (6 nm) obtained in Example 1 was isolated and washed once with water (20 mL). The Cu NP was re-dispersed in water (300 mL) and a solution of La(NO3)3 6H2O (0.43 g, 1.0 mmol) in water (60 mL) was added and the mixture was stirred (60 min.) in an argon atmosphere. The sample was isolated (12,000 rpm for 10 min) and re-dispersed in water (300 mL). To the stirring solution NaF (0.042 g, 1.0 mmol) in water (60 mL) was injected at 6 mL/min then stirred (60 min.) in an argon atmosphere. The sample was isolated via centrifuge (12,000 rpm for 10 min) and washed twice with EtOH (20 mL). XRD showed complete oxidation of the Cu core sample to Cu2O with a LaF3 shell. See
The Cu2O in the core nanoparticles obtained in Example 2 was effectively reduced to Cu by a mixture of H2 and N2 gases under heat treatment of 300° C. for six hours. The particle size of Cu NP increased during the reduction reaction. XRD spectra of 6 nm Cu core NP with a LaF3 shell after reduction reaction is shown in
(ii) Cu Nanowires (“NW”) Encapsulated in LaF3 or Ba-Doped LaF3 Shells (“Hard Shells”).
The structural design of Cu core nanowires is illustrated in
About 20 mg of Cu nanowires were re-dispersed in 50 ml toluene. A first portion of tetrabutylammonium bromide (0.322 g, 1.0 mmol) was added into the Cu nanowires toluene suspension. A solution of La(NO3)3 6H2O (0.866 g, 2.0 mmol) in water (50 mL) was injected at 5 mL/min into the toluene suspension. This mixture was stirred very rapidly for 2 hours. The water layer was removed via a separatory funnel and a second portion of tetrabutylammonium bromide (0.322 g, 1.0 mmol) was added to the toluene layer. A solution of NaF (0.084 g, 2.0 mmol) in water (50 mL) was injected at 5 mL/min into the stirring toluene suspension. This mixture was stirred very rapidly for additional 2 hours. The water layer was removed via separatory funnel and ethanol (20 mL) was added to distribute the product. The product was isolated via centrifuge (12,000 rpm for 10 min) then washed twice with EtOH (20 mL).
As set forth above, the two phase shell formation method can be applied to nanowires. However, the applications of the same coating method is not limited to nanowires or relevant applications. Even further the core material is not limited to copper. In one example, The coated structures may be used as a cathode material in a Fluoride Shuttle battery. In another example, the Fluoride Shuttle battery comprises a liquid electrolyte.
The XRD spectra of Cu nanowires, a small amount of Cu2O after shell formation, and the LaF3 shell of Cu nanowires are depicted in
In addition,
(iii) Cu Nanotubes.
The structural design of Cu nanotubes is illustrated in
(iv) Cu Nanoflakes.
Cu flakes may take many shapes, such as triangle, rectangle, square, circle, oval etc. The structure of Cu nanoflakes is illustrated in
(v) Cu Nanoframes.
The structural design of Cu nanoflakes is illustrated in
(vi) Cu Nanosheets with a Thickness No More than 20 nm.
The structural design of Cu nanosheets is illustrated in
In the present disclosure, the metal nanostructures suitable for making cathodic electrode is not limited to copper. As shown in
It should be understood that while
According to some aspects, the shell may be configured to accommodate the volume change of the electrochemically active material between charged and discharged states. For example,
Cu nanowires can be encapsulated in surfactant soft shells. The soft shells comprises at least one organic surfactant. Suitable organic surfactants comprise one or more specific functional group, which may be selected from the group consisting of —COOH, —NH2, —COH, —OH, —SH, —PO3H, —SO3H, —CN, —NC, —R2P, —COO−, —COO—OOCR, ene-diol, —C≡N, —N≡N+(BF4−), -Sac, —SR, —SSR, —CSSH, —S2O3−Na+, —SeH, —SeSeR, —R2P═O, —PO32-/—P(O)(OH)2, —PO42-, —N≡C, —HC═CH2, —C≡CH, —SiH3, —SiCl3, —OCH2CH3, formula (I), formula (II), formula (III), an alkane, an alkyne, an alkene, an aromatic ring, and combinations therefore,
wherein formula (I) is:
formula (II) is:
and formula (III) is:
wherein R′ and R″ are each independently an organic chain or an aromatic group, either alone or in combination with another R′ or R″. Examples of suitable surfactants include oleylamine, oleic acid, tris(trimethylsilyl)silane, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10, 10-heptadecafluorodecanethiol, 2-(trifluoromethoxy)-benzenethiol, P-[12-(2,3,4,5,6-pentafluorophenoxy)dodecyl]-Phosphonic acid, P-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)-Phosphonic acid, pentafluorobenzylphosphonic acid, perfluorododecanoic acid and combinations thereof. More specifically, the suitable surfactants are selected from oleylamine, oleic acid, tris(trimethylsilyl)silane, or a combination thereof. The structure of CuNW@soft shell is similar as that of
According to some aspects, the surfactant soft shells can comprise organic or organic molecule-containing polymers forming polymer shells; the structure of CuNW@soft shell comprising polymers is similar to that of
The method of synthesizing Cu nanowires has been reported in F Cui et al., Synthesis of Ultrathin Copper Nanowires Using Tris(trimethylsilyl)silane for High-Performance and Low-Haze Transparent Conductors, Nano Letters 2015, 15, 7610-7615, the entirety of which is incorporated herein by reference. In this example, a solution of CuCl2 2H2O (85 mg, 0.5 mmol) in oleylamine (5 g, 18.7 mmol) and oleic acid (0.1 g, 0.354 mmol) was sonicated in a glass vial until completely dissolved. Tris(trimethylsilyl)silane (0.5 g, 2.0 mmol) was added, and the mixture was heated up to 120° C. until the dark blue solution turned clear yellow. The mixture was heated further to 165° C. for 18 h. The Cu nanowires were isolated via centrifuge (12,000 rpm for 10 min.) and washed three times with toluene (10 mL). The XRD spectra and TEM images of the Cu nanowires produced in this example are illustrated in
A cathodic electrode was prepared using CuNW@soft shell nanomaterial of Example 5. The average cross-sectional diameter of CuNW core is about 20 nm. The voltage profile of the charge-discharge cycle of the CuNW@soft shell electrode is shown in
CuNW@soft shell electrode was further characterized by XRD and the experimental results are illustrated in
A series of cathodes having Cu nanostructures for F-shuttle batteries had been prepared. The Cu nanostructures used in the preparation of cathodes are CuNP@LaF3 with a core having an average diameter about 50 nm, CuNP@La0.97Ba0.03F2.97 with a core having an average diameter about 50 nm, CuNW@LaF3 with a core having an average cross-sectional diameter about 20 nm, and CuNW@soft shells with a core having an average cross-sectional diameter about 20 nm.
As shown in
Furthermore, the capacity delivery of cathodes in
While the aspects described herein have been described in conjunction with the example aspects outlined above, various alternatives, modifications, variations, improvements, and/or substantial equivalents, whether known or that are or may be presently unforeseen, may become apparent to those having at least ordinary skill in the art. Accordingly, the example aspects, as set forth above, are intended to be illustrative, not limiting. Various changes may be made without departing from the spirit and scope of the disclosure. Therefore, the disclosure is intended to embrace all known or later-developed alternatives, modifications, variations, improvements, and/or substantial equivalents.
Thus, the claims are not intended to be limited to the aspects shown herein, but are to be accorded the full scope consistent with the language of the claims, wherein reference to an element in the singular is not intended to mean “one and only one” unless specifically so stated, but rather “one or more.” All structural and functional equivalents to the elements of the various aspects described throughout this disclosure that are known or later come to be known to those of ordinary skill in the art are expressly incorporated herein by reference and are intended to be encompassed by the claims. Moreover, nothing disclosed herein is intended to be dedicated to the public regardless of whether such disclosure is explicitly recited in the claims. No claim element is to be construed as a means plus function unless the element is expressly recited using the phrase “means for.”
Further, the word “example” is used herein to mean “serving as an example, instance, or illustration.” Any aspect described herein as “example” is not necessarily to be construed as preferred or advantageous over other aspects. Unless specifically stated otherwise, the term “some” refers to one or more. Combinations such as “at least one of A, B, or C,” “at least one of A, B, and C,” and “A, B, C, or any combination thereof” include any combination of A, B, and/or C, and may include multiples of A, multiples of B, or multiples of C. Specifically, combinations such as “at least one of A, B, or C,” “at least one of A, B, and C,” and “A, B, C, or any combination thereof” may be A only, B only, C only, A and B, A and C, B and C, or A and B and C, where any such combinations may contain one or more member or members of A, B, or C. Nothing disclosed herein is intended to be dedicated to the public regardless of whether such disclosure is explicitly recited in the claims.
The examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how to make and use the present invention, and are not intended to limit the scope of what the inventors regard as their invention nor are they intended to represent that the experiments below are all or the only experiments performed. Efforts have been made to ensure accuracy with respect to numbers used (e.g. amounts, dimensions, etc.) but some experimental errors and deviations should be accounted for.
Moreover, all references throughout this application, for example patent documents including issued or granted patents or equivalents; patent application publications; and non-patent literature documents or other source material; are hereby incorporated by reference herein in their entireties, as though individually incorporated by reference.
This application claims priority to each of the following applications, and each of the following applications is hereby incorporated herein by reference in its entirety: U.S. Patent Application No. 62/687,653, entitled “Barium-Doped Composite Electrode Materials For Fluoride-Ion Electrochemical Cells,” filed Jun. 20, 2018; U.S. patent application Ser. No. 16/013,739, entitled “Barium-Doped Composite Electrode Materials For Fluoride-Ion Electrochemical Cells,” filed Jun. 20, 2018, which claims priority to U.S. Patent Application No. 62/676,693, entitled “Composite Electrode Materials for Fluoride-Ion Electrochemical Cells,” filed May 25, 2018; U.S. patent application Ser. No. 15/844,079, entitled “Composite Electrode Materials for Fluoride-Ion Electrochemical Cells,” filed Dec. 15, 2017, which claims priority to U.S. Patent Application No. 62/434,611, entitled “Composite Electrode Materials for Fluoride-Ion Electrochemical Cells,” filed Dec. 15, 2016; U.S. Patent Application No. 62/453,295, entitled “Core Shell,” filed Feb. 1, 2017; U.S. Provisional Application No. 62/775,748 filed Dec. 5, 2018; and U.S. patent application Ser. No. 16/444,854 filed Jun. 18, 2019 (attorney docket H1182950US02, 037110.01444).
This invention was made with government support under Grant No. 80NM0018D004 awarded by NASA Jet Propulsion Laboratory (JPL). The government has certain rights in the invention.
| Number | Date | Country | |
|---|---|---|---|
| 62687653 | Jun 2018 | US | |
| 62775748 | Dec 2018 | US | |
| 62676693 | May 2018 | US | |
| 62453295 | Feb 2017 | US | |
| 62434611 | Dec 2016 | US | |
| 62775748 | Dec 2018 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 16013739 | Jun 2018 | US |
| Child | 16445022 | US | |
| Parent | 15844079 | Dec 2017 | US |
| Child | 16013739 | US | |
| Parent | 16444854 | Jun 2019 | US |
| Child | 15844079 | US |
